Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
CHEMISTRY
for JEE MAIN
with BOARDS SCORE BOOSTER
So
lly
Fu ed
lv
F
F
F
F
F
JEE Main 2014-15 Solved Papers
Key Concepts with Illustrations
4 levels of Exercises
1200+Questions based on NCERT
1500+Past Competitive Exam MCQ's
F 3500+ Practice MCQ's for JEE Main
F Aligned as per Class 11 & 12 NCERT
• Head Office : B-32, Shivalik Main Road, Malviya Nagar, New Delhi-110017
• Sales Office : B-48, Shivalik Main Road, Malviya Nagar, New Delhi-110017
Tel. : 011-26691021 / 26691713
DISHA PUBLICATION
ALL RIGHTS RESERVED
© Copyright Author
6. Thermodynamics 145-178
Terminology used in thermodynamics; Internal energy and its transfer; Processes and their types; Thermodynamic equilibrium; First law of
thermodynamics; Factros affecting DH; Relation between DH and DE; Applications of first law; Hess’s law of constant heat summation;
Heat capacity of system; Entropy; Criteria for feasibility of a process; Zeroth law of thermodynamics; Third law of thermodynamics;
Clapeyron Clausius equation and its applications; Heat engine and its efficiency; Carnot cycle; Resonance energy; Calorific value; Types
of reactions and corresponding enthalpy changes; Laws of thermochemistry.
9. Hydrogen 257-270
Preparation and manufacturing of hydrogen and its properties; Different forms of hydrogen; Hydrides; Hydrogen peroxide; Water; Hydrates.
1. Which compound would give 5 - keto - 2 - methylhexanal 6. Which of the following compounds is not colored yellow ?
upon ozonolysis ? (a) (NH4)3 [As(Mo3O10)4 ] (b) BaCrO4
(c) Zn2[Fe(CN)6] (d) K3[Co(NO2)6]
CH3
7. Which of the following is the energy of a possible excited
CH3
state of hydrogen ?
H3C (a) –3.4 eV (b) +6.8 eV
(a) (b) (c) +13.6 eV (d) –6.8 eV
CH3 8. Which of the following compounds is not an antacid ?
(a) Phenelzine (b) Ranitidine
CH3 (c) Aluminium hydroxide (d) Cimetidine
CH3 9. The ionic radii (in Å) of N3–, O2– and F– are respectively :
(a) 1.71, 1.40 and 1.36 (b) 1.71, 1.36 and 1.40
(c) CH3 (d) (c) 1.36, 1.40 and 1.71 (d) 1.36, 1.71 and 1.40
10. In the context of the Hall - Heroult process for the extraction
CH3 of Al, which of the following statements is false ?
2. Which of the vitamins given below is water soluble ? (a) Al3+ is reduced at the cathode to form Al
(a) Vitamin E (b) Vitamin K (b) Na3AlF6 serves as the electrolyte
(c) Vitamin C (d) Vitamin D (c) CO and CO2 are produced in this process
3. Which one of the following alkaline earth metal sulphates (d) Al2O3 is mixed with CaF2 which lowers the melting point
has its hydration enthalpy greater than its lattice enthalpy ? of the mixture and brings conductivity
(a) BaSO4 (b) SrSO4 11. In the following sequence of reactions :
(c) CaSO4 (d) BeSO4 KMnO SOCl H / Pd
Toluene ¾¾¾¾
4
® A ¾¾¾
2
® B ¾¾¾®
2
C
4. In the reaction BaSO 4
the product C is :
NH2
(a) C6H5CH2OH (b) C6H5CHO
(c) C6H5COOH (d) C6H5CH3
¾¾¾¾¾
NaNO /HCl
2
® D ¾¾¾¾¾
CuCN/KCN
® E + N2 12. Higher order (>3) reactions are rare due to :
0–5° C D
(a) shifting of equilibrium towards reactants due to elastic
collisions
CH3 (b) loss of active species on collision
(c) low probability of simultaneous collision of all the
the product E is : reacting species
CH3 (d) increase in entropy and activation energy as more
CN
molecules are involved
13. Which of the following compounds will exhibit geometrical
(a) (b) isomerism ?
(a) 2 - Phenyl -1 - butene
(b) 1, 1 - Diphenyl - 1 - propene
CH3
(c) 1 - Phenyl - 2 - butene
COOH (d) 3 - Phenyl -1 - butene
14. Match the catalysts to the correct processes :
Catalyst Process
(c) (d) H3C CH3 (A) TiCl4 (i) Wacker process
(B) PdCl2 (ii) Ziegler - Natta
polymerization
CH3
(C) CuCl2 (iii) Contact process
5. Sodium metal crystallizes in a body centred cubic lattice with (D) V2O5 (iv) Deacon's process
a unit cell edge of 4.29Å. The radius of sodium atom is (a) (A) - (ii), (B) - (iii), (C) - (iv), (D) - (i)
approximately : (b) (A) - (iii), (B) - (i), (C) - (ii), (D) - (iv)
(a) 5.72Å (b) 0.93Å (c) (A) - (iii), (B) - (ii), (C) - (iv), (D) - (i)
(c) 1.86Å (d) 3.22Å (d) (A) - (ii), (B) - (i), (C) - (iv), (D) - (iii)
2 CHEMISTRY
15. The intermolecular interaction that is dependent on the 24. Which among the following is the most reactive ?
inverse cube of distance between the molecules is : (a) I2 (b) IC1
(a) London force (b) hydrogen bond (c) Cl2 (d) Br2
(c) ion - ion interaction (d) ion - dipole interaction 25. The standard Gibbs energy change at 300 K for the reaction
16. The molecular formula of a commercial resin used for
B + C is 2494.2 J. At a given time, the composition
2A
exchanging ions in water softening is C8H7SO3– Na+ (Mol.
wt. 206. What would be the maximum uptake of Ca2 + ions by
the resin when expressed in mole per gram resin ? 1 1
of the reaction mixture is [A] = , [B] = 2 and [C] = . The
2 2
2 1 reaction proceeds in the : [R = 8.314 J/K/mol, e = 2.718]
(a) (b)
309 412 (a) forward direction because Q < Kc
1 1 (b) reverse direction because Q < Kc
(c) (d) (c) forward direction because Q > Kc
103 206
17. Two Faraday of electricity is passed through a solution of (d) reverse direction because Q > Kc
CuSO4. The mass of copper deposited at the cathode is 26. Assertion: Nitrogen and oxygen are the main components in
(at. mass of Cu = 63.5 amu) the atmosphere but these do not react to form oxides of
nitrogen.
(a) 2g (b) 127 g
Reason: The reaction between nitrogen and oxygen requires
(c) 0 g (d) 63.5 g
high temperature.
18. The number of geometric isomers that can exist for square
(a) The assertion is incorrect, but the reason is correct
planar complex [Pt (Cl) (py) (NH3 ) (NH2 OH)] + is
(py = pyridine) : (b) Both the assertion and reason are incorrect
(a) 4 (b) 6 (c) Both assertion and reason are correct, and the reason is
the correct explanation for the assertion
(c) 2 (d) 3
(d) Both assertion and reason are correct, but the reason is
19. In Carius method of estimation of halogens, 250 mg of an
not the correct explanation for the assertion
organic compound gave 141 mg of AgBr. The percentage of
bromine in the compound is : 27. Which one has the highest boiling point ?
(at. mass Ag =108; Br = 80) (a) Kr (b) Xe
(a) 48 (b) 60 (c) He (d) Ne
(c) 24 (d) 36 28. Which polymer is used in the manufacture of paints and
lacquers ?
20. The color of KMnO4 is due to :
(a) Polypropene (b) Polyvinyl chloride
(a) L ® M charge transfer transition
(c) Bakelite (d) Glyptal
(b) s - s* transition
29. The following reaction is performed at 298 K.
(c) M ® L charge transfer transition
(d) d – d transition 2NO (g)
2NO(g) + O2(g) 2
21. The synthesis of alkyl fluorides is best accomplished by :
The standard free energy of formation of NO(g) is 86.6 kj/mol
(a) Finkelstein reaction (b) Swarts reaction
at 298 K. What is the standard free energy of formation of
(c) Free radical fluorination (d) Sandmeyer's reaction
NO2(g) at 298 K? (Kp = 1.6 × 1012)
22. 3 g of activated charcoal was added to 50 mL of acetic acid
solution (0.06N) in a flask. After an hour it was filtered and ln (1.6 ´ 1012 )
the strength of the filtrate was found to be 0.042 N. The (a) 86600 –
R (298)
amount of acetic acid adsorbed (per gram of charcoal) is :
(b) 0.5[2 × 86,600 – R(298) ln(1.6 × 1012)]
(a) 42 mg (b) 54 mg
(c) R(298) ln(1.6 × 1012) – 86600
(c) 18 mg (d) 36 mg
(d) 86600 + R(298) ln(1.6 × l012)
23. The vapour pressure of acetone at 20°C is 185 torr. When 1.2
g of a non-volatile substance was dissolved in 100 g of 30. From the following statements regarding H2O2, choose the
acetone at 20°C, its vapour pressure was 183 torr. The molar incorrect statement :
mass (g mol–1) of the substance is : (a) It has to be stored in plastic or wax lined glass bottles in
(a) 128 (b) 488 dark
(c) 32 (d) 64 (b) It has to be kept away from dust
(c) It can act only as an oxidizing agent
(d) It decomposes on exposure to light
JEE MAIN 2015 Solved Paper 3
SOLUTIONS
1. (d) When 1, 3-dimethylcyclopentene is heated with ozone 10. (b) In the metallurgy of aluminium, purified Al2O3 is mixed
and then with zinc and acetic acid, oxidative cleavage with Na3AlF6 or CaF2 which lowers the melting point
leads to keto - aldehyde. of the mix and brings conductivity.
11. (b)
CH3 CH3
O CH3 COOH COCl CHO
1O - 78° C
¾ ¾ ¾3¾ ¾ ¾ ¾ ® O C–H
2 - Zn- CH 3 COOH KMnO4 SOCl2 H2/Pd
BaSO 4
CH3 CH3
(A) (B) (C)
O O
|| || Rosenmund’s
CH3 — C— CH 2 — CH 2 — CH— C— H reaction
|
CH3 12. (c) Reactions of higher order (>3) are very rare due to very
less chances of many molecules to undergo effective
5- keto – 2 – methylhexanal collisions.
2. (c) Water-soluble vitamins dissolve in water and are not
stored by the body. The water soluble vitamins include H
|
the vitamin B-complex group and vitamin C.
13. (c) H3C — C = CH — CH 2
3. (d) In alkaline earth metals, ionic size increases down the |
group. The lattice energy remains constant because Ph
sulphate ion is so large, so that small change in cationic
size does not make any difference. On moving down 1- Phenyl-2-butene the two groups around each of the
the group the degree of hydration of metal ions doubly bonded carbon
decreases very much leading to decrease in solubility. Because, all are different. This compound can show
cis-and trans-isomerism.
\ BeSO 4 > MgSO 4 > CaSO 4 > SrSO 4 > BaSO 4
14. (d) (A) - (ii), (B) - (i), (C) - (iv), (D) - (iii)
4. (a) 15. (b) Hydrogen bond is a type of strong electrostatic dipole-
+ – dipole interaction and dependent on the inverse cube
NH2 N = NCl CN of distance between the molecular ion-dipole
1
¾ NaNO
¾¾¾ 2 /HCl
¾¾ ® ¾ CuCN/KCN
¾ ¾ ¾ ¾® interaction µ .
0 - 5° C D r3
16. (b) 2 mole of water softner require 1 mole of Ca 2+ ion
CH3 CH3 CH3
1
5. (c) In bcc the atoms touch along body diagonal So, 1 mole of water softner require mole of Ca2+ ion
2
\ 2r + 2r = 3a
1 1
Thus, = mol / g will be maximum uptake
3a 3 ´ 4.29 2 ´ 206 412
\ r= = = 1.857Å
4 4 17. (d) Cu 2+ + 2e – ¾¾ ® Cu
6. (c)
2F i.e. 2 × 96500 C deposit Cu = 1 mol = 63.5 g
–13.6Z2 18. (d) Square planar complexes of type M[ABCD] form three
7. (a) Total energy = eV isomers. Their position may be obtained by fixing the
n2 position of one ligand and placing at the trans position
where n = 2, 3, 4 .... any one of the remaining three ligands one by one.
Putting n = 2
HOH2N Cl HOH2N NH3
-13.6
ET = = -3.4eV
4
8. (a) Phenelzine is an antidepressant, while others are Pt Pt
antacids.
9. (a) For isoelectronic species, size of anion increases as
negative charge increases. Thus the correct order is py NH3 py Cl
trans cis
N 3- > O 2 - > F -
(1.71) (1.40) (1.36)
4 CHEMISTRY
HOH2N where w1, M1 = mass in g and mol. mass of solvent
NH3 w2, M2 = mass in g and mol. mass of solute
Let M2 = x
Pt p° = 185 torr
ps = 183 torr
CH 3Br + AgF ¾¾
® CH 3 F + AgBr 2494.2 J
Þ log KC = –
2.303 ´ 8.314 J / K / mol ´ 300 K
2CH3CH 2 Cl + Hg 2 F2 ¾¾ ® 2CH 3CH 2 F + Hg 2Cl 2 Þ log KC = – 0.4341
22. (c) Let the weight of acetic acid initially be w1 in 50 ml of KC = 0.37
0.060 N solution. Q > KC.
w 1 ´ 1000 26. (c) Nitrogen and oxgen in air do not react to form oxides of
Let the N = (Normality = 0.06 N) nitrogen in atmosphere because the reaction between
M.wt . ´ 50 nitrogen and oxygen requires high temperature.
w1 ´ 1000 27. (b) Xe. As we move down the group, the melting and boiling
0.06 = points show a regular increase due to corresponding
60 ´ 50
increase in the magnitude of their van der waal forces of
0.06 ´ 60 ´ 50 attraction as the size of the atom increases.
Þ w1 = = 0.18 g = 180 mg.
1000 28. (d) Glyptal is used in the manufacture of paints and
After an hour, the strength of acetic acid = 0.042 N lacquers.
so, let the weight of acetic acid be w2 29. (b) DG°NO(g) = 86.6k J/mol = 86600 J/mol
w ´1000 G° NO2 (g) = x J/mol
N= 2
60 ´ 50 T = 298, KP = 1.6 × 1012
w ´ 1000 DG° = – RT ln KP
0.042 = 2 Given equation,
3000
Þ w2 = 0.126 g = 126 mg 2NO (g)
2NO(g) + O2 (g) 2
So amount of acetic acid adsorbed per 3g
= 180 – 126 mg = 54 mg \ 2DG°NO – 2DG°NO = – R (298) ln (1.6 × 1012)
2
Amount of acetic acid adsorbed per g 2DG°NO – 2 × 86600 = – R (298) ln (1.6 × 1012)
2
2DG°NO = 2 × 86600 – R (298) ln (1.6 × 1012)
54 2
= = 18 mg 1
3 DG°NO = [2 × 86600 – R(298) ln (1.6 × 1012]
23. (d) Using relation, 22
= 0.5 [2 × 86600 – R (298) ln (1.6 × 1012)]
p° - ps w 2 M1
= 30. (c) H 2O2 has oxidizing and reducing properties both.
ps w1M 2
JEE MAIN 2014 CHEMISTRY
(Held on 6th April-2014)
1. The correct set of four quantum numbers for the valence 7. The equivalent conductance of NaCl at concentration C and
electrons of rubidium atom (Z = 37) is: at infinite dilution are lC and l¥ , respectively. The correct
1 1
(a) 5, 0, 0, + (b) 5,1, 0, + relationship between lC and l¥ is given as:
2 2
(Where the constant B is positive)
1 1
(c) 5,1,1, + (d) 5, 0,1, + (a) lC = l ¥ + ( B ) C (b) lC = l ¥ - ( B ) C
2 2
2. If Z is a compressibility factor, van der Waals equation at low
pressure can be written as: (c) lC = l¥ - ( B ) C (d) lC = l¥ + ( B ) C
C2 H5OH ( l ) + 3O2 ( g ) ¾¾
® 2CO2 ( g ) + 3H 2 O ( l ) ,
the amount of heat produced as measured in bomb calorimeter, The rate law for the formation of C is:
is 1364.47 kJ mol–1 at 25ºC. Assuming ideality the enthalpy dc dc
= k [ A][ B ] = k [ A] [ B ]
2
( )
2 Mn3+ + e - ® Mn 2+ ; E 0 = +1.51V
(b) K2Cr2O7
(c) CrO3
The E0 for 3Mn 2 + ® Mn + 2Mn 3+ will be: (d) PCC (Pyridinium Chlorochromate)
24. The major organic compound formed by the raction of
(a) –2.69 V; the reaction will not occur
1, 1, 1-trichloroethane with silver powder is:
(b) –2.69 V; the reaction will occur
(a) Acetylene (b) Ethene
(c) –0.33 V; the reaction will not occur
(d) –0.33 V; the reaction will occur (c) 2 - Butyne (d) 2 - Butene
JEE MAIN 2014 SOLVED PAPER 2014-3
25. Sodium phenoxide when heated with CO2 under pressure at 27. For which of the following molecule significant m ¹ 0?
125ºC yields a product which on acetylation produces C.
CI CN
ONa 125° H+
+ CO 2 ¾¾¾¾ ®B ¾¾¾® C
5 Atm Ac2 O
(i) (ii)
The major product C would be
OCOCH3 OH CI CN
COOH COCH3
(a) (b) OH SH
OH OCOCH3
OH SH
COOCH3 (a) Only (i) (b) (i) and (ii)
(c) (d)
COOH (c) Only (iii) (d) (iii) and (iv)
28. Which one is classified as a condensation polymer?
26. Considering the basic strength of amines in aqueous solution,
which one has the smallest pKb value? (a) Dacron (b) Neoprene
(a) (CH3)2NH (b) CH3NH2 (c) Teflon (d) Acrylonitrile
(c) (CH3)3N (d) C6H5NH2 29. Which one of the following bases is not present in DNA?
(a) Quinoline (b) Adenine
(c) Cytosine (d) Thymine
30. In the reaction,
LiAH PCl Alc.KOH
CH 3 COOH ¾¾¾¾
4 ® A ¾¾¾
5 ® B ¾¾¾¾® C,
SOLUTIONS
1. (a) The electronic configuration of Rubidium (Rb = 37) is
1.4 ´ meq. of acid
1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 10 4s 2 4 p 6 5s1 4. (b) % of N =
mass of organic compound
Since last electron enters in 5s orbital
1 M
Hence n = 5, l = 0, m = 0, s = ± meq. of H2SO4 = 60´ ´ 2 = 12
2 10
PV M
2. (b) Compressibility factor ( Z ) = meq. of NaOH = 20´ = 2
RT 10
(For one mole of real gas)
van der Waals equation \ meq. of acid consumed = 12 – 2 = 10
a 1.4 ´ 10
(P + )(V - b) = RT \ % of N = = 10%
2 1.4
V
At low pressure, volume is very large and hence 5. (a) Given for 0.2 M solution
correction term b can be neglected in comparison to
R = 50 W
very large volume of V.
i.e. V - b » V k = 1.4 S m–1 = 1.4 × 10–2 S cm–1
æ a ö l 1 l
Now, R = r = ´
çè P + 2 ÷ø V = RT a k a
V
a l
PV + = RT Þ = R ´ k = 50 ´1.4 ´ 10-2
V a
a For 0.5 M solution
PV = RT -
V R = 280 W
PV a k =?
= 1-
RT VRT
l
= 50 ´ 1.4 ´ 10-2
a a
Hence, Z = 1 -
VRT
l 1 l
Þ R=r = ´
3. (c) a k a
Cl – Cl –
1
Cl – Cl Þ k= ´ 50 ´ 1.4 ´ 10 -2
280
Cs+ =
1
´ 70 ´ 10-2 = 2.5 × 10–3 S cm–1
280
1 O
9. (b) SO3 (g)
SO 2 (g) + O 2 (g)
2
For a given metal ion, weak field ligands create a complex
x with smaller D, which will absorbs light of longer l and
K P = K C ( RT )
thus lower frequency. Conservely, stronger field ligands
create a larger D, absorb light of shorter l and thus
where x = Dng = number of gaseous moles in product
higher v i.e. higher energy.
– number of gaseous moles in reactant
Red < Yellow < Green < Blue
l = 650 nm 570 nm 490 nm 450 nm
æ 1ö 3 1
= 1 - ç1 + ÷ = 1 - = - So order of ligand strength is
è 2 ø 2 2
L1 < L3 < L2 < L4
d [C ] 14. (a) Nitric oxide is paramagnetic in the gaseous state
10. (d) Let rate of reaction = = k[A]x [B]y because of the presence of one unpaired electron in its
t
outermost shell.
Now from the given data
The electronic configuration of NO is
1.2 × 10 – 3 = k [0.1]x[0.1]y .....(i)
1.2 × 10 – 3 = k [0.1]x[0.2]y .....(ii) s12s s1*2s s 22 s s*2 2 2 2 *1
2 s s 2 p p 2 p x = p2 p y p 2 p x
z
2.4 × 10 – 3 = k [0.2]x[0.1]y .....(iii) 15. (d) The reducing agent loses electron during redox
Dividing equation (i) by (ii) reaction i.e. oxidises itself.
-1 -2
1.2 ´10-3 k[0.1]x [0.1] y (a) H 2O 2 + 2H + + 2e - ¾¾
® 2H 2 O (Re d.)
Þ =
1.2 ´10-3 k [0.1]x [0.2] y
-1 0
We find, y = 0
(b) ® O 2 + 2H + + 2e- (Ox.)
H 2O 2 ¾¾
Now dividing equation (i) by (iii)
-1 -2
1.2 ´10-3 k[0.1]x [0.1] y (c) H 2O 2 + 2e - ¾¾
® 2 OH - (Re d.)
Þ =
2.4 ´10 -3 k [0.2] x [0.1] y
We find, x = 1 0
(d) H 2O-2 1 + 2OH - ¾¾
® O 2 + H 2 O + 2e - (Ox.)
d [C ]
Hence = k[ A]1 [ B ]0
dt
2014-6 CHEMISTRY
16. (b) CsI3 dissociates as
CsI3 ® Cs+ + I3– Cl
|
w 24. (c) 2Cl - C - CH3 + 6Ag
17. (b) Number of moles of O 2 = |
32 Cl
4w w
Number of moles of N 2 = = 1, 1, 1-trichloroethane
28 7
¾¾
® CH 3C º CCH 3 + 6AgCl
\ Ratio = w : w = 7 : 32
32 7 2-butyne
3Mn 2+ ® Mn + + 2Mn 3+ ;
OH
H SO
0
E = EOx. + ERed. = – 1.18 + (– 1.51) = – 2.69 V ¾¾¾¾
2 4®
COOH
(–ve value of EMF (i.e. DG = +ve) shows that the
Salicylic acid
reaction is non-spontaneous)
19. (c) In equation (i) Fe2(SO4)3 and in equation (ii) Fe2(SO4)3
on decomposing will form oxide instead of Fe. (CH 3 CO) 2 O
The correct sequence of reactions is
O ,heat Co,600° C
Fe ¾¾¾¾
2 ® Fe3O 4 ¾¾¾¾¾ ®
O
D ||
Fe 2 (SO 4 )3 ¾¾® Fe O - C - CH3
+ CH3COOH
20. (b) The complex [CoCl(NH3 )5 ]+ decomposes under
COOH
acidic medium, so Aspirin
(Acetyl Salicylate)
[CoCl(NH3 )5 ]+ + 5H + ¾¾
® Co 2+ + 5NH 4 + + Cl -
21. (b) Steric congestion around the carbon atom undergoing 26. (a) Arylamines are less basic than alkyl amines and even
the inversion process will slow down the SN2 reaction, ammonia. This is due to resonance. In aryl amines the
hence less congestion faster will the reaction. So, the lone pair of electrons on N is partly shared with the
order is ring and is thus less available for sharing with a proton.
CH3Cl > (CH3)CH2 – Cl > (CH3)2CH – Cl > (CH3)3CCl In alkylamines, the electron releasing alkyl group
22. (d) R – CH2 – NH2 + CHCl3 + 3KOH (alc) ¾¾
® increases the electron density on nitrogen atom and
Carbyl amine reaction thus also increases the ability of amine for protonation.
R – CH2 – NC + 3KCl + 3H2O Hence more the no. of alkyl groups higher should be
Alkyl isocynide
the basicity of amine. But a slight discrepancy occurs
in case of trimethyl amines due to steric effect. Hence
23. (d) An excellent reagent for oxidation of 1° alcohols to
the correct order is
aldehydes is PCC.
PCC
(CH3 )2 NH > CH3 NH 2 > (CH3 )3 N > C 6 H5 NH 2
R - CH 2 - OH ¾¾¾
® R - CHO
JEE MAIN 2014 SOLVED PAPER 2014-7
27. (d)
O O
H
[CO CH 2 - CH 2 - O - ] n
H Dacron (Polyester)
Alc. KOH
HOOC COOH +
CH2 = CH2
(C)
Terephthalic acid
HO – CH2 – CH2 – OH ¾¾
® Hence the product (C) is ethylene.
Ethylene glycol
1
Some Basic Concepts
of Chemistry
PHYSICAL QUANTITIES AND SI UNITS : Physical Definition SI Unit
The 11th general conference of weights and measures in 1960 Quantity
recommended the use of international system of units. volume length cube m3
Abbreviated as SI Units (after the French expression La System area length square m2
International de units). The SI system has seven basic units of speed distance travelled ms– 1
physical quantities as follows : per unit time
Physical quantity Abbreviation Name of unit Symbol acceleration speed changed ms– 2
per unit time
time t second s
density mass per unit volume kg m–3
mass m kilogram kg
pressure force per unit area kgm–1s–2 or Nm–2
length l metre m (pressure = Pa)
temperature T kelvin K force mass times acceleration kgms–2
of object (Newton N)
electric current I ampere A
energy force times distance kgm2s–2
light intensity Iv candela Cd
travelled (Joule J)
amount of substance n mole mol frequency cycles per second s–1 (hertz = Hz)
pound lb 0.453502 kg
10 –1 deci d 10 1 Deka da
10 –2 centi c 10 2 Hecta h
10 –3 milli m 10 3 kilo k
10 –6 micro m 10 6 Mega M
10 –9 nano n 10 9 Giga G
10 –12 pico p 10 12 Tera T
10 –15 femto f 10 15 Peta P
1. Calculate the weight of Iron which will be converted into its Sol. Since terpentine oil absorbs O3, the volume of O3 absorbed
oxide by the action of 18 g of steam. by terpentine oil is 10 ml.
Sol. The required equation is 3Fe + 4H2O ¾¾ ® Fe3O4 + 4H2 Volume of O2 = 100 – 10 = 90 ml
From gas equation (m)
3 × 56 g 4 × 18 g
3´ 56 WRT
g 18 g PV =
4 M
\ Weight of Fe converted into oxide = 42 g. Mol. wt of ozonised oxygen
2. The vapour density of a mixture containing NO2 and N2O4 is WRT 1.5 ´ 0.0821´ 273
38.3 at 27°C. Calculate the moles of NO2 in 100 g mixture. = = = 33.62
PV 1´1
Sol. Molecular weight of mixture = 2 × 38.3 = 76.6
Let weight of NO2 present in mixture be x g Mol. ratio of O2 and O3 90 : 10.
M. wt. of ozonised oxygen
x 100 - x 100
then + = \ x = 20.10 g
46 92 76.6 90 ´ 32 + 10 ´ a
= = 33.62 Þ a = 48.2 .
100
20.10
Hence moles of NO2 in mixture = = 0.43 Mol. wt. of ozone = 48.2.
46
5. How many millilitre of 0.5M H2SO4 are needed to dissolve
3. A mixture of 20 ml of CO, CH4 and N2 was burnt in excess of
0.5 g of copper (II) carbonate.
O2, resulting in reduction of 13 ml of volume. The residual
gas was then treated with KOH solution to show a Sol. Millimoles of H2SO4 = Millimoles of CuCO3
contraction of 14 ml in Volume. Calculate volume of CO, CH4 0.5 ´1000
and N2 in mixture. All measurements are made at constant T and P. 0.5 ´ V = or V = 8.097 ml.
123.5
Sol. Let a, b and c be the volume of CO, CH4 and N2 in mixture.
(II) CH 4 + 2O 2 ¾
¾® CO 2 + 2 H 2 O 40 ´ 1000
Sol. Normality of NaOH = =1
b 2b b 40 ´ 1000
(III) N 2 + O 2 ¾
¾® No Reaction 39 ´ 1000 39n
Normality of acid = =
Since reduction in volume is 13. This is volume of O2 used 82
then we have ´ 1000 82
n
a n = Basicity of acid
+ 2b = 13 (I)
2 N1V1 = N2V2
Volume of CO2 formed is volume absorbed by KOH
a + b = 14 (II) 39n ´ 100
= 1 ´ 95 n = 1.99 = 2 Basicity is 2 .
\ c = 20 – 14 = 6 ml 82
Solving I & II we get a = 10 ml, b = 4 ml.
\ CO = 10 ml, CH4 = 4 ml and N2 = 6 ml 7. For the reaction N2O5 (g) 2NO2 (g) + 0.5 O2 (g).
Calculate the mole fraction of N2O5 (g) decomposed at a
4. The weight of one litre sample of ozonised oxygen at NTP
was found to be 1.5 g. When 100 ml of this mixture at NTP constant volume and temperature if the initial pressure is 600
were treated with terpentine oil the volume was reduced to mm Hg and the pressure at any time is 960 mm Hg. Assume
90 ml. Hence calculate the molecular weight of Ozone. ideal gas behaviour.
10 Chemistry
1. In the final answer of the expression How would the weight of the sample be reported?
(a) 3.93 g (b) 3g
(29.2 - 20.2)(1.79 ´ 10 )
(c) 3.9 g (d) 3.929 g
1.37 5. Dimension of pressure are same as that of
the number of significant figures is (a) Energy (b) Force
(a) 1 (b) 3 (c) 2 (d) 4 (c) Force per unit volume (d) Energy per unit volume
2. Given the numbers : 161 cm, 0.161 cm, 0.0161 cm. The number 6. The prefix 1018 is
of significant figures for the three numbers are (a) giga (b) kilo
(a) 3, 4 and 5 respectively (b) 3, 3 and 4 respectively (c) exa (d) nano
(c) 3, 3 and 3 respectively (d) 3, 4 and 4 respectively 7. Which of the following halogen can be purified by
3. One fermi is sublimation?
(a) 10–15 cm (b) 10–13 cm (a) I2 (b) Cl2
–10
(c) 10 cm (d) 10–12 cm (c) Br2 (d) F2
4. A sample was weighted using two different balances. The 8. A mixture of sand and iodine can be separated by
results were (a) crystallisation (b) distillation
(i) 3.929 g (ii) 4.0 g (c) sublimation (d) fractionation
Some Basic Concepts of Chemistry 15
9. Among the following pairs of compounds, the one that (b) 0.44 g of CO2
illustrates the law of multiple proportions is (c) 22.4 L of CO2 at STP
(a) NH3 and NCl3 (b) H2S and SO2 (d) None of these
(c) CS2 and FeSO4 (d) CuO and Cu2O 22. Number of g of oxygen in 32.2 g Na2SO4.10 H2O is
10. Irrespective of the source, pure sample, of water always yields (a) 20.8 (b) 2.24 (c) 22.4 (d) 2.08
88.89% mass of oxygen and 11.11% mass of hydrogen. This is 23. The specific heat of a metal is 0.16, its approximate atomic
explained by the law of weight would be
(a) conservation of mass (b) multiple proportions (a) 32 (b) 16 (c) 64 (d) 40
(c) constant composition (d) constant volume 24. The weight of a molecule of the compound C60H122 is
11. If NA is Avogadro's number then number of valence electrons (a) 1.09 × 10–21 g (b) 1.4 × 10–21 g
(c) 5.025 × 10 g 23 (d) 16.023 × 1023 g
in 4.2 g of nitride ions (N3–) is
(a) 4.2 NA (b) 2.4 NA 25. The number of water molecules present in a drop of water
(c) 1.6 NA (d) 3.2 NA (volume 0.0018 ml) density = 18 ml–1at room temperature is
12. Two containers P and Q of equal volume (1 litre each) contain (a) 1.084 × 1018 (b) 6.023 × 1019
(c) 4.84 × 10 17 (d) 6.023 × 1023
6 g of O2 and SO2 respectively at 300 K and 1 atmosphere.
then 26. The percentage of Se in peroxidase anhydrous enzyme is
(a) Number of molecules in P is less than that in Q 0.5% by weight (atomic weight = 78.4). Then minimum
(b) Number of molecules in P and Q is same molecular weight of peroxidase anhydrous enzyme is
(c) Number of molecules in Q is less than that in P (a) 1.568 × 103 (b) 1.568 × 104
(c) 15.68 (d) 3.136 × 104
(d) Either (a) or (b)
27. Equivalent weight of crystalline oxalic acid is
13. The number of moles of oxygen in one litre of air containing
21% oxygen by volume, under standard conditions are (a) 90 (b) 53 (c) 63 (d) 45
28. 3 g of an oxide of a metal is converted to chloride completely
(a) 0.0093 mole (b) 0.21 mole
and it yielded 5 g of chloride. The equivalent weight of the
(c) 2.10 mole (d) 0.186 mole metal is
14. The vapour density of a gas is 11.2. The volume occupied (a) 3.325 (b) 33.25 (c) 12 (d) 20
by 11.2 g of the gas at NTP will be
29. The simplest formula of a compound containing 50% of
(a) 22.4 L (b) 11.2 L element X (atomic mass 10) and 50% of element Y (atomic
(c) 1 L (d) 44.8 L mass 20) is
15. The amount of zinc required to produce 224 ml of H2 at STP on (a) XY (b) XY3 (c) X2Y (d) X2Y3
treatment with dil. H2SO4 will be 30. The hydrogen phosphate of certain metal has formula
(a) 6.5 g (b) 0.65 g MHPO4. The formula of metal chloride would be
(c) 65 g (d) 0.065 g (a) MCl (b) M2Cl2 (c) MCl2 (d) MCl3
16. The volume occupied by 4.4 g of CO2 at STP is 31. A compound contains atoms of three elements as A, B and
(a) 22.4 L (b) 0.224 L C. If the oxidation number of A is +2, B is +5 and that of C is
(c) 2.24 L (d) 0.1 L –2, the possible formula of the compound is
17. Assuming fully decomposed, the volume of CO2 released at (a) A3(B4C)2 (b) A3(BC4)2
STP on heating 9.85 g of BaCO3 (Atomic mass, Ba = 137) will (d) ABC2 (d) A2(BC3)2
be 32. If 0.44 g of a colourless oxide of nitrogen occupies 224 ml at
(a) 1.12 L (b) 2.24 L 1520 mm Hg and 273°C, then the compound is
(c) 4.06 L (d) 0.84 L (a) NO2 (b) N2O
18. 3 3
10 dm of N2 gas and 10 dm of gas X at the same temperature (c) NO4 (d) N2O2
contain the same number of molecules, the gas X is 33. The mass of a molecule of water is
(a) CO2 (b) CO (c) H2 (d) NO (a) 3 × 10–25 kg (b) 3 × 10–26 kg
19. 7.5 grams of a gas occupy 5.6 litres of volume at STP. The (c) 1.5 × 10–26 kg (d) 2.5 × 10–26 kg
gas is 34. Number of moles of KMnO4 required to oxidize one mole of
(a) N2O (b) NO (c) CO (d) CO2 Fe(C2O4) in acidic medium is
(a) 0.167 (b) 0.6 (c) 0.2 (d) 0.4
20. 1 amu is equal to
35. 100 cm3 of 0.1 N HCl is mixed with 100 cm3 of 0.2 N NaOH
1 1 solution. The resulting solution is
(a) of O-16 (b) of C-12
14 12 (a) 0.1 N and the solution is basic
(c) 1 g of H2 (d) 1.66 × 10–23 kg (b) 0.1 N and the solution is acidic
21. Which of the following contains maximum number of atoms? (c) 0.05 N and the solution is basic
(a) 6.023 × 1021 molecules of CO2 (d) 0.05 N and the solution is acidic
16 Chemistry
36. For preparing 0.1 N solution of a compound from its impure 46. The volume of water to be added to 100 cm3 of 0.5 N H2SO4 to
sample of which the percentage purity is known, the weight get deci normal concentration is
of the substance required will be (a) 400 cm3 (b) 450 cm3
(a) less than the theoretical weight (c) 500 cm 3 (d) 100 cm3
(b) more than the theoretical weight 47. 250 ml of a sodium carbonate solution contains 2.65 grams
(c) same as the theoretical weight of Na2CO3. If 10 ml of this solution is diluted to one litre,
what is the concentration of the resultant solution?
(d) none of these
(mol. wt. of Na2CO3 = 106)
37. 10 g CaCO3 gives on strong heating CO2. It gives quicklime
(a) 0.1 M (b) 0.01 M
(in grams)
(c) 0.001 M (d) 10–4 M
(a) 5g (b) 4.4 g (c) 5.6 g (d) 4 g
48. 3.92 g of ferrous ammonium sulphate crystals are dissolved in
38. Haemoglobin contains 0.33% of iron by weight. The 100 ml of water. 20 ml of this solution requires 18 ml of potassium
molecular weight of haemoglobin is approximately 67200. permaganate during titration for complete oxidation. The weight
The number of iron atoms (at. wt. of Fe = 56) present in one of KMnO4 present in one litre of the solution of
molecule of haemoglobin is (a) 3.476 g (b) 12.38 g
(a) 6 (b) 1 (c) 2 (d) 4 (c) 1.238 g (d) 34.76 g
39. The number of molecules in 16 g of methane is 49. 30 g of Magnesium and 30 g of oxygen are reacted, then the
residual mixture contains
16
(a) 3.0 × 1023 (b) ´ 10 23 (a) 50 g of Magnesium oxide and 10 g of oxygen
6.02
(b) 40 g of Magnesium oxide and 20 g of oxygen
16 (c) 45 g of Magnesium oxide and 15 g of oxygen
(c) 6.02 × 1023 (d) ´ 10 23 (d) 60 g of Magnesium oxide only
3.0
50. In order to prepare one litre normal solution of KMnO4, how
40. 50 ml 10 N H2SO4, 25 ml 12 N HCl and 40 ml 5 N HNO3 were
many grams of KMnO4 are required if the solution is to be
mixed together and the volume of the mixture was made 1000 ml
used in acid medium for oxidation?
by adding water. The normality of the resultant solution will be
(a) 158 g (b) 62.0 g
(a) 2 N (b) 1 N (c) 3 N (d) 4 N
(c) 31.6 g (d) 790 g
41. A molal solution is one that contains 1 mole of a solute in 51. In a chemical reaction
(a) one litre of the solvent K 2 Cr 2 O 7 + xH 2 SO 4 + ySO 2
(b) 1000 g of the solvent
(c) one litre of the solution ¾
¾® K 2SO 4 + zCr2 (SO 4 ) 3 + H 2 O
(d) 22.4 litres of the solution the values of x, y, z are
42. A 100 ml solution of 0.1 N HCl was titrated with 0.2 N NaOH (a) 4, 1, 4 (b) 1, 3, 1
solution. The titration was discontinued after adding 30 ml (c) 3, 2, 3 (d) 2, 1, 2
of NaOH solution. The remaining titration was completed 52. The maximum amount of BaSO4 precipitated on mixing equal
by adding 0.25 N KOH solution. The volume of KOH required volumes of BaCl2 (0.5 M) with H2SO4 (1 M) will correspond to
for completing the titration is (a) 1.0 M (b) 0.5 M
(a) 16 ml (b) 32 ml (c) 1.5 M (d) 2.0 M
(c) 35 ml (d) 70 ml 53. In the reaction
43. An aqueous solution of 6.3 g of oxalic acid dihydrate is ® 4NO(g) + 6H 2 O(l ) ,when 1 mole
4NH 3 (g) + 5O 2 (g) ¾¾
made up to 250 ml. The volume of 0.1 N NaOH required to of ammonia and 1 mole of O2 are made to react to completion
completely neutralise 10 ml of this solution is (a) 1.0 mole of H2O is produced
(a) 20 ml (b) 40 ml (b) 1.0 mole of NO will be produced
(c) 10 ml (d) 4 ml (c) all the ammonia will be consumed
44. The percentage of nitrogen in urea is about (d) all the oxygen will be consumed
(a) 85 (b) 46 (c) 18 (d) 28 54. The set of numerical coefficients that balances the equation
45. How much of NaOH is required to neutralise 1500 cm3 of 0.1 ¾® K 2 Cr2 O 7 + KCl + H 2 O is
K 2 CrO 4 + HCl ¾
N HCl? (Na = 23) (a) 2, 2, 1, 2, 1 (b) 2, 2, 1, 1, 1
(a) 60 g (b) 4 g (c) 6 g (d) 40 g (c) 2, 1, 1, 2, 1 (d) 1, 1, 2, 2, 1
Some Basic Concepts of Chemistry 17
1. The mass of carbon anode consumed (giving only 12. With increase of temperature, which of these changes?
carbondioxide) in the production of 270 kg of aluminium (a) molality [AIEEE 2002]
metal from bauxite by the Hall process is (Atomic mass: (b) weight fraction of solute
Al = 27) [CBSE-PMT 2005] (c) fraction of solute present in water
(a) 270 kg (b) 540 kg (c) 90 kg (d) 180 kg (d) mole fraction.
2. The number of moles of KMnO4 reduced by one mole of 13. Number of atoms in 558.5 gram Fe (at. wt. of Fe = 55.85
KI in alkaline medium is: [CBSE-PMT 2005] g mol–1) is [AIEEE 2002]
(a) one (b) two (c) five (d) one fifth (a) twice that in 60 g carbon (b) 6.023 ´ 1022
3. Volume occupied by one molecule of water (c) half that in 8 g He (d) 558.5 ´ 6.023 ´ 1023
(density = 1 g cm–3) is : [CBSE-PMT 2008] 14. One mole of magnesium nitride on the reaction with an
(a) 9.0 × 10–23 cm3 (b) 6.023 × 10– 23 cm3 excess of water gives : [AIEEE 2004]
(a) two moles of ammonia (b) one mole of nitric acid
(c) 3.0 × 10–23 cm3 (d) 5.5 × 10– 23 cm3
- (c) one mole of ammonia (d) two moles of nitric acid
4. Number of moles of MnO4 required to oxidize one mole of
15. If we consider that 1/6, in place of 1/12, mass of carbon atom
ferrous oxalate completely in acidic medium will be : is taken to be the relative atomic mass unit, the mass of one
[CBSE-PMT 2008] mole of the substance will [AIEEE 2005]
(a) 0.6 moles (b) 0.4 moles (a) be a function of the molecular mass of the substance
(c) 7.5 moles (d) 0.2 moles (b) remain unchanged
5. An organic compound contains carbon, hydrogen and (c) increase two fold
oxygen. Its elemental analysis gave C, 38.71% and H, 9.67%. (d) decrease twice
The empirical formula of the compound would be : 16. How many moles of magnesium phosphate, Mg3(PO4)2 will
[CBSE-PMT 2008] contain 0.25 mole of oxygen atoms? [AIEEE 2006]
(a) 1.25 × 10 –2 (b) 2.5 × 10 –2
(a) CH3O (b) CH2O (c) CHO (d) CH4O
6. How many moles of lead (II) chloride will be formed from a (c) 0.02 (d) 3.125 × 10–2
reaction between 6.5 g of PbO and 3.2 g of HCl ? –1
17. The density (in g mL ) of a 3.60 M sulphuric acid solution
[CBSE-PMT 2008] that is 29% H2SO4 (molar mass = 98 g mol–1) by mass will
(a) 0.044 (b) 0.333 (c) 0.011 (d) 0.029 be [AIEEE 2007]
7. 10 g of hydrogen and 64 g of oxygen were filled in a steel (a) 1.45 (b) 1.64
vessel and exploded. Amount of water produced in this (c) 1.88 (d) 1.22
reaction will be: [CBSE-PMT 2009] 18. In the reaction, [AIEEE 2007]
(a) 3 mol (b) 4 mol (c) 1 mol (d) 2 mol 2Al( s ) 6HCl( aq ) 2Al3 (aq) + 6Cl (aq) + 3H2 ( g)
8. The number of atoms in 0.1 mol of a triatomic gas is :(NA = (a) 11.2 L H2(g) at STP is produced for every mole HCl(aq)
6.02 ×1023 mol–1) [CBSE-PMT 2010] consumed
(a) 6.026 × 1022 (b) 1.806 × 1023 (b) 6 L HCl(aq) is consumed for every 3 L H2(g) produced
(c) 3.600 × 1023 (d) 1.800 × 1022 (c) 33.6 L H2(g) is produced regardless of temperature and
9. Which has the maximum number of molecules among the pressure for every mole Al that reacts
following ? [CBSE-PMT 2011 M] (d) 67.2 H2(g) at STP is produced for every mole Al that
reacts.
(a) 44 g CO2 (b) 48 g O3
19. The molality of a urea solution in which 0.0100 g of urea,
(c) 8 g H2 (d) 64 g SO2
[(NH2)2CO] is added to 0.3000 dm3 of water at STP is :
10. How many grams of concentrated nitric acid solution should
[AIEEE 2011 RS]
be used to prepare 250 mL of 2.0M HNO3 ? The concentrated
acid is 70% HNO3 [NEET 2013] (a) 5.55 10 4 m (b) 33.3 m
(a) 90.0 g conc. HNO3 (b) 70.0 g conc. HNO3 (c) 3.33 × 10–2 m (d) 0.555 m
(c) 54.0 g conc. HNO3 (d) 45.0 g conc. HNO3 20. A gaseous hydrocarbon gives upon combustion 0.72 g of
20
11. 6.02 × 10 molecules of urea are present in 100 mL of its water and 3.08 g. of CO2. The empirical formula of the
solution. The concentration of solution is : [NEET 2013] hydrocarbon is : [JEE Main 2013]
(a) C2H4 (b) C3H4 (c) C6H5 (d) C7H8
(a) 0.01 M (b) 0.001 M (c) 0.1 M (d) 0.02 M
18 Chemistry
21. Experimentally it was found that a metal oxide has formula 22. Consider a titration of potassium dichromate solution with
M0.98O. Metal M, present as M2+ and M3+ in its oxide. acidified Mohr's salt solution using diphenylamine as
Fraction of the metal which exists as M3+ would be : indicator. The number of moles of Mohr's salt required per
[JEE Main 2013] mole of dichromate is [IIT-JEE 2007]
(a) 7.01% (b) 4.08% (c) 6.05% (d) 5.08% (a) 3 (b) 4 (c) 5 (d) 6
1. The correctly reported answer of addition of 29.4406, 3.2 12. A compound made up of two elements A and B is found to
and 2.25 will have significant figures contain 25% A (atomic mass = 12.5) and 75% B (atomic mass
(a) 3 (b) 4 (c) 2 (d) 5 = 37.5). The simplest formula of the compound is
2. On dividing 0.25 by 22.1176 the actual answer is 0.011303. (a) AB (b) AB2 (c) AB3 (d) A3B
The correctly reported answer will be 13. On analysis a certain compound was found to contain iodine
and oxygen in the ratio of 254 gm of iodine (atomic mass
(a) 0.011 (b) 0.01 (c) 0.0113 (d) 0.013
127) and 80 gm oxygen (at mass = 16). What is the formula of
3. In which of the following number all zeros are significant? the compound.
(a) 0.0005 (b) 0.0500 (c) 50.000 (d) 0.0050 (a) IO (b) I2O (c) I5O3 (d) I2O5
4. If law of conservation of mass was to hold true, then 20.8 14. Two oxides of a metal contain 50% and 40% metal (M)
gm of BaCl2 on reaction with 9.8 gm of H2SO4 will produce respectively. If the formula of first oxide is MO2 the formula
7.3 gm of HCl and BaSO4 equal to : of second oxide will be
(a) 11.65 gm (b) 23.3 gm (a) MO2 (b) MO3 (c) M2O (d) M2O5
(c) 25.5 gm (d) 30.6 gm 15. The ratio of the molar amounts of H2S needed to precipitate
5. One of the following combination which illustrates the law the metal ions form 20 ml each of 1 M Ca(NO3)2 and 0.5M
of reciprocal proportions ? CuSO4 is
(a) N2O3, N2O4, N2O5 (b) NaCl, NaBr, NaI (a) 1 : 1 (b) 2 : 1 (c) 1 : 2 (d) indefinite
(c) CS2, CO2, SO2 (d) PH3, P2O3, P2O5 16. 12 gm of Mg (atomic mass 24) will react completely with
hydrochloric acid to give
6. If isotopic distribution of C-12 and C-14 is 98% and 2%
(a) One mol of H2
respectively then the no. of C-14 atoms in 12gm of carbon is
(b) 1/2 mol of H2
(a) 1.032 × 1022 (b) 3.0 × 1022
(c) 2/3 mol of O2
(c) 5.88 ×1023 (d) 6.02 × 1023
(d) both 1/2 mol of H2 and 1/2 mol of O2
7. Which of the following contains maximum number of atom
17. The total number of protons in 10 gm of calcium carbonate
(a) 2.0 mole of S8 (b) 6.0 mole of S is (No = 6.023 × 1023)
(c) 5.5 mole of SO2 (d) 44.8 litre of CO2 of S.T.P. (a) 1.5057 × 1024 (b) 2.0478 × 1024
8. A sample of AlF3 contains 3.0 × 1024 F– ions. The number of (c) 3.0115 × 1024 (d) 14.0956 × 1024
formula unit of this sample are 18. 2.76 gm of silver carbonate (at mass of Ag 108) on being
(a) 9 × 1024 (b) 3 × 1024 heated strongly yield a residue weighing
(c) 0.75 × 10 24 (d) 1.0 × 1024 (a) 2.16 gm (b) 2.48 gm
9. What mass of calcium chloride in grams would be enough (c) 2.32 gm (d) 2.64 gm
to produce 14.35 gm of AgCl ? 19. If 0.5 mol of BaCl2 is mixed with 0.2 mol of Na3PO4 then maximum
(a) 5.55 gm (b) 8.295 gm (c) 16.5 gm (d) 11.19 gm number of moles of Ba 3 (PO 4 ) 2 that can be formed is
10. If potassium chlorate is 80% pure, then 48 gm of oxygen (a) 0.7 (b) 0.5 (c) 0.3 (d) 0.1
would be produced from (atomic mass of K =39) 20. 1.12 ml of a gas is produced at S.T.P. by the action of 4.12 mg
(a) 153.12 gm of KClO3 (b) 122.5 gm of KClO3 of alcohol ROH with methyl magnesium Iodide. The
(c) 245 gm of KClO3 (d) 98 gm of KClO3 molecular mass of alcohol is
11. If 224 ml of a triatomic gas has a mass of 1 gm at 273K and 1 (a) 16.0 (b) 41.2 (c) 82.4 (d) 156.0
atmospheric pressure then the mass of one atom is 21. An unsaturated hydrocarbon weighing 1.68 gm has volume
(a) 8.30 × 10–23 gm (b) 2.08 × 10–23 gm of 488 ml at S.T.P. If it contains 14% of hydrogen, then the
(c) 5.53 × 10–23 gm (d) 6.24 × 10–23 gm family to which the hydrocarbon belongs is
(a) alkane (b) alkene (c) alkyl (d) benzene
Some Basic Concepts of Chemistry 19
22. The number of molecules in 8.96 litre of a gas at 0ºC and 1 32. A gas mixture of 3 litres of propane (C3H 8 ) and butane
atm. pressure is approximately
(C 4 H10 ) on complete combustion at 25° C produced 10
(a) 6.023 × 1023 (b) 12.04 × 1023
(c) 18.06 × 1023 (d) 24.08 × 1022 litre CO 2 . Find out the composition of gas mixture (Propane
20
23. If 3.01 × 10 molecules are removed from 98 mg of H2SO4, : Butane)
then the number of moles of H2SO4 left are (a) 2 : 1 (b) 1 : 2 (c) 1.5 : 1.5 (d) 0.5 : 2.5
(a) 0.1 × 10–3 (b) 0.5 × 10–3 33. On subjecting 10 ml mixture of N 2 and CO to repeated electro
(c) 1.66 × 10–3 (d) 9.95 × 10–2 spark, 7 ml of O 2 was required for combustion. What was
24. 25.4 g of I 2 and 14.2 g of Cl 2 are made to react completely the mole percent of CO in the mixture? (All volumes were
measured under identical conditions)
to yield a mixture of ICl and ICl3 . Calculate moles of ICl (a) 60 (b) 40 (c) 6 (d) 4
and ICl3 formed 34. How many of 0.1N HCl are required to react completely with
1 g mixture of Na 2CO 3 and NaHCO 3 containing equimolar
(a) 0.1, 0.1 (b) 0.2, 0.2 (c) 0.1, 0.2 (d)0.2, 0.1
amounts of two ?
25. 2 g of a mixture of CO and CO 2 on reaction with excess (a) 157.7 ml (b) 15.77 ml
I 2 O 5 produced 2.54 g of I 2 . What be the mass % of CO 2 (c) 147.7 ml (d) 14.77 ml
in the original mixture ? 35. 1 mole of mixture of CO and CO 2 requires exactly 28 g KOH
(a) 35 (b) 70 (c) 30 (d) 60 in solution for complete conversion of all the CO 2 into
26. The hydrated salt Na 2 CO 3. xH 2 O undergoes 63% loss in K 2 CO 3 . How much amount more of KOH will be required
mass on heating and becomes anhydrous. The value of x is for conversion into K 2 CO 3 . If one mole of mixture is
(a) 10 (b) 7 (c) 5 (d) 3
completely oxidized to CO 2
27. Gastric juice contains 3.0 g of HCl per litre. If a person
(a) 112 g (b) 84 g (c) 56 g (d) 28 g
produces 2.5 litre of gastric juice per day. How many antacid
36. 10 g CaCO3 were dissolved in 250 ml of M HCl or the
tablets each containing 400 mg of Al(OH )3 are needed to
solution was boiled. What volume of 2M KOH would be
neutralize all the HCl produced in one day ? required to equivalence point after boiling ? Assume no
(a) 18 (b) 14 (c) 20 (d) 17 change in volume during boiling.
28. Sulfuryl chloride (SO 2Cl 2 ) reacts with water to give a (a) 50 ml (b) 25 ml (c) 75 ml (d) 60 ml
37. 2.24 ml of a gas ‘X’is produced at STP by the action of 4.6
mixture of H 2SO 4 and HCl. How many moles of baryta mg of alcohol (ROH) with methyl magnesium iodide the
would be required to neutralize the solution formed by adding molecular mass of alcohol and the gas ‘X’ are respectively.
= Force =
Work (energy/di stance)
=
Energy M. Wt = 30.12 Hence gas is NO.
area Area Volume
6. (c) Exa = 1018 (see text.) 1
20. (b) 1 amu = of the mass of C-12.
12
Some Basic Concepts of Chemistry 21
21. (c) 22.4 L of CO2 at STP = 1 mole = 6.023 × 1023 molecules. 34. (b) The required equation is
Hence number of atoms 3 × 6.023 × 1023.
22. (c) M. Wt of Na2SO4.10 H2O is 322 g which contains 224 g 2KMnO 4 + 3H 2SO 4 ¾
¾®
oxygen. \ 32.2 g will contain 22.4 g oxygen. K 2SO 4 + 2MnSO 4 + 3H 2O + 5 [O]
6.4 nascent oxygen
23. (d) = Apx. Atomic mass
Specific heat
2Fe(C2 O 4 ) + 3H 2SO 4 + 3 [ O ] ¾¾
®
6.4 Fe 2 (SO 4 )3 + 2CO 2 + 3H 2O
\ Apx. At.wt = = 40
0.16 O required for 1 mol. of Fe(C2O4) is 1.5, 5O are obtained
24. (b) M. Wt of C60H122 = 842g from 2 moles of KMnO4
842 2
\ Wt of one molecule = 23
= 1.4 ´10 - 21 g \ 1.5 [O] will be obtained from = ´ 1.5 = 0.6 moles of
6.023 ´10 5
KMnO4.
25. (b) 0.0018 ml = 0.0018 g = 0.0001 mole of water = 10-4 mole
35. (b) Normality = N1V1 - N 2 V2 = 0.2 ´ 100 - 0.1´100
\ Number of water molecules = 6.023 ´ 10 23 ´ 10 -4 V1 + V2 100 + 100
= 6.023 × 1019
26. (b) 0.5% by weight means. If Mol. wt. is 100 then mass of Si 10
= = 0.05 N NaOH
is 0.5. If at least one atom of Se is present in the molecule 200
then 36. (b) More than theoretical weight since impurity will not
100 contribute.
M. Wt = ´ 78.4 = 1.568 ´ 10 4
0.5 37. (c) CaCO3 CaO + CO2
27. (c) Eq. Wt of crystalline oxalic acid (COOH)2. 2H2O 100 g 56 g
10 g CaCo3 will give 5.6 gCaO
M.Wt . 126
= = = 63
2 2 0.33
38. (d) Weight of Iron in 67200 = ´ 67200 = 221.76
100
P WAVE NUMBER :
(effective 1.1 1.2 1.3 1.4 It is the number of wavelengths per cm. It is equal to the inverse of
e
Nuclear charge) wavelength. Unit is cm–1 and is denoted by n .
Ionic radius (Å) 0.95 0.65 0.50 0.41
1
FAILURE OF RUTHERFORD'S MODEL : n=
l
According to classical theory of electromagnetism whenever a
charge is subjected to an acceleration around an opposite charge, AMPLITUDE :
it emits radiations continuously. Therefore the electron while It is the height of crest or trough. Square of amplitude determines
moving around nucleus in circular path must loose energy, go the amount of energy carried by the wave.
into spiral motion and ultimately fall into the nucleus. Practically it ELECTROMAGNETIC SPECTRUM :
does not happen. Arrangement of all electro-magnetic radiations in the increasing
PLANCK QUANTUM THEORY : order of their wavelengths or decreasing order of frequencies is
According to Max Planck (1901) radiant energy is emitted or called electromagnetic spectrum.
absorbed only in discrete units in form of bundle or packets of
energy called photon (quantum). Photon is not a material body. It Rays Wavelength Frequency
is massless bundle of energy (l in Å) n in Hz
Energy associated with each photon (quantum) Cosmic Rays 3×1021 to ¥
c g Rays 0.01 3×1019 to 3×1020
E = hn = h
l X Rays 1.0 2×1016 to 3×1019
h = Planck's constant = 6.626 × 10 –34 Js in S.I. units
(or 6.6726 × 10–27 ergs in c.g.s. units). n = frequency of radiation UV Rays 150 7.9×1014 to 2×1016
(each photon). Visible Light 3800 3.9×1014 to 7.9×1014
c = velocity of light, l = wavelength of radiation. Infra Red 7600 1×1011 to 3.95×1014
Thus a body can radiate energy in multiples of quantum hn, 2hn, Micro Waves 6×106 1×109 to 5×1011
3hn .... nhn where n is an integer.
Radio Waves 3×109 1×105 to 1×109
INTENSITY OF LIGHT :
ATOMIC SPECTRUM :
It is defined as number of photons falling per unit area per sec.
and depends upon wavelength of photons. Atoms of different elements emit electromagnetic radiations of
definite frequencies when excited by heating, passing current or
or it is defined as amount of energy falling per unit area per sec
electric discharge. Arrangement of these radiations in decreasing
and depends upon wavelength of photons.
order of frequencies is called atomic spectrum.
ELECTROMAGNETIC RADIATION :
Electromagnetic radiation by James maxwell (1870). An electrically DISPERSION :
changed particles moving under acceleration produces alternating Phenomenon of splitting of beam of light into radiations of different
electrical and magnetic fields mutually perpendicular to each other. frequencies after passing through a prism is called dispersion.
These fields are transmitted in the form of waves having same CONTINUOUS SPECTRUM :
wavelengths, frequency, speed and amplitude and are called It is obtained by passing sunlight (white light) through a prism.
electromagnetic waves or electromagnetic radiations. In vaccum The light is dispersed or resolved into continuous spectra of
all types of electromagnetic radiations travel at the same speed colours from Violet to Red. It contains radiations of all the
(3.0 × 108 ms–1) regardless of wavelengths. frequencies.
30 Chemistry
LINE SPECTRUM : (III) Number of Lines in a Transition : Mathematical formula for
It is an atomic spectrum of an element which consists of a number number of lines is follows as
of bright lines separated by dark bands. Atomic Spectra of most
(n 2 - n1 )(n 2 - n1 + 1)
elements is line spectrum. No. of lines =
2
ABSORPTION SPECTRUM :
BLACK BODY RADIATION :
It is obtained by passing white light through solutions or vapours
of chemical substance and then is analysed by spectroscope. It The radiation emitted by a body when heated is called black body
has few dark lines in otherwise continuous spectrum. radiation. The frequency of radiation increases with temperature.
At a given temperature the intensity of radiation emitted increases
EMISSION SPECTRUM :
with decrease of wavelength, reaches a maximum value and then
It is obtained by passing radiations from the atoms through prism. starts decreasing with further decrease of wavelength. A black
It has few bright lines against a dark back ground. body can emit and absorb all frequencies.
HYDROGEN SPECTRUM : PHOTOELECTRIC EFFECT :
It is obtained by passing light being emitted from discharge tube Phenomenon of ejection of electrons from the surface of a metal
containing hydrogen at low pressure through spectrograph. when light of suitable frequency strikes on it is called photoelectric
Hydrogen Spectrum has five Series effect.
Spectral Line Region n1 n2 (I) Threshold frequency (v0) : The minimum frequency of
Lyman Series U.V. 1 2, 3, 4..... incident radiation to cause the photoelectric effect is called
Balmer Series Visible 2 3, 4, 5..... threshold frequency.
Paschen Series I.R. 3 4, 5, 6..... (II) Work function : A part of the photons energy that is absorbed
Brackett Series I.R. 4 5, 6, 7.... by the metal surface to release the electron is known as work
Pfund Series I.R. 5 6, 7, 8.... function of the surface denoted by f. The remaining part of
the energy of photons goes into the Kinetic energy of the
éIn Balmer Series of hydrogen spectrum ù electron emitted.
ê the first line (3 ® 2) is known as L line ú
ê the second line (4 ® 2) is L line. a ú If n0 is the threshold frequency and n the frequency of incident
ë b û
light then f = hn 0 and E = hn.
Wavelength of line in spectrum is given by the expression
K.E. = E - f = hn - hn 0 = h (n - n 0 )
1 1 1 Note: • K.E. is independent of the intensity of light.
= = R H Z2 ÷
n12 n 22 ÷ • Number of photoelectrons µ Intensity of light
• K.E. is directly proportional to frequency of incident
RH = Rydberg Constant, Z = charge on nucleus, light.
n1, n2 = electronic levels involved in transition, = Wave number • E = K.E. + f is known as Einstein's photoelectric
2 equation.
2 me 4
RH = = 109677.76 cm -1 also for hydrogen • Energy required to stop the ejection of electrons is given
ch 3
by eV0 where e is the electric charge and V0 is stopping
æ 1 potential.
1 ö÷ -1
n = 3.29 ´ 1015 ç - sec where is frequency..
çn 2
è 1 n2 ø
2÷ BOHR’S MODEL OF ATOM :
Proposed by Niel Bohr to overcome the drawbacks of Rutherford’s
(I) For calculation of longest wavelength line use n 2 nearest
model.
and for shortest wavelength line use n 2 infinity e.g. value of
(i) Electrons revolve around nucleus only in certain selected
longest wave length in Balmer Series of hydrogen spectrum
circular orbits. These orbits are associated with definite
use n1 = 2 and n2 = 3.
energies and are called energy shells or levels.
(II) Last line of spectrum is called Series limit. Last line is the line
of shortest wavelength and high energy when n 2 = ¥ we (ii) Electrons can move only in those circular orbits where
get last wavelength angular momentum is a whole number and multiple of h/2p.
nh
1 R H2 n12 i.e. mvr = . or simply an integral number of wavelengths
= l (series limit) = , 2
n12 R H2
should fit in given electron orbit of radius r i.e. n =2 r.
Structure of Atom 31
(iii) Electrons energy in a particular orbit is constant. (xii) Number of revolutions per second in n th orbit,
(iv) Lowest energy state is called ground state and when electron vn velocity of electron in n th orbit
absorbs energy and jumps to higher state, it is called excited =
2prn circumference of the n th orbit
state v Velocity
(v) Electronic energy is negative because at infinite distance (xiii)Angular velocity = =
r radius
there is no interaction between electron and nucleus thus (xiv) Angular momentum = mvr
energy is zero. While when close to nucleus, attraction takes (xv) Number of spectral lines when electron jumps from the n th
place, energy is released and it becomes negative as it was
n (n - 1)
already zero. The energy of electron increases with the value to ground level = =
of n, but the difference of energy between two successive 2
orbits decreases. Thus (xvi) The electrons energy is generally expressed in kcal or kJ
E2 – E1 > E3 – E2 > E4 – E3 .......... etc. mol–1 or in electron volts eV.
(vi) Energy of electron in nth orbit 1 ergmol–1 = 1.44×1013 kcalmol–1 = 6.022×1013 kJmol–1
1eV = 1.602×10–19J
k2 2 2
me 4 z 2 -13.6Z2 (xvii)Some important values :
En = - = eV atom -1
n 2h 2 n2 In c.g.s. system,
m = 9.109×10–28g
-2.178 ´10-18 Z2 e = 4.803×10–10 esu,
= J atom -1
2
n h = 6.626×10–27 ergs,
where m = Mass of the electron, k= 1
e = Charge on the electron,
2 p 2 me 4
h = Planck's constant RH = cm - 1
ch 3
n = Principal quantum number,
k = A universal constant = 9.0 × 109 J.m/C2 In S I system,
The constant k is inverse of permitivity factor 4p 0 of the m = 9.109×10–31kg
e = 1.602×10–19C,
1
medium k = . The numerical value of permitivity factor h = 6.626×10–34 J.s,
4p 0
is 4p 0 = 1.11264 × 10–10 C2N–1m–2. In C.G.S. system k = 1. k = 9.0 × 109 Jm/C2
(vii) The radius of nth orbit
2 p 2 me 4
RH = = m -1
n2h 2 a0n 2
0.528Ån 2 2
(4 p o ) ch 3
rn = = = Å
2 2 Z Z
4 me Zk
(viii)The velocity of electron in nth orbit, e
In S I system the charge e is replaced by 4p o
nh 2 Ze 2 k 2.19 ´ 108 Z
vn = = = cm/sec. LIMITATIONS OF BOHR’S MODEL ARE :
2 mr nh n
1 (i) Explains the spectrum of elements having only one electron
The velocity of electron in first orbit of hydrogen is of (ii) Does not explain splitting of spectral lines under magnetic
137
the velocity of light. field (Zeeman effect) and electric field (stark effect)
(iii) Does not explain quantisation of angular momentum.
(ix) Kinetic energy of electron in nth orbit, (iv) It goes against the Heisenberg’s uncertainity principle.
2m p 2 e 4 Z 2 k 2 13.6 ´ Z 2 SOMMERFIELD MODEL :
Ek = = eV
n2h2 n2 (i) Motion of electrons is in closed elliptical paths of definite
(x) Potential energy of electron in nth orbit, energy levels having nucleus on either of the focii.
(ii) Angular momentum is quantized
- e2 - 4m p 2 e 4 Z 2 k 2 - 27.2 Z 2
Ep = = = eV n major axis length
r n2h2 n2 (iii) = where k = 1, 2 ---------n.
k minor axis length
(xi) Total energy of electron in nth orbit,
(iv) It does not explain distribution of electrons in extranuclear
part of atom and also does not explain for de Brogalie
k 2 2 2me4 Z2 13.6Z2
En = Ek + Ep = = eV concept.
n 2h 2 n2
32 Chemistry
QUANTUM MECHANICS : (v) has no physical significance but 2 gives intensity of
It was developed independently by Warner Heisenberg and Erwin electrons and thus gives probability of electron in a particular
Schrodinges and takes into account the dual behaviour (particle region.
and wave nature) of matter proposed by de Broglie. ORBITALS :
Planck’s Quantum theory successfully explains.
Orbitals are the regions in space around nucleus where probability
(i) Photoelectric effect
of finding the electron is maximum.
(ii) Black-body radiation
(iii) Line spectra of H-atom (i) Probability does not become zero even at infinity and is
(iv) Variation of heat capacity of solids with temperature. given by 2.
(ii) Electron orbitals in atoms arecalled atomic orbitals while
de- BROGLIE PRINCIPLE (1924) :
those in molecules are called molecular orbitals.
(i) Proposes that just as radiations have particle nature, the
(iii) Orbitals have definite energy and momentum and are
material particles are also associated with wave nature.
quantized. i.e, En = –E1/n2 thus Bohr’s concept of well
h h defined orbits is ruled out.
(ii) de Broglie wavelength is l = = h = Planck’s constant
mv p QUANTUM NUMBERS :
m = mass of object ; v= velocity and this equation is called
the de Broglie equation. (i) Four quantum numbers (n, l, m, s) help in providing complete
information about an electron in an atom.
DAVISSON AND GERMER’S EXPERIMENT :
(ii) Principal quantum number (n) determines the energy and
Confirms the wave nature of electrons.
average distance of electron. It has whole number values also
SCINTILLATION METHOD AND PHOTOELECTRIC denoted as K, L, M, N. etc. As n increases, distance of electron
EFFECT : from nucleus increases and energy increases.
Confirm the particle nature. (iii) Azimuthal quantum number (l) determines angular momentum
HEISENBERG’S UNCERTAINITY PRINCIPLE : of the electron. It also determines the shape of orbitals and it
may have all possible whole number values from 0 to n–1 for
“It is not possible to determine simultaneously the position and
each principal energy level. The sublevels are:
momentum of small moving sub-atomic e.g.,
Value of l 0 1 2 3
+
1H , He + , 1B, , n particle, such as electron with entire Sub-shell s p d f
certainty”. Magnitude of angular momentum of an electron in orbital,
h
(i) Mathematically ± Dx ´ Dp ³ h mvr = l (l + 1)
4p 2
where, D x = uncertainity in position Angular momentum of an electron in any orbit,
D p = uncertainity in momentum and h = Planck’s constant
(ii) As the mass of particle increases, the uncertainity decreases nh
mvr =
QUANTUM MECHANICAL MODEL OF ATOM : 2p
(i) Based on de Broglie's and Heisenberg’s principle. (iv) Magnetic quantum number (m) defines the orientation of
(ii) Put forward by Schrodinger (1920). Behaviour of electron electrons cloud in a particular sub shell. Values of m are the
was described in terms of equation known as Schrodinger number of orbitals associated with a particular sub shell in
wave equation main shell. Values of m lie from 0 to ± l. Total values of ‘m’
2 2 2 2
for a given n is n 2. Total values of ‘m’ for a given l is 2l +1.
m The table shows a clear relation between quantum numbers.
+ + +
(E - V) = 0 where is
2 2 2 2
x y z h Shell (n) Sub -shells (l) Orbitals (m)
amplitude of electron wave and is also called wave function.
n=1 Þ K shell l= 0 Þ 1s m= 0
x, y, z, are space coordinates, m is mass of electron, h is
Planck’s constant, E is total energy and V is potential energy n=2 Þ L shell l= 0 Þ 2s m= 0
of the electron. l= 1 Þ 2p m = –1,0, +1
(iii) Many solutions for this equation are possible for hydrogen
but only certain solutions are permissible and are called ( 2p x , 2p y , 2pz )
eigen values
n=3 Þ M shell l= 0 Þ 3s m= 0
(iv) The solution must be single valued, should satisfy the
l= 1 Þ 3p m = –1, 0, +1
l= 2 Þ 3d m = –2, –1, 0,+1, +2
relation dr = 0 and must be finite and continuous.
æ 3d , 3d , 3d , 3d 3d ö÷
0 ç xy yz zx x2 - y2 , z2 ø
è
Structure of Atom 33
(v) Spin quantum number (s) tells the spin of the electron. It Shape of d-orbitals :
+1 -1 y y z
can have two value (clockwise) and (anticlockwise).
2 2
x z x
h
Mathematically S = s(s +1) where s is amplitude of spin
2 dyz
dxy dxz
quantum angular momentum.
SHAPE OF ORBITALS : m = 0 for d
z2
(i) s orbitals are spherically symmetrical.
(ii) p orbitals are dumbell shaped. m = ± 1 for d and d xy
x 2 - y2
(iii) d orbitals have five different orientation. Three of them dxy,
dyz, dxz are identical in shape but have different orientation. m = ± 2 for d and d
x2 y2
(iv) The plane passing through nucleus where probability of
finding the electron is zero is called a nodal plane. Number z
y
of nodal planes in an orbital = l. Number of nodal planes
increases with increasing value of n. e.g. 1s has no nodal
plane. 2s has one nodal plane. For e.g. : s orbitals (l=0) have x x
no nodal plane, p orbital (l=1) have one nodal plane, d
orbitals (l=2) have two nodal planes.
d
Nodal plane = n - l - 1 x 2 - y2 d
z2
(v) Orbitals of a sub shell having same energy are called
degenerated orbitals. PAULI’S EXCLUSION PRINCIPLE :
(vi) Spherical surface within an orbital where probability of No two electrons in an atom can have same values for all the four
finding an electron is zero is called spherical or radial node. quantum numbers.
Number of spherical nodes = (n–l–1). Angular or non (i) It is not possible to accomodate more than two electrons in
spherical nodes = (l). Thus total nodes = (n – 1). an orbital. In other words. s sub shell can have maximum of
Shape of s-orbital : 2 electrons p sub shell can have maximum of 6 electrons.
z Thus max. no. of electrons in a shell can be 2n2.
(ii) Maximum number of electrons in a sub shell can be 2, 6, 10,
14 in s, p, d, f respectively and max. electrons in an atomic
x
orbital can be 2.
y Maximum number of electrons in a sub shell is equal to
4l + 2
s orbital
Shape of p-orbital : where l = 0, 1, 2, 3
px AUFBAU’S RULE :
Electrons are added to orbitals in increasing order of energies.
z The order of energies for orbitals is 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p,
z 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s.
(i) The order of energies can be calculated by (n + l) rule. i.e.
x x orbitals are filled in order of increasing (n+l) values the one
y with lower n value is filled first.
y
py (ii) The energy of atomic orbitals for H-atom depends on the
pz value of n only.
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f
34 Chemistry
HUND’S RULE OF MAXIMUM MULTIPLICITY : In case of s orbitals the number of peaks is equal to n,
The pairing of electrons in orbitals of a subshell does not take In case of p orbitals the number of peaks is equal to (n–1),
place until all orbitals of sub shell are singly occupied. In case of d, orbitals the number of peaks is equal to (n–2)
(i) This arrangement leads to lower energy level. The point at which the probability of finding the electrons is zero
(ii) Singly occupied orbitals should have same spins giving rise iscalled nodal point.
to lower energies. The distance of maximum probability increases with increase in
the value of n. hence 2s, 2p electrons are greater distance than 1s.
RADIAL PROBABILITY DISTRIBUTION CURVES :
and have greater energy also.
2
The electron density is directly proportional to . The larger ANGULAR PROBABILITY DISTRIBUTION CURVES :
the value of
2
more is the probability of finding the electrons. The total angular ( ). (f) depends only on the direction and
Schrodinger wave equation may be separated into a product of remain independent of the distance electrons from the nucleus
three functions dependent on r, q, f P
P
Q
z
R(r) ( ) ( ) O
( r, q, f ) = { 14243 O
¯ ¯ px
Radial Part Angular part
Note : ® 4 r 2 .dr is the volume of spherical shell having small Angular probability distribution curves for s and p orbitals. The
length of the line OP is proportional to the probability of finding
thickness dr.
the electrons. The length of the line OP is the same in all directions
n=1 for s orbital Hence there are equal chances for finding electrons
n=2
R .4pr .dr
R .4pr .dr
l c çx 2
y 2 ÷ø
è
2
2p
2
3p
RH = Rydberg constant
2
2
®r ®r COMPTON EFFECT :
The decrease in energy (or increase in wavelength) of X-rays
after the scattering from the surface of carbon or light element is
R .4pr .dr
n=3
2
®r
Structure of Atom 35
1. An electron beam can undergo diffraction by crystals. 4. A bulb emits light of = 4500Å . The bulb is rated as 150
Through what potential a beam of electrons be accelerated
so that its wavelength becomes equal to 1.54Å. (IIT 1997) watt and 8% of the energy is emitted as light. How many
photons are emitted by the bulb per second?
1 h Sol. Energy of one photon
Sol. mv 2 = eV and l =
2 mv
hc 6.6 ´ 10 -34 ´ 3 ´ 10 8
2 = E = hu = = = 4.42 ´ 10 -19 J
1 h l -10
\V = . 4500 ´ 10
2 ml2 e
150 ´ 8
Energy emitted by bulb = J
(6.62 ´10 -34 ) 2 100
=
2 ´ 9.108 ´10 -31 (1.54 ´ 10 -10 ) 2 ´1.6202 ´10 -19
19 150 8
= 63.3 volt. n .42 10 =
100
2. Wavelength of photon having energy 2 eV.
\ n = 27.2 ´1018 photons
-19 -12
Sol. 1 eV = 1.6 ´ 10 J or 1.6 ´ 10 ergs
5. If the critical wavelength for producing photoelectric effect
-34 8 is 2000Å. Then what wavelength of light will be required to
hc 6.62 ´10 ´ 3 ´ 10
l= = = 6.20 ´103 Å produce photoelectrons with double the K.E. of those
E -19
2 ´1.6 ´ 10
produced by light of wavelength of 1500Å.
3. The velocity of electron in a certain Bohr's orbit of
H-atom bears the ratio 1: 275 to the velocity of light. æ hc hc ö
Sol. K.E. with 1500Å = ç - ÷ (I)
(i) What is quantum number n of orbit. è 1500 2000 ø
(ii) Wave number of radiations emitted when electron jumps
from (n + 1) to ground state. æ hc hc ö
KE with xÅ = ç - ÷ (II)
è x 2000 ø
1
Sol. (i) Velocity of electron = ´ Velocity of light
275 According to question 2I = II
æ hc hc ö æ hc hc ö
2.19 ´ 108 ´ Z 2ç - ÷=ç - ÷
Again Vn = cm / sec è 1500 2000 ø è x 2000 ø
n
1 æ 1 1 ö÷ T12 R3 T1 1
For H = RH ç - \ = Þ =
l ç 2 2 ÷
T22 3 T2 8
è n1 n 2 ø 64R
14. Calculate the speed of electron in third orbit of hydrogen
1 ù é 12é 1 ù
1 atom. Also calculate the number of revolutions per second
Since l is the same Z ê 2 - 2 ú = ê 2 - 2 ú that this electron makes around the nucleus. Given
ë2 4 û êë n 1 n 2 úû
4p 0 = 1.112 ´10 -10 C 2 N -1m -2 .
é1 1 ù é 1 1 ù
Since Z = 2 ê 2 - 2 ú = ê 2 - 2 ú 2p(Ze2 / 4p 0 )
ë1 2 û êë n1 n 2 úû Sol. Speed v =
nh
n1 = 1 and n2 = 2
2 ´ 3.14(1.6 ´ 10 -19 C) 2 / 1.112 ´ 10 -10
= = 7.27 ´ 10 5 ms -1
10. Find out the number of waves by a Bohr electron in one 3 ´ 6.626 ´ 10 -34
complete revolution in its 3rd orbit. [IIT 1994]
Sol. Number of waves in an orbit v
Number of revolutions made by the electron =
2 pr
Circumference of orbit 2 r
= =
Wavelength n2 h2
r= 2
4 m( Ze2 / 4 0)
æ nh ö
2 ç ÷ 34
2 r 2 (mvr) 2 9 (6.626 10 )
= = = è ø =n =
h / mv h h 2 31 19 2 10
4(3.14) (9.1 10 kg)(1.6 10 ) / 1.112 10
(Since angular momentum mvr = nh/ 2p) Ans. 3.
= 4.782 ´ 10 -10 m
11. A compound of Vanadium has a magnetic moment of 1.73
BM. Work out the electronic configuration of the vanadium 7.27 ´ 10 5
v= = 2.42 ´ 10 4 s -1
ion in the compound. [IIT 1997] 2 ´ 3.14 ´ 4.782 ´ 10 -10
Structure of Atom 37
15. Calculate the frequency, energy and wavelength of the - 12
radiation corresponding to the spectral line of lowest D E = E ¥ - E 2 = 5.425 × 10 ergs
frequency in Lyman series in the spectra of H atom. Also
hc 6.626 ´ 10 - 27 ´ 3 ´ 1010
calculate the energy for the corresponding line in the spectra E= = 5.425 × 10 - 12 =
of Li2+ l l
4 4 1 6.626 ´ 10 - 34 ´ 3 ´ 108
l = 3R = × = 1.216 × 10 - 7 m = = 4.417 × 10 - 19 J
H 3 1.09678 ´ 107 m -1 4500 ´ 10 -10
3.00 ´ 108 ms -1
= 1.55 ´10-19 J and u = = 4.2 × 10 14 s - 1
710 ´ 10 - 9 m
1/ 2
é 2 ´ 0.97 ´ 1.602 ´ 10 -19 ù The frequency range of the human eye is 4.2 × 10 14 to
(iii) v = ê ú = 5.85 × 10 5 ms -1
êë 9.109 ´ 10- 31 úû 14
7.7 × 10 Hz.
Structure of Atom 39
1. A neutral atom (Atomic No > 1) has 4. Which of the following statements is incorrect?
(a) electron and proton (a) Cathode rays carry negative charge
(b) neutron and electron (b) Frequency of X-rays is higher than that of microwaves
(c) neutron, electron and proton (c) Unit for wave number is m–1
(d) neutron and proton. (d) Threshold frequency is the same for all metals.
2. Which of the following set of quantum numbers belong to 5. Which is not true with respect to cathode rays?
highest energy? (a) A stream of electrons
(b) Charged particles
1
(a) n = 4, l = 0, m = 0, s = + (c) Move with speed same as that of light
2 (d) Can be deflected by magnetic fields
1 6. Rutherford’s a-particle dispersion experiment concludes
(b) n = 3, l = 0, m = 0, s = + (a) all positive ions are deposited at small part
2
(b) all negative ions are deposited at small part
1 (c) proton moves around the electron
(c) n = 3, l = 1, m = 1, s = + (d) neutrons are charged particles.
2
7. Ratio of mass of proton and electron is
1 (a) infinite (b) 1.8 × 103
(d) n = 3, l = 2, m = 1, s = +
2 (c) 1.8 (d) None of these.
1-
8. Which of the following is the main cause of late discovery of
3. The number of electrons in é 19
40 ù
K is neutron?
ë û (a) Neutron is chargeless particle
(a) 20 (b) 40 (b) Neutron is highly unstable particle
(c) 18 (d) 19 (c) Neutron in the nucleus moves very fast
(d) All of these.
Structure of Atom 41
9. Which of the following does not contain number of neutrons (a) 3 : 1 (b) 2 : 1
40 (c) 1 : 2 (d) 1 : 3
equal to that of 18 Ar ? 20. The energy of a photon is given as DE/atom
(a) 41 (b) 43
19 K 21 Sc 3.03 ´10-19 J atom-1 . Then the wavelength (l) of the
(c) 40 (d) 42 photon is
21 Sc 20 Ca
(a) 65.6 nm (b) 656 nm
10. Rutherford’s experiment which established the nuclear model
of the atom used a beam of (c) 0.656 nm (d) 6.56 nm
(a) b-particles which impinged on a metal foil and got 21. If wavelength of photon is 2.2×10–11 m, h = 6.6 ×10–34 Js,
absorbed then momentum of photon is
(b) g-rays which impinged on a metal foil and ejected (a) 3 × 10–23 kg/s (b) 3.33 × 1022 kg/s
–44
electrons (c) 1.452 × 10 kg/s (d) 6.89 × 1043 kg/s
(c) helium atoms, which impinged on a metal foil and got 22. Which orbital of carbon can absorb photon but not emit it?
scattered (a) 1 s (b) 2 s
(d) helium nuclei, which impinged on a metal foil and got (c) 3 p (d) 2 p.
scattered 23. Brackett series are produced when the electrons from the
11. Number of protons, neutrons and electrons in the element outer orbits jump to
231 (a) 2nd orbit (b) 3rd orbit
89 X is (c) 4th orbit (d) 5th orbit.
(a) 89, 89, 242 (b) 89, 142, 89 24. The first emission line in the atomic spectrum of hydrogen in
(c) 89, 71, 89 (d) 89, 231, 89 the Balmer series appears at
12. An element has atomic number 11 and mass number 24. What
9R 7R
does the nucleus contain? (a) cm -1 (b) cm -1
(a) 11 protons, 13 neutrons 400 144
(b) 11 protons, 13 neutrons, 13 electrons
3R 5R
(c) 13 protons, 11 neutrons (c) cm -1 (d) cm -1
(d) 13 protons, 11 electrons 4 36
13. The number of electrons and neutrons of an element is 18 25. In hydrogen spectrum which of the following lies in the
and 20 respectively. Its mass number is wavelength range 350–700 nm?
(a) 2 (b) 17 (a) Balmer series (b) Lyman series
(c) 37 (d) 38 (c) Brackett series (d) paschen series.
14. The hydride ion is isoelectronic with 26. In Balmer series of hydrogen atom spectrum which electronic
(a) H+ (b) He+ transition causes third line?
(c) He (d) Be. (a) Fifth Bohr orbit to second one
15. Which of the following isoelectronic species has the smallest (b) Fifth Bohr orbit to first one.
atomic radius? (c) Fourth Bohr orbit to second one
(a) N 3- (b) O 2- (d) Fourth Bohr orbit to first one.
27. The spectrum of He is expected to be similar to that of
(c) F - (d) Ne. (a) H (b) Na
16. Among the following groupings which represents the (c) He +
(d) Li+
collection of isoelectronic species? 28. In hydrogen atom, energy of first excited state is –3.4eV.
(a) NO + , C 22 - , O -2 , CO (b) N 2 , C 22 - , CO, NO Then find out the KE of the same orbit of hydrogen atom
(a) + 3.4 eV (b) + 6.8 eV
(c)CO, NO + , CN - , C 22 - (d) NO, CN - , N 2 , O -2 (c) – 13.6 eV (d) + 13.6 eV
17. Which of the following is not iso electronic 29. In the Bohr’s orbit, what is the ratio of total kinetic energy
and total energy of the electron?
+
(a) Na (b) Mg 2+ (a) –1 (b) –2
(c) 1 (d) +2
2-
(c) O (d) Cl - 30. The kinetic energy of an electron accelerated from rest
18. Chloride ion and potassium ion are isoelectronic. Then through a potential difference of 5 V will be
(a) their sizes are same (a) 5 J (b) 5 erg
(b) chloride ion is bigger than potassium ion (c) 5 eV (d) 8 × 10–19eV
(c) potassium ion is relatively bigger 31. The angular momentum of an electron revolving around the
(d) depends upon the other cation or anion nucleus is integral multiple of
19. Ratio of energy of photon of wavelength 3000 Å and 6000Å (a) 2n (b) h
is (c) h / 2p (d) 2pn
42 Chemistry
32. The orbital angular momentum of an electron in 2 s orbital is 44. The radius of hydrogen atom in the ground state is 0.53Å.
The radius of Li2+ ion (atomic number = 3) in a similar state is
1 h
(a) + . (b) zero (a) 0.17 Å (b) 1.06 Å
2 2p (c) 0.53 Å (d) 0.265 Å
h h 45. The Bohr orbit radius for the H-atom (Z=1) is approximately
(c) (d) 2. 0.53 Å. The radius for the first excited state orbit is
2p 2p
(a) 0.13 Å (b) 1.06Å
33. The energy of an electron in the first Bohr orbit of H atom is
(c) 4.77 Å (d) 2.12 Å
– 13.6 eV. The possible energy value(s) of the excited state
46. The ratio of the radius of the first Bohr orbit for the electron
(s) for electrons in Bohr orbits of hydrogen is (are)
orbiting the hydrogen nucleus to that of the electron orbiting
(a) – 3.4eV (b) – 4.2eV
the deuterium nucleus (mass nearly twice that of the
(c) – 6.8 eV (d) + 6.8eV. hydrogen nucleus) is approximately
34. If the radius of first Bohr orbit be a0, then the radius of the (a) 2 : 1 (b) 1 : 1
third orbit would be (c) 1 : 2 (d) 4 : 1
(a) 3 × a0 (b) 6 × a0 47. The energy of the first electron in helium will be
(c) 9 × a0 (d) 1/9 × a0 (a) –13.6 eV (b) –54.4 eV
35. According to Bohr’s theory of hydrogen atom, which of the (c) –5.44 eV (d) zero
following is quantised for an electron? 48. Who modified Bohr’s theory by introducing eiliptical orbits
(a) Angular momentum (b) Angular acceleration for electron path?
(c) Acceleration (d) Velocity. (a) Hund (b) Thomson
36. According to Bohr’s theory the energy required for the (c) Rutherford (d) Sommerfeld.
transition of H-atom from n = 6 to n = 8 state is 49. Wavelength associated with electron motion
(a) equal to the energy required for the transition from n = (a) increases with increase in speed of electron
5 to n = 6 state (b) remains same irrespective of speed of electron
(b) larger than in (a) (c) decreases with increase of speed of e– (electron)
(c) less than in (a) (d) is zero.
(d) equal to the energy required for the transition from n = 50. If the Planck’s constant h = 6.6×10–34 Js, the de Broglie
7 to n = 9 state. wavelength of a particle having momentum of 3.3 × 10–24
37. The wave number of the light emitted by a certain source is kg ms –1 will be
2 × 106 m . The wavelength of this light is (a) 0.002 Å (b) 0.5Å
(a) 500 m (b) 200 nm (c) 2Å (d) 500Å
(c) 500 nm (d) 5 × 107 m 51. What is the wavelength associated with an electron moving
38. For which of the following species, Bohr’s theory is not with a velocity of 106 m/s?
applicable? (given h = 6.63 × 10–34 Js and m = 9.11 × 10–31 kg)
(a) Be3+ (b) Li2+ (a) 72.7 nm (b) 0.727 nm
2+
(c) He (d) H. (c) 7.27 nm (c) None of these.
39. As the nuclear charge increases from Neon to Calcium, the 52. The wavelength associated with a golf balf weighing 200 g
orbital energies and moving at a speed of 5 m/h is of the order
(a) increase (b) increase very rapidly (a) 10–10 m (b) 10–20m
–30
(c) increase very slowly (d) fall (c) 10 m (d) 10–40m
40. The ratio of ionization energy of H and Be+3 is 53. The uncertainty in the position of an electron
(a) 1 : 1 (b) 1 : 3 (mass = 9.1 × 10–28 g) moving with a velocity of 3.0 × 104
(c) 1 : 9 (d) 1 : 16 cm s–1 accurate upto 0.011% will be
41. In a Bohr model of on atom, when an electron jumps from n = (a) 1.92 cm (b) 7.68 cm
3 to n = 1, how much energy will be emitted? (c) 0.175 cm (d) 3.84 cm.
(a) 2.15 × 10–11 ergs (b) 2.389 × 10 –12 ergs 54. The uncertainty in the momentum of an electron is
(c) 0.239 × 10 ergs–10
(d) 0.1936 × 10 –10 ergs 1.0 × 10–5 kg ms –1. The uncertainty in its position will be (h =
42. In H-atom electron jumps from 3rd to 2nd energy level, the 6.62 × 10–34 kg m2 s–1)
energy released is (a) 1.05 × 10–26 m (b) 1.05 × 10–28 m
–30
(a) 3.03 × 10–19 J/atom (b) 1.03 × 10–19 J/atom (c) 5.27 × 10 m (d) 5.25 × 10–28 m
(c) 3.03 × 10–12 J/atom (d) 6.06 × 10–19 J/atom 55. Azimuthal quantum number determines the
43. The value of the energy for the first excited state of hydrogen (a) size
atom will be (b) spin
(a) –13.6 eV (b) –3.40 eV (c) orientation
(c) –1.51 eV (d) –0.85eV (d) angular momentum of orbitals
Structure of Atom 43
56. When the value of azimuthal quantum number, l = 2, value of 65. The electrons, identified by quantum numbers n and l (i) n =
‘n’ will be 4, l = 1 (ii) n = 4, l = 0 (iii) n = 3, l = 2 (iv) n = 3,
(a) 3 (b) 4 l = 1 can be placed in order of increasing energy, from the
(c) 5 (d) any one of these. lowest to highest, as
57. The values of quantum numbers n, l and m for the 5th electron (a) (iv) < (ii) < (iii) < (i) (b) (ii) < (iv) < (i) < (iii)
of Boron will be (c) (i) < (iii) < (ii) < (iv) (d) (iii) < (i) < (iv) < (ii)
(a) n = 1, l = 0, m = –1 (b) n = 2, l = 1, m = –1 66. Bohr's model of atom is in conflict with
(c) n = 2, l = 2, m = –1 (d) n = 1, l = 2, m = –1 (a) Pauli's exclusion principle
(b) Heiseinberg's uncertainity principle
58. The total number of orbitals in a shell with principal quantum
(c) Max Planck's quantum theory
number ‘n’ is
(d) All the above three
(a) 2 n (b) 2 n2
2 67. What is the maximum number of electrons that can be
(c) n (d) n.
accomodated in an atom in which the highest principal
59. Which of the following combinations of quantum numbers quantum number value is 4?
is allowed? (a) 10 (b) 18
n l m ms (c) 36 (d) 54.
(a) 3 2 1 0 68. The total number of orbitals possible for principal quantum
1 number n is
(b) 2 0 0 - (a) n (b) n 2
2
(c) 2n (d) 2n2
1 69. Which of the following is not possible ?
(c) 3 –3 –2 + (a) n = 3, l = 0, m = 0
2
(b) n = 3, l = 1, m = –1
1 (c) n = 2, l = 0, m = –1
(d) 1 0 1 +
2 (d) n = 2, l = 1, m = 0.
60. Which one of the following set of quantum numbers is not 70. For how many orbitals, the quantum numbers
possible for 4p electron? n = 3, l =2, m = +2 are possible?
(a) 1 (b) 2
1
(a) n = 4, l = 1, m = –1, mS= + (c) 3 (d) 4
2 71. The correct set of quantum numbers for a 4d electron is
1 1
(b) n = 4, l = 1, m = 0, mS = + (a) 4, 3, 2, + (b) 4, 2, 1, 0
2 2
1 1 1
(c) n = 4, l = 1, m = 2, mS = + (c) 4, 3, - 2, + (d) 4, 2,1, -
2 2 2
1 72. For a, f-orbital, the values of m are
(d) n = 4, l = 1, m = –1, mS = - (a) –2, –1, 0, +1, +2
2
(b) –3, –2, –1, 0, +1, +2, 3
61. The maximum number of electrons in subshell with
(c) –1, 0, +1
l = 2 and n = 3 is
(d) 0, +1, +2, +3
(a) 2 (b) 6
73. The values of Planck's constant is 6.63 × 10–34 Js. The velocity
(c) 12 (d) 10 of light is 3.0 × 108 m s–1. Which value is closest to the
62. An electron has principal quantum number 3. The number of wavelength in nanometres of a quantum of light with
its (i) sub-shells and (ii) orbitals would be respectively frequency of 8 × 1015 s–1?
(a) 3 and 5 (b) 3 and 7 (a) 5 × 10–18 (b) 4 × 101
7
(c) 3 and 9 (d) 2 and 5 (c) 3 × 10 (d) 2 × 10–25
63. An e– has magnetic quantum number as –3, what is its 74. The number of nodal planes ‘d’ orbital has
principal quantum number? (a) 1 (b) 2
(a) 1 (b) 2 (c) 3 (d) 0
(c) 3 (d) 4 75. What do you mean by degenerate orbitals?
64. The four quantum numbers of the valence electron of (a) Orbitals having equal energy
potassium are (b) Oribitals having equal wave function
(a) 4, 1, 1, 1/2 (b) 4, 0, 0, 1/2 (c) Oribitals having equal energy but different wave
(c) 4, 5, 0, 1/2 (d) 4, 4, 0, 1/2 function
(d) Orbitals having equal energy and equal wave function.
44 Chemistry
76. The number of nodal planes in a px orbital is 90. The number of unpaired electrons in a Nickel atom (ground
(a) one (b) two state) are (Atomic No. of Ni = 28)
(c) three (d) zero. (a) 2 (b) 5 (c) 3 (d) 7
77. A 5f orbital has 91. The element with its electronic configuration of its
(a) one node (b) two nodes atom 1 s2 2 s2 2 p6 3 s2 3 p6 3 d10 4 s1 is
(c) three nodes (d) four nodes. (a) Fe (b) Co (c) Ni (d) Cu.
78. “ No two electrons in an atom can have same set of all the 92. In Cu. (At. No. 29)
four quantum numbers” is known as (a) 13 electrons have spin in one direction and 16 electrons
(a) Hund’s rule in other direction
(b) Aufbau principle (b) 14 electrons have spin one direction and 15 electrons
(c) Uncertainty principle in other direction
(d) Pauli’s exclusion principle. (c) one electron can have spin only in the clockwise
79. Which of the following has maximum number of unpaired direction
electrons ? (d) None of the above is correct.
3+ 93. Which of the following atom has no neutron in its nucleus?
(a) Mg 2+ (b) Ti 3+ (c) V (d) Fe 2 +
(a) Helium (b) Lithium
80. An element M has an atomic mass 19 and atomic number 9, (c) Protium (d) Tritium
its ion is represented by 94. In the ground state, an element has 13 electrons in its M-
(a) M + (b) M 2 + (c) M - (d) M 2 - shell. The element is
2 2 5 1
81. The configuration 1s 2 s 2p 3 s shows (a) zinc (b) chromium
(a) ground state of fluorine (c) nickel (d) iron
(b) excited state of fluorine 95. Which one of the following pairs of ions has the same
(c) excited state of neon atom electronic configuration?
1. If uncertainty in position and momentum are equal, then 11. The value of Planck’s constant is 6.63 × 10–34 Js. The speed
uncertainty in velocity is : [CBSE-PMT 2008] of light is 3 × 1017 nm s–1.. Which value is closest to the
wavelength in nanometer of a quantum of light with frequency
1 h h 1 h h of 6 × 1015 s–1? [NEET 2013]
(a) (b) (c) (d)
2m p 2p m p p (a) 25 (b) 50 (c) 75 (d) 10
2. The measurement of the electron position is associated with 12. What is the maximum numbers of electrons that can be
an uncertainty in momentum, which is equal to 1×10–18 g cm s–1. associated with the following set of quantum numbers?
The uncertainty in electron velocity is, [CBSE-PMT 2008] n = 3, l = 1 and m = –1 [NEET 2013]
(mass of an electron is 9 × 10– 28 g) (a) 6 (b) 4 (c) 2 (d) 10
(a) 1 × 109 cm s–1 (b) 1 × 106 cm s–1 æ Z2 ö
5 –1 (d) 1 × 1011 cm s–1
(c) 1 × 10 cm s 13. Based on equation E = – 2.178 × J çç 2 ÷÷ , certain
10-18
3. The energy absorbed by each molecule (A2) of a substance èn ø
is 4.4 × 10–19 J and bond energy per molecule is 4.0 × 10–19 J. conclusions are written. Which of them is not correct ?
The kinetic energy of the molecule per atom will be: [NEET 2013]
[CBSE-PMT 2009] (a) Larger the value of n, the larger is the orbit radius.
(a) 2.2 × 10–19 J (b) 2.0 × 10–19 J (b) Equation can be used to calculate the change in energy
(c) 4.0 × 10–20 J (d) 2.0 × 10–20 J when the electron changes orbit.
4. Maximum number of electrons in a subshell of an atom is (c) For n = 1, the electron has a more negative energy than it
determined by the following: [CBSE-PMT 2009] does for n = 6 which mean that the electron is more loosely
(a) 2 l + 1 (b) 4 l – 2 (c) 2 n2 (d) 4 l + 2 bound in the smallest allowed orbit.
5. Which of the following is not permissible arrangement of (d) The negative sign in equation simply means that the
electrons in an atom? [CBSE-PMT 2009] energy or electron bound to the nucleus is lower than it
(a) n = 5, l = 3, m = 0, s = + 1/2 would be if the electrons were at the infinite distance
(b) n = 3, l = 2, m = – 3, s = – 1/2 from the nucleus.
(c) n = 3, l = 2, m = – 2, s = – 1/2 14. In a hydrogen atom, if energy of an electron in ground state is
(d) n = 4, l = 0, m = 0, s = – 1/2 13.6. eV, then that in the 2nd excited state is [AIEEE 2002]
6. A 0.66 kg ball is moving with a speed of 100 m/s. The associated (a) 1.51 eV (b) 3.4 eV (c) 6.04 eV (d) 13.6 eV.
wavelength will be ( h = 6.6 ´ 10 -34 Js) : [CBSE-PMT 2010] 15. Uncertainty in position of a minute particle of mass 25 g in
(a) 1.0 ´ 10–32m (b) 6.6 ´ 10–32m space is 10–5 m. What is the uncertainty in its velocity (in
(c) 6.6 ´ 10 m–34 (d) 1.0 ´ 10–35m ms–1)? (h = 6.6 ´ 10–34 Js) [AIEEE 2002]
7. The total number of atomic orbitals in fourth energy level of (a) 2.1 ´ 10 –34 (b) 0.5 ´ 10–34
1. Which statement is not correct ? (c) electrons come out of metal with a constant velocity
which depends on frequency and intesity of incident
æ 4 3ö -38 light.
(a) Volume of proton is approx. ç pr ÷1.5 ´ 10 cm3.
è3 ø (d) electrons come out of metal with different velocities
not greater than a certain value which depends upon
(b) Radius of e– is 42.8 × 10–13 cm3
frequency of incident light and not on intensity.
(c) Density of nucleus is 1014 g/cm3. 5. If E1, E2 and E3 represent respectively the kinetic energies of
(d) All are correct an electron and an alpha particle and a proton each having
2. The potential energy of electron present in ground state of same de-broglie wavelength then
Li2+ ion is represented by : (a) E1 > E3 > E2 (b) E2 > E3 > E1
+ 3e 2 -3e (c) E1 > E2 > E3 (d) E1 = E2 = E3
(a)
4p 0 r
(b) 4p 0 r 6. The angular speed of the electron in n th orbit of Bohr
hydrogen atom is
- 3e 2 - 3e 2 (a) directly proportional to n
(c) (d)
4p 0 r 2 4p 0 r (b) inversely proportional of n
3. Which principle/rule limits the maximum no. of electrons in (c) inversely proportional to n 2
an orbital to two ? (d) inversely proportional to n 3
(a) Aufbau principle 7. The Bohr's energy equation for H atom reveals that the energy
(b) Pauli's exclusion principle level of a shell is given by E = –13.58/n2eV. The smallest
(c) Hund's rule of max. multiplicity amount that an H atom will absorb if in ground state is
(d) Heisenberg's uncertainty principle (a) 1.0 eV (b) 3.39 eV
4. Photoelectric effect is the phenomenon in which (c) 6.79 eV (d) 10.19 eV
(a) photons come out of metal when hit by a beam of 8. If the Planck's constant h = 6.6 × 10–34 Js, the de-Broglie's
wavelength of a particle having momentum of 3.3 × 10–24
electrons
m/s will be
(b) photons come out of the nucleus of an atom under the (a) 0.02Å (b) 0.5Å
action of an electric field (c) 2Å (d) 500Å
48 Chemistry
9. Ionization potential of hydrogen atom is 13.6eV. Hydrogen 19. The angular distribution functions of all orbitals have
atom in ground state are excited by monochromatic light of (a) l nodal surfaces (b) l – 1 nodal surfaces
energy 12.1 eV. The spectral lines emitted by hydrogen (c) n + 1 nodal surfaces (d) n – l –1 nodal surfaces
according to Bohr's theory will be 20. Which of the following radial distribution graphs correspond
(a) one (b) two to l = 2 for the H atom ?
(c) three (d) four
10. The wavelength of radiations emitted when electrons
falls from 4 th Bohr's orbit to 2 nd in H atom is : (RH =
(a)
1.09678 × 10–7 m –1).
(a) 972 nm (b) 486 nm
(c) 243 nm (d) 182 nm
11. The energy of e– in first orbit of He+ is –871.6 × 10–20 J. The
energy of e– in first orbit of H is:
(a) – 871.6 × 10–20 (b) –435.8 × 10–20 J
–20 (b)
(c) – 217.9 × 10 J (d) –108.9 × 10–20
12. The wave no. of radiation of wavelength 500 nm is :
(a) 5 × 10–7 /m (b) 2 × 107/m
6
(c) 2 × 10 /m (d) 500 × 10–9/m
+
13. In ground state of Cu . The no. of shells occupied, subshells,
filled orbitals, and unpaired electrons respectively are :
(a) 4, 8, 15, 0 (b) 3, 6, 15, 1 (c)
(c) 3, 6, 14, 0 (d) 4, 7, 14, 2
14. The quantum numbers +1/2 and –1/2 for the electron spin
represent
(a) rotation of the electron in clockwise and anticlockwise
direction respectively
(b) rotation of the electron in anticlockwise and clockwise
direction respectively (d)
(c) magnetic moment of the electron pointing up and down
respectively
(d) two quantum mechanical spin states which have no
classical analogue
15. Let mp be the mass of a proton, mn that of a neutron, M1 that
of a 20 nucleus and M2 that of a 40 nucleus. Then 21. Which of the following graphs correspond to
10 Ne 20 Ca one node?
(a) M2 = 2M1 (b) M1<10(mp + mn)
(c) M2 > 2M1 (d) M1 = M2
16. Which of the following pairs have identical values of e/m?
(a) A proton and a neutron (a) (b)
(b) A proton and deuterium
(c) Deuterium and an a- particle
(d) An electron and g-rays
ao
17. The wavelength of the third line of the Balmer series for a
hydrogen atom is
21 100
(a) (b) (c) (d)
100R ¥ 21R ¥
21R ¥ 100R ¥ ao
(c) (d) ao
100 21
22. A body of mass 10 mg is moving with a velocity of
18. Which of the following electronic configurations have zero
-1
spin multiplicity ? 100 ms . The wavelength of de-Broglie's wave associated
with it would be
(a) (b)
(a) 6.63 × 10 -35 m (b) 6.63 × 10 -31 m
(c) (d) (c) 6.63 × 10 -37 m (d) 6.63 × 10 -34 m
Structure of Atom 49
23. If N 0 represents the Avogadro number, then which of the 31. The ratio of magnetic moments of Fe(III) and Co(II) is
(a) 7 : 3 (b) 3 : 7
following represent correct value of one atomic mass unit.
(c) 7 : 3 (d) 3 : 7
(a) N 0 ´ 10 - 3 kg (b) N0 g
32. The average life of an excited state of hydrogen atom is of
-1 1
(c) N 0 g (d)
16
Mass of 0-16 atom the order 10 -8 s. The number of revolutions made by an
electron when it is in state n = 2 and before it suffers a
24. If the shortest wavelength of the spectral line of H-atom in
transition to state n = 9 are
the Lyman series is X, then the longest wavelength of the
(a) 8.23 × 10 6 (b) 2.82 × 10 6
line in Balmer series of Li 2+ is
x (c) 22.8 × 10 6 (d) 2.28 × 10 6
(a) 9x (b) 33. The number of concentric spherical surfaces for 3s orbital at
9
which the probability of finding electrons is zero, are
5x 4x (a) 3 (b) 2
(c) (d)
4 5 (c) 1 (d) 0
25. If the subsidiary quantum number of a sub-energy level is 4, 34. If the second ionization potential of helium is 54.4 eV, then
the maximum and minimum values of the spin multiplicities
possible energy states of He + ion is/are
are
(a) 10, 2 (b) 4, – 4 (a) 13.6 eV (b) – 13.6 eV
(c) 10, 1 (d) 9, 1 (c) + 3.4 eV (d) None of these
35. If the uncertainties in position and momentum are equal, the
26. Li 3+ and a proton are accelerated by the same potential, uncertainty in the velocity is
then de-Broglie wavelengths l Li and l p have the ratio
1 h h
(a) (b)
(assume m Li = 9 mp ) 2m p 2p
(a) 1: 3 3 (b) 1 : 1 h
(c) 1 : 2 (d) 1 : 4 (c) (d) None of these
p
27. One Bohr magnet on is equal to
36. The de-Broglie wavelength of an electron accelerated by an
c h electric field of V volts is given by
(a) (b)
4phm e 4pem e
1.23 1.23
(a) l= nm (b) l= nm
eh hc V h
(c) (d)
4 me 4 me
1.23 1.23
(c) l= nm (d) l= nm
-1 m
28. The dissociation energy of H 2 is 430.53 KJmol . If V
hydrogen is dissociated by illumination with radiation of 37. The photoelectric current decreases if
wavelength 253.7 nm the fraction of the radiant energy which (a) the intensity of the source of light is decreased
will be converted into kinetic energy is given by (b) the frequency of incident radiation decreases below
(a) 100% (b) 8.76% threshold frequency
(c) 2.22% (d) 1.22%
(c) the exposure time decreases
29. The magnetic moment of M x + (atomic number M = 25) is (d) None of these
38. If a proton and a -particle are accelerated through the same
15 BM. The number of unpaired elections and the value
of x respectively are potential difference, the ratio of de-Broglie wavelengths l p
(a) 5, 2 (b) 3, 2 and l a is
(c) 3, 4 (d) 4, 3
30. The threshold frequency of a metal is 1 × 1015 s -1 . The ratio (a) 3 (b) 2 2
of the maximum kinetic energies of the photoelectrons when (c) 1 (d) 2
the metal is irradiated with radiations of frequencies 1.5 × 39. Which of the following pairs of nucleides are isodiaphers ?
1015 s -1 and 2.0 × 1015 s -1 respectively would be (a) 13
6 C and 16
8 O
(b) 1
1H and 12 H
(a) 4 : 3 (b) 1 : 2
(c) 3 and 42 He (d) 55 and 65
(c) 2 : 1 (d) 3 : 4 1H 25 Mn 30 Zn
50 Chemistry
40. A system irradiated for 10 min. is found to absorb 39
42. The species 19 K and 19
9 F are called
18
3 × 10 quanta per sec. If the amount of substance (a) isosters (b) isobars
decomposed is 3 × 10 -3 mol ( N A = 6 × 10 23 ). The quantum (c) isotones (d) isodiaphers
43. A particle of mass 1 micro gram is moving with a speed of
efficiency of the reaction is
1 Kms–1. The de-Broglie wavelength of the particle is
(a) 2.5 (b) 2
(c) 1.5 (d) 1 (a) 7.04 × 10 -25 m (b) 6.626 × 10 -28 m
41. If the radius of first orbit of H-atom is a 0 , then de-Broglie (c) 6.626 × 10 -15 m (d) 6.626 × 10 -31 m
wavelength of electron in 4th orbit is
a0
(a) 8pa 0 (b)
4
(c) 16a 0 (d) 2pa 0
Structure of Atom 51
–
EXERCISE 1 14. (c) Hydride ion H contains two electrons and He contains
238 234
two electrons.
1. Isotopes = U, U
92 92
15. (c)
Isobars = 234
90 Th, 234
91 Pa, 234
92 U 16. (c) The species CO, NO+, CN– and C22–. Contain 14 electrons
each.
2. First energy level.
3. s-orbital 17. (d) Na+, Mg++, O2– contain 10 electrons each Cl– has 18
electrons.
4. Interference and diffraction
18. (b) Nuclear charge of K+ (19) is more than nuclear charge of
5. There is no probability of finding a d electron right at the
Cl– (17).
nucleus.
6. Electron, because of its least mass. hc E1 2 6000
19. (b) E = ; = = = 2 :1
8. K.E. = 7.29 × 10–19J E2 1 3000
9. l = 1.24 × 10–14 m
hc
10. l = 6572 Å 20. (b) DE = hn = ;
l
13. v0= 9.81×1014 Hz.
19. (b) 20. (a) 21. (c) 22. (c) hc 6.63 ´ 10 -34 (3 ´ 108 )
\l = = = 656 nm
23. (a) 24. (b) 25. (b) 26. (d) DE 3.03 ´ 10 -19
27. (c) 28. (c)
h 6.63 ´10-34
EXERCISE 2 21. (a) p = = = 3 ´10-23 kg / s
l 2.2 ´10 -11
1. (c) A neutral atom with Z > 1 can have neutron, proton and
electron. 22. (a) It is in the lowest energy level, it can absorb and not emit
2. (d) Atomic orbitals are 4s, 3s, 3p and 3d. (n + l) values being energy.
4, 3, 4 and 5. Hence 3d has highest energy. 23. (c) See text for Brackett n 1 = 4, n2 = 5, 6, 7 etc.
3. (a) 19 + 1e– = 20 electrons.
æ 1 1 ö 5R
4. (d) Threshold frequency is not the same for all metals. 24. (d) For Balmer n1 = 2 and n2 = 3; n = R çç - ÷÷ = cm -1
2 2 36
è2 3 ø
5. (c) incorrect. (see text).
6. (a) All positive ions are deposited at small part. (nucleus of 25. (a) 350-700 nm lies in visible region hence Balmer Series.
atom). 26. (a) For Balmer n 1 = 2 and n2 = 3, 4, 5. For third line
7. (b) Ratio of mass of proton and electron is approx. n1 = 2 & n2 = 5.
1837 = 1.8 × 103. 27. (d) Li+ and He both have two electrons each.
8. (a) Neutron being chargless particle could not effect certain 13.6 ´ 1
13.6 Z 2 = +3.4 eV .
properties. 28. (a) KE = eV when n = 2. KE =
22
2
40
n
9. (c) 18Ar contains 22 neutrons and 21Sc40 contains 19
neutrons. The number of neutrons = (A – Z)
10. (d) Rutherford used doubly charged helium particle. 13.6Z2 13.6Z 2
29. (a) KE = eV and Total energy = - eV .
(a - particle) n2 n2
11. (b) Number of p = number of e – = 89 and neutrons Hence ratio = –1.
231 – 89 = 142. 30. (c)
12. (a) Z = 11, A = 24. Hence protons = 11 the neutrons
(24 – 11) = 13. nh
31. (c) Angular momentum mvr =
13. (d) For neutral atom . No. of p = No. of e– = 18 and 2p
A = Z + No. of neutrons = 18 + 20 = 38.
52 Chemistry
74. (b)
Number of nodal planes in d orbitals is 2. h
1. (a) We know Dp.Dx ³
4p
75. (a)
Degenerate orbitals have equal energy.
since Dp = Dx (given)
76. (a)
One nodal plane in the YZ plane.
h
77. (a)
Angular nodes = l, spherical nodes (n – l – 1); \ Dp.Dp =
4p
Total (n – 1). Hence spherical nodes for 5f orbits.
= ( 5 –3 –1) = 1 h
or mDv m v. = [\ Dp= mDv]
78. (d) (follow text.) 4
2 h
or ( Dv ) =
79. (d) Mg 2 + = 1s 2 , 2s 2 p 6 , Ti 3+ = 1s 2 2s 2 p 6 3s 2 p 6 d 1 , 4 pm 2
V 3+ = 1s 2 , 2s 2 p 6 , 3s 2 p 6d 2 , Fe2+ = 1s2, 2s 2p6, 3s 2p6d 6 h 1 h
or Dv = =
(4 unpaired electrons in d). 4pm 2m p
2
80. (c) Atomic number 9 is for F and ion is F–. Thus option (a) is the correct option.
81. (c) 1s2, 2s22p5, 3s1. Total electrons (10) excited state of Ne. 2. (a) Dp = mDv
Substituting the given values of Dx and m, we get
82. (d) Heisenberg's uncertainty Principle is applicable to any 1×10–18 g cm s–1 = 9×10–28 g × Dv
moving object.
1´ 10 -18
83. (d) Configuration contains 2 unpaired electrons hence most or Dv =
paramagnetic. 9 ´ 10-28
= 1.1 × 109 cm s–1 ; 1×109 cm s–1
84. (d) For Cu2+ electronic configuration is [Ar]3d9.
i.e. option (a) is correct.
85. (c) Aufbau Principle. 3. (d) K.E per atom
18 3 hc
2.178 10 = 1
4 K.E. µ
m
34
6.62 10 3 108
= V 1
6. (d) Angular speed is . Vn µ and rn µ n 2 .
r n
34
6.62 10 3 108 4 Angular speed is inversely proportional to n
=
2.178 10 18 3 7. (d) The smallest value of energy of an electron in H atom in
= 1.214 × 10–7m ground state can absorb is = E2 – E1.
43. (c) As per Bohr’s postulate,
13.58 13.58
nh = ÷ = 10.19
mvr = 4 1
2
nh h 6 .6 1 0 3 4
So, v = 8. (c) de-Broglie wavelength = = = 2Å
2 mr m 3 .3 1 0 2 4
1 2 9. (c) After absorbing 12.1 eV the electron in H atom is excited
KE = mv
2 to 3 shell.
2
1 nh 13.6
So, KE = m ÷ En E1 = ( 13.6) = 12.1
2 2 mr n2
a n2 13.6
Since, r = + 13.6 = 12.1
z n2
So, for 2nd Bohr orbit n=3
a 22 The possible transitions are (3 1) = 3
r= = 4a
1
1 1 1
1 22 h 2 10. (b) = RH = 4.86 10 7 m = 486 nm
KE = m 2 2
÷
2 2
4 2
2 4 m (4a )2 ÷
r2 2
lLi 3+ 2Vemp 1
20. (c) l = 2 represent d orbital for which \ = =
lp 6Vemp ´ 9 3 3
r
21. (b) The point at which the radial function acquirs zero value he
is called a node. Examine the graph the answer is (b). (c) 27. (c) One Bohr magneton =
4 mc
graph contains in nodes (a) and (d) none. 28. (b) Energy of 1 mole of photons,
h 6.63 ´ 10 -34 E = N0 × h u
22. (b) l = = = 6.63 × 10 -31 m
mv 10 ´ 10 -6 ´ 100
N0 ´ h ´ c
1 1 =
23. (c) 1 amu = g = N 0 -1 or × mass of C-12 atom l
N0 12
6.023 ´ 10 23 ´ 6.63 ´ 10 -34 ´ 3 ´ 10 8
1 æ ö =
24. (d) = R H Z2 ç 1 - 1 ÷ 253.7 ´ 10 -9
l çn 2 n 2 ÷ = 472.2 kJ
è 1 2 ø
Energy converted into KE = (472.2 – 430.53) kJ
To calculate shortest wavelength take n 2 = ¥ and
(472.2 - 430.53)
longest wavelength take nearest value of n 2 . % of energy converted into KE =
472.2
For H-atom,
= 8.76 %
1 29. (c) Magnetic moment
n 2 = ¥ , Z = 1, n1 = 1
l shortest
n ( n + 2) = 15
1 \ n = 3 number of unpaired electrons
\ = RH (Lyman series)
x 5 2
25 M = 3d , 4s
1
For l longest for Li 2+ , Z = 3, n1 = 2, n 2 = 3 (Balmer M x = 3d3
\ x = 4 for three unpaired electrons
series)
(KE )1 1- 0
1 1 æ 1 1 ö 5 30. (c) =
= × 3 2 çç 2 - 2 ÷÷ = (KE ) 2 2- 0
l longest x è2 3 ø 4x
(1.5 ´1015 - 1 ´1015 ) 1
4x = =
\ l longest = (2.0 ´ 10 15
- 1 ´10 ) 15 2
5
58 Chemistry
1 h
\ Dv =
2m p
3
Classification of Elements
and Periodicity in Properties
THE PERIODIC TABLE OF THE ELEMENTS
Very Short/Short Answer Questions (ii) Arrange the above five elements is order of increasing
electron gain enthalpy.
1. Name a species which is iso electronic with Al3+.
13. Predict the formula of a stable binary compound that would
2. Helium has a electronic configuration of 1s2 but it is placed
be formed by the following pairs of elements
in p-block in group 18. Explain.
(a) aluminum and phosphorous
3. Name the elements with the lowest and the highest ionisation (b) lithium and nitrogen
energy. (c) calcium and sulphur
4. Predict the position of the element in the Periodic Table
satisfying the electronic configuration (n – 1) d1 ns2 Long Answer Questions
for n = 4.
14. Name the four blocks of elements in the periodic table and
5. Write equations to demonstrate the difference between list the difference in their electronic configurations. Give
electron affinity and the reverse of ionization potential. examples of each type of elements. Write at least four
6. All the lanthanoid elements form stable characteristics of each block.
compounds containing the +3 cation. Of the few other ionic 15. Find the best choice in the following list and give brief reason
forms known, Ce forms the stable + 4 series of ionic com- for your answer
pounds and Eu the stable + 2 series. Account for these (i) highest IE1; Se, S,Te
unusual ionic forms in terms of their electronic configura- (ii) smallest radius; Cl–, Br–, I–
tions. (iii) most parmagnetic; Fe, Co, Ni
7. Nitrogen has positive electron gain enthalpy whereas oxygen (iv) smallest atom; Sn, I, Bi
has negative. However, oxygen has lower ionisation
(v) lowest IE2 ; Ar, K, Ca
enthalpy than nitrogen. Explain.
16. (i) Explain the terms (a) screening effect,
8. Explain the following : (b) penetration effect, (c) metallic character.
(a) Electronegativity of elements increase on moving from (ii) Why are electron affinities of noble gases zero ?
left to right in the periodic table. Arrange halogens in increasing order of electron
(b) Ionisation enthalpy decrease in a group from top to affinity.
bottom. 17. The second ionization enthalpy (IE2) of the elements of the
9. Give the order in which the melting points of halides of second period are given below :
sodium decrease and why ? Element : IE2 (kJ/mol) :
10. The first (IE1) and second (IE2) ionisation enthalpies (kJ Li 7294
mol–1) of three elements I, II and III are given below : Be 1756
I II III B 2430
C 2354
1E1 403 549 1142
N 2856
1E2 2640 1060 2080 O 3396
Identify the element which is likely to be (a) non-metal (b) F 3377
an alkali metal (c) an alkaline earth metal. Ne 3966
11. Show by a chemical reaction with water that Na2O is a basic (i) Explain
oxide and Cl2O7 is an acidic oxide. (a) Why is IE2 of Li so much higher than for all other
12. Consider the ground state electronic configuration of the elements of this period ?
five elements I to V given below : (b) What is the general trend from Be to Ne of
Elements Electronic Configuration increasing IE2?
I 1s2 2s2 2p5 (c) Why IE 2 of F is just about the same
or very slightly less than that of oxygen ?
II 1s2 2s2 2p4
(ii) Would you predict the IE2 of Na in kJ/mol is
III 1s2 2s2 2p6 3s2 (a) greater than 7294
IV 1s2 2s2 2p6 3s1 (b) between 3966 and 7294 or
V 1s2 2s2 2p6 (c) less than 3966 ? Explain.
(i) Which of the above configuration is associated with
the highest and which is associated with the lowest
ionisation enthalpy ?
Classification of Elements and Periodicity in Properties 65
Multiple Choice Questions 23. The period number in the long form of the periodic table is
equal to
18. Element A belongs to Group VII in p-block and element B
(a) magnetic quantum number of any element of the period.
belongs to Group I in s-block of the periodic table. Out of
(b) atomic number of any element of the period.
the following assumptions, the correct one is :
(c) maximum Principal quantum number of any element of
(a) A and B are metals
the period.
(b) A and B are non-metals
(d) maximum Azimuthal quantum number of any element
(c) A is a metal and B is a non-metal
of the period.
(d) A is a non-metal and B is a metal 24. The lightest liquid metal is
19. Examine the following elements : (a) Hg (b) Ga
N, O, F, Ne (c) Cs (d) Fr
P, S, Cl, Ar 25. Which of the following elements A, B, C, D and E with atomic
Br, Kr number 3, 11, 15, 18 and 19 respectively belong to the same
I, Xe group?
In modern periodic table, on which side these elements are (a) A, B, C (c) B, C, D
placed (c) A, D, E (d) A, B, E
(a) Top left side (b) Bottom left side 26. Which of the following statement(s) about the Modern
(c) Top right side (d) Middle side Periodic Table is/are incorrect ?
(i) The elements in the Modern Periodic Table are arranged
20. The screening effect of ‘d’ electrons is
on the basis of their decreasing atomic number
(a) Much less than s-electrons (ii) The elements in the Modern Periodic Table are arranged
(b) Much more than s-electrons on the basis of their increasing atomic masses
(c) Equal to s-electrons (iii) Isotopes are placed in adjoining group(s) in the Periodic
(d) Equal to p-electrons Table
21. Which of the following is not an actinoid ? (iv) The elements in the Modern Periodic Table are arranged
(a) Curium (Z = 96) on the basis of their increasing atomic number
(a) (i) only (b) (i), (ii) and (iii)
(b) Californium (Z = 98) (c) (i), (ii) and (iv) (d) (iv) only
(c) Uranium (Z = 92) 27. An element having electronic configuration
(d) Terbium (Z = 65)
22. Electronic configurations of four elements A, B, C and D are 1s 2 2s 2 2p 6 3s 2 3p 6 4s1 forms
given below : (a) Acidic oxide (b) Basic oxide
(i) 1s2 2s2 2p6 (ii) 1s2 2s2 2p4 (c) Amphoteric oxide (d) Neutral oxide
2 2 6
(iii) 1s 2s 2p 3s 1 (iv) 1s2 2s2 2p5 28. An element which is an essential constituent of all organic
compounds belongs to
Which of the following is the correct order of increasing
(a) group 1 (b) group 14
tendency to gain electron ?
(c) group 15 (d) group 16
(a) A < C < B < D (b) A < B < C < D
(c) D < B < C < A (d) D < A < B < C
1. As per the modern periodic law, the physical and chemical 3. The most significant contribution towards the development
properties of elements are periodic functions of their of periodic table was made by
(a) atomic volume (a) Mendeleev (b) Avogadro
(b) electronic configuration (c) Dalton (d) Cavendish
(c) atomic weight 4. Mendeleev’s periodic law is based on
(d) atomic size (a) atomic number (b) atomic weight
2. Eka-aluminium and Eka-silicon are known as (c) equivalent weight (d) valency
(a) Gallium and Germanium 5. Which of these does not reflect the periodicity of the
(b) Aluminium and Silicon elements?
(c) Iron and Sulphur (a) Bonding behaviour (b) Electronegativity
(d) Manganese and Magnesium (c) Ionization potential (d) Neutron/proton ratio
66 Chemistry
6. The statement that is not true for the long form of the periodic 18. Electronic configuration of most electronegative element is
table is (a) 1s2 2s2 2p4 3s1 (b) 1s2 2s2 2p6 3s2 3p5
(a) It reflects the sequence of filling electrons in the order of (c) 1s2 2s2 2p5 (d) 1s2 2s2 2p6 3s2 3p6
sub-energy levels s, p, d and f. 19. Going from fluorine to chlorine, bromine and iodine, the
(b) It helps to predict the stable valence states of the electronegativity
elements (a) increases
(c) It reflects trends in physical and chemical properties of (b) decreases
the elements (c) first decrease then increases
(d) It helps to predict the relative ionicity of the bond (d) changes randomly
between any two elements. 20. Which of the following is most electronegative?
7. Which of the following pairs of atomic numbers represents (a) Lead (b) Silicon
elements belonging to the same group? (c) Carbon (d) Tin
(a) 11 and 20 (b) 12 and 30 21. On going from right to left in a period in the periodic table,
(c) 13 and 31 (d) 14 and 33 the electronegativity of the elements
8. Which of the following sets of atomic number belong to that (a) increases
of alkali metals? (b) decreases
(a) 1, 12, 30, 4, 62 (b) 37, 19, 3, 55 (c) remains unchanged
(c) 9, 17, 35, 53 (d) 12, 20, 56, 88 (d) decreases first then increases
9. What is the atomic number of the next halogen if discovered? 22. The electronegativity follows the order
(a) 85 (b) 117 (a) F > O > Cl > Br (b) F > Cl > Br > O
(c) 167 (d) 104 (c) O > F > Cl > Br (d) Cl > F > O > Br
10. All the elements of a group in the periodic table have the 23. Electronegativity values for the elements help in predicting
same (a) polarity of bonds
(a) atomic weight (b) dipole moments
(b) number of protons (c) valency of elements
(c) mass number (d) position in the electrochemical series
(d) number of electrons for bonding 24. Which of the following is correctly matched?
11. The elements in which 4f orbitals are progressively filled up (a) C—C bond length — 0.077 nm
are called as (b) Ionic radius of Na+ — 0.136 nm
(a) actinides (b) transition elements (c) C—Cl bond length — 0.176 nm
(c) lanthanides (d) halogens (d) Ionic radius of F– — 0.095 nm
12. Which of the following is not a transition metal? 25. The atomic radius increases as we move down in a group
(a) Zr (b) Tc because
(c) Re (d) Np (a) effective nuclear charge increases
13. Which of the following have same number of electrons in (b) atomic mass increases
the outermost orbit? (c) additive electrons are accommodated in new electron
(a) Pb, Sb (b) N, O level
(c) As, Bi (d) P, Ca (d) atomic number increases
14. Representative elements belong to 26. The correct order of radii is
(a) s- and p-blocks (b) p- and d-blocks (a) N < Be < B (b) F - < O 2 - < N 3-
(c) f-block only (d) d- and f-blocks
15. Element with atomic number 56 belongs to which block? (c) N < Li < K (d) Fe 3+ < Fe 2 + < Fe 4+
(a) s (b) p 27. Which of the following is the smallest cation?
(c) d (d) f (a) Na+ (b) Mg2+
(c) Ca 2+ (d) Al3+
16. Which of the following remains unchanged on descending
in a group in the periodic table? 28. The ionic radii of N , O , F and Na+ are in the order
3– 2– –
(a) Valence electrons (b) Atomic size (a) N 3- > O 2 - > F - > Na +
(c) Density (d) Metallic character
17. Which is true about the electronegativity order of the (b) N 3- > Na + > O 2- > F -
following elements? (c) Na + > O 2 - > N 3- > F -
(a) P > Si (b) C > N
(c) Br > Cl (d) Sr > Ca (d) O 2- > F - > Na + > N 3-
Classification of Elements and Periodicity in Properties 67
29. Ionic radii of 41. Highest electron affinity is shown by
(a) Ti 4+ < Mn 2+ (b) 35 -
Cl < 37
Cl - (a) O– (b) F–
(c) Cl2 (d) F2
(c) K + > Cl -1 (d) P 3+ > P 5+ 42. Which of the following has least electron afinity?
30. The radii of F, F–, O and O2– are in the order (a) Oxygen (b) Argon
(a) O 2 - > F - > F > O (c) Nitrogen (d) Boron
43. Which of the following has highest electron affinity?
(b) F - > O 2 - > F > O
(a) Li+ (b) Na+
(c) O 2 - > O > F - > F (c) F– (d) Cl–
(d) O 2 - > F - > O > F 44. The element having very high ionizaiton energy but zero
electron affinity is
31. Which stable nucleus has radius half than that of 54Xe
(a) H (b) F
(a) 40Ca (b) 23Na
(c) He (d) Be
(c) 32S (d) 7Li
45. The lower electron affinity of fluorine than that of chlorine is
32. For which of the following ionic species radius would be
due to
maximum?
(a) smaller size
(a) C4– (b) N3–
2– (b) smaller nuclear charge
(c) O (d) Mg2+
(c) difference in their electronic configurations
33. The decreasing order of the size of the following ions is
(a) Li+ > H+ > H– (b) H+ > H– > Li+ (d) its highest reactivity
(c) H– > Li+ > H+ (d) H– > H+ > Li+ 46. Which of the following orders is correct for the first ionization
potential of B, C and N?
34. Chloride ion and potassium ion are isoelectronic. Then
(b) B > C > N (b) N > C > B
(a) their sizes are same
(c) N > C < B (d) N < C < B
(b) Cl– ion is bigger than K+ ion
47. Consider the following changes
(c) K+ ion is relatively bigger
(d) their sizes depend on either cation or anion A ® A + + e - : E1 and A + ® A 2 + + e - : E 2
35. Which has the smallest size? The energy required to pull out the two electrons are E1 and
(a) Na+ (b) Mg2+ E 2 respectively. The correct relationship between two
(c) Al3+ (d) P5+ energies would be
36. Which of the following is isoelectronic with carbon atom? (a) E1 < E2 (b) E1 = E2
(a) Na+ (b) Al3+ (c) E1 > E2 (d) E1 ³ E2
(c) O2– (d) N+ 48. Which of the following isoelectronic ions has the lowest
37. + ++ 3+ 4+
Na , Mg , Al and Si are isoelectronic. The order of their ionization energy?
ionic size is (a) K+ (b) Ca2+
(a) Na+ > Mg++ < Al3+ < Si4+ (c) Cl– (d) S2–
(b) Na+ < Mg++ > Al3+ > Si4+ 49. The decreasing order of the ionization potential of the
(c) Na+ > Mg++ > Al3+ > Si4+ following elements is
(d) Na+ < Mg++ > Al3+ < Si4+ (a) Ne > Cl > P > S > Al > Mg
38. Electron affinity depends on (b) Ne > Cl > P > S > Mg > Al
(a) atomic size (c) Ne > Cl > S > P > Mg > Al
(b) nuclear charge (d) Ne > Cl > S > P > Al > Mg
(c) atomic number 50. The electronic configuration of elements A, B and C are [He]
(d) atomic size and nuclear charge both 2s1, [Ne] 3s1 and [Ar] 4s1 respectively. Which one of the
39. The element with highest electron affinity among halogens following order is correct for IE1 (in kJ mol–1) of A, B and C?
is (a) A > B > C (b) C > B > A
(a) F (b) Cl (c) B > C > A (d) C > A > B
(c) Br (d) I 51. The set representing the correct order of first ionization
40. The correct order of electron affinity among the following is potential is
(a) F > Cl > Br (b) Br > Cl > F (a) K > Na > Li (b) Be > Mg > Ca
(c) Cl > F > Br (d) F > Br > Cl (c) B > C > N (d) Ge > Si > C
68 Chemistry
52. The correct order of ionization energies is 62. Consider the following statements
(a) Zn < Cd < Hg (b) Hg < Cd < Zn I. The radius of an anion is larger than that of the parent
(c) Ar > Ne > He (d) Cs < Rb < Na atom.
53. Which of the order for ionization energy is correct? II. The ionization energy generally increases with increasing
(a) Be < B < C < N < O (b) B < Be < C < O < N atomic number in a period.
(c) Be > B > C > N > O (d) B < Be < N < C < O III. The electronegativity of an element is the tendency of
an isolated atom to attract an electron.
54. First ionization potential will be maximum for
Which of the above statements is/are correct?
(a) Uranium (b) Hydrogen
(c) Lithium (d) Iron (a) I alone (b) II alone
55. The incorrect statement among the following is (c) I and II (d) II and III
(a) the first ionization potential of Al is less than the first 63. Which of the following order is wrong?
ionization potential of Mg (a) NH 3 < PH 3 < AsH 3 — Acidic
(b) the second ionization potential of Mg is greater than the
second ionization potential of Na (b) Li < Be < B < C — IE1
(c) the first ionization potential of Na is less than the first (c) Al 2 O3 < MgO < Na 2 O < K 2 O — Basic
ionization potential of Mg
(d) the third ionization potential of Mg is greater than the (d) Li + < Na + < K + < Cs + — Ionic radius
third ionization potential of Al. 64. Gradual addition of electronic shells in the noble gases causes
56. The second ionization potential of an element M is the energy a decrease in their
required to (a) ionization energy (b) atomic radius
(a) remove one mole of electrons from one mole of gaseous (c) boiling point (d) density
cations of the element
65. Which of the following elements represents highly
(b) remove one mole of electrons from one mole of gaseous electropositive as well as highly electronegative character in
anions its period?
(c) remove one mole of electrons from one mole of (a) Hydrogen (b) Nitrogen
monovalent gaseous cations of the element
(c) Fluorine (d) None of these
(d) remove 2 moles of electrons from one mole of gaseous
atoms 66. The cause of diagonal relationship is
57. Highest ionization potential is shown by (a) similar electronegativities
(a) Alkali metals (b) Transition elements (b) similar ionic or atomic radii
(c) Halogens (d) Inert gases (c) similar polarizing power of ions
58. With reference to ionization potential which one of the (d) All the three
following sets is correct? 67. Variable valency is generally exhibited by
(a) Li > K < Cs (b) B > Li > K
(a) representative elements
(c) Cs > Li > B (d) Cs < Li < K
(b) transition elements
59. Which of the following species has lowest ionization
potential? (c) non-metallic elements
(a) O (b) O2 (d) metallic elements
(c) O2 + (d) O2– 68. Which of the following elements does not belong to first
60. The factor not affecting the ionization energy is transition series?
(a) size of atom (a) Fe (b) V
(b) charge in the nucleus (c) Ag (d) Cu
(c) type of bonding in the crystalline lattice 69. In the periodic table, with the increase in atomic number, the
(d) type of electron involved metallic character of an element
61. The screening effect of inner electrons of the nucleus causes (a) decreases in a period and increases in a group
(a) decrease in the ionization energy (b) increases in a period and decreases in a group
(b) increase in the ionization energy
(c) increases both in a period and the group
(c) no effect on the ionization energy
(d) decreases both in a period and the group
(d) increases the attraction of the nucleus for the electrons
Classification of Elements and Periodicity in Properties 69
1. Identify the correct order of the size of the following: 11. Which one of the following ions has the highest value of
(a) Ca2+ < K+ < Ar < Cl– < S2– [CBSE-PMT 2007] ionic radius ? [AIEEE 2004]
2+ + – 2– (a) O2– (b) B3+
(b) Ar < Ca < K < Cl < S
(c) Li+ (d) F–
(c) Ca2+ < Ar < K+ < Cl– < S2– 12. Among Al2O3, SiO2, P2O3 and SO2 the correct order of acid
(d) Ca2+ < K+ < Ar < S2– < Cl– strength is [AIEEE 2004]
2. In which of the following electronic configuration an atom (a) Al2O3 < SiO2< SO2 < P2O3
has the lowest ionisation enthalpy? [CBSE-PMT 2007] (b) SiO2< SO2 < Al2O3 < P2O3
2 2
(a) 1s 2s 2p 3 (b) 1s 2s 2p5 3s1
2 2 (c) SO2< P2O3 < SiO2 < Al2O3
2 2 6 (d) Al2O3 < SiO2< P2O3 < SO2
(c) 1s 2s 2p (d) 1s2 2s2 2p5 13. Beyllium and aluminium exhibit many properties which are
3. Which one of the following ionic species has the greatest similar. But, the two elements differ in [AIEEE 2004]
proton affinity to form stable compound? [CBSE-PMT 2007] (a) forming covalent halides
(a) NH -2 (b) F – (b) forming polymeric hydrides
(c) exhibiting maximum covalency in compounds
(c) I– (d) HS–
(d) exhibiting amphoteric nature in their oxides
4. The stability of + 1 oxidation state increases in the sequence: 14. Which of the following oxides is amphoteric in character?
[CBSE-PMT 2009] (a) SnO 2 (b) SiO 2 [AIEEE 2005]
(a) Tl < In < Ga < Al (b) In < Tl < Ga < Al
(c) CO 2 (d) CaO
(c) Ga < In < Al < Tl (d) Al < Ga < In < Tl
15. In which of the following arrangements, the order is NOT
5. Amongst the elements with following electronic
according to the property indicated against it?
configurations, which one of them may have the highest (a) Li < Na < K < Rb : [AIEEE 2005]
ionization energy? [CBSE-PMT 2009] Increasing metallic radius
2
(a) Ne [3s 3p ] 2 (b) Ar [3d 4s24p3 ]
10
(b) I < Br < F < Cl :
2
(c) Ne [3s 3p ] 1 (d) Ne [3s23p3] Increasing electron gain enthalpy
6. Which of the following represents the correct order of (with negative sign)
increasing electron gain enthalpy with negative sign for the (c) B < C < N < O
Increasing first ionization enthalpy
elements O, S, F and Cl ? [CBSE-PMT 2010]
(a) Cl < F < O < S (b) O < S < F < Cl (d) Al3+ < Mg 2+ < Na + < F -
(c) F < S < O < Cl (d) S < O < Cl < F Increasing ionic size
7. Among the elements Ca, Mg, P and Cl, the order of increasing 16. The increasing order of the first ionization
enthalpies of the elements B, P, S and F (Lowest first)
atomic radii is : [CBSE-PMT 2010]
is [AIEEE 2006]
(a) Ca < Mg < P < Cl (b) Mg < Ca < Cl < P (a) B < P < S < F (b) B < S < P < F
(c) Cl < P < Mg < Ca (d) P < Cl < Ca < Mg (c) F < S < P < B (d) P < S < B < F
8. What is the value of electron gain enthalpy of Na+ if IE1 of 17. Following statements regarding the periodic trends of
Na = 5.1 eV ? [CBSE-PMT 2011 M] chemical reactivity of the alkali metals and the halogens are
(a) –5.1 eV (b) –10.2 eV given. Which of these statements gives the correct picture?
[AIEEE 2006]
(c) +2.55 eV (d) +10.2 eV
(a) Chemical reactivity increases with increase in atomic
9. According to the Periodic Law of elements, the variation in number down the group in both the alkali metals and
properties of elements is related to their [AIEEE 2003] halogens
(a) nuclear masses (b) In alkali metals the reactivity increases but in the halogens
(b) atomic numbers it decreases with increase in atomic number down the
(c) nuclear neutron-proton number ratios group
(d) atomic masses (c) The reactivity decreases in the alkali metals but increases
10. Which is the correct order of ionic sizes (At. No. : Ce = 58, in the halogens with increase in atomic number down the
group
Sn = 50, Yb = 70 and Lu = 71) ? [AIEEE 2003]
(d) In both the alkali metals and the halogens the chemical
(a) Ce > Sn > Yb > Lu (b) Sn > Ce > Yb > Lu reactivity decreases with increase in atomic number down
(c) Lu > Yb > Sn > Ce (d) Sn > Yb > Ce > Lu the group
70 Chemistry
18. The charge/size ratio of a cation determines its (a) Al3+ > Mg 2+ > Na + > F- > O 2 -
polarizing power. Which one of the following sequences (b) Na + > Mg 2+ > Al3+ > O2- > F-
represents the increasing order of the polarizing power of (c) Na + > F - > Mg 2 + > O 2 - > Al3+
the cationic species, K+, Ca2+, Mg2+, Be2+? [AIEEE 2007]
(d) O2- > F- > Na + > Mg 2+ > Al3+
(a) Ca2+ < Mg2+ < Be+ < K+ 21. The correct order of electron gain enthalpy with negative
(b) Mg2+ < Be2+ < K+ < Ca2+ sign of F, Cl, Br and I, having atomic number 9, 17, 35 and 53
(c) Be2+ < K+ < Ca2+ < Mg2+ respectively, is : [AIEEE 2011 RS]
(d) K+ < Ca2+ < Mg2+ < Be2+. (a) F > Cl > Br > I (b) Cl > F > Br > I
19. In which of the following arrangements, the sequence is not (c) Br > Cl > I > F (d) I > Br > Cl > F
strictly according to the property written against it? 22. The increasing order of the ionic radii of the given
[AIEEE 2008] isoelectronic species is : [AIEEE 2012]
(a) HF < HCl < HBr , HI : increasing acid strength (a) Cl–, Ca2+ , K+, S2– (b) S2–, Cl–, Ca2+ , K+
(b) NH3 < PH3 < AsH3 <SbH3 : increasing basic strength (c) Ca2+ , K+, Cl–, S2– (d) K+, S2–, Ca2+, Cl–
(c) B < C < O < N : increasing first ionization enthalpy 23. Which of the following represents the correct order of
(d) CO2 < SiO2 < SnO2 < PbO2 : increasing oxidising power increasing first ionization enthalpy for Ca, Ba, S, Se and Ar ?
20. The correct sequence which shows decreasing order of the [JEE M 2013]
ionic radii of the elements is [AIEEE 2010] (a) Ca < S < Ba < Se < Ar (b) S < Se < Ca < Ba < Ar
(c) Ba < Ca < Se < S < Ar (d) Ca < Ba < S < Se < Ar
1. An element X occurs in short period having configuration 8. The valence shell of element A contains 3 electrons while the
ns2 np1. The formula and nature of its oxide is valence shell of element B contains 6 electrons . If
(a) XO3, basic (b) XO3 acidic A combines with B, the probable formula of the compound
(c) X2O3, amphoteric (d) X2O3 basic formed will be
2. The law of triads is applicable to a group of (a) AB2 (b) A2B
(a) Cl, Br, I (b) C, N, O
(c) A2B3 (d) A3B2
(c) Na, K, Rb (d) H, O, N
9. Pauling scale of electronegativity of elements helps to
3. Elements of IA group give flame colour due to
determine
(a) low IP
(a) covalent nature of an element
(b) low m.pt.
(c) softness (b) position of an element in EMF series
(d) one electron in outermost shell. (c) dipole moment of molecules
4. The ionic radii of N3–, O2– and F– are respectively given by (d) polarity of bond.
(a) 1.36, 1.40, 1.71 (b) 1.36, 1.71, 1.40 10. The statement that is not correct for the periodic classification
(c) 1.71, 1.40, 1.36 (d) 1.71, 1.36, 1.40 of elements is
5. The first ionisation potential of aluminium is smaller than (a) The properties of elements are the periodic functions of
that of magnesium because their atomic number
(a) Atomic size of Al > Atomic size of Mg. (b) Non-metallic elements are lesser in number than metallic
(b) Atomic size of Al < Atomic size of Mg. elements
(c) Al has one electron in p - orbital (c) The first ionization energies of elements along a period
(d) None of these do not vary in a regular manner with increase in atomic
6. Which of the following halides is not oxidized by MnO2 number.
(a) F– (b) Cl– (d) For transition elements the d-sub shells are filled with
electrons monotonically with increase in atomic number
(c) Br– (d) I–
11. Which is coloured ion
7. Which species has the maximum ionic radius
(a) Na+ (b) O2– (a) [Cu ( NH 3 ) 4 ]+ (b) [Cu( NH 3 ) 4 ]2 +
(c) F– (d) Mg2+
(c) [ Zn(H 2 O) 6 ]2 + (d) [Ca (H 2 O) 6 ]2 +
Classification of Elements and Periodicity in Properties 71
12. Considering the elements from left to right in the second 17. Which transition involves maximum amount of energy
period of the periodic table, the gram atomic volume of the
elements. (a) M - (g ) ¾
¾® M (g ) + e
(a) first increases then decreases
(b) M - ( g ) ¾
¾® M + (g ) + 2e
(b) decreases
(c) increases at constant rate (c) M + (g ) ¾
¾® M 2+ (g ) + e
(d) remains unchanged
(d) M 2 + (g ) ¾
¾® M 3+ (g ) + e
13. Atomic radii of fluorine and neon in angstrom units are
respectively given by 18. A sudden jump between the values of second and third
(a) 0.72 ; 1.60 (b) 1.60 ; 1.60 ionization energies of an element would be associated with
(c) 0.72 ; 0.72 (d) None of these the electronic configuration
14. The screening effect of ‘d’ electrons is (a) 1s 2 2s 2 2p 6 3s1 (b) 1s 2 2s 2 2p 6 3s 2 3p1
(a) much less than s- electrons
(c) 1s 2 2s 2 2p 6 3s 2 3p 2 (d) 1s 2 2s 2 2p 6 3s 2
(b) much more than s- electrons
(c) equal to s- electrons 19. The element with outer electronic configuration 3d 6 4s 2 is a
(d) equal to p- electrons (a) metalloid (b) non-metal
15. An element having electronic configur ation (c) transition metal (d) noble gas
1s 2 2s 2 2p 6 3s 2 3p 6 4s1 forms 20. In the process, Cl(g) e – H
Cl (g); H is
(a) acidic oxide (b) basic oxide (a) positive (b) negative
(c) amphoteric oxide (d) neutral oxide (c) zero (d) unpredictable
16. Which pair of elements belongs to same group 21. Among the following the lowest degree of paramagnetism
per mole of the compound at 298 K will be shown by
(a) Elements with atomic no. 17 and 38
(b) Elements with atomic no. 20 and 40 (a) MnSO 4 .4H 2O (b) CuSO 4 .5H 2O
(c) Elements with atomic no. 17 and 53 (c) FeSO 4 .6H 2 O (d) NiSO 4 .6H 2 O
(d) Elements with atomic no. 11 and 33
72 Chemistry
Na +
F Mg + +
O Similarly, other than fluorine, the halogens have high covalencies
2,8 2,8 2,8 2,8 equal to 3, 5 and 7. Phosphorous shows covalencies equal to 3
and 5.
Similarly K2S and CaCl2 are isomorphous
K+ S2- K+ Cl- Ca++ Cl- The elements having no d-orbitals do not exhibit variable
2,8,8 2,8,8 2,8,8 2,8,8 2,8,8 2,8,8 covalency
VARIABLE ELECTROVALENCY : EXAMPLES OF COVALENT COMPOUNDS :
It is due to unstable atomic core and inert pair effect. When valence (i) Chlorine (Cl2)
electrons from a metal atom are removed it leaves behind the
atomic core or atomic kernel. The latter with 2 or 8 electrons are
Cl + Cl Cl Cl
stable. In case of transition elements the atomic cores are not very
stable. They may lose one or more electrons thus exhibiting 8e
–
8e
–
variable electrovalency eg. iron and copper etc. (ii) Carbon dioxide (CO2)
Fe (2, 8, 14, 2) 1s2, 2s2p6, 3s2p6 d6, 4s2
++
Fe (2, 8, 14) 1s2, 2s2p6, 3s2p6 d6
+++
Fe (2, 8, 13) 1s2, 2s2p6, 3s2p6 d5 O C O O = C =O
The energy difference between 4s and 3d subshell is not very – –
large. 8e 8e 8e
(iii) Nitrogen (N2)
INERT PAIR EFFECT :
The reluctance of s electron pair of some heavy elements
(p - block elements present at the bottom of group) to take part in N N N N
bonding is known as inert pair effect. Thus Tl (6s2, 6p1) show +1
– –
electrovalence. Similarly Sn(5s2p2) and Pb (6s2p2) show + 2 8e 8e
oxidation state commonly. In such elements the lower oxidation
state is more stable than higher oxidation state.
78 Chemistry
NATURE OF COVALENT BOND :
+ + Addition
The nature of covalent bond is explained by (a) + 1s bonding
+
(i) Heitler - london theory Valence bond theory 1s + 1s
(ii) Pauling - slater theory
(iii) Hund - mulliken theory } Molecular orbital theory + • Subtraction
(antibonding)
–
+ + – 1s
VALENCE BOND THEORY :
1s – 1s
A covalent bond is formed by the overlapping between two half
filled atomic orbitals having electrons with opposite spin. (b) p x p x or p x p x and p y p y or p y p y overlap to form
(Nb - Na ) 10 - 4 6
Bond order = = = = 3 \N º N
2 2 2
p (2Px) p (2Py)
(d) Oxygen molecule (O2) - Total number of electrons = 16
2s and electronic configuration is
2s
*(2s) 1s2 < 1s 2 < 2s 2 < 2s 2 < 2p2z
(2s) 2 * 1 * 1
< 2p 2x = 2py < 2px = 2py
N b - N a 10 - 6 4
Bond order = = = =2
1s 1s 2 2 2
*(1s) As shown by electronic configuration the O2 molecule
contains two unpaired electrons, hence it is paramagnetic
in nature
s1s < s*1s < s2s < s* 2s < s2p z < [p2p x = p2p y ] N b - Na 10 - 5 5 1
Bond order = = =2
2 2 2 2
< [p* 2p x = p* 2p y ] < s* 2p z It is paramagnetic
80 Chemistry
(h) Carbon monoxide (CO) - Total number of electrons = (6 + 8)
(f) O2– (Super oxide ion) Total number of electrons (16 + 1) = 17 .
= 14
Electronic configuration
The electronic configuration is
1s2 < 1s 2 < 2s 2 < 2s 2 < 2p2z
1s2 < 1s2 < 2s2 < 2s2 < 2p2z < 2p2x = 2p2y
< 2p2x = 2p2y < 2p2x 2p1y
Bond order Nb Na 10 4 6
Bond order = = = = 3
2 2 2
(Nb Na ) 10 7 3 1
= 1 It is paramagnetic
=
2
=
2
=
2 2 It is diamagnetic
(i) Nitric Oxide (NO) - Total number of electrons = (7 + 8) = 15
(g) Peroxide ion O 22 - Total number of electrons
1s2 < 1s2 < 2s2 < 2s2 < 2p2z <
(16 + 2) = 18 . The electronic configuration is
1s2 < 1s 2 < 2s 2 < 2s 2 < 2p2z < 2p 2x 2p2x = 2p2y < 2p1x
= 2p 2y < 2p 2x = 2p2y Nb Na 10 5 5 1
Bond order = = = = 2
2 2 2 2
Nb Na 10 8 2
Bond order = = = 1
2 2 2 It is paramagnetic.
It is diamagnetic
( * 2p x )1 ( * 2p y )1
( * 2 p x ) 2 ( * 2 p y )1
CO 14 Same as in N2 3 Diamagnetic
NO 15 Same as in O2+ 2.5 Paramagnetic
NO+ 14 Same as in N2 3 Diamagnetic
4
, ClO 4 , NH , BF , PO
+
4 4
3
ClO 2
METHOD FOR FINDING THE TYPE OF VSEPR THEORY VALENCE SHELL ELECTRON PAIR
HYBRIDISATION : REPULSION THEORY :
Apply the following formula to find the hybridisation of central The following types of repulsions between different pair of
atom. electrons change the regular geometry of the molecule.
Lone pair - lone pair repulsion > Lone pair - bond pair repulsion >
Number of valence electrons of central atom Bond pair - bond pair repulsion or lp - lp > lp - bp > bp - bp eg:
1 ÷
(i) Shape of H2O molecule - The hybridisation of oxygen is sp3
+ number of monovalent atoms attached to it ÷ = z
2 ÷ and angle should be 109º 28’. But actually the HOH angle is
+ negative charge if any – positive charge if any
104.5º. The VSEPR theory explains this fact
Value of z 2 3 4 5 6 7
O V-shape
Hybridisation sp sp 2 sp 3 sp3 d sp3d 2 sp3d 3
H H
Examples : All types of repulsions (lp–lp, lp–bp, bp–bp) are present in
1 H2O.
i) Hybridisation of NH3 = [5 + 3 + 0 - 0] = 4; sp3 (ii) Shape of NH3 molecule - The hybridisation of nitrogen is
2
1 sp3. The H–N–H angle is 107.5º instead of 109º28’. Due to
ii) Hybridisation of H2O = [6 + 2 + 0 - 0] = 4; sp3 lp–bp and bp–bp repulsions the value of angle change
2
1 N
iii) Hybridisation of SO3 = [6 + 0 + 0 - 0] = 3; sp2 H H Pyramidal
2 H
1 (iii) Structure of PCl5 : The phosphorous is in sp3d hybridised
iv) Hybridisation of SO42– = [6 + 0 + 2 - 0] = 4; sp3
2 form. The five hybrid orbitals are not equivalent. The bonds
1 pointing towards the three corners of equilateral triangle are
v) Hybridisation of CO32– = [4 + 0 + 2 - 0] = 3; sp2 known as equatorial bonds making an angle of 120° between
2
them. The remaining two bonds are at right angle to the
1
vi) Hybridisation of PCl 5 = [5 +5 + 0 - 0] = 5; sp3d plane of three make an angle of 90° and are called axial bonds.
2 The axial bonds are slightly longer and weaker then equatorial
1 bonds. Since they suffer more repulsive interaction from the
vii) Hybridisation of SF6 = [6 + 6 + 0 - 0] = 6; sp3d2
2 later. Consequently PCl5 is very reactive molecule.
Note : Species having same hybridisation are isostructral in nature.
Chemical B onding and Molecular Structure 83
Cl H–F ............ H–F ............ H–F
Cl The chains possess a Zig-Zag structure
P – –
F F
Cl Cl
+ + + +
Cl H H H H
CO-ORDINATE COVALENT BOND OR DATIVE – –
BOND : F F
When both the elctrons for sharing between two atoms are Hydrogen bond is purely electrostatic in nature. It is a weak bond,
contributed by one atom only the bond formed is known as the strength of the strongest being about 5 - 10 kcal per mole. The
coordinate bond or dative bond. more the electronegativity of atom involved in H - bonding, the
In terms of orbital theory the co-ordinate covalent bond is formed more is the bond strength eg.
by overlapping between empty and completely filled atomic H F > H O > H N
orbitals.
10 kcal/mole > 7 kcal/mole > 2.0 kcal/mole
The atom donating the pair of electrons is called donor and the
Types of hydrogen bonds - Hydrogen bond is of two types
atom which accepts the pair of electrons is called acceptor. The
compounds containing coordinate bonds are known as co- (i) Intermolecular H-bonding (Association).
ordination compounds. The bond is represented by an arrow ( ) H–bonding involving two or more molecules.
pointing head towards the acceptor. (ii) Intramolecular H-bonding (chelation). H–bonding taking
Once the coordinate bond is formed it is indistinguishable from a place within single molecule.
covalent bond. Examples (i) Applications of intermolecular H-bonding.
(i) Formation of SO2 (a) Water - Water has the lowest molecular weight among
the hydrides of group 16 elements yet it has the highest
O S O or melting and boiling points
O=S O
H2O H2S H2Se H2Te
ii) Formation of SO3
Melting point 0ºC -85.5ºC -66ºC -51.2ºC
O O Boiling point 100ºC -60.4ºC -41.5ºC +2ºC
O S O or It is due to intermolecular H - bonding through which
O=S O water molecules associate
iii) Formation of Hydroxonium ion + + + +
H H H H
H – + – + – + – +
H H O –H O– H O– H O– H
O H +
or O H or O+ H (b) Ice has less density than water - In crystal structure of
ice every water molecule is associated with four other
H H
H water molecules by H-bonding in a tetrahedral fashion
iv) NH3 and BF3 form addition product by Co-ordinate covalent
bond –
O
H F + +
| | H H
– –
H N: B F or H 3 N.BF3 O O
| | + + +
H F H H H H
–
CHARACTERITICS OF CO-ORDINATE COMPOUNDS O
Co-ordinate compounds have volatile character in between ionic + +
H H
and covalent compounds. Other properties like solubility, electrical
conductivity and stereo isomerism are similar to covalent
compounds. It gives rise to cage likes tetrahedral structure of ice with
HYDROGEN BOND : large empty spaces. On melting the ice H-bonds are
broken and space between water molecules decreases
It may be defined as the force of attraction existing between
and density of water increases upto 4ºC. Above 4ºC more
hydrogen atom covalently bonded to highly electronegative atom
H - bonds are broken, the water molecules move apart
(N, O or F) and the electronegative atom belonging to another
molecule of the same or different substance. It is represented by from each other and the density again decreases. Thus
dotted lines water has maximum density at 4ºC.
84 Chemistry
(c) Alcohols - The marked difference between the melting (c) Ethyl aceto acetate - It exists in two forms
and boiling points of alcohols and corresponding O
mercaptans is also due to association. ||
CH 3OH C2H 5OH C3H 7OHC4H 9OH CH 3 C CH 2 . COOC 2 H 5
Keto form
Boiling point 64.4ºC 78ºC 97ºC 117ºC
CH3SH C2H5SH C3H7SH C4H9SH OH
|
Boiling point 5.8ºC 37ºC 67ºC 97ºC
CH3 C = CH.COOC2 H 5
R R R R Enol form
– + – + – + – + Enolic form is more volatile due to chelation
O –H O–H O–H O–H
(d) Amides - Amides associate and have higher melting and O H
+
O
boiling points | ||
CH 3 C = CH C OC 2 H 5
R H R H R
| + | | + | | (d) Maleic acid is stronger acid than fumaric acid
H2N C = O H N C= O H N C= O
O
(e) Amines - Primary and secondary amines are associated || – +
and have higher boiling points than isomeric tertiary H C C O H
H C COOH || |
amines. ||
H C COOH H C C O
(f) Fatty acids - In organic solvents, fatty acids form ||
a dimer O
Maleic acid Chelation in maleate ion
– + – (e) Acid character of nitrophenols. It follows the following
O H O
order
R C – C R p - nitrophenol > o - nitrophenol > m - nitrophenol
+ –
O H O Acid character of o - nitrophenol is suppressed by
chelation
It is confirmed by electron diffraction method.
(ii) Applications of Intramolecular H - bonding. O +
H
When the H - bonding takes place within a single molecule –
this is known as intramolecular H - bonding. It also effects O
N
the physical and chemical properties of compound.
(a) Volatile character of nitrophenols - o-nitrophenol is O
more volatile (b.pt 214ºC) as compared to meta (b.pt
(f) Other compounds showing intramolecular
290ºC) and para (b.pt 279ºC). It is due to chelation H - bonding
– O O +
O + + H
H H
O –
O – Cl
– C
N
H
O
o-Chlorophenol o-hydroxy benzaldehyde
In meta and para isomer chelation is not possible due to O +
the formation of desired size of ring. They therefore H
O –
associate to some extent and have higher B.P C
(b) Salicylic acid is stronger acid than o - methoxy benzoic
acid OH
o-hydroxy benzoic acid
O O
METALLIC BOND :
C C
O – O It has been found that metals have generally low ionisation
H
+ CH3 energies indicating that valence electrons are weakly bound to
O O the atomic kernel (or core).
H-bonding in salicylate ion No-H-bonding in
Metals contain few valence electrons and valence orbitals which
are empty. Thus valence electrons are completely delocalised and
o-methoxy benzoate ion
are frequently exchanged between atoms. The atoms thus acquire
Chemical B onding and Molecular Structure 85
a positive charge and are arranged in a regular fashion (lattice • The greater the polarizability of a molecule, the stronger are
structure). the London forces.
• The polarizability increases with number of electrons and
e e e
their distance from the nucleus.
e e e • These forces are operative over a very short range.
• The inert gases have weak van der Waals forces of attraction
e e e
• The striaght chain hydrocarbons boil at higher temperature
The valence electrons form an “electron gas” or "sea of than isomeric branched chain hydrocarbons due to greater
electrons". The attractive interaction between the mobile magnitude of van der Waal's forces of attraction.
electrons and a number of ions constitutes a weak bond
known as metallic bond. Dipole - dipole attraction
It is the attraction between the positive end of the one molecule
CONSEQUENCES OF METALLIC BOND :
and negative end of the another molecule
1. Electrical conductivity - It is due to presence of mobile
valence electrons. + +
or
+ +
H Cl H Cl Cl H Cl H
2. Thermal conductivity - On heating one part of metal, the
K.E. of electrons is increased and they conduct heat to the This type of interaction is called dipole - dipole interaction. The
other parts of the metal. force of dipole - dipole attraction is inversely proportional to fourth
3. Metallic lustre- The mobile elctrons are promoted to excited 1
states by absorption of light and on coming back from the power of their separation of distance r. F = . The dipole dipole
excited state light of all wavelengths in the visible region is r4
emitted. The surface, therefore emits metallic lustre. attractions in gaseous molecules are particularly small since the
4 Malleability - Metals can be made thin sheets gas molecules are in continuous motion. This attraction increases
5. Ductility - Metals can be drawn into wires since metal kernels the m.pt. and b.pt. of substances and makes their liquification
can easily be shifted. easy.
6. Electrical conductivity decreases with temperature - It is Dipole-induced dipole attraction
due to random motion of mobile electrons which increases The attractive forces operate between polar molecules having
with increase of temperature. permanent dipole and non-polar molecules. The polarity in the
van der Waal's Forces : non-polar molecules is induced by the polar molecule
Attractive forces between uncharged molecules are known as
van der Waals forces. These forces may be divided into three + – + –
groups A B A–A
(i) Dispersion or London forces. These are due to transient
polarisation. Polar molecules Non-polar molecules
–
+
+
–
C C
H Cl Cl H
O
Cis ( 0 ) trans ( = 0 )
O
1
(5) Dipole moment is greatest for ortho isomer, zero for para
O 2
isomer and less than that of ortho for meta isomer.
While expressing dipole moments, generally charge is given in o > m > p. e.g.
electrostatic units (esu) and distance in angstrom units (1Aº = Cl
10–10 m). Thus dipole moment of an electron separated from unit Cl Cl
positive charge by a distance 1Aº would be (4.80 × 10–10 esu) × Cl
(10-8 cm) = 4.8 × 10–18 esu cm = 4.8 Debye.
Some compounds and their dipole moments are
Substance Moment Substance Moment Cl
Cl
(Debye) (Debye) ortho meta para
CO2 0.00 = 2.53 Debye = 1.48 Debye = 0
HBr 0.78 (6) Ionic character can be determined by using dipole moment
For e.g. experimental dipole moment for HCl is 1.03 and
CH3Cl 1.85 CH2F2 1.96
= r e
NH3 1.48 O3 0.52 as r = 1.26 and, e = 4.8 × 10-10 esu,
H2O 1.85 CO 1.11 = 6.05 Debye.
CH3I 1.35 CH3OH 1.68
1.03 1
Thus the ionic character 100%
C6H5NO2 4.08 C2H5OH 1.65 6.05 6
CH4 0.00 N2O 0.17 Thus we can say % ionic character
HF 1.91 H2S 0.92 experimental dipole moment
= 100
SO2 1.61 H2O2 1.84 theoretical dipole moment
NF3 0.24 PH3 0.59 (7) Hybridisation can be determined by dipole moment for eg.
C6H5OH 1.70 HCN 2.93 (i) If a molecule AB2 has =0, the orbitals used by
A (z < 21) must be sp hybridised e.g. BeF2
HCl 1.03 CCl4 0.0
(ii) If a molecule AB3 has =0, the orbitals used by
HI 0.38 CS2 0.0
A (z < 21) must be sp2 hybridised e.g. BF3
H2 0.95 PCl5 0.0
(iii) If a molecule AB4 has =0, the orbitals used by
Applications of dipole moment A (z < 21) must be sp3 hybridised e.g. CCl4
(1) Dipole moment is helpful in predicting the geometry of the
molecule. BOND LENGTH :
(2) Dipole moment helps in determining the polarity. It is the distance between the nuclei of two atoms between which
the bond is formed. Other names for bond length are interatomic
(3) Dipole moment can distinguish between symmetrical and
non symmetrical molecules. eg. CO2 has 0 dipole moment as distance or bond distance. It is usually expressed in angstrom
it is symmetrical whereas H2O has a dipole moment of 1.85D. unit (1Å=10-10m). Pauling’s rule states that for covalently bonded
atoms, bond length is sum of covalent radii. Thus for a covalent
O compound AB, the bond length is rA + rB. where rA and rB are
O C O 105º covalent radii of A and B
= 0 Bond length depends on:-
H
H
µ = 1 .8 5
(4) Cis and trans isomers can be distinguished by dipole i) Bond order - Bond length decreases with bond order. For
moments, usually cis isomers have higher dipole moment e.g. C - C length in CH3 - CH3 is 1.54 Å, C = C length in
and hence higher polarity e.g. CH2 = CH2 is 1.34 Å and C C length in CH CH is 1.20 Å.
Larger the s character, smaller is bond length.
Chemical B onding and Molecular Structure 87
ii) Electronegativity - If one of th e atoms is mor e 4) Hybridisation - Due to directional character of hybridised
electronegative than other, the bond length is found to be orbitals, extent of overlapping increases and hence stronger
smaller than expected value. The relation that holds true for bonds are formed.
most compounds is 5) Type or extent of overlapping - Coaxial overlappings
rAB = rA + rB - 0.09 (xA - xB) (s-s, s-p, p-p) have higher extents and hence are stronger
than collateral overlappings. Thus sigma bond (coaxial
where xA and xB are electronegativities of A and B
overlapping) is stronger than pi bond (collateral
iii) Hybridisation - Larger is s character, shorter is orbital and overlapping).As p orbitals are more directional, p - p coaxial
hence shorter is the length of bond formed by it. overlapping gives stronger bond in comparison to s - s
iv) Resonance and delocalisation - C-C bond length is 1.54Å overlapping.
and C = C bond length is 1.34 Å but in benzene, due to 6) Repulsion between lone pair - In a bonding atom having lone
pair the bond formed is weaker due to non localisation of lone
pair. Mutual repulsion takes place between lone pair clouds of
two atoms, decrease the strength and hence the bond energy.
For e.g. as lone pair at each C - C is 0, N - N is one, O - O is two,
so values of their bond energies are in order C - C > N - N >
resonance, the carbon-carbon bond is neither single nor O - O.
double but intermediate between single and double and same Determination of bond energy
holds for bond length and is equal to 1.39 Å. Bond energy is determined by thermochemical methods by
Average Bond Distance of Covalent Bonds determining either the heat of atomisation i.e. heat required to
break the molecule into its atoms or by the heat of formation of
Bond Bond Bond Bond Bond Bond
compound.
length (Å) length (Å) length (Å)
Some average Bond Energies (kcal/mole)
C-C 1.54 C-H 1.12 H- H 0.74
Bond Energy Bond Energy Bond Energy
C= C 1.34 C-F 1.42 F-F 1.42
H–H 103.4 C–N 69.3 C–F 107.0
C C 1.20 C - Cl 1.77 CI - CI 1.99
C–H 98.4 C N 135.0 C – Cl 78.0
C- N 1.47 C - Br 1.91 Br - Br 2.28
C– C 81.6 O– O 34.9 C – Br 65.0
C= N 1.28 C–I 2.13 I–I 2.67
C=C 146.1 O=O 119.0 C–I 57.0
C N 1.15 O-H 0.97 H- F 0.92
C C 192.1 N– N 39.0 H–F 132.4
C- O 1.43 N-H 1.03 H - Cl 1.27
C–O 81.5 N=N 97.6 H – Cl 102.7
C= O 1.20 S-H 1.35 H - Br 1.41
C= O 173.0 N N 225.0 H – Br 87.3
O=O 1.21 N=N 1.09 H- I 1.61
C O 256.0 N–H 92.9 H–I 71.4
BOND ENERGY :
C=S 114.0 S–H 87.5 F–F 37.0
Bond strength or bond energy is the amount of energy required
to break a bond in one gram mole of a substance in gaseous state. N=O 146.0 O–H 110.2 Cl – Cl 58.0
Bond energy is also called bond dissociation energy. Its units are
BOND ANGLE :
kJmol–1. Bond dissociation energy and (average) bond energy
are same in diatomic molecules as they have only one bond. But Bond angle is the angle between two adjacent bonds in a molecule.
in molecules having many bonds, bond dissociation energy of O
the bonds are different and bond energy is the average value of 180°
bond dissociation energy O C O H 105° H
Factors affecting the bond energy Thus bond angles in CO2 and H2O are 180º and 105º.
1) Atomic size - Strength of shorter bond is more e.g. atomic Factors affecting bond angle
size of Cl, Br, I has the order Cl < Br < I and their bond 1) Electronegativity - Cl - O- Cl bond angle in Cl2O is more
energies, Cl - Cl (243 kJ mol -1 ) > Br - Br (192 kJ mol –1 ) than F - O - F bond angle in OF2 because in Cl2O, O atom is
> I - I(151 kJmol–1) more electronegative compared to Cl atom due to which
2) Bond order - Higher bond order implies higher energy e.g. shared electrons are attracted towards O. This makes bonded
electrons of two Cl-O bonds to come close and hence more
bond energies for C C, C C and C C are 347.2, 610.0
repulsion resulting in wider bond angle. Whereas in OF2, F
and 835.1 kJ mol-1 respectively. is more electronegative than O thus bonded electrons of F-O
3) Electronegativity-Larger the difference in electronegativities bond are closer to F atom. This makes bonded electrons of
of bonded atoms, more is the attraction, shorter is bond two O - F bonds to go apart, feeling less repulsion and hence
length and hence higher is bond energy. a lower value for bond angle.
88 Chemistry
2) Hybridisation - sp3 hybridisation at central atom implies a (2) Expansion of octet : Consider the following molecules
bond angle of 109º 28 each e.g. CH4, CH3CH3 etc. sp2 .. ..
hybridisation leads to 120º bond angle as in BF3 . sp .. Cl .. F ..
..
..
..
..
hybridisation makes angle 180º e.g. BeCl2. Cl
.. F F
..
.. ..
..
..
..
.. P Cl .. .... .. .. S ..
..
3) Lone pair repulsions - Presence of lone pair at central atom Cl
..
.. ..F– Cl – F.. F
.. F
..
..
..
..
..
..
results in repulsion of shared pair of electrons. Thus bonds
Cl
.. F
..
..
..
..
..F
..
at central atom are displaced inside making the value of bond
..
..
angle smaller e.g. bond angle in ammonia is 107º even though (10 electrons around P) (10 electrons around Cl) (12 electrons around S)
hybridisation at nitrogen is sp3. It is due to presence of lone
Explanation for the failure of Octet rule : The concepts given
pair of electrons at nitrogen atom which causes more
repulsion between N and H and hence decreasing the bond below explain the failure of the octet rule :
angle. Bond angle can be measured by X-ray techniques or (a) Sidwick's rule of maximum covalency : The maximum
by I.R. spectroscopy. covalency of an element depends on the period to which
Baeyer’s strain theory states that any shift in normal bond it belongs and octet can be exceeded for n = 1 it is 2, for n
angle causes strain over the molecule making it less stable = 2 it is 4, for n = 3 it is 6 and for n > 4 it is 8.
and more reactive. Thus CH4, C2H6 are quite stable while (b) Sugden's view of singlet linkage : According to Sugden
ethylene is less stable (bond angle 120º). the octet rule is never violated. There can be one electron
OCTET RULE : bond known as Singlet linkage, Singlet or half bond is
formed by sharing of one electron between two atoms. It is
During formation of a covalent bond, the atoms attain an intert represented by half arrow ( ). Thus SF6 and PCl5 have
gas electronic configuration (ns2p6 configuration). This is known the structures :
as Octet rule. There are exceptions of octet rule.
.. ..
(1) Incomplete octet : Consider the following molecules .. F .. .. Cl
..
..
..
..
.. .. F F Cl
..
..
.. ..
..
..
..
.. .. ..F– B – F.. .. .. Cl
..
S P
..
..
..
Cl
.. – Be – Cl
.. F F Cl
..
..
..
..
..
F ..
..
..
..
..
..
..
..
..
..
..
.N ..
O
..
(7 electrons around N)
Chemical B onding and Molecular Structure 89
..
..
.. _
N = N = O :N N—O:
..
:N—N
..
O+ :
..Cl O.. ..Cl O..
I II III
.. ..
..
.. ..
.. ..
P P
5. Which of the following has higher dipole moment
H3C – CH2 – CH = CH2( 1–butene) or .. Cl.. ..Cl..
..
..
H3C – CH2 – C º CH( 1–butyne)? I II
6. Predict the dipole moment of 16. Draw all possible resonance structures for the sulfate ion,
(i) A molecule AX4 with tetrahedral geometry SO42– on the basis of formal charge
(ii) A molecule AX2 with linear geometry 17. State the hybridization and draw the molecular structure of
(iii) A molecule AX3 with distorted tetrahedral geometry. the following
7. Three elements have the following Lewis symbols: (a) PF5 (b) I3– (c) NH3 (d) XeO3 (e) CH4
A B C 18. Give reasons for following :
(a) Assign groups of the periodic table to these elements. (i) What is the decreasing order of lattice energy of
various ions?
(b) Which elements are expected to form ions and what is
the expected charge over these ions? (ii) PbSO4, BaSO4, AgCl, AgBr, AgI are insoluble in water,
(c) Write the formulae and Lewis structures of the covalent why?
compounds formed between (iii) Which is more ionic and why? FeCl 2 or FeCl3?
(i) A and B (iv) What is the decreasing order of strengths of bonds
(ii) A and C between sp3, sp2 and sp hybrid orbitals?
8. Why are lone pair-lone pair repulsions stronger than lone (v) What is the order of dipole moment of ortho, meta and
pair-bond pair? para disubstituted derivatives?
9. Account for the following : Multiple Choice Questions
(i) N2 has a higher bond dissociation energy than NO. 19. Sodium chloride is an ionic compound whereas hydrogen
(ii) N2 and CO both have the same bond order but CO is chloride is mainly covalent because
more reactive than N2. (a) sodium is less reactive
10. Account for the following : (b) hydrogen is non-metal
(i) He2 is not found to exist in nature (c) hydrogen chloride is a gas
(ii) N2+ is not a diamagnetic substance (d) electronegativity difference in the case of hydrogen
and chlorine is less than 2.1.
(iii) The dissociation energy of H+2 is almost the same as
20. Which one of the following molecules will have unequal
that of He2+.
M – F bond lengths ?
11. Which is more covalent and why : BeCl2 or MgCl2 ?
(a) NF3 (b) BF3
12. Why does Pauli’s exclusion principle permit bonding only if
the electrons are of different spins? (c) PF5 (d) SF4
90 Chemistry
21. Match List I (Molecules) with List II (Bond order) and select 25. Number of bonds and bonds in the following structure
the correct answer using the codes is H H
List I List II H H
I. Li2 A. 3
II N2 B. 1.5 H H
III Be2 C. 1.0 H H
IV O2 D. 0 (a) 6, 19 (b) 4, 20
E. 2 (c) 5, 19 (d) 5, 20
Codes 26. The states of hybridisation of boron and oxygen atoms in
(a) I - B, II - C, III - A, IV - E boric acid (H3BO3) are respectively
(b) I - C, II - A, III - D, IV - E (a) sp3 and sp2 (b) sp2 and sp 3
(c) I - D, II - A, III - E, IV - C 2
(c) sp and sp 2 (d) sp3 and sp3
(d) I - C, II - B, III - E, IV - A 27. Which of the following statement is not correct from the
22. Polarity in a molecule and hence the dipole moment depends view point of molecular orbital theory?
primarily on electronegativity of the constituent atoms and (a) Be2 is not a stable molecule.
shape of a molecule. Which of the following has the highest
dipole moment? (b) He2 is not stable but He 2 is expected to exist.
+
1. Chemical bond implies 11. Ground state electronic configuration of valence shell
(a) repulsion electrons in nitrogen molecule (N 2) is written as
(b) attraction
( 2s ) 2 ( *2s ) 2 ( 2p ) 4 ( 2p ) 2 . Hence the bond order of
(c) attraction and repulsion balanced at a particular distance
(d) attraction and repulsion nitrogen molecule is
2. The bonding is electrovalent in (a) 2 (b) 3
(a) NaCl (b) Br2 (c) 0 (d) 1
(c) PF5 (d) XeF4 12. The bond order of NO molecule is
3. Bonding in ferric chloride is (a) 1.5 (b) 2.0
(a) covalent (b) ionic (c) 2.5 (d) 3.0
(c) co-ordinate (d) None of the above 13. Which of the following cannot be formed ?
4. Which of the following species has lowest ionization (a) He2+ (b) He+
potential? (c) He (d) He2
(a) O (b) O2
14. N 2 and O 2 are converted into monoanions, N 2– and O 2
(c) O +
(d) O–
2 2
respectively. Which of the following statements is wrong ?
5. Polarization power of a cation increases when
(a) charge on the cation increases (a) In N – , N – N bond weakens
2
(d) has no relation to its size or charge (c) In O – , O - O bond order decreases
2
6. The correct order of decreasing polarisability of following
ions is (d) N – becomes paramagnetic
2
–
(a) Cl , Br , I , F – – – (b) – – – –
F , I , Br , Cl
15. N2 and O2 are converted into monocations, N +
2
and
– –
(c) F , CI , Br , l – – – –
(d) I , Br , Cl , F – –
O respectively. Which of the following statements is
+
overlapping
(d) The bond formed may or may not be polar (c) In O , paramagnetism decreases
+
(c) BeCl2 (d) BCl3 16. Which of the following molecule is paramagnetic?
9. Consider the following statements: (a) CO2 (b) SO2
(i) A sigma ( ) bond is formed when two s - orbitals overlap (c) NO (d) H2O
(ii) A pi ( ) bond is formed when two 17. In PO 34– , the formal charge on each oxygen atom and the
p- orbitals axially overlap
P - O bond order respectively are
(iii) A -bond is weaker than -bond.
Which of the above statements is/are correct ? (a) –0.75, 0.6 (b) –0.75, 1.0
(a) i and ii (b) ii and iii (c) –0.75, 1.25 (d) –3, 1.25
(c) i alone (d) ii alone 18. Which of the following ion has not bond order of 2.5 ?
10. Number of bonds in naphthalene are (a) O – (b) O +
2 2
(a) 6 (b) 3
(c) 4 (d) 5 (c) N +
2
(d) N– 2
92 Chemistry
19. Oxygen molecule is 32. The values of electronegativity of atoms A and B are 1.20
(a) diamagnetic with no unpaired electrons and 4.0 respectively. The percentage of ionic character of
(b) diamagnetic with two unpaired electrons A - B bond is
(c) paramagnetic with two unpaired electrons (a) 50% (b) 72.24%
(d) paramagnetic with no unpaired electrons (c) 55.3% (d) 43%
20. The number of electrons that are paired in oxygen molecule 33. The electronegativities of F, Cl, Br and I are 4.0, 3.0, 2.8, 2.5
is
respectively. The hydrogen halide with a high percentage of
(a) 16 (b) 12 ionic character is
(c) 7 (d) 8
(a) HF (b) HCl
21. Which of the following pairs have identical bond
order ? (c) HBr (d) HI
34. Covalent compounds have low melting point because
(a) N , O 2 +
(b) N ,O– 1
2 2 2 2
(a) covalent molecules have definite shape
(c) N – , O2 2
(d) O , N 2 +
2
(b) covalent bond is weaker than ionic bond
22. Which one of the following should be most stable? (c) covalent bond is less exothermic
(a) H +
(b) H+ (d) covalent molecules are held by weak van der Waal’s
2
forces of attraction
(c) H (d) H– 35. The number of sigma ( ) bonds in 1-butene is
23. The number of antibonding electron pairs in O – molecular
2
2
(a) 8 (b) 10
ion on the basis of molecular orbital theory are (at. no. O (c) 11 (d) 12
= 8) 36. The structure of PF5 molecule is
(a) 2 (b) 3 (a) tetrahedral
(c) 4 (d) 5 (b) square planar
24. Which of the following is not paramagnetic ?
(c) trigonal bipyramidal
(a) N +
2
(b) CO (d) pentagonal bipyramidal
(c) O – (d) NO 37. Which of the following has sp 2-hybridization?
2
(a) C2H6 (b) C2H4
25. Which of the following molecular species has unpaired
electron (s) ? (c) BeCl2 (d) C2H2
(a) N2 (b) F2 38. The structure and hybridization of Si(CH3)4 is
(a) bent, sp (b) trigonal, sp2
(c) O – (d) O –2
2 2
3
(c) octahedral, sp d (d) tetrahedral, sp3
26. Which of the following has least covalent P–H bond?
(a) PH3 (b) P2H6 39. Which of the following molecule is not linear in shape
(c) P2H5 (d) PH6+ (a) HgCl2 (b) Hg2Cl2
27. Which contains both polar and non - polar bonds? (c) CO2 (d) SnCl2
(a) NH4Cl (b) HCN 40. Among the following compounds the one that is polar and
(c) H2O2 (d) CH4 has the central atom with sp2 hybridisation is
28. Which of the following has least polarity in bond? (a) H2CO3 (b) SiF4
(a) H – F (b) H – Cl (c) BF3 (d) HClO2
(c) H – O (d) H – S 41. Which one of the following compounds has sp2 hybridisation?
29. Which of the following substances has the least ionic (a) CO2 (b) SO2
character ?
(c) N2O (d) CO
(a) FeCl2 (b) ZnCl2
(c) CdCl2 (d) MgCl2 42. The AsF5 molecule is trigonal bipyramidal. The hybrid
orbitals used by the As atoms for bonding are :
30. The correct order of increasing ionic character is
(a) BeCl2 < MgCl2 < CaCl2 < BaCl2 2
(a) d x 2 y2 , d z , s, p x , p y (b) d xy , s, p x , p y , p z
(b) BeCl2 < MgCl2 < BaCl2 < CaCl2
(c) BeCl2 < BaCl2 < MgCl2 < CaCl2
(c) s, p x , p y , p z, d 2z (d) d , s, p x , p y
(d) BaCl2 < CaCl2 < MgCl2 < BeCl2 x 2 y2
31. Which of the following contains both covalent and ionic bond? 43. The hybridization of S atom in SO42– is
(a) NH4Cl (b) H2O (a) sp (b) sp 2
(c) CCl4 (d) CaCl2 (c) sp 3 (d) sp 3 d
Chemical B onding and Molecular Structure 93
44. In piperidine , the hybrid state assumed by N is Electron Pair Repulsion (VSEPR) theory will be
N (a) planar triangular (b) pyramidal
H (c) tetrahedral (d) square planar
(a) sp (b) sp 2 56. Among the following ions, the p – d overlap could be
(c) sp 3 (d) dsp 2 present in
45. Which of the following will be octahedral ? (a) NO – (b) PO 3 –
3 4
3
3 2
–
46. The hybridization of atomic orbitals of nitrogen in 57. In NO ion, number of bond pairs and lone pairs of electrons
3
(a) 2, 2 (b) 3, 1
(a) sp2, sp3 and sp2 respectively (c) 1, 3 (d) 4, 0
(b) sp, sp2 and sp3 respectively 58. In OF2, number of bond pairs and lone pairs of electrons are
(c) sp2, sp and sp3 respectively respectively
(d) sp2, sp3 and sp respectivley (a) 2, 6 (b) 2, 8
47. The compound MX4 is tetrahedral. The number of XMX (c) 2, 10 (d) 2, 9
formed in the compound are 59. The compound containing co-ordinate bond is
(a) three (b) four (a) H2SO4 (b) O3
(c) five (d) six (c) SO3 (d) All of these
48. The shape of gaseous SnCl2 is 60. Sulphuric acid provides a simple example of
(a) tetrahedral (b) linear (a) co-ordinate bonds
(c) angular (d) t-shape (b) non-covalent compound
49. Which of the following molecule is linear ? (c) covalent ion
(d) non - covalent ion
(a) SO2 (b) NO +
72. Which of the following has the highest dipole moment? (a) 2 (b) 3
(a) AsH3 (b) SbH3 (c) 6 (d) 9
(c) PH3 (d) NH3 86. Match List I (Molecules) with List II (Bond order) and select
73. The molecule having non-zero dipole moment is the correct answer using the codes
(a) H2O2 (b) CH4 List I List II
I. Li2 A. 3
(c) C2H6 BF –
(d) 4
II N2 B. 1.5
74. Which of the following hydrocarbons has the lowest dipole III Be2 C. 1.0
moment ? IV O2 D. 0
H3C CH 3 E. 2
(a) C (b) CH C CCH Codes
3 3
H H (a) I - B, II - C, III - A, IV - E
(b) I - C, II - A, III - D, IV - E
(c) CH CH C CH (d) CH 2 = CH – C CH
3 2
(c) I - D, II - A, III - E, IV - C
75. Which of the following has zero dipole moment?
(d) I - C, II - B, III - E, IV - A
(a) ClF (b) PCl3
87. An ether is more volatile than an alcohol having the same
(c) SiF4 (d) CFCl3
molecular formula. This is due to
76. Dipole moment is shown by
(a) 1, 4-dichlorobenzene (a) dipolar character of ethers
(b) cis 1,2-dichlorobenzene (b) alcohols having resonance structures
(c) trans 1, 3-dichlorobenzene (c) inter-molecular hydrogen bonding in ethers
(d) trans 2, 3-dichloro -2- butene (d) inter-molecular hydrogen bonding in alcohols
77. Which one of the following molecules will have unequal 88. The reason for double helical structure of DNA is operation
M – F bond lengths ? of
(a) NF3 (b) BF3 (a) van der Waal’s forces (b) dipole-dipole interaction
(c) PF5 (d) SF4 (c) hydrogen bonding (d) electrostatic attraction
78. The bond length in LiF will be 89. Among the following, the molecule with the highest dipole
(a) less than that of NaF (b) equal to that of KF moment is
(c) more than that of KF (d) equal to that of NaF (a) CH3Cl (b) CH2Cl2
79. Which has the least bond angle ? (c) CHCl3 (d) CCl4
(a) NH3 (b) BeF2 90. Which of the following represents the given mode of
(c) H2O (d) CH4 hybridisation sp2 –sp2 – sp - sp from left to right ?
80. The correct sequence of decrease in the bond angles of the
following hydrides is (a) H C = CH C
2
N (b) HC C–C CH
(a) NH3 > PH3 > AsH3 > SbH3 CH2
(b) NH3 > AsH3 > PH3 > SbH3 (c) H C = C = C = CH (d) H C
2 2
2
(c) SbH3 > AsH3 > PH3 > NH3
(d) PH3 > NH3 > AsH3 > SbH3
Chemical B onding and Molecular Structure 95
1. In which of the following pairs, the two species are iso- 9. In which of the following molecules the central atom does
structure? [CBSE-PMT 2007] not have sp3 hybridization? [CBSE-PMT 2010]
(a) SO32– and NO3– (b) BF3 an NF3 (a) NH +4 (b) CH4 (c) SF4 (d) BF4–
(c) BrO3– and XeO3 (d) SF4 and XeF4
2. The correct order of increasing bond angles in the following 10. Which one of the following species does not exist under
triatomic species is : [CBSE-PMT 2008] normal conditions? [CBSE-PMT 2010]
(a) NO 2 < NO +2 < NO 2 (b) NO2 < NO2 < NO2 +
(a) Be 2 +
(b) Be2 (c) B2 (d) Li 2
(c) NO2 < NO 2 < NO2 (d) NO2 < NO2 < NO2 11. Considering the state of hybridization of carbon atoms, find
3. Four diatomic species are listed below in different sequences. out the molecule among the following which is linear ?
Which of these presents the correct order of their increasing (a) CH3– CH = CH–CH3 [CBSE-PMT 2011]
bond order ? [CBSE-PMT 2008] (b) CH3 – C C – CH3
(a) O2 < NO < C22 < He2 (b) NO < C22
+
< O2 < He 2+
(c) CH2 = CH – CH2 – C CH
(c) C 22 < He 2 < NO < O 2 (d) He2 < O2 < NO < C 22 (d) CH3 – CH2 – CH2 – CH3
4. What is the dominant intermolecular force or bond that must 12. Which of the two ions from the list given below have the
be overcome in converting liquid CH3OH to a gas? geometry that is explained by the same hybridization of
(a) Dipole-dipole interactions [CBSE-PMT 2009] orbitals, NO2–, NO3–, NH2–, NH4+, SCN– ?
(b) Covalent bonds [CBSE-PMT 2011]
(c) London dispersion forces (a) NO2– and NO3– (b) NH2– and NO3–
(d) Hydrogen bonding (c) SCN– and NH2– (d) NO2– and NH2–
5. In which of the following molecules / ions BF3, NO 2 , NH 2 13. Which of the following has the minimum bond length ?
and H2O , the central atom is sp2 hybridized ? [CBSE-PMT 2011]
[CBSE-PMT 2009] (a) O2 + (b) O2 –
(a) NH 2 and H2O (b) NO 2 and H2O (c) O2 2– (d) O2
(c) BF3 and NO2 (d) NO2 and NH 2 14. The pairs of species of oxygen and their magnetic
6. According to MO theory which of the following lists ranks behaviours are noted below. Which of the following presents
the nitrogen species in terms of increasing bond order? the correct description ? [CBSE-PMT 2011 M]
[CBSE-PMT 2009] (a) O -2 , O 22 - – Both diamagnetic
(a) N 2–
2 < N 2– < N2 (b) N 2 < N 22– < N 2– (b) O +2 ,O22 - – Both paramagnetic
(c) N 2– < N 2–
2 < N2 (d) N 2– < N2 < N 2–
2 (c) O+2 ,O2 – Both paramagnetic
7. In which one of the following species the central atom has (d) None of these
the type of hybridization which is not the same as that
15. Which one of the following pairs is isostructural (i.e., having
present in the other three? [CBSE-PMT 2010]
the same shape and hybridization) ? [CBSE-PMT 2012]
(a) SF4 (b) I3– (c) SbCl52– (d) PCl5
8. Some of the properties of the two species, NO3 and H3O+ (a) BCl3 and BrCl3 (b) NH3 and NO3
are described below. Which one of them is correct?
[CBSE-PMT 2010] (c) [ NF3 and BF3 ] (d) BF4 and NH 4+
(a) Similar in hybridization for the central atom with different 16. Bond order of 1.5 is shown by : [CBSE-PMT 2012]
structures.
(a) O +2 (b) O 2 (c) O 22 (d) O2
(b) Dissimilar in hybridization for the central atom with
different structures. 17. Which of the following species contains three bond pairs
(c) Isostructural with same hybridization for the central and one lone pair around the central atom ?
atom. [CBSE-PMT 2012]
(d) Isostructural with different hybridization for the central
atom. (a) H2O (b) BF3 (c) NH -2 (d) PCl3
96 Chemistry
18. The pair of species with the same bond order is : 29. The states of hybridization of boron and oxygen atoms in
[CBSE-PMT 2012] boric acid (H3BO3) are respectively [AIEEE 2004]
(a) O 2– (b) O +2 , NO+ (a) sp3 and sp2 (b) sp2 and sp 3
2 , B2
(c) sp2 and sp2 (d) sp3 and sp3
(c) NO, CO (d) N2, O2
30. Which one of the following has the regular tetrahedral
19. Which of the following is electron - deficient ?
structure ? [AIEEE 2004]
(a) (SiH3)2 (b) (BH3)2 [NEET 2013]
(c) PH3 (d) (CH3)2 (a) BF4 (b) SF4
20. Which one of the following molecules contains no bond?
(a) H2O (b) SO2 [NEET 2013] (c) XeF4 (d) [ Ni(CN) 4 ]2
(c) NO2 (d) CO2 (Atomic nos. : B = 5, S = 16, Ni =28, Xe = 54)
21. Which of the following is paramagnetic ? [NEET 2013] 31. The maximum number of 90º angles between bond pair-bond
pair of electrons is observed in [AIEEE 2004]
(a) O2 (b) CN–
(a) dsp2 hybridization (b) sp3d hybridization
(c) NO+ (d) CO (c) dsp3 hybridization (d) sp3d2 hybridization
22. Dipole-induced dipole interactions are present in which of 32. Which of the following species is diamagnetic in
the following pairs : [NEET 2013] nature? [AIEEE 2005]
(a) Cl2 and CCl4
(a) H 2 (b) H 2+
(d) H2O and alcohol 33. Lattice energy of an ionic compound depends upon
23. In which of the following species the interatomic bond angle (a) Charge on the ion and size of the ion [AIEEE 2005]
is 109° 28’? [AIEEE 2002] (b) Packing of ions only
(a) NH3, (BF4)1– (b) (NH4)+, BF3 (c) Size of the ion only
(c) NH3, BF4 (d) (NH2)1–, BF3. (d) Charge on the ion only
24. Which one of the following pairs of molecules will have 34. The molecular shapes of SF4 , CF4 and XeF4 are
permanent dipole moments for both members ? [AIEEE 2005]
[AIEEE 2003] (a) different with 1, 0 and 2 lone pairs of electrons on the
(a) NO2 and CO2 (b) NO2 and O3 central atom, respectively
(c) SiF4 and CO2 (d) SiF4 and NO2 (b) different with 0, 1 and 2 lone pairs of electrons on the
25. Which one of the following compounds has the smallest central atom, respectively
bond angle in its molecule ? [AIEEE 2003] (c) the same with 1, 1 and 1 lone pair of electrons on the
(a) OH2 (b) SH2 central atoms, respectively
(c) NH3 (d) SO2 (d) the same with 2, 0 and 1 lone pairs of electrons on the
central atom, respectively
26. The pair of species having identical shapes for molecules of
35. Which of the following molecules/ions does not contain
both species is [AIEEE 2003]
unpaired electrons? [AIEEE 2006]
(a) XeF2, CO2 (b) BF3, PCl3
(c) O 22
+
(c) PF5, IF5 (d) CF4, SF4 (a) N2 (b) O2 (d) B2
27. The correct order of bond angles (smallest first) in H2S, NH3, 36. Among the following mixtures, dipole-dipole as the major
BF3 and SiH4 is [AIEEE 2004] interaction, is present in [AIEEE 2006]
(a) H2S < NH3 < SiH4 < BF3 (a) KCl and water
(b) NH3 < H2S < SiH4 < BF3 (b) benzene and carbon tetrachloride
(c) H2S < SiH4 < NH3 < BF3 (c) benzene and ethanol
(d) H2S < NH3 < BF3 < SiH4 (d) acetonitrile and acetone
28. The bond order in NO is 2.5 while that in NO+ is 3. Which of 37. In which of the following molecules/ions are all the bonds
the following statements is true for these two species ? not equal? [AIEEE 2006]
[AIEEE 2004] (a) XeF4 (b) BF4 –
(a) Bond length in NO+ is equal to that in NO
(c) SF4 (d) SiF4
(b) Bond length in NO is greater than in NO+
38. Which of the following species exhibits the diamagnetic
(c) Bond length in NO+ is greater than in NO behaviour ? [AIEEE 2007]
(d) Bond length is unpredictable (a) NO (b) O2 2– (c) O2+ (d) O2
Chemical B onding and Molecular Structure 97
39. The charge/size ratio of a cation determines its polarizing 48. Which of the following is the wrong statement ?
power. Which one of the following sequences represents [JEE Main 2013]
the increasing order of the polarizing power of the cationic –
(a) ONCl and ONO are not isoelectronic.
species, K+, Ca2+, Mg2+, Be2+? [AIEEE 2007]
(b) O3 molecule is bent
(a) Ca2+ < Mg2+ < Be2+ < K+
(b) Mg2+ < Be2+ < K+ < Ca2+ (c) Ozone is violet-black in solid state
(c) Be2+ < K+ < Ca2+ < Mg2+ (d) Ozone is diamagnetic gas.
(d) K+ < Ca2+ < Mg2+ < Be2+ 49. In which of the following pairs of molecules/ions, both the
40. In which of the following ionization processes, the bond species are not likely to exist ? [JEE Main 2013]
order has increased and the magnetic behaviour has
changed? [AIEEE 2007] (a) H 2 , He 22 (b) H 2 , He 22
(a) N 2 N2 +
(b) C2 C2 +
1. Sodium chloride is an ionic compound whereas hydrogen 10. Which one of the following arrangements of molecules is
chloride is mainly covalent because correct on the basis of their dipole moments?
(a) Sodium is less reactive (a) BF3 > NF3 > NH3 (b) NF3 > BF3 > NH3
(b) Hydrogen is non-metal
(c) NH3 > BF3 > NF3 (d) NH3 > NF3 > BF3
(c) Hydrogen chloride is a gas
11. Which of the following is the correct electron dot structure
(d) Electronegativity difference in the case of Hydrogen and
of N2O molecule?
chlorine is less than 2.1. .. + ..
2. For two ionic solids, CaO and Kl. Identify the wrong (a) : N = N = O : (b) : N = N = O
.. :
statement among the following .. .. .. ..
(a) Lattice energy of CaO is much larger than that of Kl (c) N = N = O : (d) : N = N = O ..
:
..
(b) KI is soluble in benzene 12. Consider the following statements. The common features of
(c) CaO has higher melting point the molecules BF3, CO & NO are that
(d) KI has lower melting point I. all are Lewis acids
3. The correct order of increasing C - O bond length of CO, II. all are gaseous in nature
CO 2 –
, CO2 is III. all contain unpaired electrons
IV. all do not conform to the octet rule
3
–
(a) CO 2
3
< CO 2
< CO (b) CO 2
< CO 2
3
< CO Which of the above statements are correct ?
(a) I and II (b) III and IV
(c) CO < CO – < CO (d) CO < CO < CO –
2
3 2 2
2
(d) ICl is polar while Br2 is non polar 4. SeF4 and CH 4 have same shape
38. An element forms compounds of the formula ACl3 , A 2O 5 (a) 1, 2, 3 (b) 1, 3
and Mg 3A 2 but does not form ACl5 , the A could be (c) 1, 3, 4 (d) 1, 2, 4
47. Trimethylamine is a pyramidal molecule
(a) Al (b) P
(c) B (d) N N
CH 3 and formamide is a planar molecule
39. The magnitude of the lattice energy of a solid increases if H 3C CH 3
(a) charges on both the ions are small
(b) the ions are large O
(c) the ions are small ||
(d) the ions are of equal size C H
, The hybridisation of Nitrogen in both is
40. The correct representation of H-bond in solid HF H N
(a) H – F H–F H–F |
F F F
H
(b) H H H H H 3 2
F F (a) sp 2 , sp 2 (b) sp , sp
H H H H
(c) F F (c) sp 3 , sp 3 (d) sp 2 , sp
F
H H 48. If climbing of water droplets is made to occur on a coated
(d) F F F F microscope slide, the slide would have to be coated in
H which of the following way
Cl
EXERCISE 1 3 3
O O
1. Bonding molecular orbital. | |
2. Because b.p. –b.p. repulsion is less in H2S than in H2O. 17. (c) O P O O P= O
3. MgO || |
O O
4. III, because like charges reside on adjacent atoms.
5. 1 – butyne has more dipole moment. 3 3
O O
6. (i) Non-polar due to symmetric structure. || |
(ii) Non-polar due to linear molecular structure. O P O O= P O
(iii) Polar due to non-symmetric molecular structure. | |
O O
7. (a) A – group 1, B – group 14, C – group 17
(b) A, C are expected to form ions A+ and C– Bond order
A Number of bonds 5
.. = = = 1.25
(c) (i) A : B : A (ii) A : C : or A+Cl +
Number of Resonating structures 4
..
A Three unit negative charge is being shared by four O atoms.
11. BeCl2 Since Be2+ ion is small in size. Formal charge = –3/4
19. (b) 20. (c) 21. (b)
18. (a) O – has Bond order 1.5 (see text)
22. (c) 23. (c) 24. (a) 2
2
is 3 (calculate by energy level
3. (b) Covalent ( Fajan's rule see text)
diagram)
4. (d) *2px2 *2py1 antibonding molecular orbitals contain
22. (b) H+
three electrons in O – . Their energy being more and
2
23. (c)
2
* 2 2
* 2 2
*
5. (a) Polarizing power = charge/ radius. Thus µ charge.
2
* 2
6. (d) The larger the size of anion the more is its polarizability 4 pairs
7. (b) Covalent bonds are directional in nature 24. (b) CO is diamagnetic while others are paramagnetic
8. (d) BCl3 is lewis acid and electron deficient. The octet around
25. (c) O – (see text)
B is not complete 2
9. (c) Statement 1 is correct (see text) 26. (d) In PH6 , P – H bond will have ionic character due to
+
10. (d) number of bonds is 5 electron attracting tendency of P carrying +ve charge
and least covalent.
Nb8 2 Na 27. (c)
11. (b) Bond order = = 3 =
2 2 28. (d) The electronegativity of S is least among others hence H
12. (c) Bond order in NO is 2.5 (see text) -S bond is least polar in nature.
13. (d) Bond order in He2 is zero (see text) 29. (b) Polarizing power of Zn2+ is more than others, hence ZnCl2
is least ionic in nature.
14. (c) Species N2 O2 N–2
O–2 30. (a) Electropositive character and size increases down the
Bond order 3 2 2.5 1.5 group, the ionic character increases.
The O-O bond is O – decreases 31. (a) NH 4Cl contains both covalent and ionic bonds
2
+
2 + H
15. (d) b *a2 2
b( *2
2
a
1 2
b ) b (N 2 = 13electrons)
b |
it contains one unpaired electron hence paramagnetic H – N– H Cl –
|
16. (c) NO is paramagnetic H
102 Chemistry
32. (b) Electronegativity difference is 4.0 - 1.20 = 2.8 percentage (–)
ionic character is 72.24% when the electronegativity O
difference is 1.7, the % ionic character is approx 51%. O–N
57. (d) it has 4 bond pairs and none lone pair..
33. (a) Ionic character follows the order HF > HCl > HBr > HI O
34. (d)
35. (c) H3C – CH2 – CH = CH2. It has 11 bonds 58. (b) F – O – F 2 bond pairs and 8 lone pairs
36. (c) Hybridisation in PF5 is = ½ [5 + 5 + 0 –0] = 5 sp3d, hence
..
structure is trigonal bipyramidal. :O:
H .. ..
H
59. (d) All contain coordinate bond H – O
..
– S –O
..
–H ,
37. (b) C = C Hybridisation of C is sp2 ¯
:O
. .:
H H
38. (d) Hybridisation in Si(CH3)4 ( ½ [4 + 4 + 0 – 0] = 4) is sp3 ..
which is tetrahedral. :O:
..
39. (d) Hybridisation in SnCl2 (½ [4 + 2 + 0 - 0] =3) sp3. It has V- O
shape. S
,
. O :O:
..
.O
..
O
..
..
..
40. (a) H2CO3 and BF3 both have triangular planar structure
..
F H–O 60. (a) Coordinate bond
B–F C = O.
F H–O 61. (c) CO 2 – Its structure is
BF3 is symmetrical
\ m = 0 hence non polar, H2CO3 is not symmetrical
hence polar in nature. 62. (b) It is 4 See H - bonding.
41. (b) SO2 has sp2 hybridisation. 63. (d) NH3 forms intermolecular H - bonding.
64. (b) In H - bonding atoms involved are F, O and N.
42. (c) AsF5 is trigonal bipyramidal and sp3d hybridised.
65. (a) H -bonding interactions.
43. (c)
66. (c) It is due to H - bonding.
44. (c) Hybridisation of N = ½ [5 + 3 + 0 – 0] = 4 hence sp 3 67. (d) In HCl No–H–bonding, H – F form zig zag; (cage like by
45. (a) SF6 is octahedral (see text) H2O, only NH3 forms linear polymeric structures)
46. (b) NO +2 = ½ [5 + O + O –1] = 2 sp; NO 2– = ½ [5 + 0 + 1 –0] = 3 68. (a) H2O (see H - bonding)
69. (b) C2H5OH soluble in water due to H-Bonding
sp2; NH + = ½ [5 + 4 + 0 - 1] = 4 sp3 70. (d) Metallic bond is electrostatic in nature.
71. (b) Non polar molecules have dispersive forces.
X 72. (d) The electronegativity difference is maximum between N &
47. (d) M three angle below M and three above M H hence NH3 will have highest magnetic moment.
X X X
H
hence = 6 O
48. (c)
73. (d) H2O2 it is nonplanar O
49. (b) NO2+ has sp hybridisation hence linear. H
50. (c) O = C = C = C = O is sp hybridised
51. (d) In XeF2 Total number of valence electrons of Xe = 8, two The bonds are not in the plane of paper.
electrons shared with 2F atoms, 6 electrons left hence 3
74. (b) H C . C º C . CH symmetrical and linear. Hence D.M.
lone pairs, in XeF4 4 shared with 4 F atoms 4 left hence 2
lone pairs; in XeF6 6 shared with 6 F atoms 2 left hence 1 ( m ) = 0.
lone pair. 75. (c) In SiF4 DM = zero due to symmetrical structure.
52. (b) In CH3 CH2OH underlined C is forming 4 bonds, hence
Cl
sp3 hybridisation. In others it is sp2 hybridised (due to 3 Cl
bonds). 76. (b) Cis1, 2 - dichloro benzene will have some D.M.
53. (b) dsp2 hybridisation involves d x 2 - y2 . F
F
54. (b) Tetrahedral 77. (c) In PF5 the hybridisation is sp3d P–F axial. P – F bonds
55. (b) Hybridisation is sp3 and shape pyramidal
F F
56. (b) Hybridisation in PO – = ½ [5 + 0 + 3 –0] = 4 sp3. In are longer than equatorial bonds.
bonding only d orbital of P, p orbital of O can be 78. (a) It is due to small size of Li compared to size of Na and K.
involved. Since hybrid atomic orbitals do not 79. (c) Bond angles NH3 (107.5º); BeF2 (180º) H2O (104.5º) and
form bond. CH4 (109º28’)
Chemical B onding and Molecular Structure 103
80. (a) Bond angles NH PH AsH SbH 3. (d) Calculating the bond order of various species.
10 . º 2 1 0 O-2 : KK s 2s 2 , s* 2 s 2 , s2 pz2 ,
81. (d) M +2 (SO ) – Here metal atom is trivalent. Hence formula
p2 px2 = p2 p 2y , p* 2 px2 = p* 2 p1y
for phosphate will be MPO4
82. (c) Since F form H-bond [HF2]– exists. Therefore KHF2 gives 1
K+ + HF2– B.O. = (Nb - N a )
2
8-5
83. (c) It has two nodal planes. It is p*2py = or 1.5
2
NO =
84. (b) Electronic configuration reveals it is monovalent (in fact K K 2s 2 , 2s 2 ,62 p 2z , 2 p x2 = p2 p 2y , p* 2 p1x
Na) hence its oxide will be M2O.
– – Nb - N a 8 - 3
– – B.O. = = or 2.5
O O O 2 2
85. (b) C–O C=O C–O
2- 2 * 2 2
O O O = C2 : KK s2s , s 2s , p2 px = p2 p 2y , s 2 p z2
– –
Nb - N a 8 - 2
4–2 B.O. = = or 3
86. (b) B.O. = ½ [Nb – Na] Li 2 = = 1; N2 = 3; Be = 0, O2=2. 2 2
2
87. (d) In alcohol intermolecular H-bonding is possible whereas He 22+ = s1s 2 s*1s1
in ether it is not possible.
88. (c) Double helical structure of DNA is stabilised by Nb - N a 2 - 1
B. O. = = or 0.5
H - bonding. 2 2
89. (a) Dipole moment follows the order CH3Cl > CH2Cl2 > CHCl3 From these values we conclude that the correct order
> CCl4 of increasing bond order is
90. (a) CH 2 = C H - C º N He22+ < O 2- < NO < C22-
1 2 3 4
4. (d) Due to intermolecular hydrogen bonding in methanol,
3 bonds (sp 2 hybridisation);2 bonds (sp-
it exist as assosiated molecule.
hybridisation)
5. (c) On determining hybridisation from H = 1/2 (V + M – C + A).
C1 = 3 bonds, C2 = 3 bonds,
The hybridisation of BF3, NO2–, NH2– and H2O are
C3 = 2 bonds
sp2, sp2, sp3 and sp3 respectively.
EXERCISE 3 6. (a) Molecular orbital configuration of
1. (c) Both BrO3 and XeO3 have sp3 hybridization but N 2– 2 2 2 2
2 = s1s s *1s s2 s s * 2 s -
due to presence of one lp of electrons they have 2 1
ïp 2 px ï p * 2 px
trigonal pyramidal geometry. s2 p2z
2 1
2. (b) From the structure of three species we can determine ïp 2 p y ïp * 2 p y
the number of lone pair electron(s) on central atom (i.e. 10 – 6
Bond order = =2
N atom) and thus the bond angle. 2
p2 px2 1
. .N. +
N 2– = s1s 2 s *1s 2 s2 s 2s * 2 s 2 ï s2 pz2
ï p * 2 px
.. ....O.. ..O ......
N N 2 0
..O.. .... O ..O ïp2 p y ï p *2 p y
|
||
|
|
||
||
..
O
..
- + 10 5
(NO )2 NO 2 NO 2 Bond order = = 2.5
2
We know that higher the number of lone pair electron(s) 2 px2
on central atom, greater is the lp – lp repulsion. Thus N 2 = s1s 2 s *1s 2 s 2 s 2 s * 2 s 2 , 2 pz2
2 p 2y
smaller is bond angle.
The correct order of bond angle is 10 – 4
Bond order = =3
+
2
NO -2 < NO 2 < NO 2 i.e., option (b) is correct. \ The correct order is = N 2– –
2 < N2 < N2
104 Chemistry
1 2 px2 = 2 p y2 , 2 px2 = 2 p 2y
NH2– H = [5 + 2 + 1 + 0] = 4 = sp3
2
Nb - Na 10 - 8 2
1 Bond order = = =1
NH4+, H = [5 + 4 + 0 - 1] = 4 = sp 3 2 2 2
2
SCN– = sp 17. (d) PCl3
i.e., NO2– and NO3– have same hybridisation.
P
13. (a) O2 (16) 1s 2 , *1s 2 , 2s 2 , * 2s 2 , 2 p 2z , Cl
Cl
Cl
2 px2 2 p 2y , * 2 p1x * 2 p1y
18. (a) Both O2–
2 and B2 has bond order equal to 1.
B.O. = ½ (Nb – Na) = ½ (10 – 6) = 2
O2 + (15) 1s 2 , *1s 2 , 2s 2 , * 2s 2 , 2 p z2 , B2 (10) = 1s 2 *
1s 2 2s 2 * 2s 2
2 p1x = 2 p y1
2 px2 2 p 2y , * 2 p1x * 2 p0y
Nb - N a
B.O. = ½ (Nb – Na) = ½ (10 – 5) = 2.5 Bond order =
2
O2 (17) 1s 2 , *1s 2 , 2s 2 , * 2s 2 , 2 p z2 , 6-4 2
= =1
=
2 px2 2 p 2y , * 2 px2 * 2 p1y 2 2
B2 is known in the gas phase
B.O. = ½ (Nb – Na) = ½ (10 – 7) = 1.5
O22 - = (s1s )2 (s *1s)2 ( s2 s ) 2 (s * 2 s ) 2 ( s2 p z )
2
O2 2 (18) 1s 2 , *1s 2 , 2 s 2 , * 2 s 2 , 2 p z2 ,
( )( ) =( )
2 2 2
2 px2 2 p 2y , * 2 px2 * 2 p 2y ( 2 px ) =
2
2 py *
2 px *
2 py
24. (b) Both NO2 and O3 have angular shape and hence will shape-square pyramidal, one lone pair
have net dipole moment.
CF4 – Configuration of excited C-atom :
25. (b) In H2S, due to low electronegativity of sulphur the l.p. -
3
l. p. repulsion is more than bp. - bp. repulsion and hence 2s1 2p
3
the bond angle is 92º. sp
26. (a) Both XeF2 and CO2 have a linear structure. shape-tetrahedral; no lone pair
27. (a) The order of bond angles XeF6 – configuration of excited Xe atom :
BF3 > SiH 4 > NH 3 > H 2S
120º 109º 28¢ 107 º 92.5º 4 2
5s2 5p 5d
3 2
28. (b) The lower the bond order the greater the bond length sp d hybridization
and vice-versa. shape-square planar, 2 lone pairs
29. (b) In H 3BO 3 hybridisation of B is sp2 and O is sp3. 35. (c) The distribution of electrons in MOs is as follows:
F
F Vacant Filled
2p-orbital 2p -orbital
38. (b) Diamagnetic species have no unpaired electrons
O 2 2- Þ s1s2, s*1s2, s2s2, s*2s2, 2 p z ,
2
F F
+
p2px2 = p2py2, p*2px2 = p*2py2 B=F B–F
+
Whereas paramagnetic species has one or more F F
unpaired electrons as in +1/3
+
F F
O2 2
1s , 2
1s , 2 s , 2
2s ,2
2 p 2z ,{ 2 p 2x 2 p 2y , +1/3
B–F B F
+1/3
{ 2 p1x = 2 p 1y = 2 unpaired electrons F F
44. (d) Calcium carbide exists as Ca2+ and C22–. According to
O2 1s 2 , 1s 2 , 2 s 2 , 2 s 2 , 2 pz2 , the molecular orbital model, C 2 2– should have
2 molecular orbital configuration :
2 px2 = 2 p y 2 p1x * 2 p0y = 1 unpaired
unpaired electron
electron
s1 s 2 , s *1 s 2 , s 2 s 2 , s *2 s 2 ,
NO 1s 2 , 1s 2 , 2 s 2 , 2s 2 , 2 p 2z ,
{p 2 px2 = p 2 p 2y }, s 2 pz2
* *
p2 px2 = p2 p2y , p 2 p1y =p 2 pz0 = 1 unpaired electron Thus M.O. configuration suggests that it contains one
39. (d) Smaller the size and higher the charge more will be the & 2p bonds.
polarising power of cation. Since the order of the size 45. (c) All the members form volatile halides of the type
AX3. All halides are pyramidal in shape. The bond
of cation is K + > Ca ++ > Mg ++ > Be++ . So the
angle decreases on moving down the group due to
correct order of polarising power is decrease in bond pair-bond pair repulsion.
K+ < Ca2+ < Mg2+ < Be2+ 46. (c) PF5 trigonal bipyramidal
40. (c) (i) N2 : bond order = 3, diamagnetic
N2– : bond order = 2.5, paramagnetic F
F
(ii) C2 : bond order = 2, diamagnetic
F P
C2+ : bond order = 1.5, paramagnetic F
(iii) NO : bond order = 2.5, paramagnetic
F
NO+ : bond order = 3, diamagnetic
(iv) O2 : bond order = 2, paramagnetic BrF5 square pyramidal (distorted due to presence of
one lp of electrons on central atom)
O2+ : bond order = 2.5, paramagnetic
41. (c) Greater the difference between electro-negativity of F
bonded atoms, stronger will be the bond. Since F is F F
most electronegative hence F – H ...... F is the strongest Br
bond. F F
Chemical B onding and Molecular Structure 107
47. (a) & (b) The molecular orbital structures of C2 and N2 are (iii) No. of valence electrons of all atoms in N2O
N2 1s 2
*1s 2
2s 2
* 2s 2
2 px2 2 py2 2 pz2 = 2 × 5 + 6 = 16. Hence, here also all electrons are
paired. So it is diamagnetic.
C2 1s 2 *1s 2 2s 2 * 2s 2 2 py 2 2 Pz2
(iv) In KO2, we have O2 . No. of valence electrons of
Both N2 and C2 have paired electrons, hence they are
diamagnetic. all atoms in O2 = 2 × 8 + 1 = 17,
48. All options are correct,
1s 2 , *1s 2 , 2s 2 , * 2s 2 , 2 pz2
(a) ONCl = 8 + 7 + 17 = 32e not isoelectronic
ONO = 8 + 7 + 8 + 1 = 24e 2 px2 2 p 2y , * 2 px2 * 2 p1y
..
7 8Å O 1.278A° 2 Thus it has one unpaired electron, hence it is
(b) 1. 2 The central atom is sp paramagnetic.
O 116.8° O hybridized with one lone pair.
52. (a) Molecular electronic configuration of
(c) It is a pale blue gas. At – 249.7°, it forms violet black
crystals. CO: 1s 2 , *1s 2 , 2 s 2 , * 2 s 2 ,{ 2 px 2 2 p y 2 , 2 pz 2
(d) It is diamagnetic in nature due to absence of unpaired
electrons. Nb Na 10 4
Therefore, bond order = = =3
49. (c) H2+
2 = s1s s*1s
0 0 2 2
1 NO+ : 1s2 , *1s2 , 2 s 2 , * 2 s 2 , 2 pz 2 ,{ 2 px 2 2 py2
Bond order for H2+
2 =
(0 0) = 0
2
He2 = s1s2s*1s2 10 4
Bond order = =3
2
1
Bond order for He2 = (2 2) = 0
2 CN 1s 2 , *1s 2 , 2 s 2 , * 2s 2 ,
so both H22+ and He2 does not exist.
50. (b) Li2 = s1s2 s*1s2 s2s2 { 2 px 2 2 p y 2 , 2 pz 2
1
\ Bond order = (4 - 2) = 1 10 4
2 Bond order = =3
2
Li2+ = s1s2 s*1s2 s2s1
1 N2 : 1s 2 , *1s 2 , 2s2 , *2s 2 ,{ 2 p2x 2 p2y , 2 pz2
B.O. = (3 - 2) = 0.5
2 10 4
Li2– = s1s2 s*1s2s2s2s*2s1 Bond order = =3
2
1
B.O. = (4 - 3) = 0.5 NO – : 1s 2 , *1s 2 , 2 s 2 , * 2 s 2 , 2 p z2 ,
2
The bond order of Li2+ and Li2– is same but Li2+ is more { 2 p x2 2 p 2y , { * 2 p1x * 2 p1y
stable than Li2– because Li2+ is smaller in size and has 2
electrons in antibonding orbitals whereas Li2– has 3 10 6
Bond order = =2
electrons in antibonding orbitals. Hence Li2+ is more 2
stable than Li2–. \ NO– has different bond order from that in CO.
51. (d) (i) In Na2O2, we have O 22 ion. Number of valence 53. (a) Molecular orbital configuration of B2(10) as per the
electrons of the two oxygen in O 22 ion = 8 × 2 + 2 condition given in question will be
=18 which are present as follows s1s2, s* 1s2, s2s2, s* 2s2, 2 px2
6 4
2
s1s2, s*1s2, s2s2, s*2s2, 2 p z2 , { 2 px2 = 2 p y , Bond order of B2 = =1.
2
{ * 2 p x2 = * 2 p 2y B2 will be diamagnetic.
6+2
\ Number of unpaired electrons = 0, hence, O 22 is 54. (d) OSF2 : H = =4.
2
diamagnetic.
It has 1 lone pair.
(ii) No. of valence electrons of all atoms in
O3 = 6 × 3 = 18.
:
:
15. (c) H – C or Resonance Nd
H–C
d- F F d - and m ¹ 0 hence it is polar..
O F d-
O
– 24. (c) In metallic crystals the Kernels constitute the lattice and
electrons are mobile and form sea of electrons.
25. (d) Bond angles are affected by repulsions which are
O
lp – lp > lp – bp > bp – bp.
hybrid H – C due to resonance C – O bond length 26. (d) The hydrated Aluminium chloride trivalent complex ion
O
[Al.(H 2 O)6 ]3+ , formation of which is exothermic process.
is the same.
The energy released is sufficient to cause the ionisation
F :O: of Al.
| ||
16. (c) XeF2 and CO2 have linear structure Xe ; C 27. (b) Since XY2 forms 2 s , 2 p bonds and has 1 lone pair of
| ||
F :O:
electrons. It must have the structure Y = X = Y. Hence Y
1 is divalent. The hybridisation of X is
17. (b) Solubility µ . Lattice energy opposes
lattice energy æ1 ö
sp 2 ç (6 + 0 + 0 - 0)= 3 ÷ . So XY2 is trigonal planar
solubility and Solubility µ heat of hydration . Heat of è 2 ø
hydration favours solubility. For second groups ions heat .
..
of hydration is Be++ > Mg++ > Ca++ > Sr++ > Ba++ hence || X || (like SO 2 ).
solubility decreases down the group. Y Y
Cl 28. (b) For T-shape geometry the molecule must have 3 bonded
18. (b) BiCl3: Cl Bi ; sp2 - Hybridisation (Trigonal pair and 2 lone pair of electrons.
Cl 29. (a) See text
geometry); Bond angle = 120º 30. (c) Ortho-nitrophenol has intramolecular H-bonding
.
. . OH
sp3
P . O and para-nitr ophenol has
In PCl3 (Pyramidal
||
Cl Cl Cl geometry)
. N
Bond angle = O
sp3 below 109o 28’ intermolecular H-bonding.
As and decreases from
In AsCl3– (Pyramidal PCl3 to BiCl3 NO 2 NO 2 NO 2
Cl Cl Cl geometry)
sp3
In BiCl3– Bi (Pyramidal ,
Cl Cl Cl geometry) | | |
O– H O– H O– H
In these, order of bond angle : BCl3 > PCl3 > AsCl3 > BiCl3 Hence former is more volatile than latter.
19. (a) H 3 N ® BF3 where both N, B are attaining tetrahedral
31. (b) SF4 (sp 3 d) has see saw shape, XeF4 (sp 3d 2 ) square
geomerty.
planar and SiF4 (sp 3 ) is tetrahedral.
110 Chemistry
32. (d) LiCl is covalent in nature due to small size of Li + ion, -10 -8
42. (b) m cal = e × l = (4.802 ´10 esu ) (1.275 ´10 cm)
hence LiCl will ionise less than NaCl.
33. (c) Due H -bonding in H – F its boiling point is more than m obs 1.03
Percentage ionic character = ´100 = =100=17%
HCl. m cal 6.12
34. (d) Although all the factors are correct but out of these lattice
energy is the most important one. (See Born-Haber cycle). Product of charges
43. (c) Lattice energy =
35. (a) Silicon carbide is covalent solid. interionic distance
36. (c) A p bond is formed by orbitals having same symmetry
In NaCl the product of charges = 1 × 1; In CaO product of
about the internuclear axis.
charges = 2 × 2 = 4 while the inter ionic distance is almost
37. (d) The more the polar nature of molecule the more is the
same in both. Thus lattice energy of CaO is almost four
boiling point.
times the lattice energy of NaCl.
38. (d) Nitrogen can form NCl3, N 2 O5 and Mg 3 N 2 but not
44. (a) MgO has highest lattice energy, since 2 × 2 = 4 is maximum
NCl5 due to non availability of d atomic orbitals. in MgO.
39. (c) The smaller the size, the more the charge, the more is the 45. (a) m = e × d
lattice energy.
40. (b) m 1.2 D 1.2 ´ 10-18 esu cm
\ e= = =
d 1. 0 A 1.0 ´ 10-8 cm
Cl 120
1
6 Cl = 1.2 × 10 -10 esu
41. (c) 2 Dipole moments of 2Cl and 5Cl
3 Percentage of electronic charge
Cl 5 4 Cl
1.2 ´ 10 -10 esu
are vectorically cancelled. = ´ 100 = 25 %
4.8 ´ 10 -10 esu
2 2
It is due 1 Cl and 3 Cl m 2 = m1 + m 2 + 2m1 m 21 cos q 46. (a) All the statements are correct (see text).
= (1.5) 2 + (1.5) 2 + 2 ´1.5 ´1.5 cos 120 47. (b) In amine the nitrogen is sp 3 hybridised and in amide the
\ m = 1.5 D
nitrogen is sp 2 hybridised.
48. (c) Since water is polar in nature and like dissolves like, the
coating must be nonpolar to polar manner.
5
States of Matter
STATES OF MATTER : MEASURABLE PROPERTIES OF GASES :
The three important states of the matter are (i) Solid state (ii) Four measurable properties are.
(i) Mass : It is expressed in grams or kg. 1 kg=103 g moles of
Liquid state (iii) Gaseous state, which can exist together at a
particular temperature and pressure e.g. water has three states Mass in grams m
gas = =
in equilibrium at 4.58 mm and 0.0098ºC. Molar mass M
PLASMA STATE : (ii) Volume : It is equal to the volume of the container and is
expressed in terms of litres (L), millilitres (ml), cubic
It is the gaseous mixture of electrons and positive ions existing at
extremely high temperatures (in the interior of stars) or internal centimeters ( cm 3 ) , cubic meters (m3) or cubic decimeters
electrical fields in discharge tubes. (dm3).
SINGLE SUPER ATOM STATE : 1 l = 1000 ml = 1000 cm 3 = 1 dm 3
At extermely low temperature, all atoms lose their identity and get
1 m 3 = 10 3 dm 3 = 10 6 cm 3 = 10 6 ml = 10 3 l
condensed into a single entity behaving like a single super atom.
(iii) Pressure : It is equal to force per unit area and expressed in
SOME CHARACTERISTICS OF THE THREE COMMON the units such as atmosphere, millimetres (mm), centimetres
FORMS OF MATTER ARE : (cm), torr, bar etc. SI unit of pressure is pascal (Pa) or
Property Gaseous state Liquid State Solid state
kilopascal (kPa)
1 General It has definite mass It has definite It has definite
but no definite shape mass and volume mass, volume 1atm = 76cm of Hg = 760 mmof Hg = 760 torr
and volume but no definite shape and shape.
2. Forces Almost negligible Weaker than those Strongest
1atm = 101.325 kPa = 101325Pa = 101.325 Nm -2
in solids
= 1.01325 bar = 14.7lb m -2 (psi)
3. Density Low Lower than solids High
4. Motion Molecules have large Low values of No translatory 1bar = 105Pa. Pressure is measured with manometer
rotatory, vibratory motions or rotatory
and translatory motion. Possess (iv) Temperature : It is measured in celcius scale (°C)or in Kelvin
motions vibratory motion scale (K). SI unit of temperature is Kelvin (K) or absolute
5. Packing No proper packing Less closely Molecules
packed closely packed degree T (K) = t °C + 273
6. Energy Least Higher than solids Molecules possess GAS LAWS :
maximum energy
7. Thermal High Higher than solid Least
Boyle’s Law - The volume of a given mass of a gas is inversely
Expansion proportional to its pressure at constant temperature.
8. Compression High Slightly higher than Least compressibility
1
solid V or VP = k , a constant
9. Intermixing Spontaneous Spontaneous but slow Least-intermixing P
10. Pressure Exert pressure on Negligible Negligible Value of k depends on mass, temperature and nature of gas.
the walls of container
When mass and temperature are the same we have P1V1 = P2 V2
112 Chemistry
ISOCHORES :
ISOTHERMS :
A graph of P vs T at constant volume is known as Isochore
Graphs of V vs P or PV vs P at constant temperature are known as
Isotherms. GRAPHICAL REPRESENTATION OF GAY LUSSAC’S
GRAPHICAL REPERSENTATION OF BOYLES LAW : LAW :
T2 V1 V2 > V1
P P PV T1 P V2
V 1/V P T
KE of one molecule = 1 mv 2 U=
3PV ; In such case molecular volume (22400ml) is
2 M
converted into the volume under given conditions of T and
1 2 1 2
PV = mNU 2 = . mNU 2 = KE = RT
3 3 2 3 P using relation, P1V1 = P 2 V 2
T1 T2
( N = n and m ´ n = M)
MAXWELL’S DISTRIBUTION OF VELOCITIES :
3 The molecules present in a given sample of gas move with different
\ KE = RT for 1 mole of a gas
2 velocites in all possible directions. Velocities and directions of
(i) KE of n moles of gas = 3/2 nRT molecules keep on changing due to intermolecular collisions.
(ii) At absolute zero, KE is zero Hence it is impossible to find out the individual velocity of each
molecule. It is however possible to predict fraction ( DN / N ) of
MAXWELL’S GENERALISATION :
the total number of molecules having specific velocities at a
Kinetic Energy of translation of ideal gas is directly proportional
particular temperature. As shown by the curve,
to absolute temperature of gas or its pressure and is independent
of the nature of gas. The gases show ideal behavior at low presence/large volume.
Since the volume of molecules can be neglected and at high
THERMAL MOTION : temperature since intermolecular forces decrease.
KE U 2 or U 2 T U T
Most probable velocity
The molecular velocity of a gas is proportional to square root of
Fraction (percentage) of
the absolute temperature. The molecular motion is called thermal Average velocity
motion of molecules. RMS velocity
molecules
3 ´ 76 ´ 13.6 ´ 981´ 22400 (ii) Average velocity ( v ) : This is the average of the different
U=
M velocities of all the molecules.
Pc Vc 3 æ Tö
z= = = 0.375 , almost constant. (ii) When Joule Thomson Coefficient ç ÷ is negative,
RTc 8 è P øH
(heating)
JOULE THOMSON EFFECT :
2a
When a gas under high pressure is allowed to expand adiabatically Or Joule Thomson Coefficient will be negative when <b
into a region of extremly low pressure, it suffers change of temperature. RT
The phenomenon is kown as Joule -Thomson effect. æ Tö
(iii) When Joule Thomson Coefficient ç ÷ is zero, (no heating
CONDITION FOR JOULE-THOMSON EFFECT è P øH
(INVERSION TEMPERATURE): or cooling)
In Joule -Thomson effect, cooling is observed only if the gas is
2a
present below certain temperature known as inversion temperature, Or Joule Thomson Coefficient will be zero when =b
Ti. It is characteristic of each gas and related to van der Waal’s RT
Since a, b and R are constants, the sign of Joule-Thomson
2a Coefficient will depend only upon the temperature at which
constant a and b as, Ti =
Rb the gas is being allowed to expand. The temperature at which
At exact inversion temperature there is no Joule-Thomson effect. the Joule-Thomson Cofficient changes sign is known as the
Above inversion temperature, there is heating during Joule- inversion temperature.
Thomson effect. Below inversion temperature there is cooling 2a 2a
during Joule-Thomson effect. = b \ Ti =
RTi Rb
Inversion temperature for hydrogen = –80°C and for He = –240°C.
Joule-Thomson effect is zero in an ideal gas and enthalpy remains LAW OF CORRESPONDING STATES :
constant. When an ideal gas expands in vacuum, it does no work When the values of pressure, volume and temperature are
i.e. W=0 ; DE = 0 (Adiabatic condition). Hence internal energy expressed as fractions of the corresponding critical values we
of a given quantity of an ideal gas at constant temperature is P V T
have. = p, = f, =q
independent of its volume. Pc Vc Tc
æ Eö If the two substances have the same reduced temperature and the
(ii) ç ÷ =0 same reduced pressure, they will have the same reduced volume.
è V øT The statement is known as the law of corresponding states.
States of Matter 119
HEAT CAPACITY OF SYSTEM : (ii) Collision frequency (Z) : The number of collisions
For gases it can be at constant volume or at constant pressure. experienced by molecules per cc of a gas per second is known
(i) Heat capacity at constant volume (CV) is defined as the 1 2
increase in internal energy of a gas per degree rise of as collision frequency of gas, Z = vN 2
2
temperature.
v = average velocity
æ Eö 3 N = number of molecules per cm3
CV = ç ÷ = R
è T øV 2 s = collision diameter
(ii) Heat capacity at constant pressure (Cp) is defined as increase 2
in enthalpy of a gas per degree rise of temperature. At constant pressure, Z T3
æ Hö 5 At constant temperature, Z p2
Cp = ç ÷ = R
è T øP 2 (iii) Collision number (Z1) : Number of collisions undergone by
For one mole of gas, the heat capacities at constant volume a molecule with other molecules per second present in 1cm3.
and constant pressure are denoted by Cv and Cp and are Z1 = Collision number = 2 ps 2 vN
termed as molar heat capacities.
s = diameter of molecules, v = Average velocity,,
RELATION BETWEEN Cp AND Cv : N = Number of molecules per unit volume of the gas
Cp– Cv = R (iv) Mean free path (l) : The average distance travelled by the
R = 1.987 cal or 8.314 Joule molecule between two successive collisions
R= PDV = Work done by one mole of an ideal gas in expansion at 1
constant pressure when heated through 1°C. l=
2
2 N
MOLAR HEAT CAPACITIES FOR POLYATOMIC
GASES: At constant pressure, l T
3 5 1
The values C V = At constant temperature, l
R and C p = R are for monoatomic gases P
2 2
VOLUME COEFFICIENT :
like He, Ar etc. where the energy supplied increases translational
It is defined as the ratio of the increase in volume of the gas at
kinetic energy only. In polyatomic gases heat supplied is utilised
constant pressure per degree rise of temperature to its volume at
to increase vibrational and rotational energy also. Thus we have
0°C
3 5 v t -v 0
CV = R+x and C p = R+x
2 2 aV =
v0 ´ t
5 V0 =Volume of a given mass of a gas at 0°C
Cp R
5
For monoatomic gas, x = 0, g = = 2 = = 1.66 Vt= Volume of a given mass of a gas at t°C
CV 3 3
R V t = V0 (1 +a V t )
2
The value of a v is found be 1/273 for all gases (charle's law)
5
Cp R+R t
7
for diatomic gases, x = R, g = = 2 = = 1.46 Therefore, V t = V0 (1 +
273
)
CV 3 5
R+R
2 PRESSURE COEFFICIENT ( P) :
5 3 It is defined as the ratio of the increase in pressure of the gas at
C R+ R constant volume per degree rise of temperature to its pressure at
3 p
= 2 2 = 8 = 1.33
for triatomic gases, x = R , g = 0°C
2 CV 3 3 6
R+ R
2 2 P t -P 0
ap =
P 0 ´t
COLLISION PROPERTIES : P0=Pressure of given mass of gas at 0°C
(i) Molecular diameter or collision diameter : The distance Pt=Pressure of given mass of gas at t°C
between the centers of the molecules at the point of their
closest approach. P t =P 0 (1 +a p t )
The value found by Ragnault & Gay Lussac was in the vicinity of
1 æ ö t
273 for all gases and hence P t = P0 çè1 + 273 ÷ø
120 Chemistry
AMAGAT LAW OF PARTIAL VOLUME : Liquefaction is further based on the following principles
The total volume of a mixture of non reacting gases at constant (a) Cooling by freezing mixture : eg NaCl & ice (-22°C), CaCl2
temperature and pressure is equal to the sum of the individual & ice(-55°C), KOH & ice (-65°C)
partial volumes of the constituents (b) Cooling by adiabatic expansion (Claude’s Method) : The gas
in this process suffers a loss in temperature.
V(total)= V1+V2+V3+.....+Vn = Vi
DE = q + w if q = 0 then DE = w or - DE = - w
LOSCHMIDT NUMBER :
Work is done by the gas at the cost of internal energy and
It is the number of molecules present in 1cc of a gas or vapour at temeprature is lowered.
STP. Its value is 2.617×1019 per cc.
(c) Cooling by Joule-Thomson effect ( Linde’s method) :
AVERAGE MOLECULAR WEIGHT OF A GASEOUS Expansion of a gas through a small jet under adiabatic
MIXTURE : conditions results in cooling and liquefaction of gas
1. The density of a gas at 30°C and 1.3 atmosphere pressure is 2. Density of ammonia is 0.77 g/l. Calculate its vapour density.
0.027 g/cc. Calculate the molecular weight of the gas.
Densityof gas 0.77
Sol. V.D. = = =8.55
RTd Densityof H 2 0.09g / l 0.09
Sol. M = ; R = 0.0821 atm lit K -1 mol-1;
P
3. A gas cylinder containing cooking gas can withstand a
d = .027 g / cc = 27 g / l; pressure of 14.9 atmosphere. The pressure gauge of cylinder
indicates 12 atmosphere at 27°C. Due to sudden fire in the
T = 273 + 30 = 303K; P =1.3 atm
building the temperature starts rising. At what temeprature,
27 ´ .0821 ´ 303 cylinder will explode.
M= = 516 .66 g / mol
1. 3
Sol. P1 = P2 Þ 14.9 12
= Þ T1 = 372.5 K
T1 T2 T1 300
122 Chemistry
4. The total pressure exerted by a mixture of gases containing 12
0.4g H2, 2.2g of CO2, 1.4 g N2 and 3.2g SO2 is 2.5 atmosphere Second equation 1.1 ´ V = ´ .0821(t + 273 + 10)
120
. What are the partial pressures of each gas under the same
conditions? 1 t + 273
Dividing = or t = - 173°C
Sol. Partial pressure of a gas = mole fraction × total pressure 1.1 t + 283
= 273 - 173° C = 100 K
Total moles = 0.4 + 2.2 + 1.4 + 3.2 = 0.35
2 44 28 64 12
V= ´ 0.0821(100) = 0.821 litre
120
0.2
pH 2 = ´ 2.5 = 1.428 atm; 8. Calculate the molecular mass of a gas if its specific heat at
0.35
constant pressure is 0.125 and at constant volume is 0.075
0.05 Cp
pCO2 = ´ 2.5 = 0.357 atm 0.125 5
0.35 Sol. = = = 3 = 1.66 hence gas is monoatomic
Cv 0.075
0.05
pN 2 = ´ 2.5 = 0.357 atm;
0.35 Molar heat at constant volume C v = 3 2 R = 3 2 2 = 3 cal.
Very Short/Short Answer Questions 12. A bacterial culture isolated from sewage produced 41.3 ml of
1. When do real gases behave as ideal gas? methane, CH4 at 31ºC and 753 mm Hg. What is the volume of
2. The size of weather balloon becomes larger and larger as it this methane at STP?
ascends up into higher altitudes. Why? Long Answer Questions
3. What do you mean by Boyle temperature ? Give its expression 13. (i) A quantity of hydrogen is confined in a chamber of
and its relation with inversion temperature.
constant volume. When the chamber is immersed in a
4. Liquid is transferred from a large beaker to a small beaker,
bath of melting ice, the pressure of the gas is 1000atm.
what will be the effect on its vapour pressure ?
5. Explain, why the bubbles of a gas in a boiling liquid generally (a) What is the Celsius temperature when the pressure
increase in volume as they approach the upper surface ? manometer indicates an absolute pressure of 400
6. What is the effect of temperature on the vapour pressure of atm?
a liquid ? (b) What pressure will be indicated when the chamber
7. Two different gases ‘A’ and ‘B’ are filled in separate is brought to 100 ºC?
containers of equal capacity under the same conditions of (ii) A steel tank containing air at 15 atm pressure at 15° C is
temperature and pressure. On increasing the pressure
provided with a safety valve that will yield at a pres-
slightly the gas ‘A’ liquefies but gas B does not liquify even
on applying high pressure until it is cooled. Explain this sure of 30 atm. To what minimum temperature must the
phenomenon. air be heated to blow the safety valve?
8. A gas occupying a volume of 100 litres is at 20°C under a 14. (i) One mole of the CO2 occupies 1.5 L at 25ºC. Calculate
pressure of 2 bar. What temperature will it have when it is the pressure exerted by the gas using:
placed in an evacuated chamber of volume 175 litres ? The
(a) an ideal gas equation
pressure of the gas in the chamber is one-third of its initial
pressure. (b) van der Waal’s equation if:
9. The values of the van der Waal’s constants for a gas are a = a = 3.012 atm mol–2 and b = 0.04 L mol–1.
4.10 dm6 bar mol–2 and b = 0.035 dm3 mol–1. Calculate the (ii) The critical temperature and pressure for NO gas are
values of the critical temperature and critical pressure for
177 K and 64.5 atm. respectively. Calculate the van der
the gas.
Waal’s constants ‘a’ and ‘b’.
pV 15. (i) A spherical balloon of 21 cm diameter is to be filled with
10. Compressibility factor, Z, of a gas is given as Z =
nRT hydrogen at STP from a cylinder containing the gas at
(i) What is the value of Z for an ideal gas ? 20 atm at 27ºC. If the cylinder can hold 2.82 L of water,
(ii) For real gas what will be the effect on value of Z above calculate the number of balloons that can be filled up.
Boyle’s temperature ?
(ii) Two van der Waals gases A and B have volumes 0.112
11. For real gases the relation between p, V and T is given by
and 0.111 L mol –1 r espectively. Calculate the
van der Waals equation :
compressibility factors for one mole of each at 273 K
an2 and 200 atm and hence state which gas is more
p ÷ (V nb) = nRT compressible.
V2
Multiple Choice Questions
where ‘a’ and ‘b’ are van der Waals constants, ‘nb’ is
approximately equal to the total volume of the molecules of 16. Dipole-dipole forces act between the molecules possessing
a gas. permanent dipole. Ends of dipoles possess ‘partial charges’.
‘a’ is the measure of magnitude of intermolecular attraction. The partial charge is
(i) Arrange the following gases in the increasing order of (a) more than unit electronic charge
‘b’. Give reason. O2, CO2, H2, He
(b) equal to unit electronic charge
(ii) Arrange the following gases in the decreasing order of
magnitude of ‘a’. Give reason. (c) less than unit electronic charge
CH4, O2, H2 (d) double the unit electronic charge
States of Matter 127
17. A plot of volume (V) versus temperature (T) for a gas at From the above data what would be the order of liquefaction
constant pressure is a straight line passing through the of these gases ?
origin. The plots at different values of pressure are shown Start writing the order from the gas liquefying first
in figure. Which of the following order pressure is correct (a) H2, He, O2, N2 (b) He, O2, H2, N2
for this gas ? (c) N2, O2, He, H2 (d) O2, N2, H2, He
21. Atmospheric pressures recorded in different cities are as
(a) p1 > p2 > p3 > p4 p1 follows :
(b) p1 = p2 = p3 = p4 Volume (mL) p2 Cities p in N/m2
(c) p1 < p2 < p3 < p4 p3 Shimla 1.01 × 105
(d) p1 < p2 = p3 < p4 Bangalore 1.2 × 105
p4
Delhi 1.02 × 105
Mumbai 1.21 × 105
Consider the above data and mark the place at which liquid
Temperature (K) will boil first.
18. The pressure of a 1 : 4 mixture of dihydrogen and dioxygen (a) Shimla (b) Bangalore
enclosed in a vessel is one atmosphere. What would be the (c) Delhi (d) Mumbai
partial pressure of dioxygen ? 22. Which curve in figure represents the curve of ideal gas ?
(a) 0.8 × 105 atm (b) 0.008 Nm–2 (a) B only FE
4
(c) 8 × 10 Nm –2 (d) 0.25 atm (b) C and D only
19. The ratio of Boyle’s temperature and critical temperature for (c) E and F only D
a gas is : (d) A and B only
C
8 27 A
1 2
pV
(a) (b) (c) (d) B
27 8 2 1
20. Gases possess characteristic critical temperature which
depends upon the magnitude of intermolecular forces
between the particles. Following are the critical temperature 0 p
of some gases. 23. Increase in kinetic energy can overcome intermolecular
Gases H2 He O2 N2 forces of attraction. How will the viscosity of liquid be
Critical temperature 33.2 5.3 154.3 126 affected by the increase in temperature ?
in Kelvin (a) Increase (b) No effect (c) Decrease
(d) No regular pattern will be followed
1. Which one of the following statements is wrong for gases? 4. Densities of two gases are in the ratio 1:2 and their
(a) Gases do not have a definite shape and volume temperatures are in the ratio 2:1 then the ratio of their
(b) Volume of the gas is equal to the volume of the container respective pressures is
confining the gas (a) 1:1 (b) 1:2
(c) Confined gas exerts uniform pressure on the walls of its (c) 2:1 (d) 4:1
container in all directions 5. Gas equation PV = nRT is obeyed by
(d) Mass of the gas cannot be determined by weighting a (a) only isothermal process
container in which it is enclosed. (b) only adiabatic process
2. Non reacting gases have a tendency to mix with each other. (c) both (a) and (b)
This property is known as
(d) None of these
(a) diffusion (b) fusion
6. The following graph illustrates
(c) mixing (d) None of these V
(a) Dalton’s law
3. Which of the following mixtures of gases does not obey
Dalton’s law of partial pressure ? (b) Charle’s law
(a) O2 and CO2 (b) N2 and O2 (c) Boyle’s law
(c) Cl2 and O2 (d) NH3 and HCl (d) Gay-Lussac’s law
Temp. (ºC)
128 Chemistry
7. 4.4 g of a gas at STP occupies a volume of 2.24 L, the gas can 15. For an ideal gas, correct relation is-
be
(a) O2 (b) CO é dE ù é dE ù
(a) ê dV ú = 0 (b) ê dT ú = 0
(b) NO2 (d) CO2 ë ûT ë ûP
8. Which of the following volume (V) - temperature (T) plots
represents the behaviour of one mole of an ideal gas at one é dE ù
(c) ê dT ú = 0 (d) All of these
atmospheric pressure ? ë ûV
1. A weather ballon filled with hydrogen at 1 atm and 27°C has 7. A bubble of air is underwater at temperature 15°C and the
volume equal to 12000 litres. On ascending it reaches a place pressure 1.5 bar. If the bubble rises to the surface where the
where the temperature is –23°C and pressure is 0.5 atm. The temperature is 25°C and the pressure is 1.0 bar, what will
volume of the balloon is [CBSE-PMT 1991] happen to the volume of the bubble ?
(a) 24000 litres (b) 20000 litres [CBSE-PMT 2011M]
(c) 10000 litres (d) 12000 litres (a) Volume will become greater by a factor of 1.6.
2. If a gas expands at constant temperature, it indicates that : (b) Volume will become greater by a factor of 1.1.
[CBSE-PMT 2008] (c ) Volume will become smaller by a factor of 0.70.
(a) kinetic energy of molecules decreases (d) Volume will become greater by a factor of 2.5.
(b) pressure of the gas increases 8. 50 mL of each gas A and of gas B takes 150 and 200 seconds
(c) kinetic energy of molecules remains the same respectively for effusing through a pin hole under the similar
(d) number of the molecules of gas increases condition. If molecular mass of gas B is 36, the molecular
3. The pressure exerted by 6.0g of methane gas in a 0.03 m3 mass of gas A will be : [CBSE-PMT 2012]
vessel at 129°C is (Atomic masses : C = 12.01, H = 1.01 and (a) 96 (b) 128 (c) 20.25 (d) 64
R = 8.314 kpa dm3K–1 mol –1) [CBSE-PMT 2010] 9. A certain gas takes three times as long to effuse out as
(a) 31684 Pa (b) 215216 Pa helium. Its molecular mass will be : [CBSE-PMT 2012]
(c) 13409 Pa (d) 41777 Pa (a) 27 u (b) 36 u (c) 64 u (d) 9 u
4. By what factor does the average velocity of a gaseous 10. Maximum deviation from ideal gas is expected from :
molecule increase when the temperature (in Kelvin) is (a) N2(g) (b) CH4(g) [NEET 2013]
doubled ? [CBSE-PMT 2011] (c) NH3 (g) (d) H2(g)
(a) 2.0 (b) 2.8 (c) 4.0 (d) 1.4 11. For an ideal gas, number of moles per litre in terms of its
5. Two gases A and B having the same volume diffuse through presure P, gas constant R and temperature T is
a porous partition in 20 and 10 seconds respectively. The [AIEEE 2002]
molecular mass of A is 49 u. Molecular mass of B will be : (a) PT/R (b) PRT
[CBSE-PMT 2011] (c) P/RT (d) RT/P
(a) 50.00 u (b) 12.25 u (c) 6.50 u (d) 25.00 u 12. Value of gas constant R is [AIEEE 2002]
(a) 0.082 litre atm (b) 0.987 cal mol–1 K–1
6. A gaseous mixture was prepared by taking equal mole of CO
and N2. If the total pressure of the mixture was found 1 (c) 8.3 J mol–1 K–1 (d) 83 erg mol–1 K–1.
atmosphere, the partial pressure of the nitrogen (N2) in the 13. Kinetic theory of gases proves [AIEEE 2002]
mixture is : [CBSE-PMT 2011] (a) only Boyle’s law
(b) only Charles’ law
(a) 0.5 atm (b) 0.8 atm (c) 0.9 atm (d) 1 atm
(c) only Avogadro’s law
(d) All of these.
132 Chemistry
14. The heat required to raise the temperature of body by 1 K is 22. If 10–4 dm3 of water is introduced into a 1.0 dm3 flask at
called [AIEEE 2002] 300 K, how many moles of water are in the vapour phase
(a) specific heat (b) thermal capacity when equilibrium is established ? [AIEEE 2010]
(c) water equivalent (d) none of these. (Given : Vapour pressure of H2O at 300 K is 3170 Pa;
15. What volume of hydrogen gas, at 273 K and 1 atm pressure R = 8.314 J K–1 mol–1)
will be consumed in obtaining 21.6 g of elemental boron (atomic
(a) 5.56× 10–3 mol (b) 1.53 × 10–2 mol
mass = 10.8) from the reduction of boron trichloride by –2
hydrogen ? [AIEEE 2003] (c) 4.46 × 10 mol (d) 1.27 × 10–3 mol
(a) 67.2 L (b) 44.8 L 23. When r, P and M represent rate of diffusion, pressure and
(c) 22.4 L (d) 89.6 L molecular mass, respectively, then the ratio of the rates of
16. According to the kinetic theory of gases, in an ideal gas, diffusion (rA / rB ) of two gases A and B, is given as :
between two successive collisions a gas molecule travels [AIEEE 2011 RS]
(a) in a wavy path [AIEEE 2003]
(b) in a straight line path (a) ( PA / PB ) ( M B / M A )1/ 2 (b) ( PA / PB )1/ 2 ( M B / M A )
(c) with an accelerated velocity
(c) ( PA / PB ) ( M A / M B )1/ 2 (d) ( PA / PB )1/ 2 ( M A / M B )
(d) in a circular path
17. As the temperature is raised from 20ºC to 40ºC, the average 24. The molecular velocity of any gas is [AIEEE 2011 RS]
kinetic energy of neon atoms changes by a factor of which (a) inversely proportional to absolute temperature.
of the following ? [AIEEE 2004] (b) directly proportional to square of temperature.
(a) 313 293 (b) (313 / 293) (c) directly proportional to square root of temperature.
(d) inver sely proportion al to the squar e root of
(c) 1 2 (d) 2 temperature.
25. The compressibility factor for a real gas at high pressure is :
18. In van der Waals equation of state of the gas law, the constant
[AIEEE 2012]
‘b’ is a measure of [AIEEE 2004]
(a) volume occupied by the molecules RT pb pb
(b) intermolecular attraction (a) 1 + (b) 1 (c) 1 + (d) 1 –
pb RT RT
(c) intermolecular repulsions
(d) intermolecular collisions per unit volume 26. For gaseous state, if most probable speed is denoted by C*,
average speed by C and mean square speed by C, then for
19. Which one of the following statements is NOT true about
a large number of molecules the ratios of these speeds are :
the effect of an increase in temperature on the distribution
of molecular speeds in a gas? [AIEEE 2005] (a) C* : C : C = 1.225 : 1.128 : 1 [JEE Main 2013]
(a) The area under the distribution curve remains the same (b) C* : C : C = 1.128 : 1.225 : 1
as under the lower temperature (c) C* : C : C = 1 : 1.128 : 1.225
(b) The distribution becomes broader (d) C* : C : C = 1 : 1.225 : 1.128
(c) The fraction of the molecules with the most probable 27. At constant volume and temperature conditions, the rate of
speed increases diffusion DA and DB of gases A and B having densities rA
(d) The most probable speed increases and rB are related by the expression. [IIT-JEE 1993]
20. The volume of a colloidal particle, VC as compared to the
12 12
volume of a solute particle in a true solution VS , could be (a) DA = DB A (b) DA = DB B
[AIEEE 2005] B A
VC ~ 3 VC ~ - 3 12 12
(a) - 10 (b) - 10 B
VS VS (c) A (d) DA = D B
DA =DB ÷ ÷
B A
VC ~ 23 VC ~
(c) - 10 (d) -1 28. The compression factor (compressibility factor) for 1 mole
VS VS of a van der Waal’s gas at 0°C and 100 atm pressure if found
21. Equal masses of methane and oxygen are mixed in an empty to be 0.5. Assuming that the volume of gas molecules is
container at 25°C. The fraction of the total pressure exerted negligible, calculate the van der Waal’s constant 'a'.
by oxygen is [AIEEE 2007]
(a) 1/2 (b) 2/3 [IIT-JEE 2001]
(a) 0.253 L2 mol–2 atm (b) 0.53 L2 mol–2 atm
1 273
(c) ´ (d) 1/3. (c) 1.853 L2 mol–2 atm (d) 1.253 L2 mol–2 atm
3 298
States of Matter 133
29. The given graph represents the variation of Z [IIT-JEE 2009]
PV 2 2
(compressibility factor = ) versus P, for three real gases an an
nRT (a) nb (b) 2 (c)
(d) – nb –
A, B and C. Identify the only incorrect statement V V2
[IIT-JEE 2006] 31. For one mole of a van der Waals gas when b = 0 and
T = 300 K, the PV vs, 1/V plot is shown below. The value of
C the van der Waals constant a (atm. liter2 mol–2) is :
A [IIT-JEE 2012]
1
24.6
23.1
Z
1. N2O4 is 20 % dissociated at 27°C and 760 torr. The density of 5. The partial pressure of hydrogen in a flask containing 2.016
the equilibrium mixture is g of H2 and 96.0 g of O2 is
(a) 3.1 g/l (b) 6.2 g/l (a) 1/8 of the total pressure (b) 1/6 of the total pressure
(c) 12.4g/l (d) 18.6 g/l (c) 1/4 of the total pressure (d) 2/3 of the total pressure
2. Helium atom is two times heavier than a hydrogen molecule 6. At 27°C a gas was compressed to half of its volume. To what
at. 298K. The average KE of helium is temperature it must be now heated so that it occupies just
(a) 2 times of H2 molecule its original volume. The pressure remains constant
(b) same as that of H2 molecule (a) 54°C (b) 327°C
(c) 4 times that of hydrogen molecule (c) 600°C (d) 327 °C.
1 7. Equal volumes of the gases which do not react together are
(d) that of H2 molecule
2 confined in separate vessels. The pressure is
3. The units of ‘a’ in van der Waals equation of state is 200 mm and 400 mm of Hg respectively. If the two gases are
mixed together what will be the pressure of the resulting
(a) atm. litre mol–1 (b) atm. litre2 mol–2
2 2 mixture (temperature remaining constant)
(c) atm litre mol (d) atm. litre mol–2
4. A container contains certain gas of mass ‘m’ of high pressure. (a) 400 mm (b) 400 mm
Some of the gas has been allowed to escape from the container
(c) 300 mm (d) 200 mm
and after some time the pressure of the gas becomes half and
its absolute temperature 2/3 rd. The amount of the gas 8. A flask containing air (open to the atmosphere) is heated
from 300 K to 500 K. The percentage of the air escaped into
escaped is
the atmosphere is
(a) 2/3 m (b) 1/2 m
(a) 16.6 (b) 40
(c) 1/4 m (d) 1/6 m
(c) 60 (d) 20
134 Chemistry
9. A sample of O2 gas is collected over water at 23°C at a 18. A bubble of the gas released at the bottom of a lake increases
barometer pressure of water at 751 mm Hg (Vapour pressure to eight times the original volume when it reaches at the
of water at 23°C is 21 mm Hg). The partial pressure of O2 gas surface. Assuming that the atmospheric pressure is equivalent
in the sample collected is to pressure exerted by a column of water 10 m high, what is
(a) 21 mm Hg (b) 751 mm Hg the depth of the lake
(c) 0.96 atm. (d) 1.02 atm. (a) 80 m (b) 90 m
10. Which of the following is a false statement ? (c) 10 m (d) 70 m
(a) Gases having same molecular masses diffuse at the
19. SO 2 and He are kept in a container at partial pressure P1
same rate
(b) 0.5 litre of nitrogen and 1 litre of helium will have the and P2 . A thin perforation is made in the wall of the container
same number of the atoms at the same temperature and and it is observed that gases effuse at the same rate. The
pressure
ratio of P1 and P2 will be
(c) The value of molar gas constant does not vary with the
nature of the gas (a) 4 : 1 (b) 1 : 4
(d) None is false (c) 1 : 16 (d) 16 : 1
11. The density of SO2 at STP is 2.06 kg m-3. Its density at 819°C 20. Helium has the van der Waals constant b = 24 ml mol -1 . The
and 2 atmosphere is
molecular diameter of helium will be
(a) 2.86 kg m-3 (b) 1.43 kg m-3
-3
(a) 267 pm
(c) 0.715 kg m (d) 4.2686 kg m-3
(b) 133.5 pm
12. When helium is allowed to expand into vacuum, heating effect
(c) 26.7 pm
is observed. Its reason is that
(d) Data not sufficient for calculation the diameter.
(a) helium is an ideal gas
21. At 100°C and 1 atm, if the density of liquid water is
(b) helium is an inert gas
1.0 g cm–3 and that of water vapour is 0.0006 g cm–3, then the
(c) inversion temperature of helium is low volume occupied by water molecules in 1 litre of steam at
(d) the boiling point of helium is the lowest amongst the that temperature is
element. (a) 6 cm3 (b) 60 cm3
13. What would be the vapour density of a gas 260 cm3 of which (c) 0.6 cm 3 (d) 0.06 cm3
at 290 K and 100.40 KPa pressure weights 0.160g 22. Which of the following graphs is not a straight line for an
(a) 17.9 gL-1 (b) 14.2 gL-1 ideal gas?
(a) n ® T (b) T ® p
(c) 7.4 g cm -3 (d) None of these
1 1
14. Reducing the pressure from 1.0 atm to 0.5 atm would change (c) n ® (d) n®
T p
the number of molecules in one mole of ammonia to
23. A volume V of a gas at temperature T1 and a pressure p is
(a) 25% of its initial value
enclosed in a sphere. It is connected to another sphere of
(b) 50% of its initial value
volume V/2 by a tube and stopcock. The second sphere is
(c) 75% of its initial value initially evacuated and the stopock is closed. If the stopcock
(d) None of the above is opened the temperature of the gas in the second sphere
15. The ratio of diffusion of nitrogen at 25°C would be ......... becomes T2. The first sphere is maintained at a temperature
times that of carbon dioxide at 75°C T1. What is the final pressure p1 within the apparatus ?
(a) 0.90 (b) 1.16 2pT2 2pT2
(c) 1.41 (d) 1.76 (a) (b)
2T2 + T1 T2 + 2T1
16. The average kinetic energy of 28 g CO at, 300 K is E kcal.
The average kinetic energy of 2 g H2 at the same temperature pT2 2pT2
would be..... kcal. (c) (d)
2T2 + T1 T1 + T2
(a) E (b) 14 E 24. The molecular velocities of two gases at the same temperature
(c) 1/14 E (c) 28 E are u1 and u2 and their masses are m1 and m2 respectively.
17. The critical temperature of water is higher than that of O2 Which of the following expressions are correct ?
because the H2O molecule has m1 m2
(a) fewer electrons than O2 (a) = (b) m1u1 = m 2 u 2
u12 u 22
(b) two covalent bonds
(c) V-shape m1 m 2
(c) = (d) m1u12 = m 2 u 22
(d) dipole moment. u1 u2
States of Matter 135
25. At low pressure, the van der Waal's equation is reduced to 27°C. The cylinder can hold 2.82 L of water at NTP. The number
of balloons that can be filled up is
pVm aP pVm b
(a) Z = = 1- (b) Z= = 1+ p (a) 15 (b) 10
RT RT RT RT (c) 20 (d) 25
pVm a 32. The mass of N 2 in a 15 L gaseous mixture at 20°C and 740
(c) pVm = RT (d) Z= = 1-
RT RT mm pressure of the composition of the mixture by volume
26. The van der Waal's equation for n = 1 mol may be expressed is H 2 = 10%, O 2 = 20% and N 2 = 70%
æ RT ö 2 aV ab (a) 11.91 g (b) 16.2 g
as V 3 - çç b + ÷V + - =0 (c) 21.91 g (d) 28.00 g
è p ÷ø p p
33. What will be the mole fraction of N 2 in a mixture of N 2
Where V is the molar volume of the gas. Which of the
and O 2 if partial pressure of O 2 is 63 cm and total
following is correct?
(a) For a temperature less than Tc, V has three real roots pressure of the mixture is 90 cm
(b) For a temperature more than Tc, V has one real and two (a) 3.0 (b) 0.3
imaginary roots (c) 0.7 (d) 0.5
(c) For a temperature equal to Tc all three roots of V are real 34. The bottles of NH 3 and HBr gases are connected through
and identical a tube of 1 metre length. The distance of white solid formed
(d) All of these in the tube from the end of NH 3
27. According to kinetic theory of gases, for a diatomic
(a) 68.56 cm from NH 3 bottle
molecule
(b) 68.56 cm from HBr bottle
(a) the pressure exerted by the gas is proportional to the
(c) At the centre of the tube
mean velocity of the molecule.
(d) None is correct.
(b) the root mean square velocity of the molecule is 35. At a temperature TK the pressure of 4 g of argon in a bulb
inversely proportional to the temperature. is p. The bulb is put in a bath having temperature higher
(c) the pressure exerted by the gas is proportional to the by 50 K than the first one. 0.8 g of argon has to be removed
rms velocity of the molecule. to maintain original pressure. The temperature T is equal
(d) the mean translational kinetic energy of the molecule to
is proportional to the absolute temperature. (a) 510 K (b) 200 K
(c) 73 K (d) 100 K
28. A perfect gas is found to obey the relation PV 3 / 2 = 36. Let the most probable velocity of hydrogen molecules at a
constant. If the gas is compressed to half of its volume at temperature of t° C be V0 . When the temperature is raised
temperature T adiabatically, the final temperature of the
to (2t + 273)°C the new rms velocity is (suppose all the
gas will be molecules dissociate into atoms at latter temperature)
(a) 2T 2 (b) 4T (a) (b) 6V0
2 3V0
(c) T 2 (d) 2T
æ 273 ö 2
29. A vessel containing gas at pressure 60 cm of Hg was (c) 3ç 2 + ÷V0 (d) V0
è t ø 3
connected to an arm A of open end manometer. The
atmospheric pressure was recorded as 74 cm of Hg. If 37. A vessel is filled with a mixture of O 2 and N 2 . At what
mercury in arm A stands at 84.5 cm height, the mercury in ratio of partial pressures will be the mass of gases be
arm B will stand at identical
(a) 24.5 cm (b) 70.5 cm (a) p( O ) = 8.75 p( N )
2 2
(c) 88 cm (d) 74 cm
30. Three gases A, B, C have volumes V1 , V2 , V3 at pressure (b) p( O ) = 0.78 p( N )
2 2
P and temperature T are mixed keeping the temperature (c) p( O ) = 0.875 p ( N )
2 2
and pressure constant. The final volume of the gaseous
mixture will be (d) p( O 2 ) = 11.4 p( N 2 )
V1 + V2 + V3 38. A compound exists in the gaseous state both as monomer A
(a) V1 + V2 + V3 (b)
3 and dimer A 2 . The M. wt. of monomer is 48. In an experiment
96 g of the compound was confined in vessel of 33.6 L and
V1 + V2 + V3 heated to 273° C. Calculate the pressure developed, if the
(c) (d) V1 ´ V2 ´ V3
P compound exists as a dimer to the extent of 50% by weight
31. A spherical balloon of 21 cm diameter is to be filled with under the conditions
(a) 0.9 atm (b) 4.0 atm
H 2 at NTP from a cylinder containing the gas at 20 atm at (c) 2.0 atm (d) 1.0 atm
136 Chemistry
39. A mixture of 1 mol of H 2 and 1 mole of Cl 2 with little 41. A closed vessel contains He and Ozone at pressure of P
charcoal in a 10 L evacuated flask was irriadiated with light atm. The ratio of He and oxygen atoms is 1 : 1. If He is
until the reaction was completed. Subsequently 5L of water removed from the vessel, the pressure of the system will
was introduced into the flask and the flask was cooled to reduce to
27°C. The pressure exerted by the system is approximately (a) 0.25 P (b) 0.5 P
equal to (c) 0.75 P (d) 0.33 P
42. The factor that has the largest effect on vapour pressure of
2 ´ 0.0821´ 300
(a) atm a liquid is
5 (a) liquid surface area
(b) » 26 mm Hg (b) molecular dipole moment
2 ´ 0.0821 (c) presence of H-bonding
(c) atm (d) molecular mass of liquid
10
43. The molecular mass of a compound does not effected by
4 ´ 0.0821´ 300 (a) vapour pressure of a liquid
(d) atm
5 (b) vapour density
40. The relative humidity of air is 80% at 27°C. If the aqueous (c) vapour pressure of solid
tension at the same temperature is 27 mm Hg. The partial (d) molar volume of vapour
pressure of water vapour in the air will be 44. Which of the following liquids has the highest viscosity?
(a) 21.60 mm Hg (b) 27 mm Hg (a) Benzene (b) Carbon disulphide
(c) 25 mm Hg (d) 23 mm Hg (c) Acetone (d) Ethanol
States of Matter 137
P1 d T 1 2 r1 d2 16
4. (a) P d and T, = 1 1 = ´ Þ P1 : P2 = 1 : 1 18. (b) = = = 4 :1
P2 d 2 T2 2 1 r2 d1 1
138 Chemistry
3RT U CO 2 TCO 2 ´ M N 2 O
19. (c) r U and U = =
M 31. (a)
U N 2O M CO 2 ´ TN 2 O
r1 TM rN T1 ´ 64
= 1 2 or 2
= = 1.625 or
r2 T2 M1 rSO 2 323 ´ 28 x TCO2 44
= ´ TN 2O = 16TCO 2
4x 44 TN 2O
T2 = 373K
2 Mx 1
20. (a) = M x = 64 32. (d) U hence hydrogen (molecular weight being the
1 16 M
lowest) has the maximum root mean square velocity.
21. (b) For effusion of same volume,
t1 M1 t1 t2 U1 d2 1
= = 33. (c) = = =1: 4
t2 M2 U2 d1 16
M1 M2
This is clearly seen from the options that the ratio of U1 T1M 2
34. (b) Apply =
t æ U2 T2 M1
5 20 5 ö
is same for H2 and O2. ç = = ÷÷
M ç
è 2 32 2ø
3RT U1 T1 1200 1
35. (b) U = = = = 2; U2 = U1
M N2 M U2 T2 300 2
rx 28 56 1
22. (a) = = = or rN 2 = 79.19 mls -1
rN 2 Mx 56 rN 2 2 36. (d)
23. (d) NO and C2H6 both have same molecular weight. Hence 37. (b) Due to intermolecular interactions appreciable at high P
their rate of diffusion will be same. and low T, the ideal gas deviates from ideal behaviour.
1 PV
38. (b) Ideal gas strictly follows PV= nRT, Z= =1
24. (d) Rate . The smaller the value of M the more is the nRT
M
rate of diffusion 39. (c) Ideal behaviour at low P and high temperature. The larger
25. (a) At the same temperature KE is the same, as KE T.. the volume the lesser are the interactions, higher the
temperature the more is KE the lesser are interactions
26. (a) The gas molecules are tiny particles and not rigid in nature
between the molecules.
rather they are perfect elastic bodies
PV
3 3 8.313 40. (b) Z = <1 nRT > PV
27. (b) KE = kT = ´ ´ 298 = 6.17 ´10-21 J . nRT
2 2 6.023 ´1023
or 1´ 0.0821´ 273 > 1´ V or V < 22.4
(Average Kinetic energy KE = 3 kT = 3 R T )
2 2 N æ MP ö
41. (b) Higher P lower T greater the density. ç d = ÷
è RT ø
1 2 1 2 2 2
28. (d) PV = mnU = ´ mU = KE = KT .
3 3 3 3
42. (b) PV = RT , PV = w RT , 20P = 120 ´ .0821 ´ 400
M 40
The product PV will have constant value at constant
temperature. This is Boyle’s law or P = 4.92 atm
TN 2 > TH 2
States of Matter 139
44. (a) Total moles
60. (a) Avogadro number is 6.023 ´ 10 23
= 4 + 2 = 1.125 ; PV = nRT Þ P = 1.125 ´ .0821´ 273 61. (a) At higher attitudes, boiling point is low because
32 2
atmospheric pressure is low.
P = 25.215 atm 62. (b) The strength of H-bonding is in the order N....H< O....H <
x x F....H
45. (a) Let the mass be x, then moles of CH4 and H2 are & ;
16 2 63. (d) All the given phenomenon occurs due to surface tension
64. (b) Liquid drops assume spherical shape because a sphere
9x has minimum surface area.
Total moles =
16 65. (b) Surface tension decreases with increase in temperature
66. (b) Water sticks to a glass surface due to force of adhesion.
x/2 8
pH 2 = mole Fraction ´ P = .P = P 67. (c) The internal resistance of a liquid to flow is called
9 x / 16 9
viscosity.
46. (d) 6.02 ´ 10 23 molecules : 28 g N 2 = 32 g O 2 = 2 g H 2 68. (b) Visocity µ 1/temperature
69. (b) Visocity µ molecular weight
6.02 ´ 10 22 molecules : 2.8 g N 2 = 3.2 g O 2 = 0.2 g H 2
EXERCISE 3
Total mass = 2.8 + 3.2 + 0.2 = 6.2
47. (d) VD of air = mass of 11200cc of air = 11200 × density of air P T 1 250
1. (b) V2 = 1 2 .V1 = ´ ´12000 lit. = 20000 lit.
= 11200 × .00130 = 14.56 P2 T1 0.5 300
48. (b) An ideal gas obeys the gas laws under all experimental
2. (c) At any constant temperature the K.E. of gaseous
conditions.
molecules remains same (K.E. µ T). Thus option (c) is
49. (b) Boyle’s temperature by definition. At this temperature
correct answer.
the real gases obey ideal gas laws over wide range of P.
nRT 6 ´ 8.314´ 402
50. (c) He possess van der waals forces of attraction, which are 3. (d) P = = 41777 Pa
V 16 0.03´103
weak in nature.
51. (c) At low pressure and high temperature terms a and b are 8RT
negligible hence PV= nRT 4. (d) Average velocity =
pM
52. (d) Ideal gas cannot be liquefied at any value of P and T
since there are no intermolecular interactions between i.e., v µ T
molecules
v2 2T
53. (b) Boyle’s temperature, \ = = 1.41
v1 T
a 8a T 27
Tb = and critical temperature, Tc = \ b =
Rb 27Rb Tc 8 rA MB
5. (b) r = M
B A
54. (c) The higher the value of ‘a’, more the value of T c , easy is
the liquefaction
V
55. (a) Ideal gas does not exhibit Joule Thomson effect. Hence MB
20 = M B Þ 1 =
æ dT ö V 49 2 49
ç ÷ , the Joule-Thomson coefficient is zero 10
è dP ø H
1
2a MB = ´ 49 = 12.25
56. (b) Ti = Where Ti is inversion temperature. 4
Rb
57. (a) At exact inversion temperature there is neither heating 6. (a) Given nCO = n N2
nor cooling or no Joule Thomson effect
PCO + PN2 = 1 atm
1 Partial pressure of a gas
58. (c) Mean free path µ
(Radius)2 = mole fraction of gas × total pressure
PV
1 1 = P2V2 3
K ´ 313
T1 T2 K.E of neon at 40 °C 313
17. (a) = 2 =
K.E of neon at 20°C 3 293
1.5 ´V 1´V2 K ´ 293
= 2
288 298
V2 = 1.55 V i.e., volume of bubble will be almost 1.6 time 18. (a) In van der waal's equation ‘b’ is for volume correction
to initial volume of bubble. 19. (c) As temperature rises the most probable speed increases
and the fraction of molecules possessing most probable
VA VB MB speed decreases.
8. (c) =
tA tB MA
20. (a) Particle size of colloidal particle = 1m m to 100 m m
(suppose 10 ml)
200 36 4 36
Þ = Þ =
150 MA 3 MA 4 3
Vc = pr
3
16 36 81
Þ = Þ MA = = 20.25
9 MA 4 4 3
= Vc = p(10)
9. (b) t1 - Time taken by unknown gas 3
t2 - Time taken by helium
Particle size of true solution particle = 1m m
M1 - Molar mass of unknown gas
M2 - Molar mass of helium 4 3
Vs = p (1)
t1 = 3t2 3
t1 M1 3t M1 Vc
= Þ 2 = 3
t2 M2 t2 4 hence now = 10
Vs
æ 2.06 96.0
an2 ö 5. (c) Moles of H 2 = ; Moles of O 2 = = 6 Total
ç P + 2 ÷ (V - nb) = nRT 2 16
ç V ÷ø
è moles = 8
æ a ö 2 1
PH = P = (partial pressure = Mole fraction × Total
çç 100 + 2 ÷÷
(0.112 - 0) = 0.0821´ 273 2 8 4
è (0.112) ø
pressure )
a = 1.253 L2 mol–2 atm
142 Chemistry
17. (d) Critical temperature of water is higher than O2 because
V1 V2
6. (b) Let the original volume be V then = at constant H2O molecule has dipole moment which is due to its
T1 T2
V-shape.
V V 18. (d) Let V be the original volume of bubble. The final volume
P, = \ T2 = 600K = 327°C
300 ´ 2 T2 will be 8 V. Let p be the atmospheric pressure and p1 the
7. (c) When vessels are joined the volume is doubled and pressure at the bottom
pressure is reduced to half \ Pressure of mixture
\ p × 8 V = p1 × V;;
200 400
= + = 300mm 8p = p1
2 2
8. (b) P,V and R are constant p1 = atmospheric pressure + pressure due to water lake
\ n l T1 = n 2T2 ,100 ´ 300 = n 2 ´ 500, : n 2 = 60 = p + 7p
Air escaped is 40%. The p = 10 m high, the 7p will be = 70 m high
9. (c) Pressure of gas = (Total pressure of gas - aqueous So the depth = 70 m
tension ) = 751-21 = 730 mm = 0.96 atm.
1 rSO2 P1 M He
10. (d) Moles of 0.5 litre of N 2 = ´ 0.5 = 0.02, 19. (a) =
22.4 rHe P2 M SO 2
1 1 V1
24 (d) U1 and U 2 But V2 = (given)
m1 m2 2
1
U 12
m
\ = 2 \ m1 U12 = m 2 U 22
2
2
U2 m1 æ ö
ç ÷
V
\ T2 = T1 ç 1 ÷ = T1 2
æ a ö ç V1 ÷
25. (a) van der Waals eqation is ç p + ÷(Vm - b ) = RT ç ÷
ç Vm2 ÷ è 2 ø
è ø
29. (b) Let the difference in two columns be h. Since the
V
Where Vm = = molar volume. At low pressure Vm is atmospheric pressure is more.
n
\ 60 = 74 – h
high and b can be ignored
or, h = 74 – 60 = 14 cm
æ a ö
\ç p + ÷Vm = RT or pVm + a = RT Thus Hg will stand in column B = 84.5 – 14 = 70.5 cm
ç Vm2 ÷ Vm
è ø 30. (a) The final volume will be V1 + V2 + V3 (Amagat’s law).
a pVm a 4 3
\ pVm = RT - or =1- 31. (b) The volume of the balloon = pr
Vm RT RTVm 3
a aP æ 1ö 3
or Z = 1 - = 1- çè since V µ ÷ø 4 22 æ 21 ö
RTVm RT P = ´ ´ ç ÷ = 4851 ml
3 7 è2ø
26. (d) The given equation is cubic equation in the variable V
and, therefore, for a single value of P and T, there should Volume of the cylinder = 2820 ml
be three values of V, all of which may be real or one real
and two imaginary. 20 ´ 2820 ´ 273
Volume of H 2 at NTP = ml
At Tc there values of V become identical. 300 ´ 1
1 = 51324 ml
27.(d) PV = NmU 2rms
3 After filling the cylinder will have H 2 equal to its volume
1 = 2820 ml
æ 3KT ö 2
\ U rms =ç ÷ \ Volume of H 2 for filling balloons = 51324 – 2820
è m ø
= 48504 ml
1 2 3
KE = mv = KT 51324
2 2 Hence no. of balloon to be filled = = 10
3
2820
28. (c) PV 2 = constant.
15 ´ 273 ´ 740
32. (a) 15 L (20°C, 740 mm) = = 13.61 L (NTP)
nRT 293 ´ 760
Again P =
V
13.61
3 70% N 2 = ´ 70 = 9.527 L (NTP)
nRT 100
\ ´V2 = constant (K)
V
28´ 9.527
1 9.527 L (NTP) of N 2 = = 11.91 g
K 22.4
or, TV 2 = = K' (constant)
nR
33. (b) p N 2 = r - rO2 = 90 - 63 = 27 cm
1 1
2 2
For two states, T1V1 = T2 V2 p N2 = mole fraction of N 2 ´ P
1 \ 27 = X N 2 × 90
2
æV ö
T2 = T1çç 1 ÷÷ \ X N 2 = 0.3
è V2 ø
144 Chemistry
34. (a) Let the distance be x metre.
48
Moles of dimer = = 0.5
R NH3 x M HBr 81 96
\ = = =
R HBr 1- x M NH3 17
1.5 ´ 0.0821 ´ (273 + 273)
\ P= = 2.00 atm
\ x = 0.6856 = 68.56 cm 33.6
It is the branch of chemistry which deals with the energy changes EXTENSIVE PROPERTIES :
taking place during physical and chemical changes. The properties which depend upon the quantity of the substance
Terminology used in thermodynamics :- or substances present in the system e.g. volume, enthalpy, free
energy, entropy, heat capacity.
SYSTEM :
A system is that part of universe which is under investigation . INTENSIVE PROPERTIES :
The properties which are independent of the quantity of the
SURROUNDINGS :
substance present in the system e.g. density, molar volume,
The part of the universe other than the system is known as temperature, melting point, boiling point, freezing point etc.
surroundings. Note – Any extensive property if expressed as per mole or per gm
Thus universe = system + surroundings becomes intensive property e.g. mass and volume are extensive
In simple case surroundings implies air or water both. properties but density is an intensive property.
TYPES OF SYSTEM : STATE VARIABLES AND STATE FUNCTIONS :
(i) Open system - A system which can exchange matter as well These are the macroscopic properties of the system which change
as energy with surroundings. with the change in the state of system. They depend upon the
(ii) Closed system – A system which can exchange energy and initial and final state of system. They are temperature, pressure,
not matter with surroundings. volume, chemical composition, energy, entropy, free energy.
(iii) Isolated system - A system which can exchange neither INTERNAL ENERGY, INHERENT ENERGY OR
matter nor energy with surroundings. HIDDEN ENERGY (IE) :
(iv) Homogeneous system – A system consisting of one phase It is the sum of all types of energies (as given below) associated
only e.g. pure solid, a liquid or a mixture of gases. with a system or substance.
(v) Heterogeneous system – It may consists of two or more (i) Translational energy of the molecules, Et
phases e.g. a solid in contact with liquid etc. (ii) Rotational energy, Er
STATE OF SYSTEM : (iii) Vibrational energy, Ev
(iv) Electronic energy, Ee
The condition of existence of a system when its macroscopic
(v) Nuclear energy, En
properties have definite values is known as state of system e.g.
(vi) Interaction energy of molecules, Ei
at 1 atm pressure H2O is (a) Solid below 0°C, (b) liquid between
E = Et + Er + Ev + Ee + En + Ei
0°C - 100°C and (c) gas above 100°C.
It is a state function, depends upon chemical nature of the
MACROSCOPIC PROPERTIES : substance, amount, temperature, pressure etc. Its absolute
The properties which arise out of collective behaviour of large value cannot be determined but change during a chemical
number of chemical entities e.g. pressure, volume, temperature, process can be determined.
composition, colour, refractive index etc. DE = Eproducts - E reactants = EP - ER
146 Chemistry
If E P > E R DE = +ve change is endothermic (iv) Isochoric process ( DV = 0) : Volume remains constant but
If E P < E R DE = - ve change is exothermic pressure changes.
HELMHOLTZ FREE ENERGY (WORK FUNCTION) DS total = 0 , the process is reversible and system is in
(A): The maximum work obtainable from a system is given equilibrium when internal energy and volume are kept
by this energy. constant
( DS ) E, V > 0 the process is irreversible and if ( DS) E ,V = 0 ,
A = E - TS ; E= Internal energy, S = Entropy, T= Temperature
the process is reversible.
150 Chemistry
(ii) Internal energy : When entropy and volume kept constant (i) For water (liquid ) = water (vapour) we have
If (DE) S, V < 0 , the process is irreversible and if dP DH V
=
( DE) S, V = 0 , the process is reversible. dT T(Vg - Vl ) ;
(iii) Enthalpy (H) : When entropy and pressure are kept constant DH V = molar heat of vaporisation ,
( DH) S,P < 0 , the process is irreversible and if (ii) For water (Solid, Ice) = water (liquid)
( DH) S,P = 0 , the process is reversible. dP DH f
= ;
(iv) Work function : (A) when temperature and volume are kept dT T (Vl - Vs )
constant
DH f = molar heat of fusion of ice
( D ) T ,V < 0 , the process is irreversible and if (iii) For solid = vapour equilibrium
( DA) T ,V = 0 , the process is reversible. dP DH s
=
(v) Free energy (G) : When pressure and temperature are kept dT T(Vg - Vs ) ; DH s = molar heat of sublimation
constant
INTEGRATED FORM OF CLAPEYRON - CLAUSIUS
( DG ) P ,T < 0 , the process is irreversible and if
EQUATION :
( DG ) P,T = 0 , the process is reversible. For Liquid = gas system in Equilibrium
NOTE : Criteria of feasibility or spontaneity in terms of free P2 DH v é T2 - T1 ù
energy is most important since most of the processes are carried log = ê ú
P1 2.303R ë T1T2 û
out at constant temperature and pressure.
ZEROTH LAW OF THERMODYNAMICS : APP LICATIONS OF CLAPE YRON C LAUSIUS
If two bodies have separately equality of temperature with a
EQUATION :
third body, they also have equality of temperature with each (i) Calculation of molar heat of vaporisation
other. (ii) Effect of temperature on vapour pressure of a liquid
(iii) Effect of pressure on boiling point
THIRD LAW OF THERMODYNAMICS :
(iv) Calculation of molal elevation constant (kb) and molal
At absolute zero temperature, the entropy of a perfectly crystalline depression constant (kf ) of a solvent.
substance is taken as zero. This law was formulated by Nernst in
1906. 0.002T 2
kb =
Calculation of absolute value of entropy: lv
Let S0 be the entropy of substance at 0 K and S be its entropy at lv= latent heat of vaporisation per gram of solvent
T K. T= boiling point of pure solvent
T
Cp 0.002T2
DS = S0 - S = dT kf =
T lf
0
T= freezing point of solvent
Where Cp is the heat capacity of the substance at constant
lf = latent heat of fusion per gram of solvent
pressure. According to the third law
HEAT ENGINE :
T
Cp Machine which converts heat into work is called heat engine.
S0 = 0, thus S = dT .
T EFFICIENCY OF HEAT ENGINE :
0
The fraction of the heat absorbed, converted into work is called
The value of the integral can be obtained from a plot of the efficiency of machine.
CP / T Vs T. The area under the curve between 0 and T K gives the
W Work done
value of the integral and hence of S at temperature T. h= =
Q Heat absorbed
CLAPEYRON - CLAUSIUS EQUATION :
CARNOT CYCLE :
It gives the change in pressure dP accompanying change in
temperature dT or vice versa for a system containing two phases It is a process where a system after undergoing a number of
of a pure substance in equilibrium, q is heat exchanged reversibly successive changes returns to its original state. It consists of
per mole of the substance during the phase transformation at four different operations.
temperature T. (i) Isothermal expansion
(ii) Adiabatic expansion
dP q (iii) Isothermal compression
=
dT T (VB - VA ) (iv) Adiabatic compression
Thermodynamics 151
EFFICIENCY OF CARNOT CYCLE OR ENGINE : TYPES OF REACTIONS AND CORRESPONDING
ENTHALPY CHANGES :
W T -T Q - Q1
h= = 2 1= 2 (i) Heat of reaction at constant volume and certain temperature
Q T2 Q2
It is defined as the change in internal energy ( DE ) of the
system when requisite number of molecules of reactants
T2 - T1
Since is always less than unity, hence efficiency
T2 react to form the products. ( DE ) = E p - E r = q v = heat of
reaction at constant volume
is always less than unity
(ii) Heat of reaction at constant pressure and certain
CARNOT THEOREM : temperature
Efficiency of reversible heat engine is independent of the nature
It is defined as the difference in enthalpies ( DH ) of products
of working substance and depends upon the temperature of
source and sink. and reactants DH = H p - H r = q p = heat of reaction at
Or constant pressure
All machines working reversibly between the same temperature (iii) Relation between heat of reaction at constant volume ( q v )
of source and sink have same efficiency.
RESONANCE ENERGY : and at constant pressure ( q p )
1. Six moles of an ideal gas expand isothermally and reversibly Sol. Work done is irreversible as at constant pressure,
from a volume of 1litre to a volume of 10 litres at 27º C. What
DV = 5 – 3 = 2 dm3 = 2 lit.
is the maximum work done? Express the results in various
units. W = – PDV = – 3 × 2 = – 6 atm. lit. = – 6 × 101.3J
Sol. Work done = 607.8J
This work is used for heating water W = m × s × DT
V2 V
W = nRT ln = 2.303nRT log 2 607.8 = 10 × 18 × 4.184 × DT
V1 V1
Therefore DT = 0.807
10 Hence final temperature = 290 + 0.807 = 290.807 K
= 2.303 ´ 6 ´ 0.0821 ´ 300log = 340.3 lit. atm. 5. 10 g of argon gas is compressed isothermally and reversibly
1
at a temperature of 27º C from 10 litres to
If we put the value of
5 litres. Calculate q, w, DE and DH for this process. R=2.0
R= 8.314 J K–1 mol–1 W = 34464.8J cal K–1 mol–1 log 2 = 0.3010
Atomic weight of Argon = 40
R = 8.314 ´10 7 ergs K -1mol -1 W = 3.44 ´1011 ergs
R = 1.987 cal K -1 mol -1 W = 8236.91 cal V2 10 5
Sol. W =- 2.303nRT log =- 2.303 ´ ´ 2 ´ 300 log
V1 40 10
2. A system performs 101.3J of work on its surroundings and
absorbs 15 kJ of heat from surroundings. What is the change W = 103.635 cal
in internal energy of the system. For isothermal proccess DE = 0, q = –W = – 103.635 cal
Sol. Work done by the system is taken as negative DH = 0
W = –101.3J 6. Show that in an isothermal expansion of an ideal gas
Heat absorbed by the system is taken as positive (a) DE = 0 and (b) DH = 0
q = 15kJ = 15000 J Sol. (a) For one mole of a gas Cv= [ E / T]v
DE = q+w ( First law of thermodynamics) For finite change DE = Cv DT
=15000J-101.3J= 14898.7J For isothermal process DT = 0 therefore DE = 0
3. One mole of liquid water at its boiling point vapourises (b) We know that DH = DE + D( PV) = DE + D( RT)
against a constant external pressure of 1 atm. at the same
(PV = RT)
temperature. Assuming ideal behaviour and initial volume
of water vapours as zero, calculate the work done by the Therefore DH = DE + RDT. Since DT = 0, DE = 0, therefore
system. DH = 0.
7. Calculate the change in free energy at 25º C for the reaction
Sol. For ideal behaviour of water vapour PV = nRT can be applied
to find the volume. 1
CO(g) + O2 (g) ® CO2 (g) DH = -67.37 kcal
1 × V = 1 × 0.0821 × 373 2
V = 30.62 lit. and the change in entropy accompanying the process is –
DV = V2 - V1 = 30.62 lit. – 0 lit. = 30.62 lit. 20.7 cal deg–1 mol–1
Sol. DG = DH – TDS
work done = – PDV = –1 × 30.62 = – 30.62 lit atm.
= – 67.37 – 298 (–20.7 × 10–3)
= – 30.62 × 101.3J = -3101.8 J
= -61.2014 kcal mol -1
4. A gas expands from 3 dm3 to 5 dm3 against a constant
pressure of 3 atm. The work done during expansion is used 8. Calculate DH, DS, DG and DE when 1 mole of water is
to heat 10 mole of water of temperature 290 K. Calculate the vapourised at 100º C and 1 atm pressure. The latent heat of
final temperature of water. Specific heat of water is vapourisation of water is 540 cal g–1
4.184 Jg–1 K–1
154 Chemistry
Sol. (i) 1 mole of water is 18 g therefore enthalpy change (i) Latent heat of fusion for 900 g ice
DH = 18 × 540 cal = 9720 cal
900 ´ 5.99
(ii) Entropy change DS = DH/ T = 9720/373 DH fus = kJ = 299.5kJ
18
= 26.06 cal K–1
(iii) Free energy change DG = DH – TDS DH fus 299.5 ´1000
DS = = = 1097 JK -1
DG = 9720 – 373 × 26.06 = 0 T 273
(iv) DH = DE + PDV DH fus
(ii) DS for freezing of liquid water = -
therefore DE = DH – PDV = DH – P(V2 – V1) T
V1 = Volume of 1 mole of liquid water = 18 cm3 when liquid water freezes heat is evolved
V2 = Volume of 1 mole of steam at 373 K 5.99 ´ 1000
DS = - = - 21.94 Jmol -1K -1
Applying ideal gas equation, 273
11. Calculate the entropy change in isothermal reversible
P1V1T2 1´ 22400 ´ 373 expansion of 5 moles of an ideal gas from a volume of 10
V2 = =
P2 T1 1´ 273 litres to a volume of 100 litres at 300 K.
Sol. For isothermal process T1 = T2 hence the equation
V2 = 30600 cm3 T2 V
DS = C v ln + nR ln 2 is reduced to
DV= V2 – V1 = (30600 – 18) cm3 = 30600 cm3 T1 V1
(18 negligible) V2 V
3 DS = nR ln = 2.303nR log 2
PDV =1atm ´ 30600 cm = 1 ´ 30.6lit. = 30.6 lit atm. V1 V1
Given n = 5,
30.6 × 24.2 cal = 740.5 cal (1atm lit = 24.2 cal)
V1 =10 litres, V2 = 100 litres, R = 8.314JK -1mol -1
Hence DE = DH – PDV = 9720 – 740.5 = 8979.5 cal
100
9. A certain volume of dry air at NTP is expanded reversibly to DS = 2.303´ 5 ´ 8.314 log = 95.75JK -1
three times its volume (a) isothermally (b) adiabatically. 10
Calculate the final pressure and temperature in each case, 12. Calculate the temperature at which the reaction
assuming ideal behaviour. (Cp/Cv for air is 1.4) 1
Ag 2 O(s) ® 2Ag(s) + O 2 (g) at 1 atmospheric pressure
Sol. Let V1 be the initial volume of dry air at NTP 2
(a) Isothermal expansion. Since will be in equilibrium. The value of DH and DS for the
reaction are 30.58 kJ and 66.11JK–1 respectively and these
DT = 0 hence P1V1 = P2 V2 value do not change much with temperature.
Sol. DG = DH - T DS for equilibrium DG = 0
P1V1 1´ V1
P2 = = = 0.333 atm
V2 3V1 DH DH 30580
DS = T= = = 462.6 K
T DS 66.1
(b) Adiabatic expansion we have 13. Calculate the standard entropy change for the reaction
-1 1.4 -1 A B if the value of DHº = 28.40kJ mol -1 and
T1 é V2 ù 273 é 3V1 ù
=ê ú or =ê ú equilibrium constant is 1.8 × 10-7 at 298K
T2 ë V1 û T2 ë V1 û
Sol. DGº = - 2.303RT log K
c
Very Short/ Short Answer Questions (b) The entropy of a substance increases in going from
the liquid to the vapour state at any temperature.
1. Predict DH > DU or DH < DU or DH = DU.
(c) Reaction with DG° < 0 always have an equilibrium
(a) C (graphite) + O2 (g) ® CO2(g) constant greater than 1.
(b) PCl5 (g) ® PCl3(g) + Cl2 (g). 11. Give reasons for the following :
2.
In the equation N2(g) + 3H2(g)
2NH3(g), what whould (a) Why the heat produced be different if same mass of
be the sign of work done? diamond and graphite are burnt in oxygen?
3. Give an example of following energy conversions: (b) The dissolution of ammonium chloride in water is en-
(i) Radiation energy into chemical energy. dothermic still it dissolves in water
(ii) Radiation energy into electrical energy. (c) A real crystal has more entropy than an ideal crystal.
4. A system is changed from an initial state to a final state by 12. Calculate the value of log Kp for the reaction N2(g) + 3H2(g)
a manner such that DH = q. If the change from the initial 2NH3 (g) at 25°C. The standard enthalpy of
state to a final state were made by a different path, would formation of NH3(g) is – 46 kJ mol–1 and standard entropies
DH be the same as that for the first path? would q too be of N2(g) , H2(g) and NH3(g) are 191, 130, 192 JK–1 mol–1
the same? respectively.
5. What property of enthalpy provides the basis of Hess’s
Long Answer Questions
law?
6. A chemist while studying the properties of gaseous 13. Define the following terms :
C2Cl 2F2, a chlorofluorocarbon refrigerant, cooled 1.25 g (a) System
sample at constant atmospheric pressure of 1.0 atm from (b) Isothermal processes
320 K to 293 K. During cooling, the sample volume
(c) Adiabatic processes
decreased from 274 to 248 ml. Calculate DH and DU for the
chlorofluorocarbon for this process. (d) State variables/state functions
The value of molar heat capacity is 80.7 J mol –1 K–1 . (e) Work
7. Gobar gas obtained by bacterial fermentation of animal 14. (i) Calculate the standard molar entropy change for the
refuse contains mainly methane. The heat of combustion following reactions at 298 K.
of methane to CO2 and water as gas is given by (a) 4 Fe (s) + 3 O2 (g) ¾¾ ® 2 Fe2O3(s).
CH4(g) + 2O2(g) ® CO2(g) + 2H2O(g) + 809 kJ (b) Ca (s) + 2 H2O (l) ¾¾ ® Ca(OH)2 (aq) + H2 (g)
How much gobar gas would have to be produced per day Given:
for a small village community of 100 families, if we assume S° Fe(s) = 27.28, S°O2(g) = 205.14, S° Fe2O3 (s) = 87.4
that each family has to be supplied 20000 kJ of energy per
S°Ca(s) = 41.42, S°H2O(l) = 69.9, S°Ca(OH)2(aq) = 74.5,
day to meet all its needs and that the methane content in
the gobar gas is 80 percent by weight. S°H2(g) = 130.68,
8. Why is it more convenient to predict the direction of (ii) Calculate the standard molar Gibbs energy of formation
reaction in terms of DGsys instead of DStotal? Under what of CS2, given that its standard enthalpy of formation is
conditions can DGsys be used to predict the spontaneity of 89.7 kJ mol–1 and the standard molar entropies of
a reaction? graphite, S and CS2 are 5.7, 31.8 and 151.3JK–1mol–1
respectively.
9. Which of the following processes are accompanied by
increase of entropy ? 15. For the reaction
(a) Stretching of rubber band, 2H 2 (g) + O2 (g)
2H 2O(l )
(b) Boiling of an egg at 25°C, the equilibrium constant is 7.0 × 10–84.
(c) A deodrant is sprayed. (i) Calculate the standard Gibbs energy formations of
10. Comment on the following statements : water at 25°C.
(a) An exothermic reaction is always thermodynamically (ii) Dr H°H O = – 280 kJ mol–1. Calculate the entropy
2
spontaneous. change for the reaction.
158 Chemistry
Multiple Choice Questions The work can also be calculated from the pV–plot by using
the area under the curve within the specified limits. When
16. Thermodynamics is not concerned about____. an ideal gas is compressed (a) reversibly or (b) irreversibly
(a) energy changes involved in a chemical reaction. from volume Vi to Vf. Choose the correct option.
(b) the extent to which a chemical reaction proceeds. (a) w (reversible) = w (irreversible)
(c) the rate at which a reaction proceeds (b) w (reversible) < w (irreversible)
(d) the feasibility of a chemical reaction. (c) w (reversible) > w (irreversible)
17. Which of the following statements is correct? (d) w (reversible) = w (irreversible) + pex. DV
(a) The presence of reacting species in a covered beaker 21. During complete combustion of one mole of butane, 2658
is an example of open system. kJ of heat is released. The thermochemical reaction for above
(b) There is an exchange of energy as well as matter change is
between the system and the surroundings in a closed (a) 2C4H10(g) + 13O2(g) ® 8CO2(g) + 10H2O(l)
system. DcH = –2658.0 kJ mol–1
(c) The presence of reactants in a closed vessel made up
of copper is an example of a closed system. 13
(b) C4H10(g) + O (g) ® 4CO2(g) + 5H2O (g)
(d) The presence of reactants in a thermos flask or any 2 2
other closed insulated vessel is an example of a closed DcH = –1329.0 kJ mol–1
system.
13
18. Which one of the following statements is false? (c) C4H10(g) + O (g) ® 4CO2(g) + 5H2O (l)
2 2
(a) Work is a state function
DcH = –2658.0 kJ mol–1
(b) Temperature is a state function
(c) Change in the state is completely defined when the 13
(d) C4H10(g) + O (g) ® 4CO2(g) +5H2O (l)
initial and final states are specified 2 2
(d) None of the above DcH = + 2658.0 kJ mol–1
19. A heat engine absorbs heat Q1 at temperature T1 and heat 22. On the basis of thermochemical equations (1), (2) and (3),
Q2 at temperature T2. Work done by the engine is J (Q1 + find out which of the algebric relationships given in options
Q2). This data (a) to (d) is correct.
(a) violates 1st law of thermodynamics (1) C (graphite) + O2(g) ® CO2(g); DrH = x kJ mol–1
(b) violates 1st law of thermodynamics if Q1 is –ve
1
(c) violates 1st law of thermodynamics of Q2 is –ve (2) C(graphite) + O2(g) ® CO (g); DrH = y kJ mol–1
2
(d) does not violate 1st law of thermodynamics.
20. The pressure-volume work for an ideal gas can be calculated 1
(3) CO (g) + O (g) ® CO2 (g); DrH = z kJ mol–1
Vf
2 2
by using the expression w = - pex dV . (a) z = x + y (b) x = y–z
Vi (c) x = y + z (d) y = 2z – x
Thermodynamics 159
1. Consider the following reactions: [CBSE-PMT 2007] 7 From the following bond energies: [CBSE-PMT 2009]
+ –
(i) H (aq) + OH (aq) ¾¾ ® H2O(l), H – H bond energy: 431.37 kJ mol–1
DH = – X1 kJ mol–1 C = C bond energy: 606.10 kJ mol–1
C – C bond energy: 336.49 kJ mol–1
1 C – H bond energy: 410.50 kJ mol–1
(ii) H2(g) + O (g) ¾¾
® H2O(l),
2 2 Enthalpy for the reaction,
DH = – X2 kJ mol–1
H H H H
(iii) CO2(g) + H2(g) ¾¾ ® CO(g) + H2O, | | | |
DH = – X3 kJ mol–1 C = C + H - H ¾¾
® H - C- C - H
| | | |
5 H H H H
(iv) C2H 2 ( g ) + O2 ( g ) ¾¾
® 2CO2(g) + H2O(l),
2
will be:
DH = + 4X4 kJ mol–1 (a) – 243.6 kJ mol–1 (b) –120.0 kJ mol–1
Enthalpy of formation of H2O (l) is (c) 553.0 kJ mol–1 (d) 1523.6 kJ mol–1
(a) + X3 kJ mol– 1 (b) – X4 kJ mol– 1 8. Standard entropies of X2 , Y2 and XY3 are 60, 40 and
(c) + X1 kJ mol– 1 (d) – X2 kJ mol– 1 50 JK–1mol–1 respectively. For the reaction
2. Given that bond energies of H – H and Cl – Cl are [CBSE-PMT 2010]
430 kJ mol– 1 and 240 kJ mol–1 respectively and DfH for HCl
1 3
is – 90 kJ mol– 1, bond enthalpy of HCl is [CBSE-PMT 2007] X 2 + Y2 XY3 , DH = – 30 kJ
2 2
(a) 380 kJ mol–1 (b) 425 kJ mol–1 to be at equilibrium, the temperature should be:
(c) 245 kJ mol–1 (d) 290 kJ mol–1 (a) 750 K (b) 1000 K
3. Which of the following are not state functions ? (c) 1250 K (d) 500 K
[CBSE-PMT 2008] 9. For vaporization of water at 1 atmospheric pressure, the values
(I) q + w (II) q of DH and DS are 40.63 kJmol–1 and 108.8 JK–1 mol–1,
(III) w (IV) H - TS respectively. The temperature when Gibbs energy change
(a) (I) and (IV) (b) (II), (III) and (IV)
(c) (I), (II) and (III) (d) (II) and (III)
( DG ) for this transformation will be zero, is:
4. For the gas phase reaction, [CBSE-PMT 2008] [CBSE-PMT 2010]
PCl3(g) + Cl2(g) (a) 293.4 K (b) 273.4 K
PCl5(g)
(c) 393.4 K (d) 373.4 K.
which of the following conditions are correct ? 10. Match List -I (Equations) with List-II (Type of processes)
(a) DH = 0 and DS < 0 and select the correct option. [CBSE-PMT 2010]
(b) DH > 0 and DS > 0 List I List II
(c) DH < 0 and DS < 0 Equations Type of processes
(d) DH > 0 and DS < 0 (1) Kp > Q (i) Non spontaneous
5. Bond dissociation enthalpy of H2, Cl2 and HCl are 434 , 242 and (2) DG ° < RT lnQ (ii) Equilibrium
431 kJ mol–1 respectively. Enthalpy of formation of HCl is : (3) Kp = Q (iii) Spontaneous and
[CBSE-PMT 2008] endothermic
(a) 93 kJ mol –1 (b) – 245 kJmol–1 DH
(c) – 93 kJmol –1 (d) 245 kJmol–1 (4) T > (iv) Spontaneous
DS
6. The values of DH and DS for the reaction, Options:
C(graphite) + CO2 (g) ® 2CO(g) are 170 kJ and 170 JK–1, (1) (2) (3) (4)
respectively. This reaction will be spontaneous at (a) (ii) (i) (iv) (iii)
[CBSE-PMT 2009] (b) (i) (ii) (iii) (iv)
(a) 910 K (b) 1110 K (c) (iii) (iv) (ii) (i)
(c) 510 K (d) 710 K (d) (iv) (i) (ii) (iii)
164 Chemistry
11. The following two reactions are known : 18. Standard enthalpy of vapourisation Dvap H° for water at
[CBSE-PMT 2010] 100°C is 40.66 kJ mol–1. The internal energy of vaporisation
of water at 100°C (in kJ mol–1) is : [CBSE-PMT 2012 S]
Fe2O3(s) + 3CO (g) ¾¾
® 2Fe(s) + 3CO2(g); DH = –26.8 kJ (a) + 37.56 (b) – 43.76
(c) + 43.76 (d) + 40.66
FeO(s) + CO(g) ¾¾
® Fe(s) + CO2(g); DH = –16.5 kJ
(Assume water vapour to behave like an ideal gas).
The value of D H for the following reaction 19. Equal volumes of two monoatomic gases, A and B, at same
Fe2O3(s) + CO(g) ¾¾ ® 2FeO(s) + CO2(g) is; temperature and pressure are mixed. The ratio of specific
(a) + 6.2 kJ (b) + 10.3 kJ heats (Cp/Cv) of the mixture will be : [CBSE-PMT 2012]
(c) – 43.3 kJ (d) – 10.3 kJ (a) 0.83 (b) 1.50
12. Three moles of an ideal gas expanded spontaneously into (c) 3.3 (d) 1.67
vacuum. The work done will be : [CBSE-PMT 2010] 20. A reaction having equal energies of activation for forward
(a) Zero (b) Infinite (c) 3 Joules (d) 9 Joules and reverse reaction has : [NEET 2013]
13. If the enthalpy change for the transition of liquid water to (a) DG = 0 (b) DH = 0
steam is 30 kJ mol–1 at 27ºC, the entropy change for the (c) DH = DG = DS = 0 (d) DS = 0
process would be : [CBSE-PMT 2011]
21. If an endothermic reaction is non-spontaneous at freezing
(a) 10 J mol –1 K–1 (b) 1.0 J mol–1 K–1
point of water and becomes feasible at its boiling point,
(c) 0.1 J mol–1 K–1 (d) 100 J mol–1 K–1
then [AIEEE 2002]
14. Enthalpy change for the reaction, [CBSE-PMT 2011]
(a) DH is –ve, DS is +ve
4H( g ) ¾¾
® 2H 2 ( g ) is – 869.6 kJ.
(b) DH and DS both are +ve
The dissociation energy of H–H bond is :
(c) DH and DS both are –ve
(a) – 434.8 kJ (b) – 869.6 kJ
(d) DH is +ve, DS is -ve
(c) + 434.8 kJ (d) + 217.4 kJ
22. A heat engine abosrbs heat Q1 at temperature T1 and heat
15. Consider the following processes :
Q2 at temperature T2. Work done by the engine is J (Q1 +
DH (kJ/mol)
Q2). This data [AIEEE 2002]
1/2 A® B +150 st
(a) violates 1 law of thermodynamics
3B ® 2C + D –125 (b) violates 1st law of themodynamics if Q1 is –ve
E + A ® 2D +350 (c) violates 1st law of thermodynamics of Q2 is –ve
For B + D ® E + 2C, DH will be : [CBSE-PMT 2011 M] (d) does not violate 1st law of themodynamics.
(a) 525 kJ/mol (b) – 175 kJ/mol 23. For the reactions, [AIEEE 2002]
(c) – 325 kJ/mol (d) 325 kJ/mol C + O2 ® CO2 ; DH = -393 J
16. In which of the following reactions, standard entropy
2Zn + O2 ® 2 ZnO ; DH = -412 J
change (DS°) is positive and standard Gibb’s energy change
(a) carbon can oxidise Zn
(DG°) decreases sharply with increase in temperature ?
(b) oxidation of carbon is not feasible
[CBSE-PMT 2012 S]
(c) oxidation of Zn is not feasible
1 (d) Zn can oxidise carbon.
(a) C (graphite) + O (g) ® CO(g)
2 2 24. The internal energy change when a system goes from state
1 A to B is 40 kJ/mole. If the system goes from A to B by a
(b) CO(g) + O (g) ® CO2(g) reversible path and returns to state A by an irreversible path
2 2
what would be the net change in internal energy ?
1 [AIEEE 2003]
(c) Mg(s) + O (g) ® MgO(s)
2 2 (a) > 40 kJ (b) < 40 kJ
1 1 1 (c) Zero (d) 40 kJ
(d) C (graphite) + O2(g) ® CO2(g) 25. If at 298 K the bond energies of C — H, C — C, C = C and H
2 2 2
— H bonds are respectively 414, 347, 615 and 435 kJ mol–1,
17. The enthalpy of fusion of water is 1.435 kcal/mol. the value of enthalpy change for the reaction
The molar entropy change for the melting of ice at 0°C is :
H 2 C = CH 2 (g) + H 2 (g) ® H 3C — CH 3 (g)
[CBSE-PMT 2012 S]
(a) 10.52 cal / (mol K) (b) 21.04 cal / (mol K) at 298 K will be [AIEEE 2003]
(c) 5.260 cal / (mol K) (d) 0.526 cal / (mol K) (a) – 250 kJ (b) + 125 kJ
(c) – 125 kJ (d) + 250 kJ
Thermodynamics 165
26. In an irreversible process taking place at constant T and P and 34. An ideal gas is allowed to expand both reversibly and
in which only pressure-volume work is being done, the change irreversibly in an isolated system. If T i is the initial
in Gibbs free energy (dG) and change in entropy (dS), satisfy temperature and Tf is the final temperature, which of the
the criteria [AIEEE 2003] following statements is correct? [AIEEE 2006]
(a) ( D S)V, E > 0, ( D G)T, P < 0 (b) ( D S)V, E = 0, ( D G)T, P = 0 (a) (Tf)rev = (Tf)irrev
(b) Tf = Ti for both reversible and irreversible processes
(c) ( D S)V, E = 0, ( D G)T, P > 0 (d) ( D S)V, E < 0, ( D G)T, P < 0
(c) (Tf)irrev > (Tf)rev
27. The correct relationship between free energy change in a
(d) Tf > Ti for reversible process but Tf = Ti for irreversible
reaction and the corresponding equilibrium constant Kc is
process
[AIEEE 2003]
35. The standard enthalpy of formation (DfHº) at 298 K for
(a) – DG = RT ln Kc (b) DGº = RT ln Kc
methane, CH4 (g) is –74.8 kJ mol –1 . The additional
(c) – DGº = RT ln Kc (d) DG = RT ln Kc information required to determine the average energy for C
28. The enthalpy change for a reaction does not depend upon – H bond formation would be [AIEEE 2006]
[AIEEE 2003] (a) the first four ionization energies of carbon and electron
(a) use of different reactants for the same product gain enthalpy of hydrogen
(b) the nature of intermediate reaction steps (b) the dissociation energy of hydrogen molecule, H2
(c) the differences in initial or final temperatures of involved (c) the dissociation energy of H2 and enthalpy of
substances sublimation of carbon
(d) the physical states of reactants and products (d) latent heat of vapourization of methane
29. An ideal gas expands in volume from 1×10 –3 to 36. The enthalpy changes for the following processes are listed
1 × 10 –2 m 3 at 300 K against a constant pressure of below : [AIEEE 2006]
1×10 5 Nm –2 . The work done is [AIEEE 2004] Cl2(g) = 2Cl(g), 242.3 kJ mol –1
40. Identify the correct statement regarding a spontaneous 46. Consider the reaction : [AIEEE 2011 RS]
process: [AIEEE 2007] 4NO2 ( g ) + O 2 ( g ) ® 2N 2O5 ( g ),
(a) Lowering of energy in the process is the only criterion DrH = – 111 kJ.
for spontaneity.
If N2O5(s) is formed instead of N2O5(g) in the above reaction,
(b) For a spontaneous process in an isolated system, the
the DrH value will be :
change in entropy is positive.
(given, DH of sublimation for N2O5 is –54 kJ mol–1)
(c) Endothermic processes are never spontaneous.
(a) + 54 kJ (b) + 219 kJ
(d) Exothermic processes are always spontaneous.
41. Oxidising power of chlorine in aqueous solution can be (c) – 219 J (d) – 165 kJ
determined by the parameters indicated below: 47. A piston filled with 0.04 mol of an ideal gas expands
[AIEEE 2008] reversibly from 50.0 mL to 375 mL at a constant temperature
of 37.0ºC. As it does so, it absorbs 208 J of heat. The values
1
1 D H D eg H of q and w for the process will be: [JEE M 2013]
2 diss
Cl2 ( g ) ¾¾¾¾¾ ® Cl( g ) ¾¾¾¾ ® Cl– ( g )
2 (R = 8.314 J/mol K) (ln 7.5 = 2.01)
(a) q = + 208 J, w = – 208 J
D H
Hyd
¾¾¾¾ ® Cl – (aq) (b) q = – 208 J, w = – 208 J
(using the data, (c) q = – 208 J, w = + 208 J
–1 –1 (d) q = + 208 J, w = + 208 J
D diss H Cl = 240 kJ mol D eg H Cl = –349 kJ mol
2
48. B is
The value of log10 K for a reaction A
–1
D hyd H Cl – = –381 kJ mol ), will be (Given : D r H °298K = -54.07 kJ mol- 1 ,
(a) + 152 kJ mol–1 (b) – 610 kJ mol–1
(c) – 850 kJ mol–1 (d) + 120 kJ mol–1 D r S°298K = 10 JK–1 mol–1 and R = 8.314 JK–1 mol–1;
42. On the basis of the following thermochemical data : 2.303 × 8.314 × 298 = 5705) [IIT-JEE 2007]
+
[Δ f H°(H (aq) = 0)] [AIEEE 2009] (a) 5 (b) 10
(c) 95 (d) 100
H 2O(l ) ® H + ( aq ) + OH – ( aq ); DH = 57.32kJ
49. For the process H2O(l) (1 bar, 373 K) ® H2O(g) (1 bar, 373
1 K), the correct set of thermodynamic parameters is
H2 (g )+ O2 (g ) ¾¾ ® H2O(l); ΔH= –286.20kJ
2 [IIT-JEE 2007]
The value of enthalpy of formation of OH– ion at 25° C is: (a) DG = 0, DS = +ve (b) DG = 0, DS = –ve
(a) –228.88 kJ (b) +228.88 kJ
(c) DG = +ve, DS = 0 (d) DG = –ve, DS = +ve
(c) –343.52 kJ (d) –22.88 kJ
50. The species which by definition has ZERO standard molar
43. The standard enthalpy of formation of NH 3
enthalpy of formation at 298 K is [IIT-JEE 2010]
is – 46.0 kJ mol–1. If the enthalpy of formation of H2 from its
atoms is – 436 kJ mol–1 and that of N2 is – 712 kJ mol–1, the (a) Br2 (g) (b) Cl2 (g)
average bond enthalpy of N – H bond in NH3 is (c) H2O (g) (d) CH4 (g)
[AIEEE 2010] 51. Using the data provided, calculate the multiple bond energy
(a) – 964 kJ mol–1 (b) + 352 kJ mol–1 (kJ mol–1) of a C º C bond in C2H2. That energy is (take the
(c) + 1056 kJ mol–1 (d) – 1102 kJ mol–1 bond energy of a C – H bond as 350 kJ mol–1)
44. For a particular reversible reaction at temperature T, DH 2C(s) + H2(g) ¾¾ ® HC º CH(g); DH = 225 kJ mol–1
and DS were found to be both +ve. If Te is the temperature 2C(s) ¾¾ ® 2C(g) ; DH = 1410 kJ mol–1
at equilibrium, the reaction would be spontaneous when H2(g) ¾¾ ® 2H(g) ; DH = 330 kJ mol–1 [IIT-JEE 2012]
(a) Te > T (b) T > Te [AIEEE 2010] (a) 1165 (b) 837
(c) Te is 5 times T (d) T = Te
(c) 865 (d) 815
45. The value of enthalpy change (DH) for the reaction
52. The standard enthalpies of formation of CO2(g), H2O(l)
C2 H5 OH(l) + 3O2 ( g ) ® 2CO2 ( g ) + 3H 2O(l) and glucose(s) at 25°C are –400 kJ/mol, –300 kJ/mol and –
at 27° C is – 1366.5 kJ mol–1. The value of internal energy 1300 kJ/mol, respectively. The standard enthalpy of
change for the above reaction at this temperature will be : combustion per gram of glucose at 25°C is
[AIEEE 2011 RS] [JEE Advanced 2013]
(a) – 1369.0 kJ (b) – 1364.0 kJ (a) +2900 kJ (b) –2900 kJ
(c) – 1361.5 kJ (d) – 1371.5 kJ (c) –16.11 kJ (d) +16.11 kJ
Thermodynamics 167
1. For determining the spontaneity of a process which of the 9. What is the free energy change for the conversion of
following is considered ? 1 mole of water into steam at 373.2 K . The heat
(a) DS system of vaporization (DHv) of water of 373.2 K is 9.1 kcal. mol –1.
(b) DS surroundings The entropy change is 25.5 cal/mol deg.
(c) DS system + DS surroundings (a) –401.6 cal/mol (b) –416.6 cal/mol
(d) DS system – DS surroundings (c) 516.5 cal/mol (d) –516.5 cal/mol
2. Which of the following is always true for a spontaneous 10. The ‘thermite reaction’ involving the reaction between ferric
change at all temperatures ? oxide and metallic aluminium produces molten iron. Given
(a) DH > 0 ; DS < 0 (b) DH < 0 ; DS < 0 that
(c) DH < 0 ; DS > 0 (d) DH > 0 ; DS > 0 2Al + 3 / 2 O 2 ® Al 2 O 3 ; DH1 = -400 kcal/ mol
3. What is the change in entropy when ice melts at 0°C, enthalpy
of fusion of one mole of ice is 6.02 kJ ? 2Fe + 3 / 2 O 2 ® Fe 2O 3 ; DH 2 = -200 kcal/mol.
(a) 6.02 kJ K–1 mol–1 (b) 22.1 J K–1 mol–1 What is DH for the formation of 1 mole of iron ?
(c) 1 J K–1 mol–1 (d) 22.0J K–1 mol–1 (a) –100 kcal (b) –200 kcal
4. In which of the following processes, the entropy decreases (c) +100 kcal (d) +200 kcal
? 11. Given the reaction at 927°C and 1 atm.
(a) CaCO3 (s) ® CaO(s) + CO2 (g) CaO(s) + CO2 (g) DH= 176 kJ/mol; then
CaCO3 (s)
(b) 2NH 3 (g) ® N 2 (g) + 3H 2 (g) DE equals
(c) 2H 2 (g) + O 2 (g) ® 2H 2 O(l) (a) 100 kJ (b) 166.03 kJ
(c) 180.0 kJ (d) 186.4 kJ
(d) O 3 (g ) ® O 2 (g ) + O(g) 12. What is the enthalpy change for the reaction
5. For which one of the processes represented by the following H 2 (g ) + C 2 H 4 (g ) ® C 2 H 6 (g )
equations the enthalpy (heat) change is likely to be negative
The bond energies are given below:
(a) Cl - (g) + aq ® Cl - (aq) (b) Cl(g) ® Cl + (g) + e -
( H - H ) ® 103; ( C - H ) ® 99, ( C - C ) ® 80 and
(c) 1 / 2Cl 2 (g ) ® Cl(g ) (d) Cl 2 (l) ® Cl 2 (g)
( C = C ) ® 145 kcal/mol respectively
6. The enthalpy change of formation of CO 2 (g)
is – 393 kJmol–1 and that of H2O (l) is – 286 kJmol–1. The (a) –10 kcal mol–1 (b) +10 kcal mol–1
enthalpy of combustion of one mole of ethanol (C2H5OH) is (c) –30 kcal mol–1 (d) +30 kcal mol–1
–1360. The enthalpy change for the formation of one mole of 13. For the process H2O(l) H2O(g) DH = 45.0 kJ mol–1 and
ethanol form its constituent elements is DS = 1.20 × 102 J K–1 mol–1. At what temperature the above
(a) –681 kJ (b) –284 kJ process is at equilibrium?
(c) +965 kJ (d) 1360 kJ (a) 273 K (b) 373 K
7. What is Dngas for the combustion of 1 mole of benzene, when (c) 370 K (d) 375 K
both the reactants and the products are at 298 K ?
14. Third law of thermodynamics is used to determine the
(a) 0 (b) 1/2
(a) spontaneity of a process
(c) 3/2 (d) –3/2
(b) enthalpy of substance
8. Which of the following statements is false ?
(c) absolute values of entropy of a substance
(a) For 1 mole of an ideal gas, Cp – Cv = R
(d) free energy of a substance
æ Eö 15. In thermodynamics, a process is called reversible when
(b) ç ÷ = 0 for an ideal gas
è T øT (a) surroundings and system change into each other
(b) there is no boundary between system and surroundings
(c) Dq = Dw + pDV (c) the surroundings are always in equilibrium with the
(d) For reversible isothermal expansion of 1 mole of an ideal system
gas from volume V1 to V2, work done is equal to RT ln (d) the system changes in to the surroundings
(V2/V1) spontaneously
168 Chemistry
16. Which one of the following statements is false? 23. For the reaction
(a) Work is a state function
(b) Temperature is a state function 2C6 H5CO2 H(s) + 15O2 (g) ¾¾
®14CO 2 (g) + 6H 2O(g)
(c) Change in the state is completely defined when the initial DUº = –772.7 kJ mol–1 at 298 K. Calculate DHº
and final states are specified (a) +760.3 kJ mol–1 (b) –760.3 kJ mol–1
(d) Work appears at the boundary of the system (c) +670.3 kJ mol –1 (d) –790.3 kJ mol–1
17. The standard enthalpies of formation of H + and 24. 1 gram equivalent of H2SO4 is treated with 112 g of KOH for
OH– ions in water are zero and –229.6 kJ mol–1 respectively. complete neutralization. Which of the following statements
The standard enthalpy of formation of liquid water is –285.6kJ is correct?
mol–1. Then the enthalpy of neutralization of HCl(aq) by (a) 13.7 kcal of heat is evolved with the formation of
KOH(aq) is 87 g of K2SO4, leaving no KOH.
(a) 229.6 kJ mol–1 (b) –173.4 kJ mol–1
(b) 27.4 kcal of heat is evolved with the formation of
(c) 56.0 kJ mol –1 (d) –56.0 kJ mol–1 87 g of K2SO4, leaving 4 gram equivalent of KOH.
18. Which of the following salts should cause maximum cooling (c) 15.7 kcal of heat is evolved with the formation of 1 gram
when 1 mole of it is dissolved in the same volume of water ? equivalent of K2SO4, leaving 56 g of KOH.
(a) NaCl; DHº = 5.35 kJ mol–1 (d) 13.7 kcal of heat is evolved with the formation of 87g of
(b) KNO3; DHº = 53.5 kJ mol–1 K2SO4, leaving 1 gram equivalent of KOH.
(c) KOH; DHº = –56.0 kJ mol–1 25. From the following data DH of the following reactions
(d) HBr; DHº = –83.3 kJ mol–1
19. The molar enthalpies of combustion of isobutane and n-butane 1
C(s) + O 2 (g ) ¾¾® CO(g); DH = – 110 kJ and
are –2870 kJ mol–1 & –2875 kJ mol–1 respectively at 298 K and 2
1 atm. Calculate DHº for the conversion of 1 mole of n-butane
to 1 mole of isobutane C(s) + H 2 O(g) ¾¾® CO(g) + H 2 (g); DH = 132 kJ
(a) –8 kJ mol–1 (b) +8 kJ mol–1 Calculate the mole composition of the mixture of steam and
(c) –5748 kJ mol –1 (d) +5748 kJ mol–1 oxygen on being passes over coke at 1273 K, keeping the
temperature constant.
20. For the reaction
(a) 1 : 0.6 (b) 0.6 : 1
1 (c) 2 : 3 (d) 3 : 2
CO(g) + O 2 (g) ¾ ¾® CO 2 (g ); DHº = –67650 cal at
2
o -1
25 ºC. Calculate DHº at 100°C, given that the required molar 26. DHf of water is – 285.8 kJmol . If enthalpy of
heat capacities are as follows. neutralisation of monoacidic strong base is
CP(CO,g) = 6.97 cal ºC–1
–57.3 kJmol - 1 . DHf of OH - ion will be
o
CP(CO2,g) = 8.97 cal ºC–1
CP(O2,g) = 7.00 cal ºC–1 (a) – 114.25 kJmol -1 (b) 114.25 kJmol
-1
(c) 71.6 kcalmol -1 (d) – 71.6 kcalmol -1 (c) H 2S > HCOOH > CH 3COOH > HCN
(d) HCOOH > H 2S > CH 3COOH > HCN
170 Chemistry
41. When 1.8 g of steam at the normal boiling point of water is 43. The enthalpy of atomisation of CH 4 and C 2 H 6 are 360
converted into water at the same temperature, enthalpy and
entropy changes respectively will be ( DHVaporisation for and 620 kcal mol -1 respectively. The C – C bond energy is
expected to be
H 2 O = 40.8 kJ mol-1 )
-1 -1
(a) 210 k cal mol (b) 80 k cal mol
-1 -1
(a) 4.08 kJ, 10.93 J K (b) – 4.08 kJ, – 10.93 J K
-1
(c) 130 k cal mol -1 (d) 180 k cal mol
-1 -1
(c) – 4.08 kJ, – 40.8 J K (d) 4.08 kJ, 40.8 J K
44. A certain reaction is non spontaneous at 298K. The entropy
42. The enthalpy of neutralisation of a weak acid in 1 M solution
change during the reaction is 121 J K -1 . Is the reaction is
with a strong base is – 56.1 kJ mol-1 . If the enthalpy of
endothermic or exothermic ? The minimum value of DH for
ionisation of acid is 1.5 kJ mol-1 an d enthalpy of the reaction is
neutralisation of the strong acid with a strong base is –57.3
(a) endothermic, DH = 36.06 kJ
kJ eq-1 . What is the % ionisation of the weak acid in molar (b) exothermic, DH = – 36.06 kJ
solution (assume the acid is monobasic)
(c) endothermic, DH = 60.12 kJ
(a) 25 (b) 20
(c) 15 (d) 10 (d) exothermic, DH = – 60.12 kJ
Thermodynamics 171
DH (iii) H2(g) ¾¾
\ DH = TeDS or Te = ® 2H(g)
DS DH = 330 kJ mol–1
For a spontaneous reaction From equation (i) :
DG must be negative which is possible only if DH – TDS < 0
\ DH < TDS 225 = éë 2 ´ DHC(s) ¾¾
® C( g )
+ 1 ´ BE H – H ù
û
DH - [2 ´ BE C – H + 1 ´ BECº C ]
or T > ; Te < T
DS 225 = [1410 + 1 × 330] – [2 × 350 + 1 × BEC º C]
225 = [1410 + 330] – [700 + BEC º C]
45. (b) C2H5 OH(l) + 3O 2 ( g ) ® 2CO 2 ( g ) + 3H 2O(l) 225 = 1740 – 700 – BEC º C
BEC º C = 815 kJ mol–1
Dng = 2 - 3 = -1 52. (c) The standard enthalpy of the combustion of glucose
can be calculated by the eqn.
DU = DH - Dng RT C6H12O6(s) + 6O2(g) ® 6CO2(g) + 6H2O(l)
DHC = 6 × DHf(CO2) + 6 × DHf (H2O) – DHf [C6H12O6]
8.314 DH° = 6 (–400) + 6(–300) – (–1300)
= -1366.5 - ( -1) ´ ´ 300
103 DH° = –2900 kJ/mol
For one gram of glucose, enthalpy of combustion
8.314
= -1366.5 + (1) ´ ´ 300 2900
103 DH° = – = - 16.11kJ / gm
= – 1366.5 + 0.8314 × 3 = – 1364 .006 kJ 180
176 Chemistry
EXERCISE 4 14. (c) The third law of thermodynamics is about entropy.
15. (c) 16. (a)
1. (c) The criteria for the spontaneity, DS system + DS 17. (d) It is neutralisation of strong acid with strong base.
surroundings, must be + ve 18. (b) Dissolution of KNO3 is endothermic, hence heat is
2. (c) DG = DH – TDS. For spontaneous process DG < 0. To absorbed and cooling is observed.
get DG < 0. we must have DH < 0 ; DS > 0
19. (a) Isobutane + oxygen ® CO 2 + H 2 O
DH fusion 6.02 ´103
3. (d) DS = ; DS = = 22.0 JK -1 mol -1 DH = -2870 kJ mol -1 ......(i)
T 273
4. (c) Examine the chemical equations . If there is decrease in n-butane + oxygen ® CO2 + H 2O
number of moles of gaseous products, the entropy will
decrease and vice versa. DH = -2878 kJ mol -1 ....(ii)
5. (a) Gaseous ions, when dissolved in water, get hydrated (ii) - (i); n-butane – Isobutane,
and heat is evolved (heat of hydration). DH = (–2878 + 2870)
= – 8 kJ mol–1.
Cl - (g) + aq ® Cl- (aq) is such reaction .
DH 2 - DH1
6. (b) Write the proper chemical equations. 20. (d) Apply Kirchoff’s equation = C p - C R = DC p
T2 - T1
C(graphite) + O 2 (g) ® CO2 (g)
21. (b) Bond dissociation energy of PH3(g) = 228 kcal mol–1
DH = -393kJ ........(i)
228
P – H bond energy = = 76 kcal mol-1
1 3
H 2 (g) + O 2 (g) ® H 2 O(l)
2 H H
DH = -286kJ .........(ii)
P P
C2 H 5OH (l) + 3O2 (g) ® 2CO 2 (g) + 3H 2 O(l) H H
....(iii) Bond energy of 4 (P – H) + (P –P) = 355 kcal mol–1
DH = -1360kJ
or 4 × 76 + (P – P) = 355 kcal mol–1
From ( 2 ´ I + 3 ´ II ) – (III) we get P–P bond energy = 51 kcal mol–1
22. (a) DHº solution =U (lattice energy) + DHº hydration
1
2C + 3H 2 + O ® C 2 H 5 OH 23. (b) DH º = DU º + DnRT
2 2
5 ´ 8.314 ´ 298
2(-393kJ) + 3(-286kJ) - (-1360kJ) = -284kJ DHº = -772.7 + = -760.3 kJ mol -1
1000
15
7. (d) C6 H 6 (l) + O2 (g) ® 6CO 2 (g) + 3H 2O (l) 24. (d) H 2SO 4 + 2KOH ® K 2 SO 4 + 2H 2 O
2 98 112 174 2 mole
56
Dn = 6 - 15/2 = –3/2 49 87 1 mole
8. (c) C is incorrect ; The correct is DE = Dq + Dw 13.7 kcal is the heat evolved when 1 gev of strong acid is
9. (b) DG =DH – TDS neutralised by 1 gev of strong base.
DG = 9100 - 373.2 ´ 25.5 = -416.6 cal mol–1 25. (a) The first reaction is exothermic and the second reaction
10. (a) I – II, gives, 2Al + Fe2O3 ® 2Fe + Al2O3 is endothermic. If on passing the mixture of O 2 and
we have -400 - (-200) = -200; For one mole of iron H 2 O (steam) over coke while keeping the temperature
the value is –100 cal constant DH of both the reactions must be same.
11. (c) Moles of O 2 needed to evolve 132 kJ
12. (b) Enthalpy change = ( Energy required for breaking of
bonds – Energy evolved by formation of bonds) 0.5 ´ 132
= = 0.6
H H H H 110
H–H+ C=C H C–C H Hence steam : O 2 ratio must be 1 : 0.6
H H H H 1
( )- ( )
26. (d) H 2 (g) + O 2 (g ) ¾
¾® H 2 O (l);
H -H 103 80 C -C 2
C = C 145 2´99 C -H = -30 kcal mol–1
DH = – 285.8 kJ .... (i)
13. (d) DG = DH – TDS ; At equilibrium DG = 0 ; D =TDS ;
H + (aq) + OH (aq) ¾
¾® H 2 O (l);
–
DH
T= DH = – 57.3 kJ ... (ii)
DS
1
45000 ¾® H + (aq) + e - ; DH = 0
H 2 (g) + aq ¾
T= = 375K 2
1.2 ´ 10 2 (by convention) .... (iii)
Thermodynamics 177
(i) – (ii) – (iii) gives,
33. (a) CuSO 4 (s) + 5 H 2 O (g) ¾
¾® CuSO 4 .5 H 2 O (s);
1 1
H 2 (g ) + O 2 (g ) + e - + aq ¾
¾® OH - (aq) DH = – 71.5 kcal ........ (i)
2 2
5 H 2 O (l) ® 5 H 2 O (g) ;
DH = – 285.8 + 57.3 = – 228.5 kJ
27. (b) For 5 moles of gas at temperature T, DH = 5 × 10.5 k cal = 52.5 kcal ........ (ii)
(i) + (ii),
PV1 = 5RTT
For 5 moles of gas at temperature T – 2, CuSO 4 (s) + 5 H 2 O (l) ¾
¾® CuSO 4 .5 H 2 O (s)
1 1 DH = – 28136 J mol -1
30. (a) H2 + X2 ¾ ¾® HX
2 2 = – 28.136 kJ mol -1
Let the bond enthalpy of X – X bond be x.
1 3
1 1 36. (d) N 2 (g) + F2 (g) ¾
¾® NF3 ; DH = – 113 kJ
DH f (HX ) = – 50 = DH H– H + DH X - X – DH H - X 2 2
2 2
3
1 1 -x or DH N º N + DH F- F – 3 DH N - F = – 113 kJ
= 2x + x – 2x = 2
2 2 2
Let x kJ mol-1 be the bond energy of F – F bond then
-1
x = 50 × 2 = 100 kJ mol bond energy of N º N bond = 6x
The difference (114.6 – 106) = 8.6 kJ mol-1 is used to 37. (b) DH N for strong base and strong acid
-1
effect of the ionisation of oxalic acid. = – 13.7 kcal eq
32. (a) After the event the energy remained in the body of the
DH ion (CH 3COOH )
1560
athlete =
2
= 780 kJ = – 12.5 – (– 13.7) = 1.2 kcal mol-1
Weight of water to be evaporated by 780 kJ of energy DH ion ( NH 4 OH)
18 = – 10.5 – (– 13.7) – D H ion (CH 3COOH )
= × 780 = 319.1 g
44 = 13.7 – 10.5 – 1.2
= 2 kcalmol -1
178 Chemistry
CHEMICAL EQUILIBRIUM : K f [ A ]a [ B ]b = K b [C ]c [ D ]d
When a reversible reaction is carried out in a closed vessel a
Kf [C ]c [ D ]d
stage reached when the speed of the forward reaction equals the = Kc =
speed of the backward reaction and chemical equilibrium is said Kb [A]a [B]b
to be established. Kc is called the equilibrium constant.
CHARACTERISTICS OF CHEMICAL EQUILIBRIUM : FACTORS INFLUENCING EQUILIBRIUM
(i) Equilibrium can be attained from either side. CONSTANT:
(ii) Equilibrium is dynamic in nature i.e. at equilibrium, reaction (i) The equilibrium constant is not influenced by :
does not stop. (1) Concentration of reactants and products.
(iii) At equilibrium there is no change in the concentration of (2) Presence of a catalyst.
various species. (3) Pressure.
(iv) The equilibrium state remains uneffected by the presence of (4) Presence of inert materials.
catalyst. Catalyst helps to attain the equilibrium state rapidly. (5) The direction from which the equilibrium state is reached.
180 Chemistry
(ii) The equilibrium constant is influenced by : RELATION BETWEEN Kc AND Kp FOR DIFFERENT
(A) Temperature : The variation of equilibrium constant is given TYPES OF REACTIONS :
by Van't Hoff equation.
(i) When Dn = 0, Kp = Kc e.g. for reaction A B.
(K p ) 2 DH æ T 2 - T1 ö [H2(g) + I2(g) 2HI(g)]
log = ç ÷
(K p ) 1 2.303R çè T1T 2 ÷ø
(ii) When Dn = +ve, Kp > Kc e.g. for reaction A 2B.
where DH = Enthalpy change , (K p ) 1 and (K p ) 2 = [PCl5(g) PCl3(g) +Cl2(g)]
Equilibrium Constant at temperature T1 & T2 (iii) When Dn = –ve, Kp < Kc e.g. for reaction 2A B.
R = Universal gas Constant
[N2(g) +3H2(g) 2NH3(g)]
For exothermic reaction : Kp decreases with increase of temperature
æ Kf ö THE UNITS OF Kp AND Kc :
since Kf decreases. çç K p = K ÷÷ (i) Unit of Kp = (atm)Dn
è bø
For endothermic reaction. Kp increases with increase of (ii) Unit of Kc = (mol lit–1)Dn
temperature since Kf increases. CHARACTERISTICS OF EQUILIBRIUM CONSTANT :
(B) The mode of representing the reaction :
1. It has definite value for every chemical reaction at a particular
The reaction A + B C + D may be written as temperature
C+D A+ B 2. The more is the value of Kc or Kp, the more is the completion
of reaction or the more is the concentration of products.
K f [C][D] 3. When the reaction can be expressed as sum of two other
Kc = =
K b [A][B] reactions, the Kc of overall reaction is equal to the product
of equilibrium constants of individual reactions.
K ' f [A][B] 1 Illustration :
K 'c = = \ Kc =
K 'b [C][D] K 'c If K1, K2 and K3 are the quilibrium constants for the reaction
(1), (2) and (3) respectively, then prove that K1×K2=K3.
(C) Stoichiometric representation of equation :
H2S HS– + H+ ...(1)
(I) N2 + 3H2 2NH3
HS– S– – + H+ ...(2)
[ NH 3 ]2
Kc = H2S S– – + 2H+ ...(3)
[ N 2 ][H 2 ]3
[HS- ][H + ] [S-- ][H + ]
1 3 Sol. K1 = K2 =
N2 + H2 NH3 [H 2S] [HS- ]
2 2
[ NH 3 ] [S - - ][H + ]2
K' c = On multiplying K1 ´ K 2 = = K3
1 3 [H 2S]
[N 2 ] 2 [H 2
2]
4. The equilibrium constant is independent of initial
\ K c = K 'c concentrations of reacting species.
5. Independent of presence of catalyst.
USE OF PARTIAL PRES SURE INS TEAD OF 6. Kc for backward reaction is inverse of Kc for forward
CONCENTRATIONS : reaction.
For gaseous reactin g substances partial pressures are 7. Kc changes with stoichiometric representation of
conveniently used since at any fixed temperature partial pressure reaction.
is directly proportional to concentration. For a general reaction Illustration :
aA + bB cC + dD For the reaction 2SO2 + O2 2SO3 the equilibrium
constant is 49. Find the equilibrium constant for
éPC ù ´ [ PD ]
c d
K p = ë ûa 1
O2
[ PA ] ´ [ PB ]b SO2 +
2
SO3.
where [SO 3 ]
Dn = [moles of products – moles of reactants] gaseous only. Kc = (II)
1
[SO 2 ][O 2 ] 2
Chemical Equilibrium 181
taking under root of (I) PCl5 PCl3 + Cl2
[SO 3 ] a
7= = Kc Initial molar Conc. 0 0
1
[SO 2 ][O 2 ] 2 V
ê 10 ú ê 10 ú
On solving we get K''p = 0.144 × 10–4 atm. ë û ë û
6. The vapour density of PCl5 when in equilibrium with its \ [O2] = 0.1 mole
dissociation products was found to be 90. Calculate its degree 2
of dissociation. Also calculate the dissociation constant of é2ù
ê10 ú
PCl5 at this temperature if the pressure is in atmosphere. ë û = 100 ;
(ii) 2
é 1 ù é O2 ù
31 + 177.5 ê 10 ú ê 10 ú
Sol. Theoretical density D = = 104.25 ë û ë û
2
Observed density d = 90 [O2] = 0.4 mole
10. 1 mole of N2 is mixed with 3 moles of H2 in a 4 litre container.
D-d 104.25 - 90 If 0.25% N2 is converted into NH3 according to the equilibrium
Degree of dissociation x = = = 0.158
d(n - 1) 90 N2 + 3 H2 2 NH3. Calculate Kc. What will be the value of
Kp can be calculated as PCl5 PCl3 + Cl2 K 'c for the given reaction.
1 – 0.158 0.158 0.158
Total moles = 1 – 0.158 + 0.158 + 0.158 = 1.158 1 3
N2 + H2 NH3
2 2
186 Chemistry
[SO 3 ][ NO] (1 + x )(1 + x ) when the volume of the container is doubled, the pressure of
Kc = = 16 ; = 16 N2O4 and NO2 shall be reduced to half
[SO 2 ][ NO 2 ] (1 - x )(1 - x)
N2O4 2NO2
3 0.14 0.55
x = = 0.6
5 (0.14 –x ) atm (0.55 + 2x) atm At new equilibrium
\ Concentration of NO = 1 + x = 1 + 0.6 = 1.6 mole
(0.55 + 2x ) 2
Concentration of NO2 = 1– x = 1– 0.6 = 0.4 mole. Kp = = 4.32
0.14 - x
12. Kc for PCl5 PCl3 + Cl2 is 0.04 at 25°C. How many moles
of PCl5 must be added to a 3 litre flask to obtain a Cl 2 of \ x = 0.045
concentration 0.15 M. Since temperature remains the same Kp will not change
Sol. At equil. No. of mole of Cl2 in 3L = 0.15×3 = 0.45 \. p = 0.14 - 0.045 = 0.095 atm
N 2O 4
PCl5 PCl3 + Cl2
x 0 0 Initial moles
and p NO2 = 0.55 + 2 ´ 0.045 = 0.64 atm
x – 0.45 0.45 0.45 Moles at eqb.
( x - 0.45) (0.45) (0.45) 16. The value of Kp at 298 K for the reaction
Molar conc. at eqb.
3 3 3 1/ 2 N 2 + 3/ 2 H 2 NH3
[ PCl 3 ][Cl 2 ] (0.15)(0.15) is found to be 826.0, partial pressures being measured in
Kc = =
[ PCl 5 ] ( x - 0.45) atmospheric units. Calculate DG ° at 298K
3
Sol. D G ° = -2.303 RTlogK p
\ x = 2.1 mole
13. The value of Kc is 0.50 for the reaction = -2.303 ´ 1.98 ´ 298 log 826 = -3980 calories
N2 + 3H2 2NH3 17. If 50% of CO2 converts to CO at the following equilibrium
at 400°C. Calculate the value of Kp for the given reaction at C (s) + CO2 (g) 2CO (g)
the same temperature (R = 0.0821 atm litre/ deg. mol) and the equilibrium pressure is 12 atm calculate Kp .
Chemical Equilibrium 187
18. The density of an equilibrium mixture of N2O4 and NO2 at 1 Sol. DG° = 2 ´ DG °f (N 2 ) + DG °f (O 2 ) - 2 ´ DG °f (N 2O)
atm and 348K is 1.84 g/c. Calculate Kc for the equilibrium
N2O4 (g) 2 NO2 (g) = (2 ´ 0 + 0) - 2 ´104.2 = -2.084 ´105 J / mol
Sol. N2O4 2 NO2 For gas phase reaction DG° is related to Kp as follows
1–x 2x
DG° = -2.303 RT log K p
92(1 - x) + 46 ´ 2x 92
Molecular wt of mixture = =
1+ x 1+ x
- 2.084 ´105 = -2.303 ´ 8.314 ´ 298 log K p
dRT
Further P =
M \ K p = 3.3 ´1036
188 Chemistry
Very Short/Short Answer Questions If a mixture of 0.482 mol N2 and 0.933 mol of O2 is
placed in a reaction vessel of volume 10L and allowed
1. In a reaction a + b c + d the change in enthalpy is –10 to form N2O at a temperature for which Kc = 2.0 × 10–37.
kcal. If heat is added to the system in which direction the Determine the composition of the reaction mixture.
reaction would proceed? (ii) Bromine monochloride, BrCl, decomposes into bromine
2. What is meant by the statement ‘Equilibrium is dynamic in and chlorine and reaches the equilibrium
nature’? Br2(g) + Cl2(g)
2BrCl(g)
3. A + B AB; K = 1 ´ 102 for which Kc = 32 at 500 K. If initially pure BrCl is present
at a concentration of 3.30 × 10–3 mol L–1; what is its
E + F EF; K = 1 ´ 10 -3 molar concentration in the mixture at equilibrium?
Out of AB and EF, which one is more stable AB or EF ? 13. (i) How much of 0.3 M ammonium hydroxide should be
4. Which will have CO2 to more extent, hot cold drink bottle or mixed with 30 mL of 0.2 M solution of ammonium
chilled cold drink bottle, why ? chloride to give buffer solution of pH 8.65 and 10?
5. Write the expression for equilibrium constant Kp, for the [pKb = 4.75]
reaction. (ii) How much volume of 0.1 M HAc should be added to
Fe3O4(s) + 4H2(g)
3Fe(s) + 4H2O(g) 50 mL of 0.2 M NaAc solution if we want to prepare a
buffer solution of pH 4.91. (pKa = 4.76)
6. In a reaction a + b c + d will addition of c to the system
change the value of K? Multiple Choice Questions
7. The equilibrium constant for a gas phase reaction is 14. Which of the following is not a general characteristic of
4 equilibria involving physical processes ?
[CS2 ][H 2 ]
Kc = (a) Equilibrium is possible only in a closed system at a
[CH 4 ][H 2S]2 given temperature.
Write the balanced chemical equation corres- ponding to (b) All measurable properties of the system remain
this expression. constant.
8. In a gaseous reaction a + b c + 2d, 3 mol of inert gas (c) All the physical processes stop at equilibrium.
is introduced into the vessel at constant pressure. What (d) The opposing processes occur at the same rate and
will be its effect on equilibrium? there is dynamic but stable condition.
9. For the reaction 2a c + d , the equilibrium constant is 15. A reaction is A + B C + D. Initially we start with
1.0 × 10–3 . At equilibrium, the concentrations observed were equal concentrations of A and B. At equilibrium we find that
[c] = 1.2 × 10–3 M, [d] = 3.8 × 10–6 M. the moles of C is two times of A. What is the equilibrium
What was [a] at equilibrium? constant of the reaction?
10. On the reaction 2NH3 (g) N (g) + 3H (g) 1 1
2 2
DH = + 93.6 kJ. Tell us what would be effect of (a) (b)
4 2
(a) temperature (c) 4 (d) 2
(b) pressure 16. In the two gaseous reactions (I) and (II), at 25°C
11. The equilibrium constant for the following reaction is 1.6 ×
105 at 1024 K (I) NO (g) + 1 2 O 2 (g ) NO2 (g), K1
2HBr(g)
H2(g) + Br2(g)
(II) 2NO2 (g) 2NO (g) + O2 (g), K2
Find the equilibrium pressure of all gases if 10.0 bar of HBr
is introduced into a sealed container at 1024 K. the equilibrium constants K1 and K2 are related as
1 K1
Long Answer Questions (a) K 2 = (b) K2 =
K1 2
12. (i) Reaction between nitrogen and oxygen takes place as
following: 1
(c) K 2 = (d) K 2 = K12
2N2O(g)
2N2(g) + O2(g) K12
Chemical Equilibrium 189
17. For the reversible reaction, 21. On increasing the pressure, in which direction will the gas
N2(g) + 3H2(g) 2NH3(g) at 500°C, the value of Kp is phase reaction proceed to re-establish equilibrium, is
predicted by applying the Le Chatelier’s principle. Consider
1.44 ´ 10 -5 when partial pressure is measured in the reaction.
atmospheres. The corresponding value of K C, with
concentration in mole litre–1, is N 2 (g) + 3H 2 (g) 2NH3 (g)
Which of the following is correct, if the total pressure at
1.44 ´10 -5 1.44 ´10 -5
(a) (b) which the equilibrium is established, is increased without
(0.082 ´ 500)- 2 (8.314 ´ 773)- 2 changing the temperature?
(a) K will remain same
1.44 ´10 -5 1.44 ´10 -5 (b) K will decrease
(c) (d)
(0.082 ´ 773)2 (0.082 ´ 773)-2 (c) K will increase
(d) K will increase initially and decrease when pressure is
2CO(g) , the partial
18. For the reaction C(s) + CO2 (g) very high
22. In which of the following reactions, the equilibrium remains
pressures of CO2 and CO are 2.0 and 4.0 atm respectively at
unaffected on addition of small amount of argon at constant
equilibrium. The Kp for the reaction is.
volume?
(a) 0.5 (b) 4.0
(a) H2 (g) + I2 (g) 2HI (g)
(c) 8.0 (d) 32.0
19. The reaction quotient (Q) for the reaction (b) PCl5 (g) PCl3 (g) + Cl2 (g)
N2 (g) + 3H2 (g) 2NH3 (g) (c) N2 (g) + 3H2 (g) 2NH3 (g)
(d) The equilibrium will remain unaffected in all the three
[NH 3 ]2 cases.
is given by Q = . The reaction will proceed from 23. Which of the following statements is incorrect?
[N 2 ][H 2 ]3 (a) In equilibrium mixture of ice and water kept in perfectly
right to left if insulated flask mass of ice and water does not change
(a) Q < Kc (b) Q > Kc with time.
(c) Q = 0 (d) Q = Kc (b) The intensity of red colour increases when oxalic acid
where Kc is the equilibrium constant. is added to a solution containing iron (III) nitrate and
potassium thiocyanate.
20. DG° for the reaction X + Y Z is –ve 4.606 kcal. The
(c) On addition of catalyst the equilibrium constant value
equilibrium constant for the reaction at 227°C is is not affected.
(a) 100 (b) 10 (d) Equilibrium constant for a reaction with negative DH
(c) 2 (d) 0.01 value decreases as the temperature increases.
1. Which is a reversible reaction? 3. A reaction attains equilibrium when the free energy change
(a) H 2 + I 2 ¾
¾® 2HI accompanying the reaction is
(a) positive and large
(b) H 2SO 4 + Ba (OH ) 2 ¾¾® BaSO 4 ¯ +2H 2 O
(b) zero
(c) NaCl + AgNO 3 ¾
¾® NaNO 3 + AgCl ¯ (c) negative and large
(d) negative and small
(d) 2KClO 3 ¾ ¾® 2 KCl + 3O 2 4. The equilibrium constant for the reversible reaction
2. The standard state Gibb's free energy change for the
N2 + 3H2 2NH3 is K and for the reaction
isomerisation reaction
cis-2-pentene trans-2-pentene is 1 N2 + 3 H 2 NH3, the equilibrium constant is K'.
–1
–3.67 kJ mol at 400 K. If more trans-2-pentene is added to 2 2
the reaction vessel K and K' will be related as
(a) more cis-2-pentene is formed
(a) K = K' (b) K' = K
(b) equilibrium shifts in the forward direction
(c) equilibrium remains unaltered (c) K = (d) K × K' = 1
K'
(d) more trans-2-pentene is produced
190 Chemistry
5. If K1 and K2 are respective equilibrium constants for the two 12. For a chemical reaction 2A + B C, the thermodynamic
reactions equilibrium constant Kp is
XeF6 (g) + H2O (g) XeOF4 (g) + 2HF (g) (a) in atm–2 (b) in atm–3
XeO4 (g) + XeF6 (g) (c) in atm –1 (d) dimensionless
XeOF4 (g) + XeO3F2 (g) 13. When two reactants, A and B are mixed to give products C
the equilibrium constant for the reaction and D, the reaction quotient Q, at the initial stage of the
reaction
XeO4 (g) + 2HF (g) XeO3F2 (g) + H2O (g)
(a) is zero (b) decreases with time
will be
(c) is independent of time (d) increases with time
K1
(a) (b) K1.K 2 14. In the equilibrium reaction involving the dissociation of
K 22 CaCO3
K1 K2 CaCO3 (s) CaO (s) + CO2 (g)
(c) (d)
K2 K1
the equilibrium constant is given by
6. A cylinder fitted with a movable piston contains liquid water
in equilibrium with water vapour at 25°C. Which operation p CaO ´ p CO 2 p CO 2
(a) (b) C CaO ´
result in a decrease in the equilibrium vapour pressure p CaCO3 C CaCO3
(a) Moving the piston downward a short distance
(b) Removing a small amount of vapour p CaO
(c) (d) p CO2
(c) Removing a small amount of the liquid water pCaCO3
(d) Dissolving salt in the water 15. Steam reacts with iron at high temperature to give hydrogen
7. The volume of the reaction vessel containing an equilibrium gas and Fe3O4 (s). The correct expression for the equilibrium
mixture in the reaction constant is
SO2Cl2 (g) SO2 (g) + Cl2 (g)
is increased when the equilibrium is re-established PH2 (PH 2 ) 4
2
(a) (b)
(a) The amount of SO2 (g) will decrease PH2 O
2
(PH 2O ) 4
(b) The amount of SO2Cl2 (g) will increase
(c) The amount of Cl2 (g) will increase
(d) The amount of Cl2 (g) will remain unchanged (PH 2 ) 4 [Fe 3O 4 ] [Fe3O 4 ]
(c) (d)
8. In gaseous equilibrium the correct relation between Kc and 4
(PH 2O ) [Fe] [Fe]
Kp is
16. In lime kiln, the reversible reaction
(a) K c = K p ( RT) Dn (b) K p = K c ( RT) Dn
CaCO3 (s) CaO (s) + CO2 (g)
Kc Kp proceeds to completion because
(c) = ( K p ) Dn (d) = ( K c ) Dn
RT RT (a) of high temperature (b) CO2 escaped out
9. In which of the following reaction Kp > Kc (c) CaO is removed (d) of low temperature
(a) N2 + 3H2 2NH3 (b) H2 + I2 2HI 17. If 1.0 mole of I2 is introduced into 1.0 litre flask at
(c) PCl3 + Cl2 PCl5 (d) 2SO3 O2 + 2SO2 1000 K, at quilibrium (Kc = 10–6), which one is correct
(a) [I2 (g)] > [I– (g)] (b) [I2 (g)] < [I– (g)]
10. For reaction PCl3 (g) + Cl2 (g) PCl5 (g), the value of
Kc at 250°C is 26 mol–1 litre1. The value of Kp at this 1 -
(c) [I2 (g)] = [I– (g)] (d) [I2 (g)] = [I (g )]
temperature will be 2
(a) 0.61 atm–1 (b) 0.57 atm–1 18. At equilibrium, if Kp = 1, then
(c) 0.83 atm –1 (d) 0.46 atm–1 (a) DG° = 0 (b) DG ° > 1
11. The equilibrium constant for the reaction,
(c) DG ° < 1 (d) None of these
N2 (g) + O2 (g) 2NO (g)
–4
19. Van't Hoff's equation giving the effect of temperature on
is 4 × 10 at 2000 K.
chemical equilibrium is represented as
In presence of a catalyst, equilibrium is attained ten times
faster. Therefore, the equilibrium constant, in presence of the d ln F DH d ln K p DHT 2
(a) = (b) =
catalyst, at 2000 K is dT RT 2 dT R
(a) 40 × 10–4
(b) 4 × 10–4 d ln K p DH d ln K p RT 2
(c) 4 × 10–3 (c) =
2 (d) =
dT RT dT DH
(d) difficult to compute without more data
Chemical Equilibrium 191
20. Solubility of a substance which dissolves with a decrease in 28. If the equilibrium constant for the reaction
volume and absorption of heat will be favoured by 2AB A2 + B2
(a) high P and high T (b) low P and low T
(c) high P and low T (d) low P and high T is 49, what is the value of equilibrium constant for
21. In what manner will increase of pressure affect the following 1 1
equation? AB A 2 + B2 ?
2 2
C (s) + H2O (g) CO (g) + H2 (g) (a) 49 (b) 2401
(a) Shift in the forward direction (c) 7 (d) 0.02
(b) Shift in the reverse direction
(c) Increase in the yield of hydrogen 29. The reaction, SO 2 + Cl 2 ¾
¾® SO 2 Cl 2 is exothermic and
(d) No effect reversible. A mixture of SO2 (g), Cl2 (g) and SO2Cl2 (l) is at
22. In a reaction, A + 2B 2C, 2.0 mole of 'A', 3.0 mole of 'B' equilibrium in a closed container. Now a certain quantity of
and 2.0 mole of 'C' are placed in a 2.0 L flask and the equilibrium extra SO2 is introduced into the container, the volume
concentration of 'C' is 0.5 mole/L. The equilibrium constant remaining the same. Which of the following is/are true?
(K) for the reaction is (a) The pressure inside the container will not change
(a) 0.073 (b) 0.147 (b) The temperature will not change
(c) 0.05 (d) 0.026 (c) The temperature will increase
23. 4.5 moles each of hydrogen and iodine were heated in a (d) The temperature will decrease
sealed ten litre vessel. At equilibrium 3 moles of HI were
30. The rate of forward reaction is two times that of the reverse
found. The equilibrium constant of
reaction at a given temperature and identical concentration.
H2 (g) + I2 (g) 2HI (g) is Kequilibrium is
(a) 1 (b) 10 (a) 0.5 (b) 1.5
(c) 5 (d) 0.33 (c) 2.5 (d) 2.0
24. A reaction is A + B C + D. Initially we start with 31. 1 mole of hydrogen and 2 moles of iodine are taken initially in
equal concentrations of A and B. At equilibrium we find that a 2 litre vessel. The number of moles of hydrogen at
the moles of C is two times of A. What is the equilibrium equilibrium is 0.2. Then the number of moles of iodine and
constant of the reaction? hydrogen iodide at equilibrium are
(a) 1.2, 1.6 (b) 1.8, 1.0
1 1
(a) (b) (c) 0.4, 2.4 (d) 0.8, 2.0
4 2
(c) 4 (d) 2 32. For the reaction PCl5 (g) PCl3 (g) + Cl2 (g) the forward
25. In which of the following, the forward reaction is favoured reaction at constant temperature is favoured by
by use of high pressure? (a) introducing an inert gas at constant volume
(a) H2 + I2 2HI (b) introducing PCl3 (g) at constant volume
(b) N2 + O2 2NO (c) introducing PCl5 (g) at constant volume
(d) introducing Cl2 (g) at constant volume
(c) 2NH3 N2 + 3H2
33. For the chemical reaction :
(d) 2SO2 + O2 2SO3 3X (g) + Y (g) X3Y (g)
26. In a reaction A + B C + D, the initial concentrations, the amount of X3Y at equilibrium is affected by
of A and B were 0.9 mol. dm–3 each. At equilibrium the (a) temperature and pressure
concentration of D was found to be 0.6 mol dm –3. What is (b) pressure only
the value of equilibrium constant for the reaction (c) temperature only
(a) 8 (b) 4 (c) 9 (d) 3
(d) temperature, pressure and catalyst
27. On the basis of Le-Chatelier's principle, predict which of the
34. When 3 mole of reactant A and one mole of the reactant B are
following conditions would be unfavourable for the formation
of SO3? Given that mixed in a vessel of volume 1 litre, the following reaction
takes place
2SO2 + O2 2SO3; DH = –42 kcal
A (g) + B (g) 2C (g)
(a) Low pressure and low temperature
(b) High pressure and low temperature If 1.5 mole of C is formed at equilibrium, the equilibrium
(c) High temperature and low pressure constant (Kc) of the reaction is
(d) High concentration of SO2 (a) 0.12 (b) 0.50 (c)0.25 (d) 4.00
192 Chemistry
35. Kc for the reaction 42. 8 mole of a gas AB3 are introduced into a 1.0 dm3 vessel. It
N2 (g) + O2 (g) 2NO (g) dissociates as, 2AB3 (g) A2 (g) + 3B2 (g). At
–6
at 300 K is 4.0 × 10 . Kp for the above reaction will be equilibrium, 2 mole of A2 are found to be present. The
(R = 2 cal mol–1 K–1) equilibrium constant of reaction is .... in mol2L–2
(a) 2.4 × 10–3 (b) 4 × 10–6 (a) 2 (b) 3
–6
(c) 4 × 10 (RT) 2 (d) 16 × 10–12
(c) 27 (d) 36
36. Which of the following equilibria will shift to right side on
increasing the temperature? 43. DG° for the reaction X + Y Z is –ve 4.606 kcal. The
(a) CO (g) + H2O (g) CO2 (g) + H2 (g) equilibrium constant for the reaction at 227°C is
(b) 2SO2(g) + O2 (g) 2SO3 (g) (a) 100 (b) 10
(c) 2 (d) 0.01
(c) H2O (g) H2 (g) + 1 2 O 2 (g ) 44. The partial pressure of CH3OH (g), CO (g) and H2 (g) in
(d) 4HCl (g) + O2 (g) 2H2O (g) + 2Cl2 (g) equilibrium mixture for the reaction,
37. 1 mole of N2 and 2 moles of H2 are allowed to react in a 1 dm3 CO (g) + 2H2 (g) CH3OH (g) are 2.0, 1.0 and 0.1 atm
vessel. At equilibrium 0.8 mole of NH3 is formed. The respectively at 427°C. The value of Kp for the decomposition
concentration of H2 in the vessel is of CH3OH to CO and H2 is
(a) 0.6 mole (b) 0.8 mole
(a) 102 atm (b) 2 × 102 atm–1
(c) 0.2 mole (d) 0.4 mole 2
(c) 50 atm (d) 5 × 10–3 atm2
38. The equilibrium
45. Which of the following is not affected by pressure change?
SO2Cl2 (g) SO2 (g) + Cl2 (g)
is attained at 25°C in a closed container and an inert gas, (a) 2NO2 (g) N2O4 (g)
helium is introduced. Which of the following statement is (b) CO2 (g) + H2O (l) CO2 solution
correct?
(c) H2 (g) + I2 (g) 2HI (g)
(a) More chlorine is formed
(b) Concentration of SO2 is reduced (d) 2O3 (g) 3O2 (g)
(c) More SO2Cl2 is formed 46. The degree of dissociation of dinitrogen tetroxide
(d) Concentration of SO2Cl2, SO2 and Cl2 do not change
39. For which reaction high pressure and high temperature is ¾® 2 NO 2 (g ) at temperature T and total
N 2 O 4 (g ) ¾
helpful in obtaining a high equilibrium yield pressure P is a. Which one of the following is the correct
(a) 2NF3(g) N2(g) + 3F2(g) – 54.40 kcal expression for the equilibrium constant (Kp) at this temperature?
(b) N2(g) + 3H2(g) 2NH3(g) + 22.08 kcal 2a a 2P
(a) (b)
(c) Cl2(g) + 2O2(g) 2ClO2(g) – 49.40 kcal (1 - a 2 ) 1- a
(d) 2Cl2O7 (g) 2Cl2 (g) + 7O2(g) + 126.8 kcal
40. For the reversible reaction 4a 2 4a 2 P
(c) (d)
N2 (g) + 3H2 (g) 2NH3 (g) (1 - a 2 ) (1 - a 2 )
at 500°C, the value of Kp is 1.44 × 10–5 when partial pressure
47. Calculate the degree of dissociation of PCl5, the density at
is measured in atmospheres. The corresponding value of Kc
230°C is 70
with concentration in mole litre–1, is
(a) 97.8% (b) 48.9%
(a) 1.44 × 10–5 / (0.082 × 500)–2
(b) 1.44 × 10–5 / (8.314 × 773)–2 (c) 4.89% (d) 24.45%
(c) 1.44 × 10–5 / (0.082 × 773)2 48. When heated to 100°C the V.D. of N 2 O 4 becomes
(d) 1.44 × 10–5 / (0.082 × 773)–2 24.5. The degree of dissociation of N2O4 at this temp. will be
41. A 1 M solution of glucose reaches dissociation equilibrium (a) 80% (b) 87.74%
according to the equation given below (c) 40.34% (d) 60%
6HCHO C6H12O6 49. The correct relationship between free energy change in a
What is the concentration of HCHO at equilibrium if reaction and the corresponding equilibrium constant Kc is
equilibrium constant is 6 × 1022 (a) DG = RT ln K c (b) - DG = RT ln K c
(a) 1.6 × 10–8 M (b) 3.2 × 10 –6 M
–4
(c) DG° = RT ln K c (d) - DG° = RT ln K c
(c) 3.2 × 10 M (d) 1.6 × 10–4 M
Chemical Equilibrium 193
50. The reaction quotient (Q) for the reaction 51. In Haber process 30 litres of dihydrogen and 30 litres of
N2 (g) + 3H2 (g) 2NH3 (g) dinitrogen were taken for reaction which yielded only 50%
of the expected product. What will be the composition of
[ NH 3 ]2 gaseous mixture under the aforesaid conditions in the end?
is given by Q = . The reaction will proceed from
[ N 2 ][H 2 ]3 (a) 10 litres of ammonia, 25 litres nitrogen, 15 litres hydrogen
(b) 20 litres ammonia, 10 litres nitrogen, 30 litres hydrogen
right to left if
(a) Q < Kc (b) Q > Kc (c) 20 litres ammonia, 25 litres nitrogen, 15 litres hydrogen
(c) Q = 0 (d) Q = Kc (d) 20 litres ammonia, 20 litres nitrogen, 20 litres hydrogen
where Kc is the equilibrium constant.
1. The following equilibrium constants are given: 4. The value of equilibrium constant of the reaction
1 1
2NH3 ; K1
N 2 + 3H 2 [CBSE-PMT 2003, 2007] HI ( g ) H 2 ( g ) + I 2 is 8.0 [CBSE-PMT 2008]
2 2
The equilibrium constant of the reaction
2NO; K 2
N 2 + O2
H 2 ( g ) + I2 ( g ) 2HI( g ) will be:
1
H 2 O; K 2
H 2 + O 2 1 1 1
2 (a) (b) (c) 16 (d)
16 64 8
The equilibrium constant for the oxidation of NH3 by oxygen 5. In which of the following equilibrium Kc and Kp are not equal?
to give NO is
(a) 2 NO(g ) N 2 (g ) + O 2 (g ) [CBSE-PMT 2010]
K 2 K32 K 22 K3 (b) SO 2 (g )+NO 2 (g ) SO3 (g ) + NO(g )
(a) (b)
K1 K1
(c) H 2 (g )+I2 (g ) 2 HI(g )
21. The equilibrium constants K p and K p2 for the reactions (a) K1 K 2 = K3 (b) K 2 K3 = K1
1
1. The decomposition of N2O4 to NO2 is carried out at 280 K in 6. For the reaction H2(g)+I2(g) 2HI(g) at 721 K, the value
chloroform. When equilibrium has been established, 0.2 mol of equilibrium constant is 50, when equilibrium concentration
of N2O4 and 2 ´ 10 -3 mol of NO2 are present in a 2l solution. of both is 5M. Value of Kp under the same conditions will be
(a) 0.02 (b) 0.2
The equilibrium constant for the reaction, N2O4 2NO2 is
(c) 50 (d) 50 RT
(a) 1 × 10–2 (b) 2 × 10–3 7. For which one of the following systems at equilibrium, at
(c) 1 × 10–5 (d) 2 × 10–5 constant temperature will the doubling of the volume cause
2. In an equilibrium reaction for which DG° = 0 , the equilibrium a shift to the right?
constant, K , should be equal to (a) H2(g)+Cl2(g) 2HCl(g)
(b) 2CO(g)+O2 (g) 2CO2(g)
(a) 0 (b) 1
(c) N2(g)+3H2(g) 2NH3(g)
(c) 2 (d) 10
3. The pressure change due to which equilibrium is not (d) PCl5 ( g ) PCl3 ( g ) + Cl 2 ( g )
affected is 8. For the reaction C(s)+CO2(g) 2CO(g) , the partial
(a) N 2 ( g ) + O2 ( g ) 2NO ( g ) pressures of CO2 and CO are 2.0 and 4.0 atm respectively at
equilibrium. The Kp for the reaction is.
(b) 2SO2(g)+O 2(g) 2SO3(g) (a) 0.5 (b) 4.0
(c) 8.0 (d) 32.0
(c) 2O3(g) 3O2(g) 9. In a chemical reaction calculate rate constant of backward
reaction when the rate constant of forward reaction is 20 and
(d) 2NO2(g) N2O4(g)
the equilibrium constant is 50
4. A reversible chemical reaction having two reactants in (a) (0.2) (b) (0.1)
equilibrium. If the concentration of the reactants are doubled (c) (0.4) (d) None of these
then the equilibrium constant will 10. The rate constant is given by the equation K=PZe–E/RT.
(a) be doubled (b) be halved Which factor should register a decrease for the reaction to
proceed more rapidly?
(c) become one-fourth (d) remain same (a) T (b) Z
5. 3.2 moles of hydrogen iodide were heated in a sealed bulb at (c) E (d) P
444°C till the equilibrium state was reached. Its degree of 11. For the reaction CO(g) + H2O(g) CO2(g) + H2(g) at a
dissociation at this temperature was found to be 22% The given temperature the equilibrium amount of CO2(g) can be
number of moles of hydrogen iodide present at equilibrium increased by
are (a) adding a suitable catalyst
(a) 2.496 (b) 1.87 (b) adding an inert gas
(c) decreasing the volume of the container
(c) 2 (d) 4 (d) increasing the amount of CO(g).
196 Chemistry
12. At constant temperature, the equilibrium constant (Kp) for 18. By which of the following reactions, the equilibrium constant
the decomposition reaction N2O4 2NO2 is expressed is related to tempearture?
2 2
by Kp = (4x P)/(1-x ), where P = pressure, x = extent of DH º T2 æ1ö
decomposition. Which one of the following statements is (a) ln K 2 - ln K1 = dç ÷
R T1 èTø
true?
(a) Kp increases with increase of P DHº 1/ T 2 æ 1 ö
(b) ln K 2 - ln K 1 = - d
(b) Kp increases with increase of x R 1/ T1 çè T 2 ÷ø
(c) Kp increases with decrease of x
DH º T2 æ 1 ö
(d) Kp remains constant with change in P and x (c) ln K 2 - ln K1 = - dç ÷
13. Consider the following equilibrium in a closed container R T1 è T ø
N2O4(g) 2NO2(g) At a fixed temperature, the volume DHº 1/ T1 æ 1 ö
(d) ln K 2 - ln K 1 = - d
of the reaction container is halved. For this change, which of R 1/ T 2 çè T ÷ø
the following statements holds true regarding the equilibrium 19. Which of the following expressions is incorrect?
constant (Kp) and degree of dissociation ( a )?
(a) Kp does not changes, but a changes æ ln K p ö æ ln K c ö
(b) Kp changes, but a does not change (a) çç p ÷ø
÷ =0 (b) çç p
÷÷ = 0
è T è øT
(c) both Kp and a change
(d) neither Kp nor a changes æ ln K x ö - Dn
14. Which of the following is true at chemical equilibrium? (c) çç p
÷÷ =
( p / pº ) (d) All of these
è øT
(a) (DG)T, P is minimum and (DS)U,V is also minimum
20. K c for PCl5 (g) PCl3 (g) + Cl 2 (g) is 0.04 at 250°C.
(b) (DG)T,V is minimum and (DS)U,V is maximum
(c) (DG)T,V is maximum and (DS)U,V is zero How many moles of PCl 5 must be added to a 3 L flask to
(d) (DG)T,P is zero and (DS)U,V is also zero obtain a Cl 2 concentration of 0.15 M
15. For the reaction A(g) B(g)+C(g), (a) 4.2 moles (b) 2.1 moles
(a) Kp = a p3 (b) Kp = a2(Kp+p+1) (c) 5.5 moles (d) 6.3 moles
æ Kp + p ö 21. If CuSO 4 .5H 2O (s) CuSO 4 .3H2O(s) + 2H 2O(g)
(c) Kp = a2(Kp+p) (d) K p = a 2 çç ÷
÷
è p ø K p = 1 .086 ´ 10 - 4 atm 2 at 25° C. The eflorecent nature of
16. In the van’t Hoff equation CuSO 4 . 5H 2O can be noticed when the vapour pressure of
d1nK DHº H 2 O in atmosphere is
=
dT RT 2 (a) > 9.72 mm (b) < 7.92 mm
(c) < 7.92 mm (d) < 11.92 mm
(a) when dln K < 0 , the reaction is exothermic 22. In a closed system, A(s) 2B(g) + 3C(g), if partial pressure
dT of C is doubled, then partial pressure of B will be
(a) 2 2 times the original value
(b) when dln K < 0 , the reaction is endothermic
dT 1
(b) times the original value
(c) the slope of the graph is positive throughout 2
(d) the slope of graph increases and then decreases (c) 2 times the original value
17. Consider the expression DG = –RTlnKp+RTlnQp and indicate 1
the correct statement at equilibrium (d) times the original value
2 2
(a) DG = 0, Qp> Kp the equilibrium reaction will shift
from left to right 23. For the reactions
(b) DG = 0, Qp=Kp the equilibrium reaction will shift A B Kc =2
from left to right B C Kc =4
(c) DG = ¥,Qp<Kp the equilibrium reaction will shift
C D Kc =6
from right to left
(d) DG<0, Qp>Kp the equilibrium reaction will shift K c for the reaction A D is
from right to left
2´ 4
where Qp and Kp term refer to reaction quotient and (a) 2 × 4 × 6 (b)
6
equilibrium constant at constant pressure respectively.
4´ 6
(c) 2 + 4 + 6 (d)
2
Chemical Equilibrium 197
29. For the equilibrium reaction
24. 1 mol of N 2 and 3 mol of H 2 are placed in a closed container
2NOBr(g) 2NO(g) + Br2 (g)
at a pressure of 4 atm. The pressure falls to 3 atm at the same
temperature when the following equilibrium is attained P
If PBr2 = , where P is total pressure at equilibrium. The
N 2 (g) + 3H 2 (g ) 2 NH 3 (g ) . 9
Kp
The K p for the dissociation of NH 3 is ratio is equal to
P
3´3 1 1
(a) atm - 2 (b) 0.5 ´ (1.5) 3 atm 2 (a) (b)
0.5 ´ (1.5) 3 3 81
1 1
(c) (d)
0.5 ´ (1.5) 3 (1.5) 3 9 27
(c) atm 2 (d) atm - 2
3´3 0.5 30. Equilibrium constant for the reaction
25. The reactions NH 4 OH (aq) + H + (aq) NH +4 (aq) + H 2 O ( l )
PCl5 (g) PCl3 (g) + Cl 2 (g) and is 1.8 × 10 9 . Hence equilibrium constant for ionisation
COCl 2 (g ) CO(g) + Cl 2 (g) NH 3 + H 2 O NH+4 (aq) + OH- (aq) is
are simultaneously in equilibrium in a vessel at constant (a) 1.80 ´ 10 - 9 (b) 1.80 ´ 10 5
volume. If some CO is introduced into the vessel then at the
new equilibrium (c) 1.80 ´ 10 - 5 (d) 5.55 ´ 10 -10
31. The degree of dissociation of PCl5 (a) obeying the
(a) Cl 2 is greater
equilibrium PCl 5 PCl 3 + Cl 2 is related to the
(b) PCl 5 is less equilibrium pressure by
(c) PCl 3 remain unchanged 1 1
(a) a µ (b) a µ
(d) PCl 5 is greater P4 P
The instability constant of the complex is 33. I - ions react with iodine in aqueous solution to form I3- ion
as
(a) 2.0 ´ 10 - 8 (b) 5.0 ´ 10 9
I - (aq) + I 2 (aq) I3- (aq).
(c) 2.0 ´ 10 - 4 (d) 2.0 ´ 10 4 When L of solution containing 1 mol of KI and 0.25 mol of
I 2 was reacted with excess of AgNO 3 , 0.80 mol of yellow
27. The equilibrium constant for a reaction is 1´ 10 20 at 300 K.
The standard free energy change for the reaction is ppt. was obtained. The stability constant of I3- ion is
(a) + 115 KJ (b) + 166 KJ (a) 0.20 (b) 5.0
(c) – 115 KJ (d) – 166 KJ (c) 20.0 (d) 0.05
34. A reaction A + 2B 2 C + D was studied using the initial
28. At temperature T K, PCl 5 is 50% dissociated at an concentrations of B which was 1.5 times that of A. At the
equilibrium pressure of 4 atm. At what pressure it would quilibrium, concentration of A and C were found to be equal.
dissociate to 80% at the same temperature Then K c for the equilibrium is
(a) 0.75 atm (b) 0.50 atm (a) 8 (b) 4
(c) 0.60 atm (d) 2.50 atm (c) 6 (d) 0.32
198 Chemistry
35. 1.0 mol of AB5 (g) is placed in a closed container under one 41. When the reactants A and B are mixed to give products C
and D, the reaction quotient Q at the initial stage of reaction
atmosphere and at 300K. It is heated to 600K, when 20% by
is
mass of it dissociates as
(a) zero (b) independent of time
AB5 (g) ¾ ¾® AB(g) + 2 B2 (g). (c) increases with time (d) decreases with time
The resultant pressure is 42. The eqilibrium constant for the reaction
(a) 1.2 atm (b) 2.4 atm CO(g) + 2H 2 (g) CH 3OH(g)
(c) 1.4 atm (d) 2.8 atm is 4.3 at 250° C and 1.8 at 275° C. The reaction is
36. The pressure necessary to obtain 50% dissociation of PCl 5 (a) exothermic (b) endothermic
(c) Both (a) and (b) (d) Neither (a) nor (b)
at 250°C is numerically equal to
43. The element Bi melts at 271°C and has density of 9.73 g/ml
(a) three times of K p (b) 6 times of K p as a solid and 10.05 g/ml as a liquid at this temperature. For
(c) 2.5 times of K p (d) 8 times of K p the equilibrium Bi(s) Bi( l ), the melting point is
favoured in this endothermic reaction either by
37. The activation energies for the forward and reverse reactions (a) increasing temperature, decreasing pressure
in the system A B are 10.303 and 8.000 kcal respectively (b) decreasing temperature, decreasing pressure
at 500 K. Assuming that pre exponential factor to be same for (c) increasing temperature, increasing pressure
both the forward and the reverse steps and R = 2 cal K–1 mol– (d) there is no effect of pressure on melting point
1. Calculate the K of the reaction 44. Consider the gaseous equilibrium of
c
(a) 1.00 (b) 10.0 H 2 (g) + I 2 (g) 2HI (g)
(c) 0.1 (d) 100 In the following graphs the three gases are at equilibrium in
38. 28g N 2 and 6.0 g of H 2 are heated over catalyst in a closed a container. At some time t, extra I 2 is added. Which of the
one litre flask of 450°C. The entire equilibrium mixture following sets will respond to this situation ?
required 500 ml of 1.0 M H 2SO 4 for neutralisation. The value
HI HI
of K c for the reaction
N 2 (g) + 3H 2 (g ) 2 NH 3 (g) is P I2 P I2
H2 H2
(a) 0.06 mol -2 L2 (b) 0.59 mol -2 L2
t t
(c) 1.69 mol 2 L-2 (d) 0.03 mol 2 L-2
A B
39. 2 mol of SO 2 and 1 mol of O 2 are heated in a closed vessel
to reach the equilibrium
HI HI
2 SO 2 (g) + O 2 (g) 2 SO 3
The equilibrium mixture exerted a presure of 5 atm and required P I2 P I2
1/3 mol of K 2Cr2 O 7 in acidic medium. K p for the reaction H2 H2
is t
(a) 1.0 (b) 2.0 t
(c) 0.5 (d) 4.0 C D
40. A gaseous compound of molecular mass 82.1 dissociates on (a) A (b) B
heating to 400 K as (c) C (d) D
X 2 Y4 (g) X 2 (g) + 2 Y2 (g)
The density of the equilibrium mixture at a pressure of 1 atm
and temperature of 400K is 2.0gL-1 . The percentage
dissociation of the compound is
(a) 12.5% (b) 48.5%
(c) 90.1% (d) 25.0%
Chemical Equilibrium 199
( pH ) [Fe and Fe O are solids] 14. (d) Kp = pCO2 others are solids. The concentration terms for
4
2
5. Kp = solids and liquids are taken as unity.
( pH O )
4 3 4
2 15. (b) 3Fe(s) + 4H2O (steam) Fe3O4 (s) + 4 H2 (g)
6. No, K remains constant. (p H 2 ) 4
7. CH4(g) + 2H2S(g) ® 4H2(g) + CS2(g) Kp = (p 4 only gaseous products and reactants.
H 2O )
9. 4.56 × 10–6 mol2/l2
10. (a) Increase in temperature would favour the forward 16. (b) Forward reaction is favoured by removal of products.
reaction while decrease in temperature would favour 17. (a) I2 2I–
the backward reaction. 1–x 2x
(b) Increase in pressure favours the reaction towards less
number of moles of gaseous species. (2x ) 2
Kc = = 10 -6
11. pH = pBr = 2.5 × 10–2 bar (1 - x)
2 2
pHBr = 10.0 – 5.0 × 10–2
Soln. shows that (1 – x) > 2x \ éë I2 ( g ) ùû > éë I ( g ) ùû
-
» 10.0 bar
14. (c) 15. (c) 16. (c) 17. (d) 18. (c)
18. (a) DG° = –2.303 RT log Kpwhen Kp = 1, DG° = 0 since log 1 = 0
19. (b) 20. (a) 21. (a) 22. (d) 23. (b)
d ln K p DH
EXERCISE 2 19. (c) Van't Hoff's Isochore = . Relation between
dt RT 2
1. (a) The product is separated as solid or escapes as gas in an
T and Kc.
irreversible reaction.
20. (a) See Le Chatelier's principle.
2. (a) Le Chatelier's principle, equilibrium shifted in the
21. (b) Reverse reaction, Le Chatelier's principle Dn=2 – 1 = 1.
backward direction.
3. (b) DG = 0 at equilibrium. 22. (c) A + 2B 2C
Initial moles in 2 litres 2 3 2
4. (b) K ' = K
At Equilibrium moles in 2 litres 2.5 4 1
5. (d) Reaction (II) and reverse of reaction (I) gives the desired Molar conc. moles in 2 litres 1.25 2 0.5
1 K (0.5) 2
reaction hence K = K 2 ´ = 2 . Kc = = 0.05
K1 K1
(1.25)(2) 2
6. (d) Dissolution of salt lowers the V.P. It is also effected by
temperature. 23. (a) H2 + I2 2HI
7. (c) It will decrease the concentration. The equilibrium will Initial moles 4.5 4.5 0
shift in the direction where more moles are formed to Moles at eqm. 3 3 3
keep Kc constant.
(3) 2
8. (b) Relation is Kp = Kc (RT)Dn K= = 1 . Note : when there is no change in the
3´ 3
9. (d) Dn = 3 – 2 = 1; Kp = Kc (RT) hence Kp > Kc
number of moles, Dn = 0 the volume or capacity of vessel
10. (a) Q Dn = –1 \ Kp = 26 × (0.0821 × 523)–1 = 0.61 atm–1
can be ignored.
200 Chemistry
24. (c) A+ B C +D 41. (d) C6H12O6 6HCHO
At eqb. x x 2x 2x Initial 1M
At eqb. 1–x 6x
2x.2x
Kc = =4
x.x [6x]6 1- x
Kc = for reverse reaction = 6 ´ 10 22 ;
1- x 6
(6 x )
25. (d) See Le Chatelier's principle.
On solving 6x = 1.6 × 10–4 M.
26. (b) A+ B C + D
42. (c) 2AB3 A2 (g) + 3B2 (g)
Initial 0.9 0.9 0 0
Initial moles 8 0 0
At eqm. 0.3 0.3 0.6 0.6
Moles at eqb. 8–x x 3x
2 2
0.6 ´ 0.6
Kc = =4
0.3 ´ 0.3 [B2 ]3[A 2 ] (6)3 ´ 2
given x 2 = 2 \ x = 4 Kc= = = 27
27. (c) Le Chatelier's principle since reaction is exothermic hence [AB3 ]2 (4)2
low temperature will favour forward reaction also volume
is decreased by applying high pressure. 43. (a) DGo = – 2.303 RT log K
– 4.606 × 103 = – 2.303 × 2 × 500 log Kc
28. (c) Reaction (II) is 1 2 of (I). \ K = K = 49 = 7 . \ Kc = 100.
29. (c) By addition of SO2 equilibrium will shift to RHS which is p CH 3OH 2
44. (d) K p = = = 200 ;
exothermic. Hence temperature will increase. p CO ´ p H 2 1 ´ (0.1) 2
Kf 2
30. (d) Keqb = = =2 1 1
Kb 1 For reverse reaction = = 5 ´10 -3 atm 2
K p 200
31. (a) H2 + I2 2HI
45. (c) No effect of pressure when Dn = 0.
Initial 1 2 0
46. (d) N2O4 2NO2
At eqb. 0.2 2 – 0.8 = 1.2 2 × 0.8 = 1.6
1–a 2a
32. (c) Le Chatelier's principle.
Total moles at eqb=1 – a + 2a = 1 + a
33. (a) Temperature and pressure (Le Chatelier's principle)
2
Dn ¹ 0 . æ 2a ö
p 2NO ç .P ÷
1+ a ø 4a 2 P
34. (d) A + B 2C Kc = 2
=è =
p N 2O 4 1- a 1- a2
.P
Initial moles 3 1 0 1+ a
At eqb. 3 – 0.75 1 – 0.75 1.5 47. (b) Degree of dissociation
(1.5) 2 D-d 104.25 - 70 M
Kc = =4 a= = = 48.9% (D = )
(2.25)(0.25) d(n - 1) 70(2 – 1) 2
Kc =
[ AB]2 [ B2 ] or K = (2 x)2 ´ x æ ö
PZ = ç .P
è 1 + ÷ø 1
c
[AB2 ]2 {2(1 - x )}2
PT1 1 é K P1 1 ù
20. (c) SO3(g) SO 2 (g ) +
1
O 2 (g) or = êQ = given ú
2 PT2 9 ëê K P2 9 úû
[SO 2 ] [O 2 ]½
KC = = 4.9 ´10 -2 ; PT1 1
[SO 3 ] or = or 1 : 36
PT2 36
On taking the square of the above reaction
[SO 2 ]2 [O 2 ] i.e., (b) is the correct answer.
= 24.01´10 - 4 22. (c) Reaction (c) can be obtained by adding reactions (a)
2
[SO 3 ] and (b) therefore K3 = K1. K2
Now K'C for 2SO2(g) + O2(g) 2SO3 Hence (c) is the correct answer.
[SO 3 ]2 1 23. (a) 2CO
CO2 + C(graphite)
= = = 416
[SO 2 ]2 [O 2 ] 24.01´10 - 4 Pinitial 0.5atm 0
21. (b) Let the initial moles of X be ‘a’ and that of Z be ‘b’ then Pfinal (0.5 – x)atm 2 x atm
for the given reactions, we have Total P at equilibrium = 0.5 – x + 2x = 0.5 + x atm
0.8 = 0.5 + x
X
2Y \ x = 0.8 – 0.5 = 0.3 atm
Initial a moles 0 Now Kp = (PCO ) /PCO
2
2
At equi a(1 – a) 2aa
2
(moles) (2 ´ 0.3) (0.6) 2
= = = 1.8 atm
Total no. of moles = a (1 – a) + 2aa (0.5 – 0.3) (0.2)
= a – aa + 2aa 24. (d) For the reaction
= a (1 + a) N2 + O2 ¾¾ ® 2NO K = 4 × 10–4
Hence for the reaction
Dn
(n y ) 2 æ PT ö 1 1 1 1
KP = ´ç 1 ÷ NO ¾¾
® N2 + O2 K'= = = 50
Now, ç n÷ 2 2 K 4×10 – 4
1 nx
è ø
EXERCISE 4
(2aa )2 .PT1
or, K P1 = 1. (c) N2O4 2NO2
[a(1 - a)][a(1 + a)]
0.2/2 2×10–3 /2 Concentration at equilibrium
Z P + Q
[ NO 2 ]2 = 10 -3 ´ 10 -3
Kc = = 1 ´ 10 - 5
Initial b moles 0 0 [ N 2O 4 ] 0.1
At equi b(1 – a) ba ba 2. (b) D G ° = - R T ln K c for DG° = 0 , Kc = 1; since ln 1 = 0
(moles) 3. (a) When moles of gaseous reactants and the products are the
Total no . of moles = b(1 – a) + ba + ba same on both sides, their is no effect of pressure
= b – ba + ba + ba 4. (d) The equilibrium constant does not vary with any factor
other than temperature
= b(1 + a)
3.20 ´ 22
Dn
5. (a) 2HI H2+I2 .It is 22% decomposed , \ = 0.704
nQ ´ nP é PT ù 100
Now K P2 = ´ê 2 ú (3.2–0.704) is equal to HI present at equilibrium which is
n2 ëê n ûú = 2.496
6. (c) H2(g)+I2(g) 2HI(g)
(ba)(ba).PT2
or K P2 = Kp = Kc (RT) Dn ; Dn = 2 - 2 = 0; \ K p = K c
[b(1 - a)][b(1 + a)] 7. (d) When volume is increased the conc. decreases & the
equilibrium shifts in the direction where more moles are
formed.
K P1 4a 2 .PT1 (1 - a )2 4PT1
or = ´ = 2
PCO 4´4
K P2 (1 - a 2 ) PT2 .a 2 PT2 8. (c) Kp = ; Kp = = 8; C(s) = 1; The concentration
PCO2 2
of solids and liquids are taken as unity
204 Chemistry
28 6 PM 1 ´ 82.1
38. (b) Moles of N 2 = = 1, Moles of H 2 = =3 40. (a) D = = = 2.5 g L-1
28 2 RT 0.0821´ 400
500 ´ 1
= 0.5 d = 2.0 g L-1 (given)
Moles of H 2SO 4 required =
1000 D-d 2.5 - 2
Moles of NH 3 neutralised by H 2SO 4 = 1.0 a= = = 0.125 = 12.5%
d(n - 1) 2(3 –1)
( 2NH 3 + H 2SO 4 ¾¾
® (NH 4 ) 2 SO 4 ) 41. (a) The reaction quotient Q is
pC ´ pD
. In the initial stage
pA ´ pB
Hence 1 mol of NH 3 by the reaction between N 2 and
C and D are not present. So p C and p D are zero. Then
H2 .
With the passage of the time p C and p D increase and
N 2 + 3H 2 2 NH 3
1 3 0 initial p A and p B decrease.
1 – 0.5 3 – 0.5 × 3 1 at equilibrium 1
42. (a) For exothermic reaction, K c µ
1´ 1 Temperature
Kc = = 0.592
0.5 ´ (1.5) 3 43. (c) Since the melting is endothermic increasing temperature
will favour melting. Since density of solid is less
39. (a) Eq. wt. of SO 2 = Mol. wt./2 (SO 2 ¾
¾® SO 3 )
æ Mö
2- 3+ çD = ÷ , the high pressure will reduce V and increase
Eq. wt. of K 2Cr2 O 7 = Mol. wt./6 (Cr2 O 7 ® 2Cr ) è Vø
1 6 D, hence more melting.
mol of K 2 Cr2 O 7 =
3 3 p 2HI
44. (b) K p =
or, 2 geq of K 2Cr2 O 7 = 2 geq of SO 2 = 1 mol of SO 2 p H 2 ´ p I2
It means only 1 mole of SO 2 reacted with O 2 . Addition of I 2 will increase p I 2 , hence to keep K p
2 SO 2 + O 2 2SO 3
1 mol 1 mol 0 mol initial constant, either p H 2 should decrease or p HI should
1 mol (1 – 0.5) mol 1 mol at equilibrium increase. Hence the graph (B).
\ Total moles at equilibrium = 1 + 0.5 + 1 = 2.5
2
æ 1 ö
2 ç ´ 5÷
p SO 3 è 2. 5 ø
Kp = = = 1.0
2
p 2SO 2 ´ p O 2 æ 1 ö æ 0.5 ö
ç ´ 5÷ ´ ç ´ 5÷
è 2 .5 ø è 2.5 ø
7B
Ionic Equilibrium
ARRHENIUS THEORY OF IONISATION : 5. Solvation : The more the solvation, the more is the
On the basis of colligative properties of solutions of salts, acids ionisation.
and bases, Arrhenius proposed the theory of ionisation i.e. 6. Presence of the ions in the solution : Ionisation decreases
spliting of these substances into ions in solution. It is reversible in presence of common ions.
process, effects electrical conductivity, colligative properties like ELECTROLYTE :
depression in freezing point, elevation in boiling point, lowering A substance which splits into ions in solution is called electrolyte.
of vapour pressure, osmotic pressure. It can be an acid, base or salt.
EVIDENCES IN FAVOUR OF IONISATION : (i) Strong electrolyte : Which dissociates almost completely
into ions even in concentrated solution eg. NaOH, KOH,
1. X-ray diffraction studies
HCl, H2SO4, NaCl, CaCl2.
2. Ionic reactions
(ii) Weak electrolyte : Which dissociates to a small extent into
3. Heat of neutralisation ions in solution eg CH3COOH, NH4OH etc.
4. Colour of compounds and their solutions Note : Salts are always strong electrolytes.
5. Colligative properties
OSTWALD'S DILUTION LAW :
6. Conductance of electrolytes in solution
The degree of ionisation or dissociation (a) of weak electrolytes
DEGREE OF IONISATION OR DISSOCIATION (a) : increases with dilution and law of mass action can be applied to
The fraction of the total number of molecules which is ionised at them.
the equilibrium state is known as degree of ionisation or AB A+ + B–
dissociation.
C 0 0 initial conc.
Number of moles ionised C(1-a) Ca Ca equilibrium conc.
a= Ionisation constant K = Ca2
Total number of moles
K 1
FACTORS AFFECTING IONISATION OR \a = aµ
DISSOCIATION : C C
1. Nature of electrolytes : The stronger the electrolyte, the Concentration of A+ or B– = Ca
more is the ionisation and vice versa. a approaches unity with dilution.
2. Nature of solvent : The more the dielectric constant of ACIDS AND BASES :
solvent, the more is the ionisation. 1. Arrhenius concept : An acid is a substance that dissociates
3. Concentration : The lesser the concentration, the more is to give hydrogen ions when dissolved in water eg. HCl,
the ionisation. CH3COOH, H3PO4.
4. Temperature : The higher the temperature, the more is the A base is a substance that dissociates to give hydroxyl ions
ionisation. when dissolved in water eg. NaOH, Ca(OH)2.
208 Chemistry
2. Lowry and bronsted concept : An acid is a substance which Soft bases : Species having donor atom of lower
has a tendency to donate a proton (H+) to any other electronegativity and higher polarisability e.g. P, As, S, Se
substance. etc. Examples R3P, R2S, I–.
A base is a substance which has a tendency to accept a 7. Lux-flood concept of acids and bases : An oxide ion donor is
proton (H+) from any other substance. a base and an oxide ion acceptor is an acid.
Acid H+ + Base BaO + SiO 2 ¾
¾® BaSiO 3
Acid and base differing by a proton are known as conjugate base acid
pair. The weaker the acid, the stronger the base in conjugate MgO + SO 3 ¾
¾® MgSO 4
pair and vice versa. base acid
Acid1 + Base2 Acid2 + Base1 8. Ingold concept : All electrophiles are acids and nucleophiles
+ – are bases.
HCl + H2O H3O + Cl
+ –
H2SO4 + H2O H3O + HSO4 STRENGTH OF ACIDS AND BASES :
+ –
HCl + NH3 NH4 + Cl The greater the value of Ka or Kb the stronger is the acid or base.
+
Conjugate acid Conjugate base + H the smaller the value of pKa the sronger is the acid.
3. Lewis concept : An acid is a substance which can accept a pKa values of some acids (Acid strength)
pair of electrons from any other substance e.g. BF3, AlCl3 Acid Base Approximate pKa
(incomplete octet), SnCl4, SF4 (central atom has vacant d- 1. HClO4 ClO4– –10
orbital) or cations Fe3+, Cu2+ etc. 2. HI I– –10
A base is a substance capable to donating a pair of electrons –
3. H2SO4 HSO4 –9.5
to any other substance eg. anions X – , OH – ,
4. HBr Br – –9
CN– or neutral molecules having lone pair(s) of electrons on
.. .. 5. HCl Cl – –7
..
one or more atom R O
..H,
NH 3 , H 2 O
. . etc. 6. Ar. SO3H ArSO3– –6.5
Lewis acid may be any of the following types of substances 7. CH(CN)3 C–(CN)3 –5
1. Molecules having an atom with incomplete octet
2. Simple cations 8. H- C-H H- C - H –4
|| ||
3. Molecules with central atom having empty Å OH O
d-orbitals
4. Molecules with a multiple bond between atoms of Å
9. R - O- R R–O–R –3.5
different electronegativities |
Strength of some Lewis acids H
BX3 > AlCl3 > FeX3 > GaX3 > SbX5 > InX3 > SnX4 > 10. H3O+ H2O –1.74
AsX5 > ZnX2 > HgX2 11. HNO3 NO3– –1.4
4. Extended Lewis concept : When the central atom is bonded
12. HSO4– SO4 –– 1.99
to atoms of different electronegativities by multiple bonds,
the substance is known as extended Lewis acid e.g. CO2, 13. HF F– 3.17
CS2 etc. 14. HNO2 NO2– 3.29
Extended Lewis base e.g. CO and unsaturated hydrocarbons +
like alkenes, alkynes etc. are also known as border line Lewis 15. Ar NH 3 ArNH2 3.5
bases. 16. RCOOH RCOO– 4.5
5. Hard acids : Cations of lighter elements, smaller size, higher
17. H2CO3 HCO3– 6.35
charge not easily polarisable e.g. light alkali and alkaline
metal ions of B, Al, Si, Ti4+, Cr3+, Co2+, Fe3+ (lighter transition 18. H2S HS– 7.00
elements). 19. NH4+ NH3 9.24
Soft acids : Cations of heavier elements, larger size, lower 20. ArOH ArO– 8-11
charge and easily polarisable e.g. heavy transition metal 21. HCO3– CO3 –– 10.33
ions (second and third row) e.g. Hg2+, Pd2+, Cd2+, Cu+, 22. H2O OH– 15.74
Ag+, Hg+ etc.
6. Hard bases : Species having donor atoms of higher 23. RCONH2 RCONH 17
electronegativity and low polarisability e.g. N, O, F, Cl etc. 24. RCH2OH RCH2O– 18
Examples H2O, NH3, ROH.
Ionic Equilibrium 209
25. HC º CH HC º C– 25 Ionisation of polybasic acids : Polybasic acids ionise in various
26. NH3 NH2– 34 steps e.g. Orthophosphoric acid H3PO4.
K1
27. Ar. CH3 ArCH2– 35 H3PO4 H+ + H2PO4–
28. CH2=CH2 CH2=CH– 36.5
K2
29. PhH Ph– 37 H2PO4– H+ + HPO4– –
30. CH4 CH3– 40 K3
HPO4– – H+ + PO4– –
31. C2H6 C2H5– 42
32. Cyclohexane (C6H12) C6H11– 45 K1 > K2 > K3 and overall dissociation const. K = K1 × K2 × K3
(i) Relative strengths of acids: For weak acid Ka = Ca2. For AMPHOTERIC OR AMPHIPROTIC SUBSTANCE OR
AMPHOLYTES :
two acids with dissociation constants Ka1 and K a 2 at the
A substance acting as an acid as well as a base, eg. water acts as
same concentration C, an acid with ammonia and as base with acetic acid. A substance
acting as proton donor and proton acceptor.
a1 K a1 Strength of acid HA1
= = COMMON ION EFFECT :
a2 Ka2 Strength of acid HA 2
The degree of ionisation of an electrolyte is suppressed by the
(ii) Relative strengths of bases : For weak base addition of another electrolyte having a common ion. This is
known as common ion effect e.g. ionisation of CH3COOH is
Kb = Ca2. For two bases with dissociation constants
suppressed by the addition of HCl or CH3COONa.
K b1 and K b2 at the same concentration C. (i) It helps in controlling the concentration of ions furnished
by weak electrolytes.
a1 K b1 Strength of base B1OH (ii) It effects the solubility of salts.
= = Mixture of weak acid and its salt with a strong base:
a2 K b 2 Strength of base B 2 OH
The hydrogen ion (H+) concentration of a mixture of a weak acid
LEVELLING EFFECT : HA and its highly dissociated salt say NaA is given by
All the strong acids in aqueous, solution appear almost equally (I) HA H+ + A–
strong since water acts as strong base. For example HClO4, HBr, (II) NaA Na+ + A–
H2SO4, HCl and HNO3 appear equally strong.
HA + H2O H3O+ + A– [ H + ][ A - ]
Ka =
Hence relative strengths in aqueous solution cannot be compared. [ HA ]
This phenomenon is known as levelling effect.
K a [ HA ] K a [ ACID ]
EFFECT OF SOLVENT ON ACID STRENGTH : [H+] = =
- [SALT ]
[A ]
(i) In acetic acid :
HA + CH3COOH CH3COOH2+ + A– HA being weak acid and secondly due to common ion (A– )
remains almost unionized. Salts are almost 100% ionised.
As acetic acid has a little tendency to accept proton, even
Mixture of weak base and its salt with a strong acid
strong acids are feebly ionised in acetic acid. For
The hydroxyl ion (OH–) concentration of mixture of weak base
example HClO 4 > HBr > H 2 SO 4 > HCl > HNO 3 BOH and its highly dissociated salt say BCl is given by
.. (I) ionisation of BOH B+ + OH– (negligible)
(ii) In liquid NH3 : HA + N H 3 NH4 + + A–
(II) ionisation of BCl B+ + Cl– (100%)
As ammonia has a great tendency to accept proton, even
weak acids appear strong in liquid ammonia. For example [B+ ][OH - ] K [BOH]
HCl, HNO3 and CH3COOH appear equally strong in liquid Kb = ; [OH - ] = b +
[BOH] [B ]
ammonia.
(iii) In HF : Since HF is a strong acid, the other acids act as a
K b [BASE]
base when dissolved in HF eg. [OH - ] =
[SALT]
+
HNO3 + HF H 2N O3 + F- Ex.: Calculate the [H+] concentration of solution which is 0.1 M in
HA and 0.5M in NaA .Ka of HA is 1.8 × 10–6.
RELATION BETWEEN Ka AND Kb :
Ka × Kb = Kw or pKa + pKb = pKw = 14 at 25°C. + K a [ACID] 1.8 ´ 10 -6 ´ 0.1
Sol. : [H ] = = = 3.6 ´ 10 -7 M
[SALT] 0.5
210 Chemistry
Ex. :What will be the H+ ion concentration of a solution obtained --
by mixing 500 ml of 0.20 M CH3COOH and 500 ml of 0.30 M Ag2 S Ksp = [Ag+]2 [S ]
CH3COONa (Ka of CH3COOH= 1.8 × 10–5) --
Sb2S3 Ksp = [Sb3+]2 [S ] 3
Sol. :Concentration of CH3COOH in the mixture
Ex.: Ksp of AgCl is 2.8 × 10–10 at 25°C. Calculate the solubility of
0.20 ´ 500 AgCl in (I) Pure Water (II) 0.1 M AgNO3 solution (III) 0.1 M
= = 0.10 mol / l
1000 NaCl.
Concentration of CH3COONa in the mixture Sol. (I) Let S mole/l be the solubility of AgCl
Ksp = [Ag+][Cl–] = S × S = S2;
0.30 ´ 500
= = 0.15 mol / l
1000 \ S = K sp = 2.8 ´ 10 -10 = 1.67 ´10 -5 mol / l
K w .C 1 1
[H + ] = Sol. pH = (pK w + pK a - pK b ) = (14 + 3.8 - 4.8) = 6.5
(vi) Kb 2 2
BUFFERS :
1 1
(vii) pH = 7 - pK b - log C Solutions which resist the change in the value of pH when small
2 2 amount of acid or base is added to them are known as buffers.
4. Hydrolysis of salts of weak bases and weak acids : e.g. Types
CH3COONH4 (I) Simple buffers : Solution of salt of weak acid and weak base
CH3COONH4 + H2O CH3COOH + NH4OH CH3COONH4, NH4CN.
or CH3COO– + NH4+ + H2O CH3COOH + NH4OH (II) Mixed buffers :
(a) Acidic buffers : Solution of equimolar mixture of a weak
(i) The solution may be neutral, acidic or basic depending
upon the relative strength of weak acid CH3COOH acid and its salt with a strong base e.g. (CH3COOH +
and weak base NH4OH formed. The salt is said to be CH3COONa); (H2CO3 + NaHCO3); (Boric acid + borax);
hydrolysed. (H3PO4 + NaH2PO4)
(ii) Hydrolysis is known as cationic as well as anionic (b) Basic buffers : Solution of equimolar mixture of a weak
hydrolysis. base and its salt with a strong acid e.g. (NH4OH + NH4Cl)
Buffer action of simple buffer : CH3COONH4 exist as ions
Kw
(iii) Salt hydrolysis Const., Kh = CH3COO– and N + H 4 in solution. Added acid (H+) combine with
Ka ´ Kb
(iv) pH of the solution may be 7, > 7 or <7 CH3COO– to give feebly ionised CH3COOH and added base
(OH–) combine with NH4+ to give feebly ionised NH4OH. Thus
Kw pH remains unchanged
(v) Degree of hydrolysis, a =
Ka ´ K b Buffer action of mixed buffers :
(a) Acidic buffer :
K w ´ Ka
(vi) H+ = +
Kb
CH3COONa CH 3 COO - + Na CH3COOH
H+
1 1 1
(vii) pH = pK w + pK a - pK b
2 2 2 When small amount of an acid is added to the buffer the
Ex. :Calculate the degree of hydrolysis and hydrolysis constant added H+ ions combine with CH3COO– to form feebly
of decinormal solution of NaCN. The dissociation constant ionised CH3COOH and when small amount of a base is added
of HCN is 7.2 × 10–10 at 25°C. to the buffer the added OH– ions combine with H+ to form
feebly ionised H2O. In the latter case more CH3COOH ionises
Kw 1´ 10-14 to keep K a of acid constant and hence constant
Sol. a = = = 1.178 ´10 - 2
C´ Ka 0.1´ 7.2 ´10 -10 concentration of H+ ions. Thus whether we add acid or a
base, the H+ concentration remain constant and pH of
Kw 1´10 -14 solution does not change
Kh = = = 1.388 ´10 -5
K a 7.2 ´10 -10 (b) Basic buffer :
Ex. :How many grams of sodium acetate must be added NH4Cl NH 4+ + Cl - NH4OH
to 500 ml of water to give a solution of pH = 8.52 OH -
(Ka = 1.8 × 10–5)
When small amount of an acid is added to the buffer the
Sol. Sodium acetate is salt of weak acid and strong base
added H+ ions combine with OH– to form feebly ionised
1 H2O, equilibrium is disturbed. More NH4OH ionises to keep
pH = 7 + pK a + log C
2 [OH–] fixed.
1 When small amount of a base is added to the buffer the
8.52 = (14 + 4.74 + log C) added OH– ions combine with NH4+ to form feebly ionised
2
NH4OH to keep [OH–] fixed. Hence there is no change of pH
(- log K a = pK a \ - log 1.8 ´ 10-5 = 4.74) in both cases.
C = 0.02 mol/litre
Hence wt. of CH3COONa in 500 ml = 0.01 × 82 = 0.82 g
Ionic Equilibrium 213
Buffer capacity = + -
+ - + -
H Cl + Na OH Na Cl + H 2 O
Moles of acid or a base added to 1 litre of buffer
Change in pH Net reaction H+ (aq) + OH– (aq) H2O,
1. Nicotinic acid (Ka = 1.4 × 10–5) has formula HNiC. Calculate 4. A solution contains 0.1 M H2S and 0.3 M HCl. Calculate the
its percent dissociation in a solution which contains 0.10 concentration of S– – and SH– ions in solution. Given K a1 and
mole of nicotinic acid per 2.0 litre of solution.
Ka 2 for H2S are 10–7 and 1.3 × 10–13 respectively..
Sol. HNiC + H2O H3O+ + NiC–
Ka
Molar concentration of nicotinic acid = 0.05 mole/lit. 1
Sol. (I) H2S H++ HS–
% Degree of dissociation
Ka
2
-5 (II) HS– H+ + S– –
Ka 1.4 ´ 10
a= = ´100 = 1.67.
C 0.05 [H + ][HS - ] [H + ][S -- ]
K a1 = Ka2 =
2. Enthalpy of neutralisation of CH3 COOH by NaOH [H 2S] [SH - ]
is –55.9 kJ/mol. DH for the ionisation of CH3COOH is
Sol. 57.1 – 55.9 = 1.2 KJ/mol [H + ]2 [S- - ]
K a1 ´ K a 2 =
3. Calculate the amount of heat released when [H 2S]
(I) 100 ml of 0.2 M HCl soution is mixed with 200 ml of H2S is weak electrolyte in presence of HCl its ionisation is
0.2 M KOH suppressed due to common ion effect.
(II) 200 ml of 0.2 M H2SO4 is mixed with equal volume of 0.2 K a1 ´ K a 2 [H 2S]
M KOH [S - - ] =
[H + ]2
100 ´ 0.2
Sol. (I) Moles of H+ ions = = 0.02 1 .0 ´ 10 - 7 ´ 1 .3 ´ 10 -13 ´ 0 .1
1000 = = 1 .44 ´ 10 - 20 M
( 0 . 3) 2
200 ´ 0.2 Putting [S– –] in equation (II)
Moles of OH– ion = = 0.04
1000
[H + ][S - - ] 0.3 ´ 1.44 ´ 10 -20
H2O formed is = 0.02 Moles [SH–] = = = 3.3 ´ 10 -8 M
Ka2 1.3 ´ 10 -13
Hence heat released = 57.1 × 0.02 = 1.142 kJ
5. The pH of 0.1 M hydrocyanic acid solution is 5.2. What is
200 ´ 0.2 the value of Ka for hydrocyanic acid.
(II) Moles of H+ ions = = 0.04
1000 1
Sol. log = pH = 5.2
200 ´ 0.2 [H + ]
and Moles of OH– = = 0.04
1000 [H+] = 6.2 × 10–6 M, [H+] = ca = C ´ Ka
Moles of H2O formed is = 0.04
(6.3 ´10 -6 ) 2
Heat released = 57.1 × 0.04 = 2.18 kJ =K a ; \ K a = 3.96 ´10 -10 M
0.1
216 Chemistry
6. Calculate the pH of Sol. The minimum concentration of S– – ion required to precipitate
(I) 1.0 × 10–8 M HCl (II) 1.0 × 10–8 M NaOH MS is
Sol. K sp 6.0 ´10 -21
(I) [H+] conc. due to water and HCl = [1 × 10–7 + 1 × 10–8] (S- - ) = = = 1.2 ´ 10-19 M
[M + + ] 0.05
[H+] = 10–8 (10 + 1) = 10–8 × 11
–log [H+] = 8 log 10 – log 11 ionisation of H2S; H2S H+ + HS–
pH = 8 – 1.04 = 6.96. [H + ][SH - ]
(II) Total [OH–] = [1 × 10–7 + 1 × 10–8] K1 = 10–7, K1 =
[H 2S]
Solving as in case (I) pOH = 6.96. \ pH = 7.04.
7. What is the hydrogen ion concentration of 0.1 N CH3COOH HS– H+ + S– –; K2 = 1.3 × 10–13
solution. The ionisation constant of CH3COOH is 1.8 × 10–5.
What is the pH of solution. [H + ][S -- ]
K2 =
[SH - ]
+
Sol. [ H ] = C ´K a = 0.1´ 1.8 ´ 10 -5 -3
= 1.34 ´ 10 M On multiplying,
pH = – log [H+] = – log 1.34 × 10–3 = 2.8729. [H + ]2 [S- - ]
8. What volume of 0.10 M sodium formate solution should be K1 × K2 =
[H 2S]
added to 50 ml of 0.05 M formic acid to produce a buffer
solution of pH 4.0, pKa of formic acid is 3.80. [H+ ]2 ´1.2 ´10-19
10-7 ´1.3 ´10-13 =
Salt 0.1
Sol. pH = pKa + log +
Solving for [H ] = 1.04 × 10 –1
Acid
pH = – log [H+] = – log (1.04 × 10–1) = 0.98.
Let the volume added be V ml. then 11. The pH of 0.05 M aqueous solution of diethylamine is 12.
V ´ 0.10 Calculate its Kb.
4 = 3.8 + log Sol. pH + pOH = 14
0.05 ´ 50
pOH = 14 – 12 = 2; [OH–] = 10–2
Solving for V we get V = 39.5 ml. (C2H5)2 NH + H2O (C2H5)2 NH2+ + OH–
9. Freshly precipitated aluminium and magnesium hydroxides 0.05 – 0.01 0.01 0.01
are stirred vigrously in a buffer solution containing 0.05 mol
0.01´ 0.01
L–1 of NH4OH and 0.25 mol L–1 of NH4Cl. Calculate the Kb = = 2.5 ´ 10 -3
conc. of aluminium and magnesium ions in solution. Ksp of 0.04
Al(OH)3 = 6 × 10–32, Ksp of Mg(OH)2 = 6 × 10–10, Kb of NH4OH 12. Ka for butyric acid is 2 × 10–5. Calculate the pH and hydroxyl
= 1.8 × 10–5. ion concentration of 0.2 M aqs. solution of sodium butyrate.
Sol. Sodium butyrate is a salt of weak acid and
K b ´ [BASE] strong base
Sol. The [OH - ] =
[SALT]
Kw ´Ka 1´10 -14 ´ 2 ´10 -5
[H + ] = = = 10 -9
1 .8 ´ 10 -5 ´ 0.05 C 0.2
= = 0. 36 ´ 10 - 5 mol L-1
0. 25 Hence pH = 9
10–14 = [H+] [OH–]
K sp of Al(OH) 3 10–14 = 10–9[OH–]
[Al 3+ ] = [OH–] = 10–5
[OH - ]3
13. Calculate the pH of an aqueous solution of 1.0 M ammonium
formate assuming complete dissociation pK a for formic acid
6 ´ 10-32
= = 1.29 ´10 -10 mol L-1
(0.36 ´10 -5 )3 = 3.8 and pK b of ammonia = 4.8.
Sol. Ammonium formate is a salt of weak acid and weak base.
2+ K sp of Mg (OH) 2 6 ´10 -10 -1
[Mg ]= = = 46.3 mol L 1 1
[OH - ]2 (0.36 ´ 10 -5 ) 2 Hence pH = 7 + pKa – pKb
2 2
10. An aqueous solution of metal bromide MBr2 (0.05 M) is
1 1
saturated with H2S what is the minimum pH at which MS =7+ × 3.8 – × 4.8 = 6.5
will precipitate? Ksp for MS = 6.0 × 10–21. Conc. of saturated 2 2
H2S = 0.1 M. K1 = 10–7 and K2 = 1.3 × 10–13 for H2S.
Ionic Equilibrium 217
14. A certain weak acid has Ka = 1.0 × 10–4. Calculate the
1 1
equilibrium constant for its reaction with strong base. =7+ ( – log Ka) + log C
2 2
H + + A - K a = 1 ´ 10-4
Sol. HA
1 1
HA + BOH BA + H2O =7+ ( – log 1.8 × 10 - 5 ) + log 0.1 = 8.87
Weak Strong 2 2
HA + OH– A– + H2O -4
18. The Ka for formic acid and acetic acid are 2.1 × 10 and 1.1
[Salt] \ V = 78.36 ml
pOH = – log Kb + log 24. Zn salt is mixed with (NH4)2S of molarity = 0.021 M, what
[Base]
amount of Zn 2+ will remain unprecipitated in 12ml of the
solution . Ksp of ZnS = 4.51 × 10–24
0 .1
= – log 1.8 × 10 - 5 + log Sol. (NH4)2S = 0.021 M ; [S– –] = 0.021 M
0 .1
--
pOH = 4.7447 At equilibrium [ Zn + + ] [S ] = Ksp of ZnS
pH = 14 – 4.7447 = 9.2553
4.51´10 - 24
(a) Addition of 0.02 mole of HCl [ Zn + + ] = = 2.15 × 10 - 22 M
0.021
HCl + NH 4 OH ¾
¾® NH 4 Cl+ H 2 O
Ionic Equilibrium 219
[ Zn 2+ ] left in solution = 2.15 × 10 - 22 × 65 g/litre 26. Calculate pH of a saturated solution of Mg (OH ) 2 . Ksp for
25. Will a precipitate of Mg (OH ) 2 be formed in a 0.001 M Let the solubility of Mg (OH ) 2 be S mole lit -1 ;
Sol. pH = 9; \ [H + ] = 10 - 9 M S = 1.305 × 10 - 4 M
-4
or [OH - ] = 10 - 5 M [OH - ] = 2S = 2 × 1.305 × 10
pOH = 3.5832
Product of ionic conc. = [ Mg 2 + ] [OH - ]2 pH = 10.4168
= [0.001] [10- 5 ]2 = 10 - 13
Very Short/Short Answer Questions 15. (i) How much of 0.3 M ammonium hydroxide should be
1. The equilibrium constants for HCN and HAc are 4.0 ×10–10 mixed with 30 mL of 0.2 M solution of ammonium
and 1.9 ×10–5 mole/L respectively. Which acid is stronger? chloride to give buffer solution of pH 8.65 and 10?
[pKb = 4.75]
2. A certain metal sulphide MS, has a solubility product (ii) How much volume of 0.1 M HAc should be added to
1.3 ×10–18 mole2/l2 . What must be [S – 2] be in a 0.10M 50 mL of 0.2 M NaAc solution if we want to prepare a
buffer solution of pH 4.91. (pKa = 4.76)
solution of M2+ when MS just starts to precipitate.
3. pKa values of acids A, B, C, D are 1.5, 3.5, 2.0 and 5.0. Which
Multiple Choice Questions
of them is strongest acid ? 16. Which of the following can act both as Bronsted acid and
4. Which of the following is strongest Lewis acid ? CCl4, AlCl3, Bronsted base?
NCl3, OCl2. (a) Na2CO3 (b) OH–
5. Which of the following is strongest conjugate base? CH3– (c) HCO3– (d) NH3
, NH2–, OH–, F–. 17. Which equilibrium can be described as an
6. What happens to ionic product of water if temperature is acid-base reaction using the Lewis acid-base definition but
increased? not using the Bronsted-Lowry definition?
7. All Bronsted acids are not Lewis acids. Explain. (a) 2NH3 + H2SO4 2NH4+ + SO42–
8. Calculate the molar concentration of an acetic acid solution (b) NH3 + CH3COOH
which is 2% ionized? ( Ka = 1.8 × 10–5)
NH4+ + CH3COO–
9. Which has the greater molarity in water, AgCl or Mg(OH)2
(c) H2O + CH3COOH
(Ksp (AgCl) = 1.8 ´ 10 -10 ,
(KspMg(OH)2 = 1.2 × 10–11) H3O+ + CH3COO–
10. Calculate the pH of the solution produced when an aqueous (d) [Cu(H2O)4]2– + 4 NH3
solution of pH = 5 is mixed with equal volume of an aqueous [Cu(NH3)4]2+ + 4H2O
solution of pH = 3.
18. The ionisation constant of an acid, Ka, is the measure of
11. A sparingly soluble salt gets precipitated only when the strength of an acid. The K a values of acetic acid,
product of concentration of its ions in the solution (Qsp)
hypochlorous acid and formic acid are 1.74 × 10–5, 3.0 × 10–8
becomes greater than its solubility product. If the solubility
and 1.8 × 10–4 respectively. Which of the following orders
of BaSO4 in water is 8 × 10–4 mol dm–3. Calculate its
of pH of 0.1 mol dm–3 solutions of these acids is correct?
solubility in 0.01 mol dm–3 of H2SO4.
(a) acetic acid > hypochlorous acid > formic acid
Long Answer Questions (b) hypochlorous acid > acetic acid > formic acid
12. (i) A sample of orange juice was found to have a pH of 10– (c) formic acid > hypochlorous acid > acetic acid
3. 80. What were the H+ and OH– concentrations in the (d) formic acid > acetic acid > hypochlorous acid
juice?
19. K a1 , Ka2 and K a3 are the respective ionisation constants
(ii) What is the pH of a 5.0×10–4 M solution of NaOH at
25°C? for the following reactions.
13. (i) What is the pH of a solution that contains 0. 10 M HCl
H 2S H + + HS-
and 0.10 M CH3COOH? For acetic acid, Ka = 1.8×10–5.
(ii) What are the concentrations of all the species present HS- H + + S2 -
in a 0. 50 M solution of acetic acid. For CH3COOH Ka =
1.8 × 10–5. H 2S 2H + + S2 -
14. Carbonic acid, H2CO3, is a weak diprotic acid formed by the
The correct relationship between K a1 , Ka2 and Ka3 is
reaction of carbon dioxide with water, For this acid,
Ka1 = 4.3 × 10–7and K a = 5.6 × 10–11. What are the (a) K a3 = K a1 ´ K a2 (b) K a3 = K a1 + K a2
2
equilibrium concentrations of each species in a 0. 10 M K a3 = K a1 - K a2 (d) K a3 = K a1 / K a2
(c)
solution of carbonic acid?
Ionic Equilibrium 221
20. The pKa of a weak acid, HA, is 4.80. The pKb of a weak base, 23. Which of the following will produce a buffer solution when
BOH, is 4.78. The pH of an aqueous solution of the mixed in equal volumes?
corresponding salt, BA, will be (a) 0.1 mol dm–3 NH4OH and 0.1 mol dm–3 HCl
(a) 9.58 (b) 4.79 (b) 0.05 mol dm–3 NH4OH and 0.1 mol dm–3 HCl
(c) 9.22 (d) 7.01
(c) 0.1 mol dm–3 NH4OH and 0.05 mol dm–3 HCl
21. What will be the value of pH of 0.01 mol dm –3 CH3COOH
(d) 0.1 mol dm–3 CH4COONa and 0.1 mol dm–3 NaOH
(K )
= 1.74 ´ 10-5 ?
a 24. A solution which is 10–3 M each in Mn 2+, Fe2+, Zn 2+ and
(a) 3. 4 (b) 3. 6 Hg2+ is treated with 10–6 M sulphide ion. If Ksp of MnS,
(c) 3. 9 (d) 3. 0 FeS, ZnS and HgS are 10 –15, 10 –23, 10 –20 and 10 –54
22. The pH of a solution which is 0.1 M in HA and 0.5 M in NaA. respectively which one will precipitate first
Ka for HA is 1.8 × 10–6 (a) FeS (b) MgS
(a) 5.44 (b) 6.44
(c) HgS (d) ZnS
(c) 6.0 (d) 4.73
1. Which will not affect the degree of ionization? 9. Which of the following is not a Lewis base?
(a) Temperature (b) Concentration (a) CH4 (b) C2H5OH
(c) Type of solvent (d) Current (c) Acetone (d) Sec amine
2. At infinite dilution, the percentage ionisation for both strong 10. Which of the following is not a Lewis acid?
and weak electrolytes is (a) BF3 (b) AlCl3
(a) 1% (b) 20% (c) FeCl3 (d) PH3
(c) 50% (d) 100% 11. In the given anions, the strongest Bronsted base is
3. A 0.2 molar solution of formic acid is 3.2% ionized. Its (a) ClO– (b) ClO2–
ionisation constant is (c) ClO3– (d) ClO4–
(a) 9.6 × 10–3 (b) 2.1 × 10–4 12. Which of the following can act as both Bronsted acid and
(c) 1.25 × 10–6 (d) 4.8 × 10–5 Bronsted base?
4. The hydrogen ion concentration of 0.2 N CH3COOH which (a) Na2CO3 (b) OH–
(c) HCO3 – (d) NH3
is 40% dissociated is
(a) 0.08 N (b) 0.12 N 13. Which of the following is the strongest Lewis acid?
(c) 0.80 N (d) 1.2 N (a) BI3 (b) BBr3
5. Degree of dissociation of 0.1 N CH3COOH is (Dissociation (c) BCl3 (d) BF3
constant = 1 × 10–5) 14. The strongest conjugate base is
(a) 10–5 (b) 10–4 (a) NO3– (b) Cl–
(c) SO4 2– (d) CH3COO–
(c) 10–3 (d) 10–2
15. A base, as defined by Bronsted theory, is a substance which
6. A monoprotic acid in a 0.1 M solution ionizes to 0.001%. Its
can
ionisation constant is
(a) lose a pair of electrons
(a) 1.0 × 10–3 (b) 1.0 × 10–6
(b) donate protons
(c) 1.0 × 10–8 (d) 1.0 × 10–11
(c) gain a pair of electrons
7. The concentration of water molecules in one litre of water at
(d) accept protons
298 K is
16. Which of the following is strongest Lewis base?
(a) 10–7 M (b) 55.5 M
(a) CH3– (b) NH2–
(c) 5.55 M (d) 7.26 M –
(c) OH (d) F–
8. Which of the following will occur if 0.1 M solution of a weak 17. Aluminium chloride is
acid is diluted to 0.01 M at constant temperature
(a) Bronsted Lowry acid (b) Arrhenius acid
(a) [H+] will decrease to 0.01 M (c) Lewis acid (d) Lewis base
(b) pH will decrese 18. BF3 is an acid according to
(c) Percentage ionization will increase (a) Arrhenius concept (b) Bronsted-Lowry concept
(d) Ka will increase (c) Lewis Concept (d) Both (b) and (c)
222 Chemistry
19. Which of the following is not a Lewis acid? 29. A compound having the formula NH2CH2COOH may behave
(a) CO (b) SiCl4 (a) only as an acid
(c) SO3 (d) Zn 2+ (b) only as a base
20. Ammonium ion is (c) both as an acid and base
(a) a conjugate acid (d) Neither acid nor base
(b) a conjugate base 30. Water is a
(c) both an acid and a base (a) protophobic solvent (b) protophilic solvent
(d) neither an acid nor a base (c) amphiprotic solvent (d) aprotic solvent
21. Among the following, the weakest base is 31. To Ag2CrO4 solution over its own precipitate, CrO42– ions
(a) H– (b) CH3– are added. This results in
(c) CH3O – (d) Cl– (a) increase in Ag+ concentration
In the equation I 2 + I - ¾ (b) decrease in Ag+ concentration
22. ¾® I 3- , which is the Lewis base?
(c) increase in solubility product
(a) I2 (b) I–
–
(d) shifting of Ag+ ions from the precipitate into the solution
(c) I3 (d) None of these
32. To suppress the dissociation of acetic acid, the compound
23. Which one of the following compounds is not a protonic
to be added to it is
acid
(a) sodium oxalate (b) sodium acetate
(a) PO(OH)3 (b) SO(OH)2
(c) sodium carbonate (d) sodium nitrate
(c) SO2(OH)2 (d) B(OH)3
24. Which equilibrium can be described as an acid-base reaction 33. Addition of which chemical will decrease the hydrogen ion
using the Lewis acid-base definition but not using the concentration of an acetic acid solution
Bronsted-Lowry definition? (a) NH4Cl (b) Al2(SO4)3
(c) AgNO3 (d) NaCN
(a) 2NH3 + H2SO4 2NH4+ + SO42–
34. Why only As+3 gets precipitated as As2S3 and not Zn+2 as
(b) NH3 + CH3COOH ZnS when H2S is passed throgh an acidic solution containing
NH4+ + CH3COO– As+3 and Zn+2?
(c) H2O + CH3COOH (a) Solubility product of As2S3 is less than that of ZnS
H3O+ + CH3COO– (b) Enough As+3 are present in acidic medium
(c) Zinc salt does not ionise in acidic medium
(d) [Cu(H2O)4]2– + 4 NH3
(d) Solubility product changes in presence of an acid
[Cu(NH3)4]2+ + 4H2O 35. The precipitation occurs if ionic concentration is
25. Which one of the following is the strongest acid? (a) less than solubility product
(a) ClO3OH (b) ClO2 (OH) (b) more than solubility product
(c) SO(OH)2 (d) SO2(OH)2 (c) equal to solubility product
26. Why are strong acids generally used as standard solutions
(d) None of these
in acid-base titrations?
36. The solubility of AgCl will be minimum in
(a) The pH at the equivalent point will always be 7
(a) 0.001 M AgNO3 (b) pure water
(b) They can be used to titrate both strong and weak bases
(c) Strong acids form more stable solutions than weak acids (c) 0.01 M CaCl2 (d) 0.01 M NaCl
(d) The salts of strong acid do not hydrolyse 37. The solubility of PbCl2 is
27. At a certain temperature the dissociation constants (a) K sp (b) (K sp )1 / 3
of formic acid and acetic acid are 1.8 × 10 –4 and (c) (K sp / 4)1 / 3 (d) (8K sp )1/ 2
1.8 × 10–6 respectively. The concentration of acetic acid
solution in which the hydrogen ion has the same 38. The solubility of calcium phosphate in water is
concentration as in 0.001 M formic acid solution is equal to x mol L–1 at 25°C. Its solubility product is equal to
(a) 0.001 M (b) 0.01 M (a) 108 x2 (b) 36 x3
(c) 36 x5 (d) 108 x5
(c) 0.1 M (d) 0.0001 M
28. What is the decreasing order of basic strengths of 39. Which of the following sulphides has the lowest solubility
OH–, NH2–, H–C º C– and CH3 – CH2– product?
(a) FeS (b) MnS
(a) CH 3 - CH -2 > NH -2 > H - C º C - > OH -
(c) PbS (d) ZnS
(b) H - C º C - > CH 3 CH -2 > NH -2 > OH - 40. The K sp of CuS, Ag 2 S and HgS are 10 –31 ,
10–44 and 10 –54 respectively. The solubility of these
(c) OH - > NH -2 > H - C º C - > CH 3 - CH -2 sulphides are in the order
(a) Ag2S > CuS > HgS (b) AgS > HgS > CuS
(d) NH -2 > H - C º C - > OH - > CH 3 - CH -2
(c) HgS > Ag2S > CuS (d) CuS > Ag2S > HgS
Ionic Equilibrium 223
41. Which of the following on reaction with H2S does not 53. What is the minimum concentration of SO42– required to
produce metallic sulphide? precipitate BaSO 4 in a solution containing
(a) CdCl2 (b) ZnCl2 1.0 × 10–4 mole of Ba2+ ? Ksp for BaSO4 = 4 × 10–10
(c) COCl2 (d) CuCl2 (a) 4 × 10–10 M (b) 2 × 10–7 M
42. What is the correct representation for the solubility product (c) 4 × 10–6 M (d) 2 × 10–3 M
of SnS2? 54. Solubility of an MX2 type electrolyte is 0.5 × 10–4 mole/lit,
(a) [Sn 2+] [S2–]2 (b) [Sn4+] [S2–]2 then Ksp of the electrolyte is
2+
(c) [Sn ] [2S ] 2– (d) [Sn4+] [2 S2–]2 (a) 5 × 10–12 (b) 25 × 10–10
43. How do we differentiate between Fe3+ and Cr3+ in group III? (c) 1 × 10–13 (d) 5 × 10–13
(a) By taking excess of NH4OH 55. The pH of blood does not appreciably change by a small
(b) By increasing NH4+ ion concentration addition of acid or a base because blood
(c) By decreasing OH– ion concentration (a) contains serum protein which acts as buffer
(d) Both (b) and (c) (b) contains iron as a part of the molecule
44. The solubility product of barium sulphate is 1.5 × 10–9 at (c) can be easily coagulated
18°C. Its solubility in water at 18°C is (d) is body fluid
(a) 1.5 × 10–9 mol L–1 (b) 1.5 × 10–5 mol L–1 56. The pH of solutions A, B, C, D are respectively 9.5, 2.5, 3.5,
5.5. The most acidic solution is
(c) 3.9 × 10–9 mol L–1 (d) 3.9 × 10–5 mol L–1
(a) A (b) B
45. The solubility product of AgCl is 4.0 × 10–10 at 298 K. The
solubility of AgCl in 0.04 M CaCl2 will be (c) C (d) D
57. pH of 10 M solution of HCl is
(a) 2.0 × 10–5 M (b) 1.0 × 10–4 M
–9 (a) 1 (b) 0
(c) 5.0 × 10 M (d) 2.2 × 10–4 M
(c) 2 (d) less than 0
46. The solubility of AgCl at 20°C is 1.435 × 10–3 gm/lit. The
58. It is found that 0.1 M solution of four sodium salts NaA,
solubility product of AgCl is
NaB, NaC and NaD have the following pH values
(a) 1.0 × 10–10 (b) 2 × 10–10
–5
7.0, 9.0, 10.0 and 11.0 respectively.
(c) 1.035 × 10 (d) 108 × 10–3
(a) NaD (b) NaC
47. The solubility product of Ag2CrO4 is 32 ´ 10 -12 . What is (c) NaB (d) NaA
Which one of the corresponding acids is strongest ?
the concentration of CrO 4 -2 ions in that solution (in g 59. A white salt is readily soluble in water and gives a colourless
ions L–1) solution with a pH of about 9. The salt would be
(a) 2 × 10–4 (b) 8 × 10–4 (a) NH4NO3 (b) CH3COONa
(c) 8 × 10–8 (d) 16 × 10–4 (c) CH3COONH4 (d) CaCO3
48. The solubility product of silver chloride is 1.8 × 10–10 at 298 60. The value of ionic product of water at 393 K is
K. The solubility of AgCl in 0.01 M HCl solution in mol/dm3 (a) less than 1 × 10–14 (b) greater than 1 × 10–14
is (c) equal to 1 × 10–14 (d) equal to 1 × 10–7
(a) 2.4 × 10–9 (b) 3.6 × 10–8 61. Which has the highest pH?
(c) 0.9 × 10 –10 (d) 1.8 × 10–8 (a) CH3COOK (b) Na2CO3
49. –5
Ksp for HgSO4 is 6.4 × 10 , then solubility of the salt is (c) NH4Cl (d) NaNO3
(a) 8 × 10–6 (b) 8 × 10–3 62. A solution of MgCl2 in water has pH
(c) 4.6 × 10 –5 (d) None of these (a) < 7 (b) > 7
50. The maximum amount of BaSO4 precipitated on mixing BaCl2 (c) 7 (d) 14.2
(0.5 M) with H2SO4 (1M) will correspond to 63. A solution of an acid has pH = 4.70. Find out the number of
(a) 0.5 M (b) 1.0 M OH– ions (pKw = 14)
(c) 1.5 M (d) 2.0 M (a) 5 × 10–10 (b) 4 × 10–10
(c) 2 × 10 –5 (d) 9 × 10–4
51. At 20°C, the Ag+ ion concentration in a saturated solution
of Ag2CrO4 is 1.5 × 10–4 mole/litre. At 20°C, the solubility 64. The pH of a solution whose [H+] is 3.0 × 10–4 M is
product of Ag2CrO4 will be (a) 4.45 (b) 3.75
(a) 3.3750 × 10–12 (b) 1.6875 × 10–10 (c) 4.36 (d) 3.523
(c) 1.6875 × 10–12 (d) 1.6875 × 10–11 65. pH of 4.0 gm/litre NaOH solution is
52. The solubility of BaSO4 in water is 2.33 × 10–3 g L–1. (a) 13 (b) 11
Its solubility product will be (molecular weight of (c) 13.5 (d) 12
BaSO4 = 233) 66. Highest pH (14) is given by
(a) 1 × 10–5 (b) 1 × 10–10 (a) 0.1 M H2SO4 (b) 0.1 M NaOH
(c) 1 × 10 –15 (d) 1 × 10–20 (c) 1 N NaOH (d) 1 N HCl
224 Chemistry
67. The pH of 0.0001 M NaOH is 80. Which of the following solution cannot act as a buffer?
(a) 4 (b) 10 (a) NaH2PO4 + H3PO4
(c) 12 (d) 11 (b) CH3COOH + CH3COONa
68. The pOH value of a solution whose hydroxide ion (c) HCl + NH4Cl
concentration is 6.2 × 10–9 mol/litre is (d) H3PO4 + NaH2PO4
(a) 8.21 (b) 6.21 81. A buffer solution of pH 9 can be prepared by mixing
(c) 7.75 (d) 7.21 (a) CH3COONa and CH3COOH
69. The pH of a solution obtained by mixing 50 ml of 0.4 N HCl (b) NaCl and NaOH
and 50 ml of 0.2 N NaOH is
(c) NH4Cl and NH4OH
(a) – log 2 (b) – log 0.2
(d) KH2PO4 and K2HPO4
(c) 1.0 (d) 2.0
70. The pH of 1.0 M aqueous solution of a weak acid HA is 6.0. 82. Which of the following is the buffer solution of strong acidic
Its dissociation constant is nature?
(a) 1.0 × 10–12 (b) 1.0 × 10–6 (a) HCOOH + HCOO–
(c) 1.0 (d) 6.0 (b) CH 3COOH + CH 3COO -
71. The pH of a solution is increased from 3 to 6; its H+ ion (c) H2C2O4 + C2O42–
concentration will be (d) H3BO3 + BO33–
(a) reduced to half (b) doubled 83. One litre of a buffer solution containing 0.01 M NH4Cl and
(c) reduced by 1000 times (d) increased by 1000 times 0.1 M NH4OH having pKb of 5 has pH of
72. When CO2 dissolves in water, the following equilibrium is (a) 9 (b) 10
established CO2 + 2H2O H3O+ + HCO3– (c) 4 (d) 6
for which the equilibrium constant is 3.8 × 10–7 and pH = 6.0. 84. A certain buffer solution contains equal concentration of
The ratio of [HCO3–] to [CO2] would be X– and HX. The Ka for HX is 10–8. The pH of the buffer is
(a) 3.8 × 10–13 (b) 3.8 × 10–1 (a) 3 (b) 8
(c) 6.0 (d) 13.4 (c) 11 (d) 14
73. An example of a salt that will not hydrolyse is 85. In a mixture of a weak acid and its salt, the ratio of the
(a) NH4Cl (b) KCl concentration of acid to salt is increased tenfold. The pH of
(c) CH3COONH4 (d) CH3COOK the solution
74. pH of 2 M NaCl will be (a) decreases by one (b) decreases by one tenth
(a) 3 (b) 6.5
(c) increases by one (d) increases by ten-fold
(c) 7 (d) 10
86. How much sodium acetate should be added to 0.1 M solution
75. Dissociation constant of NH4OH is 1.8 × 10–5. The
of CH3COOH to give a solution of pH 5.5
hydrolysis constant of NH4Cl would be
(pKa of CH3COOH = 4.5)
(a) 1.80 × 10–19 (b) 5.55 × 10–10
(c) 5.55 × 10 –5 (d) 1.80 × 10–5 (a) 0.1 M (b) 0.2 M
76. What is the percentage hydrolysis of NaCN in N/80 solution (c) 1.0 M (d) 10.0 M
when the dissociation constant for HCN is 1.3 × 10–9 and 87. For preparing a buffer solution of pH 6 by mixing sodium
Kw = 1.0 × 10–14 acetate and acetic acid, the ratio of the concentration of salt
(a) 2.48 (b) 5.26 and acid should be (Ka = 10–5)
(c) 8.2 (d) 9.6 (a) 1 : 10 (b) 10 : 1
77. The pH of a 1 M CH3COONa solution in water will be nearly (c) 100 : 1 (d) 1 : 100
(a) 2.4 (b) 5.4 88. What is [H+] of a solution that is 0.1 M HCN and 0.2 M
(c) 7.4 (d) 9.4 NaCN? (Ka for HCN = 6.2 × 10–10)
78. A physician wishes to prepare a buffer solution at (a) 3.1 × 1010 (b) 6.2 × 105
pH = 3.58 that efficiently resists a change in pH yet contains (c) 6.2 × 10 –10 (d) 3.1 × 10–10
only small conc. of the buffering agents. Which one of the 89. The pH of a buffer containing equal molar concentrations
following weak acid together with its sodium salt would be of a weak base and its chloride
best to use?
(Kb for weak base = 2 × 10–5, log 2 = 0.3) is
(a) m-chloro benzoic acid (pKa = 3.98)
(a) 5 (b) 9
(b) p-chloro cinnamic acid (pKa = 4.41)
(c) 4.7 (d) 9.3
(c) 2,5-dihydroxy benzoic acid (pKa = 2.97)
(d) Acetoacetic acid (pKa = 3.58) 90. How many ml of 1 M H2SO4 is required to neutralise 10 ml of
79. Which one is Buffer solution? 1 M NaOH solution?
(a) [PO4–3] [HPO42–] (b) [PO43–] [H2PO4–] (a) 2.5 (b) 5.0
(c) [HPO42–] [H2PO4–] (d) All of these (c) 10.0 (d) 20.0
Ionic Equilibrium 225
91. Molar heat of neutralization of NaOH with HCl in comparison (a) 1.0 × 10–12 (b) 1.0 × 10–10
to that of KOH with HNO3 is (c) 1.0 × 10 –8 (d) 1.0 × 10–16
(a) less (b) more 97. When rain is accompanied by a thunderstorm, the collected
(c) equal (d) depends on pressure rain water will have a pH value
92. The mutual heat of neutralization of 40 g NaOH and 60 g
(a) slightly lower than that of rain water without
CH3COOH will be
thunderstorm
(a) 57.4 kJ (b) Less than 57.4 kJ
(b) slightly higher than that when the thunderstorm is not
(c) More than 57.4 kJ (d) 13.7 kJ
there
93. Heat of neutralization of NH4OH and HCl is
(c) uninfluenced by occurrence of thunderstorm
(a) equal to 13.7 kcal (b) more than 13.7 kcal
(d) depends on the amount of dust in air
(c) less than 13.7 kcal (d) more than one is correct
98. H3BO3 is
94. The pH indicators are
(a) salts of strong acids and strong bases (a) monobasic and weak Lewis acid
(b) salts of weak acids and weak bases (b) monobasic and weak Bronsted acid
(c) either weak acids or weak bases (c) monobasic and strong Lewis acid
(d) either strong acids or strong bases (d) tribasic and weak Bronsted acid
95. Identify the indicator used to titrate Na2CO3 solution with 99. A solution which is 10–3 M each in Mn 2+, Fe2+, Zn 2+ and
HCl Hg2+ is treated with 10–6 M sulphide ion. If K sp of MnS,
(a) Phenolphthalein (b) dil. H2SO4 FeS, ZnS and HgS are 10–15, 10 –23, 10 –20 and 10–54
(c) Methyl orange (d) None of these respectively which one will precipitate first
96. The solubility product of AgI at 25°C is 1.0 × 10–16 mol2 L–2. (a) FeS (b) MgS
The solubility of AgI in 10–4N solution of KI at 25°C is (c) HgS (d) ZnS
approximately (in mol L–1)
1. A weak acid, HA, has a Ka of 1.0 × 10–5. If 0.1 mole of this 6. The dissociation constants for acetic acid and HCN at 25°C
acid dissolved in one litre of water, the percentage of acid are 1.5 × 10–5 and 4.5 × 10–10 respectively. The equilibrium
dissociated at equilbrium is closest to [CBSE-PMT 2007] constant for the equilibrium [CBSE-PMT 2009]
(a) 1.0% (b) 99.9% (c) 0.1% (d) 99.0%
CN– + CH3COOH HCN + CH3COO– would be:
2. Calculate the pOH of a solution at 25°C that contains
1× 10– 10 M of hydronium ions, i.e. H3O+. [CBSE-PMT 2007] (a) 3.0 × 10– 5 (b) 3.0 × 10– 4
(a) 4.0 (b) 9.0 (c) 1.0 (d) 7.0 (c) 3.0 × 104 (d) 3.0 × 105
3. Equal volumes of three acid solutions of pH 3, 4 and 5 are 7. Which of the following molecules acts as a Lewis acid ?
mixed in a vessel. What will be the H+ ion concentration in [CBSE-PMT 2009]
the mixture ? [CBSE-PMT 2008]
–4 (a) (CH3)2 O (b) (CH3)3 P (c) (CH3)3 N (d) (CH3)3 B
(a) 1.11 × 10 M (b) 3.7 × 10–4 M
–
(c) 3.7 × 10 M 3 (d) 1.11× 10–3 M 8. The ionization constant of ammonium hydroxide is 1.77 × 10–5
4. If the concentration of OH– ions in the reaction at 298 K. Hydrolysis constant of ammonium chloride is:
1. How many gms of CaC 2O 4 will dissolve in litre of saturated 6. The solubility of CaF2 in 0.01 M solution of NaF. The Ksp of
solution. Ksp of CaF2 is 3.4 × 10–11
CaC2 O 4 is 2.5 ´10 -9 mol 2 lit -2 (a) 3.4 ´ 10-7 mol / l
(a) 0.0064 g (b) 0.0128 g
(b) 3.4 ´ 10-5 mol / l
(c) 0.0032 g (d) None of these
(c) 3.4 Mol / l
2. For NH3, Kb = 1.8 × 10–5 and Ka for NH +4 would be
(d) None of these
(a) 1.8 ´ 10 -5 (b) 5.56 ´ 10 5 7. If the reaction between CO2 and H2O is
+
(c) 1.8 ´ 1010 (d) 5.56 ´ 10 -10 CO 2+H 2O H 2CO 3 H+HCO 3.
3. The pH of a solution which is 0.1 M in HA and 0.5 M in NaA. If CO2 escapes from the system
-6 (a) pH will decrease
Ka for HA is 1.8 ´ 10
(b) H+ concentration will decrease
(a) 5.44 (b) 6.44
(c) H2CO3 concentration will be altered
(c) 6.0 (d) 4.73
4. The pH of a solution obtained by mixing of 100.0 ml of 0.1 M (d) The forward reaction is promoted
8. A solution contains 0.1 M H2 S and 0.3 M HCl, the
HCl and 100 ml of 0.2 M NH3, Kb for NH3 is 1.8 ´ 10 -5
- -7
(a) 4.74 (b) 9.26 concentration of SH ions is ( K a = 1. ´10 )
(c) Less than 7 (d) None of these
(a) 3.3 ´ 10 -8 M (b) 33 ´ 10 -8 M
5. The percentage hydrolysis of 0.15 M solution of ammonium
acetate, K a for CH 3COOH is 1.8 ´ 10 -5 and K b for (c) 3.3 ´ 10 -7 M (d) 10 -7 M
9. 20 ml of 0.2 M. NaOH are added to 50 ml of 0.2
NH 3 is 1.8 ´10 -5
M CH3COOH (K a = 1.8 ´10 -5 ) the pH of the solution is
(a) 0.556 (b) 4.72
(c) 9.38 (d) 5.56 (a) 4.56 (b) 4.73
(c) 9.45 (d) 6.78
Ionic Equilibrium 229
10. The pH at which the Mg(OH)2 begins to precipitate from a 18. An acid-base indicator has Ka = 3.0 ´ 10 -5 . The acid form of
solution containing 0.10 M Mg++ ions. The Ksp of Mg(OH)2 the indicator is red and the basic form is blue. The amount of
is 1 ´ 10 -11 change in [H+] required to change indicator from 75% red
(a) 9 (b) 5 the 75% blue is
-5
(c) 11 (d) 4 (a) 8 ´ 10 -5 M (b) 9 ´ 10 M
11. The 0.001M Solution of Mg (NO3)2 is adjusted to pH 9, Ksp -4
(c) 1 ´ 10 -5 M (d) 3 ´ 10 M
of Mg(OH)2 is 8.9 ´ 10 -12 . At this pH 19. Which of the following statements(s) is (are) correct?
(a) Mg(OH)2 will be precipitated (a) The pH of 1.0 × 10–8 M solution of HCl is 8
(b) Mg(OH)2 is not precipitated (b) The conjugate base of H2 PO -4 is HPO 24-
(c) Mg(OH)3 will be precipitated (c) Autoprotolysis constant of water decreases with
(d) Mg(OH)3 is not precipitated temperature
12. Calculate the pH of 0.5 M aqueous solution of NaCN, the (d) When a solution of a weak monoprotic acid is titrated
pKb of CN - is 4.70 against a strong base, at half-neutralisation point pH =
(1/2)pKa.
(a) 4.70 (b) 11.5
20. The pH of 0.1 M solution of the following salts increases in
(c) 7 (d) 6.5
the order.
13. The pH of aqueous solution of 1M HCOONH4, pKa of
(a) NaCl < NH4Cl < NaCN < HCl
HCOOH is 3.8 and pKb of NH3 is 4.8
(b) HCl < NH4Cl < NaCl < NaCN
(a) 6.5 (b) 4.8
(c) NaCN < NH4Cl < NaCl < HCl
(c) 3.8 (d) 8.6
(d) HCl < NaCl < NaCN < NH4Cl
14. The hydrolysis of Na2CO3 involves the reaction between
21. What will be the H+ ion concentration in a solution prepared
+ by mixing 50 mL of 0.20 M NaCl, 25 mL of 0.10 M NaOH and
(a) Na ions and water
25 mL of 0.30 N HCl?
(b) Na + and OH - ions (a) 0.5 M (b) 0.05 M
2- (c) 0.02 M (d) 0.10 M
(c) CO3 and H 2O
22. Determine the pH of the solution that results from the addition
(d) CO32 - and H + of 20.00 mL of 0.01 M Ca(OH)2 to 30.00 mL of 0.01 M HCl.
(a) 11.30 (b) 10.53
15. The solubility of BaF2 in a solution of Ba(NO3)2 will be (c) 2.70 (d) 8.35
represented by concentration term 23. Two weak solutions are isohydric when their
- (a) hydrogen-ion concentrations are the same before mixing
(a) [ Ba 2+ ] (b) éë F ùû
(b) hydrogen-ion concentrations are same before and after
_ mixing
1 é -ù
(c) F (d) 2[ NO 3 ] (c) degree of dissociation are the same
2ë û
(d) chemical properties are the same
16. The enthalpy of neutralization of HCl and HCN by NaOH are
24. The dissociation constant of monobasic acids A, B and C
–55.9 and –12.1 kJ mol–1 respectively, the enthalpy of are 10–4, 10–6 and 10–10 respectively. The concentration of
ionisation of HCN is each is 0.1 M. Which of the following has been arranged in
(a) - 43.8 kJ mol -1 order of increasing pH?
(a) A < B < C (b) C < A < B
(b) - 68.0 kJ mol -1 (c) B < C < A (d) B < A » C
25. Calculate the molar solubility of Fe(OH)2 at a pH of 8.00 [Ksp
(c) 43.8 kJ mol -1 of Fe (OH)2=1.6×10–14]
(a) 0.06 (b) 0.016
(d) 68.0 kJ mol -1
(c) 0.010 (d) 0.16
17. Ka for HCN is 5 ´ 10 -10 at 25°C. For maintaining at constant 26. K1 and K2 for oxalic acid are 6.5×10–2 and 6.1×10–5
pH of 9, the volume of 5M KCN solution required to be respectively. What will be [HO–] in a 0.01 M solution of
added to 10ml of 2M HCN solution is sodium oxalate ?
(a) 4 ml (b) 7.95 ml (a) 9.6×10–6 (b) 1.4×10–1
(c) 2 ml (d) 9.3 ml (c) 1.3×10–6 (d) 1.3×10–8
230 Chemistry
27. Calculate the pH of a solution containing 0.1 M HCO 3- and (a) 3.52 × 10 -3 (b) 6.75 × 10 -4
0.2 M CO 32- [K1(H2CO3) = 4.2×10–7×10 and K2( HCO 3- ) = (c) 5.38 × 10 -2 (d) 1.74 × 10 - 5
4.8×10–11]. 36. The degree of dissociation of 0.1M weak acid HA is 0.5%. If
2 ml of 1.0 M HA solution is diluted to 32 ml the degree of
(a) 3.18 (b) 10.62
+
(c) 6.62 (d) 9.31 dissociation of acid and H 3O ion concentration in the
28. At what pH will a 1×10–4 M solution of an indicator will (Kb resulting solution will be respectively
indicator) = 1×10–11 change colour? -4
(a) 7.0 (b) 3.0 (a) 0.02 and 3.125 × 10 (b) 1.25 × 10 - 3 and 0.02
(c) 5.5 (d) 11.0 (c) 6.02 and 1.25 × 10 - 3 (d) 0.02 and 8.0 × 10
- 12
29. Calculate the pH of a 0.01 M NaHCO3 solution [K1(H2CO3) = 37. The dissociation constants of a weak acid HA and weak
4×10–7, K2( HCO 3- ) = 4.8×10–11]. base BOH are 2 × 10 - 5 and 5 × 10 - 6 respectively. The
(a) 9.38 (b) 6.38 equilibrium constant for the neutralisation reaction of the
(c) 8.38 (d) 7.38 two is
30. Blood plasma is maintained at a pH of 7.4 largely by the
(a) 1.0 × 10 4
(b) 1.0 × 10 - 4
(a) HCO 3- / H 2 CO 3 buffer - 10
(c) 1.0 × 10 (d) 2.5 × 10 - 1
(b) HPO 24 - / PO 34- buffer 38. The ionisation constant of an acid-base indicator
(a weak acid) is 1.0 × 10 - 6 . The ionised form of the indicator
(c) HCO 3- / H 2 CO 3 is red whereas the unionised form is blue the pH change
required to alter the colour of the indicator from 80% blue to
and HPO 24 - / H 2 PO -4 buffer 80% red is
(d) HPO 24- / H 3 PO 4 and haemoglobin buffers (a) 1.40 (b) 1.20
(c) 0.80 (d) 2.00
31. In the titration of a weak diprotic acid (H2A) with a strong 39. The pH at the equivalence point in the titration of 25 ml of
base (NaOH), [H+] is given by 0.10 M formic acid with a 0.1 M NaOH solution (given that
(a) K a1 C a (b) Ka Ca1 pKa of formic acid = 3.74)
(a) 8.74 (b) 8.37
(c) K a Ca1 (d) K a1 (c) 4.74 (d) 6.06
32. The pH of a solution prepared by mixing 2.0 ml of a strong 40. In H S , I , RNH 2 , NH 3 the order of proton accepting
acid (HCl) solution of pH 3.0 and 3.0 ml of a strong base tendency will be
(NaOH) of pH 10.0
(a) 4.5 (b) 3.4 (a) H S > RNH 2 > NH 3 > I
(c) 2.5 (d) 6.5
(b) I > NH 3 > RNH 2 > H S
33. For a sparingly soluble salt ApBq, the relationship of its
solubility product Ls ® Ksp with its solubility (S) is (c) NH 3 > RNH 2 > H S > I
+ é Acid ù
If [OH– ] is decreased by
1
times then for reaction log éë H ùû = log Ka + log ê
4 ë Salt úû
equilibrium constant to remain constant, we have to
increase the concentration of [Fe3+] by a factor of 43 i.e é H + ù = K é Acid ù
ë û aê
4× 4 × 4 = 64. Thus option (c) is correct answer. ë Salt úû
5. (b) The highest pH will be recorded by the most basic 0.1
solution. The basic nature of hydroxides of alkaline earth = 1.8 × 10 -5 ´ = 9 × 10-6 M
0.2
metals increase as we move from Mg to Ba and thus the
solution of BaCl2 in water will be most basic and so it 11. (d) Kb = 10-10 ; Ka = 10-4 or pKa = 4
will have highest pH.
For the buffer solution containing equal concentration
6. (c) Given, CH3COOH CH3COO– + H+ ; of B– and HB
Ka1 , = 1.5 × 10– 5 ....(i) pH = pKa + log 1
HA- ¾¾
® H+ + A--
23. (a) Mg(OH)2 Mg ++ + 2OH- ;
S 2S
[H + ][A -- ] (Given)
Ksp = (s) (2s)2 = 4s3 \ K 2 = 5.0 ´ 10 -10 =
24. (b) An acidic solution cannot have a pH > 7. [HA - ]
25. (d) [A] = 1.0 × 10–5, [B] = [1.0 × 10–5] ,
ksp = [2.B]2 [A] = [2 × 10–5]2 [1.0 × 10–5] [H + ]2 [A 2 - ]
= 4 × 10–15 K= = K1 ´ K2
[H 2 A]
+
–H = (1.0 × 10–5) × (5 × 10–10) = 5 × 10–15
26. (d) H 2 PO–4 HPO2–
4
Acid con ugate base
conjugate é salt ù
34. (d) For acidic buffer pH = pKa + log ê ú
4+ - ë acid û
27. (d) MX4 M + 4X
S 4S
1/ 5
éA- ù
æ K sp ö ë û
or pH = pK a + log
ksp = [S] [4S]4 = 256 S5 \ S = çç ÷
÷ [ HA ]
è 256 ø
Ionic Equilibrium 237
Given pKa = 4.5 and acid is 50% ionised.
[HA] = [A–] (when acid is 50% ionised) 41. (c) H 2CO3 (aq)+ H 2O(l ) HCO3– (aq) + H3O + (aq)
0.034 x x x
\ pH = pKa + log 1
\ pH = pKa = 4.5 [HCO3- ][H 3O + ] x´ x
K1 = =
pOH = 14 – pH = 14 – 4.5 = 9.5 [H 2 CO 3 ] 0.034 - x
35. (c) Let s = solubility
7 x2
Ag + IO3
AgIO3 4.2 10 x 1.195 10 4
s s
0.034
Ksp = [Ag+] [IO3–] = s × s = s2 As H2CO3 is a weak acid so the concentration of
H2CO3 will remain 0.034 as 0.034 >> x.
Given Ksp = 1 × 10–8
x = [H+] = [ HCO3- ] = 1.195 × 10–4
\ s = K sp = -8
1´10
Now, HCO3– (aq) + H 2 O(l ) CO32– ( aq ) + H3O+ ( aq )
= 1.0 × 10–4 mol/lit = 1.0 × 10–4 × 283 g/lit x y y y
As HCO3- is again a weak acid (weaker than H2CO3)
(Q Molecular mass of Ag IO3 = 283)
with x >> y.
1.0 ´10-4 ´ 283 ´100
= gm /100ml [CO32– ][H3O+ ] y ´ (x + y)
1000 K2 = =
[HCO3– ] ( x - y)
= 2.83 × 10–3 gm/ 100 ml
36. (c) Reaction (c) can be obtained by adding reactions (a) Note : [H3O+] = H+ from first step (x) and from second
and (b) therefore K3 = K1. K2 step (y) = (x + y)
Hence (c) is the correct answer. [As x > > y so x + y ; x and x – y ; x]
37. (c) The correct order of acidic strength of the given species y´x
So, K 2 ; =y
x
HSO3 F > H 3 O + > HSO 4 - > HCO3-
(iv) (ii) (iii) (i) Þ K 2 = 4.8 ´ 10-11 = y = [CO32 - ]
or (i) < (iii) < (ii) < (iv)
So the con centration of [H + ] ; [ HCO3– ] =
It corresponds to choice (c) which is correct answer.
38. (c) In aqueous solution BA(salt) hydrolyses to give concentrations obtained from the first step. As the
dissociation will be very low in second step so there
BA + H2O BOH + HA will be no change in these concentrations.
Base acid Thus the final concentrations are
Now pH is given by
[H+] = [ HCO3- ] = 1.195 × 10–4 & [CO23 - ] = 4.8 ´ 10-11
1 1 1
pH = pK w + pKa - pK b
2 2 2 42. (b) Ag + Br
AgBr
substituting given values, we get Ksp = [Ag+] [Br–]
1 For precipitation to occur
pH = (14 + 4.80 - 4.78) = 7.01 Ionic product > Solubility product
2
K sp 5´10-13
39. (a) Na 2 CO3 ¾¾
® 2Na + + CO32- [Br- ] = = = 10-11
1 ´10-4 M 1´10-4 M 1´10-4 M [Ag+ ] 0.05
i.e., precipitation just starts when 10–11 moles of KBr
Ksp(BaCO3 ) = [Ba 2+ ][CO32– ] is added to 1l AgNO3 solution
\ Number of moles of Br– needed from KBr = 10–11
5.1 ´ 10 -9
[Ba 2+ ] = -4
= 5.1 ´ 10 -5 M \ Mass of KBr = 10–11 × 120 = 1.2 × 10–9 g
1 ´ 10
43. (b) Mg ++ + 2 OH -
Mg(OH) 2
40. (a) (i) ® H 3O + H 2 PO 4-
H3PO 4 + H 2 O ¾¾ +
Ksp = [Mg++][OH–]2
acid1 base2 acid 2 base1 1.0 × 10–11 = 10–3 × [OH–]2
-
® HPO 4-- + H 3O +
(ii) H 2 PO 4 + H 2 O ¾¾ 10-11
acid1 base 2 base1 acid 2 [OH- ] = = 10-4
10-3
- -
+ ® H3 PO 4 + O --
¾¾
(iii) H 2 PO 4 OHacid base
\ pOH = 4
base1 2 acid1 2
\ pH + pOH = 14
Hence only in (ii) reaction H2PO4– is acting as an acid. \ pH = 10
238 Chemistry
44. (d) pH = 5 M1V1 = M2V2
\ [H+] = 10–5 0.1 × 1 = 0.01 × V2
H + + A -
HA V2 = 10 litres
\ Volume of water added = 10 – 1 = 9 litres
t=0 c 0 0
50. (d) Let the weak monoacidic base be BOH, then the
teq c (1 – a) ca ca reaction that occurs during titration is
[H + ][A - ] (c ) 2 [H + ]2 BOH + HCl ® BCl + H2O
Ka = = =
[HA] c (1 – ) c - [H + ] BOH + H +
Equilibrium : B+ + H 2 O
c (1- h) c.h c.h
(As [H+]) = [A–] = ca)
But, [H+] << c Using the normality equation, N1V1 = N 2 V2
(acid) (base)
\ Ka = (10–5)2 = 10–10
45. (b) Cr 3+ (aq.) + 3OH - (aq.)
Cr(OH)3 (s) Substituting various given values, we get
s 3s 2 2
´ V1 = 2.5´
(s) (3s)3 = Ksp 15 5
27 S 4 = K sp 2 15
or V1 = 2.5´ ´ = 2.5 × 3 = 7.5 ml
1/ 4 -30 ö 1/ 4
5 2
æ K sp ö æ 1.6 ´ 10
s=ç =ç ÷ Then the concentration of BCl in resulting solution is
è 27 ÷ø è 27 ø given by
46. (a) 2CO
CO2 + C(graphite)
2
Pinitial 0.5atm 0 2.5 1
[BCl] = 5 = or 0.1 M
10 10
Pfinal (0.5 – x)atm 2 x atm
Total P at equilibrium = 0.5 – x + 2x = 0.5 + x atm [Total volume = 2.5 + 7.5 = 10 ml]
0.8 = 0.5 + x Kw
\ x = 0.8 – 0.5 = 0.3 atm Since K h =
Kb
Now Kp = (PCO ) /PCO
2
1´10-14
2
(2 ´ 0.3) 2
(0.6) 2 \ Kh = = 10–2
= = = 1.8 atm 1´10-12
(0.5 – 0.3) (0.2)
47. (d) For the reaction 0.1h 2 0.1h 2
Thus K h = or 10-2 =
N2 + O2 ¾¾ ® 2NO K = 4 × 10–4 (1- h) (1- h)
Hence for the reaction
or 10–2 – 10–2 h = 0.1 h2
1 1 1 1
NO ¾¾
® N2 + O2 K'= = = 50 or 0.1 h2 + 10–2 h – 10–2 = 0
2 2 K 4×10 – 4
(Solving this quadratic equation for h, we get)
48. H + Q
(c) HQ
é -b ± b 2 - 4ac ù
c(1–a) ca ca êx = ú
Using ê 2a ú
[H + ] ë û
[H + ] = c a ; a =
c
-10-2 ± (10-2 )2 + 4 ´10-1 ´ 10 -2
10 –3 h=
or a = = 10-2 2 ´ 0.1
0.1
s 2s
1 Kw 1 ´ 10-14
5. (a) a = = = 0.55
é K sp ù 3 Ka ´ K b 1.8 ´ 10-5 ´ 1.8 ´ 10-5
K sp = s ´ (2 s ) 2 = 4 s3 or s=ê ú
ë 4 û
Ksp 3.4 ´10 -11
3M + X
and for M 3 X + -3 6. (a) [Ca ++ ] = ; Solubility = = 3.4 ´ 10 -7
3s s [F- ]2 [0.01] 2
1
+ –
7. (b) CO2+H2O H2CO3 H +HCO3 .
é Ksp ù 4
Ksp = (3s )3 ´ s = 27 s 4 or s = ê ú If CO2 escapes, the equilibrium will shift to LHS and [H+]
ë 27 û concentration will decrease
From the given values of Ksp for MX, MX2 and – +
8. (a) H S SH + H ;
2
M3 X, we can find the solubilities of those salts at
temperature, T. [SH][H + ] 10-7 ´ 0.1
Ka = ;[SH] = = 3.3 ´ 10 -8
Solubility of MX = 4´10-8 = 2´10-4 [H 2S] 0.3
1
9. (a) NaOH + CH 3COOH CH 3COONa + H 2O
1
é 3.2 ´10-14 ù 3 é 32 -15 ù 3
20×0.2 50×0.2 0 0
Solubility of MX 2 = êê ú
ú or ê ´10 ú
êë 4 úû êë 4 úû 4 10 0 0
0 6 4 4
1 Millimoles 6 4
Conc. = ;[CH3COOH] = ;[CH3COONa] =
= éê8´10-15 ùú 3 or 2 10 5 Total Volume 70 70
ë û
1 pH = – log 1.8 ´10 -5 + log 4 / 70 , pH = 4.56
é 2.7 ´10-15 ù 4 6 / 70
Solubility of M3 X = êê ú
ú
êë 27 úû K sp 1´ 10-11
1 10. (a) [OH - ]2 = ++
= = 10-10 ;
é10-16 ù 4 –4 [Mg ] 0.1
= ê úû or 10
ë
Thus the solubilities are in the order MX > M3 X> MX2 [OH- ] = 10-5 ;[H+ ] = 10-9 ; pH = 9
i.e the correct answer is (d).
11. (b) pH = 9 ; [H+ ] = 10-9 ;[OH- ] = 10-5 ;
EXERCISE 4
2+ 2- [Mg ++ ] = 1´10 -3 ;[Mg++ ][OH - ]2 = 1´10-13
1. (a) CaC O Ca + C O ; Ksp = S2
2 4 2 4
given Ksp of Mg(OH ) 2 = 8.9 ´10 -12 which is more than
-9 -5 mol/litre
\ S = K sp = 2.5 ´ 10 = 5 ´ 10
1 ´ 10 -13 . Hence Mg(OH)2 will not precipitate
solubility = 5 ´10 -5 ´128 = 0.0064 g
240 Chemistry
12. (b) NaCN is a salt of strong base and weak acid ; pH
NH +4 + H 2 O NH 4 OH + H +
1 1
= 7 + pK a + log C
2 2 NaCN Slightly alkaline due to the reaction
pKa for HCN = 14–4.70 = 9.30 CN - + H 2 O HCN + OH -
1 1 HCl highly acidic
\ pH = 7 + ´ 9.30 + log 0.5; pH = 11.5
2 2 The pH of the solution will follow the order highly acidic
13. (a) HCOONH 4 is a salt of weak acid and weak base ; < slightly acidic < neutral < slightly alkaline
i.e. HCl < NH4Cl < NaCl < NaCN
pH = ½ pKw + ½ pKa – ½ pKb
+ (25 ´ 0.3 - 25 ´ 0.1)
1 1 1 21. (b) [H ] = meq = 0.05M
\ pH = ´ 14 + ´ 3.8 - ´ 4.8 ; pH = 6.5 100
2 2 2
- (20 ´ 0.02) - (30 ´ 0.01)
14. (c) Na2CO3 +2H2O 2NaOH+H2CO3 22. (a) [OH ] = = 0.002M
50
CO3-- + 2H 2 O 2OH - + H 2 CO3 Anionic hydrolysis – log [OH–] = pOH = – log .002 = 2.7
\ pH = 14 – 2.7 = 11.3
15. (c) BaF2 Ba ++ + 2F- , Ba(NO3 )2 23. (a) Isohydric solutions have the same [H+] concentration
24. (a) A B C
-
F- are obtained from BaF2 . Then ½ [F ] = [BaF2] Ka 10–4 10–6 10–10
16. (c) HCN is a weak acid and energy is required to affect its The higher the value of Ka, the stronger the acid and the
ionisation. Hence the enthalpy of neutralisation of HCN lower is pH. Hence order of pH A < B < C.
is less than the enthalpy of neutralisation of strong acid. 25. (b) Fe(OH) 2 Fe + + + 2 OH
The difference of enthalpy gives the enthalpy of
ionisation. 55.9 kJ-12.1 kJ = 43.8 kJ pH = 8, [H+] = 10–8, [OH–] = 10–6
17. (c) Let the volume of KCN to be added is Vml ; Conc.of KCN K sp 1.6 ´ 10-4
= S×V and Fe++ = = = 0.016
[OH - ]2 [10-6 ]2
Conc. of HCN = 10 ×2 ; pH = 9 , \ H+ = 10–9
26. (c) The hydrolysis of C 2 O 24 - is as follows
K [ACID] -9 5 ´ 10 -10 ´ 10 ´ 2
+
H = a ;10 = ;V = 2ml
[SALT] 5´ V C 2 O 24 - + H 2 O HC2 O4- + OH –
18. (c) An acid base indicator is InH. Its ionisation is as follows
K w 1.0 ´10-14 x2
InH In – + H+ Kh = = -5
=
K 2 6.0 ´10 0.01
acid form (Red) basic form (blue)
\ x = 1.3 × 10–6
+
[In][H ] K [InH] 3 ´ 10 -5 ´ 25
Ka = ;[H + ] = a ;[H + ] = = 1 ´ 10 -5 27. (b) HCO 3- ® H + + CO 32-
[InH] [In] 75
19. (b) pH of 1 ´ 10-8 M HCl is below 7. [H + ][CO32- ]
H2PO4– + H2O HPO42– + H3O+ K2 = = 4.8 ´10-11
[HCO3- ]
conjugate base of H2PO–4 is H3PO4
4.8 ´10 -11[HCO 3- ]
H 2 PO4- + H + H3PO4 [H + ] = = 4.8 ´10 -11 (0.1 / 0.2)
[CO 32- ]
K (Autoprotolysis constant of water i.e. ionic product of
water) increases with temperature. For half neutralisation pH = – log [H+] = – log (4.8 × 10–11 × 0.5) =10.62
of a weak acid by a weak base, 28. (b) The basic indicator is InOH
InOH In+ + OH–
[Salt]
pH = pKa + log
[Acid] Kb =
[In + ][OH]
[InOH]
[Salt] = [Acid], \ pH = pKa
20. (b) The characteristics of the given solutions are:
[ In + ]
NaCl neutral solution Indicator will change colour when =1
[ InOH ]
NH4Cl slightly acidic due to the reaction
\ Kb = [OH–] = 1×10–11 and [H+] = 10–3
\ pH = 3
Ionic Equilibrium 241
29. (c) 37. (a) HA + BOH BA + H 2 O BA is Salt
30. (c) The pH of blood plasma (7.4) is maintained by
Kw
HCO 3- / H 2 CO 3 and HPO 24 - / H 2 PO -4 buffers \ KH = .
Ka ´ K b
31. (a) H2A H+ + HA–
Ka ´ Kb
[H + ][HA - ] [H + ]2 The inverse of K H is Kc =
Ka = = Kw
[H 2 A] Ca
2 ´ 10 -5 ´ 5 ´ 10 -6
\[H+ ] = Ka .Ca = -14
= 1.0 × 10 4
1 ´ 10
+ -3
32. (b) pH = 3, [H ] = 10 (2.0 ml) ; pH = 10, 38. (b) HIn H + + In
+ 2 ´ 10 - 3 3 10 -10 20
\ [H ] = + ´ 10 -10 = (2 ´ 10 7 + 3) pH1 = pK In + log = pK In - 2log 2
5 5 5 80
10 -10 2 -3 pH 2 = pK In + log
80
= pK In + 2log 2
or [H + ] = ´ 2 ´ 107 = ´ 10
5 5 20
pH 2 - pH1 = pK In + 2log 2 - (pK In - 2log 2)
– log [H + ] = – log 2 + 3 log 10 + log 5
= 4 log 2 = 1.20
\ pH = – 0.3010 + 3 + 7 = 3.4
39. (b) HCOOH + NaOH HCOONa + H 2 O,
33. (b) ApBq pA + + qB
Sp Sq
HCOONa is salt of weak acid and strong base which is
0.10 M.
Let the solubility be s mol/liter
Thus, 1
pH = (K w + pK a + log C)
2
+ p – q p q p. q p+q
Ksp = [A ] [B ] = [sp] [sq] = p q (s) .
1
34. (a) The solubility decreases by common ion effect. = (14 + 3.74 + log 0.1) = 8.37
2
A[Cl - ] = 0, B[Cl - ] = 0.1 40. (d) The stronger the base, the more is proton accepting
C [Cl - ] = 0.2 D [Cl–] = 0 tendency RNH 2 is stronger than NH 3 and HI is strong
0. 3 0 .1 [H + ][HCO3- ]
at. 1/4 neutralisation K1 = = 4.5 ´10-7
4 4 [CO 2 ]
0 .1 0. 3
4 4
at 3/4 neutralisation Again pH = - log[H + ] = 7.4
1 3 \ [H + ] = 4.0 ´10 -8
pH1 = pKa + log ; pH 2 = pKa + log
3 1
[HCO3- ] 4.5 ´10-7
\ = = 11
1 [CO 2 ] 4 ´ 10-8
pH1 – pH 2 = log – log 3 = 2 log 3
3
Mol.wt of K 2Cr2 O
Eq. wt. of K2Cr2O7 =
BALANCING OF CHEMICAL EQUATIONS : (b) Balance the total number of atoms undergoing change
For balancing a chemical equation the two important methods are in oxidation state.
(1) Oxidation number method - The certain rules are as follows (c) Balance the number of electrons gained and lost.
(a) Assign oxidation number to the atoms showing a change (d) Balance [O] on both sides by adding H2O.
in oxidation state. (e) Balance H atoms by adding H+ ions
Redox Reactions 247
(f) If the reaction proceeds in basic solution add sufficient
Cr2 O 27 - + H + ® 2Cr 3+ + H 2 O
number of OH– ions on both sides.
Example 1 : Balance O and H atoms on both sides by adding H2O and H+
Balance the equation involving oxidation of ammonia ions.
by copper oxide to give Cu, N2 and H2O Cr2 O 72 - + H + ® 2Cr 3+ + H 2 O
+2 –3 +13H + + 6 H 2O
0
Solution - CuO + 2 NH 3 ® Cu + N 02 + H2O Balance charge on both sides by adding electrons
¯
3´ 2 = 6e 6e Cr2 O72- + 14H + + 6e - ® 2Cr 3+ + 7H 2O
\ 3CuO + 2NH3 ® 3Cu + N2 + H2O (ii) Oxidation half-reaction
Balance O by adding H2O to RHS
3 CuO + 2NH3 ® 3Cu + N2 + 3H2O Fe 2 + – e- ® Fe3+
Example 2 : Balance electrons of two half reactions
The reduction of permanganate ion by ferrous ion in
6Fe 2+ – 6e - ® 6Fe3+
presence of a dilute acid
Adding two half reaction (electrons are cancelled)
MnO4– + Fe 2 + + H + ® Mn 2 + + Fe 3+ + H 2 O
Cr2 O72 - + 6Fe2+ + 14H + ® 2Cr 3+ + 6Fe3+ + 7H 2O
Solution =
Example 2 :
+7 Balance the equation
MnO 4– + Fe 2+ + H + ® Mn 2+ + Fe 3+ + H 2 O
¯ H 2 C 2 O + H 2 O 2 ® CO 2 + H 2 O
5e 5´1e Solution (i) Oxidation half - reaction
H 2 C 2 O ® CO 2
MnO 4– + 5Fe 2 + + H + ® Mn 2 + + 5Fe 3+ + H 2 O
Balance C, O, H atoms and charge
Balance O and H by adding H2O and H+; 3H2O on RHS
and 7H+ on LHS H 2C 2O4 ® 2CO2 + 2H + + 2e - .......... (i)
MnO 4– + 5Fe 2 + + 8H + ® Mn 2 + + 5Fe 3+ + 4H 2 O (ii) Reduction half reactions
Example 3 : H 2 O 2 ® H 2O
The reduction of dichromate ion by an iodide in Balance O, H atoms and charge
presence of a dilute acid H 2 O2 + 2H + + 2e- ® 2H 2O .......... (ii)
Cr2 O 27 - + 3+
+ I + H ® Cr + I 2 + H 2 O Add two balanced half reactions (i) and (ii)
Solution - Balancing atoms H 2 C 2 O 4 + H 2 O 2 ® 2CO 2 + 2H 2 O
+12 Example 3 :
Cr2 O 72 - + 2I + H + ® 2Cr 3+ + I 2 + H 2 O Write the complete balanced equation for the change
¯
6e 3 ´ 2e CrO24 – + SO 32 – ® Cr(OH) 4– + SO 24 – taking place in basic
solution
\ Cr2 O27 - + 6I- + H + ® 2Cr 3+ + 3I 2 + H 2O Solution - (i) The equation is
Balance O by adding 6H2O on RHS and balance H+ by
adding 13H+ on LHS CrO24 – + SO 32 – ® Cr(OH) 4– + SO 24 – reduction half
reaction.
\ Cr2 O27 - + 6I - + 14H + ® 2Cr 3+ + 3I 2 + 7H 2O
(2) Ion electron method - The rules are as follows: CrO24 – ® Cr (OH ) 4–
(a) Split up the reaction into two half reactions showing Balancing O, H atoms and charge on both sides
oxidation and reduction separately.
CrO24 – + 4H + + 3 e ® Cr(OH) 4– (i)
(b) Balance number of atoms undergoing the change of
oxidation state. (ii) Oxidation half reaction
(c) Balance O on both sides by adding H2O. SO 32 – ® SO 24 –
(d) Balance H atoms by adding H+ ions.
Balancing O, H, charge and atoms on both sides
(e) Balance charge by adding required number of electrons
(f) Make the number of electrons equal in two half reactions SO 32 – + H 2 O – 2e ® SO 24 – + 2H + (ii)
by multiplying with suitable coefficient. Multiply (i) by 2 and (ii) by 3 and add
(g) Add the two half reactions
Example 1 : 2CrO24 – + 8H + + 3SO 32 – + 3H 2 O ® 2
Oxidation of ferrous salt by potassium dichromate in acid
solution. ® 2Cr (OH) 4– + 3SO 24 – + 6H +
or
Cr2 O 72 - + Fe 2+ + H + ® Cr 3+ + Fe3+ + H 2 O
Solution - (i) Reduction half reactions 2CrO24 – + 2H + + 3SO 32 – + 3H 2 O ®
® 2Cr(OH) 4– + 3SO 24 –
–
Again adding 2OH on both sides.
Cr2 O 27 - + H + ® Cr 3+ + H 2 O
Equalize Cr atoms CrO242–
22CrO –
SO 3232–
4 ++33SO
–
++55H O®
H 22O ® 2Cr(OH) 4– + 3SO42– + 2OH -
248 Chemistry
Very Short/Short Answer Questions (ii) Balance the following reaction by oxidation number
method
1. Why is anode called oxidation electrode whereas cathode is As2S5 + H+ NO3–(conc.) ¾¾ ®
called reduction electrode? H3AsO4 + 5H2SO4 + H2O + NO2
2. 2Cu2S + 3O2 ¾¾ ® 2Cu2O + 2SO2. In this reaction which 14. (i) Balance the following equations using the half-reaction
substance is getting oxidised and which substance is getting
method in the acidic medium.
reduced. Name reducing agent and oxidising agent.
3. Calculate oxidation number of Cr in K2Cr2O7 and S in S2O32– (a) Zn + NO3- ¾¾
® Zn 2+ + NH +4
4. Fe decomposes steam while Cu does not, why?
5. Arrange the following in order of increasing oxidation number (b) MnO 4- + H 2 C 2 O 4 ¾¾
® Mn 2 + + CO 2
of iodine. I2, HI, ICl.
6. In the reaction given below which species is called a spectator (c) Cr2 O 27 - + Cl - ¾¾
® Cr 3+ + Cl 2
ion and why? (ii) Balance the following redox reaction in basic medium
Zn( s) + Cu 2+ (aq) + SO 24- (aq ) ¾¾
® using the half-reaction method:
Zn 2+ (aq) + Cu(s ) + SO24 - (aq ) (a) Mn 2 + + ClO3- ® MnO2 + ClO2
7. Show that oxidation and reduction go side by side by taking
a suitable example. (b) Cl2 ® Cl - + ClO3-
8. MnO 24 - undergoes disproportionation reaction in acidic 15. (i) What are the highest oxidation numbers of N, S and
Cl?
medium but MnO4- does not. Give reason.
(ii) 2CrO24-+ 2H+ a redox reaction?
Is Cr2O27- + H 2O
9. Starting with the correct half-reaction, write the correct overall
net ionic reaction in the following changes. (iii) Calculate oxidation number of :
(i) Chromite ion (CrO3–) is oxidised by H2O2 in strongly (a) Cr in CrO5
basic solution. (b) S in H2SO5
(ii) Iodate ion (IO3– ) oxidises the iodide I– to I2 in acidic (c) Fe in Fe3O4.
solution.
Multiple Choice Questions
(iii) Permanganate ion MnO–4 oxidises the oxalate ion (C2O24–)
to CO2 in acidic solution. 16. Which of the following is not an example of redox reaction?
10. Is it possible to store: (a) CuO + H2 ® Cu + H2O
(i) copper sulphate solution in a zinc vessel? (b) Fe2O3 + 3CO ® 2Fe + 3CO2
(ii) copper sulphate solution in a nickel vessel? (c) 2K + F2 ® 2KF
(iii) copper sulphate solution in a silver vessel? (d) BaCl2 + H2SO4 ® BaSO4 + 2HCl
(iv) copper sulphate solution in a gold vessel? 17. The oxidation number of an element in a compound is
(Take help from electrochemical series) evaluated on the basis of certian rules. Which of the following
11. The standard electrode potential corresponding to the rules is not correct in this respect?
reaction (a) The oxidation number of hydrogen is always + 1.
Au3+(aq) + 3e– ® Au(s) is + 1.42 V. (b) The algebraic sum of all the oxidation numbers in a
Predict if gold can be dissolved in 1 M HCl solution and on compound is zero.
passing H2 gas through gold solution, metallic gold will be (c) An element in the free or the uncombined state bears
precipitated or not? oxidation number zero.
12. Arrange A, B, C, D, E and H in order of increasing electrode (d) In all its compounds, the oxidation number of fluorine is
potential in the electrochemical series: – 1.
A + H2SO4 ® ASO4 + H2 18. Which of the following arrangements represent increasing
ACl2 + C ® CCl2 + A oxidation number of the central atom?
ECl2 + C ® No reaction
2BCl + D ® DCl2 + 2B (a) CrO-2 , ClO3- , CrO24 - , MnO -4
H2SO4 + D ® No reaction
(b) ClO3- , CrO42 - , MnO -4 , CrO -2
Long Answer Questions
(c) CrO-2 , ClO3- , MnO4- , CrO42 -
13. (i) Balance the following reaction by ion–electron method
K+ MnO4 + H+ Cl– ¾¾ ® (d) CrO24 - , MnO4- , CrO2- ,ClO3-
K+Cl– + Mn2+(Cl–)2 + H2O + Cl2
Redox Reactions 249
19. Nitric oxide acts as a reducing agent in the reaction –
E Values :
–
Fe3+/Fe2+ = + 0.77; I2(s)/I = + 0.54;
(a) 4 NH 3 + 5 O 2 ® 4 NO + 6 H 2O Cu2+/Cu = + 0.34; Ag+ /Ag = + 0.80V
(b) 2 NO + 3I 2 + 4H 2O ® 2NO3– + 6 I – + 8H + (a) Fe3+ (b) I2(s) (c) Cu2+ (d) Ag+
23. Which of the following elements does not show
(c) 2 NO + H 2SO 3 ® N 2 O + H 2SO 4 disproportionation tendency?
(d) 2 NO + H 2S ® N 2 O + S + H 2 O (a) Cl (b) Br (c) F (d) I
20. What products are expected from the disproportionation 24. For the redox reaction
reaction of hypochlorous acid?
(a) HCl and Cl2O (b) HCl and HClO3 MnO – + C 2O 2 – + H + ® Mn 2+ + CO 2 + H 2 O
(c) HClO3 and Cl2O (d) HClO2 and HClO4 the correct coefficients of the reactants for the balanced
21. Thiosulphate reacts differently with iodine and bromine in reaction are:
the reactions given below:
2S2 O32 - + I2 ® S4O62- + 2I - MnO – C 2O 2 – H+
S2 O32 - + Br2 + 5H 2 O ® 2SO 42- + 2Br - + 10H + (a) 2 5 16
Which of the following statements justifies the above dual (b) 16 5 2
behaviour of thiosulphate? (c) 5 16 2
(a) Bromine is a stronger oxidant than iodine.
(d) 2 16 5
(b) Bromine is a weaker oxidant than iodine.
(c) Thiosulphate undergoes oxidation by bromine and 25. ( x) MnO – + ( y)H 2 O 2 ®
reduction by iodine in these reactions.
(d) Bromine undergoes oxidation and iodine undergoes 2Mn +2 + 5H 2 O + 13/ 2O 2 + (z)e -
reduction in these reactions.
–
22. The more positive the value of E , the greater is the tendency In this reaction, value of (x), (y) and (z) are
of the species to get reduced. Using the standard electrode (a) 2, 5, 6 (b) 5, 2, 9 (c) 3, 5, 5 (d) 2, 6, 6
potential of redox couples given below find out which of the
following is the strongest oxidising agent.
1. In the following reaction, which is the species being oxidised ? 4. Which substance serves as reducing agent in the following
reaction?
2Fe3+ (aq) + 2I- (aq) ® I 2 (aq) + 2Fe2+ (aq)
(a) Fe + (b) I– 14H + + Cr2 O 2– 3+
7 + 3Ni ® 2Cr + 7H 2O + 3Ni
2+
(c) 6 (d) 3
(c) MnO2- ®MnO2 (d) Cr2O2- ® 2Cr +
9. Of the following reactions, only one is a redox reaction.
Identify it 20. Oxidation number of nitrogen in (NH4)2SO4 is
(a) Ca (OH) 2 + 2HCl ® CaCl 2 + 2H 2 O (a) –1/3 (b) –1
(c) +1 (d) –3
(b) BaCl 2 + MgSO ® BaSO + MgCl2 21. Oxidation number of carbon in CH2Cl2 is
(a) –4 (b) +4
(c) 2S 2O 2 – + 2H 2 O ® SO 2– + H +
(c) 0 (d) –2
(d) Cu 2S + 2FeO ® 2Cu + 2Fe + SO 2 22. Which of the following elements has least oxidation number ?
10. The reaction of KMnO4 and HCl results in (a) Ni(CN)4 (b) Ni(CO)4
(a) oxidation of Mn in KMnO4 and production of Cl2 (c) Fe2O3 (d) SF6
(b) reduction of Mn in KMnO4 and production of H2 23. The oxidation number of cobalt in K3[Co(NO2)6] is
(c) oxidation of Mn in KMnO4 and production of H2 (a) 0 (b) +4
(d) reduction of Mn in KMnO4 and production of Cl2 (c) +3 (d) +6
11. The reaction, 24. The brown ring complex is formulated as
[Fe(H2O)5 NO]SO4. The oxidation number of iron is
2H 2 O(l) ® 4H + (aq) + O 2 (g) + 4e - is (a) 1 (b) 2
(a) an oxidation reaction (c) 3 (d) 0
(b) a reduction reaction 25. In which of the following complexes, oxidation state of metal
(c) a redox reaction is zero ?
(d) a hydrolysis reaction (a) [Pt(NH3)2Cl2] (b) [Cr(CO)6]
12. The chemical that undergoes self oxidation and self reduction (c) [Cr(NH3)3Cl3] (d) [Cr(en)2Cl2]
in the same reaction is 26. The oxidation state of chromium in potassium dichromate
(a) benzyl alcohol (b) acetone (K2Cr2O7) is
(c) formaldehyde (d) acetic acid (a) –5 (b) +6
13. In which of the following pairs, there is greatest difference in (c) +2 (d) –2
the oxidation number of the underlined elements ?
27. The oxidation state of osmium (Os) in OsO4 is
(a) NO 2 and N 2 O (b) P 2 O and P O10 (a) +7 (b) +6
(c) +4 (d) +8
(c) N 2 O and N O (d) SO2 and SO3
28. In H2O2, the oxidation state of oxygen is
14. Phosphorus has the oxidation state of +3 in (a) –2 (b) –1
(a) phosphorous acid (c) 0 (d) –4
(b) orthophosphoric acid 29. A, B and C are three elements forming a part of compound in
(c) hypophosphorous acid
oxidation states of +2, +5 and –2 respectively. What could
(d) metaphosphoric acid
be the compound ?
15. In which of the compounds does 'manganese' exhibit highest
(a) A2(BC)2 (b) A2(BC4)3
oxidation number ?
(c) A3(BC4)2 (d) ABC
(a) MnO2 (b) Mn 3O4
30. Among the following, identify the species with an atom in
(c) K2MnO4 (d) MnSO4
+6 oxidation state
16. One of the following has both positive and negative oxidation
states (a) MnO – (b) Cr(CN) –
(a) F (b) Cl
(c) He (d) Na (c) NiF2 – (d) CrO 2 Cl 2
Redox Reactions 251
31. On reduction of KMnO4 by oxalic acid in acidic medium, the 44. The reaction in which hydrogen peroxide acts as a reducing
oxidation number of Mn changes. What is the magnitude of agent is
this change? (a) PbS + H 2 O 2 ® PbSO + H 2 O
(a) From 7 to 2 (b) From 6 to 2
(c) From 5 to 2 (d) From 7 to 4 (b) 2KI + H 2O2 ® 2KOH + I 2
32. The oxidation number of iron in Fe3O4 is (c) 2 FeSO 4 + H 2SO 4 + H 2 O 2 ®
(a) +2 (b) +3
(c) 8/3 (d) 2/3 Fe 2 (SO 4 ) 3 + 2H 2 O
33. The oxidation number of S in H2S2O8 is (d) Ag 2 O + H 2 O 2 ® 2Ag + H 2 O + O 2
(a) +2 (b) +4
45. HNO3 acts as
(c) +6 (d) +7
(a) acid (b) oxidising agent
34. When KMnO4 acts as an oxidising agent and ultimately forms
(c) reducing agent (d) Both (a) and (b)
MnO –2 , MnO2, Mn 2O3 and Mn+2, then the number of 46. When KMnO4 reacts with acidified FeSO4
electrons transferred in each case respectively is (a) FeSO4 is oxidised and KMnO4 is reduced
(a) 4, 3, 1, 5 (b) 1, 5, 3, 7 (b) only KMnO4 is oxidised
(c) 1, 3, 4, 5 (d) 3, 5, 7, 1 (c) only FeSO4 is oxidised
35. The oxidation number of sulphur in Na2S4O6 is (d) None of these
(a) 1.5 (b) 2.5 47. Formula weight divided by the change in oxidation number
(c) 3 (d) 2 gives
36. In which of the following reactions, there is no change in (a) equivalent weight of an oxidant
valency ? (b) equivalent weight of the reductant
(a) 4KClO3 ® 3KClO4 + KCl (c) the number of electrons gained in the reaction
(b) SO2 + 2 H2S ® 2H2O + 3 S (d) the equivalent weight of the oxidant or reductant
(c) BaO2 + H2SO4 ® BaSO4 + H2O2 48. The equivalent weight of Mohr’s salt,
(d) 2 BaO + O2 ® 2 BaO2 FeSO ( NH ) 2 SO . H 2 O is equal to
37. What is the coefficient of oxalate ion in the following (a) its molecular weight
reaction ? (b) its atomic weight
MnO 4– + C 2 O 24 – + H + ® Mn 2+ + CO2 + H 2O (c) half-its molecular weight
(d) one-third its molecular weight
(a) 4 (b) 2
49. In the reaction between SO2 and O3 the equivalent weight of
(c) 3 (d) 5
ozone is
38. The compound that can work both as an oxidising as well as
(a) the same as its molecular weight
a reducing agent is
(b) half of the molecular weight
(a) KMnO4 (b) H2SO4
(c) one-third of the molecular weight
(c) BaO2 (d) H2O2
(d) one-fourth of the molecular weight
39. When SO2 is passed through the solution of potassium
50. Equivalent weight of iron in Fe2O3 would be
iodate, the oxidation state of iodine changes from
(a) 28 (b) 56
(a) + 5 to 0 (b) + 5 to – 1
(c) 18.6 (d) 112
(c) – 5 to 0 (d) – 7 to – 1
51. Atomic number of an element is 22. The highest O.S. exhibited
40. Which of the following behaves as both oxidising and
by it in its compounds is
reducing agents ?
(a) 1 (b) 2
(a) H2SO4 (b) SO2
(c) 3 (d) 4
(c) H2O (d) HNO3
52. The equivalent weight of potassium permaganate in acid
41. In the reaction
solution is
2FeCl 3 + H 2S ® 2 FeCl 2 + 2 HCl + S (a) 158 (b) 31.6
(a) FeCl3 acts as an oxidising agent (c) 52.16 (d) 79
(b) Both H2S are FeCl3 are oxidised 53. The equivalent weight of phosphoric acid (H3PO4) in the
(c) FeCl3 is oxidised while H2S is reduced reaction:
(d) H2S acts as an oxidising agent. NaOH + H PO ® NaH 2 PO + H 2 O
42. Which of the following is not a reducing agent?
(a) 59 (b) 49
(a) SO2 (b) H2O2
(c) 25 (d) 98
(c) CO2 (d) NO2
54. Equivalent mass of oxidising agent in the reaction,
43. Number of moles of K2Cr2O7 reduced by one mole of Sn2+
ions is SO 2 + 2H 2S ® S + 2H 2 O is
(a) 1/3 (b) 3 (a) 32 (b) 64
(c) 1/6 (d) 6 (c) 16 (d) 8
252 Chemistry
55. In the chemical reaction, 57. The set of numerical coefficients that balances the equation
K 2 Cr2 O + X H 2 SO + YSO 2 ® K 2 CrO + HCl ® K 2 Cr2 O + KCl + H 2 O
K 2SO4 + Cr2 (SO4 )3 + Z H 2O (a) 1, 1, 2, 2, 1 (b) 2, 2, 1, 1, 1
X, Y and Z are (c) 2, 1, 1, 2, 1 (d) 2, 2, 1, 2, 1
(a) 1, 3, 1 (b) 4, 1, 4
58. (X) MnO 4– + (Y)H 2O2 ®
(c) 3, 2, 3 (d) 2, 1, 2
56. Consider the following reaction
2Mn +2 + 5H 2 O + 9O 2 + (Z)e-
– –
5H 2 O2 + X ClO2 + 2OH ® X Cl + Y O2 + 6H 2O
In this reaction, value of (X), (Y) and (Z) are
The reaction is balanced if (a) 2, 5, 6 (b) 5, 2, 9
(a) X = 5, Y = 2 (b) X = 2, Y = 5 (c) 3, 5, 5 (d) 2, 6, 6
(c) X = 4, Y = 10 (d) X = 5, Y = 5
1. The oxidation number of phosphorus in pyrophosphoric 7. Which of the following chemical reactions depict the
acid is [CBSE-PMT 1999] oxidising beahviour of H2SO4? [AIEEE 2006]
(a) +3 (b) +1 (a) NaCl + H 2 SO 4 ¾¾® NaHSO 4 + HCl
(c) +4 (d) +5 (b) 2PCl 5 + H 2SO 4 ¾
¾® 2 POCl 3 + 2HCl + SO 2 Cl 2
2. The oxidation states of sulphur in the anions SO32–, S2O42–
and S2O62– follow the order [CBSE-PMT 2003] (c) 2 HI + H 2 SO 4 ¾
¾® I 2 + SO 2 + 2 H 2 O
(d) Ca (OH ) 2 + H 2SO 4 ¾
¾® CaSO 4 + 2 H 2 O
(a) S 2 O 6 2 - < S 2 O 4 2- < SO 3 2-
(b) S2 O 4 2 - < SO 3 2- < S2 O 6 2- 8. What products are expected from the disproportionation
reaction of hypochlorous acid? [AIEEE 2006]
(c) SO32- < S2 O4 2- < S2O 6 2- (a) HCl and Cl2O (b) HCl and HClO3
(d) S2 O 4 2 - < S 2 O 6 2- < SO 3 2- (c) HClO3 and Cl2O (d) HClO2 and HClO4
9. Consider the following reaction :
3. Oxidation numbers of P in PO3– 2–
4 , of S in SO 4 and that of
z
Cr in Cr2 O 72– are respectively [CBSE-PMT 2009] xMNO4 - + yC2O42- + zH + ® xMn 2+ + 2yCO2 + H 2O
2
(a) + 3, + 6 and + 5 (b) + 5, + 3 and + 6
The value’s of x, y and z in the reaction are, respectively :
(c) – 3, + 6 and + 6 (d) + 5, + 6 and + 6
[JEE M 2013]
4. When Cl2 gas reacts with hot and concentrated sodium
hydroxide solution, the oxidation number of chlorine (a) 5, 2 and 16
changes from : [CBSE-PMT 2012 S] (b) 2, 5 and 8
(a) zero to +1 and zero to –5 (c) 2, 5 and 16
(b) zero to –1 and zero to +5 (d) 5, 2 and 8
(c) zero to –1 and zero to +3 10. The compound YBa 2 Cu 3 O 7 which shows
(d) zero to +1 and zero to –3 superconductivity has copper in oxidation state ..........
5. Which of the following is a redox reaction? [AIEEE 2002] Assume that the rare earth element Yttrium is in its usual +3
(a) NaCl + KNO3 ® NaNO3 + KCl oxidation state
(a) 3/7 (b) 7/3 [IIT 1994]
(b) CaC2O4 + 2HCl ® CaCl2 + H2C2O4
(c) 3 (d) 7
(c) Mg(OH)2 + 2NH4Cl ® MgCl2 + 2NH4OH
11. For H3PO3 and H3PO4 the correct choice is
(d) Zn + 2AgCN ® 2Ag + Zn(CN)2
[IIT SCREENING 2003]
6. The oxidation state of chromium in the final product formed
(a) H3PO3 is dibasic and reducing
by the reaction between KI and acidified potassium
dichromate solution is: [AIEEE 2005] (b) H3PO3 is dibasic and non-reducing
(a) + 3 (b) + 2 (c) H3PO4 is tribasic and reducing
(c) + 6 (d) + 4 (d) H3PO3 is tribasic and non-reducing
Redox Reactions 253
EXERCISE 3 H
|
1. (d) Pyrophosphoric acid H4P2O7 11. (a) H - O - P - OH , hence it is dibasic. It acts as reducing
Let oxidation state of phosphorus is x
(4 × 1 + (– 2) × 7 + 2 x) = 0 O
\ 2x = 10 or x = +5 agent also.
2. (c) SO 32 - ® S is in + 4 oxidation state EXERCISE 4
S2 O 24- ® S is in + 3 oxidation state 1. (a) ON of S in S8 = 0
ON of S in S2F2 = + 1
S2 O 62- ® S is in + 5 oxidation state ON of S in H2S = -2
2. (c) K2Cr2O7 + 3SO2 + 4H2SO4 ®
3. (d) PO3–
4 = x + 4 (– 2) = – 3; x – 8 = – 3; x = + 5
K 2SO 4 + Cr2 (SO 4 )3 + 3SO 3 + 4H 2 O
SO 2– = x + 4 (– 2) = – 2; x – 8 = – 2; x = + 6 O.N.of chromium changes from +6 to +3
4
loss of 10 e
3. (c) N 2-4 H 4+4 ¾¾¾¾¾ ® N 2+6 (y);
Cr2 O72– = 2x + 7 (– 2) = – 2; 2x – 14 = – 2; N
2x =12; x = + 6 O.N.of N changes from -2 to +3
4. (b) On reaction with hot and concentrated alkali a mixture 4. (a) O.N. of C changes form 0 to + 4 by oxidation. Hence
of chloride and chlorate is formed HNO3 is oxidising agent.
Hot
3Cl2 + 3 NaOH(excess) ¾¾¾ 5. (a) CrO24 - ® Cr2 O72– O.N of Cr does not change . It remains
®
+6 on both sides . Hence there is no oxidation or reduction.
-1 +5
5NaCl + NaClO3 + 3H 2O 6. (d) Xe = 53.5 % \ F = 46.5%
Relative number of atoms Xe
5. (d) The oxidation states show a change only in
reaction (d). 53.5 46.5
= = 0.4 and F = = 2.4
131.2 19
0 +1 0 +2
-2e - Simple ratio Xe = 1 and F = 6 ; Molecular formula is XeF6
Zn + 2A gCN ¾¾¾® 2Ag + Zn(CN) 2
+2e - O.N.of Xe is +6
7. (b) In iodometry, K2Cr2O7 liberates I2 from iodides (NaI or
2- - +
6. (a) Cr2O7 + 6I + 14H ¾¾ ® 2Cr3+ +3I2 +7H 2O KI). Which is titrated with Na2S2O3 solution.
+ 3 oxidation state of Cr. K 2Cr2O7 + I – + H + ¾¾
® Cr3+ + I2
+6 +4 Here, one mole of K2Cr2O7 accepts 6 mole of electrons.
7. (c) 2HI -1 + H 2SO 4 ¾ ¾® I 02 + SO 2 + 2H 2 O molecular weight
In this reaction O.N. of S is decreasing from + 6 to +4 \Equivalent weight =
6
hence undergoing reduction and O.N. of I is increases
from –1 to 0 hence undergoing oxidation therefore H2SO4 8. (c) 4P + 3KOH + 3H 2 O ® KH 2 PO 2 + PH 3
is acting as oxidising agent. O.N of P = 0, In KH2PO2 it is + 1, In PH3 it is –3. Hence P
8. (b) During disproportionation same compound undergo is oxidised and reduced
simultaneously oxidation and reduction. 9. (a) Ozone is reducing as well as oxidising is nature
+1
Oxidation 10. (a) [Co( NH 3 ) 5 Cl.]Cl 2 , H –1 –2 +1
N — O — H,
–3 +1H
- + -1 +5
3HO Cl ¾
¾® 2HCl+ HClO 3 reduction H .. H
H N-N , Mg3N2
Reduction H H
– 1, – 2, –3
9. (c) On balancing the given equations, we get
2MnO 4- + 5C 2 O 4 2- + 16H + ¾¾
® 2Mn ++ 11. (d) In H2SO4 , sulphur is in highest oxidation state (+6),
Hence H2SO4 will be strongest by oxidising agent.
+10CO 2 + 8H 2O -1 +1
So, x = 2, y = 5 & z = 16 12. (d) Cl0 + 2NaOH ® NaCl+ NaClO+ H O
2 2
10. (b) YBa2Cu3O7
+6 +7 +4
3 + 2 × 2 + 3x – (2 × 7) = 0 3M nO-- - –
4 + 2H 2O ® 2 Mn O 4 + M nO 2 + 4OH
3 + 4 + 3x – 14 = 0
3x = 7 +4 +5 +3
2 N O 2 + H 2 O ® HN O 3 + H NO 2
7
x= . All undergo disproportionation
3 13. (c) I2 is less electronegative than Br2
9
Hydrogen
GENERAL INTRODUCTION : MANUFACTURE OF HYDROGEN :
Symbol of hydrogen is H. Electronic Configuration 1s1. Hydrogen i) From water gas (Bosch process) : By passing water gas
is the lightest and most abundant element in the universe. It was mixed with steam over heated catalyst Fe3O4 and Cr2O3 at
first prepared by Sir Henry Cavendish by the action of sulphuric 450ºC.
acid on Zinc and named by Antoine Lavoisier since it produced
Re d Hot
water on burning. H 2 O(Steam) ¾¾ ¾¾® (CO + H 2 )
Coke
water gas
(Greek : hydra= water, gennas = maker or producing)
PREPARATION OF DIHYDROGEN : Fe O , Cr O
(CO + H 2 ) + H 2 O ¾¾2¾3¾ ¾
2¾3 ® CO + 2 H
450 º C 2 2
i) From cold water : By the action of Na, K, Ca etc.
2 Na + 2H 2 O ® 2 NaOH + H 2 (highly exothermic and H2 The CO2 is removed by dissolving in water under high
pressure.
cathces fire)
ii) By Lane’s process : The superheated steam is passed over
Al-Hg and Zn-Cu couple decompose water to give nascent
heated iron at 600 - 800ºC
hydrogen
Zn + 2H 2 O ® Zn(OH) 2 + 2H 3 Fe + 4H 2 O Fe3O 4 + 4H 2
Hence Couples constitute better reducing agents Iron is regenerated by passing water gas. (H2 + CO)
ii) From hot water : By the action of Mg, Zn, Al etc. Fe 3O 4 + 4CO ® 3Fe + 4CO 2
2Al + 3H 2 O ® Al 2 O 3 + 3H 2 Fe 3O 4 + 4H 2 ® 3Fe + 4H 2 O
iii) From steam : By the action of Fe, Sn etc. In actual practice steam is passed over hot iron for 10 - 15
3Fe + 4H 2 O ® Fe3O 4 + 4H 2 minutes and then water gas is blown over heated oxide for
25 - 30 minutes.
iv) From water : By the action of metallic hydrides of alkali and iii) By electrolysis of water : By the electrolysis of acidified or
alkaline earth metals. alkaline water.
CaH 2 + 2H 2 O ® Ca (OH ) 2 + H 2
H 2O H + + OH -
v) From acids : By the action of dilute acids on Zn, Mg, Fe,
etc. placed above hydrogen in electrochemical series. At cathode 2H + + 2e - ® H 2
Sn + 2HCl ® SnCl 2 + H 2
At anode 4OH - - 4e - ® 4OH ® 2H 2 O + O 2
Zn + H 2SO 4 ® ZnSO 4 + H 2
iv) As by product : When NaOH is manufactured by electrolysis
vi) From alkalies : By the action Zn, Al, Sn etc. of NaCl in Nelson or Castner Kellner cell hydrogen is
Zn + 2NaOH ® Na 2 ZnO 2 + H 2 obtained as by product.
2Al + 2 NaOH + 2 H 2 O ® 2 NaAlO2 + 3 H 2 2 NaCl ® 2 Na + + Cl -
258 Chemistry
used for making LiAlH4, NaBH4 etc and for removing last
traces of water from organic compound. O OH
2) Molecular or covalent hydrides : These are formed by 4th,
5th, 6th, 7th group elements and boron by sharing electrons O
with hydrogen atoms. eg.: NH3, HCl, B2H6, AsH3 . These C2H5
O2
are non electrolytes and are usually gases or liquids. + H2O2
3) Metallic or interstitial hydrides : The transition elements
and rare earth metals combine with hydrogen to give O
interstitial hydrides. They exhibit metallic properties and 3) By electrolysis of ammonium sulphate solution and
are powerful reducing agents. They are non stoichiometric sulphuric acid. When aqueous solution of ammonium
compounds and their composition varies with temperature sulphate and sulphuric acid in equimolar proportion is
and pressure. eg. LaH2.76, TiH1.73 electrolysed at low temperature ammonium persulphate is
4) Polymeric hydrides : These are solids containing molecules, formed. The latter on distillation with sulphuric acid gives
linked together in two or three dimensions by hydrogen 30% solution of hydrogen peroxide.
bridge bonds. e.g.: (BeH2)n, (MgH2)n and (AlH3)n
( NH 4 ) 2 SO 4 + H 2SO 4 ® 2 NH 4 .HSO 4
HYDROGEN PEROXIDE :
Discovery : French chemist Thenard 1818. NH 4 HSO 4 NH 4SO -4 + H +
Occurrence : Traces in air, rain and plants.
At anode :
PREPARATION :
i) Lab method : From true peroxide by the action of ice cold 2 NH 4SO -4 ® ( NH 4 ) 2 S 2 O8 + 2e -
dil. H2SO4.
At cathode :
Na 2 O 2 + H 2SO 4 ® Na 2SO 4 + H 2 O 2
2 H + + 2e - ® H 2 ( g )
BaO 2 + H 2SO 4 ® BaSO 4 + H 2 O 2
( NH 4 ) 2 S2 O8 + 2H 2 O ® 2 NH 4 HSO 4 + H 2 O 2
(HNO3 is not used since it will oxidise H2O2).
260 Chemistry
CONCENTRATION OF HYDROGEN PEROXIDE : ii) Oxidising agent : It is strong oxidising agent in acidic as
It is very carefully concentrated since it decomposes on heating well as in basic medium.
or on standing.
H 2 O 2 + 2 H + + 2e - ® 2 H 2 O Eº = 1.77 V
2H 2 O 2 ® 2H 2 O + O 2 (auto-oxidation)
Decomposition is catalysed by Cu, Ag, Pt, Co, Fe, MnO2 etc. H 2 O 2 + OH – + 2e - ® 3OH - Eº = 0.88 V
The methods employed for concentration are
i) Evaporation : By careful evaporation of solution on a water or H 2O 2 ® H 2O + O
bath (50% H2O2 is obtained).
PbS + 4O ® PbSO 4
ii) Dehydration in vacuum desicator : The 50% H2O2 is
dehydrated in a vacuum desicator in presence of conc. H2SO4 2KI + H 2 O + O ® 2KOH + I 2
when 90% H2O2 is obtained. 2FeSO 4 + H 2SO 4 + O ® Fe 2 (SO 4 ) 3 + H 2 O
iii) Vacuum distillation : The 90% H2O2 obtained in step (ii) is
distilled under reduced pressure to get 100% H2O2 2K 4 [Fe(CN) 6 ] + H 2 O + O ® 2K 3 [ Fe(CN ) 6 ] + 2KOH
iv) Cooling : The traces of water left are removed by freezing in
a freezing mixture when crystals of hydrogen peroxide H 2 Cr2 O7 + 4O ® 2CrO5 + H2O
Chromic Blue peroxide
separate out. acid of chromium
STRENGTH OF HYDROGEN PEROXIDE :
C 6 H 6 + O ® C 6 H 5 OH
The strength of hydrogen peroxide is indicated in terms of the
volume of oxygen at NTP that 1 volume of H2O2 gives on heating. In basic medium
For example “20 volume H2O2 means 1 volume of H2O2 at NTP
will give 20 volume of oxygen. The normality and percentage 2Cr 3+ + 3H 2 O 2 + 10OH – ® 2CrO42 - + 8H 2 O
strength of H2O2 can be calculated as follows
Mn 2+ + H 2 O 2 + 2OH – ® MnO2 + 2H 2 O
2 H 2 O 2 ® 2H 2 O + O 2
iii) Reducing agent :
2 × 34 = 68 g 1 mole O2 = 22.4 litres of O2 at NTP
22.4 litres of O2 at NTP are evolved from 68g of H2O2 a) In acidic medium
Very Short/ Short Answer Questions 18. Complete the following reactions :
1. Why is 2-ethylanthraquinol preferred in the commercial (i) P4O10 + H2O ® (ii) AlCl3 + H2O ®
production of H2O2? (iii) SiCl4 + H2O ® (iv) Ca3P2 + H2O ®
2. Give an example to show that ionic hydrides forms (v) NaH + H2O ®
complexes. Multiple Choice Questions
3. Which gas is evolved when Mg3N2 (Magnesium nitride)
19. Hydrogen resembles halogens in many respects for which
is treated with H2O? Give chemical reaction.
several factors are responsible. Of the following factors
4. How would you prepare a sample of ND3? which one is most important in this respect?
5. How does heavy water react with Al4C3? (a) Its tendency to lose an electron to form a cation.
6. Arrange H2, D2 and T2 in the decreasing order of their boiling (b) Its tendency to gain a single electron in its valence
points. shell to attain stable electronic configuration.
7. Conc. H2SO4 cannot be used for drying H2, why? (c) Its low negative electron gain enthalpy value.
8. Why ice is less dense than water ? (d) Its small size.
9. Statues coated with white lead on long exposure to 20. Which of the following reactions increases production of
atmosphere turn black and original colour can be restored dihydrogen from synthesis gas?
on treatment with H2O2. Why?
1270 K
10. How will you show that H2O2 will act like oxidizing agent in (a) CH 4 ( g ) + H 2 O( g ) ¾¾¾¾ ® CO( g ) + 3H 2 ( g )
Ni
acidic as well as basic medium?
11. Why hard water is not used in industrial boilers for producing 1270K
(b) C( s ) + H 2 O( g ) ¾¾¾¾
® CO( g ) + H 2 ( g )
steam?
673K
12. Hydrogen forms compounds with elements having atomic (c) CO( g ) + H 2O( g ) ¾¾¾¾ ® CO2 (g) + H 2 (g)
Catalyst
number 9, 11, 12 and 17. What are their chemical formulae?
Compare their chemical behaviour. 1270K
(d) C 2 H 6 + 2H 2 O ¾¾¾¾
® 2CO + 5H 2
13. What happens when– Ni
(i) Water reacts with cyanamide of calcium 21. Which of the following reactions is an example of use of
(ii) Peroxosulphuric acid is hydrolysed. water gas in the synthesis of other compounds?
(iii) Moist silver oxide reacts with H2O2 1270K
(a) CH4(g) + H2O(g) ¾¾¾¾
Ni
® CO(g) + H2(g)
14. Describe the industrial application of H2 dependent on
673K
(i) the heat liberated when its atoms are made to combine (b) CO(g) + H2O(g) ¾¾¾¾
Catalyst
® CO (g) + H (g)
2 2
on the surface of a metal
(ii) its effect on unsaturated organic system is presence of 1270K
(c) CnH2n+2 + nH2O (g) ¾¾¾¾
Ni
® nCO + (2n + 1)H2
catalyst
(iii) its ability to combine with N2 under specific conditions Cobalt
(d) CO(g) + 2H2(g) ¾¾¾¾
Catalyst
® CH OH(l)
3
15. A mixture of hydrazine and H2O2 with Cu (II) catalyst is
used as a rocket propellant. Why? 22. Consider the following statements :
1. Atomic hydrogen is obtained by passing hydrogen
Long Answer Questions through an electric arc.
16. (i) What are the ways in which water molecules are bound 2. Hydrogen gas will not reduce heated aluminium oxide.
to an anhydrous salt to form hydrate? 3. Finely divided palladium absorbs large volume of
hydrogen gas.
(ii) Why water is an excellent solvent?
4. Pure nascent hydrogen is best obtained by reacting
17. How does dihydrogen react with Na with C2H5OH.
(i) O2 (ii) C Which of the above statements is/are correct ?
(iii) N2 (iv) F2 (a) 1 alone (b) 2 alone
(v) Cl2? (c) 1, 2 and 3 (d) 2, 3 and 4
Hydrogen 265
23. Elements of which of the following group(s) of periodic table Codes
do not form hydrides. (a) 1–C, 2–D, 3–B, 4–A
(a) Groups 7, 8, 9 (b) Group 13
(b) 1–B, 2–A, 3–C, 4–D
(c) Groups 15, 16, 17 (d) Group 14
24. Water contracts on heating (c) 1–B, 2–D, 3–C, 4–A
(a) to 100 °C (b) from 0°C to 4°C (d) 1–C, 2–A, 3–B, 4–D
(c) to 273 K (d) from 10°C to 20°C 26. Consider the reactions
25. Match list I with list II and select the correct answer using
(A) H2O2 + 2HI ® I2 + 2H2O
the codes given below the lists :
List I List II (B) HOCl + H2O2 ® H3O+ + Cl– + O2
1. Heavy water A. Bicarbonates of Which of the following statements is correct about H2O2
Mg and Ca in with reference to these reactions? Hydrogen peroxide is
water ______ .
2. Temporary B. No foreign ions
hard water in water (a) an oxidising agent in both (A) and (B)
3. Soft water C. D2O (b) an oxidising agent in (A) and reducing agent in (B)
4. Permanent hard D. Sulphates & (c) a reducing agent in (A) and oxidising agent in (B)
water chlorides of (d) a reducing agent in both (A) and (B)
Mg & Ca in water
1. Which of the following metal evolves hydrogen on reaction 8. Which one of the following pairs of substances on reaction
with cold dilute HNO3 ? will not evolve H2 gas ?
(a) Mg (b) Al (a) Iron and H2SO4 (aq)
(c) Fe (d) Cu (b) Iron and steam
2. The metal which gives hydrogen on treatment with acid as (c) Copper and HCl (aq)
well as sodium hydroxide is (d) Sodium and ethanol
(a) Fe (b) Zn 9. Which of the following will not displace hydrogen
(c) Cu (d) None of these (a) Ba (b) Pb
3. The metal that cannot displace hydrogen from dil HCl is (c) Hg (d) Sn
(a) Al (b) Fe 10. The adsorption of hydrogen by palladium is called
(c) Cu (d) Zn (a) hydration
4. Action of water or dilute mineral acids on active metals can (b) reduction
give (c) occlusion
(a) monohydrogen (b) tritium (d) hydrogenation
(c) dihydrogen (d) trihydrogen 11. Reaction of potassium with water is
5. The property of hydrogen which distinguishes it from other (a) exothermic (b) endothermic
alkali metals is (c) hydrolysis (d) absorption
(a) its electropositive character 12. Consider the following statements :
(b) its affinity for non-metals 1. Atomic hydrogen is obtained by passing hydrogen
(c) its reducing character through an electric arc.
(d) its non-metallic character 2. Hydrogen gas will not reduce heated aluminium oxide.
6. 2 g of aluminium is treated separately with excess of dilute 3. Finely divided palladium adsorbs large volume of
H2SO4 and excess of NaOH. The ratio of the volumes of hydrogen gas
hydrogen evolved is 4. Pure nascent hydrogen is best obtained by reacting Na
(a) 2 : 3 (b) 1 : 1 with C2H5OH
(c) 2 : 1 (d) 1 : 2 Which of the above statements is/are correct ?
7. Which of the following statements is correct ? (a) 1 alone (b) 2 alone
(a) Hydrogen has same IP as alkali metals (c) 1, 2 and 3 (d) 2, 3 and 4
(b) Hydrogen has same electronegativity as halogens 13. Metal hydride on treatment with water gives
(c) It has oxidation number of –1 and +1 (a) H2O2 (b) H2O
(d) It will not be liberated at anode. (c) acid (d) hydrogen
266 Chemistry
14. H2O2 is commonly prepared in lab. by the reaction of 27. When two ice cubes are pressed over each other, they unite to
(a) PbO2 + H2SO4 (b) MnO2 + H2SO4 form one cube. Which of the following forces is responsible to
(c) BaO2 + H2O + CO2 (d) Na2O2 + H2O hold them together ?
15. Calculate the normality of 10 volume H2O2 ? (a) Hydrogen bond formation
(a) 1.7 N (b) 12 N (b) van der Waals forces
(c) 30.3 N (d) 0.0303 N (c) Covalent attraction
16. Commercial 10 volume H2O2 is a solution with a strength of (d) Ionic interaction
approximately 28. The process used for the removal of hardness of water is
(a) 30% (b) 3% (a) Calgon (b) Baeyer
(c) 1% (d) 10% (c) Serpeck (d) Hoope
17. A, 6 volume sample of H2O2 29. Pure water can be obtained from sea water by
(a) will contain 6% V/V of H2O2 (a) centrifugation (b) plasmolysis
(b) will contain 6% W/V of H2O2 (c) reverse osmosis (d) sedimentation
(c) would give 6 volumes of oxygen per unit volume of H2O2 30. Polyphosphates are used as water softening agents because
sample at STP they
(d) would give 6 volumes of oxygen per unit weight of H2O2 (a) form soluble complexes with anionic species
sample at STP (b) precipitate anionic species
18. The structure of H2O2 is (c) form soluble complexes with cationic species
(a) planar (b) non planar (d) precipitate cationic species
(c) spherical (d) linear 31. What is heavy water ?
19. In which of the following reactions, H2O2 is acting as a (a) H2O18 (b) H2O16
reducing agent (c) H2O3 (d) D2O
(a) H 2 O 2 + SO 2 ® H 2SO 4 32. D2O is used in
(b) 2KI + H 2 O 2 ® 2KOH + I 2 (a) industry (b) nuclear reactor
(c) medicine (d) insecticide
(c) PbS + 4H 2 O 2 ® PbSO 4 + 4H 2 O 33. Match list I with list II and select the correct answer using
(d) Ag 2 O + H 2 O 2 ® 2Ag + H 2 O + O 2 the codes given below the lists :
List I List II
20. Which of the following is formed by the action of water on
1. Heavy water A. Bicarbonates of Mg
sodium peroxide
and Ca in water
(a) H2 (b) N2
2. Temporary B. No foreign ions
(c) O2 (d) CO2
hard water in water
21. The percentage by weight of hydrogen in H2O2 is
3. Soft water C. D2O
(a) 5.88 (b) 6.25
(c) 25 (d) 50 4. Permanent hard D. Sulphates & chlorides of
22. In which of the following reactions, H2O2 acts as a reducing water Mg & Ca in water
agent? Codes
(a) 1–C, 2–D, 3–B, 4–A (b) 1–B, 2–A, 3–C, 4–D
(a) PbO 2 (s ) + H 2 O 2 (aq ) ® PbO(s) + H 2 O(l) + O 2 (g)
(c) 1–B, 2–D, 3–C, 4–A (d) 1–C, 2–A, 3–B, 4–D
(b) Na 2 SO 3 (aq ) + H 2 O 2 (aq ) ® Na 2SO 4 (aq ) + H 2 O (l) 34. What is formed when calcium carbide reacts with heavy
(c) 2KI(aq ) + H 2 O 2 (aq) ® 2KOH (aq ) + I 2 (s) water?
(d) KNO 2 (aq ) + H 2 O 2 (aq ) ® KNO 3 (aq ) + H 2 O (l) (a) C2D2 (b) CaD2
(c) Ca2D2O (d) CD2
23. The low density of ice compared to water is due to
35. The correct order of the O–O bond length in O2, H2O2 and
(a) hydrogen bonding interactions
O3 is
(b) dipole – dipole interactions
(c) dipole – induced dipole interactions (a) O2 > O3 > H2O2 (b) O3 > H2O2 > O2
(d) induced dipole – induced dipole interactions (c) H2O2 > O3 > O2 (d) O2 > H2O2 >O3
24. The alum used for purifying water is 36. The hydride ion H– is stronger base than its hydroxide ion
(a) Ferric alum (b) Chrome alum OH–. Which of the following reactions will occur if sodium
(c) Potash alum (d) Ammonium alum hydride (NaH) is dissolved in water ?
25. The boiling point of water is exceptionally high because (a) H - (aq ) + H 2 O ® H 3O -
(a) there is covalent bond between H and O (b) H - (aq ) + H 2 O(l) ® OH - + H 2
(b) water molecule is linear (c) H - + H 2 O ® No reaction
(c) water molecules associate due to hydrogen bonding
(d) None of these
(d) water molecule is not linear
26. The H–O–H angle in water molecule is about 37. The component present in greater proportion in Coal gas is
(a) 90º (b) 180º (a) CH4 (b) CO2
(c) 102º (d) 105º (c) CO (d) H2
Hydrogen 267
1. The O – O – H bond angle in H2O2 is [CBSE-PMT 1994] 6. Which of the following statements in relation to the
(a) 106° (b) 109°28' hydrogen atom is correct ? [AIEEE 2005]
(c) 120° (d) 94.8° (a) 3s, 3p and 3d orbitals all have the same energy
2. When H2O2 is oxidised the product is [CBSE-PMT 1999] (b) 3s and 3p orbitals are of lower energy than 3d orbital
(a) OH– (b) O2
(c) 3p orbital is lower in energy than 3d orbital
(c) O2– (d) HO2–
3. Some statements about heavy water are given below: (d) 3s orbital is lower in energy than 3p orbital
(A) Heavy water is used as a moderator in nuclear reactors. 7. In context with the industrial preparation of hydrogen from
(B) Heavy water is more associated than ordinary water. water gas (CO + H2), which of the following is the correct
(C) Heavy water is more effective solvent than ordinary statement? [AIEEE 2008]
water. (a) CO and H2, are fractionally separated using differences
Which of the above statements are correct?
in their densities
[CBSE-PMT 2010]
(a) (A) and (C) (b) (A) and (B) (b) CO is removed by absorption in aqueous Cu2Cl 2
(c) (A), (B) and (C) (d) (B) and (C) solution
4. Which one of the following processes will produce hard (c) H2 is removed through occlusion with Pd
water ? [AIEEE 2003] (d) CO is oxidised to CO2 with steam in the presence of a
(a) Saturation of water with MgCO3 catalyst followed by absorption of of CO2 in alkali
(b) Saturation of water with CaSO4 8. The critical temperature of water is higher than that of O2
(c) Addition of Na2SO4 to water
because H2O molecule has [IIT 1997]
(d) Saturation of water with CaCO3
5. Which of the following species is diamagnetic in nature? (a) fewer electrons than oxygen
(b) two covalent bonds
(a) H -2 (b) H +2 [AIEEE 2005]
(c) v-shape
(c) H2 (d) He +2
(d) dipole moment
1. Hydrogen is not obtained when Zn reacts with 5. The m.pt. of most of the solid substances increase with an
(a) cold water (b) dil H2SO4 increase of pressure. However ice melts at a temperature
lower than its usual melting point when pressure is increased.
(c) dil. HCl (d) 20% NaOH
This is because
2. True peroxide is (a) ice is less denser than H2O
(a) BaO 2 (b) MnO 2 (b) pressure generates heat
(c) the chemical bonds break under pressure
(c) PbO 2 (d) NO2
(d) ice is not a true solid
3. An inorganic compound gives off O2 when heated, turns an
6. Acidified K 2 C r2 O 7 on oxidation by H 2 O 2 gives
acidic solution of KI violet and reduces acidified KMnO4.
The compound is (a) Blue solution (b) CrO5
(a) SO3 (b) KNO3 (c) Chromium peroxide (d) All of these
(c) H2O2 (d) All of these 7. Which reaction shows oxidising nature of H 2 O 2
4. Acidified solution of chromic acid on treatment with H2O2 (a) H 2 O 2 + 2 KI ¾
¾® 2 KOH + I 2
yields (b) Cl 2 + H 2 O 2 ¾
¾® 2 HCl + O 2
(a) CrO3 + H 2 O + O 2 (b) Cr2 O 2 + H 2 O + O 2 (c) H 2 O 2 + Ag 2 O ¾
¾® 2Ag + H 2 O + O 2
(c) CrO 5 + H 2 O + K 2SO 4 (d) H 2 Cr2 O 7 + H 2 O + O 2 (d) NaClO + H 2 O 2 ¾
¾® NaCl + H 2 O + O 2
268 Chemistry
of Na 2 CO 3 is treated with milk of lime, Ca (OH )2 . (b) Formation of unstable hydroxides, e.g.
2AgNO3 + 2 NaOH ® 2 NaNO3 + 2AgOH
Na 2 CO3 + Ca (OH)2 ® CaCO3 ¯ +2 NaOH
2AgOH ® Ag 2 O ¯ + H 2 O
(ii) Electrolytic process :- In this process a concentrated solution Brown
of sodium chloride is electrolysed where Cl 2 is evolved at (c) Formation of insoluble hydroxides which dissolve in
excess of NaOH e.g. Zn, Al, Sb, Pb, Sn and As.
the anode and H 2 at the cathode. However Cl2 gas reacts
with NaOH forming NaCl and sodium hypochlorite. ZnSO 4 + 2 NaOH ® Zn (OH ) 2 ¯ + Na 2SO 4
Mercury cathode process ( Castner - Kellner cell ):- This Zn (OH) 2 + 2 NaOH ® Na 2 ZnO 2 + 2H 2 O
Sodium zincate
process is used to avoid reaction between NaOH and
Cl2 .NaOH is obtained by the electrolysis of (aqueous) (d) Formation of ammonia from ammonium salts :-
solution of brine. The cell has three compartments and D
NH 4 Cl + NaOH ¾¾® NaCl + NH 3 + H 2 O
involves following reactions :-
(iii) Reaction with halogens:-
In outer compartment -
Anode - Graphite rods X 2 + 2 NaOH(cold ) ® NaX + NaXO + H 2O
Sodium hypohalite
Cathode - Mercury 3X 2 + 6 NaOH(hot ) ® 5 NaX + NaXO 3 + 3H 2 O
Electrolyte -Brine solution Sodium halate
Reaction - At Anode : (where X= Cl,Br or I)
- - (iv) Reaction with metals :- Less electropositive metals
Cl ® Cl + e ;
like Zn, Al and Sn etc. give H 2 gas with NaOH.
Cl + Cl ® Cl2
Zn + 2 NaOH ® Na 2 ZnO 2 + H 2
The s-block Elements – Alkali Metals 277
(v) Reaction with sand:- Properties :-
2NaOH + SiO 2 ® Na 2SiO3 + H 2 O (i) Heating effect :- It gives CO 2 and Na 2 CO 3 .
sodium silicate 373K
(glass) 2 NaHCO 3 ¾¾¾® Na 2 CO 3 + CO 2 + H 2 O
(vi) Reaction with CO :- (ii) In aqueous medium it is alkaline due to hydrolysis:
150° –200°C NaHCO 3 + H 2 O ® NaOH + H 2 CO 3
NaOH + CO ¾ ¾ ¾ ¾ ¾ ® HCOONa
5 - 10 atm. sodium formate (iii) It is used as a constituent of baking powder and in medicine
(vii)Reaction with non-metals e.g.with P, Si, S, F, etc. to remove acidity of the stomach (as antacid).
D
Si + 4 NaOH ¾¾® Na 4SiO 4 + 2H 2 (iv) It is present in Selidlitz powder.
D
P4 + 3NaOH + 3H 2 O ¾¾® PH 3 + 3NaH 2 PO 2
(v) Baking powder is a mixture of starch, sodium bicarbonate
sodium hypophosphite and potassium hydrogen tartarate.
S8 + 12 NaOH ¾¾®
D
4 Na 2S + 2 Na 2 S2 O3 + 6H 2 O (vi) Fire extinguishers contain
sodium sulphide sodium thiosulphate H 2SO 4 + Na 2 CO 3 + NaHCO 3
(viii) It breaks down the proteins of the skin flesh to a pasty mass (vii) Na 2SO 4 .10H 2 O is called Glauber’s salt, anhydrous
and hence it is commonly known as caustic soda.
Na 2SO 4 is called salt cake, NaNO3 is called chile salt-
SODIUM CARBONATE OR WASHING SODA
petre, NaHSO4 is called nitre cake, mixture of Na2O2 and
Na 2CO 3 .10H 2O :
dil. HCl is called oxone.
PREPARATION : (viii)When common salt is fused with a little Na2CO3 ,5% to
It is obtained by the following process - 10% Na 2SO4 and some sugar, it acquires a dark purple colour
(i) Solvay or ammonia - soda process :- In this process,NaCl and has a characteristic saline taste. It is used in medicine
(brine), ammonia and CO2 are taken as raw materials. The and is useful for digestion.It is called kala namak or black
involving reactions are salt or sulemani namak.
NH 3 + CO 2 + H 2 O ® NH 4 HCO 3 COMPOUNDS OF POTASSIUM
30 C
NH 4 HCO 3 + NaCl ¾¾ ¾®
o
NaHCO 3 ¯ + NH 4 Cl POTASSIUM HYDROXIDE,CAUSTIC POTASH, KOH
Sodium bicarbonate
o
PREPARATION :
250 C
2NaHCO 3 ¾¾ ¾® Na 2 CO 3 + H 2 O + CO 2 (i) It is prepared in a cell similar to that used for NaOH.In this
Sodium bicarbonate
cell electrolysis of an aqueous solution of KCl takes place.
2NH 4 Cl + Ca(OH) 2 ¾¾
® CaCl 2 + 2H 2 O + 2NH 3 (ii) It is also prepared by the action of soda lime
Amm. chloride Slaked lim e Cal. Chloride
(by product ) (NaOH + CaO) on potassium carbonate.
(ii) Electrolytic Process :- In this Nelson cell is used for the POTASSIUM CARBONATE, POTASH, PEARL ASH,
manufacture of NaOH, CO2 under pressure is blown with
steam K2CO3:
Preparation :- It is prepared by following two methods-
2 NaOH + CO 2 ® Na 2 CO 3 + H 2 O (i) By Leblanc process
(iii) Leblance Process:-This is now an absolute method. (ii) By Precht process (magnesia process)
Properties :-
(i) Sodium Carbonate crystallizes from water as POTASSIUM CYNAIDE, KCN:
decahydrate which effloresces on exposure to dry air Preparation :-
forming monohyrate which on heating change to (i) By heating potassium ferrocyanide with metallic potassium
anhydrous salt (soda-ash). K 4 [Fe(CN )6 ] + 2K ¾¾® 6KCN + Fe
D
dry air
Na 2 CO3 .10H 2 O ¾¾¾® Na 2 CO3 .H 2 O + 9H 2 O (ii) It is used in electroplating and due to the formation of soluble
D complexes with gold and silver, it is used in extraction of
Na 2 CO3 .H 2 O ¾¾ ® Na 2 CO3 + H 2 O these metals.
soda ash
POTASSIUM CHLORATE, KClO3 :
(ii) On hydrolysis it forms an alkaline solution
(i) Preparation :-
Na 2 CO 3 + 2H 2 O ® H 2 CO 3 + 2 NaOH
(weak acid) (strongbase) (a) By passing Cl 2 through boiling concentrated KOH
(iii) Aqueous sodium carbonate solution react with CO2 gas solution.
and forms sodium bicarbonate. 6KOH + 3Cl 2 ® 5KCl + KClO 3 + 3H 2 O
Na 2 CO 3 + H 2 O + CO 2 ® 2 NaHCO 3 (b) By the action of KCl on NaClO3 (obtained by
(iv) It is used as fusion mixture electrolysis of NaCl at 345-350K).
(Na 2 CO 3 + K 2 CO 3 ) and black ash (Na 2 CO 3 + CaS) NaClO 3 + KCl ® KClO 3 + NaCl
SODIUM BICARBONATE, BAKING SODA, (ii) It used as an oxidising agent and in the laboratory and
NaHCO3:- preparation of O 2 .
Preparation :- It is obtained as an intermediate product in Solvay KNO 3 is called Indian salt petre or nitre.
ammonia process.
278 Chemistry
1. Which of the following is a man made element? 17. Which one of the following has highest electropositive
(a) Ra (b) Fr (c) Rn (d) Lr character?
2. Which one of these is most reactive ? (a) Cu (b) Cs (c) Ba (d) Cr
(a) Na (b) K (c) Pb (d) Mg 18. Which of the following has the highest conductivity ?
3. Alkali metals are generally extracted by
(a) reduction methods (a) Li + (b) Cs + (c) Na + (d) K +
(b) double decomposition methods 19. The metal that dissolves in liquid ammonia, giving a dark
(c) displacement methods blue coloured solution is
(d) electrolytic methods (a) tin (b) lead
4. The alkali metal which is a liquid at room temperature is (c) sodium (d) silver
(a) Fr (b) Cs (c) Rb (d) Na 20. Highly pure dil. solution of Na in liquid ammonia
5. The alkali metal which can emit its outermost electron under (a) shows blue colour
the influence of even candle light is (b) exhibits electrical conductivity
(a) Na (b) Rb (c) K (d) Cs (c) produces sodium amides
6. Francium was discoverd by (d) produces hydrogen gas
(a) Arfwedson (b) Davy 21. Which of the following alkali metal form complex hydrides
(c) Perey (d) Bunsen & Kirchoff (a) Li (b) Na (c) K (d) Rb
7. Sodium is usually kept under
22. Which of the following has the highest melting point?
(a) alcohol (b) kerosene oil
(a) NaCl (b) NaF (c) NaBr (d) NaI
(c) ammonia (d) water
23. Which of the following has lowest melting point?
8. Sodium metal cannot be stored under
(a) benzene (b) kerosene oil (a) Li (b) Na (c) K (d) Cs
(c) alcohol (d) toluene 24. With the increase in atomic weights melting points of the
alkali metals
9. Among KO 2 , AlO2- , BaO2 and NO +2 , unpaired (a) increase
electron is present in (b) decrease
(a) NO 2+ and BaO 2 (b) KO 2 and AlO -2 (c) remain constant
(d) do not show definite trend
(c) KO2 only (d) BaO 2 only
25. Lithium shows diagonal relationship with
10. The one with the largest size is (a) magnesium (b) beryllium
(a) Na (b) Na + (c) K (d) K + (c) aluminium (d) boron
11. The increasing order of atomic radius for the elements Na, 26. The electronic configuration of metal M is 1s2, 2s2 2p6, 3s1.
Rb, K and Mg is The formula of its oxide would be
(a) Na < K < Mg < Rb (b) K < Na < Mg < Rb
(a) MO (b) M 2 O (c) M 2 O3 (d) MO2
(c) Na < Mg < K < Rb (d) Rb < K < Mg < Na
12. Smallest among these species is 27. Which of the following electronic configurations corresponds
(a) hydrogen (b) helium to an element with the lowest ionization energy ?
(c) lithium (d) lithium ion (a) 1s 2 2s 2 2 p 3 (b) 1s 2 2s 2 2 p 5
13. Which of the following has largest size ?
(c) 1s 2 2s 2 2 p 6 (d) 1s 2 2s 2 2 p 6 3s1
(a) Na (b) Na + (c) Na - (d) None of these
14. Which of the following alkali metal ions has the lowest 28. Solution of sodium metal in liquid ammonia is strongly
mobility in aqueous solution ? reducing due to the presence of the following in solution
(a) sodium hydride (b) sodium amide
(a) Li + (b) Na + (c) K + (d) Cs +
(c) sodium atoms (d) solvated electrons
15. Which of the following has the least ionization potential? 29. Lithium is strongest reducing agent among alkali metals due
(a) Li (b) He (c) N (d) Zn to which of the following factor?
16. In view of their low ionization energies, the alkali metals are (a) Ionization energy (b) Electron affinity
(a) weak oxidising agents (b) strong reducing agents (c) Hydration energy (d) Lattice energy
(c) strong oxidising agents (d) weak reducing agents
280 Chemistry
30. Microcosmic salt is : (c) NaCl > KCl > LiCl > CsCl
(a) Na 2 HPO 4 .2H 2 O (b) (NH 4 )2 HPO 4 .2H 2 O (d) KCl > CsCl > NaCl > LiCl
42. The order of solubility of lithium halides in non polar solvents
(c) Na (NH 4 )HPO 4 .4H 2 O (d) None of these
follows the order :
31. Which of the following has lowest thermal stability ? (a) LiI > LiBr > LiCl > LiF
(a) Li2CO3 (b) Na 2CO3 (c) K 2CO3 (d) Rb2CO3 (b) LiF > LiI > LiBr > LiCl
32. Which one of these is basic ? (c) LiCl > LiF > LiI > LiBr
(a) CO 2 (b) SiO 2 (c) Na 2O (d) SO 2 (d) LiBr > LiCl > LiF > LiI
33. Sodium nitrate decomposes above 800°C to give 43. Which among the following is most soluble in water?
(a) N 2 (b) O2 (c) NO2 (d) Na 2O (a) CsClO4 (b) NaClO 4
34. Fires , that result from the combustion of alkali metals can be (c) LiClO4 (d) KClO 4
extinguished by 44. When sodium is treated with sufficient oxygen/air the
(a) CCl4 (b) sand product obtained is
(c) water (d) kerosene (a) Na 2O (b) Na 2 O 2 (c) NaO2 (d) NaO
35. The alkali metal that reacts with nitrogen directly to from 45. Choose the compound which does not possess a peroxide
nitride is group
(a) Li (b) Na (c) K (d) Rb (a) Na 2 O 2 (b) CrO5
36. Which of the following bicarbonates does not exist as solid?
(c) Fe 2 O 3 (d) BaO 2
(a) KHCO 3 (b) NaHCO 3 46. Which of the following alkali metals burns in air to form only
(c) CsHCO3 (d) LiHCO3 monoxide ?
(a) Na (b) Li (c) K (d) Cs
37. Which of the following is most stable?
47. Alkali metals form peroxides and superoxides except
(a) Na 3 N (b) Li 3 N (c) K 3 N (d) Rb3 N (a) Na (b) Rb (c) Li (d) Cs
38. LiNO3 on heating gives 48. Which is the most basic of the following?
(a) O2 (b) NO2 (a) Na 2O (b) BaO
1. Which one of the following properties of alkali metals 2. Which of the following is known as fusion mixture?
increases in magnitude as the atomic number rises ? [CBSE-PMT 1994]
[CBSE-PMT 1989] (a) Mixture of Na2CO3 + NaHCO3
(a) Ionic radius (b) Melting point (b) Na2CO3.10H2O
(c) Electronegativity (d) First ionization energy (c) Mixture of K2CO3 + Na2CO3
(d) NaHCO3
The s-block Elements – Alkali Metals 281
3. Sodium is made by the electrolysis of a molten mixture of 9. Which of the following statements is incorrect?
about 40% NaCl and 60% CaCl2 because [CBSE-PMT 2011M]
[CBSE-PMT 1995] (a) Pure sodium metal dissolves in liquid ammonia to give
blue solution.
(a) Ca + + can reduce NaCl to Na
(b) NaOH reacts with glass to give sodium silicate
(b) Ca + + can displace Na from NaCl (c) Aluminium reacts with excess NaOH to give Al(OH)3
(c) CaCl 2 helps in conduction of electricity (d) NaHCO3 on heating gives Na2CO3
(d) this mixture has a lower melting point than NaCl 10. The ease of adsorption of the hydrated alkali metal ions on
4. Aqueous solution of sodium carbonate absorbs NO and NO2 an ion-exchange resins follows the order :
to give [CBSE-PMT 1996] (a) Li+ < K+ < Na+ < Rb+ [CBSE-PMT 2012S]
(a) CO2 + NaNO3 (b) CO2 + NaNO2 (b) Rb+ < K+ <Na+ < Li+
(c) NaNO2 + CO (d) NaNO3 + CO (c) K+ < Na+ < Rb+ < Li+
5. In crystals of which one of the following ionic compounds (d) Na+ < Li+ < K+ < Rb+
would you expect maximum distance between centres of 11. KO2 (potassium super oxide) is used in oxygen cylinders in
cations and anions? [CBSE-PMT 1998] space and submarines because it [AIEEE 2002]
(a) LiF (b) CsF (a) absorbs CO2 and increases O2 content
(c) CsI (d) LiI (b) eliminates moisture
6. In which of the following processes, fused sodium hydroxide (c) absorbs CO2
is electrolysed at a 330ºC temperature for extraction of (d) produces ozone.
sodium? [CBSE-PMT 2000] 12. The ionic mobility of alkali metal ions in aqueous solution
(a) Castner's process (b) Down's process is maximum for [AIEEE 2006]
(c) Cyanide process (d) Both (b) and (c) (a) Li+ (b) Na+
7. The sequence of ionic mobility in aqueous solution is : (c) K+ (d) Rb+
[CBSE-PMT 2008]
13. The products obtained on heating LiNO2 will be :
+ +
(a) K > Na > Rb > Cs+ +
[AIEEE 2011RS]
(b) Cs+ > Rb+ > K+ > Na+
(c) Rb+ > K+ > Cs+ > Na+ (a) Li2 O + NO2 + O2 (b) Li 3 N + O 2
(d) Na+ > K+ > Rb+ > Cs+ (c) Li 2 O + NO + O 2 (d) LiNO3 + O2
8. The alkali metals form salt-like hydrides by the direct
14. What is the best description of the change that occurs when
synthesis at elevated temperature. The thermal stability of
these hydrides decreases in which of the following orders ? Na2O(s) is dissolved in water ? [AIEEE 2011RS]
[CBSE-PMT 2008] (a) Oxide ion accepts sharing in a pair of electrons
(a) CsH > RbH > KH > NaH > LiH (b) Oxide ion donates a pair of electrons
(b) KH > NaH > LiH > CsH > RbH (c) Oxidation number of oxygen increases
(c) NaH > LiH > KH > RbH > CsH (d) Oxidation number of sodium decreases
(d) LiH > NaH > KH > RbH > CsH
1. On heating sodium metal in a current of dry ammonia gas the 3. Gun powder is
compound formed is (a) KNO3+ Charcoal + S (b) NaNO3 + KNO3 + S
(a) sodium nitrate (b) sodium hydride (c) NaNO3 + S (d) None of these
(c) sodium amide (d) sodium azide
4. Sodium carbonate is manufactured by Solvay process. The
2. The pair of compounds which cannot exits together in
products which can be recycled are
solution is
(a) CO2 and NH3 (b) CO2 and NH4Cl
(a) NaHCO3 and NaOH (b) Na2CO3 and NaHCO3
(c) Na2CO3+ NaOH (d) NaHCO3 and NaCl (c) NaCl and CaO (d) CaCl2 and CaO.
282 Chemistry
5. Which of the following statements is false for alkali metals? 14. Sodium thiosulphate, Na2S2O3. 5H2O is used in photography
(a) Lithium is the strongest reducing agent to
(b) Sodium is amphoteric in nature (a) reduce the silver bromide grains to metallic silver
(c) Li+ is exceptionally small (b) convert the metallic silver to silver salt
(d) All alkali metals give blue solution in liquid ammonia (c) remove undecomposed AgBr as soluble silver
6. Fusion of AgCl with Na2CO3 gives thiosulphate complex.
(a) Ag2CO3 (b) silver carbide (d) remove reduced silver
(c) Ag (d) Ag2O 15. The salt on heating does not give brown coloured gas is
7. A mixture of Al(OH)3 and Fe(OH)3 can be separated easily
(a) LiNO3 (b) KNO3
by treating it with :
(a) HCl (b) NH4OH (c) Pb(NO3)2 (d) AgNO3
(c) HNO3 (d) NaOH 16. Sodium carbonate solution in water is alkaline due to
8. When sulphur is heated with NaOH (aq). The compounds (a) hydrolysis of Na+
formed are
(b) hydrolysis of CO 32-
(a) Na 2S + H 2 O
(b) Na 2SO 3 + H 2 O (c) hydrolysis of both Na+ and CO 32- ions
24. If NaOH is added to an aqueous solution of Zn 2+ ions, a 27. Na 2SO 3 and NaHCO 3 may be distinguished by treating
white precipitate appears and on adding excess NaOH, the their aqueous solution with :
precipitate dissolves. In this solution zinc exists in the : (a) MgO (b) Mg SO 4
(a) both in cationic and anionic parts (c) litmus solution. (d) dil. acid
(b) there is no zinc left in the solution 28. Which hydride is most stable :
(c) cationic part (a) NaH (b) KH
(c) CsH (d) LiH
(d) anionic part.
29. A and B are two salts. A with dil. HCl and A & B with conc.
25. Sodium cannot be extracted by the electrolysis of brine
H 2SO 4 react to give reddish brown vapours, hence A & B
solution because
respectively are :
(a) electrolysis cannot take place with brine solution.
(a) NaNO3 , NaBr (b) NaBr, NaNO3
(b) sodium reacts with water to produce NaOH + H 2
(c) NaBr, NaNO 2 (d) NaNO 2 , NaBr
(c) sodium being more electropositive than hydrogen, H 2
30. When CO 2 is bubbled into an aqueous solution of
is liberated at cathode and not sodium.
Na 2 CO 3 the following is formed :
(d) None of these
26. The raw materials in Solvay Process are : (a) NaHCO 3 (b) H 2 O
EXERCISE 1
9. (c) In NO +2 odd ( unpaired ) electron is removed. In peroxides
1. Because they have low ionisation energy and can lose
electrons when light falls on them. (O 2 2– ) no unpaired electrons are present as the
antibonding pi M.O.’s acquired one more electron each
2. Alkali metals acquire, noble gas configuration after losing 1 for pairing. AlO2– containing Al3+ (2s22p6 configuration)
electron. and 2 oxide (O2–) ions each of which does not contain
3. (i) As washing soda in laundry. unpaired electron. Superoxide O2– has one unpaired
(ii) For softening of hard water. electron in pi antibonding M.O.
4. Li. 10. (c) The size increases down the group.
5. Monohydrate (Na2CO3 . H2O) is formed as a result of 11. (c) 12. (d) 13. (c)
efflorescence. 14. (a) Li+ is most highly hydrated [Li+(H2O)6]+. Therefore its
6. Due to ammoniated electrons and cations. effective size becomes greater than any other hydrated
alkali metal cation and hence has the lowest mobility .
7. It turns white due to formation of NaOH and Na2CO3.
15. (a)
10. NaNO3 is very readily soluble in water because it is ionic in
16. (b) Alkali metals are strong reducing agents and have less
nature while LiNO3 is not readily soluble in water because it value for I.P.
is covalent in nature.
17. (b) Alkali metals are more electropositive and this character
12. Alkali metals contain unpaired electrons and hence are increases down the group.
paramagnetic. But in the salts of alkali metals there are alkali 18. (b) Cs+ due to its very high ionic mobility has the highest
metal cations which don’t have unpaired electrons. Hence conductivity.
these are diamagnetic.
19. (c)
16. (d) 17. (c) 18. (b) 19. (c) 20. (b)
20. (b) Dilute solution of Na in liquid NH3 will not produce sodium
21. (d) 22. (c) 23. (a) 24. (d) 25. (c) amide and hydrogen gas instantaneously. These are
EXERCISE 2 metastable and when catalysed give hydrogen and amide.
21. (a) Li forms LiAlH4 and Na forms NaBH4 as the complex
1. (d) Lr. all transuranics ( 93 Np -103 Lr ) are man-made
hydrides besides simple hydrides of MH type.
elements.
22. (b) NaF due to its largest lattice energy has the highest
2. (b) melting point.
3. (d) Alkali metals are highly electropositive and thus highly 23. (d) Melting point of alkali metals decreases with increase in
reducing .Therefore reduction , double decomposition size.
and displacement methods for their extraction are not 24. (b)
suitable .Only electrolytic methods are useful for their 25. (a)
extraction.
26. (b) Electronic configuration indicates that the metal is
4. (a) univalent (alkali metal). Its oxide will be M2O.
5. (d) Cs, because of its low I.E. emits electron under the 27. (d) Electronic configuration of the alkali metals correspond
influence of even candle light. to lowest I.E.
6. (c) 28. (d)
7. (b) Alcohols , NH3 and H2O all react with sodium 29. (c) Li due to highest hydration energy among the alkali metals
is the strongest reducing agent.
2ROH + 2Na ® 2RONa + H 2 ; 30. (c)
31. (a) The weaker the base, the less stable is its carbonate.
Na(s) + NH3 (x + y) ® Na + (NH3 ) x + e - (NH3 ) y Since LiOH is the weakest base, hence Li2CO3 has the
lowest thermal stability.
2Na + 2H 2 O ® 2NaOH + H 2
32. (c)
Only kerosene does not react . D
33. (b) 2NaNO3 ¾¾¾¾
® 2NaNO2 + O 2
8. (c) above 800ºC
The s-block Elements – Alkali Metals 285
34. (a) In contrast, CCl4 is a low boiling highly non inflammable EXERCISE 3
heavy liquid . Its vapours surround the fire thereby 1. (a) Within a group, ionic radius increases with increase in
cutting off air supply. atomic number. The melting points decrease down the
35. (a) group due to weakning of metallic bond. The
36. (d) LiHCO3 is unstable and exists only in solution . electronegativity and the 1st ionization energy also
37. (b) Only Li3N is stable ,others are not formed at all . decreases down the group.
38. (c) LiNO3 like alkaline earth metal and heavy metal nitrates 2. (c) Mixture of K2CO3 and Na2CO3 is called fusion mixture
undergo decomposition as
3. (d) Sodium is obtained by electrolytic reduction of its
4LiNO3 ® 2Li2O + 4NO2 + O2
chloride. Melting point of chloride of sodium is high
39. (d) Na2CO3 does not decompose to form Na2O.
(803°C) so in order to lower its melting point(600°C),
40. (d)
calcium chloride is added to it.
41. (d) Stability of a compound depends upon its enthalpy of
4. (c) 2 Na 2 CO 3 + NO + 3 NO 2 ® 4 NaNO 2 + CO
formation DHf. The more negative value of DH f shows
more stability of a compound. Thus KCl is more stable 5. (c) As Cs+ ion has larger size than Li+ and I– has larger size
than LiCl , than F–, therefore maximum distance between centres of
cations and anions is in CsI.
DH f for LiCl = -408 kJ/mol
6. (a) In Castner process, for production of (Na) Sodium metal,
DH f for KCl = -436 kJ/mol Sodium hydroxide (NaOH) is electrolysed at temperature
42. (a) As the size of the anion increases from F– to I–, the 330ºC.
covalent character increase and hence the solubility in 7. (b) Smaller the ion more is its ionic mobility in aqueous
non -polar solvent increases solution. Ionic radii of the given alkali metals is in the
LiI > LiBr > LiCl > LiF order Na+ < K+ < Rb+ < Cs+ and thus expected ionic
43. (a) The high solubility of LiClO4is mainly due to high heat of mobility will be in the order Cs+ < Rb+ < K+ < Na+.
hydration of Li+ ion. However due to high degree of solvation (or hydration)
44. (b) Na in excess of O2 forms Na2O2. because of lower size or high charge density, the
hydrated ion size follows the order Cs+ < Rb+ < K+ < Na+
45. (c) Na2O2 is Na+ O– – O–Na+; Cr2 O5 is
and thus conductivity order is Cs+ > Rb+ > K+ > Na+ i.e.
O option (b) is correct answer.
O 8. (d) The stability of alkali metal hydrides decreases from Li
O
to Cs. It is due to the fact that M–H bonds become
Cr
weaker with increase in size of alkali metals as we move
O O
down the group from Li to Cs. Thus the order of stability
BaO2 is Ba 2+ ( -
)
O - O - while Fe2 O3 consists of
of hydrides is
LiH > NaH > KH > RbH > CsH
only Fe3+ and O2 - ions. Thus Fe2 O3 does not contain i.e. option (d) is correct answer.
9. (c) 2Al(s) + 2NaOH (aq) + 2H2O (l) ¾¾
® 2NaAlO2 + 3H2
a peroxide - O - O- linkage. sod. meta aluminate
46. (b) 10. (b) All alkali metal salts are ionic (except Lithium) and soluble
47. (c) Li + does not allow its O 2 - ion to combine with other O in water due to the fact that cations get hydrated by
atom(s) to form peroxides and superoxides . water molecules. The degree of hydration depends upon
48. (a) the size of the cation. Smaller the size of a cation, greater
49. (c) Because KO2 not only provides O2 but also removes is its hydration energy.
CO2 as follows Relative ionic radii :
¾® Mg 2 + + 2Cl -
MgCl 2 ¾
USES OF CALCIUM :
(i) It is used to remove air from vaccum tubes, sulphur from
At Cathode : Mg2+ + 2e- ¾¾
® Mg petroleum and oxygen from molten steel.
(ii) It is used as a reducing agent in the extraction of such metals
At anode: Cl- ¾¾
® Cl + e - ; Cl + Cl ¾¾
® Cl2 from their oxides where carbon is ineffective.
USES OF MAGNESIUM : COMPOUNDS OF CALCIUM
(i) Mg being a light metal forms alloys with Al and Zn which are
CALCIUM OXIDE, QUICK LIME, BURNT LIME, LIME,
used in aircraft construction. e.g., elektron (95% Mg + 5%
CaO :
Zn) used in construction of aircraft, magnalium (1-15% Mg +
85-99% Al) used in construction of aircraft and light Preparation:
instruments. (i) By the thermal decomposition of calcium carbonate.
(ii) Magnesium powder is used in flash bulbs used in 1070 -1270 K
CaCO 3 ¾¾ ¾ ¾ ¾
¾® CaO + CO 2 ; DH = +1080 kg
photography.
Properties:
COMPOUNDS OF MAGNESIUM (i) It is a basic oxide.
MAGNESIUM OXIDE, MAGNESIA, MgO : (ii) Its aqueous suspension is known as slaked lime Ca(OH)2.
With MgCl2, it forms a mixture of composition MgCl2.5MgO.xH2O hissing sound
CaO + H 2 O ¾¾¾¾¾ ® Ca(OH) 2 + Heat
which is known as Sorel’s cement or magnesia cement. Burnt lime Slaked lime
MAGNESIUM HYDROXIDE, MILK OF MAGNESIA, (iii) On heating with ammonium salts it gives ammonia
Mg(OH)2: D
Its aqueous suspension is used in medicine as an antacid. CaO + 2 NH 4 Cl ¾¾® CaCl 2 + 2 NH 3 + H 2 O
(iv) It reacts with carbon to form calcium carbide.
MAGNESIUM SULPHATE OR EPSOM SALT,
MgSO4.7H2O: CaO + 3C ¾¾
® CaC 2 + CO
It shows isomorphous nature with ZnSO4.7H2O, deliquesence Calcium carbide
and efflorescence. It is used as a purgative in medicine and as a (v) It is used as basic flux, for removing hardness of water for
stimulant to increase the secretion of bile. preparing mortar (CaO + Sand + Water).
292 Chemistry
CALCIUM HYDROXIDE, SLAKED LIME, LIME WATER, (ii) On heating at about 200ºC, it also forms dead burnt plaster of
Ca(OH)2 : paris (it has no tendency to set).
Preparation: CALCIUM CARBIDE OR CALCIUM ACETYLIDE, CaC2:
(i) By dissolving quick lime in water. Preparation:
CaO + H 2 O ¾¾ ® Ca(OH) 2 ; DH = -63kJ (i) By heating a mixture of quick lime (CaO) and powdered coke
in an electric furnace at 3300K.
Properties:
(i) Its suspension in water is known as milk of lime. 3300K
CaO + 3C ¾¾ ¾ ¾® CaC 2 + CO
(ii) It gives CaCO3 (milky) and then Ca(HCO3)2 with CO2.
Properties:
Ca(OH)2 + CO2 ¾¾
® CaCO3 + H 2O (i) It reacts with water to form acetylene.
Lime water (Milkiness)
CaC 2 + 2 H 2 O ¾
¾® Ca ( OH ) 2 + HC º CH
CaCO3 + H 2 O + CO 2 ¾
¾® Ca (HCO3 ) 2 (ii) When heated with nitrogen, it forms calcium cyanamide
(Excess) (Soluble) which on reaction with steam under pressure gives NH3.
(iii) It reacts with Cl2 to give bleaching powder CaOCl2. 1373K
CaC 2 + N 2 ¾¾ ¾
¾®CaCN 2 + C
14243
Ca (OH ) 2 + Cl 2 ¾
¾® CaOCl 2 + H 2 O Nitrolim
1. The one which does not show variable valency is 13. The first ionization potentials (eV) of Be and B respectively
(a) barium (b) titanium are
(c) copper (d) lead (a) 8.29, 9.32 (b) 9.32, 9.32
2. Alkaline earth metals form ions of the general formula (c) 8.29, 8.29 (d) 9.32, 8.29
(a) M2+ (b) M+ (c) M (d) M 2– 14. Which of the following has maximum ionization energy
3. The number of covalent bonds formed by beryllium is
(a) 2 (b) 3 (c) 4 (d) 5 ¾® Ba + + e -
(a) Ba ¾ ¾® Be + + e -
(b) Be ¾
4. Alkaline earth metals show typical characteristics of (c) Ca ¾¾ ® Ca 2+ + 2e- (d) Mg ¾ ¾® Mg 2 + + 2e -
(a) inner transition elements (b) noble gases
(c) representative elements (d) transition elements. 15. The alkaline earth metals Ba, Sr, Ca and Mg may be arranged
5. The elements of group-2 are called alkaline earth metals in the order of their decreasing first ionisation potential as
because (a) Mg, Ca, Sr, Ba (b) Ca, Sr, Ba, Mg
(a) they are alkaline in nature (c) Sr, Ba, Mg, Ca (d) Ba, Mg, Ca, Sr
(b) they occur in earth’s crust and form alkaline salts 16. The first ionization energy of magnesium is lower than the
(c) their oxides are alkaline and occur in earth’s crust first ionization energy of
(d) these are s-block elements. (a) lithium (b) sodium
6. Alkaline earth metals are (c) calcium (d) beryllium
(a) reducing agents (b) oxidising agents 17. The most electropositive amongst the alkaline earth metals
(c) amphoteric (d) acidic is
7. Of the following, most reactive alkaline earth metal is (a) beryllium (b) magnesium
(a) beryllium (b) barium (c) calcium (d) barium
(c) calcium (d) strontium 18. The most electronegative alkaline earth metal is
8. The oxidation state shown by alkaline earth metals is (a) Be (b) Mg
(a) +2 (b) +1, +2 (c) –2 (d) –1, –2 (c) Ca (d) Ra
9. Which of the following ions has the largest ionic radius? 19. Which of the following metals has the highest melting point ?
(a) Be2+ (b) Mg2+ (a) Be (b) Mg
(c) Ca 2+ (d) Sr2+ (c) Ca (d) Ba
10. Density is lowest for 20. Which of the following has exceptionally high melting point
(a) Mg (b) Ca (c) Sr (d) Ba (a) MgO (b) NaOH
11. The first ionization energies of alkaline earth metals are higher (c) NaCl (d) KCl
than those of the alkali metals. This is because 21. The compounds of alkaline earth metals have the following
(a) there is an increase in the nuclear charge of the alkaline magnetic nature
earth metals (a) diamagnetic (b) paramagnetic
(b) there is a decrease in the nuclear charge of the alkaline (c) ferromagnetic (d) antiferromagnetic
earth metals 22. Among the alkaline earth metals, the element forming
(c) there is no change in the nuclear charge predominantly covalent compound is
(d) None of these (a) Ba (b) Sr
12. The first ionization potential of Mg is (c) Ca (d) Be
(a) less than Al 23. As the nuclear charge increases from neon to calcium, the
(b) more than Al orbital energies
(c) equal to Al (a) increase (b) increase very rapidly
(d) can be less or more than Al (c) increase very slowly (d) decreases
296 Chemistry
24. The following compounds have been arranged in order of 38. A salt on treatment with dil. HCl gives a pungent smelling
their increasing thermal stabilities. Identify the correct order. gas and a yellow precipitate. The salt gives green flame test
K2CO3 (I) MgCO3 (II) and a yellow precipitate with potassium chromate. The salt
CaCO3 (III) BeCO3 (IV) is
(a) I < II < III < IV (b) IV < II < III < I (a) NiSO4 (b) BaS2O3
(c) IV < II < I < III (d) II < IV < III < I (c) PbS2O3 (d) CuSO4
25. One which is not dissolved by dilute hydrochloric acid is 39. A metal is burnt in air and the ash on moistening smells of
(a) ZnS (b) MnS NH3. The metal is
(c) BaCO3 (d) BaSO4 (a) Na (b) Fe
26. The hydroxide which is best soluble in water is (c) Mg (d) Al
(a) Ba(OH)2 (b) Mg(OH)2 40. The carbide of which of the following metals on hydrolysis
(c) Sr(OH)2 (d) Ca(OH)2 gives allylene or propyne?
27. The order solubility in water of alkaline earth metal sulphates (a) Be (b) Ca
down the group is Be > Mg > Ca > Sr > Ba. This is due to (c) Al (d) Mg
increases in 41. Magnesium burns in CO2 to form
(a) ionization energy (b) melting point (a) MgO + C (b) MgO + CO
(c) coordination number (d) All of these (c) MgCO3 (d) MgO
28. Which of the following are arranged in increasing order of 42. Which of the following will liberate hydrogen by its reaction
solubilities? with hydrochloric acid?
(a) CaCO3 < KHCO3 < NaHCO3 (a) Copper (b) Phosphorus
(b) NaHCO3 < KHCO3 < CaCO3 (c) Mercury (d) Magnesium
43. Alkaline earth metals are not found free in nature because of
(c) KHCO3 < NaHCO3 < CaCO3
(a) their thermal instability
(d) CaCO3 < NaHCO3 < KHCO3
(b) their low melting points
29. Which of the following is least soluble in water?
(c) their high boiling points
(a) BeSO4 (b) BaSO4
(d) their greater chemical reactivity
(c) CaSO4 (d) SrSO4
44. Ionic hydride is not formed by
30. Which of the following sulphates has highest solubility in
(a) Be (b) Ca
water?
(c) Ba (d) Sr
(a) BaSO4 (b) CaSO4
45. Which of the following alkaline earth metal hydroxides is
(c) BeSO4 (d) MgSO4 amphoteric in character
31. The ion having highest mobility in aqueous solution is (a) Be(OH)2 (b) Ca(OH)2
(a) Be 2+ (b) Mg2+ (c) Sr(OH)2 (d) Ba(OH)2
(c) Ca 2+ (d) Ba2+ 46. A chloride dissolves appreciably in cold water. When placed
32. Which one of the following is least soluble in water? on a Pt wire in Bunsen flame, no distinctive colour is noted.
(a) BaF2 (b) MgF2 Which cation could be present?
(c) CaF2 (d) SrF2 (a) Be2+ (b) Ba2+
33. The characteristic outer electronic configuration of alkaline (c) Pb 2+ (d) Ca2+
earth metals is 47. Halides of alkaline earth metals form hydrates such as
(a) ns 1 (b) ns 2 MgCl2.6H2O, CaCl2.6H2O, BaCl2.2H2O and SrCl2.2H2O. This
2
(c) ns np 2 (d) ns2 np1 shows that halides of group 2 elements
34. Which of the following is strongest base? (a) are hygroscopic in nature
(a) Al(OH)3 (b) Mg(OH)2 (b) act as dehydrating agents
(c) Ca(OH)2 (d) Ba(OH)2 (c) can absorb moisture from air
35. As the alkaline earth metals (except Be) tend to lose their (d) All of the above
valence electrons readily, they act as 48. Which of the followng has lowest melting point?
(a) weak oxidising agents (b) weak reducing agents (a) SrF2 (b) BeF2
(c) strong oxidising agents (d) strong reducing agents (c) MgF2 (d) CaF2
36. Which of the alkaline earth metals is the strongest reducing 49. Amongst LiCl, RbCl, BeCl2 and MgCl2 the compounds with
agent? greatest and the least ionic character, respectively, are
(a) Ca (b) Sr (a) LiCl and RbCl (b) RbCl and BeCl2
(c) Ba (d) Mg (c) RbCl and MgCl2 (d) MgCl2 and BeCl2
37. The correct order of increasing ionic character is 50. Melting point of calcium halides decreases in the order
(a) BeCl2 < MgCl2 < CaCl2 < BaCl2 (a) CaF2 > CaCl2 > CaBr2 > CaI2
(b) BeCl2 < MgCl2 < BaCl2 < CaCl2 (b) CaI2 > CaBr2 > CaCl2 > CaF2
(c) BeCl2 < BaCl2 < MgCl2 < CaCl2 (c) CaBr2 > CaI2 > CaF2 > CaCl2
(d) BaCl2 < CaCl2 < MgCl2 < BeCl2 (d) CaCl2 > CaBr2 > CaI2 > CaF2
The s-Block Elements – Alkaline Earth Metals 297
51. Which liberates ammonia when treated with water? 63. Which of the following is incorrect?
(a) Li3N (b) Mg3N2 (a) Mg burns in air releasing dazzling light rich in UV rays.
(c) CaCN2 (d) All of these (b) CaCl2.6H2O when mixed with ice gives freezing mixture
(c) Mg cannot form complexes
52. In the reaction Mg + H 2 O ® X + H 2 ; X is
(steam)
(d) Be can form complexes due to its very small size
64. Chemical A is used for water softening to remove temporary
(a) MgO (b) Mg(OH)2 hardness. A reacts with Na2CO3 to generate caustic soda.
(c) MgH2 (d) None of these When CO2 is bubbled through A, it turns cloudly. What is
53. The value of x is maximum for the chemical formula of A
(a) MgSO4.x H2O (a) CaCO3 (b) CaO
(b) CaSO4.x H2O (c) Ca(OH)2 (d) Ca(HCO3)2
(c) BaSO4.x H2O 65. Blanc fire used in paints is
(d) All have the same value of x. (a) finely divided BaSO4
54. Which of the following shows high tendency to form a (b) paste of Mg(OH)2
peroxide? (c) suspension of slaked lime
(a) Lithium (b) Beryllium (d) MgCl2.5MgO.5H2O
(c) Magnesium (d) Radium 66. Mg is an important component of which biomolecule occurring
55. Which of the following alkaline earth metal oxides shows a extensively in living world?
coordination number four? (a) Haemoglobin (b) Chlorophyll
(a) BeO (b) MgO (c) Florigen (d) ATP
67. A metal X on heating in nitrogen gas gives Y. Y on treatment
(c) SrO (d) CaO
with H2O gives a colourless gas which when passed through
56. The basic character of the oxides MgO, SrO, K2O, NiO, Cs2O
CuSO4 solution gives a blue colour. Y is
increases in the order
(a) Mg(NO3)2 (b) Mg3N2
(a) MgO > SrO > K2O > NiO > Cs2O
(c) NH3 (d) MgO
(b) Cs2O < K2O < MgO < SrO < NiO 68. Which of the following is the component of most of the
(c) NiO < MgO < SrO < K2O < Cs2O kidney stones?
(d) K2O < NiO < MgO < SrO < Cs2O (a) (COO)2Ca (b) (COO)2Ba
57. Which of the following has correct increasing basic strength? (c) (COONa)2 (d) (COO)2Mg
(a) MgO < BeO < CaO < BaO (b) BeO < MgO < CaO < BaO 69. A firework gives out crimson coloured light. It contains a
(c) BaO < CaO < MgO < BeO (d) CaO < BaO < BeO < MgO salt of
58. Among the following oxides, the one which is most basic is (a) Ca (b) Na
(a) ZnO (b) MgO (c) Sr (d) Ba
(c) Al2O3 (d) N2O5 70. In India at the occasion of marriages, the fire works used
59. Which of the following peroxides is thermally most stable? give green flame. Which one of the following radicals may
be present?
(a) SrO2 (b) MgO2
(a) Na+ (b) K+
(c) CaO2 (d) BaO2 2+
(c) Ba (d) Ca2+
60. Mark the compound which does not contain calcium
71. Which of the following metal ions plays an important role in
carbonate?
muscle contraction?
(a) Fluorspar (b) Iceland spar
(a) K+ (b) Na+
(c) Marble (d) Limestone
(c) Mg2+ (d) Ca2+
61. Thermal stability of alkaline earth metal carbonates decreases 72. White enamel of our teeth is
in order (a) Ca3(PO4)2 (b) CaF2
(a) BaCO3 > SrCO3 > CaCO3 > MgCO3 (c) CaCl2 (d) CaBr2
(b) BaCO3 > SrCO3 > MgCO3 > CaCO3 73. The electric cookers have a coating that protects them
(c) CaCO3 > SrCO3 > MgCO3 > BaCO3 against fire. The coating is made of
(d) None of these (a) heavy lead (b) zinc oxide
62. Which of the following metal carbonates decomposes on (c) magnesium oxide (d) sodium sulphate
heating ? 74. Which of the following is used as a scavenger in metallurgy ?
(a) MgCO3 (b) Na2CO3 (a) Be (b) Mg
(c) K2CO3 (d) Rb2CO3 (c) Ca (d) Sr
298 Chemistry
1. The correct order of increasing thermal stability of K2CO3, 9. Match List – I with List –II for the compositions of
MgCO3, CaCO3 and BeCO3 is [CBSE-PMT 2007] substances and select the correct answer using the code
(a) BeCO3< MgCO3 < CaCO3 < K2CO3 given below the lists : [CBSE-PMT 2011M]
List - I List - II
(b) MgCO3 < BeCO3 < CaCO3 < K2CO3
Substances Composition
(c) K2CO3 < MgCO3 < CaCO3 < BeCO3
(A) Plaster of paris (i) CaSO4.2H2O
(d) BeCO3 < MgCO3 < K2CO3 < CaCO3 (B) Epsomite (ii) CaSO4.½ H2O
2. In which of the following the hydration energy is higher (C) Kieserite (iii) MaSO4.7 H2O
than the lattice energy? [CBSE-PMT 2007] (D) Gypsum (iv) MgSO4. H2O
(a) MgSO4 (b) RaSO4 (v) CaSO4
(c) SrSO4 (d) BaSO4 Code :
3. Which of the following oxides is not expected to react with (A) (B) (C) (D)
sodium hydroxide? [CBSE-PMT 2009] (a) (iii) (iv) (i) (ii)
(a) CaO (b) SiO2 (b) (ii) (iii) (iv) (i)
(c) BeO (d) B2O3 (c) (i) (ii) (iii) (v)
4. Which of the following alkaline earth metal sulphates has (d) (iv) (iii) (ii) (i)
hydration enthalpy higher than the lattice enthalpy? 10. Equimolar solutions of the following substances were
prepared separately. Which one of these will record the
[CBSE-PMT 2010]
highest pH value ? [CBSE-PMT 2012S]
(a) CaSO 4 (b) BeSO 4 (a) BaCl2 (b) AlCl3
(c) LiCl (d) BeCl2
(c) BaSO 4 (d) SrSO4
11. A metal M readily forms its sulphate MSO4 which is water-
5. Property of the alkaline earth metals that increases with their soluble. It forms its oxide MO which becomes inert on heating.
atomic number is [CBSE-PMT 2010] It forms an insoluble hyroxide M(OH)2 which is soluble in
(a) solubility of their hydroxides in water NaOH solution. Then M is [AIEEE 2002]
(a) Mg (b) Ba
(b) solubility of their sulphates in water
(c) Ca (d) Be.
(c) ionization energy
12. The solubilities of carbonates decrease down the magnesium
(d) electronegativity group due to a decrease in [AIEEE 2003]
6. The compound A on heating gives a colourless gas and a (a) hydration energies of cations
residue that is dissolved in water to obtain B. Excess of CO2 (b) inter-ionic attraction
is bubbled through aqueous solution of B, C is formed which (c) entropy of solution formation
is recovered in the solid form. Solid C on gentle heating (d) lattice energies of solids
gives back A. The compound is [CBSE-PMT 2010]
13. In curing cement plasters water is sprinkled from time to
(a) CaSO4.2H2O (b) CaCO3 time. This helps in [AIEEE 2003]
(c) Na2CO3 (d) K2CO3 (a) developing interlocking needle-like crystals of hydrated
7. Which of the following compounds has the lowest melting silicates
point ? [CBSE-PMT 2011] (b) hydrating sand and gravel mixed with cement
(a) CaCl2 (b) CaBr2 (c) converting sand into silicic acid
(c) CaI2 (d) CaF2 (d) keeping it cool
14. Which of the following on thermal decomposition yields a
8. Which one of the following is present as an active ingredient
basic as well as acidic oxide ? [AIEEE 2012]
in bleaching powder for bleaching action ? [CBSE-PMT 2011]
(a) NaNO3 (b) KClO3
(a) CaOCl2 (b) Ca(OCl)2
(c) CaCO3 (d) NH4NO3
(c) CaO2Cl (d) CaCl2
The s-Block Elements – Alkaline Earth Metals 299
EXERCISE 1 10. (b) Ca contains vacant 3d orbitals which leads much increase
in atomic volume of the element hence has the lowest
1. Gypsum is added to retard the rate of setting of cement. density.
2. Anhydrous CaSO4 can absorb water to form CaSO4 . 2H2O. 11. (a)
Plaster of paris is not used as a drying agent because it sets 12. (b) Mg has more IE1 than Al since the electron has to be
into a hard mass by absorbing water. removed from completely filled s-valence shell of Mg.
3. Caves in limestone regions get formed due to the dissolution 13. (d) 14. (d) 15. (a) 16. (d)
of calcium carbonate in water containing carbon dioxide. 17. (d) 18. (a)
4. This is because alkaline earth metals have smaller size and 19. (a) Being small and hard, Be atoms pack closely in the lattice
higher nuclear charges as compared to alkali metals. and hence Be has the highest m.pt.
5. By treating quick lime with water, slaked lime is formed. 20. (a) Higher the charge on the ions, greater is the lattice energy
and hence higher the m.pt. of the ionic solid.
7. (i) 3Ca(s) + N2(g) ¾¾
® Ca3N2(s)
21. (a) M2+ ions are present in alkaline earth metal compounds
(ii) Ca(s) + H2SO4(aq) ¾¾
® CaSO4(aq) + H2(g) thus leaving all paired electrons in (n-1) s 2 p 6
configuration and are diamagnetic.
(iii) 2Ca(s) + SO2(g) ¾¾
® 2CaO (s) + S(s)
22. (d)
(iv) Ca(s) + 2H2O (l) ¾¾ ® Ca(OH)2(aq) + H2(g) 23. (d) After neon (At No-18), the next electron enters into 4s
8. (i) Plaster of paris quickly solidifies to gypsum with the orbital which has lower energy than 3d orbitals.
evolution of heat and also expands slightly. 24. (b) 25. (d) 26. (a)
473K
27. (c) In crystalline sulphates, the co-ordination number of the
(ii) CaSO 4 . 2H 2 O ¾¾¾® CaSO 4 + 2H 2 O ions increases from Be to Ba and so also the lattice energy
Dead burnt plaster hence solubility in H2O decreases.
9. (i) BeCl2 < MgCl2 < CaCl2 < SrCl2 28. (d) Lesser the lattice energy, more will be the solubility in
H2O.
(ii) Be(OH)2 < Mg(OH)2 < Sr(OH)2 < Ba(OH)2
29. (b) 30. (c)
(iii) BaSO4 < SrSO4 < CaSO4 < BeSO4. 2+
31. (d) Ba is least hydrated hence its size becomes lesser than
12. Both Na and K can react with water. But Na also reacts with any other hydrated alkaline earth metal cation and
alcohol whereas calcium does not or react slowly. therefore has the highest ionic mobility.
15. (a) 16. (d) 17. (a) 18. (b) 19. (c) 32. (b) As we move down the group, the lattice energies of
fluorides decrease more rapidly than the hydration energy
20. (a) 21. (d) 22. (a) 23. (a) 24. (a) and hence the solubilities of the fluorides increase from
top to bottom within a group.
EXERCISE 2 33. (b) 34. (d)
1. (a) Barium shows fixed valency whereas Ti and Cu (transition 35. (d) Lower the I.E. or higher the negative electrode potential,
stronger is the reducing agent.
metals) and Pb (due to inert pair effect) show variable
valency. 36. (c) 37. (a)
38. (b) Since the salt on treatment with dil. HCl gives a pungent
2. (a)
smelling gas (SO2) and a yellow ppt., it must contain
3. (a) Since Be has two valence electrons, it forms only two S2O32– (thiosulphate ion) and further since it gives green
covalent bonds. flame test, it must contain Ba2+ ion. Hence salt is BaS2O3.
4. (c) 39. (c) Mg burns in air to form Mg3N2 which then reacts with
H2O to form NH3.
5. (c) Their oxides are alkaline and occur in earth’s crust.
40. (d) 41. (a)
6. (a) Because of low I.E. and high hydration energies.
42. (d) Since the electrode potential of Mg is lower than that of
7. (b) Ba is most electropositive amongst the listed and hence hydrogen (Eº = 0.0 volt), it will reduce H+ ions to H2 gas.
most reactive. 43. (d)
8. (a) 9. (d) 44. (d) BeH2 is covalent.
The s-Block Elements – Alkaline Earth Metals 301
45. (a) Be(OH)2 is amphoteric while Ca(OH)2, Sr(OH)2 and EXERCISE 3
Ba(OH)2 are all basic.
46. (a) Due to very high I.E. of Be, its valence electrons require 1. (a) As the basicity of metal hydroxides increases down the
high energy to remove (excite) which is not available in group from Be to Ba, the thermal stability of their
Bunsen flame hence Be2+ ions do not impart colour to carbonates also increases in the same order. Further group
the flame. 1 compounds are more thermally stable than group 2
47. (d) because their hydroxide are much basic than group 2
hydroxides therefore, the order of thermal stability is
48. (b) BeF2 being covalent has the lowest melting point (800ºC)
while all other fluorides melt around 1300ºC BeCO3 < MgCO3< CaCO3< K2CO3.
49. (b) 2. (a) In alkaline earth metals ionic size increases down the
50. (a) As the size of the anion increases, the covalent character group. The lattice energy remains constant because
increases and hence the mp. decrease. sulphate ion is so large, so that small change in cationic
51. (d) All nitrides react with H2O to give NH3 but CaCN2 also sizes do not make any difference. On moving down the
react with H2O to give NH3. group the degree of hydration of metal ions decreases
very much leading to decrease in solubility
CaNCN + 3H 2 O ¾
¾® CaCO 3 + NH 3
\ BeSO 4 > MgSO 4 > CaSO 4 > SrSO 4 > BaSO 4
52. (a) Mg(OH)2 is not formed because of poor solubility of
MgO in H2O. 3. (a) NaOH is a strong alkali. It combines with acidic and
53. (a) Because of smaller size, Mg2+ ions are extensively amphoteric oxides to form salts. Since CaO is a basic
hydrated. oxide hence does not reacts with NaOH.
54. (d) Larger the size of the atom, larger is the tendency to form 4. (b) Be2+ is very small, hence its hydration enthalpy is
peroxides.
greater than its lattice enthalpy
65. (a) 56. (c)
5. (a) Lattice energy decreases more rapidly than hydration
57. (b) The basic character of oxides increases down the group.
energy for alkaline earth metal hydroxides. On moving
58. (b) N2O5 is strongly acidic, ZnO and Al2O3 are amphoteric, down a group\ solubility of their hydroxides increases.
therefore, MgO is most basic.
D
59. (d) The stability of the peroxide increases as the size of the 6. (b) CaCO3( s ) ¾¾® CO 2( g ) + CaO ( s )
metal increases.
A colourless B
60. (a) Fluorspar is CaF2 while other compounds listed are
different crystalline forms of CaCO3. ® Ca (OH )2(aq)
CaO (s) + H 2 O ¾¾
61. (a) B
62. (a) MgCO3 decomposes on heating to give MgO and CO2 ® Ca (HCO3 )2(aq)
Ca (OH )2 + 2CO2 ¾¾
while alkali metal carbonates do not. C
63. (c)
Ca (HCO3 )2(s) ¾¾
® CaCO3(s) + CO2(g) + H 2 O(g)
A
64. (c) Ca (HCO3 ) 2 + Ca (OH) 2 ¾
¾® 2CaCO 3 ¯ +2H 2 O
temp. hardness \ Correct choice : (b)
7. (c) Melting points of halides decreases as the size of the
Ca(OH)2 + Na 2CO3 ¾¾
® 2NaOH + CaCO3 halogen increases. The correct order is
A Caustic soda
CaF2 > CaCl2 > CaBr2 > CaI2
Ca (OH) 2 + CO 2 ¾
¾® CaCO 3 ¯ + H 2 O 8. (b) Active ingredient in bleaching powder for bleaching
A milkiness action is Ca (OCl)2
65. (a) 66. (b) 1
9. (b) (A) Plaster of paris = CaSO4. H 2O
D 2
67. (b) 3Mg + N 2 ¾¾® Mg 3 N 2 ;
X Y (B) Epsomite = MgSO4.7H2O
(C) Kieserite = MgSO4.H2O
Mg 3 N 2 + 6H 2 O ¾
¾® 3Mg(OH) 2 + 2 NH 3
(D) Gypsum = CaSO4.2H2O
(colourless)
10. (a) (AlCl3, LiCl & BeCl2) ) all these solutions are acidic due
CuSO 4 + 4 NH3 ¾
¾® [Cu ( NH 3 ) 4 ] SO 4 to cationic hydrolysis, whereas BaCl2, is salt of strong
Blue complex base and strong acid, hence its solution will almost
neutral i.e., pH » 7.
68. (a) 69. (c) 70. (c) 71. (d) 72. (b)
73. (c) MgO being high melting does not catch fire and hence
protects the cooker against fire. 11. (d) Beryllium shows anomalous properties due to its small
size.
74. (c)
302 Chemistry
12. (a) The solubility is governed by DH solution 13. (d) K and Mg are formed at cathode
Due to increase in size the magnitude of hydration energy Chlorine is formed at anode 2C l - 2e - ® Cl 2 .
decreases and hence the solubility.
14. (b) The mixture of MgCl2 and MgO is known as sorel’s
13. (a) Setting of cement is exothermic process which develops cement.
interlocking crystals of hydrated silicates
15. (d) K and Mg, both form oxides
14. (c) Calcium carbonate on thermal decomposition gives CaO
(Basic oxide) and CO2 (Acidic oxide) K + O 2 ® KO 2 ;2Mg + O 2 ® 2MgO
D Mg form nitride also 3Mg + N 2 ® Mg 3 N 2
CaCO 3 CaO + CO 2
Basic oxide Acidic oxide K does not form nitride.
16. (b) Statement (b) is correct.
EXERCISE 4 1
17. (c) CaSO 4 . H 2 O ¾setting
¾¾ ¾® CaSO 4 .2H 2 O
1. (c) Plaster of Paris reacts with water to form gypsum which 2
is hard. Plaster of paris Gypsum (orthorhombic)
CaSO4 .1/ 2 H 2 O + 3/ 2 H 2 O ® CaSO 4 .2H 2 O hardening
¾¾ ¾¾ ¾® CaSO 4 .2H 2O
2. (d) Hasenclever and Batchmann’s plants are used for the
Gypsum (monoclinic)
manufacture of bleaching powder (See theory).
18. (b) CaO (Quick lime) is hygroscopic in nature.
3. (a) 2CaOCl2 + dil.H 2SO4 ® CaCl2 + CaSO 4 + 2HClO
19. (a) Mg + + + Na 2 HPO 4 + NH 4 OH
HClO ® HCl + O
4. (d) Portland cement is a complex mixture of silicates and
¾® Mg(NH 4 )PO 4 + 2 Na + + H 2 O
¾
aluminates of Ca.
White ppt
5. (c) The higher the covalent character, the lower the solubility
of compound in water. 20. (a) Ca + H 2 ¾¾® CaH 2 + 2H 2 O ¾ ¾® Ca (OH ) 2 + H 2
6. (c) Mg is more reducing in nature than carbon
21. (c) Be(OH)2 is insoluble in water and thus has lowest value
CO 2 + 2Mg ® 2MgO + C of K sp .
D
7. (a) MgCl 2 .6H 2 O ¾¾® D
MgCl 2 .2H 2 O ¾¾® 22. (b) The Be(OH)2 and Al(OH)3 are amphoteric in nature.
Mg (OH )Cl ¾
¾® MgO + HCl 23. (b) CaO + CO 2 ¾
¾® CaCO 3 .
8. (a) Dicalcium silicate sets at the lowest rate. But the CO 2 does not react with NaHCO 3 .
9. (b) Ba++ with CrO -4 - give yellow BaCrO4. It is insoluble in
24. (d) CaO + CO 2 ¾
¾® CaCO 3
CH3COOH.
CaO + H 2 O ¾
¾® Ca (OH) 2
(
10. (a) CaC2 calcium carbide is ionic Ca 2+ C22- . ) hissing sound and DH = – ve
11. (b) The bicarbonates of alkaline earth metals exist in solution
only 25. (d) Na 2 Z + Ca 2 + ¾
¾® CaZ + 2 Na +
12. (c) Be2+ being small in size is heavily hydrated and heat of
hydration exceeds the lattice energy. Hence BeF2 is
soluble in water.
11A
The p-Block Elements :
Boron Family
The elements of group 13 are Element B Al Ga In Tl
B - Boron Al - Aluminium Ga - Gallium M.p. (K) 2453 933 303 430 576
In - Indium Tl - Thallium
B.p. (K) 3923 2740 2676 2353 1730
Amongst the elements of this group, Al is the third most abundant
element found in the earth’s crust after oxygen and silicon. (b) The m. p. decreases from B to Ga and then increases,
due to structural changes in the elements
GENERAL CHARACTERISTICS (i.e., PHYSICAL
PROPERTIES) OF BORON FAMILY : (c) Boron has a very high m. p. because of its three
(i) Electronic configuration : The elements of group 13 belong dimensional (B12- icosahedral) structure in which B
to p-block of the periodic table and these elements contain atoms are held together by strong covalent bonds.
three electrons in the valence shell, therefore, their valence (d) Low m. p. of Ga is due to the fact that it consists of only
shell electronic configuration is ns2np1. Ga2 molecules, and Ga remains liquid upto 2273K
Element At. No. Electronic Valence therefore it is used in high temperature thermometry.
Confg. Shell Confg.
(v) Ionisation energy :
B 5 [He] 2s2, 2p1 2s 22p 1
(a) The first I.E. values of group 13 elements are lower than
Al 13 [Ne] 3s2, 3p1 3s 23p 1
the corresponding values of the alkaline earth metals,
Ga 31 [Ar]3 3d10, 4s24p1 4s 24p 1
due to the fact that removal of electron is easy in former
In 49 [Kr] 4d10, 5s25p 1 5s 25p 1
case (p-electron) than latter (s-electron)
Tl 81 [Xe] 4f14, 5d10, 6s2p 1 6s 26p 1
This results in the increase of nuclear charge.
(ii) Atomic radii and ionic radii : Consequently the valence electrons are more tightly
(a) Atoms and their ions of group 13 elements have smaller held leading to high I.E. Similarly we can explain the
size than those of alkaline earth metals of group-2, due irregularity in case of Tl on the basis of ineffective
to greater nuclear charge of former group than latter shielding of intervening electrons
group.
(b) On moving down the group IE, decreases from B to Al
(b) Atomic radii increase on going down in the group with
but the next element Ga has slightly higher IE, than Al,
an abnormaly at gallium and the unexpected decrease in
it again decreases in In and increases in the last element
the atomic size of Ga is due to the presence of electrons
Tl as follows :
in d- orbitals which do not screen the nucleus effectively.
(c) The ionic radii regularly increases from B 3+ Element B Al Ga In Tl
to Tl3+ IE, (kJ mol–1) 800 577 578 558 590
(iii) Density : It increases regularly on moving down the group
from B to Tl (c) The irregularity observed in case of Gallium is due to
(iv) Melting and boiling points : the ineffective shielding of nuclear charge because of
(a) M.P. and b. p. of group 13 elements are much higher intervening d electrons, which cause the increase in
than those of group 2 elements nuclear charge leading to high I.E.
304 Chemistry
(vi) Inert pair effect : (ii) Reaction with nitrogen : The elements of group 13 form
(a) It is the reluctance of the s-electrons of the valence their corresponding nitrides with the reaction of nitrogen.
shell to take part in bonding and occurs due to These nitrides undergo hydrolysis with steam and evolve
ineffective shielding of the ns 2 electrons by the NH3
intervening d and f electrons.
(b) It increases down a group and thus the lower elements 2B + N 2 ¾¾®
D
2BN
of group show lower oxidation states. Boron nitride
(vii) Oxidation states :
(a) B and Al show an oxidation state of +3 only while Ga, In D
2Al + N 2 ¾¾® 2AlN
and Tl show oxidation states of both +1 Aluminium nitride
and +3.
(b) As we move down in the group 13, due to inert pair BN + 3H 2 O ® H3 BO3 + NH3
effect, the tendency to achieve +3 oxidation state goes orthoboric acid
on decreasing and the tendency to acquire +1 oxidation
state goes on increasing. (iii) Action of water :
(c) Stability of +1 oxidation state follows the order Ga < In (a) Both B and Al do not react with water but amalgamated
< Tl aluminium does react with H2O evolving H2.
(d) Tl+ compounds are more stable than Tl3+ compounds. 2Al(Hg) + 6H2O ® 2Al(OH)3 + 3H2 +Hg
(viii) Electropositive (metallic) character : Aluminium amalgam
(a) These elements are less electropositive than the (b) Ga and In do not react with pure cold or hot water but Tl
elements of the group 1 and 2 due to their smaller size
forms an oxide on the surface.
and higher ionisation energies.
(b) On moving down the group, the electropositive (iv) Reaction with alkalies :
character first increases from B to Al and then decreases (a) Boron dissolves in alkalies on fusion and gives borates.
from Ga to Tl, due to the presence of d and f orbitals in
latter elements. 2B + 6NaOH ¾fuse¾¾® 2Na3BO3 + 3H2
(ix) Reducing character : It decreases down the group from Al (b) Al and Ga dissolve in concentrated alkalies on heating
to Tl because of the increase in electrode potential values and form meta-aluminate and gallate respectively.
for M3+/M. Therefore it follows the order.
D
Al + 2NaOH + 2H2O ¾¾® 2NaAlO2 + 3H2
Al > Ga > In > Tl
Element B Al Ga In Tl Sod. metaaluminate
Eº (V) at 298 K for M3+/M –1.66 –0.56 –0.34 +1.26
(x) Complex formation : Due to their smaller size and greater Ga + 2NaOH + 2H2O ¾¾® D 2NaGaO +3H
2 2
charge, these elements have greater tendency to form Sod. gallate
complexes than the s-block elements.
(xi) Nature of compounds : (v) Reaction with carbon :
(a) The tendency of formation of ionic compounds (a) B and Al form carbides with carbon on heating.
increases from B to Tl. D
(b) Boron forms only covalent compounds where as Al can 4B + C ¾¾® B4C
;
form both covalent (e.g., anhydrous AlCl3) and ionic Boron carbide
compounds (e.g., hydrated AlCl 3 ) because when
anhydrous AlCl3 is hydrated, the hydration energy 4Al + 3C ¾
¾® Al 4 C3
released is sufficient to overcome the ionisation energy Aluminium carbide
of Al.
(b) Aluminium carbide is ionic and forms methane with
(c) Gallium forms mainly ionic compounds although
anhydrous GaCl3 is covalent . water, while boron carbide is covalent having molecular
CHEMICAL PROPERTIES : formula B12C3 and it is very hard, hence used as an
Crystalline B is unreactive whereas amorphous B is reactive. It abrasive.
reacts with air at 700ºC as follows : (vi) Hyrides :
(a) 4B + 3O2®2B2O3; (a) Elements of group 13 do not combine directly with H2 to
2B + N2 ®2BN form hydrides, therefore, their hydrides have been
(b) Al is stable in air due to the formation of protective oxide prepared by indirect methods for example.
film. Some properties are given below
dry ether
(i) Action of Air : BF3 + 3LiBH4 ¾¾¾¾® 2B2H6 + 3LiF
(a) 4Al + 3O2 ®2 Al2O3 diborane
(b) Thallium is more reactive than Ga and In, due to the (b) Boron forms a number of hydrides which are called
formation of unipositive ion Tl+. boranes with general formula BnHn+4(e.g., B2H6) and
4Tl + O2 ®2 Tl2O BnHn+6 (e.g., B4H10)
The p -Block Elements – Boron Family 305
(c) Boranes catch fire in the presence of oxygen with the 373K
evolution of heat energy 2H 3 BO3 ¾¾¾® 2HBO 2
orthoboric acid - 2 H 2O Metaboric acid
B2H6 + 3O2 ® B2O3 + 3H2O ; DH = – 2008 kg/mol
(d) Boranes are hydrolysed by water as follows : ¾¾¾¾
®
red heat
B2O3 + H 2O
B2H6 + 6H2O ® 2H3BO3 + 6H2 Boric acid
or boron sesquioxide or
(e) Boranes are quite stable but the stability of hydrides of Boric anhydride
Al, Ga, In, and Tl decreases on moving down the group
because the strength of the M–H bond decreases with 2Al(OH)3 ® Al2O3 + 3H2O
increasing size of the element. 4Al(NO3)3 ® 2Al2O3 + 12NO2 + 3O2
(f) Structure of diborane : The simplest boron hydride, i.e. (d) The hardest alumina, a–Al2O3, which is stable at high
BH3 does not exist as such but exists as a dimer, B2H6, temperature, resistant to hydration and attacked by
having following structure acids, is called corundum and is used as an abrasive
where as g –Al2O3 is known as activated alumina and
Ha 11 Hb Ha used in column chromatography.
9p
m (viii) Hydroxides :
B 178pm B Amalgamated aluminium reacts with H2O and forms its hydroxide.
120º or
97º 2Al(Hg) + 6H2O ® Al(OH)3 + 3H2 + Hg
13
Aluminium amalgam
4p
Hb Ha
m
Hb
Ha Ha (b) On moving down the group, there is a change from
acidic to amphoteric and then to basic character of
In above structure B atoms are in sp3 hybrid state. There oxides and hydroxides of group 13 elelments.
are six B-H bonds out of which four B-Ha bonds are (x) Preparation of halides :
normal convalent bonds (two centre electron - pair (a) All the elements of boron family (except thallium which
bonds i.e, 2c–2e) present in the same plane while rest forms thallous monohalides ) form trihalides of type
two B-Hb bonds behave as bridges containing three MX3 where X= F, Cl, Br and I.
centre two electron pairs bonds i.e., 3c–2e (known as B2O3 + 3C + 3Cl2 ® 2BCl3 + 3CO
banana bonds) and present above and below the plane Al2O3 + 3C + 3Cl2 ® 2AlCl3 + 3CO
of the molecules which do not have sufficient number (b) All the boron trihalides, BX3 and aluminium trihalides
of electrons to form normal covalent bonds are called AlX 3 (except AlF 3 which is ionic) are covalent
electron - deficient molecules. Ex. B2H6. compounds whereas former exist as only monomers and
(g) Aluminium forms a polymeric hydride of general formula latter as dimers, because boron atom is too small to co-
(AlH3)x which decomposes into its elements on heating. ordinate with four large halide ions and in case of much
(h) B, Al and Ga form complex anionic hydrides, like lithium smaller F– ion , the energy released during the formation
borohydride, Li[BH4], lithium aluminium hydride , of the bridge structure is not sufficient for the cleavage
Li[AlH4] etc. due to the presence of a vacant p-orbital in of the typical pp-pp bond in BF3.
their outermost shells which accepts electron pair from
X
H– ion.
XH3 + H– ® [XH4]– where X= B, Al and Ga.
B X
(vii) Oxides :
(a) Except Tl all the elements of group 13 form oxides
(general formula, M2O3) on heating with oxygen X
BX3
4M + 3O2 ¾¾® D 2M2O3 (M = B to In)
X X X
(b) Tl forms thallium (I) oxide, Tl2O which is more stable
than thallium (III) oxide, Tl2O3 because of inert pair
Al Al
effect.
(c) B2O3 and Al2O3 can also be prepared by following
X X X
method :
Al2X6
306 Chemistry
(c) BF3 is a colourless gas, BCl3 and BBr3 are colourless (viii)It does not react with steam but other elements decompose
fuming liquids whereas BI3 is a white fusible solid at steam.
room temperature. (ix) It can be oxidised by concentrated HNO3 while aluminium is
(d) The covalent character of trihalides decreases on passive due to the formation of oxide layer on the surface.
moving from Ga to Tl. 2B +6HNO3 ® 2H3BO3 + 6NO2
(e) Hybridisation of Boron in BCl3 is sp2
Boric acid
(xi) Nature of Trihalies :
DIAGONAL RELATIONSHIP BETWEEN BORON AND
(a) Trihalides of group 13 elements behave as lewis acids
due to having a strong tendency to accept a pair of
SILICON :
electrons. Boron shows resemblance with its diagonal element silicon of
group 14. Some of the important points are given below :
(b) The relative strength of lewis acids of boron trihalides
(i) Both B and Si are non- metals.
increases in the order :
(ii) Both are semi- conductor.
BF3 < BCl3 < BBr3 < BI3. (iii) Both do not form ions, i.e., B 3+ and Si4+.
(c) The halides of group 13 elements behave as lewis acids (iv) Both B and Si form covalent hydrides : boranes i.e., B2H6,
and the acidity character decreases as follows: B4H6 etc. and silanes, i.e., SiH4, Si2H6 etc. respectively, which
BX3 > AlX3 > GaX3 > InX3 (where X=Cl, Br or I) catch fire when exposed to air.
(d) BF3 and anhydrous AlCl3 are used as a catalyst in Friedel B2H6 + 3O2 ® B2O3 + 3H2O
Crafts reactions. SiH4 + 2O2 ® SiO2 + 2H2O
(e) TlCl3 decomposes to TlCl and Cl2 above 40ºC and hence (v) Both form covalent, and volatile halides which fume in moist
acts as an oxidising agent, whereas TlBr3 converts into air due to release of HCl fumes.
Tl[TlBr4] at room temperture. BCl3 + 3H2O ® H3BO3 + 3HCl
SiCl4 + 4H2O ® H4SiO4 + 4HCl
D (vi) Both form solid oxides which are acidic and dissolve in
TlCl3 ¾¾® TlCl + Cl2 ; 2TlBr3 ® Tl[TlBr4] +Br2 alkalies forming borates and silicates respectively.
> 40 º C
B2O3 + 2NaOH ® 2NaBO2 + H2O
While TlI3 is an ionic compound containing Tl(I) and
SiO2 + 2NaOH ® Na2SiO3 + H2O
I 3- ions. (vii) Both react with electropositive metals and form binary
compounds, which yield mixture of boranes and silanes on
ANOMALOUS BEHAVIOUR OF BORON : hydrolysis. Both B and Si form hydroxides boric acid B(OH)3
Boron shows anomalous behaviour as compared to other member and silicic acid Si(OH)4 respectively which are weak acids.
of the group, due to the following reasons. D
3Mg + 2B ¾¾® Mg3B2
(i) It has smallest size in the group.
(ii) It has high ionisation energy. H O / H+
Mg3B2 ¾¾2 ¾ ¾
¾® Mixture of boranes
(iii) It has highest electronegativity in the group.
D
(iv) It does not have any vacant d-orbital in valance shell 2Mg + Si ¾¾® Mg2Si
A few points of difference are : +
Mg2Si ¾H O/H
¾2 ¾ ¾
¾® mixture of silanes
(i) It is a non-metal while other members of the group are metallic
in character. METALLURGY OF BORON
(ii) It shows allotropy as crystalline and amorphous while other OCCURRENCE AND IMPORTANT MINERALS OF
members do not. BORON :
(iii) It has the highest m. p. and b.p. amongst the elements of It does not occur in the free state in nature. It forms electron
group 13. deficient compounds.
(iv) It forms only covalent compounds while other members form Its important minerals are
both ionic and covalent compounds. (a) Borax (or Tincal), Na2B4O7.10H2O or
(v) It forms a number of hydrides which are quite stable while Na2[B4O5(OH)4]8H2O
those of other members are less stable. (b) Kernite, Na2B4O7.2H2O or Na2[B4O5(OH)4]
(vi) The halides of boron exist as monomers while AlCl3 exists (c) Orthoboric-acid H3BO3
as a dimer. (d) Colemanite, Ca2B6O11.5H2O or Ca2[B3O4(OH)3]2 2H2O
(e) Boracite, 2Mg3B8O15. MgCl2
(vii)The oxides and hydroxides of boron are weak acidic while
those of aluminium are amphoteric and those of other ISOLATION :
elements are basic. Elemental boron in the form of dark brown powder is obtained by
following methods :
The p -Block Elements – Boron Family 307
(i) By reduction of boric oxide with highly electropositve metals Heat , swells
like K, Mg, Al, Na etc. in the absence of air (iii) Action of heat : Na2B4O7.10H2O ¾¾ ¾ ¾¾®
-10H 2O
B2O3 + 6K ¾Heat
¾¾® 2B + 3K2O 740º C
(ii) By the reaction of boron halides with hydrogen at high Na2B4O7 ¾¾¾® 2NaBO2 + B2O3
temperature. Anhydrous Sodium Boric
Metaborate anhydride
2BCl3 + 3H2 ¾1270K
¾® 2B + 6HCl
¾¾ Glassy mass (Borax bead)
(iii) By thermal decomposition of boron triiodide over red hot Borax bead is used for the detection of coloured basic
tungsten filament. radicals under the name borax bead test in which on heating
W heat borax bead combines readily with a number of coloured
2BI3 ¾¾¾ ¾ ® 2B + 3I 2 transition metal oxides such as Co, Ni, Cr, Cu, Mn etc. to
(iv) By thermal decomposition of boron hydrides form the corresponding metaborates which possess
D characteristic colours.
B 2 H 6 ¾¾® 2B + 3H 2
D
USES OF BORON : CoSO4 ¾¾® CoO +SO3 ;
(i) As a semiconductor CoO +B2O3 ® Co(BO2)2
(ii) Boron steel or boron carbide rods are used to control the cobalt metaborate (blue)
nuclear reactions. Basic radical of a salt Cu Fe Co Cr Ni
10
5B + 0 n1 ®5 B11 Colours of metaborates Blue Green Blue Green Brown
Uses : It is used in making optical and hard glasses and in
COMPOUNDS OF BORON the borax bead test.
BORON HYDRIDES OR BORANES : BORIC ACID OR ORTHOBORIC ACID, H 3 BO 3
Boron forms hydrides of the type BnHn+4 and BnHn+6 which are OR B(OH) 3 :
called Boranes.
Preparation
Preparation :
(i) By treating borax with dil HCl or dil H2SO4
(i) 8BF3 + 6LiH ® B2H6 + 6LiBF4
(ii) 4BCl3 + LiAlH4 ® 2B2H6+ 3AlCl3 + 3LiCl Na2B4O7 + 2HCl + 5H2O ® 2NaCl +4H3BO3
Properties : (ii) By passing SO2 through a mixture of powdered mineral
(i) All boranes are called as electron – deficient compounds colemanite in boiling water.
because boron in boranes never completes its octet. Ca2B6O11 + 4SO2 + 11H2O ® 2Ca(HSO3)2 +6H3BO3
(ii) On reaction with water boric acid is formed. Properties :
BORAX OR SODIUM TETRABORATE DECAHYDRATE, (i) It is a very weak monobasic acid. It does not act as a proton
Na2B4O7.10H2O OR Na2[B4O5(OH)4]8H2O : donor but accepts a hydroxyl ion i.e., it behaves as a lewis
Preparation : acid.
(i) It occurs naturally as tincal in dried up lakes of Sri Lanka , H3BO3 + H2O ® [B(OH)4]– + H +
USA and India. (ii) With C2H5OH and conc. H2 SO4, it gives triethylborate.
(ii) By the boiling of mineral colemanite with a solution of
H3BO3 + 3C2H5OH¾Conc. H SO4
¾¾¾2 ¾ ¾® B(OC2H5)3 +3H2O
Na2CO3.
Ca2B6O11 + 2Na2CO3 ® 2CaCO3 + 2NaBO2 + Na2B4O7 (iii) With NaOH, it gives sodium metaborate
Colemanite Borax H3BO3 + NaOH ® NaBO2 + 2H2O
Above NaBO2 can be reconverted by passing CO2 through (iv) Heating effect :
it.
4NaBO2 + CO2 ® Na2CO3+ Na2B4O7 H3BO3¾273K
¾¾® HBO¾
433K red
2 ¾¾® H2B4O7¾¾®
¾ B2O3
hot
Properties : Orthoboric Metaboric Tetraboric Boron
(i) Its aqueous solution is basic in nature due to hydrolysis. acid acid acid trioxide
Na2B4O7+ 7H2O ® 2NaOH + 4H3BO3 (Boric anhydride)
(ii) On heating with ethyl alcohol and conc. H2SO4, it gives
Uses : As an antiseptic and eye lotion under the name Boric
volatile vapours of triethylborate which burn with a green
lotion, and as a food preservative.
edged flame.
Na2B4O7+ H2SO4 + 5H2O ® Na2SO4+ 4H3BO3 Structure : It has a layer structure in which planar BO 33-
H3BO3 + 3C2H5OH ® B(OC3H5)3 + 3H2O units are linked by H- bonding, as shown in fig.
Triethylborate
308 Chemistry
H METALLURGY OF ALUMINIUM
O OCCURRENCE AND IMPORTANT MINERALS :
H B It is the most abundant metal found in the earth’s crust. It does
O O not occur in the free state in nature.
H H Its important minerals are :
O OH H (a) Bauxite, Al2O3. 2H2O
OH B O (b) Diaspore, Al2O3. H2O
(c) Corundum, Al2O3
B HO H B (d) Cryolite, Na3 AlF6
H
O O O O (e) Alunite or alum stone, K2SO4. Al2(SO4)3. 3Al(OH)3
(f) Feldspar, K2O. Al2O3 6SiO2
H H H (g) Mica, KAl3Si3O10(OH)2
BORON HALIDES , BX3, (WHERE, X= F, Cl, Br OR I): (h) Kaolinite, Al2O3. 2SiO2 .2H2O
Preparation : By the reaction of boron and halogens at high EXTRACTION :
temperature.
Aluminium metal is extracted from bauxite. It involves following
2B + 3X2 ¾heat
¾ ¾® 2BX3 steps.
Properties : (i) Purification of bauxite : Bauxite usually contains silica as
(i) BF3 and BCl3 are gases, BBr3 is a volatile liquid and BI3 is a impurity. These impurities must be removed before
solid at room temperature. electrolysis, since aluminium, once prepared, cannot be freed
(ii) These are covalent in nature and act as lewis acids. The of other metals by refining it. The bauxite is first purified by
decreasing order of acid strength is. any of the following processes depending upon the nature
BI3 > BBr3 > BCl3 > BF3 of impurities present in it.
(a) Bayer’s process :
BORAZINE OR BORAZOLE OR TRIBORINE
Roasted
TRIAMINE, B3N3H6 : Finely powdered bauxite ¾¾ ¾¾® Roasted ore
FeO ®Fe 2O 3
It is a colourless liquid having a six membered ring of alternating
B and N atoms. It is also called inorganic benzene. It is prepared Caustic soda solution
¾¾¾¾¾¾¾¾
heat
® Al(OH) 3 ¾¾¾® Al 2O 3
by B2H6 as follows: High pressure(150ºC,80atm) pure
filtered, Fe2O3 as residue
3B2H6 + 6NH3 ¾180 ºC
¾ ¾® 2B3N3H6 + 12H2 The reactions involved are given below.
The p electrons in borazine are only partially delocalised. It is Al2O3.2H2O +2NaOH ® 2NaAlO2 + 3H2O
much more reactive than benzene, because there is a retention of
Bauxite Sod. meta
partial negative charge by nitrogen atoms in latter case. It is
aluminate
isosteric (presence of same number of atoms and electrons) with
benzene. NaAlO2 + 2H2O ® Al(OH)3 ¯ + NaOH
H
2Al(OH)3 ¾1473
¾¾
K
¾® Al2O3 + 3H2O
H B
– Alumina
B (b) Hall’s process :
H N: :N H H N+ +N H
2 3 + Na CO
Bauxite (Fine powder) ¾¾¾¾¾¾¾® solution
H B B H H B– –B H fused,extracted with water
r esidueSiO 2 , Fe 2 O 3
N +
N
CO Heat
¾¾ ¾ ¾2¾¾® ppt. Al(OH)3 ¾¾¾® PureAl2O3
H H 50 - 60 º C and filtraed
Borazine filtrate ( Na 2CO 3 )
H
The reactions involved are given below.
C Al2O3. 2H2O + Na2CO3 ®
2NaAlO2 + CO2 + 2H2O
H C C H
2NaAlO2 + 3H2O+ CO2 ¾323 -333K
¾ ¾¾ ¾®
H C 2Al(OH)3 ¯ + Na2CO3
C H
(c) Serpek’s process : This process is employed when silica
C content of ore is high.
H
Benzene Finely powdered bauxite ¾+¾coke
¾ ¾¾
+ N2
®
Heated to1800º C
The p -Block Elements – Boron Family 309
USES :
silica reduced to Si which volatalises
(i) A mixture of aluminium powder and aluminium nitrate is
+ Alumina form aluminium nitride AlN known as Ammonal and is used in bombs.
(ii) A mixture of Al powder in linseed oil is used as silver paint.
hydrolysis
(iii) The reduction of metal oxides by aluminium is called
aluminothermy or thermite process or Goldschmidt
Heated aluminothermite process.
Pure Al2O3 ¬¾ ¾
¾¾ Al(OH)3
(ppt) COMPOUNDS OF ALUMINIUM
ANHYDROUS ALUMINIUM CHLORIDE, AlCl3 (OR
Al2Cl6) :
Filtrate Preparation : It can not be prepared by heating AlCl3. 6H2O
(sod. aluminate + sod. silicate) because of its hydrolysing tendency by its own water as below.
The involving reactions are given below.
D
2AlCl3. 6H2O ¾¾® 2Al(OH)3 + 6HCl
Al2O3. 2H2O + N2 + 3C ¾2000
¾¾ ¾®
K
2Al(OH)3 ¾heat
¾¾® Al2O3 + 3H2O
2AlN + 3CO + 2H2O
¾® Si + 2CO
SiO2 + 2C ¾ However, it can be prepared by following methods:
AlN + 3H2O ¾
¾® Al(OH)3 ¯ + NH3 (i) By passing dry chlorine or HCl gas over
(ii) Electrolysis of fused alumina (Hall and Heroult’s process) heated Al.
: Since pure alumina is a bad conductor of electricity, 2Al + 3Cl2 ¾heat
¾¾® 2AlCl3
therefore it is dissolved in molten cryolite. Na3AlF6 and
2Al + 6HCl ¾heat
¾¾® 2AlCl3 + 3H2
fluorspar, CaF2 to decrease its fusion temperature. The
molten electrolyte is covered with a layer of powdered coke (ii) By heating a mixture of alumina and carbon in a current of
to prevent oxidation and loss of heat due to radiation. dry chlorine.
The reactions are : Al2O3 + 3C + 3Cl2 ¾heat
¾¾® 2AlCl3 + 3CO
Na3AlF6 3NaF + AlF3
AlF3 Al3+ + 3F– Properties :
At cathode : Al3+ + 3e– ® Al (i) It fumes in moist air due to hydrolysis
AlCl3 + 3H2O ® Al(OH)3 + 3HCl
At anode : F– ® e– + F
The resulting solution is acidic due to the formation of HCl.
2Al2O3 + 12F ® 4AlF3 + 3O2
(ii) It behaves as lewis acid.
2C + O2 ® 2CO ;
(iii) It is a covalent solid and dissolves in organic solvents like
2CO + O2 ¾
¾® 2CO2 C6H6 etc.
(iii) Refining of aluminium : It is refined by Hoope’s electrolytic Structure : It exists as dimer Al2Cl6 in which each Al atom is
process, which is carried out in a graphite lined bath which terahedrally surrounded by four Cl atoms as below.
acts as the anode and carbon cathodes are used. The refining Cl Cl Cl
cell consists of three fused layer’s of different densities. Al Al
(a) The bottom layer is of molten impure aluminium (anode) Cl Cl Cl
(b) The middle layer is of fused cryolite and barium fluoride
(c) The upper layer is of pure aluminium (cathode) USES :
There is a new method of extraction of Aluminium in which the (i) As a catalyst in Friedel - Craft reactions
purification of the oxide is not of much importance. In this method, (ii) As a mordant in dyeing
AlCl3 vapour is passed through the fused oxide at 1000ºC ALUMINIUM OXIDE OR ALUMINA Al2O3 :
2Al2O3 + 2AlCl3 ® 6AlCl + 3O2 It is the most stable compound of aluminium and occurs in nature
Aluminium monochloride as colourless corundum and several coloured oxides, (when
The above aluminium monochloride vapour is unstable when present in combination with different metal oxides) like ruby (red),
cooled and disproportionates below at 800ºC. topaz (yellow), sapphire (blue), amethyst (voilet) and emerald
3AlCl ® AlCl3 + 2Al (green), which are used as precious stones (gems).
310 Chemistry
THERMITE :
A mixture of aluminium powder and ferric oxide in the ratio 1: 3.
ALUMINIUM SULPHATE, Al2(SO4)3 :
It is used for obtaining H2S in pure form and for making fire proof clothes.
ALLOYS OF ALUMINIUM :
Alloy Composition Properties Uses
(iv) Magnalium Al + Mg + Ca Light, tough and strong Balance beams and machinery
(83%) (15%) ( 2%)
1. The state of hybridization of B in BCl3 is 11. Which of the following hydroxide is acidic ?
(a) sp 3 (b) sp 2 (a) Al(OH)3 (b) Ca(OH)3
(c) sp (d) sp 3d 2 (c) Tl(OH)3 (d) B(OH)3
2. The type of hybridization of boron in diborane is 12. BF3 acts as an acid according to the concept of
(a) sp (b) sp 2 (a) Lewis (b) Bronsted
(c) sp 3 (d) sp 3d 2 (c) Arrhenius (d) None of these
3. Specify the coordination geometry around and hybridization 13. Which of the following is electron deficient ?
of N and B atoms in a 1: 1 complex of BF 3 and NH3 (a) NH3 (b) BCl3
(a) N : tetrahedral, sp3; B : tetrahedral, sp3 (c) PCl3 (d) None of these
(b) N : pyramidal, sp3; B : pyramidal, sp3 14. NH3 and BF3 form an adduct readily because they form
(c) N : pyramidal, sp3; B : planar, sp3 (a) a coordinate bond
(d) N : pyramidal, sp3; B : tetrahedral, sp3 (b) a hydrogen bond
(c) an ionic bond
4. Which one of the following elements has the highest melting
point ? (d) a covalent bond
15. BF3 is used as a catalyst in several industrial processes due
(a) Boron (b) Aluminium
to its
(c) Gallium (d) Thallium
(a) strong reducing nature
5. The element which shows least metallic character is
(b) weak reducing action
(a) Indium (b) Boron
(c) strong Lewis acid nature
(c) Aluminium (d) Gallium
(d) weak Lewis acid character
6. Which of the following does not form M3+ ion? 16. Among the halides of the elements of group 13 the one
(a) Boron (b) Aluminium which is most acidic is
(c) Indium (d) Gallium (a) BF3 (b) AlCl3
7. Which of the following does not react with aqueous (c) BCl3 (d) BBr3
NaOH ? 17. In diborane
(a) B (b) Al (a) 4–bridged hydrogens and two terminal hydrogens are
(c) Ga (d) Tl present
8. B2O3 is (b) 2– bridged hydrogens and four terminal hydrogens are
(a) acidic (b) basic present
(c) amphoteric (d) None of these (c) 3–bridged and three terminal hydrogens are present
9. Boric acid is polymeric due to (d) None of these
(a) its acidic nature 18. Identify the statement that is not correct as far as structure
(b) the presence of hydrogen bonds of diborane is concerned
(c) its monobasic nature (a) There are two bridging hydrogen atoms and four terminal
(d) its geometry hydrogen atoms in diborane
10. B(OH)3 is (b) Each boron atom forms four bonds in diborane
(c) The hydrogen atoms are not in the same plane in
(a) monobasic acid (b) dibasic acid
diborane
(c) tribasic acid (d) triacidic base
(d) All, B – H bonds in diborane are similar
The p -Block Elements – Boron Family 313
19. BCl3 does not exist as dimer but BH3 exists as dimer (B2H6) 32. A lake can be obtained by making a mixture of a coloured
because dye with
(a) chlorine is more electronegative than hydrogen (a) NH4OH (b) Ba(OH)2
(b) there is pp-pp back bonding in BCl3 but BH3 does not (c) Al(OH)3 (d) NaOH
contain such multiple bonding 33. AlCl3 is
(c) large sized chlorine atoms do not fit in between the (a) anhydrous and covalent
small boron atoms where as small sized hydrogen atoms
(b) anhydrous and ionic
get fitted in between boron atoms
(d) None of these (c) covalent and basic
20. Diborane upon hydrolysis gives (d) coordinate and acidic
(a) boric anhydride (b) metaboric acid 34. Anhydrous AlCl3 is prepared from
(c) orthoboric acid (d) boron oxide (a) conc. HCl and Al metal
21. In reaction (b) aluminium and Cl2
BF3 + 3LiBH4 ® 3LiF + X ; X is (c) dry HCl gas + heated Al metal
(a) B4H10 (b) B2H6 (d) dil. HCl and Al metal
(c) BH3 (d) B3H8 35. Aluminium chloride is a/an
22. Which of the following mineral does not contain Al ? (a) Bronsted - Lowry acid (b) Arrhenius acid
(a) Cryolite (b) Mica (c) Lewis acid (d) Lewis base
(c) Feldspar (d) Fluorspar 36. Which member of group 13 does not exhibit the group
23. In the thermite welding process we use valency in its compounds ?
(a) Al powder (b) Fe powder (a) Boron (b) Aluminium
(c) Ca powder (d) (Al + Fe) mixture
(c) Gallium (d) Thallium
24. In aluminates, the coordination number of Al is
37. The highly toxic element of group 13 is
(a) 4 (b) 6
(a) Al (b) B
(c) 3 (d) 1
(c) Ga (d) Tl
25. Aluminium is
(a) a reducing agent 38. Which of the following oxides is strongly basic ?
(b) an oxidising agent (a) B2O3 (b) Al2O3
(c) amphoteric (c) Ga2O3 (d) Tl2O3
(d) highly electronegative element 39. Which out of the following compounds does not exist?
26. Al is more reactive than Fe but Al is less easilly corroded (a) BF3 (b) TlCl3
than Fe because (c) TlCl5 (d) Both (b) and (c)
(a) it is a noble metal 40. Which of the following does not give a borax bead
(b) oxygen forms a protective oxide layer test ?
(c) iron undergoes reaction easily with water (a) Chromium (b) Ferrous salt
(d) Fe form mono and divalent ions. (c) Sodium (d) Cobalt
27. Corundum is 41. Borazole is known as
(a) Al2(SO4)3 (b) Al2O3.H2O (a) organic benzene (b) organic xylene
(c) Al2O3.2H2O (d) Al2O3
(c) inorganic benzene (d) inorganic xylene
28. Although Al has a high oxidation potential it resists
42. The I.E1 among the group 13 member follows as
corrosion because of the formation of a tough, protective
coat of (a) B > Al < Ga < Tl (b) B > Al > Ga > Tl
(a) Al(NO3 )3 (b) AlN (c) B > Ga > Al > Tl (d) B > Ga < Al < Tl
(c) Al2O3 (d) Al2(CO3)3 43. The melting pt. of group 13 follows the order
29. AlCl3 on hydrolysis gives (a) B > Al > Ga > In > Tl (b) B > Al < Ga > In > Tl
(a) Al2O3. H2O (b) Al(OH)3 (c) B > Al > Tl > In > Ga (d) B > Al < Ga < In < Tl
(c) Al2O3 (d) AlCl3.6H2O 44. The compounds of boron and hydrogen are collectively
30. Action of caustic soda on aluminium hydroxide gives a called
compound having formula (a) diboranes (b) borazoles
(a) Al2(OH)4 (b) Na2Al(OH)4
(c) boracits (d) boranes
(c) NaAlO2 (d) Na3AlO3
45. The bonds present in borazole or inorganic benzene are
31. Al(OH)3 is
(a) 9 s, 6p (b) 12 s, 3p
(a) acidic (b) basic
(c) amphoteric (d) neither acidic nor basic (c) 6 s, 9p (d) 15 s only
314 Chemistry
46. The aluminium salt commonly used to stop bleeding is (b) washing soda gets easily decomposed
(a) aluminium sulphate (b) potash alum (c) washing soda reacts with aluminium to form soluble
(c) aluminium chloride (d) aluminium fluoride aluminate
47. The nature of the solution of Potash alum is (d) washing soda reacts with aluminium to form insoluble
(a) basic (b) acidic aluminium oxide
(c) neutral (d) amphoteric 49. Which out of the following is potash alum ?
48. Aluminium vessels should not be washed with materials
containing washing soda because (a) K2SO4.Al2(SO4)3.24H2O (b) K2SO4. Cr2(SO4)3.24H2O
(a) washing soda is expensive (c) K2SO4.Fe2(SO4)3.24H2O (d) [NH4]2SO4.FeSO4.6H2O
1. On adding ammonium hydroxide solution to 10. The two type of bonds present in B2H6 are covalent and
Al2(SO4)3 (aq) : (a) ionic (b) co-ordinate
(a) A precipitate is formed which does not dissolve in excess (c) hydrogen bridge bond (d) None of these
of ammonium hydroxide 11. Orthoboric acid when heated to red hot gives
(b) A precipitate is formed which dissolves in excess of (a) metaboric acid (b) pyroboric acid
ammonia solution (c) boron and water (d) boric anhydride
(c) No precipitate is formed 12. Anodised aluminium is
(d) None of these (a) Al obtained at anode
2. The purification method used for mineral Al 2 O 3 .2H 2 O is (b) Al prepared electrolytically
(a) froth floatation (b) leaching (c) Alloy of Al containing 95% of Al
(c) liquation (d) magnetic separation (d) Al electrolytially coated with aluminium oxide
3. The process used for purification of bauxite ore containing 13. Which statement regarding H3BO3 is not correct ?
high silica content as impurity is (a) It is a strong tribasic acid
(a) Baeyer’s process (b) Hall’s process (b) It is prepared by acidifying an aqueous solution of borax
(c) Hoope’s process (d) Serpeck’s process (c) It has a layer structure in which planar BO3 units are
4. Hydrogen forms a bridge in the chemical structure of : joined by H- bonds
(a) sodium peroxide (b) diborane (d) It does not act as proton donor but acts on lewis acid by
(c) hydrogen peroxide (d) lithium hydride accepting OH– ions
14. The precious Ruby stone is
5. The role of fluorspar ( CaF2) which is added in small quantities
in the electrolytic reduction of alumina dissolved in fused (a) alumina
cryolite (Na3AlF6) is (b) aluminium silicate
(a) as a catalyst (c) sodium aluminium silicate
(b) to make the fused mixture very conducting (d) sodium silicate
(c) to increase the temperature of the melt. 15. The hybridisation of boron atom in orthoboric acid is
(d) to decrease the rate of oxidation of carbon at the anode. (a) sp (b) sp 2
6. In Gold Schmidt reaction, certain metallic oxides are reduced (c) sp 3 (d) sp 3 d
to the metallic state by heating with 16. Which of the following statements is not correct ?
(a) metallic magnesium (b) metallic aluminium (a) Al acts as a reducing agent
(c) metallic iron (d) sodium metal (b) Al does not react with steam even at higher temperature
7. The dissolution of Al(OH)3 by a solution of NaOH results in (c) Al forms a number of alloys with other metals
the formation of (d) Al is ionic in all its compounds
17. Which of the following processes does not involve a catalyst?
(a) [Al(H 2 O) 4 (OH)]2 + (b) [Al(H 2 O) 2 (OH) 4 ]-
(a) Thermite process (b) Ostwald process
(c) [Al(H 2 O) 3 (OH) 3 ] (d) [Al(H 2 O) 6 (OH)3 ] (c) Contact process (d) Haber process
8. Which of the following is pseudo alum ? 18. The factor responsible for weak acidic nature of B–F bonds
in BF3 is
(a) (NH 4 )2 SO 4 .Fe2 (SO4 )3.24H 2O
(a) large electronegativity of fluorine
(b) K 2SO 4 .Al2 (SO4 )3 .24H 2O (b) three centred two electron bonds in BF3
(c) pp - dp back bonding
(c) MnSO 4 .Al2 (SO4 )3 .24H 2O
(d) pp - pp back bonding
(d) None of these 19. An aqueous solution of FeSO4, Al2(SO4)3 and chrome alum
9. Which of the following statements about anhydrous is heated with excess of Na2O2 and filtered. The materials
aluminium chloride is correct ? obtained are :
(a) It exist as AlCl3 molecule (a) a colourless filtrate and a green residue
(b) It is a strong lewis base (b) a yellow filtrate and a green residue
(c) It sublimes at 100°C under vaccum (c) a yellow filtrate and a brown residue
(d) It is not easily hydrolysed. (d) a green filtrate and a brown residue
316 Chemistry
20. Which of the following has the minimum heat of dissociation: 22. Which reaction cannot give anhydrous AlCl3 :
(a) Passing dry Cl2 over heated aluminium powder.
(a) (CH3 )3 N : ® BF3
(b) Heating a mixture of alumina and coke in a current of dry
Cl2.
(b) (CH3 )3 N : ® B(CH3 )2 F
(c) Passing dry HCl over heated aluminium powder.
(c) (CH3 )3 N : ® B(CH 3 ) 3 (d) Heating of AlCl3 .6H 2 O .
23. The process used for purification of bauxite ore containing
(d) (CH3 )3 N : ® B(CH 3 )F2 iron oxide impurity is known as :
21. Purification of alumina is essential because : (a) Hoope’s process (b) Serpeck’s process
(c) Baeyer’s process (d) Electrolytic process
(a) impure alumina has a very high melting point. 24. Which statement is not true about potash alum ?
(b) impure alumina is a very poor conductor of electricity. (a) On heating it melts and loses its water of crystallization.
(c) impure alumina cannot react with the oxidizing agent. (b) It’s aqueous solution is basic in nature.
(c) It is used in dyeing industries.
(d) it is difficult to purify aluminium metal.
(d) It’s empirical formula is KAl(SO 4 )2 .12H 2 O .
N+ +N N Al Al
– +
–B B B– –B Cl Cl Cl
CH2–OH
–
HO–CH2
– 9. (c) AlCl3 is Lewis acid, exists as dimer (Al2Cl6) and easily
HO OH CH2–O O–CH2
+ B + B hydrolysed
CH2–OH HO OH HO–CH2 CH2–O O–CH2
10. (c) B2H6 contains hydrogen bridge bonds. These are one
Stable chelated complex ion
electron bonds also known as banana bonds.
EXERCISE 4 °C 160°C
11. (b) H 3 BO 3 ¾100
¾ ¾® HBO 2 ¾¾ ¾® H
1. (a) Al2 (SO 4 )3 + 6NH 4 OH ® 2Al(OH)3 + 3(NH 4 ) 2 SO 4
3. Producer gas : Burning coke + limited air ® producer gas ( Al 2 O 3 .2SiO 2.2H 2 O ) .
Composition : CO = 31.7%, N2 = 65.7%, CO2 = 2.5% PREPARATION OF AMORPHOUS FORM
Properties and uses : Poisonous, combustible but non supporter It is very common and may be obtained by heating powdered
of combustion, has low calorific value. Mainly employed as fuel. quartz or finely divided silica with Mg powder.
4. Coal gas :
SiO 2 + 2Mg ® Si + 2MgO
Preparation : By destructive distillation of coal
324 Chemistry
PREPARATION OF CRYSTALLINE FORM (x) Silica garden- Aqueous solution of sodium silicate containing
crystals of various coloured salts e.g. copper sulphate, cobalt
By reduction of SiCl 4 with molten Al
nitrate , manganese chloride, nickel chloride etc.
3SiCl 4 + 4Al ® 3Si + 4AlCl3 (xi) Hydro flurosilicic acid H2SiF6
By reduction of highly purified SiCl4 with hydrogen 3SiF4 + 4H 2 O ® H 4SiO 4 ¯ +2H 2SiF6 soluble
SiCl4 + 2H 2 ® Si + 4HCl (xii)Permutit -Artificially perpared sodium aluminium silicate
containing varying composition of sodium ,aluminium and
ZONE-REFINING
silica Na 2Al2Si 2O8 .xH 2O .Used for softening hard water..
Silicon is purified by Zone-refining process because the impurities
present in it are more soluble in the liquid phase than in the solid (xiii)Zeolites -They have honey comb like structure and have the
Mx
phase.
general formula
n
( AlO2 ) x .(SiO2 ) y .zH2O
PROPERTIES
Crystalline form possesses metallic lustre. It is very hard and M = Na + , K + or Ca ++
scratches glass. Crystalline silicon is isomorphous with diamond. n = Charge on metal
CHEMICAL REACTIONS OF AMORPHOUS SILICON : They act as ion exchanger and molecular sieves. They can
be artificially perpared by heating China clay, Silica and
Burns in air Si + O 2 ® SiO 2 Na2CO3 .
Si + 2F2 ® SiF4 (xiii)Ultramarines - Zeolite type silicates, containing ions like
Si + 2Cl2 ® SiCl4 Cl - , SO 24 - , S 2 - and not water, are known as ultramarines
Si + 2NaOH + H 2 O ® Na 2 SiO 3 + 2H 2 e.g. Na 2 (Al6Si6O24 )S2 Many of them are coloured and
used as pigments and calicoprinting.
Si + 2H 2 O (steam) ® SiO 2 + 2H 2
(xiv)Carborundum - silicon carbide
USES SiO 2 + 2C ® Si + 2CO
Silicon chips used for computing devices are doped with P,As, Al Si + C ® SiC
or Ga to enhance the semiconductor properties. It is nearly as hard as diamond .
COMPOUNDS OF SILICON GLASS
Amorphous, hard, brittle, transparent, transluscent super cooled
(i) SiO 2 (silica) - It exists in three crystalline forms Quartz,
solution of various silicates and borates of K, Ca and Pb . It has
Trydimite and crystobalite. Further each form has a and no definite formula but roughly can be represented as
b form. At low temperature the a form is stable and at high M '2 O.M ''O.xSiO 2 where M ' = Na, K and M " = Ba, Zn, Pb
temperature the b form is stable . Raw material used in the manufacture of glass.
(ii) Sand - It is crushed form of quartz produced in nature by (i) SiO2
weathering of rocks . (ii) Na 2CO3, K 2CO3 or NaNO3 or KNO3
(iii) Flint - It is amorphous silica associated with quartz .
(iv) Kiesulguhr - Siliceous rock composed of the remains of sea (iii) Alkaline earth metals e.g. CaCO3 , BaCO3
organisms. Used as absorbent for nitroglycerine. (iv) oxides of heavy metals
(v) Quartz or rock crystal - It is purest form of silica It is optically (v) Cullets (pieces of glass)
active. (vi) Colouring matter
(vi) Silicic acid Colouring materials -
(a) Ortho silicic acid H 4SiO 4 or Si(OH) 4 Colour Substances Colour Substances
(b) Meta silicic acid H 2SiO 3 or SiO(OH) 2 Yellow Ferric iron, Lemon yellow CdS
uranate of Na
Na 2SiO3 + 2HCl ® 2NaCl + H 2SiO3
Purple MnO2 Black NiO
(vii) Silicic acid sol -Colloidal solution of silicic acid.
(viii)Silica gel -Transparent gel of bluish white colour Ruby AuCl3 Milky white Na 3 AlF6
SiO2 .xH 2 O . Blue CuO, CoO Peacock Blue cupric Salts
(ii) Hard or potash glass Sand+lime stone + K 2CO3 Hard Hard glass apparatus
(iii) Flint glass Sand +Red lead+ K 2CO3 High refractive index Optical instrument, prisms
(iv) Pyrex glass Na 2 O.B2 O3 Al2 O3 SiO2 Low coefficient Glass ware
(v) Jena glass Zn and Barium Borosilicate Low coefficient of expansion Glass wares
(vi) Crookes glass K 2O.PbO.CeO 2 .SiO 2 Cuts off U.V. rays Eye lenses
(vii) Quartz glass or silica glass Pure SiO 2 Low coefficient of expansion Scientific wares
(viii) Safety glass or Between two glass layers Automobile wind
shatter proof a transparent plastic layer shields, goggles etc.
glass of vinyl acetate resin is placed
Annealing - The process of slow cooling of glass is known as Chemical properties - With acids
annealing .The glass becomes soft.
Sn + 2HCl ® SnCl2 + H 2
TIN ( Sn ) :
Sn + dilH 2SO4 ® SnSO 4 + H 2
[Kr]4d 10 4 s 2 4 p 2 Sn + 4H 2SO 4 (Conc.) ® Sn(SO 4 ) 2 + 2SO2 + 4H 2 O
Principal ores of tin - (i) Cassiterite or Tin stone, Sn O 2 (ii)Tinpyrites, 4Sn + 10HNO3 (dil.) ® 4Sn(NO3 ) 2 + NH 4 NO3 + 3H 2 O
SnS.Cu2S. FeS.
Extraction - Sn + 4HNO3 (conc.) ® H 2SnO3 + 4NO2 + H 2 O
(i) Concentration - By gravity process washing with water
Meta stannic acid
and then magnetic separation.
(ii) Roasting -To remove volatile impurities With alkali : Sn + 2NaOH + H 2O ® Na 2SnO3 + 2H 2
S + O2 ® SO2 o
WithO2 at 1500 C: Sn + O2 ® SnO2
4As + 3O2 ® 2As2O3 With steam : Sn + 2H2 O ® SnO2 + 2H 2
(iii) Smelting - It is carried out in reverberatory furnace with COMPOUNDS OF TIN :
coal (powdered anthracite )and lime stone.
SnO2 + 2C ® Sn + 2CO (i) Stannic Oxide ( SnO2 ) - It occurs naturally as cassiterite.
(slag)
CaCO3 + SiO2 ® CaSiO3 + CO2 Preparation - Sn + O 2 D
¾¾® SnO 2
Sn so obtained contains iron and other metals and called D
black tin . H 2SnO 3 ¾¾® SnO 2 + H 2 O
(iv) Refining by (a) Liquation (b) Poling and (c) Electrolytic Properties - White solid, insoluble in water and amphoteric in
Properties - Soft silvery white metal, ductile and malleable. It has nature.
maximum number of isotopes and three allotropic forms.
SnO 2 + 2H 2SO 4 ® Sn ( SO 4 ) 2 + 2H 2 O
18°C 161° C
Grey
White
Rhombic SnO 2 + 2NaOH ® Na 2SnO3 + H 2 O
Tin cry - It produces a peculiar cracking sound on bending which is
Uses - As polishing powder, in glass and pottery manufacture.
known as tin cry.
(ii) Stannous oxide (SnO) -
Tin plague - It is the conversion of white tin to grey tin at low
temperature which crumbles into powder. D
Preparation - SnC 2 O 4 ¾¾ ® SnO + CO + CO 2
Tinning - Since tin is not attacked by organic acids the utensils are
Sn(II) oxalate
protected by thin layer of tin .A pinch of NH 4 Cl is sprinkled over
Properties : It is black solid and amphoteric in nature.
hot and clean surface, when HCl liberated removes the oxide film.Tin
then rubbed over the clean surface with the help of rag dipped in SnO + 2H + ® Sn 2 + + H 2 O
NH 4 Cl powder. The utensil is immediately dipped in water to avoid
SnO + 2OH - ® SnO 22 - + H 2 O
oxide formation .
Tin plating - It involves the depositing of thin protective layer of tin (iii) Sulphides - SnS precipitated by H 2 S .It is dark brown solid,
over sheets of iron electrolytically. soluble in yellow ammonium sulphide forming (NH 4 ) 2 SnS3
326 Chemistry
Very Short/ Short Answer Questions (ii) (a) Why N(CH3)3 is pyramidal but N(SiH3)3 is planar?
1. Explain why silicon shows a higher covalency than carbon? (b) Why (SiH3)3N is a weaker base than (CH3)3N ?
2. Why is diamond a bad conductor of electricity but a good (iii) Account for the following:
conductor of heat? PbO2 is a stronger oxidizing agent than SnO2.
3. Which oxide of carbon is an anhydride of carbonic acid ? Or
4. Why carbon forms covalent compounds whereas lead forms
ionic compounds? PbO2 can act as an oxidizing agent.
5. What name is given to the compounds formed by more 16. Glass made up of SiO2 reacts with HF to form SiF62– anion.
electropositive elements with carbon? The analogous CF62– anion does not form. Why?
6. What are silicates?
7. Silanes gets hydrolysed by water whereas alkanes do not, Multiple Choice Questions
why? 17. Which of the following is most stable?
8 (CH3)3N is basic but (CF3)3N is not basic. Explain.
9. (a) CO2 is a gas while SiO2 is a solid. Explain.
(a) Sn 2+ (b) Ge2+
(b) Give one chemical reaction to show that: (c) Si 2+ (d) Pb 2+
(i) Tin (II) is a reducing agent whereas Pb (II) is not. 18. Cement, the important building material is a mixture of oxides
(ii) Tin (II) reduces mercuric salt to mercurous salt. of several elements. Besides calcium, iron and sulphur, oxides
10. (a) Carbon monoxide is readily absorbed by ammonical of elements of which of the group (s) are present in the
cuprous chloride solution but carbon dioxide is not. mixture?
Explain. (a) Group 2
(b) Silanes are few in number whereas alkanes are large in (b) Groups 2, 13 and 14
number. Explain. (c) Groups 2 and 13
(c) Diamond is covalent, yet it has high melting point. Why? (d) Groups 2 and 14
11. Give reason : 19. The most commonly used reducing agent is
(a) Silicon form compounds with coordination number of (a) AlCl3 (b) PbCl2
5 and 6.
(c) SnCl4 (d) SnCl2
(b) Si—F bond is stronger than C—F bond although Si is
20. Lead pipes are not suitable for drinking water because
larger in size than C.
(a) lead forms basic lead carbonate
12. Arrange the following in increasing order of the property
indicated: (b) lead reacts with water containing air to form Pb(OH)2
(a) CCl2, SiCl2, GeCl2, SnCl2 and PbCl2 (c) a layer of lead dioxide is deposited over lipes
(stability) (d) lead reacts with air to form litharge
(b) CO, SiO, SnO, GeO, PbO (basicity) 21. Catenation i.e., linking of similar atoms depends on size and
(c) SiF4, SiCl4, SiI4, SiBr4 (stability) electronic configuration of atoms. The tendency of
catenation in Group 14 elements follows the order :
13. Out of CCl4 and SiCl4 which one reacts with water?
(a) C > Si > Ge > Sn (b) C >> Si > Ge » Sn
14. [SiF6]2– is known whereas [SiCl6]2– is not. Give possible
reasons. (c) Si > C > Sn > Ge (d) Ge > Sn > Si > C
22. Graphite is a soft solid lubricant extremely difficult to melt.
Long Answer Questions The reason for this anomalous behaviour is that graphite
15. (i) C and Si are almost always tetravalent but Ge, Sn and (a) is an allotropic form of diamond
Pb show bivalency. Why? (b) has molecules of variable molecular masses like
Or polymers
Why the tendency to exhibit + 2 oxidation state (c) has carbon atoms arranged in large plates of rings of
increases with increasing atomic number in group 14. strongly bound carbon atoms with weak inter plate
Or
bonds
+ 2 oxidation of lead is more stable than + 4 oxidation
state. Give reasons. (d) is a non-crystalline substance
The p -Block Elements –Carbon Family 329
23. Which statement is false (a) MeSiCl3 (b) Me2SiCl2
(a) Water gas is a mixture of hydrogen and carbon dioxide. (c) Me3SiCl (d) Me4Si
(b) Producer gas is a mixture of CO and nitrogen 25. Dry ice is
(c) Water gas is a mixture of water vapour and hydrogen. (a) solid NH3 (b) solid SO2
(d) Natural gas consists of methane, ethane and gaseous (c) solid CO2 (d) solid N2
hydrocarbons. 26. Quartz is extensively used as piezoelectric material, it
24. Silicon has a strong tendency to form polymers like silicones. contains __________ .
The chain length of silicone polymer can be controlled by (a) Pb (b) Si
adding (c) Ti (d) Sn
1. Which of the following is most electronegative? 10. The element that does not form a monoxide is
(a) Pb (b) Si (a) lead (b) tin
(c) C (d) Sn (c) germanium (d) silicon
2. The most stable +2 oxidation state is exhibited by 11. Pyrosilicate ion is
(a) Fe (b) Sn
(c) Pb (d) Si (a) SiO 22 - (b) SiO 24 -
3. The electronic configuration of four different elements is
(c) Si 2 O67 - (d) Si 2 O76 -
given below. Identify the group 14 element among these
12. Freon -12 is used as a
(a) [He] 2s1 (b) [Ne] 3s 2
(a) refrigerant (b) insecticide
(c) [Ne] 3s 2 3 p 2 (d) [Ne] 3s 2 3 p 5 (c) fungicide (d) herbicide
4. The catenation tendency of C,Si and Ge is in the order Ge 13. Which one of the following allotropic forms of carbon is
-1
isomorphous with crystalline silicon?
<Si<C.The bond energies (in kJ mol ) of C-C,Si-Si and Ge- (a) Graphite (b) Coal
Ge bonds, respectively are (c) Coke (d) Diamond.
(a) 167,180,348 (b) 180,167,348
(c) 348,167,180 (d) 348,180,167 14. The structure and hybridization of Si ( CH 3 ) 4 is
5. Ge(II)compounds are powerful reducing agents
whereas Pb(IV)compounds are strong oxidants .It is because (a) Bent, sp (b) Trigonal, sp 2
(a) Pb is more electropositive than Ge
(c) Octahedral, d 2 sp 3 (d) Tetrahedral, sp 3
(b) ionization potential of lead is less than that of Ge
(c) ionic radii of Pb2+ and Pb4+ are larger than those of Ge2+ 15. Silicon is an important constituent of
and Ge4+ (a) rocks (b) minerals
(d) of more pronounced inert pair effect in lead than (c) alloys (d) vegetables.
in Ge 16. In laboratory, silicon can be prepared by the reaction of
6. Which among CH4, SiH4, GeH4, SnH4 is most volatile? (a) SiO2 with Mg
(a) CH4 (b) SiH4 (b) by heating C in electric furnace
(c) GeH4 (d) SnH4 (c) by heating potassium fluorosilicate with potassium
7. Which of the following halides is the most stable? (d) None of these
(a) CF4 (b) CI4 17. Silica is soluble in
(c) CBr4 (d) CCl4 (a) HCl (b) HNO3
8. Which of the following conceivable structures for CCl4 will
(c) H2SO4 (d) HF
have a zero dipole moment ?
18. Quartz is a crystalline variety of
(a) Square planar
(a) Si (b) SiO2
(b) Square pyramid (carbon at apex)
(c) Irregular tetrahedron (c) Na2SiO3 (d) SiC
(d) None of these 19. Carborundum is
9. PbF4, PbCl4 exist but PbBr4 and PbI4 do not exist because of (a) Al2(SO4)3 (b) Al2O3. 2H2O
(a) large size of Br– and I– (c) AlCl3 (d) SiC
(b) strong oxidising character of Pb4+ 20. Which one of the following is a correct set for SiO2?
(c) strong reducing character of Pb4+ (a) Linear acidic (b) Linear,basic
(d) low electronegativity of Br– and I–. (c) Tetrahedral, acidic (d) Angular, basic.
330 Chemistry
21. A pseudo solid is 35. White lead is
(a) diamomd (b) glass (a) Pb3O4
(c) rock salt (d) CaCO3
(b) PbO
22. Pyrex glass is a mixture of
(a) sodium borosilicate and aluminium borosilicate (c) 2PbCO3 .Pb ( OH ) 2
(b) sodium silicate and calcium silicate
(c) sodium silicate and lead silicate (d) Pb ( CH 3COO ) 2 .Pb ( OH ) 2
(d) sodium silicate and aluminium borosilicate 36. The oxide which cannot act as reducing agent is
23. The variety of glass used in making lenses and prisms is
(a) SO2 (b) NO2
(a) soda glass (b) borosilicate glass
(c) flint glass (d) crooke’s glass (c) CO2 (d) ClO2
24. Cassiterite is an ore of
37. A solid element (symbol Y) conducts electricity and forms
(a) Mn (b) Ni
two chlorides YCln (colourless volatile liquid) and YCln - 2
(c) C (d) Sn
25. The shape of gaseous SnCl2 is (a colourless solid). To which one of the following groups of
the periodic table does Y belong?
(a) tetrahedral (b) linear
(c) angular (d) T-shaped (a) 13 (b) 14
26. Butter of tin is (c) 15 (d) 16
(a) SnCl4 .6H 2 O (b) SnCl4 .4H 2 O 38. Which of the following bonds has the most polar
(c) SnCl4 .5H 2 O (d) SnCl4 .2H 2 O character?
27. An alloy of Pb and Sn in equal proportion is called (a) C-O (b) C-Br
(a) pewter (b) type metal (c) C-S (d) C-F
(c) solder (d) constantan 39. The ion that can be precipitated by HCl as well as H2S is
28. Red lead is
(a) Pb 2 + (b) Fe3+
(a) PbO (b) Pb3O4
(c) PbO 2 (d) Pb 4 O3 (c) Zn2+ (d) Cu 2+
29. An oxide of lead which is used in lead storage battery, in 40. Which of the following is most dense?
safety matches and is a powerful oxidising agent is
(a) Fe (b) Cu
(a) PbO (b) PbO 2
(c) B (d) Pb
(c) Pb3O4 (d) 2PbO.PbO 2
41. C and Si have
30. Lead sulphate is soluble in
(a) conc. HNO3 (a) Same physical properties
(b) conc. HCl (b) Different physical properties
(c) solution of ammonium acetate (c) Same physical but different chemical properties
(d) water (d) Different chemical and physical properties
31. The percentage of lead in lead pencil is 42. Mark the oxide which is amphoteric in character
(a) zero (b) 20 (a) CO2 (b) SiO 2
(c) 80 (d) 70
32. The important ore of lead is (c) SnO2 (d) CaO
(a) chalcopyrites (b) haematite 43. Which of the following sulphate is insoluble in water?
(c) galena (d) bauxite (a) CuSO4 (b) CdSO4
33. Which of the following lead oxides is present in ‘Sindhur’?
(a) PbO (b) PbO 2 (c) PbSO4 (d) Al 2 ( SO 4 )3
(c) Pb 2 O3 (d) Pb3O4
44. Which of the following molecule has highest bond energy?
34. Which of the following reactions occurs at the cathode during
the charging of a lead storage battery? (a) F-F (b) C-C
(c) N-N (d) O-O
(a) Pb 2 + + 2e - ® Pb
45. The metal used for making radiation shield is
(b) Pb 2 + + SO 24 - ® PbSO 4 (a) Al (b) Fe
(c) Zn (d) Pb
(c) Pb ® Pb 2 + + 2e -
1. The straight chain polymer is formed by: [CBSE-PMT 2009] 8. In silicon dioxide [AIEEE 2005]
(a) hydrolysis of CH 3 SiCl3 followed by condensation (a) there are double bonds between silicon and oxygen
polymerisation atoms
(b) hydrolysis of (CH3)4Si by addition polymerisation (b) silicon atom is bonded to two oxygen atoms
(c) hydrolysis of (CH3)2SiCl2 followed by condensation (c) each silicon atom is surrounded by two oxygen atoms
polymerisation and each oxygen atom is bonded to two silicon atoms
(d) hydrolysis of (CH3)3 SiCl followed by condensation (d) each silicon atom is surrounded by four oxygen atoms
polymerisation and each oxygen atom is bonded to two silicon atoms.
4. Name the type of the structure of silicate in which one oxygen 9. A metal, M forms chlorides in its +2 and +4 oxidation states.
2tom of [SiO4]4– is shared ? [CBSE-PMT 2011] Which of the following statements about these chlorides is
correct? [AIEEE 2006]
(a) Linear chain silicate (b) Sheet silicate
(a) MCl2 is more ionic than MCl4
(c) Pyrosilicate (d) Three dimensional (b) MCl2 is more easily hydrolysed than MCl4
3. The basic structural unit of silicates is : [NEET 2013] (c) MCl2 is more volatile than MCl4
(a) SiO 44- (b) SiO32- (d) MCl2 is more soluble in anhydrous ethanol than MCl4
10. The stability of dihalides of Si, Ge, Sn and Pb increases
(c) SiO 24- (d) SiO steadily in the sequence [AIEEE 2007]
4. Graphite is a soft solid lubricant extremely difficult to melt. (a) PbX 2 << SnX 2 << GeX 2 << SiX 2
The reason for this anomalous behaviour is that graphite
(b) GeX2 << SiX2 << SnX2 << PbX2
[AIEEE 2003]
(a) is an allotropic form of diamond (c) SiX2 << GeX2 << PbX2 << SnX2
(b) has molecules of variable molecular masses like polymers (d) SiX2 << GeX2 << SnX2 << PbX2.
(c) has carbon atoms arranged in large plates of rings of 11. In context with the industrial preparation of hydrogen from
strongly bound carbon atoms with weak interplate bonds water gas (CO + H2), which of the following is the correct
(d) is a non-crystalline substance statement? [AIEEE 2008]
5. Glass is a [AIEEE 2003] (a) CO is oxidised to CO2 with steam in the presence of a
(a) super-cooled liquid (b) gel catalyst followed by absorption of of CO2 in alkali
(c) polymeric mixture (d) micro-crystalline solid (b) CO is removed by absorption in aqueous Cu2Cl2
6. For making good quality mirrors, plates of float glass are used. solution
These are obtained by floating molten glass over a liquid metal (c) H2 is removed through occlusion with pd
which does not solidify before glass. The metal used can be (d) CO and H2, are fractionally separated using differences
[AIEEE 2003] in their densities
(a) tin (b) sodium 12. Among the following substituted silanes the one which will
(c) magnesium (d) mercury give rise to cross linked silicone polymer on hydrolysis is
7. The soldiers of Napolean army while at Alps during freezing [AIEEE 2008]
winter suffered a serious problem as regards to the tin buttons (a) R4Si (b) R2SiCl2
of their uniforms. White metallic tin buttons got converted (c) RSiCl3 (d) R3SiCl
to grey powder. This transformation is related to
13. In view of the signs of D r G ° for the following reactions :
[AIEEE 2004]
(a) a change in the partial pressure of oxygen in the air PbO 2 + Pb ® 2PbO, D r G° < 0
(b) a change in the crystalline structure of tin SnO 2 + Sn ® 2SnO , D r G° > 0
(c) an interaction with nitrogen of the air at very low Which oxidation states are more characteristics for lead and
temperature tin ? [AIEEE 2011RS]
(d) an interaction with water vapour contained in the humid
(a) For lead + 2, for tin + 2 (b) For lead + 4, for tin + 4
air
(c) For lead + 2, for tin + 4 (d) For lead + 4, for tin + 2
332 Chemistry
14. Name of the structure of silicates in which three oxygen atoms 16. The species present in solution when CO2 is dissolved in
of [SiO4]4– are shared. [IIT-JEE 2005 S] water are [IIT-JEE 2006]
(a) Pyrosilicate (a) CO 2 , H 2CO3 ,HCO3- ,CO32-
(b) Sheet silicate
(b) H 2CO3 ,CO32 -
(c) Linear chain silicate
(d) Three dimensional silicate (c) CO32- , HCO3
15. When PbO2 reacts with conc. HNO3 the gas evolved is (d) CO2, H2CO3
[IIT-JEE 2005 S]
(a) NO2 (b) O2 (c) N2 (d) N2O
1. On addition of excess of sodium hydroxide solution to 10. Which gas is essential constituent of almost all fuel gases ?
stannous chloride solution, we obtain : (a) CO2 (b) N2
(a) Sn( OH)2 (b) SnO2 .H2O (c) CO (d) H2O
(c) Na2SnO2 (d) None of these 11. Which does not exist
2. Lead pipes are readily corroded by
(a) [SnCl 6 ]2- (b) [GeCl 6 ]2-
(a) H 2SO 4 (b) HCl
(c) CH 3COOH (d) pure water (c) [SiCl 6 ]2- (d) [CCl 6 ]2-
3. A salt which gives CO2 with hot H2SO4 and also decolourises 12. Newly shaped glass articles when cooled suddenly become
acidified KMnO4 on warming is brittle, therefore these are cooled slowly, this process in
(a) bicarbonate (b) carbonate known as
(c) oxalate (d) acetate (a) tempering (b) annealing
4. Which halide is least stable and has doubtful existence (c) quenching (d) galvanising
(a) CI4 (b) GeI4 13. Mark the correct statement
(c) SnI4 (d) PbI4 (a) Water gas is used in manufacture of methyl alcohol
5. R3SiCl on hydrolysis forms (b) Water gas has highest calorific value
(c) Water gas burns with luminous flame
(a) R3SiOH (b) R 3Si - O - SiR 3
(d) The production of water gas is exothermic process.
(c) R 2Si = O (d) None of these 14. H2SO4 is not used for preparation of CO2 from marble chips
6. Which melts in boiling water ? because
(a) Gun metal (b) Wood’s metal (a) it does not react
(c) Monel metal (d) Bell metal (b) huge amount of heat is evolved
7. Incomplete combustion of petrol or diesel oil in automobile (c) the reaction is vigorous
engines can be best detected by testing the fuel gases for (d) calcium sulphate is sparingly soluble and gets deposited
the presence of on marble chips and stops the reaction.
(a) CO + H 2 O (b) CO 15. CO2 is used for extinguishing fire because
(c) NO 2 (d) SO 2 (a) it has a relatively high critical temperature
8. Which of the following is/ are methanide (s) ? (b) in solid state, it is called dry ice
(a) Be2C (b) Al4C3 (c) it is neither combustible nor a supporter of combustion
(c) Mg2C3 (d) Both (a) and (b) (d) it is a colourless gas
9. Which of the following statements is false? 16. Lead pipes are not suitable for drinking water because
(a) Water gas is a mixture of hydrogen and carbon monoxide (a) lead forms basic lead carbonate
(b) Producer gas is a mixture of CO and nitrogen (b) lead reacts with water containing air to form
(c) Water gas is a mixture of water vapour and hydrogen Pb(OH)2
(d) Natural gas consists of methane, ethane and gaseous (c) a layer of lead dioxide is deposited over pipes
hydrocarbons. (d) lead reacts with air to form litharge
The p -Block Elements –Carbon Family 333
17. CO2 and N2 are non-supporters of combustion. However for (b) PbO film is formed which resists chemical attack by acid
putting out fires CO2 is preferred over N2 because CO2 (c) PbCl2 protective coating gets formed on Pb surface
(a) does not burn (d) PbO2 film is always present on Pb surface, which resist
(b) forms non-combustible products with burning chemical attack
substances 28. Which of the folllowing is not correct?
(c) is denser than nitrogen (a) Ge (OH)2 is amphoteric
(d) is a more reactive gas (b) GeCl2 is more stable than GeCl4
18. When sodium oxide is heated in a current of CO2 at 360°C we (c) GeO2 is weakly acidic
get (d) GeCl4 in HCl forms [ GeCl2]2– ion
(a) sodium formate (b) sodium oxalate 29. Producer gas, a fuel and also a source of nitrogen is obtained
(c) sodium acetate (d) sodium carbonate by
19. Tin plague is the (a) passing a mixture of steam and air over incandescent
(a) conversion of stannous to stannic coke.
(b) conversion of white tin to grey tin (b) spraying oil into hot retorts.
(c) emission of sound while bending a tin rod (c) restricted supply of air through a bed of incandescent
(d) atmospheric oxidation of tin coke.
20. A gas does not turn lime water milky, supports combustion (d) passing steam over incandescent coke.
of burning magnesium. It has no smell and is colourless. It 30. Which of the following shows bond in silicone :
extinguishes a glowing splint but under some circumstances (a) Si – Si – Si – Si (b) – Si – O – Si – O – Si
reacts with oxygen and hydrogen. It is not poisonous. The (c) Si – C – Si – C – Si (d) Si – C – Si – O – Si
gas is likely to be 31. Which type of forces bind together the carbon atoms in
(a) water vapours (b) nitrogen diamond ?
(c) CO2 (d) helium (a) Coulombic forces (b) van der Waal’s forces
21. The correct statement with respect to CO is (c) Dipole-Dipole forces (d) Covalent forces
32. Which is the best absorbing material for carbon dioxide?
(a) it combines with H2O to give carbonic acid
(a) Cold, solid calcium chloride
(b) it reacts with haemoglobin in RBC (b) Heated charcoal
(c) it is powerful oxidising agent (c) Heated copper oxide
(d) it is used to prepare aerated drinks (d) Cold, solid calcium hydroxide.
22. Tin cry refers to 33. Water gas cannot be prepared by a continuous process
(a) conversion of white to grey tin because
(b) tin plating (a) the reaction ceases when coke is too cool.
(c) conversion of white tetrahedral tin to white rhombohedral (b) it cannot be manufactured without producer gas.
tin (c) the furnace must be allowed to cool occasionally.
(d) emission of sound while bending a tin rod. (d) hot coke must be added from time to time.
23. Plumbo - solvency means dissolution of lead in 34. A kettle which becomes furred-up in use has inside it a deposit
(a) hot water (b) acids composed mainly of :
(c) ordinary water (d) alkalies (a) magnesium bicarbonate (b) magnesium sulphate
24. The reducing power of divalent species decreases in the (c) sodium sulphate (d) calcium carbonate
order 35. The substance used to impart green colour to glass is :
(a) Ge > Sn > Pb (b) Sn > Ge > Pb (a) Cu 2 O (b) SnO2
(c) Pb > Sn > Ge (d) None of these
(c) Cr2 O 3 (d) CdS
25. Which is formed when SiCl4 vapours are passed over
36. On doping Ge metal with a little of In, one gets :
hot Mg
(a) insulator (b) rectifier
(a) SiCl 2 + MgCl 2 (b) Si + MgCl 2 (c) n-type semiconductor (d) p-type semiconductor.
(c) Mg 2Si + Cl 2 (d) MgSiCl 6 37. Water gas is produced by :
(a) saturating hydrogen with moisture.
26. Mg2C3 possess which of the following characteristics? (b) passing steam through a red hot coke bed.
(a) Is called magnesium allylide (c) mixing oxygen and hydrogen in the ratio of 1 : 2
(b) It contain Mg2+ and C 34- ions (d) heating a mixture of CO 2 and CH 4 in petroleum
(c) It on hydrolysis gives propyne refineries.
(d) All of these 38. Which of the following is similar to graphite
27. Lead is not affected by dil. HCl in cold because (a) B (b) BN
(a) Pb is less electronegative than H (c) B 2 H 6 (d) B4C
334 Chemistry
EXERCISE 3 9. (a) Metal atom in the lower oxidation state forms the ionic
bond and in the higher oxidation state the covalent bond
1. (c) Hydrolysis of substituted chlorosilanes yield because higher oxidation state means small size and great
corresponding silanols which undergo polymerisation. polarizing power and hence greater the covalent character.
Hence MCl2 is more ionic than MCl4.
CH3 Cl H OH – 2HCl CH3 OH
Si + Si 10. (d) Reluctance of valence shell electrons to participate in
CH3 Cl H OH CH3 OH bonding is called inert pair effect. The stability of lower
Dialkyl silandiol oxidation state (+2 for group 14 element) increases on
going down the group. So the correct order is
Polymerisation of dialkyl silandiol yields linear
SiX2 < GeX2 < SnX2 < PbX2
thermoplastic polymer.
11. (a) On the industrial scale hydrogen is prepared from water
CH3 CH3 gas according to following reaction sequence
catalyst 2NaOH
HO — Si — OH + H O —Si — OH CO + H 2 + H 2 O ¾¾¾¾
® CO 2 + 2H 2 ¾¾¾¾ ® Na 2 CO3 + H 2 O
1424 3 (alkali)
water gas
CH3 CH3
From the above it is clear that CO is first oxidised to CO2
which is then absorbed in NaOH. So the correct answer
CH3 CH3 in option (a)
12. (c) The cross linked polymers will be formed by RSiCl3
HO — Si — O — Si — OH
OH
CH3 CH3 |
3nH O
nRSiCl3 ¾¾¾¾
2 ® nR - Si - OH ¾¾
®
-3nHCl |
O– O– OH
| |
2. (c) O O
Si Si | |
–
O O O– R - Si - O - Si
| |
O
– O– O O
| |
Pyrosilicate [Si2O7]6– R - Si - O - Si - R
| |
3. (a) SiO44– is basic structural unit of silicates. O O
| |
4. (d) Statement (c) is correct (Cross linked polymer)
5. (a) Glass is a transparent or translucent super cooled liquid. The correct choice is (c)
6. (d) It is because mercury exists as liquid at room °
13. (c) Negative D r G value indicates that + 2 oxidation state
temperature.
is more stable for Pb. Also it is supported by inert pair
7. white tin. Grey tin is brittle and crumbles
(b) Grey tin effect that + 2 oxidation state is more stable for Pb and
as DrG° value is positive in second reaction it indicates
down to powder in very cold climate.
that + 4 oxidation state is more stable for Sn.
8. (d) In SiO2 (quartz), each of O-atom is shared between two
i.e., Sn++ < Pb++, Sn4+ > Pb4+
SiO44– tetrahedra.
14. (b) Two dimensional sheet structures of the formula
— —
— —
— —
— —
— Si — O —Si — O — Si — O —Si — (SiO5 ) n2n - are formed when tetrahedral are shared.
O O O O 16. (a)
— —
— —
— —
— —
Structure of SiO2
336 Chemistry
14. (d) Sparingly soluble CaSO4 deposits on marble and stops 34. (d) The bicarbonates of Ca and Mg are decomposed to Ca
the reaction. and Mg carbonates by boiling.
15. (c) CO2 is incombustible and non supporter of combustion. 35. (c) Cr2 O 3 impart green colour to glass.
16. (b) 2Pb + 2H 2 O + O 2 ® 2Pb(OH ) 2 36. (d) Doping of Ge with In produces p-type semiconductor.
17. (c) CO2 being more dense covers the igniting material more 37. (b) H 2 O (steam) + C (coke) ¾
¾® CO + H 2
effectively than N2.
38. (b) Graphite and boron nitride have similar structure.
12A
Purification,
Qualitative and Quantitative
Analysis of Organic Compounds
The organic compounds obtained from natural sources or conditions of temperature and pressure without
synthesised in the lab are often contaminated with impurities. decomposition and containing non volatile impurities are
They are purified by specialised methods purified by simple distillation.
METHODS OF PURIFICATION OF SOLIDS (ii) Fractional distillation: It is employed for separating two or
(i) Cystallisation: A saturated solution of impure substance is more volatile liquids having boiling points close to each
prepared in hot solvent and is heated with vegetable or other eg. acetone (bpt 60ºC) and methanol (bpt 65ºC). The
animal charcoal which adsorbs the impurities . The solution vapours of the liquids pass through the fractionating column
is filtered while hot through a hot water funnel. The filtrate which provides greater space for their cooling. The vapours
on cooling deposits crystals of pure compound. Success of of high boiling fractions condense and fall back into
the process depends upon the selection of the solvent. The distillation flask. The process is repeated till fractions of
impurities must be least soluble while hot and most-soluble high volatility go up followed by of lower volatility. They
while cold. The quick cooling gives tiny but pure crystals are collected separately.
while slow cooling gives bigger but impure crystals. When (iii) Distillation under reduced pressure or vacuum distillation:
crystal formation is initiated by adding crystals of substance Some liquids decompose when heated to their boiling points
it is called “Seeding”. eg. glycerol. Such liquids can be purified by distillation under
(ii) Fractional crystallisation : It is based on the differential reduced pressure much below their boiling points. The lower
solubilities of different compounds in a solvent. The the pressure lower is the boiling point and vice versa.
compound having less solubility crystallises out first on (iv) Steam distillation: The liquids insoluble in water, steam
cooling leaving behind others in solution. Sometimes mixture volatile in nature, having high molecular weight and having
of two solvents eg. Alcohol & water; Chloroform & high vapour pressure are purified by steam distillation
Petroleum ether, Alcohol or ether give better results. provided the impurities present are not steam volatile.
(iii) Sublimation: Some solids directly pass into vapour when Theory of steam distillation: The liquid boils when its
heated and vapour directly pass into solid when cooled vapour pressure becomes equal to the atmospheric
without the intermediate formation of liquid. This is known pressure. For a mixture of liquid (pl) and steam (ps) we have
as sublimation. The substances which sublime can be at boiling point
purified by this method provided the impurities present do P = pl + ps \ pl = (P – ps)
not sublime.
Hence liquid will boil at lower temperature than its normal
Camphor, napthalene, anthracene, benzoic acid, phthalic
boiling point. Examples Aniline, o-nitrophenol,
anhydride and anthraquinone are purified by sublimation.
bromobenzene, salicyaldehyde, essential oils etc.
METHODS OF PURIFICATION OF LIQUIDS
CHROMATOGRAPHIC METHODS
(i) Simple distillation: The vapourisation of a liquid by heating
It was discovered by Tswett (1906) and developed by Kuhn,
and subsequent condensation of vapours by cooling is
Winterstein and Karrer.
known as distillation. The liquids boiling under ordinary
338 Chemistry
(i) Principle: Selective adsorption or distribution of various EXTRACTION
components of mixture beween the two phases - fixed phase The process of removing a substance from its aqueous solution
and mobile phase. by shaking with a suitable solvent is known as extraction. (partition
(ii) Classification: law) The greater the number of operations the greater is the
(a) Adsorption chromatography: Fixed phase - Solid or recovery of substance. Soxhlet extractor is used for continuous
ion exchange resin extraction.
Mobile phase - Liquid or gas DRYING OF ORGANIC SUBSTANCES
Hence it is further known as liquid - solid Stable solids may be dried in a steam or air oven; by heating on a
chromatography, gas-solid chromatography or ion free flame. In a vacuum desicator using anhy. CaCl , conc H SO
2 2 4
exchange chromatography. or P2O5 etc.
(b) Partition Chromatography: Fixed phase - liquid Alcohols are dried over : Quick lime, anhy. K CO , MgSO or
2 3 4
supported on inert solid Na2SO4
Mobile phase - liquid or gas Aldehydes and Ketones : Anhy. MgSO4, Na2SO4 or CaCl2
Hence we have liquid - liquid partition chromatography Organic acids: Anhy. MgSO , Na SO or P O
4 2 4 2 5
and liquid gas partition chromatography
Organic bases: Solid KOH, Quick lime or Soda lime
Paper chromatography is the example of partition
chromatography CRITERIA OF PURITY
(iii) Column chromatography: (i) Mixed melting point: The purified substance is mixed with
Example of Adsorption chromatography pure substance (100%) and melting point is taken. If it is
sharp the substance is pure otherwise not. Impurities lower
Adsorbents used are: alumina, silica gel, cellulose powder,
the melting point.
sucrose, animal charcoal, magnesium oxide or keiselguhr
etc. (ii) Boiling Point : The boiling point of a liquid is defined as the
temperature at which its vapour pressure becomes equal to
Liquid Solvents used are : benzene, petrolium ether,
atomospheric pressure. Sharp and concordant boiling point
chloroform, alcohol etc.
is the criteria of purity of organic substance. Impurities
When the solvent is poured over the mixture present at the increase the boiling point.
top of a column packed with adsorbent the components are
separated into number of layers called Zones, bands or DETECTION OF CARBON AND HYDROGEN
chromatograms due to preferential adsorption. The process Strong
(C) organic compound + CuO ¾¾ ¾ ¾®
being known as development. D
(i ) Exploded (ii ) Coo l Contraction in volume (iii) KOH contraction in (iv) Remaining
¾¾ ¾ ¾ ¾® CO 2 ¾¾ ¾¾® ¾¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾® ¾¾ ¾ ¾ ¾ ¾ ¾ ¾¾® ® ¾¾¾¾¾¾¾¾¾¾®
gives volume of H 2O volume gives volume of CO 2 volume is of uncreated O2
H 2O
O 2 (unreacted)
It is absorbed by alkaline pyrogallol. Hence volume of O2 reacted can be known and molecular formula can be calculated with the
help of following equation
æ yö y
C x H y + ç x + ÷ O 2 ® XCO 2 + H 2 O
è 4 ø 2
(x) Aromatic 1° amines : Give diazo compound with NaNO 2 and HCl.
(xiv) Isocyanide : On reduction with Na + C 2 H 5 OH give 2° amines. On acid hydrolysis give 1° amine and formic acid.
(xv) 1° amine : Give isocyanides with CHCl 3 + NaOH, which have unpleasant odour..
(xvi) Nitro compounds : Give 1° amine with Sn + HCl.
(xvii) Amides : Give NH 3 when heated with NaOH.
(xviii) Anilides : They are hydrolysed to 1° amines.
Purification, Qualitative and Quantitative Analysis of Organic Compounds 343
1. 0.280 gm. of an organic substance gave on combustion 0.560 4. 0.147 gm. of an organic compound containing chlorine was
gm. of carbon dioxide and 0.14 gm. of water. Calculate the heated with nitric acid and silver nitrate which gave 0.287
percentage of carbon, hydrogen and oxygen present in the gm. of silver chloride. Calculate the percentage of chlorine
compound. in the compound.
Sol. Percentage of carbon Sol. Percentage of chlorine
12 Wt. of CO 2 ´ 100 12 ´ 0.560 ´ 100 35.5 ´ Wt. of AgCl ´ 100 35.5 ´ 0.287 ´ 100
= ´ = = 54.54% = = = 48.29%
44 Wt. of substance 44 ´ 0.280 143.5 ´ Wt. of substance 143.5 ´ 0.147
0.22 æ yö
= ´ 22400 = 121.1 gm. \ 20 + 20ç x + ÷ - 20 x = 50
40.7 è 4 ø
Hence molecular weight of the substance = 121.1
10. The molal freezing point constant of benzene is 4.90 and its y
20 ´ = 30 \y = 6
melting point is 5.51°C. A solution of 0.816 g of a compound 4
A dissolved in 7.5 g of benzene freezes at 1.59°C. Calculate the Hence formula of hydrocarbon = C2H6.
molecular weight of compound A. 14. A dibasic acid gave the following results on analysis
Sol. DTf = 5.51°C - 1.59°C = 3.92°C (a) 0.177 gm. of acid gave on combustion 0.2642 gm. of CO2
K f ´ w ´ 1000 4.9 ´ 0.816 ´ 1000 and 0.081 gm. of water.
m= = = 136 (b) 0.2988 gm. of its Ag salt left 0.1944 gm. of Ag on ignition.
DTf ´ W 3.92 ´ 7.5
Determine the molecular formula of the acid and write
11. The boiling point of pure acetone is 56.38°C at normal down the structural formula of its possible isomers.
pressure. When 0.707 gm. of a substance is dissolved in 10
gm. acetone, the solution boils at 56.88°C. Calculate the 12 0.2642 ´ 100
Sol. % of C = ´ = 40.70
molecular weight of the substance. Ebullioscopic constant 44 0.177
Kb for acetone is 1.67.
Sol. Molecular weight M 2 0.081´ 100
% of H = ´ = 5.07
K b ´ w ´ 1000 1.67 ´ 0.707 ´1000 18 0.177
= = = 236.13 % of O = 100 – (40.70 + 5.07) = 54.23
DTb ´ W (56.88 - 56.38) ´ 10
Element % At. wt. Relative Simple
12. 0.177 gm. of a monobasic acid requires 30 cc of N/10 NaOH
for complete neutralisation. Calculate the molecular weight no. of atoms ratio
of the acid. 40.70 3.39
C 40.70 12 = 3.39 = 1´ 2 = 2
1 1 12 3.39
Sol. geq. of NaOH used = 30 ´ ´ = 0.003
10 1000 5.07 5.07
H 5.07 1 = 5.07 = 1.5 ´ 2 = 3
geq. of acid neutralised by NaOH = 0.003 1 3.39
0.003 geq. º 0.177 g. of acid 54.23 3.39
O 54.23 16 = 3.39 = 1´ 2 = 2
16 3.39
1 geq. º 0.177 = 59 g of acid,
0.003 Empirical formula of dibasic acid = C2H3O2
Hence equivalent of acid = 59 Empirical formula weight of the acid = 59
Since the acid is monobasic. Therefore molecular weight of
acid = 59 × 1 = 59.
Purification, Qualitative and Quantitative Analysis of Organic Compounds 345
Mol. wt. of acid
æ Wt. of Ag Salt ´ 108 ö
Mol. wt. of acid = basicity × çç - 107 ÷÷ æ Wt. of Silver salt ´ 108 ö
è Wt. of Ag ø = Basicity × çç - 107 ÷÷
è Wt . of Silver ø
æ 0.2988 ´ 108 ö
= 2ç - 107 ÷ = 118 æ 0.91´108 ö
è 0.1944 ø = 2´ç - 107 ÷ =150
è 0.54 ø
Molecular formula =
Molecular weight Mol.wt 150
(Empirical formula) n= = =2
Empirical formula weight Empirical wt 75
15. 0.56 g of an organic compound gave 0.589 g of silver iodide. CO 2 and 0.324 g H 2 O . 0.295 g compound gives 56 cc
Calculate the % of I in the compound. N 2 by Dumas method . The compound is monoacidic
127 wt. of AgI base and its platinichloride contains 36.89% platinum. Find
Sol. % I = × × 100
235 wt. of organic compound the mol. formula of the compound.
12 0.528
127 0.589 Sol. %C= × × 100 = 61.02
= × × 100 = 56.84 44 0.236
235 0.56
16. 2.79 g of an organic compound was heated in a Carius tube 2 0.324
%H= × × 100 = 15.25
with conc HNO 3 and H 3PO 4 formed was 18 0.236
converted into Mg NH 4 PO 4 ppt. The precipitate on heating 28 56´ 100
%N= × = 23.74
gave 1.332 g of Mg 2 P2 O 7 . What is the % of P in the 22400 0.295
compound? Element % At. wt. Relative Simple
62 wt. of Mg 2 P2 O 7 no. of atoms ratio
Sol. % P = × × 100
222 wt. of organic compound 61.02 5.08
C 61.02 12 = 5.08 =3
12 1.69
62 1.332
= × × 100 = 13.33%
222 2.79 15.25 15.25
H 15.25 1 = 15.25 =9
17. A dibasic acid contain C = 32%, H = 4%. 0.91 g silver salt of 1 1.69
the acid gives 0.54 g silver on ignition. Determine the
molecular formula of the compound. 23.74 1.69
N 23.74 14 = 1.69 =1
Sol. 14 1.69
Empirical formula of compound C 3 H 9 N .
Element % At. wt. Relative Simple
no. of atoms ratio Mol. wt. of compound
1. For the separation of two immiscible liquids which method (a) sodium hydroxide (b) sodium sulphate
(or apparatus) is used? (c) calcium chloride (d) sodium bicarbonate
(a) chromatography (b) fractionating column 12. In sodium fusion test of organic compounds, the nitrogen
(c) fractional distillation (d) separating funnel of the organic compound is converted into
2. A mixture of benzene and chloroform is separated by (a) sodamide (b) sodium cyanide
(a) sublimation (b) separating funnel (c) sodium nitrite (d) sodium nitrate
(c) crystallization (d) distillation 13. The Lassaigne’s extract is boiled with dil. HNO3 before
3. Which of the following has molecular weight of 92 ? testing for halogens because
(a) Toluene (b) Benzene (a) silver halides are soluble in HNO3
(c) Methylene (d) Propene (b) Na2S and NaCN are decomposed by HNO3
4. Aniline is usually purified by (c) Ag2S is soluble in HNO3
(a) chromatographic technique (d) AgCN is soluble is HNO3
(b) steam distillation 14. Which of the following compounds does not show
Lassaigne’s test for nitrogen ?
(c) by addition of oxalic acid
(a) Urea (b) Hydrazine
(d) fractional crystallization
(c) Phenylhydrazine (d) Azobenzene
5. An organic compound contains 49.3% carbon, 6.84%
hydrogen and its vapour density is 73. Empirical formula of 15. When pieces of human hair are heated strongly with soda-
the compound is lime, smell of ammonia can be detected. Which one of the
following conclusion can be drawn form this observation?
(a) C3H5O2 (b) C6H10O4
(a) Ammonia is present in the human hair
(c) C3H10O2 (d) C4H10O4
(b) Ammonium salt is present in hair
6. Distillation under reduced pressure is employed for
(c) Hair contains amino acids
(a) C6H6
(d) None of the above
(b) petrol
16. Which of the following is the best scientific method to test
(c) CH2OHCHOHCH2OH
presence of water in a liquid ?
(d) organic compounds used in medicine
(a) Smell
7. Impure glycerine is purified by
(b) Taste
(a) steam distillation (b) simple distillation
(c) Use of litmus paper
(c) vacuum distillation (d) None of these
(d) Use of anhydrous copper sulphate
8. Absolute alcohol is prepared by
17. Liebig’s method is used for the estimation of
(a) fractional distillation (b) Kolbe’s method
(a) nitrogen (b) sulphur
(c) azeotropic distillation (d) vacuum distillation
(c) carbon and hydrogen (d) halogens
9. The latest technique used for purification of organic
18. 0.765 g of an acid gives 0.535 g of CO2 and 0.138 g of H2O.
compounds is
Then the ratio of the percentage of carbon and hydrogen is
(a) chromatography (b) vacuum distillation
(a) 19 : 2 (b) 18 : 11
(c) fractional distillation (d) crystallization
(c) 20 : 17 (d) 1 : 7
10. In paper chromatography
19. Nitrogen in an organic compound can be estimated by
(a) moving phase is liquid and stationary phase in solid
(a) Kjeldahl’s method only (b) Duma’s method only
(b) moving phase is liquid and stationary phase is liquid
(c) Both (a) and (b) (d) Neither (a) nor (b)
(c) moving phase is solid and stationary phase is solid
20. Duma's method involves the determination of nitrogen
(d) moving phase is solid and stationary phase is liquid content in the organic compound in form of
11. A is a lighter phenol and B is an aromatic carboxylic acid. (a) NH3 (b) N2
Separation of mixture of A and B can be carried out easily by
(c) NaCN (d) (NH4)2SO4
using a solution of
Purification, Qualitative and Quantitative Analysis of Organic Compounds 349
21. Molecular mass of a volatile substance may be obtained by (a) 65.0 (b) 64.0
(a) Kjeldahl’s method (b) Duma’s method (c) 63.8 (d) 62.5
(c) Victor-meyer’s method (d) Liebig’s method 33. The equivalent weight of an acid is equal to
22. The percentage of sulphur in an organic compound whose (a) Molecular weight × acidity
0.32 g produces 0.233 g of BaSO4 [At. wt. Ba = 137, S = 32] is (b) Molecular weight × basicity
(a) 1.0 (b) 10.0 (c) Molecular weight/basicity
(c) 23.5 (d) 32.1 (d) Molecular weight/acidity
23. If 0.2 gram of an organic compound containing carbon, 34. Simple distillation can be used to separate liquids which
hydrogen and oxygen on combustion, yielded 0.147 gram differ in their boiling points at least by
carbon dioxide and 0.12 gram water. What will be the content (a) 5ºC (b) 10ºC
of oxygen in the substance ? (c) 30º – 50ºC (d) 100ºC
(a) 73.29% (b) 78.45% 35. Empirical formula of a compound is CH2O. If its vapour
(c) 83.23% (d) 89.50% density is 90, then the molecular formula of the compound
24. If a compound on analysis was found to contain is
C = 18.5%, H = 1.55%, Cl = 55.04% and O = 24.81.%, then its (a) C5H10O5 (b) C3H6O3
empirical formula is (c) C6H12O6 (d) C4H8O4
(a) CHClO (b) CH2ClO 36. The empirical formula of an acid is CH2O2, the probable
(c) C2H2OCl (d) ClCH2O2 molecular formula of the simplest acid may be
25. An organic compound contains C = 40%, H = 13.33% and N (a) CH2O (b) CH2O2
= 46.67%. Its empirical formula would be (c) C2H4O4 (d) C3H6O6
(a) CHN (b) C2H2N 37. A gaseous hydrocarbon has 85% carbon and vapour
(c) CH4N (d) C3H7N density of 28. The possible formula of the hydrocarbon will
be
26. Two elements X (atomic weight = 75) and Y (atomic weight
(a) C3H6 (b) C2H4
= 16) combine to give a compound having 75.8% X. The
formula of the compound is (c) C2H2 (d) C4H8
(a) XY (b) X2Y 38. A hydrocarbon has C= 85.72% and remaining H. The
hydrocarbon is
(c) X2Y2 (d) X2Y3
(a) C2H4 (b) C2H6
27. On analysis, a saturated hydrocarbon is found to contain
(c) C2H2 (d) CH4
83.70% carbon and 16.30% hydrogen. The empirical formula
39. An organic compound containing carbon, hydrogen and
will be (at wt. of C= 12; at. wt. of H = 1)?
oxygen contains 52.2% carbon and 13.04% hydrogen.
(a) C3H6 (b) C3H8
Vapour density of the compound is 23. Its molecular formula
(c) C3H4 (d) C6H12 will be
28. Empirical formula of a hydrocarbon containing 80% carbon (a) C2H6O (b) C3H8O
and 20% hydrogen is (c) C4H8O (d) C5H10O
(a) CH (b) CH2 40. Percentage of Se(at. wt. = 78.4) in peroxidase anhydrase
(c) CH3 (d) CH4 enzyme is 0.5% by weight, then minimum molecular weight
29. An organic compound with C = 40% and H = 6.7% will have of peroxidase anhydrase enzyme is
the empirical formula (a) 1.568 × 104 (b) 1.568 × 103
(a) CH4 (b) CH2O (c) 15.68 (d) 2.136 × 104
(c) C3H6O3 (d) C2H4O2 41. The empirical formula of a compound is CH 2. One mole of
30. In a hydrocarbon, mass ratio of hydrogen and carbon is 1:3, the compound has a mass of 42 g, its molecular formula is
the empirical formula of hydrocarbon is (a) CH2 (b) C2H2
(a) CH4 (b) CH2 (c) C3H6 (d) C3H8
(c) C2H (d) CH3 42. In a compound, C, H and N atoms are present in 9 :1: 3.5 by
31. 0.24 g of a volatile liquid on vaporization gives 45 ml of weight . If molecular weight of the compound is 108, then
vapours at NTP. What will be the vapour density of the molecular formula of the compound is
substance ? (Density of H2 = 0.089 g L–1) (a) C2H6N2 (b) C3H4N
(a) 95.39 (b) 39.95 (c) C6H8N2 (d) C9H12N3
(c) 99.53 (d) 59.93 43. The following is the percentage composition of a compound
32. 0.1914 g of an organic acid is dissolved in about 20 ml of : Na = 16.08%, C = 4.19%, O = 16.78% and H2O = 62.95% . Its
water. 25 ml of 0.12 N NaOH is required for the complete molecular formula is
neutralization of the acid solution. The equivalent weight of (a) Na2CO3 (b) Na2CO3H2O
the acid is (c) Na2CO3.10H2O (d) Na2CO3.5H2O
350 Chemistry
1. Lassaigne’s test is used in qualitative analysis to detect 7. The best method for the separation of naphthalene and
[CBSE-PMT 1989] benzoic acid from their mixture is:
(a) Nitrogen (b) Sulphur [CBSE-PMT 2005]
(c) Chlorine (d) All of these (a) distillation (b) sublimation
2. Kjeldahl’s method is used in the estimation of
(c) chromatography (d) crystallisation
[CBSE-PMT 1990]
8. The compound formed in the positive test for nitrogen with
(a) Nitrogen (b) Halogens the Lassaigne solution of an organic compound is
(c) Sulphur (d) Oxygen
[AIEEE-2004]
3. In sodium fusion test of organic compounds, the nitrogen of
(a) Fe4[Fe(CN)6]3 (b) Na3[Fe(CN)6]
the organic compound is converted into
[CBSE-PMT 1991] (c) Fe(CN)3 (d) Na4[Fe(CN)5NOS]
(a) Sodamide (b) Sodium cyanide 9. In a compound C, H and N atoms are present in 9 : 1 : 35 by
weight. Molecular weight of compound is 108. Molecular
(c) Sodium nitrite (d) Sodium nitrate
formula of compound is [AIEEE 2002]
4. A is a lighter phenol and B is an aromatic carboxylic acid.
Separation of a mixture of A and B can be carried out easily (a) C2H6N2 (b) C3H4N
by using a solution of [CBSE-PMT 1992] (c) C6H8N2 (d) C9H12N3.
(a) Sodium hydroxide 10. The ammonia evolved from the treatment of 0.30 g of an organic
(b) Sodium sulphate compound for the estimation of nitrogen was passed in 100
(c) calcium chloride mL of 0.1 M sulphuric acid. The excess of acid required 20 mL
of 0.5 M sodium hydroxide solution for complete neutralization.
(d) Sodium bicarbonate
The organic compound is [AIEEE 2004]
5. The most suitable method for separtion of a 1 : 1 mixture of ortho
and para nitrophenols is [CBSE-PMT 1994] (a) urea (b) benzamide
(a) Sublimation (b) Chromatography (c) acetamide (d) thiourea
(c) Crystallization (d) Steam distillation 11. Sodium nitroprusside, when added to an alkaline solution
6. The first organic compound, synthesized in the laboratory, of sulphide ions, produces purple colour ion due to the
was [CBSE-PMT 1995] formation of [IIT 1995, Orissa JEE 2008]
(a) alcohol (b) acetic acid (a) Na[Fe(H2O)5 NOS] (b) Na2[Fe(H2O)5 NOS]
(c) urea (d) none of these (c) Na3[Fe(CN)5NOS] (d) Na4[Fe(CN)5NOS]
Purification, Qualitative and Quantitative Analysis of Organic Compounds 351
1. In Kjeldahl’s method nitrogen present is estimated as 11. Liquid benzene burns in oxygen according to
(a) N2 (b) NH3
2C6H6 (l) +15O2 (g) ®12CO2 (g) + 6H2O(g) . How many litre
(c) NO2 (d) None of these
2. Lassaigne’s test for the detection of nitrogen will fail in of O2 at STP are needed to complete the combustion of 39g
case of of liquid benzene:
(a) 11.2 litre (b) 22.4 litre
(a) NH 2 CONH 2 (b) H 2 NCONHNH 2 .HCl
(c) 84 litre (d) 74 litre
(c) H 2 N.NH 2 .2HCl (d) H 6 C5 NHNH 2 .2HCl 12. 0.75 g platinic chloride of a mono- acidic base on ignition
3. The most suitable method of separation of 1:1 mixture of gives 0.245 g platinum. The molecular weight of the base is
ortho and para nitrophenols is (a) 75.0 (b) 93.5
(a) distillation (b) crystallisation (c) 100 (d) 80.0
(c) sublimation (d) chromatography 13. An organic compound has C and H percentage in the ratio 6
4. In kjeldahl's method of estimation of nitrogen, K2SO4 acts as : 1 and C and O percentage in the ratio 3:4 the compound is
(a) oxidising agent (b) catalytic agent (a) HCHO (b) CH3OH
(c) hydrolysing agent (d) boiling point elevator (c) CH3CH2OH (d) (COOH)2
5. For detection of sulphur in an organic compound sodium 14. Before testing halogens the sodium extract is boiled with
nitroprusside is added to the sodium extract. A violet colour conc. HNO 3 to
is obtained due to formation of (a) bring common ion effect
(a) Fe(CN ) 2 (b) K 3 Fe(CN ) 5 NS (b) make solution clear
(c) destroy CN– and S– – ions
(c) Na 4 [Fe(CN ) 5 NOS] (d) Na 4 Fe(CN ) 6
(d) make the solution acidic
6. Which of the following reagents is useful for separating 15. The sodium extract prepared from sulphanilic acid, contains
aniline and nitrobenzene?
SCN - . It gives blood red colouration with
(a) NaOH (aq) (b) H 2 O
(a) a mixture of Na 2S and CS 2
(c) NaHCO3 (d) HCl (aq)
7. 0.5g of an organic compound containing nitrogen on (b) FeCl 3
Kjeldahlising required 29 mL of N/5 H2SO4 for complete
neutralization of ammonia. The percentage of nitrogen in the (c) FeSO 4
compound is (d) Na 2SO 3
(a) 34.3 (b) 16.2
(c) 21.6 (d) 14.8 16. An organic compound is treated with NaNO 2 and dil. HCl
8. Kjeldahl’s method cannot be used for the estimation of at 0°C. The resulting solution is added to an alkaline solution
nitrogen in of b -naphthol where by a brilliant red dye is produced. It
(a) pyridine (b) nitro compounds shows the presence of
(c) azo compounds (d) All of these
(a) – NO 2 group (b) aromatic – NH 2 group
9. A compound contains 38.8% C, 16% H and 45.2% N. The
formula of compound would be : (c) – CONH 2 group (d) aliphatic – NH 2 group
(a) CH 3 NH 2 (b) CH 3CN 17. Methanol and ethanol can be distinguished by
(a) iodoform reaction (b) Esterification
(c) C 2 H 5 CN (d) C H2(NH2)2
(c) Victor Meyer test (d) Acrolein test
10. 0.22 g of organic compound C x H y O which occupied 112 ml 18. 0.532 g of the chloroplatinate of an organic base (M. wt. 264)
gave 0.190 g of Pt on ignition. Then the number of nitrogen
at NTP and on combustion gave 0.44 g CO2. The ratio of x to
atoms per molecule of the base is
y in the compound is
(a) 4 (b) 3
(a) 1 : 1 (b) 1 : 2
(c) 1 (d) 2
(c) 1 : 3 (d) 1 : 4
352 Chemistry
19. 0.59 g of an organic substance when treated with caustic 27. To detect iodine in presence of bromine, the sodium extract
soda evolved ammonia which required 20 cc of N/2 sulphuric is treated with NaNO 2 + glacial acetic acid + CCl 4 . Iodine
acid for neutralisation. The percentage of nitrogen is
is detected by the appearance of
(a) 26.32% (b) 40%
(c) 53.6% (d) 63.6% (a) yellow colour of CCl 4 layer
20. Which of the following compounds will give foul odour (b) purple colour of CCl 4
of isocyanide when heated with chloroform and alcoholic
KOH ? (c) brown colour in the organic layer of CCl 4
(a) Sulphanilic acid (b) Para toluidine
(d) deep blue colour in CCl 4
(c) Glycine (d) Anthranilic acid
21. 10.0 ml mixture of methane and ethylene was exploded with 28. Which of the following compounds will give silver mirror
30 ml (excess) of oxygen. After cooling the volume was 21.0 test ?
ml. On treatement with KOH solution the volume was reduced (a) CH 3COOH (b) HCOOH
to 7.0 ml. The amount of methane and ethylene in the mixture
respectively are (c) CH 3 CO. COOH (d) None of these
(a) 5 ml CH 4 + 5 ml C 2 H 4 29. Benzaldehyde and acetone can be distinguished by
(c) CH 3COOC 2 H 5 (d) CH 3COCH 3 31. In Kjeldahl’s method for the estimation of N 2 , potassium
24. Beilstein’s test is given by which of the following? sulphate and copper sulphate are used. On the basis of their
(a) Halogens (b) Thiourea functions which of the following statement(s) is/are correct?
(c) Pyridine (d) All of these I. Potassium sulphate raises the bpt. and ensures complete
25. The molecular mass of an organic compound which contains reaction.
only one nitrogen atom can be II. Copper sulphate acts as catalyst.
(a) 152 (b) 146 III. Potassium sulphate acts as catalyst and copper sulphate
(c) 76 (d) 73 raises the bpt.
26. Which of the following observations is correct and useful in (a) Only III is correct (b) I and II are correct
identifying carboxylic acids ? (c) Only II is correct (d) None is correct
(a) Carboxylic acids liberate CO 2 gas from NaHCO 3 32. 2.79 g of an organic compound when heated in Carius tube
solution with conc. HNO 3 and H 3PO 4 formed converted into
(b) Acids liberate I 2 from a mixture of KIO 3 and KI MgNH 4 .PO 4 ppt. The ppt. on heating gave 1.332 g of
(c) They produce fruity smell of esters when heated with Mg 2 P2 O 7 . The percentage of P in the compound is
alcohol in presence of conc. H 2SO 4
(a) 23.33% (b) 13.33%
(d) All of these (c) 33.33% (d) 26.66%
Purification, Qualitative and Quantitative Analysis of Organic Compounds 353
EXERCISE 1 Na 2S + 2AgNO 3 ¾
¾® 2 NaNO 3 + Ag 2S ¯
1. By fractional distillation. Black
2. o–nitrophenol is steam volatile while p–nitro phenol is not NaCN + AgNO 3 ¾
¾® NaNO3 + AgCN ¯
and hence these can be separated by steam distillation. White
3. Vacuum distillation and steam distillation. NaCl + AgNO 3 ¾
¾® NaNO3 + AgCl ¯
5. Fractional crystallisation using benzene as a solvent. white
6. Al2O3 (alumina). boil
Na 2S + 2HNO 3 ¾¾¾® 2 NaNO 3 + H 2S
7. V.D. is 42, Mol. wt. = 2 × V.D. = 2 × 42 = 84 therefore, molecular boil
formula is C6H12. NaCN + HNO 3 ¾¾
¾® NaNO 3 + HCN
8. Every pure substance has fixed melting point and refractive 14. (b) Hydrazine (NH2NH2) does not contain carbon and hence
index. Impurities reduce the melting point and change on fusion with Na metal, it cannot form NaCN;
refractive index. consequently hydrazine does not show Lassaigne’s test
9. Tap water usually contains dissolved chlorine which gives for nitrogen.
test for halogens. 15. (c) Hair contains amino acids which upon fusion with soda
13. Percentage of Br = 34.04% lime (NaOH + CaO) evolve NH3.
14. Percentage of nitrogen = 56% 16. (d) Hydrated CuSO4 is blue in colour, while anhydrous is
17. (b) 18. (d) 19. (d) 20. (d) white.
21. (d) 22. (b) 23. (b) 24. (a) CuSO 4 + 5H 2 O ¾
¾® CuSO 4 .5H 2 O
White Blue
EXERCISE 2 17. (c)
1. (d)
2 (d) Benzene (b.p. 80ºC) and chloroform (b.p. 61.5ºC) have 18. (a) % of C = 12 ´ 0.535 ´ 100 = 19.07 %
44 0.765
different boiling points.
2 0.138
3. (a) Mol. wt. of toluene, C6H5CH3 = 72 + 5 + 12 + 3 = 92 % of H = ´ ´ 100 = 2.004 %
4. (b) Aniline is miscible in steam and has b.p. lower than water, 18 0.765
hence it is collected as distillate along with steam. Ratio of C : H = 19 : 2
5. (a) % of O = 100 – (49.3 + 6.84) = 43.86 19. (c) 20. (b) 21. (c)
Relative ratio of C : H : O =
49.3 6.84 43.86
: : 22. (b) % of S = 32 ´ 0.233 ´ 100 = 10 %
12 1 16 233 0.32
= 4 : 6.84 : 2.74 12 0.147
23. (a) % of C = ´ ´ 100 = 20.045 %
= 1.49 : 2.49 : 1 44 0 .2
= 3 : 5 : 2 (multiplying by 2) 2 0.12
\ Empirical formula = C3H5O2 % of H = ´ ´ 100 = 6.666 %
18 0.2
6. (c) Glycerol decomposes at its boiling point, hence it should
be purified by distillation under reduced pressure. % of O = 100 - (20.045 + 6.666) = 73.29 %
7. (c) Vaccum distillation means distillation under reduced 24. (a) Relative ratio of wts.
pressure. C H Cl O
8. (c) Since alcohol and water form a constant boiling mixture 18.5 1.55 55.04 24.81
(azeotrope). 35.5 16
12 1
9. (a) 10. (b) = 1.55 = 1.55 = 1.55 = 1.55
11. (d) Carboxylic acids dissolve in sodium bicarbonate, while
\ Relative No. of atoms
phenol does not.
12. (b) 1 1 1 1
13. (b) Na2S and NaCN, formed during fusion with metallic Hence empirical formula is CHClO
sodium, must be removed before adding AgNO 3 , 25. (c) As in above question,
otherwise black ppt. due to Na2S or white precipitate due
to AgCN will be formed and thus white precipitate of 40 13.33 46.67
C= = 3.33; H = = 13.33; N = = 3.34
AgCl will not be identified easily. 12 1 14
354 Chemistry
Relative No. of atoms, 85.72 14.28
38. (a) C : H = : = 7.15 : 14.28 = 1 : 2
3.33 13.33 3.34 12 1
C= = 1; H = = 4; N = =1
3.33 3.33 3.33 \ Empirical formula = CH2
\ Empirical formula = CH4N From the give options, simple multiple of CH2 is only C2H4
75 . 8 24 . 2 39. (a) % of O = 100 – (52.2 + 13.04) = 34.76%
26. (d) Relative No. of atoms : X = = 2;Y = = 3 Relative ratio of
75 16
C H O
\ Empirical formula = X2Y3
27. (b) Relative No. of atoms 52.2 13.04 34.76
C H 12 1 16
83.70 16.30 4.35 13.04 2.17
=7 = 16.30
12 1 2 6 1
\ Empirical formula = C2H6O
7 16.30
or =1 = 2.33
7 7 2 ´ 23
Mol. formula = ´ C 2 H 6O = C 2 H 6 O
or 1 × 3 = 3 2.33 × 3 = 8 24 + 6 + 16
\ Empirical formula = C3H8 At. wt. of Se
40. (a) % of Se = ´100
80 20 6.66 20 Min. mol. wt.
28. (c) C : H or = 6.66 ; = 20 or =1; =3
12 1 6.66 6 .66
\ Empirical formula = CH3 \ Min. mol. wt. = At. wt. of Se ´100
29. (b) % of O = 100 – (40 + 6.7) = 53.33 % of Se
78.4 ´ 100
40 6.7 53.33 = = 1.568 ´ 10 4
C:H:O = : : = 3.33 : 6.7 : 3.33 = 1 : 2 : 1 0.5
12 1 16 41. (c) Mol. wt. of the compound
\ Empirical formula = CH2O = Mass of 1 mole of the compound = 42
30. (a) Mass ratio of H : C = 1 : 12 empirical formula wt. of CH2 = 12 + 2 = 14
However, given mass ratio of H : C = 1 : 3
Therefore, for every C atom, there are 4 H atoms, hence 42
\ Molecular formula = CH 2 ´ = C3 H 6
empirical formula = CH4 14
42. (c) Relative ratio of wts. of C : H : N = 9 : 1 : 3.5
31. (d) V.D. = Wt. of 45 ml. of vapours at NTP
Wt. of 45 ml. of H 2 at NTP 9 1 3.5
Relative No. of atoms : : =0.75:1: 0.25=3: 4:1
12 1 14
0.24 g \ Empirical formula = C3H4N
= = 59.93
45 ml. ´ 0.000089 g ml -1 Mol. wt.(given) = 108
32. (c) 25 ml of 0.12 N NaOH = 0.1914 g of acid 108
\ Mol. formula = ´ C3 H 4 N = C 6 H8 N 2
0.1914 ´ 1000 36 + 4 + 14
1000 ml of 1 N NaOH = = 63.8 43. (c) Relative No. of atoms or molecule
25 ´ 0.12
\ Eq. wt. of the acid = 63.8 16.08 4.19 16.78 62.95
Na : C : O : H 2 O = : : :
33. (c) 34. (c) 23 12 16 18
35. (c) Mol. wt. = 2 × V.D. = 2 × 90 = 180 = 0.70 : 0.35 : 1 : 3.50
Empirical formula wt. = 12 + 2 + 16 = 30 = 2 : 1 : 3 : 10
Mol. wt. \ Empirical formula = Na2CO3.10H2O
\ Molecular formula = EF wt. ´ empirical formula
EXERCISE 3
180 1. (d) Nitrogen, sulphur and halogens are tested in an organic
= ´ CH 2 O = C6 H12 O6
30 compound by Lassaigne's test. The organic compound
36. (b) The simplest acid is HCOOH whose mol. formula is CH2O2 is fused with sodium metal as to convert these elements
which coincides with the given empirical formula. into ionisable inorganic substances,
85 15 Na + C + N ¾¾
® NaCN
37. (d) C : H = : = 7 : 15 » 1 : 2
12 1
\ Empirical formula = CH2 2Na + S ¾¾
® Na 2S
Mol. wt. = 2 × 28 = 56
2Na + X 2 ¾¾
® 2NaX
56
Mol. Formula = ´ CH 2 = C 4 H 8 The cyanide, sulphide or halide ions can be confirmed in
12 + 2 aqueous solution by usual test.
Purification, Qualitative and Quantitative Analysis of Organic Compounds 355
2. (a) Kjeldahl's method is suitable for estimating nitrogen in 4. (d) To increase the bpt of H2SO4,K2SO4 is added
those compounds in which nitrogen is linked to carbon
and hydrogen. The method is not used in case of nitro, 5. ( c) Na 2S + Na 2 [Fe(CN)5 NO] ¾¾
® Na 4[Fe(CN)5 NOS]
azo and azoxy compound. This method is basically used Sodium nitroprusside Sodium thionitroprusside
for estimating nitrogen in food fertilizers and agricultural + –
products. 6. (d) C6 H 5 NH 2 +HCl ® C6 H 5 NH 3 Cl
Soluble salt
3. (b) Sodium cyanide (Na + C + N ® NaCN).
(Lassaigne's test) Nitrobenzene remains unaffected
4. (d) Carboxylic acids dissolve in NaHCO 3 but phenols do 1.4 ´ N ´ V 1.4 ´ 29 ´ 1/ 5
7. (b) N% = = = 16.24%
not. wt.of organic compound 0.5
NaHCO3
RCOOH ¾¾¾¾ ® RCOONa + H 2O + CO2 8. (d) Kjeldahl’s method is not suitable for heterocylclic ring
by evolving CO2 gas. with N atom, azo, azoxy and nitro compounds
5. (d) The boiling point of o-nitrophenol is less than para-
9. (a) % of element Relative Simple ratio
nitrophenol due to presence of intramolecular hydrogen
bonding. Since p-nitrophenol is less volatile in than o- no. of atoms
nitrophenol due to presence of inter molecular hydrogen 38.8
bonding hence they can be separated by steam distillation. C 38.8 = 3.2 1
12
6. (c)
7. (b) Among the given compounds naphthelene is volatile 16
H 16.0 = 16.0 5
but benzoic acid is non-volatile (it forms a dimer). So, 1
the best method for their separation is sublimation, 45.28
which is applicable to compounds which can be N 45.28 = 3.2 1
14
converted directly into the vapour phase from its solid
state on heating and back to the solid state on cooling. 10. (b) M.wt of compound = 0.22 ´ 22400 = 44
Hence it is the most appropriate method. 112
8. (a) Prussian blue Fe 4 [Fe(CN ) 6 ]3 is formed in lassaigne 12 0.44 ´ 100
test for nitrogen. % of C = ´ = 54.54
44 0.22
3Na 4 [Fe(CN)6 + Fe3+ ¾¾
®
Fe 4 [Fe(CN) 4 ]3 + 12Na +
Amount of C in compound = 44 ´ 54.54 = 24
Prussian blue 100
9. (c) According to given molecular weight.
\ molecular formula is C2HyO or C2H4O
10. (a) H 2SO 4 is dibasic.
It corresponds to M.wt 44. Hence x : y is 1 : 2
0.1 MH 2SO 4 = 0.2 NH 2SO 4 11. (c) 2 × 78 g C6H6 requires 15 × 22.4 litre O2
Meq of H 2SO 4 taken = = 100 ´ 0.2 = 20
Meq of H 2SO 4 neutralised by NaOH = 20 ´ 0.5 = 10 \ 39 g C6H6 will require = 15 ´ 22.4 ´ 39 = 84 litre
2 ´ 78
Meq of H 2SO 4 neutralised by NH3 = 12 - 10 = 10
12. (b) Apply the formula M.wt
1.4 ´ Meq of acid neutrialised by NH3
% of N 2 = Acidity æ wt of Pt salt ´195 ö
wt. of organic compound = ç - 410 ÷÷
1.4 ´ 10 2 çè wt of Pt ø
= = 46.6
0.3
% of nitrogen in urea = 14 ´ 2 ´ 100 = 46.6 \ M.wt = 1 æç 0.75 ´ 195 - 410 ö÷ = 93.5
60 2 è 0.245 ø
11. (d) Na 2 [Fe(CN)5 NO] + S2- ® Na 4 [Fe(CN)5 NOS] 13. (a) % ratio of C : H is 6 : 1 and C : O is 3 : 4 or 6 : 8
Sodium thio-nitroprusside
(violet) \ % ratio of C : H : O is 6 : 1 : 0 ( Total = 15)
EXERCISE 4 % of C = 6 ´ 100 = 40 40 / 12 = 3 . 33 = 1
15
1. (b) In Kjeldahl’s method nitrogen is converted into
1
(NH4)2 SO4, then to NH3 %H= ´ 100 = 6.6 6.6 / 1 = 6.6= 2
2. (c) For detection of nitrogen by Lassaigne’s method, the 15
8
compound must contain C and N both to form NaCN. % O = ´100 = 53.3 53.3 / 16 = 3 . 3= 1
3. (a) o- nitrophenol is more volatile due to intramolecular H- 15
bonding . p - nitrophenol is less volatile due to simple ratio CH2O
intermolecular H-bonding \ The compound is H.CHO
356 Chemistry
14. (c) It decomposes NaCN and Na 2S to avoid their Vol. of CO 2 produced + O 2 left = 21 ml
interference Vol. of CO 2 produced = 21 – 7 = 14 ml
NaCN + HNO 3 ¾
¾® NaNO3 + HCN CO 2 produced is
Na 2S + 2 HNO 3 ¾
¾® 2 NaNO3 + H 2S a + 2(10 – a) = 14
\ a=6
NaCN + AgNO 3 ¾
¾® AgCN ¯ + NaNO3 \ Vol. of CH 4 = 6 ml and vol. of C 2 H 4 = 4 ml
22. (d)
Na 2S + 2 AgNO 3 ¾
¾® Ag 2S ¯ + 2 NaNO3
NO 2
- +++
15. (b) SCN + Fe ¾
¾® Fe(SCN ) 3
blood red ppt. 23. (d) C = O + H 2 N.NH NO 2 ¾
¾®
OH
16. (b) N 2 Cl + NO 2
¾
¾®
C = NNH NO 2
OH
N=N orange red ppt.
24. (d) Pyridine and thiourea form volatile cupric cyanide and
Red dye also give bluish green flame like volatile cupric halides.
I 2 / NaOH
25. (d) The compounds with odd number of N-atoms have odd
17 (a) CH 3COCH 3 ¾¾¾¾ ¾® CHI3 (iodoform) masses and with even number of N-atoms have even
18. (a) The equivalent wt. of base masses. This is “nitrogen rule”.
26. (d) All the points are correct.
1 æ 0.532 ö
E= ç ´ 195 - 410 ÷ = 68
2 è 0.190 ø 27. (b) 2NaI + 2 NaNO 2 + 4 CH 3COOH ¾
¾®
I 2 + 2NO + 4 CH 3COONa + 2 H 2 O
264
Acidity = =4 28. (b) HCOOH is reducing in nature
68
Acidity of base = number of N atoms per molecule of Ag 2 O + HCOOH ¾ ¾® 2Ag + H 2 O + CO 2
base = 4 silver mirror
19. (a) Percentage of nitrogen by Kjeldahl’s method 29. (d) Benzaldehyde does not give iodoform test while acetone
1.4 ´ N ´ V 1.4 ´ 20 1 forms CHI3 .
= = ´ = 26.32%
Wt. of organic compound 0.532 2 30. (d) When organic compound contains nitrogen, upon
combustion it will produce oxides of nitrogen soluble in
20. (b) H 3 C – NH 2 + CHCl3 + 3KOH ¾
¾®
KOH solution. The copper will convert them into N 2
CH 4 + 2 O 2 ¾
¾® CO 2 + 2 H 2 O (liquid) 62 wt. of Mg 2 P2 O 7
32. (b) Percentage of P = × × 100
a ml 2a ml a ml negligible volume 222 wt. of compound
C2H 4 + 3 O2 ¾ ¾® 2 CO 2 + 2 H 2O 62 1.332
= × × 100 = 13.33%
(10 – a) ml 3(10 – a) ml 2(10 – a) ml negligible 222 2.79
12B
Classification and
Nomenclature of Organic
Compounds
CLASSIFICATION OF ORGANIC COMPOUNDS (iii) Homocyclic : The ring system is made up of one type of
The ability of carbon to combine with large number of elements atoms generally carbon
especially O, N, S, X etc, to undergo catenation to form chains of (a) Alicyclic : The cyclic compounds resembling open chain
varying lengths and shapes and existance of isomers has led to aliphatic compounds.
the formation of more than five million organic compounds. These For example: Cycloalkanes
have been classified into the following main groups (b) Aromatic : The benzene, napthalene and their derivatives
etc are homocyclic aromatic compounds
Organic
Compounds
NH2
Homocyclic
Benzene Aniline
Heterocyclic
OH
n-Butane Isobutane n-Butanol
Napthalene Anthracene
2, 4-Dimethyl pent-1-ene
O – OH – ol Alkanol
|| –CHO – al Alkanal
Acids — C— O — H
>C = O – one Alkanone
O – COOH – oic acid Alkanoic acid
||
Amides –COX – oyl halide Alkanoyl halide
— C — NH 2
– CONH2 – amide Alkanamide
Classification and Nomenclature of Organic Compounds 359
– COOR – alkyl -- – oate Alkyl alkanoate – NO2 Nitro
– (CO)2O – oic anhydride Alkanoic anhydride – NO Nitroso
– CN – nitrile Alkane nitrile + ..
-Nº N Diazo
– SH – thiol Alkanethiol
– NH2 – amine Alkanamine
æR = ö
(iii) Prefix : They are of two types – OR ç CH3 , C2 H5 , C3 H 7 , etc. ÷ Alkoxy
è ø
(a) Primary prefix : It is for cyclic nature of the compound
and primary prefix cyclo is used immediately before the –R (CH3, C2H5, C3H7, etc) Alkyl
word root. eg.: Thus the complete IUPAC name of an organic
compound consists of the following parts
Sec. prefix Prim. prefix
word root Prim. suffix
Sec. suffix
Primary Word Prim. Sec. IUPAC
prefix root suffix suffix name 2 3
Cyclo hex ane – Cyclohexane For example: HO 4 Br
1
(b) Secondary prefix : The certain atoms and groups which 6 5
are not considered as functional groups but are treated 4-Bromo-cyclo-Hex-2-ene-1-ol
as substituents are called secondary prefixes. They are
IUPAC name is 4-Bromocyclohex-2-ene-1-ol or 4-
added before the word root in case of acyclic compounds
Bromo-2-Cyclohexenol
and before the primary prefix in case of cyclic compounds
in alphabetical order. word root = hex
The important secondary prefixes are Prime suffex = ene
Sec. suffex = ol
Substituent Sec. prefix
Prime prefex = Cyclo
– X (F, Cl, Br, I) Halo Sec. prefex = 4bromo
ALKYL GROUPS :
Univalent groups formed by the removal of one hydrogen atom from an alkane are known as alkyl groups or alphyl groups. Their
names are obtained by changing the suffix –ane of parent hydrocarbon by –yl.
Alkane Group Short-hand notation IUPAC name
Methane Methyl CH3– Me Methyl
Ethane ethyl C2H5– Et Ethyl
Propane n-propyl CH3CH2CH2– n-Pr, Pra or Pr 1-propyl
|
Iso propyl CH 3 – C H – CH 3 Iso- Pr , Prb , Pri 2-propyl
CHCl 2
Ethylidine Chloride 1,1-dichloroethane
CH 3
Geminal
6. Trihalogen CHCl3 CnH2n–1X3 Chloroform 1,1,1-trichloromethane
derivatives
7. Tetra halogen CCl4 CnH2n–2X4 Carbon tetra 1,1,1,1-tetra-
derivatives chloride chloromethane
8. Alcohols CH3OH CnH2n+1OH Methyl Alkanol Methanol
(Monohydric) alcohol
11. Acid chlorides CH3COCl R–COCl Acetyl chloride Alkanoyl halide Ethanoyl chloride
O
12. Esters CH3 – C – OC2H5 RCOOR' Ethyl acetate Alkyl alkanoate Ethyl ethanoate
(here alkyl
O O attached to oxygen)
O O
||
17. Ketones CH3–C–CH3 R – C– R Acetone Alkanone Propan-2-one
O
CH3–C–CH2–CH3 Ethylmethyl Butan-2-one
ketone
18. Cyanides HC º N R–CN Hydrogen cyanide Alkanenitrile Methanenitrile
CH3C º N Methyl cyanide Ethanenitrile
CH2 – CN Butan-1, 4 dinitrile
CH2 – CN
Propanl-1, 2,
CH2 – CN
3-tricarbonitrile
CH – CN
CH2 – CN
362 Chemistry
LINE ANGLE FORMULA (iv) If two or more of the same alkyl groups are present, use the
Bonds are represented by lines, carbon atoms are assumed to be prefixes di, tri etc to avoid repetition
present at the start and finish of a line. Nitrogen, oxygen and 5 1
halogens are labelled, but hydrogens are only shown when 3
bonded to a drawn atom. Each atom is assumed to have sufficient 4 2
hydrogen atoms around it to make it neutral. For example: 3, 3-Dimethylpentane
6 4 2 (v) Alphabetical order : The side chains are cited in alphabetical
n-Hexane CH3(CH2)4CH3 order
7 5 1
5 3 1
4 3
CH2 O 6 2
6 O
CH2 C 5
1 4-Ethyl-3, 3-dimethylheptane
2-Cyclohexenone CH2 CH 4 2
(vi) Longest chain with maximum number of side chains : If two
CH 3
or more chains of the same length are possible, choose the
one with maximum number of side chains.
But-1, 3-diene CH 2 = CH – CH = CH 2
2 4 6
1
3
3
1 5
4 2
CH3 OH
| |
3-methyl but-2-ol CH 3 – C H – CH – CH 3
(vii) Locant sum : Sum of the locants must be minimum. But out
of two sets of the sum of the locants, the set having the
3 1 lowest number when compared by term is preferred. For
4 2 example out of (2+6+7=15) and (3+4+7=14), the first set is
OH correct.
4
NOMENCLATURE OF COMPLEX HYDROCARBONS 6
3 2
The following rules are followed
5 1
(i) Longest chain rule : The longest continuous chain of carbon
atoms is picked up which forms the base name of the 2,3, 5-Trimethylhexane (not 2,4,5-Trimethylhexane)
compound. (viii) The name of a complex radical is considered to begin with
(ii) Numbering : The longest chain is numbered by arabic the first letter of its complete name
numerals beginning with the end nearest a substituent.
i.e. including the numerical affix (di, tri, tetra etc are numerical
(iii) If two or more side chains are in equivalent positions, then affix) for alphabetical order.
the one cited first in the name is assigned the lower number.
12 10 8 6 4 2
11 9 7
8 6 4 2 13 3 1 5 3 1
5
5 2
7 3 1 4
8 6 2 2 4
4
4 3 2 1
5
1 3
7 3 1
12 10 8 6 4 2
4-isopropyl-5-propyl octane 13 11 9 7 5 3 1
(not 5-Isopropyl-4-propyloctane) 6-(1-Methylbutyl)-8-(2-methyl butyl) tridecane
(not 6-(2-Methylbutyl)-8-(1-Methylbutyl) tridecane)
Classification and Nomenclature of Organic Compounds 363
(x) The numerical prefixes bis, tris tetrakis are used to indicate NOMENCLATURE OF CYCLOALKANES : (Alicyclic
the multiplicity of substituted substituent Compounds)
(i) The base name is decided by the number of carbon atoms
2 4 6 which the cyclic or acyclic portion contains. If the ring
3 5 contains more or equal number of carbon atoms as alkyl then
1 7
it is regarded as derivative of cycloalkane
2-Methyl-4-bis(1-methylethyl)heptane
Nomenclature of complex alkenes and alkynes : (ii) Carbons are numbered to give lowest numbers to substituted
(i) Selection of longest chain containing maximum number of carbons. For example
double or triple bonds (sometimes longest chain rule is
violated) 2
CH3
3
1
4 6
5
3-n-propylhexa-1,5-diene methyl cyclo pentane
It contains longest chain of 7C atoms, but both the double
bonds are not included. Hence longest chain of 6C catoms CH3 CH3
is picked up)
(ii) If both, the double and triple bonds, are present the — CH — CH — CH3
compound is regarded as derivative of alkyne. In such cases 1 2 3
the terminal 'e' of -ene is dropped if it is followed by suffix (1, 2-dimethyl propyl) cyclohexane
starting with a,i,o,u,y. For example :
(iii) When there are more acyclic than cyclic carbons the cyclic
6 4 2
part becomes cycloalkyl substituent
7 5 3 1
Hept-4-en-1-yne 2 6 8
(not Hept-4-ene-1-yne) 4
3
(iii) If double and triple bonds are at equidistance from either 1 5 7
side, the preference is given to double bond. 4-Cyclopropyl-3-methyloctane
2 4 6 8 (iv) When acyclic portion contains a multiple bond or a functional
1 3
group, the cyclic portion is treated as substituent.
5 7
oct-1-en-7-yne
(not oct-7-en-1-yne)
O
(iv) If the compound contains two or more double or triple bonds CH = CH – C – CH3
4 3 2 1
a terminal "a" is added to the word root.
2 4 6 2 4 6
4-Cyclohexyl but-3-en-2-one
1 3 5 1 3
5 7
Hexa-2,4-diene Hepta-2,5-diyne
(v) In case when both contain the same functional group, the
(not Hex-2,4-diene) (not Hept-2,5-diyne) base name is decided by the number of c-atoms.
(v) The terminal 'a' is not added to the word root when the OH
complete primary suffix do not start with a numerical affix 1 3
1 2
2 4 6 2 4 6 6
2
5 3 OH
1 3 5 7 1 3
5 7 4
Hepta-1,6-dien-3-yne Hept-3-ene-1,6-diyne 2-(2-Hydroxy propyl) cyclohexan-1-ol
(Note that di, tri, tetra.. are numerical affix) (vi) When both contain the different functional groups, the base
(vi) Side chains containing multiple bonds are named as follows name is decided by principal characteric group
CH2= CH2=CH–CH2– CH3–CH= CH2=CH–
Allyl Ethylidene Vinyl 5 6
3 2 1
HO 4 CH2–CH2–COOH
2 6 2 6 1
8
4 4 2
3
Examples : 1 3 7 5 1 3 5 7 3-(4-Hydroxyclohexyl)propanoic acid
4-Vinylocta-1,7-diene 4-Methylidenhepta-1,6-diene
364 Chemistry
(vii) When the acylic ring is directly attached to benzene ring, it Numbering of C-atoms in fused rings and bridge rings : The
is named as derivative of benzene numbering starts from bridge head carbon, proceeds along the
longest bridge passing through the second bridge head atom,
proceeds to the next longest bridge and completed along the
shortest path.
Numbering of C-atoms in spiro compounds : The numbering
Cyclohexyl benzene
(viii)Presence of certain groups starts from the carbon atom, next to spiro atom, present in the
Functional gp. Suffix smaller ring giving minimum number to atoms containing functional
–COOH Carboxylic acid groups.
–COOR Alkyl carboxylate (i) Fused Rings : Fused rings share two adjacent carbon atoms
and the bond between them eg. :
–COX Carbonyl halide
–CONH2 Carboxamide
-C º N Carbonitrile
–CHO Carbaldehyde Bicyclo [4.4.0]decane
(ii) Bridged Rings : These share two non adjacent carbon atoms
(the bridgehead carbons) and one or more carbon atoms
between them 7
1
6
2
5 4
3
CONH 2
CHO Bicyclo [2.2.1]heptane
6 1
2
CH 3 More examples of bridge Compounds
2
5 3 1
OH 3
4 6
2-Methylcyclohexane-1-carboxamide 3-hydroxy cyclohexane carbaldehyde
C N COCl 7
4
5
CH 3
2, 6, 6-Trimethyl bicyclo[3.1.1]hept-2-ene
1
7
2-Methyl cyclohexane carbonitrile cyclohexane-1-carbonyl chloride 1
2 4 2
NOMENCLATURE OF POLYCYCLIC ALKANES 6
There are three ways that rings can be joined. 3 4
3 5
Bicyclo [1.1.0] butane Bicyclo[2.2.1]hept-2-ene
(i) Fused rings (iii) Spirocyclic Compounds : The two rings share one carbon
atom 1 5 6
4
(ii) Bridged rings 2 7
3 8
Spiro [4.3] octane
(iii) Spirocyclic compounds
More examples of spiro Compounds
The carbon atoms common to both the rings are called bridge
7 6 1
head atoms. The chain of carbon atoms connecting the bridge 2 Br
5
head atoms is called a bridge.
3
8 9 4
2-Bromo spiro[4.4] nonane
7 6 1
2 CH3
1 5
5 6 8
4 3
2 7 10
9 4
3 9
spiro atom
8 2-methyl spiro[4.5]deca-1, 6-diene
Classification and Nomenclature of Organic Compounds 365
Nomenclature of compounds containing identical cyclic units (i) Presence of only two similar terminal groups : The carbon
joined by a single bond atoms of such groups are included in the principal chain. For
No. of cyclic hydrocarbon units Two Three Four example
Prefix bi ter quarter
Numbering of C-atoms : The numbering starts from the
C-atom joining the rings.
2 1 1' 2'
2 2'
1 1'
O
4
O
3 4' 3' 3 3'
1,1'-Bicyclopropane 3
1,1'-Bicyclobutane
1 5
H 5C 2O OC2H5
4' 3' 2 4
Diethyl pentanedioate
2 1 1'' 2''
1' 2' O O
3 4 4'' 3'' 3
1,1',2',1''-Tercyclobutane 1 5
H 2N NH2
2 4
3 2 2' 3' Pentanediamide
1 1'
4 4'
(ii) Presence of more than two similar terminal groups attached
5 6 6' 5' to the main principal chain : In this case special suffixes are
1,1'-Biphenyl
used and carbons of terminal groups are not counted in the
principal chain
Functional groups Suffix
–COOH - Carboxylic acid
–CHO - Carbaldehyde
–COX - Carbonylhalide
–CONH2 - Carboxamide
NOMENCLATURE OF COMPOUNDS CONTAINING
TERMINATING FUNCTIONAL GROUPS –COOR - Alkyl carboxylate
–CN - Carbonitrile
If only one group such as –COOH, –CHO, –COOR, –CONH2, –
COCl or – C º N is present in the molecule it is always given HOOC 2 4
COOH
3
number 1 and 1 is never writen when there is no ambiguity.
1
COOH 5
5 3 Pentane-1,3,5-tricarboxylic acid
3 5
4 2 2
6 4 NC 2 4
1 CN
O 1 OH 3
OH 2-Ethylpent-2-enoic acid 1
O CN
5
Pentane-1,3,5-tricarbonitrile
2-Ethylhaxenoic acid
Presence of more than two similar terminal groups not
NH2 directly attached to the principal chain : In such case the
2 longest chain with two similar terminal groups is selected
1
3 and carbons of groups are counted in the principal chain.
O
HOOC 1 3
7
5
2-Methylpropanamide COOH 4
2 6
4 2 CH2COOH
4 2 OMe 5
1 4-(Carboxymethyl)heptanedioic acid
3 1 3 CHO
Pent-2-enal CH2COOH
5 (terminal e of ene is removed
HOOC 3 5
O as it comes before a) COOH
1 4
Methylpentanoate 2 CH2COOH
–C º C – – yne Ethyl-3-hydroxybutanoate
–N=N Azo – CH3
6 4 3 2 1
– NO2 Nitro – 9.
5
HO–CH2–C–CH=CBr–CH2–CHO
– NO Nitroso –
– X (Cl, Br, I) Halo (Cl, Br, I)
The terminal e of the primary suffix is replaced by the suffix
name of functional group.
3-Bromo-5-cyclopentyl-6-hydroxy-5-
Alphabetical order for substituents : These should be placed in methylhex-3-en-1-al
alphabetical order.
Classification and Nomenclature of Organic Compounds 367
Benzene
4-Carbethoxypent-3-en-1-oic acid Methyl benzne Ethyl benzne
O NH2
CH3 CH3
1 CH3
12. Br 4
2
3
5
CH3
O
1, 2-dimethylbenzene 1, 3-dimethylbenzene
2-(Bromomethyl)-3-oxopentanamide (o-xylene) (m-xylene)
13. MeO 2 OEt CH3
3 1
1-ethoxy-3-methoxypropane CH
3
2 4 1, 3-dimethylbenzene CH3
14. 1, 4-dimethylbenzene
1 5
6 (p.xylene)
CH3 H3 C – CH – CH3
2-Ethenyl-3-methylcyclohexa-1, 3-diene
3 OH
4 H3C CH3
2
15. 1, 3, 5-trimethylbenzene 2-propylbenzene
5 1
6 (mesitylene) (cummene)
H – – CH CH = CH2
4-ethylhex-4-en-2-ol
CH2– CH OH
OH
1, 2-dihydroxy benzene 1, 3-dihydroxybenzene
(Catechol) (Resorinol)
Phenyl Benzyl Benzal
OH
Phenol 2-methylphenol
(o-cresol) Benzenamine 2-methylbenzenamine
(Aniline) (o-Toluidine)
NH2
CH3 CH3
NH2
OH
(ix) Aldehydes:
—
—
—
(v) Br OH
CHO CH3
7. Write IUPAC names for 12. Give IUPAC names of
(i) CH3 – CH = C(NO2) CH2CH3 CH3 O
CH3 +
Cl N -
| OH O
(ii) H 2 C = CHCH - CHCH - CHCHMe2 (a) Cl (b)
|
CH(Me)CH2CH3
CH3
HO
CH3
(iii) (c)
C2H5
OH
(iv) (H2C = CH)2 CHCH2CH = CHCH3
8. Write the condensed structural formula of
Multiple Choice Questions
(a) 4-ethyl-3-methyl heptane 13. Correct IUPAC name of
(b) 3, 3-dimethyl octane H3C - CH - CH - CH 3 is _________ .
| |
9. Write the structural formula of C2 H5 C2 H5
(i) o-methoxyethylbenzene
(a) 2 –ethyl-3-methylpentane
(ii) 2,3-dibromo-1-phenylpentane
(b) 3,4-dimethylhexane
(iii) 4-ethyl-1-fluoro-2-nitrobenzene
(c) 2-sec-butylbutane
10. Name the compounds whose line formulae are given below:
(d) 2, 3-dimethylbutane
O NO2 14. Which of the following is the correct IUPAC name?
(a) 3-Ethyl-4, 4-dimethylheptane
(i) (ii) (b) 4,4-Dimethyl-3-ethylheptane
(c) 5-Ethyl-4, 4-dimethylheptane
(d) 4, 4-Bis(methyl)-3-ethylheptane
Classification and Nomenclature of Organic Compounds 371
15. The IUPAC name for (a) 3, 3-dimethyl - 1- cyclohexanol
(b) 1, 1-dimethyl-3-hydroxy cyclohexane
O O
|| || (c) 3, 3-dimethyl-1-hydroxy cyclohexane
CH3 — C — CH 2 — CH 2 — C — OH
(d) 1, 1-dimethyl-3-cyclohexanol
is ___. 19. The IUPAC name of the compound shown below is :
(a) 1-hydroxypentane-1, 4-dione
Cl
(b) 1,4-dioxopentanol
(c) 1-carboxybutan-3-one
(d) 4-oxopentanoic acid Br
16. The IUPAC name for (a) 3-bromo-1-chlorocyclohexene
(b) 1-bromo-3-chlorocyclohexene
Cl
(c) 2-bromo-6-chlorocyclohex-1-ene
NO2
(d) 6-bromo-2-chlorocyclohexene
20. Name of the following compound is :
CH3 CH 3CH 2 CH 3
C
(a) 1-Chloro-2-nitro-4-methyl benzene CH 3 CH 2 OH
(b) 1-Chloro-4-methyl-2-nitrobenzene (a) 2-ethylbutan-2-ol
(c) 2-Chloro-1-nitro-5-methyl benzene (b) 1-ethyl-1-methylpropan-1-ol
(d) m-Nitro-p-chlorotoluene (c) 3-methyl pentan-3-ol
17. Which of the following compounds has wrong IUPAC name? (d) diethylethanol
(a) CH3–CH2–CH2 –COO–CH2CH3 ® ethyl butanoate 21. The IUPAC name for
1. The kind of valency that exists in CaH2 & C2H2 is 8. The IUPAC name of this compound
(a) electrovalency in CaH2 and covalency in C2H2 CH 3 - C H - CH 2CH 2CH 3 is
(b) electrovalency in both |
CH(CH3 ) 2
(c) covalency in CaH2 and electrovalency in C2H2
(a) 2- isopropylpentane (b) 2, 3 -dimethylhexane
(d) covalency in both
(c) Isononane (d) 2, 4- dimethylhexane
2. The compound which has one isopropyl group is
9. The IUPAC name of the compound
(a) 2, 2, 3, 3 - Tetramethylpentane
CH 3 - CH - CH2- CH 2 - Cl
(b) 2, 2 - Dimethylpentane |
(c) 2, 2, 3- Trimethylpentane CH 3
(d) 2- Methypentane (a) 1-chloro -3- methylbutane
3. Which of the following statements is false for isopentane ? (b) 2- methyl-4- chlorobutane
(a) It has three CH3 groups (c) 2-methyl-4-chlorobutane
(b) It has one CH2 group (d) 1-chloropentane
(c) It has one CH group 10. IUPAC name of the given compound will be
(d) It has a carbon which is not bonded to hydrogen (CH3)2C(CH2CH3)CH2CH(Cl)CH3
4. Which of the following IUPAC names is correct? (a) 5-chloro-3-, 3-dimethylhexane
(a) 2-Methyl-3-ethylpentane (b) 4-chloro-2-ethyl-2-methylpentane
(b) 3-Ethyl-2-methylpentane (c) 2-chloro-4-ethyl-4-methylpentane
(c) 2-Ethyl-3-methylpentane (d) 2-chloro-4, 4- dimethylhexane
(d) 3-Methyl-2-ethylpentane 11. The IUPAC name of (CH3)3 C – CH = CH2 is
5. The correct IUPAC name of the compound with molecular (a) 2 , 2- dimethylbut -3-ene
formula, (CH3)3 C – CH3 is (b) 2, 2- dimethylpent -4-ene
(a) Pentane (c) 3, 3- dimethylbut - 1- ene
(b) 1, 1, 1 -trimethylethane (d) Hex -1-ene
(c) 2, 2- dimethylpropane 12. The IUPAC name of the following
(d) Neopentane CH3C(CH3)2CH2CH=CH2 is
6. The IUPAC name of (a) 2, 2- dimethyl -4- pentene
CH 3 - CH - CH - CH 2 CH 2 - C H - CH 3 (b) 4, 4- dimethyl -1- pentene
| | | (c) 1, 1, 1- trimethyl -3- butene
CH 3 CH 3 CH 3
(d) 4, 4, 4- trimethyl -1- butene
(a) 2, 5, 6- trimethylhexane 13. The IUPAC name of the compound
(b) 2, 3, 6- trimethylheptane
(c) 2, 3, 6- trimethylhexane CH3 – CH – C – CH 2 CH 3
| ||
(d) 2, 5, 6- trimethylheptane CH 3 CH 2
7. The IUPAC name of
(a) 2- ethyl -3- methylbut -1- ene
H C 4H9 (b) 2- isopropylbut -1- ene
| |
CH 3CH 2 - C - C - CH 3 is (c) 2- methyl - 3 ethyl - 3- butene
| | (d) 2- (1- methylethyl) but -1- ene
CH 3 CH3
14. CH3CH2CH2CH(CH=CH2)CH2CH2CH3 is
(a) 3, 4, 4- trimethylheptane (a) 4-ethenylheptane
(b) 3, 4, 4- trimethyloctane (b) 3-n-propyl-1-hexene
(c) 2- butyl -2-methyl-3-ethylbutane (c) 4-ethenylhexane
(d) 2-ethyl-3, 3- dimethylheptane (d) 3-ethenylheptane
Classification and Nomenclature of Organic Compounds 373
15. IUPAC name of the following compound will be 24. IUPAC name of the compound
CH 3 - CH = C - CH 2 - CH 3
| CH 3 - C H - CH 2 - CHOH - CH 3 is
CH 2 -CH 2 -CH 3 |
CH 2 -CH 3
(a) 3-propyl-3-hexene (b) 3-propyl-2-hexene
(c) 3-ethyl-2-hexene (d) 4-ethyl-4-hexene (a) 4- methyl -3- hexanol (b) Heptanol
(c) 4- methyl - 2- hexanol (d) None of these
16. The IUPAC name of CH 3 - C = CHCH3 is
| 25. The correct nomenclature (IUPAC) for the following alcohol
C2 H 5 is
(a) 2-ethylbutene (b) 2-ethylbut-2-ene CH3CH2 CH3
(c) 3-methylpent-2-ene (d) 2-ethylpent-2-ene C
17. The IUPAC name of CH3–CºC–CH(CH3)2 is OH
CH3CH2
(a) 4- methyl -2-pentyne
(b) 4, 4 - dimethyl -2 butyne (a) 2-ethyl-2-butanol
(c) Isopropylmethylacetylene (b) 3-methyl-3-pentanol
(d) 2-Methyl-4-pentyne (c) 3-ethyl-3-methyl-3-pentanol
18. The IUPAC name of (d) 1, 1 - diethylethanol
26. The IUPAC name of
CH 3 - C= C - C H - CH 2 - C º CH is
| | |
Cl CH3 C2H5 H Br
| |
(a) 6-chloro-4-ethyl-5-methylhept-5-en-1-yne CH 3 - C - CH 2 - CH 2 - CH 2 - C - CH 3 is
| |
(b) 6-chloro-4-ethyl-5-methylhept-1-yn-5-ene OH Br
(c) 2-chloro-4-ethyl-3-methylhept-2-en-6-yne
(d) 2-chloro-4-ethyl-3-methylhept-6-yn-2-ene (a) 6, 6- dibromoheptan -2- ol
19. The IUPAC name of CH3OC2H5 is (b) 2, 2- dibromoheptan -6- ol
(a) Methyl ethyl ether (b) Ethyl methyl ether (c) 6, 6- dibromoheptan -2- al
(c) Methoxyethane (d) Ethoxymethane (d) None of these
20. Which of the following represents the correct IUPAC name 27. The IUPAC name of the compound
of the compound
CH2 = CH – CH2 Cl?
CH3
|
(a) Allyl chloride (b) 1- chloro -3- propene CH3 - CH - CH2 - C - CH3 is
(c) 3- chloro-1- propene (d) Vinyl chloride | |
OH OH
21. The name of ClCH 2 - C = C - CH 2 Cl according to
| | (a) 1, 1- dimethylbutane -1, 3-diol
Br Br (b) 1, 3. 3- trimethylpropane -1, 3-diol
IUPAC nomenclature system is (c) 2- methylpentane -2, 4- diol
(a) 2, 3- dibromo -1, 4- dichlorobutene-2 (d) 1, 3, 3- trimethyl -1, 3- propanediol
(b) 1, 4- dichloro-2, 3- dibromobutene-2 28. Choose the correct IUPAC name for
(c) Dichlorodibromobutene
(d) Dichlorodibromobutane CH3 - C H - CHO
|
22. IUPAC name of (C2H5)2CHCH2OH is CH2 -CH 3
(a) 2- ethylbutanol - 1 (b) 2- methylpentanol -1
(a) Butan - 2- aldehyde
(c) 2- ethylpentanol -1 (d) 3- ethylbutanol -1
(b) 2- methylbutanal
23. The IUPAC name of
(c) 3- methylisobutyraldehyde
OH
| (d) 2- ethylpropanal
CH 3 - C - CH 2 - C H - CH 3 is
| | 29. The IUPAC name of the compound having the molecular
CH 3 CH 3 formula Cl3C –CH2CHO is
(a) 2, 4- dimethylpentanol -2 (a) 3, 3, 3- trichloropropanal
(b) 2, 4- dimethylpentanol -4 (b) 1, 1, 1- trichloropropanal
(c) 2, 2- dimethylbutanol-2 (c) 2, 2, 2- trichloropropanal
(d) Butanol -2 (d) Chloral
374 Chemistry
30. The incorrect IUPAC name is 36. The IUPAC name of CH3CH=CHCOOC2H5 is
(a) CH 3 - C - C H - CH 3 (a) Ethyl but-1-enoate (b) Ethyl but-2-enoate
|| | (c) Ethyl prop-2-enoate (d) None of these
O CH3
37. The IUPAC name of the compound
2-methyl-3-butanone
CH 3CH = CHCH 2 C HCH 2 COOH is
(b) CH3 – C H – C H – CH 3 |
| | NH 2
CH3 CH 2 CH 3
(a) 5- amino - 2 - heptenoic acid
2, 3 -dimethylpentane (b) b - amino- d - heptanoic acid
(c) CH3– C º CCH(CH3)2 (c) 5- amino hex - 2- enecarboxylic acid
4-methyl-2-pentyne
(d) 3- amino -5- heptenoic acid
(d) CH3 - CH - CH - CH3 38. Indicate the wrongly named compound
| |
Cl Br (a) CH 3- C H - CH 2 - CH 2 - CHO
3-chloro-2-bromobutane |
CH 3
31. The systematic name of (CH3)2 CH – COOH is
(a) 2- propanoic acid (4-methyl -1- pentanal)
(b) isobutanoic acid (b) CH 3- CH - C º C - COOH
(c) 2- methylpropanoic acid |
CH 3
(d) 2- methylbutanoic acid
32. The IUPAC name of the formula, (4- methyl -2- pentyne -1- oic acid)
CH3 O CH2OH
| ||
CH 3- C H - C - CH 2 - CH 2 OH is (c) (d) None of these
1. 2-Methyl 2-butene will be represented as [CBSE-PMT 1992] 6. IUPAC name for the compound [CBSE-PMT 1998]
CH 3 Cl CH2CH3
| C=C
(a) CH 3 - CH - CH 2 CH 3 is
H3C I
(b) CH 3 - C = CH - CH 3 (a) trans-3-iodo-4-chloro-3-pentene
|
CH 3 (b) cis-2-chloro-3-iodo-2-pentene
(c) trans-2-chloro-3-iodo-2-pentene
(c) CH 3 - CH 2 - C = CH 2
(d) cis-3-iodo-4-chloro-3-pentene
|
CH 3 7. The correct structure of trans-2 hexenal is
[CBSE-PMT 1999]
(d) CH 3 - CH - CH = CH 2
| CHO
CH 3
(a) (b) CHO
2. The IUPAC name of [CBSE-PMT 1992]
(c) CHO (d)
CHO
CH 3 - CH - CH = C - CHO 8. The incorrect IUPAC name is [CBSE-PMT 2001]
| |
OH CH 3 (a) CH 3 - C - C H - CH 3
|| |
(a) 4-Hydroxy-1-methylpentanal O CH 3
(b) 4-Hydroxy-2-methylpent-2-en-1-al 2-Methyl-3-butanone
(c) 2-Hydroxy-4-methylpent-3-en-5-al
(b) CH 3 - CH - C H - CH 3
(d) 2-Hydroxy-3-methylpent-2-en-5-al | |
3. Which of the following IUPAC names is correct for the CH3 CH 2CH 3
compound? [CBSE-PMT 1994] 2,3-Dimethylpentane
H 3C - C H - CH - CH 2 - CH 3
| | (c) CH 3 C H - C H - CH 3
CH3 CH 2CH3 | |
Cl Br
(a) 2-Methyl-3-ethylpentane 2-Bromo-3-chlorobutane
(b) 3-Ethyl-2-methylpentane
(d) CH 3 - C º CCH (CH 3 ) 2
(c) 2-Ethyl-3-methylpentane
4-Methyl-2-pentyne
(d) 3-Methyl-2-ethylpentane
9. Name of the compound given below is [CBSE-PMT 2003]
4. The first organic compound, synthesized in the laboratory,
was [CBSE-PMT 1995]
CH3
(a) alcohol (b) acetic acid
H3C
(c) urea (d) none of these CH3
5. The IUPAC name of [CBSE-PMT 1996]
H 3C — C H — CH — CH 2 —CH 2— C H — CH 3 is CH3
| | |
CH3 CH3 CH3
(a) 5-ethyl-6-methyloctane
(a) 1, 3-isopropyl-3-methylpropane
(b) 4-ethyl-3-methyloctane
(b) 2, 3, 6-trimethylheptane
(c) 3-methyl-4-ethyloctane
(c) 2, 5, 6-trimethylheptane
(d) 2, 3-diethylheptane
(d) 2, 6, 3-trimethylheptane
Classification and Nomenclature of Organic Compounds 377
10. Names of some compounds are given. Which one is not
correct in IUPAC system? [CBSE-PMT 2005]
COOH
(c)
CH3
| OH
(a) CH 3 - CH 2 - CH 2 - C H - CH - CH 2 CH 3
|
CH 2CH3 OH
3-Methyl-4-ethyl heptane
(d) COOH
(b) CH3 - CH - CH - CH3
| |
OH CH3
3- Methyl - 2- butanol 14. The structure of isobutyl group in an organic compound is
CH 3
is [CBSE-PMT 2011] (d) CH - CH 2 -
CH 3
(a) 4-Ethyl-3-propyl hex-1-ene 15. Which of the following compounds has wrong IUPAC name?
(b) 3-Ethyl-4-ethenyl heptane [AIEEE 2002]
(c) 3-Ethyl-4-propyl hex-1-ene (a) CH3–CH2–CH2 –COO–CH2CH3 ® ethyl butanoate
(d) 3-(1-ethylpropyl) hex-1-ene
(b) CH3 - CH - CH 2 - CHO ® 3-methyl-butanal
12. The IUPAC name of the following compound is |
CH3
Cl CH2CH3
(c) CH3 - C H - CH - CH3 ® 2-methyl-3-butanol
C C | |
OH CH3
CH3 I
18. The IUPAC name of the compound is 21. The IUPAC name of is
HO
Br
CN
(a) 3-bromo-1-chlorocyclohexene Br
(b) 1-bromo-3-chlorocyclohexene (a) 4-Bromo-3-cyanophenol
(c) 2-bromo-6-chlorocyclohex-1-ene (b) 2-Bromo-5-hydroxybenzonitrile
(d) 6-bromo-2-chlorocyclohexene (c) 2- Cyano-4-hydroxybromobenzene
(d) 6-Bromo-3-hydroxybenzonitrile
Cl
Cl H
(c) H 2 N H CH 2 CH 3
OEt O
(a) cis – 2 – ethyl – 3 – methyloxirane
(b) trans – 1 – ethyl – 2 – methyl oxycyclopropane
(c) trans – 2 – ethyl – 3 – methyloxirane
(d) Me 2 N (d) trans – 1 – ethyl – 2 – methyl ethane epoxide
OEt
380 Chemistry
16. The IUPAC name of the following compound (a) 1, 1 – dimethyl – 1 – cyclopentyl methane
(b) 2 – cyclopentyl propane
(c) 1 – (1 – methyl) ethyl cyclopentane
(d) Cumene.
(a) E – 1 – cyclopentyl – 2 – hexene 22. The accepted IUPAC name of the following compound.
(b) E – 2 – cyclohexyl – 2 – hexene
(c) Z – 1 – cyclopentyl – 1 – hexene
(d) Z – 2 – cyclopentyl – 2 – hexene
17. The IUPAC name of the following compounds is
O
N (a) Propanoic anhydride
| (b) Butanoic propanoic anhydride
H O (c) Ethyl butanoate
(a) N – phenyl ethanamide (b) N – phenyl ethanone (d) 4, 6 – dioxo heptane
(c) N – phenyl methanamide (d) None of these 23. The IUPAC name of the compound
18. What is the name of the following compound ?
H COOH
O
||
O O
H CHO
Cl
(a) 4-formyl-3-oxo cyclohexane-1-carboxylic acid
(a) 2 – chlorohexyl ethanoate
(b) 2, 4-dioxo cyclohexanoic acid
(b) ethyl – 2 chloro hexanoate
(c) 2, 4-dioxo heptanoic acid
(c) 1 – chlorohexyl ethanoate
(d) None of these
(d) ethyl – 1 chloro hexanoate
24. The correct IUPAC name of the compound
19. The IUPAC name of the following compound.
HC CH 3 CH 3
||
HO CH 3
O
OH
(a) 2, 6 – dimethyl octa – 2, 6 – dien – 1 – al
(a) 4 – hydroxy – 3 – methyl butanoic acid
(b) 3, 7 – dimethyl hepta – 2, 6 – dien – 1 – al
(b) 1 – hydroxy – 2 – methyl butanoic acid
(c) 3, 7 – dimethyl octa – 2, 6 – dien – 1 – al
(c) 3 – hydroxy – 2 – methyl butanoic acid
(d) 2, 6 – dimethyl – 2, 6 – dien – 8 – al
(d) 3 – (hydroxymethyl) butanoic acid
25. The IUPAC name of the compound
20. What is the IUPAC name of the following compound ?
CONH 2
COOH CHO
Br
COOH NH 2
(a) o, o’ – diamino – o, o’ – dicarboxy biphenyl (a) Tetraphenyl methane
(b) 6, 6’ – diamino diphenyl – 2, 2’ – dicarboxylic acid (b) 1, 1, 1, 1 – tetra phenyl methane
(c) diamino dicarboxy biphenyl (c) 1, 1, 1, 1 – tetra cyclohexyl methane
(d) None of these (d) Neophenyl
32. The IUPAC name of 38. Which of the following numberings is correct ?
OH FF 1 2 FF 3 2
C A 3 B 1
|| Br Br
5 4 4 5
O
(a) 3 – phenyl prop – 2 – enoic acid F 5 4 FF 5 1
(b) Cinnamic acid C 3 D 2
1 Br Br
(c) 1 – Styrene acid 2 4 3
(d) 3 – Cyclohexyl – 2 – propenoic acid (a) A (b) B (c) C (d) D
382 Chemistry
CH 3 CH3
CH3 CH3 5 4 3 2 1
| | |
12. (b) CH3 CCH2CH = CH2
CH 3 C - C HCH 2 CH 3 CH 3 C HCH 2 CH 2CH 3
| CH3
CH3 (d )
(c ) 4 3 2
13. (a) CH3 – CH – C – CH2CH3
3. (d) In isopentane, (CH3)2CH CH2 CH3, every carbon is having
hydrogen atom(s). CH3 CH2
1
4. (b) When the sum of locants is same, viz. 2 + 3 = 5, lower
Here numbering should be done in a way that simpler
alkyl group should be given lower numeral number, i.e.,
alkyl group(s) is (are) present on the main chain
here it should be 2-methyl and 3-ethyl and not the reverse.
Classification and Nomenclature of Organic Compounds 383
2 1 O CH3
CH=CH2 1 2 3 4
14. (b) 6 5 4 3 30. (a) CH3 – C – CH – CH3
CH3CH2CH2CHCH2CH2CH3
3-Methyl-2-butanone
4 5 6
CH2 CH2CH3 31. (c) 32. (c)
15. (c)
1 2 3 3 2 1
CH3 – CH = C – CH2CH3 33. (d) CH = CH – CN
2
Double bond should be present on the minimum possible Nitrile carbon is also counted in the carbon chain
number in the lengthiest possible carbon chain. 34. (a) 35. (a)
4 5
16. (c) CH2CH3 4 3 2 1
3 2 1
36. (b) C H 3 - C H = C H - C OOC2 H 5
CH3 – C = CH CH3 37. (d)
1 2 3 4 5
17. (a) CH3 C º C CH CH3 O
6 5 || 1
4 3 2
CH3 38. (d) CH CH CH = CH – C–C H
3 2 3
7 6 5 4 3 2 1
18. (a) CH3 – C = C – CH – CH2 – C º CH 1
CH3
Cl CH3 CH2CH3 39. (d) tert - Butyl chloride is CH3 – C – Cl
2
EXERCISE 3 1 2 3 4
8. (a) CH3 C CH CH3
CH3
| O CH3
1. (b) 1 CH3 - 2C = 3CH - 4 CH3 3 Methyl-2- butanone
2-Methyl-2-butene 1 2 3
CH3 CH CH CH3
2. (b) 5 CH - 4 CH - 3CH = 2
C - 1CHO 4 5
3 CH3 CH2 CH3
| |
OH CH 3 2,3dimethyl pentane
4-Hydroxy-2-methylpent-2-en-1-al 4 3 2 1
CH3 CH CH CH3
3. (b) 1 CH 3 - 2 CH - 3CH - 4 CH 2 - 5 CH 3 Cl Br
| |
H 3C CH 2 CH 3 2 Bromo 3 chlorobutane
5CH
3-Ethyl-2-methylpentane 3
1 2 3 4
4. (c) The vital force theory suffered first death blow in 1828 CH3 C C CH
when Wohler synthesized the Ist organic compound
urea in the laboratory from inorganic compounds CH3
reported below : 4 - Methyl-2-pentyne
to isomeric charge 9. (b) CH3 CH3 5 7
NH 4 CNO ¾¾ ¾ ¾ ¾ ¾ ¾¾® NH 2 CONH 2 1 3
4
rearrangement leading CH3
Urea 2 6
Later on a further blow to vital force theory was given CH3
by Kolbe (1845) who prepared acetic acid, the first
organic compound, in laboratory from its elements. 4 ethyl - 3 methyl octane
10. (a) Correct IUPAC name of
5. (b) When many substituents are present, the numbering is
done from the end where the sum of locants is the lowest CH 3
|
(lowest sum rule)
CH 3 CH 2 CH 2 - C H - C H - CH 2 CH 3
|
7 6 5 4 3 2 1
CH 2CH 3
C H3 - CH - CH - C H 2 - C H 2 - C H - C H3
| | | is 4-Ethyl-3–methyl heptane
CH3 CH3 CH3
11. (a) The given compound is
2, 5, 6 trimethyl heptane (wrong)
2 1
2 + 5 + 6 = 13 CH = CH2
1 2 3 4 5 6 7
CH3 — CH — CH — CH 2 — CH 2 — CH — CH3 Ch3 — CH2 — CH2 — CH — CH — CH2 — CH3
| | | 3 4
CH3 CH3 CH3 CH2 – CH3
5 6
2 + 3 + 6 = 11
4 ethyl- 3-propyl hex – 1 – ene
2, 3, 6 TriMethyl Heptane (correct)
4 5
Cl CH2 – CH3 12. (a) Cl CH2CH3
6. (c) C C C=C
H3C I 2 3
CH3 I
1
As in this compound the common groups i.e highly
electronegative halogen atoms are on opposite side, Correct IUPAC name of above compound is trans-2-
hence it is a trans isomer. chloro-3-iodo-2-pentene
Thus its name is trans-2-chloro-3-iodo-2-pentene. OH
7. (a) When similar atoms are on opposite side the compound 1
3 2
is in trans-form H3C COOH
13. (a) 4
6
H CHO CH 3
5
C C
IUPAC name of the structure is 3-ethyl-2-hydroxy-4-
C3H7 H methylhex-3-en-5-ynoic acid
Classification and Nomenclature of Organic Compounds 385
CH 3 EXERCISE 4
14. (d) CH - CH 2 - (iso-butyl group) 1. (b) The compound contains longest chain of 5C - atoms and
CH 3 e of ene is retained as the suffix name starts with constant
2. (d) The compound is an enol containing chain of 5C atoms.
15. (c) The correct name is 3 - methylbutan 2-ol
3. (b) The compound is a derivative of butane
O CH3 4. (b) It contains longest chain of three C atoms having CHO
1 2| | 3| 4
16. (c) CH3 - C - CH - CH3 ; 3- methyl-2-butanone and double bond
5. (d) The compound contains longest chain of 5 C - atoms
having > C = O and - NH2 groups
17. (a) CnH2nO2 is general formula for carboxylic acid
6. (d) The compound contains longest chain of 3 C - atoms and
three -COOH groups and one -OH group attached to it
(latest convention).
18. (a) 1 3
2 7. (b) The compound contains longest chain of 6C atoms and
HO amino group. Hence it is an alkanamine.
IUPAC name – 3, 3-Dimethyl -1 cyclohexanol 8. (c) The compound is derivative of aniline. The positions of
19. (b) The compounds containing two similar assymmetric C- groups are shown by numbering the nuclear C-atoms.
atoms have plane of symmetry and exist in meso from 9. (d) The compound is an ester. Its IUPAC name is derived
from alkyl alkanoate.
10. (a) Select the longest chain of C-atoms which includes both
plane of symmetry the double bonds. Further ethenyl and methyl groups at
C3 and C 4 are on the same side. Hence it is Z-isomer..
11. (a) It contains chain of 4C atoms. Double bond is given
meso 2, 3 dichlorobutane preference over Cl-atom.
12. (b) The compound is a ketone containing longest chain of
Cl 7C-atoms and side chains.
1
6 2 13. (d) The compound is an aldehyde containing longest chain
20. (a)
5 of 6 C-atoms and side chains.
3 Br
4 14. (b) The compound is a derivative of benzaldehyde. Start
3-bromo-1chlorocyclohexene numbering C-atoms of benzene nucleus from C-atom
bearing – CHO group.
CH 3
7 6 5 4| 3 2 1 *
15. (c) The compound is derivative of oxyrane CH * .
2 - CH 2
21. (a) CH3 - CH 2 - CH 2 - C - CH - CH 2 - CH3
| |
CH3 CH 2 O
| *
CH3 The hydrogen atoms attached to C –atom are on the
3- ethyl - 4,4 - dimethylheptane opposite side hence it is trans isomer.
16. (b) When acyclic portion contains a multiple bond or
22. (a) The correct order of priority for the given functional functional group, the cyclic portion is treated as
group is substituent.
O O 17. (a) It is derivative of ethanamide having N-phenyl group.
|| ||
–COOH > –SO3 H > – C - NH 2 > - C - H 18. (b) The compound is an ethyl ester of hexanoic acid.
19. (a) The compound is a derivative of butanoic acid.
23. (a) CH3 20. (b) The compound is a derivative of benzoic acid. The
|
1
positions of substituents attached to benzene nucleus
3 2
H3C- C - CH3 are represented by number of C-atoms and not by ortho,
|
CH3 meta and para.
Neopentane 21. (c) The cyclic portion contains more C-atoms than
or 2, 2- Dimethylpropane acyclic portion. Hence it is derivative of cyclopentane.
22. (b) The compound is anhydride of butanoic and propanoic
24. (b) – CN has highest priority. Further the sum of locants is acid.
7 in (b) and 9 in (d). 23. (a) It is derivative of cyclohexane. The C-atom bearing
– COOH group is to be assigned the number 1.
386 Chemistry
24. (c) The compound is an aldehyde containing longest chain 32. (a) It is derivative of propanoic acid
of 8 C-atoms. O
25. (a) The compound is an amide containing longest chain of 5 ||
C-atoms – CHO is substituent group. CH = CH - C - OH
3 2 1
26. (d) The compound is derivative of ethane.
3-phenyl prop-2-enoic acid
27. (b) It is spiro compound. The numbering begins with the
33. (b) In such compounds the numbering is done as follows
ring atom next to the spiro atom around the smaller ring
and then to the spiro atom and finally around the large 3'
ring. The total number of C-atoms decides the parent 2 2' '
hydrocarbon. 1 1' 2' 1' '
1 2 CH 3 3' '
7 6 3
1, 1' , 2' , 1' ' tercyclopropane
8
5 2 1 6 7
9 10 4 3
34. (a) 5 8 spiro [4.5] decane
Hence it is 2-methyl spiro[4.5] deca-1-ene. 3 4 10 9
28. (b) When – CHO is treated as side chain, its name is 35. (c) It is an ester of ethanoic acid
carbaldehyde.
O
3 2 1 6 || 2
C H2 - C H - C H2 1 O - C - CH 3
5
| | | 1
Hence CHO CHO CHO is propane – 1, 2, 3 tri 2
4 COOH
carbaldehyde. 3
29. (a) It is derivative of cyclopentanone having 2-carboxy phenyl ethanoate
36. (a) It is an ethyl ester of butanoic acid
O
|| CH 3 O
– C– O – C2 H5 carbethoxy group at 2C. | ||
CH 3 - CH - CH - C - O - C 2H 5
30. (a) It is a bridge compound 4 3 2 1
1 6 1 2
6 O
7 2 3
5 NO 2
5 3 4
4 ethyl-3-methyl-2-(3-nitro) phenyl butanoate
1, 7, 7-trimethyl bicyclo [2. 2. 1] heptan-2-one 37. (c) It is derivative of methane 1, 1, 1, 1-tetracyclohexyl
31. (b) It is biphenyl derivative methane.
38. (d) F *1
NH 2 COOH 5
5' 6' 2 3
Br
2
4' 4 **
1' 1 4 3
3' 2' 6 5 * **
The numbering of C-atom starts from C or C . But
COOH NH 2 *
numbering from C give minimum locant (2) to Br which is
correct.
12C
Hybridisation & Shapes
of Organic Molecules
HYBRIDISATION
Sigma bonds are the most common bonds in organic chemistry.
All single bonds are sigma (s) bonds and formed by the
C
overlapping between s-s, s-p and p-p (head on) atomic orbitals
present on different atoms. A pi (p) bond results from the overlap
of two p-orbitals that are oriented perpendicular to the axis of the
nuclei. A p bond is not cylindrically symmetrical. A s bond is These hybrid orbitals can overlap with four s atomic orbitals
stronger than p bond due to better overlap. All multiple bonds provided by four hydrogen atoms to form methane molecule.
contain one s bond and others p bond(s).
To have more efficient overlapping and to provide more H
symmetrical structure to the molecule the atomic orbitals on the H
same atom interact to provide hybrid atomic orbitals and the
interaction is known as hybridisation. The hybrid atomic orbitals H 109.5°
have enhanced electron density. C
9Å C
HYBRIDISATION OF CARBON
H 1. 0 H
H
The ground state electronic configuration of carbon is
H
2 2 H
1s , 2s 2p1x 2p1y 2p 0z . The electronic configuration of carbon in
sp3 hybridisation:
H H
If we superimpose one s and three p atomic orbitals we get 4sp3
hybrid orbitals.
3 4 H
s-atomic p-atomic C C
hybrid H
orbital orbital orbital
Each hybrid orbital contains single electron, has 25% s character
and 75% p character. They are directed towards the four corners H H
of a regular tetrahedron with the carbon located in the centre. The
angle between any two sp3 hybrid orbitals is 109º 28' (109.5º). Bonding in Ethane
388 Chemistry
sp hybridisation:
H H
If we superimpose one s and one p atomic orbitals we get 2sp
hybrid orbitals.
109.5°
1.54Å
9Å C C
1. 0 H 1
H s-atomic orbital p-atomic orbital
H H
sp2 hybridisation: If we superimpose one s and two p atomic 1 2
orbitals we get 3sp2 hybrid orbitals
hybrid orbital
2 Each sp hybrid orbital has 50% s character and 50% p character.
s-atomic orbital p-atomic orbital They are diagonally present with their axis forming an angle of
180º. The unhybridised 2p y and 2p z atomic orbitals are
perpendicular to each other and perpendicular to hybrid orbitals
2 3 also.
hybrid orbital pz
Each sp2 hybrid orbital has 33% s character and 67% p character. • • py
They lie in the same plane with their axis directed towards the • •
sp
corner of an equilateral triangle and are 120º apart from each other.
The unhybridised pz atomic orbital is perpendicular to the plane
of sp2 hybrid orbitals. BONDING IN ACETYLENE
pz
• • • • py
H • • • • H
C
sp
H—C C—H
pz
HYBRIDISATION OF NITROGEN
The ground state electronic configuration of nitrogen is
BONDING IN ETHYLENE
Consider two sp2 hybridised carbon atoms approaching to each 7N = 1s 2 , 2s 2 2p1x 2p1y p1z
other and four hydrogen atoms which provide four s atomic
orbitals One s and three p atomic orbitals superimpose and give 4 sp3 hybrid
orbitals. These are tetrahedrally present.
C C
N
N H
H H H 107°
H
H H H
H BOND LENGTHS
Some importants bond lengths are as follows
C N
C–C sp3 – sp3 1.54 Å C–O sp3 – O 1.41 Å
sp3 – sp2 1.50 Å sp2 – O 1.34 Å
sp3 – sp 1.46 Å C=O sp2 – O 1.20 Å
H H
sp2 – sp2 1.48 Å sp – O 1.16 Å
Carbon Nitrogen
sp2 – sp 1.43 Å C–N sp3 – N 1.47 Å
H sp – sp 1.38 Å sp2 – N 1.36 Å
p
s C=C sp2 – sp2 1.34 Å C=N sp2 – N 1.28 Å
C N
sp2 – sp 1.31 Å CºN sp – N 1.16 Å
H H sp – sp 1.28 Å
sp hybridisation: when nitrogen is attached to only one atom its CºC sp – sp 1.21 Å
hybridisation is sp. In H - C º N both carbon and nitrogen are in C–H sp3– H 1.11 Å
sp hybridised form
sp2 – H 1.10 Å
• • • •
sp – H 1.08 Å
H • • • •• H—C N BOND ANGLES IN SELECTED MOLECULES
H Cl
Carbon Nitrogen
HYBRIDISATION OF OXYGEN C C
H H Cl Cl
2 2 109.5° 109.5°
The electronic configuration of oxygen is 1s 2s 2p 2x 2p1y 2p1z . H Cl
sp3hybridisation : When oxygen is attached to two atoms the CH3 Cl
hybridisation is sp3.
112° 112°
C C
H CH3 H Cl
106° 112°
H H
.. CH3
O .O.
N
111° H H
O
H H 104.5° H CH3 H 107°
H H H H
sp2 hybridisation: When oxygen is attached to one atom as in 104.5° 118° C C
O
case of aldehydes and ketones e.g. in Formaldehyde carbon and H H 121° H
oxygen, both are in sp2 hybrid form.
Cl Cl 120°
CH3
H
114° C C 120° C O
Cl 123° Cl CH3
C O 127° 121°
CH3 CH3
110° C O 114° C O
Cl 123° CH3HN 125°
H
AROMATICITY AND AROMATIC COMPOUNDS
Carbon Oxygen Aromatic indicates a stable system which undergoes substition
H rather than addition, retaining the closed p-electron system. Many
..
C O such systems contain only six p electrons, but generally they
.. contain (4n+2) p electrons, where n is an integer.
H
390 Chemistry
In general, higher polyclic aromatic compounds are somewhat
n=1 less stable than benzene.
n = 0 cyclopropenyl cation contains 2p - electrons and is aromatic
H
Benzene Cyclopentadienyl
anion H
+
ANTIAROMATICITY
H The less stability of monocyclic compounds containing (4n)p
electrons than their acyclic analogues is called anti aromaticity.
H For example
Cycloheptatrienyl
cation Cyclobutadiene is less stable than 1,3-Butadiene
(Tropylium cation)
Nonbenzenoid heterocyclic compounds with 6p electrons are Here Resonance is the cause of destabilisation (hence the concept
aromatics of antiaromaticity)
¬¾
®
N O S N
More examples of antiaromatic compounds
Pyridine H
Furan Thiophene Pyrrole
H
The hetero atom contributes to non bonded electrons, to complete –
the sextet.
n=2
Cyclooctatetraene
(8 p electrons) Cycloheptatrienyl anion
Naphthalene Cyclo octatetraenyl (8p electrons)
dianion
H + H –
n=3
Very Short/ Short Answer Questions 9. Will the following compound be aromatic. Explain.
1. Out of ethylene and acetylene which is more acidic and
why?
2. Write the type of hybridisation involve in CH4, C2H4 and
C2H2.
3. What types of hybridisation are involved with the central
atom of a molecule having following shapes:
(i) planar, (ii) a regular tetrahedral, (iii) an equilateral Multiple Choice Questions
triangle. 10. Butyne-2 contains :
4. State the hybridisation of the carbon labelled (x) and (y) in
(a) sp hybridised carbon atoms only
acetic acid.
(b) sp 3 hybridised carbon atoms only
H O
H— C — C — O —H (c) both sp and sp 2 hybridised carbon atoms
y x
H (d) both sp and sp 3 hybridised carbon atoms
5. How hybridization of ‘C’ atom changes when ethene is 11. The correct order towards bond length is
hydrogenated? (a) C - C < C = C < C º C (b) C º C < C = C < C - C
6. Ethane is stable while ethene is quite reactive, explain why?
(c) C = C < C º C < C - C (d) C = C < C - C < C º C
7. Give hybridisation state of each carbon atom in the following
compounds. 12. The C–H bond length is minimum in the bond formed by
(i) CH2 = C = O (a) sp-s overlapping (as in alkynes)
(ii) CH3CH = CH2 (b) sp2-s overlapping (as in alkenes)
(iii) (CH3)2 CO (c) sp3-s overlapping (as in alkanes)
(iv) CH3CH2– (d) None of these
13. Triple bond of ethyne is made of or Cylindrical shape of an
Long Answer Questions alkyne is due to
8. The ring systems having following characteristics are (a) Three s – bonds
aromatic. (b) Three p – bonds
(i) Planar ring containing conjugated p bonds. (c) Two s and one p – bond
(ii) Complete delocalisation of the p-electrons in ring (d) Two p and one s – bond
system i.e, each atom in the ring has unhybridised p-
14. The hybridization of carbon atom in benzene is:
orbital, and
(iii) Presence of (4n + 2) p-electrons in the ring where n is (a) sp (b) sp2 (c) sp3 (d) dsp2
an integer (n = 0, 1, 2 ...........) [Huckel rule] 15. The conditions for aromaticity is :
Using this information classify the following compounds (a) molecule must have cyclic clouds of delocalised p
as aromatic /non-aromatic. electrons
(b) molecule must contain (4n + 2) p electrons
(c) Both (a) and (b)
N – (d) None of the above
+
(A) (B) (C) 16. Which one of the following has the shortest carbon carbon
bond length ?
(a) Benzene (b) Ethene (c) Ethyne (d) Ethane
17. Shape of methane molecule is
(a) tetrahedral (b) pyramidal
+
(D) (c) octahedral (d) square planar
(E)
392 Chemistry
18. Which of the following has the shortest C – C bond length? (a) sp3 orbital (b) sp2 orbital
(a) C2H5OH (b) C2H6 (c) sp orbital (d) sp3 and sp respectively
(c) C2H2 (d) C2H4 21. In ethene, the bond angle(s) is/ are
19. The compound 1, 2 - butadiene has (a) 109°28 (b) 120°
(a) only sp hybridized carbon atoms (c) 180° (d) Both (a) and (c)
(b) only sp2 hybridized carbon atoms 22. Electronegativity of carbon atoms depends upon their state
(c) both sp and sp2 hybridized carbon atoms of hybridisation. In which of the following compounds, the
(d) sp, sp2 and sp3 hybridized carbon atoms carbon marked with asterisk is most electronegative?
20. In the following molecule, the two carbon atoms marked by (a) CH3 – CH2 – *CH2 – CH3
asterisk (*) possess the following type of hybridized orbitals (b) CH3 – *CH = CH – CH3
(c) CH3 – CH2 – C º *CH
H3C - C*º C*- CH3
(d) CH3 – CH2 – CH = *CH2
(a) (b)
(a) (b)
+
+
(c) (d)
+ –
(c) (d) N
30. As the s - character of hybrid orbital increases, the bond
21. The change in the state of hybridization of the asterisked angle
carbon in the following reaction. (a) increases (b) decreases
(c) does not change (d) becomes zero
* H O *
CH3 CN ¾¾¾
2 ® CH CONH
3 2 is 31. Which of the following bonds is strongest ?
(a) sp3 to sp2 (b) sp3 to sp (a) – C – C– (b) > C = C <
(c) sp to sp2 (d) sp2 to sp3
22. Which of the following carbon atoms is most |
(c) - C - C = (d) – C º C –
electronegative? | |
394 Chemistry
32. sp3-hybridization
leads to which shape of the molecule ? 34. The maximum number of carbon atoms arranged linearly in
(a) Tetrahedral (b) Octahedral the molecule,
(c) Linear (d) Trigonal planar CH3 – C º C – CH = CH2 is
33. The cylindrical shape of alkynes is due to (a) 5 (b) 4
(a) three sigma C – C bonds (c) 3 (d) 2
(b) three p C – C bonds 35. Which of the following is planar in shape ?
(c) two s C – C and p C – C bonds (a) Methane (b) Acetylene
(d) one sigma C – C and two p C – C bonds (c) Benzene (d) Isobutane
1. The Cl – C – Cl angle in 1,1,2,2- tetrachloroethene and (a) CH3C º CCH2 – CH = CHCH = CH2
tetrachloromethane respectively will be about (b) CH3CH2– CH = CHCH = CHC º CH
[CBSE PMT 1988] (c) CH3CH = CHCH2 – C º CCH = CH2
(a) 120° (b) 90° and 109.5° (d) CH3CH = CHCH2 – CH = CH = C º CH.
(c) 109.5° and 90° (d) 120° and 109.5° 8. When the hybridization state of carbon atom changes from
2. Which of the following possesses a sp-carbon in its sp3 to sp2 and finally to sp, the angle between the hybridized
structure? [CBSE PMT 1989] orbitals [CBSE PMT 1993]
(a) CH2 = CCl – CH = CH2 (a) decreases gradually
(b) CCl2 = CCl2 (b) decreases considerably
(c) CH2 = C = CH2 (c) is not affected
(d) CH2 = CH – CH = CH2. (d) increases progressively.
3. Cyclic hydrocarbon ‘A’ has all the carbon and hydrogen
9. The restricted rotation about carbon carbon double bond in
atoms in a single plane. All the carbon carbon bonds have
2-butene is due to [CBSE PMT 1993]
the same length, less than 1.54 Å, but more than 1.34 Å. The
C – C – C bond angle will be [CBSE PMT 1989] (a) Overlap of one s- and sp 2 - hybridized orbitals
(a) 109°28' (b) 100°
(b) Overlap of two sp 2 - hybridized orbitals
(c) 180° (d) 120°
4. An organic compound X (molecular formula C 6 H 7 O 2 N ) (c) Overlap of one p- and one sp 2 - hybridized orbitals
has six carbon atoms in a ring system, two double bonds and (d) Sideways overlap of two p- orbitals.
a nitro group as substituent, X is [CBSE PMT 1990] 10. Huckel's rule states that a monocyclic conjugated compound
(a) Homocyclic but not aromatic will be aromatic if it contains [CBSE PMT 1996]
(b) Aromatic but not homocyclic (a) (4n + 2p) electrons
(c) Homocyclic and aromatic
(b) (4p + 2n) electrons
(d) Heterocyclic and aromatic
(c) 4p electrons
5. The shortest C – C bond distance is found in
(d) (4n + 2)p electrons
(a) Diamond (b) Ethane [CBSE PMT 1991]
11. The structural formula of a compound is CH3 – CH = C = CH2.
(c) Benzene (d) Acetylene
The types of hybridization at the four carbons from left to
6. An sp3 hybrid orbital contains [CBSE PMT 1991]
right are [CBSE PMT 1999]
(a) 1/4 s-character (b) 1/2 s-character
(a) sp , sp , sp , sp (b) sp , sp , sp2, sp2
2 2 2 3 2 3
(c) 1/3 s-character (d) 2/3 s-character.
(c) sp3, sp2, sp, sp2 (b) sp3, sp2, sp2, sp2
7. A straight chain hydrocarbon has the molecular formula
C8H10. The hybridization of the carbon atoms from one end 12. The correct order regarding the electronegativity of hybrid
of the chain to the other are respectively sp3, sp2, sp2, sp3, orbitals of carbon is [CBSE PMT 2006]
sp2, sp2, sp and sp. The structural formula of the hydrocarbon (a) sp > sp2 > sp3 (b) sp < sp2 > sp3
would be : [CBSE PMT 1991] (c) sp < sp2 < sp3 (d) sp > sp2 < sp3
Hybridisation & Shapes of Organic Molecules 395
13. In the hydrocarbon .
15. The radical, CH2 is aromatic because it has :
CH3 – CH = CH – CH2 – C º CH
6 5 4 3 2 1 [NEET 2013]
(a) 7 p-orbitals and 6 unpaired electrons
The state of hybrization of carbons 1, 3 and 5 are in the (b) 7 p-orbitals and 7 unpaired electrons
following sequence : [CBSE-PMT 2008] (c) 6 p-orbitals and 7 unpaired electrons
(a) sp2, sp, sp3 (b) sp, sp3, sp2 (d) 6 p-orbitals and 6 unpaired electrons
16.. In which of the following species is the underlined carbon
(c) sp, sp2, sp3 (d) sp3, sp2, sp
having sp3 hybridisation? [AIEEE 2002]
14. The state of hybridization of C2, C3, C5 and C6 of the (a) CH3 COOH (b) CH3 CH2 OH
hydrocarbon, [CBSE-PMT 2009] (c) CH3 COCH3 (d) CH2 = CH –CH3
CH3 CH3 17. Which one of the following does not have sp2 hybridized
| | carbon ? [AIEEE 2004]
CH3 C CH = CH CH C º CH (a) Acetonitrile (b) Acetic acid
7 6| 5 4 3 2 1
CH3 (c) Acetone (d) Acetamide
18. In allene (C3H4), the type(s) of hybridisation of the carbon
is in the following sequence: atoms is (are) : [IIT-JEE 2012]
(a) sp3, sp2, sp2 and sp (b) sp, sp2, sp2 and sp3 (a) sp and sp3 (b) sp and sp2
(c) sp, sp2, sp3 and sp2 (d) sp, sp3, sp2 and sp3 (c) only sp3 (d) sp2 and sp3
1. The bond between carbon atom (1) and carbon atom (2) in 6. Allyl isocyanide has
1 2 (a) 9 s and 4 p - bonds
compound N º C - C H = CH 2 involves the hybridisation (b) 8 s and 5 p - bonds
(a) sp2 and sp2 respectively (a) sp3 and sp respectively (c) 9 s , 3 p and 2 non- bonded electrons
(c) sp and sp2 respectively (d) sp and sp respectively (d) 8 s , 3 p and 4 non - bonded electrons
x 7. During elimination reactions, the hybrid state of carbon
2. The compound in which C uses its sp3 - hybrid orbitals for atoms involved change as shown below:
bond formation is (a) sp3 to sp2 nature
X X
(a) HCOOH (b) (H2 N)2 CO (b) sp3 to sp nature
(c) No change in hybridised state
X X (d) Either (a) or (b)
(c) (CH 3 )3COH (d) CH 3C HO
8. In the dehydration reaction,
3. Of the following compounds which will have a zero dipole
P O
5 ® CH C º N ,
moment CH 3CONH 2 ¾¾
2¾
3
(a) 1, 1 - dichloroethylene the hybridisation state of carbon changes from
(b) Trans -1, 2 - dichloroethylene (a) sp3 to sp2 (b) sp to sp
(c) Cis - 1 , 2 - dichloroethylene (c) sp2 to sp (d) sp to sp3
(d) None of these ·
4. The number of s - and p - bonds in but- 1 - ene - 3 - yne are 9. Unpaired electron in CH3 occupies
(a) 5s - and 5p - (b) 7s - and 3p - (a) sp - hybrid orbital (b) sp3 - hybrid orbital
(c) p - orbital (d) sp2 - hybrid orbital
(c) 8s - and 2p - (d) 8s - and 4p - 10. The hybridisation of carbon atom in C - C single bond of
5. The species which use sp2 - hybrid orbitals in its bonding H - C º C - CH = CH 2 is
(a) PH 3 (b) NH 3 (a) sp3 - sp3 (b) sp2 - sp2
(c) CH 3+ (d) CH 4 (c) sp - sp2 (d) sp3 - sp
396 Chemistry
11. Which of the following represents the given mode of 15. Which of the following species would be expected to exhibit
hybridisation sp2 – sp2 – sp – sp from left to right? aromatic character ?
(a) H 2 C = CH – C º CH . –. +
(b) HC º C – C º CH
(c) H 2 C = C = C = CH 2 (i) (ii)
CH2
(d) H C . –. +
2
12. The structure of H2C = C = CH2 is
(a) linear (iii) (iv)
(b) planar
(c) non-planar (a) (i) and (iv) (b) (ii) and (iv)
(d) has several resonance structures (c) (i) and (iii) (d) (ii) and (iii)
13. Aromatic character of benzene is proved by 16. Which among the following is aromatic ?
(a) resonance theory (b) aromatic sextet theory 2– –
(c) orbital theory (d) All of these
14. Which of the following will show aromatic behaviour ?
I II III IV V
(a) I (b) II and V
(a) (b) (c) III (d) IV
17. Which of the following is not aromatic ?
+ (a) Benzene
(b) Cyclooctatetraenyl dianion
(c) Tropylium ion
(c) (d) (d) Cyclopentadienyl cation
EXERCISE 1 EXERCISE 2
1. Acetylene, due to greater electronegativity of the
1º
sp–hybridized carbon. CH3
1º 2º 3º 4º 2º 2º 1º
2. CH4 = sp3 1. (c) CH – CH – CH – C – CH – CH – CH ;
3 2 2 2 3
C2H4 = sp2 CH3 CH3
1º 1º
C2H2 = sp
Thus there are five 1º carbon atoms.
3. (i) sp2, (ii) sp3, (iii) sp2.
4. The carbon atom x is sp2 and carbon atom y is sp3 hybridised. 1º 1º
CH3 CH3
5. Ethene (C2 H 4 ) has sp 2 hybridized carbon atoms. On 1º 4º 2º 1º
2. (b) CH3 – CH – C – CH2 – CH3 ;
hydrogenation, it changes to ethane (C2H6) in which carbon 3º
atoms are sp3 hybridized. Cl
10. (d) 11. (b) 12. (a) 13. (d) 14. (b) 15. (c) Thus all the four types of carbon atoms are present in
16. (c) 17. (a) 18. (c) 19. (d) 20. (c) 21. (b) this compound.
O O
sp3 || sp3 sp sp3 ||
; CH3 - C - OH ; CH3 - C º N ; C H 3 - C - NH 2
2
sp 2
sp
Aromatic Alicyclic
Acetic acid Acetonitrile Acetamide (conjugated 6p electrons)
sp 2 sp sp 2 +
18. (b) Allene (C3H4) is H 2 C = C = CH 2
EXERCISE 4
1. (c) The C1 forms 2s bonds and 2p - bonds (sp-hybridisation) Antiaromatic
(conjugated 4p electrons)
and C2 forms 3s bonds and 1p bond (sp2 hybridisation)
x 15. (d) (ii) and (iii) have delocalized six p electrons and hence
2. (c) See the number of s bonds formed by C in each case. In
x x x x these are aromatic; (i) has 8 conjugated p electrons, while
HCOOH , (H 2 N)2CO and CH3C HO, C forms 3s (iv) has 4 conjugated p electrons.
bonds and 1 p bond, hybridisation is sp 2 . In 16. (a) Only structure I has 8 + 2 = 10p electrons, hence it is
x x aromatic; II has 4, III has 8, IV has 9 and V has 4 electrons,
(CH3 )3C OH , C forms 4s bonds, hence hybridisation thus II to V are not aromatic.
is sp3 17. (d) No. of delocalized p electrons in benzene (a),
s- cyclooctatetraenyl dianion (b), and tropylium ion (c) are
Cl H
3. (b) C= C s- has zero dipole moment 6, 10 and 6 respectively. Further all the three species are
H Cl cyclic, hence all of these are aromatic. Cyclopentadienyl
cation (d) has 4 p electrons, hence it is not aromatic but
4. (b) H2C = CH- C º CH has 7s and 3p actually it is antiaromatic.
+
5. (c) CH3 is sp2 hybridised
12D
General Organic
(Basic Concepts)
ELECTRONEGATIVITY Hence transmission can be ignored after the second C-atom. An
A covalent bond, where the electrons are shared equally is called atom or group which attracts electrons more strongly than
a non-polar bond (eg H–H) and an unequal sharing of the pair of hydrogen is said to have a negative inductive effect (–I). An atom
bonding electrons results in a polar bond. The unequal sharing of or group which attracts electrons less strongly than hydrogen is
electrons is due to the ability of an atom to attract electrons said to have a positive inductive effect (+I).
towards itself which is known as Electronegativity. + +
Elements with higher electronegativity values have greater N R 3 > N H 3 > NO 2 > CN > COOH > F > Cl > Br > I
attraction for bonding electrons.
> OAr > OR > OH > C º CR > Ar > H
H
2.2 ¬
¾¾ Increasing – I effect (Electrons attracting )
Li Be B C N O F
1.0 1.6 1.8 2.5 3.0 3.4 4.0 O - > COO - > CR 3 > CHR 2 > CH 2 R > CH 3 > D > H
Na Mg Al Si P S Cl
0.9 1.3 1.6 1.9 2.2 2.6 3.2 ¬
¾¾ Increasing + I effect (electrons repelling)
Br Inductive effect does not change the covalency. The more the
3.0 inductive effect between a bond, the more is the ionic character of
I the bond.
2.7 Applications :
Electronegativity increases from left to right and decreases from (I) Acid character of Acids : Formic acid is stronger than acetic
top to bottom. acid.
INDUCTIVE EFFECT (I)
O d+ O
The displacement of shared pair of electrons towards the more H–C CH3 C d–
electronegative atom in a molecule is called inductive effect. It is O–H O–H
a permanent effect e.g. Formic acid Acetic acid
d+ d- The oxygen atom in acetic acid holds the hydrogen atom
H ® Cl more tightly after acquiring negative charge due to +I effect
• It develops polarity in a bond or molecule. of methyl group. Hence it is less ionised
• It is transmitted along a chain of atoms but the intensity Acid character of halogens substituted acids. Chloro
goes on decreasing with the increase in the size of chain. For substituted acetic acids follow the following order for acid
example,
character.
d+
C ® C ®® C ®®® X d -
400 Chemistry
(II) Reactivity of Alkyl halides. It follows the following order
d–
Cl R R
O
d– –
Cl C C O H R C Cl R C Cl
d–
Cl R H
3° 2°
Trichloro acetic acid
H H
d– R C Cl H C Cl
Cl
O
d– – H H
Cl C C O H 1°
H R .N. H R N:
.. H
Monochloro acetic acid Acetic acid
¬
¾¾ Increasing acid character 2ºamine 1ºamine
·
The attack of Br on terminal carbon atom (see step III) results in
..
the formation of more stable secondary free radical. This is the
reason that addition takes place anti to markownikoff's rule. HCl ..
•
and HI do not show peroxide effect. HCl does not give Cl atoms
and HI gives molecular I2. ..
RESONANCE :O: :O: :O: :O: :O:
Representation of certain molecules by various electronic ..
configurations is known as Resonance. Electronic configurations
differ only in location of electrons, the atoms must stay in the
same conditions. e.g.
(a) NO 3- ion
Due to resonance the unshared pair of electrons present on
nitrogen atom is delocalised within benzene nucleus and not
available for protonation (to accept H+). Hence basic
character is suppressed.
III. Stability of cations : Methoxy methyl cation is more stable
by 76 kcal/mole than methyl Cation.
4
H H B.O. = = 1.33
.. | Å | 3
CH 3 - O
. . - C- H ¬¾® CH 3 - O
. . = C- H
Å
(b) CO3- - ion
More stable (every atom has octet)
ER = E0 – EC
ER = Resonance energy, E0 = Observed heat of formation (II) Extra stability : Each C-atom in 1, 3-butadiene is sp2
and EC = Calculated heat of formation of the most stable of hybridised and contains one pz atomic orbital parallel to each
the resonating structures. other and perpendicular to the plane of hybrid atomic orbitals.
In case of unsaturated compunds, Resonance energy is the By sidewise overlapping these pz atomic orbitals form a
difference between a measured and calculated heat of delocalised p molecular orbital which provides the extra
hydrogenation e.g., stability to the molecule.
Benzene Cyclohexane
(III) Bond length : Conjugation affects the bond length. The C2 –
C3 bond length in 1,3-butadiene is 1.47 Å and C1 – C2 bond
Calculated value of heat of hydrogenation of benzene length is 1.35Å due to conjugation.
= 28.6 × 3 = 85.8 kcal/mole, RE = 36.0 kcal / mole. (IV) Heat of hydrogenation :
The greater the RE, the more is the stability. Calculated heat of hydrogenation of 1,3 butadiene
MESOMERIC EFFECT (ME) : = 28.6 × 2 = 57.2 kcal.
It is a permanent effect and similar to electromeric effect. Like Observed heat of hydrogenation of 1,3-butadiene
Inductive effect it may be +ME or –ME. = 53.7 kcal.
+ME atoms or groups donate electrons to the double bond or R.E. = 57.2 – 53.7 = 3.5 kcal/mole
conjugated system e.g. –Cl, –Br, –I, NH2, –NHR, –NR2, –OH, – Thus due to conjugation 1,3-butadiene is stabilised by 3.5
OR, –SH, –SR etc. kcal/mol.
.. – + HYPERCONJUGATION :
CH2 = CH – Cl:
.. CH2 – CH = Cl
. .:
Introduced by Baker and Nathan (1935). The electron release by
–ME atoms or groups withdraw electrons eg. –NO2, CN, COOH, C–H bond by the effect similar to electromeric effect is known as
CHO, HSO3. hyperconjugation. It is a permanent effect.
Å ..
CH 2 = CH - C º N ¾
¾® C H 2 - CH = C = N
.. H
| H+ ..
- C - C = C- ¬¾® - C = C - C-
CONJUGATION : | | | | |
The compounds containing alternate single and double bonds (I) (II)
Hyperconjugated forms
are known as conjugated compounds. Such compounds exhibit
certain abnormal properties due to interaction between single and Since there is no apparent bond between C and H + , the
double bonds, known as conjugation hyperconjugation is also known as No bond Resonance. The
(I) Abnormal addition reactions : Addition of HBr to 1,3- magnitude of inductive effect and hyperconjugation follows the
butadiene. order.
–CH , - C H , - CH (CH ) , - C ( CH )
Increasing Hyperconju gation ¬¾ ¾3 ¾ ¾
2¾5 ¾¾ ¾¾
3 2¾ ¾ ¾ ¾
3¾
3®
H + / Br -
CH 2 = CH - CH = CH 2 ¾¾ ¾¾®
Electrophilic Increasing Inductive effect
+
attack of H
404 Chemistry
Effects of hyperconjugation : Types of reagents :
(I) Heat of hydrogenation of Substituted Olefins : (I) Electrophilic reagents : They have high affinity for electrons
+ + + + + + ..
The greater the number of H.C. forms the more is the stability. H + , H 3O + , N O 2 , H S O 3 , X (Cl, Br, I), R + , R C O, NO, - N º N
Compound Heat of hydrogenation They may be neutral in nature also AlCl3, BF3, ZnCl2, FeCl3,
CH2 = CH2 Ethylene 32.8 kcal/mol SnCl4 etc.
CH3–CH = CH2 Propylene 30.1 kcal/mol (II) Nucleophilic reagents : Electron rich species and have
(Due to H.C. forms) affinity towards nucleus (which is positively charged).
.. ..
CH 2 = CH - C H 2 ¬¾® C H 2 - CH = CH 2
Benzyl Carbanion
+
CH2 CH2
:CH2 CH2 CH2
:
The order of stability of different carbonium ions
+ + +
(C 6 H 5 ) 3 C > (C 6 H 5 ) 2 C H > (C 6 H 5 ) C H 2 >
+ + + + + CH2 :CH2
CH 2 = CH . CH 2 > R 3 C > R 2 CH > R CH 2 > C H 3
:
CH2 CH2
Multiplicity is A = 2 × 1 + 1 = 3
æ 1 1 ö
ç S = + = 1, Two unpaired electrons have parallel spin ÷
è 2 2 ø
Order of stability of various free radicals
Triplet is more stable than singlet.
g g g g g g g g
(C6 H5 )3 C > (C6 H 5 ) 2 C H > C6 H 5 CH 2 > CH 2 = CH - CH 2 > (CH 3 )3 C > (CH 3 ) 2 CH
. . > CH 3 CH 2 > CH 3
Nitrenes : R - N
. . Nitrenes are nitrogen analogs of carbenes,
g g g g g g
C6 H5 CH 2 > CH 2 = CH - CH 2 > (CH3 )3 C > (CH3 ) 2 CH > CH3 CH 2 > CH 3
nitrogen is sp2 hybridised.
¬
¾¾ Stability
.. .. ..
D or hv
Generation R - N
..- N º N
. . ¾¾ ¾¾® R - N
. . + N2
CARBENES C : These are uncharged reactive intermediates
Azide
that contain a divalent carbon atom which is sp2 hybridised. There
is a perpendicular vacant p-orbital. Structure singlet :
Generation :
2pz
U.V.
(I) CH 2 N 2 ¾¾¾® : CH 2 + N 2
Diazomethane Carbene
R R
N OR N N
U.V.
(II) CH 2 = C = O ¾¾¾® : CH 2 + CO
Ketene
OH - Multiplicity A = 2s + 1 = 2 × 0 + 1 = 1
(III) CHCl3 ¾¾¾® : CCl 2 + HCl
Chloroform Dichloro carbene
Singlet carbenes :
R
2pz Triplet : N OR N
C Or C
Multiplicity A = 2s + 1 = 2 × 1 + 1 = 3
Arynes : The derivatives of benzyne are called arynes :
°
Z
H H
C Or C Benzyne Aryne
H H
Generation :
H
NH2 –
+ NH3 + Cl
æ 1 1 ö
Multiplicity is A = 2s + 1 = 2 × 0 + 1 = 1 çs = + 2 - 2 = 0÷ Cl
è ø
General Organic (Basic Concepts) 407
Types of reactions : (III) Addition reactions :
(I) Substitution reactions or replacement reactions : (a) Electrophilic Addition reactions, initiation by electrophile
(a) S N 1 : Substitution nucleophilic unimolecular reactions : e.g.
Such reactions take place in two stages H + / X-
+
X-
R - CH = CH 2 ¾¾ ¾¾® R - C H - CH 3 ¾¾®
¾ R - C H - CH 3
Slow + - + – Fast First attack
R – X ¾¾¾® R + X ; R + Y ¾¾
¾® R - Y by erectrophile
|
X
(b) S N 2 : Substitution nucleophilic bimolecular reactions :
(b) Nucleophilic addition reactions, initiation by nucleophile
d- d+ d- e.g.
Y - + R - X ¾¾¾®[ Y × × × × × R × × × × × X ] ¾¾
¾® Y - R + X -
Slow Fast
Transition State
H + / CN - H+
¾® > C - O - ¾¾
> C = O ¾¾ ¾ ¾ ¾® > C - OH
First attack by | |
SN 1 SN 2 Nucleophile
CN CN
• 3°> 2°> (1° and CH3 X do not go) CH 3 X >1°> 2°> 3°
(c) Free radical addition reactions, initiation by free radical
• Strength of nucleophile Strong nucleophiles required
Peroxide
not important R - CH = CH 2 + H · / Br · ¾¾¾¾® R - CH 2CH 2 Br
• Good ionising solvent May go faster in less polar (IV) Rearrangement reactions :
required solvent
• Rate = K [RX] Rate = K [RX] [Nu–] NHOH NH2
• Possible rearrangements No rearrangements
• Lead to recemisation Lead to inversion.
(c) S N 1 : Substitution nucleophilic internal. Example
Phenyl hydroxylamine OH p-amino phenol
ROH + SOCl 2 ¾
¾® RCl + SO 2 + HCl O
NH4CNO NH–
2 C–NH2
ROH + SOCl 2 ¾
¾® RO.SOCl + HCl
Amm. Cynate Urea
–
Slow + Fast
ROSOCl ¾¾¾® R + O ¾¾
¾® R - Cl + SO 2 (V) Polymerisation reactions :
S=O
Cl nCH 2 = CH 2 ¾¾
® -(CH 2 - CH 2 -) n
Ethylene Polythene
(II) Elimination reactions :
DIRECTIVE INFLUENCE OF ATOMS AND GROUPS :
(a) E1 : Elimination unimolecular (For electrophilic substitution reactions)
When monosubstitution product of benzene is converted into di-
X substitution product, the position of second incoming group is
| | + |
- C - C - ¾¾¾® X - + - C- C - ¾¾ ¾
Slow :B Fast decided by the atom or group already present in the benzene
¾® > C = C < + B : H
| | | | nucleus. This is known as directive influence of atoms and groups.
H H
A carbocation Directive influence is governed by three effects :
(I) Inductive effect (I) (II) Electromeric effect (E)
(b) E2 : Bimolecular elimination (III) Resonance (M)
Any effect that pushes the electrons towards the benzene nucleus
X is taken as positive and activates the benzene nucleus for further
| | substitution. The effect that pushes the electrons away from
- C - C - ¾¾® X - + > C = C < + H : B
:B
benzene nucleus is taken as negative and deactivates the benzene
| |
H nucleus for further substitution.
Here we will consider Inductive effect and Mesomeric effect
E1 (comparison) E2 (Resonance) to decide the directive influence of atoms and groups.
The electromeric effect is similar to Mesomeric effect and always
• Good ionising solvent Solvent polarity not so
operate in the same direction, the only difference is the former is
required important temporary and latter is permanent.
• Base strength not Strong bases are required (I) Directive influence of OH group :
important (a) Inductive effect (I)
OH
• Rate = K [RX] Rate = K [RX] [B–]
• Saytzeff orientation Saytzeff orientation –I deactivation
• Rearrangements are No rearrangements
common
408 Chemistry
(b) Mesomeric effect (M) (b) Mesomeric effect (M)
:O – H O–H O–H
C N C N C N
+
O–H O–H :O – H
C N C N
+M
+ +
activation –M
deactivation
Ortho and para positions become the points of high The o,p-positions become the points of low electron
electron density as + M > > – I. The electrophilic reagent density, therefore the electrophilic reagent will attack at
will attack at o- and p- positions. Hence OH gp. is o, p- the m position. Hence CN is meta directing in nature
directing in nature with activation of benzene nucleus.
with deactivation of benzene nucleus.
.. .. .. ..
Other examples are - NH 2 , - NHR, - NR2 , - OR Other examples are : - NO 2 , COOH , HSO 3 , CHO
..
(IV) Directive influence of –Cl atom :
(II) Directive influence of –CH3 group :
(a) Inductive effect (I)
(a) Inductive effect (I) ..
:Cl:
CH3
– I deactivation
+ I activation
..
:
.. .. .. ..
:Cl + :Cl :Cl:
H H +M
H–CH H–C–H activation
..
+ HC
activation By mesomeric effect the o,p positions become the points
of high electron density. Further –I > +M, hence Cl is
The o, p-positions become the points of high electron o, p directing in nature with deactivation of benzene
density. The electrophilic reagent will attack at o- and p- nucleus.
positions. Hence methyl group is o,p-directing in nature Other examples are : –F, Br, I
with activation of benzene nucleus.
EASE OF ELECTROPHILIC SUBSTITUTION OF
Other examples are : -C 2 H 5 , - C3 H 7 , - C 4 H 9 etc. BENZENE AND ITS DERIVATIVES :
(III) Directive influence of –CN group : 1. Strongly activating (o, p directing) :
(a) Inductive effect (I) .. .. ..
CN
- N H 2 , - NHR, - N R 2 , - O
..
H
2. Moderately activating (o, p directing) :
– I deactivation
.. .. ..
-O
..
CH 3 , - O C H , -N
.. 2 5 ..
HCOCH3
General Organic (Basic Concepts) 409
3. Weakly activating (o, p-directing) : (IV) Friedel Craft's alkylation
-CH 3 , - C 2 H 5 , - C 3 H 7 , C 6 H 5 ¾® R + + AlCl -4
RX + AlCl 3 ¾ Electrophile R+
4. Benzene itself. (V) Friedel crafts acylation
5. Deactivating (o, p - directing) : F, Cl, Br, I +
¾® R C O + AlCl 4-
RCOCl + AlCl3 ¾
6. Deactivating (m-directing) : +
+ Electrophile R C O
NO 2 , - N (CH 3 ) 3 , CN , COOH , COOR , SO 3 H, CHO, - COR
Again NUCLEOPHILIC SUBSTITUTION OF BENZENE
It does not occur with benzene itself, but it does occur with some
NH 2 > OH > OCH 3 > NHCOCH 3 > C 6 H 5 > CH 3 substituted benzenes.
¬
¾¾ activation of benzene nucleus
–
O2N + N(C6H5)2
COMMON ELECTROPHILIC SUBSTITUTION
REACTIONS
(I) Nitration –
O2N N(C6H5)2 + H
+ +
® NO 2 + H 3O + 2HSO -4
HNO3 + 2H 2SO 4 ¾¾
+
Electrophile NO 2 –
O2N + OH
(II) Sulphonation
® HSO 4- + H 2 O + HS+ O3
2H 2SO 4 ¾¾
+ –
Electrophile HSO 3 or SO3 O2N OH + H
(III) Halogenation
H– much less stable hence some oxidising reagent with which H–
¾® FeCl 3 X - + X +
X 2 + FeCl 3 ¾ Electrophile X +
can react facilitate the nucleophilic substitution.
410 Chemistry
g
HS– , BF3, ROH
g g
(i) C6H5 CHCH3 , C6H5 C HCH = CH2, C6H5CH2CH 2 , Multiple Choice Questions
g
C6H5 C(CH 3) 2 in order of increasing stability.. 16. Select the most stable carbocation from amongst the
following
(ii) CH3CH2+, C6H5CH2+, (CH3)3C+, CH2 = CHCH2+ in
order of decreasing stability. +
(a)
(iii) HC º C–, CH2 = CH–, CH3CH2–, CH3–, (CH3)2CH–,
C6H5CH2– in order of increasing stability. (b)
5. What are carbocations (carbonium ion)? Discuss their types. +
6. What are free radicals ? Discuss their types.
7. How does (i) an electron withdrawing group (EWG) and (ii)
an electron donating group (EDG) influence the acid strength (c) +
of carboxylic acid?
8. Which of the following species behaves as (i) a nucleophile,
(ii) an electrophile, (iii) both, or (iv) neither? (d) +
....I ..– , H N, BeCl , NO+ , CH C º N :,
.. 3 2 2 3 17. What is the correct order of decreasing stability of the
... following cations ?
H , H C = C., CH
2 2 4 Å
9. What are carboanions? Discuss their types. I. CH3 — CH— CH3
10. The structure of triphenylmethyl cation is given below. This
Å
is very stable and some of its salts can be stored for months. II. CH3 — CH— OCH3
Explain the cause of high stability of this cation.
Å
III. CH3 — CH— CH 2 — OCH3
(a) II > I > III (b) II > III > I
C (c) III > I > II (d) I > II > III
18. The order of decreasing stability of the carbanions
(CH3 )3 C - (I) ; (CH3 ) 2 CH - (II) ; CH3CH -2 (III);
11. Identify the most stable species in the following set of ions C 6 H 5 CH -2 ( IV ) is
giving reasons: (a) I > II > III > IV (b) IV > III > II > I
+ + + + (c) IV > I > II > III (d) I > II > IV > III
(i) CH 3 , CH 2 Br , CH Br2 , CBr3 19. The most stable free radical among the following is
– – – – · ·
(ii) CH 3 , CH 2Cl , CHCl2 , CCl3 (a) C6 H 5 CH 2 CH 2 (b) C 6 H 5 CHCH 3
1. Which of the following is correct regarding the – I effect of 8. Select the most stable carbocation from amongst the following
the substituents?
+
(a) – NR2 < – OR < – F (b) – NR2 > – OR < – F (a)
(c) – NR2 < – OR > – F (d) – NR2 > – OR > – F
2. Polarization of electrons in acrolein may be written as (b)
d- d+ d- d+ +
(a) CH 2 = CH - CH = O (b) CH 2 = CH - CH = O
d- d- d+ d-
(c) CH 2 = CH- CH = O (d) CH 2 = CH - CH = O (c) +
3. Heterolytic fission of a covalent bond in organic molecules
gives
(a) free radicals (b) cations and anions
(c) only cations (d) only anions (d) +
4. In which of the following homolytic bond fission takes place ?
(a) Alkaline hydrolysis of ethyl chloride 9. The most stable carbonium ion among the following is
(b) Addition of HBr to double bond
(c) Photochlorination of methane + +
(d) Nitration of benzene (a) C6 H5 CHC6 H5 (b) C6 H5CH 2
5. Homolytic fission of C–C bond in ethane gives an
+ +
intermediate in which carbon is (c) CH3 CH 2 (d) C6 H5CH2CH 2
(a) sp3-hybridised (b) sp2-hybridised
(c) sp-hybridised (d) sp2d-hybridised 10. Which of the following is most stable?
6. Among the following, the true property about (a) Ph3C+ (b) Ph2CH+
CH3 (c) PhCH2+ (d) Tropylium cation
+
C – CH3 is 11. Consider the following carbocations
CH3 + +
I. C6 H5 CH 2 II. C6 H5 CH 2CH 2
(a) it is non-planar
(b) its C+ is sp2-hybridized
+ +
(c) an electrophile can attack on its C+ III. C6 H5CHCH3 IV. C6 H5C(CH3 )2
(d) it does not undergo hydrolysis
7. Which of the following is the most stable carbocation The correct sequence for the stability of these carbocations
(carbonium ion)? is
+
(a) CH 3CH 2 + (b) (CH ) CH (a) II < I < III < IV (b) II < III < I < IV
3 2
+ +
(c) III < I < II < IV (d) IV < III < I < II
(c) (CH 3 )3 C (d) C6 H5CH 2
412 Chemistry
12. The most stable carbanion among the following is 22. Which of the following has the highest nucleophilicity?
(a) F - (b) OH -
CH2 – CH2– CH2–
(c) CH 3- (d) NH -2
23. The correct nucleophilicity order is
(a) (b)
(a) CH 3- < NH -2 < HO - < F -
(b) CH 3- ~
- NH -2 > HO - ~- F-
CH2– CH2– (c) CH 3- > NH -2 > HO - > F -
(d) NH -2 > F - > HO - > CH 3-
24. What is the decreasing order of strength of the bases
(c) (d)
OH - , NH -2 , HC º C - and CH 3CH -2 ?
OCH3 NO2 (a) CH 3 CH -2 > NH -2 > HC º C - > OH -
13. The order of decreasing stability of the carbanions (b) HC º C - > CH 3CH -2 > NH -2 > OH -
(CH 3 )3C - (I) ; (CH 3 ) 2 CH - (II); CH 3CH 2- (III); (c) OH - > NH 2- > HC º C - > CH 3CH -2
(a) I > II > III > IV (b) IV > III > II > I 25. Which is the correct symbol relating the two Kekule
structures of benzene ?
(c) IV > I > II > III (d) I > II > IV > III
14. The most stable free radical among the following is (a) ®¬ (b) ®
(c) º (d) «
· ·
(a) C 6 H 5 CH 2CH 2 (b) C6 H 5 CHCH 3 26. Point out the incorrect statement about resonance?
(a) Resonance structures should have equal energy
· ·
(c) CH 3CH 2 (d) CH 3CHCH 3 (b) In resonating structures, the constituent atoms must be
in the same position
15. Intermediate involved in Reimer-Tiemann reaction is (c) In resonating structures, there should not be same
(a) carbocation (b) carbanion number of electron pairs
(c) carbene (d) free radical (d) Resonating structures should differ only in the location
16. For the reaction of phenol with CHCl3 in presence of KOH, of electrons around the constituent atoms
the electrophile is 27.
-
: CH 2 - C - CH3 and CH 2 = C - CH 3 are
(a) +
CHCl 2 (b) : CCl2 || |
O. .: :O -
. .:
·
(c) CHCl (d) CCl4 (a) resonating structures (b) tautomers
2
17. In the mechanism of Hofmann reaction which intermediate (c) geometrical isomers (d) optical isomers
rearranges to alkyl isocyanate? 28. The most unlikely representation of resonance structures of
(a) Bromamide (b) Nitrene p-nitrophenoxide ion is
(c) Nitroso (d) Amide –O
+ O –O O–
18. Which of the following is an electrophile? +
N N
(a) H2O (b) NH3
(c) AlCl3 (d) C2H5NH2
19. Which of the following is not a nucleophile? (a) (b)
(a) CN– (b) OH–
(c) NH3 (d) BF3 O– O
20. Which of the following is not a nucleophile?
(a) H2O (b) CH3OH –O
O + O O
(c) H2 (d) NH3 +
N N
21. Which of the following behaves both as a nucleophile and
as an electrophile ?
(c) (d)
(a) CH 3C º N (b) CH 3OH
–
(c) CH 2 = CHCH 3 (d) CH 3 NH 2 O– O
General Organic (Basic Concepts) 413
29. In which of the following, resonance will be possible? 32. Resonance in most of the organic molecules
(a) CH3 - CH 2 - CH 2 - CHO (a) increases stability (b) decreases stability
(c) increases reactivity (d) None of these
(b) CH 2 = CH - CH = O
33. The kind of delocalization involving sigma bond orbitals is
(c) CH 3COCH 3 called
(a) inductive effect
(d) CH 2 = CH - CH 2 - CH = CH 2
(b) hyperconjugation effect
30. Which of the following statements regarding the resonance (c) electromeric effect
energy of benzene is correct? (d) mesomeric effect
(a) Resonance energy is the energy required to break the 34. The reaction,
C–H bond in benzene
¾® CH 3CHBrCH 3 is
CH 2 = CH - CH 3 + HBr ¾
(b) Resonance energy is the energy required to break the
(a) nucleophilic addition
C–C bond in benzene
(b) electrophilic substitution
(c) Resonance energy is a measure of stability of benzene
(c) electrophilic addition
(d) Resonance energy is the energy required to convert
(d) free radical addition
35. The addition of HCN to a carbonyl compound is an example
of
(a) nucleophilic substitution
31. The heat of hydrogenation of 1-hexene is 126 kJmol–1, When (b) electrophilic addition
a second double bond is introduced in the molecule, the (c) nucleophilic addition
heat of hydrogenation of the resulting compound is 230 kJ (d) electrophilic substitution
mol–1. The resulting compound (diene) is 36. Acetaldehyde is the rearrangement product of
(a) 1, 3-Hexadiene (b) 1, 4-Hexadiene (a) methyl alcohol (b) allyl alcohol
(c) 1, 5-Hexadiene (d) Nothing certain (c) vinyl alcohol (d) All are correct
1. For (i) I–, (ii) Cl–, (iii) Br–, the increasing order of nucleophilicity 4. Base strength of : [CBSE-PMT 2008]
would be [CBSE-PMT 2007] (A) H 3CCH 2 ,– (B) H 2C = CH and
(a) Cl– < Br– < I– (b) I– < Cl– < Br– (C) H - C º C
(c) Br– < Cl– < I– (d) I– < Br– < Cl– is in the order of :
2. The order of decreasing reactivity towards an electrophilic (a) (B) > (A) > (C) (b) (C) > (B) > (A)
reagent, for the following would be [CBSE-PMT 2007]
(c) (A) > (C) > (B) (d) (A) > (B) > (C)
(i) benzene (ii) toluene 5. The stability of carbanions in the following :
(iii) chlorobenzene (iv) phenol
(a) (ii) > (iv) > (i) > (iii) (b) (iv) > (iii) > (ii) > (i) (I) RC = C (II)
(c) (iv) > (ii) > (i) > (iii) (d) (i) > (ii) > (iii) > (iv)
(III) R 2C = CH (IV) R 3C - CH 2
3. Which one of the following is most reactive towards
electrophilic attack ? [CBSE-PMT 2008] is in the order of : [CBSE-PMT 2008]
CH2OH (a) (I) > (II) > (III) > (IV) (b) (II) > (III) > (IV) > (I)
(a) (b) (c) (IV) > (II) > (III) > (I) (d) (I) > (III) > (II) > (IV)
6. Cyclohexanol (I), acetic acid (II), 2, 4, 6-trinitrophenol (III)
Cl and phenol (IV) are given. In these the order of decreasing
OH acidic character will be : [CBSE-PMT 2010]
(a) III > II > IV > I (b) II > III > I > IV
(c) (d)
(c) II > III > IV > I (d) III > IV > II > I
414 Chemistry
7. The correct order of increasing reactivity of C – X bond 12. Some meta-directing substituents in aromatic substitution
towards nucleophile in the following compounds is: are given. Which one is most deactivating? [NEET 2013]
[CBSE-PMT 2010] (a) –SO3H (b) –COOH
X (c) –NO2 (d) –C º N
X
NO2 13. Arrangement of (CH3)3 – C –, (CH3)2 – CH –, CH3 – CH2 –
(CH3)3 C – X, (CH3)2CH – X when attached to benzyl or an unsaturated group in
increasing order of inductive effect is [AIEEE 2002]
(a) (CH3)3 –C – < (CH3)2 – CH – < CH3 – CH2–
NO2 (b) CH3 –CH2– < (CH3)2– CH – < (CH3)3 –C –
(I) (II) (III) (IV) (c) (CH3)2 – CH– < (CH3)3 –C – < CH3—CH2–
(a) I < II < IV < III (b) II < III < I < IV (d) (CH3)3 – C– < CH3 –CH2 – < (CH3)2 –CH –
(c) IV < III < I < II (d) III < II < I < IV 14. The reaction:
H O
8. Among the given compounds, the most susceptible to (CH3)3C – Br ¾¾2¾® (CH3)3 – C –OH is a/an
nucleophilic attack at the carbonyl group is: [AIEEE 2002]
[CBSE-PMT 2010] (a) elimination reaction (b) substitution reaction
(a) CH3COOCH3 (b) CH3CONH 2 (c) free radical reaction (d) displacement reaction.
15. In the anion HCOO– the two carbon-oxygen bonds are found
(b) CH3COOCOCH3 (d) CH 3 COCl
to be of equal length. what is the reason for it ?
9. Which one of the following is most reactive towards [AIEEE 2003]
electrophilic reagent ? [CBSE-PMT 2010, 2011] (a) The C = O bond is weaker than the C — O bond
CH3 CH3 (b) The anion HCOO– has two resonating structures
(a) (b) (c) The anion is obtained by removal of a proton from the
OCH3 OH acid molecule
(d) Electronic orbitals of carbon atom are hybridised
CH3 CH3 16. Rate of the reaction [AIEEE 2004]
(c) (d) O O
NHCOCH3 CH2OH R – C + Nu R–C +Z
Z Nu
10. Which one is a nucleophilic substitution reaction among the
is fastest when Z is
following ? [CBSE-PMT 2011]
(a) OC2H5 (b) NH2
(a) CH3 – CH = CH2 + H2O CH3 – CH – CH3 (c) Cl (d) OCOCH3
OH 17. Due to the presence of an unpaired electron, free radicals
(b) RCHO + R¢ MgX R – CH – R¢ are: [AIEEE 2005]
(a) cations (b) anions
OH (c) chemically inactive (d) chemically reactive
CH 3 18. The decreasing order of nucleophilicity among the
(c) CH3 – CH2–CH–CH2Br + NH 3 nucleophiles [AIEEE 2005]
(a) CH 3C - O -
CH3
||
CH 3–CH 2–CH–CH2NH 2 O
(b) CH 3O -
(d) CH3CHO + HCN ¾¾ ® CH3CH (OH) CN
11. Which of the following compounds undergoes nucleophilic (c) CN -
O
substitution reaction most easily ? [CBSE-PMT 2011 M] ||
(d) H 3C S – O – is
Cl ||
Cl O
(a) (b) (a) (c), (b), (a), (d) (b) (b), (c), (a), (d)
NO2 (c) (d), (c), (b), (a) (d) (a), (b), (c), (d)
CH3 19. The reaction [AIEEE2005]
O
O
||
||
Cl R–C + Nu R–C +X
Cl X Nu
is fastest when X is
(c) (d)
(a) OCOR (b) OC 2 H 5
NO2
O
H Å
(b)
+ E Å N
(a) (b) +
O
H E
NO2 NO2 O
H (c) Å
E Å N
(c) + (d) + H
E O
23. Arrange the carbanions, [AIEEE 2009]
(b) CCl3 > C6 H5 CH2 > (CH3 )2 CH > (CH3 )3 C 28. Hyperconjugation involves overlap of the following orbitals
[IIT-JEE 2008]
(c) (CH3 )3 C > (CH3 )2 CH > C6 H5 CH 2 > C Cl3 (a) s-s (b) s - p (c) p- p (d) p-p
29. The correct stability order for the following species is
(d) C6 H5 CH2 > CCl3 > (CH3 )3 C > (CH3 )2 CH
[IIT-JEE 2008]
24. The correct order of increasing basicity of the given conjugate
+ + +
bases (R = CH3) is [AIEEE 2010]
O O +
(a) RCOO < HC º C < R < NH 2 (I) (II) (III) (IV)
(a) (II) > (IV) > (I) > (III) (b) (I) > (II) > (III) > (IV)
(b) R < HC º C < RCOO < NH 2
(c) (II) > (I) > (IV) > (III) (d) (I) > (III) > (II) > (IV)
(c) RCOO < NH 2 < HC º C < R 30. In the following carbocation, H/CH3 that is most likely to
migrate to the positively charged carbon is [IIT-JEE 2009]
(d) RCOO < HC º C < NH 2 < R H H
1 2 4 5
25. A solution of ( – ) – 1 – chloro –1– phenylethane in toluene H3C — C
+
—3C — C — CH3
racemises slowly in the presence of a small amount of SbCl5,
due to the formation of : [JEE M 2013] HO H CH3
(a) carbanion (b) carbene
(a) CH3 at C-4 (b) H at C-4
(c) carbocation (d) free radical
(c) CH3 at C-2 (d) H at C-2
416 Chemistry
31. Among the following compounds, the most acidic is O
[IIT-JEE 2011] Cl
H3C – Cl Cl Cl
(a) p-nitrophenol (b) p-hydroxybenzoic acid
(c) o-hydroxybenzoic acid (d) p-toluic acid
32. KI in acetone, undergoes SN2 reaction with each of P, Q, R P Q R S
and S. The rates of the reaction vary as (a) P > Q > R > S (b) S > P > R > Q
(JEE Advanced 2013) (c) P > R > Q > S (d) R > P > S > Q
1. In E2 elimination, some compounds follow Hofmann’s rule (a) Carbanion (b) Carbene
which means (c) Free radical (d) Carbocation
(a) the double bond goes to the most substituted position 8. Which of the following is singlet carbene ?
(b) the compound is resistant to elimination ..
(c) no double bond is formed (a) (CH3)3C+ (b) C 2 H 5 C CH 3
(d) the double bond goes mainly towards the least – +
substituted carbon (c) CH3CHCH 3 (d) CH 2 = CH - CH 2
2. SN1 reaction on optically active substrates mainly gives 9. The reaction,
(a) retention in configuration
C 2 H 5 I + KOH ® C 2 H 5 OH + KI is called
(b) inversion in configuration
(c) racemic product (a) hydroxylation substitution
(d) No product (b) electrophilic substitution
3. Which of the following contains only three pairs of electrons? (c) nucleophilic substitution
(a) Carbocation (b) Carbanion (d) dehydroiodination
(c) Free radical (d) None of these 10. An organic compound C5H11X an dehydrohalogenation
4. The addition of HBr on butene -2 in presence of peroxide gives pentene - 2 only. What is halide
follows the (a) CH 3CH 2 CHXCH 2 CH 3
(a) electrophilic addition (b) free radical addition
(c) nucleophilic addition (d) None of these (b) (CH 3 )2CHCHXCH3
5. The stability of 2, 3 - dimethyl-but - 2- ene is more than 2- (c) CH3CH 2 CH 2 CHXCH3
butene. This can be explained in terms of
(a) resonance (b) hyperconjugation (d) CH3CH 2 CH 2 CH 2 CH 2 X
(c) electromeric effect (d) inductive effect 11. Sulphur trioxide is
6. (CH3)4N+ is neither an electrophile, nor a nucleophile because (a) an electrophile (b) a nucleophile
it (c) a homolytic reagent (d) a base
(a) does not have electron pair for donation as well as cannot 12. Intermediate product formed in the acid catalysed
attract electron pair dehydration of n- propyl alcohol is
(b) neither has electron pair available for donation nor can
(a) CH 3 - CH 2 - CH 3 (b) CH 3 - CH = CH 2
accommodate electron since all shells of N are fully
occupied + +
(c) can act as Lewis acid and base (c) CH 3 - C H - CH 3 (d) CH 3 - CH 2 - C H 2
(d) None of these 13. Which of the following is most stable
7. A solution of (+) - 2 - chloro - 2 - phenylethane in toluene
(a) CCl 3CH (OH ) 2 (b) (CH3)2.C.(OH)2
racemises slowly in the presence of small amounts of SbCl5
due to the formation of (c) CH3C.Cl(OH)2 (d) CH3CH(OH)2
General Organic (Basic Concepts) 417
14. Chlorine in vinyl chloride is less reactive because 21. The intermediate during the addition of HCl to propene in
(a) sp2 - hybridised carbon has more acidic character than the presence of peroxide is
· +
sp3 - hybridised carbon (a) CH3CHCH 2 Cl (b) CH 3CHCH 3
· +
(b) C - Cl bond develops partial double bond character (c) CH3CH 2CH 2 (d) CH3CH 2CH 2
(c) of resonance
22. Which of the following acids has the smallest dissociation
(d) All are correct constant ?
15. The compound which gives the most stable carbonium ion (a) CH3CHFCOOH (b) FCH2CH2COOH
on dehydration :
(c) BrCH2CH2COOH (d) CH3CHBrCOOH
CH3 23. One of the equivalent energy resonance structures for
| formate anion is shown below
(a) CH3 - CH - CH 2 OH (b) H 3 C - C - OH
|
: :
| O
A
CH3 CH3
H –C
: :
(c) CH3– CH 2 – CH 2 – CH 2 OH (d) CH3 - CH - CH 2 - CH3 O:
| B
OH Which C – O bond is longer ?
16. Among the following compounds which is most reactive (a) A
towards nitration (b) B
(a) Benzene (b) Nitrobenzene (c) Both are equal
(c) Toluene (d) Chlorobenzene
(d) Structure shown is not correct
17. Example of chlorinolysis is
24. Which of the following resonance structure is lowest in
(a) CH 2 = CH 2 ¾¾
® C 2 H 4 Cl 2 energy?
(b) CCl4 + H 2 O ¾¾
® COCl2 + 2HCl
H O
:
H O : : : :
(c) CHCl3 + 4NaOH | || |
(A) H – C – C (B) H – C – C
¾¾
® HCOONa + 3NaCl + 2H 2 O +
| |
: :
Cl2 O– H O– H
(d) C3 H8 ¾¾¾ ® CCl 4 + C 2 Cl6 + 8HCl HB HB
:
18. During debromination of meso - dibromobutane, the major
:
H O : :
compound formed is : | |
(a) n - butane (b) 1 - butene (C) H – C – C
| +
: :
26. How many degrees of unsaturation are there in benzene 31. Which of the followings is most stable ?
CH 3
CH3
? |
(a) 2 (b) 3 (a) H (b) +
(c) 4 (d) More than 4
Y
27. Which is incorrect for the following pairs ? H Y
Column I Column II CH 3 CH3
| H |
(a) resonance +
(c) Y (d)
+
O O
|| H Y
(b) equilibrium
OH OH
Å 32. The stable resonating form of vinyl methyl ketone is
: O: -
:
(c) equilibrium Å |
(a) CH2 – CH = C –CH3
O OH : O:
|| |
(d) equilibrium Å - ||
(b) C H 2 – C H – C – CH 3
28. What is the mechanistic intermediate in the following reaction
:O: -
:
O O O O |
|| (i ) NaOMe || (c) CH 2 = CH - C - C H 3
Å
¾¾¾¾¾® OEt
OEt (ii ) MeI | :O:
:
(d) Å
:
O O CH 2 - CH - C - C H 3
O– O
|| || | || 33. Hyperconjugation involves
(a) OEt (b) OEt
| (a) s - p conjugation (b) s - p delocalisation
OMe (c) no bond resonance (d) All of these
34. The following reaction
O O
Br
|| + HBr ¾
¾®
(c) OEt (d) None of these
| is an example of
(a) elimination reaction (b) nucleophilic subsitution
29. In the reaction shown below the six membered ring is (c) electrophilic addition (d) nucleophilic addition
generated by shifting which bond 35. Which of the following reactions is elimination reaction?
(a) O + Ph 3 P = CH 2 ¾
||
B ¾®
CD HBr
¾¾¾® Br
A
| CH 2 + Ph 3 PO
||
H
OH
(b) C 2 H 5 Cl + KOH ® C 2 H 5 OH + KCl
(a) A (b) B (c)
(c) C (d) D H
30. When HI is added on to propene in presence of peroxide the |
Alc KOH
:
CH 3
+ (ii)
H3 O (i)
CH - CH 3 ¾¾¾ ® Product.
| D + –
OH NH3 O
CH 3
CH 3
(a) (b) CH = CH 2
CH 3 (iii) ( iv)
(b) +
|| || O
O O
CH 3
Anhy. ZnCl 2 + NaOH
(c) R 3COH ¾¾ ¾ ¾ ¾
¾® Turbidity
Conc. HCl O
(d) All of these
O O–
40. Which of the following reactions cannot proceed by SN1
mechanism ? CH 3 CH 2
:
(a) (b)
CH 2 Cl O
O
| O– O–
(a) (b) Cl CH 3 CH 3
(c) (d)
(c) (d) Cl O O–
Cl
420 Chemistry
EXERCISE 1 EXERCISE 2
1. No. It is 1°. 1. (a) Greater the electronegativity, higher is the -I effect. Thus
2. (i) –NO2 > –CN > –COOH > –F > –I – F > –OR > – NR2
(ii) –C(CH 3 ) 3 > –CH(CH 3 ) 2 > –CH 2 CH 3 > 2. (d) Due to – I effect of the – CHO group, oxygen acquires-d
–CH3 > –D. - charge and the terminal carbon acquires d + charge.
. . d+ d-
4. (i) C6H5CH2 C H 2 < C6H5CHCH3 < C6H5 C (CH3)2 < CH2 = CH – C = O
. H
C6H5 CH –CH=CH2.
(ii) (CH3)3C+ > C6H5CH2+ > CH2 = CHCH2+ > CH3CH2+ 3. (b) 4. (c)
5. (b) Homolytic fission of the C – C bond gives free radicals
(iii) (CH3)2CH– < CH3CH2– < CH3– < CH2 = CH–
in which carbon is sp2- hybridised.
< C6H5CH2– < HC º C–. 6. (b) In carbocations, carbon bearing positive charge is
.. –
8. (i) Nucleophiles : ....I .. , H3N .. always sp2-hybridised
7. (d) Higher the possibility of delocalisation of the positive
(ii) Electrophiles : BeCl2 and NO +2 charge, greater is stability of the species. Thus
.. + + +
(iii) Both : CH3C º N.. and H2C = C .. C6H5 C H2 > (CH3 )3 C+ > (CH3 ) 2 C H > CH3 C H2
(iv) Neither : CH4 and H2. Benzyl carbocation is more stable than tert-butyl due to
10. Stabilised due to nine possible canonical structures. resonance in the former.
8. (b) Structure (b) is a 3º carbocation, while (a) is 2º and (c)
and (d) are 1º carbocations; thus (b) is the most stable.
9. (a) Higher the possibility of delocalisation, greater is its
C +
stability; in C6 H5CHC6 H5 , +ve charge can delocalise
over two benzene rings.
10. (a) Same as above, in Ph3C+, +ve charge can delocalise over
three benzene rings.
Other + +
C canonical 11. (a) I. C6 H5 CH 2 II. C6 H5 CH 2CH 2
structures 1º Benzylic 1º
+ +
16. (b) 17. (a) 18. (b) 19. (b) 20. (d) 21. (b) III. C6 H 5 CHCH3 IV. C6 H 5 C(CH3 )2
2º benzylic 3º benzylic
22. (a) 23. (b) 24. (b)
3º Benzylic (IV) > 2º Benzylic (III) > 1º Benzylic
(I) > 1º (II)
12. (d) –NO 2 group, being strong electron-withdrawing,
disperses the –ve charge, hence stabilizes the concerned
carbanion.
General Organic (Basic Concepts) 421
13. (b) C6H5CH2– > CH3CH2– > (CH3)2 CH– >(CH3)3C– 31. (a) Since the given heat of hydrogenation of the diene is
Dispersal of –ve Intensification of –ve charge due less (230 kJ mol–1) than the heat of hydrogenation of
charge due to to + I effect of CH3 gps. two isolated double bonds, i.e. 126 × 2 = 252 kJ mol–1,
the diene must be conjugated, i.e., it should be 1,3 -
resonance and - I effect
hexadiene, CH2 = CH – CH= CH CH2 CH3.
. 32. (a) 33. (b) 34. (c)
14. (b) C6 H 5CHCH3 is a 2º benzylic free radical, hence
stabilized most due to resonance.
15. (c) 35. (c)
16. (b) Dichlorocarbene, : CCl2 (a carbene) is the electrophile
formed as an intermediate in Reimer-Tiemann reaction. Since first attack is nuclephilic in nature (by CN –) hence
17. (b) 18. (c) the addition is nuclophilic addition.
19. (d) BF3 has electron deficient B, hence it is an electrophile.
H
20. (c) H2 has no lone pair of electrons, hence cannot function |
rearrangement or Tautomersin
36. (c) H 2 C = CH OH ¾¾¾¾¾¾¾¾¾¾¾® H3C- C = O
as a nucleophile. Acetaldehyde
Vinyl alcohol
21. (a) Due to the presence of a lone pair of electrons on N,
CH3C º N: acts as a nucleophile. Further due to greater
electronegativity of N than C, the C atom of – C º N EXERCISE 3
carries a positive charge and hence behaves as an
1. (a) Nucleophilicity increases down the periodic table.
electrophile.
22. (c) I - > Br - > Cl- > F-
23. (c) Nucleophilicity increases with the decrease in 2. (c) Electrophiles have high affinity for electrons. They attack
electronegativity of the central atom. Since at the site where electron-density is highest. Electron
electronegativity follows the order: F > O > N > C; donating groups increases the electron density. The
nucleophilicity of the concerned group will follow the electron donating tendency decreases in the order :
reverse order i.e., –OH > –CH3 > –H > –Cl
Therefore, the correct order of reactivity towards
CH 3 - > NH 2 - > OH - > F -
electrophile is
24. (a) Stronger the acid, weaker the conjugate base. Since acid C6H5OH > C6H5CH3 > C6H6 > C6H5Cl
character follows the order
3. (c) Out of the given compounds the most reactive towards
H 2 O > NH 3 > HC º CH > CH 3 - CH 3 OH
(Acid character), electrophilic attack is . Phenol forms phenoxide
the basic character of their conjugate bases decreases
in the reverse order, i.e., ion which is stable due to resonance i.e. the correct
answer is option (c).
CH 3CH -2 > HC º C - > NH 2 - > OH - (Basic character)
4. (d) The amount of s-character in various hybrid orbitals is
25. (d) as follows.
26. (c) All resonating structures should have same number of sp = 50%, sp2 = 33% and sp3 = 25%
electron pairs. Therefore s character of the C – H bond in acetylene (sp)
27. (a) The two structures involve only movement of electrons is greater than that of the C – H bond in alkene (sp2
and not of atoms or groups, hence these are resonating hybridized) which in turn has greater s character of the C
structures. – H bond than in alkanes. Thus owing to a high s
28. (c) In structure (c), nitrogen has 10 electrons in the valence character of the C – H bond in alkynes, the electrons
shell which is not possible. constituting this bond are more strongly held by the
carbon nucleus with the result the hydrogen present on
29. (b) Only structure (b) has a conjugated system, which is
such a carbon atom can be easily removed as proton.
necessary for resonance.
The acidic nature of three types of C – H bonds follows
30. (c) the following order
422 Chemistry
increases the reactivity of the – Cl towards nucleophiles. Hence, the correct order of nucleophilic substitution
reactions
(CH3)3 – C – X > (CH3)2 – CH2 – X >
General Organic (Basic Concepts) 423
Cl Cl Cl
Cl
Cl – – – –
23. (b) C Cl > C6H5CH2 > (CH3)2 CH > (CH3)3C
> > >
Cl
–ve charge –M effect +I effect of CH3 group
highly dispersed delocalises intensifies the –ve charge
NO2 CH3 OCH3 –ve charge
due to – I effect
12. (c) Decreasing order of deactivating effect of the given
m-directing group is 24. (d) The correct order of basicity is
> NO2 > – CN > – SO3H > – COOH RCOO - < CH º C - < - NH 2 < R -
—NO2 group is most deactivating group due to strong 25. (c) Carbocations are planar hence can be attacked on
– E, – I and – M effects. either side to form racemic mixture.
13. (b) –CH3 group has +I effect, as number of –CH3 group Å
SbCl
5 ® Ph - C H - CH + SbCl- ¾¾
increases, the inductive effect increases. Cl - CH - CH3 ¾¾¾¾ 3 6 ®
Toluene
| (carbocation)
14. (b) The reaction is nucleophilic sustitution reaction
Ph
(-)
O O
15. (b) H–C–O H–C=O
Ph - CH - CH3 + SbCl5
16. (c) Cl– is the best leaving group among the given options. |
Cl
17. (d) Free radicals are electrically neutral, unstable and very (d + l) mixture
reactive on account of the presence of odd electrons.
26. (d) Higher stability of allyl and aryl substituted methyl
18. (b) The stronger the base the more is the nucleophilic
carbocation is due to dispersal of positive charge due
character and vice versa.
to resonance
Basic character
+ +
CH 2 = CH - C H 2 ¬¾® CH 2 - CH = CH 2
CH 3O - > CN - > CH 3 COO - > H 3C - Resonating structures of allyl carbocation
–
SO3
+
Hence the nucleophilic character. CH2 CH2 CH2 CH2
Å Å
O
||
19. (d) R - C - X ; when X is Cl the C–X bond is more polar
Å
and ionic which leaves the compound more reactive for Resonating structures of benzyl carbocation
nucleophilic substitution reaction.
20. (b) The order of stability of free radicals whereas in alkyl carbocations dispersal of positive charge
on different hydrogen atoms is due to hyperconjugation.
• • • •
(C6 H5 )3C > (C6 H5 ) 2CH > (CH3 )3C > (CH3 ) 2CH Hence the correct order of stability will be
Å
The stabilisation of first two is due to resonance and last CH2
two is due to inductive effect. Å Å
21. (a) Nitro group is electron withdrawing group, so it > CH 2 = CH - CH2 > CH3 - CH 2 - CH 2
Allyl, I Propyl, II
deactivates the ring towards electrophilic substitution. Benzyl, III
22. (b) In option (b) the complex formed is with benzene 27. (a) Due to similar charges on adjacent atoms, the
whereas in other cases it is formed with nitrobenzene structure (a) is least stable.
with –NO2 group in different position (o-, m-, p-). The
28. (b) Alkyl groups with at least one hydrogen atom on the
complex formed with nitrobenzene in any position of
a-carbon atom, attached to an unsaturated carbon
–NO2 group is less stable than the complex formed
atom, are able to release electrons in the following
with benzene so the correct answer is (b). The most
way.
stable complex has lowest energy.
424 Chemistry
32. (b)
O
Cl
Compounds : CH3 – Cl : Cl : Cl
Note that the delocalisation involves s and p bond orbitals S P R Q
(or p orbitals in case of free radicals) ; thus it is also known
Relative reactivities 1,00,000 : 200 : 79 : 0.02
as s – p conjugation. This type of electron release due to towards SN 2 reaction
the presence of the system H—C—C = C is known as
hyperconjugation
29. (d) The correct stability order is EXERCISE 4
I > III > II > IV 1. (d) During E2 elimination the double bond goes mainly
toward the least hindered carbon
+ +
O O 2. (c) The intermediate planar carbonium ion has equal chances
I III to be attacked from either side leading to racemisation
+ M effect, 6 hyper- +
conjugative H’s, + M, 3 hyperconjugative
. H’s, one CH 3 group 3. (a) R 3 C has three pairs of electrons in three bonds
2 CH 3 groups
(+ I effect) 4. (b) It is free radical addition (See mechanism of peroxide
effect)
+
+
IV CH3 CH3
II | |
5 hyperconjugative 5 hyperconjugative H’s 5. (b) H 3C - C = C - CH 3 . The more substituted alkenes
H’s 2 R groups one R group
have greater number of hyperconjugated forms. Hence
30. (d) Migrating tendency of hydride is greater than that of
they are more stable
alkyl group. Further migration of hydride from C–2 gives
more stable carbocation (stabilized by +R effect of OH 6. (b) The octet around N is complete, hence it has no
group and +I and hyperconjugative effects of methyl electrophilic character. N has no unshared pair of electrons
group). to act as nucleophile
:
–
O O O O
|| || || ||
- MeI
.. .. +
OEt ¾¾
¾® OEt
14. (c) CH 2 = CH - Cl: « CH 2 - CH = Cl: a double bond is
.. ..
Na
formed between C and Cl. Hence it is less reactive due to
resonance 29. (a) Five membered ring is being converted into six membered
ring. Hence the sixth bond must come from within the
15. (b) (CH 3 ) 3 COH gives tert (CH 3 ) 3 C + . The order of ring.
+ 30. (a) HI does not add on to propene by peroxide effect. Even
stability of carbonium ions is 3° > 2° > 1° > CH 3
in presence of peroxide the addition is according to
16. (c) Due to hyperconjugation toluene is most reactive for Markownikoff’s rule forming intermediate carbonium ion.
electrophilic substitution reaction ( see theory)
17. (d) Chlorinolysis is substitution by chlorine CH 3
18. (d) It gives trans - 2 - butene
+
19. (d) In I the unshared pair of electrons on N always available 31. (d) The structure carring +ve charge nearest to
for protonation in III due to presence of electronegative
O atom the electron density on N is decreased . In II and
IV resonance suppresses the basic character H Y
20. (b) The more the electrons withdrawing groups attached to
electrons repelling -CH 3 group is most stable.
- O atom, the more is the ease of leaving
21. (b) The addition of HCl to propene proceeds by ionic 32. (a) In (a) the separation of charges is maximum and
mechanism and not by free radical mechanism. Hence it electronegative atom oxygen carry –ve charge.
forms intermediate carbonium ion 33. (c) correct. (See text.)
22. (c) BrCH2CH2CO2H is the weakest acid as Br has less -I 34. (c) Addition reactions of alkenes are known as electrophilic
effect compared to F and is also far from -CO2H group. addition reactions.
23. (c) Formate ion 35. (c) The reaction (c) is Hoffmann elimination (see Reaction
Mechanisms.)
O O – 36. (d) The second ring has o/p directing O-atom and first ring
H–C H–C
O – O has m-directing -C - group. o/p directing group activate
||
Hence A, B bonds are of same length. O
24. (a) The order of stability of resonating structures carrying the benzene nucleus.
no charge > carrying minimum charge and each atom
having octet complete. – –
37. (a) ¬
¾® ¬
¾® ¬
¾®
25. (d) In A nitrogen is bivalent, in B and C carbon is pentavalent.
–
26. (c) The degree of unsaturation is equal to number of
hydrogen molecules needed to convert the given –
compound into an alkane. – –
¬
¾® ; ¬
¾®
27. (b) In (b) the pair has resonance. –
O O
|| || MeO- –
28. (b) ¾¾¾¾® –
OEt - MeOH RCH 2 (1°); (2°)
426 Chemistry
-
CH 3 43. (b) CH3C H 2 > HC º C - > CH 3CH 2 O - basic character..
CH 3
-H O CH - CH 3 + The acid character being
¾¾¾
2¾®
+
2° CH 3 CH 3CH 2 OH > HC º CH > CH 3CH 3 . The weaker the
3° H
acid, the stronger the base (conjugate pair)
44. (b) (a),(c) and (d) are resonating structures.
+
CH 3
-H
O
–O
CH 3
CH 3 CH 3
Anhy. ZnCl
39. (c) R 3COH ¾¾ ¾ ¾ ¾
¾2®
R 3C.Cl
Conc. HCl O O
(ii) Functional isomerism : This is due to difference in the (v) Ring chain isomerism : Cyclic/acyclic Isomerism
functional groups
C2H5OH CH 3OCH 3 CH 3 - CH = CH 2
ethyl alcohol dimethyl ether Propene
Cyclopropane
CH3COOH HCOOCH3
Acetic acid Methyl formate
CH 3CH 2 CHO CH 3COCH 3 CH 3 - CH 2 - CH = CH 2
Propionaldehyde Acetone. But -1-ene Cyclobutane
(iii) Position or region isomerism : This is due to difference in
the positions of the same functional groups (vi) Tautomerism (Tauto = Same, Mers = Parts) : It is due to the
presence of a mobile atom in the molecule and the same
OH
| substance behaves in such a way as if it is a mixture of two or
CH 3 – CH 2 – CH 2 OH CH 3 – C H – CH 3 more compounds. Further we have
n- Propyl alcohol Iso - Propyl alcohol
428 Chemistry
(a) Dyad system : When the mobile atom oscillates between
S SH
two adjascent atoms eg || |
H-C º N H–N C H 2 N - C- NH 2 HN = C - NH 2
Thio Urea Enolic form
Hydrocyanic acidIso-hydrocyanic acid
(b) Triad system : When the mobile atom oscillates between
atoms one position ahead eg. NO O= N – OH
HO
O OH
|| | p-Nitrosophenol Keto form
CH 3 - C - CH 2 .COOC 2 H 5 CH3 - C = CH.COOC2 H5
Types of stereo isomerism :
93% Keto form 7% Enol form
(I) Optical Isomerism
Aceto acetic ester Aceto acetic ester
(II) Geometrical Isomerism and
Aceto acetic ester reacts with HCN, NH 2 OH,
(III) Conformational Isomerism
C6H5NHNH2 showing the properties of a ketone and
(I) Optical isomerism : The compounds having the same
also reacts with CH 3COCl, PCl5, Na showing the
molecular formula, the same structural formula but different
properties of OH group.
behaviour towards the plane polarised light are known as
It gives colour change with 1% FeCl3 a characteristic Optical Isomers.
Terminology used in optical isomerism.
æ OH ö
test of ç | ÷ (enol group) • Plane polarised light : Light having vibrations restricted
çè - C| = C| -÷ø to one plane only is called plane polarised light.
• Optically active compounds : The compounds capable
There exists an equilibrium between the two forms which of rotating the plane of polarisation of plane polarised
is dynamic in nature. light are known as optically active compounds.
• Optical activity : It is the ability of a substance to rotate
O OH the plane of polarisation of plane polarised light.
|| |
CH 3 - C - CH 3 CH 3 - C = CH 2 • Dextrorotatory compounds (d or +) : The compounds
which rotate the plane of polarisation of plane polarised
Acetone 99.5% Acetone (enol form) 0.5% light towards the right hand side are called dextro rotatory.
• Laevo rotatory compounds (l or –) : The compounds
O OH
|| | which rotate the plane of polarisation of plane polarised
CH3 - C- CH2 .COCH3 CH 3 - C = CH.CO CH 3 light towards the left hand side are called laevo rotatory.
• Specific rotation : The rotatory power of optically active
Acetyl acetone (keto form) Acetyl acetone (enol form)
compounds is compared in terms of specific rotation.
Specific rotation
OH O
Observed rotation in degrees
H =
Length of tube in decimeter ´ Concentration of solution in g/ml
H
q
[a]Dt =
Phenol l´C
Keto form of Phenol
• D corresponds to D line of Sodium light (l = 5893Å)
Triad system containing nitrogen • t corresponds to temperature
• Rotation is observed and measured with a polarimeter
O O–H
CH 3 - CH 2 - N CH3 – CH = N The specific rotation varies with light l and temperature.
O O • Optical activity due to crystalline strcuture : Some
Nitro ethane Aci Nitro ethane compounds are optically active only in crystalline form.
It dissolves in NaOH on account of aci form. Tautomeric They loss their optical activity when dissolved or fused
form which is less stable is called labile form. e.g. Quartz.
• Optical activity due to molecular structure : Some
O OH compounds are optically active in solid as well as in
|| |
H 2 N - C - NH 2 HN = C - NH 2 solution e.g. tartaric acid. Hence their optical activity is
Urea ( Keto form ) Enolic form due to their molecular structure which remains the same
in solid form and in solution.
Isomerism 429
• Asymmetric carbon atom : A carbon atom attached to
four different atoms and groups is called asymmetric COOH COOH
*
carbon atom. e.g. CH C . H OH HO H
3 H OH COOH
• Chirality : If the mirror image of the molecule is different
from the molecule it is said to be a chiral molecule. In CH3 CH3
such case if one configuration of the molecule is placed Dextrorotatory (d or +) Laevorotatory (lor –)
above its mirror image configuration, the similar atoms Lactic acid Lactic acid
and groups do not fall over each other and the (Source meat extract) (Obtained during
fermentation of
configurations are said to be nonsuperimposable.
Sucrose)
If object and mirror image configurations are superimposable
Racemic Lactic acid : It is an equimolar mixture of
(similar atoms and groups fall over each other) the molecule
d- and l- forms. It is optically inactive due to external
is said to be "achiral”.
Chirality is the necessary condition for a compound to be compensation of optical rotation. It is present in sour milk. It
optically active. can be resolved.
Enantiomers : Pairs of nonsuperimposable mirror images Examples of optically active compounds containing one
are called enantiomers. asymmetric C-atom.
Fischer Projections : Fischer projections are drawn with a
COOH COOH C2H5
cross, with chiral atom at the centre of the cross.
H OH H OH H CH2OH
A A A
D CH2 COOH C6H5 CH3
B C B C Malic acid Mandelic acid Amyl alcohol
B C D
D Number of optically active forms is given by 2n where n is
The horizontal line represents wedges (bonds) coming out number of asymmetric C-atoms different in nature.
of the plane of the paper. The vertical line represents dashed Resolution : The separation of d- and l- forms present in a
lines (bonds) in the plane of the paper (Bow-tie convention). racemic mixture is known as resolution.
The carbon chain is drawn along the vertical line of the Conditions for Chirality : Absence of (I) Plane of symmetry
projection with most highly oxidised carbon substituent at (II) Centre of symmetry and (III) Alternating axis of
the top. Fischer projections are very useful to determine symmetry.
chirality of a compound. Plane of Symmetry : A plane which divides the molecule in
Lebel and Van't Hoff’s theory about optical isomerism :
two portions in such a way that one portion is the mirror
The tetrahedral structure of a compound containing
asymmetric carbon atom (*Cabed) gives two configurations image of the other eg. Tartaric acid.
related to each other as object and its mirror image but are COOH
non-superimposable. H OH
Plane of symmetry
H OH
d d
COOH
c c
e b b e Meso tartaric acid
a a It is optically inactive due to internal compensation of optical
d or + l or – rotation. It can not be resolved.
Enantiomers or Enantiomorphs
Centre of Symmetry : It is a point from which lines, when
drawn on one side to meet the groups and produced to an
d d
equal distance on the other side of the point will meet the
same original groups.
e b b e
H NH CO CH3
a a
d or + l or –
(I) (II) C C
Enantiomers or Enantiomorphs CO NH
CH3 H
* Trans:1,4-dimethyl diketo piperazino (Inactive)
Optical isomerism of Lactic acid : CH 3 CHOH.COOH
Contains centre of symmetry
430 Chemistry
erazino (Inactive) cis: 1,4-dimethyldiketo piperazino (Active) • l-tartaric acid is prepared by resolving racemic acid. Its
No centre of symmetry mpt is 170°C.
Alternating axis of symmetry : If a molecule is rotated • Meso-tartaric acid is obtained by oxidation of maleic
acid, heating d-tartaric acid with water at 170°C. Its mpt
360° is 143°C.
through an angle of about the axis and then reflected
n
• Racemic tartaric acid (dl or ±). It is obtained from Argol.
in a plane perpendicular to the axis, gives back the original Its mpt is 206°C. It is an equimolar mixture of d and l
molecule it is said to possess the n fold alternating axis of forms.
symmetry.
• Racemic tartaric acid can be resolved into d and l forms.
90° It is a mixture of two compounds.
CH3 H H CH3
• Meso-tartaric acid cannot be resolved. It is a single
2 1 1 4 compound.
H CH3 CH3 H
Optical Isomerism of the compound containing two dissimilar
H H3C H3C H C-atoms : Example a,b-dibromo cininamic acid and 2,3-
3 4 2 3 dihydroxy butanoic acid.
CH3 H H CH3
1,2,3,4-tetramethyl cyclo butane Mirror
CH3 H
H CH3
H H3C
CH3 H
H OH HO H
H OH HO H
COOH COOH
Meso tartaric acid
(I) (II)
l
COOH COOH COOH
Let optical rotation due to chiral centre C3 and C2 be A and B
and further A > B. In the above case I-II and III-IV are pairs of
H OH HO H enantiomers where as I-III; I-IV, II-III, and II-IV are pairs of
HO H H OH diastereo-isomers.
Diastereo Isomers : Stereo isomers which are not mirror
COOH COOH COOH images of each other are called diastereo isomers. They have
different physical properties (mpt, bpt, solubility) and are
d-tartaric acid l-tartaric acid
often easy to separate by distillation, recrystallisation,
(III) (IV)
chromatography etc.)
Isomerism 431
The same compound pair are called the meso diastereoisomer (II) Substituted allenes : Unsymmetrically substituted allene
(I-II in case of Tartaric acid see above). Most diastereo- (CH2 = C = CH2) are optically active.
isomers are either geometric isomers or compounds with two a x a a
or more chiral atoms. C=C=C C=C=C
b y b b
Enantiomers : Enantiomers are non superimposable mirror (I) (II)
image isomers. They have identical physical properties (bpt, active Inactive
mpt, density etc.) except for their rotation of plane polarised
a x a a a x a b
light. They are much more difficult to separate. In nature C=C=C C=C=C
very often only one enantiomer
b y
is produced. Living organisms
b b b x b a
(I)
are one of the best sources of optically active compounds (III) (IV)
Inactive Active
(plants, enzymes, animals, cells etc.).
Enantiomeric excess (Optical Purity) : It is given by
Asymmetric synthesis : The synthesis of an optically active Optical purity = O.P.
compound from optically inactive compound under the
Observed rotation d -l
influence of an optically active compound without resolution = ´ 100% Or O.P. = ´ 100%
Pure enantiomer rotation d+l
is known as asymmetric synthesis.
where d and l are ratio of two forms
Geometrical isomerism : Alkenes with double bonds cannot
ROH
CH 3COCOOH ¾¾¾¾¾¾® CH 3COCOOR ¾¾¾
2H undergo free rotation
® CH 3CHOH.COOR ¾¾¾
H Oand can have different geometrical shapes
® CH CHOH.COOH
Pyruvic acid Optically active alcohol Optically active ester with two
Active lac different groups on3 each end of the double bond. e.g.
molecules C2a2b2, C2a2bd or C2abde.
2H H O a a a b a a
OCOOR ¾¾¾
® CH 3CHOH.COOR ¾¾¾
2 ® CH CHOH.COOH
3
y active ester Active lactic ester l -lactic acid
C=C C=C ; C=C
b b b a b d
(I) (II) (III)
Racemisation : The transformation of an optically active
a
isomer under the influence a light
of heat, a or some breagents
a a a d a d a e
into an inactive isomer is called racemisation. C=C ; C=C C=C
b b b a b d b a b e b d
Walden inversion / Optical (I)inversion : The conversion of (III) (IV) (V) (VI)
an enantiomer into another is called Walden inversion. I-II, III-IV and V-VI are pairs of geometrical isomers.
Nomenclature :
CH2 COOH CH2 COOH Cis Isomer : Contains the similar atoms or groups on the same
PCl5 side.
HO H H Cl Trans Isomer : Contains the similar atoms or groups on the
KOH
COOH COOH opposite side.
Examples :
d-Malic acid l-Chlorosuccinic acid CH3 CH3 CH3 H
C=C C=C
H H H CH3
CH2COOH
Cis-But-2-ene Trans But-2-ene
AgOH
H OH
H–C–COOH H–C–COOH
COOH
H–C–COOH HOOC–C–H
-Chlorosuccinic acid l-Malic acid
Cis-But-2-ene Trans But-2-ene Maleic acid Fumaric acid
Geometrical Isomerism of Oximes
Optical isomerism due to restricted rotation : Aldoximes :
(I) Diphenyls :
R H2NOH R
C=O C = NOH
H –H2O H
SO3H SO3H
H H
Aldehyde Aldoxime
R R H R H
C = NOH C C
SO3H SO3H H
H H
N N
OH HO
Enantiomers of diphenyl disulphonic acid
Syn Aldoxime Anti Aldoxime
432 Chemistry
Ketoximes : (III) By Oxidation :
COOH
R H2NOH R H COOH
C=O C = NOH C H OH
–H2O Dil. aq. KMnO4
R' R'
Unsymmetrical Ketone Ketoxime C or OsO4
H OH
H COOH
Maleic acid COOH
R R R' R R' meso-Tartaric acid
C = NOH H COOH
C C C Dil. aq. KMnO4
N N C or OsO4
OH HO HOOC H
Syn (R', OH) Anti (R', OH) Fumaric acid
COOH
COOH
Geometrical isomerism of azo compounds : Example azobenzene
COOH
H OH HO H
+
C6H5 HO H H OH
N=N HOOCN = N
C6H5 C6H5 C6H5 COOH COOH
d-Tartaric acid l-Tartaric acid
Syn-azo benzene Anti-azo benzene
Hence Maleic must be cis and fumaric must be trans.
E,Z system of Nomenclature for Geometrical Isomers:
Geometrical isomerism in cyclo alkanes : Cyclo alkanes also
If two high-priority groups are on the same side, the configuration
cannot undergo free rotation.
is Z (German, Zus ammen = togehter). If they are on opposite side,
the configuration is E (German; entgegen = opposite)
H (2S, 3R)
(S) enantiomer
b - hydroxybutyric aldehyde
434 Chemistry
(i) Acids are chain isomers 4 Write all possible isomers of each formula and report what
(ii) Acids,esters and aldol are functional isomers type of isomerism exists in each
(iii) Aldol contains asymmetric C-atom and can exist in (a) C4H11N (b) C4H8
two optically active forms and one racemic form Sol.
NH 2
OH |
|
CH 3 - CH 2 - CH 2 - CH 2 - NH 2 CH3 - CH 2 - C H - CH3
CH 3 - C*- CH 2 .CHO
| 1- amino butane (I) 2 - amino butane (II)
H
CH 3
2. Write the possible isomers of C 4 H 8 O and type of CH 3 |
CH 3 - C - CH3
isomerism | |
CH 3 - C H - CH 2 - NH 2 NH 2
CH 3 CH 3
Sol. C = O n - C3H 7 | 1 - amino 2- methyl propane (III) 2- amino 2- methyl propane (IV)
C2 H5 C=O CH 3 - CH - CHO
H CH3
|
(I) (II) (III)
CH 3 - CH 2 - CH 2 - NH - CH 3 CH3 - CH - NH - CH3
Ethyl methyl Ketone n -butyraldehyde Isobutyraldehyde
Methyl propylamine (V) methyl isopropylamine (VI)
Functional isomers I and II, I and III
Chain isomers II and III CH3
3. Write the possible isomers of C3 H 6 O 3 and type of isom- |
C2H5 - NH - C2 H5 CH3 - N - C 2 H5
erism existing between them
diethyl amine (VII) ethyl dimethylamine (VIII)
Sol. (HCHO) 3 CH 3CHOHCOOH CH 2 OH.CH 2 COOH Position isomers I and II, III and IV
(I) (II) (III) Chain isomers I and III, I and IV
Functional isomers 1°, 2° and 3° amines are functional iso-
Meta formaldehyde a - hydroxy b- hydroxy mers
propionic acid propionic acid Metamers :- VI, V, VII
Functional isomers I and II, I and III
C 4H8 :
Position isomers II and III
Ring chain isomers I and II, 1 and III (i) CH 3CH 2 .CH = CH 2 but -1-ene
(ii) CH 3CH = CH CH 3 but - 2 - ene
CH 2
O O CH 3 H CH 3 CH 3
C=C C= C
CH 2 CH 2 H CH 3 H H
O trans (A) cis (B)
CH 3
Trioxane (meta formaldehyde) (iii) C = CH 2 2 - methyl propene
Stereoisomers :- II will show optical isomerism due to the CH 3
presence of an asymmetric C- atom.
(iv) Cyclobutane
COOH COOH
CH 3
H OH HO H
(v) methyl cyclopropane
CH 3 CH 3 Chain isomers I and III, II and III
Position isomers I and II
Ring chain isomers I and IV, II and IV
It will have the one racemic formed (dl, ± ) Geometrical isomers A and B forms of II
Isomerism 435
CH 3
CH - O - CH 3
CH 3
N -methyl aniline Benzylamine
methyl iso-propyl ether
6. Write possible isomers of C8 H 8 O 2
9. Write Keto-enol tautomers of phenol C 6 H 5 OH
CH 3 CH 3 CH 3 O
OH
COOH H
Sol. Sol. H
COOH
COOH enol form Keto form
o- Toluic acid m - Toluic acid p - Toluic acid 10. Write possible isomers of C 4 H 4 O 4 and type of isomerism
exhibited by them
COOCH 3 OCOCH 3 CH 2COOH
Sol. H - C - COOH HOOC - C - H
|| ||
H - C - COOH H - C - COOH
Maleic acid Fumaric acid
methylbenzoate phenyl acetate phenylacetic acid
These are Geometrical isomers.
436 Chemistry
45. Which one of the following compounds is not optically (a) A and B are identical
active ? (b) A and B are diastereomers
(a) CH3CH2CH(CH3)CH2Cl (b) CH3CH2CH(CH3)2 (c) A and C are enantiomers
(c) CH3–CHOH–COOH (d) CH3–CHCl–CH2Br (d) A and B are enantiomers
46. An optically active compound is 56. How many optically active stereoisomers are possible for
(a) 1-bromobutane butane-2, 3- diol ?
(b) b-bromobutyric acid (a) 1 (b) 2
(c) 2-bromo-2-methylpropane (c) 3 (d) 4
(d) 1-bromo -2-methylpropane 57. The number of possible enantiomeric pairs that can be
produced during monochlorination of 2-methylbutane is
47. Which of the following is optically active ?
(a) 2 (b) 3
(a) butane (b) 4-methylheptane
(c) 4 (d) 1
(c) 3-methylheptane (d) 2-methylpentane
58. The number of enantiomers of the compound
48. Which of the following compounds exhibits stereoisomerism ? CH3CHBrCHBrCOOH is
(a) 2-methylbutene-1 (b) 3-methylbutyne-1 (a) 0 (b) 1
(c) 3-methylbutanoic acid (d) 2-methylbutanoic acid (c) 3 (d) 4
440 Chemistry
59. Which of the following has a chiral carbon? 67. Which one of the following is the stablest structure of
(a) 2,3-dimethylpentane cyclohexatriene ?
(b) CH3–CH2–CH2–CHO (a) Chair form (b) Boat form
(c) (CH3)3CCH2CH2CH3 (c) Half chair form (d) Planar form
(d) (CH3)2CHCH2CH2CH2CH3 68. The isomers which can be converted into another form by
rotation of the molecule around single bond are
60. Me (a) geometrical isomers (b) conformers
Me H H (c) enantiomers (d) diastereomers
69. The most stable conformation of n-butane is
(a) skew-boat (b) eclipsed
Me H
(c) gauche (d) staggered -anti
Hydrogenation of the above compound in the presence of 70. In the following structures, which two forms are staggered
poisoned palladium catalyst gives conformations of ethane ?
(a) optically active compound
(b) an optically inactive compound H
H
H H H
(c) a racemic mixture H
H
(d) a diastereomeric mixture H
H
H H H
61. HO– H H
– CH = CH – CH – COOH will show.. H H
H H
OH (1) (2) (3)
(a) geometrical isomerism
(b) optical isomerism
H
(c) geometrical and optical isomerism H
(d) neither geometrical nor optical isomerism H
H H H
62. Number of stereoisomers of the compound, 2-chloro-4-
(4)
methylhex-2-ene is/are
(a) 1 (b) 2 (a) 1 and 4 (b) 2 and 3
(c) 4 (d) 6 (c) 1 and 2 (d) 1 and 3
63. The number of stereoisomers for pent-3-en-2-ol is 71. Which of the following is the most stable form of
(a) 2 (b) 4 cyclohexane ?
(c) 3 (d) 5 (a) boat (b) chair
H (c) twist boat (d) half chair
|
64. C6 H 5 CHO + HCN ¾¾
® C6 H 5 - C - CN 72. In the boat conformation of cyclohexane, the most
| destabilizing interaction is
OH
The product would be (a) eclipsing (b) 1, 3-diaxial
(a) a racemate (c) 1, 3-diequatorial (d) flagpole -flagpole
(b) optically active 73. The stability of the compounds
(c) a meso compound
(d) a mixture of diastereomers
65. The process of separation of a racemic modification into d -
and l- enantiomers is called
(i) (ii) (iii) (iv)
(a) resolution (b) dehydration
(c) revolution (d) dehydrohalogenation (a) (iv) > (iii) > (i) > (ii) (b) (i) > (iii) > (ii) > (iv)
66. An important chemical method to resolve a racemic mixture (c) (ii) > (iii) > (i) > (iv) (d) (iv) > (i) > (iii) > (ii)
makes use of the formation of 74. The Baeyer’s angle strain is expected to be maximum in
(a) a meso compound (b) enantiomers
(a) cyclodecane (b) cyclopentane
(c) diastereomers (d) racemate
(c) cyclohexane (d) cyclooctane
Isomerism 441
1. CH3 – CHCl – CH2 – CH3 has a chiral centre. which one of the 7. Which of the following does not show geometrical
following represents its R-configuration? [CBSE-PMT 2007] isomerism? [AIEEE 2002]
(a) 1,2-dichloro-1-pentene (b) 1,3-dichloro-2-pentene
C 2 H5 C2 H5 (c) 1,1-dichloro-1-pentene (d) 1,4-dichloro-2-pentene
| |
(a) H - C - CH3 (b) Cl - C - CH3 8. Racemic mixture is formed by mixing two [AIEEE 2002]
| | (a) isomeric compounds (b) chiral compounds
Cl H (c) meso compounds (d) optical isomers.
9. Among the following four structures I to IV, [AIEEE 2003]
CH3 C2 H5 O CH3
| | CH3 || |
|
(c) H - C - Cl (d) H 3C - C - Cl C 2 H 5 - CH - C3 H 7 , CH 3 - C - C H - C 2 H 5 ,
| |
C 2 H5 ( I) ( II )
H
<
O O |
|| || (a) CH3 - C -
CH3 - C- CH 2 - C- CH 3 |
C2H5
II
CH3
OH O |
| || (b) CH3 - CH 2 - CH - CH3
CH 3 - C = CH - C - CH 3
III (c) CH 3 - CH 2 - CH 2 - CH 3
(d) CH 3 - CH 2 - C º CH
(a) III > II > I (b) II > I > III
(c) II > III > I (d) I > II > III 11. Which of the following compounds is not chiral?
5. The type of isomerism present in nitropentamine chromium [AIEEE 2004]
(III) chloride is [AIEEE 2002] (a) 1-chloro-2-methyl pentane
(a) linkage (b) ionization (b) 2-chloropentane
(c) polymerisation. (d) optical (c) 1-chloropentane
6. A similarity between optical and geometrical isomerism is (d) 3-chloro-2-methyl pentane
that [AIEEE 2002] 12. Increasing order of stability among the three main
(a) each forms equal number of isomers for a given conformations (i.e. Eclipse, Anti, Gauche) of 2-fluoroethanol
compound is [AIEEE 2006]
(b) if in a compound one is present then so is the other
(c) both are included in stereoisomerism (a) eclipse, anti, gauche (b) anti, gauche, eclipse
(d) they have no similarity. (c) eclipse, gauche, anti (d) gauche, eclipse, anti
442 Chemistry
13. Which of the following molecules is expected to rotate the (a) S, S (b) R, R (b) R, S (c) S, R
plane of plane-polarised light? [AIEEE 2007] (a) 3-methyl-2-pentene (b) 4-methyl-1-pentene
COOH CHO (c) 3-methyl-1-pentene (d) 2-methyl-2-pentene
16. The alkene that exhibits geometrical isomerism is :
(a) H2N H (b) HO H
[AIEEE 2009]
H (a) 2- methyl propene (b) 2-butene
CH2OH
(c) 2- methyl -2- butene (d) propene
H2N NH2
17. The number of stereoisomers possible for a compound of the
(c) (d) H H molecular formula
Ph Ph CH3 – CH = CH – CH(OH) – Me is: [AIEEE 2009]
SH
14. Which one of the following conformations of cyclohexane is (b) 2 (c) 4 (d) 6 (d) 3
chiral? [AIEEE 2007] 18. Out of the following, the alkene that exhibits optical isomerism
(a) Boat (b) Twist boat is [AIEEE 2010]
(c) Rigid (d) Chair. (a) 3-methyl-2-pentene (b) 4-methyl-1-pentene
15. The absolute configuration of [AIEEE 2008] (c) 3-methyl-1-pentene (d) 2-methyl-2-pentene
HO2C CO2H 19. The number of stereoisomers obtained by bromination of
trans-2-butene is [IIT-JEE 2007]
OH
(a) 1 (b) 2 (c) 3 (d) 4
HO H H
1. The molecular formula of a saturated compound is 5. The maximum number of stereoisomers possible for
C 2 H 4 Br2 . This formula permits the existence of 3 - hydroxy - 2 -methyl butanoic acid is
(a) 1 (b) 2
(a) functional isomers (b) optical isomers
(c) positional isomers (d) cis-trans isomers (c) 3 (d) 4
2. The production of an optically active compound from a 6. The optically active tartaric acid is named as D - (+) - tartaric
symmetric molecule without resolution is termed acid because it has a positive
(a) Walden inversion (b) Partial racemisation (a) optical rotation and is drived from D - glucose
(c) Asymmetric synthesis (d) Partial resolution (b) pH in organic solvent
3. Which of the following is optically active (c) optical rotation and is derived from D - (+) -
(a) n - propanol (b) 2 - chlorobutane glyceraldehyde
(c) n - butanol (d) 3 - hydroxy pentane (d) optical rotation when substituted by deuterium
4. Geometrical isomerism is not shown by 7. The enol form of acetone after treatment with D2O gives:
CH3 O
OD
| | ||
(a) CH 3CH 2 C = C CH 2 CH 3 (a) CH 3 - C = CH 2 (b) CH 3 - C - CD 3
|
CH3
OH OD
| |
(b) C 2 H 5 - C = C - CH 2 I (c) CH 2 = C - CH 2 D (d) CD 2= C - CD 3
| |
H H 8. Two geometrical isomers are given by the following
compound
(c) CH 2 = C(Cl)CH3
(a) ethylidene bromide (b) acetylene tetrachloride
(d) CH 3 - CH = CH - CH = CH 2 (c) acetylene tetrabromide (d) acetylene dibromide
Isomerism 443
9. Only two isomeric monochloro derivatives are possible for : 16. How many stereoisomers are possible for the molecule?
(a) n - butane
(b) 2, 4 - dimethylpentane H CH 3
(c) benzene C=C OH
H C=C
(d) 2 - methylbutane
10. Keto-enol tautomerism is observed in CH 3
HO–C
O O
|| ||
(a) C 6 H 5 - C - H (b) C 6 H 5 - C - CH 3
O
(a) 2 (b) 4
(c) C 6 H 5 - C - C 6 H 5 (d) (d) None of these
|| (c) 6 (d) 8
O 17. The configuration of the compound
11. Ethoxy ethane and methoxy propane are
Cl
(a) geometrical isomers (b) optical isomers
(c) functional group isomers (d) metamers
12. The number of structural and configurational isomers of a (a) E (b) Z
bromo compound, C5H9Br, formed by the addition of HBr to (c) Both (a) and (b) (d) Neither (a) nor (b)
2 - pentyne respectively are 18. The alcohol product(s) of the reduction of 2-methyl-3-
(a) 1 and 2 (b) 2 and 4 pentanone with LiAlH4 is (are)
(c) 4 and 2 (d) 2 and 1 O
13. The structure, (i ) LiAlH diethyl ether
¾¾ ¾ ¾4¾ ¾ ¾ ¾¾®
CH3 H (ii) H 2O
C=C H
CH3 C (a) a single enantiomer (b) racemic mixture
COOH shows :
CH3 (c) two diastereoisomers (d) two structural isomers
19. How many stereoisomers of phenyl propylene oxide are there ?
(a) geometrical isomerism
H O H
(b) optical isomerism
(c) geometrical and optical isomerism
(d) tautomerism CH 3
14. Which of the alkenes shown below are member of a pair of E
- Z isomers ? (a) 1 (b) 2
H Cl (c) 4 (d) None of these
20. What is the R and S configuration for each stereogenic centre
(A) Cl (B) Cl in this sugar from top to bottom ?
O H
H H
H Cl H OH
HO H
(C) (D) H OH
H H CH 2 OH
H Br (a) R, R, S (b) R, S, S
(a) A and C only (b) B and C only (c) R, S, R (d) S, S, R
(c) A and D only (d) None of these 21. How many isomers have the compound bromomethyl
15. The correct priorities for the substituents shown below, cyclopentane (ignoring chirality) ?
according to the E-Z sequence rule is (a) 4 (b) 5
I. – CN II. – CBr (CH 3 ) 2 (c) 6 (d) 7
O 22. The structure shown below has the configuration
|| CH 2 CH 3
III. – COOH IV. – CH 2 - C - OCH3
|
O
C C(CH 3 ) 3
||
V. – C - H CH(CH 3 ) 2
(a) II, III, V, I, IV (b) V, II, I, IV, III (a) R (b) S
(c) III, IV, I, II, V (d) II, V, I, IV, III (c) Both (a) and (b) (d) Neither (a) nor (b)
444 Chemistry
23. The structure of allene is 29. Which of the following optically active compounds racemizes
CH 2 = C = CH 2 in dil. KOH/ CH 3OH solution ?
(a) staggered (b) planar O O
(c) eclipsed (d) None of these H CH 3
(a) (b)
24. The compound showing geometrical isomerism
CH 3 C6 H5
Br
(a) C 6 H 5 CH = NOH (b)
Br O
O
H 3C C6 H 5
(c) (d) All of these (c) (d)
H CH 3
25. Which of the following will show tautomerism ?
30. How many stereoisomeric aldohexoses are there ?
O (a) four (b) eight
(c) sixteen (d) eighteen
31. What is the relationship between open chain forms of D-
(a) glucose and D-altrose ?
(a) enantiomers
O (b) constitutional isomers
(c) diastereomers
(d) different conformations of the same compound
(b) O = = =O 32. Which of the following compounds will not have diastereo
isomers ?
O (a) COOH (CHOH ) 2 COOH
(b) CH 3 CHOH.COOH
(c)
(c) CH 2 OH (CHOH ) 4 CHO
O (d) CH 2 OH (CHOH ) 4 CH 2 OH
33. The correct number of chiral centres in
O C 2 H5 C 2 H 5
(d)
(a) 1 (b) 3
O (c) 4 (d) 2
34. Give the correct relationship among the followings :
26. Identify the Keto form of the following enol
CHO CH 2 OH CHO
H OH H OH H OH
OH H OH H OH HO H
(a) 1-penten-3-one (b) (E)-3-penten-2-one CH 2 OH CH 2 OH CH 2 OH
(c) 2-pentanone (d) (E)-3-pentanal
(A) (B) (C)
27. What is the relationship between keto and enol tautomers? (a) A and B are identical
(a) Resonance forms (b) A and B are diastereomers
(b) Constitutional isomers (c) A and C are diastereo isomers
(c) Stereoisomers (d) A and C are enantiomers
(d) Different conformations of the same compound 35. The number of metamers given by the compound
28. Which of the following has the highest percentage of enol in
a Keto-enol equilibrium ? – O – CH 2 .CH 3
(a) Hexanal (b) 2-hexanone (a) 3 (b) 4
(c) 2, 4-hexanedione (d) 2, 5-hexanedione (c) 5 (d) 6
Isomerism 445
36. The number of asymmetric C-atom created and number of 39. The stereo isomers formed when cis-2-butene is reacted with
possible stereoisomers when benzil (Ph.CO.CO.Ph) is reduced Br2 .
with LiAl H 4 . (a) meso-2, 3-dibromo butane
(a) 2, 3 (b) 2, 2 (b) racemic 2, 3-dibromo butane
(c) pair of diastereomers
(c) 2, 4 (d) 3, 2
(d) cannot be predicted
37. An optically active compound (A) is treated with NaI/acetone 40. Which of the followings is Z-isomer ?
(B) is obtained
Cl CH 3
(a) C=C
CH 3 CH 3 FF C 2 H5
NaI
H I ¾¾ ¾
¾® I H FF Br
acetone (b) C=C
C2 H5 C2 H 5 Cl H
O
(A) (B)
What is true about (B) ? CHO C–H
(c)
(a) optically active C=C
H H
(b) optically inactive and racemic form
CH 3OOC CH 3
(c) optically inactive
(d) C=C
(d) None of these H OH
38. The following compounds A, B, C have R or S configurations 41. The two compounds given below are
5. (c) C5H10 has 1º degree of unsaturation since the isomers 9. (b) 2, 2, 4, 4 - Tetramethylhexane has 10 carbon atoms, only
are acyclic, all of these are alkenes. For writing the 4-isopropylheptane has also 10 carbon atoms so these
isomers, first introduce the double bond at different two are isomers.
possible positions, and then consider the possibility of 10. (c) Convert these Newmann projections into open chain
branching in the alkyl group. structures.
CH3CH2CH2CH =CH2 CH3CH2CH=CHCH3 CH3 CH3
1-pentene (i) 2- pentene, (cis,- trans) (ii), (iii) H Cl H H
H H H H
CH 3 CH3
| | CH3 CH2Cl
CH 3- C H - CH = CH 2 CH 3CH 2 C = CH 2 Both structures have same molecular formula C4H9Cl,
thus these are isomers. However, the two have different
3-methyl-1-butene, (iv) 2-methyl-1-butene, (v)
groups, viz CH 3 and CH 2Cl, so these are neither
CH 3 enantiomers nor diastereomers. Hence these are
| structural isomers.
CH 3 - C = CHCH 3
11. (b) 12. (b) 13. (a) 14. (a) 15. (c)
2-methyl-2-butene, (vi) 16. (d) 17. (a) 18. (b) 19. (d)
Isomerism 447
20. (d) Introduce - NH2 at various possible positions to get
C6H5
different isomers which is possible only, on C1 and C2. |
Now observe isomerism in the alkyl part C 6 H 5 CH 2 CH = CHCH 3 CH 2 = CH CHCH3
(C4H9–) of the amine which is three
1-phenyl-2-butene 3-phenyl-1-butene
NH 2
| C6 H 5
CH3CH2CH2CH2NH2 CH 3CH 2 C HCH 3 |
CH 2= C CH 2 CH 3 (C6H5)2C=CHCH3
(CH3)2CHCH2NH2 (CH3)3CNH2
2-phenyl-1-butene 1, 1- diphenyl -1-propene
21. (d) Molecular formula C7H8O points out the presence of
one benzene ring (relatively less number of H atoms); so Note that only in first structure both of the doubly
it can be C6H5CH2OH and its other isomers. bonded carbon atoms have different groups.
C6H5CH2OH C6H5OCH3 OH.C6H4.CH3 31. (b) 32. (d) 33. (b) 34. (c)
Benzylalcohol (i) Anisole (ii) o -, m-, p- Cresols, (iii), 35. (d) The given structure has three double bonds whose each
(iv) and (v) carbon atom is differently substituted hence number of
22. (c) Alcohol may be 1º, 2º and 3º; further analyse the geometrical isomers will be 2n = 23’ = 8, where n is the
possibility of isomerism in each type of alcohol number of double bonds whose each carbon atom is
differently substituted.
CH 3 36. (d) Consider one doubly bonded carbon atom first, attach
|
CH3CH2CH2CH2OH CH 3CH 2 C HO H any one halogen atom (say F) on this C on one bond,
and then attach the three remaining halogen atoms, of
1-butanol, 1º 2-methylpropanol, 1 º course one by one, on the other bond.
OH CH3 F F F
| | C=C ; C=C ; C=C
CH 3CH 2 C HCH 3 CH 3- C - OH Cl Br I
|
CH3 Now attach the remaining two halogen atoms in each of
the above structures, for which there are two possibilities
2-butanol, 2º 2-methyl-2-propanol, 3º for every structure; so on the whole there will be 6
23. (c) There are four isomeric alcohols (mentioned in geometrical isomers.
the above question) and three isomeric ethers
F Br F I F Cl
corresponding to the formula C4H10O; CH3OC3H7–n; C=C C=C C=C
CH3OC3H7–iso and C2H5OC2H5 Cl I Cl Br Br I
24. (d) Only RCH2NO2 has a -hydrogen atom (I) (II) (III)
O OH F I F Cl F Br
+ + C=C C=C C=C
RCH2 – N RCH = N Br Cl I Br I Cl
O– O– (IV) (V) (VI)
25. (a) 26. (c) 37. (a) 38. (a) 39. (a)
27. (b) Replace three different types of hydrogen atoms,one by 40. (a) None of the carbon atoms in DCH2CH2CH2Cl is chiral
one. i.e., each carbon atom is achiral (symmetric).
1 2 3 4 5 6 7
CH3 C=CH2 CH3 CH=CH2 CH2CH=CH2 41. (b) C H 3 - C H 2 - C H 2 - C H 2 - C H 2 - C H 2 - C H 3
CH3
COOCH3 COOCH3 |
CH 3 - CH - CH 2 CH 2 CH 2 CH 3
OH H H OH
HO H H OH 2 - Methylhexane
(No chiral carbon)
COOH COOH
(D) (A)
* EXERCISE 3
63. (b) CH 3 - CH - CH = CH CH 3 ;
|
OH 2
Pent - 3 - en - 2 - ol C2H5
3
As in above question, total number of stereoisomers
1. (b) Cl — C — CH3
=2×2=4 1
64. (a) Since during the reaction, a chiral carbon is created and
further since the CN– ion can attack the planar aldehyde H 4
group both from the top and the bottom face of the R-configuration
aldehyde group with equal ease, therefore, a 50:50 mixture
of the two enantiomers, i.e. a racemic mixture is obtained. 2. (a) In the molecule
65. (a)
CH3CH = CH CH 2 CH - CH3,
66. (c) Diastereomers have different solubility, m.p. and b.p., |
hence they can be separated by fractional crystallisation. Br
67. (d) Since all the six carbon atoms of cyclohexatriene the number of stereoisomers is given by sum of
(benzene) are sp2 hybridized, therefore its stablest geometrical isomers (because of presence of C = C) and
structure is planar form. optical isomers (because of presence of chiral carbon
68. (b) 69. (d) atom).
70. (c) Note that in structures 1 and 2, every two adjacent Number of geometrical isomers = 2 (one C = C is present).
hydrogen atoms are at maximum possible distance from Number of optical isomers = 2 (one chiral carbon atom).
each other (staggered conformation). Total number of stereoisomers = 2 + 2 = 4
71. (b) 3. (d) Alkenes with double bonds cannot undergo free rotation
72. (d) Boat conformation of cyclohexane has two types of and can have different geometrical shapes with two
destabilizing interactions, i.e. eclipsing and flagpole- different groups on each end of the double bond.
flagpole. Out of these flagpole-flagpole interaction is
the most destabilizing. CH3 CH3 CH3 H
C=C C=C
73. (a) Cyclohexane (iv) is non-planar and has chair H H H CH3
conformation. In this conformation, the bond angle is cis-But-2-ene trans-But-2-ene
the normal tetrahedral angle (109°, 28’) and thus has no
4. (a) Enolic form predominates in compounds containing
angle strain and hence is most stable. The rest of the
two carbonyl groups separated by a – CH2 group. This
molecules are nearly planar and hence their stability
is due to following two factors.
depends upon the angle strain in accordance with
Baeyer’s strain theory. Since cyclopropane has higher (i) Presence of conjugation which increases stability.
(ii) Formation of intramolecular hydrogen bond
æ 109° 28'– 60° ö
angle strain ç = 24°, 44' ÷ than between enolic hydroxyl group and second
è 2 ø carbonyl group which leads to stablisation of the
molecule. Hence the correct answer is III > II > I.
æ 109° 28'–108° ö
cyclopentane ç = 0°, 44' ÷ . Therefore 5. (b) The nitro group can attach to metal through nitrogen as
è 2 ø (–NO2) or through oxygen as nitrito (–ONO).
cyclopentane (iii) is more stable than cyclopropane (i). 6. (c) Optical and geometrical isomers are stereoisomers
Further, because of the presence of a double bond in a
three membered ring, cyclopropene (ii) is the least stable. Cl
7. (c) C = CH-CH 2 - CH 2 CH3 does not show geometrical
Thus the order of stability is (iv) > (iii) > (i) >(ii). Cl
74. (a) As the size of the ring increases, the internal angle isomerism due to presence of two similar Cl atoms on the
increases accordingly. As a result, the deviation from same C-atom.
the tetrahedral angle and hence the angle strain increases 8. (d) Racemic mixture is formed when enantiomers are mixed in
as the size of the ring increases. Thus, planar equimolar proportion
cyclodecane is expected to have the maximum angle
9. (a) A chiral object or structure has four different groups
strain.
attached to the carbocation.
450 Chemistry
10. (a) Only 2- cyclopropyl butane has a chiral centre. 18. (c) For a compound to show optical isomerism, presence
11. (c) 1-chloropentane is not chiral while others are chiral in of chiral carbon atom is a necessary condition.
nature
H
Cl Cl |
C–C–C–C–C; C–C–C–C–C; H 2 C = CH — C* — CH 2 - CH3
1–chloropentane *
2–chloropentane |
CH3
3- methyl-1-pentene
Cl C C Cl
C–C–C–C–C C–C–C–C–C
*
1–chloro-2-methyl pentane
*
3–chloro-2-methyl pentane
19. (a) Anti addition of Br2 on trans alkene provides meso
compound.
12. (c) The greater the distance between the atoms or groups
CH3
the more is the stability of conformers. Hence the order
H 3C H H Br
of stability is C= C + Br2 ¾CCl
¾¾ 4®
H CH 3 H Br
F F H F CH3
H H HO H
Therefore, no. of stereoisomers = 1
HO
H H H H H H
OH H H EXERCISE 4
anti or staggered eclipsed Skew or
Gauche 1. (c) C 2 H 4 Br2 represents 1, 1-dibromoethane and 1, 2 -
dibromethane which are position isomers
13. (b) The organic compounds which have chiral carbon atom 2. (c) It is definition of asymmetric synthesis
(a carbon atom attached to four different group or atoms
and do not have plane of symmetry rotate plane Cl
|
polarised light. 3. (b) CH3 - CH - CH 2 CH3 contains asymmetric C - atom
CHO
| 4. (c) The condition for geometrical isomerism is
HO - C*- H (C* is asymmetric carbon) a a a e
| c=c
CH 2 OH
or c=c
b b b d
OH N C CH 3
| |
7. (a) The enol form of acetone is CH3 - C = CH 2 with | |
15. (a) - C - N , - C - CH 3 ,
| | |
OD N C Br
|
D2O it gives CH 3 - C = CH 2
(i) (ii)
a a
8. (d) BrCH = CHBr . It fulfills the condition of c=c OH H O-C
b b | | |
- C - O, - C - C - OCH 3 ,
| | | |
Cl O C H O
|
9. (a) CH3 - CH 2 CH - CH3 , CH3CH 2 CH 2CH 2 - Cl (2 from (iii) (iv)
n-butane)
O-C
Cl | |
-C-O
(1from benzene) (All positions are the same) |
H
C C
(v)
C–C–C–C–C
o Arrange (NNN), (BrCC), (OOO), (CHH), (OOH) in
(3 from 2, 4 - dimethylpentane) ( there are three different increasing atomic number. The order is ii, iii, v, i, iv.
positions, ·, c, and o) 16. (a)
·C
17. (a) The groups of higher priority Cl and – C 2 H 5 are on
|
opposite sides.
· C- C - C- C
* o
18. (b) The resulting compound is C3 H 7 .CHOH.C 2 H 5 which
(4 from 2 - methyl butane) ( there are 4 different is optically inactive and reaction leads the racemisation.
positions, ·, c, o and *)
11. (d) There are metamers Each structure will have two configurations.
Br
| O H C - O
12. (b) C - C = C - C - C structural : 1, geometrical : 2 C 2
| H OH O - C - H
H 20. (c) HO H 4 H - C - OH 1
H OH HO - C - H
H CH 2 OH
| H - C - OH 3
C - C = C - C - C structural : 1, geometrical : 2.
| CH 2 OH
Br
3 OCH 3 OCH 3
CH 3 , ,
2 C 1 R configuration CH 3
4
H 3C – OCH 3
H H
23. (a) Allene has the structure C=C=C staggered
H H OH OH
| |
24. (d) Write cis and trans configuration for each. 36. (a) Ph.CO.CO. Ph ¾LiAlH
¾ ¾¾ 4®
Ph - C x - C x - Ph The
| |
O OH H H
product contains two similar asymmetric carbon atoms
25. (a) are tautomers. and two optically active and one optically inactive meso
form.
O O CH3
|
37. (b) The reaction proceeds through planar CÅ
3 5 H C2 H 5
26. (b) 1
| 2 4 leading to racemisation.
OH O 38. (d)
The keto form has E configuration. Br Br
27. (b) The keto enol tautomers are constitutional isomers. CH 3 CH 3 | |
39. (b) Br2
C=C ¾¾
¾® CH3 - C - C - CH3
28. (c) Enol form of 2, 4-hexane dione
H H | |
O H O H H
CH 3C = CH - C - CH 2 - CH 3 Racemic form
40. (c)
is stabilised by H-bonding.
41. (a) The given compounds are identical.
O 42. (d) None can have the enol form due to absence of H-atom
||
29. (d) The compounds containing - C - group adjacent to O
||
asymmetric carbon atom carrying a hydrogen easily on the carbon adjacent to - C - group.
racemise.
13
Hydrocarbons
SATURATED HYDROCARBONS, PARAFFINS OR (II) Derived names : In this system the higher hydrocarbons are
ALKANES : considered as derived from methane, eg.
They are open chain compounds of carbon and hydrogen having
all the atoms linked together by single covalent bonds, least H H CH3
reactive in nature | |
CH 3 - C - CH 2 - CH 3 CH 3 - C - CH
(Parum = little; affins = affinity) and having general formula CnH2n+2 | | CH3 ;
;
H H
NOMENCLATURE : ethyl m ethyl m ethane methyl iso propyl methane
(I) Trivial names : The first four members have the trivial names
derived from their preparation from corresponding alcohols (III) IUPAC system
containing same number of carbon atoms eg. methane from Types of carbon atoms :
methyl alcohol, ethane from ethyl alcohol and so on. After
(I) Primary (1°) - It is attached to one carbon atom only.
butane they are named according to Latin or Greek numerals
(II) Secondary (2°) - It is attached to two carbon atoms.
of the number of Carbon atoms present in them with class
suffix-ane. eg. Pentane (penta = 5) : hexane (hexa = 6) and so (III )Tertiary (3°) - It is attached to three carbon atoms.
on. (IV) Quaternary (4°) - It is attached to four carbon atoms.
The straight chain hydrocarbons are called normal (n) and
1° 1°
contain 1° or 1° & 2° carbon atoms. The branched chain C C
1° 2° 1°
hydrocarbons containing the group (CH 3 ) 2 CH - are called C – C 4°
–C–C–C
3°
Iso and contain 1° & 3° or 1°, 2° and 3° carbon atoms. The C1°
hydrocarbons containing a quaternary carbon atom are
called neo (new). Isomerism : They exhibit chain isomerism
CH 3 - CH 2 - CH 2 - CH 3 CH 3 - C H - CH 3
; | ;
n -Bu tan e
CH 3
Iso - butane n-Pentane Isopentane Neopentane
Ni / H Be 2 C + 4H 2 O ¾
¾® 2Be(OH ) 2 + CH 4
C n H 2n - 2 + 2H 2 ¾¾ ¾
¾2® C H
n 2n + 2
300°C
(XII) From carbon monooxide
(II) By heating anhydrous sodium salt of fatty acid with soda
lime (Lab method). Ni + C
CO + 3H 2 ¾¾¾® CH 4 + H 2 O
255°C
CaO
RCOONa + NaOH ¾¾¾ ® RH + Na 2 CO 3 (XIII) By reduction of alcohols, aldehydes, ketones and
Δ
carboxylic acids :
(III) By reduction of alkyl halides with nascent hydrogen.
Red P
ROH + 2HI ¾¾ ¾® RH + I 2 + H 2 O
RX + 2H ¾
¾® RH + HX 200°C
• Ease of replacement of hydrogen atom 3° > 2° > 1°. The relative rates being 5:3.8:1
• Order of reactivity of halogens F2 > Cl2 > Br 2 > I 2
• Iodination is reversible CH4 + I 2 CH3I + HI
5HI + HIO3 3I2 + 3H2O
It requires the use of oxidising agent such as HNO3, HIO3 etc.
• Fluro compounds are obtained from bromo or chloro compounds
2RBr + HgF2 2RF + HgBr2
• Chlorination and bromination proceed by free radical mechanism.
Sulphuryl Chloride
R – Cl + SO2 + HCl (Chlorination)
SO2Cl2+ light or peroxide
NO2
Nitration HNO3 |
CH 3CH 2 CH 2 NO 2 + CH 3 C H - CH 3 + CH 3 CH 2 NO 2 + CH 3 NO 2 (from propane)
450°C vapour phase
2CH 3 COOH + CO 2 + H 2 O (from neopentane)
Sulphonation
RSO3H + H 2O
H2SO4 400°C Alkyl sulphonic acid
,
Oxidation O2 Cu tube 100 atm.
CH 3OH ü
200°C ï
MoO / O2 ï
ï
RH HCHO + H 2 O ý From methane
Alkane (CH3COO)2 Mn/O2 ï
ï
HCOOH + H 2 Oþï
Alk. KMnO4 [O]
R 3COH (From Isobutane)
Alkanes containing 2° and 1° H atoms are generally not
oxidised by K2Cr2O7 and KMnO4
Combustion
CO 2 + H 2 O
O2 Excess D
CH 3
Isomerisation |
Anhy. AlCl3 + Conc. HCl CH 3 - C H - CH 3 (from n - butane)
Aromatisation Cr2O3
+ 4H2 (from n-Hexane)
450–500°C
Dehydrogenation
CH 3 - CH = CH 2 + H 2 (from propane)
Cr2O3 / Al2O3 D
CH 3 CH3
Alkylation | |
CH 3 - C - CH 2 - C H - CH 3
Isobutane + Isobutylene |
CH 3
2,2,4 - trimethyl pentane (common name isoctane)
Cracking D
CH 3 - CH = CH 2 + CH 4 + CH 2 = CH 2 + CH 3 - CH3
n-butane gives
CH3 CH3
(CH 3 ) 3 CH + CH3 COCH 3 | |
CH 3 - C - C - CH 3
Conc. H2SO4 | |
CH3 OH
2,3,3- trimethyl butanol - 2
456 Chemistry
CONFORMATIONAL ANALYSIS :
H H
Ethane – H
H H H
C
C
H H H
H H H
Sawhorse projection Newman projection
Different arrangements of atoms in a molecule convertible into one another by rotation about single bond are called conformers
or conformations. Their study is known as conformational analysis. If the energy barrier to the rotation is nil or small, the rotation
is said to be free or almost free. Ethane can exist in an infinite number of conformations. They are
HH H H H
H H
H
H H
H HH H
H H H H
Eclipsed q = 60° Staggered q < 60° > 0 Skew
q = It is dihedral angle between C–H bonds on the front of a Newman projection and those on the back.
Order of stability : Staggered > Skew > Eclipsed
Energy barrier between eclipsed and staggered is 2.8 kcal/mol.
Conformations of Propane C3H8 :
H3C CH
3
H3C CH
3
CH3 CH3 H CH3
H CH3 H H
H H
H H H H
HH CH3
H H H H H
H
CH3
H H
q = 0° q < 60° > 0 q = 60° Gauche q = 180° Anti or Trans q= 120 ° Eclipsed
Fully Eclipsed Skew
Staggered
Order of stability : Anti > Gauche > Skew > Eclipsed > Fully Eclipsed
Energy barrier between fully eclipsed and fully staggered (anti) is 5.3 kcal / mol or 22 kJ/mol.
Conformations of Cyclohexane : It exists in two nonplanar, strainless forms, the boat and the chair form.
a Axial a a
e e
e e e
e
a a equatorial
a a
e
e
e e
e e
a a
Move up Move Down
Move Down a a
HX
CH 3 .CH 2 X (Order of reactivity of HX HI > HBr > HCl)
(Anti and Syn addition)
HOX hypohalous acid
CH 2 OH.CH 2 Cl ethylene chlorohydrin
CH2Cl . CH2NO
Ethylene nitroso chloride
O3 O
CH2 CH2 H2O
Ozone 2HCHO + H2O2 2HCOOH
O O H2/Zn
2HCHO + H2O
CH2
O
CH2
Ethylene Oxide
1% alk. KMnO4 Cold CH2OH
(Test for unsaturation)
Baeyer's reagent CH2OH
Hydroxylation
Ethylene glycol (Syn. addition)
Hydrocarbons 459
[O]acid KMnO4
or acid K2Cr2O7 CH2 OH [O]
2HCOOH
CH2OH
The double bond is completely cleaved; the molecule is split into two
molecules. If carbon has two hydrogens it will become CO 2. If carbon has one
hydrogen it will become carboxylic acid. If carbon has no hydrogens it will
become a ketone. For example,
CH3 + CH3
KMnO4/H
C = CH2 C = O + CO2
CH3 CH3
CH3 H +
KMnO4/H CH3 OH
C=C C=O+O=C
Periodic acid HIO4 CH3 CH3 CH3 CH3
or lead tetra acetate
(H2O + O) CH3 CH3
COH C = O + HCHO
CH3 CH3
CH2 OH
H2O2 / CH3COOH CH2OH
CH2OH
C6H5.CO.OOH H2 O
C–C C–C
Perbenzoic acid 160
O OH OH
Oxide Glycol
Oxy-mercuration - demercuration
R-CH-CH3 (from R-CH= CH)2
OH
or (Addition of H2O according to
H2O + acid or Catalyst BF3,Mn phosphate Markownikoffs rule)
Cl(500–
2 600ºC)
Cl CH2– CH = CH2 (from propene)
Allylic substitution Allyl chloride
CH2
methyl cyclopropane
460 Chemistry
Isomerisation Al2(SO4)3
at 200 – 300ºC
CH 3 - CH 2 - CH = CH 2 ¾
¾® CH 3 - CH = CH - CH 3
or D above 500º – 700º C
But-1-ene gives But-2-ene
Polymerisation
–(CH2 – CH2)n polythene
O2 D
Combustion
CO2 + H2O + heat
Addition of HX CH 2 HX
CH 3
|| ¾¾¾® |
CHX CHX 2
Ethylidene halide
CH 3 CH 3
H O
R–C CH | ¾¾2¾® |
CH(HSO 4 ) 2 CHO
Ethylidene hydrogen Sulphate ( Acetaldehyde)
HCN / Ba (CN)2
CH2= CHCN
Acrylonitrile
CH3COOH / Hg2+
CH 2 = CHOOC.CH 3 ¾
¾® CH 3 - CH(OOCCH 3 ) 2
Vinyl acetate Ethylidene acetate
Addition of CO + HO
2
CH2= CH.COOH
Ni (CO)4 Acrylic acid
Cl
CuCl (aq.) + NH4Cl HCl
|
CH 2 = CH - C º CH ¾¾
¾® CH 2 = CH - C = CH 2
Vinyl acetylene Chloroprene
( monomer of Neoprene rubber )
Polymerisation
hot copper tube
Benzene
HCHO under pressure Partial
HC º C.CH 2 OH ¾¾¾
¾® CH 2 = CH.CH 2 OH
Propargyl alcohol reduction Allyl alcohol
K2Cr2O7 + H2SO4[O]
CH3COOH
Acetic acid
SeO2 CHO
| glyoxal
CHO
N2 electric spark
2HCN
Na or NaNH2 (alc.)
HC º CNa ¾
¾® NaC º CNa
Sod. acetylide di Sod. acetylide
Cu2Cl 2/ NHO4H
Cu.C º C.Cu
Copper acetylide (Red ppt.)
O O O O Formic acid
Ozonide Glyoxal
Combustion
CO2 + H2O
S
Thiophene
H
Pyrrole
All the products obtained in the above reactions are from acetylene.
Hydrocarbons 463
AROMATIC HYDROCARBONS : distill
Benzene C6H6 ¾¾¾® Benzene + Some toluene + Thiophene
110°C
A Benzene
Preparation - A Small scale preparation : Again distill
¾¾ ¾ ¾ ¾® Almost pure benzene
(I) From acetylene : at 80-82°C
OH SO3H
Sulphonation Conc. HS2O4
Zn dust + ZnO +
distillation Electrophile SO3 or HSO3
Benzene
Sulphonic acid
(IV) From Chlorobenzene : Cl
Cl Halogenation Cl / Fe2Cl3
+
Mg/dil. HCl Electrophile Cl Chlorobenzene
+ 2H + HCl
CH 3
Friedel Crafts's Alkylation
(V) From benzene sulphonic acid : CH3Cl/Anhy Al3Cl
+
SO3H Electrophile CH
(Carbonium ion) Toluene
200°C + H2SO4
+ 2H2O COCH 3
Friedel Crafts's Acylation
Steam CH3COCl/Anhy AlCl3
(VI) From benzene diazonium chloride : +
Electrophile CH3CO
acylium ion Acetophenone
N2Cl
(B) Addition reaction :
H3PO2
+ N2 + HCl 3H2/Ni
+
Cu
Cyclohexane
(B) Large Scale preparation :
(I) From Petroleum : n-hexane fraction of petroleum
Cl
3Cl2, UV light Cl Cl
Cr2O3 / Al2O3
CH3 (CH 2 )CH3 ¾¾¾¾¾¾
® + 4H2
n - Hexane 550°C Cl Cl
Cl
(II) From light-oil fraction of Coal tar BHC - Benzene Hexa Chloride,
Gammexane,Lindane used as insecticide.
Conc. H SO
2 4 ® ¾¾¾¾ NaOH
Light oil fraction ¾¾¾¾¾¾ ® ¾¾¾® + +
- pyridene - phenol 110°
464 Chemistry
4 or
benzene a planar compound whereas above structure
is non planar.
delocalised p
. M.O.
Hydrocarbons 465
PETROLEUM
CaC 2 + 2H 2 O ¾
¾® C 2 H 2 + Ca (OH ) 2
Petroleum (petra = rock, oleum = oil). A thick dark coloured
complex liquid, mixture of organic compounds obtained from below Polymerisa tion
3C 2 H 2 ¾¾ ¾ ¾ ¾¾® C 6 H 6 ;
the surface of the earth is petroleum. The chief components of
petroleum are hydrocarbons, aliphatic, alicyclic (naphthalenes) C2H 2 + H 2 ¾
Polymerisa tion
¾® C 2 H 4 ¾¾ ¾ ¾ ¾¾® C 6 H12
or aromatic in varying proportions and 1 to 6 percent of Sulphur,
Nitrogen and Oxygen compounds. The theory was supported by Moissan, Sabatier and
Senderens. It fails to explain the presence of optically active
Natural Gas : Found along with petroleum and roughly contains
compounds, Compounds of N and S, chlorophyll and haemin
60 to 80 percent methane 5 to 9 percent ethane, 3 to 18 percent
derivatives.
propane, 2 to 14 percent higher hydrocarbons. It is used as fuel.
(II) Engler's Theory : Petroleum is a product of slow
Partial combustion of natural gas yields Carbon blocks (reinforcing
decomposition of dead marine animals under high
agents for rubber).
temperature and pressure. It explains the presence of brine,
Theories of origin :
fossils, compounds of N and S.
(I) Mendeleef 's Carbide Theory :
It explains the presence of all the above mentioned
¾® Al 4 C 3 ;
4Al + 3C ¾ compounds including chlorophyll. Hence petroleum is of
animal as well as vegetable origin.
Ca + 2C ¾
¾® CaC 2 (III)Modern Theory : Petroleum is produced by partial
decomposition of marine animals and sea weeds etc.
¾® 3CH 4 + 4Al(OH ) 3 ;
Al 4 C 3 + 12 H 2 O ¾ Mining and Refining : Recovery from oil wells and separation
of individual components.
Flash Point : The minimum temperature at which an oil gives Anti Knock Compounds : 59% Tetra ethyl lead, 13% Ethylene
off sufficient vapours to form an explosive mixture with air is bromide, 24% Ethylene chloride, 4% Kerosene and dye is
called Flash Point. anti knock mixture.
Knocking : A sharp metallic sound emitted by internal In presence of aromatic compounds tetramethyl lead is more
combustion engine owing to immature ignition of the air effective.
gasoline mixture. Knocking is maximum in presence of straight Octane number : The percentage of iso octane (2, 2, 4-
chain hydrocarbons and minimum in presence of aromatic trimethyl pentane) in a mixture of iso octane and n-heptane
and branched chain hydrocarbons. having the same knocking properties as the fuel under
consideration.
466 Chemistry
The higher the octane number, the better is the fuel. (V) Aromatisation :
Octane number of compunds : Aromatic Compounds > Cyclo
alkanes > Olefins > Branched chain alkanes > Straight
Chain alkanes. CH 3 - (CH 2 ) 4 - CH 3 ¾
¾® + 4H2
Cetane number : It is the percentage of cetane
(n-hexadecane) in a cetane and a-methylnaphthalene mixture
that has the same ignition qualities as the fuel. (VI) Chain Fission :
Cracking : The conversion of less valuable higher fraction
C16 H 34 ¾
¾® C 8 H18 + C 8 H16 or C 6 H14 + C10 H 20
to the more valuable lower fraction by the application of heat
is known as cracking. Synthetic Petrol :
(I) Liquid Phase Cracking : (I) Bergins Process :
475° -530°C
Heavy Oil (C18 - C 43 ) ¾¾ ¾ ¾ ¾ ¾ ¾ ¾
¾®(C 4 - C10 )
Catalyst 1000-1200 lbs psi
Sn, Pb or Mo Compounds
Catalyst : Silica, titanium dioxide, zinc oxide, ferric oxide, Powdered Coal + Heavy Oil ¾¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾
¾®
H 2 400 -500°C, 200 -700 Atm
alumina etc. High pressure keeps the oil in liquid state.
Octane number of product : 65-70.
(II) Vapour phase Cracking :
600-800°C Petrol
Kerosene oil or gas oil ¾¾¾ ¾¾® Lower fractions
50-150 lbs psi
F.D. Middle Oil
(III) Cracking in presence of hydrogen : Product ¾ ¾¾ ®
Catalyst
R - R + H 2 ¾¾ ¾¾® 2RH ü Heavy Oil
ï
ROH + H 2 ¾ ¾® RH + H 2 O ïï
ý Product free from O, S & N Heavy oil is reused.
¾® 2RH + H 2S ï
R 2S + 2H 2 ¾
ï (II) Fischer-Tropsch Process :
¾® 2RH + NH 3 þï
R 2 NH + 2H 2 ¾
S team + Coke (Red hot) ¾¾® CO + H 2
water gas
Reactions taking place during cracking :
cold dilute
+
cold dilute (D)
(i) (ii) KMnO4
(E)
KMnO4
17. Convert the following :
hot (a) Ethyne to ethanal
(iii) K2Cr2O7/H2SO4 (b) Tert. butyl chloride to 2,2,3,3 tetra methyl butane.
(c) Ethyne to benzene.
13. You are given three jars containing ethane, ethylene and
(d) Benzoic acid to benzene
acetylene, respectively. How will you identify each of them
by chemical test? (e) But 1–ene to butane 1,2– diol.
468 Chemistry
Multiple Choice Questions 23. Arrange the following alkyl halides in decreasing order of
the rate of b–elimination reaction with alcoholic KOH.
18. Arrange the following in decreasing order of their boiling
points. H
— —
(A) n–butane (B) 2-methylbutane
(C) n-pentane (D) 2, 2–dimethylpropane (A) CH3—C—CH2Br
(a) A > B > C > D (b) B > C > D > A CH3
(c) D > C > B > A (d) C > B > D > A
19. Arrange the halogens F2, Cl2, Br2, I2, in order of their (B) CH3—CH2—Br
increasing reactivity with alkanes. (C) CH3—CH2—CH2—Br
(a) I2 < Br2 < Cl2 < F2 (b) Br2 < Cl2 < F2 < I2 (a) A > B > C (b) C > B > A
(c) F2 < Cl2 < Br2 < I2 (d) F2 < I2 < Cl2 < F2 (c) B > C > A (d) A > C > B
20. An alkene having molecular formula C7H14 was subjected
24. The addition of HBr to 1-butene gives a mixture of products
to ozonolysis in the presence of zinc dust. An equimolar
A, B and C
amount of the following two compounds was obtained
CH3 CH3 Br C2H5
C = O and C=O
CH3 CH3CH2 C C
(A) H5C2 CH3 (B) H CH3
The IUPAC name of the alkene is H Br
(a) 3, 4-dimethyl-3-pentene (b) 3, 4-dimethyl-2-pentene
(C) CH3—CH2—CH2—CH2—Br
(c) 2, 3-dimethyl-3-pentene (d) 2, 3-dimethyl-2-pentene
21. Which of the following reactions of methane is incomplete The mixture consists of
combustion ? (a) A and B as major and C as minor products
Cu / 523K /100atm 2CH OH
(a) 2CH4 + O2 ¾¾¾¾¾¾¾® (b) B as major, A and C as minor products
3
Mo2O3 HCHO + H O (c) B as minor, A and C as major products
(b) CH4 + O2 ¾¾¾¾ ® 2
(d) A and B as minor and C as major products
(c) CH4 + O2 ® C(s) + 2H2O(l)
25. Among the following compounds, the decreasing order of
(d) CH4 + 2O2 ® CO2 (g) + 2H2O(l)
22. The correct IUPAC name of following alkane is reactivity towards electrophilic substitution is
H2C—CH2—CH—CH2—CH2—CH—CH2—CH3
—
— —
CH CH2
CH3 CH3 CH3
CH3 OCH3 CF3
(a) 3,6 – Diethyl – 2 – methyloctane I II III IV
(b) 5 – Isopropyl – 3 – ethyloctane
(c) 3 – Ethyl – 5 – isopropyloctane (a) III > I > II > IV (b) IV > I > II > III
(d) 3 – Isopropyl – 6 – ethyloctane (c) I > II > III > IV (d) II > I > III > IV
1. Successive alkanes differ by 4. When petroleum is heated gradually, the first batch of
(a) CH2 (b) CH vapours evolved will be rich in
(c) CH3 (d) C2H4 (a) kerosene (b) petroleum ether
2. An alkyne has the general formula (c) diesel (d) lubricating oil
(a) CnH2n (b) CnH2n+2 5. The order of appearance of the following with rising
temperature during the refining of crude oil is
(c) CnH2n–2 (d) CnH2n+1
(a) kerosene oil, gasoline, diesel
3. Which of the following is not a mixture of hydrocarbons?
(b) diesel, gasoline, kerosene oil
(a) Candle wax (b) Kerosene (c) gasoline, diesel, kerosene oil
(c) Vegetable oil (d) Paraffin oil (d) gasoline, kerosene oil, diesel
Hydrocarbons 469
6. LPG contains 20. Formation of alkanes by action of Zn on alkyl halides is
(a) methane (b) ethane called
(c) butane (d) None of these (a) Frankland's reaction (b) Cannizaro's reaction
7. Petrol for aviation purposes must contain (c) Wurtz's reaction (d) Kolbe’s reaction
(a) straight chain hydrocarbons 21. For preparing an alkane, a concentrated solution of sodium or
(b) aromatic hydrocarbons potassium salt of a saturated carboxylic acid is subjected to
(c) olefinic hydrocarbons (a) hydrolysis (b) oxidation
(d) highly branched chain paraffins (c) hydrogenation (d) electrolysis
8. In commercial gasoline, the type of hydrocarbons which are 22. Pure methane can be produced by
desirable is (a) Wurtz reaction
(a) Branched hydrocarbons (b) Kolbe’s electrolytic method
(b) Straight chain hydrocarbons (c) Soda-lime decarboxylation
(c) Linear unsaturated hydrocarbons (d) Reduction with H2
(d) All of these 23. Which of the following liberates methane on treatment with
9. Fischer-Tropsch process is used in the manufacture of water ?
(a) synthetic petroleum (b) ethanol (a) Silicon carbide (b) Calcium carbide
(c) benzene (d) ethanoic acid (c) Beryllium carbide (d) Magnesium carbide
10. Octane number is zero for 24. Which of the following methods is most appropriate for the
(a) isoheptane (b) n-heptane manufacture of methane ?
(c) isooctane (d) n-octane (a) Reduction of CH2Cl2
11. Which of the following has lowest octane number ? (b) Wurtz reaction
(a) Iso-octane (b) n-Heptane (c) Liquefaction of natural gas
(c) n-Hexane (d) n-Hexadecane (d) None of these
12. Which of the following has highest octane number ? 25. The reaction/method that does not give an alkane is
(a) n-Hexane (b) n-Heptane (a) catalytic hydrogenation of alkenes
(c) n-Pentane (d) 2, 2, 4-Trimethylpentane (b) dehydrohalogenation of an alkyl halide
13. The process in which higher hydrocarbons are broken down
(c) hydrolysis of alkylmagnesium bromide
into lower hydrocarbons by controlled pyrolysis is called
(d) Kolbe’s electrolytic method
(a) Hydrolysis (b) Cracking
26. Ethyl bromide on treatment with alcoholic KOH gives
(c) reforming (d) Both (a) and (b)
(a) ethylene (b) ethanol
14. A fuel has the same knocking property as a mixture of 70%
(c) acetic acid (d) ethane
isooctane (2,2,4-trimethylpentane) and 30% n-heptane by
volume. The octane number of the fuel is 27. When n-propyl iodide is heated with alcoholic KOH, one of
the products is
(a) 100 (b) 70
(c) 50 (d) 30 (a) Propene (C3H6) (b) Cyclopropane (C3H6)
15. Cetane number of a diesel fuel will increase with the addition (c) C3H4 (d) C3H8
of 28. 1-Chlorobutane, on reaction with alcoholic potash (KOH),
(a) n-Decane (b) n-Hexadecane gives
(c) n-Pentane (d) a-Methylnaphthalene (a) 1-Butene (b) 1-Butanol
16. Which one is used as an antiknock in petrol fuel ? (c) 2-Butene (d) 2-Butanol
(a) Basic lead carbonate (b) Lead tetraacetate 29. In preparation of alkene from alcohol using Al2O3 which is
(c) Tetraethyl-lead (d) Basic lead sulphate effective factor ?
17. Wurtz reaction involves the interaction of alkyl halides in (a) Porosity of Al2O3 (b) Temperature
dry ether with (c) Concentration (d) Surface area of Al2O3
(a) sodium (b) zinc 30. Which one of the following heptanols can be dehydrated to
(c) copper (d) platinum hept-3-ene only ?
18. Ethane is formed by the reaction of methyl iodide and (a) Heptan-3-ol (b) Heptan-4-ol
sodium metal in dry ether solution. The reaction is known (c) Heptan-2-ol (d) Heptan-1-ol
as 31. Which of the principle is applied in the following reaction ?
(a) Clemmensen reduction (b) Kolbe’s reaction alc. KOH
CH 3CHBrCH 2 CH 3 ¾¾ ¾ ¾®
(c) Wurtz reaction (d) Cannizzaro's reaction
19. Which one of the following cannot be prepared by Wurtz CH 3CH = CHCH 3 + CH 2 = CHCH 2 CH 3
reaction ? ( Major ) ( Minor )
(a) CH4 (b) C2H6 (a) Markovnikov’s rule (b) Saytzeff's rule
(c) C3H8 (d) C4H10 (c) Kharasch's effect (d) Hofmann's rule
470 Chemistry
32. The conversion of 2, 3-dibromobutane to 2-butene with Zn 44. How many monochlorobutanes will be obtained on
and alcohol is chlorination of n-butane?
(a) redox reaction (b) a-elimination (a) 5 (b) 2
(c) b-elimination (d) Both (a) and (b) (c) 3 (d) 4
33. Coal-tar is a main source of 45. Conversion of CH4 to CH3Cl is an example of ......... reaction
(a) aromatic compounds (b) aliphatic compounds (a) electrophilic substitution
(c) cycloalkanes (d) heterocyclic compounds (b) nucleophilic substitution
34. Which of the following metal powder is used to convert (c) free radical substitution
trichloromethane into acetylene by heating the latter with it ? (d) free radical addition
(a) Na (b) Mg 46. The molecule having dipole moment is
(c) Ca (d) Ag (a) 2,2-dimethylpropane
35. Tetrabromoethane on heating with Zn gives (b) trans-2-pentene
(a) ethyl bromide (b) ethane (c) hexane
(c) ethene (d) ethyne (d) 2,2,3,3-tetramethylbutane
36. What is formed when calcium carbide reacts with heavy 47. Olefins can be hydrogenated by
water ? (a) zinc and hydrochloric acid
(a) C2D2 (b) CaD2 (b) raney nickel and hydrogen
(c) Ca2D2O (d) CD2 (c) nascent hydrogen
37. Monosodium acetylide reacts with an alkyl halide to form (d) lithiumaluminium hydride in ether
(a) an alkane 48. Which one of the following compounds would have the
(b) an alkene highest heat of hydrogenation ?
(c) an unsymmetric higher alkyne (a) CH 2 = CH 2
(d) a symmetric higher alkyne
38. Fractional distillation of coal-tar produces the following (b) CH 3 - CH 2 - CH = CH 2
fractions. Phenol is the main component of which fraction ? (c) CH 3CH = CHCH 3
(a) Light oil (b) Middle oil
(c) Heavy oil (d) Green oil (d) (CH3 ) 2 C = C(CH3 ) 2
39. Benzene is obtained by fractional distillation of 49. The reaction,
(a) light oil (b) middle oil CH 2 = CHCH 3 + HBr ® CH 3CHBrCH 3 is a type of
(c) anthracite oil (d) heavy oil
(a)electrophilic addition reaction
40. Heating a mixture of sodium benzoate or benzoic acid and
(b)nucleophilic addition reaction
soda-lime gives
(c)free radical addition reaction
(a) benzene (b) methane
(d)electrophilic substitution reaction
(c) sodium benzoate (d) calcium benzoate
41. Crude naphtha is a mixture of 50. CH 3 - CH = CH 2 + HI ¾ ¾® X , X is
(a) alkanes (b) conjugated dienes (a) CH3–CH2–CH2–I (b) CH3–CHI–CH3
(c) alkynes (d) alkyl halides (c) CH3CH2CH3 (d) None of these
42. Hydrocarbon which is liquid at room temperature is 51. When propene is treated with HBr in the dark and in absence
(a) pentane (b) butane of peroxide, the main product is
(c) propane (d) ethane (a) 1-Bromopropane (b) 2-Bromopropane
43. Which of the following isomers will have the highest boiling (c) 1,2-Dibromopropane (d) 1,3-Dibromopropane
point ? 52. Pentene-1 with HCl gives
(a) 3-Chloropentane (b) 2-Chloropentane
(a) CH 3 - CH 2 - CH 2 - CH 2 - CH 2 - CH 3 (c) 1,2-Dichloropentane (d) 1-Chloropentane
(b) CH 3 - CH - CH 2 - CH 2 - CH 3 53. Addition of HI to double bond of propene yields isopropyl
| iodide and not n-propyl iodide as the major product, because
CH3 addition proceeds throughs
(a) a more stable carbonium ion
(c) CH 3 - CH - CH - CH 3
| | (b) a more stable carbanion
CH 3 CH 3 (c) a more stable free radical
(d) homolysis
CH 3 54. Propene is reacted with HBr in presence of peroxides, the
|
(d) CH 3 - C - CH 2 - CH 3 product is
| (a) 2-Bromopropane (b) 1-Bromopropane
CH 3 (c) 3-Bromopropane (d) None of these
Hydrocarbons 471
55. The principal organic product formed in the reaction, 64. Ozonolysis of C7H14 gave 2-methyl-3-pentanone. The alkene
peroxide is
CH 2 = CH(CH 2 )8 COOH + HBr ¾¾¾ ¾® is
(a) 2-ethyl-3-methyl-1-butene
(a) CH3CHBr(CH2)8COOH (b) 3-ethyl-2-methyl-3-butene
(b) CH2 = CH(CH2)8COBr (c) 2,5-dimethyl-3, 4-dimethylhex-3-ene
(c) CH2BrCH2(CH2)8COOH (d) 3-ethyl-2-methyl-1-butene
(d) CH2 = CH(CH2)7CHBrCOOH 65. Which one of the following is a free-radical substitution
56. Markovnikov’s rule is applicable to reaction ?
(a) CH2 = CH2 (b) CH3–CH2–CH3
CH3 CH3 Anh. AlCl3 CH3
(c) CH3–CH = CH–CH3 (d) C=C (a) + CH3Cl
CH3 C2H5
57. Which of the following compound gives similar products
obeying Markovnikov’s rule and peroxide effect ? CH2Cl CH2NO2
(b) + AgNO2
(a) CH3–CH=CH2 (b) CH3CH = CH–CH3
(c) C2H5–CH = CH–CH3 (d) C2H5–CH = CH2
58. The addition of HBr is easiest in (c) CH 3CHO + HCN ® CH 3CH (OH)CN
(a) CH2=CHCl (b) ClCH=CHCl
CH3 Boiling CH2Cl
(c) CH3–CH=CH2 (d) (CH3)2C=CH2
(d) + Cl2
59. 1, 3-Butadiene when treated with Br 2 gives
(a) 1, 4-dibromo-2-butene (b) 1, 3-dibromo-2-butene
(c) 3, 4-dibromo-1-butene (d) 2, 3-dibromo-2-butene 66. Ethylene reacts with 1% cold alkaline KMnO4 to form
60. Ozonolysis of 2, 3-dimethyl-1-butene followed by reduction (a) oxalic acid (b) ethylene glycol
with zinc and water gives (c) ethyl alcohol (d) HCHO
(a) methanoic acid and 3-methyl-2-butanone 67. Baeyer’s reagent is used in the laboratory for
(b) methanal and 2-methyl-2-butanone (a) detection of double bond
(c) methanal and 3-methyl-2-butanone (b) reduction process
(d) methanoic acid and 2-methyl-2-butanone (c) oxidation process
61. Position of double bond in alkenes can be identified by (d) detection of glucose
(a) bromine water 68. Baeyer’s reagent is
(b) ammonical silver nitrate solution (a) saturated KMnO4 soln. (b) neutral KMnO4 soln.
(c) ozonolysis (c) alkaline KMnO4 soln. (d) acidic KMnO4 soln.
(d) None of these 69. Which of the following has the lowest dipole moment ?
62. Which alkene on ozonolysis gives CH3 CH3
CH3CH2CHO and CH3COCH3 (a) C=C (b) CH 3C º CCH 3
H H
CH3
(a) CH3CH2CH = C (c) CH 3CH 2 C º CH (d) CH 2 = CH - C º CH
CH3 70. 3-Hexyne reacts with Na/liq. NH3 to produce
(b) CH3CH2CH = CHCH2CH3 (a) cis-3-Hexene (b) trans-3-Hexene
(c) CH3CH2CH=CHCH3 (c) 3-Hexylamine (d) 2-Hexylamine
(d) CH 3 - C = CHCH 3 71. The most suitable catalyst for the hydrogenation of
| 2-Hexyne ¾ ¾® 2-cis-Hexene is
CH 3 (a) Pd–BaSO4 (b) (Ph3P)3RhCl
63. An alkene having molecular formula C7H14 was subjected (c) 10% Pd—C (d) Raney Ni
to ozonolysis in the presence of zinc dust. An equimolar 72. Lindlar’s catalyst is
amount of the following two compounds was obtained (a) Na in alcohol (b) Raney nickel
CH3 CH3 (c) Pd/BaSO4 (d) Na/liq. NH3
C = O and C=O 73. Acetylene when reacts with two molecules of HBr, then it
CH3 CH3CH2
gives
The IUPAC name of the alkene is (a) Br - C º C - Br (b) Br - CH = CH - Br
(a) 3, 4-dimethyl-3-pentene (b) 3, 4-dimethyl-2-pentene
(c) 2, 3-dimethyl-3-pentene (d) 2, 3-dimethyl-2-pentene (c) Br2 CH - CHBr2 (d) CH 3 - CHBr2
472 Chemistry
74. In the following reaction, 84. Propyne and propene can be distinguished by
(a) conc. H2SO4 (b) Br2 in CCl4
H 2O
C2H2 X CH3CHO (c) dil. KMnO4 (d) AgNO3 in ammonia
HgSO 4/H 2SO 4, 60ºC 85. Identify the reagent from the following list which can easily
what is X ? distinguish between 1-butyne and 2-butyne
(a) bromine, CCl4
(a) CH3CH2OH (b) CH3–O–CH3 (b) H2, Lindlar catalyst
(c) CH3CH2CHO (d) CH2 = CHOH (c) dilute H2SO4, HgSO4
75. When 2-pentyne is treated with dil. H2SO4 and HgSO4, the (d) ammonical Cu2Cl2 solution
product formed is 86. An organic compound, on treatment with Br2 in CCl4 gives
bromoderivative of an alkene. The compound will be
(a) 1-pentanol (b) 2-pentanol
(a) CH3 - CH = CH 2 (b) CH 3 CH = CHCH 3
(c) 2-pentanone (d) 3-pentanone
(c) HC º CH (d) H 2 C = CH 2
76. In which of the following hydrogen is most acidic?
87. Which of the following will yield a mixture of 2-chlorobutene
(a) Acetylene (b) Methane
and 3-chlorobutene on treatment with HCl ?
(c) Ethane (d) Ethylene
77. Match List I (Reagents used with ethyne) with List II (a) CH 2 = C = CH – CH3 (b) H 2 C = C - CH = CH 2
|
(products) and select the correct answer using the codes CH3
given below in the lists.
(c) CH 2 = CH - CH = CH 2 (d) HC º C - CH = CH 2
List I List II
88. An unknown compound A has a molecular formula C4H6,
I. Hydrogen chloride A Benzene
when A is treated with an excess of Br2, a new substance B
II. Hydrogen in presence B Acetaldehyde with formula C4H6Br4 is formed. A forms a white precipitate
of Ni at 573 K with ammonical silver nitrate solution. A may be
III. Hydrogen in presence C Ethene (a) Butyne-1 (b) Butyne-2
of Pd and BaSO4 at (c) Butene-1 (d) Butene-2
473 K 89. The hydrocarbon which decolourises alkaline KMnO 4
IV. Water in presence of D Ethane solution, but does not give any precipitate with ammonical
silver nitrate is
H2SO4 and HgSO4
(a) benzene (b) acetylene
Codes :
(c) propyne (d) butyne-2
(a) I-B, II-C, III-D, IV-A (b) I-A, II-D, III-C, IV-B 90. Select the true statement about benzene from amongst the
(c) I-A, II-D, III-B, IV-C (d) I-D, II-A, III-C, IV-B following
78. In its reaction with silver nitrate, acetylene shows (a) Because of unsaturation benzene easily undergoes
(a) oxidising property (b) reducing property addition
(c) basic property (d) acidic property (b) There are two types of C—C bonds in benzene molecule
(c) There is cyclic delocalisation of pi-electrons in benzene
79. When an alkyne, RC º CH , is treated with cuprous ion in
(d) Monosubstitution of benzene gives three isomeric
an ammonical medium, one of the products is
products
(a) RC º CCu (b) CuC º CH 91. Aromatic hydrocarbons undergo
(c) CuC º CCu (d) RC º CR (a) nucleophilic addition reactions
80. Which of the following does not give a white precipitate (b) electrophilic addition reactions
with AgNO3 solution ? (c) electrophilic substitution reactions
(d) None of these
(a) Propyne (b) 1-Butyne
92. Benzene on treatment with a mixture of conc. HNO3 and
(c) 2-Butyne (d) 1-Pentyne conc. H2SO4 at 100ºC gives
81. A compound is treated with NaNH2 to give sodium salt. (a) Nitrobenzene (b) m-Dinitrobenzene
Identify the compound (c) p-Dinitrobenzene (d) o-Dinitrobenzene
(a) C2H2 (b) C6H6 93. Which species represents the electrophile in aromatic
(c) C2H6 (d) C2H4 nitration ?
82. KMnO4 will oxidise acetylene to (a) NO -2 (b) NO +2
(a) ethylene glycol (b) ethyl alcohol (c) NO 2 (d) NO 3-
(c) oxalic acid (d) acetic acid 94. In the Friedel-Craft's synthesis of toluene, reactants in
83. Which one of the following gives Tollen’s reagent test ? addition to anhydrous AlCl3 are
(a) 1-Butanol (b) 2-Butanol (a) C6H6 + CH4 (b) C6H6 + CH3Cl
(c) 1-Butyne (d) 2-Butyne (c) C6H5Cl + CH3Cl (d) C6H5Cl + CH4
Hydrocarbons 473
95. When CH3Cl and AlCl3 are used in Friedel-Craft's reaction, 106. The correct order of reactivity towards the electrophilic
the electrophile is substitution of the compounds aniline (I), benzene (II) and
nitrobenzene (III) is
(a) Cl + (b) AlCl-4
(a) II > III > I (b) I < II > III
(c) CH 3+ (d) AlCl+2 (c) I > II > III (d) III > II > I
96. Benzene reacts with CH3COCl + AlCl3 to give 107. Addition of Br2 to 1-butene would give 1, 2-dibromobutane
(a) chlorobenzene (b) toluene which is
(c) benzyl chloride (d) acetophenone (a) achiral (b) racemic
97. Which of the following is not a meta-directing group ? (c) meso (d) optically active
(a) SO3H (b) NO2
(c) CN (d) NH2 108. Addition of Br2 to trans-2-butene would give a product
98. In the reaction of C 6 H 5 Y, the major product which is
( > 60%) is m-isomer, so the group Y is (a) chiral (b) meso
(a) —COOH (b) —NH2 (c) racemic (d) optically active
(c) —OH (d) —Cl 109. Name of following reaction is
99. A group which deactivates the benzene ring
towards electrophilic substitution but which directs the
incoming group principally to the o- and p-positions is + || ¾
¾®
(a) –NH2 (b) –Cl CN CN
(c) –NO2 (d) –C2H5 (a) Claisen Condensation
100. The most reactive compound for electrophilic nitration is (b) Diel’s Alder reaction
(a) benzene (b) nitrobenzene
(c) Dieckmann cyclisation
(c) benzoic acid (d) toluene
101. Which of the following will be most easily attacked by an (d) Michael addition reaction
electrophile? 110. The cycloalkane having the lowest heat of combustion per
Cl CH 2 group
(a) (b)
(a) (b)
OH CH3
(c) (d) (c) (d)
C º C-H
(b)
I II III
(a) II > III > I (b) III < I < II
(c) I > II > III (d) I = II > III CºC
103. The most reactive among the following towards (c)
sulphonation is
(a) toluene (b) chlorobenzene
(c) nitrobenzene (d) m-Xylene (d) CH 3 - C º C - CH 3
104. Which of the following is the most reactive towards ring 112. Which of the following will give alkene in Kolbe’s electrolytic
nitration ? method ?
(a) Benzene (b) Mesitylene
CH. COOK
(c) Toluene (d) m-Xylene ||
105. Aromatic compounds burn with a sooty flame because (a) CH 3 - C. COOK (b) CH 3CH 2 COOK
(a) they have a ring structure of carbon atoms
(b) they have a relatively high percentage of hydrogen CH 2 COOK
(c) they have a relatively high percentage of carbon |
(c) CH 3 - CH COOK (d) All of these
(d) they resist reaction with oxygen of air
474 Chemistry
10. In the following reaction : [CBSE-PMT 2012 S] 17. Acid catalyzed hydration of alkenes except ethene leads to
the formation of [AIEEE 2005]
CH3
+
(a) mixture of secondary and tertiary alcohols
H 2O/H (b) mixture of primary and secondary alcohols
C CH —
— CH2
(c) secondary or tertiary alcohol
CH3 (d) primary alcohol
18. Which one of the following conformations of cyclohexane
A B is chiral? [AIEEE 2007]
Minor Product + Major Product
(a) Boat (b) Twist boat
The major product is :
(c) Rigid (d) Chair.
CH3 19. The compound formed as a result of oxidation of ethyl
benzene by KMnO4 is [AIEEE 2007]
(a) C CH CH3 (a) benzyl alcohol (b) benzophenone
(c) acetophenone (d) benzoic acid.
OH CH3 20. Which of the following reactions will yield
CH3 2, 2-dibromopropane? [AIEEE 2007]
(a) CH3 – CH = CH2 + HBr ®
(b) C CH2 CH3 (b) CH3 – C º CH + 2HBr ®
(c) CH3CH = CHBr + HBr ®
OH CH3 (d) CH º CH + 2HBr ®
21. The reaction of toluene with Cl2 in presence of FeCl3 gives
CH3
predominantly [AIEEE 2007]
(c) (a) m-chlorobenzene (b) benzoyl chloride
C CH CH3
(c) benzyl chloride (d) o- and p-chlorotoluene.
CH3 OH 22. Toluene is nitrated and the resulting product is reduced
with tin and hydrochloric acid. The product so obtained is
CH3 diazotised and then heated wth cuprous bromide. The
reaction mixture so formed contains [AIEEE 2008]
(d) C CH2 CH2 (a) mixture of o- and p-bromotoluenes
(b) mixture of o- and p-dibromobenzenes
CH3 OH (c) mixture of o- and p-bromoanilines
11. Which of these will not react with acetylene? [AIEEE 2002] (d) mixture of o- and m-bromotoluenes
(a) NaOH (b) ammonical AgNO3 23. In the following sequence of reactions, the alkene affords
(c) Na (d) HCl. the compound ‘B’
12. What is the product when acetylene reacts with hypochlorous O H O
acid? [AIEEE 2002] CH 3 - CH = CH - CH 3 ¾¾3¾
® A ¾¾¾
2 ® B.
Zn
(a) CH3COCl (b) ClCH2CHO The compound B is [AIEEE 2008]
(c) Cl2CHCHO (d) ClCHCOOH. (a) CH3CH2CHO (b) CH3COCH3
13. On mixing a certain alkane with chlorine and irradiating it (c) CH3CH2COCH3 (d) CH3CHO
with ultraviolet light, it forms only one monochloroalkane. 24. The hydrocarbon which can react with sodium in liquid
This alkane could be [AIEEE 2003] ammonia is [AIEEE 2008]
(a) pentane (b) isopentane
(a) CH 3CH 2 CH 2 C º CCH 2 CH 2CH3
(c) neopentane (d) propane
14. Butene-1 may be converted to butane by reaction (b) CH 3CH 2 C º CH
with [AIEEE 2003]
(c) CH 3CH = CHCH3
(a) Sn – HCl (b) Zn – Hg
(c) Pd/H2 (d) Zn – HCl (d) CH 3CH 2 C º CCH 2CH3
15. Which one of the following has the minimum boiling point ?
25. The treatment of CH3MgX with CH 3C º C - H produces
[AIEEE 2004]
(a) 1 - Butene (b) 1 - Butyne [AIEEE 2008]
(c) n- Butane (d) isobutane (a) CH 3 - CH = CH 2
16. 2-Methylbutane on reacting with bromine in the presence of
(b) CH 3C º C - CH3
sunlight gives mainly [AIEEE 2005]
(a) 1-bromo-3-methylbutane H H
(b) 2-bromo-3-methylbutane | |
(c) 2-bromo-2-methylbutane (c) CH 3 - C = C - CH3
(d) 1-bromo-2-methylbutane (d) CH4
476 Chemistry
26. One mole of a symmetrical alkene on ozonolysis gives two
moles of an aldehyde having a molecular mass of 44 u. The
alkene is [AIEEE 2010] (a) CHO (b) CHO
(a) propene (b) 1-butene
(c) 2-butene (d) ethene CO 2 H
27. Ozonolysis of an organic compound 'A' produces acetone (c) COOH (d)
CO 2 H
and propionaldhyde in equimolar mixture. Identify 'A' from
the following compounds: [AIEEE 2011] 31. The synthesis of 3-octyne is achieved by adding a
(a) 1 – Pentene bromoalkane into a mixture of sodium amide and an alkyne.
(b) 2 – Pentene The bromoalkane and alkyne respectively are
(c) 2 – Methyl – 2 – pentene [IIT-JEE 2010]
(d) 2 – Methyl – 1 – pentene (a) BrCH2CH2CH2CH2CH3 and CH3CH2C º CH
28. The non aromatic compound among the following is : (b) BrCH2CH2CH3 and CH3CH2CH2C º CH
[AIEEE 2011RS] (c) BrCH2CH2CH2CH2CH3 and CH3C º CH
(d) BrCH2CH2CH2CH3 and CH3CH2C º CH
32. The bond energy (in kcal mol–1) of a C–C single bond is
(a) (b) approximately [IIT-JEE 2010]
S (a) 1 (b) 10
(c) 100 (d) 1000
33. The number of optically active products obtained from the
(c) (d) complete ozonolysis of the given compound is :
[IIT-JEE 2012]
–
CH3 H
29. 2-Hexyne gives trans-2-Hexene on treatment with :
(a) Pt/H2 (b) Li / NH3 [AIEEE 2012]
CH3 CH CH C CH CH C CH CH CH3
(c) Pd/BaSO4 (d) Li AlH4
30. Cyclohexene on ozonolysis followed by reaction with zinc
dust and water gives compound E. Compound E on further H CH3
treatment with aqueous KOH yields compound F. (a) 0 (b) 1
Compound F is [IIT-JEE 2007] (c) 2 (d) 4
1. To prepare a pure sample of n-hexane using sodium metal as 5. An alkane C7H16 is produced by the reaction of lithium di(3-
one reactant, the other reactant will be pentyl) cuprate with ethyl bromide. The structural formula
(a) Ethyl chloride and n-butyl chloride of the product is
(b) Methyl bromide and n-pentyl bromide (a) 3-ethylpentane (b) 2-ethylpentane
(c) n-Propyl bromide (c) 3-methylhexane (d) 2-methylhexane
6. When ethyl alcohol is heated with conc. H2SO4 at 443 K,
(d) Ethyl bromide and n-butyl bromide
ethylene is formed by
2. Indicate the expected structure of the organic product when
(a) intramolecular hydration
ethyl magnesium bromide is treated with heavy water (D2O)
(b) intermolecular hydration
(a) C2H5–C2H5 (b) C2H5OD (c) intermolecular dehydration
(c) Sodium benzoate (d) C2H5D (d) intramolecular dehydration
3. (CH3)3CMgCl on reaction with D2O produces 7. Electrolysis of cold concentrated aqueous solution of
(a) (CH3)3CD (b) (CH3)3COD potassium succinate yields
(c) (CD)3CD (d) (CD)3COD (a) ethane (b) ethyne
4. The reagent used for the conversion, (c) ethene (d) ethane-1, 2-diol
8. When CH3CH2CHCl2 is treated with NaNH2, the product
CH 3CH 2 COOH ® CH 3CH 2 CH 3 is formed is
(a) LiAlH4 (a) CH 3 – CH = CH 2 (b) CH 3 – C º CH
(b) Soda-lime
NH2 Cl
(c) Red P and concentrated HI (c) CH3CH2CH (d) CH3CH2CH
(d) Zn – Hg/conc. HCl NH2 NH2
Hydrocarbons 477
9. 1,2-Dibromopropane on treatment with X moles of NaNH2 17. Which of the following alkenes will react fastest with H2
followed by treatment with ethyl bromide gave pentyne. under catalytic hydrogenation conditions ?
The value of X is R R R H
(a) 1 (b) 2 (a) (b)
H H R H
(c) 3 (d) 4
R R R R
10. In the reaction, (c) (d)
R H R R
oxidation NaOH Soda - lim e 18. The conversion of ClCH=CHCl to Cl2CH–CHCl2 can be
C6 H 5CH3 ¾¾¾¾® A ¾¾¾® B ¾¾¾¾¾
®C,
D carried out with
the product C is (a) Cl2 (b) Cl2/hn
(a) C6H5OH (b) C6H6 (c) Cl2/AlCl3 (d) Cl2/aq. NaOH
(c) C6H5COONa (d) C6H5ONa 19. The products formed by the action of chlorine on ethene in
11. Reactivity of hydrogen atoms attached to different carbon saturated solution of KBr is/are
atoms in alkanes has the order (a) ClCH2CH2Cl + ClCH2CH2Br
(a) Tertiary > Primary > Secondary (b) ClCH2CH2Cl
(c) ClCH2CH2Cl + BrCH2CH2Br
(b) Primary > Secondary > Tertiary
(d) ClCH2CH2Cl + BrCH2CH2Br + ClCH2CH2Br
(c) Tertiary > Secondary > Primary
20. In methyl alcohol solution, bromine reacts with ethylene to
(d) Both (a) and (b) yield BrCH2CH2OCH3 in addition to 1, 2-dibromoethane
12. In the free radical chlorination of methane, the chain initiating because
step involves the formation of (a) the ion formed initially may react with Br – or CH3OH
(a) chlorine atom (b) hydrogen chloride (b) the methyl alcohol solvates the bromine
(c) methyl radical (d) chloromethyl radical (c) the reaction follows Markovnikov’s rule
13. Consider the following reaction, (d) this is a free-radical mechanism
·
21. The intermediate during the addition of HCl to propene in
H 3C - CH - CH - CH 3 + Br ®' X '+ HBr the presence of peroxide is
| |
D CH3 ·
+
(a) CH3CHCH 2 Cl (b) CH 3CHCH 3
Identify the structure of the major product ‘X’ +
·
(c) CH3CH 2CH 2 (d) CH 3CH 2C H 2
· ·
(a) CH3 - CH - CH - CH 2 (b) CH 3 - CH - C - CH 3 22. In presence of peroxide, hydrogen chloride and hydrogen
| | | |
D CH3 iodide do not give anti-Markovnikov’s addition to alkenes
D CH 3
because
· ·
(a) both are highly ionic
(c) CH 3 - C - C H - CH 3 (d) CH3 - C H - CH - CH3 (b) one is oxidising and the other is reducing
| | |
D CH 3 CH3 (c) one of the steps is endothermic in both cases
(d) all steps are exothermic in both cases
14. A hydrocarbon with molecular formula C8H18 gives only 23. Arrange the following compounds in increasing order of
one monochloro derivative. The hydrocarbon is reactivity towards the addition of HBr.
(a) n-Octane RCH=CHR, CH2=CH2, R2C=CHR, R2C=CR2
(b) 2-Methylheptane (a) CH2=CH2<RCH=CHR<R2C=CHR <R2C=CR2
(c) 2,2,4-Trimethylpentane (b) R2C=CHR<RCH=CHR<CH2=CH2 <R2C=CR2
(d) 2,3,3,3-Tetramethylbutane (c) RCH=CHR<R2C=CR2<R2C=CHR <CH2=CH2
15. Which of the following compounds has the lowest boiling (d) R2C=CR2<R2C=CHR<RCH=CHR <CH2=CH2
point ? 24. Which of the following is the predominant product in the
reaction of HOBr with propene?
(a) CH3CH2CH2CH2CH3
(a) 2-Bromo-1-propanol (b) 3-Bromo-1-propanol
(b) CH3CH = CHCH2CH3
(c) 2-Bromo-2-propanol (d) 1-Bromo-2-propanol
(c) CH3CH = CH–CH = CH2
25. The reaction of propene with HOCl proceeds via the addition
(d) CH3CH2CH2CH3 of
16. Among the following alkenes : 1-butene(I), cis-2-butene(II), (a) H+ in the first step
trans-2-butene(III), the decreasing order of stability is (b) Cl+ in the first step
(a) III > II > I (b) III > I > II (c) OH– in the first step
(c) I > II > III (d) II > I > III (d) Cl+ and OH– in a single step
478 Chemistry
26. The products obtained via oxymercuration (HgSO4 + H2SO4) 34. Indicate the organic structure for product expected when 2-
of 1-butyne would be methylpropene is heated with acetyl chloride in the presence
of anhydrous ZnCl2 ?
(a) CH 3 - CH 2 - CO - CH 3
CH 3
(b) CH 3 - CH 2 - CH 2 - CHO |
(a) CH 3 - C - C = CH 2 (b) CH 3 - C - C - CH 3
(c) CH 3 - CH 2 - CHO + HCHO || | || |
O CH 3 O CH 3
(d) CH 3CH 2 COOH + HCOOH
27. Which set of products is expected on reductive ozonolysis CH 3 H
| |
of the following diolefin ? (c) CH 3 - C - CH 2 COCH 3 (d) CH 3 - C - CH 2 - COCH 3
| |
CH3 Cl CH 3
|
CH3CH = C - CH = CH 2 Hg2+ / H +
35. Ph - C º CCH3 ¾¾¾¾
¾® A , A is
(a) CH 3CHO ; CH 3COCH = CH 2 O
(a) Ph (b) Ph
(b) CH3CH = C - CHO ;CH 2O O
|
CH3 (c) Ph OH (d) Ph
OH
(c) CH 3CHO ; CH 3COCHO ; CH 2 O
36. Excess of CH3COOH is reacted with CH º CH in presence
(d) CH 3CHO ; CH 3COCH 3 ; CH 2 O of Hg2+, the product is
28. The alkene C6H10 producing (a) CH 3CH (OOCCH 3 ) 2
OHC(CH2)4CHO on ozonolysis is
(a) Hexene-1 (b) Hexene-3 (b) CH 2 = CH (OCOCH 3 )
(c) Cyclohexene (d) 1-Methylcyclohexene (c) (CH 3COO )CH 2 - CH 2 (OOCCH 3 )
29. 2.8 g of pure alkene containing only one double bond per (d) None of these
molecule, react completely with 8 g of bromine (in an inert 37. When acetylene reacts with arsenic trichloride in the
solvent). What is the molecular formula of the alkene ? presence of anhydrous aluminium chloride it produces
(a) C2H4 (b) C4H8 (a) b-Chlorovinyldichloroarsine
(c) C3H4 (d) C6H12 (b) Lewisite
(c) Nitrobenzene
CH 3 (d) Both (a) and (b)
|
30. The compound CH 3 - C = CH - CH 3 on reaction with 38. Which one of the following compounds will react with
methylmagnesium iodide ?
NaIO4 in the presence of KMnO4 gives
(a) CH3CH2CH2CH2CH3 (b) CH3CH=CH–CH=CH2
(a) CH3COCH3 + CH3COOH
(c) CH 3C º CCH 2 CH 3 (d) CH 3 CH 2 CH 2 C º CH
(b) CH3COCH3 + CH3CHO
(c) CH3CHO + CO2 39. Propyne on polymerization gives
(a) mesitylene (b) benzene
(d) CH3COCH3
(c) ethylbenzene (d) propylbenzene
+
CH3 H Br2, CCl4
40. 1-Butyne reacts with cold alkaline KMnO4 to produce
[F] C4H8Br2 (a) CH3CH2COOH
31. H3C OH –H 2O
(b) CH3CH2CH2COOH
5 such products
are possible (c) CH3CH2COOH + CO2
How many structures of F are possible ? (d) CH3CH2COOH + HCOOH
41. Two gases, P and Q decolourise aqueous bromine but only
(a) 2 (b) 5
one of them gives a white precipitate with aqueous ammonical
(c) 6 (d) 3 silver nitrate solution. P and Q are likely to be
32. When CH2 = CH – COOH is reduced with LiAlH4, the (a) ethane and ethyne (b) But-1-yne and but-2-yne
compound obtained will be (c) ethane and but-2-yne (d) ethyne and propyne
(a) CH3–CH2–COOH (b) CH2=CH–CH2OH 42. The compound X (C5H8) reacts with ammonical AgNO3 to
(c) CH3–CH2–CH2OH (d) CH3–CH2–CHO give a white precipitate, and on oxidation with hot alkaline
33. Ethyne can be oxidised to oxalic acid by using KMnO4 gives the acid, (CH3)2CHCOOH. Therefore, X is
(a) chromic acid (b) alkaline KMnO4 (a) CH2 = CHCH = CHCH3 (b) CH 3 (CH 2 ) 2 C º CH
(c) hypochlorous acid (d) Any of these
(c) (CH 3 ) 2 CH - C º CH (d) (CH3)2C = C = CH2
Hydrocarbons 479
43. Choose the compound which can react with [Ag(NH3)2 ]+ 52. Two organic compounds A and B both containing only
and on treatment with alk. KMnO4 gives (CH3)3CCOOH carbon and hydrogen, on quantitative analysis gave the
(a) CH 3CH 2 CH 2 - C º C - CH 3 same percentage composition by weight :
C = (12/13) × 100%, H = (1/13) × 100%
(b) (CH 3 ) 2 CHCH 2 - C º CH
A decolourises bromine water but B does not. A and B
(c) (CH 3 ) 3 C - C º CH respectively are
(a) C2H2 and C6H6 (b) C6H6 and C2H2
(d) (CH 3 ) 3 C - C º C - CH 3
(c) C2H4 and C2H6 (d) C2H2 and C2H6
44. Which of the following possesses the highest melting point
53. What is the correct product of reaction ?
?
(a) Chlorobenzene (b) o-Dichlorobenzene CH 3
(c) m-Dichlorobenzene (d) p-Dichlorobenzene 1. BH , THF
¾¾ ¾3¾ ¾® ?
45. The function of AlCl3 in the Friedel-Craft's reaction is 2. H 2O 2 , OH -
(a) to absorb water (b) to absorb HCl
(c) to produce electrophile (d) to produce nucleophile CH 3 CH 3
46. Which one of the following will undergo metasubstitution
(a) H (b)
on monochlorination ? H
(a) Ethoxybenzene (b) Chlorobenzene H
(c) Ethyl benzoate (d) Phenol H
47. Which of the following deactivates benzene towards further
substitution reaction ? CH 3 CH 3
(a) —NHR (b) —OH (c) (d) H
H H
(c) —COOR (d) —OR
48. Which of the following will have fastest rate of reaction H
with Br2/FeBr3? 54. Choose the correct alkyne and reagents for the preparation
NO2
(a) (b) of
CH3 OCH3
(a) , HgSO 4 , H 2SO 4 , H 2 O
(c) (d)
CH 2
¾
¾® ||
CH I , Zn (Cu )
¾¾ ¾
2 2¾ ¾ ¾
¾®
Diethyl ether
O
||
(a) Hg (O - C - CF3 ) 2
(c) BH 3 , NaOH / H 2 O 2
CH 3 C º CH C CH 3
CH 2 HO C
NBS, CCl ( heat )
HO
NaOH
¾¾ ¾ ¾ ¾
4 ¾¾®
¾¾¾¾®
benzoyl peroxide
CH 3 (c) (d)
CH 3
61. The major product obtained in the following reaction
Method II : O
|| Br
CH 3 ¾¾
¾2®
?
FeBr3
Br / FeBr Mg / ethane
(i ) H C = O
3 ® ¾¾ ¾¾¾®
¾¾2¾¾¾ ¾¾ ¾2¾ ¾¾® O
(ii ) H 3O + ||
(a) Br
CH 3
O
(a) Method I ||
(b) Method II (b) Br
(c) Both (I) and (II) are equally good
(d) Neither (I) nor (II) O
||
58. The reaction of cis-2-butene with CH 2 I 2 and Zn(Cu) to
(c) Br Br
give cis-1, 2-dimethyl cyclopropane is
(a) stereospecific reaction
O
(b) enantiospecific reaction ||
(c) diastereoselective reaction (d)
(d) regioselective reaction Br
Hydrocarbons 481
62. The unsaturated hydrocarbon which on ozonolysis gives 69. Bromination of ethyl benzene in presence of light gives
one mole each of formaldehyde, acetaldehyde and methyl
C2 H5 C2 H5
glyoxal ( CH 3 CO.CHO)
Br
(a) CH 3 – CH = C( CH 3 ) – CH 3 (a) (b)
(b) CH 2 = CH – CH 2 – CH = CH 2
(c) CH 2 = CH – C( CH 3 ) = CH – CH 3 Br
(d) (CH 3 ) 2 C = CH - CH 3 Br
63. Which of the following is not the mechanistic step during
CH - CH 3
chlorination of methane by Cl2 / hn ? (c) (d) Both (a) and (b)
·
(a) Cl 2 ® 2Cl
· ·
70. Pair of enantiomers of 1, 2-dimethylcyclopentane having
(b) Cl + CH4 ® CH3 + HCl structures
· ·
(c) Cl + CH 4 ® CH 3Cl + H
· · H CH 3 H H
(d) Cl + CH3 ® CH3Cl CH 3 H
The X may be H H
(a) cyclohexene (b) cyclohexadiene
(c) cyclogexatriene (d) None of these HgSO 4 / H 2SO 4
X
Na liquid NH 3 72. 1- Pentyne
68. R - CH = CH 2 ¾¾ ¾ ¾ ¾¾ ® R. CH 2 . CH 3 Y
Et. OH BF3 , THF, H 2 O 2 , OH -
The reaction is called X and Y can be distinguished by
(a) Birch's reduction (b) Clemensen's reduction (a) silver-mirror test (b) iodoform test
(c) Catalytic reduction (d) None of these
(c) Both (a) and (b) (d) Neither (a) nor (b)
482 Chemistry
73. Which of the following change is correct 76. PhCH 3 on reaction with Cl2 / hn followed by Na/ether will
I 2 , CH3COOAg give
(a) C=C ¾¾ ¾ ¾¾ ¾
¾® C -C
wet CH3COOH
OH OH
OH (a)
I , CH COOAg
(b) C=C ¾¾
2 ¾¾
3 ¾¾
¾® C -C
dry CH3COOH Me Me
OH
(c) Both (a) and (b) one correct (b)
(d) Neither (a) nor (b)
74. Choose the correct among the following (c) Me Me
H
H (d) - CH 2 - CH 2 -
(a) H
H 77. In the following changes which is correct.
S - trans (transoid), less stable Reagent HCOOOH
A ¾¾ ¾¾® B ¾¾ ¾¾
¾® Erythroracemic
R
(b) H H
H H (a) A is 2-hexyne and R is Na-liquid NH 3
S - cis (cisoid), more stable (b) A is 3-hexyne and R is H 2 – Lindlar
(c) S-refers to geomectrical isomerism with respect to single
(c) B is 2-hexene and R is H 2 – Lindlar
bond.
(d) All are correct (d) A is 3-hexyne and R is H 2 /Ni
75. Choose the correct product of the following reaction
O
O ||
||
Cl 78. The compound reacts with MeMgI to give A and
(1) OOH
CH 3
? Cl
(2) H3 O +
CH 3 with Me 2 CuLi to give B. What are A and B ?
O O Me OMgI O
CH 3 || || ||
OH
(a) CH 3 (b) OH
(a) (b)
CH 3 OH
H CH 3
Me Me Me Cl Me
CH 3 OH Me OMgI Me Me OMgI Me O Li
(c) OH (d) CH 3
CH 3 H (c) (d)
OH CH 3
Cl Me Me Cl
Hydrocarbons 483
+
101. (c) Phenol as well as toluene have electron-releasing groups,
87. (a) CH 2 = C = CH - CH 3 ¾H
¾
¾® however –OH group, in phenol, is more electron-releasing
(due to +R effect) than the –CH3 group in toluene, so
+ + phenol is more easily attacked by an electrophile.
é ù
= C = CH - CH3 ¾¾¾
® êCH 2 = C- CH 2CH3 + CH 2 = CH - CHCH3 ú
ë û 102. (c) OCH3 NO2
Cl-
¾¾¾
® CH 2 = C - CH 2CH3 + CH 2 = CH - CHCH3
| | > >
Cl Cl
2- Chlorobutene 3- Chlorobutene
Electron-releasing No group Electron withdrawing
88. (a) Conversion of C 4H 6 to C 4H 6Br 2 indicates that the group present is present group is present
compound is either butyne-1 or butyne-2. However, white
precipitate with ammonical silver nitrate solution indicates
that it is a terminal alkyne, i.e. butyne-1 and not butyne-
2 103. (d) Cl NO2 CH3
89. (d) Since the hydrocarbon decolourises KMnO4 solution, it
must be unsaturated, i.e. alkene or alkyne. However, it
does not give any precipitate with ammonical AgNO3, it
must be a non-terminal alkyne, i.e. butyne-2 (b) (c) (a)
90. (c) Electron-withdrawing One electron-
91. (c) groups are present releasing group
92. (b) Mononitration occurs at about 60º C, but at 100ºC
dinitration occurs. Since –NO 2 is m-directing,
m-dinitrobenzene is formed at 100ºC CH3
93. (b)
94. (b)
95. (c) RCl + AlCl3 ® R+ + AlCl -4
Electrophi le CH3
(a) (d)
96. (d)
One electron- Two electron-releasing groups, hence
97. (d) releasing group most reactive towards sulphonation
98. (a) Since the major product (>60%) is a m-isomer, the group
Y must be m-directing which is –COOH
104. (a) Mesitylene (1,3,5-trimethylbenzene) has three electron-
99. (b) –Cl group is o-, p-directing due to +R effect ; however it
releasing (–CH3) groups, while m-xylene, toluene and
is deactivating due to strong –I effect of Cl (difference
from other o-, p-directing groups which are activating). benzene have 2, 1 and 0 electron-releasing (–CH3) groups
The net result is that chlorobenzene undergoes o-, p- 105. (c)
substitution, but with difficulty 106. (c)
100. (d) NO2 COOH 107. (b) CH3 - CH 2 - CH = CH 2 + Br2 ¾
¾®
Br
|
CH3 - CH 2 - CH - CH 2 Br Racemic mixture.
Benzene Nitrobenzene Benzoic acid
108. (b) Always remember cis 2-butene + Br2 ® Racemic 2, 3-
No group is present Deactivating group present
dibromobutane \ Trans 2-butene + Br2 ® Meso 2, 3-
CH3 dibromobutane.
109. (d) The given reaction is Diel’s Alder reaction
110. (a) More is the stability, lower is the heat of combustion
(See Baeyer’s strain theory). Cyclohexane is more stable.
111. (b) Only 1-Alkynes form alkynides
Benzoic acid Toluene 112. (c) K salt of succinic acid or its derivatives give alkenes by
ivating group present Activating group present Kolbe’s electrolytic method.
486 Chemistry
EXERCISE 3 8. (a) Due to hydrogen bonding between the two OH groups,
1. (c) This reaction occurs according to Markownikoff’s rule gauche conformation of ethylene glycol (a) is the most
which states that when an unsymmetrical alkene undergo stable conformation.
hydrohalogenation, the negative part goes to that
C-atom which contain lesser no. of H-atom. H
O
CH3 - CH 2 - C º CH + HCl H O
H
¾¾
® CH3 - CH 2 - C = CH 2
|
Cl
H H
I H
|
HI
¾¾® CH3 - CH 2 - C - CH3 \ Correct choice : (a)
|
Cl
CH3
2. (d) H3C — C = CH — CH3 9. (b) CH3 — CH — CH — CH3 H+/ Heat
CH3 OH
H3C O H
O3
C C CH3 CH3
H3C CH3 H / Heat
O CHO — CH — CH — CH CH3 — C = CH — CH3 + CH3 — CH — CH = CH2
2 methyl 3 methyl
O O butene-1 (20%)
H 2O
butene-2
CH3 – C – CH3 + CH3 – C – H (80%) (B)
–H2O 2 acetone acetaldehyde (A)
+
H
C 6 H 5 CH 2 Mg Br ¾¾¾ CH3
® C H CH + MgBr(OH)
H OH 6 5 3 HBr, dark
(CH3)2 — CH — CH — CH3 + CH3 — C — CH2 – CH3
6. (c) When both double and triple bonds are present, then Br Br
triple bond is considered as the principal group. (Minor) (Major)
CH3 H / Pd
14. (c) Butene - 1 ¾¾2 ¾ ¾® Butane
15. (d) Bpt. follows the order
10. (a) C CH CH2 Alkynes > Alkenes > Alkanes (Straight chain) > Alkanes
(branched chain) of comparable molecular weights.
CH3
CH3 CH3
| |
+ Br
H 16. (c) CH3 - CH - CH 2 - CH3 ¾¾¾
2 ® CH - C - CH CH
3 2 3
sunlight |
Br
2 - bromo - 2 - methyl butane
CH3
H2O
Ease of replacement of H-atom 3° > 2° > 1°.
C CH CH3 +
Å –H
H SO
CH3 17. (c) CH3 - CH = CH 2 + H 2 O ¾¾¾¾
2 4 ® CH - CH - CH
3 3
|
1,2-methyl shiftting OH
2° alcohol
CH3 CH3
CH3 CH3 | |
H 2SO 4
Å
CH3 - C = CH 2 + H 2 O ¾¾¾¾
® CH3 - C - CH3
CH3 C CH CH3 |
C CH CH3 OH
3° alcohol
CH3 H3C OH Addition follows Markownikoff’s rule.
3° carbocaction
(more stable)
A (Minor) 18. (b) Chiral conformation will not have plane of symmetry. Since
twist boat does not have plane of symmetry it is chiral.
H2O 4 1
OH CH3
3 6
C CH CH3
CH3
B (Major) 5 2
11. (a) Acetylene reacts with the other three as: 19. (d) When alkyl benzene are oxidised with alkaline KMnO4,
(strong oxidising agent) the entire alkyl group is oxidised
CH2
CH º CNa Na
CH º CH +HCl to –COOH group regardless of length of side chain.
liq. NH3
CHCl CH2CH3 COOH
CH2 CH3 ( O ), KMnO4 / OH -
+HCl ¾¾¾¾¾¾¾¾ ®
CHCl CHCl2 Benzoic acid
Ethyl benzene
[AgNO3+NH4OH]
CH º CH AgCºCAg + NH4NO3 20. (b) The reaction follows Markownikov’s rule which states
white ppt. that when unsymmetrical reagent adds across
CHOH unsymmetrical double or triple bond the negative part
12.(c) CH º CH + HOCl adds to carbon atom having lesser number of hydrogen
® ||
¾¾¾¾ atoms.
CHCl
HBr
CH 3 - C º CH + HBr ® CH3 - C = CH2 ¾¾¾ ®
+ HOCl é CH(OH) 2 ù -H O CHO |
¾¾¾¾® ê | 2 ® |
ú ¾¾¾¾ Br
êëCHCl2 úû CHCl2
Br
dichloroacetaldehyde |
13. (c) In neopentane all the H atoms are same (1º). CH3 - C - CH3
|
CH3 Br
|
CH 3 - C - CH 3 2, 2-dibromopropane
|
CH3
488 Chemistry
21. (d) FeCl 3 is Lewis acid. In presence of FeCl 3 o- and 25. (d) Writing the reaction we get
p-chlorotoluene is formed.
CH 3 MgX + CH 3 – C º C – H ¾¾
®
CH3 CH3 CH3
Cl CH3 – C º CMgX + CH 4 ( g )
FeCl3
+ Cl2 ¾¾¾® + So we find that CH4 is produced in this reaction.
Toluene o-chlorotoluene
Cl 26. (c) The given molecular formula suggests that the aldehyde
p-chloro toluene formed will be acetaldehyde hence the alkene will be
CH3CH = CHCH3
CH3 2-butene
CH3 O
NH2
|
anilines when diazotized and then treated with CuBr forms CH3 - C = O + CH 3 - CH 2 - C
o-, p- bromotoluenes.
23. (d) Completing the sequence of given reactions, H
Acetone Propionaldehyde
CH 3 – CH = CH - CH 3 ¾¾3¾
®
O
H H
28. (d) sp3 Carbon
O
Zn / H O
CH3– CH CH – CH3 ¾¾¾¾®
2
CH 3 CH 3
H CH3 | |
CH 3 - C - C - CH 3
O3/Zn/H2O | |
CH 3 CH3
15. (d) Option (d) has the lowest number of carbon atoms
CH3
16. (a)
17. (a) See the order of stability of substituted alkenes. Lesser
2 H3C CH O + 2O CH C CH O the stability more is the reactivity.
(achiral) 18. (a)
H 19. (a) Reaction of chlorine on ethene is an electrophilic addition
(achiral) and involves the formation of carbocation which is
29. (a) 8g Br2 react with 2.8g of alkene Ethoxybenzene Chlorobenzene Phenol
\ 80g Br2 react with 28g alkene
Thus the molecular wt. of alkene is 28 which indicates o-p-directing
C2H4 COOC2H5
30. (a) 31. (d) 32. (b) 33. (b)
é + ..
+ - ù
34. (c) CH 3COCl + ZnCl 2 ® êCH 3 - C = O
. . « CH 3 - C º O ú + ZnCl 3
êë úû
Acylium ion
é OH OH ù
Most electron- Electron releasing
ê
cold alk.
| | ú releasing due to due to –OH group
40. (c) CH 3CH 2 C º CH ¾¾ ¾¾®ê CH 3CH 2 C - C - H ú –ve charge on O
KMnO 4 ê | | ú
ë OH OH û O O
–
oxidation OH O – C – CH3 C – CH3
® CH 3CH 2 COCHO ¾¾¾¾® CH 3CH 2COOH + CO 2
41. (b) Since both gases decolourise KMnO4 solution, both must
be unsaturated, i.e. alkene or alkyne ( >option b or d). > >
However, only one of them gives a white precipitate with
ammonical AgNO3 solution, it must be terminal alkyne
Electron releasing Less electron releasing due to presence of Electron-
and thus the other should be either a non-terminal alkyne –CO grouping which shows resonance withdrawing group
or an alkene. The datas coincide with the option b with the electrons on O
Hydrocarbons 491
NO2
CH3 CH3
> H C = O
¾¾2 ¾ ¾
¾®
MgBr H 3O +
Electron-releasing Strong electrons
CH 2OH
as welll as electron- withdrawing group CH3 CH3
O
NaH
¾¾¾® ||
CH3I - C - CH 2 - - Br
492 Chemistry
O O
62. (c) CH 2 = CH - C(CH 3 ) = CH - CH 3 ¾¾3¾
® ||
Zn H 2O 72. (c) In the reactions X is CH 3 - CH 2 - CH 2 - C - CH 3
| Me
Cl
14
Environmental
Chemistry
POLLUTION (iv) Mesosphere : The region of the earth’s atmosphere above
Pollutant :- Any material affecting the life is known as pollutant the stratosphere and below the thermosphere. It is the
and the phenomenon is known as pollution. The pollutants may coldest region (temp. –2 to –92ºC) of atmosphere.
be inorganic, biological or radiological in nature. (v) Exosphere : The uppermost region of atmosphere. It
(i) Primary pollutants : These are emitted directly from the contains atomic and ionic O2, H2 and He.
sources. eg. inorganic gases such as H2S, SO2, CO, NO, HF, (b) Hydrosphere :- The aqueous envelop of the earth eg. oceans,
NH3 radioactive substancs or particulates such as smoke, lakes etc.
ash, dust, fumes. (c) Lithosphere :- The solid rocky portion of the earth.
(ii) Secondary pollutants : These are formed in the atmosphere (d) Biosphere :- The biological envelop which supports the life.
by chemical interactions among primary polluntants eg. SO3, AIR POLLUTION :
NO2, CH4, aldehydes, ketones, nitrates, sulphates, phenols.
(I) Major air pollutants: The major air pollutants are following:-
(iii) Bio-degradable pollutants : These are domestic wastes which
(a) Carbon monoxide (CO) :- It is produced by incomplete
are rapidly decomposed by micro-organisms.
combustion of gasoline in motor vehicles, wood, coal,
(iv) Non-degradable pollutants : These include chemicals,
inceneration and forest fires.
mercuric salts, lead compounds, pesticides etc.
It is treacherous and deadly poisonous gas. It induces
(v) Natural pollution : It is caused by radioactive substances,
headache, visual difficulty coma and death. It blocks
volcanic eruptions, forests and mines fires, floods etc.
the normal transport of oxygen from the lungs to other
(vi) Artificial pollution : It is caused by industries, thermal plants, parts of the body.
automobile exhausts, sewage etc.
(b) Sulphur dioxide ( SO 2 ) :- It is produced by petrol
ENVIRONMENT :
combustion, coal combustion, petrol refining and
The conditions existing around animal or human life. It is further
smelting operations.
classified as
It hinders the movement of air in and out of lungs. It is
(a) Atmosphere :- The gaseous envelop surrounding the earth.
particularly poisonous to trees causing chlorosis and
(i) Stratosphere : The layer of the earth’s atmosphere above
the troposphere and below the mesosphere. dwarfing. In presence of air it is oxidised to SO 3 which
(ii) Troposphere : The lowest region of the atmosphere is also irritant.
extending from earth’s surface to the lower boundary of
2 SO 2 + O 2 (air) ¾
¾® 2 SO 3
the stratosphere. It contains water vapour and is greatly
affected by air pollution. In presence of moisture SO 3 is converted into highly
(iii) Thermosphere : The upper region of the atmosphere corrosive sulphuric acid.
above the mesosphere. It is the hottest region (temp
upto 1200ºC). SO 3 + H 2 O (moisture ) ¾
¾® H 2SO 4
494 Chemistry
It attacks marble, limestone,vegetation, paper and textiles Hydrocarbons + O2, NO2, NO, O, O3 ® Peroxides,
and injurious to human beings. formaldehyde, peroxyacetylnitrate (PAN), acrolein etc.
(c) Oxides of nitrogen :- NO 2 and NO It is oxidising in nature and causes irritation to eyes,
lungs, nose, asthamatic attack and damage plants.
(Source - combustion of coal, gasoline, natural gas,
(IV) Acid rain :- The oxides of C, N and S present in the atmosphere,
petroleum refining, chemical plants manufacturing
dissolve in water and produce acids and lower the pH of
explosives and fertilizers, tobacco smoke.
water to below 5.5.
Breathing NO 2 causes chlorosis to plants and
2-
H 2 O + CO 2 ¾
¾® H 2 CO 3 2 H + + CO3
chronic lung conditions leading to death. NO 2 reacts
with moisture to form acids. 2 H 2 O + 2 SO 2 + O 2 ® 2 H 2SO 4
2 NO 2 + H 2 O ¾
¾® HNO 2 + HNO 3 2 H + + SO 24 -
3 HNO 2 ¾ ¾® 2 NO + HNO 3 + H 2 O -
2 H 2 O + 4 NO 2 + O 2 ® 4 HNO 3 4H + + 4NO3
(d) Smoke, dust :-
The acids are toxic to vegetation, react with marble and
Sources foundries, cement works, iron and steel works,
damage buildings.
gas works, power generating stations.
(e) Ammonia : Ammonia works CaCO 3 + H 2SO 4 ¾
¾® CaSO 4 + H 2 O + CO 2
(f) Chlorine and hydrogen chloride : Chlorine works Acids corrode water pipes and produce salts with heavy
(g) Chlorinated hydrocarbons : Dry cleaning works metals ions viz Cu, Pb, Hg and Al toxic in nature.
(h) Mercaptans : Oil refineries, coke ovens (V) Green House effect :- The retention of heat by the earth and
(i) Zn and Cd : Zinc industries atmosphere from the sun and its prevention to escape into
(j) Freon : Refrigeration works. the outer space is known as green house effect. Green house
(II) Photochemical pollutants :- The nitrogen dioxide by gases such as CO 2 , ozone, methane, the chlorofluoro carbon
absorbing sunlight in blue and U. V. region decomposes into compounds and water vapour form a thick cover around the
nitric oxide and atomic oxygen followed by a series of other earth which prevents the IR rays emitted by the earth to
reactions producing O 3 formaldehyde, acrolein and escape. It gradually leads to increase in temperature of
peroxyacylnitrates. atmosphere.
Ozone causes bronchial irritation even at 1 ppm level. Ozone Consequences of green house effect
affects tobacco plants, spinach, tomato, potato etc. The (i) Global warming would result in rise in sea level due to
photochemical pollutants are powerful eye irritants. The increased rate of melting of glaciers and floods.
reactions are as follows (ii) Increase in infectious diseases like malaria, dengue etc.
(VI) Ozone layer and its depletion :- The ozone layer, existing
NO 2 + h u ¾
¾® NO + O, O + O2 ¾
¾® O 3
between 20 to 35 km above the earth’s surface, shield the
earth from the harmful U. V. radiations from the sun. The U. V.
¾® RO · ,
RH + O ¾ ¾® RO ·3
RO · + O 2 ¾
radiations cause skin cancer, cataract of eye, and harmful to
RO ·3 + RH ¾
¾® Aldehydes + Ketones vegetation.
Depletion of ozone is caused by oxides of nitrogen
RO ·3 + NO ¾
¾® RO ·2 + NO 2 N 2O + h u ¾ ¾® NO + N
reactive nitric oxide
RO ·2 + NO 2 ¾
¾® Peroxyacylnitrate
NO + O 3 ¾
¾® NO 2 + O 2
(III) Smog : It is a mixture of smoke (composed to tiny particles of
carbon, ash and oil etc. from coal combustion) and fog in O3 + h u ¾
¾® O 2 + O
suspended droplet form. It is of two types :
(a) London smog or classical smog : It is coal smoke plus NO 2 + O ¾
¾® NO + O 2
fog. The fog part is mainly SO2 and SO3. It has sulphuric 2 O3 + h u ¾
¾® 3 O 2 (Net reaction)
acid aerosol. It causes bronchial irritation and acid rain.
The presence of oxides of nitrogen increase the
It is reducing in nature.
decomposition of O 3 . Depletion of ozone by chlorofluoro
(b) Photochemical smog or Los Angeles smog : The
oxidised hydrocarbons and ozone in presence of carbons.
humidity cause photochemical smog.
Environmental Chemistry 495
(iii) Sulphates : Sulphates of Na, K, Mg cause diarrihoea
C F2 Cl 2 + h u ¾
¾® CF2 Cl + Cl
(iv) Sodium chloride : It imparts bad taste to water
CFCl 3 + h u ¾
¾® CFCl 2 + Cl (v) Iron and manganese : Stain fabrics, bad taste, modify
colours
Cl + O 3 ¾
¾® ClO + O2
(vi) Lead : It damages kidney, liver, brain and central nervous
ClO + O ¾
¾® Cl + O 2 system
(vii) Cadmium and Mercury : Cause kidney damage
O3 + O ¾
¾® 2 O 2 (Net reaction)
(viii) Zn : Causes vomitting, dizziness and diarrhoea
(VII) Control of air pollution :- It can be controlled by
(ix) Arsenic can cause cramps, paralysis and death
1. Dissolving HCl, HF, SiF4 in water and SO 2 , Cl 2 , H 2S (x) Phosphates from fertilizers : They promote algae growth
in alkaline solution. and reduce D.O. concentration of water. This process is
2. Adsorbing gas and liquids molecules over activated known as eutrophication.
charcoal and silica gel. (xi) Anionic detergents (eg. alkyl benzene sulphonates, ABS)
3. Chemical reactions : They produce stable foam, stabilise colloidal impurities
and inhibit oxidation of organic compounds like phenol.
2CuO + O 2 + 2 S O 2 ¾
¾® 2 CuSO 4 ABS is not bio-degradable.
(xii) Hydrogen sulphide : Acidic, rotten-egg odour and
2 CaCO 3 + O 2 + 2 SO 2 ¾
¾® 2 CaSO 4 + 2 CO 2
corrosive to metals.
4 NO + 4 NH 3 + O 2 ¾ ¾® 2 N 2 + 6 H 2 O (xiii) Polychlorinated biphenyls : They are resistant to
4. Use of precipitators to settle charge particles oxidation and cause skin disorders and are carcinogenic.
5. Use of settling chambers under the action of gravity (xiv) Acid polluted water (pH < 3) : H2SO4 produced by
oxidation of Iron pyrites (FeS2) harmful to life.
6. Use of natural gas in place of diesel, petrol etc.
Suspended impurites :
WATER POLLUTION
(i) Parasitic worms : They cause infections
A. Water Pollution : The contamination of water by foreign
(ii) Bacterias : Cause dysentery, typhoid, cholera
substances which would constitute a health hazard and make
it harmful for all purposes (domestic, industrial or agriculture (iii) Viruses : Cause entroviral infections
etc.) is known as water pollution. The polluted water may (iv) Algae : Cause foul odour, taste, turbidity
have affensive odour, bad taste, unpleasant colour, murky D. International standards for drinking water :
oily etc. S.No. Characteristics Acceptable Rejection
B. Sources of water pollution : (mg/l) limit limit
(i) Domestic sewage : Discharges from kitchens, baths, 1. pH value 7 - 8.5 6.5 - 9.5
lavatories etc. 2. Total dissolved solids 500 1500
(ii) Industrial waters : Wastes from manufacturing 3. Total hardness (as CaCO3) 200 600
processes which includes acids, alkalies, pesticides, 4. Fluorides 1.0 1.5
insecticides, metals like copper, Zinc, lead, mercury,
5. Chlorides 200 1000
fungicides etc.
6. Sulphates 200 400
(iii) Oil : from oil spills or washings of automobiles
7. Nitrates 45 45
(iv) Atomic explosion and processing of radioactive
8. Magnesium 30 150
materials
9. Calcium 75 200
(v) Suspended particles (organic or inorganic) viruses,
10. Zinc 5.0 15.0
bacterials algae protozoa etc.
11. Anionic detergents 0.2 1.0
(vi) Wastes from fertilizer plants such as phosphates,
nitrates ammonia etc. 12. Iron 0.1 1.0
13. Manganese / Copper 0.05 0.5
(vii) Clay : Ores, minerals, fine particles of soil.
14. Phenolic compounds 0.001 0.002
C. Effects of impurities in water : Dissolved substances
15. Toxic Materials
(i) Hardness : Corrossive effect on boils, alkalinity, laxative
eg. As, Cd, Cr, CN–, Pb, Se 0.05 - 0.001 0.05 - 0.001
effect
(ii) Fluorides : Motting of teeth enamel, nervous and
skeleton disorders, above 1 mg/litre causes fluorosis.
496 Chemistry
AEROBIC AND ANAEROBIC OXIDATION : SEWAGE TREATMENT :
The oxidation of organic compounds present in sewage in The artificial treatment is called sewarage and involves the
presence of good amount of dissolved or free oxygen (approx. 8.5 following steps :
ml/l) by aerobic bacterials is called aerobic oxidation. When (i) Preliminary process : Passing sewage through screens to
dissolved or free oxygen is below a certain value the sewage is remove large suspended matter and then through mesh
called stale anaerobic bacterias bring out purification producing
screens to remove solids, gravels, silt etc.
H2S, NH3, CH4, (NH4)2S etc. This type of oxidation is called
anaerobic oxidation. (ii) Settling process (sedimentation) : The residual water when
The optimum value of D.O. for good quality of water is 4-6 ppm (4- allowed to stand in tanks, the oils and grease float on the
6 mg/l). The lower the concentration of D.O., the more polluted is surface and skimmed off and solids settle down. The colloidal
the water. meterial is removed by adding alum, ferrous sulphate etc.
BIOLOGICAL OXYGEN DEMAND (BOD) : and we get primary sludge.
It is defined as the amount of free oxygen required for biological (iii)Secondary treatment or Biological treatment : It is aerobic
oxidation of the organic matter by aerobic conditions at 20°C for chemical oxidation or aeration which converts carbon of the
a period of five days. Its unit is mg/l or ppm. An average sewage organic matter to CO2, nitrogen into NH3 and finally into
has BOD of 100 to 150 mg/l. nitrites and nitrates, dissolved bases form salts such as
CHEMICAL OXYGEN DEMAND (COD) : NH4NO2, NH4NO3 and Ca(NO3)2 etc. and secondary sludge
It is a measure of all types of oxidisable impurities (biologically is obtained.
oxidisable and biologically inert organic matter such as cellulose) The primary and secondary sludge (combined) is
present in the sewage. COD values are higher than BOD values.
subjected to anaerobic digestion to CO2 and CH4
COD DETERMINATION :
A known volume of sample is refluxed with known volume of 2[CH 2 O] ¾
¾® CO 2 + CH 4
standard K2Cr2O7 + dil. H2SO4 in presence of Ag2SO4 (catalyst)
(iv) Tertiary treatment : It is treatment of waste water with lime
for 1½ hours. The unreacted K2Cr2O7 is then titrated against
FeSO4.(NH4)2SO4.6H2O solution. The oxygen equivalent of for removal of phosphate which is coagulated by adding
K2Cr2O7 consumed is taken as a measure of COD. alum and ferric chloride and removed by filtration. Water is
1 ml. of 1 N K2Cr2O7 º 0.008 g oxygen disinfected by adding chlorine.
SOIL OR LAND POLLUTION : Secondarty sludge forms a good fertilizer for soil as it contains
nitrogen and phosphorous compounds.
The addition of substances in an indefinite proportion changing
the productivity of the soil is known as soil or land pollution. PESTICIDES :
Sources of soil pollution : The chemical substances used to kill or stop the growth of
(i) Agricultural pollutants : Chemicals like pesticides, fertilizers, unwanted organisms are called pesticides. They are further
fumigants, insecticides, herbicides, fungicides. classified as
(ii) Domestic refuge and industrial wastes (a) Insecticides : They are used to kill insects. The most common
(iii) Radioactive wastes from research centres, and hospitals insecticides are
(iv) Soil conditioners containing toxic metals like Hg, Pb, As, Cd
Cl
etc. Cl
Cl
(v) Farm wastes from poultries, dairies and piggery forms Cl
(vi) Improper disposal of human and animal excreta. (i) Cl3C.CH (ii)
Cl Cl
(vii) Pollutants present in air from chemical works Cl Cl
CONTROL OF WATER POLLUTION : BHC, 666, gamexane
D.D.T.
The water pollution can be reduced by following techniques OCONHCH3
(i) Recycling of waste water : by aeration and use of trickling OCONHCH3
filter (iii) CH(CH3)2 (iv)
(ii) Use of chemicals : Effective filtration and chlorination
Sevin, Carbaryl
(iii) Special techniques : Such as adsorption, ion-exchangers, Baygon
reverse osomosis, electrodialysis etc. S
||
(iv) Waste-water reclamation : Sewage water can be directly (v) (C 2 H 5 ) 2 - P - O - NO
used for irrigation and fish farms. Since it contains N, P and K.
Parathion
Environmental Chemistry 497
(c)Fungicides : They are used to stop or kill fungus e.g.
OCH3
OH
Cl Cl
Very Short/ Short Answer Questions 19. Which of the following is not a consequence of green-
house effect?
1. In what regions of the atmosphere, the temperature (a) Climatic conditions will be changed resulting in
increases with altitude and in which regions it decreases? (b) Plants in warmer climates with adequate rainfall would
2. What is the most important sink of CO pollutant? grow faster
3. What is marine pollution? (c) The incidence of infectious diseases is likely to
increase
4. Why COD is preferred over BOD ?
(d) Malaria will be controlled as the mos
5. What should be the tolerable limit of fluoride ions in drinking quitoes will not survive.
water? What happens if it is higher than10 ppm ? 20. Which of the following statements is not true about classi-
6. Name any four methods for waste management. cal smog?
7. Write the name of gas produced in Mathura refineries which (a) Its main components are produced by the action of
can damage the great historical monument “Taj Mahal”? sunlight on emissions of automobiles and factories.
8. What are 'asbestosis' and 'silicosis'? (b) Produced in cold and humid climate.
9. (i) Why there is ozone depletion mainly over Antarctica? (c) It contains compounds of reducing nature.
(ii) In which season the depletion of ozone on Antarctica (d) It contains smoke fog and sulphur dioxide
takes place and when is it replenished? 21. Which of the following statements is wrong?
10. Depending upon the nature of pollutants, how can the (a) Ozone is not responsible for green house effect.
pollution be classified into different types ? (b) Ozone can oxidise sulphur dioxide present in the atmo-
sphere to sulphur trioxide.
11. How plant nutrients and pesticides acts as water pollutants?
(c) Ozone hole is thinning of ozone layer present in strato-
12. Fish do not always grow in warm as well as in cold water, sphere.
why?
(d) Ozone is produced in upper stratosphere by the action
13. On the basis of chemical reactions involved, explain how of UV rays on oxygen.
do chlorofluorocarbons cause thinning of ozone layer in 22. Which of the following statements is correct?
stratosphere.
(a) Ozone hole is a hole formed in stratosphere from which
14. How can lead poisoning be cured? ozone oozes out.
(b) Ozone hole is a hole formed in the troposphere from
Long Answer Questions which ozone oozes out.
15. What is the strategy for control of Environmental pollution? (c) Ozone hole is thinning of ozone layer of stratosphere
16. List industrial wastes which contaminate water. at some places.
Multiple Choice Questions (d) Ozone hole means vanishing of ozone layer around
the earth completely.
17. Dinitrogen and dioxygen are main constituents of air but
these do not react with each other to form oxides of nitrogen 23. Which among the following statements is false?
because __________. (a) Oil slick in sea water increases D.O. value.
(a) the reaction is endothermic and requires very high (b) The main reason for river water pollution is industrial
temperature. and domestic sewage discharge.
(b) the reaction can be initiated only in presence of a (c) Surface water contains a lot of organic matter mineral
catalyst. nutrients and radioactive materials.
(c) oxides of nitrogen are unstable. (d) Oil spill in sea water causes heavy damage to fishery.
(d) N2 and O2 are unreactive 24. Sewage containing organic waste should not be disposed
18. The pollutants which came directly in the air from sources in water bodies because it causes major water pollution.
are called primary pollutants. Primary pollutants are Fishes in such a polluted water die because of
sometimes converted into secondary pollutants. Which of (a) large number of mosquitoes
the following belongs to secondary air pollutants?
(b) increase in the amount of dissolved oxygen
(a) C O
(b) Hydrocarbon (c) decrease in the amount of dissolved oxygen in water
(c) Peroxyacetyl nitrate (d) clogging of gills by mud.
(d) NO
Environmental Chemistry 499
25. Which of the following practices will not come under green 26. Water is often treated with chlorine to
chemistry? (a) remove hardness
(a) If possible, making use of soap made of vegetable oils (b) increase oxygen content
instead of using synthetic detergents. (c) kill germs
(b) Using H2O2 for bleaching purpose instead of using (d) remove suspended particles
chlorine based bleaching agents.
(c) Using bicycle for travelling small distances instead of
using petrol/ diesel based vehicles.
(d) Using plastic cans for neatly storing substances.
1. The uppermost region of the atmosphere is called 11. Formation of photochemical smog takes place in
(a) ionosphere (b) stratosphere (a) winter during day time
(c) troposphere (d) exosphere (b) summer during morning time
2. Which of the following is the coldest region of atmosphere? (c) summer during day time
(a) thermosphere (b) mesosphere (d) winter during morning time
(c) troposphere (d) stratosphere 12. Which of the following statement is false?
3. The region which is greatly affected by air pollution is (a) London smog is oxidising in nature
(a) thermosphere (b) stratosphere (b) Photochemical smog causes irritation in eyes
(c) troposphere (d) mesosphere (c) London smog is a mixture of smoke and fog
4. The region containing water vapour is (d) Photochemical smog results in the formation of PAN
(a) thermosphere (b) stratosphere
13. The viable particulate among the following is
(c) troposphere (d) mesosphere
(a) fumes (b) algae
5. In which of the following regions hydrogen and helium are
found (c) smoke (d) mist
(a) stratosphere (b) mesosphere 14. The non-viable particulate among the following is
(c) exosphere (d) troposphere (a) dust (b) bacteria
6. The substance which is a primary pollutant? (c) moulds (d) fungi
(a) H2SO4 (b) CO 15. Which of the following acts as a sink for CO?
(c) PAN (d) Aldehydes (a) Plants
7. Which of the following is most abundant hydrocarbon (b) Haemoglobin
pollutant? (c) Microorganisms present in the soil
(a) Butane (b) Ethane
(d) Oceans
(c) Methane (d) Propane
16. Which forms the part of hazy fumes of photochemical smog?
8. The aromatic compounds present as particulates are
(a) SO2 (b) Nitrogen dioxide
(a) polycyclic aromatic hydrocarbons
(b) benzene (c) PAN formation (d) Aldehydes
(c) toluene 17. Depletion of ozone layer causes
(d) nitrobenzene (a) breast cancer (b) blood cancer
9. The biggest particulate matter is (c) lung cancer (d) skin cancer
(a) HNO3 droplets (b) soot 18. The gas responsible for ozone depletion :
(c) H2SO4 droplets (d) fly ash (a) NO and freons (b) SO2
10. Formation of London smog takes place in (c) CO2 (d) CO
(a) winter during day time 19. The reaction caused by U.V. radiations from sun produces
(b) summer during day time (a) ozone (b) carbon monoxide
(c) summer during morning time
(c) sulphur dioxide (d) fluorides
(d) winter during morning time
500 Chemistry
20. Which of the following chemical, harmful to ozone, is 28. Water pollution is caused by
released by chlorofluoro carbon? (a) pesticides (b) fly ash
(a) Sulphur dioxide (b) Fluorine (c) auto exhausts (d) aeroplanes
(c) Chlorine (d) Nitrogen dioxide 29. Which causes death of fishes in water bodies polluted by
sewage?
21. Ozone hole refers to
(a) Foul smell (b) Pathogens
(a) increase in concentration of ozone
(c) Clogging of gills by silt (d) Decrease in D.O.
(b) hole in ozone layer 30. Phosphate pollution is caused by
(c) reduction in thickness of ozone layer in troposphere (a) sewage and agricultural fertilizers
(d) reduction in thickness of ozone layer in stratsophere (b) weathering of phosphate rocks only
22. Ozone layer of stratosphere requires protection from (c) agricultural fertilizers only
indiscriminate use of (d) phosphate rocks and sewage
(a) baloons 31. Sewage water is purified by
(b) pesticides (a) aquatic plants (b) micro-oganisms
(c) atomic explosions (c) light (d) fishes
(d) aerosols and high flying jets 32. Water is often treated with chlorine to
(a) remove hardness
23. Phosphate fertilizers when added to water leads to
(b) increase oxygen content
(a) increased growth of decomposers
(c) kill germs
(b) reduced algal growth
(d) remove suspended particles
(c) increased algal growth
33. Ozone is an important constituent of stratosphere because it
(d) nutrient enrichment (eutrophication)
(a) destroys bacteria which are harmful to human life
24. The type of pollution caused by spraying of DDT
(b) prevents the formation of smog over large cities
(a) air and soil (b) air and water (c) removes poisonous gases of the atmosphere by reacting
(c) air (d) air, water and soil with them
25. Pollution in large cities can be checked only by (d) absorbs ultraviolet radiation which is harmful to human
(a) shifting of factories out of the residential area life
(b) less use of insecticides 34. Which is the major air pollutant
(c) proper disposal of organic wastes, sewage and industrial (a) He (b) O2
effluents (c) CO2 (d) CO
(d) All the above 35. The ozone layer is present in
26. Sewage mostly constitutes (a) stratosphere (b) troposphere
(a) non-biodegradable pollutants (c) thermosphere (d) mesosphere
(b) biodegradable pollutants 36. The green house effect is caused by
(c) effluents (a) CO2 (b) NO2
(d) air pollutants (c) NO (d) CO
27. Chief source of soil and water pollution is 37. Surface water contains
(a) mining (b) agro industry (a) suspended impurity (b) salt + organic matter
(c) thermal power plant (d) All the above (c) only salt (d) organic matter
Environmental Chemistry 501
1. The greenhouse effect is because of the 7. When rain is accompanied by a thunderstorm, the collected
[CBSE-PMT 1996] rain water will have a pH value
[AIEEE 2003]
(a) presence of gases, which in general are strong infrared (a) slightly lower than that of rain water without
absorbers, in the atmosphere thunderstorm
(b) presence of CO2 only in the atmosphere (b) slightly higher than that when the thunderstorm is not
(c) pressure of O3 and CH4 in the atmosphere there
(d) N2O and chlorofluorohydrocarbons in the atmosphere (c) uninfluenced by occurrence of thunderstorm
2. Which of the following is/are the hazardous pollutant(s) (d) which depends upon the amount of dust in air
present in automobile exhaust gases? [CBSE-PMT 1996] 8. The smog is essentially caused by the presence of
(i) N2 (ii) CO (a) Oxides of sulphur and nitrogen [AIEEE 2004]
(iii) CH4 (iv) Oxides of nitrogen (b) O2 and N2
(a) (ii) and (iii) (b) (i) and (ii)
(c) O2 and O3
(c) (ii) and (iv) (d) (i) and (iii)
(d) O3 and N2
3. Green chemistry means such reactions which :
9. Identify the wrong statement in the following: [AIEEE 2008]
(a) produce colour during reactions [CBSE-PMT 2008]
(b) reduce the use and production of hazardous chemicals (a) Chlorofluorocarbons are responsible for ozone layer
depletion
(c) are related to the depletion of ozone layer
(d) study the reactions in plants (b) Greenhouse effect is responsible for global warming
4. Which one of the following statement is not true ? (c) Ozone layer does not permit infrared radiation from the
[CBSE-PMT 2011] sun to reach the earth
(a) pH of drinking water should be between 5.5 – 9.5. (d) Acid rain is mostly because of oxides of nitrogen and
(b) Concentration of DO below 6 ppm is good for the sulphur
growth of fish. 10. Identify the incorrect statement from the following :
(c) Clean water would have a BOD value of less than 5 [AIEEE 2011RS]
ppm. (a) Ozone absorbs the intense ultraviolet radiation of the
(d) Oxides of sulphur, nitrogen and carbon are the most sun.
widespread air pollutant.
(b) Depletion of ozone layer is because of its chemical
5. Which one of the following statements regarding reactions with chlorofluoro alkanes.
photochemical smog is not correct? [CBSE-PMT 2012]
(c) Ozone absorbs infrared radiation.
(a) Carbon monoxide does not play any role in
(d) Oxides of nitrogen in the atmosphere can cause the
photochemical smog formation.
depletion of ozone layer.
(b) Photochemical smog is an oxidising agent in character.
11. What is DDT among the following ? [AIEEE 2012]
(c) Photochemical smog is formed through photochemical
(a) Greenhouse gas
reaction involving solar energy.
(b) A fertilizer
(d) Photochemical smog does not cause irritation in eyes
and throat. (c) Biodegradable pollutant
6. Frequent occurrence of water blooms in a lake indicates (d) Non-biodegradable pollutant
(a) nutrient deficiency [AIEEE 2003] 12. The gas leaked from a storage tank of the Union Carbide
plant in Bhopal gas tragedy was : [JEE M 2013]
(b) oxygen deficiency
(a) Methyl isocyanate (b) Methylamine
(c) excessive nutrient availability
(c) Ammonia (d) Phosgene
(d) absence of herbivores in the lake
502 Chemistry
1. The substance which is not regarded as a pollutant? 9. Minamata disease is due to pollution of
(a) NO2 (b) CO2 (a) aresenic into the atmosphere
(c) O3 (d) Hydrocarbons (b) organic waste into drinking water
2. The greatest affinity for haemoglobin is shown by which of (c) oil spill in water
the following : (d) industrial waste mercury into fishing water
(a) NO (b) CO 10. BOD is connected with
(c) O2 (d) CO2 (a) microbes and organic matter
3. The substance having the largest concentration in acid rain? (b) organic matter
(a) H2CO3 (b) HNO3 (c) microbes
(c) HCl (d) H2SO4 (d) None of the above
4. Which of the following is not involved in the formation of 11. Eutrophication causes reduction in
photochemical smog? (a) dissolved oxygen (b) nutrients
(a) Hydrocarbon (b) NO (c) dissolved salts (d) All the above
(c) SO2 (d) O3 12. Which among the following statements is false?
5. The statement which is not true (a) Oil slick in sea water increases D.O. value
(a) NO2 does not play any role in photochemical smog (b) The main reason for river water pollution is industrial
(b) SO3 is more harmful air polluntant than SO2 and domestic sewage discharge
(c) SO2 dos not affect larynx (voice box) (c) Surface water contains a lot of organic matter mineral
(d) NO is more toxic to living tissues than NO2 nutrients and radioactive materials
6. The false statement among the followings : (d) Oil spill in sea water causes heavy damage to fishery
(a) The average residence time of NO is one month 13. Presence of which of the following fuel gas in the exhaust
(b) Limestone acts as a sink for SOx fumes shows incomplete combustion of fuel?
(c) SOx can be removed from flue gases by passing through (a) Sulphur dioxide
a solution of citrate ions (b) Carbon monoxide and water vapour
(d) Ammonia acts as a sink for NOx (c) Carbon monoxide
7. The statement which is not correct about control of (d) Nitrogen dioxide
particulate pollution 14. Which one of the following statements about ozone and
(a) In electrostatic precipitator, the particulates are made to ozone layer is true?
acquire positive charge which are then attracted by the (a) Ozone layer is beneficial to us because ozone cuts out
negative electrode and removed the ultraviolet radiation of the sun
(b) Gravity settling chamber removes larger particles from (b) The conversion of ozone to oxygen is an endothermic
the air reaction
(c) Cyclone collector removes fine particles in the diameter (c) Ozone has a triatomic linear molecule
range 5-20 microns (d) None of the above
(d) Wet scrubbers are used to wash away all types of
particulates
8. Which of the following statements about polar stratosphere
clouds (PSCs) is not correct?
(a) PSCs do not react with chlorine nitrate and HCl
(b) Type I clouds are formed at about –77ºC and contain
solid HNO3 . 3H2O
(c) Type II clouds are formed at about –85ºC and contain
some ice
(d) A tight whirlpool of wind called Polar Vortex is formed
which surrounds Antarctica
Environmental Chemistry 503
EXERCISE 1 hn •
20. (c) CF2 Cl 2 ¾¾® CF2 Cl + Cl
1. Temperature increases in stratosphere and thermosphere,
• •
it decreases in troposphere and mesosphere. Cl + O 3 ¾
¾® Cl O + O 2
2. Soil micro–organism.
21. (d) Ozone hole is reduction in ozone layer in stratosphere.
3. Pollution of sea water due to discharge of wastes into it. 22. (d) Aerosols use CFC an flying jets release NO. Both causes
4. COD can be found in a few minutes whereas BOD requires depletion of ozone layer.
at least 5 days. 23. (d) Addition of phosphate fertilizers to water leads to
5. 1 ppm or 1 mg dm–3. Higher concentration is harmful to nutrient enrichment (eutrophication)
bones and teeth. 24. (d) DDT causes water, air and soil pollution.
6. Recycling, burning incineration and sewage treatment. 25. (d)
7. Sulphur dioxide 26. (c) Domestic sewage constitute biodegradable pollutants.
8. The lung disease caused by particulates of asbestos is 27. (d)
'asbestosis' and that caused by silica is 'silicosis'. 28. (a) Pesticides cause water pollution.
29. (d) Decrease in D.O causes death of fish
14. By feeding the patient with an aqueous solution of calcium
complex of EDTA. 30. (a) Phosphate pollution is caused by sewage and
agricultural fertilizers.
17. (a) 18. (c) 19. (d) 20. (a) 21. (a)
31. (b) Sewage water is purified by micro-organisms.
22. (c) 23. (a) 24. (c) 25. (d) 26. (c)
32. (c) Water is often treated with Cl2 to kill germs.
EXERCISE 2 33. (d) Ozone absorbs U.V. radiations harmful to human life.
1. (d) The uppermost region of atmosphere is exosphere. 34. (d) CO is major air pollutant.
2. (b) The coldest region is mesosphere 35. (a) Ozone layer is present in stratosphere.
(temp. –27ºC to –92ºC) 36. (a) CO2 causes green house effect.
3. (c) Air pollution greatly affect the troposphere. 37. (b) Surface water contains salts + organic matter.
4. (c) Troposphere contains water vapour. EXERCISE 3
5. (c) H2, He and ionic oxygen are present in exosphere. 1. (a) Green house gases such as CO2, ozone, methane, the
6. (b) CO is primary pollutant. chlorofluorocarbon compounds and water vapour form
7. (c) Most abundant hydrocarbon pollutant is methane. a thick cover around the earth which prevents the IR
8. (a) PAH (Poly Aromatic Hydrocarbon) rays emitted by the earth to escape. It gradually leads
to increase in temperature of atmosphere.
9. (d) Fly ash.
2. (c) CO and oxides of Nitrogen are poisnous gases present
10. (d) London smog is formed in morning during winter.
in automobile exhaust gases.
11. (b) Photochemical smog is formed in noon in summer.
3. (b) Green chemistry may be defined as the programme of
12. (a) London smog is reducing in nature. developing new chemical products and chemical
13. (b) Algae processes or making improvements in the already
14. (a) Dust existing compounds and processes so as to make less
15. (c) CO is converted into CO2 by microorganism present in harmful to human health and environment. This means
soil. the same as to reduce the use and production of
16. (b) NO2 forms a part of photochemical smog. hazardous chemicals.
i.e. correct answer is option (b).
17. (d) Depletion of ozone layer causes skin cancer.
18. (a) NO and freons are responsible for ozone depletion. 4. (b) The ideal value of D.O for growth of fishes is 8 mg/ l .
7mg /l is desirable range, below this value fishes get
¾® O + O ; O + O 2 ¾
19. (a) O 2 ¾ ¾® O 3 susceptible to disease. A value of 2 mg/ l or below is
lethal for fishes.
504 Chemistry
5. (d) The oxidised hydrocarbons and ozone in presence of 11. (d) DDT is a non-biodegradable pollutant.
humidity cause photochemical smog. 12. (a) Methyl isocyanate, CH3 – N = C = O
Hydrocarbons + O2, NO2, NO, O, O3 ® Peroxides, EXERCISE 4
formaldehyde, peroxyacetylnitrate (PAN), acrolein etc.
1. (b) CO2 is generally not regarded as an pollutant.
It is oxidising in nature and causes irritation to eyes,
lungs, nose, asthamatic attack and damage plants. 2. (a) Haemoglobin has great affinity for NO.
6. (b) 3. (d) Acid rain contains H2SO4 > HNO3> HCl.
4. (c) Photochemical smog does not involve SO2.
7. (a) Normal rain water has pH 5.6 Thunderstorm results in
the formation NO and HNO3 which lowers the pH. 5. (b) SO3 is more harmful pollutant than SO2.
8. (a) Smog is caused by oxides of sulphur and nitrogen. 6. (a) The average residence time of NO is 4 days.
9. (c) Ozone layer acts as a shield and does not allow 7. (a) Particulates acquire negative charge and are attracted
ultraviolet radiation from sun to reach earth. It does by the positive electrode.
not prevent infra-red radiation from sun to reach earth. 8. (a) PSCs react with chlorine nitrate and HCl to give HOCl
Thus option (c) is wrong statement and so it is the and Cl2.
correct answer. 9. (d) Minamata is caused by Hg poisoning.
10. (c) The ozone layer, existing between 20 to 35 km above 10. (a) BOD is connected with microbes and organic matter
the earth’s surface, shield the earth from the harmful 11. (a) Eutrophication causes reduction in D.O
U. V. radiations from the sun.
12. (a) Oil slick in sea water decreases D.O value.
Depletion of ozone is caused by oxides of nitrogen
13. (c) Presence of CO in the exhaust fumes shows incomplete
N 2O + h u ¾ ¾® NO + N
combustion.
reactive nitric oxide
14. (a) Statement (a) is correct.
NO + O 3 ¾
¾® NO 2 + O2
qqq
O3 + h u ¾
¾® O 2 + O
NO 2 + O ¾
¾® NO + O 2
2 O3 + h u ¾
¾® 3 O 2 (Net reaction)
The presence of oxides of nitrogen increase the
decomposition of O3.
15
The Solid State
molecules or ions) are closely packed and held together by strong Binding Electrostatic Shared Vander Waals' Electrostatic
forces attraction electrons Dipole-dipole between +ve
forces. ions and
negative
CRYSTALLINE SOLIDS : electrons
The constituent particles are arranged in definite geometrical Properties High melting Very high Low mpt Moderate to
pattern i.e. they have lattice structure. points mpt high mpt.
Hard & brittle Very hard Very soft Hard & Soft
AMORPHOUS SOLIDS : Semi Non Insulators good
They have random arrangement of the constituent particles Conductors Conductors Conductors
(amorphous - means without any form). Examples NaCl, CaF2 Diamond, H2O, CO2 Cu, Fe
Silica
DIF FERENCES BETWEEN CRYSTALLINE AND
CRYSTAL LATTICE :
AMORPHOUS SOLIDS ARE :
The three dimensional orderly arrangement of constituent particles
Crystalline Amorphous of a crystalline solid is known as Crystal lattice.
• Have lattice structure • Do not have lattice structure UNIT CELL :
• Have sharp melting point • No sharp mpt The smallest geometrical portion of the crystal lattice which can
be used as repetitive unit to build up the whole crystal is called
• They are anisotropic i.e. • They are isotropic i.e. their
unit cell.
their physical properties are physical properties are the
different along different same along all directions TYPES OF UNIT CELL :
(i) Simple or primitive : Unit cell in which the particles are
directions
present at the corners only
• They are symmetrical • They are non symmetrical.
(iv) End face centred : In which the particles are present at the F
corners and at the centre of two opposite faces.
E D
Atoms touch each other along the face diagonal. Hence r =
2a
(length of face diagonal = 2a )
4
1 1 F C
4. End face Centred 8 × 2× – 2 b
8 2 a
E a D
PACKING FRACTION : Atoms touch each other along the body diagonal. Hence
It is defined as the ratio of the volume of the unit cell that is
occupied by the spheres to the volume of the unit cell. 3a
r= (length of body diagonal = 3 a )
(i) Primitive cubic unit cell : Number of atoms per unit 4
cell = 1
4
G 2 ´ pr 3
B 3 = 0.68
Therefore P.F. = 3
æ 4r ö
H A çç ÷÷
è 3ø
(iv) Hexagonal primitive unit cell : Each corner atom is being
F shared by 6 other unit cells therefore their contribution to one
C
1
E D unit cell would be .
6
The Solid State 507
1 1 MILLER INDICES :
Total number of atoms per unit cell ´ 12 + 3 + ´ 2 = 6 Reciprocals of Weiss indices and multiplying throughout by
6 2
smallest number to make integers are known Miller indices and
a = 2r represented by h, k and l and the plane as (hkl). For example, in
(112) plane h = 1, k = 1 and l = 2.
The distance between the parallel planes in a crystal is designated
as dhkl. For different cubic lattices the interplanar distances are
C a
given by d hkl =
h + k 2 + l2
2
è ø angles.
c c c
b a
g
b a b a
b b
g g a b
a a
Simple Cubic Tetragonal Rhombohedral
The Solid State 509
c c (b) Hexagonal close packing : Space occupied by spheres
is 60.4%. Hence it is more efficient.
b a b a
b
g g
a a
Orthorhombic Monoclinic b
c c
b b a
a b (ii) Close packing in three dimensions : Following the
b g
g hexagonal close packing here, we have two layers.
a
a
Triclinic Hexagonal
Bravais showed from geometrical considerations that there
are only seven shapes in which unit cells can exist. c
c c c
These are
(i) Cubic a a a
a
(ii) Orthorhombic
c c c
(iii) Rhombohedral
(iv) Hexagonal
(v) Tetragonal
(vi) Monoclinic
(vii) Triclinic
On the basis of presence of particles there are four types For third layer there are two types of voids, marked a
of unit cells tetrahedral voids and marked c octahedral voids. If spheres
(i) Primitive or simple are placed over a, first layer is repeated and we have AB- AB
(ii) Face centred arrangement. This is known as hexagonal close packing
(iii) Body centred (hcp). If spheres for third layer are placed over c, a different
(iv) End centred
layer is formed and we have ABC-ABC arrangement. This is
He also showed that out of possible twenty eight unit cells. (Seven
knwon as cubic close packing (ccp).
shapes × four types in each shape = 28) only fourteen actually
Both hcp and ccp are equally efficient and space occupied
exist. These are called BRAVAIS LATTICES.
by spheres is 74.0%. The cubic close packing has face
CO-ORDINATION NUMBER : centered cubic (fcc) unit cell.
It is defined as the number of particles immediately adjacent to Following the square close packing in three dimensions,
each particle in the crystal lattice. we have AB, AB arrangement of spheres.
In simple cubic lattice C.N. is 6
In body centred lattice C.N. is 8 and
In face centred cubic lattice C.N. is 12.
High pressure increases C.N. and high temperature decreases
the C.N.
PACKING OF CONSTITUENT PARTICLES IN
CRYSTALS :
Generally the particles of larger size do the packing and particles
The resulting structure in this arrangement is referred to as
of smaller size occupy interstitial places
body-centred cube (bcc). In this arrangement only 68% of
(i) Close packing in two dimensions : It is of two types
(a) Square close packing : Space occupied by spheres is the available space is occupied by spheres and occur in
52.4% many solids.
INTERSTITIAL VOIDS :
The space left after hcp and ccp (74.0% in each case) is known as
interstitial voids. They are of two types:
(i) Tetrahedral voids : The vacant space touching four spheres
is called tetrahedral void. The radius ratio is
rvoid
= 0.225
rsphere
510 Chemistry
rvoid
= 0.414
rsphere
(a) (b)
(a) (b)
(a) Eight tetrahedral voids per unit cell of ccp structure
Location of octahedral voids per unit cell of ccp or fcc lattice
(b) one tetrahedral void showing the geometry.
(a) at the body centre of the cube and
The number of tetrahedral voids is twice the number of (b) at the centre of each edge (only one such void is shown).
spheres (atoms). The number of octahedral voids is equal to the number of
(ii) Octahedral voids : The vacant space touching six spheres is spheres (atoms).
called octahedral void. The radius ratio is
Cations tend to get surrounded by the largest number of anions therefore the larger the rvoid ratio, the larger is the coordination
rsphere
number.
Limiting radius ratio(r+/r–) Shape Coordination number Example
0.155 – 0.225 Planar triangle 3 B2O3
0.225 – 0.414 Tetrahedral 4 ZnS
0.414 – 0.732 Square planar 4
0.414 – 0.732 Octahedral 6 NaCl
0.732 – 1.000 Body Centred Cubic 8 CsCl
1. Sodium metal crystallises in a body centred cubic lattice with Sol. The arrangement of atoms shows a simple cubic cell.
the cell edge a = 4.29 Å. What is the radius of sodium atom.
1
Sol. In bcc the atoms touch along body diagonal Number of X atoms = ´ 8 = 1 (at corners)
8
3 ´ 4.29
\ 2r + 2r = 3 . a ; r = = 1.857 Å 1
4 Number of O atoms = ´12 = 3 (at edges)
2. Chromium metal crystallizes with a body centred cubic lattice. 4
The length of the unit cell edge is found to be 287 pm. Calculate Number of Na atoms = 1 (at centre)
the atomic radius. What would be the density of chromium Hence formula NaXO3
in g/cm3.
+ –
3 .a 3 ´ 287 6. A solid A B has NaCl type close packed structure. If the
Sol. In bcc lattice r = = = 124.24 pm anion has a radius of 250 pm; What should be the ideal
4 4
radius for the Cation? Can a cation C+ having radius 180 pm
Z´M + –
Density = N ´ a 3 be slipped into the tetrahedral void of the crystal A B ? Give
A
reasons for your answer.
2 ´ 51.99
r= = 7.30 g / ml + –
6.023 ´ 10 23 ( 287 ´ 10 -10 ) 3 Sol. Since A B has NaCl type close packed structure it must
3. Gold has closed packed structure which can be viewed as belong to a crystal system having coordination number 6.
spheres occupying 0.74 of the total volume. If the density of Hence limiting radius ratio
gold is 19.3 g/ml. Calculate the approximate radius of gold r+
ion in the solid (gold = 197 amu). = 0.414 - 0.732
Sol. Packing fraction = 0.74. It has fcc type cell. r-
So number of gold ions per cell = 4
r– = 250 pm ; r + ³ 0.414 ´ 250 = 103.5 pm
Z´M 4 ´ 197 Ideal radius for cation.
r= = = 19 .3 ;
NA ´ a3 a 3 ´ 6 .023 ´ 10 23 (II) Cation C+ having radius 180 pm cannot be slipped into
\ a = 4.07 ´10 -8 cm + – r+
the tetrahedral site of crystal A B because should be
For fcc cell, r-
2 .a 2 ´ 4.07 ´ 10 -8 r+
r= = = 1.439 ´10 -8 cm 0.225 – 0.414. In the given case
180
=
= 0.72 .
4 4 r 250-
4. A metal crystallizes into two cubic phases. (fcc and bcc)
7. In an ionic crystalline solid AB, r + = 0.74 Å and
whose unit cell lengths are 3.5 and 3.0 Å respectively.
r– = 1.84Å. The atomic weights of A and B are 70 and 40 amu
Calculate the ratio of densities of fcc and bcc.
respectively. Find (a) Coordination number of A & B (b)
Z´M Density in g/cc of solid.
Sol. r =
NA ´ a3
r+ 0.74
Sol. Given = = 0.402 < 0.414 therefore coordination
4´ M 2´ M r - 1.84
For fcc, r1 = ; For bcc, r2 =
N A (3.5 ´10-8 ) 3 N A (3.0 ´10 -8 )3 number = 4 (tetrahedral)
2r+ + 2r– = a
r1 4 (3.0 ´10 -8 ) 3
= = 1.259 \ a = 2(0.74 + 1.84) = 5.16Å
r 2 2 (3.8 ´10 -8 )3
5. A solid has a structure in which X atoms are located at the 4 ´ 110
= = 5.33 g / cc
cube corners of the unit cell. O atoms are located at the 6.023 ´ 10 23 (5.16 ´ 10-8 )3
centre of cube edges and Na atom at the cube centre. What
8. What is the concentration of cation vacancies when NaCl is
type of lattice is represented by this compound. Also suggest
a molecular formula for the compound. doped with 10–3 mole % of SrCl2.
The Solid State 515
Sol. The number of cation vacancies created in the lattice of NaCl l 154
is equal to the number of divalent Sr2+ ion added d 200 = = = 280 pm
2 sin q 2 sin 16°6'
Concentration of Sr 2+ ions = 10 –3 mole per cent
a
= 10 -3 100 = 10 -5 mol d 200 =
1 mole of Sr 2+ contains 6.023 × 1023 Sr2+ ions 22 + 02 + 02
10–5 mole of Sr2+ ions contains 6.023 × 1023 × 10–5 ions. \ a = 2 ´ 280 = 560 pm
Therefore the number of cation vacancies in NaCl crystal is + -
6.023 × 1018. 15. A solid A B has an NaCl type closest packed structure. If
9. In Fe0.93O, find the % of Fe+++ ions. the radius of the anion is 250 pm. What is the radius of the
Sol. Iron 93% and O is 100%. cation?
Let Fe+++ be x% then Fe++ (93 – x)% then rc
Positive charge = Negative charge Sol. For NaCl type structure, = 0.414
ra
2(93 - x ) + 3x = 2 ´100
\ rc = (0.414) ra = 0.414 × 250 pm = 103.5 pm
\ x = 14
14
16. KF has NaCl structure. What is the distance between K +
+++
\ % of Fe = ´ 100 = 15.2% .
93 and F - in KF, if the density of KF is 2.48 g cm - 3 .
10. X-rays of wavelength 1.54Å strike a crystal and are observed [At. wt. of K = 39 and F = 19]
to be deflected at an angle of 22.5°. Assuming that n = 1. Calculate Sol. For NaCl type structure the rank of unit cell = 4
the placing between the planes of atoms that are responsible Z´ M 4 ´ 58
a3 = =
for the reflection. r´ NA 2.48 ´ 10 - 30
´ 6.023 ´ 10 23
Sol. Bragg's equation is nl = 2d sin q Edge length a = 538 pm
1.54 ´ 1 a
\d = = 2.01Å So the distance between K + and F - ion =
= 269.0 pm
2 sin 22.5° 2
17. The unit cell of an element of atomic mass 96 and density
11. At what glancing angle would be first order diffraction from
(110) plane of KCl observed using X-ray of wavelength of 10.3 g cm - 3 is a cube with edge length of 314 pm. Find the
154 pm. The dimensions of the unit cell is 315 pm. structure of the crystal lattice.
Sol. For the first order diffraction; l = 2d sin q
r ´ N A ´ a 3 10.3 ´ 6.023 ´10 23 ´ (314 ´ 10 -10 ) 3
l = 154 pm ; d = 315 pm Sol. Z= = =2
M 96
154 = 2 ´ 315 sin q ; \ q = 14.1° The number of atoms per unit cell is two. Hence the crystal
lattice has bcc unit cell.
12. The planes in a crystalline solid intersect the crystal axes at 18. KCl crystallises in the same type of lattice as does NaCl.
(2a, b, c) (–a, b, c) (a, 2b, 3c), (3a, b, c), (–a, b, ¥ ). Calculate
the miller indices for these planes. rNa + r
Na +
Sol. Given that, = 0.5 and = 0.7
rCl- r
Intercepts 2a, b, c –a, b, c a, 2b, 3c 3a, b, c –a, b, ¥ K+
Weiss indices 211 –111 123 311 –11 ¥ Calculate (a) the ratio of the side of the unit cell for KCl to
Reciprocal of weiss indices that for NaCl and (b) the ratio of density of NaCl to that of
KCl.
1 11 1 11 11 1 1 11 1 11 Sol. NaCl crystallises in the fcc unit cell such that
2 11 -1 1 1 123 3 11 -1 1 ¥ a
Clear fractions 122 –111 632 133 –110 ( rNa + + rCl- =
2
)
Miller indices 122 111 632 133 110
Where a is the edge of length of unit cell. Since
13. Determine the interplanar spacing between the (220) planes
of a cubic lattice of length 450 pm. r r
Na + Na +
= 0.5 and = 0.7
a 450 450 r r
Sol. d hkl = = = = 159 pm Cl- K+
h2 + k 2 + l 2 22 + 22 + 02 8
r +r
Na + Cl -
14. First order X-ray reflection (l = 154) maximum from a set of We have, = 1.5 ....(i)
r
(200) planes of a body centred cubic lattice was observed at Cl -
16°6'. Calculate the length of the edge of unit cell.
r rK + 0. 5 0.5
Sol. For first order reflection n = 1. K+
and = = =
r rNa + / 0.5 r + /r 0.7
\ l = 2d sin q Cl- Na K+
516 Chemistry
Adding 1 on both sides
Z´ M 4 ´ 108
rK + + rCl - Hence density r = =
=
1.2 NA ´ a 3 6.023 ´ 10 23 (3.53 ´ 10- 8 )3
rCl - 0. 7 ...(ii)
= 16.3 g cm - 3
Dividing (ii) by (i)
22. LiI occurs as a cubical closest packing . If the edge length of
r +r
K+ Cl -
=
1.2
×
1 the unit cell is 624 pm, determine the ionic radii of Li + and
r +r 0.7 1 .5
Na + Cl - I - ions
a KCl / 2 1.2 a KCl 1 .2 Sol. The cubical closest packing has fcc unit cell. I - ions occupy
or = or = the corner and the face centers. These ions touch each other
a NaCl / 2 0.7 ´ 1.5 a NaCl 1 . 05
along the face diagonal of the cube. Hence
Z´ M 4r - =
Now since r = I
2 .a
NA ´ a3
a 624pm
3 or r- = = = 220.65 pm
I
r NaCl æa ö æ M NaCl ö 2 2 2(1.414)
We will have = çç KCl ÷÷ ç ÷
ç M ÷
r KCl è a NaCl ø è KCl ø Along the edge we have I - Li + I - arrangement where I -
æ 1.2 ö æ 58.5 ö
3 are at the corners and Li + at the centre of the edge
=ç ÷ ´ç ÷ = 1.172 (Octahedral void)
è 1.05 ø è 74.5 ø
\ 2r - +2r =a
-3 I Li+
19. The density of CsBr which has bcc structure is 4.4 g cm .
The unit cell has edge length a pm. Calculate the inter ionic a æ 624 ö
r = – rI- = ç - 220.65 ÷ pm = 91.35 pm
distance in crystals of CsBr (Atomic mass Cs = 133, Br = 80) Li+ 2 è 2 ø
é Z´ M ù 23. Calculate the packing fraction for Ca unit cell, given that Ca
3 2 ´ 213 êFormula r = ú
Sol. a = crystallises in face centred cube unit cell
4.4 ´ 6.023 ´10 23 êë N A ´ a 3 úû
Sol. The rank of fcc unit cell = 4
a = 5.438 × 10 - 8 cm 2.a
The atomic radius r =
For bcc lattice the interionic distance 4
(The atoms touch along face diagonal)
3 1.732 ´ 5.438 ´ 10- 8
r+ + r- = ×a= = 470.9 pm Volume of 4 atoms
2 2
3
20. If the radius of Cs + is 169 pm and that of Cl - is 181 pm. 4 3 4 æ 2 .a ö÷ 2 pa3
= 4 × p r = 4 × pç =
Predict the structure of CsCl. What is the coordination 3 3 çè 4 ÷ø 6
number of Cs + ion?
2 p a3 3
rc 169 Packing fraction = a = 0.74
Sol. = = 0.94 6
ra 181
24. The first order reflection of a beam of X -rays of wavelength
Since the value is greater than 0.732, the structure of CsCl is 1.54Å from the (100) plane of a crystal of the simple cubic
bcc. Its coordination number is 8. type occurs at an angle of 11.29. Calculate the length of the
21. The nearest neighbour Ag atoms in the silver crystal are unit cell (sin 11.29° = 0.1991)
2.5 × 10 - 8 cm. Presuming fcc structure of the crystal, what Sol. nl = 2 d sin q
will be the density of the silver? [At. wt. of Ag = 108 mol -1 ] 1 × 1.54 × 10 - 8 cm = 2 × d × sin11.29
Sol. We know that the nearest neighbour distance between the d = 3.68 × 10 - 8 cm
silver atoms is half of the face diagonal which is related to Further
2.a a
the edge length a by a
2 d= or 3.68 × 10 - 8 =
h 2 + k 2 + l2 12 + 0 2 + 0 2
2.a
= 2.5 × 10 - 8 cm or a = 3.53 × 10 - 8 cm
2 or a = 3.68 × 10 - 8 cm
The Solid State 517
1. Which of the following is not a crystalline solid? 10. A match box exhibits
(a) KCl (b) CsCl (a) cubic geometry
(c) Glass (d) Rhombic S (b) monoclinic geometry
2. Among solids, the highest melting point is exhibited by (c) tetragonal geometry
(a) Covalent solids (b) Ionic solids (d) orthorhombic geometry.
(c) Pseudo solids (d) Molecular solids
11. When molten zinc is cooled to solid state, it assumes hcp
3. The major binding force of diamond, silicon and quartz is
structure. Then the number of nearest neighbours of zinc
(a) electrostatic force
atom will be
(b) electrical attraction
(a) 4 (b) 6
(c) covalent bond force
(d) non-covalent bond force (c) 8 (d) 12
+
4. The maximum proportion of available volume that can be 12. Co-ordination number of Na in NaCl is
filled by hard spheres in diamond is (a) 4 (b) 3
(a) 0.52 (b) 0.34 (c) 6 (d) 5
(c) 0.32 (d) 0.68 13. A crystal lattice with alternate +ve and –ve ions has radius
5. The packing fraction for a body-centred cubic is ratio 0.524. Its co-ordination number is
(a) 0.42 (b) 0.53 (a) 4 (b) 3
(c) 0.68 (d) 0.82 (c) 6 (d) 12
6. In a solid AB having the NaCl type structure, ‘A’ atoms 14. How many unit cells are present in a cube-shaped ideal
occupy the corners of the cubic unit cell. If all the face- crystal of NaCl of mass 1.00 g?
centred atoms along one of the axes are removed, then the [Atomic masses : Na = 23, Cl = 35.5]
resultant stoichiometry of the solid is
(a) 2.57 × 1021 unit cells (b) 5.14 × 1021 unit cells
(a) AB2 (b) A2B 21
(c) A4B3 (d) A3B4 (c) 1.28 × 10 unit cells (d) 1.71 × 1021 unit cells
7. A substance AxBy crystallizes in a face centred cubic (fcc) 15. Which of the following is example of body centred
lattice in which atoms ‘A’ occupy each corner of the cube cube ?
and atoms ‘B’ occupy the centres of each face of the cube. (a) Mg (b) Zinc
Identify the correct composition of the substance AxBy (c) Copper (d) Sodium
(a) AB3 16. Which of the following describes the hexagonal close packed
(b) A4B3 arrangement of spheres?
(c) A3B (a) ABCABA (b) ABCABC
(d) Composition can’t be specified (c) ABABA (d) ABBABB
8. Crystals can be classified into basic crystal habits, equal to 17. A metallic crystal crystallizes into a lattice containing a
(a) 7 (b) 4 sequence of layers AB AB AB......Any packing of spheres
(c) 14 (d) 2 leaves out voids in the lattice. What percentage of volume
9. Tetragonal crystal system has the following unit cell of this lattice is empty space?
dimensions (a) 74% (b) 26%
(a) a = b = c, a = b = g = 90° (c) 50% (d) none of these.
(b) a = b ¹ c, a = b = g = 90° 18. In crystal structure of sodium chloride, the arrangement of
Cl– ions is
(c) a ¹ b ¹ c, a = b = g = 90° (a) fcc (b) bcc
(d) a = b c, = b = 90° = 120° (c) Both fcc and bcc (d) None of these.
The Solid State 519
19. The intermetallic compound LiAg crystallizes in cubic lattice 32. When electrons are trapped into the crystal in anion vacancy,
in which both lithium and silver have co-ordination number the defect is known as :
of eight. The crystal class is (a) Schottky defect (b) Frenkel defect
(a) simple cubic (b) body centred cubic (c) Stoichiometric defect (d) F-centres
(c) face-centred cubic (d) None of these 33. In the laboratory, sodium chloride is made by burning sodium
20. In the crystals of which of the following ionic compounds in the atmosphere of chlorine. The salt obtained is yellow in
would you expect maximum distance between the centres of colour. The cause of yellow colour is
the cations and anions? (a) Presence of Na+ ions in the crystal lattice
(a) LiF (b) CsF
(b) Presence of Cl– ions in the crystal lattice
(c) CsI (d) LiI
21. Potassium crystallizes with a (c) Presence of electrons in the crystal lattice
(a) body-centred cubic lattice (d) Presence of face centred cubic crystal lattice.
(b) face-centred cubic lattice 34. Schottky defect in crystals is observed when
(c) simple cubic lattice (a) unequal number of cations and anions are missing from
(d) orthorhombic lattice the lattice
22. The range of radius ratio (cationic to anionic) for an (b) equal number of cations and anions are missing from the
octahedral arrangement of ions in an ionic solid is lattice
(a) 0 – 0.155 (b) 0.155 – 0.225 (c) an ion leaves its normal site and occupies an interstitial
(c) 0.225 – 0.414 (d) 0.414 – 0.732 site
23. The interionic distance for cesium chloride crystal will be (d) density of the crystal is increased
a 35. Which of the following has Frenkel defects?
(a) a (b) (a) Sodium chloride (b) Graphite
2
(c) Silver bromide (d) Diamond
3a 2a
(c) (d) 36. Which of the following crystals does not exhibit Frenkel
2 3 defect?
24. Which of the following has hcp crystal stucture? (a) AgBr (b) AgCl
(a) NaCl (b) CaCl (c) KBr (d) ZnS
(c) Zn (d) RbCl 37. Due to Frenkel defect, the density of ionic solids
35. In the fluorite structure, the coordination number of Ca2+ ion (a) decreases (b) increases
is :
(c) neither (a) nor (b) (d) does not change
(a) 4 (b) 6
38. A solid with high electrical and thermal conductivity from
(c) 8 (d) 3
the following is
26. For an ionic crystal of the general formula AX and co-
ordination number 6, the radius ratio value will be (a) Si (b) Li
(a) greater than 0.73 (b) between 0.73 and 0.41 (c) NaCl (d) Ice
(c) between 0.41 & 0.22 (d) Less than 0.22 39. If we mix a pentavalent impurity in a crystal lattice of
27. In CsCl, if coordination number of Cs+ is 8, then coordination germanium, what type of semiconductor formation will occur?
number of Cl– ion is : (a) p-type (b) n-type
(a) 4 (b) 6 (c) both (a) and (b) (d) None of the two.
(c) 8 (d) 12 40. The addition of arsenic to germanium makes the latter a
28. The number of unit cells in 58.8 g of NaCl is nearly (a) metallic conductor (b) intrinsic semiconductor
(a) 6 × 1020 (b) 3 × 1022 (c) mixed conductor (d) extrinsic semiconductor
23
(c) 1.5 × 10 (d) 0.5 × 1024
41. A semiconductor of Ge can be made p-type by adding
29. An element has bcc structure having unit cells 12.08×1023.
The number of atoms in these cells is (a) trivalent impurity (b) tetravalent impurity
(a) 12.08 × 1023 (b) 24.16 × 1023 (c) pentavalent impurity (d) divalent impurity
(c) 48.38 × 10 23
(d) 12.08 × 1022 42. On doping Ge metal with a little of Ga, one gets
30. An element (atomic mass = 100 g / mol) having bcc structure (a) p-type semi conductor (b) n-type semi conductor
has unit cell edge 400 pm. Then, density of the element is (c) insulator (d) rectifier
(a) 10.376 g/cm3 (b) 5.188 g/cm3 43. The pure crystalline substance on being heated gradually
3
(c) 7.289 g/cm (d) 2.144 g/cm36 first forms a turbid liquid at constant temperature and still at
31. The edge length of face centred unit cubic cell is 508 pm. If higher temperature turbidity completely disappears. The
the radius of the cation is 110 pm, the radius of one anion is behaviour is a characteristic of substance forming.
(a) 144 pm (b) 288 pm (a) Allotropic crystals (b) Liquid crystals
(c) 618 pm (d) 398 pm (c) Isomeric crystals (d) Isomorphous crystals.
520 Chemistry
44. If one end of a piece of a metal is heated the other end becomes 48. The existence of a substance in more than one solid
hot after some time. This is due to modifications is known as
(a) Energised electrons moving to the other part of the metal (a) Isomorphism
(b) resistance of the metal (b) Polymorphism
(c) mobility of atoms, in the metal
(c) Amorphism
(d) minor perturbation in the energy of atoms.
45. Which of the following is ferroelectric compound? (d) Allotropy
(a) BaTlO3 (b) K4[Fe(CN)6] 49. The second order Bragg diffraction of X-rays with l = 1.0Å
(c) Pb2O3 (d) None of these from a set of parallel planes in a metal occurs at an angle of
46. Which of the folliowing metal oxides is anti-ferromagnetic in 60°. The distance between the scattering planes in the crystal
nature? is
(a) MnO2 (b) TiO2 (a) 0.575Å (b) 1.00Å
(c) VO2 (d) CrO2
(c) 2.00Å (d) 1.15Å
47. Among the following which compound will show the highest
lattice energy? 50. Superconductors are derived from compounds of
(a) KF (b) NaF (a) p-block elements (b) lanthanides
(c) CsF (d) RbF (c) actinides (d) transition elements
1. If NaCl is doped with 10– 4 mol % of SrCl2, the concentration 7. A solid compound XY has NaCl structure. If the radius of the
of cation vacancies will be (NA = 6.02 × 1023 mol–1) cation is 100 pm, the radius of the anion (Y–) will be :
[CBSE-PMT 2007] [CBSE-PMT 2011 M]
16
(a) 6.02 × 10 mol –1 (b) 6.02 × 1017 mol–1 (a) 275.1 pm (b) 322.5 pm (c) 241.5 pm (d) 165.7 pm
14
(c) 6.02 × 10 mol –1 (d) 6.02 × 1015 mol–1 8. A metal crystallizes with a face-centered cubic lattice. The
2. The fraction of total volume occupied by the atoms present edge length of the unit cell is 408 pm. The diameter of the
in a simple cube is [CBSE-PMT 2007] metal atom is : [CBSE-PMT 2012]
(a) 288 pm (b) 408 pm
p p p p
(a) (b) (c) (d) (c) 144 pm (d) 204 pm
3 2 4 2 4 6
9. A metal has a fcc lattice. The edge length of the unit cell is 404
3. If ‘a’ stands for the edge length of the cubic systems : simple pm. The density of the metal is 2.72 g cm-3. The molar mass of
cubic, body centred cubic and face centred cubic, then the the metal is : (NA Avogadro’s constant = 6.02 × 1023 mol-1)
ratio of radii of the spheres in these systems will be [NEET 2013]
respectively, [CBSE-PMT 2008] (a) 30 g mol -1 (b) 27 g mol -1
12 3 16 3
(a) pr (b) pr
3 3 M
X
20 3 24 3
(c) pr (d) pr
3 3
17. In a compound, atoms of element Y form ccp lattice and those
of element X occupy 2/3rd of tetrahedral voids. The formula
of the compound will be [AIEEE 2008]
(a) X4Y3 (b) X2Y3 (c) X2Y (d) X3Y4
18. Copper crystallises in fcc with a unit cell length of 361 pm.
(a) MX (b) MX2 (c) M2X (d) M5 X14
What is the radius of copper atom? [AIEEE 2009]
25. The arrangement of X–ions around A+ion in solid AX is
(a) 127 pm (b) 157 pm
given in the figure (not drawn to scale). If the radius of X– is
(c) 181 pm (d) 108 pm 250 pm, the radius of A+ is [JEE Advanced 2013]
19. The edge length of a face centered cubic cell of an ionic
substance is 508 pm. If the radius of the cation is 110 pm, the
radius of the anion is [AIEEE 2010] –
X
(a) 288 pm (b) 398 pm (c) 618 pm (d) 144 pm
20. Percentages of free space in cubic close packed structure A+
and in body centered packed structure are respectively
[AIEEE 2010]
(a) 30% and 26% (b) 26% and 32%
(c) 32% and 48% (d) 48% and 26% (a) 104 pm (c) 183 pm (b) 125 pm (d) 57 pm
522 Chemistry
28. NH 4 Cl crystallises in a bcc lattice with edge length of unit 32. Al (at. wt 27) crystallizes in the cubic system with a cell edge
of 4.05 Å . Its density is 2.7 g per cm 3 . Determine the unit
-
cell equal to 387 pm. If the radius of the Cl ion is 181 pm, cell type calculate the radius of the Al atom
+ (a) fcc, 2.432 Å (b) bcc, 2.432 Å
the radius of N H 4 ions is (c) bcc, 1.432 Å (d) fcc, 1.432 Å
33. The ratio of inner planar distancess of three types of planes
(a) 366.3 pm (b) 154.1 pm (d100 , d110 , d111 ) for simple cubic lattice are
(c) 92.6 pm (d) None of these
1 1
(a) 1 : 1 : 1 (b) : :1
29. A metal crystallizes in 2 cubic phases fcc and bcc whose unit
2 3 3 2
cell lengths are 3.5 Å and 3.0Å respectively. The ratio of their
densities is (c) 3 : 2 :1 (d) 1 : 2 : 3
(a) 0.72 (b) 2.04 34. In mineral MX 2 , M 2 + does ccp and X - occupy the
(c) 1.46 (d) 3.12 tetrahedral voids. The number of cations and anions per unit
cell, the coordination number of cation and percent of
30. In a cubic closed packed structure of mixed oxides, the lattice tetrahedral voids occupied are
is made up of oxide ion, 20% of tetrahedral voids are occupied (a) 8, 4, 8, 100 % (b) 8, 4, 8, 50%
(c) 4, 8, 8, 50% (d) 4, 8, 8, 100%
by divalent X 2 + ions and 50% of the octahedral voids are
35. Iron crystallizes in several modifications. At about 911°C,
occupied by trivalent Y 3 + ions. The formula of the oxide is the bcc ' a ' form undergoes a trasition to fcc ' g ' form. If the
distance between the two nearest neighbours is the same in
(a) X.Y2O 4 (b) X 4 Y5O10 the two forms at the transition temperature, the ratio of the
(c) X 5 Y4 O10 (d) X 2 YO 4 density of iron in fcc form (r2 ) to that of iron of bcc form
(r1 ) at the transition temperature
31. The ranks of atoms in face centred cubic and hexagonal unit
cells respectively are r1 r1
(a) = 0.918 (b) = 0.718
(a) 6, 4 (b) 4, 6 r2 r2
(c) 1, 6 (d) 2, 6 r1 r1
(c) = 0.518 (d) = 0.318
r2 r2
The Solid State 525
EXERCISE 1
14. (a) Number of unit cells = N A ´ Weight of subs tan ce
High Pressure M. Wt. ´ Z
¾¾¾¾¾
NaCl structure ¬¾¾¾¾¾ ® CsCl structure
1.
(CN 6 : 6) Heat to 760K (CN8 : 8) 6.023 ´ 10 23 ´ 1
= = 2.57 ´ 10 21 unit cells .
3. In the face-centred unit cell, there are eight tetrahedral voids. 58.5 ´ 4
Of these, half are occupied by silver cations. 15. (d) Na has Body centred cubic lattice.
4. Electrical conductivity increases with decrease of 16. (c) ABAB is hexagonal close packing.
temperature. 17. (b) In AB AB packing spheres occupy 74%. 26% is empty.
8. 128 pm. 18. (a) Arrangement of Cl– ions is fcc in NaCl
9. The formula of the compound will be = N3 M2 or M2N3. 19. (b) In bcc each atom has C. No. = 8.
18. (c) 19. (c) 20. (d) 21. (d) 22. (a) 20. (c) In CsI since Cs+ and I– have largest size.
23. (b) 24. (d) 25. (c) 26. (a) 27. (b) 21. (a) Potassium crystallises in BCC lattice.
22. (d) For octahedral r+ / r– = 0.414 – 0.732.
EXERCISE 2
23. (c) CsCl is body centred. Therefore 2r + + 2r – = 3.a body
1. (c)
Glass is amorphous solid. diagonal.
2. (a)
Covalent as in case of diamond.
3a
3. (c)
Covalent bond force (see text). \ r+ + r - = .
4. (b)
The volume to be filled by hard spheres in diamond is 2
0.34. 24. (c) Zn has hcp lattice.
5. (c) The p.f. for body centred cube = 0.68 (see text). 25. (c) In fluorite structure the C.No. of Ca++ is 8. See structure
6. (d) In NaCl structure we have particles at (8 corners + 6 faces) of simple ionic compounds.
one type. (12 edges + 1 in body) other type.
r+
A atoms are at eight corners. Removal of atoms along one 26. (b) Since C.No. is 6 it is octahedral and = 0.414 - 0.73 .
axis from face means removal of two A atoms. r-
27. (c) It is bcc hence, C. No. of each ion is 8.
1 1
\ Number of A atoms = ´8 + ´4 = 3
8 2 28. (c) Number of unit cells = N A ´ Wt. of subs tan ce
M. Wt. ´ Z
1
Number of B atoms = ´12 + 1 = 4 . \ A 3B 4 . 6.023 ´ 10 23 ´ 58.8
4 = = 1.5 ´10 23
58.8 ´ 4
1
7. (a) Number of A atoms = ´8 =1 Total number of molecules
8 29. (b) Number of unit cells =
(Z)
1
Number of B atoms = ´6 = 3 \Number of atoms = 12.08 ´ 1023 ´ 2 = 24.16 ´ 10 23
2
\ Formula AB3 (for bcc Z = 2)
8. (a) Seven crystal systems.
30. (b) r = Z ´ M = 2 ´ 100
9. (b) For tetragonal a = b ¹ c , a = b = g = 90° 3
NA ´ a 6.023 ´ 10 23
´ (400 ´ 10 -10 ) 3
2Cu + + + Fe (CN ) 46 - ¾
¾® Cu 2 [ Fe( CN ) 6 ] ¯
It is not suitable for non aqueous solution as it gets dissolved.
p = pA + pB 0
pA Another artificial semipermeable membrane is Ca3(PO4)2.
V.P.
pB
0
pA OSMOTIC PRESSURE (p) :
The hydrostatic pressure developed on the solution which just
pB prevents the osmosis of pure solvent into the solution through a
semipermeable membrane is called osmotic pressure.
xA = 0 xA = 1
xB = 1 Mole fraction xB = 0
p
Solvent
0
V.P. pA Solution
pB
0
p = p A + pB
pA Semipermeable
membrane
pB p = hrg
xA = 0 xA = 1
xB = 1 Mole fraction xB = 0
=hrg
COLLIGATIVE PROPERTIES : Or
Properties which depend upon the number of particles irrespective The minimum external pressure applied to the solution to just
of their nature (ions or molecules) are called colligative properties. stop the process of osmosis is known as osmotic pressure.
Solutions 533
RELATION BETWEEN OSMOTIC PRESSURE (p) AND
patm p patm LOWERING OF VAPOUR PRESSURE :
Relative lowering of vapour pressure is directly proportional to
osmotic pressure
po - p p´M po - p æ M ö
o
= \ o
µ p ç since Constant ÷
p dRT p è dRT ø
SPM
OSMOLARITY :
Solution Solvent Osmotic behaviour of solutes undergoing association or
dissociation is equal to molarity × number of particles produced
Or per formula unit of solute known as osmolarity.
The minimum external pressure applied on solution to make its REVERSE OSMOSIS :
vapour pressure equal to that of solvent is known as osmotic When the external pressure applied on the solution is more than
pressure. osmotic pressure, the solvent flows from the solution to the pure
DETERMINATION OF OSMOTIC PRESSURE : solvent which is called reverse osmosis. Desalination of sea water
(i) Pfeffer's method is done by reverse osmosis to make it potable.
(ii) Berkeley and Hartley's method (most common) PLAMOLYSIS :
(iii) Morse and Frazer's method The flow of the fluid from the plant cell when placed in a hypertonic
(iv) Townsend's negative pressure method solution is called plamolysis. The plant cell undergoes shrinkage.
(v) De. Vries method EXO-OSMOSIS :
ISOTONIC SOLUTIONS : Outward osmotic flow of fluid from a cell through semipermeable
Solutions having the same osmotic pressure. 0.91% NaCl solution memberane e.g. grape in conc. NaCl solution.
is isotonic with human RBC's. ENDO-OSMOSIS :
HYPOTONIC SOLUTION : Inward osmotic flow of fluid from a cell through semipermeable
Solution having lower Osmotic pressure. membranes e.g. grape in water.
HYPERTONIC SOLUTION : SILICA GARDEN :
Solution having higher osmotic pressure. When coloured salts e.g. Copper Sulphate, Cobalt Nitrate,
Manganese Chloride, Nickel Chloride and Ferrous sulphate etc.
VAN'T HOFF'S THEORY OF DILUTE SOLUTIONS : are placed in Sodium silicate solution of density 1.1, a colloidal
Dilute solutions behave like gases and gas laws can be applied to and semipermeable shell of Silicates is formed round the crystal.
them. Inside this, there is strong solution of salt and outside weak
BOYLE-VAN'T HOFF LAW : solution of sodium silicate. Water permeates into the shell, pressure
rises and the shell bursts out, the salt solution escapes but
Osmotic pressure of a solution is directly proportional to its
immediately reacts with sodium silicate to form again
concentration at constant given temperature.
semipermeable shell of the metallic silicate. The process is repeated
1 again and again and projection of coloured silicates continues to
pµCµ
V grow.
nt
K ´ w ´ 1000 solve
DTb µ m or DTb = K b ´ m = b id
M´W liqu tion
Kb = molal elevation constant or ebullioscopic constant. It is solu
nt
characteristic for given solvent. When olve
s
Vapour pressure
RT02 M A RT02 1
Kf = = Units of Kf = K . Kg mol–1 Colligative property µ , hence higher
1000 lf DH fusion ´ 1000 Molecular mass of solute
values are obtained for molecular masses in case of association.
R = gas constant,
Acetic acid in benzene associates and its observed molecular
T0 = normal freezing point, mass is 120.
lf = heat of fusion per gram of solvent.
O--H—O
Kf is freezing point constant for a given solvent.
MOLAL DEPRESSION CONSTANTS OF SOME CH3–C C–CH3
COMMON SOLVENTS :
O—H--O
Water 1.86 Naphthalene 6.90
Acetic acid
Acetic acid 3.90 Bromoform 14.40
Phenol 7.27 Cyclohexane 20.00 Benzoic acid in benzene associates and its observed molecular
mass is 244.
Benzene 5.12 Camphor 37.70
DETERMINATION OF MOLECULAR WEIGHT BY O--H—O
DEPRESSION IN FREEZING POINT :
C6H5–C C–C6H5
K ´ w ´1000
M= f O—H--O
DTf ´ W
Benzoic acid
Kf = Molal depression constant, w = weight of non-volatile solute,
DTf = depression in freezing point,W = weight of solvent KCl in water dissociates and its observed molecular mass
The method employed is known as Cryoscopic method. The is 37.25.
common methods are + –
KCl K + Cl
(i) The Beckmann method
These observed values are corrected by multiplying by Van't Hoff
(ii) The Rast Method
factor i.
RELATION BETWEEN OSMOTIC PRESSURE AND
VAN'T HOFF FACTOR (i ) :
OTHER COLLIGATIVE PROPERTIES :
Its value is obtained by any of the following expression
æ p o - p ö dRT
(i) p = ç A o A ÷´ Normal molecular mass
ç p ÷ M Relative lowering of vapour pressure (i) i=
è A ø B
Observed molecular mass
25 3
Moles fraction of Na2S2O3 = = 0.065
Moles of ethanol n B = = 0.543 46.1
46
Solutions 537
(III) Number of moles of Na+ ions = 2 × 3 = 6
17.3555 - 17.2350 10 18
6 ´ 1000 or = ´
Molality of Na+ = = 7.73 m 17.3555 m 100
776
Number of moles of S2O32– ions = 3 1.8
0.006943 =
3 ´ 1000 m
Molality of S2O32– = = 3.86 m
776 \ m = 259.25
5. 0.080575 kg of Glauber's Salt is dissolved in water to obtain
1 dm3 of solution of density 1.0772 kgdm–3. Calculate the p o - ps w´M
(b) =
molarity, molality and mole fraction of Na2SO4 in solution. p o m´ w
Sol. Molecular mass of Glauber's salt = 322 g/mol = 0.322
kg mol–1 23.62 - Ps 1.5 ´ 18
or =
0.080575 23.62 60 ´ 50
Moles of Glauber's salt = = 0.2502
0.322
\ Ps = 23.407 mm Hg
Moles of Na2SO4 will be same i.e. 0.2502.
8. The vapour pressure of water at 20°C is 17.54 mm Hg. When
0.2502 20g of solute was added in 50 g water, the V.P. was found to
\ Molarity of solution = = 0.2502 M
1 lower by 0.30 mm Hg. Calculate M wt of solute.
Mass of 1 litre solution = V × d = 1 dm 3 × 1.0772 kg dm–3
= 1.0772 kg po - ps w´M
Sol. =
Mass of Na2SO4 = 0.2502 × 142 (M. wt of Na2SO4 = 142) p o m´ W
= 0.03552 kg
Mass of solvent = (1.0772 – 0.0355) Kg = 1.0417 kg 0.30 20 ´ 18
or =
0.2502 17.54 m ´ 50
Molality m = = 0.24 m
1.0417
\ m = 420.96
1041.7 9. Find the molality of a solution containing non volatile solute
Moles of solvent = = 57.87
18 if the vapour pressure is 2% below the vapour pressure of
pure water. (DHANBAD 1990)
0.2502
Mole fraction of Na2SO4 = = 4.3 ´ 10 -3
0.2502 + 57.87 p o - ps m´M
Sol. Apply o
=
6. How much concentrated H2SO4 of density 1.84 g cm–3 which p 1000
contains 98 mass percent of H2SO4 must be diluted to prepare
where m = molality of solution;
100 cm3 of the 20 mass percent H2SO4 of density 1.14 g cm–
3.
M = Molecular weight of solvent.
p o - ps w M 7 ´ 18
14. 0.85%, aqueous solution of NaNO3 is apparently 90% Now = ´ = = 0.0184
p o m W 68.33 ´ 100
dissociated at 27°C. Calculate the osmotic pressure.
(R = 0.0821 atm K–1 mol–1)
Sol. Molecular weight of NaNO3 = 85 po - ps
= 0.0184
po
Wt ´1000 0.85 ´ 1000
Molarity = = = 0.1 mol lit -1
M. wt ´ V 85 ´ 100 760 - ps
= 0.0184
NaNO3 solution is 90% dissociated 760
NaNO3 Na+ + NO3– \ ps = 746.01 mm Hg
1 – 0.9 0.9 0.9 17. To 500 cm3 of water 3.0 × 10–3 Kg of acetic acid is added. If
23% acetic acid is dissociated, what will be the depression in
Van't Hoff factor i = 1 – 0.9 + 0.9 + 0.9 = 1.9
freezing point? Kf and density of water are 1.86K kg–1 mol–1
\ p = 1.9 ´ 0.1 ´ 0.0821 ´ 300 = 4.68 atm and 0.997 g cm–3 respectively.
Solutions 539
Sol. Mass of acetic acid = 3 × 10–3 kg = 3.0 g
x 2 ´1000
Molecular mass of acetic acid = 60 g now apply the formula m =
x1M1
Mass of Solvent = 500 × 0.997 = 498.5 g
CH3COOH CH3COO– + H+ 1000 ´ 0.012
m= ;
1 – 0.23 0.23 0.23 i = 1.23 0.988 ´ 78
3 ´ 1000 m = 0.156 mol kg -1
\ DTf = K f ´ molality ´ i = 1.86 ´ ´ 1.23 = 0.229
60 ´ 498.5
21. Addition of 0.643 g of a compound to 50 ml of benzene
18. Calculate the molality of a 1 litre solution of 93%
(density 0.879 g mol -1 ), lower the freezing point from 5.51°C
H 2SO 4 (mass/volume). The density of the solution is 1.84
g/ml to 5.03°C. If Kf for benzene is 5.12 kg mol -1 , Calculate the
molecular mass of the compound
93 ´ 1000
Sol. Molarity of 93% H 2SO 4 is = = 9.48
98 ´ 100 K f ´ w ´ 1000
Sol. Molecular mass =
The relation between M and m is as follows DTf ´ W
m´ d 5.12 ´ 0.643 ´ 1000
M= ; =
m M2 0.48 ´ 50 ´ 0.879
1+
1000 = 156.06 g/mol
m ´1.84 ( DTf = (5.51 – 5.03) = 0.48 and Mass of solvent
9.48 =
m ´ 98
1+ = V ´ d = 50 × 0.879)
1000 22. At 100°C benzene and toluene have vapour pressure of 1375
On solving and 558 torr, respectively. Assuming these two form an ideal
m = 10.30 solution calculate the composition of the solution that boils
19. What mass of non volatile solute urea ( NH 2 CONH 2 ) must at 1 atm and 100°C. What is the composition of vapour issuing
at these conditions.
be dissolved in 100 g of water in order to decrease the vapour
pressure of water by 25%. What will be the molality of the Sol. Let xAand xB be the mole fraction of benzene and toluene
solution? respectively
Sol. Let the mass of urea be w g o
then, P = x A p A + (1 - x A )p Bo
Now use the alternate formula
760 = x A × 1375 + (1 – x A ) 558
p0 - p n
= x A = 0.247
p N
Mole fraction of benzene in the vapour phase
100 - 75 W / 60 o
= x ApA 0.247 ´ 1375
75 100 / 18 = = = 0.447
P 760
6000 Mole fraction of toluene in solution
or w = = 111.11 g
54 (1 – 0.247) = 0.753
111.11´ 1000 Mole fraction of toluene in vapour
Molality of urea = (1 – 0.447) = 0.553
60 ´ 100
23. The vapour pressure of pure benzene at a certain temperature
= 18.5 mol kg -1 is 640 mm Hg. The non volatile solid weighing 2.175 g is
20. The vapour pressure of pure benzene at 25°C is 639.7 mm Hg added to 39.0 g of benzene. The vapour pressure of the
and the vapour pressure of a solution of a solute in benzene solution is 600 mm Hg. What is the molar mass of the solid
at the same temperature is 631.9 mm Hg. Calculate the molality substance?
of the solution. Sol. Apply the formula
o
Sol. From Raoult’s law p A = x A PA P° - P n
=
P N
631.9
\ x1 = = 0.988 640 - 600 2.175 / M
639.7 =
600 39 / 78
\ Mole fraction of solute = ( 1 – 0.988) = 0.012 = x 2
M = 65.25 g/mol
540 Chemistry
24. A 0.1 molar solution of NaCl is found to be isotonic with 1%
NaCl Na + + Cl -
urea solution. Calculate
(a) degree of dissociation of sodium chloride. 1– a a a
(b) Van’t Hoff factor and 1- a + a + a
i= ; 1 + a = 1.87
-3 1
Assume density of 1% urea equal to 1 g cm
\ a = 0.87 or 87%
Sol. (a) NaCl Na + + Cl - 27. The freezing point of a solution containing 0.2 g of ethanoic
C(1 – a ) Ca Ca acid in 20 g of benzene is lowered by 0.45°C. Calculate the
Total concentration of species in solution degree of association of ethanoic acid in benzene. Assume
= C(1 + a ) = 0.1(1 + a )
ethanoic acid dimerises in the solvent benzene. Kf for
Osmotic pressure of NaCl
= 0.1 (1 + a ) RT
T benzene = 5.12 K mol -1 kg
Osmotic pressure of urea solution
K f ´ w ´ 1000 5.12 ´ 0.2 ´ 1000
1 Sol. M = = = 113.77
= RT
T DTf ´ W 0.45 ´ 20
60 ´ 0.1
Since two solutions are isotonic, then Van’t Hoff factor
1 Normal M.wt 60
0.1 (1 + a ) RT = RT
T i= = = 0.53
60 ´ 0.1 Observed M.wt 113.77
\ a = 0.667 2 CH 3COOH (CH3COOH)2
(b) Again Van’t Hoff's factor
a
C(1 + a) 1–a
i= = 1.667 2
C
25. What minimum weight of ethane -1, 2-diol must be mixed 1- a + a / 2
Van’t Hoff factor i = = 0.53
with 10 gallons of water to protect it from freezing at – 24°C? 1
Ethane 1, 2 - diol is an antifreeze addition
a
(1 gallon = 3.785 liters, Kf for H 2 O = 1.86 K mol -1 kg) or 1 – = 0.53
2
Sol. DTf = Kf × m (m = Molality) \ Degree of association a = 0.94 = 94%
28. The degree of dissociation of calcium nitrate in dilute solution
24 containing 7 g per 100 g of water at 100°C is 70%. Calculate
\ m= = 12.90
1.86 the vapour pressure of solution.
Freezing point of water = 0.0°C
\ 1 kg of water should contain 12.90 mole of Sol. Ca ( NO 3 ) 2 Ca + + + 2 NO 3-
ethane-1, 2-diol 1– a a 2a
10 gallons of water = 10 × 3.785 Moles at equilibrium
= 37.85 liters 1 – a + a + 2 a = 1 +2 a
Moles of ethane – 1, 2-diol in 37.85 liters = 1 + 2 × 0.7 = 2.4
= 12.9 × 37.85mol Again
1. Which of the following modes of expressing concentration (a) more than the theoretical weight
is independent of temperature? (b) less than the theoretical weight
(a) Molarity (b) Formality (c) same as theoretical weight
(c) Normality (d) Molality (d) None of the above
2. The solubility of a gas in water depends on
7. What is the molarity of H2SO4 solution that has a density
(a) nature of the gas (b) temperature
1.84 gm/cc at 35°C and contains 98% H2SO4 by weight?
(c) pressure of the gas (d) All of these
(a) 4.18 M (b) 8.14 M
3. If one mole of a substance is present in 1 kg of solvent, then
its concentration is called (c) 18.4 M (d) 18 M
(a) Molar conc. (b) Molal conc. 8. The amount of oxalic acid (mol. wt. 63) required to prepare
(c) Normality (d) Strength wt/wt. 500 ml of its 0.10 N solution is
4. Equal volumes of 0.1 M HCl and 0.1M NaOH are mixed. The (a) 0.315 g (b) 3.150 g
concentration of the resulting solution will be (c) 6.300 g (d) 63.00 g
(a) 0.1 M (b) 0.05 M 9. The molarity of the solution containing 7.1 g of Na2SO4 in
(c) 0.2 M (d) 0.0 M 100 ml of aqueous solution is
5. When the solute is present in trace quantities the following (a) 2 M (b) 0.5 M
expression is used (c) 1 M (d) 0.05 M
(a) gram per million (b) milligram percent 10. A solution of CaCl2 is 0.5 mol/litre, then the moles of chloride
(c) microgram percent (d) parts per million ions in 500 ml. will be
6. For preparing 0.1 N solution of a compound from its impure (a) 0.25 (b) 0.50
sample of which the percentage purity is known, the weight
(c) 0.75 (d) 1.00
of the substance required will be
Solutions 543
11. What will be the molality of a solution having 18 g of glucose 20. The vapour pressure of a solvent A is 0.80 atm. When a non-
(mol. wt. = 180) dissolved in 500 g of water? volatile substance B is added to this solvent its vapour
(a) 1 m (b) 0.5 m pressure drops to 0.6 atm. the mole fraction of B in the solution
(c) 0.2 m (d) 2 m is
12. 50 ml of 10N H2SO4, 25 ml of 12 N HCl and 40 ml of 5 N HNO3 (a) 0.25 (b) 0.50
were mixed together and the volume of the mixture was made (c) 0.75 (d) 0.90
1000 ml by adding water. The normality of the resulting 21. At a particular temperature, the vapour pressures of two
solution will be liquids A and B are respectively 120 and 180 mm of mercury.
(a) 1 N (b) 2 N If 2 moles of A and 3 moles of B are mixed to form an ideal
(c) 3 N (d) 4 N solution, the vapour pressure of the solution at the same
13. An aqueous solution of 6.3 g oxalic acid dihydrate is made temperature will be (in mm of mercury)
upto 250 ml. The volume of 0.1 N NaOH required to completely (a) 156 (b) 145
neutralize 10 ml of this solution is (c) 150 (d) 108
22. At room temperature, the mole fraction of a solute is 0.25 and
(a) 40 ml (b) 20 ml
the vapour pressure of a solvent is 0.80 atm. Then the lowering
(c) 10 ml (d) 4 ml
of vapour pressure is
14. 2.5 litre of 1 M NaOH solution are mixed with another 3 litre
(a) 0.75 (b) 0.60
of 0.5 M NaOH solution. Then the molarity of the resulting (c) 0.20 (d) 0.80
solution is 23. Which of the following is not correct for ideal solution?
(a) 0.80 M (b) 1.0 M (a) DSmixing = 0 (b) DVmixing = 0
(c) 0.73 M (d) 0.50 M (c) DHmixing = 0 (d) It obeys Raoult's law
15. 12g of urea is dissolved in 1 litre of water and 68.4 g of 24. Which of the following does not show positive deviation
sucrose is dissolved in 1 litre of water. The lowering of vapour from Raoult's law?
pressure of first case is (a) Benzene-Chloroform
(a) equal to second (b) greater than second (b) Benzene-Acetone
(c) less than second (d) double that of second (c) Benzene-Ethanol
16. Which of the following statement is correct if the (d) Benzene-Carbon tetrachloride
intermolecular forces in liquids A, B and C are in the order 25. Identify the mixture that shows positive deviation from
A < B < C? Raoult's law
(a) B evaporates more readily than A (a) CHCl3 + (CH3)2CO
(b) B evaporates less readily than C (b) (CH3)2CO + C6H5NH2
(c) A and B evaporates at the same rate (c) CHCl3 + C6H6
(d) A evaporates more readily than C (d) (CH3)2CO + CS2
26. Azeotropic mixture of HCl and H2O has
17. The aqueous solution that has the lowest vapour pressure
(a) 48% HCl (b) 22.2% HCl
at a given temperature is
(c) 36% HCl (d) 20.2% HCl
(a) 0.1 molal sodium phosphate 27. Which of the following is not a colligative property?
(b) 0.1 molal barium chloride (a) Depression in freezing point
(c) 0.1 molal glucose (b) Elevation of boiling point
(d) 0.1 molal acetic acid (c) Osmotic pressure
18. Vapour pressure of CCl4 at 25°C is 143 mm Hg. 0.5 g of a non- (d) Modification of refractive index
volatile solute (mol. wt. 65) is dissolved in 100 ml of CCl4. 28. Which of the following is a colligative property?
Find the vapour pressure of the solution. (Density of CCl4 = (a) Change in free energy (b) Change in pressure
1.58 g/cm3) (c) Heat of vapourisation (d) Osmotic pressure
29. Which of the following colligative properties can provide
(a) 141.93 mm Hg (b) 94.39 mm Hg
molar mass of proteins (or polymers or colloids) with greatest
(c) 199.34 mm Hg (d) 143.99 mm Hg precision?
19. The vapour pressure of solvent decreases by 10 mm of (a) Depression in freezing point
mercury when a non-volatile solute was added to the solvent. (b) Osmotic pressure
The mole fraction of the solute in the solution is 0.2. What (c) Relative lowering of vapour pressure
should be the mole fraction of the solvent if the decrease in (d) Elevation of boiling point
vapour pressure is to be 20 mm of mercury ? 30. Isotonic solutions have same
(a) 0.8 (b) 0.6 (a) molar concentration (b) molality
(c) 0.4 (d) 0.4 (c) normality (d) None of these
544 Chemistry
31. When mango is placed in dilute aqueous solution of 42. If the solution boils at a temperature T1 and the solvent at a
hydrochloric acid, it temperature T2 the elevation of boiling point is given by
(a) shrinks (b) swells (a) T1 + T2 (b) T1 – T2
(c) bursts (d) Nothing happens (c) T2 – T1 (d) T1 + T2
32. As a result of osmosis, the volume of the solution
43. Which of the following will have highest boiling point at 1
(a) gradually decreases (b) gradually increases
atm pressure?
(c) is not affected (d) Any of the three
33. The relationship between osmotic pressure at 273 K when (a) 0.1 M NaCl (b) 0.1 M Sucrose
10g glucose (P1), 10 g urea (P2), and 10g sucrose (P3) are (c) 0.1 M BaCl2 (d) 0.1 M Glucose
dissolved in 250 ml of water is 44. A solution of 1 molal concentration of a solute will have
(a) P1 > P2 > P3 (b) P3 > P1 > P2 maximum boiling point elevation when the solvent is
(a) ethyl alcohol (b) acetone
(c) P2 > P1 > P3 (d) P2 > P3 > P1
(c) benzene (d) chloroform
34. 0.1 M NaCl and 0.1 M CH3COOH are kept in separate
45. The normal boiling point of water is 373 K (at 760 mm Hg).
containers. If their osmotic pressures are P 1 and P 2
Vapour pressure of water at 298 K is 23 mm Hg. If enthalpy of
respectively then what is the correct statement?
vaporisation is 40.656 kJ mol–1, the boiling point of water at
(a) P1 > P2 (b) P1 = P2
23 mm Hg pressure will be
(c) P1 < P2 (d) P1 = P2 = 0 atm.
35. What happen when isotonic solution of A (mol. wt. 342) and (a) 250 K (b) 294.4 K
B (mol. wt. 60) are put into communication through (c) 51.6 K (d) 12.5 K
semipermeable membrane? 46. If the elevation in boiling point of a solution of 10 gm of
(a) Transference of solvent from solution of A to that of B solute (mol. wt. = 100) in 100 gm of water is DTb, the
takes place ebullioscopic constant of water is
(b) Transference of solvent from solution of B to that of A (a) 10 (b) 10 DTb
takes place
(c) No transference of solvent from solution of A to that of DTb
(c) DT b (d)
B takes place 10
(d) Change in temperature of the solutions takes place 47. The rise in the boiling point of a solution containing 1.8 g of
36. Which among the following will show maximum osmotic glucose in 100 g of solvent is 0.1°C. The molal elevation
pressure? constant of the liquid is
(a) 1 M NaCl (b) 1 M MgCl2 (a) 0.01 K/m (b) 0.1 K/m
(c) 1 M (NH4)3PO4 (d) 1 M Na2SO4 (c) 1 K/m (d) 10 K/m
37. Isotonic solutions have 48. The boiling point of a solution of 0.11 g of a substance in 15
(a) same boiling point (b) same vapour pressure g of ether was found to be 0.1°C higher than that of pure
(c) same melting point (d) same osmotic pressure ether. The molecular weight of the substance will be (Kb =
38. An aqueous solution of sucrose, C12H22O11, containing 34.2 2.16°K kg mol–1)
g/ litre has an osmotic pressure of 2.38 atmospheres at 17°C. (a) 148 (b) 158
For an aqueous solution of glucose, C6H12O6 to be isotonic (c) 168 (d) 178
with this solution, it would have 49. The boiling point of 0.1 molal K4[Fe(CN)6] solution will be
(a) 34.2 g/lit of glucose (b) 17.1 g/lit of glucose (Given Kb for water = 0.52°K kg mol–1)
(c) 18.0 g/lit of glucose (d) 36.0 g/lit of glucose (a) 100.52°C (b) 100.104°C
39. The osmotic pressure of 5% (mass-volume) solution of cane (c) 100.26°C (d) 102.6°C
sugar at 150°C (mol. mass of sugar = 342) is 50. The freezing point of equimolal aqueous solution will be
(a) 4 atm (b) 5.07 atm highest for
(c) 3.55 atm (d) 2.45 atm (a) C6H5NH3+Cl– (b) Ca(NO3)2
40. A 1% aqueous solution (mass by volume) of a certain (c) La(NO3)2 (d) C6H12O6
substance is isotonic with a 3% solution of dextrose i.e. 51. If all the following four compounds were sold at the same
glucose (molar mass 180) at a given temperature. The molar price, which would be cheapest for preparing an antifreeze
mass of the substance is solution for a car radiator?
(a) 60 (b) 120 (a) CH3OH (b) C2H5OH
(c) 180 (d) 360 (c) C2H4(OH)2 (d) C3H5(OH)3
41. A 5% solution of cane sugar (mol. wt. = 342) is isotonic with 52. Which of the following 0.10 m aqueous solution will have
1% solution of substance X. The molecular weight of X is the lowest freezing point?
(a) 34.2 (b) 171.2 (a) Al2(SO4)3 (b) C6H10O5
(c) 68.4 (d) 136.8 (c) KI (d) C12H22O11
Solutions 545
53. Which of the following aqueous solution will have highest 61. The van't Hoff factor for 0.1 M Ba(NO3)2 solution is 2.74.
depression in freezing point? The degree of dissociation is
(a) 0.1 M Urea (b) 0.1 M Sucrose (a) 91.3% (b) 87%
(c) 0.1 M AlCl3 (d) 0.1 M K4 [Fe(CN)6] (c) 100% (d) 74%
54. The depression in freezing point for 1 M urea, 1 M glucose 62. Formation of a solution from two components can be
and 1 M NaCl are in the ratio considered as
(a) 1 : 2 : 3 (b) 3 : 2 : 2 (i) pure solvent ® separated solvent molecules, DH1
(c) 1 : 1 : 2 (d) None of these
(ii) pure solute ® separated solute molecules, DH2
55. Which one of the following aqueous solutions will have the
lowest freezing point? (iii) separated solvent and solute molecules ®
(a) 0.1 molal solution of urea solution, DH3
(b) 0.1 molal solution of sucrose Solution so formed will be ideal if
(c) 0.1 molal solution of sodium chloride
(a) DHsoln = DH1 + DH 2 - DH3
(d) 0.1 molal solution of calcium chloride
56. The depression of freezing point is directly proportional to (b) DHsoln = DH1 - DH 2 - DH3
(a) mole fraction of the solution
(b) molarity of the solution (c) DHsoln = DH3 - DH1 - DH 2
(c) molality of the solution
(d) molarity of the solvent (d) DHsoln = DH1 + DH 2 + DH3
57. A 0.5 molal solution of ethylene glycol in water is used as 63. If liquids A and B form an ideal solution
coolant in a car. If the freezing point constant of water be
(a) the enthalpy of mixing is zero
1.86°C per mole, the mixture shall freeze at
(a) 0.93°C (b) –0.93°C (b) the entropy of mixing is zero
(c) 1.86°C (d) –1.86°C (c) the free energy of mixing is zero
58. An aqueous solution freezes at –0.186°C (Kf = 1.86, Kb = (d) the free energy as well as the entropy of mixing are each
0.512) what is the elevation in boiling point? zero
(a) 0.186 (b) 0.512
64. 25 ml of a solution of barium hydroxide on titration with a 0.1
(c) 0.86 (d) 0.0512
molar solution of hydrochloric acid gave a titre value of 35
59. The molal freezing point constant for water is 1.86°C/m.
Therefore, the freezing point of 0.1 M NaCl solution in water ml. The molarity of barium hydroxide solution was
is expected to be (a) 0.07 (b) 0.14
(a) –1.86°C (b) –0.186°C (c) 0.28 (d) 0.35
(c) –0.372°C (d) + 0.372°C 65. During depression of freezing point in a solution the
60. The molecular weight of benzoic acid in benzene as
following are in equilibrium
determined by depression in freezing point method
corresponds to (a) liquid solvent, solid solvent
(a) ionization of benzoic acid (b) liquid solvent, solid solute
(b) dimerization of benzoic acid (c) liquid solute, solid solute
(c) trimerization of benzoic acid (d) liquid solute, solid solvent
(d) solvation of benzoic acid
1. A 0.0020 m aqueous solution of an ionic compound (a) Addition of NaCl (b) Addition of Na 2SO4
Co(NH3)5(NO2)Cl freezes at – 0.00732 °C. Number of moles
of ions which 1 mol of ionic compound produces on being (c) Addition of 1.00 molal KI (d) Addition of water
dissolved in water will be (Kf = – 1.86°C/m) 3. A solution of sucrose (molar mass = 342 g mol–1) has been
[CBSE-PMT 2009] prepared by dissolving 68.5 g of sucrose in 1000 g of water.
The freezing point of the solution obtained will be
(a) 3 (b) 4 (c) 1 (d) 2
(Kf for water = 1.86 K kg mol–1). [CBSE-PMT 2010]
2. An aqueous solution is 1.00 molal in KI. Which change will
cause the vapour pressure of the solution to increase? (a) – 0.372°C (b) – 0.520°C
[CBSE-PMT 2010] (d) + 0.372°C (d) – 0.570°C
546 Chemistry
4. 25.3 g of sodium carbonate, Na 2 CO3 is dissolved in enough 12. In mixture A and B components show -ve deviation as
water to make 250 mL of solution. If sodium carbonate (a) D Vmix > 0 [AIEEE 2002]
dissociates completely, molar concentration of sodium ions, (b) D Hmix < 0
Na + and carbonate ions, CO 32– are respectively (Molar mass (c) A – B interaction is weaker than A – A and B – B interaction
of Na2CO3 = 106 g mol–1) [CBSE-PMT 2010] (d) A – B interaction is stronger than A – A and B – B
(a) 0.955 M and 1.910 M (b) 1.910 M and 0.955 M interaction.
(c) 1.90 M and 1.910 M (d) 0.477 M and 0.477 M 13. A pressure cooker reduces cooking time for food because
[AIEEE 2003]
5. The freezing point depression constant for water is
– 1.86ºC m–1. If 5.00 g Na2SO4 is dissolved in 45.0 g H2O, the (a) boiling point of water involved in cooking is increased
freezing point is changed by – 3.82ºC. Calculate the van’t (b) the higher pressure inside the cooker crushes the food
Hoff factor for Na2SO4 [CBSE-PMT 2011] material
(a) 2.05 (b) 2.62 (c) 3.11 (d) 0.381 (c) cooking involves chemical changes helped by a rise in
temperature
6. The van’t Hoff factor i for a compound which undergoes
(d) heat is more evenly distributed in the cooking space
dissociation in one solvent and association in other solvent
is respectively : [CBSE-PMT 2011] 14. In a 0.2 molal aqueous solution of a weak acid HX the degree
of ionization is 0.3. Taking kf for water as 1.85, the freezing
(a) less than one and greater than one.
point of the solution will be nearest to [AIEEE 2003]
(b) less than one and less than one. (a) – 0.360º C (b) – 0.260º C
(c) greater than one and less than one. (c) + 0.480º C (d) – 0.480º C
(d) greater than one and greater than one. 15. Which one of the following aqueous solutions will exihibit
7. Mole fraction of the solute in a 1.00 molal aqueous solution is highest boiling point ? [AIEEE 2004]
[CBSE-PMT 2011] (a) 0.015 M urea (b) 0.01 M KNO3
(a) 0.1770 (b) 0.0177 (c) 0.01 M Na2SO4 (d) 0.015 M glucose
(c) 0.0344 (d) 1.7700 16. 6.02 × 1020 molecules of urea are present in 100 ml of its
solution. The concentration of urea solution is
8. A 0.1 molal aqueous solution of a weak acid is 30% ionized. If
[AIEEE 2004]
Kf for water is 1.86°C/m, the freezing point of the solution will
be : [CBSE-PMT 2011 M] (a) 0.02 M (b) 0.01 M
(a) – 0.18°C (b) – 0.54°C (c) 0.001 M (d) 0.1 M
(Avogadro constant, NA = 6.02 × 1023 mol–1)
(c) – 0.36°C (d) – 0.24°C
17. To neutralise completely 20 mL of 0.1 M aqueous solution of
9. 200 mL of an aqueous solution of a protein contains its 1.26 g.
phosphorous acid (H3PO3), the value of 0.1 M aqueous KOH
The osmotic pressure of this solution at 300 K is found to be
solution required is [AIEEE 2004]
2.57 × 10–3 bar. The molar mass of protein will be (R = 0.083 L
(a) 40 mL (b) 20 mL
bar mol–1 K–1) [CBSE-PMT 2011 M]
(c) 10 mL (d) 60 mL
(a) 51022 g mol–1 (b) 122044 g mol–1
18. For which of the following parameters the structural isomers
(c) 31011 g mol–1 (d) 61038 g mol–1 C2H5OH and CH3OCH3 would be expected to have the same
10. PA and PB are the vapour pressure of pure liquid components, values? [AIEEE 2004]
A and B, respectively of an ideal binary solution. If XA (Assume ideal behaviour)
represents the mole fraction of component A, the total pressure
(a) Boiling points
of the solution will be. [CBSE-PMT 2012]
(b) Vapour pressure at the same temperature
(a) PA + XA (PB – PA) (b) PA + XA (PA – PB)
(c) Heat of vapourization
(c) PB + XA (PB – PA) (d) PB + XA (PA – PB)
(d) Gaseous densities at the same temperature and pressure
11. Freezing point of an aqueous solution is 19. Which of the following liquid pairs shows a positive
(–0.186)°C. Elevation of boiling point of the same solution is deviation from Raoult’s law ? [AIEEE 2004]
Kb = 0.512°C,Kf = 1.86°C, find the increase in boiling point.
(a) Water - nitric acid
[AIEEE 2002]
(b) Benzene - methanol
(a) 0.186°C (b) 0.0512°C
(c) Water - hydrochloric acid
(c) 0.092°C (d) 0.2372°C.
(d) Acetone - chloroform
Solutions 547
20. Which one of the following statements is FALSE? 28. A 5.25% solution of a substance is isotonic with a 1.5% solu-
[AIEEE 2004] tion of urea (molar mass = 60 g mol–1) in the same solvent. If the
(a) The correct order of osmotic pressure for 0.01 M densities of both the solutions are assumed to be equal to
aqueous solution of each compound is 1.0 g cm–3, molar mass of the substance will be [AIEEE 2007]
BaCl 2 > KCl > CH3COOH > Sucrose (a) 210.0 g mol–1 (b) 90.0 g mol–1
(b) The osmotic pressure (p) of a solution is given by the (c) 115.0 g mol–1 (d) 105.0 g mol–1.
equation p = MRT, where M is the molarity of the solution 29. At 80° C, the vapour pressure of pure liquid ‘A’ is 520 mm Hg
(c) Raoult’s law states that the vapour pressure of a and that of pure liquid ‘B’ is 1000 mm Hg. If a mixture solution
component over a solution is proportional to its mole of ‘A’ and ‘B’ boils at 80° C and 1 atm pressure, the amount of
fraction ‘A’ in the mixture is (1 atm = 760 mm Hg) [AIEEE 2008]
(d) Two sucrose solutions of same molality prepared in
(a) 52 mol percent (b) 34 mol percent
different solvents will have the same freezing point
depression (c) 48 mol percent (d) 50 mol percent
30. The vapour pressure of water at 20°C is 17.5 mm Hg. If 18 g of
21. If a is the degree of dissociation of Na 2SO 4 , the Vant
glucose (C6H12O6) is added to 178.2 g of water at 20°C, the
Hoff’s factor (i) used for calculating the molecular mass is
vapour pressure of the resulting solution will be [AIEEE 2008]
[AIEEE 2005]
(a) 1 – 2 a (b) 1 + 2 a (a) 17.325 mm Hg (b) 15.750 mm Hg
(c) 1 – a (d) 1 + a (c) 16.500 mm Hg (d) 17.500 mm Hg
22. Benzene and toluene form nearly ideal solution. At 20°C, the 31. A binary liquid solution is prepared by mixing n-heptane and
vapour pressure of benzene is 75 torr and that of toluene is ethanol. Which one of the following statements is correct
22 torr. The partial vapour pressure of benzene at 20°C for a regarding the behaviour of the solution? [AIEEE 2009]
solution containing 78 g of benzene and 46 g of toluene in (a) The solution is non-ideal, showing – ve deviation from
torr is [AIEEE 2005]
Raoult’s Law.
(a) 53.5 (b) 37.5
(b) The solution is non-ideal, showing + ve deviation from
(c) 25 (d) 50
Raoult’s Law.
23. Two solutions of a substance (non electrolyte) are mixed in
the following manner. 480 ml of 1.5 M first solution + 520 ml (c) n-heptane shows + ve deviation while ethanol shows
of 1.2 M second solution. What is the molarity of the final – ve deviation from Raoult’s Law.
mixture ? [AIEEE 2005] (d) The solution formed is an ideal solution.
(a) 2.70 M (b) 1.344 M 32. Two liquids X and Y form an ideal solution. At 300 K, vapour
(c) 1.50 M (d) 1.20 M pressure of the solution containing 1 mol of X and 3 mol of Y
24. Equimolar solutions in the same solvent have is 550 mm Hg. At the same temperature, if 1 mol of Y is further
[AIEEE 2005] added to this solution, vapour pressure of the solution
(a) different boiling and different freezing points
increases by 10 mm Hg. Vapour pressure ( in mm Hg) of X and
(b) same boiling and same freezing points
Y in their pure states will be, respectively: [AIEEE 2009]
(c) same freezing point but different boiling point
(d) same boiling point but different freezing point (a) 300 and 400 (b) 400 and 600
25. Density of a 2.05M solution of acetic acid in water is (c) 500 and 600 (d) 200 and 300
1.02 g/mL. The molality of the solution is [AIEEE 2006] 33. If sodium sulphate is considered to be completely dissociated
(a) 2.28 mol kg–1 (b) 0.44 mol kg–1 into cations and anions in aqueous solution, the change in
(c) 1.14 mol kg –1 (d) 3.28 mol kg–1
freezing point of water (DTf ), when 0.01 mol
26. 18 g of glucose (C6H12O6) is added to 178.2 g of water. The
of sodium sulphate is dissolved in 1 kg of water, is (Kf = 1.86
vapour pressure of water for this aqueous solution at 100ºC
is [AIEEE 2006] K kg mol–1) [AIEEE 2010]
(a) 76.00 Torr (b) 752.40 Torr (a) 0.372 K (b) 0.0558 K (c) 0.0744 K (d) 0.0186 K
(c) 759.00 Torr (d) 7.60 Torr 34. On mixing, heptane and octane form an ideal solution. At
27. A mixture of ethyl alcohol and propyl alcohol has a vapour 373 K, the vapour pressures of the two liquid components
pressure of 290 mm Hg at 300 K. The vapour pressure of (heptane and octane) are 105 kPa and 45 kPa respectively.
propyl alcohol is 200 mm Hg. If the mole fraction of ethyl Vapour pressure of the solution obtained by mixing 25.0 g of
alcohol is 0.6, its vapour pressure (in mm Hg) at the same heptane and 35 g of octane will be (molar mass of heptane
temperature will be [AIEEE 2007] = 100 g mol–1 and of octane = 114 g mol–1) [AIEEE 2010]
(a) 360 (b) 350 (c) 300 (d) 700 (a) 72.0 kPa (b) 36.1 kPa (c) 96.2 kPa (d) 144.5 kPa
548 Chemistry
35. A 5% solution of cane sugar (molar mass 342) is isotonic with [IIT-JEE 2009]
1% of a solution of an unknown solute. The molar mass of
(a) 4.0× 10– 4 (b) 4.0 × 10–5
unknown solute in g/mol is : [AIEEE 2011RS]
(c) 5.0 × 10– 4 (d) 4.0 × 10–6
(a) 171.2 (b) 68.4 (c) 34.2 (d) 136.2
40. Dissolving 120 g of urea (mol. wt. 60) in 1000 g of water gave
36. Kf for water is 1.86 K kg mol–1. If your automobile radiator
a solution of density 1.15 g/mL. The molarity of the solution
holds 1.0 kg of water, how many grams of ethylene glycol
is [IIT-JEE 2011]
(C2H6 O2) must you add to get the freezing point of the
solution lowered to –2.8ºC ? [AIEEE 2012] (a) 1.78 M (b) 2.00 M (c) 2.05 M (d) 2.22 M
(a) 72 g (b) 93 g (c) 39 g (d) 27 g 41. The freezing point (in °C) of a solution containing 0.1 g
of K3[Fe(CN)6] (Mol. wt. 329) in 100 g of water (Kf = 1.86 K
37. The molarity of a solution obtained by mixing 750 mL of 0.5(M)
kg mol–1) is [IIT-JEE 2011]
HCl with 250 mL of 2(M) HCl will be : [JEE M 2013]
(a) –2.3 × 10–2 (b) –5.7 × 10–2
(a) 0.875 M (b) 1.00 M (c) 1.75 M (d) 0.975 M
(c) –5.7 × 10–3 (d) –1.2 × 10–2
38. When 20 g of naphthoic acid (C11H8O2) is dissolved in 50 g
of benzene (Kf = 1.72 K kg mol–1), a freezing point depression 42. For a dilute solution containing 2.5 g of a non-volatile non-
of 2 K is observed. The Van't Hoff factor (i) is [IIT-JEE 2007] electrolyte solute in 100 g of water, the elevation
in boiling point at 1 atm pressure is 2°C. Assuming
(a) 0.5 (b) 1 (c) 2 (d) 3
concentration of solute is much lower than the concentration
39. The Henry’s law constant for the solubility of N2 gas in water of solvent, the vapour pressure (mm of Hg) of the solution is
at 298 K is 1.0 × 105 atm. The mole fraction of N2 in air is 0.8. (take Kb = 0.76 K kg mol–1) [IIT-JEE 2012]
The number of moles of N 2 from air dissolved in
(a) 724 (b) 740 (c) 736 (d) 718
10 moles of water at 298 K and 5 atm pressure is
1. An X molal solution in carbon tetrachloride show the mole (a) 6.2 g (b) 8.5 g
fraction of solute equal to 0.23527 . The value of X is (c) 12.6 g (d) 14.0 g
(a) 1.55 (b) 1.82 6. At 30°C and 40°C the vapour pressure of a liquid are 0.025
(c) 2.00 (d) 2.16 and 0.050 atm respectively. Calculate the heat of vaporization
2. 3.0 molal sodium hydroxide solution has a density of of the liquid.
1.110 gm L-1 . The molarity of this solution is (a) 14.06 cal/mol (b) 13060 cal/mol
(a) 2.97 (b) 3.05 (c) 140.8 cal /mol (d) 2160 cal/ mol
(c) 3.65 (d) 4.11 7. The equilibrium vapour pressure of water vapour over a 0.20
mole sample of water (l) is 35 torr at 27°C. If the amount of the
3. For a solution of two liquids A and B it was proved that
liquid water is decreased to 0.10 mole, the equilibrium vapour
PS = x A (p°A - p°B ) + p°B . The resulting solution will be pressure of it would be
(a) Non -ideal (b) ideal (a) 17.5 torr (b) 35.0 torr
(c) semi-ideal (d) None of these (c) 51.5 torr (d) None of these
4. The vapour pressure of water at 50°C is 92.5 torr. What will 8. A flask is partially evacuated to 400 torr pressure of air. A
be the vapour pressure of solution which consists of 1 mole small amount of benzene is introduced into the flask in order
of nonvolatile solute in 100 g of water at 50°C that some liquid will remain after equilibrium has been
(a) 906 .5 torr (b) 94.2 torr established. The vapour pressure of benzene at 25°C is 220
torr. . What is the total pressure in the flask at equilibrium at
(c) 91.8 torr (d) 90.8 torr.
25°C ?
5. When 200g of 10% solution was cooled part of the solute
(a) 120 torr (b) 510 torr
precipitated and the concentration of solution become 6% .
The mass of the precipitated solute is (c) 620 torr (d) 480 torr
Solutions 549
9. Which of the following solutions will have the highest 15. Consider the following statements
boiling point?
1. Isotonic solutions have the same molar concentration at
(a) 0.5 molal BaCl2 a given temperature
(b) 1.0 molal KBr 2. The molal elevation constant Kb is a characteristic of a
(c) 1.8 × 1024 glucose molecules per litre. solvent, and is independent of the solute added
3. The freezing point of a 0.1 M aqueous KCl solution is
(d) 100 g powdered glucose in one litre water
more than that of a 0.1 M aqueous AlCl3 solution.
10. Two 1-litre flask A and B are connected to each other by a
Which of these statements is correct?
valve which is closed. Flask A has benzene in equilibrium
with its vapours at 30°C. The flask B, is evacuated, and the (a) 1 and 2 (b) 2 and 3
valve is opened. Which of the following is true. If temperature (c) 1 and 3 (d) 1, 2 and 3
is kept constant.’ 16. The vapour pressure of pure liquid is 70 torr at 300 K. It forms
(a) Some of the benzene molecules would move to flask B an ideal solution with another liquid Y. The mole fraction of Y
from flask A. in the solution is 0.2 and total pressure of solution is 84 torr
at 300 K. The vapour pressure of pure liquid Y at 27° C
(b) Vapour pressure will be half the initial value.
(a) 70 torr (b) 560 torr
(c) The vapour pressure remains unchanged
(c) 140 torr (d) 154 torr
(d) Some more of the liquid benzene in flask A would
17. The molecular mass of a solute cannot be calculated by which
evaporate.
of the following?
11. The vapour pressure of ethanol and methanol are 42.0 mm
and 88.5 mm Hg respectively . An ideal solution is formed at WB ´ RT po WB MA
the same temperature by mixing 46.0 g of ethanol with 16.0 g (a) M B = (b) M B =
pV (po - p)WA
of methanol. What is the mole fraction of methanol vapour ?
(a) 0.467 (b) 0.502 DTb WB ´ 1000 K b WB ´1000
(c) 0.513 (d) 0.556 (c) M B = (d) M B =
K b WA DTb ´ WA
12. Which of the following solutions will have the maximum
lowering of vapour pressure at 300 K 18. At certain hill station pure water boils at 99.725 ° C. If K b for
(a) 1 M CaCl2 (b) 1 M NaCl water is 0.513 ° C kg mol-1 , the boiling point of 0.69 m solution
(c) 1 M Phenol (d) 1 M sucrose of urea will be
13. Two Aqueous solutions S1 and S2 are separated by a (a) 103 °C (b) 100.079 °C
semipermeable membrane . Solution S1 has got a greater (c) 100.359 °C (d) unpredictable
vapour pressure than solution S2 . Water will be flowing 19. Two elements A and B form compounds of formula AB2 and
(b) from S2 to S1 lowers F. pt. by 2.3° C whereas 1.0 g of AB4 lowers F. pt. by
(c) in both the directions 1.3° C. The K f for benzene is 5.4. The atomic masses of A
(d) in either direction depending upon the nature of the and B are
solute (a) 25, 42 (b) 42, 25
14. What is the degree of dissociation of sodium chloride, if the (c) 52, 48 (d) 48, 52
molar mass determined by a cryoscopic method was found to
20. The heat of vaporisation of benzene is 7353 cal mol -1 . The
be 31.80 g mol-1 [ Atomic mass Na = 23 g mol–1 Cl = 35.5 g mol–
1] ? approximate bpt. of benzene is
EXERCISE 1
50 ´ 10 + 25 ´ 12 + 40 ´ 5
= = 1N
7. (a) 0×322 mol/kg. 1000
(b) 373×165 K.
(c) 0×137 mm Hg. 13. (a) Normality of oxalic acid = 6.3 ´ 1000 = 0.4
63 ´ 250
8. 177×38 g mol–1
N1V1 = N2V2; 0.1 ×V1 = 0.4 × 10. \ V1 = 40 ml
9. (i) They will shrink due to plasmolysis.
14. (c) M3V3 = M1V1 + M2V2
(ii) They will swell and may even burst.
\ M3 × 5.5 = 2.5 × 1 + 3 × 0.5. \ M3 = 0.727.
14. Sucrose < NaCl < Glucose
12
20. (a) 21. (a) 22. (c) 23. (c) 24. (d) 15. (a) Moles of urea = = 0.2
60
25. (a) 26. (b) 27. (c)
68.4
EXERCISE 2 Moles of sucrose = = 0. 2
342
1. (d) Molality involves weight of solute and solvent, hence it Both are non electrolyte hence lowering of V.P. will be
is independent of temperature. same.
2. (d) All are correct. See Henry's law. 16. (d) Lesser the intermolecular forces, the more the volatile
3. (b) If one mole of solute is present in 1 Kg of solvent the character.
conc. is 1 m. 17. (a) 0.1 m Na3PO4 = 0.4 m (Van't Hoff factor i = 4)
4. (b) Solution will be neutral. Concentration of each will be \ Lowering of vapour pressure will be maximum.
0.05 M since volume got doubled. 18. (a) Relative lowering of V.P. = mole fraction of Solute
5. (d) For very dil. solution the concentration is expressed in
p o - ps
ppm. = x2
po
6. (a) Since the compound is impure more than theoretical
weight is required. 143 - p s 0.5 / 65
= ; p s = 141.93 mm Hg
143 158 / 154
Wt ´1000 98 ´ 1000
7. (c) M = = ´1.84 = 18.4
M. Wt ´ V 98 ´100 19. (b) Dp = x ; Dp = x 2 ; 10 = 0.2 ;
2
po Dp ' x '2 20 x '2
Wt ´ 1000 Wt ´1000
8. (b) M = ; 0.10 = ;
E.wt. ´ V 63 ´ 500 \ x '2 = 0.4, x '1 = 1– 0.4 = 0.6
sum of mole fractions is always 1
Wt = 3.150 g
20. (a) 0.80 - 0.6 = x B ; x B = 0.25
9. (b) M = Wt ´ 1000 ; M = 7.1 ´ 1000 = 0.5M 0.80
M.Wt . ´ V 142 ´ 100
21. (a) Vapour pressure of solution = PA + PB
10. (b) CaCl2 Ca++ + 2Cl–. 120 ´ 2 180 ´ 3
= p oA x A + p oB x B = + = 156 mm Hg
Moles of CaCl2 in 500 ml = 0.25 and Cl– = 0.50. 5 5
Wt. ´1000g Dp
11. (c) Apply m = 22. (c) = xB; \ Dp = 0.25 ´ 0.80 = 0.20
M.Wt ´ Wt. of Solvent po
N1V1 + N 2 V2 + N 3 V3 23. (a) DSmixing ¹ 0 for ideal solution. On mixing two solutions
12. (a) N =
Total volume the entropy increases.
552 Chemistry
24. (a) Benzene + chloroform, show negative deviation.
P2 DH v æ T2 - T1 ö
25. (d) CH3COCH3 + CS2 45. (b) Clapeyron Clausius equation log = ç ÷.
P1 2.303R è T1T2 ø
26. (d) Azeotrope of HCl + H2O contains 20.2% HCl.
27. (d) Modification of refractive index is not a colligative 760 40656 æ 373 - T1 ö
log = ç ÷
property. 23 2.303 ´ 8.314 çè 373T1 ÷ø
28. (d) Osmotic pressure.
29. (b) Osmotic pressure. T1 = 294.4K
30. (a) Isotonic solutions have same molar concentration at K b ´ w ´ 1000 DTb ´ 100 ´ 100
given temperature provided the Van't Hoff factor (i) is 46. (c) DTb = ; \Kb = = DTb
M´W 10 ´ 1000
same
31. (b) Mango swells due to osmosis. 0.1 ´ 180 ´ 100
47. (c) K b = =1 K/ m
32. (b) Increases 1.8 ´1000
DTb ´ WB ´1000 1 po 1 æ po ö
17. (c) M B = is wrong. The correct form is or, = Ao . + çç 1 - Ao ÷÷
K b ´ WA xA p B yA è pB ø
K b ´ WB ´1000
MB = p oA 1 po - po
DTb ´ WA = . + B o A
p oB yA pB
18. (b) DTb = K b × m = 0.513 × 0.69 = 0.3539° C
This is equation of straight line.
\ bpt. of solution = 99.725° C + 0.3539° C
= 100.079° C p oA p oB - p oA
Slope = , Intercept =
19. (a) Let the masses of A and B be a and b. The mass of AB2 p oB p oB
will be (a + 2b) g mol -1 and AB4 will be (a + 4b) g mol -1 23. (c) B. pt. = 100 + D T b = 100 + K b m
F. pt. = 0 – D Tf = 0 – Kf m
5.1´1´1000
For AB2, 2.3 = ............ (I)
(a + 2b) ´ 20 Tb – Tf = 100 + K b m – (– K f m)
105 = 100 + 0.51 m + 1.86 m
5.1´1´1000
For AB4, 1.3 = ............ (II) 5
(a + 4b) ´ 20 \ m= = 2.11
2.37
On solving (I) and (II),
Weight of sucrose to be dissolved in 100 g water
a = 25.49 and b = 42.64
2.11´ 342 ´ 100
D H evp = = 72 g
-1 -1 1000
20. (a) Trouton’s rule is = 21 cal. K mol
Tb
24. (b) DTf = 0.3° C
7353
Tb = = 350.1 K = 77.1° C K f ´ WB ´ 1000
21 DTf = 0.3° C =
M B ´ WA
o o
21. (b) Ptotal = p A ´ x A + p B ´ x B
1.86 ´ WB ´ 1000
= 80.0 × 0.4 + 120.0 × 0.6 = 104 mm Hg =
62 ´ 5000
The observed Ptotal is 100 mm Hg which is less than
\ WB = 50 g
104 mm Hg. Hence the solution shows negative deviation.
The amount used should be more than 50 g.
o
22. (c) p A = pA ´ x A = Total pressure × yA 25. (c) XA = 0.70 \ X B = 0.30;
p B = poB ´ x B = Total pressure × yB YA = 0.35 \ YB = 0.65
Where x and y represent mole fraction in liquid and vapour
600 ´ 0.35
phase respectively. p A = 600 × 0.35 \ = p oA
0.70
p oB x B yB p oA = 300 torr
\ = , \
p oB xA yA
600 ´ 0.65
p B = 600 × 0.65 \ = p oB
1 - yA 0.30
poB (1 - x A )
=
poA x A yA
\ p oB = 1300 torr
558 Chemistry
26. (a) Ostwald and Walker’s method When 1 mole of A is added
2 1 2 1
po - ps W2 W2 / m xA = = and x B = =
= = 4 2 4 2
po W1 + W2 W2 / m + W1 / M
1 o 1
W1 = loss of weight of solution, \ p oA . + p B . = 300
2 2
W2 = loss of weight of solvent
\ p oA + p oB = 600 ............. (ii)
0.0345 2.64 / m From (i) and (ii),
\ =
0.645 + 0.0345 2.64 / m + 30 / 74
p oB = 150 and p oA = 450
m = 122 g
When 1 mole of B is added
o o
27. (b) V. P. of solution P = p A x A + pB xB
1 3
xA = , xB =
1 2 4 4
or 250 = p oA . + p oB .
3 3 3 1
\ P = 150 × + 450 × = 225
4 4
p oA + 2 p oB = 750 ............... (i)
17
Electrochemistry
ELECTROLYTES AND ELECTROLYSIS : Z is a constant known as Electrochemical equivalent
A substance which decomposes as a result of the passage of When I = 1 amp., t = 1 sec. then Q = 1 coulomb, then W = Z.
electric current is called an electrolyte and phenomenon of Thus Electrochemical equivalent is the amount of the
decomposition by electricity is called electrolysis. substance deposited or liberated by 1 ampere current
passing for 1 second (i.e. 1 coulomb, I × t = Q)
ELECTROLYTIC CELL :
(II) Second law : When the same quantity of electricity is passed
The apparatus used to carry out electrolysis is known as
through different electrolytes, the amounts of the products
electrolytic cell. The main features of electrolytic cell are :
obtained at the electrodes are directly proportional to their
Feature Cathode Anode chemical equivalents or equivalent weights. Thus
Sign Negative since attached to Positive since attached to Mass of A Eq. wt of A m1 E1 Z1Q Z1
negative end of external positive end of external = ; = = =
battery battery
Mass of B Eq. wt of B m 2 E 2 Z 2 Q Z 2
Direction of into the cell out of the cell Hence electrochemical equivalent µ Equivalent wt.
movement of
electrons ONE FARADAY :
Direction of Cations Anions E µ Z; E = FZ F = Known as Faraday's constant
movement of ions
Half-Reaction Reduction Oxidation One Faraday is the quantity of charge carried by one mole of
electrons
OXIDATION :
Loss of electrons is called oxidation. IF = 1.6023 ´ 10 -19 ´ 6.023 ´ 10 23 = 96500 Coulombs
¾® O 2 + 4H + + 4e -
2H 2 O ¾ AMOUNT OF THE SUBSTANCE 'm' LIBERATED OR
DEPOSITED AT AN ELECTRODE :
REDUCTION :
Gain of electrons is called reduction. Eq . wt of the Sub . ´ I ´ t Eq. wt ´ Q
m= =
96500 96500
2 H 2 O + 2e - ¾
¾® H 2 + 2OH -
Ex.1: Three electrolytic cells A, B and C containing electrolytes
FARADAY'S LAWS OF ELECTROLYSIS : AlCl3, CuSO4 and AgNO3 respectively were connected in
(I) First law : The amount of the substance deposited or series. A steady current of 1.287 ampere was passed through
liberated at an electrode is directly proportional to the the cells for a definite time. After electrolysis 2.158 g of
quantity of electricity passed through an electrolyte silver were deposited at the cathode of cell. Calculate.
W µ I´ t = I´ t ´ Z = Q´ Z (I) total charge passed during electrolysis.
I = Current strength in amp., t = time in sec., (II) time period for which the current is passed
Q = Quantity of charge (coulombs) (III) Mass of aluminium deposited at cathode of cell A
(IV) Mass of Copper deposited at cathode of cell B
560 Chemistry
Eq. of Zn++ deposited =
Eq. wt ´ total charge (Q)
Sol.: (I) Amt. deposited =
96500 i´ t 1.70 ´ 90 ´ 230
= = 3.646 ´ 10 -3
96500 100 ´ 96500
107.9
2.158 = ´ total charge Meq. of Zn++ deposited = 3.646
96500
Initial Meq of Zn++ = 300 × 0.160× 2 = 96
2.158 ´ 96500 (Q M × 2 = N for Zn++)
\Q = = 1930 C
107.9 Meq. of Zn++ left in solution 96 – 3.646 = 92.354
1930 C 92.354
(II) Charge = Current × time; \ time = = 1499.6 s [ ZnSO 4 ] = = 0.154M
1.287 A 2 ´ 300
31.75 ´ 2.158 3. Chemical property No change in chemical property there is chemical change
(IV) Mass of copper deposited = = 0.635 g 4. Resistance Resistance is offered Resistance is offered by
107.9 by atomic Kernels interionic attractions,
viscosity of solvent
Ex.2 : The same quantity of electrical charge that deposited
5. Temperature decreases with increase increases with increase of
0.583 g of Ag was passed through solution of gold salt and of temperature temperature
0.355 gold was deposited. Find the oxidation state of gold in 6. Magnitude generally high generally low
the solution. 7. Solvation No solvation Ions are solvated
Sol.: Au n + + ne- ¾
¾® Au FACTORS AFFECTING ELECTROLYTIC
CONDUCTION :
197 Please refer to the properties discussed above viz. viscosity,
Eq. wt. of Au =
n temperature, solvation of ions etc.
m1 E1 0.583 107.9 OHM'S LAW :
= ; = ; The potential difference across the conductor is directly
m 2 E 2 0.355 197
proportional to the current flowing through it.
n
Potential difference µ current
\ n = 3, \ Oxidation state of gold = 3
V µ I; V = RI
Ex.3: Calculate the quantity of electricity that would be
where R is a constant and known as resistance of the conductor
required to reduce 12.3 g of nitrobenzene to aniline if current
efficiency is 50%. If the potential drop across the cell is 3.0 V
R=
volt, how much energy will be consumed. I
Law is applicable to metallic as well as electrolytic conductors. R
Sol.: C 6 H 5 NO 2 + 6H + + 6e - ¾
¾® C 6 H 5 NH 2 + 2H 2 O
is expressed in Ohms also designated as W.
M 123 RESISTANCE (R) :
Eq. wt of nitrobenzene = =
6 6 It offers obstruction to the passage of electric current. It is directly
proportional to the length (l) and inversely proportional to the
E´i´t 123 i ´ t ´ 50 æ 2 ´ 50 ö
W= Þ 12.3 = ´ çi = ÷ area of cross section (a) of the conductor.
96500 6 100 ´ 96500 è 100 ø
l l
(given current efficiency is 50 %) Rµ
= r´
a a
Q = i × t = 115800 coulombs where r is a constant, called resistivity or specific resistance.
Now energy used = Q × V = 115800 × 3 = 347.4 kJ
when l = 1 cm and a = 1 cm2 then r = R
Ex.4: A current of 1.70 amp. is passed through 300 ml of 0.160 M
solution of ZnSO4 for 230 sec with a current efficiency of SPECIFIC RESISTANCE (r) :
90%. Find the molarity of Zn++ after the deposition of Zn The resistance offered by 1 cm3 of the conductor is known as
assuming no change in volume during electrolysis. specific resistance.
1.70 ´ 90 R.a Ohm ´ cm 2
Sol. i = amp. Units of r = = = Ohm cm or W cm
100 l cm
Electrochemistry 561
CONDUCTANCE (C) : RELATION BETWEEN EQUIVALENT CONDUCTIVITY
It is ease of flow of electric current through the conductor ( L eq ) AND SPECIFIC CONDUCTIVITY ( k)
and reciprocal of resistance R.
k ´ 1000 k ´ 1000
C=
1
units ohm–1, mhos or W–1 L eq = k ´ V = =
R Normality of solution N
SPECIFIC CONDUCTIVITY k (KAPPA) : where V is the volume in cm3 or ml containing 1 gev. of the
It is the reciprocal of specific resistance. electrolyte.
UNITS OF EQUIVALENT CONDUCTIVITY :
1 l l æl ö Ohm–1 cm2 eq–1 or W–1 cm2 eq–1 or S cm2 eq–1
k= = = C ´ = C ´ cell constant ç = cell constant ÷
r R.a a èa ø EFFECT OF DILUTION ON EQUIVALENT
Hence specific conductivity k (Kappa) = Conductance × cell CONDUCTIVITY :
constant Since the degree of dissociation of the electrolyte increases with
Units k = Ohm–1 cm–1 = W–1 cm–1 = S cm–1 (W–1 = S, Seimens) dilution, the equivalent conductivity also increases. The increase
is more in case of weak electrolytes than strong electrolytes.
EFFECT OF DILUTION ON CONDUCTANCE :
The equivalent conductivity increases and specific conductivity
The number of current carrying particles or ions per ml decrease
decreases with dilution.
on dilution and specific conductivity, being the conductance of
IMPORTANCE OF EQUIVALENT CONDUCTIVITY :
one centimetre cube of solution, decreases with dilution.
It helps to compare the conductivity of different electrolytes,
CELL CONSTANT AND ITS DETERMINATION : since solutions of different electrolytes having 1 gram equivalent
l each in the same volume will have the same total charge of
The quantity is known as cell constant. Its direct measurement electricity. One mole of NaCl yields ions carrying 2 faradays of
a
electricity and one mole of Na2SO4 yields ions carrying 4 faradays
is very difficult. It is measured by using standard solution of KCl
of electricity. But 1 gram equivalent of each will produce ions
whose conductivity is known at different concentrations and
carrying 2 faradays of electricity
temperatures. Specific conductance of KCl solutions :
Concentration Specific conductance (W–1 cm–1) at Mol wt. of Na 2SO 4
(Equivalent wt. of Na2SO4 = ).
0°C 18°C 25°C 2
0.1M 0.007154 0.011192 0.012886 Hence conductivity of different electrolytes can only be compared
0.01M 0.0007751 0.0012227 0.0014114 if their solutions have equivalent concentrations.
MOLAR CONDUCTIVITY (Lm) :
Specific conductance
Hence cell constant = Measured conductance The conductivity of all the ions produced when 1 mole of an
electrolyte is dissolved in V ml of solution is known as molar
Ex.5: Specific conductance of a decinormal solution of KCl at conductivity.
18°C is 0.0112 Ohm–1 cm–1. The resistance of the cell or
containing the solution at 18°C was found to be 55 Ohm. 'The conductance of a solution containing one gram-mole of
What is the cell constant. electrolyte placed between two large electrodes one centimeter
apart'.
Specific conductance
Sol. Cell constant = RELATION BETWEEN MOLAR CONDUCTIVITY (Lm)
Measured conductance
AND SPECIFIC CONDUCTIVITY ( k) :
0.0112
= 0.616 cm -1 k ´ 1000
= Lm = k ´ V =
1 M
55 where V is the volume in cm3 or ml containing 1 mole of the
electrolyte.
EQUIVALENT CONDUCTIVITY ( L eq ) :
UNITS OF MOLAR CONDUCTIVITY (Lm) :
The conductivity of all the ions produced when 1 gram equivalent Ohm–1 cm2 mol–1 or W–1 cm2 mol–1 or S cm2 mol–1
of an electrolyte is dissolved in V ml of solution is known as
equivalent conductivity EFFECT OF DILUTION ON MOLAR CONDUCTIVITY:
or Since the degree of dissociation of electrolyte increases with
'The conductance of a solution containing 1 gm. equivalent of dilution, L m also increases but less in case of strong electrolytes
electrolyte placed between two large electrodes one centimetre and more in case of weak electrolytes.
apart'.
562 Chemistry
DEBYE-HUCKEL ONSAGAR EQUATION : 1
Sol. Conductance of solution C = ohm–1
Relation between molar conductivity L m at a particular 45
¥
concentration and molar conductivity L m at infinite dilution l 2.3
is given by Cell constant = = 0.6052
a 3.8
L m = L ¥m - b C Specific conductance
where b is constant. It depends upon nature of solvent and
1
temperature. = 0.6052 ´ = 0.01345 Ohm-1cm-1
45
FACTORS AFFECTING THE MOLAR
0.01345 ´1000
CONDUCTIVITY Lm : L eq = = 26.90 Ohm -1cm 2 eq -1
1
(I) Nature of electrolyte : The strong electrolytes like KNO3,
KCl, NH4NO3, HCl, H2SO4, NaOH, KOH etc are completely 2
ionised in aqueous solution and have high values of Lm. N
Ex.7: The specific conductance of an solution of KCl at
The weak electrolytes are ionised to lesser extent in aqueous 50
solution and have lower values of Lm. 25°C is 0.002765 mho. If the resistance of a cell containing
(II) Concentration of the solution : The concentrated solutions this solution is 400 ohms, what is the cell constant.
of strong electolytes have significant inter-ionic attractions,
which reduce the speed of ions and lower the value of Lm. Sol.: Cell constant=
0.002765
= 0.002765 ´ Resistance
The dilution decreases such attractions and increases the Conductance
value of L m. The limiting value L m( L¥m the molar = 0.002765 ´ 400 = 1.106
conductivity at zero concentration or at infinite dilution) KOHLRAUSCH'S LAW :
can be obtained by extrapolating the graph.
At infinite dilution the molar conductivity of an electrolyte is the
L¥m sum of the ionic conductivities of the cations and anions. e.g. for
KCl AxBy.
Lm
CH3 COOH
( )
L ¥m (A x By ) = xl¥ A+ + yl¥ B- ( )
It is important to note that the source of cations (A+) and anions
C (B–) may be electrolyte itself or any other electrolyte.
¥ ¥
In case of weak electrolytes, the degree of ionisation Thus L¥m (CH3COOH) = l CH3COO- + l H +
increases which increases the value of Lm. The limiting value
L¥m cannot be obtained by extrapolating the graph. The ¥ ¥ ¥
(II) L m (Al2 (SO4 )3 ) = 2l Al3+ + 3lSO24-
limiting value, L¥m , for weak electrolytes is obtained by APPLICATIONS OF KOHLRAUSCH'S LAW :
Kohlrausch law. (I) Calculation of molar conductivities of weak electrolytes at
(III) Temperature : The increase of temperature decreases inter- infinite dilution.
ionic attractions, solvation of ions, viscosity and increases Ex.8:Calculate the degree of dissociation of 0.01 M NH4OH
kinetic energy of ions and their speed. Thus Lm increases solution when its molar conductivity is 9.4 Ohm–1 cm2 mol–
with temperature. 1. The molar conductivities at infinite dilution of NaCl, NH Cl
4
(IV) Viscosity of solvent : The higher the value of viscosity the and NaOH are 126, 130 and 217 Ohm–1 cm2 mol –1
lower is the value of Lm. respectively.
(V) Dielectric constant of solvent : The higher the value of
Sol. Lm (NaCl) = lNa+ + lCl- = 126 Ohm cm mol ( I)
¥ ¥ ¥ -1 2 -1
dielectric constant of solvent, the more is the value of Lm.
The former decreases interionic attractions.
L¥m (NH4Cl) = l¥NH+ + lCl
¥ -1
- = 130 Ohm cm mol
2 -1 (II)
DEGREE OF DISSOCIATION (a) : 4
– +
+ –
– + –
– +
– +
–
– +
M ® M n+ + n e M n+ + ne - ® M
Anode Cathode
1. Assembly It is a combination of two half cells, It is a single cell containing the same electrodes
containing the same or different present in the same electrolyte.
electrodes in the same or different electrolytes.
2. Nature of electrodes Anode is negative, Cathode is positive Anode is positive, Cathode is negative
3. Movement of From anode to cathode in Electrons enter through cathode and
electrons external circuit leave through anode.
4. Energy It converts chemical energy It converts electrical energy into chemical
into electrical energy, produced energy. Energy is supplied to the electrolytic
as a result of redox reaction. solution to bring about the redox reaction.
5. Spontaneity Cell reaction is spontaneous. Cell reaction is non-spontaneous.
6. Salt bridge Salt bridge is required. No salt-bridge is required.
564 Chemistry
DANIELL CELL : Cr3+/Cr Cr 3+ + 3e - ¾
¾® Cr –0.74
An electrochemical cell of Zinc and copper metals is known as
Daniell Cell. It is represented as Fe3+/Fe Fe3+ + 3e - ¾
¾® Fe –0.41
Cd++/Cd Cd + + + 2e - ¾
¾® Cd –0.40
Zn plate Voltmeter Cu plate
Ni + + + 2e - ¾
Anode Cathode Ni++/Ni
Salt ¾® Ni –0.25
bridge
0.1 M 0.1 M Sn++/Sn Sn + + + 2e - ¾
¾® Sn –0.14
ZnSO4 CuSO 4
1 1
H+/ H 2 H + + e- ¾
¾® H 2 0.00
2 2
Zn (s) | Zn++ (aq.) | | Cu2+ (aqs.) | Cu (s)
Cu++/Cu Cu + + + 2e - ¾
¾® Cu 0.34
¾® Zn 2+ + 2e -
LHS oxidation : Zn ¾
1 1
I2 / I I2 + e- ¾
¾® I 0.54
RHS reduction : Cu 2+ + 2e - ¾
¾® Cu 2 2
Overall reaction :
Ag+/Ag Ag + + e - ¾
¾® Ag 0.80
2+ 2+
Zn + Cu (aq) ¾¾
® Zn (aq) + Cu
Hg++/Hg Hg + + + 2e - ¾
¾® Hg 0.85
By convention cathode is represented on the RHS and anode
on the LHS. Two vertical lines represent the salt bridge.
1 1
Br2 / Br - Br2 + e - ¾
¾® Br - 1.09
FUNCTION OF SALT BRIDGE : 2 2
(I) Completes the circuit and allows the flow of current (II) It
1
maintain the electrical neutrality on both sides. Salt-bridge Cr2 O 72- / Cr 3+ 1
Cr2 O72- + 7H + + 3e - ¾¾
7
® Cr 3+ + H 2 O 1.33
generally contains solution of strong electrolyte such as KNO3, 2 2 2
KCl etc. KCl is preferred because the transport numbers of K+
1 1
and Cl– are almost same. Cl 2 / Cl - Cl 2 + e - ¾
¾® Cl - 1.36
2 2
ELECTRODE POTENTIAL :
When an electrode is in contact with the solution of its own ions in MnO -4 / Mn + + MnO 4- + 8H + + 5e - ¾
¾® Mn + + + 4H 2 O 1.51
a half cell, it has a tendency to lose or gain electrons which is known
as electrode potential. It is expressed in volts. H2O2/H2O H 2 O 2 + 2H + + 2e - ¾
¾® 2H 2 O 1.77
Some standard electrode potentials (E° Red) at 298K (ECS)
1 1
Couple Half-Reaction E° Volts F2 / F - F2 + e - ¾
¾® F - 2.87
2 2
Li+/Li Li + + e - ¾
¾® Li –3.05
Hg +2 + / 2Hg Hg 2+ + + 2e - ¾
¾® 2Hg 0.79
M+/M M + + e- ¾
¾® M –2.94
NO 3- / NO, H 2 O NO 3- + 4H + + 3e - ¾
¾® NO + 2H 2 O 0.97
(K, Rb or Cs)
Ba++/Ba Ba + + + 2e - ¾
¾® Ba –2.90 Au3+/Au Au 3+ + 3e - ¾
¾® Au 1.42
OXIDATION POTENTIAL :
Sr++/Sr Sr + + + 2e - ¾
¾® Sr –2.89
The tendency to lose electrons in above case is known as
Ca++/Ca Ca + + + 2e - ¾
¾® Ca –2.76 Oxidation potential.
Oxidation potential of a half-cell is inversely proportional to
Na+/Na Na + + e - ¾
¾® Na –2.71 the concentration of ions in the solution.
REDUCTION POTENTIAL :
Mg++/Mg Mg + + + 2e - ¾
¾® Mg –2.38
The tendency to gain electrons in above case is known as
1 1 reduction potential.
H2 / H- H 2 + e- ¾
¾® H - –2.23 It is not possible to determine the absolute value of electrode
2 2
potential. For this a reference electrode is required. The
Al3+/Al Al3+ + 3e - ¾
¾® Al –1.67 electrode potential is only the difference of potentials between
two electrodes that we can measure by combining them to give
Zn++/Zn Zn + + + 2e - ¾
¾® Zn –0.76 a complete cell.
Electrochemistry 565
Reduction :
STANDARD REDUCTION POTENTIAL ( Eo ):
Mn+ /M
Hg 2 Cl 2 (s) ® Hg 22 + + 2Cl -
According to latest convention the electrode potential is always
represented as reduction potential. If its value is negative, it means Hg 22+ + 2e - ® 2Hg(l)
electrode has oxidation potential. The standard conditions are 1 Overall reaction :
molal solution, 298K temperature and 1 atm. pressure. According
2Hg(l) + 2Cl
– –
to IUPAC convention, the reduction potential alone be called as Hg2Cl2(s) +2e E ºRe d = 0.2422 V
the electrode potential unless it is specifically mentioned. (iii) Silver-silver salt electrode
REFERENCE ELECTRODE : Half cell is Ag, AgCl(s), Cl– (KCl or HCl)
The following electrodes are used as reference electrodes for Oxidation :
determining the standard reduction potentials.
Ag ®Ag+ + e-
(i) Standard hydrogen electrode (SHE) : Standard hydrogen
Ag + + Cl - ® AgCl(s)
electrode (SHE) also known as Normal Hydrogen Electrode
(NHE), consists of platinum wire, carrying platinum foil
coated with finely divided platinum black. The wire is sealed Ag + Cl - ® AgCl(s) + e -
into a glass tube, placed in a beaker containing 1M HCl. The
hydrogen gas at 1 atm pressure is bubbled through the Reduction :
solution at 298K. Half cell is Pt, H2(1 atm)/H+ (1M)
AgCl(s) ® Ag + + Cl -
In SHE, at the surface of platinum, either of the following
reactions can take place Ag + + e - ® Ag
AgCl(s) + e - ® Ag + Cl -
EoRed = 0.2225 V
H2(g) at
1 bar ELECTROMOTIVE FORCE (EMF) OF A CELL :
It is the difference between the electrode potentials of two half-
cells and cause of flow of current from electrode at higher
potential to electrode at lower potential. It is also the measure of
free energy change. Standard EMF of a cell
E ocell = E ocathode - E oanode = E oright - E oleft
1.00 MH
+ Finely divided
platinum coated
ELECTROCHEMICAL SERIES :
on platinum foil It is the arrangement of electrodes in the increasing order of their
o
+ - Standard Reduction potential E M n + / M .
2H (aq) + 2e ® H 2 (g) Reduction
APPLICATIONS OF ELECTROCHEMICAL SERIES :
H 2 (g) ¾¾ ® 2H + (aq) + 2e - Oxidation
(I) The lower the value of E°, the greater the tendency to form
The electrode potential of SHE has been fixed as zero.
cation
All other single electrode potentials are referred to as
potentials on hydrogen scale. M – ne ¾ ¾® M n +
Drawbacks of SHE (II) Replacement (or evolution) of H2 from hydro acids by metals.
1. It is difficult to maintain H2 at 1 atm. pressure.
Metals placed below hydrogen in E.C.S. can not replace
2. It is difficult to maintain H+ ion concentration at 1M
hydrogen from dil. acids but metals placed above hydrogen
3. The platinum electrode is easily poisoned by traces of
can replace hydrogen from dil. acids.
impurities.
Hence calomel and silver chloride electrodes are Ca + H 2SO 4 ¾
¾® CaSO 4 + H 2
conveniently used as reference electrodes.
possible
(ii) Calomel electrode (Hg, Hg2Cl2, KCl)
Half cell is Hg, Hg2Cl2(s) KCl(solution) (Ca + 2H + ® Ca + + + H 2 )
Oxidation :
Cu + H 2SO 4 ¾
¾® CuSO 4 + H 2
2Hg(l) ® Hg 22+ + 2e - not possible
Hg 22 + + 2 Cl -
® Hg 2 Cl 2 (Cu + 2H + ® Cu + + + H 2 )
(III) Metals placed above hydrogen evolve H2 with H2O or steam,
2Hg (l) + 2Cl ® Hg 2 Cl 2 (s) + 2e - but metals placed below hydrogen cannot.
566 Chemistry
(IV) Oxides of metals placed above hydrogen are not reduced
by H2 but oxides of iron and metals placed below iron are Ag(s) + Br - (aq) ® AgBr(s) + e -
reduced by H2
SnO, PbO, Fe3O4, CuO are reduced with H2 AgBr(s) + e - ¾¾
® Ag(s) + Br - (aq)
CaO, MgO, K2O are not reduced with H2 Cl–(aq) / Hg2Cl2(s) / Hg (Pt) :
(V) Oxides of Ag and metals below Ag are decomposed
2Hg(l) + 2Cl- ® Hg 2 Cl2 (s) + 2e -
2HgO ¾
¾® 2Hg + O 2
Hg 2 Cl 2 (s) + 2e - ¾¾
® 2Hg(l) + 2Cl - (aq)
2 Ag 2 O ¾
¾® 4Ag + O 2
OH–(aq) / Cu(OH)2(s) / Cu :
(VI) Reducing character decreases down the series.
(VII) Reactivity decreases down the series. Cu(s) + 2OH - (aq) ® Cu(OH) 2 + 2e -
(VIII)Feasibility of redox reaction : A redox reaction can occur if
the species losing the electrons lie above that which gains Cu(OH) 2 (s) + 2e - ¾¾
® Cu(s) + 2OH - (aq)
the electrons.
(IX) Determination of emf : Emf is the difference of reduction SO--
4 (aq) / PbSO 4 (s) / Pb :
potentials of two half cells.
Eemf = ERHS – ELHS
Pb(s) + SO 4-- (aq) ® PbSO 4 (s) + 2e -
If the value of e.m.f. is positive the reaction can take place
spontaneously, otherwise not.
PbSO 4 (s) + 2e- ¾¾
® Pb(s) + SO --
4 (aq)
FUNCTIONING OF ELECTROCHEMICAL CELL :
With the passage of time the electrode potential of the cathode (IV) Redox electrodes half cells : An inert metal such as platinum
decreases and that of anode increases the difference becomes wire dipped in a solution of ions of the same metal in different
zero, the driving force of emf becomes zero and reaction stops. oxidation states
TYPES OF ELECTRODES AND HALF-CELLS : Fe3+(aq), Fe2+(aq) / Pt : Fe 2+ (aq) ® Fe3+ (aq) + e-
(I) Gas electrodes or gas Ion half cells :
Half-cell Reaction Fe3+ (aq) + e - ¾¾
® Fe 2 + (aq)
Oxidation
Sn4+(aq), Sn2+(aq) / Pt: Sn 2+ (aq) ® Sn 4+ (aq) + 2e-
H + (aq) / H 2 (g) / Pt : H 2 (g ) 2H+ + 2e–
2.303RT 1
Ag + + e - ¾
¾® Ag E M n + / M = E oM n + / M - log
nF [M n + ]
Cu++(aq) / Cu : Cu ® Cu ++ + 2e-
2.303 ´ 8.314 ´ 298 1
Cu + + + 2e - ¾
¾® Cu E M n + / M = E oM n + / M - log
n ´ 96500 [M n + ]
(III) Metal-metal insoluble Salt-Salt anion :
Cl–(aq) / AgCl / Ag:
0.059 1
E M n + /M = E oM n+ /M - log n +
Ag(s) + Cl – (aq) ® AgCl(s) + e - n [M ]
AgCl(s) + e - ¾¾
® Ag(s) + Cl - (aq) If we write the elcetrode reaction, in general, as
Br–(aq) / AgBr / Ag : Oxidised state + ne– Reduced State
Electrochemistry 567
The potential of electrode is given by RELATIONSHIP BETWEEN FREE ENERGY CHANGE
AND EQUILIBRIUM CONSTANT :
RT [Reduced state]
E cell = E cell
o
- 2.303 log
nF [Oxidised state] DGo = -2.303RT log Kc
aA + bB ¾
¾® cC + dD Zn, Zn + + (c1 ) | | Zn + + (c 2 ); Zn c 2 > c1
2.303 c 0.0591 c
2.303RT [C]c [D]d E cell = RT log 2 = log 2
E cell = E cell
o
- log nF c1 n c1
nF [A]a [B]b
Concentration of solids and liquids is taken as unity, APPLICATIONS OF THE CONCENTRATION CELLS :
concentration of ions Mol L–1 and concentration of gases as (I) Determination of valency
partial pressures in Atmosphere. (II) Determination of solubility of sparingly soluble salts.
NERNST EQUATION AND EQUILIBRIUM (III) Determination of transition point.
CONSTANT (Kc) : OVERVOLTAGE :
When Ecell drops to zero the concentration of ions will be The difference between the voltage at which a gas is actually
equilibrium concentrations. We have for general cell reaction evolved and theoretical value at which it ought to have been
evolved during electrolysis is known as overvoltage.
aA + bB cC + dD
REVERSIBLE CELL :
2.303RT [C] [D] c d When the cell reaction can be stopped or reversed by applying
E cell = E cell
o
- log an emf exactly equal to or infinitesimally greater than that of the
nF [A]a [B]b
cell, it is called reversible cell.
Examples of reversible electrodes
2.303RT
E ocell = log K c [Since at equilibrium Ecell = 0] 1. Metal-metal ion electrode : Metal rod dipped into a solution
nF
of its own ions.
0.0591 + –
E ocell = log Kc at 298K. M M +e
n The negative electrode (electrode reaction involving
RELATION BETWEEN ELECTRICAL ENERGY AND oxidation) increases M+ ions in solution
FREE ENERGY (DG) : The positive electrode (electrode reaction involving
reduction) decreases M+ ions in solution.
If n is the number of electrons liberated (or taken up) in a particular
Thus, electrode is reversible with respect to M+ ions
cell reaction, then n faradays (nF) of electricity will be generated
in the complete reaction. If E is the EMF of the cell, then 2. Gas electrodes :
(a) Hydrogen electrode : Pt, H2(g), H+
Electrical energy supplied by the cell = nFE
Reaction
According to Gibbs and Helmholtz, the decrease of free energy
1 H (g) H+ + e–
(–DG) of the reaction occuring in the cell is equal to electrical 2 2
energy The electrode is reversible with respect to H+ ions
Hence, –DG = nFE (b) Chlorine electrode : Pt, Cl2(g), Cl–
Reaction
The standard free energy and E ocell are related as
1 – –
Cl (g) + e Cl (aq)
2 2
DG = o
- nFE ocell The electrode is reversible with respect to Cl– ion.
568 Chemistry
(c) Metal - Metal Salt Ion Electrode : (I) Electrolysis of aqueous NaOH :
¾® Na + + OH -
i) Calomel Electrode
NaOH ¾ Completely dissociated
Hg, Hg2Cl2(s) ; KCl(solution)
Oxidation : ¾® H + + OH - Slightly dissociated
H 2O ¾
2Hg(l )
2+
Hg 2 + 2e
– At cathode : 2 H + + 2e - ¾
¾® 2H ¾
¾® H 2
2+ –
Hg 2 + 2Cl Hg2Cl2(s) At anode : 2OH - - 2e - ¾ ¾® H 2 O + O; O + O ¾
¾® O 2
2Hg + 2Cl
–
Hg2Cl2(s) + 2e
– Current is carried by Na+ and OH– ions.
(II) Electrolysis of aqueous H2SO4
Oxidation decreases concentration of chloride ions.
¾® 2H + + SO 24 -
H 2SO 4 ¾ Completely dissociated
Reduction :
2+ – ¾® H + + OH -
H 2O ¾ Slightly dissociated
Hg2Cl2(s) Hg + 2e
–
2
At cathode : 2H + + 2e - ¾
¾® 2H ¾
¾® H 2
2Hg(l )
2+
Hg + 2e
2
At anode : 2OH - - 2e - ¾
¾® 2OH ¾
¾® H 2 O + O;
2Hg(l ) + 2Cl
– –
Hg2 Cl2(s) + 2e
O+O¾
¾® O 2
Reduction increases the concentration of chloride ions
(III) Electrolysis of aqueous NaCl
The electrode is reversible with respect to Cl– ions.
ii) Silver-Silver Chloride Electrode : Ag, AgCl(s), Cl–(KCl ¾® Na + + Cl -
NaCl ¾ Completely dissociated
or HCl)
¾® H + + OH -
H 2O ¾ Slightly dissociated
Oxidation :
+ – At cathode : 2 H + + 2e - ¾
¾® 2H ¾
¾® H 2
Ag Ag + e
+
Ag + Cl
–
AgCl(s) At anode : 2Cl - - 2e - ¾
¾® 2Cl ¾ ¾® Cl 2
– Although the oxidation potential of OH– is more than Cl–
Ag + Cl AgCl(s)+ e– yet Cl2 is formed at anode due to overvoltage.
Oxidation decreases the concentration of Cl– ions. (IV) Electrolysis of aqueous CuSO4 using Pt electrodes
Reduction : ¾® Cu + + + SO -4 -
CuSO 4 ¾
+ –
AgCl(s) Ag + Cl ¾® H + + OH -
H 2O ¾
+ –
Ag + e Ag At cathode Cu + + + 2e - ¾
¾® Cu
– –
AgCl(s) + e Ag + Cl At anode 2OH - - 2e - ¾
¾® 2OH ¾
¾® H 2 O + O;
Reduction increases the concentration of Cl– O+O¾ ¾® O 2
(d) Oxidation - Reduction Electrodes : Such electrodes (V) Electrolysis of CuSO4 solution using copper electrodes
are set up by inserting unattackable metal (eg Platinum)
into a solution of ions in different oxidation states. The ¾® Cu + + + SO -4 - ;
CuSO 4 ¾ ¾® H + + OH -
H 2O ¾
metal acquires a potential due to tendency of ions in
one oxidation state to change into another stable
At Cathode Cu + + + 2e - ¾
¾® Cu
oxidation state. At Anode ¾® Cu + + + 2e -
Cu ¾
Electrode reaction :
Oxidation potential Cu > OH - > SO 4- -
n+ – (n+m)+ - 3. 4 -1.23 - 2.01
M – me M
2+ – 3+
Fe – e Fe FACTORS GOVERNING THE DISCHARGE
2+ – 4+
Sn – 2e Sn POTENTIAL :
(I) Position in the electrochemical series
IRREVERSIBLE CELL : (II) Concentration of ions in the solution
When the cell reaction cannot be stopped or reversed it is called (III) Nature of electrodes
irreversible cell e.g. cell of Zn and Ag electrodes immersed in Discharge potential of some ions
solution of H2SO4.
Criteria of the formation of products in Electrolysis - Li + < K + < Na + < Ca + + < Mg + + < Al + + < Zn + + < Fe + +
=
Current carried by the cation
=
Uc
NiO 2 ( s ) + 2H 2 O ( l ) + 2e - ® Ni ( OH )2 ( s ) + 2OH - ( aq )
Total current U c + Ua
Net Reaction :
Ua Cd ( s ) + NiO2 ( s ) + 2H 2 O ( l )
Transport number of anion na =
Uc + Ua
® Cd(OH)2 ( s ) + Ni(OH)2 ( s )
Uc = speed of cation and Ua = speed of anion.
Cell potential = 1.4 V.
Further na + nc = 1
FUEL CELLS :
SOME COMMERCIAL CELLS AND THEIR TYPES :
They convert chemical energy into electrical energy and the
They are broadly classified into two groups. reactants are continuously fed and products are removed.
(I) Primary cells : They cannot be recharged and used again. (a) Hydrogen-Oxygen-Fuel Cell : Electrodes are made of porous
Examples are graphite impregnated with catalyst (Pt, Ag or a metal oxide).
(a) Dry cell or Leclanche cell : Particulars are
Anode - Zinc Container H2O
Cathode - graphite rod surrounded by MnO2 powder Anode Cathode
Electrolyte - paste of NH4Cl + ZnCl2
Aqueous electrolyte
Cathode Reaction : MnO2 + NH +4 + e– ¾¾® MnO(OH) + NH3
Anode Reaction : Zn – 2e - ¾
¾® Zn + +
H2 O2
Zn 2 + + 2 NH 3 ¾
¾®[ Zn ( NH 3 ) 2 ]2+
Cell potential 1.25V to 1.5V
(b) Mercury Cell :
Anode - Zn-Hg amalgam
Cathode - paste of (HgO + C) Fuel cell using H2 and O2 produces electricity.
Electrolyte - moist paste of KOH-ZnO
Cathode Reaction : Electrolyte-aqueous solution of KOH or NaOH
- -
HgO(s) + H 2 O( l ) + 2e ¾¾
® Hg(l) + 2OH Oxygen and hydrogen are continuously fed into the cell.
Oxidation (half-cell reaction) :
Anode Reaction : Zn + 2OH - ¾¾
® ZnO + H 2 O(l) + 2e - Reaction : H 2 + 2OH - ¾
¾® 2H 2 O + 2e -
® ZnO(s) + Hg(l)
Net Reaction : Zn(Hg) + HgO(s) ¾¾ Reduction (half-cell reaction) :
cell potential = 1.30 volt O 2 + 2H 2 O + 4e - ¾
¾® 4OH -
(II) Secondary cells : It can be recharged and can be used again
and again. Examples Net Reaction : 2H 2 + O 2 ¾
¾® 2H 2 O
(a) Lead storage battery : EMF of the cell 1 volt.
Anode - Spongy lead (b) Hydrocarbon-oxygen fuel cell : Based upon the combustion
Cathode - grid of lead packed with PbO2 of hydrocarbons such as methane, ethane propane etc.
Electrolyte - 38% H2SO4 by mass Oxidation (half cell reaction) :
Anode Reaction : Pb + SO 4- - ¾
¾® PbSO 4 + 2e - C 3 H 8 + 20 OH - ¾¾
® 3CO 2 + 14H 2 O + 20e -
Cathode Reaction : Reduction (half cell reaction) :
( O 2 + 2 H 2 O + 4e - ¾
¾® 4OH - ) ´ 5
PbO 2 + SO 4- - + 4H + + 2e - ¾
¾® PbSO 4 + 2H 2 O
Net Reaction : Net Reaction C 3 H 8 + 5O 2 ¾
¾® 3CO 2 + 4 H 2 O
Pb + PbO 2 + 4H + + 2SO 4- - ¾
¾® 2PbSO 4 + 2H 2 O ADVANTAGES OF FUEL CELLS :
When recharged the cell reactions are reversed. I. Pollution free II. High efficiency
570 Chemistry
THERMODYNAMIC EFFICIENCY OF FUEL CELLS : 1
Net Reaction, Fe + 2H + + ¾® Fe + + + H 2 O
O2 ¾
-DG -nFEocell 2
h= =
DH DH
1
For H2–O2 fuel cells it is 95%. At surface 2Fe + + + O 2 + 2H 2 O ¾
¾® Fe 2 O 3 + 4H +
2
CORROSION :
Slow formation of undesirable compounds such as oxides, Fe 2 O 3 + xH 2 O ¾
¾® Fe 2 O 3 .xH 2 O
sulphides or Carbonates at the surface of metals by reaction with
moisture and other atmospheric gases is known as corrosion. Net reaction at surface
FACTORS AFFECTING THE CORROSION : 1
2Fe + + + O 2 + ( x + 2)H 2 O ¾
¾® Fe 2 O 3 xH 2 O+ 4H +
(I) Reactivity of metals 2 Rust
(II) Presence of moisture and atmospheric gases like CO2, SO2
etc. PREVENTION OF CORROSION :
(III) Presence of impurities (I) Barrier protection : By painting, coating, electroplating
(IV) Strains in the metal (II) Sacrificial protection : By galvanization, Sherardising
(V) Presence of electrolyte (III) Electrical protection
RUSTING OF IRON-ELECTROCHEMICAL THEORY : (IV) Use of anti rust compounds.
An electrochemical cell known as corrosion cell is developed at
CALCULATION OF POTENTIAL OF INTERMEDIATE
the surface of iron.
Anode ® Pure iron
REACTION :
Cathode ® Impure Surface When two half-reactions having potential E1 and E2 which are
Electrolyte : combined to yield a third half reaction having potential E3. Then
E3 is given by
CO 2 + H 2 O ¾
¾® H 2 CO 3 H + + HCO 3-
SO 2 + H 2 O ¾
¾® H 2SO 3 H + + HSO 3- n1E1 + n 2 E 2
E3 =
n
Anode Reaction ¾® Fe + + + 2e -
Fe ¾
Remember : The cell potentials are not thermodynamic functions
Cathode Reaction 2 H + + 2e - ¾
¾® 2H
and should not be added.
1
2H + O2 ¾
¾® H 2 O
2
Electrochemistry 571
1. Which of the following is the use of electrolysis? 6. A current of 2.0 A passed for 5 hours through a molten metal
(a) Electrorefining (b) Electroplating salt deposits 22.2 g of metal (At wt. = 177). The oxidation
(c) Both (a) and (b) (d) Neither (a) nor (b) state of the metal in the metal salt is
2. Which of the following will form the cathode with respect to
(a) +1 (b) +2
iron anode in an electrolytic cell?
(a) Mg (b) Al (c) +3 (d) +4
(c) Cu (d) Zn 7. A 5 ampere current is passed through a solution of zinc
3. The number of coulombs required for the deposition of sulphate for 40 minutes. Find the amount of zinc deposited
107.870 g of silver is at the cathode
(a) 96500 (b) 48250 (a) 40.65 g (b) 4.065 g
(c) 193000 (d) 10000
(c) 0.4065 g (d) 65.04 g
4. An electrolytic cell contains a solution of Ag2SO4 and has
platinum electrodes. A current is passed until 1.6 gm of O2 8. On passing a current of 1.0 ampere for 16 min and 5 sec
has been liberated at anode. The amount of silver deposited through one litre solution of CuCl2, all copper of the solution
at cathode would be was deposited at cathode. The strength of CuCl2 solution
(a) 107.88 gm (b) 1.6 gm was (Molar mass of Cu = 63.5, Faraday constant = 96500 C
(c) 0.8 gm (d) 21.60 gm mol–1).
5. 1.08 g of pure silver was converted into silver nitrate and its (a) 0.07 M (b) 0.2 N
solution was taken in a beaker. It was electrolysed using
platinum cathode and silver anode. 0.01 Faraday of electricity (c) 0.005 M (d) 0.02 N
was passed using 0.15 volt above the decomposition 9. In a solution of CuSO4 how much time will be required to
potential of silver. The silver content of the beaker after the precipitate 2 g copper by 0.5 ampere current ?
above shall be (a) 12157.48 sec (b) 102 sec
(a) 0 g (b) 0.108 g (c) 510 sec (d) 642 sec
(c) 1.08 g (d) None of these
Electrochemistry 573
10. What is the amount of chlorine evolved when 2 amperes of 21. The unit of equivalent conductivity is
current is passed for 30 minutes in an aqueous solution of (a) ohm cm
NaCl? (b) ohm–1 cm+2 (g equivalent)–1
(a) 66 g (b) 1.32 g (c) ohm cm2 (g equivalent)
(c) 33 g (d) 99 g (d) S cm–2
11. When 9.65 coulombs of electricity is passed through a 22. The conductivity of a saturated solution of BaSO 4
solution of silver nitrate (atomic mass of Ag = 108 is 3.06 × 10–6 ohm–1 cm–1 and its equivalent conductance is
g mol–1), the amount of silver deposited is
1.53 ohm–1 cm2 equiv–1. The Ksp for BaSO4 will be
(a) 16.2 mg (b) 21.2 mg
(a) 4 × 10–12 (b) 2.5 × 10–9
(c) 10.8 mg (d) 6.4 mg –13
12. The charge required to deposit 9 g of Al from Al3+ solution (c) 2.5 × 10 (d) 4 × 10–6
is (At. wt. of Al = 27.0) 23. The resistance of 0.1 N solution of a salt is found to be 2.5×
(a) 3216.3 C (b) 96500 C 103 ohm . The equivalent conductance of the solution is
(c) 9650 C (d) 32163 C (cell constant = 1.15 cm–1)
13. The quantity of electricity needed to deposit 127.08 g of (a) 4.6 (b) 5.6
copper is (c) 6.6 (d) 7.6
(a) 1 Faraday (b) 4 Coulombs 24. Specific conductance of 0.1 M sodium chloride solution is
(c) 4 Faraday (d) 1 Ampere 1.06 × 10 –2 ohm –1 cm –1 . Its molar conductance in
14. Silver is monovalent and has atomic mass of 108. Copper is ohm–1 cm2 mol–1 is
divalent and has an atomic mass of 63.6. The same electric (a) 1.06 × 102 (b) 1.06 × 103
current is passed for the same length of time through a (c) 1.06 × 10 4 (d) 5.3 × 102
silver coulometer and a copper coulometer. If 27.0 g of silver 25. Molar conductivity of a solution is 1.26 × 102 W–1 cm2 mol–1.
is deposited, then the corresponding amount of copper Its molarity is 0.01. Its specific conductivity will be
deposited is (a) 1.26 × 10–5 (b) 1.26 × 10–3
(a) 63.60 g (b) 31.80 g (c) 1.26 × 10 –4 (d) 0.0063
(c) 15.90 g (d) 7.95 g
26. Molar ionic conductivities of a two-bivalent electrolytes
15. By passing 0.1 Faraday of electricity through fused sodium
chloride, the amount of chlorine liberated is x 2+ and y 2- are 57 and 73 respectively. The molar
(a) 35.45 g (b) 70.9 g conductivity of the solution formed by them will be
(c) 3.545 g (d) 17.77 g (a) 130 S cm2 mol–1 (b) 65 S cm2 mol–1
16. The unit of specific conductivity is 2 –1
(c) 260 S cm mol (d) 187 S cm2 mol–1
(a) ohm cm–1 (b) ohm cm–2
27. The equivalent conductivity of 0.1 M weak acid is 100 times
(c) ohm–1 cm (d) ohm–1 cm–1
less than that at infinite dilution. The degree of dissociation
17. The cell constant of a given cell is 0.47 cm–1. The resistance
of a solution placed in this cell is measured to be 31.6 ohm. of weak acid will be
The conductivity of the solution (in S cm–1 where S has (a) 100 (b) 10
usual meaning) is (c) 0.01 (d) 0.001
(a) 0.15 (b) 1.5 28. An electrochemical cell is set up as follows :
(c) 0.015 (d) 150 Pt (H2, 1 atm)/0.1 M HCl/0.1 M acetic acid/(H2, 1 atm) Pt
18. The specific conductivity of N/10 KCl solution at 20°C is EMF of this cell will not be zero because
0.212 ohm–1 cm–1 and the resistance of the cell containing (a) the temperature is constant
this solution at 20°C is 55 ohm. The cell constant is (b) the pH of 0.1 M HCl and 0.1 M acetic acid is not the
(a) 4.616 cm–1 (b) 11.66 cm–1 same
(c) 2.173 cm–1 (d) 3.324 cm–1 (c) acids used in the two compartments are different
19. The resistance of 1 N solution of acetic acid is 250 ohm, (d) EMF of a cell depends on molarities of the acids used
when measured in a cell of cell constant 1.15 cm–1. The 29. Which one of the following reaction occurs at the cathode?
equivalent conductance (in ohm–1 cm2 equiv–1) of 1 N acetic
(a) 2OH - ¾ ¾® H 2 O + O + 2e -
acid will be
(a) 4.6 (b) 9.2 ¾® Ag + + e -
(b) Ag ¾
(c) 18.4 (d) 0.023
(c) Fe 2 + ¾
¾® Fe 3+ + e -
20. The equivalent conductance at infinite dilution of a weak
acid such as HF (d) Cu 2 + + 2e - ¾
¾® Cu
(a) can be determined by extrapolation of measurements of 30. Which of the following statements is true for an
dilute solutions of HCl, HBr and HI electrochemical cell?
(b) can be determined by measurement of very dilute HF
(a) Reduction occurs at H2 electrode
solutions
(b) H2 is cathode and Cu is anode
(c) can be determined from measurements of dilute
solutions of NaF, NaCl and HCl (c) H2 is anode and Cu is cathode
(d) is an undefined quantity (d) Oxidation occurs at Cu electrode
574 Chemistry
31. On the basis of the information available from the reaction 39. The standard electrode potential (E°) for OCl– /Cl– and
1
Cl - / Cl 2 respectively are 0.94 V and –1.36 V. The E° value
4 2
Al + O 2 ¾¾® Al 2 O 3 , D G = - 827 kJmol - 1 of O , the
3 3 2 2
minimum e.m.f. required to carry out electrolysis of Al2O3 is 1
(F = 96500 C mol–1) for OCl - / Cl 2 will be
2
(a) 4.28 V (b) 6.42 V (a) –0.42 V (b) –2.20 V
(c) 8.56 V (d) 2.14 V (c) 0.52 V (d) 1.04 V
32. In the electrochemical reaction 40. The standard reduction potential for Fe 2+ / Fe and
Sn2+/ Sn electrodes are –0.44 and –0.14 volt respectively.
2Fe3+ + Zn ¾ ¾® Zn 2+ + 2Fe 2+ , For the cell reaction
on increasing the concentration of Fe2+
(a) increases cell emf Fe 2+ + Sn ¾
¾® Fe + Sn 2+
(b) increases the current flow the standard emf will be
(a) +0.30 V (b) –0.58 V
(c) decreases the cell emf
(c) +0.58 V (d) –0.30 V
(d) alters the pH of the solution
41. The emf of the cell
33. In the cell reaction
Ni / Ni 2+ (1.0 M ) | | Au 3+ (1.0 M) / Au is [E° for Ni2+ / Ni = –
+ 2+
Cu(s) + 2Ag (aq) ¾¾
® Cu (aq) + 2Ag(s) , 0.25 V; E° for Au3+ / Au = 1.5 V]
Eo 0.46 V. By doubling the concentration of Cu2+, Eocell (a) +1.25 V (b) +1.75 V
cell =
will become (c) –1.25 V (d) –1.75 V
(a) doubled 42. An unknown metal M displaces nickel from nickel (II)
sulphate solution but does not displace manganese from
(b) halved
manganese sulphate solution. Which order represents the
(c) increases but less than double
correct order of reducing power?
(d) decreases by a small fraction (a) Mn > Ni > M (b) Ni > Mn > M
34. If salt bridge is removed from two half-cells the voltage (c) Mn > M > Ni (d) M > Ni > Mn
(a) drops to zero (b) does not change 43. Electrode potentials (E° red ) of four elements A, B, C, D are
(c) increases gradually (d) increases rapidly
–1.36, –0.32, 0, –1.26 V respectively. The decreasing reactivity
35. In a salt bridge KCl is used because order of these elements is
(a) it is an electrolyte (a) A, D, B and C (b) C, B, D and A
(b) it is good conductor of electricity (c) B, D, C and A (d) C, A, D and B
(c) the transport number of K+ and Cl– ions are nearly same 44. Chlorine cannot displace
or both have same ionic mobility (a) Fluorine from NaF (b) Iodine from NaI
(d) it is ionic compound (c) Bromine from NaBr (d) None of these
36. The reference electrode is made by using 45. Standard potentials (E°) for some half-reactions are given
(a) ZnCl2 (b) CuSO4 below :
(c) HgCl2 (d) Hg2Cl2 (I) Sn 4 + + 2e ¾¾
® Sn 2 + ; E° = +0.15V
37. The standard hydrogen electrode potential is zero, because
(a) there is no potential difference between the electrode (II) 2Hg 2 + + 2e ¾
¾® Hg 22+ ; E° = 0.92 V
and the solution
(III) PbO 2 + 4H + + 2e ¾
¾® Pb 2+ + 2 H 2 O;
(b) hydrogen ions acquire electrons from a platinum
electrode E° = +1.45V
(c) it has been measured accurately based on the above, information which one of the following
(d) it has been defined that way statements is correct?
38. The standard reduction potentials E° for the half reactions (a) Sn4+ is a stronger oxidising agent than Pb4+
are as (b) Sn2+ is a stronger reducing agent than Hg22+
(c) Pb2+ is a stronger oxidising agent than Pb4+
¾® Zn 2+ + 2e - ; E° = 0.76 V
Zn ¾ (d) Pb2+ is a stronger reducing agent than Sn2+
46. The oxidation potentails of A and B are +2.37 and +1.66 V
¾® Fe 2+ + 2e - ; E° = 0.41V
Fe ¾ respectively. In chemical reactions
(a) A will be replaced by B
The EMF for the cell reaction will be
(b) A will replace B
(a) –0.3 V (b) 0.35 V
(c) A will not replace B
(c) 1.17 V (d) –1.17 V (d) A and B will not replace each other
Electrochemistry 575
47. Electrode potential data are given below : 53. The e.m.f. of a Daniell cell at 298 K is E1
Fe +3 (aq) + e - ¾¾
® Fe +2 (aq); E° = +0.77 V ZnSO 4 CuSO 4
Zn Cu
(0.01M) (1.0 M)
3+ -
Al (aq) + 3e ¾¾
® Al (s) ; E° = – 1.66 V
When the concentration of ZnSO4 is 1.0 M and that of CuSO4
Br2 (aq) + 2e - ¾¾
® 2Br - (aq); E° = + 1.08V
is 0.01 M, the e.m.f. changed to E2. What is the relationship
between E1 and E2?
Based on the data, the reducing power of Fe2+, Al and Br–
(a) E1 < E2 (b) E1 = E2
will increase in the order
(c) E2 = 0 ¹ E1 (d) E1 > E2
(a) Br– < Fe2+ < Al (b) Fe2+ < Al < Br–
54. The metal that cannot displace hydrogen from dilute
(c) Al < Br– < Fe2+ (d) Al < Fe2+ < Br–
hydrochloric acid is
48. Choose the correct statement from the following which is
related to the electrochemical series (a) aluminium (b) Iron
(a) Electrochemical series is not the arrangement of metals (c) copper (d) zinc
and ions according to their reactivity 55. Which reaction is not feasible?
(b) The metal ions at the top of the electrochemical series (a) 2 KI + Br2 ¾
¾® 2KBr + I 2
are highly electronegative
(c) Strongly electropositive metals can displace weakly (b) 2 KBr + I 2 ¾
¾® 2KI + Br2
electropositive metals from their salt solution
(d) All metals above hydrogen in the series do not displace (c) 2KBr + Cl 2 ¾
¾® 2KCl + Br2
hydrogen from dilute acids
49. The standard reduction potentials of four elements are given (d) 2H 2 O + 2F2 ¾
¾® 4HF + O 2
below. Which of the following will be the most suitable
reducing agent? 56. Which of the following will form a cell with the highest
I = –3.04 V II = – 1.90 V voltage?
III = 0 V IV = 1.90 V (a) 1 M Ag + ,1 M Co 2+ (b) 2 M Ag + , 2 M Co 2+
(a) III (b) II
(c) I (d) IV (c) 0.1 M Ag + , 2 M Co 2+ (d) 2 M Ag + , 0.1 M Co 2+
50. The standard reduction potentials at 298K for the following
half reactions are given against each 57. E° of a cell aA + bB ¾
¾® cC + dD is
Fe3+ (aq) + e Fe2+ (aq) ; 0.770 V 58. The standard EMF for the cell reaction,
æ C2 ö ¾® Pb 2+ + 2e -
(c) Pb ¾
(a) ln (C1) (b) ln çç C ÷÷
è 1ø ¾® 2PbO 2 + 4H + + SO 24- + 2e -
(d) PbSO 4 + 2H 2 O ¾
(c) ln (C1 + C2) (d) ln (C2) 71. Reaction that takes place at graphite anode in dry cell is
62. The relationship between standard reduction potential of a (a) Zn 2 + + 2e - ¾¾
® Zn(s)
cell and equilibrium constant is shown by
® Zn 2 + + 2e -
(b) Zn(s) ¾¾
n 0.059
(a) E ocell = log k c
o
(b) E cell = log k c (c) Mn 2 + + 2e - ¾¾
0.059 n ® Mn(s)
log k c ® Mn + + e - + 1.5V
(d) Mn(s) ¾¾
(c) E ocell = 0.059 n log k c (d) E cell =
o
n 72. Which one of the following cells can convert chemical energy
63. E° for the cell, of H2 and O2 directly into electrical energy?
(a) Mercury cell (b) Daniell cell
Zn | Zn 2+ (aq) | | Cu 2+ (aq)| Cu is 1.10 V at 25°C. The (c) Fuel cell (d) Lead storage cell
equilibrium constant for the cell reaction 73. Hydrogen-Oxygen fuel cells are used in space craft to supply
(a) power for heat and light (b) power for pressure
Zn + Cu 2+ (aq) Cu + Zn 2+ (aq) (c) oxygen (d) water
is of the order of 74. As lead storage battery is charged
(a) 10–37 (b) 1037 (a) lead dioxide dissolves
(c) 10 –17 (d) 1017 (b) sulphuric acid is regenerated
64. The standard EMF of Daniell cell is 1.10 volt. The maximum (c) lead electrode becomes coated with lead sulphate
electrical work obtained from the Daniell cell is (d) the concentration of sulphuric acid decreases
(a) 212.3 kJ (b) 175.4 kJ 75. The thermodynamic efficiency of cell is given by
(c) 106.15 kJ (d) 53.07 kJ (a) DH/DG (b) nFE/DG
65. The emf of Daniell cell is 1.1 volt. If the value of Faraday is (c) nFE/DH (d) nFE
96500 coulombs per mole, the change in free energy in kJ is 76. The electroplating with chromium is undertaken because
(a) 212.30 (b) –212.30 (a) electrolysis of chromium is easier
(c) 106.15 (d) –106.15 (b) chromium can form alloys with other metals
66. Pure water does not conduct electricity because it (c) chromium gives protective and decorative coating to
the base metal
(a) has low boiling point (b) is almost unionised
(d) of the high reactivity of metallic chormium
(c) is neutral (d) is readily decomposed
77. Prevention of corrosion of iron by Zn coating is called
67. At cathode, the electrolysis of aqueous Na2SO4 gives
(a) galvanization (b) cathodic protection
(a) Na (b) H2
(c) electrolysis (d) photoelectrolysis
(c) SO3 (d) SO2
78. Which of the following statements is correct?
68. At anode in the electrolysis of fused NaCl
(a) Oxidation number of oxygen in KO2 is +1
(a) Na+ is oxidized (b) Cl– is oxidized (b) The specific conductance of an electrolyte solution
(c) Cl is reduced (d) Na is reduced decreases with increase in dilution
69. In electrolysis of NaCl when Pt electrode is taken then H2 is (c) Sn2+ oxidises Fe3+
liberated at cathode while with Hg cathode, it forms sodium (d) Zn/ZnSO4 is a reference electrode
amalgam 79. In the electrolytic cell, flow of electrons is from
(a) Hg is more inert than Pt (a) cathode to anode in solution
(b) More voltage is required to reduce H+ at Hg than at Pt (b) cathode to anode through external supply
(c) Na is dissolved in Hg while it does not dissolve in Pt (c) cathode to anode through internal supply
(d) Conc. of H+ ions is larger when Pt electrode is taken (d) anode to cathode through internal supply
Electrochemistry 577
1. Zn gives H2 gas with H2SO4 and HCl but not with HNO3 M
because [CBSE-PMT 2002] 9. The equivalent conductance of solution of a weak
32
(a) Zn acts as an oxidising agent when it reacts with HNO3 2
monobasic acid is 8.0 mho cm and at infinite dilution is 400
(b) HNO3 is weaker acid than H2SO4 and HCl mho cm2. The dissociation constant of this acid is:
(c) in electrochemical series, Zn is above hydrogen
[CBSE-PMT 2009]
(d) NO3– is reduced in preference to hydronium ion
(a) 1.25 × 10–6 (b) 6.25 × 10–4
2. The efficiency of a fuel cell is given by [CBSE-PMT 2007]
(c) 1.25 × 10–4 (d) 1.25 × 10–5
DG DS DH
(a) DG (b) (c) (d) 10. For the reduction of silver ions with copper metal, the standard
DS D H DG DG cell potential was found to be + 0.46 V at 25°C.
3. The equilibrium constant of the reaction: The value of standard Gibbs energy, D G° will be
Cu( s) + 2Ag+ (aq)
Cu 2+ (aq) + 2Ag( s) ;
(F = 96500 C mol –1 ) [CBSE-PMT 2010]
E° = 0.46 V at 298 K is [CBSE-PMT 2007]
(a) – 89.0 kJ (b) – 89.0 J (c) – 44.5 kJ (d) – 98.0 kJ
(a) 2.0 × 1010 (b) 4.0 × 1010 (c) 4.0 × 1015 (d) 2.4 × 1010
4. On the basis of the following E° values, the strongest oxidizing 11. An increase in equivalent conductance of a strong electrolyte
agent is : [CBSE-PMT 2008] with dilution is mainly due to: [CBSE-PMT 2010]
[Fe(CN)6]4– ® [Fe(CN)6]3– + e– ; E° = – 0.35 V (a) increase in ionic mobility of ions
Fe2+ ® Fe3+ + e–; E° = – 0.77 V (b) 100% ionisation of electrolyte at normal dilution
(a) [Fe(CN)6]4– (b) Fe2+ (c) increase in both i.e. number of ions and ionic mobility of
(c) Fe3+ (d) [Fe(CN)6]3– ions
5. Kohlrausch’s law states that at : [CBSE-PMT 2008] (d) increase in number of ions
(a) finite dilution, each ion makes definite contribution to 12. Which of the following expressions correctly represents the
equivalent conductance of an electrolyte, whatever be equivalent conductance at infinite dilution of Al2(SO4)3,
the nature of the other ion of the electrolyte.
° 2-
(b) infinite dilution each ion makes definite contribution to Given that L °Al3+ and LSO are the equivalent
4
equivalent conductance of an electrolyte depending on
the nature of the other ion of the electrolyte. conductances at infinite dilution of the respective ions?
(c) infinite dilution, each ion makes definite contribution to [CBSE-PMT 2010]
conductance of an electrolyte whatever be the nature of
(b) 2L°Al3+ + 3LSO
° 2-
1 ° 1
the other ion of the electrolyte. (a) L 3+ + L° 2-
3 Al 2 SO4 4
(d) infinite dilution, each ion makes definite contribution to
æ ° 2- ö ´ 6
equivalent conductance of an electrolyte, whatever be (c) L°Al3+ + LSO
° 2- (d) èL °Al3+ + LSO
4 4 ø
the nature of the other ion of the electrolyte.
6. Standard free energies of formation (in kJ/mol) at 298 K are 13. Consider the following relations for emf of a electrochemical
– 237.2, – 394.4 and – 8.2 for H2O(l), CO2(g) and pentane (g), cell: [CBSE-PMT 2010]
respectively. The value E°cell for the pentane-oxygen fuel cell (i) emf of cell = (Oxidation potential of anode) –
is : [CBSE-PMT 2008] (Reduction potential of cathode)
(a) 1.968 V (b) 2.0968 V (c) 1.0968 V (d) 0.0968 V (ii) emf of cell = (Oxidation potential of anode) + (Reduction
7. Given: [CBSE-PMT 2009] potential of cathode)
(i) Cu2+ + 2e– ® Cu, Eo = 0.337 V (iii) emf of cell = (Reduction potential of anode) + (Reduction
(ii) Cu2+ + e– ® Cu+, Eo = 0.153 V potential of cathode)
Electrode potential, Eo for the reaction, (iv) emf of cell = (Oxidation potential of anode) – (Oxidation
Cu + + e– ® Cu, will be : potential of cathode)
(a) 0.90 V (b) 0.30 V (c) 0.38 V (d) 0.52 V
Which of the above relations are correct?
8. Al2O3 is reduced by electrolysis at low potentials and high
currents. If 4.0 × 104 amperes of current is passed through (a) (ii) and (iv) (b) (iii) and (i)
molten Al 2 O 3 for 6 hours, what mass of aluminium is (c) (i) and (ii) (d) (iii) and (iv)
produced? (Assume 100% current efficiency. At. mass of 14. Standard electrode potential of three metals X, Y and Z are
Al = 27 g mol–1) [CBSE-PMT 2009] – 1.2 V, + 0.5 V and – 3.0 V, respectively. The reducing power
(a) 8.1 × 104 g (b) 2.4 × 105 g of these metals will be : [CBSE-PMT 2011]
(c) 1.3 × 104 g (d) 9.0 × 103 g (a) Y > Z > X (b) X > Y > Z (c) Z > X > Y (d) X > Y > Z
578 Chemistry
15. The electrode potentials for [CBSE-PMT 2011] 23. At 25°C molar conductance of 0.1 molar aqueous solution
Cu2+(aq) + e– ¾¾ ® Cu+(aq) of ammonium hydroxide is 9.54 ohm-1 cm2mol-1 and at
and Cu+(aq) + e– ¾¾ ® Cu(s) infinite dilution its molar conductance is 238 ohm-1cm2 mol-1.
are + 0.15 V and + 0.50, respectively. The value of The degree or ionisation of ammonium hydroxide at the
E°Cu 2+ / Cu will be : same concentration and temperature is : [NEET 2013]
(a) 20.800% (b) 4.008%
(a) 0.500 V (b) 0.325 V (c) 0.650 V (d) 0.150 V
(c) 40.800% (d) 2.080%
16. Standard electrode potential for Sn4+ / Sn2+ couple is + 0.15 V
24. A button cell used in watches functions as following
and that for the Cr3+ / Cr couple is – 0.74 V. These two couples
in their standard state are connected to make a cell. The cell Zn(s) + Ag2O(s) + H2O(l)
potential will be : [CBSE-PMT 2011] 2Ag(s) + Zn2+(aq) + 2OH–(aq)
(a) + 1.19 V (b) + 0.89 V (c) + 0.18 V (d) + 1.83 V If half cell potentials are :
17. If the E°cell for a given reaction has a negative value, then Zn2+(aq) + 2e– ® Zn(s); Eo = – 0.76 V
which of the following gives the correct relationships for the Ag 2 O(s) + H 2 O (l) + 2e – ® 2Ag(s) + 2OH – (aq);
values of DG° and Keq ? [CBSE-PMT 2011] Eo = 0.34 V
(a) DG° > 0 ; Keq > 1 (b) DG° < 0 ; Keq > 1 The cell potential will be : [NEET 2013]
(c) DG° < 0 ; Keq < 1 (d) DG° > 0 ; Keq < 1 (a) 0.42 V (b) 0.84 V
18. A solution contains Fe2+, Fe3+ and I– ions. This solution (c) 1.34 V (d) 1.10 V
was treated with iodine at 35°C. E° for Fe3+ / Fe2+ is + 0.77 V 25. Conductivity (unit Siemen’s S) is directly proportional to
and E° for I2/2I– = 0.536 V. The favourable redox reaction is : area of the vessel and the concentration of the solution in it
(a) I2 will be reduced to I– [CBSE-PMT 2011 M] and is inversely proportional to the length of the vessel
(b) There will be no redox reaction then the unit of the constant of proportionality is
(c) I– will be oxidised to I2 [AIEEE 2002]
(d) Fe2+ will be oxidised to Fe3+ (a) Sm mol–1 (b) Sm2 mol–1
19. Limiting molar conductivity of NH4OH [CBSE-PMT 2012 S] (c) S–2m2 mol (d) S2m2 mol–2.
(i.e., L° ) is equal to :
26. EMF of a cell in terms of reduction potential of its left and
m(NH4OH right electrodes is [AIEEE 2002]
(a) E = Eleft - Eright (b) E = Eleft + Eright
(a) L°m( NH Cl) + L°m( NaCl) -L°m NaOH (c) E = Eright - Eleft (d) E = -(Eright + Eleft).
4 ( )
27. If f denotes reduction potential, then which is true?
(b) L°m( NaOH ) + L°m( NaCl) -L°m( NH Cl) [AIEEE 2002]
4
(a) E°cell = f right – f left (b) E°cell = f left + f right
(c) L°m( NH 4OH ) + L °m( NH 4Cl) -L°m( HCl)
(c) E°cell = f left – f right (d) E°cell = – ( f left + f right).
(d) L°m( NH 4Cl) + L°m( NaOH)-L°m( NaCl) 28. What will be the emf for the given cell
Pt | H2 (P1) | H+ (aq) | | H2 (P2) | Pt [AIEEE 2002]
20. Standard reduction potentials of the half reactions are given P P
RT RT
below : [CBSE-PMT 2012 M] (a) log 1 (b) log 1
F2(g) + 2e– ® 2F– (aq); E° = + 2.85 V f P2 2f P2
Cl2(g) + 2e– ® 2Cl–(aq); E° = + 1.36 V RT P
Br2(l) + 2e– ® 2Br–(aq); E° = + 1.06 V (c) log 2 (d) None of these.
f P1
I2(s) + 2e– ® 2I–(aq); E° = + 0.53 V
The strongest oxidising and reducing agents respectively 29. Which of the following reaction is possible at anode?
are : [AIEEE 2002]
(a) F2 and I– (b) Br2 and Cl– (a) 2 Cr3+ + 7H2O ® Cr2O72– + 14H+
(c) Cl2 and Br – (d) Cl2 and I2 (b) F2 ® 2F –
21. Molar conductivities ( L° m ) at infinite dilution of NaCl, HCl (c) (1/2) O2 + 2H+ ® H2O
and CH3COONa are 126.4, 425.9 and 91.0 S cm2 mol–1 (d) None of these.
respectively. L°m for CH3COOH will be : 30. For a cell reaction involving a two-electron change, the
[CBSE-PMT 2012 M] standard e.m.f. of the cell is found to be 0.295 V at 25ºC. The
(a) 425.5 S cm2 mol–1 (b) 180.5 S cm2 mol–1 equilibrium constant of the reaction at 25ºC will be
(c) 290.8 S cm2 mol–1 (d) 390.5 S cm2 mol–1 (a) 29.5 × 10–2 (b) 10 [AIEEE 2003]
22. A hydrogen gas electrode is made by dipping platinum (c) 1 × 1010 (d) 1 × 10–10
wire in a solution of HCl of pH = 10 and by passing hydrogen 31. Standard reduction electrode potentials of three metals A, B
gas around the platinum wire at one atm pressure. The & C are respectively + 0.5 V, – 3.0 V & –1.2 V. The reducing
oxidation potential of electrode would be ? [NEET 2013] powers of these metals are [AIEEE 2003]
(a) 0.59 V (b) 0.118 V (a) A > B > C (b) C > B > A
(c) 1.18 V (d) 0.059 V (c) A > C > B (d) B > C > A
Electrochemistry 579
32. When during electrolysis of a solution of AgNO3 9650 41. Aluminium oxide may be electrolysed at 1000°C
coulombs of charge pass through the electroplating bath, to furnish aluminium metal (At. Mass = 27 amu; 1 Faraday =
the mass of silver deposited on the cathode will be 96,500 Coulombs). The cathode reaction is–
(a) 10.8 g (b) 21.6 g [AIEEE 2003]
(c) 108 g (d) 1.08 g Al3+ + 3e- ® Al
33. For the redox reaction : [AIEEE 2003] To prepare 5.12 kg of aluminium metal by this method we
Zn(s) + Cu 2+ (0.1 M) ® Zn 2+ (1 M) + Cu (s) require [AIEEE 2005]
º
taking place in a cell, E cell is 1.10 volt. Ecell for the cell will (a) 5.49 × 101 C of electricity
4
(b) 5.49 × 10 C of electricity
be æç 2.303 RT = 0.0591 ö÷
è F ø 7
(c) 1.83 × 10 C of electricity
(a) 1.80 volt (b) 1.07 volt
(c) 0.82 volt (d) 2.14 volt (d) 5.49 × 10 7 C of electricity
34. Several blocks of magnesium are fixed to the bottom of a
ship to [AIEEE 2003] Electrolyte: KCl KNO3 HCl NaOAc NaCl
42.
(a) make the ship lighter 2
^¥ (S cm mol ) : 149.9
–1
145 426.2 91 126.5
(b) prevent action of water and salt
(c) prevent puncturing by under-sea rocks Calculate L ¥
HOAC using appropriate molar conductances
(d) keep away the sharks
35. In a hydrogen-oxygen fuel cell, combustion of hydrogen of the electrolytes listed above at infinite dilution in H 2 O
occurs to [AIEEE 2004] at 25°C [AIEEE 2005]
(a) produce high purity water (a) 217.5 (b) 390.7
(b) create potential difference between two electrodes
(c) 552.7 (d) 517.2
(c) generte heat
o o
(d) remove adsorbed oxygen from electron surfaces 43. The molar conductivities L NaOAc and L HCl at infinite
36. Consider the following Eº values [AIEEE 2004]
dilution in water at 25ºC are 91.0 and 426.2 S cm2/mol
Eº = +0.77V ; E º Sn 2+ / Sn = -0.14V o
Fe3+ /Fe2 + respectively. To calculate L HOAc , the additional value
Under standard conditions the potential for the reaction required is [AIEEE 2006]
Sn (s) + 2Fe3+ (aq) ® 2Fe 2+ (aq) + Sn 2+ (aq) is o o
(a) L NaOH (b) L NaCl
(a) 0.91 V (b) 1.40 V
o o
(c) 1.68 V (d) 0.63 V (c) LH (d) L KCl
2O
37. The standard e.m.f. of a cell involving one electron change
is found to be 0.591 V at 25ºC. The equilibrium constant of 44. Resistance of a conductivity cell filled with a solution of an
the reaction will be electrolyte of concentration 0.1 M is 100 W. The conductivity
(F = 96,500 C mol–1; R = 8.314 JK–1 mol–1) [AIEEE 2004] of this solution is 1.29 S m–1. Resistance of the same cell
(a) 1.0 × 1010 (b) 1.0 × 105 when filled with 0.2 M of the same solution is 520 W. The
(c) 1.0 × 101 (d) 1.0 × 1030 molar conductivity of 0.02 M solution of electrolyte will be
38. The limiting molar conductivities L º for NaCl, KBr and KCl [AIEEE 2006]
are 126, 152 and 150 S cm2 mol–1 respectively. The L º for (a) 1.24 × 10–4 S m2 mol–1 (b) 12.4 × 10–4 S m2 mol–1
NaBr is [AIEEE 2004] (c) 124 × 10–4 S m2 mol–1 (d) 1240 × 10–4 S m2 mol–1
(a) 278 S cm2 mol–1 (b) 176 S cm2 mol–1 45. The equivalent conductances of two strong electrolytes at
(c) 128 S cm2 mol–1 (d) 302 S cm2 mol–1 infinite dilution in H2O (where ions move freely through a
39. The E º values for Cr, Mn, Fe and Co are – 0.41, + solution) at 25°C are given below : [AIEEE 2007]
M 3+ / M 2 +
1.57, + 0.77 and + 1.97V respectively. For which one of these LoCH3COONa = 91.0 S cm2 / equiv.
metals the change in oxidation state from +2 to +3 is easiest?
L o HCl = 426.2 S cm 2 / equiv.
(a) Fe (b) Mn [AIEEE 2004]
(c) Cr (d) Co What additional information/ quantity one needs to calcu-
40. The highest electrical conductivity of the following aqueous late L o of an aqueous solution of acetic acid?
solutions is of [AIEEE 2005] (a) L o of chloroacetic acid (ClCH2COOH)
(a) 0.1 M difluoroacetic acid
(b) L o of NaCl
(b) 0.1 M fluoroacetic acid
(c) 0.1 M chloroacetic acid (c) L o of CH3COOK
(d) 0.1 M acetic acid (d) the limiting equivalent coductance of H + (l° ).
H+
580 Chemistry
54. Resistance of 0.2 M solution of an electrolyte is 50 W. The
46. The cell, Zn | Zn 2+ (1 M) || Cu 2+ (1 M) | Cu ( E °cell = 1.10 v)
specific conductance of the solution is 1.3 S m–1. If resistance
was allowed to be completely discharged at 298 K. The of the 0.4 M solution of the same electrolyte is 260 W, its molar
æ [Zn 2+ ] ö conductivity is : [AIEEE 2011RS]
relative concentration of Zn2+ to Cu2+ çç 2+ ÷
÷ is (a) 6.25 × 10–4 S m2 mol–1 (b) 625 × 10–4 S m2 mol–1
è [Cu ] ø (c) 62.5 S m2 mol–1 (d) 6250 S m2 mol–1
[AIEEE 2007] 55. The standard reduction potentials for Zn 2+ /Zn,
(a) 9.65 × 104 (b) antilog (24.08) Ni2+/Ni and Fe2+/Fe are –0.76,–0.23 and –0.44 V respectively.
(c) 37.3 (d) 1037.3. The reaction X + Y 2 + ¾¾ ® X 2+ + Y will be spontaneous
47. Given Eº = –0.72 V, Eº 2+ = – 0.42 V. The when : [AIEEE 2012]
Cr 3+ / Cr Fe / Fe (a) X = Ni, Y = Fe (b) X = Ni, Y = Zn
potential for the cell (c) X= Fe, Y = Zn (d) X= Zn, Y = Ni
Cr|Cr3+ (0.1M)|| Fe2 + (0.01 M)| Fe is [AIEEE 2008]
(a) 0.26 V (b) 0.336 V (c) – 0.339 (d) 0.26 V 56. Given : E° 3+ = -0.74 V; E° - = 1.51 V
Cr / Cr MnO4 / Mn 2 +
48. In a fuel cell methanol is used as fuel and oxygen gas is used
as an oxidizer. The reaction is E° 2- 3+ = 1.33 V; E° - = 1.36 V
Cr2O7 / Cr Cl / Cl
CH 3OH(l ) + 3/2O 2 (g) ¾¾ ® CO 2 (g) + 2H 2 O(l ) Based on the data given above, strongest oxidising agent
At 298 K standard Gibb’s energies of formation for CH3OH(l), will be : [JEE M 2013]
H2O(l) and and CO2 (g) are –166.2 –237.2 and –394.4 kJ mol–1 (a) Cl (b) Cr3+
respectively. If standard enthalpy of combustion of methonal (c) Mn2+ (d) MnO4 –
is – 726 kJ mol–1, efficiency of the fuel cell will be: 57. Four successive members of the first row transition elements
[AIEEE 2009] are listed below with atomic numbers. Which one of them is
(a) 87% (b) 90% (c) 97% (d) 80% expected to have the highest E° 3+ 2+ value ?
49. Given: M /M
[JEE M 2013]
E° 3+ = –0.036V, (a) Cr(Z = 24) (b) Mn(Z = 25)
Fe / Fe
(c) Fe(Z = 26) (d) Co(Z = 27)
E° = –0.439V
Fe2+ / Fe 58. Electrolysis of dilute aqueous NaCl solution was carried out
The value of standard electrode potential for the change, by passing 10 milli ampere current. The time required to liber-
ate 0.01 mol of H2 gas at the cathode is (1 Faraday = 96500
Fe3+ ( aq ) + e – ¾¾
® Fe 2+ ( aq ) will be: [AIEEE 2009]
C mol–1)
(a) 0.385 V (b) 0.770 V (c) –0.270 V (d) –0.072 V [IIT-JEE 2008S]
50. The Gibbs energy for the decomposition of Al2O3 at 500°C is (a) 9.65 × 104 sec (b) 19.3 × 104 sec
as follows : (c) 28.95 × 104 sec (d) 38.6 × 104 sec
2 4 59. AgNO3(aq.) was added to an aqueous KCl solution gradually
Al2 O3 ® Al + O2 , D r G = + 966 kJ mol -1 and the conductivity of the solution was measured. The plot
3 3
The potential difference needed for electrolytic reduction of of conductance ( L ) versus the volume of AgNO3 is
Al2O3 at 500°C is at least [AIEEE 2010] [IIT-JEE 2011]
(a) 4.5 V (b) 3.0 V
(c) 2.5 V (d) 5.0 V
51. The correct order of E ° 2+ values with negative sign for
M /M
the four successive elements Cr, Mn, Fe and Co is
[AIEEE 2010]
(a) Mn > Cr > Fe > Co (b) Cr < Fe > Mn > Co
(c) Fe > Mn > Cr > Co (d) Cr > Mn > Fe > Co
52. The reduction potential of hydrogen half-cell will be negative
if : [AIEEE 2011]
(a) p(H2) = 1 atm and [H+] = 2.0 M
(b) p(H2) = 1 atm and [H+] = 1.0 M
(c) p(H2) = 2 atm and [H+] = 1.0 M
(d) p(H2) = 2 atm and [H+] = 2.0 M
53. Consider the following cell reaction: [AIEEE 2011]
2Fe( s) + O2 ( g) + 4H+ (aq) ® 2Fe2+ (aq) + 2H2O(l);E° = 1.67V
At [Fe2+] = 10–3 M, p(O2) = 0.1 atm and pH = 3, the cell
potential at 25ºC is (a) (P) (b) (Q)
(a) 1.47 V (b) 1.77 V (c) 1.87 V (d) 1.57 V (c) (R) (d) (S)
Electrochemistry 581
1. Which of the following solutions of KCl will have the highest 7. What is the reaction taking place at the anode when an
value of specific conductance? aqueous solution of copper sulphate is electrolysed using
(a) 1.0 N (b) 0.1 N Pt–electrodes (inert) ?
(c) 1.0 ×10–2N (d) 1.0 ×10–3N (a) Cu 2 + + 2e - ® Cu
2. Which of the following statements is not correct? (b) 2 H + + 2 e - ® H 2
(a) The equivalent conductance of an electrolyte increases
(c) 2H 2 O ® O 2 + 4H + + 4e -
on dilution.
(b) The equivalent conductance of an electrolyte decreases (d) 2SO 24 - ® S 2 O 82 - + 2e -
on dilution 8. The specific conductance at 298 K of AgCl is
(c) The degree of ionization of a weak electrolyte is given -1 -1
1.826 × 10–6 ohm cm . The ionic conductances of Ag+
by a = l c / l 0 , where l c and l 0 are equivalent
conductances at concentration c and zero respectively and Cl– are 61.92 and 76.34 respectively. What is the solubility
(d) In case of a weak electrolyte on dilution,, specific of AgCl in water ?
conductance decreases but its equivalent conductance (a) 1.1´10 -2 g -1 (b) 1.9 ´ 10 -3 g L-1
increases
3. Which of the following statements is wrong ? (c) 2.1´ 10 -5 g L-1 (d) 2.1´ 10 -6 g L-1
(a) Electrolysis of an aqueous sodium hydroxide solution 9. The potential of a hydrogen electrode at pH=10 is
liberates H2 gas at the cathode and O2 gas at the anode. (a) 0.59 V (b) zero volt
(b) Electrolysis of dil. H2SO4 liberates H2(g) at cathode (c) –0.59 V (d) 0.059 V
10. Equivalent conductance at infinite dilution, l° of NH4Cl,
and O2 (g) at the anode
NaOH and NaCl are 128.0, 217.8 and 109.3 ohm–1 cm2 eq–1
(c) DG°= nFE° for a spontaneous reaction
respectively. The equivalent conductance of 0.01 N NH4OH
0.059 is 9.30 ohm–1 cm2 eq–1, then the degree of ionization of
(d) E=E° - log Q , Where Q = reaction quotient.
n NH4OH at this temperature would be
4. In the electrolysis of CuCl2 solution, the mass of the cathode (a) 0.04 (b) 0.1
increased by 3.2g. What occured at the copper anode ? (c) 0.39 (d) 0.62
(a) 0.12 litre of Cl2 was liberated 11. What is the standard cell potential E° for an electrochemical
cell in which the following reaction takes place
(b) 0.56 litre of O2 was liberated spontaneously ?
(c) 0.1 mol Cu2+ passed into the solution.
Cl2 (g) + 2Br - ® Br2 (aq) + 2Cl- DG° = -50.6 kJ
(d) 0.05 mol of Cu2+ passed into the solution.
(a) 1.2 V (b) 0.53 V
5. Copper can be deposited from acidified copper sulphate (c) 0.26 V (d) –0.53 V
and alkaline copper cyanide both. If the same current is 12. When electric current is passed through acidified water, 112
passed for the definite time, which of the following is correct? ml of hydrogen gas at STP collected at the cathode in 965
(a) The amount of copper deposited from acidic copper seconds. The current passed in amperes is
sulphate will be higher (a) 1.0 (b) 0.5
(b) The amount of copper deposited from alkaline copper (c) 0.1 (d) 2.0
-
cyanide will be more. 13. If the half cell reaction is A + e ® A- has a large negative
(c) The same amount of Cu will be deposited reduction potential , it follows that.
(d) No Cu will be deposited (a) A is readily reduced (b) A is ready oxidised
6. The EMF of the cell Tl/Tl+ (0.001M) || Cu2+ (0.01M) /Cu is (c) A- is readily reduced (d) A- is readily oxidised
0.83. The cell EMF can be increased by 14. The electrochemical equivalent of silver is 0.001180 g. When
(a) Increasing the concentration of Tl+ ions. an electric current of 0.5 amp is passed through an aqueous
silver nitrate solution for 200 sec., the amount of silver
(b) Increasing the concentration of Cu2+ ions. deposited is
(c) Increasing the concentration of Tl + and Cu2+ ions. (a) 1.1180 g (b) 0.1180 g
(d) None of these (c) 5.590 g (d) 0.5598 g
582 Chemistry
15. A gas X at 1 atm is bubbled through a solution containing a 21. The mathematical expression for law of independent
mixture of 1 M Y– and M Z– at 25°C. If the reduction potential migration of ions and Ostwald’s dilution law are given by
of Z > Y > X, then,
(a) Y will oxidize X and not Z (a) L = Lom - BC½ (b) L o = F( U + + U - )
(b) Y will oxidize Z and not X
(c) Y will oxidize both X and Z Lo 1 Lmc
(c) Lom = n+ l + + n- l- (d) L = o +
(d) Y will reduce both X and Z m L m K a (L om )2
16. For the electrochemical cell, M | M + || X - | X, 22. The variation of equivalent conductance of a weak electrolyte
o – with (concentration)½ is represented as
E o M + / M = 0.44V and E (X/X ) = 0.33V..
From this data one can deduce that
(a) M+X®M++X– is the spontaneous reaction
(b) M++X–®M+X is the spontaneous reaction (a) l (b) l
(c) Ecell = 0.77 V
(d) Ecell = - 0.77 V Öc Öc
17. Standard electrode potential data are useful for understanding
the suitability of an oxidant in a redox titration. Some half cell
reactions and their standard potentials are given below:
(c) l (d) l
MnO -4 (aq.) + 8H + (aq.) + 5e - ® Mn 2 + (aq.) + 4H 2 O(l)
Öc Öc
E° = 1.51 V
23. The ionic mobility of ions at infinite dilution is related to
Cr2 O 72 - (aq.) + 14H + (aq.) + 6e - ® 2Cr 3+ (aq.) + 7H 2 O(l) ionic conductance by
E° = 1.38 V (a) L o = Fk (b) L o F = U++U–
Fe3+ (aq.) + e - ® Fe2 + (aq.) E° = 0.77 V (c) L o = U++ U– (d) L o = F(U++ U–)
24. The variation of equivalent conductance of strong
Cl2 (g) + 2e- ® 2Cl- (aq.) E° = 1.40 V electrolyte with (concentration)½ is represented by
Identify the only incorrect statement regarding the
quantitative estimation of aqueous Fe(NO3)2
(a) MnO-4 can be used in aqueous HCl
(a) l (b) l
(b) Cr2O72 - can be used in aqueous HCl c c
EXERCISE 1 E´i´ t
10. (b) Apply m =
1. Iron ions. 96500
2. No, we cannot use nickel spatula to stir a solution of CuSO4.
7. (a) Standard electrode potential = 0.46V E´Q
11. (c) Apply m = where Q = coulombs
(b) Ecell = 0×37 V. 96500
8. 2×886 × 10–3 cm. E´Q 27
17. (a) 18. (d) 19. (c) 20. (d) 21. (c) 12. (b) Apply m = . E. wt of Al = =9.
96500 3
22. (c) 23. (d) 24. (b)
127.08
EXERCISE 2 13. (c) geq of copper to be deposited is = =4
31.75
1. (c) Electrorefining and electroplating are done by 1F deposits 1 geq, 4F will deposit 4 geq.
electrolysis.
WA WB W
2. (c) In cell the cathode is of higher reduction potential. 14. (d) = ; 27 = Cu ; \ WCu = 7.95g
3. (a) Amount of substance deposited EA EB 108 31.8
15. (c) 0.1 F will liberate 0.1 gev of Cl2 = 3.545 g
= m = E. wt ´ Q ; 16. (d) Ohm–1 cm–1
96500
1 0.47
107.870 17. (c) k = ´ Cell constant = = 0.01487
107.870 = ´ Q; R 31.6
96500
\ Q = 96500C 18. (b) Cell constant = k ´ R
= 0.212 ohm -1 cm -1 ´ 55 ohm
4. (d) WA = WB ; 1.6 = Wt. of Ag
EA EB 8 108 = 11.66 cm -1
\ Wt. of Ag = 21.6 g Cell constant 1.15
19. (a) k = =
5. (a) Ag + + e - ¾ R 250
¾® Ag
1F 108 g 1.15 1000
L eq = ´ = 4.6
1 F = 1 mole of electrons = 96500 C 250 1
0.01F = 1.08 g Ag; Ag left = 1.08 – 1.08 = 0
20. (c) Kohlrausch Law. Leq (NaF)+ Leq (HCl)– Leq (NaCl) =
6. (c) m = E.Wt ´ Q ;
96500 Leq (HF)
21. (b) Ohm–1 cm2 geq–1
m ´ 96500 22.2 ´ 96500
\ E. wt = = = 60.3
Q 2 ´ 5 ´ 60 ´ 60 k ´ 1000 3.06 ´ 10-6 ´ 1000
22. (d) Solubility = = = 2 × 10–3
L eq 1.53
At wt . 177
Oxidation state = = =3 Ksp = S2 = 4 × 10–6
Eq. wt. 60.3
23. (a) Specific conductance = Conductance × Cell constant
7. (b) m = E ´ Q = 32.68 ´ 5 ´ 40 ´ 60 = 4.065 g
96500 96500 1
k= ´1.15 ;
2.5 ´103
31.75 ´ 1´ 965 .3175
8. (c) m = = 0.3175 g = = 0.005 moles in
96500 63 1.15 1000
L eq = ´ = 4.6
one litre. \ 0.005 M. 2.5 ´ 10 3 0.1
E´i´ t 31.75 ´ .5 ´ t
9. (a) m = ;2= , \ t = 12157.48 sec . k ´ 1000 1.06 ´ 10-2 ´ 1000
96500 96500 24. (a) L m = = = 1.06 ´ 10 2
M 0.1
586 Chemistry
47. (a) Fe Al Br
L m ´ M 1.26 ´ 10 -2 ´ 0.01
25. (b) k = = = 1.26 ´ 10 -3 0.77 –1.66 1.08 E°Red
1000 1000 –0.77 1.66 –1.08 E°Oxi
26. (a) L¥m = 57 + 73 = 130 S cm 2 mol -1 X 2+ Y 2 - Hence Reducing power Al > Fe > Br
48. (c) On the basis of ECS strongly electropositive metals can
x displace less electropositive metals from their salt
Lcm solutions.
27. (c) Degree of dissociation = ¥ = 100 = 0.01 . 49. (c) I has the highest oxidation potential hence most reducing.
Lm x
50. (a) Since oxidation potential of Zn is highest hence strongest
28. (b) It is an example of concentration cell, Ecell cannot be zero reducing agent.
since [H+] are different (HCl is strong and CH3COOH
51. (d) The reduction potential of NO3- ion is more than H+
weak acid).
29. (d) Reduction occurs at cathode. ion. (see ECS).
30. (c) Consult ECS. Reduction potential of Cu is more 52. (c) Gold having higher E oRed and oxidises Fe ¾
than H2. ¾® Fe + + .
53. (d) Cell reaction Zn + Cu + + ¾ ¾® Zn + + + Cu
31. (d) 4 2 DG = –827 kJ mol–1
¾® Al 2 O 3 ;
Al + O 2 ¾ 0.059 0.01
3 3 o
E1 = E cell - log
2 1.0
æ2 ö o
Number of electrons involved is 4 ç ´ 6 = 4 ÷ \ E1 = (E cell + 0.059) V
è 3 ø
o 0.059 1.0
E 2 = E cell - log
827000 2 0.01
DGo = –nFE o or = Eo
4 ´ 96500 o
\ E 2 = (Ecell - 0.059) V E1 > E2.
o
\ E = 2.14V 54. (c) Copper is below in ECS hence cannot displace hydrogen
2+ 2 from HCl.
RT ln[Fe ] é 2+ ù
32. (c) Nernst equation Ecell = E ocell - Zn HCl H+ + Cl–
nF [Fe3+ ]2 ë û
2H + 2e ® H2
+ –
increasing [Fe2+] will decrease the Ecell. Cu ® Cu++ + 2e–
33. (d) Emf will decrease. not possible. Hence evolution of H2 is not possible.
34. (a) Salt bridge allows the flow of current by completing 55. (b) I2 is less reactive than Br2.
circuit. No current will flow and voltage will drop to zero, 56. (d) Oxidation potential of Co is more than Ag, hence cell
if salt bridge is removed. reaction will be
35. (c)
Co + 2 Ag + ¾
¾® Co 2 + + 2 Ag
36. (d) Calomel electrode is used as reference electrode.
37. (d) Though it is not zero but has been fixed as zero. o RT ln [Co 2 + ] , the lesser the value of
E cell = E cell -
38. (b) E ocell = E ored (Zn) + E oxi
o
(Fe) = 0.76 - 0.41 = 0.35V nF [Ag + ]2
2+
39. (a) OCl - ¾
¾® Cl - ; E° = 0.94 V (I) the factor [Co ] greater will be value of Ecell. .
[ Ag + ]2
1
Cl - ¾
¾® Cl 2 + e - ; E° = 1.36 V (II)
2 o RT [C]c [D]d
57. (b) E cell = E cell - ln .
nF [A]a [B]b
- 1
Add (I) + (II) OCl ¾¾® Cl 2 ; E° = 0.94 – 1.36 = –0.42 V
2 RT [C]c [D]d
Hence E ocell = E cell + ln
40. (d) E ocell = E oRe d (Fe) + E oxi
o
(Sn) = –0.44 + 0.14 = –0.30V nF [A]a [B]b
58. (a) Since concentration of ions is the same hence
41. (b) E ocell = E oRe d (Au) + E oxi
o
(Ni) = 1.5 + 0.25 = 1.75V
Ecell = E o cell.
42. (c) Oxidation potential of M is more than Ni and less than
Mn. Hence reducing power Mn > M > Ni 59. (a) The Half cell reaction is Zn + + + 2e - ¾
¾® Zn .
43. (a) The greater the oxidation potential greater is reactivity o 0.059 1
E cell = E cell - log
A > D > B > C. 2 [Zn ++ ]
44. (a) Chlorine is less reactive than fluorine.
45. (b) Follow ECS, more the reduction potential, the stronger = - 0.763 - 0.059 log 1 = -0.822 V
the oxidising power and vice versa. 2 0.01
46. (b) Follow ECS, A will replace B. Eoxi = 0.822 V
Electrochemistry 587
60. (d) 2 H + + 2e - ¾
¾® H 2 o 0.0591
3. (c) As Ecell = log Kc
n
0.059 1
E Red = E oRe d - log + 2 ; 0.0591
n [H ] \ 0.46 = log Kc
2
0.059 1 2 ´ 0.46
E Re d = 0 - log ; ERed = –0.059 V,,
2 (0.1) 2 \ log K c = = 15.57
0.0591
Eoxi = 0.059 V. or Kc = Antilog 15.57 = 3.7 × 1015 » 4 × 1015
RT C 4. (c) From the given data we find Fe 3+ is strongest
o
61. (b) E cell = E cell - ln 2 and DG = –nFE°cell oxidising agent. More the positive value of E°, more is
nF C1
the tendency to get oxidized. Thus correct option is
C (c).
Hence DG is a function of ln 2 . 5. (d) Kohlrausch’s Law states that at infinite dilution, each
C1
ion migrates independent of its co-ion and contributes
0.059 to the total equivalent conductance of an electrolyte a
o
62. (b) At equilibrium Ecell = 0. E cell = log K C definite share which depends only on its own nature.
n
From this definition we can see that option (d) is the
o 0.059 1.10 ´ 2 correct answer.
63. (b) E cell = log K C or = log K C
6. (c) Writing the equation for pentane-oxygen fuel cell at
2 0.059
respective electrodes and overall reaction, we get
\ K C = 1.9 ´ 1037 At Anode:
64. (a) DG = –nF E°cell = –2 × 96500 × 1.1 J = 212.3 kJ. C5 H12 + 10H 2 O ® 5CO 2 + 32H + + 32e -
65. (a) Q Change in free energy = maximum electrical work done (pentane)
66. (b) Water is weak electrolyte and remains almost unionised.
At Cathode:
67. (b) Cathode Anode
Aqs. soln. of Na2SO4 2 Na+ SO4– – 8O 2 + 32H + + 32e - ® 16H 2O
Ionisation of H2O ® H+ OH– Overall :C5H12 + 8O2 ® 5CO 2 + 6H 2O
+ - 1 Calculation of DG° for the above reaction
E°Red of H is more hence H + e ¾ ¾® H 2
2 DG° = [5×(–394.4) + 6× (–237.2)]
68. (b) Cl– is oxidised to Cl2 at anode. – [–8.2]
69. (b) 70. (d) 71. (b) 72. (c) = – 1972.0 – 1423.2 + 8.2 = – 3387.0 kJ
73. (b) H2 – O2 fuel cell supply power for pressure. = – 3387000 Joules.
74. (b) H2SO4 regenerated follow text. From the equation we find n = 32
-nFE ° and substituting
75. (c) Thermodynamic efficiency is given by Using the relation, DG° = – nFEcell
DH
76. (c) various values, we get
77. (a) Galvanization ° (F = 96500C)
– 3387000 = –32×96500× Ecell
78. (b) Specific conductance decreases with dilution
(follow text). 3387000
° =
or Ecell
79. (d) In electrolytic cell the flow of electrons is from anode to 32 ´ 96500
cathode through internal supply.
3387000 3387
EXERCISE 3 = or V = 1.0968 V
3088000 3088
1. (d) Zinc gives H2 gas with dil H2SO4/HCl but not with HNO3 Thus option (c) is correct answer.
because in HNO3, NO3– ion is reduced and give NH4NO3, 7. (d) Cu2+ + 2e– ® Cu; DGo = – nEoF
N2O, NO and NO2 (based upon the concentration of = – 2 × F × 0.337
HNO3) = – 0.674 F ....(i)
4Zn+10HNO 3 ¾¾ ® 4Zn(NO 3 ) 2 +NH 4 NO 3 +3H 2 O Cu+ ® Cu2+ + e– ; DGo = – nEoF
= – 1 × F × – 0.153
Zn is on the top position of hydrogen in electrochemical
= 0.153 F ....(ii)
series. So Zn displaces H2 from dilute H2SO4 and HCl
On adding eqn (i) & (ii)
with liberation of H2.
Cu+ + e– ® Cu ;
Zn + H2SO4 ® ZnSO4 + H2
DGo = – 0.521 F = – nEoF;
DG Here n = 1 \ Eo = + 0.52 V
2. (b) Efficiency of a fuel cell (h ) =
DH
588 Chemistry
8. (a) Q Q = i × t 16. (b) Given ESn +4 = + 0.15 V
Sn +2
\ Q = 4.0 × 104 × 6 × 60 × 60 C
= 8.64 × 10 8 C E Cr+ 3 Cr = – 0.74 V
3+ -
Al + 3e ¾¾
® Al
3´96500C 27g E °cell = E °ox + E °red
[3 × 96500 C liberates = 27 g of Al] = 0.74 + 0.15
\ 96500 C liberates 9 g of Al = 0.89 V
9 17. (d) Standard Gibbs free energy is given as DG° = – nE°F
8.64 × 108 C liberates = ´ 8.64 ´ 108 g Al
96500 If E°cell < 0 i.e., – ve
= 8.1 × 104 g of Al DG° > 0
9. (d) Degree of dissociation Further DG° = – RT ln Keq
L 8.0 \ DG° > 0 and Keq < 0
a= = = 2 ´ 10-2 18. (c) Given Fe+3/Fe2+ = + 0.77 V
L ¥ 400
and I2/2I– = 0.536V
2 (e– + Fe+3 ¾¾ ® Fe+2) E° = 0.77 V
ca 2 1
( )
2
Ka = » ca 2 = ´ 2 ´ 10 -2 2I – ¾¾ ® I2 + 2e – E° = – 0.536 V
(1 - a ) 32
2Fe+3 + 2I– ¾¾ ® 2Fe+2 + I2
= 1.25 ´ 10-5 E° = E°ox + E°red
10. (a) Cu + 2 Ag+ (aq) ¾¾
® Cu 2+ (aq ) + 2 Ag (s ) = 0.77 – 0.536
= 0.164 V
Here, n = 2 , E°cell = + 0.46 V \ Since value of E° is + ve reaction will take place.
25. (b) S =
K m 2 mol
\ K = Sm 2 mol-1
( )
38. (c) L o NaCl = l o Na + + lCl- ....(i)
3
m´m
26. (c) Ecell = Reduction potential of cathode (right)
Lo KBr = lo ( K ) + l ( Br )
+ o -
....(ii)
- reduction potential of anode (left)
= Eright - Eleft. L o KCl = l o ( K ) + l ( Cl )
+ -
....(iii)
27. (a) Ecell = Eright (cathode) - Eleft (anode). (i) + (ii) - (iii)
28. (d) If p1 > p2 then E cell =
2.303
nF
p
RT log 1
p2
(
L o NaBr = l o Na + + lo Br - ) ( )
29. (a) 2Cr 3+ + 7H 2 O ® Cr2 O 72- + 14H + = 126 + 152 - 150 = 128 S cm 2 mol -1
O.S. of Cr changes from + 3 to + 6 by loss of electrons. 39. (c) The given values show that Cr has maximum oxidation
At anode oxidation takes place. potential, therefore its oxidation will be easiest. (Change
30. (c) The equilibrium constant is related to the standard emf the sign to get the oxidation values)
of cell by the expression 40. (a) Thus difluoro acetic acid being strongest acid will furnish
maximum number of ions showing highest electrical
n 2
log K = Eº cell ´ = 0.295 ´ conductivity. The decreasing acidic strength of the
0.059 0.059
carboxylic acides given is difluoro acetic acid >
590 fluoro acetic acid > chloro acetic acid > acetic acid.
log K = = 10 or K = 1 × 1010
59 41. (d) 1 mole of e– = 1F = 96500 C
31. (d) A B C 27g of Al is deposited by 3 × 96500 C
+ 0.5C –3.0V –1.2V 5120 g of Al will be deposited by
The higher the negative value of reduction potential, 3 ´ 96500 ´ 5120
the more is the reducing power. Hence B > C > A. = = 5.49 ´ 10 7 C
27
9650 1
32. (a) No. of moles of silver = = moles 42. (b) L ¥
96500 10 HCl = 426.2 (i)
Eocell being +ve, DG ° will be -ve and hence the above 29. (a) Ar NO 2 + 6H + + 6e - ¾
¾® ArNH 2 + 2H 2 O
31.8 Cathode : 2H 2 O + 2e - ¾
¾® H 2 + 2OH -
geq of Cu deposited = = 1 .0
63.6 / 2
1´ 5 ´ 965
Moles of OH - formed = Z × i × t = = 0.05
0.6 ´100 96500
\ Current efficiency = = 60 %
1
0.05
34. (d) Ionic mobility is the velocity of an ion under a potential [OH - ] = = 1 ´ 10 -1
0 .5
gradient of 1Vm -1 .
[H + ] = 10 -13 pH = 13
- -
35. (a) MX(s) + e ¾
¾® M(s) + X (aq); E° = 0.207 V .......(i)
40. (a) Wmax = – n.FE;
+ - ......(ii)
M ( aq ) + e ¾
¾® M (s ); E ° = 0 .799 V Wmax = – 2 × 96500 × 0.65 = – 1.25 ´ 10 5 J
From (i) – (ii),
0.5g H 2 = 0.25 mole.
¾® Ms+ (aq) + Xs- (aq);
MX(s) ¾
Hence Wmax = – 1.25 ´ 10 5 ´ 0.25 = –3.12 ´ 10 4 J
594 Chemistry
reactions.
RATE OF REACTION : d[P]
It is defined as the change in concentration of a reactant or a dt
product in a particular interval of time. The change in concentration [P1]
of a substance say A is represented by D[A] D[P]
D[A] = [Final concentration – Initial concentration] [P2] rav D[P] {[P2]–[P1]}
For a reactant : Final concentration < Initial concentration Dt Dt (t2 – t1)
Thus D[A] will have negative sign
For a product : Final concentration > Initial concentration
Thus D[A] will have positive sign t Time t1 t2
Average rate in terms of products (b)
D[A ] Total change in concentration Instantaneous and average rate of a reaction
= = The minus sign indicates the decrease in concentration and plus
Dt Total change in time sign increase in concentration. The above expressions give the
D[ A ] average rate of reaction.
Average rate in terms of reactants = - FEATURES OF THE RATE OF REACTION :
Dt
The negative sign in the expression make the rate positive. Hence (I) Rate of reaction is proportional to the concentration of the
rate of a reaction is never negative. reactants
Consider the decomposition of N2O5 (II) Rate of a reaction is always a positive quantity
(III) Rate of a reaction is determined by measuring the
2 N 2 O 5 (g ) ¾
¾® 4 NO 2 (g ) + O 2 (g )
concentration of a reactant or a product as a function of time
1 DN 2 O 5 1 DNO 2 DO 2 (IV) Property related to concentration is selected e.g. volume,
Rate = - . = =
2 Dt 4 Dt Dt pressure, thermal or electrical conductivity, colour change,
pH, etc.
[R]0 UNITS OF RATE OF REACTION :
Mol L–1 time–1 and for gaseous reaction atm time–1
INSTANTANEOUS RATE :
Concentration of reactants
1
T
Chemical Kinetics 597
TEMPERATURE COEFFICIENT : FEATURES OF ORDER OF REACTION :
It is the ratio of two rate constants differing by a temperature of (I) The order of a reaction is experimentally determined
10 °C. Generally the temperatures are 298K & 308 K. quantity.
(II) It cannot be written from balanced chemical equation.
Rate constant at 308K
Temperature Coefficient = (III) It can be written from the rate law equation.
Rate constant at 298K
(IV) It depends upon the molecules undergoing change in
The value of temperature coefficient is generally 2 and 3. In rare concentration.
cases the value is 4, 5 etc. (V) Order may be zero, whole number, fractional or negative
RATE LAW EQUATION : even
The mathematical expression, which practically relates the rate of (VI) Reaction with order ³ 3 are rare.
a chemical reaction and concentration of reactants is called rate RATE DETERMINING STEP :
law equation e.g. for a hypothetical reaction.
Some reactions take place in more than one step. Each step has
aA + bB cC + dD its own rate. The slowest step is called the rate determining step
Rate µ [A]a [B]b. It is law of mass action or rate controlling step e.g.
Rate µ [A]x [B]y It is rate law..
2 NO 2 + F2 ¾
¾® 2 NO 2 F
If rate actually vary according to this equation practically then
this is rate law equation. For decomposition of N2O5.
Mechanism NO 2 + F2 ¾
¾® NO 2 F + F (slow )
2N2O5 2N2O4 + O2
NO 2 + F ¾
¾® NO 2 F (fast )
Rate µ [ N 2 O 5 ] and not Rate µ [ N 2 O 5 ]2
\ Rate law equation is, Rate = k[N2O5] 2 NO 2 + F2 ¾
¾® 2 NO 2 F
Rate law equation for reversible reaction
First step is the rate determining step. The rate law equation is
k1 always written from slow step.
H2 + I2 2HI
k2 \ The rate law is given as rate = k [ NO2 ][ F2 ]
1 d[HI] Remember that reaction intermediate are never shown in rate law
Rate = = k1[H 2 ][I 2 ] - k 2 [HI]2
2 dt equation.
dx
( Rate) = [ A ] x [ B] y ; HOOBr + HBr ¾
¾® 2HOBr Molecularity two
dt
( HOBr + HBr ¾
¾® H 2 O + Br2 ) ´ 2 Molecularity two
Order w.r.t. A is x, Order w.r.t. B is y
Overall order is x + y
4HBr + O 2 ¾
¾® 2H 2 O + 2Br2 Molecularity five
598 Chemistry
PSEUDO UNIMOLECULAR REACTIONS : The half-life period of the first order reaction is independent
Reactions like hydrolysis of an ester or cane sugar, which though of the initial concentration of reacting substances.
bimolecular and yet following the kinetics of first order are called The time taken for the completion of any fraction of the
pseudo unimolecular reactions. reaction is independent of the initial concentration.
First order growth kinetics : It is used in population growth
CH 3COOC 2 H 5 + H 2 O CH 3COOH + C 2 H 5 OH
and bacteria multiplication
dx
= k[CH 3 COOC 2 H 5 ] 2.303 a+x
k= log
dt t a
C12 H 22 O11 + H 2 O C 6 H12 O 6 + C 6 H12 O 6 where a is initial population and (a + x) population after time
t.
dx (2) Second order reaction : The reaction rate is determined by
= k[C12 H 22 O11 ] .
dt the variation of two concentration terms. They are of two
In above reactions the rate is independent of concentration types
of H2O being present in excess. Hence [H2O] is constant. (a) 2A ¾
¾® Products
DIFFERENCES BETWEEN ORDER AND
MOLECULARITY OF REACTION : Rate µ [A]2
1 a 2.303 a (c) A + B + C ¾
¾® Products
k = .ln = log
t (a - x) t a-x Rate µ [A][B][C]
This is called the kinetic equation of a first order reaction.
Units of k = time–1 eg h–1, m–1 or s–1 x ( 2a - x )
Consider the type (a) k =
Half-life period (t1/2). The time taken for the completion of 2 t a 2 (a - x ) 2
half of the reaction is known as half-life period. When Unit of k = (mol L–1)–2 s–1 = mol–2 L2 s–1
t = t1 / 2 , x = a / 2 . When t = t1/2, x = a/2
0.693 3 1
t1/ 2 = Half-life period (t1/2) = (Q t1/ 2 µ )
2
k 2ka a2
Chemical Kinetics 599
The time taken for the completion of half of the reaction is (II) Conversion of para hydrogen to ortho hydrogen at high
inversely proportional to the square of the initial temperature.
concentration of reactants.
Rate µ (PH )3/2
Note :The time taken for the completion of any fraction of 2
the reaction is inversely proportional to the square of the
initial concentration of reactants. \ Rate = k(PH 2 )1.5 . Order w.r.t. H2 is 3/2.
(4) Zero order reaction : The reaction rate is independent of NEGATIVE ORDER REACTIONS :
the concentration of the reactants.
Conversion of ozone into oxygen.
A¾
¾® Product Rate = K [O3]2 [O2]–1
Order with respect to oxygen is –1.
dx
Rate = k[A]0 or = k on integration DETERMINATION OF ORDER OF REACTION :
dt
(1) Fractional change method : The time required to complete
x = kt + c
a definite fraction of reaction is given by
when t = 0, x = 0 so c = 0
t1 / 2 µ (a)1- n where n is order of reaction
x
Hence x = kt or k = The following graphs are obtained between t1/2 and initial
t
concentration 'a'.
Unit of k = Conc. time–1 = mol L–1 s–1
When the reaction is complete, C = 0
Co
\ E completion = I. t1/2 II. t1/2
k
Co - C
For zero order reaction k = a
t a
Zero order t1/2 µ a First order t1/2 µ a0
Co = initial concentiation
C = conc. at any time t
III.
When t = t1 / 2 , x = a / 2
t1/2
a
Half life period (t1/2) = (t µ a )
2k 1 / 2
n–1
The time taken for the completion of half of the reaction is a
directly proportional to the initial concentration of reactants. Second & Third Order
For zero order reaction, where n = 2 & 3
(I) Rate is independent of concentration of reactant (s) 1 1
(II) Concentration of reactants do not vary with time t1 / 2 µ
and t1 / 2 µ
a a2
(III) Rate does not vary with time. (2) Graphical method : (a) The graphs between concentration
(IV) Rate is always equal to rate constant. of any reactant Vs. time or concentration of any product Vs.
(V) t ½ < a time are plotted. The slope of the tangent to the curve gives
(VI) If we double the amount of reactants then time for the rate of reaction at that time.
completion will be doubled.
HALF-LIFE PERIOD FOR THE nTH ORDER Product
REACTION : dx
When the order of reaction is n, t1/2 is given by dt
Concentration
1 é 2n -1 - 1 ù
t1/ 2 = ê ú
k(n - 1) êë a n -1 úû Reactant
dx
1 dt
\ t1 / 2 µ
n -1
a time
Unit of k = (conc)1–n. time–1
FRACTIONAL ORDER REACTIONS : dx
The new graphs between Vs. (a – x), (a – x)2 or
(I) Reaction between H2 and D2. dt
Rate = k PH (PD )1/2. Order w.r.t. D2 is 1/2. (a – x)3 are plotted.
2 2
600 Chemistry
1
For II order slope = ; k can be calculated
Zero order k
dx dx
dt dt 1
For III order slope = ; k can be calculated
I order 2k
(3) Use of differential rate equations.
(a – x) (a – x)
(4) Use of integral rate equations – hit and trial method
(5) Ostwald's isolation method.
Examples of reactions of different order :
(a) Reactions of zero order :
dx dx
hn
dt dt (I) H 2 (g ) + Cl 2 (g ) ¾¾® 2HCl (g )
II order III order
MO
(II) 2NH 3 (g) ¾¾¾
® N 2 (g) + 3H 2 (g)
hn
2 3
(a – x) (a – x) Au
(III) 2HI(g) ¾¾¾ ® H 2 (g) + I 2 (g)
(b) Making use of integrated form of rate expression : (b) Reactions of Ist order :
(I) 2 N 2O5 ¾
¾® 4 NO 2 + O 2
(II) 2H2 O2 ¾¾
® 2H2 O + O2
t t I order
Zero order
(III) NH 4 NO 2 ¾
¾® N 2 + 2H 2 O
x Log (a – x) (IV) SO 2 Cl 2 ¾
¾® SO 2 + Cl 2
x
(V) (CH 3 ) 3 CO . OC(CH 3 ) 3 ¾¾® 2CH 3COCH 3 + C 2 H 6
x
Zero order t = COOH
k
(VI) O2N NO2
a
For first order kt = 2.303 log
a-x
2.303 2.303
or t= log a - log(a - x) NO2
k k
O2N NO2
+ CO2
-2.303 ® CH 3COONa + C 2 H 5 OH
For I order slope = ; k can be calculated
k
(V) NO + O 3 ¾
¾® NO 2 + O 2
Chemical Kinetics 601
(VII) Fe 3+ + 3I - ¾
¾® FeI 3
GRAPHICAL REPRESENTATION OF EXOTHERMIC
REACTION :
(e) Reactions of fractional order :
(I) H 2 + Br2 ¾
¾® 2HBr A(Reactant) ® B (Product)
E a(F.R.) + DH = E a(B.R.)
Rate = k[H 2 ][Br2 ]1/ 2 Order = 1.5
DH = - ve
(II) CO + Cl 2 ¾
¾® COCl 2 where F.R. = Forward reaction and B.R. = Backward reaction
Rate = k[CO] [Cl 2 ]
2 1/ 2
Order = 2.5
Threshold energy
(III) COCl 2 ¾
¾® CO + Cl 2
(a - x ) µ rt - r¥ a
The value of k = t.a (a - x)
Sol. 2 N 2 O 5 ¾
¾® 2 N 2 O 4 + O 2 \ k = 2.35 ´10-5 sec-1
a -x x x/2
604 Chemistry
9 ´10 -3 = [0.05]m [0.15]n (III) 11. When the initial concentration is changed from 0.50 to 1.0
mole lit–1, the time of half completion for a certain reaction is
Divide II by I, found to change from 50 sec. to 25 sec. Calculate the order
of reaction.
Chemical Kinetics 605
n -1
Sol. k = 2.303 log a
Sol. T1 = æç a 2 ö÷ t a-x
T2 çè a1 ÷ø
2.303 5.0
n -1 6= log
50 æ 1.0 ö t 0.05
=ç ÷ 2 = (2)n – 1 or 21 = (2)n – 1
25 è 0.5 ø 2.303
t= log100 = 46.06 sec.
\ 1 = n – 1. Hence n = 1 + 1 = 2. Reaction is of second order. 6 min -1
12. Find the 3/4 th life (t 3/4) of a first order reaction. The rate
16. For the reaction, 2A + B + C ® A 2 B + C , rate law has been
constant k = 7.4 ´ 10 -5 sec-1
determined to be rate = k[A][B] 2. If the rate constant
2.303 a 2.303 1 k = 2.0 ´ 10 -6 mol L sec , what will be initial rate
–2 2 –1
Sol. t 3 = log = log
4
k a-x k 1-
3 of the reaction with [A] = 0.1 mol L–1 and [B] = 0.2 mol L–1
4 and [C] = 0.8 mol L–1.
2.303 Sol. For 2A + B + C ® A 2 B + C
t3 = log 4 = 1.84 ´104 sec
4
7.4 ´ 10-5 Rate = k[A][B]2
13. For a reaction it takes 10 min. for the initial concentration of = 2.0 ´10 -6 ´ 0.1´ [0.2]2
2.0 mol L–1 to become 1.0 mol L–1 and another 10 min to
become 0.50 mol L–1. Calculate the rate constant of the = 8.0 ´ 10 -9 mol L-1 s -1
reaction. 17. At some temperature, the rate constant for
Sol. The time taken for the concentration to fall to half the decomposition of HI on the surface of gold is 0.08 mol L –
1 s–1
concentration is constant in both the cases. Hence the
reaction is of first order 2HI (g) ® H 2 (g ) + I 2 (g)
0.693 0.693 what is the order of the reaction. How long will it
\ k= = = 0.0693 min -1
t½ 10 take for the concentration of HI to drop from 1.50 M to 0.30
M.
14. The rate of reaction 2 NO + Cl 2 ® 2 NOCl is doubled when
Sol. From the unit of k, the reaction is of zero order.
concentration of Cl2 is doubled and it becomes 8 times
when concentration of both NO and Cl2 are doubled. Deduce C0 - C
k=
the order of reaction. 2t
Sol. Rate is doubled when [Cl2] is doubled
1.5 - 0.30 1.2
Rate w.r.t. Cl2 = k[Cl2]1 0.08 = or t=
2t 0.08 ´ 2
Rate becomes 8 times when concentration of both NO and
Cl2 is doubled \ t = 7.5 s
Rate = k[Cl2 ][NO]x 18. The following data were obtained at a certain temperature
for the decomposition of ammonia in contact with tungsten
8 = k[2][2]x p (mm Hg) 50 100 200
\x=2 t½ 3.64 1.82 0.90
Find the order of the reaction.
Rate law is Rate = K[Cl 2 ][ NO]2
n -1 n -1
( t½)1 æ a1 ö 3.64 æ 100 ö
Total order 1 + 2 = 3 Sol. =ç ÷ or =ç ÷
15. A reaction that is of the first order with respect to ( t½) 2 çè a 2 ÷ø 1.82 è 50 ø
reactant A has a rate constant of 6 min–1. If we start with [A]
= 5.0 mol L–1 when would [A] reach the value of 0.05 mol L–1. 2 = (2) n -1 or n -1 = 1
\n = 2
606 Chemistry
2k1 3 d[ A] 2 d[ A]
(a) [ NO 2 ]2 (a) - (b) -
k2 2 dt 3 dt
(b) 2k1[ NO 2 ]2 - 2k 2 [ N 2 O 4 ] 1 d[ A ] d[ A ]
(c) - (d) + 2
3 dt dt
(c) 2k1[ NO 2 ]2 - k 2 [ N 2 O 4 ] 4. Consider the chemical reaction,
(d) (2k1 – k2) [NO2]
N 2 (g ) + 3H 2 (g ) ¾¾® 2 NH 3 (g ) . The rate of this reaction
2. The rate of the reaction intermediates can be determined by
the study of can be expressed in terms of time derivative of concentration
of N2 (g), H2 (g) or NH3 (g). Identify the correct relationship
(a) catalyst effects
amongst the rate expressions
(b) concentration of the reactants
608 Chemistry
13. In Arrhenius plot, intercept is equal to
-d[ N 2 ] -1 d[H 2 ] 1 d[ NH 3 ]
(a) Rate = = =
dt 3 dt 2 dt Ea
(a) - (b) ln A
R
-d[ N 2 ] d[ H 2 ] d[ NH 3 ]
(b) Rate = = -3 =2 (c) ln k (b) log10a
dt dt dt
14. A chemical reaction was carried out at 300 K and 280 K. The
d[ N 2 ] 1 d[H 2 ] 1 d[ NH 3 ] rate constants were found to be k1 and k2 respectively. then
(c) Rate = = =
dt 3 dt 2 dt (a) k1 = 4k1 (b) k2 = 2k1
(c) k2 = 0.25 k1 (d) k2 = 0.5 k1
d[ N 2 ] d[ H 2 ] d[ NH 3 ]
(d) Rate = - =- = 15. The decomposition of a substance follows first order kinetics.
dt dt dt
Its concentration is reduced to 1/8th of its initial value in 24
5. The rate of a gaseous reaction is given by the expression minutes. The rate constant of the decomposition process is
k(A)(B). If the volume of the reaction vessel is suddenly
reduced to 1/4 of the initial vol. the reaction rate relative to 0.692
(a) 1/24 min–1 (b) min -1
the original rate will be 24
1 1
2.303 æ1ö 2.303 æ8ö
log ç ÷ min -1 log ç ÷ min -1
(a) (b)
16 8 (c) (d)
24 è8ø 24 è1ø
(c) 8 (d) 16
6. The units for the rate constant of first order reaction is 16. The rate of chemical reaction is doubled for every 10°C rise
in temperature because of
(a) s –1 (b) mol L–1 s–1
(c) mol s –1 (d) L mol–1 s–1 (a) increase in the activation energy
7. The rate constant of reaction depends upon (b) decrease in the activation energy
(a) temperature (b) pressure (c) increase in the number of molecular collisions
(c) volume (d) All the these (d) increase in the number of activated molecules
8. The rate constant of a reaction is 10.8 × 10 –5 17. The temperature coefficient of most of the reactions lies
mol dm–3 s–1. The order of the reaction is between
(a) zero (b) 1 (a) 1 and 3 (b) 2 and 3
(c) 2 (d) 3 (c) 1 and 4 (d) 2 and 4
9. If concentration of reactants is increased by 'x', then k 18. The velocity of a reaction is doubled for every 10°C rise in
becomes temp. If the temp. is raised to 50°C the reaction velocity
k k increases by about
(a) ln (b) (a) 12 times (b) 16 times
x x
(c) k + x (d) k (c) 32 times (d) 50 times
10. Rate constant in the case of first order reaction is
19. For the reaction A ¾ ¾® B , the rate law expression is : rate
(a) inversely proportional to the concentration units
= k [A]. Which of the following statements is incorrect?
(b) independent of concentration units
(a) The reaction follows first order kinetics
(c) directly proportional to the concentration units
(b) The t1/2 of reaction depends on initial concentration of
(d) inversely proportional to the square of the concentration
reactants
units
11. The Arrhenius equation expressing the effect of temperature (c) k is constant for the reaction at a constant temperature
on the rate constant of the reaction is (d) The rate law provides a simple way of predicting the
conc. of reactants and products at any time after the
Ea
(a) k = e - E a / RT (b) k = start of the reaction.
RT
20. For a reaction of type A + B ¾¾® products , it is observed
Ea
(c) k = log e (d) k = Ae - E a / RT that doubling concentration of A causes the reaction rate to
RT
be four times, but doubling amount of B does not affect the
12. For the following homogeneous reaction, rate. The rate equation is
k
A + B ¾¾ ®C k
(a) Rate = k [A] [B] (b) Rate = [A]2
the unit of rate constant is 4
(a) sec –1 (b) sec–1 mol L–1 (c) Rate = k [A]2 [B] (d) Rate = k [A]2 [B]2
(c) sec–1 mol–1 L (d) sec–1 mol–2 L2
Chemical Kinetics 609
21. Select the rate law that corresponds to the data shown for 29. A first order reaction does not depend upon
the following reaction A + B ¾
¾® C (a) volume (b) pressure
(c) temperature (d) All of these
Expt. No. (A) (B) Initial Rate
1 0.012 0.035 0.10 30. 2A ¾¾ ® B + C, would be a zero order reaction when
2 0.024 0.070 0.80 (a) the rate of reaction is proportional to square of conc.
3 0.024 0.035 0.10 of A
4 0.012 0.070 0.80 (b) the rate of reaction remains same at any conc. of A
(a) Rate = k[B]3 (b) Rate = k [B]4 (c) the rate remains unchanged at any conc. of B and C
(c) Rate = k [A] [B]3 (d) Rate = k [A]2 [B]2 (d) the rate of reaction doubles if conc. of B is increased to
22. The chemical reaction 2O 3 ¾
¾® 3O 2 proceeds as follows double
31. Which of the following is correct for a first order reaction?
:
Fast Slow (a) t1 / 2 µ a (b) t1 / 2 µ 1 / a
O 3 ¾¾ ¾® O 2 + O ; O + O 3 ¾¾¾® 2O 2 the rate law
expression should be (c) t1 / 2 µ a 0 (d) t1 / 2 µ 1 / a 2
(a) r = k[O3]2 (b) r = k [O3]2[O2]–1 32. Order of reaction is decided by
(c) r = k3 [O3][O2]2 (d) r = [O3][O2]2 (a) temperature
23. For the reaction 2 H 2 O 2 ¾¾® 2H 2 O + O 2 , r = k [H2O2]. It (b) mechanism of reaction as well as relative concentration
of reactants
is
(c) molecularity
(a) zero order reaction (b) first order reaction
(d) pressure
(c) second order reaction (d) third order reaction
24. If the rate of the reaction is equal to the rate constant, the 33. Half-life of a reaction is found to be inversely proportional to
order of the reaction is the cube of initial concentration. The order of reaction is
(a) 1 (b) 2 (a) 4 (b) 3
(c) 3 (d) 0 (c) 5 (d) 2
25. For the reaction A + B ¾ ¾® C , it is found that doubling 34. The reaction L ¾ ¾® M is started with 10.0 g of L. After 30
the concentration of A increases the rate 4 times, and and 90 minutes 5.0 g and 1.25 g of L respectively are left. The
doubling the concentration of B doubles the reaction rate. order of the reaction is
What is the overall order of the reaction? (a) 0 (b) 1
(a) 3/2 (b) 4 (c) 2 (d) 3
(c) 1 (d) 3 35. If initial concentration is reduced to 1/4th in a zero order
26. For a first-order reaction, the half life period is independent reaction, the time taken for half the rection to complete
of (a) remains same (b) becomes 4 times
(a) initial concentration (c) becomes one-fourth (d) doubles
(b) cube root of initial concentration 36. A first order reaction is half-completed in 45 minutes. How
(c) first power of final concentration long does it need for 99.9% of the reaction to be completed?
(d) square root of final concentration (a) 20 hours (b) 10 hours
27. For a first order reaction, the plot of log K against 1/T is a
straight line. The slope of the line is equal to 1
(c) 7 hours (d) 5 hours
2
Ea 2.303
(a) - (b) - E R 37. A reaction which is of first order w.r.t. reactant A, has a rate
R a constant 6 min–1. If we start with [A] = 0.5 mol L–1, when
-E a would [A] reach the value of 0.05 mol L–1
Ea
(c) - (d) 2.303R (a) 0.384 min (b) 0.15 min
2.303
(c) 3 min (d) 3.84 min
28. For a first order reaction, a plot of log (a – x) against time is 38. The rate constant for the reaction
a straight line with a negative slope equal to
-k 2 N 2O5 ¾ ¾® 4 NO 2 + O 2 , is 3.0 × 10–5 sec–1. If the rate is
(a) (b) – 2.303 k 2.40 × 10–5 mol litre–1 sec–1, then the concentration of N2O5
2.303
(in mol litre–1) is
2.303 Ea (a) 1.4 (b) 1.2
(c) (d) - 2.303 R (c) 0.04 (d) 0.8
k
610 Chemistry
39. The reaction, 47. According to the collision theory of reaction rates, the rate
1 of reaction increases with temperature due to
N 2 O 5 (ln CCl 4 ) ¾¾® 2 NO 2 + O 2 (g) (a) greater number of collision
2
(b) higher velocity of reacting molecules
is first order in N2O5 with rate constant 6.2 × 10–4 s–1. What
(c) greater number of molecules having the activation
is the value of rate of reaction when [N2O5] = 1.25 mol L–1? energy
(a) 7.75 × 10–4 mol L–1 s–1 (b) 6.35 × 10–3 mol L–1 s–1 (d) decrease in the activation energy
(c) 5.15 × 10–5 mol L–1 s–1 (d) 3.85 × 10–4 mol L–1 s–1 48. Which of the following has been used to explain the subject
40. The time taken for 90% of a first order reaction to complete of chemical kinetics
is approximately (a) Collision theory of bimolecular reactions
(a) 1.1 times that of half-life (b) The activated complex theory
(b) 2.2 times that of half-life (c) Arrhenius equation
(c) 3.3 times that of half-life (d) All of these
(d) 4.4 times that of half-life 49. Which of the following statements is incorrect?
41. The rate of a certain reaction at different time intervals are (a) Activation energy for the forward reaction equals to
as follows activation energy for the reverse reaction
Time Rate (b) For a reversible reaction, an increase in temperature
0 sec. 1.8×10–2 mol l–1 s–1 increases the reaction rate for both the forward and the
10sec. 1.82×10–2 mol l–1 s–1 backward reaction
(c) The larger the initial reactant concentration for a second
20 sec. 1.79×10–2 mol l–1 s–1
order reaction, the shorter is its half-life.
The reaction is of
(d) When Dt is infinitesimally small, the average rate equals
(a) zero order (b) first order the instantaneous rate
(c) second order (d) third order 50. Activation energy of a chemical reaction can be determined
42. A substance initial concentration (a) reacts according to by
zero order kinetics. What will be the time for the reaction to (a) evaluating rate constant at standard temperature
go to completion (b) evaluating velocities of reaction at two different
a k temperatures
(a) (b) (c) evaluating rate constants at two different temperatures
k a
(d) changing concentration of reactants
a 2k 51. A catalyst increases rate of reaction by
(c) (d) (a) decreasing enthalpy
2k a
(b) decreasing internal energy
43. The hypothetical reaction A 2 + B 2 ¾
¾® 2AB ; follows (c) decreasing activation energy
(d) increasing activation energy
Fast
the following mechanism A 2 ¾¾¾® A + A , 52. The activation energy for a simple chemical reaction A ® B
Fast is Ea in forward direction. The activation energy for reverse
A + B 2 ¾¾¾® AB + B , A + B ¾¾
¾® AB .
Slow
reaction
The order of the overall reaction is (a) is always less than Ea
(a) 0 (b) 1 (b) can be less than or more than Ea
(c) 2 (d) 3/2 (c) is always double of Ea
44. The reaction (d) is negative of Ea
2N2O5 2N2O4 + O2 is 53. A graph plotted between log k Vs 1/T for calculating
activation energy is shown by
(a) bimolecular and of second order
(b) unimolecular and of first order
(c) bimolecular and of first order log k
log k
(d) bimolecular and of zero order (a) (b)
45. The given reaction
2FeCl 3 + SnCl 2 ¾
¾® 2 FeCl 2 + SnCl 4 1/T 1/T
is an example of
(a) first order reaction (b) second order reaction
(c) third order reaction (d) None of these log k
log k
46. Collision theory is applicable to
(c) (d)
(a) first order reactions (b) zero order reactions
(c) bimolecular reactions (d) intra-molecular reactions
1/T
1/T
Chemical Kinetics 611
54. Activation energy of the reaction is 58. The temperature dependence of rate constant (k) of a
(a) the energy released during the reaction chemical reaction is written in terms of Arrhenius equation, k
(b) the energy evolved when activated complex is formed = A . e - E a Activation energy (Ea) of the reaction can be
calculated by plotting
(c) minimum amount of energy needed to overcome the
potential barrier 1 1
(a) k vs. log T (b) log k vs
(d) the energy needed to form one mole of the product T
55. The activation energy for a hypothetical 1
reaction, A ® Product, is 12.49 kcal/mole. If temperature is (c) log k vs. log T (d) k vs. T
raised from 295 to 305, the rate of reaction increased by
59. The reaction A ® B follows first order kinetics. The time
(a) 60% (b) 100% taken for 0.8 mole of A to produce 0.6 mole of B is 1 hour.
(c) 50% (d) 20% What is the time taken for conversion of 0.9 mole of A to
produce 0.675 mole of B?
56. In a reaction, the threshold energy is equal to
(a) 0.5 hour (b) 0.25 hour
(a) activation energy + normal energy of reactants (c) 2 hours (d) 1 hour
(b) activation energy - normal energy of reactants 60. According to the adsorption theory of catalysis, the speed
(c) normal energy of reactants - activation energy of the reaction increases because
(a) in the process of adsorption, the activation energy of
(d) average kinetic energy of molecules of reactants
the molecules becomes large
57. When two reactants A and B are mixed to give products C (b) adsorption produces heat which increases the speed of
and D, the reaction quotient, 'Q', at the initial stages of the the reaction
reaction (c) adsorption lowers the activation energy of the reaction
(a) is zero (b) decreases with time (d) the concentration of product molecules at the active
(c) is independent of time (d) increases with time centres of the catalyst becomes high due to adsorption.
would be : –2
IV 0.4 0.1 2.40 × 10
(a) 4 × 10–4 mol L–1 s–1 (b) 6 × 10–4 mol L–1 s–1
(c) 1 × 10–4 mol L–1 s–1 (d) 3 × 10–4 mol L–1 s–1 Based on the above data which one of the following is correct?
7. In the reaction [CBSE-PMT 2009] [CBSE-PMT 2010]
(a) rate = k [A]2 [B] (b) rate = k[A] [B]
BrO3– (aq) + 5Br - ( aq ) + 6H + ( aq) ® 3Br2 (l ) + 3H 2O(l )
2 2
The rate of appearance of bromine (Br2) is related to rate of (c) rate = k [A] [B] (d) rate = k [A] [B]2
disappearance of bromide ions as following: 13. The rate of the reaction 2NO + Cl 2 ¾¾ ® 2NOCl is given
by the rate equation rate = k [NO]2 [Cl2] [CBSE-PMT 2010]
d[Br2 ] 5 d[Br – ] d[Br2 ] 5 d[Br – ] The value of the rate constant can be increased by:
(a) =– (b) =
dt 3 dt dt 3 dt (a) increasing the concentration of NO.
(b) increasing the temperature.
d[Br2 ] 3 d[Br – ] d[Br2 ] 3 d [Br – ] (c) increasing the concentration of the Cl2
(c) = (d) =-
dt 5 dt dt 5 dt (d) doing all of these
8. Half life period of a first-order reaction is 1386 seconds. The 14. Which one of the following statements for the order of a
specific rate constant of the reaction is : [CBSE-PMT 2009] reaction is incorrect ? [CBSE-PMT 2011]
(a) 0.5 × 10–2 s–1 (b) 0.5 × 10–3 s–1 (a) Order can be determined only experimentally.
–2 –1 (b) Order is not influenced by stoichiometric coefficient of
(c) 5.0 × 10 s (d) 5.0 × 10–3 s–1
the reactants.
9. For the reaction A + B ¾¾ ® products, it is observed that: (c) Order of reaction is sum of power to the concentration
[CBSE-PMT 2009] terms of reactants to express the rate of reaction.
(d) Order of reaction is always whole number.
(1) On doubling the initial concentration of A only, the rate
15. The rate of the reaction 2N2O5 ® 4NO2 + 2O2 can be written
of reaction is also doubled and
in three ways : [CBSE-PMT 2011 M]
(2) On doubling the initial concentrations of both A and B,
- d[N 2O5 ]
there is a change by a factor of 8 in the rate of the reaction. = k [N 2O5 ]
dt
The rate of this reaction is given by:
(a) rate = k [A] [B]2 (b) rate = k [A]2 [B]2 d[NO 2 ]
= k ¢ [N 2 O5 ]
(c) rate = k [A] [B] (d) rate = k [A]2 [B] dt
[AIEEE 2007]
(a) 20 (b) 300 (c) 120 (d) 280
2.0 38. Consider the reaction, 2A + B ® products. When
1.5 ´10 -3 1 (k -1 ) 2.0 ´10 -3 concentration of B alone was doubled, the half-life did not
T change. When the concentration of A alone was doubled, the
The reaction must be rate increased by two times. The unit of rate constant for this
(a) highly spontaneous at ordinary temperature reaction is [AIEEE 2007]
(b) one with negligible enthalpy change (a) s –1 (b) L mol–1 s–1
(c) endothermic
(c) no unit (d) mol L–1 s–1.
(d) exothermic
33. t1/4 can be taken as the time taken for the concentration of a 39. A radioactive element gets spilled over the floor of a room. Its
half-life period is 30 days. If the initial velocity is ten times the
3
reactant to drop to of its initial value. If the rate constant permissible value, after how many days will it be safe to enter
4
the room? [AIEEE 2007]
for a first order reaction is K, the t1/4 can be written as
[AIEEE 2005] (a) 100 days (b) 1000 days
(a) 0.75/k (b) 0.69/k (c) 300 days (d) 10 days.
(c) 0.29/k (d) 0.10/k
1
34. A reaction was found to be second order with respect to the 40. For a reaction A ® 2B, rate of disappearance of ‘A’ is
concentration of carbon monoxide. If the concentration of 2
carbon monoxide is doubled, with everything else kept the related to the rate of appearance of ‘B’ by the expression
same, the rate of reaction will [AIEEE 2006] [AIEEE 2008]
(a) increase by a factor of 4
d[A] 1 d[B]
(b) double (a) – = (b) – d[A] = 1 d[B]
(c) remain unchanged dt 2 dt
dt 4 dt
(d) triple
35. Rate of a reaction can be expressed by Arrhenius equation d[A] d[B]
(c) d[A ] d[B]
– =
(d) – =4
as : [AIEEE 2006] dt dt dt dt
k = A e–E/RT
41. The half life period of a first order chemical reaction is 6.93
In this equation, E represents
minutes. The time required for the completion of 99% of the
(a) the total energy of the reacting molecules at a
temperature, T chemical reaction will be (log 2 = 0.301) [AIEEE 2009]
(b) the fraction of molecules with energy greater than the (a) 23.03 minutes (b) 46.06 minutes
activation energy of the reaction (c) 460.6 minutes (d) 230.03 minutes
Chemical Kinetics 615
42. The time for half life period of a certain reaction 47. The rate of a reaction doubles when its temperature changes
A ¾¾ ® Products is 1 hour. When the initial concentration from 300 K to 310 K. Activation energy of such a reaction will
of the reactant ‘A’, is 2.0 mol L–1, how much time does it take be : (R = 8.314 JK–1 mol–1 and log 2 = 0.301) [JEE Main 2013]
for its concentration to come from 0.50 to 0.25 mol L–1 if it is (a) 53.6 kJ mol –1 (b) 48.6 kJ mol–1
a zero order reaction ? [AIEEE 2010] (c) 58.5 kJ mol –1 (d) 60.5 kJ mol–1
(a) 4 h (b) 0.5 h (c) 0.25 h (d) 1 h 48. Consider a reaction aG + bH ® Products. When
43. Consider the reaction : concentration of both the reactants G and H is doubled, the
rate increases by eight times. However, when concentration
Cl2 (aq ) + H 2S( aq ) ® S( s) + 2H + ( aq) + 2Cl - ( aq) of G is doubled keeping the concentration of H fixed, the rate
is doubled. The overall order of the reaction is
The rate equation for this reaction is
[IIT-JEE 2007]
rate = k[Cl2 ][H 2S] (a) 0 (b) 1
Which of these mechanisms is/are consistent with this rate (c) 2 (d) 3
equation? [AIEEE 2010] 49. Under the same reaction conditions, initial concentration of
1.386 mol dm–3 of a substance becomes half in 40 seconds
A. Cl2 + H 2S ® H + + Cl - + Cl+ + HS- (slow)
and 20 seconds through first order and zero order kinetics,
Cl + + HS- ® H + + Cl - + S (fast) respectively. Ratio (k1/k0) of the rate constant for first order
(k1) and zero order (k0) of the reaction is [IIT-JEE 2008]
B. H 2S H + + HS- (fast equilibrium) (a) 0.5 mol–1 dm3 (b) 1.0 mol dm–3
(c) 1.5 mol dm –3 (d) 2.0 mol–1 dm3
Cl2 + HS- ® 2Cl - + H + + S (Slow) 50. For a first order reaction A®P, the temperature (T) dependent
(a) B only (b) Both A and B rate constant (k) was found to follow the equation
(c) Neither A nor B (d) A only 1
log k = – (2000) + 6.0 . The pre-exponential factor A and
44. A reactant (A) froms two products : [AIEEE 2011RS] T
k the activation energy Ea, respectively, are [IIT-JEE 2009]
A ¾¾
1 ® B,
Activation Energy Ea1
(a) 1.0 × 106 s–1 and 9.2 kJ mol–1
k2
A ¾¾® C, Activation Energy Ea2 (b) 6.0 s–1 and 16.6 kJ mol–1
(c) 1.0 × 106 s–1 and 16.6 kJ mol–1
If Ea2 = 2 Ea1, then k1 and k2 are related as : (d) 1.0 × 106 s–1 and 38.3 kJ mol–1
51. Plots showing the variation of the rate constant (k) with
(a) k2 = k1e Ea1 / RT (b) k2 = k1e Ea2 / RT
temperature (T) are given below. The plot that follows
(c) k1 = Ak2 e Ea1 / RT (d) k1 = 2k2 e Ea2 / RT Arrhenius equation is [IIT-JEE 2010]
45. The rate of a chemical reaction doubles for every 10°C rise of
temperature. If the temperature is raised by 50°C, the rate of
the reaction increases by about : [AIEEE 2011]
(a) 10 times (b) 24 times (c) 32 times (d) 64 times (a) (b)
46. For a first order reaction (A) ® products the concentration of
A changes from 0.1 M to 0.025 M in 40 minutes.
The rate of reaction when the concentration of A is 0.01 M is :
[AIEEE 2012]
(a) 1.73 × 10–5 M/min (b) 3.47 × 10–4 M/min (c) (d)
(c) 3.47 × 10–5 M/min (d) 1.73 × 10–4 M/min
616 Chemistry
1. Two substances R and S decompose in solution Rate in terms of N2. Rate in terms of H2
independently, both following first order kinetics. The rate
(mol L–1sec–1 ) (mol L–1sec–1 )
constant of R is twice that of S. In an experiment, the solution
initially contained 0.5 millimoles of R and 0.25 millimoles of (a) 2×10–4 2×10–4
S. The molarities of R and S will be equal just at the end of (b) 3×10–4 1×10–4
time equal to (c) 1×10–4 3×10–4
(a) twice the half life of R (b) twice the half life of S (d) 2×10–1 2×10–3
(c) the half life of S (d) the half life of R 8. The rate constant , the activation energy and the Arrhenius
2. For a reaction, the rate constant at particular temperature parameter of a chemical reaction at 25°C are 3×10–4 s–
has a value of 2.0 × 10–3 mol lit-1s -1 . The order of the reaction
1,104.4kJ /mol and 6×1014 s–1 respectively. The value of the
is rate constant as T ® ¥ is
(a) –1 (b) 0 (a) 2.0×1018 s–1 (b) 6.0×1014 s–1
(c) 1 (d) 2 (c) Infinity (d) 3.6×1030 s–1
3. For the gas phase decomposition A ® 2B, the rate 9. A substance ‘A’ decomposes in solution following first order
constant is 6.93 × 10–3 min–1 at 300 K. The percentage of a kinetics. Flask I contains l L of a 1M solution of A and flask
remaining at the end of 300 minutes is II contains 100 ml of a 0.6 M solution. After 8 hours the
concentration of A in flask I has become 0.25. What will be
(a) 75 (b) 50
the time taken for concentration of A in flask II to become
(c) 25 (d) 12.5 0.3M ?
4. For a first order reaction t 0.75 is 1368 seconds, therefore, (a) 0.4 h
the specific rate constant in sec–1 is (b) 2.4 h
(c) 4.0 h
(a) 10–3 (b) 10–2 (d) Can’t be calculated since rate constant is not given
(c) 10–9 (d) 10–5 10. A reaction rate constant is given by
5. Consider the following reactions at 300 K k = 1.2 ´ 1014 e-25000/RT sec-1 . It means
(a) log k versus log T will give a straight line with a slope as
X ¾¾ ¾
¾® Y (uncatalysed reaction)
–25000
catalyst
X ¾¾¾
¾® Y (catalysed reaction) (b) log k versus T will give a straight line with slope as
25000
The energy of activation is lowered by 0.314 KJ mol -1 for (c) log k versus log 1/T will give a straight line with slope as
the catalysed reaction. The rate of reaction is –25000
(a) 38 times (d) log k versus 1/T will give a straight line
(b) 15 times 11. Consider a general chemical change 2A + 3B ® products.
(c) 25 times The rate with respect to A is r1 and that with respect to B is
(d) 22 times that of uncatalysed reaction. r2. The rates r1 and r2 are related as
6. For a reaction A ® B , the rate increases by a factor of 2.25 (a) 3 r1=2r2 (b) r1 = r2
when the concentration of A is increased by 1.5. What is the (c) 2r1 = 3r2 (d) r12 = 2r22
order of the reaction?
12. In case of first order reaction,the ratio of the time required for
(a) 3 (b) 0
99.9% completion to 50% completion is
(c) 2 (d) 1 (a) 2 (b) 5
7. The reactions rate N 2 (g) + 3H 2 (g) ® 2 NH 3 (g) was (c) 10 (d) None of these
13. For the exothermic reaction A + B ® C + D, DH is the heat
measured d[ NH 3 ] = 2 ´ 10 - 4 mol sec –1 . The rates of of reaction and Ea is the energy of activation. The energy of
dt
activation for the formation of A + B will be
reactions expressed in terms of N2 and H2 are (a) Ea (b) DH
(c) Ea + DH (d) DH – Ea
Chemical Kinetics 617
14. The following statement(s) is (are) correct : 20. For a reaction following first-order kinetics, which of the
(i) A plot of log kp versus 1/T is linear following statements are correct?
(ii) A plot of log [X] versus time is linear for a first order (a) The time taken for the completion of 50% of the reaction
is twice of t½
reaction, X ® P
(b) A plot of the reciprocal of the concentration of the
(iii) A plot of log p versus 1/T is linear at constant volume
reactants against time gives a straight line.
(iv) A plot of p versus 1/V is linear at constant temperature (c) The degree of dissociation is equal to 1–e–kt.
(a) (i) only (b) (ii) only (d) A plot of [A]0/[A] versus time gives a straight line.
(c) (i) & (iv) (d) (i), (ii) & (iv) 21. An endothermic reaction has a positive internal energy
15. The decomposition of A follows two parallel first order change DU. In such a case, what is the minimum value that
reactions the activation energy can have ?
–4 –1
(a) DU (b) DU = DH + DnRT
k1 1.26 ´ 10 sec (c) DU=DH–DnRT (d) DU=Ea+RT
B
–5 –1 22. At 400 K the half-life of a sample of a gaseous compound
A k2 3.8 ´ 10 sec
C initially at 56.0 kPa is 340 s. When the pressure is 28.0 kPa, the
The percentage distribution of B and C are half-life is 170s. The order of the reaction is
(a) 0 (b) 2
(a) 90 % B and 10 % C
(c) 1 (d) ½
(b) 80 % B and 20 % C
23. Consider the reaction mechanism
(c) 60 % B and 40 % C
A2 2A (fast)
(d) 76.83 of B and 23.17 % C A + B ® P (slow)
16. In a first order reaction the concentration of where A is the intermediate. The rate for the reaction is
reactant decreases from 800 mol/dm3 to 50 mol/dm3 in 2 x 104 (a) k2[A][B] (b) k2k½[A2]½[B]
sec. The rate constant of reaction in sec-1 is: ½
(c) k2k [A][B] (d) k2k½[A]2[B]
(a) 2 × 104 (b) 3.45 × 10-5 24. N2O2(g) ® 2NO(g) is a first-order reaction in terms of the
(c) 1.386 × 10-4 (d) 2 × 10-4 concentration of N2O2(g). Which of the following is valid,
17. Which of the following graphs best describes the rate at [N2O2] being constant ?
which N2O4 decomposes to NO2 if the reaction is first-order (a) [NO] = [N2O2]0 e–kt (b) [NO] = [N2O2]0 (1–e–kt)
in N2O4? (c) [NO] = [N2O2]0 (e–kt–1) (d) [NO] = [N2O2]0 (1–e–kt)
25. The reaction A(g) + 2B(g) ® C(g) + D(g) is an elementary
process. In an experiment involving this reaction, the initial
(a) [N2O4] (b) [N2O4] partial pressures of A and B are pA = 0.60 atm and pB= 0.80
atm respectively. When pC= 0.20 atm, the rate of the reaction
relative to the initial rate is
Time Time
(a) 1/6 (b) 1/12
(c) 1/36 (d) 1/18
(c) [N2O4] (d) [N2O4] 26. In acidic medium the rate of reaction between BrO3 - and
(a) 8 mm Hg min -1 (b) 2 mm Hg min -1 37. The half life of the first order reaction
(i) A + B ¾¾® X (slow) (ii) X ¾ ¾® AB (fast) pressure at the end of 20 minutes is 120 mm Hg
(a) 80 min (b) 120 min
The progress of the reaction can be best described by
(c) 20 min (d) 40 min
k1 14. (c) The rate constant doubles for 10º C rise in temperature.
1. (b) 2 NO2 N2O4,
k2 For 20º C rise, the rate constant will be 4 times
\ k1 = 4k2 or k2 = 0.25 K1
For forward reaction rate = - 1 dNO2 = dN2 O4
2 dt dt
2.303 a 2.303 1 2.303
15. (d) k = log = log = log 8
= k1[NO 2 ] 2 t a-x 24 1 24
8
For backward reaction
16. (d) With temperature the number of activated molecules
dN 2 O 4 1 dNO 2
Rate = - = = k 2 [N 2 O 4 ] . increase.
dt 2 dt
17. (b) Between 2 and 3.
Rate of disappearance of NO2 = (Rate of disapperance of 18. (c) There are 5 tens hence (2)5 = 32.
NO2 – Rate of appearence of NO2)
19. (b) For 1st order rection t 1/2 independent of initial
= 2k1[NO2]2 – 2k2[N2O4].
concentration.
2. (b) By concentration of reactants.
20. (c) Let the rate law equation be r = k[A]x[B]y................(1)
3. (b) 3A ® 2B
when A = 2A, 4r = k[2A]x[B]y........................(2)
Rate of reaction - 1 dA = 1 dB or - 2 dA = dB
4r k[2A]x [B] y
3 dt 2 dt 3 dt dt Divide(2) by (1) =
r k[A]x [B] y
4. (a) N 2 (g ) + 3H 2 (g ) ¾
¾® 2 NH 3 (g )
\ 4 = (2)x, Hence x = 2
Rate = -
dN 2 1 dH 2 1 dNH 3 when B = 2B, r = k[A]x [2B]y.........................(3)
=- =
dt 3 dt 2 dt
r k[A]x [2B] y
5. (d) If volume is reduced to 1/4th concentration will \ 1 = Divide (3) by (1) = (2)y \ y = 0
be increased 4 times hence reaction rate will r k[A]x [B]y
increase by 16. Rate = k[A][B].
\ Rate = k[A]2[B]0
New rate = k[4A][4B] = 16k[A][B]
620 Chemistry
21. (a) Let the rate law be r =k [A]x[B]y
1
34. (b) After every 30 minutes the amount is reduced to
x y 2
0.10 [0.024] [0.035]
Divide (3) by (1) =
0.10 [0.012] x [0.035] y therefore t1/2 is 30 minutes. In 90 minutes the amount is
\ 1 = [2]x, x = 0 1 1
reduced to i.e. . Here n = 3. True for 1st order reaction.
8 2n
0.80 [0.024] x [0.070] y
Divide (2) by (3) = a
0.10 [0.024]x [0.035] y 1 1
35. (c) t = for zero order, t = and t1 = , \ t1 = 2t
k 4k 2k
\ 8 = (2)y , y = 3
Hence rate equation, R = k[A]0[B]3 =k[B]3 0.693 2.303 100
36. (c) k = further t = ´ 45 log
45 0.693 100 - 99.9
22. (b) O 3 ¾Fast
¾
Slow
¾® O 2 + O; O + O 3 ¾¾¾® 2O 2
2.303 ´ 45 ´ 3 1
= = 7 hours .
[O ][O] 0.693 2
k= 2 (I), Rate = k' [O3][O] put [O] from (I)
[O 3 ]
2.303 a 2.303 0 .5
37. (a) t = log = log = 0.384 min .
k '[O3 ]k[O3 ] k a-x
= k[O3 ]2 [O2 ]-1
6 0.05
r=
[O2 ] 38. (d) Rate = k [N2O5] ;
Note intermediates are never represented in rate law 2.4 ´10 -5 = 3.0 ´ 10 -5 [ N 2 O 5 ]
equation.
23. (b) 1st order reaction. \ [ N 2 O 5 ] = 0 .8
24. (d) Rate = k [A]0 39. (a) Rate = k [N2O5]
\ Rate = k for zero order. = 6.2 ×10–4×1.25 = 7.75 × 10–4 mol L–1s–1
25. (d) Order with respect to A is 2 and B is 1.
2.303 100
\ Order of reaction = 2+1 = 3 40. (c) t 90% = log (I)
k 100 - 90
26. (a) t1/2 for 1st order is independent of initial concentration.
2.303 100
Ea t 50% = log (II)
27. (d) k = Ae - Ea / RT log k = log A – .
1 k 100 - 50
2.303R T
t log10
-E a Dividing 90% = \ t 90% = 3.3t 50%
Equation of straight line slope = . t 50% log 2
2.303R
41. (a) Since rate is constant throughout. It is zero order.
2.303 a
28. (a) t = log 42. (a) For zero order reaction tcompletion = a/k.
k a-x
43. (d) A 2 + B 2 ¾
¾® 2AB ; A 2 ¾
¾® A + A ( Fast );
2.303 2.303
or t = log a - log(a - x)
k k A + B2 ¾
¾® AB + B (Slow )
29. (d) Order of reaction is independent of given factors.
Rate law = k[A][B 2 ] put value of [A] from Ist reaction
30. (b) For zero order the rate does not change with
concentration. since A is intermediate k[A 2 ] = A
31. (c) t1/2 µ aº. t1/2 is independent of initial concentration.
32. (b) The order of a chemical reaction is given by \ Rate law equation = K k[A 2 ][B2 ]
concentration of reactants appearing in the lowest step.
1 3
\ Order = +1 =
1
33. (a) t1 / 2 µ a1- n
2 2
t1 / 2 µ hence n = 4.
a3 44. (c) It is bimolecular first order reaction since Rate µ [N2O5]
Chemical Kinetics 621
45. (c) Third order
a 0.9
46. (c) Applicable to bimolecular reactions. In second case = =4
a - x 0.225
47. (a)
Since the ratio is the same, hence time will be same.
48. (d) All the statements are correct (see text).
Therefore 1 hr.
49. (a) E a (F.R .) ¹ E a (B.R .) Ea can be calculated. 60. (c) Adsorption lowers the activation energy.
EXERCISE 3
k2 E a (T2 - T1 )
50. (c) log = ; Ea can be calculated.
k1 2.303R T1T2
1. (d) As the slowest step is the rate determining step thus
51. (c) Activation energy is lowered in presence of +ve catalyst. the mechanism B will be more consistent with the given
52. (b) Since the nature of reaction (i.e. exothermic or information also because it involve one molecule of
endothermic) not given therefore Ea for reverse reaction H2 and one molecule of ICl it can expressed as
can be more or less. r = k [H2][ICl]
53. (b) In accordance with Arrhenius equation. Which shows that the reaction is first order w.r.t. both
54. (c) Statement (c) see text. H2 & ICl.
55. (b) For 10°C rise of temperature the rate is almost doubled. 2. (c) For a first order reaction
56. (a) Threshold Energy = Energy of activation + Internal 2.303 a
energy k= log
t a- x
[C][D] [Products] when t = t½
57. (d) Q = = ; Q = increases with time
[A][B] [Reactants]
2.303 a
k= log
Ea 1 t½ a - a/2
58. (b) k = Ae - Ea / RT log k = log A - .
2.303R T
2.303 ln 2
or t½ = log 2 =
1 k k
Plot of log k Vs.
T 3. (a) For a first order reaction
-E a 2.303 a
Straight line Slope = k= log
2.303R t a- x
2000 1000 M to 0.20 M but the rate has changed from 1.2× 10 –4 to
- -
or 10 ´ 10 .e
15 T 15
= 10 .e T 3.1×10–4. This is due to change in concentration of
CH3COCH3 from 0.30 M to 0.40 M. Thus the rate is
2000 1000 directly proportional to [CH3 COCH3]. We now get
- -
T T
or 10.e =e
rate = k [CH3COCH3]1[Br2]0[H+]1
2000 1000 = k [CH3COCH3][H+].
or ln 10 - =-
T T 6. (d) Rate of disappearance of H2 = rate of formation of
NH3.
2000 1000
or ln 10 = - 1 d[H2 ] 1 d[NH3 ]
T T – =
3 dt 2 dt
1000
or 2.303 log 10 = – d[H 2 ] 3 d[NH3 ] 3 –4
T Þ = = × 2×10
dt 2 dt 2
or 2.303 ×1×T=1000 [\ log 10= 1]
= 3×10 –4 mol L–1s –1
1000
or T = K 7. (d) Rate of disappearance of Br–
2.303
= rate of appearance of Br2
5. (a) Rewriting the given data for the reaction
1 d[Br – ] 1 d[Br2 ]
H+ Þ– =
CH 3COCH 3 ( aq ) + Br2 ( aq ) ¾¾® 5 dt 3 dt
CH3COCH 2 Br(aq) + H + (aq) + Br - ( aq) 1 d[Br2 ] 1 d[Br – ]
Þ =-
3 dt 5 dt
S. Initial concent Initial concentr Initial concentr Rate of
d[Br2 ] 3 d[Br – ]
No. -ration of -ation of Br2 -ation of H + disappearance Þ =-
dt 5 dt
CH3 COCH3 in M in M of Br2 in Ms -1
in M d dx 8. (b) For a first order reaction
i.e. - [Br2 ]or
dt dt
0.693 0.693
1 0.30 0.05 0.05 5.7 ´ 10-5 t1/2 = ; k= = 0.5 × 10–3s–1
k 1386
2 0.30 0.10 0.05 5.7 ´ 10-5
3 0.30 0.10 0.10 1.2 ´ 10-4 9. (a) When concentration A is doubled, rate is doubled.
4 0.40 0.05 0.20 3.1 ´ 10-4 Hence order with respect to A is one.
When concentrations of both A and B are doubled,
rate increases by 8 times hence order with respect to B
Actually this reaction is autocatalyzed and involves
is 2.
complex calculation for concentration terms.
\ rate = k [A]1 [B]2
We can look at the above results in a simple way to
find the dependence of reaction rate (i.e., rate of Total order = 1 + 2 = 3
disappearance of Br2).
10. (b) N 2 O5 (g) ¾¾
® 2NO2 (g) + 1/2 O 2 (g)
From data (1) and (2) in which concentration of
CH3COCH3 and H+ remain unchanged and only the
[ N2 O5 ] = + [ NO2 ] = 2 [O2 ]
concentration of Br2 is doubled, there is no change in d 1d d
–
rate of reaction. It means the rate of reaction is dt 2 dt dt
independent of concentration of Br2.
[ NO2 ] = 1.25 ´ 10-2 mol L–1s–1 and
d
Again from (2) and (3) in which (CH3CO CH3) and (Br2)
dt
remain constant but H+ increases from 0.05 M to 0.10
i.e. doubled, the rate of reaction changes from 5.7×10–5
[O2 ] = 3.125 ´ 10-3 mol L–1s–1
d
to 1.2 × 10–4 (or 12 × 10–5), thus it also becomes almost
dt
doubled. It shows that rate of reaction is directly
proportional to [H+]. From (3) and (4), the rate should 11. (b)
have doubled due to increase in conc of [H+] from 0.10
Chemical Kinetics 623
12. (d) In case of (II) and (III), keeping concentration of [A]
k Ea æ 1 1ö
constant, when the concentration of [B] is doubled, 19. (b) log 2 = ç - ÷
the rate quadruples. Hence it is second order with k1 2.303R è T1 T2 ø
respect to B. In case of I & IV Keeping the
concentration of [B] constant. when the concentration Ea é 1 1 ù
-
2.303 ´ 8.314 ë 293 308 úû
ê
of [A] is increased four times, rate also increases four log 2 =
times. Hence, the order with respect to A is one. hence
[ A0 ]
keeping concentration of B constant.
2
\ Order of reaction = 1 + 1 = 2 and units of second or k = = = 1 mol lit –1 hr–1
2 t1/ 2 2 ´1
order reaction are L mol–1 sec–1.
Chemical Kinetics 625
Further for a zero order reaction 46. (b) For a first order reaction
43. (d) Since the slow step is the rate determining step hence Rate = k[A] = 3.47 × 10–2 × 0.01
if we consider option (A) we find
= 3.47 × 10–4 M/min
Rate = k [ Cl2 ][ H 2S] 47. (a) Activation energy can be calculated from the equation
Now if we consider option (B) we find log k2 -Ea æç 1 1ö
= çç - ÷÷÷÷
log k1 2.303R è T2 T1 ø
Rate = k [ Cl2 ] éë HS ùû
-
...(i)
For equation, k
Given 2 = 2 ; T2 = 310 K ; T1 = 300 K
H+ + HS–
H S k1
2
é H + ù é HS- ù -Ea æ 1 1 ÷ö
= log 2 = çç - ÷
K = ë ûë 2.303´8.314 èç 310 300 ÷ø
û
H 2S
Ea = 53598.6 J/mol = 53.6 kJ/mol.
- K [ H 2S ] 48. (d) Overall order = sum of orders w.r.t each reactant.
or éë HS ùû =
H+ Let the order be x and y for G and H respectively
Ea1 / RT 0.693
k1 = k2 A ´ e and k1 =
t1/ 2
45. (c) Since for every 10ºC rise in temperature rate doubles Substituting various given values, we get
for 50ºC rise in temperature increase in reaction rate
= 25 = 32 times 1.386 mol litre –1
k0 = ... (i)
2 ´ 20 sec
626 Chemistry
0.693
and k1 =
40sec
... (ii) 4. (a) k = 2.303 log 100 On solving we get . k = 10–3
1386 100 - 75
Dividing (ii) by (i), we get
5. (c) k un cat = A e E uncat / RT ......... (i)
k1 0.693 2´ 20 0.693
= ´ k cat = A e E cat / RT ......... (ii)
1.386 mol dm-3
40 = = 0.5
k0 1.386
Let the Ea for uncatalysed reaction be A then for catalysed
= 0.5 mol–1 dm3
reaction it will be (A - 8.314 ´ 103 ) cal/mole
Thus the correct answer is (a).
Dividing (ii) by (i),
Ea
50. (d) log k = log A - …(1) 3
2.303RT k cat e ( A -8.314´10 ) / RT
8.314´10 3
/ RT
= =e
k un cat e A / RT
1
Also given log k = 6.0 - (2000) …(2)
T k cat
= e 3.33 = 28 (take log then antilog)
On comparing equations, (1) and (2) k un cat
log A = 6.0 Þ A = 106 s–1
6. (c) Let the rate law equation be
Ea
and 2.303 R = 2000 ; r = k[A]x ...................(i)
25000 1
\ T = 2 t 1 / 2 . 2t1/2 is half life of S and twice the half - log k = log 1.2 × 10 -
14
.
R T
life of R
2. (c) Units of k = (Mol lit–1) time –1 ; Hence n = 1 order
0.693 Logk
3. (d) For first order t½ = = 100 min ; 300 = 100 × n
-3
6.93 ´10
1/T
100 Equation of straight line
Percentage left = = 12.5%
( 2) 3
2500
slope = -
R
Chemical Kinetics 627
11. (a) For the change 2A + 3B ® products 17. (d) N 2 O 4 2NO 2 . Decomposition of N2O4 is first
order and its concentration will will decrease with time.
1 d[ A ] 1 d[ B] 1 1
- =- , r1 = r2 ; 3r1 = 2r2
2 dt 3 dt 2 3 18. (b) For zero order
2.303 100 Co - C t
12. (c) t 99.9% = log k=
k 100 - 99.9 t
-5
Rate = k[A][B]2 = k(0.60)(0.80)2 .......................(i)
kC 3.8 ´ 10
The fractional yield of C = =
k av 1.64 ´ 10 - 4 when p c = 0.20 atm p A is reduced to 0.40 and
pB = 0.40 (See stoichiometric representation)
= 0.2317 = 23.17 %
Rate = k[0.40] [0.40]2..............................(ii)
2.303 [A]0 2.303 800
16. (c) k = log = log = 1.386 ´ 10 4 s -1 0.40 ´ 0.40 ´ 0.40 1
t [A]t 2 ´ 10 4 50 \ (ii) divide by (i) = =
0.60 ´ 0.80 ´ 0.80 6
628 Chemistry
26. (a) The rate law equation contains [H + ]2 , term. The rate k2 E a (T2 - T1 )
36. (d) ln =
k1 R T2 ´ T1
will change with change in pH and new rate will be [2]2
= 4 times the old rate 3.07 ´10-3 E a (510.1 - 457.6)
ln =
Ea 2.2 ´10 -5 R 510.1´ 457.6
1
27. (b) log k = log A – .
2.303 T \ Ea = (510.1 × 457.6) / 52.5 × R ln 307/2.2 cal.
The value of k increases with the increase of temperature.
37. (c) CH 3CHO (g ) ¾
¾® CH 4 (g) + CO (g)
28. (c) Generally the rate of reactions is doubled by 10°C rise in
temperature i.e. the increase is » 100 %.
When t = 0 p0 0 0
29. (b) The curve Y shows the increase in concentration of
products with time. When t = t p0 - p p p
30. (a) The increase in pressure shows the increase in conc. of Z.
120 - 100 \ p 0 - p + p + p = 120 mm Hg
Rate of appearance of Z = = 4 mm Hg min -1
5
or, p 0 + p = 120 mm Hg;
Rate of disappearance of X 2 = 2 × rate of appearance of
p = 120 – 80 = 40 mm Hg
Z = 2 × 4 mm Hg min -1 = 8 mm Hg min -1
31. (c) A dip in the curve shows the formation of X (reaction 1 p0 1 80 1
k= ln = ln = ln 2
taking place in two steps). Since the reaction is exothermic t p -p
0 20 80 - 40 20
Ea of X must be less.
ln2
K 310 Again, t1 / 2 =
32. (b) Temperature coefficient = = 2.3 k
K 300
ln2
K 310 = 2.3 K 300 \ t1 / 2 = ´ 20 = 20 min.
ln2
1
33. (c) t1 / 2 µ
6 ´ 10 -7
where n is the order of reaction
( p) n -1 38. (b) [H + ] = = 1.2 ´ 10 -2 M
-3
0.05 ´ 10
n -1 n -1
2 æ 50 ö 1 æ1ö
=ç ÷ or =ç ÷ DX DX 1.2 ´ 10 -2 M
4 è 100 ø 2 è2ø Rate r = ; Dt = =
Dt r 6 ´ 105 M s -1
\ n=2
-8
C0 - C \ T = 2 ´ 10 s
34. (a) For zero order reaction k = or C = C0 – kt
t
k 2 E 2 + k 1 E1
The equation has negative slope and non zero intercept. 39. (c) Ea =
k 2 + k1
n -1
t1 / 2 (1) é p (2) ù
35. (c)
t1 / 2 (2) êë p (1) úû
= , 1.0 ´10 - 2 ´ 60 + 3.0 ´10 - 2 ´ 70
=
1.0 ´10 - 2 + 3.0 ´10 - 2
n -1
880 é 364 ù Ea = 67.5 k J mol -1
= ê ú ;
410 ë 170 û
[2.14]1 = [2.1]n -1
19
Surface Chemistry
Thomas Graham divided the solids into two types. TYPES OF COLLOIDAL SYSTEMS :
CRYSTALLOIDS : Dispersed Dispersion Name Examples
The substances whose solution readily diffuse through a phase medium
parchment membrane eg sugars, salts, acid and base. Gas Liquid Foam Shaving Cream,
COLLOIDS : Soda Water froth
The substance whose solution diffused at very slow rate through Gas Solid Solid foam Pumice stone,
a parchment membrane eg glue, gelatin, gum arabic etc. corck, foam rubber
Later on it was found that crystalloids and colloids differed only Liquid Gas Aerosol Mist , cloud, fog
in their size of particles. They can be interconverted, hence Liquid Liquid Emulsion Hair cream, milk
colloidal is a state.
Liquid Solid Gel Cheese, butter
On the basis of the size of particles we have
Solid Gas Smoke Occluded gases,
1nm 100nm dust soot in air
1Å 10Å 1000Å 10,000Å Solid Liquid Sol Colloidal gold
Solid Solid Solid sol alloys
2 N 2 + 3H 2 ¾¾ ¾
Fe / Mo
¾® 2 NH 3 2SO 2 + O 2 + [ NO] ® 2SO 3 + [ NO]
(vi) Catalyst poisoning - The substance which destroys the Intermediate mechanism
activity of a catalyst is called a poison and process is called O2 + 2NO ® 2NO 2
catalytic poisoning eg. Catalyst Intermediate
pt
2SO 2 + O 2 ¾¾ ¾ ¾ ¾
¾® 2SO 3 [SO 2 + NO 2 ® SO 3 + NO] ´ 2
poisoned by As 2O 3
2SO 2 + O 2 + [2NO] ® 2SO 3 + 2[ NO]
pt
2H 2 + O 2 ¾¾ ¾ ¾
¾® 2H 2 O
poisoned by CO Catalytic oxidation of hydrochloric acid by atmospheric
oxygen in presence of cupric chloride (Deacon’s process)
CHARACTERISTICS OF CATALYST :
CuCl
The following are some important features for a catalyst or HCl + O 2 ¾¾¾2 ® 2Cl 2 + 2H 2 O
catalysis. Mechanism - (2CuCl2 ® Cu2Cl2 + Cl2) × 2
(i) Small quantity - Generally small amount of a catalyst is 2Cu 2Cl 2 + O 2 ® 2Cu 2 .OCl 2
required but sometimes the large quantity of catalyst is Intermediate
effective eg anhydrous AlCl3 in Friedel Craft’s reaction is
needed upto 30%. (Cu 2 OCl 2 + 2HCl ® 2CuCl 2 + H 2 O) ´ 2
(ii) Unchangeabiliy - Although there is no change in the chemical 4HCl + O 2 + [4CuCl 2 ] ® 2Cl 2 + 2H 2 O + [4CuCl 2 ]
compostion and mass, there may be a change in physical Limitations of intermediate theory-
state of catalyst eg granular MnO2 changes to fine powder (a) Action of promoters and poisons.
in decomposition of potassium chlorate (b) Participation of catalyst in chemical reaction.
(iii) Specific action of catalyst - From the same reactants the (ii) Adsorption theory - By the adsorption of the reactants at the
different products are obtained with different catalysts eg. surface of a catalyst, their concentrations are increased. The
(a) C 2 H 5 OH ¾Al
¾2¾
O3
¾® C 2 H 4 + H 2 O ( Dehydratio n ) rate being directly proportional to concentration, is increased.
D (iii) Modern theory - It is the combination of intermediate theory
C2H5OH ¾¾¾
hot
® CH3CHO + H 2 (Dehydrogenation) and adsorption theory. At the surface of a catalyst there are
Cu,300ºC residual or free valencies and reactant molecules are retained
at the surface in distorted or strained positions. These
(b) 4 NH 3 + 3O 2 ¾Cu
¾® 2 N 2 + 6H 2 O molecules then react vigrously to give products and make
500º C
space for other reactant molecules. The greater the surface
Pt
4 NH 3 + 5O 2 ¾¾® 4 NO + 6 H 2 O area of the catalyst, the more is its activity. Further catalysts
800º C
with rough surface, having greater number of corners, peaks,
(iv) Initiation of reaction - In general a catalyst does not start a cracks have more active centres and more effective e.g. finely
chemical reaction, but there are reactions initiated by catalysts divided nickel or platinum
eg.
Active spot
H 2 + O 2 ¾Room
¾ ¾Temp
¾¾.® No reaction
Pt Black Ni
2H 2 + O 2 ¾¾ ¾¾® 2 H 2 O
(v) Equilibrium - A catalyst does not affect the state of Ni Ni Active spot Ni
equilibrium, it simply helps to attain it quickly.
Ni Ni Active spot Ni Ni Ni Ni
(vi) Optimum temperature - The rate of reaction is maximum at a
particular temperature which is fixed for every reaction. Ni Ni Ni Ni Ni Ni
(vii) Physical state of catalyst - Finely divided catalyst gives better
yield in a short period than lumps.
(viii) Activation energy - A positive catalyst lowers the activation ACTION OF PROMOTERS :
energy of a chemical reaction. It can be assumed that a loose compound is formed between the
catalyst and the promoter which possesses an increased capacity
THEORY OF CATALYSIS : of adsorption.
There are following main theories Action of catalytic poison - It may be due to the preferential
(i) Intermediate theory adsorption of poison on the active spots of the catalyst thus
(ii) Adsorption theory reducing the number of free active spots for reacting molecules.
(iii) Modern theory
636 Chemistry
ACID BASE CATALYSIS :
A large number of reactions catalysed by acids or bases are known
ADSORPTION
eg. ADSOPRTION :
(a) Hydrolysis of an ester in presence of an acid Adsorption is the phenomenon of higher concentration of
H+
molecular species at the surface than in the bulk of a solid or
CH 3COOC 2 H 5 + H 2 O ¾¾
¾® CH 3COOH + C 2 H 5 OH
liquid. Forces involved are van der waal’s forces.
(b) Cyanides are hydrolysed by acids or alkalis The unbalanced or residual forces acting along the surface of a
solid or liquid attract the moleculs of other species when brought
H+ +H O
RCN + H2O ¾¾¾
®RCONH2 ¾¾¾
2 ¾
®RCOOH + NH3 into their contact. These molecules remain at surface and do not
-
or OH
go into bulk, hence making the concentration more at surface.
Such reactions are called acid base catalysis and H+ or OH–
ADSORBATE :
ions act as catalyst.
The substance that concentrates at the surface is called adsorbate.
MODERN CONCEPT OF ACID BASE CATALYSIS:
ADSORBENT :
According to this concept
(i) A reaction which is catalysed by an acid is also catalysed by Adsorbent is the solid or liquid at whose surface the concentration
all substances having tendency to lose protons (H+) occurs.
(ii) A reaction which is catalysed by a base is also catalysed by ABSORPTION :
all substances having a tendency to gain protons. Absorption is the phenomenon of uniform distribution of a
ENZYMES OR BIOLOGICAL CATALYSTS : substance throughout the body of a solid or liquid. For eg water
Many complex chemical reactions like oxidation, reduction or vapour is absorbed by a sponge or anhydrous CaCl2 while it is
hydrolysis take place in presence of enzymes which are highly adsorbed by silicagel. The pressure of gases (SO2, Cl2, NH3)
complex, nitrogenous non living organic substances. They are pressure decreases when treated with powdered charcoal in a
highly specific in nature eg. closed vessel due to adsorption of gas on charcoal surface.
(a) Starch is catalysed by diastase maltose is formed and then SORPTION :
maltose by maltase
Adsorption and absorption go hand in hand thus making it tough
Diastase
2(C 6 H10 O5 ) n + n H 2 O ¾¾ ¾¾® n C12 H 22 O11 to distinguish between them. The general term sorption was
Maltose introduced by McBain to include both processes.
Maltase
CHARACTERISTICS OF ADSORPTION :
C12H 22O11 + H 2O ¾¾¾¾
® 2C6H12O6
(i) It is a surface phenomenon.
Glucose
(ii) It is a spontaneous process.
(b) Urea is converted into ammonium carbonate by Urease (iii) Adsorption is accompanied by evolution of heat as the
H 2 N.CO.NH 2 + 2 H 2 O ¾¾ ¾
Urease
¾®( NH 4 ) 2 CO 3 residual forces acting along the surface of adsorbent
decrease.
MECHANISM OF ENZYME ACTION : Heat evolved on adsorption of 1 mole of a gas is molar heat
Enzyme can increase the rate of biochemical reactions by 106 to of adsorption.
1012 times. They are highly selective and specific and act on
(iv) Adsorption is accompanied by decrease in enthalpy. i.e. D H
certain molecules called substrates and leave the rest of the system
= -ve
unaffected (LOCK AND KEY THEORY). Michaelis and Menten
proposed the following mechanism for enzyme catalysis (v) Adsorption is accompanied by decrease in entropy i.e. TDG
is negative.
E + S ES ¾
¾® P + E
Enzyme Substrate Activated Complex Product Enzyme Also, DG = DH - TDS. As D H is negative and so is DS,
Þ DG is negative. But experimentally DH becomes less
CHARACTERISITCS OF ENZYME CATALYSIS :
negative as the adsorption progresses and ultimately
1. Enzymes are most efficient catalysts.
becomes zero as the equilibrium is reached.
2. Enzymes are very selective and specific.
Adsorption of gases at the surface of metals like Ni, Pt, Pd
3. Enzymes require optimum condition of temperature and pH etc is called Occlusion.
of the medium.
4. Enzymes are easily poisoned by addition of other substances PHYSICAL ADSORPTION :
particularly heavy metal ions (Hg2+ or Ag+) It is also called van der Waal’s adsorption which involves weak
5. Activity of enzymes is increased by activators (certain metal forces, physical in nature, with small heat of adsorption. For
ions Co2+, Mn2+, Na+, Cu++ etc) or coenzymes. example adsorption of H2 or O2 on charcoal.
Surface Chemistry 637
CHEMICAL ADSORPTION :
x
Forces of attraction between adsorbate and adsorbent being of The relation = k ( P )T solid, gas is called adsorption
m
the same strength as chemical bonds, given the name
isotherm. Such isotherms are obtained when adsorbate forms
chemisorption. It may involve covalent or ionic bonds. e.g. H2 is
a unimolecular layer on surface of adsorbent.
chemisorbed on Ni. Hydrogen is first adsorbed by van der waal’s
forces and then dissociates. Hence hydrogen atoms are
chemisorbed on Ni.
x/m
Ps
Often adsorption involves combination of two types of P
adsorption
At low pressure, x/m µ p 1 or x/m = kp 1 where
POINTS OF DISTINCTION BETWEEN PHYSICAL
k = constant
AND CHEMICAL ADSORPTION :
At high pressure, beyond saturation x/m is independent of p
Physical Chemical and x/m µ pº.
(i) Forces van der waals Chemical bonds At intermediate pressures, x/m µ p1/n where n > 1
(ii) Temperature at low temperature at high temperature
x 1
(iii) Layer multimolecular monomolecular or log = log k + log p where k = constant.
m n
(iv) Pressure increases with decrease with P. Infact
p 1 æ Bö C1
= + ç ÷p where A and B are constant A
w A èAø
B X C2
p/w q
B 1 Concentiation of X in A C1
slope = , intercept = = a constant or = KD
A A Concentiation of X in B C2
p
COMPETING ADSORPTION : (Where KD = distribution coefficient or partition coefficient or
Different adsorbates compete among themselves to adsorb on distribution ratio)
the adsorbent. Strongly adsorbable substance can displace a Distribution of Succinic acid between ether and water illustrates
weakly adsorbable substance. For e.g. Cl2 and NH3 can replace the consistancy of the ratio of concentrations in each layer
O2 and N2 already adsorbed on charcoal. Moisture is also strongly C1 in ether C2 in water C1 /C2
adsorbed by silica though it is present in small proportion in air
and charcoal adsorbs polluting gases present in air in small 0.013 0.069 0.188
amounts. 0.022 0.119 0.184
Surface Chemistry 639
Since the solubility also represents concentration, the HENRY’S LAW :
distribution law can also be written as It states that at a constant temperature the solubility of a gas in
a liquid is directly proportional to the pressure of the gas above
C1 S1
= = KD it
C 2 S2
C a P or C = KHP
Where S1 and S2 are the solubilities of the solute in two solvents. Where C is the solubility or concentration of the gas, KH is a
LIMITATIONS OF DISTRIBUTION LAW : constant known as Henry’s constant and p is the pressure of
The law holds good when the following conditions are fulfilled. the gas.
(i) Molecular State : The molecular state of the solute must • The law holds good for dilute solutions of gases which do
remain the same in both the solvents i.e. there should be no not react with the solvent.
association or dissociation of solute molecules. • When mixture of gases is there, the solubility of each gas is
(ii) Constant temperature : The temperature is kept contant proportional to its partial pressure.
(iii) Non-miscibility of solvents : The two solvents must be APPLICATIONS OF DISTRIBUTION LAW :
immiscible and the non miscibility must not change on (i) Solvent extraction : The separation of organic substances
addition of solute. from aqueous solutions by the use of organic solvent
(iv) Dilute solutions : The law is applicable to dilute solutions generally ether is based on partition law. The aqueous
only solution of organic substance is shaken with ether. The
(v) Equilibrium concentrations : The C1 and C 2 are the organic substance distributes itself in both the liquids
equilibrium concentrations which are separated by separating funnel. The solvent layer
on evaporation leaves behind organic substance.
MODIFICATIONS :
For more recovery of the substance, the number of
The following modifications are applied under different
operations should be more. The amount of organic
conditions
substance left in aqueous solution is given by
(i) When solute associates : Apply the following formula
n
æ KV ö
No change
xn = A ç ÷
è KV + v ø
C1 X Solvent A
= k ( constant ) n = Number of operations
n C2 nX Xn Solvent B
Association K = Distribution constant
V= Volume of aqueous solution
Where n is the number of molecules undergoing association
v = Volume of organic solvent
(ii) When solute dissociates : Apply the following formula
A = Amount of solute
1. If the solubility of iodine in water is 0.8 g/l at 25º C, calculate 3. The solubility of pure oxygen in water at 20º C and 1.00 atm
the solubility of I2 in CCl4. The kD of iodine in between CCl4
pressure is 1.38 ´ 10 -3 mole/litre. Calculate the concentration
and water is 85 in favour of CCl4 at 25º C.
of O2 (mole/litre) at 20º C and partial pressure of 0.21 atm.
[I 2 ]in CCl 4 layer Sol. Calculation of Henry’s constant
Sol. k D = = Let the solubility of I2 in CCl4 be
[I 2 ]in water layer
Conc. of O 2 1.38 ´10 -3
a g/litre kH or k = mole / litre
pressure of O 2 1.00 atm
a
85 = mole / litre
0.8 = 1.38 ´ 10 - 3
atm
a = 68 g litre–1 Calculation of concentration of O2
2. Succinic acid has normal molecular weight in water. Succinic
mole / litre
acid was allowed to distribute in water and benzene by C = kP = 1.38 ´ 10 - 3 ´ 0.21 atm
atm
shaking. The concentiation of acid in water and benzene
are C1 and C2 having values. = 2.9 × 10–4 mole/litre
(i) (ii) (iii) 4. The distribution coefficient of an alkaloid between
C1 g/100 ml 0.150 0.195 0.289 chloroform and water is 20 in favour of chloroform. Compare
the weights of the alkaloid remaining in aqueous solution
C2 g/100 ml 2.420 4.120 9.600
when 100 ml containing 1 gram has been shaken with (a)
Find the molecular weight of acid in benzene 100 ml chloroform and (b) two successive 50 ml portion.
Sol. Calculating the value of kD by applying the relation C1/C2
C water 1
and C1/ÖC2 Sol. K = =
C chloroform 20
C1 0.152 C1 0.150
In (i) = = 0.062 ; = = 0.096 (a) When 100 ml is used in one lot, the amount unextracted is
C 2 2.420 C2 2.420
æ KV ö
X1 = 1 ´ ç ÷
C1 0.195 C1 0.195 è KV + v ø
In (ii) = = 0.047 ; = = 0.096
C 2 4.120 C2 4.120
æ 1 / 20 ´ 100 ö 5
= 1´ ç ÷= = 0.0476 g
è 1 / 20 ´ 100 + 100 ø 105
C1 0.289 C1 0.289
In (iii) = = 0.030 ; = = 0.093 (b) When 50 ml chloroform is used in each of two stages the
C 2 9.600 C2 9.600 amount unextracted is
Since constant value of K D is obtained by relation 2 2
C1/ÖC2 hence succinic acid forms a dimer in benzene æ 1 / 20 ´ 100 ö æ 5 ö
X 2 = 1´ ç ÷ = ç ÷ = 0.0083 g
è 1 / 20 ´ 100 + 50 ø è 55 ø
Therefore its molecular weight in benzene = 2 × 118 = 236
Surface Chemistry 641
Very Short Answer Questions 19. Which one of the following in not a colloidal solution?
(a) Smoke (b) Ink
1. Which of the following is adsorbed most preferably:
(c) Blood (d) Air
O2, NH3, CO?
2. Can crystalloid be brought into colloidal state? Give one 20. Which of the following statements is not true about the oil-
example. in-water type emulsion?
3. Why are colloids good adsorbents? (a) On addition of small amount of water, no separate layer
4. Write the names of two gases which are adsorbed by of water appears
transition metals such as nickel and cobalt. (b) On addition of oil, separate layer of oil is formed
5. Can a gas mixed with another gas form a colloidal solution? (c) Addition of an electrolyte causes the conductivity of
Give reasons. the emulsion to increase
6. Account for the following: (d) Addition of small amount of oil soluble dye renders the
(a) Ferric hydroxide sol is positively charged. entire emulsion coloured.
(b) The extent of physical adsorption decreases with rise
21. Suspensions are
in temperature.
(a) Visible to naked eye
(c) A delta is formed at the point where river enters the sea.
(b) Not visible by any means
7. Detergents with straight chain hydrocarbons are preferred
(c) Invisible under electron microscope
to branched chain hydrocarbons. Explain.
(d) Invisible through microscope
8. Smoke is passed through charged plates before allowing it
to pass through chimneys in industries. 22. Which of the following terms is not related with colloids ?
9. Comment on sign of DH, DS and DG for adsorption process. (a) Brownian movement
10. What is demulsification? Name two demulsifiers. (b) Dialysis
11. Out of NH3 and CO2, which gas will be absorbed more readily (c) Ultrafiltration
on the surface of activated charcoal and why? (d) Wavelength
12. What is meant by chemisorption? 23. A colloid always :
13. Explain the following terms : (a) Contains two phases
(i) Electrophoresis (b) Is a true solution
(ii) Dialysis (c) Contains three phases
(iii) Tyndall effect. (d) Contains only water soluble particles
14. What is meant by coagulation of colloidal solution? 24. When a colloidal solution is observed under an
Describe briefly and three methods by which coagulation of ultramicroscope, we can see
lyophobic sols can be carried out. (a) Light scattered by colloidal particles
15. Explain the following terms giving a suitable example for each: (b) Size of the particle
(i) Aerosol (c) Shape of the particle
(ii) Emulsion (d) Relative size
(iii) Micelle 25. One desires to prepare a positively charged sol of silver
16. Write the dispersed phase and dispersion medium of the iodide. This can be achieved by
following colloidal systems: (a) adding small amount of AgNO3 solution to KI solution
(i) Smoke in slight excess
(ii) Milk (b) adding small amount of KI solution to AgNO3 solution
17. What are lyophilic and lyophobic colloids? Which of these in slight excess
sols can be easily coagulated on the addition of small (c) mixing equal volumes of equimolar solutions of AgNO3
amounts of electrolytes? and KI
Multiple Choice Questions (d) None of these
26. Cod Liver oil is
18. Which one of the following statements is incorrect in the (a) fat dispersed in water (b) water dispersed in fat
case of heterogeneous catalysis ?
(c) water dispersed in oil (d) fat dispersed in fat.
(a) The catalyst lowers the energy of activation
27. Colloid of which one of the following can be prepared by
(b) The catalyst actually forms a compound with the
electrical dispersion method as well as reduction method ?
reactant
(a) Sulphur (b) Ferric hydroxide
(c) The surface of the catalyst plays a very important role
(c) Arsenious sulphide (d) Gold
(d) There is no change in the energy of activation.
642 Chemistry
1. The size of colloidal particles is between 13. When H 2 S gas is passed thr ough nitric acid, the
(a) 10-7 - 10-9 cm (b) 10-9 - 10-11 cm product is
-5
(c) 10 - 10 cm-7 (d) 10-2 - 10-3 cm (a) Rhombic S (b) Prismatic S
2. The size of colloidal particles is of the order (c) Amorphous S (d) Monoclinic S
(a) > 0.1 m (b) 1mm to 0.2m 14. Colloid of which one of the following can be prepared by
(c) < 1 mm (d) > 10 mm electrical dispersion method as well as reduction method ?
3. Butter is a colloid formed when (a) Sulphur (b) Ferric hydroxide
(a) fat is dispersed in water (c) Arsenious sulphide (d) Gold
(b) fat globules are dispersed in water 15. The formation of colloid from suspension is
(c) water is dispersed in fat (a) Peptisation (b) Condensation
(d) None of the these (c) Sedimentation (d) Fragmentation
4. Milk is a colloid in which 16. Which one of the following substances is not used for
(a) A liquid is dispersed in liquid preparing lyophillic sols ?
(b) A solid is dispersed in liquid (a) Starch (b) Gum
(c) A gas is dispersed in liquid (c) Gelatin (d) Metal sulphide
(d) some sugar is dispersed in water 17. Blood may be purified by
5. Cod Liver oil is (a) Dialysis (b) Electro osmosis
(a) Fat dispersed in water (b) Water dispersed in fat (c) Coagulation (d) Filtration
(c) Water dispersed in oil (d) Fat dispersed in fat. 18. The cause of Brownian movement is
6. Cloud or fog is a colloidal system in which the dispersed (a) Heat changes in liquid state
phase and the dispersion medium are
(b) Convectional currents
(a) Gas, Liquid (b) Liquid, gas
(c) The impact of molecules of the dispersion medium on
(c) Liquid, liquid (d) Solid, Liquid
the colloidal particles.
7. Which one among the following sols is hydrophobic ?
(d) Attractive forces between the colloidal particles and
(a) Gum (b) Gelatin
molecules of dispersion medium.
(c) Starch (d) Sulphur
19. Brownian movement is found in
8. Which of the following constitutes irreversible colloidal
(a) Colloidal solution (b) Suspension
system in water as dispersion medium?
(c) Saturated solution (d) Unsaturated solution
(a) Clay (b) Platinum
20. Random motion of colloidal particles is known as
(c) Fe(OH)3 (d) All of these
9. Which of the following is a lyophillic colloid ? (a) Dialysis (b) Brownian movement
(a) Milk (b) Gum (c) Electroosmosis (d) Tyndall effect
(c) Fog (d) Blood 21. Milk can be preserved by adding a few drops of
10. Surface tension of lyophillic sols is (a) Formic acid solution (b) Formaldehyde solution
(a) lower than that of H2O (c) Acetic acid solution (d) Acetaldehyde solution.
(b) more than that of H2O 22. In which of the following Tyndall effect is not
(c) equal to that of H2O observed ?
(d) can either lower or more than H2O. (a) Suspensions (b) Emulsions
11. Peptization denotes (c) Sugar solution (d) Gold sol
(a) Digestion of food 23. Point out the false statement
(b) Hydrolysis of proteins (a) Brownian movement and Tyndall effect are shown by
(c) Breaking and dispersion into the colloidal state colloidal systems.
(d) Precipitation of solid from colloidal dispersion (b) Gold number is a measure of the protective power of a
12. Colloidal gold is prepared by lyophillic colloid
(a) Mechanical dispersion (b) Peptisation (c) The colloidal solution of a liquid in liquid is called gel
(c) Bredig’s Arc method (d) Hydrolysis (d) Hardy - Schulze rule is related with coagulation.
Surface Chemistry 643
24. Tyndall effect is shown by 37. The Rubin number which was proposed by Ostwald as an
(a) Sol (b) Solution alternative to the Gold number in order to measure the
(c) Plasma (d) Precipitate protective efficiency of a lyophillic colloid may be defined as
25. Gold number is associated with the
(a) Electrophoresis (b) Purple of caslus (a) Mass in milligrams of a colloid per 100 c.c. of solution
(c) Protective colloids (d) Amount of pure gold which just prevents the colour change of standard sol
of dye Congo - Rubin from red to violet when 0.16 g eq.
26. In Brownian movement or motion, the paths of the particles
KCl is added to it.
are
(b) Mass in grams of a colloid per 100 c.c. of solution which
(a) Linear (b) Zig-zag
just prevents the colour change of standard sol of dye
(c) Uncertain (d) Curved
Congo - Rubin from red to violet when 0.1 M KCl is
27. The migration of colloidal solute particles in a colloidal added to it
solution, when an electric current is applied to the solution is
(c) Mass in grams of a colloid per 100 c.c. of solution which
known as
just prevents the colour change of standard sol of dye
(a) Brownian movement (b) Electroosmosis Congo - Rubin from red to violet when 0.2 M KCl is
(c) Electrophoresis (d) Electrodialysis added to it.
28. When a strong beam of light is passed through a colloidal (d) Mass in grams of a colloid per 100 c.c. of solution which
solution, the light will just prevents the colour - change of standard sol of dye
(a) be reflected (b) be scattered Congo - Rubin from red to violet when 1 M KCl is added
(c) be refracted (d) give a rainbow to it
29. The simplest way to check whether a system is colloidal is by 38. The function of gum arabic in the preparation of an Indian
(a) Tyndall effect (b) Brownian movement ink is
(c) Electrodialysis (d) Finding out particle size (a) Coagulation (b) Peptization
30. A colloidal solution is subjected to an electrical field. The (c) Absorption (d) Protective action
particles move towards anode. The coagulation of same sol 39. At CMC the surfactant molecules
is studied using NaCl, BaCl2 and AlCl3 solutions. Their (a) Decompose
coagulating power should be (b) Become completely soluble
(a) NaCl > BaCl2 > AlCl3 (b) BaCl2 > AlCl3 > NaCl (c) Associate
(c) AlCl3 > BaCl3 > NaCl (d) BaCl2 > NaCl > AlCl3 (d) Dissociate
31. In coagulating the colloidal solution of As2S3 which has the 40. Which one of the following is correctly matched?
minimum coagulating value ? (a) Emulsion - curd (b) Foam - mist
(a) NaCl (b) KCl (c) Aerosol - smoke (d) Solid sol - cake
(c) BaCl2 (d) AlCl3 41. Alum helps in purifying water by
32. Which of the following ions can cause coagulation of (a) forming Si complex with clay particles
proteins ?
(b) sulphate part which combines with the dirt and removes
(a) Ag + (b) Na+ it
(c) Mg2+ (d) Ca2+ (c) aluminium which coagulates the mud particiles
33. Which is used for ending charge on colloidal solution (d) making mud water soluble
(a) Electrons (b) Electrolytes 42. The process which is catalysed by one of the products is
(c) Positively charged ions (d) Compounds called
34. Which of the following is most effective in causing the (a) Acid - base catalysis (b) Auto catalysis
coagulation of ferric hydroxide sol?
(c) Negative catalysis (d) Positive catalysis
(a) KCl (b) KNO3
43. Which one of the following is an example of homogeneous
(c) K2SO4 (d) K3[Fe(CN)6]
catalysis ?
35. Arsenic sulphide is a negative sol. The reagent with least
(a) Haber’s process of synthesis of ammonia
precipitating power is
(a) AlCl3 (b) NaCl (b) Catalytic conversion of SO2 to SO3 in contact process
(c) CaF2 (d) Glucose (c) Catalytic hydrogenation of oils
36. The stablity of lyophillic colloids is due to which of the (d) Acid hydrolysis of methyl acetate
following? 44. In the case of auto catalysis
(a) Charge on their particles (a) reactant catalysis
(b) Large size of their particles (b) heat produced in the reaction catalysis
(c) Small size of their particles (c) product catalysis
(d) A layer of dispersion medium (d) solvent catalysis
644 Chemistry
45. Which of the following statements about a catalyst is/are 57. Which one of the following is an incorrect statement for
true ? physisorption ?
(a) A catalyst accelerates the reaction by bringing down the (a) It is reversible process
free energy of activation (b) It requires less heat of absorption
(b) A catalyst also takes part in the reaction mechanism (c) it requires activation energy
(c) A catalyst makes the reaction more feasible by making (d) It takes place at low temperature
the DGº more negative 58. Which is adsorbed in maximum amount by activated charcoal
(d) A catalyst makes the equilibrium constant of the reaction ?
more favourable for the forward reaction. (a) N2 (b) CO2
46. The role of a catalyst in a reversible reaction is to (c) Cl2 (d) O2
(a) Increase the rate of forward reaction 59. Which among the following statements is false?
(b) Decrease the rate of backward reaction (a) Increase of pressure increases the amount of adsorption
(c) alter the equilibrium constant of the reaction (b) Increase of temperature may decrease the amount of
(d) Allow the equilibrium to be achieved quickly adsorption.
47. Which of the following kind of catalysis can be explained by (c) The adsorption may be monolayered or multilayered
the adsorption theory ? (d) Particle size of the adsorbent will not affect the amount
(a) Homogeneous catalysis of adsorption.
(b) Acid - base catalysis 60. Rate of physisorption increases with
(c) Heterogeneous catalysis (a) decrease in temperature (b) increase in temperature
(d) Enzyme catalysis (c) decrease in pressure (d) decrease in surface area
48. A biological catalyst is essentially 61. Distribution law was given by
(a) An enzyme (b) A carbohydrate (a) Van’t Hoff (b) Henry
(c) An amino acid (d) A nitrogenous base (c) Nernst (d) Ostwald
49. In Zeigler - Natta polymerisation of ethylene, the active species 62. When is the Distribution Law applicable?
is (a) Temperature remains constant
(a) AlCl3 (b) Et3Al (b) Dilute solutions are employed
(c) Two solvents are mutually insoluble
(c) CH2CH2 (d) Ti3+
(d) All of these
50. Adsorbed acetic acid on activated charcoal is:
63. The relation between pressure and solubility of a gas was
(a) Adsorber (b) Absorber given by
(c) Adsorbent (d) Adsorbate (a) Henry (b) Nernst
51. Which of the following is less than zero during adsorption. (c) Both (a) and (b) (d) Neither (a) nor (b)
(a) D G (b) D S 64. The solubility of iodine in water is 0.35 g/ litre at 25°C. If
(c) D H (d) All of these distribution coefficient of iodine between CS2 and water is
52. The heats of adsorption in physisorption lie in the range (in 600, the solubility of iodine in CS2 in g/ litre will be
kJ/mol) (a) 210 (b) 510
(a) 40 - 400 (b) 40 - 100 (c) 195 (d) 250
(c) 10 - 40 (d) 1 - 10 S1
65. Partition coefficient, K = is valid
53. In physical adsorption, gas molecules are bound on the solid S2
surface by (a) when dissociation takes place
(a) Chemical forces (b) Electrostatic forces (b) when association takes place
(c) Gravitational forces (d) van der waal’s forces (c) when there is a complex formation
54. How many layers are adsorbed in chemical adsorption ? (d) in case of normal distribution
(a) One (b) Two 66. When a solute is shaken with two immiscible liquid, it
(c) Many (d) Zero associates in one of the liquids. The distribution constant is
55. In physical adsorption, the forces associated are given by
(a) ionic (b) covalent C1 C1
(a) (b)
(c) van der Waal (d) H - bonding C2 C 2 (1 - a )
56. Adsorption due to strong chemical forces is called
S1 C1
(a) Chemisorption (b) Physiosorption (c) (d)
S2 n C2
(c) Reversible adsorption (d) Both (b) and (c)
Surface Chemistry 645
67. The condition under which Nernst distribution law will not 72. You are given 100 ml of CCl4 to extract iodine from 200 ml of
hold true is its aqueous solution. For extracting the maximum amount of
(a) The molecular state of the solute is same in both iodine, which one of the following process would you use
solvents (a) Use 100 ml of CCl4
(b) Temperature is constant (b) Use 50 ml of CCl4 twice
(c) The solute does not cause any change in the mutual (c) Use 10 ml of CCl4 ten times
solubility of the two solvents
(d) Use 25 ml of CCl4 4 times
(d) None of these
68. When benzoic acid is shaken with a mixture of 100 ml water 73. Distribution law cannot be applied to I2 distributed between
and 50 ml ether, the ether layer was found to contain 0.127 g (a) H2O and C2H5OH (b) H2O and CCl4
of acid and water layer 1.843 g of the acid. The partition (c) H2O and CS2 (d) H2O and C2H5OC2H5
coefficient between water and ether is 74. Which of the following applications is not shown by
(a) 72.5 (b) 7.25 distribution law?
(c) 725 (d) 0.725 (a) Pallison’s process
69. If in a pair of immiscible liquids, a common solute dissolves (b) Partition Chromatography
in both and equilibrium is reached, then the concentration (c) Solvent extraction
of the solute in the upper layer is (d) Parke’s process
(a) same as in lower 75. Which one of the following statements is false for
(b) in fixed ratio with that in the lower layer distribution law?
(c) lower than in the lower layer (a) The two solvents must be mutually immiscible
(d) higher than in the lower layer (b) The concentration of the solute in both the solvents
70. The partition coefficient of a solute for ether and water is in must be kept high
the ratio 5:1. The amount of solute extracted from 100 cc of (c) The substrate must not react with any of the solvents
its aqueous solution with 100 cc of ether in one time will be (d) The temperature should not change during
(a) 90% (b) 87.3% experimentation
(c) 91.8% (d) 83.3% 76. When solution of 5g of iodine in CS2 was shaken with the
71. The partition coefficient of X between liquids A and B is 10. same volume of water. The amount of iodine in water is
The partition coefficient of X between B and A is (Distribution coefficient C CS2 / C H 2O = 420.0)
(a) 100 (b) 1 (a) 1.19 (b) 0.0019
(c) 0.1 (d) 10 (c) 0.0119 (d) 0.119
1. The Langmuir adsorption isotherm is deduced by using the 3. In Freundlich Adsorption isotherm, the value of 1/n is :
assumption [CBSE-PMT 2007] (a) between 0 and 1 in all cases [CBSE-PMT 2012S]
(b) between 2 and 4 in all cases
(a) the adsorption sites are equivalent in their ability to adsorb
(c) 1 in case of physical adsorption
the particles
(d) 1 in case of chemisorption
(b) the heat of adsorption varies with coverage 4. Which one of the following, statements is incorrect about
(c) the adsorbed molecules interact with each other enzyme catalysis? [CBSE-PMT 2012S]
(d) the adsorption takes place in multilayers. (a) Enzymes are mostly proteinous in nature.
(b) Enzyme action is specific.
2. If x is amount of adsorbate and m is amount of adsorbent,
(c) Enzymes are denaturated by ultraviolet rays and at high
which of the following relations is not related to adsorption
temperature.
process ? [CBSE-PMT 2011] (d) Enzymes are least reactive at optimum temperature.
(a) x / m = f (p) at constant T. 5. The protecting power of lyophilic colloidal sol is expressed in
(b) x / m = f (T) at constant p. terms of : [CBSE-PMT 2012S]
(c) p = f (T) at constant (x / m). (a) coagulation value
(b) gold number
x (c) critical miscelle concentration
(d) p T
m (d) oxidation number
646 Chemistry
6. Which of the following is not the property of hydrophilic 10. Gold numbers of protective colloids A, B, C and D are 0.50,
solutions ? 0.01, 0.10 and 0.005, respectively. The correct order of their
(a) High concentration of dispersed phase can be easily protective powers is [AIEEE 2008]
obtained (a) D < A < C < B (b) C < B < D < A
(b) Coagulation is reversible (c) A < C < B < D (d) B < D < A < C
11. Which of the following statements is incorrect regarding
(c) Viscosity and surface tension are nearly the same as
physisorptions? [AIEEE 2009]
that of water.
(a) More easily liquefiable gases are adsorbed readily.
(d) The charge of the particle depends on the pH of the
(b) Under high pressure it results into multimolecular layer
medium and it may be positive, negative or zero. on adsorbent surface.
7. Which one of the following characteristics is not correct for (c) Enthalpy of adsorption ( DH adsorption) is low and positive.
physical adsorption ? [AIEEE 2003] (d) It occurs because of van der Waal’s forces.
(a) Adsorption increases with increase in temperature 12. According to Freundlich adsorption isotherm which of the
(b) Adsorption is spontaneous following is correct? [AIEEE 2012]
(c) Both enthalpy and entropy of adsorption are negative x
(d) Adsorption on solids is reversible (a) µ p°
m
8. The disperse phase in colloidal iron (III) hydroxide and
x
colloidal gold is positively and negatively charged, (b) µ p1
respectively. Which of the following statements is NOT m
correct ? [AIEEE 2005] x
(a) Coagulation in both sols can be brought about by (c) µ p1/n
m
electrophoresis
(d) All the above are correct for different ranges of pressure
(b) Mixing the sols has no effect 13. The coagulating power of electrolytes having ions Na+, Al3+
(c) Sodium sulphate solution causes coagulation in both and Ba2+ for arsenic sulphide sol increases in the order :
sols [JEE M 2013]
(d) Magnesium chloride solution coagulates, the gold sol (a) Al3+ < Ba2+ < Na+ (b) Na+ < Ba2+ < Al3+
more readily than the iron (III) hydroxide sol (c) Ba2+ < Na+ < Al3+ (d) Al3+ < Na+ < Ba2+
9. In Langmuir's model of adsorption of a gas on a solid surface 14. Among the following, the surfactant that will form micelles in
[AIEEE 2006] aqueous solution at the lowest molar concentration at ambient
(a) the mass of gas striking a given area of surface is condition is : - [IIT-JEE 2009S]
proportional to the pressure of the gas (a) CH3(CH2)15N+(CH3)3Br– (b) CH3(CH2)11OSO–3 Na+
(c) CH3(CH2)6COO–Na+ (d) CH3(CH2)11N+(CH3)3Br–
(b) the mass of gas striking a given area of surface is
15. Among the electrolytes Na 2 SO4, CaCl 2, Al 2 (SO4 )3 and
independent of the pressure of the gas
NH4Cl, the most effective coagulating agent for Sb2S3 sol is
(c) the rate of dissociation of adsorbed molecules from [IIT-JEE 2009S]
the surface does not depend on the surface covered (a) Na2SO4 (b) CaCl2
(d) the adsorption at a single site on the surface may (c) Al2(SO4)3 (d) NH4Cl
involve multiple molecules at the same time
1. For the adsorption of a gas on a solid, the plot of 3. Adsorption is accompanied by the evolution of heat. So
log(x/m) versus log p is linear with slope equal to according to Le-Chatelier principle the amount of substance
(a) k (b) log k adsorbed should
(c) n (d) 1/n (a) increase with decrease in temperature
(where, p= pressure of gas, m = mass of the adsorbent, (b) increase with increase in temperature
x = mass of the gas adsorbed) (c) decrease with decrease in temperature
2. Which of the following gas molecules have maximum value (d) decrease with increase in temperature
of enthalpy of physisorption? 4. At low pressure, the fraction of the surface covered follows
(a) C2H6 (b) Ne (a) zero-order reaction (b) second-order reaction
(c) H2O (d) H2 (c) first-order reaction (d) fractional order
Surface Chemistry 647
5. At high pressure, the entire surface gets covered by a 9. The critical micelle concentration (CMC) is
monomolecular layer of the gas follows
(a) the concentration at which micellization starts
(a) three-halved order (b) second-order
(b) the concentration at which the true solution is formed
(c) first-order (d) zero-order
6. Which of the following statements is incorrect ? (c) the concentration at which one molar electrolyte is
(a) Adsorption always leads to a decrease in enthaply and present per 1000 g of the solution
entropy of the system (d) the concentration at which DH=0
(b) Adsorption arises due to unsaturation of valence forces 10. The isoelectric-point of a colloidally dispersed material is
of atoms or molecules on the surface
the pH value at which
(c) Adsorption increases with rise in the temperature
(d) Adsorption decreases the surface energy (a) the dispersed phase migrate in an electric field
7. During adsorption (b) the dispersed phase does not migrate in an electric field
(a) TDS is positive (b) DH–TDS is negative (c) the dispersed phase has pH equal to 7
(c) DH is positive (d) TDS and DG become zero (d) the dispersed phase has pH equal to zero
8. Which of the following statements is not correct?
11. Peptization involves
(a) Decrease of temperature and increase of pressure, both
tend to cause increase in the magnitude of adsorption of (a) precipitation of colloidal particles
a gas on a solid. (b) disintegration of colloidal aggregates
(b) The easily liquefiable gases adsorb more on solid (c) evaporation of dispersion medium
(c) Greater the surface area per unit mass of the adsorbent,
(d) impact of molecules of the dispersion medium on the
the greater is its capacity of adsorption
colloidal particles
(d) None of these
648 Chemistry
17. (a) Blood is purified by dialysis. 41. (c) Alum. coagulates mud particles and helps in purifying
water.
18. (c) It is due to impact of molecules of dispersion medium on
the colloidal particles. 42. (b) In auto catalysis one of the products act as catalyst
43. (d) In acid hydrolysis of methyl acetate all are present in one
19. (a) Brownian movement is exhibited by colloidal system.
phase (liquid)
Surface Chemistry 649
44. (c) 45. (a) 46. (d)
a
47. (c) Adsorption theory is applied to heterogeneous catalysis 70. (d) Let the amount extracted be a then, k D = = 5,
100 - a
48. (a) Enzymes are biological catalysts.
\ a = 83.3%
49. (d) Ti3+ Ziegler Natta catalyst is a mixture of
(C2H5)3 Al + TiCl3. C ether
71. (c) Partition coefficient k D = , k D is in favour of
50. (d) The substance which is adsorbed is called adsorbate C w ater
51. (a) Adsorption is spontaneous process. Hence DG must be ether. The value is reversed if we change it in favour of
negative water.
52. (c) For physiosorption the D H value is 10 - 40 kJ/mol. 72. (c) The greater the number of operations, the more is the
53. (d) In physisorption, gas molecule is held on the solid surface recovery of the substances to be extracted.
by weak van der Waal’s forces. 73. (a) H2O and C2H5OH are miscible liquids, the law is applicable
54. (a) Chemical adsorption is monolayer to immiscible liquids.
55. (c) In physical adsorption the forces between adsorbate and 74. (a) Pallison process is not based on distribution law.
adsorbent are weak van der waal’s forces. 75. (b) The concentration of the solute in both the solvents must
56. (a) Chemisorption involves strong chemical forces. be kept low and not high.
57. (c) Physical adsorption does not require any activation 76. (c) Let the amount of iodine in water be a gm., C1 = 5g in x ml
energy. of CS2, C2 = 5 – a g in x ml of H2O. Then
58. (b) The gases having higher values for critical temperature 5-a
= 420, \= 0.0118
are easily liquified and are adsorbed to the greater extent. a
59. (d) Statement (d) is wrong (see text) EXERCISE 3
1 1. (a) Langmuir adsorption isotherm is based on the
60. (a) Physical adsorption µ . assumption that every adsorption site is equivalent
Temperature
and the ability of a particle to bind there is independent
61. (c) The distribution law was given by Nernst. of whether nearby sites are occupied or not.
62. (d) All the conditons are correct. 2. (d)
63. (a) Henry gave the relation between pressure and solubility 3. (a) According to Freundlich Adsorption isotherm
of a gas as, solubility a pressure. 1
x
64. (a) Let the solubility of iodine in CS2 be a then = KP n
m
S1 a 1
= KD , = 600 , \ a = 210 at low pressure =1
S2 0.35 n
x
S \ µ P1
65. (d) K D = 1 is valid only when their is no association or m
S2
dissociation of solute dissolved and no change of 1
at high pressure =0
temperature. There is no complex formation. n
x
C1 µ P°
66. (d) In case when solute associate, k D = m
n C2 i.e., the value of n varies between 0 to 1
67. (d) All the statements are correct. 4. (d) Enzymes are most reactive at optimum temperature. The
optimum temperature for enzyme activity lies between
C1 1.843 0.127 1.843 / 100
68. (b) k D = , C1 = and C 2 = ,\ k D = = 7.25 40°C to 60°C.
C2 100 50 0.127 / 50
5. (b) The lyophobic sols are less stable than lyophilic sols.
1.843 0.127 The lyophilic sols are thus used to protect the
1= and C 2 = ,
100 50 lyophobic sols. This property of lyophilic sols is known
as protective action of lyophilic sols which is
1.843 /100
\ kD = = 7.25 represented by gold number.
0.127 / 50
6. (c) See properties of hydrophilic sols.
C
69. (b) At equilibrium stage 1 = k D ; where C1 & C2 are the 7. (a) As adsorption is an exothermic process.
C2
concentrations of the solute in the upper and lower layer. \ Rise in temperature will decrease adsorption.
650 Chemistry
8. (b) When oppositely charged sols are mixed their charges 14. (b)
are neutralised. Both sols may be partially or completely 15. (c) As Sb2S3 is a negative sol, so Al2(SO4)3 will be the
precipitated.
most effective coagulant due to higher positive charge
9. (a) According to Langmuir's model of adsorption of a gas
on a soild surface the mass of gas adsorbed(x)per gram on Al (Al3+) – Hardy-Schulze rule.
of the adsorbent (m) is directly proportional to the EXERCISE 4
pressure of the gas (p) at constant temperature i.e.
x x 1
µp 1. (d) Freundlich equation is log = log K + P where
m m n
10. (c) For a protective colloid lesser the value of gold number 1
= slope .
more will be the protective power. Thus the correct n
order of protective power of A, B, C and D is 2. (c) The more the liquefiable nature of a gas, the more is the
Þ (A) < (C) < (B) < (D) enthalpy of adsorption. Water is more liquefiable.
Gold number 0.50 0.10 0.01 0.005 3. (a) The extent of adsorption increases with decrease in
temperature.
Hence (c) is the correct answer
4. (c) At low pressure the extent of adsorption is directly
11. (c) Adsorption is an exothermic process, hence DH will
proportional to pressure which follows first order kinetics.
always be negative.
5. (d) At high pressure the extent of adsorption follows zero
12. (d) The Freundlich adsorption isotherm is mathematically order kinetics.
represented as 6. (c) Adsorption increases with decrease in temperature.
x 7. (b) DG = DH – TDS. Adsorption is spontaneous process DG
= kP1/n
m should be negative. Hence DH – TDS should be negative.
At high pressure 1/n = 0. Hence, x / m µ P° 8. (d) All statements are correct
At low pressure 1/n = 1 Hence, x/m µ P1 9. (a) CMC is the concentration at which micellization starts
13. (b) According to Hardy Schulze rule, greater the charge i.e. surfactant molecules aggregate.
on cation, greater is its coagulating power for negatively 10. (b) At isoelectric point there is no migration of dispersed
charged sol (As2 S3 ), hence the correct order of phase in an electric field.
coagulating power : Na+ < Ba2+ < Al3+ 11. (b) Peptisation is disintegration of colloidal aggregate.
20
General Principles
& Processes of
Isolation of Elements
METALLURGY : CONCENTRATION OR DRESSING :
The science and technology of isolation of pure metals from their The process of the removal of gangue or matrix from the ore is
ores and preparing them for practical use. The process includes. known as concentration. It is achieved by
(i) Mining - getting the ore out of ground. (i) Hand picking
(ii) Concentration - preparing for further treatment. (ii) Gravity separation (hydraulic -washing )
(iii) Reduction - to obtain the metals in zero oxidation state. (iii) Magnetic separation
(iv) Refining - to obtain the pure metal. (iv) Electrostatic separation
(v) Mixing with other metals - to form an alloy. (v) Froth flotation process -for sulphide ores.
MINERALS : (vi) Leaching
Most metals are found in nature in the form of solid inorganic Froth flotation process - Finely divided ore is mixed with oil (pine
compounds called minerals. Names of minerals are based on the oil, eucalyptus oil or camphor oil) and agitated with water
location of their discovery, the person who discovered them or containing a detergent (foaming agent). When air is bubbled
some characteristics of the mineral. through the mixture, the air bubbeles are stabilised by the detergent
.These adsorb mineral particles wetted with oil and rise to the
ORE : surface. The earthy matter wetted by water settles down at the
The mineral from which the metal can be extracted economically. bottom.
Hence all minerals can not be classified as ores. The most Collectors - Which increase the non wettability of ore particles
important ores are oxide,sulphide and carbonate minerals. e.g. pine oil, xanthates and fatty acids.
GANGUE OR MATRIX : Froth stabiliser -Which stabilise the froth e.g. cresoles and aniline.
The unwanted rocky,earthy or sandy materials almost always Depressants - Depressants prevent the formation of froth eg
associated with the ores as impurities are called gangue or matrix. NaCN, when added to ore containing ZnS and PbS form a complex
FLUX AND SLAG : with ZnS as Na 2 [ Zn (CN )4 ] and prevent it from forming froth.
Flux is a substance added to the ores before heating which PbS is then easily separated from ZnS.
combines chemically with earthy impurities (gangue) and form a Leaching- Leaching is the selective dissolution of the desired
fusible mass known as slag . mineral leaving behind the impurities in a suitable dissolving agent
Flux can be Acidic e.g. SiO2 (silica), Na2 B4O7 .10H 2O (borax); eg bauxite when treated with strong solution of
Basic e.g. CaO, MgO ; or Neutral - neutral compounds, and they NaOH, Al 2O 3 dissolves leaving behind Fe 2O 3 .SiO 2 .
decrease the melting point and make the order conducting in an
Al2O3 + 6NaOH ® 2Na 3AlO3 + 3H 2O
electrolytic cell e.g. CaF2 , Na3 AlF6 , KF etc.
Slag consists mostly of molten silicates ,aluminates, phosphates, Na 3 AlO 3 + 3H 2 O ® 3 NaOH + Al(OH )3
fluorides and another inorganic materials. The formation of slag is 2Al(OH )3 ® Al 2 O 3 + 3H 2 O
known as slagging .
652 Chemistry
Leaching is also employed in Ag ore and native gold. (iii) Self reduction -Cu, Pb and Mg are obtained by self
reduction in roasting.
Ag2S + 4NaCN® 2Na[Ag(CN)2 ] + Na2S
3
4Au + 8KCN + 2H2O + O2 ® 4K[Au(CN)2 ] + 4KOH Cu 2S + O2 ® Cu 2O + SO2
2
CALCINATION : Cu 2S + 2Cu 2O ® 6Cu + SO 2
It is the heating of the ore in a suitable furnace in absence of air 2PbS + 3O 2 ® 2PbO + 2SO 2
much below its melting point to cause decomposition and PbS + 2PbO ® 3Pb + SO 2
elimination of volatile products.
(iv) Electrolytic reduction -Oxides of very active metals like
PbCO 3 ® PbO + CO 2 alkali or alkaline earth are not easily reduced by chemical
The process is generally applied to hydrated oxide or carbonate reducing agents e.g. Na, Mg, Al etc. They are obtained
ores. by electrolytic reduction.
Fusion
ROASTING : ® 2Na + + 2Cl -
2NaCl ¾¾¾¾
It is the heating of the concentrated ore in a suitable furnace At anode : 2Cl - - 2e - ® Cl 2
strongly in presence of air with or without certain substances
below the melting point which causes chemical reaction to expel At Cathode : 2Na + + 2e- ® 2Na
volatile impurities eg oxides of S, As and Sb. (v) Amalgamation process - Ag and Au are obtained by
leaching process using solution of KCN or NaCN to
2ZnS + 3O 2 ® 2ZnO + 2SO 2 form argento cyanide or aurocyanide . Ag and Au is
2MoS 2 + 7O 2 ® 2MoO 3 + 4SO 2 precipitated by adding Zn dust.
REDUCTION : 2Na[Ag(CN )2 ] + Zn ® Na 2 [Zn(CN )4 ] + 2Ag
After calcination or roasting, the metal oxides are reduced and 2K[Au(CN )2 ] + Zn ® K 2 [Zn(CN )4 ]+ 2Au
impurities are removed as slag. Reduction and slagging take place Soluble complex
together.
(a) Removal of impurities as slag - For acidic impurities viz. REFINING :
SiO 2 , P2 O5 basic flux is added. The methods employed for the refining of metals are
SiO 2 + CaO ® CaSiO 3 (i) Liquation -Impurities present must be less fusible than the
metal to be purified . Impure metal is placed on the slopping
For basic impurities like MnO acidic flux is added.
hearth of reverberatory furnace at a temperature just above
MnO + SiO 2 ® MnSiO3 the melting point of the metal . The pure metal flows down
(b) Reduction of oxides - leaving behind the impurities . Sn ,Pb, Bi are purified by this
(i) Decomposition of oxides by heating - For thermally method.
unstable oxide. (ii) Distillation - Zn and Hg are purified by distillation under
HgS + O 2 ® Hg + SO 2 reduced pressure provided the impurities are non volatile.
Hg is obtained from its sulphide ore cinnabar directly in (iii) Fractional crystallisation - (Zone refining ).
the roasting step.
(ii) Chemical Reduction -
• Reduction by carbon - Sn from oxide ore cassiterite Molten zone
SnO2 is obtained by heating with coke.
SnO 2 + C ® Sn + 2CO Recrystallized metal Metal rod
Zn from sulphide ore Zinc blende (ZnS).
Roasting Circular heater
2ZnS + 3O 2 ¾¾ ¾¾® 2ZnO + 2SO 2
ZnO + C ® Zn + CO
Impure metal rod is heated with the help of circular heater at
Iron is obtained from oxide ore haematite ( Fe2O3 ). one end. The metal melts and on cooling the pure metal gets
Fe 2 O 3 + 3C ® 2Fe + 3CO solidified while impurities pass on into the molten zone. The
• Reduction by H2 and CO- process is repeated twice or thrice to get the pure metal.
(iv) Polling -The molten metal is stirred with green poles of wood,
MoO 3 + 3H 2 ® Mo + 3H 2 O
which liberates gas like methane. The latter reduces any oxide
CuO + CO ® Cu + CO 2
present in the metal eg CuO in the blister copper is reduced
• Reduction by other metals e.g. Al and Mg - to copper.
Cr2 O 3 + 2Al ® 2Cr + Al 2 O 3 (v) Electrolytic refining- The blocks of impure metal form the
3Mn 3 O 4 + 8Al ® 4Al 2 O3 + 9Mn anode and pure metal form the cathode. Aqueous
Rb 2 O 3 + 3Mg ® 3MgO + 2Rb
General Principles
General Principles & Processes of Isolation of Elements 653
solution of appropriate salt is then electrolised. On oxidised and carried away by blast air .
electrolysis at a suitable voltage the pure metal is deposited (viii)Desilverisation of lead -Lead obtained from galena (PbS)
at cathode. contains impurities of silver, removal of which is called
desilverisation .The processes employed are
At anode M - ne- ® M n + (a) Parke’s process -Lead containing silver is melted in iron
At cathode M n + + ne- ® M pots and 1% Zn is added then cooled. Zn -Ag alloy
solidifies and being light floats over molten lead and
Cu, Sn, Ag, Pb, Cr, Ni are refined by this process. removed .
(vi) Vapour phase refining - Metal is removed as volatile ( Pb and Ag ) + Zn ® ( Zn - Ag ) alloy + Pb
compound which is then decomposed by heating to get pure
(b) Pattison’s process -Lead containing less than 2.5% of
metal. e.g.
Ag melts at lower temperature than lead. Thus when an
(a) Mond’s process - Ni is purified by this process. alloy of Pb-Ag containing more lead is melted then
allowed to cool slowly, pure lead separates.
Ni(s ) + 4CO(g) ¾¾¾ ¾¾® Ni (CO) 4 (g)
300 -350K
450- 470K (ix) Chromatographic methods - It is based on the preferential
Ni(CO) 4 (g) ¾¾ ¾¾¾® Ni(s) + 4CO(g) adsorption of different compunds on an adsorbent. The
(b) Van Arkel process-Zr, Hf , Si,Ti and Be are refined by mixture is put in the liquid or gaseous medium which is moved
this process. through the adsorbent. The different compounds are
adsorbed at different levels on adsorbent in column
Zr s + 2 I 2 g ® ZrI 4 g chromatography and recoverd by using suitable solvent
ZrI4(g ) On hot
Zr(s) + 2 I 2(g) (eluent). The common adsorbent as Al2O3 or SiO2 (silica).
filament The least adsorbed component is recoverd first. The method
(vii) Cupellation - This is the method of purifying silver containing is very useful for purification of elements available in minute
lead as impurity. Impure silver is heated in a shallow (Cupel) quantities.
which is made of bone ash under blast of air. Lead is easily
Flow meter
Detector
Mixture of
compounds
C
O
L
U Oven
Stationary Coloured
M
N phase bands
Flow injector
Pump
Solvent
tank (a) (b)
Industrial method Laboratory method
Schematic diagrams showing column chromatography
There are several chromatographic techniques such as gas chromatography, paper chromatography, etc.
METAL SOURCE MAIN METHOD OFEXTRACTION
Metal Occurrence (ore) Common method of extraction
Li Spodumene LiAl (SiO 3 ) 2 Electrolysis of fused LiCl with KCl .
K Carnallite KCl MgCl2 . 6H2O ; Kaenite KCl MgSO4 3H2O, Electrolysis of fused KCl with CaCl 2 added to it.
Sylvine KCl ; Nitre KNO3 ; Feldspar K2O Al2O3 6SiO2 ;
Mical KH2Al3(SO4)3 ;
654 Chemistry
2K éë Au ( CN ) 2 ùû + Zn ® K 2 éë Zn ( CN ) 4 ùû + 2Au.
(v) Thermit - It is mixture of Fe2O3 (3 parts ) and Al powder (e) Metals obtained by precipitation method are - Ag ,Au
(f) Metals obtained by reduction with Co, Fe
(1part) when ignited with the help of barium peroxide, Fe2O3
(g) Metals obtained by reduction with water gas are - Ni
is reduced to iron and an enormous amount of heat is
produced due to exothermic nature of the reaction. (xv) Alloys -Alloys contain more than one element and have the
characteristics of metals.
Fe2 O3 + 2Al ® Al2 O3 + 2Fe + 2500o C · Pure metals and alloys have different physical properties.
The molten is utilised for welding and the process is known · Solution alloys are homogeneous mixtures and they are of
as thermit welding known as Goldschmidt Alumino thermic two types
process. (a) Subtitutional alloys (Solute atoms take the positions of
(vi) Refractory materials - The substance capable of solvent atom)
withstanding at very high temperature without undergoing (b) Interstitial alloys (Solute atoms occupy interstitial sites)
any deformation is called refractory material. · Heterogeneous alloys - Components are not dispersed
Acidic refractories -silica, quartz and sand stone uniformally e.g. pearlite steel .
Basic refractories - lime ,dolomite and magnesite RELATIVE ABUNDANCE :
Neutral refractories - chromite, bone ash and graphite. Abundance of elements in the earth’s crust (by weight)
(vii) Matte or regulus - Artificially obtained sulphides are known O > Si > Al > Fe > Ca > Na > K > Mg > H > Ti > Cl > F
as matte or regulus e.g. Cu 2S in extraction of copper..
Abundance of elements in the earth’s crust (in terms of number of
(viii)Sulphating roasting - It is partial oxidising roasting. Roasting atoms per 100 atoms)
of galena gives mixture of lead oxide and lead sulphate O > Si > Al > H > Na > Ca > Fe > Mg >
2 PbS + 3O 2 ® 2 PbO + 2SO 2 > K > Ti > C > Mn > S > F > Cl > Cr
PbS + 2O 2 ® 2 PbSO 4 THERMODYNAMIC PRINCIPLES OF METALLURY :
Theory of metallurgical transformations can be interpreted by
(ix) Chlorinating roasting- Silver ores mixed with common salt
Gibb’s free energy change at any specified temp.
when heated in presence of air, the chloride is obtained.
DG = DH - TDS or DGº = - RT lnK
Ag 2S + 2 NaCl ® 2AgCl + Na 2S
where, DH = enthalpy change and
(x) Bessemerisation -The oxidation of impurities by passing the
DS = entropy change
hot blast of air through molten metal in bessemer converter
is called bessemerisation . Pig iron and copper are purified K = equilibrium constt. at temp. T
by this method. The reducing agent is oxidised and metal oxide is reduced. The
(xi) Sintering-The conversion of small pieces of a substances role of reducing agent is to provide DGº negative.
into larger one by partial fusion is known as sintering. During reduction the metal oxide decomposes.
(xii)Pulverisation- The conversion of large pieces of a substance
M x O(s) ¾¾® xM (Solid or liquid) +12 O 2 (g)
into small fine pieces or powder is known as pulverisation.
(xiii)Anodizing-The process of forming an oxide coating on metal The reducing agent (C or CO) is oxidised
surface by making it an anode by electrolytic method in called 1
anodizing. C(s) + O 2 (g) ¾¾
® CO(g)
2
(xiv)Mode of extraction of some metals- 1
CO(g) + O 2 (g) ¾¾
® CO 2 (g)
(a) Metals obtained by electrolytic reduction are - Li, Na, K, 2
Mg, Ca , Al, Sr, Ba
C(s) + O 2 (g) ¾¾
® CO 2 (g)
(b) Metals obtained by reduction of oxides by carbon are -
Zn from ZnO, Sn from SnO2. If net DG of two possible reactions (Reduction/Oxidation) is
negative, the overall reaction will occur.
(c) Metals obtained by reduction of oxides by thermite
process, (Alumino thermic process) are Cr from Cr 2O3, H.J.T. Elligham diagram (plots of DG Vs T) provides a sound basis
Mn from Mn3O4. for considering the choice of reducing agent in the reduction of
oxides.
(d) Metals obtained by air reduction method are - Hg from
HgS, Pb from PbS.
General Principles
General Principles & Processes of Isolation of Elements 657
Note: Although thermodynamically feasible the magnesium metal,
is not used for the reduction of aluminas. The temperature required
would be so high and the process would be technologically difficult
and uneconomic.
EXTRACTION OF IRON FROM ITS OXIDES:
The two simple reactions are
1
(i) ® Fe(s / l) + O 2 (g); DG(FeO, Fe)
FeO (s) ¾¾
2
1
(ii) C(s) + O (g) ® CO(g); DG(C, CO)
2 2
Adding the two reactions, we get
FeO(s) + C(s) ® Fe(s/l) + CO(g)
DG(FeO, Fe) + DG (C, CO) = DG
The resultant DG is –ve above 1073K (approx).
If the metal is obtained in liquid state the reduction becomes easier.
Fig. Gibbs energy (DGº) vs T plots (schematic) for formation of (entropy increases and DG decreases).
some oxides (Ellingham diagram) LIMITATIONS OF ELLINGHAM DIAGRAM :
When alumina is reduced by magnesium, the two equations are 1. It fails to predict the kinetics of reduction processes i.e. how
(i) ® 2Al2 O 3 (ii) 2 Mg + O 2 ¾¾
4 Al + 3O 2 ¾¾ ® 2MgO fast it could be
2. When the reactant/product are solid DG° cannot be
DG becomes ZERO at the point of intersection of the Al2O3 and
interpreted by the equation DG° = – RT log K
MgO curves (marked “A”). Above this point the magnesium can
reduce alumina.
658 Chemistry
Very Short/Short Answer Questions 14. Explain the role of each of the following:
1. Write the names of two oxides which cannot be reduced with (i) NaCN in the extraction of silver.
carbon but can be reduced with aluminium powder to get the (ii) SiO2 in the extraction of copper.
corresponding metals. 15. (a) Which solution is used for the leaching of silver metal
2. Why are metal carbonates and sulphides first converted into in the presence of air in the metallurgy of silver?
corresponding oxides for finally obtaining the corresponding (b) Out of C and CO, which is a better reducing agent at the
metals? lower temperature range in the blast furnace to extract
3. Copper and silver lie below in the electrochemical series and iron from the oxide ore?
yet they are found in the combined state as sulphides in 16. (a) Which of the following ores can be concentrated by
nature. Comment. froth floatation method and why?
4. Indicate the temperature at which carbon can be used as a Fe2O3, ZnS, Al2O3
reducing agent for FeO.
(b) What is the role of silica in the metallurgy of Copper?
5. What is the metal extracted from malachite and azurite? Give
one important use of the metal.
Multiple Choice Questions
6. Name two metals each of which can be obtained 17. The metal always found in the free states is
(a) by thermite process (a) Au (b) Ag
(b) by electrolytic reduction (c) Cu (d) Na
(c) refined by liquation, and
18. Bronze is a mixture of
(d) refined by electrolysis.
(a) Pb + Sn (b) Cu + Sn
7. Name the type of reduction processes by which the following
metals are obtained from their oxides: (c) Cu + Zn (d) Pb + Zn
(a) Metal x which is low in the reactivity series. 19. Which reagent is used in Bayer’s process?
(b) Metal y which is in the middle of the reactivity series. (a) Na2CO3 (b) Carbon
(c) Metal z which is high up in the reactivity series.
(c) NaOH (d) Silica
8. What method for concentration of ore is preferred in each of
20. Matrix is defined as –
the following cases and why:
(a) The ore has higher density particles interspersed with a (a) the unwanted foreign material present in the ore
large bulk of low density impurities. (b) the flux added to remove the unwanted impurities from
(b) The ore consists of copper sulphide intermixed with ore
clay particles. (c) the slag formed as a result of the reaction of flux with
9. At a site, low grade copper ores are available and zinc and gangue
iron scraps are also available. Which of the two scraps will (d) the material used in the reduction of metal oxide to
be more suitable for reducing the leached copper ore and metal
why? 21. The process to heat the ore in the presence of excess supply
10. Although thermodynamically feasible, in practice, of air below its melting point is called –
magnesium metal is not used in for the reduction of alumina (a) roasting (b) calcination
in the metallurgy of aluminium. Why?
(c) smelting (d) liquation
11. Differentiate between a mineral and an ore.
22. Thomas slag is
12. Describe the principle controlling each of the following
processes: (a) Ca3(PO4)2
(i) Zone refining of metals (b) CaSiO3
(ii) Electrolytic refining of metals (c) Mixture of (a) and (b)
13. Which methods are usually employed for purifying the (d) FeSiO3
following metals? 23. Blister copper is
(i) Nickel
(a) Impure Cu (b) Cu alloy
(ii) Germanium
(c) Pure Cu (d) Cu having 1% impurity
General Principles
General Principles & Processes of Isolation of Elements 659
24. Which of the following fluxes is used to remove acidic Codes:
impurities in metallurgical process? (a) I-C, II-A, III-D, IV-B
(a) Silica (b) I-D,II-B,III-C,IV-A
(b) Lime stone (c) I-C,II-B,III-D, IV-A
(c) Sodium chloride (d) I-D,II-A,III-C,IV-B
(d) Sodium carbonate 26. In forth flotation process many chemicals (frother , collector,
25. Match list I with list II and select the correct answer using activator, and depressant) are used . Which is called a frother:
the codes given below the lists: (a) CuSO 4 (b) NaCN+ alkali
List I List II
(c) Pine oil (d) Potassium xanthate.
I. Cyanide process A. Ultrapure Ge
II. Floatation process B. Pine oil
III. Electrolytic reduction C. Extraction of Al
IV. Zone refining D. Extraction of Au
1. An example of an oxide ore is 9. Which of the following fluxes is used to remove acidic
(a) bauxite (b) malachite impurities in metallurgical process?
(c) zinc blende (d) feldspar (a) Silica (b) Lime stone
2. The natural materials from which an element can be extracted (c) Sodium chloride (d) Sodium carbonate
economically are called 10. Cryolite is
(a) ores (b) minerals
(a) Na 3AlF6 and used in the electrolysis of alumina for
(c) gangue (d) None of these
3. The impurities associated with mineral used in decreasing electrical conductivity
metallurgy are called collectively? (b) Na 3AlF6 and used in the electrolysis of alumina for
(a) Slag (b) Flux lowering the melting point of alumina
(c) Gangue (d) Ore
(c) Na 3AlF6 and used in the electrolytic purification of
4. The most abundant metal on the surface of the earth is
alumina
(a) Fe (b) Al
(c) Ca (d) Na (d) Na 3AlF6 and used in the electrolysis of alumina
5. The most abundant element in the earth’s crust (by weight) 11. Flux is used to
is
(a) remove all impurities from ores
(a) Si (b) Al
(b) reduce metal oxide
(c) O (d) Fe
(c) remove silica
6. During smelting an additional substance is added which
combines with impurities to form a fusible product. It is known (d) remove silica and undesirable metal oxide
as 12. Cassiterite is concentrated by
(a) slag (b) mud (a) levigation
(c) gangue (d) flux (b) electromagnetic separation
7. When a metal is to be extracted from its ore and the gangue (c) floatation
associated with the ore is silica, then (d) liquefaction
(a) an acidic flux is needed 13. Froth floatation process is used for the metallurgy of
(b) a basic flux is needed
(a) chloride ores (b) amalgams
(c) both acidic and basic fluxes are needed
(c) oxide ores (d) sulphide ores
(d) Neither of them is needed
14. Electromagnetic separation is used in the concentration of
8. A basic lining is given to a furnace by using
(a) calcined dolomite (b) lime stone (a) copper pyrites (b) bauxite
(c) haematite (d) silica (c) cassiterite (d) cinnabar
660 Chemistry
15. For which ore of the metal, froth floatation method is used 29. Use of electrolysis is
for concentration? (a) Electroplating (b) Electrorefining
(a) Horn silver (b) Bauxite (c) Both (a) and (b) (d) Neither (a) nor (b)
(c) Cinnabar (d) Heamatite 30. In electrorefining of copper some gold is deposited as
16. Which of the following metal is leached by cyanide process (a) anode mud (b) cathode mud
(a) Ag (b) Na (c) electrolyte (d) None of these
(c) Al (d) Cu 31. Purification of silicon element used in semiconductors is
17. Which one of the following ores is not concentrated by done by
(a) zone refining (b) heating
froth floatation process?
(c) froth floatation (d) heating in vacuum
(a) Copper pyrites (b) Pyrargyrite
32. Silver containing lead as an impurity is removed by
(c) Pyrolusite (d) Zinc blende
(a) poling (b) cupellation
18. Calcination is used in metallurgy for removal of?
(c) lavigation (d) distillation
(a) Water and sulphide (b) Water and CO2
33. Nickel is purified by thermal decomposition of its
(c) CO2 and H 2S (d) H 2 O and H 2S (a) hydride (b) chloride
19. Which of the following reactions is an example for calcination (c) azide (d) carbonyl
process ? 34. The chief source of iodine, in which it is present as sodium
(a) 2Ag + 2HCl + (O ) ® 2AgCl + H 2 O iodate, is
(a) Carnallite (b) Sea weeds
(b) 2Zn + O 2 ® 2 ZnO (c) Caliche
(d) Iodine never exists as sodium iodate.
(c) 2ZnS + 3O 2 ® 2ZnO + 2SO 2
35. Malachite is an ore of
(d) MgCO3 ® MgO + CO 2 (a) iron (b) copper
20. Heating of ore in the absence of air below its melting point is (c) mercury (d) zinc
called 36. The important oxide ore of iron is
(a) leaching (b) roasting (a) siderite (b) haematite
(c) smelting (d) calcination (c) pyrites (d) bauxite
21. Heating pyrites to remove sulphur is called 37. In the commercial electrochemical process for aluminium
(a) smelting (b) calcination extraction the electrolyte used is
(c) liquation (d) roasting
22. The process of converting hydrated alumina into (a) Al(OH )3 in NaOH solution
anhydrous alumina is called (b) An aqueous solution of Al 2 (SO 4 )3
(a) roasting (b) smelting
(c) dressing (d) calcination (c) A molten mixture of Al2 O 3 and Na 3 AlF6
23. Mac Arthur process is used for
(a) Ag (b) Fe (d) A molten mixture of Al 2 O 3 and Al(OH )3
(c) Cl (d) O2 38. Cassiterite is an ore of
24. In Goldschmidt aluminothermic process, reducting agent is (a) Mn (b) Ni
used
(c) Sb (d) Sn
(a) coke (b) Al powder
39. Which of the following element is extracted commercially by
(c) Na (d) Ca
the electrolysis of an aqueous solution of its compound?
25. Aluminothermic process is used for metallurgy of
(a) Pb (b) Ag (a) Chlorine (b) Bromine
(c) Al (d) None of these (c) Sodium (d) Aluminium
26. Which metal can’t be obtained from electrolysis? 40. Galena is an ore of
(a) Ca (b) Mg (a) Pb (b) Hg
(c) Cr (d) Al (c) Zn (d) Zn
27. Which of the following metals is obtained by 41. Which one of the following element does not exits in the
electrolytic reduction process? native form?
(a) Fe (b) Cu (a) Au (b) Pt
(c) Ag (d) Al (c) Fe (d) S
28. The common method of extraction of metals from oxide ores 42. The most electropositive metals are isolated from their ores by
is (a) high temperature reduction with carbon
(a) reduction with carbon
(b) self reduction
(b) reduction with hydrogen
(c) thermal decomposition
(c) reduction with aluminium
(d) electrolytic method (d) electrolysis of fused ionic salts
General Principles
General Principles & Processes of Isolation of Elements 661
43. The metal always found in the free states is 49. Match list I with list II and select the correct answer using
(a) Au (b) Ag the codes given below the lists:
(c) Cu (d) Na List I List II
44. Pyrolusite is a/an I. Cyanide process A. Ultrapure Ge
(a) oxide ore (b) sulphide ore II. Floatation process B. Pine oil
(c) carbide ore (d) Not an ore III. Electrolytic reduction C. Extraction of Al
45. Which of the following metals is extracted by the IV. Zone refining D. Extraction of Au
electrometallurgical method ? Codes:
(a) Cu (b) Fe (a) I-C, II-A, III-D, IV-B (b) I-D,II-B,III-C,IV-A
(c) Na (d) Ag (c) I-C,II-B,III-D, IV-A (d) I-D,II-A,III-C,IV-B
46. Among the following statements the incorrect one is 50. Which of the following condition favours the reduction of
a metal oxide to metal?
(a) Calamine and siderite are carbonates
(a) DH = +ve, TDS = + ve at low temperature
(b) Argentite and cuprite are oxides
(b) DH = +ve, TDS = – ve at any temperature
(c) Zinc blende and iron pyrites are sulphides (c) DH = –ve, TDS = – ve at high temperature
(d) Malachite and azurite are ores of copper. (d) DH = –ve, TDS = + ve at any temperature
47. When an aqueous solution of sodium chloride is electrolysed 51. Ellingham diagram normally consists of plots of
using platinum electrodes, the ion (a) DSº vs T (b) D fGº vs DSº
discharged at the electrodes are (c) DGº vs T (d) DHº vs DT
(a) sodium and hydrogen (b) sodium and chloride 52. A coupled reaction is takes place as follow–
(c) hydrogen and chloride (d) hydroxyl and chloride A + B ––––® C + D, D Gº = + x kj
48. In the extraction of iron , slag is produced.Slag is D + E ––––® F D Gº = – y kj
(a) CO (b) FeSiO3 for the spontaneity of reaction A + B + E –––® C+F,
which of the following is correct?
(c) MgSiO 3 (d) CaSiO 3 (a) 2x = y (b) x < y
(c) x > y (d) x = (y)× TDS
1. Which of the following statements, about the advantage of (a) Manganese (b) Carbon
roasting of sulphide ore before reduction is not true?
[CBSE-PMT 2007] (c) Silicon (d) Phosphorus
4. Which of the following pairs of metals is purified by van
(a) The DG of of the sulphide is greater than those for CS2 Arkel method ? [CBSE-PMT 2011]
and H2S. (a) Ga and In (b) Zr and Ti
(b) The DG of is negative for roasting of sulphide ore to oxide. (c) Ag and Au (d) Ni and Fe
5. The following reactions take place in the blast furnace in the
(c) Roasting of the sulphide to the oxide is thermodynamically
feasible. preparation of impure iron. Identify the reaction pertaining to
the formation of the slag. [CBSE-PMT 2011 M]
(d) Carbon and hydrogen are suitable reducing agents for
reduction of metal sulphides. (a) Fe2O3(s) + 3 CO(g) ®2 Fe (l) + 3 CO2 (g)
2. Sulphide ores of metals are usually concentrated by froth (b) CaCO3 (s) ®CaO (s) + CO2 (g)
flotation process. Which one of the following sulphide ores (c) CaO (s) + SiO2(s) ® CaSiO3(s)
offer an exception and is concentrated by chemical leaching?
(d) 2C(s) + O2 (g) ®2 CO(g)
[CBSE-PMT 2007]
6. Aluminium is extracted from alumina (Al2O3 ) by electrolysis
(a) Galena (b) Copper pyrite
of a molten mixture of : [CBSE-PMT 2012 S]
(c) Sphalerite (d) Argentite
(a) Al2O3 + HF + NaAlF4 (b) Al2O3 + CaF2 + NaAlF4
3. Which of the following elements is present as the impurity to
the maximum extent in the pig iron ? [CBSE-PMT 2011] (c) Al2O3 + Na3AlF6 + CaF2 (d) Al2O3 + KF + Na3AlF6
662 Chemistry
7. Which one of the following is a mineral of iron ? (c) Metal sulphides are less stable than the corresponding
[CBSE-PMT 2012 S] oxides
(a) Malachite (b) Cassiterite (d) CO2 is more volatile than CS2
(c) Pyrolusite (d) Magnetite 12. Pb and Sn are extracted from their chief ore by
8. In the extraction of copper from its sulphide ore, the metal is [IIT-JEE 2004S]
finally obtained by the reduction of cuprous oxide with : (a) carbon reduction and self reduction.
(a) Copper (I) sulphide (Cu2S) [CBSE-PMT 2012 S] (b) self reduction and carbon reduction.
(b) Sulphur dioxide (SO2) (c) electrolysis and self reduction.
(c) Iron sulphide (FeS) (d) self reduction and electrolysis.
(d) Carbon monoxide (CO) 13. Extraction of zinc from zinc blende is achieved by
9. Which one of the following ores is best concentrated by (a) electrolytic reduction [IIT-JEE 2007]
froth-flotation method ? [AIEEE 2004] (b) roasting followed by reduction with carbon
(a) Galena (b) Cassiterite (c) roasting followed by reduction with another metal
(c) Magnetite (d) Malachite (d) roasting followed by self-reduction
10. Heating mixture of Cu 2 O and Cu 2 S will give 14. In the cyanide extraction process of silver from argentite ore,
[AIEEE 2005] the oxidising and reducing agents used are [IIT-JEE 2012]
(a) Cu2SO3 (b) CuO + CuS (a) O2 and CO respectively
(c) Cu + SO3 (d) Cu + SO2 (b) O2 and Zn dust respectively
11. Which of the following factors is of no significance for (c) HNO3 and Zn dust respectively
roasting sulphide ores to the oxides and not subjecting the (d) HNO3 and CO respectively
sulphide ores to carbon reduction directly? [AIEEE 2008] 15. Sulfide ores are common for the metals
(a) Metal sulphides are thermodynamically more stable than (JEE Advanced 2013)
CS2 (a) Ag, Cu and Pb (c) Ag, Mg and Pb
(b) CO2 is thermodynamically more stable than CS2 (b) Ag, Cu and Sn (d) Al, Cu and Pb
1. Which process represents the change, (a) absorbance of ultraviolet light- and reemission of white light
Ti + 2I 2 ® TiI 4 ® Ti + 2I 2 (b) shock cooling by contact with a shower of molten lead.
(a) Cupellation (b) Van Arkel (c) X-ray method
(c) Polling (d) Zone Refining (d) smelting.
2. In froth flotation process many chemicals (frother , collector, 6. Among the following groups of oxides, the group containing
activator, and depressant) are used . Which of the folloiwng oxides that cannot be reduced by carbon to give the
is a frother:
respective metals is
(a) CuSO 4 (b) NaCN+ alkali
(a) Cu 2 O, SnO 2 (b) Fe 2O 3 , ZnO
(c) Pine oil (d) Potassium xanthate.
3. Froth flotation process is based on (c) CaO, K 2O (d) PbO, Fe3O 4
(a) wetting properties of ore particle
7. The electrolytic reduction technique is used in the extraction of
(b) specific gravity of ore particles
(c) magnetic properties of ore particles (a) highly electronegative elements
(d) electrical properties of ore particles . (b) highly electropositive elements
4. In the electrolysis of alumina, cryolite is added to: (c) metalloids
(a) lower the melting point of alumina and to increase the (d) transition metals.
electrical conductivity
8. In electro-refining of metal the impure metal is made the
(b) minimise the anode effect
anode and a strip of pure metal, the cathode, during the
(c) remove impurities from alumina
electrolysis of an aqueous solution of a complex metal salt.
(d) None of these
This method cannot be used for refining of
5. In the metallurgy of Zn the Zn dust obtained from roasting
and reduction of zinc sulphide contains some ZnO. It is (a) silver (b) copper
removed by (c) aluminium (d) sodium
General Principles
General Principles & Processes of Isolation of Elements 663
9. In the froth flotation process of concentration of ores, the 18. D G° Vs T plot in the Ellingham’s diagram slopes downward
ore particles float because they: for the reaction
(a) are light
1 1
(b) are insoluble (a) Mg + O 2 ® MgO (b) 2Ag + O 2 ® Ag 2O
2 2
(c) have the surface which is not wetted easily
(d) have a constant electrical charge 1 1
(c) C + O2 ® CO (d) CO + O 2 ® CO 2
10. Thomas slag is 2 2
(a) calcium silicate 19. Which of the following reactions taking place in the bast
(b) calcium phosphate furnace during extraction of iron is endothermic?
(c) tricalcium phosphate and calcium silicate (a) CaCO3 ® CaO + CO 2
(d) calcium ammonium phosphate
(b) 2C + O2 ® 2CO
11. Extraction of Ag from commercial lead is possible by
(a) Parke’s process (b) Clarke’s process (c) C + O 2 ® CO 2
(c) Pattinson’s process (d) Electrolytic process
(d) Fe 2O3 + 3CO ® 2Fe + 3CO 2
12. Iron is obtained on large scale from Fe2O3 by
20. Consider the following reactions at 1000°C
(a) Reduction with CO (b) Reduction with Al
1
(c) Calcination (d) Passing H2 A. Zn(s) + O 2 (g) ® ZnO(s); DG° = -360 kJ mol-1
13. After partial roasting the sulphide of copper is reduced by 2
(a) cyanide process (b) electrolysis
1
(c) reduction with carbon (d) self reduction B. C(gr) + O 2 (g) ® CO(g); DG° = -460 kJ mol –1
2
14. Before introducing FeO in blast furnace , it is converted to
Choose the correct statement at 1000°C
Fe2O3 by roasting so that
(a) zinc can be oxidised by carbon monoxide.
(a) it may not be removed as slag with silica
(b) zinc oxide can be reduced by graphite
(b) it may not evaporate in the furnace
(c) carbon monoxide can be reduced by zinc.
(c) presence of it may increase the m.pt. of charge (d) both statements (a) and (b) are true
(d) None of these. 21. The substance not likely to contain CaCO3 is
15. The phenomenon of removing layers of basic oxides from (a) calcined gypsum (b) sea shells
metals before electroplating is called (c) dolomite (d) a marble statue
(a) galvanising (b) anodising 22. The value of Df Gº for formation of Cr2 O3 is – 540 kJmol–1 and
(c) pickling (d) poling. that of Al2O3 is – 827 kJ mol–1 What is the value of DrG° for
16. Aluminothermic process is used for the extraction of metals the reaction?
, whose oxides are
4 2 2 4
(a) fusible Al(s) + Cr2 O 3 (s) ® Al 2 O3 (s) + Cr(s).
3 3 3 3
(b) not easily reduced by carbon
(c) not easily reduced by hydrogen (a) – 574 kJ mol –1
(b) –287kJ mol–1
(c) + 574 kJ mol –1
(d) +287kJ mol–1
(d) strongly basic.
23. Which of the following statement is not correct about
17. When the sample of copper with zinc impurity is to be purified
Ellingham diagram?
by electrolysis, the appropriate electrodes are
cathode anode (a) D G increases with an increase in temperature
(a) pure zinc pure copper (b) It consists of plots of DfGº Vs T for formation of
oxides
(b) impure sample pure copper
(c) A coupling reaction can be well expressed by this
(c) impure zinc impure sample diagram
(d) pure copper impure sample. (d) It express the kinetics of the reduction process
664 Chemistry
EXERCISE 1 15. (c) Cinnabar is sulphide ore (HgS). Hence purified by froth
floatation process.
1. Manganese oxide (MnO2) and chromium oxide (Cr2O3). 16. (a) Ag is leached by cyanide process (see text).
2. Reduction of oxides is easier 17. (c) Pyrolusite is MnO2. Hence not concentrated by froth
3. This is due to high polarising power of Cu and Ag ions floatation process.
4. Carbon can be used as a reducing agent above 1123 K. 18. (b) Calcination is used for removal of volatile impurities and
5. Copper is extracted from malachite and azurite. decompose carbonates.
19. (d) Decomposition of carbonates and hydrated oxides.
6. (a) Chromium and manganese
20. (d) It is definition of calcination (see text).
(b) Sodium and mangnesium
21. (d) Pyrites are sulphur ores and are converted into oxide by
(c) Tin and lead
roasting.
(d) Copper and silver
22. (d) Al2O 3.2H 2O ® Al 2O3 + 2H 2O is calcination.
7. (a) x is obtained by heating metal oxide alone.
23. (a) Mac Arthur process is used for Ag and Au (see text).
(b) y is obtained by the reducing its oxide with carbon. 24. (b) In Goldschmidt aluminothermic process reducing agent
(c) z is obtained by electrolytic reduction. is Al powder.
25. (d)
10. Because magnesium is a more costlier metal than aluminium
26. (c) Chromium is obtained by reduction with Al.
17. (a) 18. (b) 19. (c) 20. (a) 21. (a) 27. (d) Al is obtained by electrolytic reduction of Al2O3 in
presence of cryolite (see text).
22. (c) 23. (d) 24. (b) 25. (b) 26. (c) 28. (a) The common method for the extraction of metal from oxide
EXERCISE 2 ore is by reduction with carbon.
29. (c) Electrolysis is used for electroplating and
1. (a) Bauxite ore of aluminium is Al 2 O3 .2H 2 O . electrorefining both.
2. (a) Ores (see text). 30. (a) Gold is deposited as anode mud (see refining of copper).
3. (c) Impurities associated with minerals are called gangue or 31. (a) Silicon is purified by zone refining . Metals of high purity
matrix. are always purified by zone refining.
4. (b) Al, see text. 32. (b) Silver containing lead is purified by cupellation (see text).
5. (c) O, see text. 33. (d) Ni is purified by Mond’s process by decomposition of
6. (d) Flux is added which combines with impurities to form Ni(CO)4.
slag.
34. (c) Caliche is crude chilesaltpetre (NaNO3) and contains
7. (b) Since silica is acidic impurity the flux must be basic.
NaIO3, source of iodine.
CaO + SiO2 ® CaSiO3
8. (a) Dolomite on calcination gives CaO.MgO which provides 35. (b) Malachite is an ore of copper Cu ( OH ) 2 .CuCO3 .
basic lining in furnace. 36. (b) Important ore of iron is Haematite Fe 2 O3 .
9. (b) To remove acidic impurities basic flux is added which
37. (c)
is CaCO3 .
38. (d)
Cassiterite is an ore of Sn also known as tin stone SnO2.
10. (b) Na 3 AlF6 is cryolite and used in the electrolysis of 39. (a)
Cl2 is obtained by electrolysis of (aqueous) NaCl.
alumina to lower the melting point and increase electrical 40. (a)
Galena is an ore of lead. It is PbS.
conductivity. 41. (c)
Fe does not exist native.
11. (d) Flux removes acidic or basic impurities e.g. silica and 42. (d)
Most electropositive metals are obtained by electrolysis
other metal oxides etc. of their fused ionic salts.
12. (b) Cassiterite contains the magnetic impurities of FeSO 4 43. (a) Gold being least reactive found native.
and concentrated by electromagnetic separation. 44. (a) MnO2 is pyrolusite (oxide ore).
13. (d) Froth floatation process is used for the concentration of 45. (c) Na is obtained by elctrolytic reduction being
sulphide ores. electropositive in nature.
14. (c)
46. (b) Cuprite is Cu2O and Argentite is Ag 2 S .
General Principles
General Principles & Processes of Isolation of Elements 665
5. (c) In blast furnace at about 1270 K, calcium carbonate is
47. (c) almost completely decomposed to give CaO which acts
as a flux and combines with SiO2 present as impurity
(gangue) in the ore to form calcium silicate (fusible
slag)
(At cathode) (At anode) CaO(s) (basic flux) + SiO2 (s) (acidic flux) ¾¾ ®
CaSiO3 (s) (slag)
Reduction potential of H is more than Na. 6. (c) Fused alumina (Al2O3) is a bad conductor of electricity.
Therefore, cryolite (Na3AlF6) and fluorspar (CaF2) are
48. (d) Slag formed in the extraction of iron is CaSiO3 .
added to purified alumina which not only make alumina
49. (b) Cyanide process is for gold (I-D); floatation process - a good conductor of electricity but also reduce the
pine oil (II-B); Electrolytic reduction - Al (III-C); Zone melting point of the mixture to around 1140 K.
refining -Ge (IV-A).
7. (d) Fe3O4 – Magnetite
50. (d)
CuCO3 · Cu(OH)2 – Malachite
51. (c) Ellingham diagram normally consists of plots of DfGº
Vs T for the formation of oxides of elements. Pyrolusite – MnO2 and Cassiterite – SnO2.
52. (d) For a spontaneous reaction , D Gº must be negative 8. (a) Cuprous oxide formed during roasting of cuprous
and it can be possible only in this case when x < y sulphide is mixed with few amount of cuprous sulphide
and heated in a reverberatory furnace to get metallic
EXERCISE 3
copper.
1. (d) The sulphide ore is roasted to oxide before reduction
because the DGof of most of the sulphides are greater 2Cu 2O + Cu 2S ® 6Cu + SO2
than those of CS2 and H2S, therefore neither C nor H 9. (a) Galena is PbS and purified by froth floatation method
can reduce metal sulphide to metal. Further, the standard 10. (d) During bessemerisation, cuprous sulphide
free energies of formation of oxide are much less than
is oxidised which combines with remaining cuprous
those of SO2. Hence oxidation of metal sulphides to
sulphide to form free copper metal
metal oxide is thermodynamically favourable.
2. (d) Leaching is the selective dissolution of the desired 2Cu 2 O + Cu 2S ¾
¾® 6Cu + SO 2
mineral leaving behind the impurities in a suitable
dissolving agent e.g., 11. (c) The reduction of metal sulphides by carbon reduction
process is not spontaneous because DG for such a
Argentitie or Silver glance, Ag2S is an ore of silver.
process is positive. The reduction of metal oxide by
Silver is extracted from argentite by the mac-Arthur
carbon reduction process is spontaneous as DG for
and Forest process (leaching process).
such a process is negative. From this we find that on
Ag 2S + 4NaCN ® 2Na[Ag ( CN )2 ] + Na 2S thermodynamic considerations CO2 is more stable than
CS2 and the metal sulphides are more stable than
4Au + 8KCN + 2H 2O + O 2 ® 4K[Au ( CN ) 2 ] + 4KOH corresponding oxides.
3. (b) Pig iron or cast iron contains 3 – 5% carbon and varying In view of above the factor listed in choice (c) is incorrect
amounts of Mn, Si, P and S which makes the iron hard and so is of no significance.
and brittle. 12. (b) PbO & PbSO4 get reduced by PbS itself which is already
4. (b) Zr and Ti are purified by van Arkel method. present in mixture so because the reduction took place
870K by itself, hence is known as self reduction.
Zr( s ) + 2I 2 ( g ) ¾¾¾® ZrI 4 ( g )
D
2PbO + PbS ¾¾
® 3Pb + SO 2
2075K
ZrI4 ( g ) ¾¾¾¾¾¾¾ ® Zr(s ) + 2I 2 ( g )
Tugsten filament
D
PbSO 4 + PbS ¾¾
® 2Pb + 2SO 2
523K
Ti(s) + 2I2(s) ¾¾¾ ® TiI4(g) 13. (b) Extraction of Zn from ZnS (Zinc blende) is achieved by
1700K roasting followed by reduction with carbon.
2ZnS + 3O2 ¾¾
® 2ZnO + 2SO2
Ti(s) + 2I2(g)
Pure titanium ZnO + C ¾¾
® Zn + CO
666 Chemistry
14. (b) The reactions involved in cyanide extraction process 10. (c) Tricalcium phosphate and calcium silicate is Thomas slag
are : 11. (a) See Parke’s process
12. (a) Fe2O3 + 3CO ® 2Fe + 3CO2 ( in blast furnace)
Ag 2 S + 4NaCN ® 2Na [Ag(CN)2] + Na2S
(argentite) 13. (d) 2CuO + CuS ® 3Cu + SO 2 (Self - reduction)
14. (a) FeO is capable forming slag with SiO2
4Na2S + 5O 2 + 2H2O ® 2Na2SO4 + 4NaOH + 2S
Oxiding SiO 2 + FeO ® FeSiO 3
agent
15. (c) Pickling is removel of basic oxide layers on metals before
electroplating.
2Na[Ag(CN)2] + Zn ® Na2 [Zn(CN)4] + 2 Ag ¯ 16. (b) When reduction by carbon is not satisfactory in case of
(reducing
agent) metals having high m.pt., aluminothermic process is used
.
15 (a) Silver, copper and lead are commonly found in earth's
17. (d) Pure metal always deposits at cathode.
crust as Ag2S (silver glance), CuFeS2 (copper pyrites)
18. (c) 19. (a) 20. (b)
and PbS (galena)
21. (a) Gypsum is CaSO4.2H2O
EXERCISE 4 22. (b) The two equation are:
1. (b) The given reaction is the method named as Van Arkel for 4 2
the purification of titanium Al(s) + O 2 (g) ® Al2 O3 (s), D f Gº = -827kJ mol -1
3 3
2. (c) Froth reduces the surface tension of water and the
… (1)
solution forms froth.
3. (a) Froth flotation process is based on wetting properties of 4 2
Cr(s) + O 2 (g) ® Cr2 O3 (s), D f Gº = -540kJ mol -1
ore particles. 3 3
4. (a) Cryolite lowers the m.p of alumina and increases the … (2)
electrical conductivity Subtracting equation (ii) from equation (i) we have,
5. (d) See metallurgy of Zn 4 2
6. (c) Ca and K are strong reducing agents, hence their oxides Al(s) + Cr2 O 3 (s),
3 3
cannot be reduced with carbon
7. (b) Highly electropositive elements are obtained by 2 4
® Al2 O3 (s) + Cr(s), D r G° = -287kJ mol -1
electrolytic reduction. 3 3
8. (d) Na reacts vigorously with water (exothermic process ) 23. (d) Ellingham diagrams are based on thermodynamic con-
9. (c) The surface of particles not wetted hence they float at cepts. It does not tell anything about the kinetics of the
the surface reduction process.
21A
Oxides of As As 2 O 5 As 2 O 3 Uses :
Amphoteric i) For manufacturing of nitric acid
ii) For detection of Oxygen
Oxides of Sb Sb 2 O 5 Sb 2 O 3 iii) For manufacturing of sulphuric acid as catalyst (Lead
Amphoteric chamber process)
Bi 2O 5 Bi 2 O3 Structure :
Oxides of Bi . .. .-. +.
Basic :N =O
..¬¾® N
.. =O:
N2O (dinitrogen oxide or nitrous oxide) known as laughing NO2 (nitrogen dioxide)
gas Preparation :
Preparation :
i) 2NO + O 2 ® 2 NO 2
(i) Priestley’s method :
ii) 2Pb ( NO 3 ) 2 ® 2PbO + 4 NO 2 + O 2
2 NO + H 2 O + Fe ® N 2O + Fe(OH) 2
(Common method)
(ii) Bertholet’s (common method) :
iii) Cu + 4HNO3 (conc.) ® Cu( NO3 )2 + 2H2O + 2NO2
D
NH 4 NO 3 ¾¾® N 2 O + 2 H 2 O Properties : Highly toxic, paramagnetic, reddish brown gas
(iii) 2NaNO3 + ( NH 4 ) 2 SO 4 ® N 2O + 2H 2O + Na 2SO 4 with choking odour, acidic
Reactions :
Properties :
Colourless, fairly unreactive, pleasing odour, sweet taste, i) 2NO 2 + H 2O ® HNO 2 + HNO 3 (Hence it is mixed
supports combustion. It is neutral. anhydride of HNO2 and HNO3)
D
2 N 2 O( g ) ¾¾® 2 N 2 (g ) + O 2 ( g ) ii) 2NO 2 N 2O4
brown colourless, solid / liquid, acidic
.-. + .. .. + .. -
.. = N =O
Structure : Linear N .. ¬
¾® N º N — O
.. : hn
iii) NO 2 ¾¾® NO + O
Uses : Mixed with oxygen it is used as anaesthetic iv) It is combustible and supports the combustion of
NO (nitrogen oxide or nitric oxide) : burning P, Mg or charcoal. Burning S or candle is
Preparation : extinguished.
Common method v) It is oxidising and reducing in nature
2NaNO2 + 2FeSO 4 + 3H 2SO4 Uses :
i) For Manufacturing of HNO3
® Fe 2(SO 4 )3 + 2NaHSO 4 + 2H 2O + 2NO
ii) As Catalyst in lead chamber process for Sulphuric acid
(i) D
N 2 (g ) + O 2 ( g ) ¾¾® 2 NO (g ) (commercial) Structure :
(ii) 3Cu (s) + 8HNO 3 (dil) ® 3Cu ( NO 3 ) 2 + 4H 2 O + 2 NO
(Lab method)
D , Pt N2O3 (dinitrogen trioxide) Nitrogen sesquioxide
(iii) 4NH3 + 5O2 ¾¾¾¾¾
750°C,6atm
® 4NO + 6H 2O
253K
Common method : 2NO + N 2 O 4 ¾¾¾ ® 2N 2 O 3
(Ostwald’s process)
Properties : Colourless, paramagnetic, slightly toxic gas, Preparation : NO + NO 2 ® N 2 O 3
blue in liquid state. It is combustible and supports Properties : It is blue solid, acidic
combustion. It is neutral.
N 2O 3 + H 2O ® 2HNO 2
D
FeSO 4 + NO ® FeSO 4 .NO ¾¾® FeSO 4 + NO Hence it is anhydride of HNO2
dark brown pure gas
Absorbed by sulphuric acid
D N 2 O 3 + 2H 2SO 4 ® 2 NO[HSO 4 ]2 + H 2 O
[Fe (H 2 O) 6 ]SO 4 + NO ® [Fe(H 2 O)5 NO]SO 4 ¾¾®
Hydrated nitrosyl Nitroso
complex sulphuric acid
:
:
O:
O
.
O:
O
.
..
O NITROGEN :
|| Discovered by Daniel Rutherford. Abundance in air is 78.15% by
P volume. It occurs in combined state as saltpetre (KNO3) and Chile
O O Saltpetre (NaNO3). It is also known as Azote (without life)
O Preparation :
Structure : O=P P=O
O i) NH 4+ + NO 2- ® N 2 + 2H 2 O
P
O || O ii) 2 NH 3 + 3CuO ® N 2 + 3H 2 O + 3Cu
O iii) 8 NH 3 + 3Cl 2 ® N 2 + 6 NH 4 Cl
The p-Block Elements - Nitrogen Family 671
D NITRIC ACID (HNO3) (ALSO KNOWN AS AQUA
iv) ( NH 4 ) 2 Cr2 O 7 ¾¾® N 2 + 4H 2 O + Cr2 O 3 . It is violent
FORTIS) :
reaction with flashes of light (volcano experiment)
Preparation :
v) H 2 NCONH 2 + 2HNO 2 ® 2N 2 + CO 2 + 3H 2 O Lab method :
Preparation of very pure N2 : By heating Sodium azide 2NaNO3 + H 2SO 4 (conc.) ® Na 2SO 4 + 2HNO 3
2 NaN3 ® 2 Na + 3N 2 Manufacturing :
Manufacturing : By Linde’s or Claude’s process (a) Birkland - Eyde process : Air is passed through an electric
Atmospheric air is compressed and then released into a bigger arc (3000ºC) when N2 combines with O2 to form NO. It is
area when liquid air is obtained (Joule Thomson effect) which is cooled and allowed to combine with O2 to form NO2. The
mainly mixture of N2 and O2. They are separated by fractional latter is passed in water in presence of excess of air to give
distillation. HNO3.
Properties : It is colourless, odourless, tasteless, slightly lighter N 2 + O 2 ® 2 NO
than air, slightly soluble in water, non poisonous gas.
It is incombustible and non supporter of combustion. It combines 2NO + O 2 ® 2 NO 2
with metals and non metals to form number of compounds. 4 NO 2 + 2H 2 O + O 2 ® 4HNO 3
Uses : To decrease concentration of oxygen in air and make
(b) Ostwald’s Process : From ammonia
combustion less rapid. To create inert atmosphere and in the
preparation of NH3, HNO3, CaCN2, etc. Pt gauge
4NH 3 + 5O 2 ¾¾¾¾® 4NO + 6H 2O
800ºC
AMMONIA (NH3) :
Preparation : Lab method : 2NO + O 2 ® 2 NO 2
2NH 4Cl + Ca (OH) 2 ® CaCl 2 + 2 NH 3 + 2H 2O 4 NO 2 + 2H 2 O + O 2 ® 4HNO 3
Manufacturing : Properties : Syrupy, colourless, pungent liquid usually
(a) Haber’s process : available as 68% and 15.7 M. Aqueous solution is often
Fe/Mo
yellow due to small concentrations of NO2
N 2 + 3H 2 ¾¾¾¾
® 2NH 3
450ºC, 245 Atm. FUMING NITRIC ACID (HNO3 + NO2)
Other catalysts employed are Chemical properties : As an acid - It is a strong acid and in
aqueous solution the ionisation is virtually complete.
(i) finely divided Os or U
(ii) Finely divided Ni deposited over pumice stone HNO 3 + H 2 O H 3 O + + NO 3-
(iii) Fe(OH)3 with traces of SiO2 and K2O Thus it reacts with basic oxides, hydroxides, carbonates etc.
(b) Cyanamide process :
CaO + 2H 3 O + ® Ca 2+ + 3H 2 O
CaC2 + N 2 ® (CaCN 2 + C)
Nitrolim As oxidising agent
Mixture of Calcium Cyanamide and graphite under the name
NO 3- + 2 H 3O + + e - ¾¾¾® NO 2 + 3H 2 O
conc .
of nitrolim is used as fertilizer.
NO 3 + 4H 3O + + 3e - ¾¾® NO + 6 H 2 O
dil.
CaCN 2 + 3H 2O ® CaCO 3 + 2 NH 3
(c) Serpeks process : As by product during hydrolysis of AlN or 2HNO 3 ® H 2O + 2 NO 2 + O (concentrated HNO3)
AlN + 3H 2O ® Al(OH )3 + NH 3
2HNO 3 ® H 2 O + 2 NO + 3O (dil. HNO3)
Properties : Colourless gas, characteristic pungent odour,
brings tears into eyes, collected by downward displacement Oxidation of non metals, - ic acids are formed eg.
of air. Extremely soluble in water due to H-bonding. It is a S + H 2O + 3O ® H 2SO 4 (Sulphuric acid)
strong lewis base.
C + H 2O + 2O ® H 2 CO 3 (Carbonic acid)
* Ammonia is dried over any metal oxide but CaO is
cheaper. 2P + 3H 2 O + 5O ® 2H 3PO 4 (Phosphoric acid)
* When passed through alkaline solution of Nesslers
I 2 + H 2 O + 5O ® 2HIO 3 (Iodic acid)
reagent a brown coloured complex known as Millon’s
base is formed. 3As + 3H 2 O + 5O ® 2H 3AsO 4 (Arsenic acid)
2K2HgI4 + 3KOH + NH3
Sn + H 2 O + 2O ® H 2SnO3 (meta stannic acid)
I
Hg Hg + 7KI + 2H2O Se + H 2 O + 2O ® H 2SiO 3 (selenious acid)
I O NH2
Millon’s base Te + H 2 O + 2O ® H 2TeO 3 (Tellurous acid)
672 Chemistry
Oxidation of compounds : Conc. HCl). eg.:
2HNO 3 ® H 2O + 2 NO 2 + O , SO 2 + H 2 O + O ® H 2SO 4 HNO 3 + 3HCl ® NOCl + 2 H 2 O + 2Cl
nascent
H 2S + O ® H 2 O + S , 2HBr + O ® H 2O + Br2 chlorine
..
H O H O
ï .. .. .. ..
2HNO3 + 8H ® N 2 O + 5H 2O ý secondary reactions O N
.. O
.. N
2HNO3 + 10H ® N 2 + 6H 2 O ï
.. .
O
.. .
O
ï
.
..
.
2HNO3 + 16H ® 2NH3 + 6H 2O ïþ Uses : In the manufacture of fertilizers ii) For purification of silver
and gold iii) In the manufacture of explosives iv) oxidising reagent
Factors affecting the secondary reactions v) As nitrating reagent
i) Nature of the metal ii) Concentration of the acid NITROUS ACID (HNO2) :
iii) Temperature iv) Presence of impurities Preparation :
Action of nitric acid on zinc under different conditions
(i) Cold and very dil. acid evolves ammonia which reacts with (i) Ba ( NO 2 ) 2 + H 2SO 4 (dil.) ® BaSO 4 ¯ +2HNO 2
HNO3 forming ammonium nitrate (ii) 2NaNO 2 + H 2SO 4 ® Na 2SO 4 + 2HNO 2
4Zn + 10HNO 3 ® 4Zn( NO3 ) 2 + 3H 2 O + NH 4 NO3
(iii) N 2O 3 + H 2O ® 2HNO 2
(ii) Cold and dil HNO3
(iv) NH 3 + 3H 2O 2 ® HNO 2 + 4H 2 O
4Zn + 10HNO 3 ® 4Zn ( NO 3 ) 2 + 5H 2O + N 2 O
Properties : It has slight bluish colour in solution may be due to
(iii) Cold and moderately conc.
anhydride N2O3. It is very unstable.
3Zn + 8HNO 3 ® 3Zn( NO3 ) 2 + 4H 2O + 2 NO (i) Decomposition :
(iv) Cold and concentrated
3HNO 2 ® 2 NO + HNO 3 + H 2 O (auto oxidation)
Zn + 4HNO 3 ® Zn( NO3 ) 2 + 2H 2O + 2NO 2
(ii) Action of heat :
Action of nitric acid on Copper under different conditions
2HNO 2 ® H 2O + N 2 O3 ® NO 2 + NO
(i) Cold and dil.
4Cu + 10HNO 3 ® 4Cu( NO3 ) 2 + 5H 2O + N 2O (iii) Oxidising nature : 2HNO 2 ® 2 NO + H 2O + O
(ii) Cold and moderately concentrated H + + HNO 2 + e - ® H 2 O + NO (electron acceptor)
3Cu + 8HNO 3 ® 3Cu ( NO 3 ) 2 + 4H 2O + 2NO
(iv) Reducing nature : HNO 2 + O ® HNO 3
(iii) Cold and concentrated
Cu + 4HNO 3 ® Cu( NO3 ) 2 + 2H 2O + 2 NO 2 H 2 O + HNO 2 ® HNO 3 + 2H + + 2e - (electron donor)
(iv) Hot and conc. (v) Reaction with ammonia :
5Cu + 12HNO 3 ® 5Cu ( NO 3 ) 2 + 6H 2O + N 2 NH 3 + HNO 2 ® NH 4 NO 2 ® N 2 + 2H 2O
Metals like Mg and Mn give hydrogen with dil. HNO3 (vi) Formation of diazonium compounds :
Mg + 2HNO 3 ® Mg( NO3 ) 2 + H 2 C 6 H 5 NH 2 HCl + HNO 2 ® C6 H 5 N = NCl + 2H 2O
Uses : In the manufacture of azo dyes.
Mn + 2HNO 3 ® Mn ( NO 3 ) 2 + H 2
Structure : It is a tautomeric mixture of the following forms
Passivity : Metals like, Fe, Cr, Ni, Al or Co become inactive or ..
passive due to stable oxide layers. O
..
.. .. .. ..
Noble Metals like Pt, Pd, Os, Ir and Au do not react with nitric H O
.. N O
.. H N
.. .
acid. They react with aqua regia (1 vol. Conc. HNO3 + 3 vol. O
.
The p-Block Elements - Nitrogen Family 673
PHOSPHOROUS : (ii) With metals :
Discovered by Brand 3Na + P ® Na 3P 3Ca + 2P ® Ca 3P2
Occurence : It occurs in combination only as phosphates (iii) With compounds :
(i) Phosphorite Ca3(PO4)2
4P + 3NaOH + 3H 2 O ® 3NaH 2 PO 2 + PH 3
(ii) Chlorapatite CaCl2.3Ca3(PO4)2
(iii) Fluorapatite CaF2.3Ca3(PO4)2. P + 5HNO 3 ® H 3PO 4 + H 2O + 5NO 2
In phosphoproteins of brain, bones, teeth, milk, egg, nervous 2P + 5H 2SO 4 ® 2H 3PO 4 + 2H 2O + 5SO 2
tissues of animal and plants.
Uses :
Manufacturing : By reduction of calcium phosphate with carbon
In matches, explosives, as rat poison and in fertilizers and alloys.
in presence of SiO2 in an electric furnance
Match box :
2Ca 3 (PO 4 ) 2 + 6SiO 2 ® 6CaSiO 3 + P4 O10 Side contains : Red P or P2S3 + Sand + Glue
P4O10 + 10C ® P4 + 10CO On tip : Red P + Oxidising agent like KClO3 or KNO3 or Pb3O4
+ glass powder or chalk for friction + glue
Purification : By melting under acidified solution of K2Cr2O7.
The impurities are oxidised and redistilled. PHOSPHINE (PH3) :
Properties : Freshly prepared phosphorous is colourless. On Preparation :
standing acquires pale lemon colour due to formation of red (i) Any phosphide +H2O ® PH3
phosphorus on the surface. It is therefore called yellow
phosphorous. Due to its poisonous nature the jaw bones decay Ca3P2 + H2O ® 2PH3 + Ca(OH)2
and disease is known as “Phossy jaw” Na3P + 3H2O ® PH3 + 3NaOH
Allotropic forms of phosphorous and their preparation :
i) Red phosphorous : It is prepard by carefully heating yellow 2AlP + 3H 2SO 4 ® 2PH 3 + Al 2 (SO 4 )3
phosphorous in an inert atmosphere for about 8 days. (ii) Decomposition of H3PO3 :
ii) Violet phosphorous : By crystallisation of white 4H 3 PO 3 ® 3H 3PO 4 + PH 3
phosphorous from molten lead
(iii) Lab. method :
iii) Scarlet :
1. By exposing the solution of red P in PBr 3 to light or by 4P + 3NaOH + 3H 2 O ® 3NaH 2 PO 2 + PH 3
boiling.
(iv) Pure PH3 : PH 4 I + NaOH ® PH 3 + NaI + H 2 O
2. By heating PBr 3 with Hg at 513 K
Properties : Colourless, highly poisonous, with rotten fish odour
4PBr3 + 6Hg ® 6HgBr2 + P4 gas, slightly soluble in water
iv) Black : By heating white P to 473K under 1000kg/sq. cm.. It Chemical properties :
is the most stable form, good conductor of electricity.
(i) Basic nature : PH 3 + HI ® PH 4 I
Some points of distinction between white and red phosphorous
Property White Red (ii) Decomposition : 4PH 3 ¾311K
¾¾® P4 + 6 H 2
P P P P
Very Short/Short Answer Questions 19. If you touch concentrated HNO3 with your finger and
immediately wash it with water, then the skin at the place
1. On being slowly passed through water, PH3 forms bubbles where it came into contact with HNO3 becomes yellow. This
but NH3 dissolves. Why is it so? is because of :
2. What is the difference between the nature of pi-bonds present (a) the formation of Xanthoprotein
in H3PO3 and HNO3? (b) the absorption of HNO3 by skin
3. NO2 is coloured but its dimer is colourless. Why? (c) the blood absorbing HNO3
4. N atom possesses 5 valence electrons but does not form (d) the absorption of yellow/brown NO2 gas
20. PCl5 is possible but NCl5 does not exist :
NCl5. Why?
(a) in N, d-sub-shell is absent
5. NF3 is an exothermic compound but NCl3 is an endothermic (b) ionization energy of N is very high
compound. Explain. (c) it does not like Cl
6. What is laughing gas? How is it prepared? (d) none of these
7. PCl5 is ionic in nature in the solid state. Why? 21. The boiling points of the following hydrides follow the order
8. In trimethylamine, nitrogen has a pyramidal geometry of
whereas in trisilylamine N(SiH3)3 it has a planar geometry? (a) SbH 3 > NH 3 > AsH 3 > PH 3
9. Molecular nitrogen N2 is not particularly reactive. Explain. (b) NH 3 > AsH 3 > PH 3 > SbH 3
10. NH3 is more basic than PH3. Explain.
(c) SbH 3 > AsH 3 > PH 3 > NH 3
11. Present a comparative account of proton affinities of NH3
and PH3. (d) NH 3 > PH 3 > AsH 3 > SbH 3
12. Which of the following is/are not known and why: PCl3, 22. Which of the following statements is not correct for
AsCl3, SbCl3, NCl5, BiCl5 nitrogen ?
(a) Its electronegativity is very high
13. Both PCl+4 and SiCl4 have tetrahedral structures. Explain.
(b) d-orbitals are available for bonding
Long Answer Questions (c) It is a typical non-metal
(d) Its molecular size is small
14. In what ways nitrogen differs in its chemical behaviour from 23. The structural formula of hypophosphorous acid is
that of its heavier congeners? O O
15. Discuss the pattern of variation in the oxidation states of P P P
to Bi (a) H (b) H
OH OH
H OH
Multiple Choice Questions O O
16. Which one of the following statements is true for HNO2 ? P P
(c) HO (d) H
(a) It can not act as reducing agent OH OOH
(b) It can not act as oxidising agent OH OH
24. Producer gas is a mixture of :
(c) It can not act both as oxidant reductant
(a) CO and N 2 (b) CO 2 and H 2
(d) It is stable only in aqueous solution.
17. Of the following which is paramagnetic and has three (c) N 2 and O 2 (d) CH 4 and N 2
electron bond in its structure 25. Which of the following oxides of nitrogen is a coloured
(a) N2O (b) NO gas?
(a) N2O (b) NO
(c) N2O3 (d) N2O5
(c) N2O5 (d) NO2
18. With respect to protonic acids, which of the following 26. Which is the most thermodynamically stable allotropic form
statements is correct ? of phosphorus?
(a) PH3 is more basic than NH3 (a) Red (b) White
(b) PH3 is less basic than NH3 (c) Black (d) Yellow
(c) PH3 is equally basic as NH3 27. The number of P – O – P bonds in cyclic metaphosphoric
acid is
(d) PH3 is amphoteric while NH3 is basic.
(a) zero (b) two (c) three (d) four
676 Chemistry
1. Which one of the following elements is most metallic ? 13. The one which does not form pentachloride is
(a) P (b) As (a) nitrogen (b) phosphorus
(c) Sb (d) Bi (c) arsenic (d) antimony
2. In NH3 and PH3 the common is 14. Which of the following compounds does not exist?
(a) odour (b) combustibility (a) AsCl5 (b) SbCl3
(c) basic nature (d) None of these (c) BiCl5 (d) SbCl5
3. Which element from group 15 gives most basic compound 15. What is hybridization of P in PCl5 ?
with hydrogen (a) sp3 (b) sp3d 2
(a) Nitrogen (b) Bismuth
(c) sp3d (d) sp2
(c) Arsenic (d) Phosphorus
16. Nitrous oxide is
4. Ionic radii (in Å) of As3+, Sb3+ and Bi3+ follow the order
(a) soluble in cold water (b) soluble in hot water
(a) As3+ > Sb3+ > Bi3+ (b) Sb3+ > Bi3+ >As3+
3+ 3+
(c) Bi > As > Sb 3+ (d) Bi3+ > Sb3+ > As3+ (c) acidic in nature (d) None of these
5. The three important oxidation states of phosphorus are 17. Which of the following oxides of nitrogen reacts with FeSO4
(a) –3, +3 and +5 (b) –3, +3 and –5 to form a dark brown compound
(c) –3, +3 and +2 (d) –3, +3 and +4 (a) N2O (b) NO
6. The basic character of hydrides of the group 15 elements (c) NO2 (d) N2O3
decreases in the order 18. Which of the following oxides is the most acidic?
(a) SbH3 > PH3 > AsH3 > NH3 (a) N2O5 (b) P2O5
(b) NH3 > SbH3 > PH3 > AsH3 (c) As2O 5 (d) Sb2O5
(c) NH3 > PH3 > AsH3 > SbH3 19. In the reaction
(d) SbH3 > AsH3 > PH3 > NH3 4HNO 3 + P4 O10 ® 4HPO 3 + X , the product X is
7. The stability of the hydrides follows the order
(a) NH3 > PH3 > AsH3 > SbH3 (a) N2O5 (b) N2O3
(b) NH3 < PH3 < AsH3 < SbH3 (c) NO2 (d) H2O
(c) PH3 > NH3 > AsH3 > SbH3 20. Which oxide of nitrogen is obtained on heating ammonium
(d) AsH3 > NH3 > PH3 > SbH3 nitrate at 250ºC ?
8. In nitrogen family, the H-M-H bond angle in the hydrides (a) Nitric oxide (b) Nitrous oxide
gradually becomes closer to 90º on going from N to Sb. This (c) Nitrogen dioxide (d) Dinitrogen tetraoxide
shows that gradually
(a) the basic strength of the hydrides increases 21. Which of the following can be used as an anaesthesia ?
(b) almost pure p-orbitals are used for M-H bonding (a) N2O (b) NO
(c) the bond energies of M-H bonds increases (c) NCl3 (d) NO2
(d) the bond pairs of electrons become nearer to the central
atom 22. The brown ring test for NO -2 and NO 3- is due to the
9. The boiling points of the following hydrides follow the order formation of complex ion with a formula
(a) SbH3 > NH3 > AsH3 > PH3 (a) [Fe(H2O)6]2+ (b) [Fe(NO)(CN)5]2+
(b) NH3 > PH3 > AsH3 > SbH3 (c) [Fe(H2O)5NO] 2+ (d) [Fe(H2O)(NO)5]2+
(c) NH3 > AsH3 > PH3 > SbH3 23. A deep brown gas is formed by mixing two colourless gases
(d) SbH3 > AsH3 > NH3 > PH3 which are
10. Which of the following has highest dipole moment? (a) NO2 and O2 (b) N2O and NO
(a) NH3 (b) PH3 (c) NO and O2 (d) NH3 and HCl
(c) AsH3 (d) SbH3 24. Which one of the following oxides of nitrogen is blue solid ?
11. The correct sequence of decrease in the bond angle of the (a) NO (b) N2O3
following hydrides is
(c) N2O (d) N2O5
(a) NH3 > PH3 > AsH3 > SbH3
25. Of the following compounds, the most acidic is
(b) NH3 > AsH3 > PH3 > SbH3
(a) As 2O30 (b) P2O5
(c) SbH3 > AsH3 > PH3 > NH3
(d) PH3 > NH3 > AsH3 > SbH3 (c) Sb2O3 (d) Bi2O3
12. Among the trihalides of nitrogen which one is most basic ? 26. Which of the following is a cyclic phosphate ?
(a) NF3 (b) NCl3 (a) H3P3O10 (b) H6P4O13
(c) NI3 (d) NBr3 (c) H5P5O15 (d) H7P5O16
The p-Block Elements - Nitrogen Family 677
27. The structural formula of hypophosphorous acid is 39. Ammonia can be dried by
O O (a) conc. H2SO4 (b) P4O10
(c) CaO (d) anhydrous CaCl2
P P 40. The shape of ammonia molecule is
(a) H OH (b) H OH (a) tetrahedral (b) pyramidal
H OH
(c) planar triangle (d) octahedral
O O 41. P4O10 is not used to dry NH3 gas because
P (a) P4O10 reacts with moisture in NH3
P
(c) HO OH (d) OH OOH (b) P4O10 is not a drying agent
OH OH (c) P4O10 is acidic and NH3 is basic
28. P—O—P bond is present in (d) P4O10 is basic and NH3 is acidic
(a) H4P2O6 (b) H4P2O5 42. When ammonia is heated with cupric oxide, a molecule of
(c) Both (a) and (b) (d) Neither (a) nor (b) ammonia will
29. Orthophosphoric acid is (a) gain 3 electrons (b) lose 3 electrons
(a) monobasic (b) dibasic (c) gain 2 electrons (d) lose 2 electrons
(c) tribasic (d) tetrabasic 43. Brown colour in HNO3 can be removed by
30. The oxyacid of phosphorous in which phosphorous has the (a) adding Mg powder
lowest oxidation state is (b) boiling the acid
(a) hypophosphorous acid (c) passing NH3 through acid
(b) orthophosphoric acid (d) passing air through warm acid
(c) pyrophosphoric acid 44. HNO2 acts as an/a
(d) metaphosphoric acid (a) acid (b) oxidising agent
31. The number of P—O—P bonds in cyclic metaphosphoric (c) reducing agent (d) All the above
acid is 45. Which of the following phosphorus is most reactive ?
(a) zero (b) two (a) Red phosphorus (b) White phosphorus
(c) three (d) four (c) Scarlet phosphorus (d) Violet phosphorus
32. The triple bond between N atoms of nitrogen molecule 46. White phosphorus is
( N º N ) consists of (a) a monoatomic gas
(b) P4, a tetrahedral solid
(a) three s-bonds
(c) P8, a crown
(b) two s-bonds and one p-bond
(d) a linear diatomic molecule
(c) one s-bond and two p-bonds
47. One mole of calcium phosphide on reaction with excess of
(d) three p-bonds
water gives
33. The molecule having bond order 3 is
(a) one mole of phosphine
(a) H2 (b) N2
(b) two moles of phosphoric acid
(c) O2 (d) He +2 (c) two moles of phosphine
34. An element (X) forms compounds of the formula XCl3, X2O5 (d) one mole of phosphorus oxide
and Ca3X2 but does not form XCl5. Which of the following is 48. PH3, the hydride of phosphorus is
the element X ? (a) metallic (b) ionic
(a) B (b) Al (c) non-metallic (d) covalent
(c) N (d) P 49. The acid which forms two series of salts is
35. Which of the following is obtained when N2 reacts with (a) H3PO4 (b) H3PO3
calcium carbide ? (c) H3BO3 (d) H 3 PO -2
(a) Calcium cyanate (b) Calcium acetate 50. The equivalent weight of phosphoric acid (H3PO4) in the
(c) Calcium cyanamide (d) Calcium carbonate reaction
36. On heating ammonium dichromate, the gas evolved is
(a) oxygen (b) ammonia NaOH + H 3PO 4 ® NaH 2 PO 4 + H 2O is
(c) nitrous oxide (d) nitrogen (a) 25 (b) 49
37. What causes nitrogen to be chemically inert ? (c) 59 (d) 98
(a) Multiple bond formation in the molecule 51. In the following reaction
(b) Absence of bond polarity H O
PCl 5 ¾¾2¾® HCl + A
(c) Short internuclear distance
(d) High bond energy the product ‘A’ is
38. In which the NH3 is not used ? (a) H2P2O4 (b) H2P2O7
(a) Cold storage (c) H3PO4 (d) H3PO3
(b) Anaesthetic 52. Which of the following undergoes sublimation
(c) Manufacture of rayon and plastic (a) ZnCl2 (b) CuCl2
(d) None of these (c) AgCl (d) NH4Cl
678 Chemistry
53. BCl3 is a planar molecule whereas NCl3 is pyramidal because 63. The nitride ion in lithium nitride is composed of
(a) BCl3 has no lone pair of electrons but NCl3 has a lone (a) 7 Protons + 10 electrons (b) 10 Protons + 10 electrons
pair of electrons (c) 7 Protons + 7 electrons (d) 10 Protons + 7 electrons
(b) B—Cl bond is more polar than N—Cl bond 64. Which of the following leaves no residue on heating ?
(c) nitrogen atom is smaller than boron atom (a) Pb(NO3)2 (b) NH4NO3
(d) N—Cl bond is more covalent than B—Cl bond (c) Cu(NO3)2 (d) NaNO3
54. The electronic configuration of an elements is 1s2 2s2 2p6 65. Which of the following molecules is linear ?
3s2 3p6 3d10 4s2 4p3. Its properties would be similar to which (a) SO2 (b) NO +2
(c) NO 2 - (d) SCl2
of the following elements ?
(a) Boron (b) Oxygen 66. A metal X on heating in nitrogen gas gives Y. Y on treatment
(c) Nitrogen (d) Chlorine with H2O gives a colourless gas which when passed through
55. Which of the following has least covalent P—H bond ? CuSO4 solution gives a blue colour. Y is
(a) Mg(NO3)2 (b) Mg3N2
(a) PH3 (b) P2 H 62+ (c) NH3 (d) MgO
67. Which one of the following molecules will have bonds of
(c) P2 H 5+ (d) PH +4 unequal lengths ?
56. Among the followng species, identify the isostructural pairs (a) NF3 (b) BF3
(c) PF5 (d) SF6
NF3 , NO 3- , BF3 , H 3 O + , HN 3 68. In which of the following the bond angle is maximum ?
(a) [ NF3 , NO 3- ] and [BF3 , H 3 O + ] (a) NH3 (b) NH +4
(c) PCl3 (d) SCl2
(b) [ NF3 , HN 3} and [ NO3- , BF3 ]
69. One of the oxidants used with liquid propellants is
+
(c) [ NF3 , H 3O ] and [ NO3- , BF3 ] (a) ammonium perchlorate (b) nitrocellulose
(c) sulphuric acid (d) nItrogen tetroxide (N2O4)
(d) [ NF3 , H 3O + ] and [HN 3 , BF3 ] 70. The aqueous solution/liquid that absorbs nitric oxide to a
considerable extent is
57. In PO 34- ion, the formal charge on each oxygen atom and (a) lead nitrate (b) nitric acid
P—O bond order respectively are (c) ferrous sulphate (d) sodium hydroxide
(a) –0.75, 1.25 (b) –3, 1.25 71. Which one of the following arrangements of molecules is
(c) –0.75, 1.0 (d) –0.75, 0.6 correct on the basis of their dipole moments ?
58. In nitroprusside ion, the iron and NO exist as Fe++ and NO+ (a) BF3 > NF3 > NH3 (b) NF3 > BF3 > NH3
(c) NH3 > BF3 > NF3 (d) NH3 > NF3 > BF3
rather than Fe+++ and NO. These forms can be differentiated
72. Sodium hexametaphosphate is known as
by
(a) calgon (b) permutit
(a) estimating the concentration of iron
(c) natalite (d) nitrolim
(b) measuring the concentration of CN - 73. The oxidation number of As in H 2 AsO -4 is
(c) measuring the solid state magnetic moment (a) +6 (b) +5
(d) thermally decomposing the compound (c) –7 (d) +9
59. Nitrogen atom has an atomic number of 7 and oxygen has an 74. Which of the following compounds is explosive in nature ?
atomic number 8. The total number of electrons in a nitrate (a) Phosphorus trichloride (b) Nitrogen trichloride
ion will be (c) Hyponitrous acid (d) Nitrosyl chloride
(a) 8 (b) 16 75. Among the 15th group elements, as we move from nitrogen
(c) 32 (d) 64 to bismuth, the pentavalency becomes less pronounced and
60. If HNO3 changes into N2O, the oxidation number is changed trivalency becomes more pronounced due to
by (a) Non metallic character (b) Inert pair effect
(a) 2 (b) 6 (c) High electronegativity (d) Large ionization energy
(c) 0 (d) +4
61. The hybridized state of N in R2NH is 76. In NO 3- ion, the number of bond pair and lone pair of
(a) sp3 (b) sp2 electrons on nitrogen atom are
(c) sp (d) dsp 2 (a) 2,2 (b) 3, 1
(c) 1, 3 (d) 4, 0
62. The hybridization of atomic orbitals of nitrogen in NO +2 , 77. Pentavalence in phosphorus is more stable when compared
to that of nitrogen even though they belong to same group.
NO 3- and NH +4 are
This is due to
(a) sp, sp3 and sp2 respectively (a) dissimilar electronic configuration
(b) sp, sp2 and sp3 respectively (b) due to presence of vacant d-orbitals
(c) sp2, sp and sp3 respectively (c) reactivity of phosphorus
(d) sp2, sp3 and sp respectively (d) inert nature of nitrogen
The p-Block Elements - Nitrogen Family 679
1. Which of the following is a nitric acid anhydride? 11. H3PO2 is the molecular formula of an acid of phosphorus. Its
(a) NO (b) NO2 [CBSE PMT 1988] name and basicity respectively are [CBSE PMT 1992]
(c) N2O5 (d) N2O3. (a) Phosphorus acid and two
2. Which of the following metal evolves hydrogen on reacting (b) Hypophosphorous acid and two
with cold dilute HNO3 ? [CBSE PMT 1989] (c) Hypophosphorous acid and one
(a) Mg (b) Al (d) Hypophosphoric acid and two
(c) Fe (d) Cu. 12. Which of the following fertilizers has the highest nitrogen
3. Each of the following is true about white and red phosphorus percentage ? [CBSE PMT 1993]
except that they [CBSE PMT 1989] (a) Ammonium sulphate
(a) Are both soluble in CS2 (b) Calcium cyanamide
(b) Can be oxidised by heating in air (c) Urea
(c) Consist of the same kind of atoms (d) Ammonium nitrate
(d) Can be converted into one another 13. Which of the following oxides will be the least acidic?
4. When orthophosphoric acid is heated to 600°C, the product (a) As4O 6 (b) As 4O10 [CBSE PMT 1996]
formed is [CBSE PMT 1989]
(c) P4O10 (d) P4O6
(a) PH3 (b) P2O5
14. Which of the following oxy-acids has the maximum number
(c) H3PO3 (d) HPO3
of hydrogens directly attached to phosphorus?
5. Which of the following statements is not correct for nitrogen?
(a) H4P2O7 (b) H3PO2 [CBSE PMT 1999]
[CBSE PMT 1990]
(c) H3PO3 (d) H3PO4
(a) Its electronegativity is very high
15. Nitrogen forms N2, but phosphorus is converted into P4 from
(b) d-orbitals are available for bonding
P, the reason is [CBSE PMT 2001]
(c) It is a typical non-metal
(a) Triple bond is present between phosphorus atom
(d) Its molecular size is small
(b) pp – pp bonding is strong
6. P2O5 is heated with water to give [CBSE PMT 1991]
(c) pp – pp bonding is weak
(a) Hypophosphorous acid
(d) Multiple bond is formed easily
(b) Phosphorous acid
(c) Hypophosphoric acid 16. Oxidation states of P in H4 P2O5 , H4 P2O6 , and H4 P2O7 ,
(d) Orthophosphoric acid are respectively: [CBSE-PMT 2010]
7. PCl3 reacts with water to form [CBSE PMT 1991] (a) + 3, + 5, + 4 (b) + 5, + 3, + 4
(a) PH3 (b) H3PO3, HCl (c) + 5, + 4, + 3 (d) + 3, + 4, + 5
(c) POCl3 (d) H3PO4 17. In which of the following compounds, nitrogen exhibits
8. PH4I + NaOH forms [CBSE PMT 1991] highest oxidation state ? [CBSE-PMT 2012 S]
(a) PH3 (b) NH3 (a) N2H4 (b) NH3
(c) P4O6 (d) P4O10 (c) N3H (d) NH2OH
9. Pure nitrogen is prepared in the laboratory by heating a 18. Which of the following statements is not valid for oxoacids
mixture of [CBSE PMT 1991] of phosphorus? [CBSE-PMT 2012 S]
(a) NH4OH + NaCl (b) NH4 NO3 + NaCl (a) Orthophosphoric acid is used in the manufacture of triple
(c) NH4 Cl + NaOH (d) NH4 Cl + NaNO2. superphosphate.
10. Sugarcane on reaction with nitric acid gives (b) Hypophosphorous acid is a diprotic acid.
(a) CO2 and SO2 [CBSE PMT 1992] (c) All oxoacids contain tetrahedral four coordinated
(b) (COOH)2 phosphorus.
(c) 2 HCOOH (two moles) (d) All oxoacids contain atleast one P = O and one P — OH
(d) No reaction. group.
680 Chemistry
19. In case of nitrogen, NCl3 is possible but not NCl5 while in 24. The decreasing values of bond angles from NH3 (106º) to
case of phosphorous, PCl3 as well as PCl5 are possible. It is SbH3 (101º) down group-15 of the periodic table is due to
due to [AIEEE 2002] (a) decreasing lp-bp repulsion [AIEEE 2006]
(a) availability of vacant d orbitals in P but not in N (b) decreasing electronegativity
(b) lower electronegativity of P than N (c) increasing bp-bp repulsion
(c) lower tendency of H-bond formation in P than N (d) increasing p-orbital character in sp3
(d) occurrence of P in solid while N in gaseous state at room 25. Regular use of which of the the following fertilizers increases
temperature.
the acidity of soil? [AIEEE 2007]
20. Number of sigma bonds in P4O10 is [AIEEE 2002]
(a) Ammonium sulphate
(a) 6 (b) 7
(b) Potassium nitrate
(c) 17 (d) 16.
(c) Urea
21. What may be expected to happen when phosphine gas is
(d) Superphosphate of lime.
mixed with chlorine gas ? [AIEEE 2003]
(a) PCl3 and HCl are formed and the mixture warms up 26. The reaction of P4 with X leads selectively to P4O6. The X is
(b) PCl5 and HCl are formed and the mixture cools down (a) Dry O2 [IIT-JEE 2009]
(c) PH3 . Cl2 is formed with warming up (b) A mixture of O2 and N2
(d) The mixture only cools down (c) Moist O2
22. Which one of the following substances has the highest (d) O2 in the presence of aqueous NaOH
proton affinity? [AIEEE 2003] 27. Extra pure N2 can be obtained by heating [IIT-JEE 2011]
(a) H2S (b) NH3 (a) NH3 with CuO (b) NH4NO3
(c) PH3 (d) H2O (c) (NH4)2Cr2O7 (d) Ba(N3)2
23. The number of hydrogen atom(s) attached to phosphorus 28. Concentrated nitric acid, upon long standing, turns yellow
atom in hypophosphorous acid is [AIEEE 2005] brown due to the formation of [JEE Advanced 2013]
(a) three (b) one (a) NO (b) NO2
(c) two (d) zero (c) N2O (d) N2O4
1. Phosphine on reaction with hydrobromic acid gives 5. The nitrate which when heated gives off a gas or a mixture of
(a) PBr3 (b) PH4Br gases which cannot relight a glowing splinter is
(c) PBr5 (d) P2H4 (a) sodium nitrate (b) ammonium nitrate
2. An inorganic compound producing organic compound on (c) lead nitrate (d) potassium nitrate
heating is 6. Liquid ammonia bottles are opened after cooling them in ice
(a) sodamide for sometime. It is because liquid NH3
(b) ammonium cyanate (a) Brings tears to the eyes
(c) sodalime (b) Has a high vapour pressure
(d) potassium cyanide (c) Is a corrosive liquid
3. Which is not correct for N2O ? (d) Is a mild explosive
(a) It is laughing gas and is used as anaesthetic agent. 7. Ammonia is generally manufactured for fertilizers by the
(b) It is nitrous oxide reaction
(c) It is not a linear molecule. (a) 2 NH 4 Cl + Ca (OH ) 2 ® CaCl 2 + 2H 2 O + 2 NH 3
(d) It is least reactive of all the oxides of nitrogen
(b) By passing an electric discharge in a mixture of N 2 and
4. An important method of fixation of atmospheric N2 is
H2
(a) Fisher- Tropsch’s process
(c) By passing a mixture of N2 and H2 under high pressure
(b) Haber’s process
and moderate temperature over a catalyst
(c) Frasch’s process
(d) None of these
(d) Solvay’s process
The p-Block Elements - Nitrogen Family 681
8. Nitrogen can be purified from the impurities of oxides of 19. Ammonia, on reaction with hypochlorite anion, can form
nitrogen and ammonia by passing through (a) NO (b) NH4Cl
(a) conc. HCl (c) N2H4 (d) HNO2
(b) alkaline solution of pyrogallol 20. The catalyst used in the manufacture of HNO 3 by Ostwald’ss
(c) a solution of K2Cr2O7 acidified with H2SO4
process is :
(d) a solution of KOH
(a) platinum gauze (b) vanadium pentoxide
9. Ammonium dichromate is used in some fire works. The green
(c) finely divided nickel (d) platinum black .
coloured powder blown is
21. The deep blue colour produced on adding excess of ammonia
(a) CrO3 (b) Cr2O3
to copper sulphate is due to presence of
(c) Cr (d) CrO(O2)
2+
10. Phosphine is not obtained by which of the following reaction (a) Cu 2 + (b) Cu ( NH 3 ) 4
(a) White P is heated with NaOH
(c) Cu ( NH 3 ) 26 + (d) Cu( NH3 ) 22 +
(b) Red P is heated with NaOH
(c) Ca3P2 reacts with water 22. Ammonia on catalytic oxidation gives an oxide from which
(d) Phosphorus trioxide is boiled with water nitric acid is obtained. The oxide is :
11. Phosphine is not evolved when (a) N 2 O3 (b) NO
(a) white phosphorus is boiled with a strong solution of
(c) NO 2 (d) N 2 O5
Ba(OH)2
(b) phosphorus acid is heated 23. The dipole moment of NF3 is less than NH 3 because
(c) calcium hypophosphite is heated
(a) NH 3 forms associated molecules.
(d) metaphosphoric acid is heated.
(b) F is more reactive than H.
12. Pure phosphine is not combustible while impure phosphine
is combustible, this combustibility is due to presence of (c) The resultant of bond polarity is less.
(d) The resultant of individual polarities is opposed by the
(a) P2 H 4 (b) N2 polarity of lone pair.
(c) PH 5 (d) P2 O5 24. Which property of white phosphorus is common to
red P
13. A white precipitate is obtained on hydrolysis of
(a) It burns when heated in air.
(a) PCl5 (b) NCl3 (b) It reacts with hot caustic soda solution to give
(c) BiCl 3 (d) AsCl3 phosphine.
(c) It shows chemiluminescence.
14. Calcium cyanamide on treatment with steam under pressure
gives NH3 and (d) It is soluble in carbon disulphide.
25. Fixation of nitrogen means :
(a) CaCO3 (b) Ca (OH) 2
(a) reaction of nitrogen with oxygen.
(c) CaO (d) CaHCO3 (b) conversion of free atmospheric nitrogen into nitrogen
15. Which of the following statements is not true ? compounds.
(a) NO2 can be prepared by heating Pb(NO3)2 (c) the action of denitrifying bacteria on nitrogen
compounds.
(b) NO2 is red - brown gas
(d) decomposition of nitrogenous compounds to yield free
(c) NO2 is diamagnetic
nitrogen.
(d) NO2 readily dimerises to N2O4
16. Hydrolysis of PI3 yields 26. Conc. HNO 3 is heated with P2 O5 to form :
(a) monobasic acid and a salt (a) NO 2 (b) NO
(b) monobasic acid and dibasic acid
(c) dibasic acid and tribasic acid (c) N 2 O5 (d) N 2 O
(d) monobasic acid and tribasic acid 27. Superphosphate of lime is obtained from the reaction of :
17. If 20% nitrogen is present in a compound its minimum (a) Bones with gypsum
molecular weight can be (b) Calcium phosphate with sulphuric acid
(a) 144 (b) 70 (c) Calcium phosphate with HCl
(c) 100 (d) 140 (d) Calcium carbonate with phosphoric acid
18. Blasting of TNT is done by mixing it with 28. Orthophosphoric acid on heating gives :
(a) NH4Cl (b) NH4NO3 (a) metaphosphoric acid (b) phosphine
(c) NH4NO2 (d) (NH4)2SO4 (c) phosphorus pentoxide (d) phosphorus acid
682 Chemistry
EXERCISE 1 14. (c) Due to inert pair effect the lower O.S. is more common at
the bottom of group
1. This is because PH3 is much weaker base than NH3.
NH3 dissolves in water forming NH4OH. 1
15. (c) Hybridisation in PCl5 = (5 + 5 + 0 - 0) = 5 sp3d
NH + H O NH + + OH– 2
3 2 4
2. In H3PO3, there is pp – dp bond whereas in HNO3 there is 16. (a) N2O is soluble in cold and not in hot water
pp – pp bond. pp – pp bond in HNO3 is stronger than pp – 17. (b) FeSO 4 + NO ® FeSO 4 .NO
dp bond in H3PO3.
18. (a) In N2O5 nitrogen is present in the highest O.S. and it is
3. NO2 has unpaired electron and due to this, it has brown most electronegative in nature than others
colour. N2O4 does not have unpaired electron and thus it is
19. (a) See preparation of N2O5
colourless.
20. (b) N2O (see text)
4. N atom does not have d-orbitals and thus it cannot have all
21. (a) N2O is used as anaesthetic
five valence electrons as unpaired.
22. (c) [Fe(H2O)5NO]2+ ion is formed
5. F is highly electronegative and N – F bond energy is higher
than N – Cl bond energy. 23. (c) 2NO + O 2 ® 2 NO 2 brown
6. N2O is laughing gas prepared by heating NH4NO 3 . 24. (b) N2O3 is blue solid
D 25. (b) P2O5 ;P is electronegative and present in highest O.S. of
NH 4 NO3 ¾¾® N 2 O + 2H 2 O
5, hence P2O5 is most acidic
7. PCl5 is ionic in the solid state because it exists as [PCl4]+
26. (c) H5P5O15 (HPO3)5. It is metaphosphoric acid which is a
[PCl6]–.
cyclic phosphate.
16. (d) 17. (b) 18. (b) 19. (a) 20. (a)
27. (b) See structures of oxy acids of phosphorous
21. (a) 22. (b) 23. (a) 24. (a) 25. (d)
28. (b) H4P2O5 is pyrophosphorous acid it contains P–O–P
26. (c) 27. (c) bond
EXERCISE 2 29. (c) H3PO4 is tribasic
30. (a) Hypophosphorous acid is H3PO2 in which O.S. of P is
1. (d) Metallic character increases down the group, Bi is most +1
metallic
31. (c) See structure of metaphosphoric acid.
2. (c) Basic nature
32. (c) One s and two p
3. (a) Nitrogen; NH3 is most basic .. ..
4. (d) Ionic radii increases down the group 33. (b) It is N º N
5. (a) –3, +3, +5 (see text) 34. (c) Nitrogen can form NCl3, N2O5 Ca3N2 and not NCl5 since
6. (c) it has no d atomic orbitals in valence shell
7. (a) 35. (c) CaC2 + N 2 ® (CaCN 2 + C)
8. (b) With the decrease in the electronegativity of central atom Calcium cyanamide
the bond angle decreases
D
9. (a) 36. (d) (NH 4 ) 2Cr2 O 7 ¾¾
® Cr2 O3 + 4H 2 O + N 2
10. (a) Dipole moment decreases with decrease in 37. (d) The cause of inert nature of N2 is the presence of triple
electronegativity of central metal atom .. ..
11. (a) bond N º N
12. (c) The lesser the electronegativity of halogen in NX3 the 38. (b) NH3 is not used as anaesthetic
more is the basic character. N can donate more electrons 39. (c) Ammonia is dried over CaO. Others will react with it
in that case. 40. (b) Ammonia has pyramidal shape with sp3 hybridisation.
13. (a) Nitrogen does not contain vacant d orbitals in valence NH
41. (c) P4 O10 + 2 H 2 O ¾
¾® 4HPO 3 ¾¾¾
3 ® NH PO
4 3
shell hence cannot extend its coordination number more basic
Acidic meta phosphoric meta ammonium
than 3 acid phosphate
The p-Block Elements - Nitrogen Family 683
54. (c) The valence shell electronic configuration is 4s24p3 67. (c) PF5 has trigonal pyramidal shape in which axial and
similar to nitrogen 2s2p3 equitorial bonds have different lengths
55. (b) For this calculate the formal charge distributed on each 68. (b) Bond angle in NH +4 is 109º28' due to sp3 hybridisation
P–H bond which is given by = Total charge . and symmetrical structure
No. of P - H bonds 69. (d) N2O4 is used as an oxidant with liquid propellants
The more the formal charge the lesser is the covalent 70. (c) FeSO 4 + NO ® FeSO 4 .NO
character. 71. (d) NH3 > NF3 > BF3. NH3 and NF3 have pyramidal shape.
In BF3 is planar.
+2 +1 +1 d–
P2 H 26 + = = +0.33 ; P2 H 5+ = = +0.2 ; PH 4+ = = +0.25 .. F
6 5 4 N N d+
B F
Hence lowest covalent character of P–H bond is d+H H H d– F
d– F F
F m=0
d–
in P2 H 62+
72. (a) It is calgon (Sodium hexametaphosphate)
56. (c) In NF3 and H3O+ the hybridisation is sp3 and both are
73. (b) H 2 AsO -4 2(1) + x +4(–2)= –1 , \ x = +5
pyramidal. In NO 3- and BF3 the hybridisation is sp2 and
74. (b) NCl3 is explosive in nature.
both are planar 75. (b) Inert pair effect (follow text)
684 Chemistry
.. 12. (c) Urea (46.6%N). % of N in other compound are :
– O
..
( NH 4 ) 2 SO 4 = 21.2%;
..
76. (d) O
.. N .. , Bond pairs = 4, lone pair = 0
O..
CaCN 2 = 35.0% and NH 4 NO 3 = 35.0%
..
77. (b) Phosphorous can achieve coordination number 5 due to 13. (a) As the O.N of the central atom of the compounds
vacant d atomic orbitals in valence shell which is not increases acidic strength of that compound also
possible in nitrogen increases and on moving from top to bottom in groups
acidic strength of oxides also decrease due to decreasing
EXERCISE 3 electronegativity in groups.
1. (c) N 2 O 5 + H 2 O ¾¾® 2 HNO 3 +5 +3 +5 +3
2. (a) Magnesium and manganese are the metals that produce P4O10 > P4O6 > As 4O10 > As 4O6
hydrogen with dilute nitric acid 14. (b)
Mg + 2HNO3 ¾ ¾® Mg (NO3)2 + H2 OH OH
3. (a) Both white and red phosphorus are not soluble in CS2
(a) H4P2O7 ÞO P O P O
only white P is soluble.
OH OH
600°C
4. (d) 2H 3 PO 4 ¾¾¾¾ ® 2HPO 3 Pyrophosphoric acid
ortho phosphoric -2H 2 O meta phosphoric
acid acid O
5. (b) In case of nitrogen, d-orbitals are not available. P
(b) H3PO2 Þ OH H
6. (d) P2O5 have great affinity for water. The final product is H
orthophosphoric acid. Hypophosphorous acid
2H2O O
P4O10 4HPO3
Metaphosphoric (c) H3PO3 Þ HO – P – OH
acid H
2H2O
Phosphorous acid
2H 2O
4H3PO4 2H4P2O7 O
orthophosphoric Pyrophosphoric
acid acid (d) H3PO4 Þ HO – P – OH
OH
7. (b) PCl3 + 3H 2 O ® H 3PO 3 + 3HCl orthophosphoric acid
8. (a) PH 4 I + NaOH ® NaI + PH 3 + H 2 O 15. (c) Nitrogen form N2 (i.e. N º N) but phosphorus form P4,
because in P2, pp — pp bonding is present which is a
9. (d) Pure nitrogen in the lab can be obtained by heating
weaker bonding.
ammonium nitrate. Ammonium nitrate is not a stable
16. (d)
compound it dissociate to give nitrogen.
17. (c) Compound Oxidation number of nitrogen
Heat
NH 4 Cl + NaNO 2 ¾¾¾® NH 4 NO 2 N2H4 = –2
NH3 = –3
Heat
¾¾¾® N 2 + 2 H 2 O. N3H = –1/3
10. (b) Cane sugar is oxidised to oxalic acid NH2OH = –1
(2HNO 3 ¾¾
® H 2 O + 2NO 2 + O)18
O
C12 H 22 O11 + 18[O] ¾
¾® 6 (COOH) 2
Cane sugar From HNO3 Oxalic acid 18. (b) H P H Hypophosphorous acid (H3PO2) is a
+ 5H 2O. O
H
C12H22O11 + 36HNO3 ¾¾®
6(COOH)2 + 36NO2 + 23H2O monobasic acid. i.e., it has only one ionisable hydrogen
atom or one OH is present.
11. (c) H3 PO2 is named as hypophosphorous acid. As it 19. (a) 7N = 1s2 2s2 2p3; 2 2 6
15P = 1s 2s 2p 3s 3p
2 3
contains only one P – OH group, its basicity is one. In phosphorous the 3 d- orbitals are available.
The p-Block Elements - Nitrogen Family 685
EXERCISE 4
20. (d) O
||
P 1. (b) PH 3 + HBr ® PH 4 Br Phosphorium bromide
O O
D
O P
O
P O 2. (b) NH 4 CNO ¾¾
® NH 2 CONH 2 . Urea is an organic
||
||
O
O P compound
|| O
O 3. (c) N2O has linear structure ( see structure)
4. (b) By Haber’s Process atmospheric nitrogen is converted
21. (a) PH 3 + 3Cl 2 ¾
¾® PCl 3 + 3HCl into NH3.
.. 5. (b) NH 4 NO3 ® N 2O + 2H 2O.
22. (b) Among the given compounds, the NH 3 is most basic.
N2O is non combustible an d non supporter of
Hence has highest proton affinity
combustion. Other nitrates give O2 which supports
H combustion.
|
23. (c) Hypophosphorous acid H - O - P ® O 6. (b) Liquid ammonia has high vapour pressure which is
| lowered down by cooling, otherwise the liquid will bump.
H
7. (c) By Haber’s process
Two H-atoms are attached to P atom. 8. (d) The oxides of nitrogen being acidic in nature are soluble
24 (b) The bond angle decreases on moving down the group in KOH which is an alkali.
due to decrease in bond pair-bond pair repulsion. 9. (b) (NH 4 ) 2 Cr2 O 7 ® N 2 + Cr2O 3 + 4H 2O
NH3 PH3 AsH3 SbH3 BiH3 green
107º 94º 92º 91º 90º
10. (b) Red P does not react with NaOH to give PH3.
This can also be explained by the fact that as the size of
11. (d) PH3 is not obtained when metaphosphoric acid is heated.
central atom increases sp3 hybrid orbital becomes more
12. (a) The combustibility of PH3 is due to presence of P2H4.
distinct with increasing size of central atom i.e. pure
The pure PH3 is not combustible.
p-orbitals are utilized in M–H bonding.
25. (a) (NH4)2SO4 + 2H2O¾¾ ® 2H2SO4 + NH4OH 13. (c) BiCl 3 + H 2O ® BiOCl + 2HCl . BiOCl gives white ppt.
H2SO4 being strong acid increases the acidity of soil. In which is used as white pigment, under the name of pearl
case of potassium nitrate and superphosphate of lime on white.
hydrolysis strong base also form along with strong acid 14. (a) CaCN 2 + 3H 2O ® CaCO3 + 2NH3
on hydrolysis results into neutralisation.
15. (c) NO2 is paramagnetic and readily dimerises to N2O4 which
In presence of N 2
26. (b) P4 + 3O 2 ¾¾¾¾¾¾¾® P4 O 6 is diamagnetic.
16. (b) PI 3 + 3H 2 O ® H 3 PO 3 + 3HI
Here N2 acts as a diluent and thus retards further
Dibasic acid Monobasic acid
oxidation. Reaction of P4 under other three conditions.
2O
17. (b) 20% nitrogen means if 20 g N then M.wt = 100
(a) P4 + 3O 2 ¾¾
® P4 O 6 ¾¾¾
2® P O
4 10
(c) In moist air, P4O6 is hydrolysed to form H3PO3 if 14 g N then M.wt = 100 ´ 14 = 70
20
P4 O 6 + 6H 2 O ¾¾
® 4H 3 PO 3
At least one N atom must be present in the molecule.
(d) In presence of NaOH,
18. (b) TNT when mixed with NH4NO3 , gives blasting mixture.
P4 + 3OH - + 3H 2O ¾¾
® PH 3 + 3H 2 PO 2- 19. (c) 2NH3 + OCl– ® NH2.NH2 + H2O + Cl–
27. (d) Very pure N2 can be obtainted by thermal decomposition Pt . gauge
20. (a) 4NH 3 + 5O 2 ¾¾¾¾® 4NO + 6H 2 O
of sodium or barium azide. Ba(N 3 ) 2 ¾¾
® Ba + 3N 2
28. (b) The slow decomposition of HNO3 is represented by the 21. (b) CuSO 4 + 4NH 3 ® [Cu( NH 3 ) 4 ] SO 4
eqn.
4HNO3 ® 4NO2 + 2H2O + O2 Blue complex due to Cu(NH3 )2 +
4
(yellow-brown)
22. (b) 4NH 3 + 5O 2 ® 4NO + 6H 2O
686 Chemistry
24. (a) Except (a) all other properties are shown by white
23. (d) NH 3 N d- phosphorous.
25. (b) The conversion of atmospheric nitrogen to nitrogen
d+
H H d+ compounds is known as fixation of nitrogen.
Hd+
26. (c) P2O 5 + 2HNO 3 ® N 2O 5 + 2HPO 3
S O 119.5 O O O O O
2
SO3. is a gas, sp hybridised and planar in nature.
F F
O O O
F
(b) Tetrahalides - With the exception of SBr4, SI4 and SeI4 S S S
all tetrahalides are known. SF4 is gaseous, SeF4 is liquid
and TeF4 is solid. SCl4 is unstable liquid. These have O O O O O O
The p-Block Elements - Oxygen Family 689
In solid state it exist as a cyclic trimer (SO3)3 a-form or as a 2. Sulphuric acid series
linear chain cross linked sheets
O O O
S O O O
O O
S S S (i) Sulphuric acid H2SO4 HO – S – OH
O S S O
O O O O O O
O
O O O
(ii) Thiosulphuric acid H2S2O3
a-form b- and g- form
SeO2 volatile solid consists of non planar infinite chains
:
O
: :
:
98º O
: :
O O
O O O O
: :
: :
: :
: :
Se 125º Se Se Se H – O – S – O– H or H – O – S – S– H
90º
O O
S
: : O
: :
SeO3 has tetrameric cyclic structure
:
:
O O O O
Se
O O O O (iii)Pyrosulphuric acid H2S2O7 HO – S – O – S – OH
Se Se
O O O O O O
3. Thionic acid series
Se
:
:
O O
: :: :
O O
Oxy acids - Sulphur forms four series of oxy acids
: :
: :
(i) Dithionic acid H2S2O6 HO – S – S – OH
Name Formula Structure
1. Sulphurous acid series O O
: :: :
(ii) Polythionic acid H2SnO6
:
:
(i) Sulpurous acid H2SO3
O O
S HO – S – S n – S – OH
: :
: :
HO OH
O O
:O : (n=3, 4, 5, 6)
(ii) Thiosulphurous acid 4. Peroxy acid series
(i) Peroxomonosulphuric acid
S H2SO5
H2S2O2 HO OH
S O
O HO – S – O – OH
O
(iii)Hyposulphurous acid H2S2O4 HO – S – S – OH
(Caro’s Acid)
O (ii) Peroxodisulphuric acid H2S2O8
O
O O
(iv) Pyrosulphurous acid H2S2O5 HO – S – S – OH HO – S – O – O – S – OH
O O O O
(Marshall’s acid)
Oxy acids of selenium - Selenous acid H2SeO3, Selenic acid
H2SeO4
690 Chemistry
Oxy acids of Tellurium Tellurous acid H2TeO3; Telluric acid (4) Manufacture of KMnO4 and artificial silk.
H2TeO4 Tests:-
OZONE (O3) : (1) Turns starch iodine paper blue.
Discovered by Van Marum by passing electric discharge through (2) Tailing of Hg. Mercury loses its meniscus in contact with O3
air, named by Schonbien (azo - I smell) and Sorret established the and sticks to the surface of glass due to formation of Hg2O
formula O3 as allotrope of oxygen (3) Clean silver foil blackened by O3
It is formed in atmosphere by action of UV rays on O2. It is also (4) It turns benzidene paper brown and tetramethyl base violet
+
formed by (i) slow oxidation of phosphorous in air (ii) Reaction of +
O
O
fluorine with water at low temperature (iii) Electrolysis of water Structure – –
(iv) SO2 reacts with H2O2 O O O O
Preparation lab method : By passing silent electric discharge Oxidation state of O is +1 and –1
through cold, dry oxygen in ozoniser Oxides: Oxides are the binary compounds of oxygen with metals
3O2 2O3 + 284.5 kJ and non metals. Based on their oxygen content they have been
classified as
The ozonisers used are
(1) Normal oxides - Oxides containing oxygen according to
1. Siemen’s ozoniser 2. Brodie’s ozoniser normal oxidation number of M eg. H2O, MgO, Al2O3.
Manufacture. For the manufacture of ozonised air Siemen and (2) Polyoxides - These contain more oxygen than normal
Halske’s ozoniser is employed. oxidation number of M and M – O and O – O bonds. They
Electrolytic method. When acidified water, using high current are further classified as
density and Pt. anode, is electrolysed 95% O3 is obtained at anode
rest being O2. (i) Peroxides - They contain O22- ion, produce hydrogen
Properties - Pale blue gas, dark blue liquid and violet black solid peroxide with dil. acids and O2 with concentrated acids
with characteristic strong smell, slightly soluble in water but more eg BaO2, Na2O2
soluble in turpentine oil, glacial acetic acid and carbon tetrachloride. ( dil.)
Decomposition BaO 2 + H 2SO 4 ¾¾¾® BaSO 4 + H 2 O 2
573K (Conc )
2O3 ¾¾¾ ® 3O 2 DH = 284 kJ / mole 2 BaO 2 + 2H 2SO 4 ¾¾ ¾
¾® 2BaSO 4 + 2H 2 O + O 2
Oxidising action (ii) Super oxides - They contain O 2– ion. With water they
O 3 ® O 2 + O (nascent oxygen hence powerfully oxidising) give hydrogen peroxide and oxygen
PbS + 4O ® PbSO 4 2KO 2 + 2H 2 O ® 2KOH + H 2O 2 + O 2
H 2S + O ® H 2 O + S (iii)Dioxides - They give chlorine with conc HCl and oxygen
with Conc H2SO4 eg MnO2, PbO2 etc.
2FeSO 4 + H 2SO 4 + O ® Fe 2 (SO 4 ) 3 + H 2O
2MnO 2 + 4HCl(Conc) ® MnCl 2 + 2H 2 O + Cl 2
2K 4 [Fe(CN) 6 ] + H 2 O + O ® 2K 3[Fe(CN) 6 ] + 2KOH
2MnO 2 + 2H 2SO 4 (Conc) ® 2MnSO 4 + 2H 2 O + O 2
2I 2 + 9O ® I 4O9 [I2 , P,S, As] + O3 ® ic acid
(iv) Suboxides - They contain lower percentage of oxygen
Reducing action eg N2O, C3O2
H 2 O 2 + O 3 ® H 2O + 2O 2 BaO 2 + O 3 ® BaO + 2O 2 They have M – M and M – O bonds. For example O
= C = C = C = O (carbon suboxide)
NaOCl + O 3 ® NaCl + 2O 2
(v) Mixed oxides - Formed by the combination of two simple
Alkaline oxides eg Red lead, Pb3O 4 (PbO 2.2PbO), Fe 3O 4
K 3 [ Fe( CN ) 6 ] ¾¾ ¾¾® K 4 [ Fe( CN ) 6 ]
(FeO+Fe2O3)
O Classification on the basis of chemicals behaviour
Addition reactions CH 2 = CH 2 + O3 ® H 2C CH2 (i) Acidic oxides - Oxides of non metals which give acids
when dissolved in water are called acidic oxides eg.
O O CO2, NO2, P2O5, SO2, SO3, Cl2O7 etc.
Ozonide
CO 2 + H 2 O ® H 2CO 3 carbonic acid
Uses:- The metallic oxides of high oxidation state eg Mn2O7,
(1) Bleaching ivory, oils, flour etc. V2O5 and CrO3
(2) As germicide and disinfectant, for sterilising water (ii) Basic oxides
(3) For improving atmosphere in crowded places (a) Ionic in nature. Oxides of alkali and alkaline earth
The p-Block Elements - Oxygen Family 691
metals eg Na2O, CaO, BaO. In water they give basic 2K 2Cr2O7 + 8H 2SO4 (conc) ® 2
solutions
2K 2SO4 + 2Cr2 (SO4 )3 + 8H 2O + 3O2
Na 2 O + H 2 O ® 2 NaOH
(3) By electrolysis of water either acidified with H2SO4 using
(b) Covalent oxides - Oxides of transition metals are platinum electrodes or by making it alkaline with NaOH
covalent in nature eg CuO, FeO. Insoluble in water. or Ba(OH)2 using nickel electrodes.
(iii) Amphoteric oxides - The oxides which react with both -2e 1
2H 2 O 2H + 2OH - ¾¾¾ ® 2OH H 2 O + O2
acids and alkalies are known as amphoteric oxides eg 2
ZnO, Al2O3, SnO etc. (4) By decomposition of steam by chlorine.
ZnO + 2 NaOH ® Na 2 ZnO2 + H 2 O 2H 2O + 2Cl 2 ® 4HCl + O 2
ZnO + 2HCl ® ZnCl 2 + H 2O Manufacture - By fractional distillation of liquid air
Properties - It is colourless, odourless, tasteless slightly heavier
(iv) Neutral oxides - Such oxides do not combine with an than air, sparingly soluble in water, soluble in pyrogallol.
acid or a base eg NO, N2O, CO, H2O etc. Chemical properties - On heating it combines directly with metals
OXYGEN : and non metals.
Chinese observed the presence of oxygen in air. Priestly & C + O 2 ® CO 2
Scheely prepared oxygen by heating suitable oxygen compounds.
P4 + 5O 2 ® 2P2O 5
1 S + O 2 ® SO 2
Occurrence - About th of the atmosphere is free of elemental
5 3000º C
N 2 + O 2 ¾¾ ¾
¾® 2 NO
oxygen. In the combined state it is present in water 89% by weight,
earth’s crust about 50% and plants and animal tissues 50–70%. 2Mg + O 2 ® 2MgO 3Fe + 2O 2 ® Fe 3O 4
Preparation - 4 Na + O 2 ® 2 Na 2O ® Na 2 O 2
(1) By action of heat on oxygen rich compounds
(i) From oxides Pb + O 2 ® PbO 2
D
Combination with O2 is accelerated by using catalyst. Platinum is
2HgO ¾¾® 2Hg + O 2 particularly active.
2Ag 2 O ® 4 Ag + O 2 Pt
2H 2 + O 2 ¾¾® 2 H 2 O
(ii) From peroxides and other oxides
Pt
MnO 4NH 3 + 5O2 ¾¾ ® 4NO + 6H 2 O (Ostwald's process)
2H 2 O 2 ¾¾ ¾
¾2 ® 2H O + O
2 2
V O (Contact process)
D 2SO 2 + O 2 ¾¾2 ¾
5 ® 2SO
3
2BaO 2 ¾¾® 2 BaO + O 2
2CH 3OH + O 2 ® 2HCHO + 2H 2 O
D
2PbO 2 ¾¾® 2PbO + O 2
CuCl
4HCl + O 2 ¾¾ ¾
¾2 ® 2Cl + 2 H O (Deacon' s process)
2 2
D
2Pb 3 O 4 ¾¾® 6PbO + O 2 Uses
D (1) For breathing
3MnO 4 ¾¾® Mn 3 O 4 + O 2
(2) In welding and cutting – oxy-hydrogen or oxy - acetylene
(iii)From certain compounds torch is used.
D (3) In iron and steel industry – to increase the content of blast in
2KClO3 ¾¾® 2KCl + 3O2
MnO2 the Bessemer and open hearth process.
(4) As a fuel in rockets.
2KNO3 ® 2KNO2 + O2
Tests
2CaOCl 2 ® 2CaCl 2 + O 2 (1) With NO it gives reddish brown fumes of NO2.
2KMnO4 ® K 2 MnO4 + MnO2 + O 2 (2) Absorbed by alkaline pyrogallol.
(3) A smouldering wood splinter bursts into flames in a jar of O2.
D
4K 2 Cr2 O 7 ¾¾® 4K 2 CrO 4 + 2Cr2 O 3 + 3O 2
(2) By the action of some chemical reagent on compound Structure
rich in O2. It is paramagnetic with following electronic configuration
2 Na 2O 2 + 2H 2 O ® 2NaOH + O 2 s1s2 s*1s2 s2s 2 s* 2s2 s2p 2 p2p 2x = p2p 2y p* 2p1x = p* 2p1y
692 Chemistry
discharge tube As2O3 is precipitated as As2S3 by passing H2S
Atomic oxygen : O2 ¾¾¾¾¾¾ ® O + O DH = 489.6kJ
1 mm pressure As 2 O 3 + 3H 2S ® As 2S3 + 3H 2 O
Isotopes O16 O17 O18 PbSO4 is insoluble in water and settles down on
10000: 1: 8 dilution and filtered off.
NO and NO 2 are removed by heating with
SULPHUR :
Occurence - It occurs free in volcanic regions. In combined state ( NH 4 ) 2 SO 4
it occurs as ( NH 4 ) 2 SO 4 + NO + NO 2 ® 3H 2 O + H 2SO 4 + 2 N 2
(i) Gypsum CaSO4.2H2O
(f) Concentration - The sulphuric acid is concentrated
(ii) S-Celesite SrSO4 by evaporation
(iii) Galena PbS (2) Contact process - The steps involved are
(iv) Zinc blende ZnS (i) Production of SO2 - It is produced by burning sulphur
(v) Copper pyrites Cu2SFe2S3 and iron pyrites and purified by treating with steam to
(vi) Iron pyrites FeS2 remove dust particles. The arsenic is removed by ferric
Properties - Ordinary sulphur is pale yellow, insoluble in water hydroxide, water vapour removed by conc H2SO4. The
but dissolves in CS2, C6H6 and turpentine gases are filtered through coke filters and purity is tested
Allotrophic forms - Its important allotrophic forms are by Tyndal box.
Crystalline - Rhombic, monoclinic (ii) Conversion of SO2 to SO3 - It is done in contact or
Amorphous - Plastic, milk of sulphur, colloidal sulphur. catalyst chamber after being preheated to 450ºC.
COMPOUNDS OF SULPHUR : 2SO 2 + O 2 == 2SO 3 + x cal
1. Sulphuric acid - It is also known as oil of vitriol and king of 450° - 500ºC 1.6 to 1.7 atm Pressure
chemicals. Catalyst - Formerly platinised asbestose was used which
Manufactures of sulphuric acid is costly and easily poisoned. Now a days V2O5 is used.
(1) Lead chamber process - The various steps involved are (iii)SO3 is absorbed by conc H2SO4 and then water is added
(a) Production of SO2 : By burning S or iron pyrites. to produce the acid of desired concentration
D
S + O 2 ¾¾® SO 2 H 2SO 4 + SO 3 ® H 2S 2O 7
(oleium or pyrosulphuric acid)
4FeS2 + 11O2 ® 2Fe2O3 + 8SO2
H 2S 2O 7 + H 2O ® 2H 2SO 4
(b) Production of catalyst - Oxides of nitrogen
If SO3 is absorbed by water it liberates large amount of
2 NaNO3 + H 2SO 4 ® Na 2SO 4 + 2HNO 3
heat producing acid fog.
2HNO 3 ® H 2O + NO + NO 2 + O 2 Properties - Its specific gravity is 1.8 and it is 98% by weight
(c) Reaction in lead chamber normality is 36N.
Chemical properties
SO 2 + NO 2 ® SO 3 + NO
(i) Action of heat H 2SO 4 ® H 2O + SO 2 + O
SO 3 + H 2 O ® H 2SO 4
Hence it acts as oxidising agent
2NO + O 2 ® 2 NO 2 (used again) Non metals are oxidised to their oxides
Gay-Lussac Tower : The residual gases (mainly air + oxides C + 2O ® CO 2 S + 2O ® SO 2
of nitrogen) from lead chambers + conc. H2SO4 from glover
tower give nitrated acid. 2P + 5O ® P2O 5
2H 2SO 4 + NO + O 2 ® 2 NO.HSO 4 + H 2 O 2KI + 2H 2SO 4 ® K 2SO 4 + SO 2 + I 2 + 2H 2 O
Glover Tower : The nitrated acid from Gay-Lussac tower is 2KBr + 2H 2SO 4 ® K 2SO 4 + SO 2 + Br2 + 2H 2 O
denitrated in this tower.
(ii) Displacement reactions - It displaces volatile acids from
2 NO.HSO 4 + H 2 O ® 2H 2SO 4 + NO + NO 2 their salts.
Nitroso Na 2S + H 2SO 4 ® H 2S + Na 2SO 4
sulphuric acid
(d) Conditions - Temperature 50ºC, excess of steam, lead NaCl + H 2SO 4 ® HCl + NaHSO 4
chamber since lead is not attacked H2SO4. NaNO3 + H 2SO 4 ® HNO 3 + NaHSO 4
(e) Purification - The acid obtained contains the
impurities of PbSO4, AS2O3, NO and NO2 which are Ca 3 (PO 4 ) 2 + 3H 2SO 4 ® 2H 3PO 4 + 3CaSO 4
removed as follows
The p-Block Elements - Oxygen Family 693
Metals above hydrogen in ECS react with dil. H2SO4 (ii) Roasting iron pyrites in excess of air
with evolution of H2.
4FeS2 + 11O 2 ® 2Fe 2O 3 + 8SO 2
M(Fe, Sn, Zn, Al, Mn, Mg) + H2SO4 ® MSO4 + H2
Conc. H2SO4 reacts with all metals except Au and Pt with (iii)Lab method : By heating Cu with conc H2SO4
evolution of SO2. Cu + 2H 2SO 4 ® CuSO 4 + SO2 + 2H 2O
Metal + Conc. H2SO4 ® MSO4 + SO2 + H2O
Properties -
(iii)Dehydrating agent - It is strong dehydrating in nature
(i) As reducing agent
C12 H 22O11 ® 12C + H 2SO 4 .11H 2 O
SO 2 + Cl 2 + 2H 2O ® H 2SO 4 + 2HCl
C 2 H 5OH ® C 2 H 4 + H 2SO 4 .H 2 O
SO 2 + 2FeCl 3 + 2H 2 O ® H 2SO 4 + 2FeCl 2 + 2HCl
HCOOH ® CO + H 2SO 4 .H 2 O
2KIO3 + 5SO 2 + 4H 2O ® 2KHSO 4 + 3H 2SO 4 + I 2
(COOH) 2 ® CO + CO 2 + H 2SO 4 .H 2 O
(iv) Reaction with PCl5 2KMnO4 + 5SO 2 + 2H 2O ® K 2SO 4 + 2MnSO 4 + 2H 2SO 4
HO.SO2.OH + PCl5 ® Cl.SO2 .OH + POCl3 + HCl It decolorises the solution of KMnO4
Chlorosulphonic K 2Cr2 O 7 + H 2SO 4 + 3SO 2 ® K 2SO 4 + Cr2 (SO 4 ) 3 + H 2 O
acid green
HO.SO 2 .OH + 2PCl5 ® Cl.SO 2 .Cl + 2POCl 3 + 2HCl (ii) As oxidising agent
Sulphuryl 2H 2S + SO 2 ® 2H 2 O + 3S ¯
Chloride
(v) Sulphonation of aromatic compounds SO 2 + 2Mg ( burning ) ® 2MgO + S ¯
C6 H6 + H 2SO4 ® C6 H5 .SO2 OH + H2O 3Fe + SO 2 ® 2FeO + FeS
Benzene
sulphonic acid PbO 2 + SO 2 ® PbSO 4
(vi) Precipitation - Barium and lead are precipitated as (iii)Burning of potassium - Potassium burns in SO2 giving
sulphates sulphate and thiosulphate
BaCl 2 + H 2SO 4 ® BaSO 4 + 2HCl 4K + 3SO 2 ® K 2SO3 + K 2S2O3
Pb( NO 3 ) 2 + H 2SO 4 ® PbSO 4 + 2HNO 3 (iv) Bleaching action - Its bleaching action is due to
Hence these are gravimetrically estimated reduction
Fuming sulphuric acid [H2SO4.SO3] SO 2 + 2H 2O ® H 2SO 4 + 2H
With ammonia it forms (NH4)2 SO4 hence NH3 can not
Structure : It is sp2 hybridised and has V- shape.
be dried over H2SO4
Uses - It is used as oxidising, dehydrating agent and for the
S S S
preparation of dyes, drugs, explosives, volatile acids etc.
Structure - It has tetrahedral structure O 120º O O O or O O
120º
O O S- in excited state
S S
HO OH or HO OH
O O sp2
hybridisation
S- in doubly excited state s bond from sp2 -p overlap
one p bond from pp-pp bond overlap
other p bond from pp-dp overlap
SULPHUR TRIOXIDE (SO3) :
sp3 hybridisation These orbitals form two Preparation
p-bonds with two oxygen (i) By heating conc H2SO4 with P2O5
SULPHUR DIOXIDE (SO2) H 2SO 4 + P2 O 5 ® SO 3 + 2HPO 3
Preparation (ii) Manufacture : It is done by contact process
D
(i) By heating sulphur in air S + O 2 ¾¾® SO 2 2SO 2 + O 2 == 2SO 3
694 Chemistry
Properties - It dissolves in water with loud hissing sound and (ii) Reducing nature
evolution of heat 2KMnO 4 + 3H 2SO 4 + 5H 2S ® K
Chemical properties
K 2SO 4 + 2MnSO 4 + 8H 2 O + 5S
1. Action of heat 2SO 3 == 2SO 2 + O 2
K 2Cr2 O 7 + 4H 2SO 4 + 3H 2S ®
2. Water SO 3 + H 2 O == H 2SO 4 K 2 Cr2O7 + 4H 2SO4 + 3H 2S ® K 2SO4 + Cr2(SO 4 )3 + 7H 2O + 3S
1. Hypo is used in photography to [CBSE-PMT1988] 11. By passing H 2S gas in acidified KMnO4 solution, we get
(a) Reduce AgBr grains to metallic silver [CBSE-PMT 1995]
(b) Convert metallic silver to silver salt (a) S (b) K2S
(c) Remove undecomposed silver bromide as a soluble (c) MnO2 (d) K2SO3
complex 12. Oxidation of thiosulphate by iodine gives
(d) Remove reduced silver [CBSE-PMT 1996]
2. Oxygen will directly react with each of the following elements (a) tetrathionate ion (b) sulphide ion
except [CBSE-PMT 1989] (c) sulphate ion (d) sulphite ion
13. During its reactions, ozone [CBSE-PMT 1999]
(a) P (b) Cl (c) Na (d) S.
(a) can only combine with hydrogen atoms
3. The gases respectively absorbed by alkaline pyrogallol and (b) accepts electrons
oil of cinnamon are [CBSE-PMT 1989] (c) loses electrons
(a) O3, CH4 (b) O2, O3 (c) SO2,CH4 (d) N2O, O3. (d) shows the role of electrons to be irrelevant
4. It is possible to obtain oxygen from air by fractional distillation 14. Which of the following is the most basic oxide?
because [CBSE-PMT 1989] (a) Sb2O3 (b) Bi2O3 [CBSE-PMT 2006]
(a) oxygen is in a different group of the periodic table from (c) SeO2 (d) Al2O3
nitrogen 15. Which one of the following compounds is a peroxide ?
(b) oxygen is more reactive than nitrogen [CBSE-PMT 2010]
(c) oxygen has higher b.p. than nitrogen (a) KO 2 (b) BaO2
(d) oxygen has a lower density than nitrogen.
5. Which would quickly absorb oxygen ? (c) MnO 2 (d) NO 2
[CBSE-PMT1991, 92] 16. Match List - I (substances) with List - II (processes) employed
(a) Alkaline solution of pyrogallol in the manufacture of the substances and select the correct
(b) Conc. H2SO4 option. [CBSE-PMT 2010]
(c) Lime water List - I List - II
(d) Alkaline solution of CuSO4 Substances Processes
6. Oleum is [CBSE-PMT 1991] (A) Sulphuric acid (i) Haber’s process
(a) Castor Oil (b) Oil of vitriol (B) Steel (ii) Bessemer’s
(c) Fuming H2SO4 (d) None of them process
7. A certain compound (X) when treated with copper sulphate
(C) Sodium hydroxide (iii) Leblanc process
solution yields a brown precipitate. On adding hypo solution,
(D) Ammonia (iv) Contact process
the precipitate turns white. The compound is
(a) K2CO3 (b) KI [CBSE-PMT 1994] Options:
(c) KBr (d) K3PO4 (A) (B) (C) (D)
8. Polyanion formation is maximum in [CBSE-PMT 1994] (a) (iv) (ii) (iii) (i)
(a) Nitrogen (b) Oxygen (b) (i) (iv) (ii) (iii)
(c) Sulphur (d) Boron (c) (i) (ii) (iii) (iv)
9. The acid which has a peroxy linkage is [CBSE-PMT 1994] (d) (iv) (iii) (ii) (i)
(a) Sulphurous acid (b) Pyrosulphuric acid 17. Which of the following oxide is amphoteric ?
(c) Dithionic acid (d) Caro’s acid [CBSE-PMT 2011 M]
10. About 20 km above the earth, there is an ozone layer. Which (a) SnO2 (b) CaO (c) SiO2 (d) CO2
one of the following statements about ozone and ozone layer
18. Sulphur trioxide can be obtained by which of the following
is true? [CBSE-PMT 1995]
reaction : [CBSE-PMT 2012 S]
(a) ozone has a triatomic linear molecule
(b) Fe 2 ( SO4 )3 ¾¾
Δ Δ
(b) it is harmful as it stops useful radiation (a) CaSO 4 + C ¾¾ ® ®
(c) it is beneficial to us as it stops U.V radiation
Δ Δ
(d) conversion of O3 to O2 is an endothermic reaction (c) S + H 2SO 4 ¾¾ ® (d) H 2SO 4 + PCl5 ¾¾ ®
The p-Block Elements - Oxygen Family 699
19. Roasting of sulphides gives the gas X as a by product. This 23. Excess of KI reacts with CuSO4 solution and then Na2S2O3
is colorless gas with choking smell of burnt sulphur and solution is added to it. Which of the statements is incorrect
caused great damage to respiratory organs as a result of for this reaction ? [AIEEE 2004]
acid rain. Its aqueous solution is acidic, acts as a reducing (a) Na2S2O3 is oxidised
agent and its acid has never been isolated. The gas X is : (b) CuI2 is formed
(a) SO2 (b) CO2 [NEET 2013] (c) Cu2I2 is formed
(c) SO3 (d) H2S (d) Evolved I2 is reduced
20. Which of the following does not give oxygen on heating? 24. Which of the following statements regarding sulphur is
(a) Zn(ClO3)2 (b) K2Cr2O7 [NEET 2013] incorrect? [AIEEE 2011]
(c) (NH4)2Cr2O7 (d) KClO3 (a) S2 molecule is paramagnetic.
21. Which one of the following is an amphoteric
(b) The vapours at 200°C consists mostly of S8 rings.
oxide ? [AIEEE 2003]
(c) At 600°C the gas mainly consists of S2 molecules.
(a) Na2O (b) SO2
(d) The oxidation state of sulphur is never less than +4 in its
(c) B2O3 (d) ZnO
compounds.
22. KO2 (potassium super oxide) is used in oxygen cylinders in
25. Aqueous solution of Na2S2O3 on reaction with Cl2 gives –
space and submarines because it [AIEEE 2002]
[IIT-JEE 2008]
(a) absorbs CO2 and increases O2 content
(a) Na2S4O6 (b) NaHSO4 (c) NaCl (d) NaOH
(b) eliminates moisture
(c) absorbs CO2
(d) produces ozone.
1. When SO2 gas is passed through an acidified solution of 7. Which reaction represents the oxidizing behaviour of H2SO4
K2Cr2O7 (a) 2PCl 5 + H 2SO 4 ® 2POCl 3 + 2HCl + SO 2Cl 2
(a) the solution becomes blue
(b) 2NaOH + H 2SO 4 ® Na 2SO 4 + 2H 2O
(b) the solution becomes colourless
(c) SO2 is reduced (c) NaCl + H 2SO 4 ® NaHSO 4 + HCl
(d) green Cr2(SO4)3 is formed
(d) 2HI + H 2SO 4 ® I 2 + SO 2 + 2H 2 O
2. FeCl3 solution on reaction with SO2 changes to
(a) FeCl2 (b) Fe2(SO4)3 8. Which characteristic is not correct about H2SO4 ?
(c) Fe2(SO3)3 (d) FeSO4 (a) Reducing agent (b) Oxidising agent
3. A considerable part of the harmful ultraviolet radiation of the (c) Sulphonating agent (d) Highly viscous
sun does not reach the surface of the earth . This is because 9. Which of the following is a saline oxide ?
high above the earth’s atmosphere there is a layer of (a) Na2O2 (b) BaO2
(a) CO2 (b) hydrogen (c) Na2O (d) Fe2O3
(c) ozone (d) ammonia 10. In the manufacture of H2SO4 the nitrated acid from the Gay -
4. On passing H2S through acidified FeCl3 solution FeCl3 is Lussac’s tower is chemically
converted into (a) H2SO4.NO2 (b) H2SO4.NO
(a) FeCl2 (b) Fe2( SO4)3 (c) H2SO4. 2NO (d) HSO4. NO
(c) FeS (d) FeSO4 11. Potassium chlorate on heating with conc H2SO4 gives
5. H2SO4 is added while preparing a standard solution of (a) chlorine dioxide (b) HClO4
Mohr’s salt to prevent (c) KHSO4 (d) All of these
(a) hydration (b) reduction 12. Sulphur forms the chlorides S2Cl2 and SCl2. The equivalent
(c) hydrolysis (d) complex formation mass of sulphur in SCl2 is 16g /mol . Therefore the equivalent
6. Concentrated H2SO4 is not used to prepare HBr from KBr mass of sulphur in S2Cl2 is
because it (a) 32 g / mol (b) 16 g /mol
(a) oxidizes HBr (c) 64 g/mol (d) 8 g/ mol
(b) reduces HBr 13. Reagent used to distinguish H2O2 and O3 is
(c) causes disproportionation of HBr (a) PbS (b) starch and iodine
(d) reacts too slowly with KBr (c) KMnO4 (d) bleaching powder
700 Chemistry
14. Which of the following does not react with AgCl 22. Which of the following statements is correct :
(a) Na2S2O3 (b) NH4OH (a) Ozone is a resonance hybrid of oxygen
(c) NaNO3 (d) Na2CO3 (b) Ozone is an isomer of oxygen
15. When KBr is treated with conc. H2SO4 reddish brown gas is
(c) Ozone has no relationship with oxygen
evolved . The gas is
(a) Br2 (b) Br2 + HBr (d) Ozone is an allotropic modification of oxygen
(c) NO2 (d) H2O2 23. The crystals of ferrous sulphate on heating give :
16. One gas bleaches the colour of the flowers by reduction (a) FeO + SO 2 + H 2 O
while the other by oxidation. The gases are
(a) CO and CO2 (b) H2S and Br2 (b) FeO + SO 3 + H 2SO 4 + H 2O
(c) SO2 and Cl2 (d) NH3 and SO3
17. Which oxide is of different type than others (c) Fe 2 O 3 + SO 2 + H 2SO 4 + H 2O
(a) MnO2 (b) PbO2
(d) Fe 2O 3 + H 2SO 4 + H 2 O
(c) TiO2 (d) Na2O2
18. In which reaction does SO2 act as oxidising agent 24. In the upper layers of atmosphere ozone is formed by the
(a) Acidified KMnO4 (b) Acidified K2Cr2O7 (a) action of ultraviolet rays on oxygen
(c) Acidified C2H5OH (d) H2S (b) action of electric discharge on oxygen molecules
19. Hydrogen sulphide reacts with lead acetate forming a black
(c) combination of oxygen molecules
compound which reacts with H2 O2 to form another
compound . The colour of the compound is (d) None of these
(a) black (b) yellow 25. When sugar is treated with conc. sulphuric acid, the sugar is
(c) white (d) pink charred. In this process, sugar is
20. Hydrolysis of one mole of peroxodisulphuric acid produces (a) reduced (b) oxidized
(a) two moles of sulphuric acid (c) sulphonated (d) dehydrated
(b) two moles of peroxomonosulphuric acid
(c) one mole of sulphuric acid and one mole of 26. H 2SO 4 and H 2SO 3 can be distinguished by the addition
peroxomonosulphuric acid of :
(d) one mole of sulphuric acid, on e mole of
peroxomonosulphuric acid and one mole of hydrogen (a) magnesium powder (b) NaHSO 4 solution
peroxide.
(c) FeCl3 solution (d) litmus solution
21. Oxygen gas can be prepared from solid KMnO4 by :
27. Yellow ammonium sulphide is
(a) treating the solid with H 2 gas
(a) ( NH 4 ) 2 S8 (b) ( NH 4 ) 2 S
(b) strongly heating the solid
(c) dissolving the solid in dil. H 2SO 4 (c) ( NH 4 ) 2 S x (d) ( NH 4 ) 2 S 4
(d) dissolving solid in dil. HCl
The p-Block Elements - Oxygen Family 701
20. (c) HO S O O S OH + H2O 26. (c) FeCl 3 acts as oxidant and H 2SO 3 as reductant.
peroxodisulphuric acid
O O O
O S OH + H O HO S O OH + HO S OH
O O O
2. Oxy acids - All form oxy acids of the type HOX, HXO2, HXO3 and HXO4 as shown below
Name O. N. of X Fluorine Chlorine Bromine Iodine Salt’s name
Hypohalous acid, HXO +1 HOF HOCl HOBr HOI Hypohalite
Halous acid, HXO2 +3 - HClO2 - - Halite
Halic acid, HXO3 +5 - HClO3 HBrO3 HIO3 Halate
Perhalic acid, HXO4 +7 - HClO4 HBrO4 HIO4 Perhalate
Trend for following properties
HXO4 > HXO3 > HXO2 > HXO 2X – + XO3–
3 – OX
¬ Thermal stability Rate of disproportionation
¬ Acid strength
IO - > BrO - > ClO -
Oxidising nature ®
The conjugate bases obtained from above acids are The structure of HClO and HFO are
O O
XO – , XO2– , XO3– and XO4– . Their stability increases with
H F H Cl
the increase of oxygen atoms due to greater chances of 97° 103°
dispersal of negative charge. The more is the stability of Bleaching powder CaOCl2 is a mixed salt of HOCl and
conjugate base, the more is the acid character. HCl
(ii) Halic acids - HClO3 and HBrO3 exist in aqueous solution
XO4– > XO3– > XO2– > XO –
and HIO3 is a white solid. The stability follows the order
(i) Hypohalous acids (HOX) - They are formed in aqueous
HIO3 > HBrO3 > HClO3 ® Acid strength
solution by disproportionation of halogens
They are strong oxidising in nature
X2 + H2O HOX + HX
Acid character and thermal stability follows the order XO3– + 5X – + 6H + ® 3X 2 + 3H 2O
HClO > HBrO > HIO Their salts, NaClO3 is a powerful weed killer and KClO3
Hypohalites disproportionate in aqs. solution to halides (Berthelot’s salt) is used in fire works and matches as
and halates. oxidising agent.
The p-Block Elements - Halogens 707
(iii)Perhalic acids - Perhalates are obtained by electrolytic Examples IBr, BrCl,ClF3, BrF3, ICl3BrF5, IF5, IF7 ClF, BrF,
oxidation of halates ICl
4ClO 3– ® Cl – + 3ClO 4– , 4IO3– ® I – + 3IO 4- Properties - They are covalent, more reactive, strong
oxidising and diamagnetic in nature.
Perborate is obtained by oxidation with F2 in basic
Preparation - The are prepared by direct combination of
solution
halogens
BrO3– + F2 + 2OH – ® BrO4- + 2F – + H 2O
500K
Cl 2 + F2 ¾¾¾® 2ClF
They are strong oxidising agents following the order
By the action of halogens on lower interhalogen
ClO - < BrO - > IO -
4 4 4 ClF3 + F2 ® ClF5
Structure of oxyacids
Polyhalide ions - The ions containing more than two halogen
(a) Hypochlorous acid (b) Chlorous acid atoms are known as polyhalide ions eg.
(HOCl) (HClO2)
_
H H KI + I 2 ® KI3 K+ + I 3
O O
Other examples are
Cl Cl _
Br3– , C l3 , IC12– , IBr2– , ICl4– , BrF4– , I 5– , IF6–
.. ..
..
..
..
O Iodine Cation - Iodine also forms I+ and I3+ cations due to less
(c) Chloric acid (d) Perchloric acid ionisation energy as (CH3COO)3I, I (ClO4)3 and IPO4 have been
(HClO3) (HClO4) isolated.
H H Pseudohalogens and pseudohalides - The substances behaving
O O like halogens are known as pseudohalides.
Some examples are
Cl Cl Pseudo halogen Pseudohalide ion
..
X
X X X 2F – - 2e – ® F2 (At anode)
X
708 Chemistry
(2) Whytlaw Gray’s method - Electrolysis of fused KHF2 is (7) With NH 3 - 2 NH 3 + 3F2 ® N 2 + 6HF and some NF3
carried out in Cu cell (electrically heated) which serves
( not explosive)
the purpose of cathode, Anode is of graphite
(3) Modern method - Electrolysis of fused mixture of KF (8) With H2S - H 2S + 4F2 ® SF6 + 2HF
and HF is carried out in steel vessel (cathode). Anode is (9) With hydrocarbons - It reacts with hydrocarbons
of graphite violently eg CH4
Properties - It is pale greenish yellow gas can be condensed to CH 4 + 4F2 ® 4HF + CF4
pale yellow liquid and then pale yellow solid. It is very reactive.
Hence fluorination is carried out in presence of N2 (it
(1) Most active - It directly combines with metals and non dilutes F2) and calalyst copper gauge.
metals eg Al, Mg, C, P, S, As, Sb, Br2, I2 etc to from
Uses
fluorides, Cu and Hg form a protective coating of
(1) Fluoro derivatives are solvents, lubricants, refrigerants,
fluoride.
fire extinguishers, fungicides, germicides, dyes and
(2) Reaction with Xe - With Xenon it forms three definite plastics etc.
halides
(2) For separation of U235 by forming UF6 from natural
XeF2, XeF4 and XeF6 having the following structure uranium
F (3) Preparation of Teflon (C2F4)n
FREONS :
:
: Xe
:
XeF2 hybridisation sp3d Chlorofluoro compounds of methane and ethane are known as
freons. They are extremely, unreactive, non corrosive, easily
F
liquefiable compounds. Freon-12 (CCl2F2) is most common and
Linear symmetrical prepared as
D
3CCl 4 + 2SbF3 ¾¾® 3CCl 2 F2 + 2SbCl 3
F F They are used as refrigerants and propellants .
Magic acid - FSO3H SbF5 is strongest acid and known as magic
XeF4 hybridisation sp3d2 Xe acid.
Chlorine :
F F It was discovered by Scheele by heating HCl acid (muriatic acid)
with MnO2 and named it oxymuriatic gas. Davy established its
nature and called it chlorine.
Square planar Occurrence - Being very reactive does not occur free in nature. It
is widely distributed as chlorides. Common salt NaCl is most
F important chloride present in sea water and as rock salt.
F F Preparation - By oxidation of Conc HCl
XeF6 sp3d3 hybridisation Xe MnO2 + 4HCl ® MnCl 2 + 2H 2 O + Cl 2
2+
_ _ Hydrogen halide Composition Boiling
solution contains Ca , C l and OC l ions. point ºC
Uses
H2F2 36% 120
(i) It is used as disinfectant and germicide
(ii) For the manufacture chloroform HCl 20.4% 110
(iii) For the sterlisation of drinking water HBr 47.0% 126
(iv) For making unshrinkable wool
HI 57.0% 127
(v) For bleaching cotton, wood pulp.
712 Chemistry
1. Among F, Cl, Br and I the lowest ionization potential will be 15. Hydrochloric acid at 25ºC is
of (a) ionic and liquid (b) covalent and liquid
(a) fluorine (b) chlorine (c) ionic and gas (d) None of these
(c) bromine (d) iodine 16. Which of the following is most volatile ?
2. The electron affinity of the halogens follows the order (a) HI (b) HBr
(a) F > Cl > Br > I (b) F < Cl < Br < I (c) HCl (d) HF
(c) F < Cl > Br > I (d) F < Cl < Br > I 17. Which of the following sets gives the correct arrangement of
3. The electronegativity follows the order the compounds involved based on their bond strengths ?
(a) F > O > Cl > Br (b) F > Cl > Br > O (a) HF > HCl > HBr > HI (b) HI > HBr > HCl > HF
(c) O > F > Cl > Br (d) Cl > F > O > Br (c) HF > HBr > HCl > HI (d) HCl > HF > HBr > HI
4. The bond energies of F2 , Cl2, Br2 and I2 are 155, 244, 193 and
18. At room temperature, HCl is a gas while HF is a low boiling
151 kJ mol–1 respectively. The weakest bond will be in
liquid. This is because
(a) Br2 (b) Cl2
(a) H- F bond is covalent (b) H- F bond is ionic
(c) F2 (d) I2
(c) HF has metallic bond (d) HF has hydrogen bond
5. The correct order of reactivity of halogens with alkalies is
(a) F > Cl > Br > I (b) F < Cl > Br < I 19. Which of the following has the highest bond strength?
(c) F < Cl < Br < I (d) F < Cl < Br > I (a) HI (b) HCl
6. The correct order of increasing oxidising power is (c) HF (d) HBr
(a) F2 > Br2 > Cl2 > I2 20. Which of the following is the strongest acid ?
(b) F2 < Cl2 < Br2 < I2 (a) HOCl (b) HOClO2
(c) Cl2> Br2 > F2 > I2 (c) HOClO3 (d) HOClO
(d) I2 < Br2 < Cl2 < F2 21. The geometry of ClO3- according to valence shell electron
7. Which of the following halogen does not exhibit positive
oxidation state in its compounds? pair repulsion (VSEPR) theory will be
(a) Cl (b) Br (a) planar triangle (b) pyramidal
(c) I (d) F (c) tetrahedral (d) square planar
8. The halogen that is most easily reduced is 22. Oxidation state of chlorine in hypochlorous acid is
(a) F2 (b) Cl2 (a) + 1 (b) + 2
(c) Br2 (d) I2 (c) – 1 (d) – 2
9. The bond energies of F2 , Cl2, Br2 and I2 are 37, 58, 46 and 36 23. The correct decreasing order of acidic character is
kcal mol–1 respectively. The strongest bond is present in (a) HClO > HBrO > HIO (b) HIO > HBrO > HClO
(a) Br2 (b) I2 (c) HBrO > HIO > HClO (d) HClO > HIO > HBrO
(c) Cl2 (d) F2 24. The element which never acts as reducing agent in a
10. Which one of the following order is correct for the bond chemical reaction is
energies of halogen molecules ? (a) O (b) Li
(a) I2 > Cl2 > Br2 (b) Br2 > Cl2 > I2 (c) F (d) C
(c) I2 > Br2 > Cl2 (d) Cl2 > Br2 > I2 25. Unlike other halogens, fluorine does not show higher
11. Which one of the following elements shows different oxidation states because
oxidation states ? (a) it is highly electronegative
(a) Sodium (b) Fluorine (b) it has no d- orbitals
(c) Chlorine (d) Potassium
(c) its atomic radius is very small
12. Which of the following halogens exhibit only one oxidation
(d) the F– ion is stable and isoelectronic with neon
state in its compounds ?
26. An element M has an atomic mass 19 and atomic number 9.
(a) Bromine (b) Chlorine
Its ion is represented by
(c) Fluorine (d) Iodine
13. Which has the highest bond energy ? (a) M+ (b) M2 +
(c) M – (d) M2 –
(a) F2 (b) Cl2
(c) Br2 (d) I2 27. Which one of the following halogen liberates oxygen when
14. Which is the weakest out of HF, HCl, HBr and HI? passed through hot concentrated KOH solution ?
(a) HF (b) HCl (a) I2 (b) Cl2
(c) HBr (d) HI (c) Br2 (d) F2
714 Chemistry
28. One mole of fluorine is reacted with two moles of hot and 40. The reaction of KMnO4 and HCl results in
concentrated KOH. The products formed are KF, H2O and (a) oxidation of Mn in KMnO4 and production of Cl2
O2. The molar ratio of KF, H2O and O2 respectively is (b) reduction of Mn in KMnO4 and production of H2
(a) 1 : 1 : 2 (b) 2 : 1 : 0.5 (c) oxidation of Mn in KMnO4 and production of H2
(c) 1 : 2 : 1 (d) 2 : 1 : 2 (d) reduction of Mn in KMnO4 and production of Cl2
41. Chlorine acts as a bleaching agent only in
29. Fluorine oxidizes HSO -4 to (a) dry air (b) sunlight
(c) moisture (d) oxygen
(a) S2 O32 - (b) S2 O82 -
42. In the reaction
(c) S4 O 26 - (d) SO 2 - -
3Br2 + 6CO 32 - + 3H 2 O ¾
¾® 5Br + BrO 3 + 6HCO 3
30. Chlorine cannot displace (a) bromine is oxidised and carbonate is reduced
(a) Fluorine from NaF (b) bromine is both oxidised and reduced
(b) Iodine from NaI (c) bromine is reduced and water is oxidised
(c) Bromine from NaBr (d) bromine is neither oxidised nor reduced
(d) None of these 43. The solubility of I2 increases in water in presence of
31. Cl2 gas is dried over (a) KI (b) H2SO4
(a) CaO (b) NaOH (c) KMnO4 (d) H2S
(c) KOH (d) conc. H2SO4 44. Oxidation of thiosulphate with iodine gives
32. The outer electronic structure of 3s2 3p5 is possessed by (a) sulphate ion (b) sulphite ion
(a) O (b) Cl (c) tetrathionate ion (d) sulphide ion
(c) Br (d) Ar 45. Which of the following cann ot work as oxidizing
agent ?
33. Chlorine acts as a bleaching agent only in the presence of
(a) O2 (b) KMnO4
(a) dry air (b) moisture
(c) H2O2 (d) I–
(c) sunlight (d) None of these 46. On boiling an aqueous solution of KClO3 with I2 the products
34. When chlorine reacts with cold and dilute solution of sodium obtained are
hydroxide, the products obtained are (a) KIO3+Cl2 (b) KCl+I2O5
(a) Cl– + ClO– (b) Cl– + ClO -2 (c) KIO4+Cl2 (d) No reaction takes place
47. When KI and CuSO4 solutions are mixed, it gives
(c) Cl– + ClO3- (d) Cl– + ClO -4 (a) K2SO4 + I2 (b) Cu2I2 + K2SO4
(c) CuI2 + K2SO4 (d) Na2SO4 + I2
35. In the reaction
48. When I2 is passed through KCl, KF and KBr solutions
2Br + X2 ® Br2 ,2X- ,X2 is (a) Cl2 and Br 2 are evolved
(a) Cl2 (b) Br2 (b) Cl2 is evolved
(c) I2 (d) N2 (c) Cl2, Br 2 and F2 are evolved
36. Chlorine is liberated when we heat (d) None of these
(a) KMnO4 + NaCl (b) K2Cr2O7 + MnO2 49. Sea weeds are an important source of
(c) Pb(NO3)2 + MnO2 (d) K2Cr2O7 + HCl (a) iodine (b) bromine
37. Which of the following is correct about the reaction? (c) chlorine (d) Both (a) and (b)
50. Which of the following elements exhibits the most basic
heat
3NaClO ¾¾¾ ® NaClO3 + 2NaCl properties ?
(a) It is disproportionation reaction (a) F (b) Cl
(b) Oxidation number of Cl decreases as well as increases in (c) Br (d) I
this reaction 51. Which of the following is used as an antiseptic?
(c) This reaction is used for the manufacture of halates (a) I (b) Br
(d) All of these (c) Cl (d) F
52. In the presence of cobalt chloride (CoCl2), bleaching powder
38. Which of the following is used in the preparation of chlorine ?
decomposes to form
(a) Only MnO2 (b) Only KMnO4
(a) CaCO3 and O3 (b) ClO2 and CaO
(c) Both MnO2 and KMnO4 (d) Either MnO2 or KMnO4 (c) Cl2O and CaO (d) CaCl2 and O2
39. A greenish yellow gas reacts with an alkali metal hydroxide 53. In the reaction
to form a halate which can be used in fire works safety
matches. The gas and halate respectively are ® H 2+ NO 3 + F - base is
HNO 3 + HF ¾¾
(a) Br2 KBrO3 (b) Cl2, KClO3 (a) HF (b) HNO3
(c) I2, NaIO3 (d) Cl2, NaClO3 (c) HF and HNO3 (d) None of these
The p-Block Elements - Halogens 715
54. The aqueous solution of which of the following has 58. The hybridization in ICl7 is
maximum pH ? (a) sp3d 3 (b) d2sp 3
(a) NaClO (b) NaClO2 (c) sp3d (d) sp3
(c) NaClO3 (d) NaClO4 59. Which of the following bond is strongest ?
55. Which of the following is not the characteristic of
(a) F – B (b) F – Cl
interhalogen compounds ?
(a) They are more reactive than halogens (c) F – Br (d) Cl –Br
(b) They are quite unstable but none of them is explosive 60. “Fluorosis” disease is caused due to the reaction of .............
(c) They are covalent in nature with excess of fluoride in the body.
(d) They have low boiling points and are highly volatile. (a) Ca (b) Mg
56. Which bond is most polar ? (c) Fe (d) K
(a) Cl - F (b) Br - F 61. Hydrogen bond is strongest in
(c) I - F (d) F - F (a) F – H...........O
57. On heating KClO3 we get (b) F – H...........N
(a) KClO2 + O2 (b) KCl + O2 (c) F – H...........F
(c) KCl + O3 (d) KCl + O2 + O3
(d) All are equally strong
1. Which among the following is paramagnetic ? 7. Which is the best description of the behaviour of bromine in
(a) Cl 2 O (b) ClO2 [CBSE-PMT 1994] the reaction given below ? [ CBSE-PMT2004]
(c) Cl 2O 7 (d) Cl 2O 6 H 2 O + Br2 ® HOBr + HBr
2. Which one of the following oxides of chlorine is obtained by (a) Proton acceptor only
passing dry chlorine over silver chlorate at 90°C ? (b) Both oxidized and reduced
[CBSE-PMT 1994] (c) Oxidized only
(d) Reduced only
(a) Cl2 O (b) ClO3
8. Which one of the following orders correctly represents the
(c) ClO2 (d) ClO4 increasing acid strengths of the given acids?
3. The formula for calcium chlorite is [CBSE-PMT 1994] [CBSE-PMT 2007]
(a) Ca(ClO )
4 2 (b) Ca(ClO )
3 2
(a) HOClO < HOCl < HOClO3 < HOClO2
(b) HOClO2 < HOClO3 < HOClO < HOCl
(c) CaClO 2 (d) Ca(ClO 2 ) 2
(c) HOClO3 < HOClO2 < HOClO < HOCl
4. Regarding F– and Cl– which of the following statements is/
(d) HOCl < HOClO < HOClO2 < HOClO3
are correct? [ CBSE-PMT1996]
(i) Cl– can give up an electron more easily than F– 9. Which one of the following arrangements does not give the
(ii) Cl– is a better reducing agent than F– correct picture of the trends indicated against it ?
(iii) Cl– is smaller in size than F– [CBSE-PMT 2008]
(iv) F– can be oxidized more readily than Cl– (a) F2 > Cl2 > Br2 > I2 : Oxidizing power
(a) (i) and (ii) (b) (i), (ii) and (iv) (b) F2 > Cl2 > Br2 > I2 : Electron gain enthalpy
(c) (iii) and (iv) (d) only (i) (c) F2 > Cl2 > Br2 > I2 : Bond dissociation energy
5. Which one is the correct order of the size of iodine species? (d) F2 > Cl2 > Br2 > I2 : Electronegativity.
[CBSE-PMT 1997] 10. In the case of alkali metals, the covalent character decreases
(a) I > I+ > I– (b) I > I– > I+ in the order: [CBSE-PMT 2009]
(c) I+ > I– > I (d) I– > I > I+
(a) MF > MCl > MBr > MI
6. Which of the following statements is not true ?
[CBSE-PMT 2003] (b) MF > MCl > MI > MBr
(a) HF is a stronger acid than HCl (c) MI > MBr > MCl > MF
(b) Among halide ions, iodide is the most powerful reducing (d) MCl > MI > MBr > MF
agent 11. Among the following which is the strongest oxidising agent?
(c) Fluorine is the only halogen that does not show a variable [CBSE-PMT 2009]
oxidation state (a) Br2 (b) I2
(d) HOCl is a stronger acid than HOBr (c) Cl2 (d) F2
716 Chemistry
12. The correct order of increasing bond angles in the following 16. Which among the following factors is the most important in
species are : [CBSE-PMT 2010] making fluorine the strongest oxidizing halogen ?
(a) Hydration enthalpy [AIEEE 2004]
(a) Cl 2 O < ClO 2 < ClO 2– (b) ClO2 < Cl 2O < ClO 2–
(b) Ionization enthalpy
(c) Cl 2O < ClO 2– < ClO2 (d) ClO 2– < Cl2 O < ClO2 (c) Electron affinity
13. Which is the strongest acid in the following : [NEET 2013] (d) Bond dissociation energy
(a) HClO3 (b) HClO4 17. Among the properties (a) reducing (b) oxidising (c)
(c) H2SO3 (d) H2SO4 complexing, the set of properties shown by CN– ion towards
14. Which of the following is a polar molecule ? [NEET 2013] metal species is [AIEEE 2004]
(a) SF4 (b) SiF4 (a) c, a (b) b, c
(c) XeF4 (d) BF3 (c) a, b (d) a, b, c
15. Concentrated hydrochloric acid when kept in open air 18. The correct order of the thermal stability of hydrogen halides
sometimes produces a cloud of white fumes. The explanation (H–X) is [AIEEE 2005]
for it is that [AIEEE 2003] (a) HI > HCl < HF > HBr
(a) oxygen in air reacts with the emitted HCl gas to form a (b) HCl< HF > HBr < HI
cloud of chlorine gas (c) HF > HCl < HBr > HI
(b) strong affinity of HCl gas for moisture in air results in (d) HI < HBr > HCl < HF
forming of droplets of liquid solution which appears like a 19. Identify the incorrect statement among the following.
cloudy smoke. [AIEEE 2007]
(c) due to strong affinity for water, concentrated (a) Br2 reacts with hot and strong NaOH solution to give
hydrochloric acid pulls moisture of air towards itself. NaBr and H2O.
This moisture forms droplets of water and hence the
(b) Ozone reacts with SO2 to give SO3.
cloud.
(c) Silicon reacts with NaOH(aq) in the presence of air to
(d) concentrated hydrochloric acid emits strongly smelling
give Na2SiO3 and H2O.
HCl gas all the time.
(d) Cl2 reacts with excess of NH3 to give N2 and HCl.
:
:
:
2. This is because A – X bond in interhalogens in weaker than
:
the X – X bond in halogens. 22. (a) In HClO the O.S of Cl is + ve (+1)
3. CaOCl2 + H2SO4 ¾¾ ® CaSO4 + H2O + Cl2. 23. (a) Since the electronegativity of halogens follow the order
4. It is most electronegative and is smallest in its atomic size, Cl > Br > I the strength of acids follow the order HClO >
and has relatively less bond energy. HBr > HIO
5. HF reacts with silica (SiO2) present in glass and forms water 24. (c) Fluorine has highest reduction potential hence it is
soluble acid. strongest oxidising agent in nature
SiO2 + 4HF ¾¾ ® SiF + 2H O
4 2
25. (b) Due to absence of d atomic orbitals the fluorine does
not exhibit higher O.S.
SiF4 + 2HF ¾¾
® H SiF
2 4 26. (c) The element is F and ion is represented by M–
(Water soluble)
27. (d) F2 reacts with KOH to give O2 and O3 (see text)
6. F being the most electronegative element does not show
28. (b) 2F2 + 4KOH ® 4KF + O 2 + 2H 2 O for 1 mole of F2 the molar
positive oxidation states.
7. (i) Cl – Cl > Br – Br > F – F > I – I ratio.
(ii) HI > HBr > HCl > HF F2 KOH KF O2 H2O
(iii) M – F > M– Cl > M – Br > M – I 1
(iv) BrO4– > ClO4– > IO4– 1 2 2 1
2
15. (a) 16. (a) 17. (d) 18. (b) 19. (c) 20. (c)
21. (d) 22. (b) 23. (d) 24. (d) 25. (a) 26. (c) 29. (b) HSO -4 - e ® HSO 4 ® H 2S 2 O8 ® S2 O8 2 -
27. (b) 30. (a) Chlorine cannot displace F from NaF. The reactivity
EXERCISE 2 follows the order F > Cl > Br > I
31. (d) Cl2 will react with CaO, NaOH and KOH (See text). It will
1. (d) Ionisation potential decreases down the group. not react with conc. H2SO4 hence can be dried over it.
2. (c) Since fluorine has small size the electron affinity of Cl is 32. (b) 3s2 3p5 is electronic configuration of Cl
more than F 33. (b) In presence of moisture only, chlorine will give O;
3. (a) Follow text
Cl 2 + H 2O ® HCl + HOCl
4. (d) The lesser the bond energy, the weaker is the bond
5. (a) (See text) Reactivity follows the order F > Cl > Br > I 34. (a) 2NaOH + Cl2 ® NaCl + NaOCl + H 2 O
6. (d) See text
7. (d) Fluorine exhibit -ve oxidation state hence Cl- and OCl-
8. (a) Since F2 is most oxidising, it is easily reduced _ _
35. (a) 2Br + Cl 2 ® Br2 + 2Cl Chlorine is more oxidising is
9. (c) The more the bond energy the stronger is the bond
10. (d) See text nature
11. (c) Chlorine shows O.S. from –1,+1 to +7, whereas others 36. (d) K 2 Cr2 O 7 + Conc HCl ® Cl 2 See text
show O.S. as Na® +1 ; K® +1 ; F® –1
+1 +5 -1
12. (c) Fluorine always –1 37. (d) NaClO ® NaClO3 + 2NaCl All statements are correct
13. (b) See text
as evident from the reaction
14. (a) HF, due to intermolecular H-bonding is weakest among
38. (d) MnO2 or KMnO4 with conc HCl give Cl2 (see text)
HX acids
15. (d) HCl acid at 25º C is a gas and polar in nature 39. (b) 3Cl 2 + 6KOH ® KClO3 + 5KCl + 3H 2O
16. (c) Volatile character HCl > HBr >HI > HF KClO3 is used in fire works and safety matches and Cl2
17. (a) See text is greenish yellow gas
18. (d) Due to hydrogen bonding HF is a liquid +7 +2
19. (c) Follow text 40. (d) 2 KMnO 4 + 16HCl ® 2 MnCl 2 + 2KCl + 8H 2 O + 5Cl 2
20. (c) Oxy acids having higher + O.S for halogen are
O.S of Mn changes from +7 to +2 hence reduction occurs
more stronger in nature . Hence the order
and Cl2 is formed.
HClO4 > HClO3 > HClO2 > HClO
The p-Block Elements - Halogens 719
41. (c) Cl 2 + H 2O ® HCl + HOCl 4. (d) The halide ions act as reducing agents . F– ion does not
_ show any reducing nature but Cl–, Br– & I– ion act as
42. (b) 3Br2 + 6CO32 - + 3H 2 O ® 5Br + BrO3- + 6HCO 3- reducing agents and their reducing nature is in increasing
O.S. of Br2 changes from 0 to –1 and +5 which is reduction order
as well as oxidation. Cl – Br – I –
¾¾¾¾¾¾¾¾¾¾¾¾ ®
43. (a) KI + I 2 ® KI3 (Soluble complex) Re ducing nature increases
5. (d) We know that positive ion is always smaller and negative
44. (c) 2 Na 2 S2 O3 + I 2 ® Na 2 S4 O 6 + 2 NaI ion is always larger than the corresponding atom.
Sodium
tetrathion ate Therefore the correct order of the size is I - > I > I +
6. (a) F is more electronegative than Cl therefore HF bond is
45. (d) I- can act as reducing agent only and not oxidising stronger than HCl and hence proton is not given off easily
since its O.S. can change from 0 to +7 only and hence HF is a weakest acid.
46. (a) 2KClO3 + I 2 ® 2KIO3 + Cl 2 0 +1 -1
+5 O.S. of iodine is more stable than chlorine 7. (b) H 2 O + B r2 ¾¾
® HOBr+ HBr
47. (b) 2KI + CuSO 4 ® K 2SO 4 + CuI 2 Thus here oxidation number of Br increases from 0 to +1
and also decreases from 0 to –1. Thus it is oxidised as
2CuI 2 ® Cu 2 I 2 + I 2 well as reduced.
48. (d) Reactivity follows the order F > Cl > Br > I 8. (d) HO Cl < HO Cl O < HO Cl O 2 < HO Cl O3
49. (a) See text +1 +3 +5 +7
50. (d) Basic character increases down the group In case of oxyacids of similar element as the oxidation
number of the central atom increases, strength of acid
51. (a) Iodine is used as an antiseptic
also increases.
52. (d) 2CaOCl 2 ¾CoCl
¾¾ ¾ 2 ® 2CaCl + O (see text )
2 2 9. (b, c) From the given options we find option (a) is correct.
The oxidising power of halogens follow the order
+
F2 > Cl2 > Br2 > I2. Option (b) is incorrect because it in
53. (b) In HNO3 + HF ® H 2 NO3 + F- HNO3 accepts H+ hence
not the correct order of electron gain enthalpy of
it is a base halogens.
54. (a) NaClO is a salt of strong base and weak acid hence on The correct order is Cl2 > F2 > Br 2 > I2. The low value of
hydrolysis the solution will be most basic, therefore F2 than Cl2 is due to its small size.
maximum pH. Option (c) is incorrect. The correct order of bond
55. (d) Interhalogen compounds are not highly volatile dissociation energies of halogens is
56. (c) I – F is most polar. The more the electronegativity Cl2 > Br2 > F2 > I2.
difference, the more is polar character of bond Option (d) is correct. It is the correct order of
57. (b) 2KClO3 ® 2KCl + 3O 2 electronegativity values of halogens. Thus option (b)
and (c) are incorrect.
1
58. (a) ICl7. The hybridisation is (7 + 7 + 0 - 0) = 7 (sp3d3 ) 10. (c) MI > MBr > MCl > MF. As the size of the anion decreases
2 covalent character also decreases.
59. (a) When atomic orbitals present in the same principle energy 11. (d) Since all the halogens have a strong tendency to accept
level overlap, a strong bond is formed. In case of F and electrons. Therefore halogens act as strong oxidising
B, atomic orbitals are from second principle energy levels. agents and their oxidising power decreases from fluorine
60. (a) Fluorosis is caused due to reaction of Ca with excess of to iodine.
fluoride in the body 12. (c) The correct order of increasing bond angle is
61. (c) The strength of H- bonding follows the order Cl2 O < ClO 2- < ClO 2
F>O>N
Cl2O2 ClO2 2
ClO2 2
EXERCISE 3 ..
O . Cl . .
..
..
Cl
1. (b) ClO2 contains 7 + 12 i.e. 19 electrons (valence) which is
an odd number, i.e. there is (are) free electron(s). Hence it . . 110° . . . . 118°
Cl Cl .O. O O O
..
..
..
..
..
..
..
..
.. ..
..
is paramagnetic in nature.
..
–
* In ClO2 there are 2 lone pairs of electrons present on
2. (c) Pure ClO2 is obtained by passing dry Cl2 over AgClO3 at
90°C. the central chlorine atom. Therefore the bond angle in
90°C ClO2– is less than 118° which is the bond angle in ClO2
2AgClO 3 + Cl 2 (dry ) ¾¾¾® 2AgCl + 2ClO 2 + O 2
which has less number of electrons on central chlorine
3. (d) Calcium chlorite is Ca (ClO2 ) 2 atom.
720 Chemistry
13. (b) HClO4 is the strongest acid amongst all because the
11. (b) 6CaOCl 2 ® Ca (ClO3 ) 2 + 5CaCl 2
oxidation state or Cl is maximum (+7).
14. (a) SF4 has 4 bond pairs and 1 lone pair of electrons, sp3d (disproportionation or auto oxidation)
12. (d) All the factors are responsible for the greater reactivity
F of F2
| F
hybridisation leads to irregular shape S and
| 13. (c) SO 2 + Cl 2 ® SO 2 Cl 2
F Sulphuryl chloride
F
resultant m ¹ 0. 14. (b) NaF + HF ® NaHF2
15. (a) 4HCl + O 2 ® 2Cl 2 + 2H 2 O 15. (d) The reactivity of halogens follows the order
cloud of white fumes F2 > Cl 2 > Br2 > I 2 Hence I2 cannot replace Br 2 from
16. (d) The fluorine has low dissociation energy of F - F bond KBr.
and reaction of atomic fluorine is exothermic in nature
16. (a) In ClO -4 the Cl is present in its highest O.S of +7 hence
17. (a) CN - ion acts good complexing as well as reducing it can undergo reduction and not oxidation
agent.
17. (a) KF + HF ® KHF2
18. (c) The H–X bond strength decreases from HF to HI. i.e.
HF > HCl > HBr > HI. Thus HF is most stable while HI is 18. (b) 2KI + Cl 2 ® 2KCl + I 2
least stable. This is evident from their decomposition
I 2 + CCl 4 ® Violet Colour
reactions. The decreasing stability of the hydrogen halide
is also reflected in the values of dissociation energy of Note: The excess of Cl2 should be avoided. The layer
the H–X bond may become colourless due to conversion of I 2 to HIO 3
9. (c) 2KClO3 + 4HCl ® 2KCl + Cl 2 + 2ClO 2 + 2H 2O 27. (b) Except ionisation potential other factors are true to explain
The mixture of (Cl 2 + ClO 2 ) is known as ‘euchlorine”. the oxidising (strong) behaviour of F2 .
10 (b) 2CaO + 2Cl 2 ® CaCl 2 + Ca (ClO) 2 28. (b) 2KMnO 4 + 16HCl ® 2KCl + 2MnCl 2 + 8H 2 O + 5Cl 2
21D
The p-Block Elements-
Noble Gases
INTRODUCTION : 6. Melting and boiling points- Due to the increase in magnitude
The group 18 of the periodic table consists of colourless, odourless of Van der waals forces, the mpt and bpt increases from He
gases at room temperature, isolated by William Ramsay and lord to Rn.
Rayleigh in 1898 from air. They realized that a sample of nitrogen 7. Atomic radii- The atomic radii increases from He to Rn and
formed synthetically had a different density than obtained from air it corresponds to the vander waals radii.
after removing oxygen, water vapour and carbon dioxide. The 8. Critical temperature/critical pressure- The critical
sample from air was heavier and it was found to contain 1.0% temperature (Tc) and Critical pressure (Pc) of noble gases
mixture of inert gases by volume (except Rn). Radon was obtained increase down the group
by radioactive disintegration of radium.
Element He Ne Ar Kr Ye Rn
Helium is second most abundant element in the universe.
Argon is the most abundant of all the inert gases in the Tc(K) 5.1 44.3 150.6 211.0 256.4 373.5
atmosphere. Pc(Atm) 2.26 26.86 47.99 54.3 58.2 62.4
GENERAL CHARACTERISTICS : 9. Density- The density of noble gases increases down the
1. Electronic configuration : group.
Element Sym bol At No. Valence shell electronic confg. 10. Heat of vaporisation - They have very low values of heat of
vaporisation due to weak van der waals forces of attraction.
Helium He 2 1s 2
The value increases down the group.
Neon Ne 10 [He] 2s 22p 6
11. Solubility in water- They are slightly soluble in water and
Argon Ar 18 [Ne] 3s 23p 6
solubility increases from He te Rn.
Kr yp to n Kr 36 [Ar] 3d104s 24p 6
12. Liquefication - It is extremely difficult to liquefy inert gases
Xenon Xe 54 [Kr] 4d10, 5s 25p 6 due to weak van der waals forces of attraction among their
Radon Rn 86 [Xe] 4f14, 3d10, 6s26p 6 molecules. Hence they possess low value of critical
temperature also.
2. Physical state - They are all gases under ordinary conditions
of temperature and pressure. 13. Ionisation energy- All noble gases possess very stable (ns2
3. Presence - Except Radon all occur in atmosphere in dry air and ns2p6) electronic configuration. Therefore, ionisation
10% by volume. Main commercial source of helium is natural energy of noble gases is very high and decreases down the
gas . group.
4. Abundance- In 1.0% air the abundance follows the order 14. Electron affinity- Due to the presence of stable electronic
configuration they have no tendency to accept additional
Ar> Ne>He>Kr> Xe
electron. Therefore electron affinity is almost zero.
5. Atomicity- The Cp/Cv =1.67 shows their monoatomic nature.
722 Chemistry
15. Polarizability- The polarizability increases with the size and SEPARATION OF RARE GASES BY DEWAR’S
hence follows the order. METHOD:
He< Ne< Ar< Kr< Xe It is as follows
16. Adsorption by charcoal- Except helium all are adsorbed by [He, Ne, Ar, Kr, and Xe] + Coconut charcoal at 171K
coconut charcoal at low temperature. The extent of
adsorption increases down the group.
DISCOVERY : He, Ne unadsorbed Ar, Kr, Xe Absorbed
+ charcoal at 93K +Coconut charcoal
(i) Argon- It was isolated by Rayleigh and confirmed by at liquid air temperature
Ramsay, from air (free from O2, moisture and CO2). Due to its
Ne He Ar Kr, Xe
inertness the gas was named as argon (meaning lazy). diffused Remain in first
Adsorbed unadsorbled
(ii) Helium- It was observed in the spectrum of the sun hence in another Charcoal
Charcoal Temperature
name helium, from helios, which means sun, by Lockyer raised to 183K
and Frankland. Ramsay obtained it from gases occluded in
Kr Xe
uranium minerals. evolved remains
adsorbed
(iii) Neon, Krypton and Xenon- These were obtained by
fractional distillation of liquid air under reduced pressure.
These were named as neon means “new” krypton means From liquid air - The difference in the boiling points of
“hidden” and Xenon means “stranger or foreigner”. various constituents of liquid air make possible their
separation by fractional distillation.
(iv) Radon- Spectroscopically was noticed by Dorn and isolated
by disintegration of radium by Rutherford and Soddy. Element He Ne N2 Ar O2 Kr Xe
B.pt (K) 4 27 77 87 90 121 124
Ra 226 ¾
¾® Rn 222 + He 4
88 86 2 HELIUM FROM OTHER SOURCES:
ISOLATION OF RARE GASES : He is also obtained by heating mineral clavite to 1273K . The gas
The following methods are employed for the isolation of Rare evolved is collected over potash solution to free from any CO2.
gas mixture. It may also be obtained from mineral by heating with dil.H2SO4
or KHSO4.
(i) Ramsay and Rayleigh’s first method-
Properties- The noble gases are inert in nature because of their
Air (dry and free from CO2)
completely filled s and p subshells. In 1962 the first compound of
D D noble gases was prepared. It is hexa fluoroplatinate prepared by
¾¾® 2Cu + O 2 ¾
¾® CuO ¾¾®
Cu Mg Bartlett.
Residual gas - mixture of inert gases. Now many compounds of Xe and Kr are known with fluorine and
(ii) Ramsay and Rayleigh’s second method oxygen.
No compounds of He, Ne or Ar exist, except under very special
discharge NaOH conditions (very unstable, not neutral compounds)
Air + O 2 ¾¾¾¾® N 2 + O 2 ® 2NO ¾¾¾® 2NO 2
6000 -8000V Rn is known to react with fluorine but its radio activity makes the
2NO + O 2 ® 2NO 2 study of its compounds difficult and dangerous. Kr forms one
(CO2 and NO2 are absorbed by NaOH and O2 if any is stable neutral molecule, KrF2. A, Kr- N bond has also been
removed by alkaline pyrogallol) reported, stable only below –50º C.
(iii) Fischer and Ringe’s method- Xe forms several compounds with fluorine and oxygen and Xe-N
and Xe-C bonds have been reported.
90%CaC2 D
R Air 10%CaCl ¾¾® CaC2 + N 2 ® [CaCN 2 + C ] 673K
Xe + F2 ¾¾¾® XeF2 673K
Xe + 2F2 ¾¾¾® XeF4
2 373K Nitrolium (C is graphite)
5- 6Atm
2 :1
C + O 2 ® CO 2 1: 5
..
XeF2 hybridization sp3d Xe Linear
..
oxygen dilutant) for divers. Mixture of O2 and He is used in
the treatment of asthma. It is also used for inflating the tyres
..
F of aeroplanes.
.. (2) Neon - When an electric current is passed through a sample
F F
of the gas, it has a characteristic orange - red glow. Neon
XeF4 hybridization sp3d2 Xe square planar lighting is used for advertising. The noble gases argon
F .. F (purple), Xenon (blue green) and Krypton (pale violet) are
also used in “neon” lighting.
F
F .. F (3) Argon - It is used primarily to create an inert atmosphere in
XeF6 Hybribisation sp3d3 Xe light bulbs, welding and fluorescent bulbs. It is also used in
geiger counters, as it becomes ionised in the presence of
F F radiation. The ratio of 40K to 40Ar can be used to date the
F
Pentagonal pyramidal or distorted octahedral age of rocks since argon is obtained by radioactive decay
XeO3 is the anhydride of Xenic acid H2XeO4 - The structures of of an isotope of potassium.
oxyfluorides and oxides of Xenon are as follows. (4) Krypton - The light emitted by Krypton in an electric
O discharge tube is used for runway and approach lights in
..
F F airports.
Xe Xe (5) Xenon - It is used in electrical flash bulbs for high speed
.. O O photography.
F F
O (6) Radon - In radiotherapy of cancer.
XeOF4 XeO3
CLATHRATES :
Square pyramidal trigonal pyramidal
A number of organic and inorganic compounds having noble
(sp3d2) (sp3)
gases trapped into the cavities of crystal lattices are called
enclosure or clathrate compounds. They are known as cage
F
compounds also.
Xe = O The substance having cavities in crystal lattices is called the
host and atom of noble gases entraped in it is called the guest
F which are held by Van der waals forces of attraction. The clathrates
XeOF2 are non stoichiometric compounds. When clathrates are heated
T – shaped or dissolved the guest atom escapes from the host.
(sp3d)
He and Ne do not form clathrates due to their small size.
F Types of Clathrates - They are of two types.
(i) Gas hydrates - Solid water having entraped Ar, Kr, or Xe
Xe Xe
(ii) Quinol Clathrates - Quinol having entraped Ar, Kr, and Xe
F
Uses of Clathrates
XeO2F2 XeO4
See-Saw (i) Separation of noble gases - Since Ne does not form a
Tetrahedral
(sp3d) clathrate with Quinol it is separated from Ar, Kr and Xe. The
(sp3)
latter form a clathrate with quinol.
(ii) Xe- 133 clathrate is a source of g- radiations
F F
Xe F (iii) Kr - 85 clathrate is a source of b - radiations
F F (iv) As an anaesthetic - Xe clathrate is used for this
– (v) For transporting isotopes of noble gases.
XeF5
Pentagonal planar
3 3
(sp d )
724 Chemistry
Very Short/Short Answer Questions 14. In XeF2, XeF4, XeF6 the number of lone pairs on Xe are
1. Why do noble gases form compounds with fluorine and respectively
oxygen only? (a) 2, 3, 1 (b) 1, 2, 3 (c) 4, 1, 2 (d) 3, 2, 1.
2. Which compound led to the discovery of noble gas 15. Total number of lone pair of electrons in XeOF4 is
compounds. (a) 0 (b) 1 (c) 2 (d) 3
3. Among the noble gases, Xe forms maximum noble gas 16. Which of the following is least polarisable ?
compounds with fluorine. Why is it so? (a) Ne (b) He (c) Xe (d) Kr
4. Why do boiling points of noble gases increases from helium 17. End-product of the hydrolysis of XeF6 is
to radon? (a) XeF4O (b) XeF2O2 (c) XeO3 (d) XeO3 –
5. Neon is generally used for warning signals. Why? 18. For advertisement, the coloured discharge tubes contain :
6. Give equations for the following : (a) He (b) Ne (c) Ar (d) Kr
(i) XeF2 + H2O ¾¾ ® 19. Which one of the following noble gases is not found in the
(ii) XeF6 + H2O ¾¾ ® atmosphere?
(iii) XeF6 + PF5 ¾¾ ® (a) Rn (b) Kr (c) Ne (d) Ar
(iv) XeF6 + NaF ¾¾ ® 20. Noble gases are group of elements which exhibit
7. How is XeO3 prepared? Write chemical equation. (a) high chemical activity
8. Solubility of noble gases in water increases as we more down (b) low chemical activity
the group. Explain. (c) minimum electronegativity
9. Why noble gases have low boiling point? (d) paramagnetic properties
10. Xenon does not form fluorides, such as XeF3 and XeF5. 21. Which one of the following statements regarding helium is
Why? incorrect ?
(a) It is used to produce an d sustain powerful
Multiple Choice Questions
superconducting magnets.
11. Which of the following fluorides of xenon is impossible?
(b) It is used as a cryogenic agent for carrying out experiments
(a) XeF2 (b) XeF3 (c) XeF4 (d) XeF6
at low temperatures.
12. The structure of XeF6 is (c) It is used to fill gas balloons instead of hydrogen because
(a) distorted octahedral (b) pyramidal it is lighter and non-inflammable.
(c) tetrahedral (d) None of these (d) It is used in gas-cooled nuclear reactors.
13. Which of the following statements is false ? 22. Which inert gas show abnormal behaviour on liquefaction
(a) Radon is obtained from the decay of radium (a) Xe (b) He (c) Ar (d) Kr
(b) Helium is inert gas 23. The ease of liquefaction of noble gases increases in the order
(c) Xenon is the most reactive among the rare gases (a) He < Ne < Ar < Kr < Xe (b) Xe < Kr < Ne < Ar < He
(d) The most abundant rare gas found in the atmosphere is (c) Kr < Xe < He < Ne < Ar (d) Ar < Kr < Xe < Ne < He
helium
1. The last member of the family of inert gases is (a) Neon (b) Radon
(a) argon (b) radon (c) Argon (d) Helium
(c) xenon (d) neon 4. Number of unpaired electrons in inert gas is
2. Which of the following is the correct sequence of the noble (a) zero (b) 8
gases in their group in the periodic table? (c) 4 (d) 18
(a) Ar, He, Kr, Ne, Rn, Xe (b) He, Ar, Ne, Kr, Xe, Rn 5. In the following four elements, the ionisation potential of
(c) He, Ne, Kr, Ar, Xe, Rn (d) He, Ne, Ar, Kr, Xe, Rn which one is the highest ?
3. Which of the following noble gases do not have an octet of (a) Oxygen (b) Argon
electrons in its outermost shell? (c) Barium (d) Cesium
The p-Block Elements -Noble Gases 725
6. The elements which occupy the peaks of ionisation energy 21. What are the products formed in the reaction of xenon
curve are hexafluoride with silicon dioxide ?
(a) Na, K, Rb, Cs (b) Na, Mg, Cl, I (a) XeSiO4 + HF (b) XeF2 + SiF4
(c) Cl, Br, I, F (d) He, Ne, Ar, Kr (c) XeOF4 + SiF4 (d) XeO3 + SiF2
7. Gradual addition of electronic shells in the noble gases 22. XeF6 on complete hydrolysis gives
causes a decrease in their (a) Xe (b) XeO2
(a) ionisation energy (b) atomic radius (c) XeO3 (d) XeO4
(c) boiling point (d) density 23. XeF4 involves which hybridization
8. Which of the following noble gas is least polarisable? (a) sp (b) sp 2
2
(c) sp d (d) sp 3d 2
(a) He (b) Xe
(c) Ar (d) Ne 24. Shape of XeOF4 is
9. In which of the following groups, when He is placed, its all (a) octahedral (b) square pyramidal
the properties are satisfied (c) pyramidal (d) T-shaped
(a) with alkali metals (b) with halogens 25. The hybridization of Xe in XeF2 is
(c) with inert gases (d) None of these (a) sp 3 (b) sp 2
3
(c) sp d (d) sp 2 d
10. The most abundant inert gas in the atmosphere is
(a) He (b) Ne 26. Which is a planar molecule ?
(c) Ar (d) Kr (a) XeO4 (b) XeF4
11. The lowest boiling point of helium is due to its (c) XeOF4 (d) XeO2F2
(a) inertness 27. Which of the following has sp3 hybridization ?
(b) gaseous nature (a) XeO3 (b) BCl3
(c) high polarisability (c) XeF4 (d) BBr3
28. Which of the following two are isostructural ?
(d) weak van der Waals forces between atoms
12. Which one of the following elements is most reactive ? (a) XeF2, IF2- (b) NH3, BF3
(a) He (b) Ne
(c) Ar (d) Xe (c) CO32 - ,SO32 - (d) PCl5, ICl5
13. Which of the noble gas has highest polarisability? 29. The number of lone pair of electrons present on Xe in XeF2
(a) He (b) Ar is
(c) Kr (d) Xe (a) 3 (b) 4
14. What is the atomic number (Z) of the noble gas that reacts (c) 2 (d) 1
with fluorine ? 30. Match List I with List II and select the answer using the
(a) 54 (b) 10 codes given below :
(c) 18 (d) 2 Code List I Code List II
15. Noble gases are group of elements which exhibit very A XeF4 1 Distorted octahedral
(a) high chemical activity
B XeF6 2 Tetrahedral
(b) low chemical activity
C XeO3 3 Square planar
(c) minimum electronegativity
(d) much paramagnetic properties D XeO4 4 Trigonal pyramidal
16. The correct order of solubility in water for He, Ne, Ar, Kr, Xe (a) A-4, B-1, C-3, D-2 (b) A-2, B-3, C-1, D-4
is (c) A-1, B-4, C-2, D-3 (d) A-3, B-1, C-4, D-2
(a) He > Ne > Ar > Kr > Xe (b) Ne > Ar > Kr > He > Xe 31. Hybridization and structure of XeF4 is
(c) Xe > Kr > Ar > Ne > He (d) Ar > Ne > He > Kr > Xe (a) sp3d, trigonal bipyramidal(b) sp3, tetrahedral
17. The noble gas which was discovered first in the sun and (c) sp3d2, square planar (d) sp3d2, hexagonal
then on the earth 32. Number of lon e pairs of electrons on Xe atoms
(a) argon (b) xenon XeF2, XeF4 and XeF6 molecules are respectively
(c) neon (d) helium (a) 3, 2 and 1 (b) 4, 3 and 2
18. XeF4 on partial hydrolysis produces (c) 2, 3 and 1 (d) 3, 2 and 0
(a) XeF4 (b) XeOF2 33. Which one of the following is correct pair with respect to
(c) XeOF4 (d) XeO3 molecular formula of Xenon compound and hybridization
19. Which element out of He, Ar, Kr and Xe forms least number state of Xenon in it?
of compounds ? (a) XeF4, sp3 (b) XeF2, sp
(a) He (b) Ar (c) XeF2, sp3d (d) XeF4, sp2
(c) Kr (d) Xe 34. The coloured discharge tubes for advertisement mainly
20. The element which has not yet been reacted with F2 is contain
(a) Ar (b) Xe (a) xenon (b) helium
(c) Kr (d) Rn (c) neon (d) argon
726 Chemistry
35. Sea divers go deep in the sea water with a mixture of which 37. In the clathrates of xenon with water, the nature of bonding
of the following gases between xenon and water molecule is
(a) O2 and He (b) O2 and Ar (a) covalent
(c) O2 and CO2 (d) CO2 and Ar (b) hydrogen bonding
36. Which of the following is the life saving mixture for an (c) co-ordinate
asthmas patient ? (d) dipole-induced dipole interaction
(a) Mixture of helium and oxygen 38. Which of the following cannot be formed ?
(b) Mixture of neon and oxygen (a) He2+ (b) He+
(c) Mixture of xenon and nitrogen (c) He (d) He2
(d) Mixture of argon and oxygen
1. Noble gases do not react with other elements because (c) It is used to fill gas balloons instead of hydrogen because
(a) they are mono atomic [CBSE PMT 1994] it is lighter and non-inflammable
(b) they are found in abundance (d) It is used in gas-cooled nuclear reactors
(c) the size of their atoms is very small 5. Which one of the following reactions of xenon compounds
(d) they are completely paired up and stable electron shells is not feasible? [AIEEE 2009]
2. Which of the following statements is false ? (a) 3XeF4 + 6H 2 O ¾¾ ® 2Xe + XeO 3 +12HF +1.5O 2
[CBSE PMT 1994] (b) 2XeF2 + 2H 2 O ¾¾ ® 2Xe + 4HF + O 2
(a) Radon is obtained from the decay of radium
(c) XeF6 + RbF ¾¾ ® Rb[XeF7 ]
(b) Helium is inert gas
(c) Xenon is the most reactive among the rare gases (d) XeO3 + 6HF ¾¾ ® XeF6 + 3H 2 O
(d) The most abundant rare gas found in the atmosphere is 6. Which of the following has maximum number of lone pairs
helium associated with Xe ? [AIEEE 2011 RS]
3. XeF2 is isostructural with : [NEET 2013] (a) XeF4 (b) XeF6
(a) ICl2– (b) SbCl3 (c) XeF2 (d) XeO3
(c) BaCl2 (d) TeF2 7. Total number of lone pair of electrons in XeOF4 is
4. Which one of the following statement regarding helium is (a) 0 (b) 1 [IIT-JEE 2004]
incorrect ? [AIEEE 2004] (c) 2 (d) 3
(a) It is used to produce and sustain powerful 8. The shape of XeO2F2 molecule is [IIT-JEE 2012]
superconducting magnets (a) trigonal bipyramidal (b) square planar
(b) It is used as a cryogenic agent for carrying out (c) tetrahedral (d) see-saw
experiments at low temperatures
1. Density of nitrogen gas prepared from air is slightly greater 4. If two liters of air is passed repeatedly over heated copper
than that of nitrogen prepared by chemical reaction from a and heated Mg till no further reduction in volume takes place
compound of nitrogen due to the presence of the volume finally obtained will be approximately
(a) argon (a) 200 mL (b) 20 mL
(b) carbon dioxide (c) zero (d) 10 mL
(c) some N3 molecules analogous to O3 5. The atomic weight of noble gases is obtained by using the
(d) greater amount of N2 molecules derived from N-15 relationship
isotope (a) Atomic weight = equivalent weight × valency
2. A radioactive element X decays to give two inert gases X is (b) Atomic weight = equivalent weight/ valency
(c) At. weight = valency/ equivalent weight
(a) 238 (b) 226
92 U 88 Ra (d) 2 × V.D. = molecular weight = atomic weight
(c) Both (a) and (b) (d) Neither (a) nor (b) 6. Compounds formed when the noble gases get entrapped in
3. Coconut charcoal at 100°C adsorbs a mixture of the cavities of crystal lattices of certain organic and inorganic
(a) He and Kr (b) Ar, Kr and Xe compounds are known as
(c) Kr and Xe (d) He and Ne (a) Interstitial compounds (b) Clathrates
(c) Hydrates (d) Picrates
The p-Block Elements -Noble Gases 727
7. The noble gas which behaves abnormally in liquid state is 11. Which is called lazy gas?
(a) Xe (b) Ne (a) Kr (b) Ar
(c) He (d) Ar (c) He (d) Ne
8. Which is called stranger gas 12. Which statement about noble gases is not correct?
(a) Kr (b) Xe (a) Xe forms XeF6
(c) He (d) Ne (b) Ar is used in electric bulbs
9. In order to prevent the hot metal filament from getting burnt, (c) Kr is obtained during radioactive disintegration
when the electric current is switched on, the bulb is filled (d) He has the lowest b.pt among all the noble gases
with 13. Which has the same electronic configuration as of inert gas?
(a) CH4 (b) An inert gas (a) Ag3+ (b) Cu2+
(c) CO2 (d) Cl2 4+
(c) Pb (d) Ti4+
10. In Kroll and IMI process of the production of titanium, the
14. Which noble gas does not form clathrates?
inert gas used is
(a) Xe (b) Kr
(a) Ne (b) Ar
(c) He (d) Ar
(c) Kr (d) Xe
EXERCISE 1 11. (d) Due to weak van der Waal’s forces, He has lowest boiling
point
2. Formation of O2+ [PtF6]–
led to the discovery of first noble
12. (d) Xe forms maximum compounds hence it is most reactive
gas compound Xe[PtF6].
13. (d) The larger the size the more is the polarisiability
5. Neon lights are visible from distance even in fog and mist
14. (a) Atomic number Xe is 54. Xe reacts with F2 and forms
and hence neon is generally used for warning signals. many compounds
6. (i) 2XeF2 + 2H2O ¾¾ ® 2Xe + 4HF + O2 15. (b) Noble gases exhibit low chemical activity
(ii) XeF6 + 3H2O ¾¾ ® XeO3 + 6HF 16. (c) Solubility increases from He to Rn
(iii) XeF6 + PF5 ¾¾ ® [XeF5]+ [PF6]– 17. (d) He was observed in the spectrum of the sun
(iv) XeF6 + NaF ¾¾ ® Na+ [XeF7]–
18. (b) XeF4 + H 2O ® 2HF + XeOF2
7. XeO3 is prepared by hydrolysis of XeF6 or XeF4.
Hydrolysis 19. (a) No compound of He as yet been reported
XeF6 + 3H2O ¾¾¾¾ ¾ ® XeO3 + 6HF
20. (a) No compound of Ar as yet been reported with F2
6XeF4 + 12H2O ® 4Xe + 2XeO3 + 24HF + 3O2
11. (b) 12. (a) 13. (d) 14. (d) 15. (b) 16. (b) 21. (c) 2XeF6 + SiO 2 ® SiF4 + 2XeOF4
17. (c) 18. (b) 19. (a) 20. (b) 21. (c) 22. (b) 22. (c) XeF6 + 3H 2 O ® 6HF + XeO 3
23. (a)
1
23. (d) Hybridisation in XeF4 = (8 + 4 + 0 - 0) = 6 sp3d 2
EXERCISE 2 2
1. (b) Radon is the last member of family 24. (b) XeOF4 square pyramidal
2. (d) He, Ne, Ar, Kr, Xe, Rn 25. (c) Hybridisation of XeF2 is sp3d
3. (d) Electronic configuration of He is 1s2 26. (b) XeF4 is planar (see text)
4. (a) Inert gases do not contain unpaired electrons 27 (a) In XeO3 the hybridisation is sp3
5. (b) Ionization potential of inert gases is highest in periodic 28. (a) XeF2 and IF2- both are linear and have hybridisation
table due to stable electronic configuration.
sp 3 d
6. (d)
7. (a) Ionisation energy decreases as we move away from F
nucleus due to less electrostatic attraction between
electrons and nucleus 29. (a) XeF2 has Xe structure hence number of lone pair
8. (a) The smaller the size the least is the polarisability
F
9. (c) The differentiating electron enter in s subshell in case of
of electrons 3
He, hence it is s- block element. Its electronic
configuration l s2 makes it inert in nature hence it is 30. (d) XeF4 is square planar (A-3) ; XeF6 is distorted octahedral
placed with inert gases. (B-1); XeO3 trigonal pyramidal (C-4) and XeO4 is
tetrahedral (D-2).
10. (c) Ar is the most abundant in atmosphere
728 Chemistry
31. (c) Hybridisation of XeF4 is sp3d2 and structure is square F
planar F
32. (a) XeF2 XeF4 XeF6
Valence electrons of Xe 8 8 8
XeF6 : F Xe F
Electrons involved 2 4 6
in bond formation
Lone pairs left 3 2 1 F F
33. (c) Hybridisation in each case is XeF4sp3d2, XeF2sp3d,
34. (c) Coloured discharge tubes mainly contain Neon
35. (a) Breathing mixture is (O2 + He) Xe
36. (a) Mixture of (He + O2) is used for asthma patient
37. (d) In clathrates the forces are dipole - induced dipole XeO3 : O O
interaction O
1 1p
38. (d) He2 Bond order = (2 - 2) = 0 Hence cannot be formed.
2 Hence XeF2 has maximum no. of lone pairs of electrons.
EXERCISE 3 7. (b) In XeOF4, Xenon is sp3d2 hybridised and has one lone
1. (d) On account of highly stable ns2np6 configuration in the pair.
valence shell. These elements have no tendency either 8. (d) XeO2F2 has trigonal bipyramidal geometry, but due to
to lose gain or share electrons with atoms of other presence of lone pair of electrons on equitorial position,
elements i.e., their combining capacity or valency is zero. its actual shape is see-saw.
Further all the orbitals in the atoms of these elements are F
doubly occupied i.e electrons are not available for O
sharing. Xe
2. (d) The most abundant rare gas found in the atmosphere is
argon and not helium. O
F
3. (a) F ¾ Xe ¾ F sp3d and Linear EXERCISE 4
1. (a) Air contains about 1% inert gases, mainly Ar. (At.wt
– sp3d and Linear
Cl ¾ I ¾ Cl 40) The atomic wt of N2 is 28
4. (c) Helium is heavier than hydrogen although it is non- 226
inflammable
2. (b) 88 Ra ®86 Rn 222 + 2 He 4 . Both are inert gases
5. (d) The products of the concerned reaction react each 3. (b) Coconut charcoal at 100°C absorbs Ar, Kr and Xe
other forming back the reactants. air
4. (b) Cu and Mg ¾¾ ¾ ¾ ¾¾® CuO, MgO and Mg3N2
® XeO3 + 6HF .
XeF6 + 3H 2 O ¾¾ mainly N 2 and O 2
Xe 13. (d) 22 Ti = 1s 2 , 2s 2 p 6 , 3s 2 p 6 d 2 , 4s 2 ; Ti 4+ = 1s 2 , 2s 2 p 6 , 3s 2 p 6
14. (c) He does not form clathrates due to small size and low
XeF4 : F F molecular weight. Ne also does not form clathrates for
the same reason
2 p
22
The d & f Block Elements
GENERAL CHARACTERISTICS : Zn ,Cd, Hg ,the end members of first three series have their
1. Transition elements :- Elements where the last orbitals filled general electronic configuration (n - 1)d 10 ns 2 . These do not
are the d orbitals known as transition elements. They have
been placed in the middle of the periodic table between show properties of transition elements to any appreciable
electropositive s-block and electronegative p-block elements. extent and are called non-typical transition elements.
3. Classification - Transition elements consist of the following
2. General Electronic Configuration :- Transition metals have four series
the electronic configuration (n - 1)d1-10 ns0 - 2 . When
3d series 21 Sc to 30 Zn 3d1-10 4s1- 2
electrons fill orbitals, ns-orbital is filled first than (n - 1) d- 4d series 39 Y to 48Cd 4d 1-105s0 - 2
orbital.When losing during oxidation ,ns electrons are lost 5d series 57 La 72 Hf to 80 Hg 5d1-10 6s1- 2
first than (n-1)d electrons. 6d series 89 Ac 104 Rf to 111Rg
–1
Pd
kJ mol
8
cm3 ), lustrous, malleable, ductile thermal and electrical Hf W Fe Co
Ta Re Cu 3d
conductors.
–2
There is gradual decrease in electropositive character from Ni
1E1 × 10
left to right Mn Ag
Rh 4d
(ii) Melting and boiling point - Due to strong metallic 7 Mo Ru
Tc
bond , they have high mpts and bpts. The mpts of these Zr Nb
elements rise to a maximum and then fall with the increase Ti
in atomic number the manganese and technitium show Cr
V
abnormal values as shown by graph) Sc
6
W
Transition elements
3500
Re First ionization energies of 3d-4d- and 5d-
Ta transition series
3000
Mo Os
Tc
Ir
2500 Nb (iv) Electrode potential ( E 0 ) ( E 0 M n+ M ) is governed by
Ru
three factors
Melting Point (K)
Zr Cr Rh
2000 Ti
V Pt (a) Heat of sublimation
Hf Fe
Y Pd (b) Heat of ionisation
(c) Heat of hydration
)
Co Ni
ies eries
1500
s)
Sc Cu
serie
s
Mn
For the 3d transition metals the E 0 M 2 + / M values are
(4d
Au
Ag
(5d
ser
1000
La V Cr Mn Fe Co Ni Cu
(3d
Zn
-1.18 -0.91 -1.18 -0.44 -0.28 -0.25 0.35
500 (Volts)
Cd The irregular trend is due to variation in ionization energies
and sublimation energies. Except copper
Hg 3d elements are good reducing agents but weaker than s-
1 2 3 4 5 6 7 8 9 10 11 12
block elements.
(v) Oxidation states -In different types of compounds ,
Periodic Groups
Melting point of Transition metals transition metals exhibit different oxidation states. The
highest oxidation state is exhibited in fluorides and oxides.
(iii) Ionisation energy- The ionisation energy increases with
In lower oxidation state the compounds formed are ionic
the increase in the atomic number but not in regular manner.
and in higher oxidation state they are covalent in nature.
The ionisation energies of 5d elements are higher than
Osmium exhibit +8 O.S. (highest)often but Ru exhibit +8
those of 4 d and 3d elements due to greater effective nuclear
oxidation state rarely. Transition metals also show oxidation
charge which in turn is due to poor shielding of nucleus by
states +1 and zero.
4f electrons.
Fe3+ is more stable than Fe2+. Hence Fe2+ act as reducing
Formation of Ni ++ requries 2.49 kJ mol-1 and formation agent Cr3+ is more stabe than Cr2+. Hence Cr2+ act as
Pt ++ requries 2.66 kJ mol -1 . Hence Ni (II) compounds reducing. Mn2+ is more stable than Mn 3+ Hence Mn3+ act
are thermodynamically more stable than Pt (II) Compounds. as oxidising agent
(vi) Atomic and Ionic radii - The values for atomic radii and
Formation of Ni 4 + requires 11.29 kJ mol-1 and ionic radii are in between the values for s and p-block
elements. In 3d transition series the ionic radii for
formation of Pt 4 + requires 9.36 kJ mol-1 . Hence Pt
M 2 + ion decreases upto the middle of the period then
(IV) compounds are relatively more stable than nickel (IV)
becomes almost constant (see table)
compounds. Thus K 2 PtCl6 is well known where as the Due to lanthanide contraction the second and third member
corresponding nickel compound is not known. (Ionisation of each group have atomic redii close to each other (Zr.160
energy graph is sketched here for ready reference) pm ,Hf 159pm)
The d & f-Block Elements 731
TABLE
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radii (pm) 144 132 122 117 117 117 116 115 117 125
I. E. kJ mol–1 631 656 650 652 717 762 758 736 745 906
Oxidation State +3 (+2) +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 (+3) +3 +3 (+3) +2
+5 (+5) (+6)
+6 +7
Element Y Zr Nb Mo Tc Ru Ph Pd Ag Cd
Atomic radii 180 160 160 146 136 134 134 137 144 154
(pm)
I.E. (kJ mol–1) 616 674 664 685 703 711 720 804 731 876
Oxidation State +3 (+3) (+2) (+2) +4 +2 +3 +2 +1 +2
+4 (+3) +3 (+5) +3 +4 (+3) (+2)
(+4) +4 +7 +4 (+6) +4 (+3)
+5 +5 (+5)
+6 (+6)
(+7)
(+8)
Element La Hf Ta W Re Os Ir Pt Au Hg
Atomic radii (pm) 187 159 146 139 137 135 136 138 144 157
I.E. (kJ mol–1) 541 760 760 770 759 840 900 870 889 1007
Oxidation State +3 (+3) (+2) +2 +3 (+2) (+2) +2 +1 +1
+4 (+3) (+3) +4 (+3) +3 (+3) +3 +2
(+4) +4 +5 +4 +4 +4
+5 +5 +6 +6 (+6) (+5)
+6 +7 +8 (+6)
(vii)Density - d-block elements have high density because of their small atomic sizes and strong metallic bonding.
Density Sc Ti V Cr Mn Fe Co Ni Cu Zn
g/ml 3.0 4.54 6.10 7.19 7.40 7.87 8.70 8.90 8.92 7.13
(viii)Atomic volume - Atomic volume decreases along the Colour of a complex depends on the metal, its oxidation
period due to decrease in size. state and its ligands. e.g.
(ix) Reactivily -d-block elements are less reactive due to high 2+
ionisation energies. Some are almost inert and known as é Cu ( H 2O ) ù is Pale blue
ë 4û
noble metals, e.g. Au, Pt, Ru, Rh, Os, Ir etc.
2+
(x) Complex formation - They are well known to form a large éCu ( NH3 ) ù is Dark blue
ë 4û
number of complex compounds mainly due to
(i) Small atomic size and higher nuclear charge. CuSO 4 .5H 2 O is blue in colour and anhydrous CuSO4 is
(ii) Presence of partly filled or vacant orbitals colourless. In absence of ligands all d orbitals are degenerate
eg. K 4 [Fe (CN )6 ] (same energy) and the possbility of d-d excitation is no
(xi) Coloured ions - The colour exhibited by transition metal more. In presence of ligand d and d have higher
x 2 -y2 z2
ions is due to the presence of unpaired electrons in d- energy, d-d transition take place by absorption of light,
orbitals which permits the d-d excitation of electrons. hence the colour.
732 Chemistry
(xii) Magnetic properties -They are 2. Extraction - It is extracted from haematite Fe2 O3 in a blast
(i) Paramagnetic- This is due to the presence of unpaired
furnace by reduction with carbon and carbon monoxide. The
electrons in d-orbitals. Paramagnetic character increases
steps inolved are-
with the number of unpaired electrons.
(ii) Diamagnetic - Diamagnetic substances are repelled (a) Concentration - The crushed ore is agitated with water
and then concentrated by electromagnetic method.
by an applied magnetic field.
(iii) Ferromagnetism - In this case permanent magnetic (b) Roasting or Calcination- To remove volatile substances
moment is acquired by substance e.g. Fe. Magnetic and organic matter. FeO changes to Fe2 O3
moment is given by
S + O 2 ® SO2
= n(n + 2 ) B.M. where n = number of unpaired 4As + 3O2 ® 2As2 O3
electrons and B.M. = Bohr magneton (unit of magnetic
moment) FeCO 3 ® FeO + CO 2
(xiii)Catalytic properties - The transition metals and their 4FeS 2 + 11O 2 ® 2Fe 2 O 3 + 8SO 2
compounds behave as catalyst due to 4FeO + O 2 ® 2Fe 2 O 3
(a) The presenc of partly filled d-orbitals and exhibiting (c) Smelting - Roasted or calcinated ore is mixed with lime
various oxidation states. stone and coke and fed into blast furnace. Reactions taking
(b) Their formation of intermediate complex with reactants place in the blast furnace.
and thus lowering the energy of activation (i) Lower region C + O 2 ® CO 2 + 97, 000 cal.
(c) Their rough surface area provides active sites for
adsorption of reactant molecules. eg. (ii) Middle region
Iron in the preparation of NH 3 (Habers process) CO2 + C ® 2CO - 39000 cal.
Finely divided nickel for hydrogenation CaCO3 ® CaO + CO2 - heat
Pt or V 2 O5 in the preparation of H 2 SO4 CaO + SiO 2 ® CaSiO3 (Slag )
(Contact process)
Fe 2 O 3 + 3CO ® 2Fe + 3CO 2
Pt in the preparation of nitric acid (Ostwald’s process)
Fe 2 O 3 + CO ® 2FeO + CO 2
(xiv)Formation of alloys -d block elements have a strong (iii) Upper region Fe3O 4 + CO ® 3FeO + CO 2
tendency to form alloys since their atomic sizes are very FeO + C ® Fe + CO
similar and in the crystal lattice one metal can be readily The gases leaving the furnace contain CO and used to heat
replaced by another. Alloys so formed are hard, have high incoming air blast.The two layers in the blast furnace are-
m.pts. The metals Mo, W, Cr, Ni, and V are used for the
Upper layer - Molten Iron - It is poured out in moulds and
production of stainless steel and alloy steel.
known as PIG IRON or CAST IRON.It contains 3-5% carbon
Amalgam is an alloy formed by mercury with other metals.
and varying amounts of Mn, Si, P and S which make the
Iron and platinum do not form any alloy with mercury. iron hard and brittle.
(xv) Interstitial compounds - The empty space persent in a
crystal lattice is known as interstitial place. The non metal Lower layer - Molten CaSiO 3 ( slag )
atoms due to their small size (eg H, B, N, C etc.) when 3. Wrought -Iron -It is obtained by heating cast iron with haematite.
occupy such place the resulting compound is known The impurities are oxidised.
interstitial compound. Such compounds are hard and rigid Fe 2 O 3 + 3C ® 2Fe + 3CO
e.g. cast iron and steel.
(xvi)Non stoichiometric compounds -The compounds not 2Fe 2 O 3 + 3Si ® 4Fe + 3SiO 2
having the elements in the exact ratio as shown by the
Fe 2O3 + 3Mn ® 2FeO + 3MnO
moleculer formula are known as non stoichiometric
compouds e.g., FeO, CuO etc. In FeO the Fe : O is approx. MnO + SiO 2 ® MnSiO 3 ( slag )
0.94 : 1 and not exactly 1:1. It containes carbon 0.2-0.5% and traces of P and Si. It is pure
form of Iron and soft , malleable, ductile. It is used to make
IRON [Fe, At.No.26, [Ar]3d 4s ]
6 1
magnets in electric cranes and dynamos, railway carriage
Being reactive in nature it does not occur in free state. couplings being corrosion resistant.
1. Ores of Iron- 4. Steel - It contains carbon 0.1-1.5%and manufactured by
Haematite Fe2 O3 following methods.
Magnetite Fe3 O4 (a) Bessemer process - Molten pig iron is heated in large pear
shaped furnace lined with silica bricks at 1873K when
Limonite or hydrated ferric oxide Fe 2 O3 .3H 2 O
impurities such as Mn, Si, C burn off. When all carbon is
Iron pyrites FeS 2 completely burn off the requisite amount of carbon is added.
Siderite FeCO3 Bessemer converter is lined with lime (CaO) or magnesia
(MgO) when pig iron contains high percentage of
copper pyrites CuFeS2
phosphorous.
The d & f-Block Elements 733
(5) Types of steel -
P4 + 5O2 ® P4 O10 (i) Soft steel- contains carbon 0.25%
P4O10 + 6CaO ® 2Ca 3 ( PO 4 )2 (ii) Mild steel - contains carbon 0.25-0.5%
(iii) Hard steel- contains carbon 0.5-1.5 %
Thomas slag (iv) Alloy steel- contains varying percentage of Ni, Cr, Mn,
Co,W, V e.g. stainless steel is an alloy of Fe, Cr and Ni.
(b) Open hearth process- The cast iron, scrap iron , haematite (6) Heat treatment of steel - The hardness of steel depends on its
ore and lime are mixed together and melted in open hearth carbon content and heat treatment.
(i) Quenching- It involves the heating of steel to red hot
furnace lined with SiO 2 or calcined dolomite (MgO. CaO) (1123K) and cooling it by plunging into cold water or oil. It
depending upon the nature of impurities. makes the steel hard and brittle.
(ii) Annealing- The steel is heated well below red heat and
2Fe 2 O3 + 3Si ® 4Fe + 3SiO 2 then cooled slowly. The steel becomes soft.
Fe 2 O 3 + 3Mn ® 2 Fe + 3MnO (iii) Tempering - In this process the quenched steel is reheated
MnO + SiO 2 ® MnSiO 3 (slag ) to 504 to 574K and allowed to cool slowly. The brittleness
P4 + 5O 2 ® P4 O10 disappears and hardness is retained.
P4 O10 + 6CaO ® 2Ca 3 (PO 4 )2 (slag ) (iv) Nitriding- It involves the heating of steel in an atmosphere
of ammonia when surface is coated with iron nitride. The
(c) Electric furnace process - It is combination of Bessemer steel becomes hard.
(v) Case hardening-The steel is heated in charcoal and then
and open hearth process. quenched.The steel becomes hard.
(7) Alloys of steel-The important alloy steels are
Name Composition Uses and Properties
(i) Tungsten steel Fe 94%, W 5%, C 1% It is very hard, resistant to water and used for making
Rock drills and Safetys
(ii) Stainless steel Fe 73% Cr 18%, Ni 8%, C 1% It is resistant to corrosion. Used for making cutlery
(iii) Manganese steel Fe 86%, Mn 13%, C 1% It is hard, used for manufacturing high speed cutting tools
(iv) Invar Fe 64%, Ni 36% It has small coefficent of expansion, used in watches,
meter scales and pendulum rods
(v) Permalloy Fe 21%, Ni 78%, C 1% It is strongly magnetised by electric current and lose
magnetism when current is let off, used for manufacturing
electromagnets and ocean cable.
(vi) Nickel steel Fe96-98%, Ni 2-4% Resistant to corrosion, hard and elastic wire, used for
making cables, gears and drive shafts.
(8) Some chemical properties of Iron- (9) Passivity - The inertness exhibited by metals under conditions
(i) Red hot iron burns in O2 giving sparks when chemical activity is to be expected is called passivity.Iron
becomes passive with conc. HNO3 , Chromic acid ,
3Fe + 2O 2 ® Fe3O 4
(ii) When steam is passed over red hot iron, hydrogen is conc. H2SO4 and KMnO4 etc. It is due to the formation of a
liberated and megnetic oxide of iron (ferroso ferric oxide) is thin layer of oxide at the surface of iron.
formed- (10) Compounds of Iron :
3Fe + 4H 2 O ® Fe3O 4 + 4H 2 (1) Ferric chloride -
(i) It is FeCl3 .6H 2 O
(iii) Action of dil. H 2SO4 -
(ii) Preparation - (i) By passing dry chlorine over heated iron,
Fe + H 2SO 4 ® FeSO 4 + H 2 anhydrous ferric chloride is obtained
(iv) Hot and conc. H 2SO 4 - 2Fe + 3Cl2 ® 2FeCl3 ® Fe 2 Cl6
Fe + 2H 2SO 4 ® FeSO 4 + SO 2 + H 2 O (iii) By the action of hydrochloric acid on ferric hydroxide or
ferric oxide
(v) Action of dil. HNO3 -
Fe ( OH )3 + 3HCl ® 2FeCl 3 + 3H 2 O
4Fe + 10HNO 3 ® 4Fe ( NO3 )2 + NH 4 NO3 + 3H 2O Fe 2 O 3 + 6HCl ® 2FeCl 3 + 3H 2 O
734 Chemistry
It is soluble in water , alcohol and ether. FeCl3 .6H 2 O is yellow.. · Reducing nature - It is strong reducing is nature.
Its aqueous solution is acidic. Sublimes at 300ºC, covalent and 2 KMnO 4 + 3H 2 SO 4 ® K 2 SO 4 + 2MnSO 4 + 3H 2 O + 5O
dissociates above 973K first into FeCl3 then FeCl 2 and Cl2 2 FeSO 4 + H 2 SO 4 + O ® Fe 2 (SO 4 )3 + H 2 O
e.g. · Addition compound with NO which is dark brown
973K 973K
Fe2Cl6 2 FeCl3 2 FeCl2 + Cl2 D
above FeSO 4 + NO ® FeSO 4 .NO ¾¾® FeSO 4 + NO
(vi) Structure of CuSO 4 .5H 2 O - Uses - In gas analysis for absorbing C 2 H 2 and CO. In
· AuCl3 auric chloride forms red crystals. Soluble in water and · Chemical properties -
(i) Action with acids
decomposed on heating. Zn + H 2SO4 ( dilute ) ® ZnSO4 + H 2
AuCl3 ® AuCl + Cl 2 4Zn + 5H 2SO 4 ( 20%H 2SO4 ) ® 4ZnSO 4 + H 2S + 4H 2 O
light yellow powder 3Zn + 4H 2SO4 ( 20%H 2SO 4 ) ® 3ZnSO 4 + S + 4H 2 O
ZINC (Zn) : Zn + 2H 2SO4 ( hot and conc.) ® ZnSO 4 + SO2 + 2H 2 O
Zinc - It is not found free in nature.The principal ores are - 4Zn + 10HNO3 ( cold and dilute ) ® 4Zn ( NO3 )2 + NH 4 NO3 + 3H 2 O
(i) Zinc blende (sphalerite) ZnS
3Zn + 8HNO 3 (mode. conc. ) ¾
¾® 3Zn (NO )3 + 2 NO + 4H 2 O
(ii) Zincite or Red zinc oxide ZnO
Zn + 4HNO 3 (conc. hot ) ¾
¾® ZnNO 3 + 2 NO 2 + 2 H 2 O
(iii) Franklinite ZnO.Fe 2O3
Zn + 2 NaOH ¾ ¾® Na 2 ZnO 2 + H 2
(iv) Calamine or Zinc spar ZnCO3 · Displacement reactions
(v) Willemite 2ZnO.SiO2 Zn + CuSO 4 ® ZnSO4 + Cu ¯
Extraction - It is extracted by reduction process from ZnS (Zinc Zn + Pb ( NO3 )2 ® Zn ( NO3 ) 2 + Pb
blende).
Concentration - The ore is concentrated by froth flotation Zn + 2Na éë Ag ( CN )2 ùû ® Na 2 éë Zn ( CN ) 4 ùû + 2Ag
process.
Roasting - The concentrated Zinc blende is roasted in a current Zn + 2Na éë Au ( CN )2 ùû ® Na 2 éë Zn ( CN ) 4 ùû + 2Au
of air.
· With non metals
2ZnS + 3O2 ® 2ZnO + 2SO2
Zn + Cl 2 ® ZnCl 2
( SO2 is utilised for the manufacturing of H 2SO4 ) Zn + S ® ZnS
If calamine ore is used, it is calcined. · It is powerful reducing in nature.
ZnCO3 ® ZnO + CO2 Fe 2 ( SO 4 )3 + Zn ® 2FeSO 4 + ZnSO 4
Reduction - The ZnO is reduced by mixing with carbon and Uses- Galvanising, sherardizing, in Parke’s process for
heating in fire clay retort. desilverisation of lead , for extraction of Ag and Au
(Cyanide proces). Zinc compounds are used in paints, filling
ZnO + C ® Zn + CO rubber etc.
Purification - Zinc so obtained contains the impurities of Fe, Compounds of Zn
Pb, Cd, As or Sb. It is purified by ZnO - Zinc oxide, Philospher’s wool, zinc white or chinese white.
(a) Distillation or buring
(b) Electrolytic method Preparation - (i) Zn + air ¾¾¾¾ ® ZnO
D
Anode impure ( Zn ) Zn - 2e- ® Zn ++ (ii) ZnCO3 ¾¾ ® ZnO + CO2
D
Cathode pure ( Zn ) Zn ++ + 2e ® Zn (iii) Zn ( NO3 )2 ¾¾ ® ZnO + NO 2 + O 2
Properties - It is white powder becomes yellow on heating but
Electrolyte - Acidic solution of ZnSO4 .
again white on cooling. It sublimes at 673K.
(c) Liquation - Molten Zn is allowed to flow down on sloping · With alkali - It forms zincate.
hearth when non fusible impurities are left behind.
ZnO + 2NaOH + H 2O ® Na 2 éë Zn (OH )4 ùû
Electrolytic method - Pure ZnSO4 is electrolysed when Zn is
deposited on aluminium cathode. It is scrapped off and melted Sodium Zincate
to obtain 99.95% pure metal. · Reduction ZnO + H 2 ® Zn + H 2 O
· Zinc dust -It is prepared by atomising molten zinc with
ZnO + C ® Zn + CO
blast of air.
· Dissolves in acids to form corresponding salts.
· Granulated Zinc - It is prepared by pouring molten Zinc
into cold water. ZnO + H 2SO4 ® ZnSO 4 + H 2 O
Properities- It is bulish white metal, stable in air. Uses - As a white paint , in medicines, glaze in ceramics and filler
· In moist air a protective covering of basic zinc carbonate is in rubber industry.
ZnSO 4 .7H 2O (White vitriol) -
formed at its surface 2ZnCO3 .3Zn ( OH ) 2 .H 2O
· Action of heat -When heated to 500ºC it catches fire with Preparation - By the action of dil. H 2SO4 on Zinc metal, ZnO
bluish white flames forming ZnO which is very light and or ZnCO3
called philospher’s wool.
( Zn, ZnO or ZnCO 3 ) + dil. H 2 SO 4 ® ZnSO 4 .7H 2 O
740 Chemistry
Properties - Colourless, crystalline compound, highly soluble
· It forms mercuric oxide at 300o C .
in water.
Action of heat - 2Hg + O 2 ® 2HgO
373K 723K
ZnSO4 .7H 2 O ¾¾¾® ZnSO4 .H 2 O + 6H 2 O ¾¾¾® ZnSO 4 anhydrous
· Dilute acids have no +action
ZnO SO 2 +onOmercury
2 except dil. HNO3 .
6 Hg + 8HNO 3 ® 3Hg 2 (NO 3 )2 + 2 NO + 4H 2 O
H 2 O + 6H 2O ¾¾¾® ZnSO 4 ( anhydrous ) Strong
¾¾¾
D
® ZnO + SO 2 + O 2
· With concentrated acids
Very Short/Short Answer Questions 16. Complete the following chemical equations:
1. Why is HCl not used to acidify a permanganate solution in (i) MnO-4 ( aq ) + S2O32 - ( aq ) + H 2 O ( l ) ®
volumetric estimations of ferrous ion (Fe2+) or oxalate ion
(C2O42–)? (ii) Cr2 O72- ( aq ) + Fe 2+ ( aq ) + H + ( aq ) ®
2. Why does V2O5 act as catalyst?
3. What is the oxidation state of chromium in (a) potassium 17. State reason for the following :
dichromate (b) potassium chromate? (i) Cu (I) ion is not stable in an aqueous solution.
4. The d-electronic configuration of Co2+ and Cu2+ is d7 and d9 (ii) Unlike Cr3+, Mn2+, Fe3+ and the subsequent other M2+
respectively. Which one of these ions will be more ions of the 3d series of elements, the 4d and the 5d
paramagnetic? series metals generally do not form stable cationic
5. Lanthanum (Z = 57), gadolinium (Z = 64) and lutetium (Z = species.
71) are extra-ordinarily stable in + 3 oxidation state. Explain. 18. How would you account for the following:
6. Why KMnO4 is used in clearing surgical instruments in (i) Among lanthan oids, Ln (III) compounds are
hospitals? predominant, However, occasionally in solutions or in
7. Write chemical equation for the conversion of: solid compounds, + 2 and + 4 ions are also obtained.
(a) Chromite ore to sodium chromate
(ii) The E° for copper is positive (0.34 V). Copper
(b) Pyrolusite to potassium manganate M 2 + /M
(c) Potassium permanganate to manganese dioxide is the only metal in the first series of transition elements
8. There is only a very small increase in IE of an element in a showing this behaviour.
transition series (or d-block elements) when we move along (iii) The metallic radii of the third (5d) series of transition
the period as compared to s and p-block elements. Explain, metals are nearly the same as those of the correspond-
why. ing members of the second series.
9. Among lanthanides, why are ions like Sm2 +, Eu2+ and Yb2+ 19. (a) Which metal in the first transition series (3d series)
in aqueous solutions good reducing agents but an aqueous exhibits + 1 oxidation state most frequently and why?
solution of Ce4+ is a good oxidising agent? Explain. (b) Which of the following cations are coloured in aque-
10. (a) Which oxidation state of Mn is most stable and why? ous solutions and why?
(b) Which transition element show highest oxidation state
Sc3+, V3+, Ti4+, Mn2+
and in which compound?
(At. nos. Sc = 21, V = 23, Ti = 22, Mn = 25)
(c) Which is the densest transition element?
11. Which of the following oxides is basic, amphoteric and acidic Long Answer Questions
oxide: Sc2O3, MnO, FeO, Cu2O, MnO2, CuO, TiO2, Mn2O7,
CrO3. Cr2O3 20. The sums of first and second ionisation energies and those
12. A substance is found to have a magnetic moment of 4×89 of third and fourth ionisation energies of nickel and platinum
BM. How many unpaired electrons does it contain? are given below:
Element IE1 + IE2 (kJ mol–1) IE3 + IE4 (kJ mol–1)
13. Write the IUPAC name of éëCo ( NH3 )5 Cl ùû Cl 2 . [Atomic no. Ni 2×49 8×80
of Co = 27] Pt 2×66 6×70
14. Compare the chemistry of the actinoids with that of Taking these values in account, write
lanthanoids with reference to (a) the most common oxidation states of Ni and Pt and its
(i) electronic configuration reason.
(ii) oxidation states (b) the name of the metal (Ni or Pt) which can form
(iii) chemical reactivity compounds is + 4 oxidation state more easily and why?
15. Write the structures and names of all the stereoisomers of 21. Explain the following:
the following compounds: (a) Transition elements show similarity in properties along
the period as well as down the group (i.e., horizontal as
(i) é Co ( en ) ù Cl3 well as vertical similarities).
ë 3û
(b) In transition series, it is observed that melting point
(ii) é Pt ( NH3 ) Cl2 ù first increases and then starts decreasing.
ë 2 û
(c) Copper is a transition element but not sodium.
(iii) éë Fe ( NH3 ) 4 Cl 2 ùû Cl (d) Zinc atom is bigger than copper atom.
(e) Transition metals have low reactivity.
746 Chemistry
22. (a) Describe with the help of chemical equations the 26. Cuprous compounds such as CuCl, CuCN and CuSCN are
preparation of potassium dichromate from chromite ore. the only salts stable in water due to
(b) Give balanced chemical equations for what happens (a) high hydration energy of Cu+ ions
when acidified potassium dichromate solution reacts
(b) their inherent tendency not do disproportionate
with
(i) ferrous sulphate solution. (c) diamagnetic nature
(ii) hydrogen sulphide gas. (d) insolubility in water
(c) Draw the structure of Cr2O72–. 27. The addition of excess of aqueous HNO3 to a solution
containing [Cu(NH3)4]2+ produces
Multiple Choice Questions (a) Cu+
23. Which element belongs to d-block ? (b) [Cu(H2O)4]2+
(a) Na (b) Ca (c) Cu(OH)2
(c) Cu (d) Ar (d) Cu(NO3)2
24. (n - 1)d 10ns 2 is the general electronic configuration of 28. An extremely hot copper wire reacts with steam to give
(a) Fe, Co, Ni (b) Cu, Ag, Au (a) CuO (b) Cu 2O
(c) Zn, Cd, Hg (d) Se, Y, La (c) Cu 2 O 2 (d) CuO2 .
25. Which of the following is not property of the transition 29. Which is not amphoteric ?
elements?
(a) Al 3+ (b) Cr 3 +
(a) Colour (b) Paramagnetism
(c) Fixed valency (d) None of these (c) Fe 3+ (d) Zn 2+
1. How many ‘d’ electrons are present in Cr 2 + ion? (b) All three are colourless
(a) 4 (b) 5 (c) All three are coloured
(c) 6 (d) 3 (d) Only Ni 2 + is coloured an d Zn 2+ and Cr 3+ are
2. Which of the following ions having following electronic colourless
structure would have maximum magnetic moment?
7. (n - 1)d 10ns 2 is the general electronic configuration of
(a) 1s 2 2 s 2 2 p 6 3s 2 3 p 6 3d 3 (b) 1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 5
(a) Fe, Co, Ni (b) Cu, Ag, Au
2 2 6 2 6 7 2
(c) 1s 2s 2 p 3s 3 p 3d (d) 1s 2s 2 p 3s 3 p 3d 2 6 2 6 9 (c) Zn, Cd, Hg (d) Se, Y, La
8. Common oxidation state of scandium, a transition element
3. Which of the following element does not belong to first
transition series? is/are [Ar.No.of Sc = 21]
(a) Fe (b) V (a) +4 (b) +1
(c) Ag (d) Cu (c) +2 and +3 (d) +4 and +1
4. The transition metals have a less tendency to form ions 9. Which of the following is not correct about transition metals?
due to (a) Their melting and boiling points are high
(a) high ionisation energy (b) Their compounds are generally coloured
(b) low heat of hydration of ions (c) They can form ionic or covalent compounds
(c) high heat of sublimation (d) They do not exhibit varialbe valency
(d) All of these 10. Which of the following has maximum unpaired
5. Which of the following oxides of manganese is amphoteric? electrons?
(a) Scandium (b) Chromium
(a) MnO 2 (b) Mn 2O3
(c) Manganese (d) Iron
(c) Mn 2O7 (d) MnO 11. The last electron in d-block elements goes to
(a) (n-1) d (b) nd
6. Of the ions Zn 2+ , Ni 2+ and Cr 3+ (c) np (d) (n-1) s
( At.Nos Zn = 30, Ni = 28,Cr = 24) 12. Which of the following ions is coloured?
(a) Cu + (b) Cu 2+
(a) Only Zn 2+ is colourless and Ni 2 + and Cr 3+ are
coloured (c) Ti4+ (d) V5+
The d & f-Block Elements 747
13. What is wrong about transition metals? 26. Elements which generally exhibit multiple oxidation states
(a) Diamagnetic and whose ions are usally coloured are
(b) Paramagnetic (a) metalloids (b) non-metals
(c) Form complexes (c) transition elements (d) gases
(d) Shows variable oxidation state 27. Transition metals mostly are
14. In 3d-series atomic number (Z) varies from (a) diamagnetic
(a) Z = 21- 30 (b) Z = 22 - 30 (b) paramagnetic
(c) Z = 20 - 30 (d) Z = 31 - 40 (c) neither diamagnetic nor paramagnetic
15. The first element in the 3d-transition series is (d) both diamagnetic and paramagnetic
(a) Sc (b) Ti 28. Transition metals usually exhibit highest oxidation states in
(c) V (d) Ca their
16. Which one of the following ionic species will impart colour (a) chlorides (b) fluorides
to an aqueous solution? (c) bromides (d) iodides
(a) Ti 4+ (b) Cu + 29. Which one of the following ions exhibit highest
magnetic moment?
(c) Zn 2 + (d) Cr 3+ (a) Cu 2+ (b) Ti3+
17. Formation of interstitial compound makes the
transition metal (c) Ni 2 + (d) Mn2+
(a) more soft (b) more ductile 30. Which of the following is colourless in water?
(c) more metallic (d) more hard
18. The elements which exhibit both vertical and horizontal (a) Ti3+ (b) V 3+
similarites are (c) Cu 3+ (d) Sc3+
(a) inert gas elements (b) representative elements
31. The valence shell of transition elements consists of
(c) rare elements (d) transition elements
(a) nd orbitals (b) (n-1) d orbitals
19. Oxidation state of osmium (Os) in OsO4 is (c) ns np nd orbitals (d) (n-1) d ns orbitals
(a) +4 (b) +6 32. Which one of the following is diamagnetic ion?
(c) +7 (d) +8 (a) Co 2+ (b) Cu 2+
20. Which of the following transition element shows the
highest oxidation state ? (c) Mn2+ (d) Sc3+
(a) Mn (b) Fe 33. Which group contains coloured ions out of
(c) V (d) Cr
21. Which of the following has more unpaired d-electrons? 1. Cu 2+ 2. Ti 4+
(a) Zn + (b) Fe 2 + 3. Co 2+ 4. Fe 2 +
(c) Ni + (d) Cu + (a) 1, 2, 3, 4 (b) 1, 3, 4
(c) 2, 3 (d) 1, 2
22. An atom has electronic configuration
34. If a non metal is added to the interstital sites of a metal, then
1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 3 4s 2 in which group would it be the metal becomes
placed? (a) softer (b) less tensile
(a) Fifth (b) Fifteenth (c) less malleable (d) more ductile
(c) Second (d) Third 35. Transition metal with low oxidation number will act as
23. Iron loses its magnetic property at (a) a base (b) an acid
(a) Curie point (b) Boiling point (c) an oxidising agent (d) None of these
(c) Melting point (d) 1000 K 36. Which of the following elements does not show
24. The number of unpaired electrons in a nickel atom in ground variable oxidation states?
state are (At. No. of Ni = 28) (a) Copper (b) Iron
(a) 2 (b) 5 (c) Zinc (d) Titanium
(c) 3 (d) 7 37. Which one of the following is an example of non-typical
25. Zinc and mercury do not show variable valency like d-block transition elements ?
element because (a) Li, K, Na (b) Be, Al, Pb
(a) they are soft (c) Zn, Cd, Hg (d) Ba, Ga, Sr.
(b) their d-shells are complete 38. Super conductors are derived from compounds of
(c) they have only two electrons in the outermost shell (a) p-Block elements (b) lanthanides
(d) their d-shells are incomplete (c) actinides (d) transition elements
748 Chemistry
39. Corrosion of iron can be prevented by coating the surface 52. The oxidation number of Fe in Fe3O 4 is
with
(a) +2 (b) +3
(a) Zn (b) Sn
(c) 8/3 (d) 2/3
(c) Ni (d) Any of these
53. The iron obtained from blast funace is
40. Which of the following compound is called Turnbull’s blue?
(a) pig iron (b) silver
(a) Ferricyanide (b) Ferrous ferricyanide
(c) soft iron (d) steel
(c) Ferrous cyanide (d) Ferri-ferrocyanide
54. Which of the following gives blood red colour with
41. In an octahedral crystal field splitting the number of orbitals
KCNS?
pushed down in energy is
(a) 3 (b) 2 (a) Cu 2+ (b) Fe3+
(c) 5 (d) zero
(c) Al3+ (d) Zn 2 +
42. Which one of the following pairs of ions have the same
55. The protection of steel by chrome plating is due to
electronic configuration?
(a) cathodic protection
(a) Cr3+ ,Fe3+ (b) Fe3+ , Mn 2+ (b) anodic protection
(c) covering of steel surface
(c) Fe3+ , Co3+ (d) Sc3+ ,Cr3+ (d) formation of alloy with iron
43. Bonding in ferric chloride is 56. The nature of an aqueous solution of FeCl 2 is
(a) covalent (b) ionic (a) acidic (b) basic
(c) co-ordinate (d) None of these (c) amphoteric (d) neutral
44. Which one of the following elements constitutes a major 57. Which one of the following is the correct configuration of
impurity of pig iron?
Fe3+ ( Z = 26 ) ?
(a) Silicon (b) Oxygen
(c) Sulphur (d) Graphite (a) [Ar ]4s 2 3d 6 (b) [Ar ]4s 2 3d 3
45. A compound of a metal ion M x + ( Z = 24 ) has a spin (c) [Ar ]3d 5 (d) [Ar ]4s 2 3d 4
only magnetic moment of 15 Bohr Magnetons. The number 58. The number of ions formed on dissolving one molecule of
of unpaired electrons in the compound are FeSO 4 ( NH 4 )2 SO 4 .6H 2O
(a) 2 (b) 4
(Mohr’s salt) is/are
(c) 5 (d) 3
(a) 6 (b) 3
46. Which of the following configuration is correct for iron?
(c) 5 (d) 4
(a) 1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 5 59. If steel is heated to a temperature well below red heat and is
then cooled slowly the process is called
(b) 1s 2 2s 2 2 p 6 3s 2 3 p 6 4s 2 3d 5 (a) tempering (b) hardening
(c) softening (d) annealing
(c) 1s 2 2s 2 2 p 6 3s 2 3 p 6 4s 2 3d 7
60. Which of the following is obtained when Fe reacts with
(d) 1s 2 2s 2 2 p 6 3s 2 3 p 6 4s 2 3d 6 dil. HNO3 ?
47. Stainless steel contains (a) N 2O (b) NO
(a) Fe + Cr + Cu (b) Fe + C + Ni
(c) NO2 (d) None of these
(c) Fe + Cr + Ni + C (d) Fe + Ni + Cu 61. Wrought iron, pig iron and steel differ in properties due to
48. Which of the following is not an element? (a) carbon content (b) malleability
(a) Graphite (b) Diamond (c) conductivity (d) softness
(c) 22-Carat gold (d) Rhombic sulphur 62. Green vitriol is
49. Which of the following elements does not exist in the native
(a) FeSO 4 .7H 2O (b) ZnSO 4 .7H 2O
form?
(a) Au (b) Pt (c) CaSO 4 .2H 2O (d) CuSO 4 .5H2O
(c) Fe (d) S 63. Which of the following is not an ore of iron?
50. In the extraction of iron, slag is produced which is (a) Limonite (b) Magnetite
(a) CO (b) FeSiO3 (c) Casiterite (d) All of these
64. Corrosion is basically a
(c) MgSiO3 (d) CaSiO3
(a) altered reaction in presence of H2O
51. The nature of an aqueous solutionof FeCl3 is (b) electrochemical phenomenon
(a) acidic (b) basic (c) interaction
(c) amphoteric (d) neutral (d) union between light metal and heavy metal
The d & f-Block Elements 749
65. Which of the following are the constituents of gun metal?
76. A metal which does not liberate H2 ( g ) from acids is
(a) Cu, Sn (b) Cu, Sn, Zn
(c) Zn, Sb, Pb (d) Cu, Ca, Pb (a) Cu (b) Fe
(c) Mn (d) Zn
66. When Cu reacts with AgNO3 solution, the reaction takes
77. Cuprous ion is colourless while cupric ion is coloured
place is because
(a) oxidation of Cu (b) reduction of Cu (a) both have half filled p-and d-orbitals
(c) oxidation of Ag + (d) reduction of NO3- (b) cuprous ion has incomplete d-orbital and cupric ion has
a complete d-orbital
67. Bordeaux used as fungicide is a mixture of
(c) both have unpaired electrons in the d-orbitals
(a) CuSO 4 + Ca (OH )2 (b) CaSO 4 + Cu (OH )2 (d) cuprous ion has complete d-orbital and cupric ion has
an imcomplete d-orbital.
(c) CuCO3 + Cu (OH )2 (d) CuO + CaO
78. In Cu ( Z = 29)
68. Which of the following ions will liberate iodine when
treated with KI? (a) 13 electrons have spin in one direction and 16 electrons
in other direction
(a) Cu 2+ (b) Fe 2 + (b) 14 electrons have spin in one direction and 15 electrons
(c) Pb 2 + (d) Sn 2+ in other direction
(c) All the electrons have spin in one direction
69. Which one of the following pairs of substances on
(d) None of these
reaction will not evolve H2 gas? 79. Cuprous ore among the following is
(a) Iron and H 2SO 4 (aq.) (a) chalcopyrites (b) azurite
(c) cuprite (d) malachite
(b) Iron and steam
80. The white anhydrous copper sulphate decomposes to give
(c) Copper and HCl ( g ) (a) CuSO 4 .5H2O (b) CuSO4.H 2O
(d) Sodium and ethyl alchohol
(c) CuO + SO3 (d) Cu
70. Which of the following metals is sometimes found in native
state in nature? 81. An important ore of copper is
(a) Al (b) Cu (a) bauxite (b) galena
(c) Fe (d) Mg (c) siderite (d) chalcopyrites
71. Which of the following is ionic in nature? 82. When the sample of copper with zinc impurity is to be purified
by electolysis, the appropriate electordes are
(a) CuF2 (b) CuCl2 Cathode Anode
(c) CuBr2 (d) None of these (a) Pure zinc Pure copper
(b) Impure sample Pure copper
72. CuSO4 reacts with KCN solution and forms
(c) Impure zinc Impure sample
(a) Cu (CN ) (b) Cu (CN )2 (d) Pure copper Impure sample
83. Which of the following compounds gives red
(c) K 3 éëCu (CN )4 ùû (d) K 4 [Cu (CN )6 precipitate with AgNO3 ?
73. When KI and CuSO4 solutions are mixed, it gives (a) KI (b) K 2CrO 4
(a) K 2SO 4 + I2 (b) Cu 2 I2 + K 2SO 4 (c) NaBr (d) NaNO3
(c) CuI2 + K 2SO4 (d) Na 2SO4 + I2 84. When silver nitrate is heated to red hot, what is formed?
74. The final step in the metallurgical extraction of Cu metal from (a) Ag (b) Ag 2O
Cu pyrites takes place in a Bessemer converter. The reaction
taking place is (c) Ag 2O3 (d) AgO 2
85. When horn silver ore is dissolved in excess of sodium
(a) Cu 2S + O 2 ® 2Cu + SO2
cyanide solution compound formed is
(b) 4Cu 2O + FeS ® 8Cu + FeSO4
(a) AgCN (b) Na [ AgCN)2 ]
(c) 2Cu 2O + Cu 2S ® 6Cu + SO 2
(c) Na 2 éë Ag (CN )3 ùû (d) Na 4 éë Ag (CN )5 ùû
(d) Cu 2S + 2FeO ® 2CuO + 2Fe + SO2
75. Matte contains mainly 86. In the chemical reaction
(a) Cu 2S and FeS (b) CuS and Fe 2S3 Ag 2O + H2O + 2e- ® 2Ag + 2OH-
(a) water is oxidised (b) water is reduced
(c) Fe (d) Cu 2S (c) silver is oxidised (d) silver is reduced
750 Chemistry
87. AgCl is soluble in NH4OH solution. The solubility is due to 98. Acidified solution of chromic acid on treatment with
the formation of H 2O2 gives blue colour which is due to
(a) AgOH (b) Ag 2O (a) CrO3 + H 2O + O2 (b) CrO5 + H 2O
+ (c) H 2Cr2O7 + H 2O + O2 (d) None of these
(c) éë Ag ( NH3 )2 ùû (d) NH 4Cl
99. In the extraction of zinc, the formation of blue flame is due
88. The compound that is soluble in water is the burning of
(a) AgF (b) AgCl (a) ZnO (b) C
(c) AgBr (d) AgI (c) Zn (d) CO
89. In the metallurgy of which of the following cupellation 100. Which of the following compounds turns black on
process is used? addition of NH 4OH ?
(a) Copper (b) Silver
(a) PbCl2 (b) Hg2Cl2
(c) Iron (d) Aluminium
90. When potassium ferrocyanide crystals are heated with (c) HgCl 2 (d) AgCl
conc. H 2SO 4 the gas evolved is 101. Mercury is the only metal which is liquid at 0°C. This is due
to its
(a) SO2 (b) NH3 (a) very high ionisation energy and weak metallic bond
(c) CO2 (d) CO (b) low ionisation potential
91. In the extraction of silver, Ag 2S is dissolved in (c) high atomic weight
(d) high vapour pressure
(a) HCl (b) HNO3
102. Which one of the following is false for Hg?
(c) KCN (d) H2SO4 (a) It can evolve hydrogen from H2S
92. Parke’s process is used (b) It is metal
(a) to extract Ag using NaCN (c) It has high specific heat
(b) to extract Cu using CuFeS2 (d) It is less reactive than hydrogen.
(c) to extract Ag from argentiferrous lead 103. Mercury sticks to the surface of the glass when it comes in
(d) to extract Ag by forming amalgam contact with
93. In the equation (a) Hg2O (b) HNO3
(c) O3 (d) grease
-
4M + 8CN - + 2H 2O + O2 ® 4 éë M (CN )2 ùû + 4OH - 104. Which compound is volatile on heating?
(a) MgCl2 (b) Hg Cl2
Identify the metal M. It is (c) ZnCl2 (d) None of these
(a) copper (b) iron 105. Which ion is detected by Nessler’s reagent?
(c) gold (c) zinc
(a) NH +4 (b) MnO-4
94. A metal which is not affected by conc. H 2SO 4 , HNO3
or alkalies forms an compound X This compound X can be (c) PO34- (d) CrO24 -
used to give a complex which finds its application for tonning 106. Mercurous ion is represented as
in photography. The metal is (a) Hg 22 + (b) Hg 2 +
(a) Au (b) Ag
(c) Hg (d) Cu (c) Hg + Hg 2 + (d) 3Hg3+
95. Which of the following is not the characteristic of zinc? 107. Nessler’s reagent is
(a) It is a volatile metal (a) potassium iodide in mercuric iodide
(b) It dissolves in alkali forming sodium zincate (b) TiCl 4
(c) It is brittle at very high temperatures
(d) Zinc dust is used as reducing agent (c) anhydrous AlCl3
96. Galvanization of iron denotes coating with (d) Al 2O3 / Cr2O3
(a) Al (b) Sn 108. The equivalent weight of KMnO4 (formula weight = M )
(c) Cd (d) Zn when it is used as an oxidant in neutral medium is
97. When Zn is treated with excess of NaOH, the product
M
obtained is (a) M (b)
2
(a) Zn (OH )2 (b) ZnOH
M M
(c) (d)
(c) Na 2 ZnO2 (d) None of these 3 5
The d & f-Block Elements 751
109. The starting material for the manufacture of KMnO4 is 120. The colour of CuCr2O7 solution in water is green because?
(a) pyrolusite (b) manganite (a) Cr2 O72 - ions are green
(c) magnatite (d) haematite
110. An explosion take place when conc. H2SO4 is added to (b) Cu 2+ ions are green
KMnO4. Which of the following is formed? (c) Both Cr2O2– 2+
7 and Cu ions are green
(a) Mn 2O7 (b) MnO 2 (d) Cu2+ ions are blue and Cr2 O72 - ions are yellow
(c) MnSO4 (d) M 2O3 121. The most common lanthanide is
(a) lanthanum (b) cerium
111. If KMnO4 is reduced by oxalic acid in an acidic
(c) samarium (d) plutonium
medium then oxidation number of Mn changes from
122. Total number of inner transition elements in the periodic table
(a) 4 to 2 (b) 6 to 4 is
(c) +7 to +2 (d) 7 to 4 (a) 10 (b) 14
112. The correct formula of permanganic acid is (c) 28 (d) 30
(a) HMnO4 (b) HMnO5 123. The electronic configuration of gadolinium (At. No. 64) is
(c) H 2 MnO4 (d) H 2 MnO3 (a) [ Xe]4 f 8 5d1 6s 2 (b) [ Xe]4 f 7 5d1 6s 2
113. In the preparation of KMnO4 pyrolusite (MnO2 ) is first (c) [ Xe]4 f 3 5d 5 6s 2 (d) [ Xe]4 f 6 5d 2 6 s 2
converted to potassium manganate ( K 2MnO4 ). In this 124. Which of the following element is responsible for oxidation
of water to O2 in biological process?
conversion, the oxidation state of manganese changes from
(a) Fe (b) Mn
(a) +1 to +3 (b) +2 to +4 (c) Cu (d) Mo
(c) +3 to +5 (d) +4 to +6 125. Which of the following compounds is not coloured?
114. Which of the following oxides of Cr is amphoteric
(a) Na 2CuCl4 (b) Na 2CdCl4
(a) CrO2 (b) Cr2O3
(c) CrO5 (d) CrO3 (c) K 4 Fe(CN)6 (d) K3Fe(CN)6
115. In potassium manganate the oxidation state of 126. The +3 ion of which one of the following has half filled 4f
manganese is subshell?
(a) +5 (b) +6 (a) La (b) Lu
(c) +7 (d) +8 (c) Gd (d) Ac
127. Which of the following metal is found in gun metal, monel
116. Number of electrons transfered in each case when KMnO4 metal and constant alloys?
acts as an oxidising agent to give MnO2, Mn2+, Mn(OH)3 (a) Zn (b) Hg
(c) Fe (d) Cu
and MnO 24- are respectively
128. Non-lanthanide atom is
(a) 3,5,4 and 1 (b) 4,3,1 and 5 (a) La (b) Lu
(c) 1,3,4 and 5 (d) 5,4,3 and 1 (c) Pr (d) Pm
117. In an alkaline condition KMnO4 reacts as follows: 129. In which of the following lanthanides oxidation state +2 is
most stable?
2KMnO 4 + 2KOH ® 2K 2 MnO4 + H 2O + O (a) Ce (b) Eu
Its equivalent weight is (c) Tb (d) Dy
(a) 31.6 (b) 52.7 130. Which of the following elements shows maximum number of
different oxidation states in its compounds?
(c) 49 (d) 158
(a) Eu (b) Ld
118. In which of the following compounds manganese has
(c) Gd (d) Am
oxidation number equal to that of iodine in KIO4 ?
131. The alloy best suited for making meter scales is
(a) Potassium manganate
(a) stainless steel (b) invar
(b) Potassium permanganate (c) alnico (d) tungsten steel
(c) Manganous chloride 132. Which metal is present in brass, bronze and German silver?
(d) Manganese chloride (a) Zn (b) Mg
119. Which of the following compounds has colour but no (c) Cu (d) Al
unpaired electrons? 133. Brass is an alloy of
(a) KMnO4 (b) K2MnO4 (a) Al and Zn (b) Cu and Al
(c) MnSO4 (d) MnCl2 (c) Ni and Zn (d) Cu and Zn
752 Chemistry
1. Which one of the following ions is the most stable in aqueous 11. Acidified K2Cr2O7 solution turns green when Na2SO3 is
solution? [CBSE-PMT 2007] added to it. This is due to the formation of :
(a) V3+ (b) Ti3+ (c) Mn 3+ (d) Cr3+ [CBSE-PMT 2011]
(At.No. Ti = 22, V = 23, Cr = 24, Mn = 25) (a) Cr2(SO4)3 (b) CrO42– (c) Cr2(SO3)3 (d) CrSO4
2. Identify the incorrect statement among the following : 12. Which of the statements is not true? [CBSE-PMT 2012]
[CBSE-PMT 2007] (a) On passing H2S through acidified K2Cr2O7 solution, a
(a) Lanthanoid contraction is the accumulation of successive milky colour is observed.
shrinkages. (b) Na 2Cr 2 O7 is preferred over K2 Cr 2O7 in volumetric
(b) As a result of lanthanoid contraction, the properties of analysis.
4d series of the transition elements have no similarities (c) K2Cr2O7 solution in acidic medium is orange.
with the 5d series of elements. (d) K2Cr2O7 solution becomes yellow on increasing the pH
(c) Shielding power of 4f electrons is quite weak. beyond 7.
(d) There is a decrease in the radii of the atoms or ions as 13. Which one of the following does not correctly represent the
one proceeds from La to Lu. correct order of the property indicated against it?
3. The correct order of decreasing second ionisation enthalpy [CBSE-PMT 2012]
of Ti (22), V(23), Cr(24) and Mn (25) is : [CBSE-PMT 2008] (a) Ti < V < Cr < Mn : increasing number of oxidation states
(a) Cr > Mn > V > Ti (b) V > Mn > Cr > Ti (b) Ti3+ < V3+ < Cr3+ < Mn3+ : increasing magnetic moment
(c) Mn > Cr > Ti > V (d) Ti > V > Cr > Mn (c) Ti < V < Cr < Mn : increasing melting points
4. Which one of the elements with the following outer orbital (d) Ti < V < Mn < Cr : increasing 2nd ionization enthalpy
configurations may exhibit the largest number of oxidation 14. Four successive members of the first series of the transition
states? [CBSE-PMT 2009] metals are listed below. For which one of them the standard
(a) 3d 54s1 (b) 3d 54s2 (c) 3d 24s2 (d) 3d 34s2
5. Out of TiF62– , CoF63– , Cu2Cl2 and NiCl2– 4 (Z of Ti = 22,
( º
)
potential E M 2 + / M value has a positive sign?
1. In nitroprusside ion the iron and NO exist as FeII and NO+ 4. Titanium shows magnetic moment of 1.73 B.M. in its
rather than FeIII and NO. These forms can be differentiated compound. What is the oxidation number of Ti in the
by compound?
(a) estimating the concentration of iron (a) +1 (b) +4
(b) measuring the concentration of CN (c) +3 (d) +2
(c) measuring the solid state magnetic moment 5. Which of the following is paramagnetic?
(d) thermally decomposing the compound. 4-
2. Anhydrous ferric chloride is prepared by (a) é Fe (CN ) ù
ë 6û
(b) éë Ni (CO )4 ùû
(a) heating hydrated ferric chloride at a high temperature in
2-
a stream of air (c) é Ni (CO ) ù
ë 4û
(d) [CoF6 ]3-
(b) heating metallic iron in a stream of dry chlorine gas
6. If an aqueous solution of KCN is added to a solution of
(c) reaction of metallic iron with hydrochloric acid
ferrous salt then the complex formed is represented by
(d) reaction of metallic iron with NaCl solution
4- 3-
3. When MnO2 is fused with KOH, a coloured compound is (a) é Fe (CN ) ù (b) éë Fe (CN )6 ùû
ë 6û
formed, the product and its colour is:
(a) K2MnO4, purple green (b) KMnO4, purple 3+ 2+
(c) é Fe (H 2 O) ù (d) éë Fe (H 2 O)6 ùû
(c) Mn2O3, brown (d) Mn3O4, black ë 6û
The d & f-Block Elements 755
7. The temperature of blast furnace to produce iron from its 12. In the extraction of copper, the reaction which takes place in
Bessemer converter is
ore Fe2 O3 varies from 500o C at the top of the furnace to
(a) 2CuFeS2 + O 2 ® Cu 2S + 2FeS + SO 2
about 1900o C at the bottom of the furnace. The reaction
(b) 2Cu 2O + Cu 2S ® 6Cu + SO 2
between the ore Fe 2O3 and CO at the lowest temperature
(c) 2Cu 2S + 3O2 ® 2Cu2O + 2SO2
( ~ 500 C ) is
o
(d) 2FeS + 3O 2 ® 2FeO + 2SO2
13. Copper is extracted from copper pyrites ore by
(a) 3Fe 2O3 + CO ® 2Fe3O4 + CO 2 heating in a blast furnace. The method is based on the
principle that
(b) Fe 2O3 + CO ® 2FeO + CO 2
(a) copper has more affinity for oxygen than sulphur at
(c) Fe2O3 + 3CO ® 2Fe + 3CO2 high temperature
(b) iron has less affinity for oxygen than sulphur at high
(d) Fe 2O3 + CO + CaCO3 ® Fe2O3 + CO + CO2 + CaO temperature
(c) sulphur has less affinity for oxygen at high temperature
8. The blue complex formed on addition of conc.
(d) copper has less affinity for oxygen than sulphur at high
NH 4OH solution to a Cu 2+ salt solution has the temprature
structure? 14. Colourless solutions of the following four salts are placed
separately in four different test tubes and a strip of copper is
2+ 2+ dipped in each one of these. Which solution will turn blue?
(a) éCu ( NH 4 ) ù
ë 4û
(b) éëCu ( NH3 )2 ùû
(a) KNO3 (b) AgNO3
2+ 2+
(c) éCu ( NH3 ) ù (d) éëCu ( NH 4 )2 ùû (c) Zn(NO3)2 (d) ZnSO4
ë 4û
15. Which of the following does not react with AgCl?
9. When CuSO4 solution is added to K 4 éë Fe (CN 6 )ùû the (a) Na 2S2O3 (b) NH 4OH
formula of the product formed is? (c) NaNO3 (d) Na 2CO3
Cu 2 Fe (CN )6 16. Which of the following reactions represents “developing”
(a) (b) KCN
in photography
(c) Cu (CN )3 (d) Cu (CN )2 (a) AgNO3 + NaBr ® AgBr + NaNO3
10. In order to refine “blister copper” it is melted in (b) AgBr + 2Na 2S2O3 ® Na 3 éë Ag (S2O3 )2 ùû + NaBr
furnace and is strirred with green logs of wood. The
purpose is (c) AgBr + hv ® AgBr*
(a) to expel the dissolved gases in the blister copper
(d) C6 H 4( OH ) + +2AgBr* ® C6 H 4O 2 + 2HBr + 2Ag
(b) to bring the impurities to surface and oxidise them 2
(c) to increase the carbon content of copper 17. In the extraction of silver from argentite ore the ore i s
treated with dilute solution of NaCN in water in the presence
(d) to reduce the metallic oxide impurities with hydrocarbon of Y, whereby the following reaction takes place
gases liberated from the wood.
11. Identify the incorrect statement Ag 2 X + 4NaCN + 2Y ® 2Na éëAg (CN )2 ùû + Na 2XO 4
(a) CuSO4 reacts with KCl in aqueous solution to give X and Y in this reaction are represented by
(a) Cl and S (b) S and O2
Cu 2Cl2 (c) O and O2 (d) O and S
(b) CuSO4 r eacts with KI in aqueous solution to 18. The black compound formed during the reaction
between sodium thiosulphate and silver nitrate is
give Cu 2 I2
(a) silver thiosulphate ( Ag2S2O3 )
(c) CuSO4 react with NaOH and glucose in aqueous
(b) silver sulphide ( Ag 2S)
medium to give Cu 2O
(c) silver sulphate ( Ag 2SO 4 )
(d) CuSO4 on strong heating gives CuO
(d) silver sulphite ( Ag 2SO3 )
756 Chemistry
19. Zn gives H2 gas with H2SO4 and HCl but not with HNO3 (b) 10 ml of 1M KMnO 4 solution oxidises
because
10 ml of 5N FeSO 4 solution
(a) Zn acts as an oxidising agent when react with HNO3
(c) 10 ml of 1M KMnO 4 solution oxidises
(b) HNO3 is weaker acid than H 2SO4 and HCl
10 ml of 1M FeSO4 solution
(c) In electrochemical series Zn is above hydrogen
- (d) 10 ml of 1N KMnO 4 solution oxidises
(d) NO3 ion is reduced in preference to hydronium ion
20. Which of the following is used in the preparation of 10 ml of 0.1M FeSO4 solution
chlorine? 22. Number of moles of K 2Cr2O7 reduced by one mole of Sn 2+
(a) Only MnO 2 ions is
(b) Only KMnO4 1
(a) (b) 3
(c) Both MnO 2 and KMnO4 3
1
(d) Either MnO 2 or KMnO4 (c) (d) 6
6
21. In acidic medium KMnO4 oxidises FeSO4 solution. Which
23. CrO3 dissolves in aqueous NaOH go give
of the following statements is correct?
(a) 10 ml of 1N KMnO 4 solution oxidises (a) CrO24 - (b) Cr (OH )3
EXERCISE 1 14. (a) 3d series starts from Sc(Z - 21) and ends with
3. In both K2Cr2O7 and K2CrO4, Cr is in + 6 oxidation state. Zn(Z –30).
4. Co2+ contains three unpaired electrons \ more paramagnetic 15. (a)
5. The extra-ordinary stability of La, Gd and Zu is due to the
16. (d) Only Cr 3+ [ Ar ]3d 3 contains unpaired electrons hence
empty, half-filled and fulley filled 4f-orbitals respectively.
6. This is because KMnO4 has a germicidal action. will give coloured solution
10. (a) + 2 oxidation state (exactly half-filled d-orbitals) 17. (d) A covalent bond is formed between small interstial
(b) Osmium, (Os) in osmium tetraoxide (OsO4). non-metal and transition metal which make it hard
(c) Osmium (Os) is the densest transition element. 18. (d) Transition element due to similar (almost) sizes exhibit
11. Acidic: Mn2O7 Cr O3 (oxides in higher oxidation states). both vertical and horizontal similarities.
Amphoteric: MnO2, CuO, TiO2 (oxides in moderate oxidation 19. (d) O.S. of Os in OsO4 is + 8
states). 20. (a) Highest O.S. by Mn (+7)
Basic: MnO, Cr2O3 (oxides in higher oxidation states).
12. n = 4. 21. (b) Zn + [ Ar ] 3d10 4s1 , Fe 2+ [ Ar ] 3d 6 4s0 , Ni + [ Ar ] 3d 8 4s1,
20. (b) Pt can form compounds of + 4 oxidation state more easily
21. (e) This is because of Cu + [ Ar ] 3d10 4s0 ;
(i) high heat of atomisation, and
(ii) high ionisation energies Fe 2 + contain maximum number of unpaired electrons.
23. (c) 24. (c) 25. (c) 26. (a) 27. (b) 22. (a) Group number is given by [ns + (n - 1)d ] electrons.
28. (b) 29. (c)
\ [2 + 3] = 5
EXERCISE 2 23. (d) Iron loses magnetic properties at 1000K.
24. (a) Ni ( 28) Ni [ Ar ]3d8 4s 2 contain 2 unpaired electrons.
1. (a) Cr 2 + electronic configuration is [ Ar ]3d , hence number
4
25. (b) Zn and Hg have d-shells completely filled hence they do
of d electrons is 4.
not exhibit variable valency.
2. (b) The more the number of unpaired electrons, the more is
26. (c) The statement is true for transition elements.
magnetic moment.Therefore the answer is (b).
27. (b) Transition metals are generally paramagnetic since they
3. (c) Ag belongs to second transition series.
contain unpaired electrons.
4. (d) All statements are correct.
28. (b) Since reduction potential of fluorine is highest transition
5. (a) The more the oxidation state, the more is the acid
metals exhibit highest oxidation state with fluorine.
character, MnO, Mn 2O3 are basic, MnO 2 is amphoteric 29. (d) Since Mn2+ contains maximum number of unparied
and Mn 2O7 is acidic. electrons hence it has maximum magnetic moment
30. (d) Since Sc3+ does not contain any unpaired electron it is
6. (a) Electronic configuration of
colourless in water.
Zn 2+ [ Ar ] 3d10 4s 0 ; Ni 2 + [ Ar ] 3d8 , 4s 0 ; 31. (d) Since transition metals can lose electrons from
Cr3+[Ar]3d3, 4s0Zn2+ colourless (no unpaired electrons) (n - 1)d ns orbitals hence they are valence orbitals.
Ni2+ and Cr 3+ coloured due to unpaired electrons 32. (d) Sc3+ is diamagnetic as it does not contain any unpaired
7. (c) electron while others contain.
8. (c)
9. (d) Transition metals exhibit variable valency 33. (b) Cu 2+ [ Ar ] 3d 9 Ti 4+ [ Ar ] 3d 0 Co 2+ [ Ar ]3d 7 Fe2+ [Ar ]3d 6
10. (b) Cr has maximum unparied electrons .The number is 6. 1,3,4 are coloured ions hence the answer is b.
34. (c) If non metal is added to the interstital site the metal
24 Cr : [Ar]3d 5 4s1 becomes less malleable due to formation of covalent bond
11. (a) between metal and non metal
35. (b) Transition metal in lower oxidation state will exist as cation
12. (b) Cu + [ Ar ] 3d10 , Cu 2+ [ Ar ] 3d9 , Ti 4+ [ Ar ] 3d 0 , V5+ [ Ar ] 3d 0 .
which are lewis acids.
only Cu2+ contains unpaired electron hence it is coloured 36. (c) Zinc does not show variable oxidation state due to
13. (a) They may or may not be diamagnetic completely filled d-orbitals
758 Chemistry
37. (c) Zn, Cd, Hg do not show properties of transition elements 62. (a) Green vitrol is FeSO 4 .7H 2O
hence they are known as non typical transition elements
63. (c) Cassiterite is not an ore of iron. Liomite and magnetite
38. (d) Super conductors are derived from compounds of
are the ores of iron. Cassiterite is an ore of Sn.
transition metals
64. (b) Corrosion is electrochemical phenomenon (See chapter
39. (d) Corrosion can be prevented by Zn (galvanizing or
on electrochemistry)
sherardizing) with Sn (known as tinning) and Ni by 65. (b) Gun metal is alloy of Cu, Zn, Sn.
electroplating
2+
40. (b) Ferrous ferricyanide is known as Turbull’s blue 66. (a) Cu 0 + 2AgNO3 ® Cu ( NO3 ) + 2Ag .
41. (a) In octahedral crystal field the d - orbitals split in to t2g 2
and eg orbitals. eg (dxy ,dyz and dzx ) occupy lower level
(
It is oxidation of copper Cu 0 ® Cu 2 + )
( )
and eg d x 2 - y2 , d z2 occupy higher energy level.
67. (a) CuSO 4 + Ca(OH) 2 is Bordeaux mixture
42. (b) 24 Cr , 26 Fe , 27 Co , 25 Mn , 21Sc 68. (a) 2Cu 2+ + 4KI ® Cu 2 I 2 + I 2 + 4K +
Electonic configuration
69. (c) Cu + HCl ® No reaction (others will give H2) See
Cr : [ Ar ] 3d5 4s1 , Fe :[ Ar ] 3d 6 4s2 , Co : [ Ar ] 3d 7 4s 2 , applications of ECS (electrochemistry).
70. (b) Cu is found in native state
Mn : [ Ar ] 3d5 4s 2 , Sc :[Ar ] 3d1 4s 2 71. (a) CuF2 is ionic in nature (Fajan’s rule ), for fixed cation the
Configuration of ions smaller the anion, the more is ionic character.
Cr3+ Fe3+ Co3 + Mn 2 + Sc3+ 72. (c) 2CuSO 4 + 10KCN ® 2K 3 éëCu (CN )4 ùû + 2K 2SO 4 + (CN )2
[Ar] 3d3 [Ar] 3d5 [ Ar] 3d6 [Ar ] 3d5 [Ar] 3d0 73. (b) Correct (see text)
74. (c)
Fe3+ , Mn 2+ have same electronic configuration 75. (a) Matte contains Cu2S and FeS
43. (a) Due to small size of Fe3+ the bonding in FeCl3 is covalent. 76. (a) Cu has more reduction potential than hydrogen. Cu does
44. (d) The impurity in pig iron is due to carbon hence graphite not evolve H2 with acids (See application of ECS in
chapter of elctrochemistry)
45. (d) Magetic moment = n (n + 2 ) where n = number of
77. (d) In Cu [ Ar ] 3d
+ 10
there is no unpaired electron,
unpaired electrons 15 = n(n + 2 ) \ n = 3
46. (d) Cu 2 + [ Ar ] 3d 9 contains one unpaired electron hence
47. (c) Stainless steel contains Fe, Cr, Ni and C. coloured
48. (c) 22 carat gold is an alloy (see text ) 78. (b) Out of 29 electrons, 14 electrons have spin in one
49. (c) Iron does not exist in native form direction and 15 electrons in other direction.
50. (d) Slag is CaSiO3 79. (c) Cuprite Cu 2O
51. (a) Acidic due to cationic hydrolysis
D
80. (c) CuSO 4 ¾¾ ® CuO + SO3
Fe(OH) + 3HCl
FeCl3 + 3H2O
81. (d) Chalcopyrites CuFeS2 , Bauxite ( Al2O3.2H 2O) ,Galena
3
1. Primary linkages - Which are satisfied by the negative ions, C5 H 5 N Pyridine SO 24 Sulphato O22- peroxo
ionisable and their number is equal to the O . N of central
metal atom. PH 3 Phosphine NO -2 nitro NH -2 Amido
They are always represented by dotted lines
2. Secondary linkages - Which are satisfied by the negative,
P(C 6 H 5 ) 3 CO 32- Carbonato N 3- nitrido
Cl
[Co( NH 3 ) 6 ]3+ + 3Cl - +
NO nitrosonium
H3N (NH2NH3)+ hydrazinium
NH3 NH3
Coordination Compounds 765
Name of some complex compounds - Following the above rules (iii) Hydration Isomers-Exchange water as ligand and hydrate
here are names of some complex compounds. [Cr(H2O)6 ]Cl3, [Cr(H 2O)5 Cl]Cl2.H 2O and Cr(H 2O) 4 Cl2 C
[Cr(H2O)5 Cl]SO4 Pentaaquachlorochromium
Cr(H 2O)6 Cl3 Cr(H 2O)5 Cl Cl 2H 2O and [Cr(H 2O) 4 Cl 2 ]Cl 2.H 2O
(III) Sulphate
[Co(NH3 )5 H2O]Cl3 and [Co(NH3 )5 Cl]Cl3.H 2O
[Cr(H2O)4 Cl2 ]Cl Tetraaquadichlorochromium (iv) Linkage Isomers - ligands that can bond at more than one
atomic site
(III) Chloride
(ambidentate) : CN– : NC–
K 2 [PtCl 4 ] Potassiumtetrachloroplatinate
[Cr(H 2O)5 CN]2+ and [Cr(H 2 O)5 NC]2 +
(II)
: NCS– and : SCN –
[Co(en) 2 Cl2 ]Cl Dichlorobis (ethylene -
[Co( NH 3 )5 NCS]2+ and [Co( NH 3 )5 SCN ]2 +
diammine) cobalt (III) Chloride
.. .. ..
IV II : NO-2 and : O
.. — N = O
[Pt ( NH3 )4Cl 2 ] [ Pt Cl 4 ] Tetraamminedichloro ..
platinum (IV) [Pt ( NH 3 )3 NO 2 ]+
and [Pt ( NH 3 ) 3 ONO]+
tetrachloroplatinate (II) (v) Coordination Isomerism - Occurs when cationic and anionic
3+ complexes of different metal ions are present in a salt.
NH Interchange of ligand between the complexes give isomers eg
(en)2Co Co(en)2 Bisethylenediaminecobalt (III)
OH [Co( NH3 ) 6 ][Cr (CN) 6 ] is an isomer of [
-m-amido -mhydroxobis
ethylenediaminecobalt (III) ion [Co(CN) 6 ] [Cr ( NH3 ) 6 ]
(vi) Ligand isomerism-Occurs when more than one isomer of
[Fe(H 2 O) 4 (C 2 O 4 )]2 SO 4 Tetraaquaoxalato iron (III) the ligand is possible eg 1, 2 diamino propane and 1,3-diamino
sulphate propane.
(vii) Polymerisation Isomerism - The isomers have the same
[ Ag( NH 3 ) 2 ]Cl Diamminesilver (I) chloride
empirical formula but different molecular weights eg.
[Cu(NH3 ) 4 ]SO4 Tetramminecopper (II) sulphate [Co(NO 2 )3 (NH 3 )3 ] and [Co(NH 3 ) 6 ][Co(NO 2 ) 6 ] .
Triamminetrinitrocobalt (III) Hexamminec obalt (III)
[ Ni(CN) 4 ]2 - Tetracyanonickelate (II) ion Hexanitroc obalt (III)
The molecular weight of the second is twice as that of the
K 2 HgI 4 Potassiumtetraiodomercurate (II) first.
[Cr( NH3 ) 6 ] [Co(C 2O 4 ) 3 ] Hexammine chromiun (III) (viii) Valence Isomerism - In this the same coordinating group is
held by different types of valence bonds. The valence state
trioxalato cobaltate (III)
of the central metal atom then differ in the two isomers. eg.
NH2 [Co( NO)(NH 3 ) 5 ]2 + and [Co( NH 3 ) 5 ( NO)]2 + .
(en)2Co Co(en)2 SO Bis (ethylenediammine)
4 In the first compound the NO group is a negative group and
OH
cobalt (III) m - amido m - oxidation state of Co is +3. In the second compound the NO
hydroroxo bis (ethylene group is neutral and oxidation state of Co is +2.
(ix) Coordination position isomerism - In this coordinating
diammine) cobalt (III)
groups occupy different positions and the isomerism occurs
sulphate
generally in bridged complex. eg.
ISOMERISM IN COORDINATION COMPOUNDS : 2+
NH2
Isomers - two or more forms of a compound having the same (NH3)4 Co Co (Cl)2 (NH3)2 and
composition O2
(i) Structural Isomers - (have different bonding) . They are of
2+
the following types NH2
(ii) Ionization Isomers - Exchange ion between ligand and anion (NH3)3 (Cl) Co Co (Cl) (NH3)3
eg. O2
(x) Stereo isomerism - It is due to different spatial arrangement
[Co(NH3 )4 ClBr ]Cl and [Co(NH3 ) 4 Cl2 ] Br of atoms and groups in a molecule. It is of two types.
(a) Geometrical - It is due to different geometrical
[ Pt(NH3 )3 Cl] NO2 and [Pt(NH3 )3 NO2 ]Cl arrangements of ligands around central metal atom and
is shown by
766 Chemistry
(I) Square planar complexes of the type X X
MA2X2 ; MABX2 ; MABXY A X A A
M M
Type MA2 X-
2 A X A X
[Co(NH3 )2 Cl2 ], [Pt(NH3 )2 Cl2 ] A X
2 H3N Cl Fac (facial) Mer (meridranal)
H3N 1 Cl
The geometrical isomerism is not possible in square planar
Pt Pt MA4, MAB3 and tetrahedral MA4, MA2B2 and MABCD
H3N 4 3 Cl Cl NH3 and Octahedral MA6, MA5B.
Pale yellow Dark yellow Facial (fac) meridional (mer) isomerism - The octahedral
Cis isomer trans isomer coor dination compounds of the type MA 3 B 3 eg.
Positions 1,2 and 1,4 are cis while 1,3 and 2,4 are trans. Co(NO2)3(NH3)3 exhibit this type of geomerical isomerism
Type MABX2 - [Co ( NH 3 ) 2 Cl Br ] of each trio of donor atoms occupy adjacent positions at
the corners of an octahedral face the isomer is known as
H3N Br Br NH3 facial (fac) isomerism. When the positions are around the
Co Co meridian of the octahedron we have meridional (mer) isomer.
H3N Cl H3N Cl NH3 NH3
Cis Trans O2N NH3 H3N NO2
Type MABXY - Co Co
Example is éëPt(NH 3 )(NH 2OH) (NO2 )(py) ùû NO 2 . Its three O2N NH3 O2N NO2
NO2 NH3
isomers are possible.
Fac. Mer.
Type M(AA1)2 - Where AA1 is unsymmetrical bidentate eg
(b) Optical isomerism - Non superimposable mirror images
.. are called optical isomers and may be described as
[Pt(Gly)2], here gly = H 2 N CH 2COO
“chiral’. They are also called enantiomers and they rotate
H2C H2N NH2 CH2 plane polarised light in opposite directions.
Pt
OC O O CO N N N
Cis - isomer N
N Co Cl Cl Co N
H2C H2N O CO
N N
Pt
Cl Cl
OC NH2
O CH2
Trans - isomer Optical isomerism - It is given by octahedral complexes of
(II) Octahedral of the type : MA4XY, MA4X2 MA3X3 the type
MA2X2Y2. M(AA)2X2 and M(ABCDEF). In the last M(AA')3 (Cis or trans) M(AA)3 ; M(AA)2 B2 (Cis not
type 15 geometrical isomers are possible.
trans) ; M(AA)2 BC (Cis form) ; M(AA)B2C2 , MA2B2C2
AA= symmetrical bidentate eg
(Cisform), MA2B2CD, MA2BCDE, MABCDEF.
2+
Type MA4X2 - [Pt ( NH 3 ) 4 Cl 2 ] , [Co ( NH 3 ) 4 Cl 2 ]+ , All exist in three forms two optically active and one
optically inactive. Examples are
[Pt ( NH 3 ) 2 Cl 4 ]
3+ + + +
X1 X ëé Co(en)3 ûù , [ Co(en) 2 Cl2 ] , [Rh(en) 2 Cl2 ] ,, Co(en) 2 CIBr ,
5
A X2 A A
+ + +
M ëé Co(en)
M 3 ûù ; Co(en) 2 Cl2 Rh(en) 2 Cl2 [Co(en)2 ClBr ]+ , ëéCo(en)2 (NH3 )2 Cl2 ûù +
A A3 A A
4 Tetrahedal Complexes - Tetrahedral complexes of the type
A6 X (M(AA 1 ) 2 show optical activity. Examples are
Cis Trans Bis(benzoylacetonato) Be (ii) and Bis (glycinato) Ni (ii)
Note : The positions 1,6 and 2,4 and 3,5 are trans. Tetrahedral complexes can have optical isomers if all four
ligands are different eg MABCD
Type MA3X3 - [Pt ( NH 3 )3 Cl3 ] +, [Co ( NH 3 ) 3 Cl 3 ]
Coordination Compounds 767
VALENCE BOND THEORY : Outer electronic configuration of Fe(At. No 26)
Features of this theory are
1. Uses hybrid orbitals to hold the donated electron pairs for 3d 4s 4p
the formation of the coordinate bonds. Outer electronic configuration of Fe2+
2. Can explain the structure and magnetic properties eg
consider the ions
3- 3+ 3d 4s 4p 4d
ëé Co(CN)6 ûù or ëé Co(NH3 ) 6 ûù 3 2
sp d
Outer electronic configuration of Co At . No. 27 The coordination number is six. We need six empty valence
atomic orbitals.
3d 4s 4p H2O is a weak ligand, pairing of electrons is not possible
Outer electronic configuration of Co3+
hence hybridisation sp 3 d 2 . Hen ce [Fe(H 2 O) 6 ]2 + is
octahedral, paramagnetic in nature, outer complex and high
spin complex.
(CN - and NH3 are strong ligands and do pairing of Third example - Structure of [CuX 4 ]2-
electrons).
The coordination number is six. We need six empty atomic Cu2+ has electronic configuration
orbitals to accomodate electrons donated by CN or NH3.
sp3
[Ni(CN)4]2- : : : : : +2 dsp2 Square planar 0 Diamagnetic
2
Rearrangement dsp
768 Chemistry
Fe 0 Trigonal 4 Paramagnetic
®
®
®
®
®
®
®
Thus bonding in the complex may be ion-ion attraction or
ion dipole attraction. Hybridisation sp3 \ tetrahedral
(ii) Ligands are treated as point of negative charges COLOURS OF METAL COMPLEXES :
(iii) There is no interaction between metal orbitals and ligand It is due to electronic transitions between t2g and eg energy levels.
orbitals The energy of an electron is increased by absorbing light energy
(iv) The d-orbitals present in metal have the same energy in the
and it moves to a higher energy level.
free state. This is called degenerate state of d-orbital. But,
Energy of a photon = Energy difference between the ground
when a complex is formed the ligands destroy the degen-
eracy of these orbitals. This effect is Known as Crystal field state and an excited state
splitting of d- orbitals. c
It accounts for both the colour and the magnetic properties of E = hn = h
l
complexes. It is based on d- orbital energy level splitting
h = Planck’s constant (6.63x10-34 J.sec.) u = frequency of light. E
2 2 2
eg = energy of photon (measured with UV. or visible spectroscopy)
dz dx – y
MAGNETIC PROPERTIES OF METAL COMPLEXES :
D = crystal field
splitting energy • Paramagnetic - unpaired electrons
energy
dxy dxz dyz
t2g • Diamagnetic - no unpaired electrons
• Determined from crystal field splitting diagrams
d orbitals of the free splitting of d-orbitals of the metal ion
metal ion in an octahedral field of ligands STABILITY OF COORDINATION COMPOUNDS IN
SOLUTION :
The size of D depends on -
(i) The nature of the ligand “Spectro chemical series” D Consider the following equilibrium between undissociated
complex ion and dissociated ion.
decreases as shown below
[MLn]b+ Ma+ +nLx-
I – < Br – < Cl – < OH – < F- < C2O 42- < H 2O < CNS– <
[M a + ][Lx - ]n
weak ligands The equilribrium constant Kc =
[(MLn ) b + ]
< NH 3 < en < NO2 – < CN – < CO
strong ligands The smaller the value of Kc, the greater is the stability of complex
(ii) The oxidation state of the metal D is greater for M3+ than ion and vice versa. The reciprocal of equilibrium constant is called
stability constant.
for M2+
(iii) The row of the metal in the periodic table. For a given ligand 1 [MLn]b +
and oxidation state of the metal, D increases going down in Ks = =
K c [M a + ][Lx - ]n
a group eg.
D is greater in [Ru (NH3)6]3+ than in [Fe(NH3)6]3+ The higher the value of Ks, the more is the stability of complex
Effect of strong field ligands and weak field ligands– Strong field ion. The value of Ks depends on.
ligands forces the electrons of central metal for pairing and the 1. Nature of central metal atom - The more the polarizing power
complex formed is known as low spin complex. While weak field of the central metal ion the more is the stability of complex
ligands do not forces the electron of central atom for pairing and ion.
the compelx formed is known as high spin complex. For example– charge
In [Ni (CN)4], CN is a strong field ligand which forces electrons of The polarising power f =
radius
Ni 2+ for pairing Thus complex of Fe3+ is more stable then Fe2+
2. Nature of ligand - Since ligand is a Lewis base the more the
Ni 2+; [Ar] 3d8
®
®
®
®
®
®
®
®
®
®
®
constant.
[Ni(H 2 O)6 ]2+ ¾¾¾ ®[Ni(NH3 )6 ]2 + , K f = 4x108
36NH
–
electrons provided by 4CN
Hybridisation: dsp 2 (square planar)
[Ni(H 2 O)6 ]2+ ¾¾
3en
¾®[Ni(en)3 ]2+ , K f = 2x1018
770 Chemistry
Perfect or penetrating complexes : They are fairly stable and ORGANOMETALLIC COMPOUNDS :
dissociate negligibly or not at all e.g.
The organic compounds having metal atom directly attached to
the carbon are known as organometallic compounds. They can
Imperfect or normal complexes : The complex ion is reversibly be
dissociated
1. Sigma bonded -
• R - Mg - X Alkyl magnesium halide commonly known as
IMPORTANCE OF COORDINATION COMPOUNDS : Grignard’s reagent
1. Biological processes
Haemoglobin - Oxygen carrier is a complex of Iron (II) 2. -bonded
Chlrorophyll - Green colouring matter of plants is a complex (CH3)4 Sn (Tetramethyl tin), (C2H5)2 Zn (Diethyl Zinc), n–
of Mg C4H9Li (n–butyl lithium)
Vitamin B 12 - It is a complex of cobalt K [PtCl3–h2 –(C2H4)] (Zeise’s salt)
2. Analytical chemistry - Many metal ions are quantitatively
estimated by complex formation eg Cu++, Ni2+, Fe3+, Al3+ CH2
OH OH Cl
CH2 +
Pt K
CH3 C= N N=C CH3
Ni Cl Cl
CH3 C= N N= C CH3
OH OH
Red precipitate of nickel with dimethyl glyoxime
Fe[h5– C5H5]2 Ferrocene Fe
• Separation of Ag+ and Hg 22 + , Ag+ form soluble
complex
AgCl + 2NH4OH ® [Ag (NH3)2]Cl + 2H2O
Soluble complex
Hg 2 Cl 2 + NH 4OH ® Hg ( NH 2 )Cl + Hg + HCl + H 2 O
142
4 43 4 Cr
Black inso lub le Cr[h6– C6H6]2 Dibenzene chromium
3. Metallurgical processes
(a) Bauxite ore of aluminium is purified by soluble complex SYNTHESIS OF ORGANOMETALLIC COMPOUNDS:
formation
1. Synthesis of Grignard’s reagent - By reaction between an
Al2O3 + 3H2 O + 2OH – ® 2 Al(OH) 4 alkyl halide and Mg in presence of ether
Impurites of Fe2O3 are left behind in solution.
ether
(b) Extraction of silver and gold by cyanide process involves R - X + Mg ¾¾¾® R - Mg - X
complex formation
Other metals like Li, Na, Zn, Cd can also be used.
Ag + (aq) + 2NaCN(aq) ® Na[Ag(CN) 2 ](aq) + Na + 2. Synthesis of other organometallic compounds using
+ + Grignand’s reagent
Au (aq) + 2NaCN(aq) ® Na[Au(CN) 2 ](aq) + Na
(c) Nickel is purified by Mond’s process forming volatile ether
PbCl 4 + 4C 2 H 5 Mg - Br ¾¾¾®(C 2 H 5 ) 4 Pb + 4MgBrCl
nickel carbonyl
ether
D
Ni + 4CO ® Ni (CO ) 4 ¾¾® Ni + 4CO PCl 3 + 3C 6 H 5 MgCl ¾¾¾® P( C 6 H 5 ) 3 + 3MgCl 2
s Bond
772 Chemistry
Very Short/Short Answer Questions 11. Arrange the following complexes in order of increasing
electrical conductivity:
1. What is the oxidation state of Co in complex [Co (NH3)2
[Co (NH3)3 Cl3], [Co (NH3)5 Cl] Cl2 , [Co (NH3)6] Cl3, [Co
(NO2) Cl] [Au (CN)2]?
(NH3)4 Cl2] Cl.
2. Write IUPAC name of complex,
12. Write the correct formula for the following compounds :
NO2 3+ (a) CrCl 3×6H2 O (violet, with three chloride ions/unit
(NH 3) Co Co (NH3) . formula)
NH (b) CoCl3×6H2O (light green colour with two chloride ions/
3. When copper sulphate solution is mixed with liquid ammonia unit formula)
(in molar ratio of 1 : 4), the resultant solution does not give (c) CrCl3×6H2O (dark green colour with one chloride ion
the test of Cu2+ ion. Why? (unit formula)
4. How many moles of Cl– ions are formed by one mole of each 13. Write the name, the state of hybridization, the shape and
of the following in aqueous solution : the magnetic behaviour of the following complexes:
(a) K2 [PtCl6]
2- -
(b) [Pt (NH3)3 Cl3]Cl [CoCl4 ]2- , éë Ni ( CN )4 ùû , éëCr ( H 2 O )2 ( C 2 O 4 ) 2 ùû
(c) [Pt (NH3)4 Cl2]Cl2 (At. No.: Co = 27, Ni = 28, Cr = 24)
5. How is tetrabutyl lead is prepared? 14. Write the name, stereochemistry and magnetic behaviour
6. Among Ag(NH3)2Cl, [Ni (CN)4]2– and [CuCl4]2–, which of the following:
(a) has square planar geometry? (At nos. Mn = 25, Co = 27, Ni = 28)
(b) remains colourless in aqueous solution and why? (i) K 4 éë Mn ( CN )6 ùû
[Ag (Z = 47), Ni (Z = 28), Cu (Z = 29)].
7. Assign the formula to complex formed by Fe2+ with following (ii) éë Co ( NH 3 )5 Cl ùû Cl2
ligands:
(a) three cyanide ion and three ammonia molecules. (iii) K 2 éë Ni ( CN ) 4 ùû
(b) one hydroxy ion and two ammonia molecules and three 15. Write the name, the structure and the magnetic behaviour
chloride ions. of each one of the following complexes:
8. Answer the following questions referring to [Al (H2O)6 ]3+ :
(i) éë Pt ( NH 3 ) Cl ( NO 2 ) ùû
(a) Coordination number of Al
(b) Oxidation state of Al (ii) éë Co ( NH 3 ) 4 Cl2 ùû Cl
(c) Hybridisation involved in complex formation
(iii) Ni(CO)4
(d) Shape of complex ion
[Al nos, Co = 27, Ni = 28, Pt = 78)
(e) Paramagnetic or diamagnetic
16. Write the IUPAC names of the following coordination
9. Give (a) linkage isomer of [Cr (CN) (H2O)5]2+ compounds:
(b) ionisation isomer of [Pt Cl2 (NH3)4] Br2
(i) éë Cr ( NH 3 )3 Cl3 ùû
(c) coordination isomer of [Pt (NH3)4] [CuCl4]
10. Mention the application of organometallic compounds in
(ii) K3 éë Fe ( CN )6 ùû
the following areas:
(a) Homogeneous catalysis +
(b) Heterogeneous catalysis (iii) é CoBr2 ( en ) ù , (en = ethylenediamine)
ë 2û
(c) Organic synthesis.
Coordination Compounds 773
Multiple Choice Questions (a) [MA5B] (b) [MA2B4]
17. An example of double salt is (c) [MA3B3] (d) [MA4B2]
(a) Bleaching powder (b) K 4 [Fe(CN) 6 ] 23. Considering H 2 O as a weak field ligand, the number of
(c) Hypo (d) Potash alum unpaired electrons in [Mn (H 2 O) 6 ]2 + will be (At. no. of
18. The number of unpaired electrons in the complex ion
[CoF6]3– is (Atomic no.: Co = 27) Mn = 25)
(a) zero (b) 2 (a) three (b) five
(c) 3 (d) 4 (c) two (d) four
19. Hybridization of Ag in the linear complex [Ag(NH3 )2 ]+ is 24. The complex, [Pt(Py)(NH3)BrCl] will have how many
geometrical isomers ?
:
(a) 3 (b) 4
(a) dsp 2 (b) sp (c) 0 (d) 2
(c) sp
2
(d) sp
3 25. On mixing conc. NH 4OH to a Cu 2 + salt, the following
20. Ammonia will not form complex ions with blue complex is formed :
1. Which of the following is odd one out ? 6. In the compound lithium tetrahydridoalumninate, the ligand
(a) potassium ferricyanide is
(b) ferrous ammoniumsulphate (a) Al+ (b) H
(c) H – (d) None of these
(c) potassium ferrocyanide
(d) tetraamminecopper (II) sulphate 7. In which of the following coordinate compounds the central
metal atom obeys the EAN rule.
2. CuSO4 dissolves in NH3 due to formation of
(a) K3[Fe(CN)6] (b) K4[Fe(CN)6]
(a) Cu (OH)2 (b) [Cu(NH3)4]SO4
(c) [Cu(NH3)4]SO4 (d) All of these
(c) [Cu(NH3)4(OH)2] (d) CuO 8. The EAN of iron in [Fe(CN)6]3– is
3. K4[Fe(CN)6] is a (a) 34 (b) 36
(a) double salt (b) complex compound (c) 37 (d) 35
(c) neutral molecule (d) None of these 9. Coordination number of Ni in [Ni(C2O4)3]4– is
4. AgCl is soluble in NH4OH solution. The solubility is due to (a) 3 (b) 6
formation of (c) 4 (d) 5
(a) AgOH (b) Ag2O 10. The coordination number of Fe(II) in oxyhaemoglobin is
(c) [Ag(NH3)2]+ (d) NH4Cl (a) 6 (b) 4
5. Some salts although containing two different metallic (c) 8 (d) 10
elements give test for only one of them in solution. Such 11. Correct formula of the complex formed in the brown ring test
salts are for nitrates is
(a) complex (b) double salts (a) FeSO4.NO (b) [Fe(H2O)5NO]2+
(c) [Fe(H2O)5NO] + (d) [Fe(H2O)5NO]3+
(c) normal salts (d) None of these
774 Chemistry
12. According to Lewis, the ligands are 22. The hypothetical complex chloro-diaquatriamminecobalt (III)
(a) acidic in nature chloride can be represented as
(b) basic in nature (a) [CoCl(NH3)3(H2O)2 ]Cl2
(c) some are acidic and others are basic (b) [Co(NH3)3(H2O)Cl3]
(d) neither acidic nor basic (c) [Co(NH3)3(H2O)2Cl]
13. According to the postulates of Werner for coordination
(d) [Co(NH3)3(H2O)3]Cl3
compounds
23. The oxidation state of Fe in K4[Fe(CN)6] is
(a) primary valency is ionizable
(b) secondary valency is ionizable (a) +2 (b) +6
(c) primary and secondary valencies are non-ionizable (c) +3 (d) +4
(d) only primary valency is non-ionizable. 24. Which of the following complex will show geometrical as
14. In [Co(NH3)6]Cl3, the number of covalent bonds is well as optical isomerism (en=ethylenediammine)
(a) 3 (b) 6 (a) Pt(NH3)2Cl2 (b) [Pt(NH3)Cl4]
(c) 9 (d) 18 (c) [Pt(en)3] 4+ (d) [Pt(en)2Cl2]
15. When AgNO3 is added to a solution of Co(NH3)5Cl3, the 25. The number of geometrical isomers from [Co(NH3)3(NO2)3]
precipitate of AgCl shows two ionisable chloride ions. This is
means : (a) 2 (b) 3
(a) Two chlorine atoms satisfy primary valency and one
(c) 4 (d) 0
secondary valency
26. The total number of possible isomers of the complex
(b) One chlorine atom satisfies primary as well as secondary
valency compound [CuII(NH3)4][PtIICl4] is
(c) Three chlorine atoms satisfy primary valency (a) 3 (b) 6
(d) Three chlorine atoms satisfy secondary valency (c) 5 (d) 4
16. The formula dichlorobis (urea) copper (II) is 27. A coordination complex compound of cobalt has molecular
(a) [Cu{O = C(NH2)2}2]Cl2 (b) [CuCl2 {O = C(NH2)2}2] formula containing five ammonia molecules, one nitro group
(c) [Cu{O=C(NH2)2}Cl]Cl (d) [CuCl2{O=C(NH2)2}H2] and two chlorine atoms for one cobalt atom. One mole of
17. Chemical formula for iron (III) hexacyanoferrate (II) is this compound produces three mole ions in an aqueous
(a) Fe[Fe(CN)6] (b) Fe3[Fe(CN)6] solution. On reacting this solution, with excess of AgNO3
(c) Fe3[Fe(CN)6]4 (d) Fe4[Fe(CN)6]3 solution two moles of AgCl get precipitated. The ionic
18. IUPAC name of Na3[Co(NO2)6] is formula of this complex would be
(a) sodium cobaltinitrite (a) [Co(NH3)4NO2Cl] [(NH3)Cl]
(b) sodium hexanitritocobaltate (III) (b) [Co(NH3)5Cl] [Cl(NO)2]
(c) sodium hexanitrocobalt (III) (c) [Co(NH3)5(NO2)]Cl2
(d) sodium hexanitrocobaltate (III) (d) [Co(NH3)5][(NO2)2Cl2]
19. Ligand in a complex salt are 28. The number of isomers exhibited by [Cr(NH3)3Cl3] is
(a) anions linked by coordinate bonds to a central metal (a) 2 (b) 3
atom or ion
(c) 4 (d) 5
(b) cations linked by coordinate bonds to a central metal or
ion 29. For the square planar complex [M (a) (b) (c) (d)] (where M =
(c) molecules linked by coordinate bonds to a central metal central metal and a, b, c and d are monodentate ligands), the
or ion number of possible geometrical isomers are
(d) ions or molecules linked by coordinate bonds to a central (a) 1 (b) 2
atom or ion (c) 3 (d) 4
20. The IUPAC name of K3[Ir(C2O4)3] is 30. Which of the following will exhibit optical isomerism ?
(a) potassium trioxalatoiridium (III) (a) [Cr(en) (H2O)4]3+
(b) potassium trioxalatoiridate (III) (b) [Cr(en)3]3+
(c) potassium tris (oxalato) iridium (III) (c) trans-[Cr(en)(Cl2)(NH3)2]+
(d) potassium tris (oxalato) iridate (III) (d) [Cr(NH3)6]3+
21. In Zeigler- Natta polymerisation of ethylene, the active 31. Which of the following will give maximum number of isomers?
species is
(a) [Co(NH3)4Cl2] (b) [Ni(en)(NH3)4]2+
(a) AlCl3 (b) Et3Al
(c) [Ni(C2O4)(en)2] (d) [Cr(SCN)2(NH3)4]2+
(c) CH2CH2 (d) TiIII
Coordination Compounds 775
32. The compounds [PtCl2(NH3)4]Br 2 and [PtBr 2(NH3)4]Cl 2 45. The valency of Cr in the complex [Cr(H2O)4Cl2]+ is
constitutes a pair of
(a) 1 (b) 3
(a) coordination isomers (b) linkage isomers
(c) 5 (d) 6
(c) ionization isomers (d) optical isomers
33. Which of the following compounds exhibits linkage 46. Which of the following is expected to be a paramagnetic
isomerism ? complex ?
(a) [Co(en)2]Cl3 (b) [Co(NH3)6][Cr(en)3] (a) [Ni(H2O)6]2+ (b) [Ni(CO)4]
(c) [Zn(NH3)4] 2+ (d) [Co(NH3)6]3+
(c) [Co(en)2NO2Cl]Br (d) [Co(NH3)5Cl]Br2
34. Both geometrical and optical isomerisms are shown by 47. Which statement is incorrect ?
(a) [Co(en)2Cl2]+ (b) [Co(NH3)5Cl]2+ (a) [Ni(CO) 4 ] – Tetrahedral, paramagnetic
(c) [Co(NH3)4Cl2] + (d) [Cr(ox)3]3–
35. Which one of the following will not show geometrical (b) [ Ni(CN) 4 ]2 - – Square planar, diamagnetic
isomerism ?
(c) [Ni(CO) 4 ] – Tetrahedral, diamagnetic
(a) [Cr(NH3)4Cl2]Cl (b) [Co(en)2Cl2]Cl
(c) [Co(NH3)5NO2]Cl2 (d) [Pt(NH3)2Cl2 ] (d) [ NiCl4 ]2 - – Tetrahedral, paramagnetic
36. A similarity between optical and geometrical isomerism is
that 48. The geometry of the compound [Pt(NH3)2Cl2] is
(a) each gives equal number of isomers for a given (a) square planar (b) pyramidal
compound (c) tetrahedral (d) octahedral
(b) if in a compound one is present then so is the other 49. The shape of cuprammonium ion is
(c) both are included in stereoisomerism (a) octahedral (b) tetrahedral
(d) they have no similarity
(c) trigonal (d) square planar
37. The type of isomerism present in nitr openta-
50. Which of the following species represent the example of
amminechromium (III) chloride is
dsp2 - hybridisation ?
(a) optical (b) linkage
(c) ionization (d) polymerization (a) [Fe(CN)6]3– (b) [Ni(CN)4]2–
38. Which of the following has square planar structure? (c) [Ag(CN)2]– (d) [Co(CN)6]3–
51. Consider the following complex [Co(NH3)5CO3]ClO4. The
(a) [Ni(CO)4] (b) [NiCl4]2–
coordination number, oxidation number, number of d-
2+
(c) [Ni(CN)4]2– (d) é Ni ( H 2O) ù electrons and number of unpaired d-electrons on the metal
ë 6û are respectively
39. The unpaired electrons in Ni(CO)4 are
(a) 6, 3, 6, 0 (b) 7, 2, 7, 1
(a) zero (b) one
(c) 7, 1, 6, 4 (d) 6, 2, 7, 3
(c) three (d) four
40. Which of the following species represent the example of 52. Atomic numbers of Cr and Fe are respectively 24 and 26.
dsp2 – hybridisation ? Which of the following is paramagnetic with the spin of the
(a) [Fe(CN)6]3– (b) [Ni(CN)4]2– electron ?
(c) [Zn(NH3)4] 2+ (d) [FeF6]3– (a) [Cr(CO)6] (b) [Fe(CO)5]
41. The correct structure of Fe(CO)5 is (Z=26 for Fe) (c) [Fe(CN)6]4– (d) [Cr(NH3)6]3+
(a) octahedral (b) tetrahedral 53. Which of the following will exhibit maximum ionic
(c) square pyramidal (d) trigonal pyramidal conductivity ?
42. The shape of [Cu(NH3)4] is2+
(a) K4[Fe(CN)6] (b) [Co(NH3)6]Cl3
(a) tetrahedral (b) square planar (c) [Cu(NH3)4Cl2] (d) [Ni(CO)4]
(c) pyramidal (d) octahedral
54. Which of the following is organo-metallic compound ?
43. Which one of the following is an example of octahedral (a) Ti(C2H4)4 (b) Ti(OC2H5)4
complex ? (c) Ti(OCOCH3)4 (d) Ti(OC6H5)4
(a) [FeF6]3– (b) [Zn(NH3)4]2+
55. Which is not p - bonded complex ?
(c) [Ni(CN)4]2– (d) [Cu(NH3)4]2+
(a) Zeise’s salt (b) Ferrocene
44. Which of the following is paramagnetic ?
(c) Dibenzene chromiun (d) Tetraethyl lead
(a) [Fe(CN)6]4– (b) [Ni(CO)4]
(c) [Ni(CN)4]2– (d) [CoF6]3–
776 Chemistry
1. Which of the following will give a pair of enantiomorphs? 9. The existence of two different coloured complexes with the
[CBSE-PMT 2007]
composition of [Co(NH3 )4 Cl2 ]+ is due to :
(a) [Cr(NH3)6][Co(CN)6]
(b) [Co(en)2Cl2]Cl [CBSE-PMT 2010]
(c) [Pt(NH3)4] [PtCl6] (a) linkage isomerism (b) geometrical isomerism
(d) [Co(NH3)4Cl2]NO2. (en =NH2CH2CH2NH2) (c) coordination isomerism (d) ionization isomerism
2. The d electron configurations of Cr 2+, Mn2+, Fe2+ and Ni2+ 10. Which one of the following complexes is not expected to
are 3d 4, 3d 5, 3d 6 and 3d 8 respectively. Which one of the exhibit isomerism? [CBSE-PMT 2010]
following aqua complexes will exhibit the minimum
2+
paramagnetic behaviour?
2+
[CBSE-PMT 2007] (a) [ Ni(en)3 ]2+ (b) éë Ni ( NH3 )4 ( H 2O ) 2 ùû
(a) [Fe(H2O)6] (b) [Ni(H2O)6]2+
(c) éë Pt ( NH3 )2 Cl 2 ùû (d) éë Ni ( NH3 ) 2 Cl 2 ùû
(c) [Cr(H2O)6] 2+ (d) [Mn(H2O)6]2+
(At. No. Cr = 24, Mn = 25, Fe = 26, Ni = 28)
11. Of the following complex ions, which is diamagnetic in nature?
3. Which of the following complexes exhibits the highest
[CBSE-PMT 2011]
paramagnetic behaviour ? [CBSE-PMT 2008]
(a) [V(gly)2(OH)2(NH3)2]+ (b) [Fe(en)(bpy)(NH3)2]2+ (a) [NiCl4]2– (b) [Ni(CN)4]2–
(c) [Co(ox)2(OH)2]2– (d) [Ti(NH3)6]3+ (c) [CuCl4]2– (d) [CoF6]3–
where gly = glycine, en = ethylenediamine and bpy = bipyridyl 12. The complexes [Co(NH3 )6] [Cr(CN)6 ] and [Cr(NH3 )6 ]
moities) [Co(CN)6] are the examples of which type of isomerism?
(At.nosTi = 22, V = 23, Fe = 26, Co = 27) [CBSE-PMT 2011]
4. In which of the following coordination entities the magnitude (a) Linkage isomerism (b) Ionization isomerism
D0 (CFSE in octahedral field) will be maximum? (c) Coordination isomerism (d) Geometrical isomerism
[CBSE-PMT 2008] 13. The complex, [Pt(py)(NH3)BrCl] will have how many
(a) [Co(H2O)6] 3+ (b) [Co(NH3)6]3+ geometrical isomers ? [CBSE-PMT 2011]
(c) [Co(CN)6] 3– (d) [Co (C2O4)3]3– (a) 3 (b) 4 (c) 0 (d) 2
(At. No. Co = 27)
14. The d-electron configurations of Cr , Mn , Fe2+ and Co2+
2+ 2+
5. Which of the following does not show optical isomerism?
are d 4 , d 5 , d 6 and d 7, respectively. Which one of the
[CBSE-PMT 2009]
0
following will exhibit minimum paramagnetic behaviour?
(a) [Co(NH3)3Cl3] (b) [Co (en) Cl2 (NH3)2]+
3+
[CBSE-PMT 2011]
(c) [Co (en)3] (d) [Co (en)2Cl2]+ 2+
(a) [Mn(H2O)6] (b) [Fe(H2O)6]2+
(en = ethylenediamine)
(c) [Co(H2O)6]2+ (d) [Cr(H2O)6]2+
6. Which of the following complex ions is expected to absorb
visible light? [CBSE-PMT 2009] (At, nos. Cr = 24, Mn = 25, Fe = 26, Co = 27)
(a) [Ti (en)2(NH3)2]4 + (b) [Cr (NH3)6]3 + 15. Which of the following carbonyls will have the strongest
(c) [Zn (NH3)6]2 + (d) [Sc (H2O)3 (NH3)3]3+ C – O bond ? [CBSE-PMT 2011 M]
(a) [Mn (CO)6] + (b) [Cr (CO)6]
(At. no. Zn = 30, Sc = 21, Ti = 22, Cr = 24)
7. Which of the following complex ion is not expected to absorb (c) [V (CO)6] – (d) [Fe (CO)5]
visible light ? [CBSE-PMT 2010] 16. Which of the following complex compounds will exhibit
highest paramagnetic behaviour? [CBSE-PMT 2011M]
(a) [ Ni(CN)4 ]2- (b) [Cr(NH3 )6 ]3+ (At. No. : Ti = 22, Cr = 24, Co = 27, Zn = 30)
(c) [ Fe(H2 O)6 ]2+ (d) [ Ni(H 2O)6 ]2+ (a) [Ti (NH3)6]3+ (b) [Cr (NH3)6]3+
(c) [Co (NH3)6]3+ (d) [Zn (NH3)6]2+
8. Crystal field stabilization energy for high spin d 4 octahedral
17. Which one of the following is an outer orbital complex and
complex is: [CBSE-PMT 2010]
exhibits paramagnetic behaviour ? [CBSE-PMT 2012 S]
(a) – 1.8 D 0 (b) – 1.6 D 0 + P (a) [Ni(NH3)6]2+ (b) [Zn(NH3)6)]2+
(c) [Cr(NH3)6] 3+ (d) [Co(NH3)6]3+
(c) – 1.2 D 0 (d) – 0.6 D 0
Coordination Compounds 777
18. Red precipitate is obtained when ethanol solution of (b) the number of ligands around a metal ion bonded by pi-
dimethylglyoxime is added to ammoniacal Ni(II). Which of bonds
the following statements is not true ? [CBSE-PMT 2012 M] (c) the number of ligands around a metal ion bonded by
(a) Red complex has a square planar geometry. sigma bonds
(b) Complex has symmetrical H-bonding (d) the number of only anionic ligands bonded to the metal
ion.
(c) Red complex has a tetrahedral geometry.
27. Which one of the following complexes is an outer orbital
(d) Dimethylglyoxime functions as bidentate ligand.
complex ? [AIEEE 2004]
(a) [Co(NH3)6]3+ (b) [Mn(CN)6]4–
OH
H3C C N (c) [Fe(CN)6]4– (d) [Ni(NH3)6]2+
dimethylglyoxime = (Atomic nos. : Mn = 25; Fe = 26; Co = 27, Ni = 28)
H3C C N
OH 28. Coordination compounds have great importance in biological
systems. In this context which of the following statements is
19. Low spin complex of d 6 -cation in an octahedral field will incorrect ? [AIEEE 2004]
have the following energy : [CBSE-PMT 2012 M] (a) Cyanocobalamin is B12 and contains cobalt
(b) Haemoglobin is the red pigment of blood and contains
-12 -12
(a) D0 + P (b) D 0 + 3P iron
5 5
(c) Chlorophylls are green pigments in plants and contain
-2 -2 calcium
(c) D 0 + 2P (d) D0 + P (d) Carboxypeptidase - A is an enzyme and contains zinc.
5 5
29. Which one of the following has largest number of
(D0= Crystal Field Splitting Energy in an octahedral field,
isomers ? [AIEEE 2004]
P = Electron pairing energy)
20. An excess of AgNO3 is added to 100 mL of a 0.01 M solution (a) [Ir(PR 3 ) 2 H(CO)]2 + (b) [Co( NH 3 )5 Cl]2+
of dichlorotetraaquachromium (iii) chloride. The number of
moles of AgCl precipitated would be : [NEET 2013] (c) [Ru ( NH 3 ) 4 Cl 2 ]+ (d) [Co(en ) 2 Cl 2 ]+
(a) 0.002 (b) 0.003 (R = alkyl group, en = ethylenediamine)
(c) 0.01 (d) 0.001 30. The correct order of magnetic moments (spin only values in
21. A square planar complex is formed by hybridisation of which B.M.) is [AIEEE 2004]
atomic orbitals? [AIEEE 2002]
(a) [Fe(CN ) 6 ]4 - > [MnCl 4 ]2 - > [CoCl 4 ]2 -
(a) s, px , py , dyz (b) s, px , p y , d x2 - y 2
(b) [MnCl 4 ]2- > [Fe(CN) 6 ]4 - > [CoCl 4 ]2 -
(c) s, px , p y , d (d) s, py , pz, dxy
z2
(c) [MnCl 4 ]2- > [CoCl 4 ]2 - > [Fe(CN) 6 ]4 -
22. CH3 – Mg – Br is an organometallic compound due to
[AIEEE 2002] (d) [Fe(CN ) 6 ]4 - > [CoCl 4 ]2- > [MnCl 4 ]2 -
(a) Mg – Br bond (b) C – Mg bond
(Atomic nos. : Mn = 25, Fe = 26, Co = 27)
(c) C – Br bond (d) C – H bond.
23. The most stable ion is [AIEEE 2002] 31. The oxidation state Cr in [Cr ( NH 3 ) 4 Cl 2 ]+ is
(a) [Fe(OH)3]3- (b) [Fe(Cl)6]3- [AIEEE 2005]
(c) [Fe(CN)6]3- (d) [Fe(H2O)6]3+.
(a) 0 (b) + 1
24. One mole of the complex compound Co(NH3)5Cl3, gives 3
moles of ions on dissolution in water. One mole of the same (c) + 2 (d) + 3
complex reacts with two moles of AgNO3 solution to yield 32. The IUPAC name of the coordination compound
two moles of AgCl (s). The structure of the complex is K 3[Fe(CN ) 6 ] is [AIEEE 2005]
[AIEEE 2003] (a) Tripotassium hexacyanoiron (II)
(a) [Co(NH3)3Cl3]. 2 NH3 (b) [Co(NH3)4Cl2] Cl . NH3
(b) Potassium hexacyanoiron (II)
(c) [Co(NH3)4Cl] Cl2. NH3 (d) [Co(NH3)5Cl] Cl2
25. In the coordination compound, K4[Ni(CN)4], the oxidation (c) Potassium hexacyanoferrate (III)
state of nickel is [AIEEE 2003] (d) Potassium hexacyanoferrate (II)
(a) 0 (b) +1 33. Which of the following compounds shows optical isomerism?
(c) +2 (d) –1 [AIEEE 2005]
26. The coordination number of a central metal atom in a complex
(a) [Co(CN) 6 ]3 - (b) [Cr(C 2 O 4 )3 ]3 -
is determined by [AIEEE 2004]
(a) the number of ligands around a metal ion bonded by
(c) [ ZnCl4 ]2 - (d) [Cu ( NH 3 ) 4 ]2 +
sigma and pi-bonds both
778 Chemistry
34. Which one of the following cyano complexes would exhibit 44. A solution containing 2.675 g of CoCl3. 6 NH3 (molar mass =
the lowest value of paramagnetic behaviour ? 267.5 g mol–1) is passed through a cation exchanger. The
[AIEEE 2005] chloride ions obtained in solution were treated with excess of
AgNO3 to give 4.78 g of AgCl (molar mass = 143.5 g mol–1).
(a) [Co(CN) 6 ]3 - (b) [Fe(CN) 6 ]3 -
The formula of the complex is [AIEEE 2010]
(c) [Mn (CN) 6 ]3 - (d) [Cr (CN) 6 ]3 - (At. mass of Ag = 108 u)
(At. Nos : Cr = 24, Mn = 25, Fe = 26, Co = 27) (a) [Co(NH3 )6 ]Cl3 (b) [CoCl2 (NH3 )4 ]Cl
35. The value of the ‘spin only’ magnetic moment for one of the
(c) [CoCl3 (NH3 )3 ] (d) [CoCl(NH3 )5 ]Cl2
following configurations is 2.84 B.M. The correct one is
[AIEEE 2005] 45. Which one of the following has an optical isomer?
(a) d5 (in strong ligand field) [AIEEE 2010]
(a) [Zn(en) (NH3)2]2+ (b) [Co(en)3]3+
(b) d3 (in weak as well as in strong fields)
(c) [Co(H2O)4(en)]3+ (d) [Zn(en)2]2+
(c) d4 (in weak ligand fields)
(en = ethylenediamine)
(d) d4 (in strong ligand fields)
46. Which one of the following complex ions has geometrical
36. The IUPAC name for the complex [Co(NO2)(NH3)5]Cl2 is : isomers ? [AIEEE 2011]
[AIEEE 2006] (a) [Ni(NH3)5Br]+ (b) [Co(NH3)2(en)2]3+
(a) pentaammine nitrito-N-cobalt(II) chloride (c) [Cr(NH3)4(en)2]3+ (d) [Co(en)3]3+
(b) pentaammine nitrito-N-cobalt(III) chloride (en = ethylenediamine)
(c) nitrito-N-pentaamminecobalt(III) chloride 47. Which of the following facts about the complex [Cr(NH3)6]Cl3
(d) nitrito-N-pentaamminecobalt(II) chloride is wrong? [AIEEE 2011]
37. In Fe(CO)5, the Fe – C bond possesses [AIEEE 2006] (a) The complex involves d 2 sp 3 hybridisation and is
(a) ionic character (b) s-character only octahedral in shape.
(b) The complex is paramagnetic.
(c) p-character (d) both s and p characters
(c) The complex is an outer orbital complex
38. How many EDTA (ethylenediaminetetraacetic acid)
(d) The complex gives white precipitate with silver nitrate
molecules are required to make an octahedral complex with
solution.
a Ca2+ ion? [AIEEE 2006]
48. Among the ligands NH3, en, CN– and CO the correct order of
(a) One (b) Two their increasing field strength, is : [AIEEE 2011]
(c) Six (d) Three
(a) NH3 < en < CN - < CO
39. Which of the following has a square planar geometry?
[AIEEE 2007] (b) CN - < NH3 < CO < en
(a) [PtCl4]2– (b) [CoCl4]2– (c) [FeCl4]2– (d) [NiCl4]2–
-
(At. nos.: Fe = 26, Co = 27, Ni = 28, Pt = 78) (c) en < CN < NH3 < CO
40. The coordination number and the oxidation state of the
(d) CO < NH3 < en < CN -
element ‘E’ in the complex
[E (en)2 (C2O4)]NO2 (where (en) is ethylene diamine) are, 49. Which among the following will be named as dibromidobis
respectively, [AIEEE 2008] (ethylene diamine) chromium (III) bromide? [AIEEE 2012]
(a) 6 and 2 (b) 4 and 2 (c) 4 and 3 (d) 6 and 3 (a) [Cr (en)3]Br3 (b) [Cr(en)2Br2]Br
41. In which of the following complexes of the Co (at. no. 27), will (c) [Cr(en)Br4]– (d) [Cr(en)Br2]Br
the magnitude of Do be the hightest? [AIEEE 2008] 50. Which of the following complex species is not expected to
(a) [Co(CN)6] 3– (b) [Co(C2O4)3]3– exhibit optical isomerism ? [JEE M 2013]
(c) [Co(H2O)6] 3+ (d) [Co(NH3)6]3+ (a) [Co(en)3]3+ (b) [Co(en)2 Cl2]+
42. Which of the following has an optical isomer [AIEEE 2009] (c) [Co(NH3)3 Cl3] (d) [Co(en) (NH3)2 Cl2]+
(a) [Co(en) (NH3)2]2+ (b) [Co(H2O)4(en)]3+ 51. Among the following metal carbonyls, the C–O bond order is
(c) [Co(en)2 (NH3)2] 3+ (d) [Co(NH3)3Cl] + lowest in [IIT-JEE 2007]
(a) [Mn(CO)6] + (b) [Fe(CO)5]
43. Which of the following pairs represent linkage isomers?
[AIEEE 2009] (c) [Cr(CO)6] (d) [V(CO)6]–
(a) [Pd(PPh3)2(NCS)2] and [Pd ( PPh3)2 (SCN)2] 52. The IUPAC name of [Ni (NH3)4] [NiCl4] is [IIT-JEE 2008]
(b) [Co(NH3)5NO3] SO4 and [Co(NH3)5SO4]NO3 (a) Tetrachloronickel (II) - tetraamminenickel (II)
(c) [PtCl2(NH3)4] Br2 and [Pt Br 2 (NH3)4] Cl2 (b) Tetraamminenickel (II) - tetrachloronickel (II)
(d) [Cu(NH3)4][Pt Cl4] and [Pt(NH3)4][CuCl4] (c) Tetraamminenickel (II) - tetrachloronickelate (II)
(d) Tetrachloronickel (II) - tetrachloronickelate (0)
Coordination Compounds 779
53. Both [Ni(CO)4] and [Ni(CN)4]2– are diamagnetic. The 57. The complex showing a spin-only magnetic moment of
hybridisations of nickel in these complexes, respectively, are 2.82 B.M. is : [IIT-JEE 2010]
[IIT-JEE 2008] (a) Ni(CO)4 (b) [NiCl4]2–
(a) sp3, sp3 (b) sp3, dsp2 (c) dsp2, sp3 (d) dsp2, sp2 (c) Ni(PPh3)4 (d) [Ni(CN)4]2–
54. The spin only magnetic moment value (in Bohr magneton 58. Among the following complexes (K-P)
units) of Cr(CO)6 is [IIT-JEE 2009] K3[Fe(CN)6] (K), [Co(NH3)6]Cl3 (L), Na3[Co(oxalate)3] (M),
(a) 0 (b) 2.84 (c) 4.90 (d) 5.92 [Ni(H2O)6]Cl2 (N), K2[Pt(CN)4] (O) and [Zn(H2O)6](NO3)2 (P)
55. The ionisation isomer of [Cr(H2O)4Cl(NO2)]Cl is the diamagnetic complexes are [IIT-JEE 2011]
[IIT-JEE 2010] (a) K, L, M, N (b) K, M, O, P
(a) [Cr(H2O)4(O2N)]Cl2 (c) L, M, O, P (d) L, M, N, O
(b) [Cr(H2O)4Cl2](NO2) 59. As per IUPAC nomenclature, the name of the complex
(c) [Cr(H2O)4Cl(ONO)]Cl [Co(H2O)4(NH3)2]Cl3 is : [IIT-JEE 2012]
(d) [Cr(H2O)4Cl2(NO2)].H2O (a) Tetraaquadiaminecobalt (III) chloride
56. The correct structure of ethylenediaminetetraacetic acid (b) Tetraaquadiamminecobalt (III) chloride
(EDTA) is [IIT-JEE 2010] (c) Diaminetetraaquacoblat (II) chloride
(d) Diamminetetraaquacobalt (III) chloride
HOOC – H2C CH2– COOH
(a) N – CH = CH – N 60. [NiCl2 {P(C2H5)2(C6H5)}2] exhibits temperature dependent
HOOC – H2C CH2– COOH magnetic behaviour (paramagnetic/diamagnetic). The
HOOC COOH coordination geometries of Ni2+ in the paramagnetic and
(b) N – CH2 – CH2 – N diamagnetic states are respectively [IIT-JEE 2012]
HOOC COOH
(a) tetrahedral and tetrahedral
HOOC–H2C CH2–COOH (b) square planar and square planar
(c) N – CH2 – CH2 – N
HOOC–H2C CH2–COOH (c) tetrahedral and square planar
(d) square planar and tetrahedral
COOH
CH2 61. Consider the following complex ions, P, Q and R.
(d) HOOC–H2C H P = [FeF6]3–, Q = [V(H2O)6]2+ and R = [Fe(H2O)6]2+
N–CH–CH–N
H CH2–COOH The correct order of the complex ions, according to their
CH2 spin-only magnetic moment values (in B.M.) is
HOOC [JEE Advanced 2013]
(a) R < Q < P (b) Q < R < P
(c) R < P < Q (d) Q < P < R
1. Which one is the most likely structure of CrCl3. 6H2O if 1/3 3. Pick a poor electrolytic conductor complex in solution
of total chlorine of the compound is precipitated by adding (a) K 2 [PtCl 6 ] (b) [Co ( NH 3 ) 3 ]( NO 2 ) 3
AgNO3
(c) K 4 [ Fe (CN ) 6 ] (d) [Co ( NH 3 ) 4 ]SO 4
(a) CrCl3. 6H2O
4. Which is correct in the case of [Fe(CN) 6 ]4- complex ?
(b) [ Cr (H2O)3 Cl3]. (H2O)3
(c) [ CrCl2 (H2O)4 ] Cl . 2H2O (a) Diamagnetic (b) Octahedral
(c) d2sp3 - hybridisation (a) All are correct
(d) [ CrCl (H2O)5 ] Cl2 . H2O
5. IUPAC name of Na 3[Co(ONO) 6 ] is
2. Which will give a white precipitate with AgNO3 in aqueous
solution (a) Sodium cobaltinitrite
(b) Sodium hexanitrito cobaltate (III)
(a) [Co(NH3 )5 Cl](NO2 )2 (b) [Pt ( NH 3 ) 6 ]Cl 4
(c) Sodium hexanitrocobalt (III)
(c) [Pt (en )Cl 2 ] (d) [Cu ( NH 3 ) 4 ]SO 4 (d) Sodium hexanitritocobaltate (II)
780 Chemistry
7. Which is not true ligands metal complex ? (a) Na2[CuCl6] (b) Na2[CdCl4]
(a) Larger the ligand, the more stable is the metal - ligand (c) K4[Fe(CN)6] (d) K3[Fe(CN)6]
complex 14. Which is paramagnetic ?
(b) Highly charged ligand forms stronger bonds (a) [Ni(H2O)6]2+ (b) [Fe(CN)6]4–
(c) Larger the permanent dipole moment of ligand , the more (c) [Ni(CO)4] (d) [Ni(CN)4]2–
stable is the bond. 15. In the complexes [Fe(H2O)6]3+ , [Fe(CN)6]3–, [Fe(C2O4)3]3–
(d) Greater the ionisation potential of central metal, the and [FeCl6]3–, more stability is shown by
stronger the bond (a) [Fe(H2O)6]3+ (b) [Fe(CN)6]3-
8. In solid CuSO 4 .5H 2O copper is coordinated to (c) [Fe(C2O4)6]3- (d) [FeCl6]3-
(a) 4 water molecules (b) 5 water molecules 16. The most stable complex among the following is
(c) one sulphate molecule (d) one water molecule (a) K3[Al(C2O4)3] (b) [Pt(en)2]Cl
9. The catalyst used for the polymerization of olefins is (c) [Ag(NH3)2]Cl (d) K2[Ni(EDTA)]
(a) Ziegler - Natta catalyst (b) Wilkinson’s catalyst 17. In the silver plating of copper, K[Ag(CN)2] is used instead
(c) Pd- catalyst (d) Zeise’s salt catalyst of AgNO3. The reason is
10. Which of the following hydrate is diamagnetic? (a) a thin layer of Ag is formed on Cu
(a) [Mn(H2O)6]2+ (b) [Cu(H2O)6]3+ (b) more voltage is required
(c) [Co(NH3)6]3+ (d) [Co(H2O)6]2+ (c) Ag+ ions are completely removed from solution
11. The geometry of Ni(CO)4 and Ni(PPh3)2Cl2 are (d) less availability of Ag+ ions, as Cu cannot displace Ag
from [Ag(CN)2]– ion.
(a) both square planar
18. Which of the following organometallic compound is s and
(b) tetrahedral and square planar
p -bonded ?
(c) both tetrahedral
(d) None of these (a) [Fe(h5 - C5 H 5 ) 2 ] (b) [PtCl3 (h2 - C 2 H 4 )]
en en eg —
= 5 unpaired e–.
Fe++ (3d 6) =
= 4 unpaired e–.
trans (green)
Ni++ (3d 8) =
Cl +
= 2 unpaired e–. HN
3 Cl
As Ni++ has minimum no. of unpaired e– thus this is
least paramagnetic. Co
3. (c)
4. (c) In octahedral field the crystal field splitting of d- orbitals
HN
3 NH3
of a metal ion depends upon the field produced by the NH3
ligands. In general ligands can be arranged in a series cis (violet)
in the order of increasing fields and splittings which
they produce around a central metal ion. A portion of 10. (d) In éë Ni ( NH3 ) 2 Cl 2 ùû , Ni 2 + is in sp3 hybridisation,
the series is given below. thus tetrahedral in shape. Hence the four ligands are
cyanide > ethylene - diamine > ammonia > pyridine > not different to exhibit optical isomerism. In tetrahedral
thiocyanate > water > oxalate > hydroxide > fluoride > geometry all the positions are adjacent to one another
chloride > bromide > iodide. \ geometrical isomerism is not possible.
Out of the given ligands water, ammonia, cyanide and 11. (b) Ni++ = 3d 8 4s0
oxalate, we can find from the above series of ligands that
the maximum splitting will occur in case of cyanide (CN–
) i.e. the magnitude of D0 will be maximum in case of Since, the coordination number of Ni in this complex is
[Co(CN)6]3+. 4, the configuration of Ni ++ at first sight shows that
5. (a) The octahedral coordination compounds of the type the complex is paramagnetic with two unpaired
MA3B3 exhibit fac-mer isomerism. electron. However, experiments show that the complex
6. (b) Since Cr3+ in the complex has unpaired electrons in the is diamagnetic. This is possible when the 3d electrons
d orbital, hence it will absorb visible light and will be rearrange against the Hund’s rule as shown below. This
coloured is in accordance with the fact that the ligand involved
here is strong i.e., CN– ion.
784 Chemistry
Ni++ (after rearrangement) 15. (a) As positive charge on the central metal atom increases,
4s 4p the less readily the metal can donate electron density
into the p* orbitals of CO ligand (donation of electron
density into p* orbitals of CO result in weakening of
C – O bond). Hence, the C – O bond would be strongest
in [Mn(CO)6]+.
Hence, now dsp2 hybridization involving one 3d, one
4s and two 4p orbitals, takes place leading to four dsp2 16. (b)
hybrid orbitals, each of which accepts four electron (a) [Ti(NH3)6]3+ : 3d1 configuration and thus has one
pairs from CN– ion forming [Ni (CN)4]2– ion. unpaired electron.
[Ni (CN)4]2– (b) [Cr(NH3)6]3+ : In this complex Cr is in +3 oxidation
state.
×× ×× ×× ×× ××
Cr3+ : 3d 3 4s0
[Co(NH3)6]3+
M M
12
= - D + 3P 33. (b) Cr
5 0 Cr C2O4 C2O4
® AgCl +
20. (d) [Cr(H2O)4Cl2] Cl + AgNO3 ¾¾ C2O4
C2O4
[Cr(H2O)4Cl2]NO3
Non-superimposable mirror images, hence optical
wt 1000 isomers.
Molarity = ´ 34. (a) No. of unpaired electron
mol. mass vol.
a) Co3+ 4
b) Fe3+ 1
wt vol. 0.01 ´100
= molarity ´ = c) Mn 3+ 4
mol. mass 1000 1000 d) Cr3+ 3
= 0.001 Lower the number of unpaired electrons in a substance,
the lower is its magnetic moment in Bohr – Magneton
21. (b) A square planer complex is formed by hybridisation of s,
and lower shall be its paramagnetism
px, py and d 2 2 atomic orbitals 35. (d) d5 –––– strong ligand field
x -y
22. (b) Bond between C of organic molecule and metal atom.
23. (b) A more basic ligand forms stable bond with metal ion, Cl- t2g eg
is most basic amongst all.
m = n(n + 2) = 3 = 1.73BM
24. (d) Co (NH3)5 Cl3 [Co(NH3)5Cl]+2 + 2Cl- d3–– in weak as well as in strong field
\ Structure is [Co (NH3)5 Cl] Cl2.
25. (a) 4 (+ 1) + x + (–1) × 4 = 0
Þ 4+x-4=0 t 2g eg
x= 0
m = 3(5) = 15 = 3.87 B.M.
26. (c) The coordination number of central metal atom in a
d4– in weak ligend field
complex is equal to number of monovalent ligands, twice
the number of bidentate ligands and so on, around the
metal ion bonded by coordinate bonds t2g eg
27. (d) Hybridisation
m = 4(6) = 24 = 4.89
[Fe(CN)6 ]4 -, [Mn(CN)6 ]4- , d4– in strong ligand field
d 2sp3 d 2sp3
en Co Co en
3+
NH 3
en en
en Co en
Enantiomers of cis- éë Co(en) 2 (NH 3 ) 2 ùû 3+
43. (a) The SCN– ion can coordinate through S or N atom
giving rise to linkage isomerism
M ¬ SCN thiocyanato NH 3
M ¬ NCS isothiocyanato. trans-
44. (a) ® x Cl-
CoCl3 .6NH3 ¾¾
2.675g
47. (c) [Cr (NH3)6]Cl3 is an inner orbital complex, because in
this complex inner d-orbital is used for hybridisation
x Cl- + AgNO3 ¾¾
® x AgCl ¯ (d2 sp3 )
4.78g 48. (a) Ligands can be arranged in a series in the orders of
Number of moles of the complex increasing field strength as given below :
2.675 Weak field ligands :
= = 0.01 moles
267.5 I- < Br - < S2 - < SCN < Cl - < N3- , F -
Number of moles of AgCl obtained < Urea, OH– < oxalate
4.78 Strong field ligands
= = 0.03 moles
143.5 O -- < H 2O < NCS- < EDTA < Py, NH3 <
\ No. of moles of AgCl obtained
= 3 × No. of moles of complex en = SO 3 – < bipy, Phen < NO2- < CH3-
0.03 < C6 H 5- < CN - < CO
\n= =3
0.01 Such a series is termed as spectrochemical series. It is
Coordination Compounds 787
an experimentally determined series based on the 3d 4s 4p
absorption of light by complexes with different ligands.
49. (b) [Cr(en)2Br2]Br
dibromidobis (ethylenediamine) chromium (III) bromide.
50. (c) Octahedral coordination entities of the type Ma3b3
exhibit geometrical isomerism. The compound exists
3d 4s 4p
both as facial and meridional isomers, both contain
plane of symmetry
NH3 NH3
Cl NH3 NH3 Cl sp3
3. (d) The complex furnishing least number of ions in solution of of e - in d atomic orbitals therefore it is paramagnetic.
will be poor electrolytic conductor. 13. (b) Na2[CdCl4] does not contain any unpaired electron hence
4. (d) [Fe(CN)6 ] 4- complex ion contains 2+ E.C is colourless
26 Fe
14. (a) [Ni (H2O)6]2+ is paramagnetic.
= 1s 2 , 2s 2 p6 ,3s 2 p6 d6 15. (c) [Fe(C2O4)3]3–. The iron is present in the highest oxidation
3d 4s 4p
state Fe3+ and C2 O 24 - is a chelating ligand. Chelates are
( due to strong CN - ligand, the electrons in 3d shell are always form more stable complexes
paired ) 16. (d) K2[Ni(EDTA)]. Since EDTA is hexadentate and chelating
C.N is 6 , hybridisation d sp 2 3 , octahedral, diamagnetic and coordinates from six sides forming more stable
complex
since no unpaired electron is present.
17. (d) In silver plating K[Ag(CN)2] is used which provides
5. (b) Na 3[Co(ONO) 6 ] IUPAC name is constant and required supply of Ag+ ions as Ag(CN)2–
sodium hexanitritocobaltate (III) is very stable. But if AgNO3 is used concentration of
6. (b) [Ag+] in solution will be very large. In that case Ag will
be deposited at faster rate without any uniformity.
[Cr (H 2 O) 6 ]3+ [Fe(H 2 O) 6 ]2+ [Cu (H 2 O) 6 ]2 + [Zn (H 2 O) 6 ]2+
18. (c) In [Co(CO)5NH3]2+ CO is bonded to cobalt through s
EC 3d3 3d 6 3d 9 3d1 0
and p bonding
Unpaired 3 4 1 0
electrons
(c) Benzylic hydrogens (hydrogen present on C attached Alkyl fluorides have lowest boiling point of all the alkyl
directly to benzene) are more reactive, hence easily halides, hence can be removed by distillation.
Swarts reaction
replaced than 1°, 2° or 3° hydrogen.
Alkyl chloride/ bromide is heated in presence of a metallic
fluoride such as AgF, Hg2F2, CoF2 or SbF3
light
CH2CH2CH3 + Br2 CH3–Br + AgF ® CH3F + AgBr
For alkyl iodides : (Finkelstein reaction)
n-Propylbenzene acetone
CH 3CHXCH 3 + NaI ¾¾¾
¾®
(X =Cl, Br) Soluble in acetone
light
CHBrCH2CH3
® CH 3CHICH 3 + NaX ¯
Insoluble in acetone
1-Bromo-1-phenylpropane
(v) Hunsdiecker method (suitable for bromides) :
(d) Halogenation of hydrocarbons in presence of light, heat
CH 3 COOAg + Br 2 ¾¾® CH 3 Br + CO 2 + AgBr
and absence of halogen carrier takes place through free-
radical mechanism. (i) Reaction involves free radical mechanism.
(e) More reactivity of benzylic and allylic hydrogens is due (ii) Reaction gives an alkyl halide having one carbon atom
to stability of the corresponding free radical due to less.
resonance.
(iii) Yield of alkyl bromides follows the order : 1° > 2° > 3°.
(f) Bromination at allylic and benzylic positions
may best be carried by N-bromosuccinimide, NBS (iv) Yield is very low in case of chlorides, while iodine in
(Wohl-Ziegler Reaction). such cases react differently.
(iii) Addition of hydrogen halides to alkenes is an example of
electrophilic addition involving carbocations as intermediates 2 RCOOAg + I 2 ¾
¾® RCOOR + CO 2 + 2 AgI
(ionic mechanism). PHYSICAL PROPERTIES :
Markownikoff's rule (i) Alkyl halides, although polar, are insoluble in water due to
(i) When an unsymmetrical alkene or alkyne reacts with inability to form hydrogen bonds with water molecules.
unsymmetrical reagent, then negative part of reagent
(ii) Density :
attach with that carbon atom which contains lesser
number of hydrogen atom during the addition. RI > RBr > RCl (For the same R– or Ar– group)
For example: CH3I > C2H5I > C3H7I (For the same halogen)
(iii) Methyl iodide is densest halide because contribution of alkyl
Br
| part is minimum.
CH3 - CH = CH 2 + HBr ® CH3 - CH - CH3 (iv) Boiling points :
Pr opene 2 - bromopropane
(a) RI > RBr > RCl > RF (When R is same)
CH 2 = CH 2 + HBr ¾
¾® CH 3 - CH 2 Br (b) CH3CH2CH2Cl > CH3CH2Cl > CH3Cl
(For the same halide)
CH 3CH = CH 2 + HBr ¾
¾® CH 3 .CHBr.CH 3 (c) CH3CH2CH2CH2Cl > CH3CH2CHClCH3
Propene > (CH3)2 CHCH2Cl > (CH3)3 CCl
(unsymmetr ical alkene)
(For isomeric halides, b.p. decreases with the increase
(Markownikoff's addition)
in branching)
(ii) Addition of HBr (not HCl, HI and HF) on alkenes in
presence of peroxides takes place in (v) Dipole moment : Except fluoride, dipole moment decreases
anti-Markownikoff's way (Peroxide effect). with the decrease in electronegativity from Cl to I. Fluorides,
Here addition takes place via free-radical mechanism. although having highest electronegativity have lower dipole
peroxide moment than chloride due to the very small size of F and
CH3CH = CH 2 + HBr ¾¾¾¾® CH3CH 2CH 2Br
hence very small C–F bond length which outweighs the effect
(iv) Halide exchange method (anti-Markownikoff's addition)
of electronegativity (recall that m = d × e). Thus the order for
is considered to be best for alkyl fluorides and alkyl iodides.
For alkyl fluorides : dipole moment is CH3Cl > CH3F > CH3Br > CH3I.
ethylene glycol
(vi) Stability order : R – F > R – Cl > R – Br > R – I
RCH 2 X + KF ¾¾¾ ¾¾¾® RCH 2 F + KX (Similar to C – X bond length)
( X =Cl, Br, I) 120°C
Haloalkanes and Haloarenes 791
CHEMICAL PROPERTIES :
1. Nucleophilic substitution :
(i) Alkyl halides undergo nucleophilic substitution very easily.
+ -
¾® R - Z+ : X -
R - X + : Z (nucleophi le) ¾
Source of :Z Product R–Z and its Name
Na+OH– R – OH Alcohols
H2O (water) R – OH Alcohols
Na+OR' R – OR' (Williamson Ethers synthesis)
I– R–I Alkyl iodides
Source of :Z Product R–Z and its Name
RCOO– R – OOCR' Esters
K+CN– R – CN Nitriles
AgCN (covalent) R – CN + R – NC Nitriles and Isonitriles
N 3- R – N = N+ = N– Azides
NH3 R – NH2 Primary amines
R' NH2 R – NHR' Secondary amines
– –
OH OH
CH3 CH3
| |
CH 3 - C - CH 2 OH CH 3 - C - CH 2 CH 3
| |
CH3 OH
Expected (but not formed) Unexpected (but formed)
(c) If the alkyl halide is optically active, the product formed in S reaction is always a racemic mixture. This is due to the
N1
formation of carbocations as intermediates which, being planar (sp2 hybridised) can be equally attacked by the nucleophile
on either side of the face forming two enantiomers.
R2
– |
+X :+X : R1 - C - Z
R2 R R2 |
| R1 + 1 R+2 R3
R1 - C - X C C
|
R2
|
R3 R3 Z - C - R1
R3
|
R3
Alkyl halide Carbocation Enantiomers in
equal amounts
(sp 3 hybridised C) (sp2 hybridised)
However, remember that the departing halide shields to some extent, the frontal attack of the carbocation, recemization is
only partial and the inverted configuration predominates.
(iii) SN2 (Bimolecular Nucleophilic Substitution) : The rate of SN2 reactions depends on the concentration of alkyl halide
as well as nucleophile, i.e. r = k [RX ][ Nu ] . This implies that both the reactants are involved in the rate-determining
step, i.e. the reaction occurs in one step only or it is a concerted reaction. Concerted reactions occur through a transition
state (an imaginary state in which both the reactant molecules are partially linked to each other).
H H
é HH HH ù ù
H ê d - d-d-úú -X :
H
Nu : + C–X ê N u - - - - C| -------XXú ú ¾¾¾® Nu – C
H ê úú H
ë H ûû
Transition state Inverted product
Remember that the nucleophile attacks from the back side of the halide ion, bulkier the alkyl group present on the carbon bearing
halogen lesser will be its tendency to undergo SN2 reaction. Thus the reactivity of alkyl halides towards SN2 mechanism is
CH3
n- C4 H9CH2 X > CHCH2X > (CH3)3C.CH2X > (CH 3)2CHX > (CH3)3CX
2 5
1° Alkyl halides 2° 3°
Since the nucleophile attacks from the back side and the halide ion leaves from the front side, the product obtained will
have an inverted configuration [Walden inversion]. This implies that if the alkyl halide is optically active, the product
will also be optically active, although the sign of rotation may be same or different. All primary alkyl halides undergo
substitution via SN2 pathway.
Haloalkanes and Haloarenes 793
Remember : 3. Reaction with metals :
(a) Polar solvents favour SN1 reactions while non-polar
(i) dry ether
solvents favour SN2 reactions. R – X + 2Li ¾¾ ¾¾® R - Li + LiX
(b) Low concentration of nucleophile favours SN1 reactions,
while high concentration favours SN2. (ii) R - X + Mg ¾dry ether
¾ ¾¾® R - MgX
(c) Rate of reaction in SN1 mechanism is independent of the (Grignard reagent)
nature of the attacking nucleophile because it is not
(iii) 4CH 3CH 2Cl + 4 Pb / Na ¾dry ether
¾ ¾¾® (C 2 H 5 ) 4 Pb + 4 NaCl + 3Pb
involved in rate-determining step; while rate of SN2
TEL
reactions depends upon the strength of the nucleophile.
Strength of some common nucleophiles is (iv) dry ether
CH 3Cl + 2 Na ¾¾¾¾® [CH 3 Na ] ¾¾¾
3¾® CH CH CH Cl
3 3
– – – – Very reactive dry ether
: CN > : OR > : OH > CH 3COO > H 2 O
(d) Primary alkyl halides undergo SN2 reactions, 3° halides (Wurtz reaction)
SN1, while 2° halides may undergo SN2 and/or SN1 Tetraethyl lead, commonly known as TEL, is used as an
mechanism. anti-knocking agent in petrol.
2. Elimination reactions : (a) Solvent used must be perfectly anhydrous because
(i) Alkyl halides lose a molecule of hydrogen halide even a trace of water or alcohol reacts with metals to
(dehydrohalogenation) when heated with alcoholic form insoluble hydroxide or alkoxide that coat the
potash. Dehydrohalogenation is a b-elimination reaction surface of the metal. Moreover, water or alcohol may
in which halogen and hydrogen atoms are lost from the react with the product (organometallic compound)
two adjacent carbon atoms. to form hydrocarbon.
CH 3CH 2CH 2 Br or CH 3CHBrCH 3 ¾ (b) Alkyl lithiums react with copper halides to form
1- Bromopropane 2 - Bromopropane higher alkanes (Corey-House synthesis)
CuI R 'X
alc. KOH 2RLi ¾¾
¾® R 2 CuLi ¾¾
¾® R - R '
¾¾¾¾® CH 3CH = CH 2 + HBr ( - LiI) (1° halide )
heat Propene
(c) Among alkyl halides, order of reactivity is
(ii) Dehydrohalogenation is governed by Saytzeff rule
according to which more highly substituted alkene is I > Br > Cl > F.
the major product, i.e. hydrogen atom is lost from the (d) The reactivity of a metal toward an alkyl halide depends
carbon atom carrying minimum number of hydrogen upon its reduction potential; more easily a metal is
atoms (poor becomes poorer). reduced, more reactive it is, e.g. Mg > Zn.
CH 3CH 2 CHBrCH 3 ¾¾¾ ¾®
alc. KOH 4. Reduction
2 - Bromobutane heat
(a) R - X + Zn + HX ¾
¾® R - H + ZnX 2
® CH 3CH 2CH = CH 2 + CH 3CH = CHCH 3 In this reaction, zinc atoms transfer electrons to the carbon
1- Butene (minor) 2- Butene (major)
atom of the alkyl halide. Zinc is a good reducing agent
(iii) Ease of dehydrohalogenation among halides is : because it has two electrons in an orbital far from the
3° > 2° > 1° nucleus, which are readily donated to an electron
(iv) Elimination reactions dominate over substitution when acceptor.
strong Bronsted base [e.g. NH 2- , Me 3CO - , OC 2 H 5 LiAlH
(b) R - X ¾¾¾¾
4®R - H
etc.) is used and alkyl halide is 3° or 2°.
Remember: Ni
(c) R - X + H 2 ¾¾® R - H + HX
(a) 1° Halides undergo SN2 reactions except when a
Mg H O
hindered strong base like Me 3 CO - is used. (d) R - X ¾¾
¾® R - MgX ¾¾2¾® RH (or RD)
or D 2O
(b) 2° Halides undergo SN2 reactions with weak base
like I–, CN–, RCOO– etc., and elimination reaction
with strong base like RO–. (e) R - I + HI ¾red P
¾¾® R - H + I 2
423 K
(c) 3° Halides undergo SN1 reaction in absence of a
strong base and only solvent acts as a base/ 5. Halogenation :
nucleophile (solvolysis), however in presence of Cl , hv Cl , hv Cl , hv
CH 3 Cl ¾¾2¾
¾® CH 2 Cl 2 ¾¾2¾
¾® CHCl 3 ¾¾2¾¾® CCl 4
strong base (–OR) elimination reaction predominates.
794 Chemistry
6. Isomerisation : Cl
573 K
CH 3CH 2CH 2 Br ¾¾¾® CH 3CHBrCH 3 FeCl
1- Bromopropane anhy. AlCl3 2 - Bromopropane + Cl 2 ¾ ¾ ¾3 ®
inyl halides Alkyl halides Allyl halides Benzyl halides CH Cl CHCl2 CCl3
dised C, C–X
r because of Cl , 383 K Cl2, 383 K Cl 2, 383 K
Sunlight Sunlight
3. The strength of the C–X bonds causes aryl halides to react Benzyl Chloride Benzal chloride Benzo trichloride
very slowly in reactions in which cleavage of C–X bond is Remember halogenation of toluene at low
rate determining, i.e. nucleophilic substitution. temperature, in the absence of light and in presence
PREPARATION : of catalyst, gives nuclear substituted products.
By direct halogenation of aromatic hydrocarbons. CH3 CH3 CH3
(a) Nuclear halogenation (suitable for aryl chlorides and Cl
Cl2, FeCl3
bromides) +
Cl
Toluene o-Chlorotoluene p-Chlorotoluene
Haloalkanes and Haloarenes 795
Generally, p-isomer predominates due to steric 3. Hunsdiecker method :
hindrance in the o-position.
C 6 H 5 COOAg + Cl 2 (or Br2 ) ¾
¾® C 6 H 5 Cl + CO 2 + AgCl
(ii) Side chain halogenation occurs by free radical
4. Industrial method for chlorobenzen (Raschig process)
mechanism.
CuCl
(iii) In case, the side chain is larger than methyl group, 2C 6 H 6 + 2HCl + O 2 ¾¾ ¾
¾2 ® 2C H Cl + 2 H O
6 5 2
500 K
side chain halogenation mainly occurs at the benzylic
carbon (carbon directly attached to benzene Physical Properties :
nucleus). This is due to stability of benzylic free (i) Like alkyl halides, aryl halides are insoluble in water due
radical due to resonance. to their incapability of forming H-bonds.
(ii) Aryl halides are less polar than alkyl halides because in
•
CH2CH3 CH2 CH2 aryl halides, halogen is present on sp2 hybridised carbon
which is more electronegative than the sp3 hybridised
Br2, heat carbon of alkyl halides or halocyclohexanes.
Sunlight Consequently, the electroneg ativity difference between
C and Cl is low in aryl halides than in alkyl halides.
2-phenylethyl radical
(less stable, 1° free radical, (iii) Possibility of resonance in chlorobenzene makes the C–
2º benzylic radical)
Cl bond shorter and hence, its dipole moment is less
• than that of cyclohexyl chloride.
2 2 CHCH3 CHBrCH3
or Br 2
Cl Cl
(b) The C–Cl bond acquires some double bond (b) Those in which halogen is present on sp2-hybridised
character (structures III, IV and V) and thus becomes carbon atom, such halogens are relatively inert. For
shorter and stronger than the C–Cl bond in alkyl example,
halides.
On the same ground, low reactivity of vinyl chloride X CH3
is explained
X
+ Cl Cl
(–Cl –)
>
CH2 CH2 NO2 NO2
+ 2,4,6-Trinitrochlorobenzene 2,4-Diinitrochlorobenzene
Cl Cl Cl
+
Similar is the case of allyl carbocation formed from allyl NO
halides.
> >
+
CH 2 = CHCH 2 Br ¾¾ ¾
¾-
® CH 2 = CH - C H 2 ¬¾® NO2
Allyl bromide ( - Br )
2,4,6-Trinitrochlorobenzene p-Nitrochlorobenzene Chlorobenzene
+
C H 2 - CH = CH 2 Remember that the electron-withdrawing groups activate
(iii) Thus halogen derivatives can be categorised into two chlorine of chlorobenzene towards nucleophilic
main groups on the basis of reactivity of the halogen substitution, they deactivate the benzene nucleus
towards electrophilic substitution.
atom.
(v) Since electron-withdrawing groups activate halogen
toward nucleophilic substitution, electron-releasing
Haloalkanes and Haloarenes 797
groups (like –OH, –NH2, –OCH3, –R etc.) deactivate
Cl NH2
toward nucleophilic substitution.
(vi) Aromatic nucleophilic substitution proceeds through (ii)
NH 3, Cu2O
(Dow’s process)
mechanisms different from the SN2 and SN1 mechanism 573K, presure
of alkyl halides.
(a) Bimolecular mechanism is applicable to reactions of
Cl NH2
aryl halides having electron-withdrawing groups
with the usual nucleophiles like NaOH, CH3ONa etc. NO2 NO2
NH , 543K
Here carbanion is formed as an intermediate.
note mild conditions
(b) Benzyne mechanism is applicable when aryl halides
are treated with a strong base like NH 2- or with the NO2 NO2
usual nucleophiles like NaOH, NH3, CH3ONa etc.
under drastic conditions.
Br CN
(vii) Relative reactivity of halogens towards nucleophilic
substitution. The order of reactivity of the halogen atom CuCN, 475K, pyridine
in aryl halides is opposite to that observed in alkyl halides (iii)
(R – I > R – Br > R – Cl > R – F). In aromatic nucleophilic
substitution, fluoride is the most reactive and iodide the Benzonitrile
* Cl *
OH KNH2
dil. HCl
(Dow’s process)
Chlorobenzene Benzyne
Cl NH2
Cl
Aniline having C–NH 2 Aniline having C–NH 2
NO2
where * indicates isotopically labelled carbon, i.e. C-14.
Benzyl chloride does not form benzyne intermediate.
NO2 NO2 (a) Remember triple bond of benzyne is different from
Requires 15% NaOH Requires weak base the triple bond of alkynes, in benzyne one of the p
and 433K Na2CO3 and 403K
bonds is formed by p–p overlap while the other by
Cl
sp2–sp2 overlap.
NO2 3. Electrophilic substitution : Remember that halogens are
O2 N
deactivating but o, p–directing. Thus chlorination, nitration,
sulphonation and Friedel-Craft reaction forms a mixture of o-
NO2 and p-chlorosubstituted derivatives, e.g.
Undergoes hydrolysis even by
warming with H 2O
798 Chemistry
Cl 4. Other reactions :
(i) Formation of Grignard reagent : Since chlorobenzene
anhy. AlCl 3 is less reactive than methyl chloride, THF (a higher
+ CH3Cl
boiling solvent) is used.
Cl Cl Tetrahydrofuran ( THF)
C 6 H 5Cl + Mg ¾¾ ¾ ¾ ¾ ¾ ¾ ¾
¾® C 6 H 5 MgCl
CH3 Chlorobenzene
dry ether
CH3 C 6 H 5Cl + 2Na + ClC6 H 5 ¾¾ ¾¾® C 6 H 5C 6 H 5
Diphenyl
o-Chlorotoluene p-Chlorotoluene
Cl (iii) Wurtz-Fittig reaction :
dry ether
anhy. AlCl 3 C 6 H 5 Cl + 2 Na + ClCH 3 ¾¾ ¾¾® C 6 H 5 CH 3
+ CH 3COCl Toluene
COCH3 Zn / Cu
(v) Reduction : C 6 H 5 Cl + 2[H ] ¾¾¾ ¾¾
¾® C 6 H 6
o-Chloroacetophenone p-Chloroacetophenone or Ni - Al / NaOH Benzene
However, unlike CH3Cl, chlorobenzene does not undergo Benzyl chloride undergoes all the above reactions forming
Friedel-Craft reaction with benzene. This is because of C 6 H 5CH 2 MgCl, C 6 H 5CH 2 CH 2 C6 H 5 (dibenzyl),
unstability of C6H5+ cation.
Benzyl chloride also undergoes electrophilic substitution C 6 H 5CH 2 CH 3 , C 6 H 5CH 2 CH 2 C 6 H 5 and
easily and mainly in the o- and p-positions. However, here
percentage of m- too is significant (10-15%) as compared to C 6 H 5CH 3 respectively..
that in toulene. Formation of m-isomer is due to the presence (vi) Condensation with chloral to form DDT, 2,2-bis
of Cl as -CH 2 Cl which decreases the electron- (4-chlorophenyl) –1, 1, 1-trichloroethane.
releasing power of the parent methyl group due to its electron
withdrawing nature. Thus we can explain the increased
Cl3C–C=O + conc. H2SO4
percentage of the m-isomer with the increase in number of Cl Cl2C–CH
atoms in the –CH3 group. H Cl
Cl DDT
CH3 CH2—Cl H–C—Cl
on standing
Cl2C=C
Toluene Benzyl chloride Benzal chloride (–HCl)
% of m-isomer (2-5%) (10-15%) (30-35%)
DDT
Cl Cl
CH Cl H–C—Cl Cl—C—Cl DDT is non-biodegradable and slowly loses a molecule
of HCl to form another compound p, p'–dichloro-
diphenyldichloroethene (DDE) which hinders with the
egg shell formation of birds with the result eggs break
off before hatching.
Toluene Benzyl chloride Benzal chloride Benzo trichloride
(30-35%) (60-65%)
Haloalkanes and Haloarenes 799
(vii) Oxidation of the side chain : 3. Properties :
(i) Dehydrohalogenation : Both give alkynes.
CH3 COOH
alc. KOH
Cl Cl ClCH2 - CH 2Cl or CH 3CHCl 2 ¾¾¾ ¾®
HNO3 Ethylene chloride Ethylidene chloride
alc. KOH
o-Chlorotoluene o-Chlorobenzoic acid (–Cl is present)
CH 2 = CHCl or ¾¾ ¾¾ ¾¾
¾® HC º CH
Vinyl chloride preferably NaNH2 Acetylene