Chemistry Times March 19

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Chemistry Times March 19

By: P. BRAHMA REDDY

(Alumni from IIT Delhi)
Introduction
 The process of extraction of metal from its ores in
profitable manner is called metallurgy.
 Mineral is a substance in which metal is present
in either native state or in combined state.
 Ore is the mineral from which the metal can be
economically and conveniently extracted.
 Gangue or matrix is the impurities present in the
ore.
 Extraction of pure metal from its ore done in various
steps, which are given in the flow chart.

In this article much focus given towards the

extraction of some metals based on thermodynamic
principles i.e., pyrometallurigcal process.

Thermodynamic principles in extraction of metals

 In metallurgical operations the selection of a
suitable, reducing agent for reduction of a particular
oxide can be decided on the basis of
thermodynamic principles.
 The optimum temperature at which reduction can
occur smoothly can also be predicted using
thermodynamic principle.
 The Gibbs free energy change G of a reaction is
a measure of the thermodynamic driving force that
makes a reaction occur. A negative value for G
indicates that a reaction can proceed
spontaneously without any external inputs, while
a positive value indicates that it will not.

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 Chemistry Times March 19

 For feasibility of any reaction at any temperature Extraction of Iron

the value of G must be negative at that  Ores : Haematite – Fe2O3 Limonite – 2Fe2O3. 3H2O;
temperature. Siderite FeCO3 ; Magnetite – Fe3O4, Pyrite- FeS2.
 Process:

H :  Measure of actual energy that is liberated

when the reaction occurs.
S :  Measure of the change in the possibilities
for disorder in the products compared to the
reactants.
 Greater the negative value of G , higher is the
reducing power of an element.
 For the reduction of a metal oxide with a reducing
agent, the plot of G o vs temperature is studied,
which is called Ellingham diagram.

Characteristics of Ellingham diagram

 G o becomes more positive when temperature
increases, i.e., stability of oxides decreases.
 A metal will reduce the oxide of other metals which
lie above it in Ellingham diagram, i.e., the metals for
which the free energy of formation ( G o ) of their
oxides is more negative can reduce those metal
oxides which has less negative G o . Thus, Al
reduces FeO, CrO and NiO in thermite reduction
but it will not reduce MgO at temperature below
1773K.
 CO is more effective reducing agent below 1073K  Reactions :
and above 1073K coke is more effective reducing (i) Roasting : FeO changes to Fe2O3 to prevent the
agent, e.g., CO reduces Fe2O3 below 1073K but loss of iron during smelting.
above it, coke reduces Fe2O3.
4 FeO  O2  2 Fe2 O3
(ii) Smelting (In blast furnace) :
In reduction zone :
At 400°C, 3Fe 2 O3 + CO  2Fe3O4  CO2
Fe3 O4 +CO  3FeO  CO2
At 600°C, FeO  CO  Fe  CO2
CaCO3  CaO  CO2
In central zone:
FeO  3CO  2CO2  C  Fe
(900 – 1200°C) Fe acts as catalyst here and ‘C’ so
formed is dissolved in Fe.

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Chemistry Times March 19

CaO  SiO2  CaSiO3 2Cu2 S  3O2  2Cu2O  2SO2

( flux ) ( impurity ) ( slag )

In fusion zone Cu2 S  2Cu2 O  6Cu  SO2 (self reduction)

 Poling : Molten Cu is stirred with poles of green
CO2  C  2CO, H  ve
wood to reduce any copper oxide in Copper
(1100 – 1200°C) melting of iron takes place  Electrolytic refining : Anode – impure Cu ; cathode
In combustion zone – pure Cu ; electrolyte - CuSO4 + H2SO4.
2C  O2  2CO, H  ve Note : Copper can be extracted by hydrometallurgical
(1500 – 1600ºC) process also
 Pig Iron: C - 3.1 – 4.5%, small amounts of Si, S, P ;
hard and brittle, obtained from blast furnace Extraction of Zinc
 Wrought Iron: C - 0.15 – 0.28%, purest form ;
malleable, fibrous
 Steel: C - 0.15 – 1.5%, strength is high.

Extraction of Copper
 Ores : Copper pyrites CuFeS2 ; Cuprite or ruby
copper Cu2O ; Copper glance Cu2S ; Malachite
Cu (OH)2 . CuCO3 ; Azurite Cu (OH)2 . 2CuCO3.
 Process:

1. Composition of azurite mineral is

 Reactions : (a) CuCO3 .CuO (b) Cu ( HCO3 ) 2 .Cu (OH ) 2
(i) Roasting : (c) 2CuCO3 .Cu (OH ) 2 (d) CuCO3 .2Cu (OH ) 2
2CuFeS2  O2  Cu2 S  2 FeS  SO2 2. The process is used to remove reductible oxides
2 FeS  3O2  2 FeO  2SO2 from metals. Molten impure metal is stirred by a
wooden rods. The hydrocarbon gases reduce the
2Cu2 S  3O2  2Cu2 O  2 SO2 oxides. The process is called
(ii) Smelting : (a) Zone refining (b) Cupellation
Cu2 O  FeS  Cu2 S  FeO (c) Poling (d) Leaching
3. Roasted copper pyrite on smelting with sand
FeO  SiO2  FeSiO3 produces
(iii) Bessemerisation : (a) FeSiO3 as fusible slag and Cu2S as matte
2 FeS  3O2  2 FeO  2SO2 (b) CaSiO3 as infusible slag and Cu2O as matte
(c) Ca3(PO4)2 as fusible slag and Cu2S as matte
FeO  SiO2  FeSiO3 (d) Fe3(PO4)2 as infusible slag and Cu2S as matte

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 Chemistry Times March

4. Which series of reactions correctly represents

chemical relations related to iron and its
compound?
o o
O ,heat CO,600 C CO,700 C
(a) Fe  2
 Fe3O4   FeO   Fe
dil.H2SO4 H2SO4 ,O2 heat
(b) Fe  FeSO4  Fe2  SO4 3   Fe
O2 ,heat dil.H2 SO4 heat
(c) Fe   FeO   FeSO4    Fe
Cl2 ,heat heat ,air Zn
(d) Fe    FeCl3  FeCl2   Fe
5.
(a) A (b) B (c) C (d) D
8. In the extraction of iron metal from haematite ore,
CaCO3 (lime stone) is one of the constituents of
the charge. The role of CaCO3 in the extraction
process is to
(a) reduce oxides of iron by providing CO2 gas
(b) oxidize the metallic impurities to respective
oxides
(c) lower the temperature at which haematite gets
reduced to iron
(d) provide CaO to gangue which is separated as
slag
9. Which is NOT true for both (A) extraction of iron
from haematite ore and (B) extraction of tin from tin
stone (cassiterite)?
From the given Ellingham diagram which is a better
(a) The ore is an oxide ore
reducing agent at 673k?
(b) Pyrometallurgical extractive method is used for
(a) C (b) CO
extraction of the metal from the ore
(c) CO2 (d) Any of these
(c) The function of C is to act as a reducing agent
6. Why are the slopes of many of the lines on the
(d) Purification is carried out by zone melting
Ellingham diagram almost identical?
10. Highly electropositive metals cannot be extracted
(a) Most reactions involve the elimination of one
by carbon reduction process because these:
mole of gas, so there is a similar standard
(a) Metals do not react with carbon
enthalpy change of a reaction.
(b) Metals do not combine with carbon to form
(b) Most reactions involve the elimination of one
carbides
mole of gas, so there is a similar standard
(c) Metal oxides are not reduced by carbon
entropy change of a reaction.
(d) Loss of metal is more by vaporisation
(c) The activity of the most of the metals is same.
11. Statement-I: Carbon monoxide is capable of
(d) The partial pressure of the reacting gas is the
reducing FeO to Fe at certain temperature.
same for all reactions.
Statement-II: At the given temperature, standard
7. For Fe3O4 (solid), standard enthalpy of formation
is -1120 kJ mol-1. Change in entropy, under standard free energy of reaction, 2 Fe  O2  2 FeO is more
conditions, for the formation of 1 mol of Fe3O4 is negative compared to the standard free energy of
-350 J K-1 mol-1. Which of the following graphs is the reaction, 2CO  O2  2CO2
the Ellingham diagram for Fe3O4?
(a) Statement-I and Statement-II are true and
Statement-II is the correct explanation of
Statement-I.
(b) Statement-I and Statement-II are true, but
Statement-II is not the correct explanation of

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Chemistry Times March 19

Statement -I 15. Column- I Column-II

(c) Statement-I is true, but Statement -II is false (Reaction) (Temperature)
(d) Statement-I is false, but Statement -II is true (i) CaO  SiO2  CaSiO3 (P) 1000oC
12. Statement-I: The precious metal, silver present as
impurity in the metal lead may be recovered by (ii) C  CO2  2CO (Q) 900oC
treating molten impure lead with molten zinc. (iii) CaCO3  CaO  CO2 (R) 400oC
Statement-II: Under equilibrium conditions, in a
mixture of two immiscible liquids (molten lead and (iv) 3Fe2 O3  CO  2 Fe3O4  CO2 (S) 1800oC
molten zinc), when silver is dissolved, the
concentration of silver in molten zinc is much
higher than its concentration in molten lead.
(a) Statement-I and Statement-II are true and
Statement-II is the correct explanation of 1. c 2. c 3. a 4. a
Statement-I. 5. b 6. b 7. c 8. d
(b) Statement-I and Statement-II are true, but 9. d 10. d 11. c 12. a
Statement-II is not the correct explanation of 13. b 14. a
Statement -I 15. (i)  (Q), (ii)  (P), (iii)  (Q), (iv)  (R)
(c) Statement-I is true, but Statement -II is false
(d) Statement-I is false, but Statement -II is true
13. Consider the following reactions at 1000oC
1 o 1
(1) Zn s  O2  g   ZnO s G  360 kJ mol 1.Sol: Azurite is a basic copper carbonate ore having
2
composition 2CuCO3 .Cu (OH ) 2 .
1 o 1
(2) C( s )  O2  g   CO g  G  460 kJ mol 3.Sol: During smelting, silica combines with FeO to
2 form fusible FeSiO3 slag and Cu2S as matte.
Choose the correct statement at 1000oC 4.Sol:Combustion of Fe to give Fe3O4 which upon
(a) Zinc can be oxidized by CO. reduction with CO first gives FeO and finally Fe.
(b) Zinc oxide can be reduced by carbon Option (b) and (c) are wrong because FeSO4 and
(c) Both statements A and B are true Fe2(SO4)3 on heating gives Fe2O3.SO2.SO3 and not
(d) Both statements A and B are false Fe.
14. Consider the oxidation reaction 
Fe2  SO4 3   Fe2O3  3SO3
2x 2
M  O2  M x Oy 2FeSO4  
 Fe2 O3  SO3  SO2
y Metal( s ) ( g ) y Metal oxide( s )
Option (d) is wrong because in presence of air,
Choose the incorrect statement.
reduction of FeCl3 to FeCl2 cannot occur.
(a) Oxygen has higher entropy than the metal but
lesser entropy than the metal oxide. 5.Sol: From the diagram G o for formation of CO2
(b) S o for the oxidation reaction would be from CO is more -ve than formation of CO (or) CO2
from carbon at 673K.
negative
Hence CO is a better reductant than C at 673K.
(c) G o would become less and less negative with
6.Sol: Most of the reactions have similar S o value.
increase in temperature
11.Sol: At the given temperature, free energy of
(d) If the temperature is very high, G o may reaction, 2 Fe  O2  2 FeO, is LESS negative.
become zero, and even positive.

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 Chemistry Times March 19

MOLECULAR ORBITAL THEORY

1. While filling electrons in  2 p x and  2 p y the (d) They are formed when the lobes of the
combining atomic orbitals have the same sign.
electronic configuration rules that has to be followed 8. The wavelength of the wave function of a bonding
is molecular orbital formed by LCAO is
(a) Pauli’s exclusion principle (a) Equal to the wave function of atomic orbital
(b) Aufbau principle (b) Less than the wave function of atomic orbital
(c) Both Pauli’s and Hund’s rule (c) Greater than the wave function of atomic orbital
(d) All the above (d) Double the wave function of atomic orbital
2. The paramagnetic nature of oxygen is best explained 9. Which of the following order of energies of
by molecular orbitals of N2 is correct?
(a) V.B.theory (b) Hybridisation
(a)  2 p y    2 p z     2 p x     2 p y 
* *
(c) M.O.theory (d) VSEPR theory
3. Maximum number of electrons that can be present
(b)  2 p y    2 pz     2 p x     2 p y 
* *
in any molecular orbital is
(a) 3 (b) 6 (c) 8 (d) 2
(c)  2 p y    2 p z     2 px     2 p y 
* *
4. Which molecule/ion out of the following does not
contain unpaired electrons?
(d)  2 p y    2 pz     2 px     2 p y 
* *

(a) N 
2
(b) O2 (c) O2
2
(d) B2 10. Which one is paramagnetic and has a bond order
5. Which of the following cannot be formed?
1
(a) He2 (b) He (c) He (d) He2 of ?
2
6. A bonding molecular orbital is produced by
(a) Destructive interference of wave functions (a) O2 (b) N 2 (c) F2 (d) H 2
(b) Constructive interference of wave functions 11. Which of the following options represents the
(c) Pairing of electrons with opposite spins correct bond order?
(d) Combination of +ve and –ve wave functions (a) O2  O2  O2 (b) O2  O2  O2
7. Which of the following statements is not correct
regarding bonding molecular orbitals ? (c) O2  O2  O2 (d) O2  O2  O2
(a) Bonding molecular orbitals possess less energy 12. In which pair, the stronger bond found in the first
than the atomic orbitals from which they are species
formed.
(I) O2 , O2 (II) N2 , N2 (III) NO  , NO 
(b) Bonding molecular orbitals have low electron
density between the two nuclei. (a) (I) only (b) (II) only
(c) Electron in bonding molecular contibutes to the (c) (I) and (III) only (d) (II) and (III) only
attraction between atoms.

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Chemistry Times March 19
13. The bond length of H 2 , H 2 and H 2 are in the
order
(a) H 2  H 2  H 2 (b) H 2  H 2  H 2
(c) H 2  H 2  H 2 (d) H 2  H 2  H 2
14. Which of the following statement is not correct
from the view point of molecular orbital theory?
(a) Be2 is not a stable molecule.
(b) He2 is not stable but He2 is expected to exist.
(c) Bond strength of N2 is maximum amongst the
homonuclear diatomic molecules belonging to
the second period.
(d) The order of energies of molecular orbitals in
N2 molecule is
2s  * 2s  2 pz   2 px  2 py    * 2 px   *2 py   * 2 pz
15. Which of the following statement is correct about
N 2 molecule?
(a) It has a bond order of 3
(b) The number of unpaired electrons present in it
is zero and hence it is diamagnetic
(c) The order of filling of MOs is
  2 p x     2 p y  ,   2 pz 
(d) All statements are correct
16. The electron probability density  2BMO is higher
than the sum for individual atomic orbitals
(  2A   2B ) by a factor of
(a) 2 A (b) 2 B (c) 2 A  B (d)  2A  2B
17. Among the following the one that has two nodal
planes is
(a)  ns*
*
(b)  npz
*
(c)  2 px
18. The incorrect statement among the following is
(a) In C2 , there is a double bond and both the
bonds are   bonds
(b) Bond order of CO and CO  are respectively
3.0 and 3.5
(c) CO, NO  and N 2 all have the same bond order
value
(d) The B.O of CO  2, NO   2.5 & N 2  3
19. Four diatomic species are listed below in different
sequences. The correct order of their bond orders
is
8
(a) C22   He2  NO  O2
(b) He2  O2  NO  C22 
(c) O2  NO  C22   He2
(d) NO  C22   O2  He2
20. The diagram shows:
*
(a)  ns (b)  ns* (c)  npz (d)  npz
21. The decreasing order of bond length for N2 and its
ions is correctly shown in
(a) N 2  N 2  N 2  N 22   N 22 
(b) N 22   N 22   N 2  N 2  N 2
(c) N 22   N 21  N 2  N 22   N 2
(d) N 22   N 2  N 2  N 2  N 22 
22. O2 and N 2 if converted to O2 and N 2
respectively. The incorrect statement is
*
(a) Electron in O2 goes form  2 p y
(b) Electron in N 2 goes from  2 pz
(c) Bond length O  O  bond length (O  O ) 
(d) Bond length N  N  bond length ( N  N ) 
23. The common features among the species
CN  , CO and NO are
(a) bond order three and isoelectronic
(d)  2 px (b) bond order three and weak field ligands
(c) bond order two and   acceptors
(d) isoelectronic and weak field ligands
24. What is the effect of the following processes on
the bond order in N2 and O2?
i) N 2  N 2  e  ii) O2  O2  e 
(a) Decreases in both (i) & (ii)
(b) Increases in both (i) & (ii)
(c) Increases in (i) but decreases in (ii)
(d) Decreases in (i) but increases in (ii)
25. In which set of molecules all the species are
paramagnetic ?
(a) B2 , O2 , N 2 (b) B2 , O2 , NO
(c) B2 , F2 , O2 (d) B2 , O2 , Li2
 Chemistry Times March 19

26. A m o n g KO2 , AlO2 , BaO2 and NO2 , u n p a i r e d 7.Sol: Bonding M.O. has maximum electron density
between two nuclei.
electron is present in
10.Sol: Ions B.O.
(a) NO2 and BaO2 (b) KO2 and AlO2 O2- 1.5
(c) KO2 only (d) BaO2 only N2+ 2.5
F2 1
27. A molecule may be represented by three structures
H2+ 0.5
having energies E1 , E2 and E3 respectively. The 11.Sol: Ions B.O.
energies of these structures follow the order O2- 1.5
E3  E2  E1 respectively. If the experimental O2 2
O2+ 2.5
energy of the molecule is E0 , the resonance energy 12.Sol: B.O. is directly proportional to the strength of
is the bond.
13.Sol: Higher is the B.O. lower is the bond length.
(a)  E1  E2  E3   E0 (b) E0  E3
17.Sol: ABMO px have two nodal planes
(c) E0  E1 (d) E0  E2 19.Sol: Bond orders are : He2  0.5; O2  1.5;
NO  2.5; C22   3.0
21.Sol: Bond order of N 22  and N 22  is 2

1. c 2. c 3. d 4. c 5. d Bond order of N 2 and N 2 is 2.5

6. b 7. b 8. a 9. a 10. d Bond order of N 2 is 3.
11. b 12. d 13. d 14. d 15. d
16. c 17. c 18. d 19. b 20. d 23.Sol: CN  , CO and NO  are Isoelectronic 14e  
21. b 22. d 23. a 24. d 25. b
26. c 27. b and has bond order 3.
26.Sol: KO2 has K  and O2 structure having one
un paired electron.
27.Sol: The difference in energy of the actual molecule
(experimental value) and energy of the most stable
3.Sol: According to Pauli’s exclusion principle. resonating structure is called resonance energy.
5.Sol: He2 cannot be formed because bond order is
5.Sol:
zero.

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Chemistry Times March

1. Which one of the following arrangements represents

(a) PCO  PCO2 (b) PCO  PCO2
the correct order of electron gain enthalpy (with
negative sign) of given atomic species? (c) PCO  PCO2 (d) zero
(a) F< Cl < O < S
(b) S < O < Cl < F 7. The average speed at temperature T C of CH 4 ( g )
(c) O < S < F < Cl
28
(d) Cl < F < S < O is  103 ms 1 . What is the value of T?
2. The pair of amphoteric hydroxides is 88
(a) Al (OH )3 , LiOH (a) 24055C (b) 32.45C
(c) 3000C (d) 24.055C
(b) Be(OH )2 , Mg (OH ) 2
8. Which of the following behaviour is true regarding
(c) B (OH )3 , Be(OH ) 2 the coefficient of viscosity (  ) of a liquid?
(d) Be(OH ) 2 , Zn(OH )2 (a) Plot of  versus T is non linear
3. The dipole moment of o,p and m-dichlorobenzene 1
will be in the order (b) Plot of  versus is linear
T
(a) o  p  m (b) p  o  m
E
(c) m  o  p (d) o  m  p (c)  
RT
4. Between any two of the following molecules,
hydrogen bonding is not possible 1
(a) Two primary amine molecules (d) Plot of log  versus is non linear
T
(b) Two secondary amine molecules 9. Ionic product of water at 310 K is 2.7×10–14. What
(c) Two tertiary amine molecules is the pH of neutral water at this temperature?
(d) Two ammonia molecules (a) 7 (b) 7.3 (c) 6.3 (d) 6.8
5. The common features among the species
10. The solubility of Ca (OH ) 2 is 3 . The solubility
CN  , CO and NO are
product of Ca (OH ) 2 is
(a) Bond order three and isoelectronic
(b) Bond order three and weak field ligands (a) 3 (b) 27 (c) 3 (d) 12 3
(c) Bond order two and   acceptors 11. In the reaction :
(d) Isoelectronic and weak field ligands
CS2 l  +3O2 g   CO2 g  +2SO2 g  ; ΔH=  265 kcal
6. Equal number of moles of CO and CO2 are filled in
The enthalpies of formation for both CO2 and SO2
a chamber at room temperature. The correct
are negative and are in the ratio 4 : 3. The enthalpy
relationship w.r.t their partial pressure PCO and PCO2 of formation for CS2 is + 26 kcal/mol. The enthalpy
is

10
 Chemistry Times March 19

of formation for SO2 is 17. Railway wagon axles are made by heating rods of
(a) 90 kcal/mol (b) 52 kcal/mol iron embedded in charcoal powder. The process is
known as
(c) 78 kcal/mol (d) 71.7 kcal/mol
(a) Case hardening (b) Sherardising
12. Consider the following reaction between zinc and
(c) Annealing (d) Tempering
oxygen and choose the correct options out of the
18. Gun metal contains
options given below :
(a) Cu, Sn, Zn (b) Cu, Ni
(a) The enthalpy of two moles of ZnO is less than
(c) Cu, Ni, Fe (d) Cu, Sn, P
the total enthalpy of two moles of Zn and one
mole of oxygen by 693.8 kJ.
(b) The enthalpy of two moles of ZnO is more than 19.
the total enthalpy of two moles of Zn and one
mole of oxygen by 693.8 kJ.
(c) 598.3 kJ mol–1 energy is evolved in the reaction. Product is
(d) 693.8 kJ mol–1 energy is absorbed in the reaction. (a) Vinyl chloride (b) Vinyl iodide
(c) Allyl chloride (d) Allyl iodide
20. What amount of bromine will be required to convert
13. 2g of phenol into 2,4,6-tribromophenol?
(a) 10.22 (b) 20.44 (c) 4.00 (d) 6.00
21. Which is lyophobic in nature?
The common name of given ester is
(a) Gelatin (b) Phosphorus
(a) Neo butyl iso butyrate
(c) Starch (d) Agar-Agar
(b) t-Butyl n- butyrate
22. Which of the following is not a gel?
(c) t- Butyl iso butyrate
(a) Cheese (b) Jelly (c) Curd (d) Milk
(d) iso butyl iso butyrate
23. Conductance of 0.1 M KCl (conductivity = X ohm-
14. IUPAC name of the following compound is 1
cm-1) filled in a conductivity cell is Y ohm-1. If the
conductance of 0.1 M NaOH filled in the same cell
is Z ohm-1, the molar conductance of NaOH will be
(a) 103 XZ/Y (b) 104 XZ/Y
(c) 10 XZ/Y (d) 0.1 XZ/Y
24. In the button cell widely used in watches and other
(a) 1-Bromo-3,5-epoxy-4,4-dimethyl-2- hexanone devices the following reaction takes place:
(b) 1-Bromo-3,3-dimethyl-2-oxo-2-hexanone
Zns +Ag 2Os +H2O l  Zn 2 aq  +2Ags +2OH aq 
(c) 1-Bromo-3,3-dimethyl acetone
(d) 1-Bromo-4,4-dimethyl-5-oxo-hexanone Determine Δ r G o for the reaction.
15. How many geometrical isomers possible for the
compound? (Given E ocell = 1.11 V)
(a) -2.14 x 104 J (b) -2.14 x 104 kJ
(c) -214 kJ (d) -214 J
25. For a first order reaction A  B the reaction rate
at which reactant concentration of 0.01 M is found
to be 2.0  105 M sec 1 . The half -life period of the
(a) 0 (b) 2 (c) 3 (d) 4
reaction is :
16. The magnetic nature of elements depends on the
(a) 30 s (b) 300 s (c) 220 s (d) 347s.
presence of unpaired electrons. Identify the
26. Two substances A and B are present such that
configuration of transition element, which shows
highest magnetic moment? [ A]0  4[ B]0 and half life of A is 5 minute and that
(a) 3d7 (b) 3d5 (c) 3d8 (d) 3d2 of B is 15 minute. If they start decaying at the same
time following first order kinetics how much time
will the concentration of both of them would be

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Chemistry Times March 19

the same? 32. The bond length of C  O bond in carbon

(a) 15 minute (b) 10 minute 
(c) 5 minute (d) 12 minute monoxide is 1.28 A . The C  O bond in Fe(CO)5
27. M=molarity of the solution is:
m=molality of the solution
   
d=density of the solution (in g. ml 1 ) (a) 1.15 A (b) 1.128A (c) 1.118A (d) 1.72A
33. D-Glucose reacts with phenylhydrazine to make
M 1  gram molecular weight of solute osazone. How many molecules of phenylhydrazine
Which of the following relations is correct? are used for this reaction per molecule of D-glucose
M ?
(a) m  (a) One (b) Two (c) Three (d) Four
1000d  MM 1
34. Amino acids exist in zwitter ion form. What is the
M  1000 structure of glycine at pH = 4 ?
(b) m 
d  MM 1 (a) H 3 N   CH 2  COO 
M 1000 (b) H 3 N   CH 2  COOH
(c) m  (1000  d )  MM1
(c) H 2 N  CH 2  COOH
m1000 (d) H 2 N  CH 2  COO 
(d) M  (1000 d)  MM1
35. The proteins with a prosthetic group are called
28. X is non volatile solute and Y is a volatile solvent. (a) Pseudo proteins (b) Complex proteins
Following V.P. are observed by dissolving X in Y. (c) Polypeptides (d) Conjugated proteins
X(M) 0.10 0.25 0.01 36. Compounds X and Y are obtained by the reaction
Y (mm of Hg) P1 P2 P3 of Cl2 with cold and dilute solution of NaOH and
(a) P1 < P2 < P3 (b) P3 < P2 < P1 compounds X and Z are formed with hot and
(c) P3 < P1 < P2 (d) P2 < P1 < P3 concentrated solution of NaOH.
29. Equimolal solutions of potassiumhexacyanoferrate The compounds Y and Z respectively are
(II), (represented as X) and potassium (a) NaCl, NaClO (b) NaClO, NaClO3
hexacyanoferrate (III), (represented as Y) are (c) NaCl, NaClO3 (d) NaClO, HCl
considered, which are at equal degree of 37. By adding gypsum to cement
dissociation. Which of the following statement is (a) setting time of cement becomes less.
correct? (b) setting time of cement increases.
(a) The boiling point of X is greater than Y. (c) colour of cement becomes light.
(b) X and Y have the same boiling point. (d) shining surface is obtained.
(c) The boiling point of X is less than Y. 38. In the carbon family the melting points of the
(d) X and Y have the same freezing point. elements decrease on descending the group
30. The spin only magnetic moment of [MnBr4]2– is because the interatomic bonds become:
5.9BM. The geometry of the complex ion is (a) Stronger as the size of the atom increases
(a) Tetrahedral (b) Square planar (b) Weaker as the size of the atom decreases
(c) Pyramidal (d) Octahedral (c) Stronger as the size of the atom decreases
31. Which of the following complexes exhibit optical (d) Weaker as the size of the atom increases
isomerism? 39. Carbogen is
(a) Trans-tetraamminedithiocyanatochromium (III) (a) Mixture of 90  95% O2  5  10% CO2
ion (b) Used by pneumonia patients for respiration
(b) Cis-diamminedicarbonatacobaltate (III) ion (c) Used by victims of CO for respiration
(c) Trans-diamminedicarbonatacobaltate (III) ion (d) All of these
(d) Cis-bis (glycinato) platinum (II) 40. Pyrex glass is a mixture of

12
 Chemistry Times March

(a) sodium borosilicate and barium borosilicate and has bond order 3.
(b) sodium silicate and calcium silicate 6.Sol: They are non-reacting gases.
(c) sodium silicate and lead silicate
(d) sodium silicate and aluminium borosilicate 8RT 28 7
7.Sol:  
41. The number of cis-trans isomers with molecular M 88 22
formula C2 BrClFI is 8  8.314  T 7
  106
(a) 4 (b) 6 (c) 7 (d) 8  16  103 22
42. A compound (X) when passed through dil. H 2 SO4
1000  2
gives compound (Y), which on reaction with HI T  240.55 K
8.314
and red phosphorous gives C2 H 6 . The compound
T C  240.55  273  32.45C
(X) is +  14
(a) Ethane (b) Ethyne 9.Sol: K w =  H 3 O  . OH   2.7  10 at 310K
(c) 2-Butene (d) 2-Butyne
H 2 O+H 2 O   H 3 O +  OH  
43. In the reaction of p-chlorotoluene with KNH 2 in
liquid NH 3 , the major product is  H 3 O +   OH  
(a) o-Toluidine (b) m-Toluidine Therefore,
(c) p-Toluidine (d) p-Chloroaniline
 H3 O +   2.7 1014  1.643  107 M
44. Aniline on treatment with sodium hypochlorite
gives
pH=  log  H 3 O +    log1.643  10 7
(a) p-aminophenol (b) phenol
(c) sodium salt of aniline (d) anilinium chloride pH = 7+  0.2156   6.7844 .
45. The compound which on reaction with aqueous
10.Sol: Ca (OH ) 2  Cas  2OH
2 
nitrous acid at low temperature produces an oily
2s
nitrosoamine is
(a) methylamine (b) ethylamine K sp  ( s ) (2s )2  4s 2 , s  3
(c) diethylamine (d) triethylamine
K sp  4( 3)3  12 3

11.Sol: CS2 l +3O2 g   CO2 g +2SO g 

H=  265 kcal
1. c 2. d 3. d 4. c 5. a Hf  CO2 , g  =4x
6. c 7. b 8. a 9. d 10. d
11. d 12. a 13. c 14. a 15. b Hf  SO2 , g  = 3x
16. b 17. a 18. c 19. c 20. a
Δ r H=  Δ f Hproducts - Δf Hreactants
21. b 22. d 23. b 24. c 25. d
26. a 27. c 28. d 29. a 30. a 265  4 x  6 x  26
31. b 32. d 33. c 34. b 35. d 10 x  239
36. b 37. b 38. d 39. d 40. a
x  23.9
41. b 42. b 43. b 44. a 45. c
Hf  SO2 , g  =  71.7 kcal/mol
13.Sol: Iso–octane is

3.Sol: Bond angle increases dipole moment decreases.

5.Sol: CN  , CO and NO  are Isoelectronic 14e  

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Chemistry Times March

17.Sol: Case hardening: The process of hardening the

surface of wrought iron by depositing a surface
layer of steel on it is called case-hardening. It is
done by heating wrought iron in contact with
potassium ferrocyanide.
Alternatively, case hardening can also be done by
heating wrought iron with charcoal and then
plunging it a suitable oil.
19.Sol:
0.693
 t 12 =  347 s
2.0  103
28.Sol: Amount of solute or concentration of the solute
increases vapour pressure of volatile solvent
decreases.
30.Sol: Since the coordination number of Mn2+ ion in
the complex ion is 4, it will be either tetrahedral (sp3
hybridisation) or square planar (dsp2 hybridisation).
But the fact that the magnetic moment of the complex
ion is 5.9 BM, it should be tetrahedral in shape
rather than square planar because of the presence
of five unpaired electrons in the d-orbitals.
31.Sol:

(Note: CO32  acts as bidented in this complex)

32.Sol: Due to synergic bond formation, bond order
20.Sol: decreases and bond length increases a little.

34.Sol:
94 g of phenol reacts with 480 g of Br2 .

480
2 g of phenol reacts with  2  10.22 g of 35.Sol: Simple protein and Prosthetic group (non-
94 protein material gives conjugated proteins.
Br2 . 36.Sol: Cl2  2 NaOH  2 NaCl  NaClO  H 2 O
23.Sol: Conductivity (X) = conductance  cell (cold dil.) (X) (Y)
constant
3Cl2  6 NaOH (hot )  5 NaCl  NaClO3  3H 2 O.
Cell constant = X/Y
Conductivity of NaOH = XZ/Y (X) (Y)
41.Sol: Six isomers are :
 m (NaOH) = 104 XZ/Y
24.Sol: NH3 produced due to cathodic reaction,
MnO2 +NH4 + e  MnO  OH  +NH3 combines
2
With Zn2+ to form Zn  NH 3  4
1
25.Sol: rate = k  A 

2.0  105
k=  2.0  103
0.01

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 Chemistry Times March 19

42.Sol: The compound (X) is likely to be alkyne which 43.Sol:

reacts with water in the presence of H 2 SO4 and
HgSO4 as catalyst to form a carbonyl compound.
HI and red phosphorous can reduce a carbonyl
compound to alkane having same number of carbon
atoms.
Therefore (Y) is likely to be acetaldehyde, which is
the hydration product of ethyne.
H 2 SO4
HC  CH  H 2 O 
HgSO4
  CH 2  CH  OH 
(X)
 CH 3  CHO
(Y)
red P
CH 3CHO + 4HI   CH 3CH 3  2I 2 +H 2 O This reaction proceeds through benzyne
Therefore, (X) is ethyne. mechanism.
45.Sol: 2 amine.

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Chemistry Times March 19

     7. EQUILIBRIUM

(1) Chemical equilibrium

  At equilibrium, rate of forward reactions is equal to kf
c
[C] [D]
d

the rate of backward reaction. K a b
 At  equilibrium,  concentration  of  reactant  and kb [A] [B]
products  remains  constant. (3) Relationship between KP and KC
 At equilibrium, state  G  0 . Δn
K P =K C ×(RT)
(2) Equilibrium Constant (K)
n   (c + d) – (a + b)
 cC(g)  dD(g)
aA (g)  bB(g) 

(4) Expressions for KC and K P for some reactions

                 

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 Chemistry Times March

(5)Factors influencing equilibrium number of  moles while decrease in pressure in

constant, K the direction of higer volume or no. of moles.
 Equilibrium constant depends on (IV) Addition  of  Catalyst
(I)  Temperature  Addition of catalyst lowers the activation
energy of reaction.  It increases rate of both
K2 ΔH  T2 -T1  forward and backward reactions to the same
log =   extent.  Hence, equilbrium is not distrubed but
K1 2.303R  T1 T2 
is attained quickly.
(II) Mode of writing the equation (8) Relation between degree of
 For the reactions, dissociation and vapour density

A B 
B A 1 Dd 

if     KC= K         then      KC=1/K n  1  d 
(III)  Stoichiometric  coefficients
N o .of m oles dissociated

A B 
2A  2B 1 A  1 B
2  2
 
Total N o .of m oles taken
2
    if KC= K         then KC= K       &  KC=  K (9) Ionic equilibrium
Ostwald’s Dilution Law

 A B 
B C 
A C 2
 if KC= K1  &  KC= K2 then KC= K1.K2 C
K eq  , for   weak electrolyte 1    1
(6) Applications of equilibrium constant, K 1 
(I)Predicting the direction of the reaction
If QC > KC - Backward reaction is favoured. 2
K eq
If QC < KC - Forward reaction is favoured. K eq  C ,  
C
If QC=  KC  - Reaction mixture is at equilibrium.
(II) Predicting the extent of a reaction (10) Ionisation Constant of Water
If KC > 103, products predominate over reactants, Kw =[H+][OH-] or Kw = [H3O+][OH-]
If KC > 10-3, reactants predominate over products, (11) pH scale
If KC is in the range of 10-3 to 103 appreciable  1
concentrations of both reactants and  products  aH  [ H ] mol.Lit .


are present.
1
(7) Le Chatelier prinicple
 pH  log10  (or)  [ H + ] = 10-pH
(I) Effect of Concentration  H 
 If concentration of reactants is increased, the
 pH + pOH = pKw at any temperature
equilibrium shifts in forward direction.
 At 25o C or 298K  for any aqueous solution.
 If concentration of products is increased, the
pH   +  pOH  =  14
equilibrium shifts in backward direction.
 At 250C for pure water or neutral solution
(II) Effect of Temperature
pH = pOH =  7.
 Equilibrium will shift backward in exothermic
and forward in endothermic when T is
(12) Calculation of pH of weak acids and
increased. weak bases
 Equilibrium will shift forward in exothermic and pH = –log [H+]                 pOH = – log [OH-]
backward in endothermic when T is decreased.
      = – log10  [ K a C ]              = – log10 K b C
(III) Effect of Pressure
 Pressure change does not affect the gaseous (13) Salts Hydrolysis
reaction equilibrium where  n  0 , i.e., nP= nR  Salts  of  strong  acids  and  strong  bases  do  not
undergo hydrolysis and the resulting solutions is
 But, when  n P  n R , increase in pressure shifts neutral.
equilbrium in the direction of lower volume or

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Chemistry Times March

(14) Buffer solutions (15) Solubility Product

(I)Henderson - Hasselbalch equation  AxBy     xAy+  + yBx 
(i) pH of Acid Buffer y x x y

Mixture of CH3COOH + CH3COONa  is an acid K sp  [A ] [B ]
buffer. Let the solubility of AxBy is S then
[Salt] x y
K sp  [xS] [yS]  Ksp  x .y [S ]
x y xy
pH  pK a  log
[Acid]
(ii) pH of Basic Buffer
K sp K sp
Mixture of  NH4OH + NH4Cl is a basic buffer. S
xy
 S x y
x y  then x
x y
y

[Salt] x y
 pOH  pKb  log [Base]
 Ionic product  and  Solubility  product
pH of buffer after adding H+  = i)Ionic product = KSP - This is Saturated solution.
Salt  x
 
ii) Ionic product < KSP - This means the solution
pK a + log Acid  x 
 
is unsaturated and more salt can be dissolved
in it.
using AAA rule pH of buffer decreases.
iii) Ionic product > KSP  - This means solution is
(II)Buffer capacity or Buffer Index (  ) holding more salt than it can dissolve in.
The ability of the buffer to resist changes in pH.

8. REDOX REACTIONS

(1) Oxidation and Reduction reactions  All neutral compound or ion in which element

(I) Oxidant or oxidising agent shows their higher oxidation no. or state are act
Species, which oxidise other species, which is as oxidant or oxidising agent
present in a reaction and reduce itself. (II) Reductant or Reducing agent
Some Important oxidising agent or oxidant Species which reduce other element in a reaction
 All elements with high electronegative character and oxidise itself to donate electrons and show
like N, O, F, Cl, etc. increase in its oxidation no. is called reductant
  All metallic oxides like or reducing agent.
Some Important reducing agents or reductants
Li2 O, Na2 O, Na2 O2 , CO2 , CaO,   MgO, BaO2
All metals like, K, Mg, Ca, etc.
etc.
 All metallic hydrides like   NaH , CaH 2 , LiAlH 4 ,
Some nonmetallic oxides like
CO2 , SO2 , H 2 O2 , O3 . NaBH 4 , AlH 3 ,  etc.

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 Chemistry Times March

 All hydroacids like  HF , HCl , HBr , H 2 S  etc. (II) Intramolecular redox reaction

5 2 1 0
 Some organic compounds like aldehyde, formic 2K Cl O3  2K Cl  3O2
acid, oxalic acid, tartaric acid.
 All neutral compounds or ions, which show their (III) Disproportion Redox Reaction
lower oxidation state. In this type of redox reactions same element acts
as both oxidising & reducing agent.
(2) Oxidation number
0 +1 -1
 It represents the number of electron gained or lost Cl2 + H2 O  H ClO + H Cl
by atom when it changes in compound from a free
state. (6) Balancing redox reactions
 Maximum oxidation no. of an element is equal to (I) Half reaction method
group no. in the periodic table consider the example,
 Minimum oxidation no. of an element is equal to H
Cr2 O72   C2 O42  

Cr 3  CO2
group no. – 8 (i) Write both the half reactions.
(3) Oxidation state Cr2 O72   Cr 3  (Reduction half reaction)
Oxidation state of an atom is defined as oxidation
number per atom for all practical purposes. C2 O42   CO2  (Oxidation half reaction)
 The rules to derive oxidation number or (ii) Atoms other than H and O are balanced
oxidation state are as follows Cr2 O72   2Cr 3
 The O.S. of an element in its free state is zero.
C2 O42   2CO2
Example O.S.’ s of  Na, Cu, I 2 , Cl2 , O2  etc. are
zero (iii) Balance O–atoms by the addition of  H 2 O  to
 Sum of O.S.’ s of all the atoms in neutral molecule   another side
is zero. Cr2 O72   2Cr 3  7 H 2 O
 Sum of O.S.’ s of all the atoms in a complex ion is
equal number of charge present on it. C2 O42   2CO2
 In complex compounds, O.S. of some neutral (iv) Balance H–atoms by the addition of  H   ions
molecules (ligands) is zero.
  to  another side
Example  CO, NO, NH 3 , H 2 O.
Cr2 O72   14 H   2Cr 3  7 H 2 O
 Generally O.S. of oxygen is –2 but in  H 2O2  it is
C2 O42   2CO2
–1 and in O2F2 it is +1, in  OF2  it is +2. (v) Now, balance the charge by the addition of
 Generally O.S. of Hydrogen is +1 but in metallic
  electrons  (e  ).
hydrides it is –1.
 Generally O.S. of halogen atoms is –1 but in Cr2 O72   14 H   6e   2Cr 3  7 H 2 O
interhalogen compounds it changes.
C2 O42   2CO2  2e 
(4) Redox Reactions
(I) The reactions in which oxidation and reduction (vi) Multiply equations by a constant to get
both occur simultaneously are called redox    number of electrons same in both side. In the
reactions.    above case second equation is multiplied by 3
(II) Any redox reaction may be divided in two parts:    and then added to first equation.
(i) Oxidation half reaction Cr2 O72   14 H   6e   2Cr 3  7 H 2 O
(ii) Reduction half reaction
(5) Types of redox reactions 3C2 O42   6CO2  6e 
    
(I) Intermolecular redox reaction Cr2 O72   3C2 O42   14 H   2Cr 3  6CO2  7 H 2 O
6 0 2 4
2H 2 S O4 (conc.)  C u  CuSO4  SO2  2H 2O In Alkaline medium
 Consider the reaction

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Chemistry Times March

OH
Cr (OH )3  IO3   I   CrO42 
(i) Separate the two half reactions.
Cr (OH )3  CrO42   (Oxidation half reaction)
 
IO  I  (Reduction half reaction)
3
(ii) Balance O– atoms by adding  H 2 O.
H 2 O  Cr (OH )3  CrO42  ,
IO3  I   3H 2 O
(iii) Balance H–atoms by adding  H 2 O  to side
   having deficiency and  OH   to other side
   having deficiency of H–atoms.
5OH   H 2 O  Cr (OH )3  CrO42   5 H 2 O or
5OH   Cr (OH )3  CrO42   4 H 2 O
IO3  6 H 2 O  I   3H 2 O  6OH  or
IO3  3H 2 O  I   6OH 
(iv) Balance the charges by electrons
5OH   Cr (OH )3  CrO42   4 H 2 O  3e 
   
IO  6 H 2 O  6e  I  3H 2 O  6OH
3 The final balanced equation should be checked
(v) Multiply first equation by 2 and add to second
 to give
9. HYDEOGEN
(1) Hydrogen
(I) Resemblance with alkali metals due to
 Electronic configuration  ( ns1 ) :1s1  i.e., it has
one electron in s - orbital of valence shell
 Oxidation state  (1) : H  Cl , Na  Cl
(II) Resemblance with halogens due to
 Electronic configuration: One electron less than
the nearest inert gas configuration
 Electronegative character: Both have tendency
to accept one electron to form anions
 Ionisation energy: Comparable with halogens.
(III) Differences from alkali metals and halogens
 Less electropositve than alkali metals and less
electronegative  than  halogens
Size of ions:  H   is much smaller than alkali
metal ions and H- is much larger than halide
ions.
20
10OH   2Cr (OH )3  2CrO42   8H 2 O  6e
IO3  6 H 2 O  6e   I   3H 2 O  6OH 
4OH   2Cr (OH )3  IO3  5 H 2 O  2CrO42   I 
(II) Oxidation number method
(i) Write the skeleton equation (if not given, frame
it) representing the chemical change.
(ii) Assign oxidation numbers to the atoms in the
equation and find out which atoms are
undergoing oxidation and reduction. Write
separate equations for the atoms undergoing
oxidation and reduction.
(iii) Find the change in oxidation number in each
    equation. Make the change equal in both the
   equations by multiplying with suitable
   integers. Add both the equations.
(iv) Complete the balancing by inspection.
First balance those substances which have
undergone change in oxidation number and
then other atoms except hydrogen and oxygen.
Finally balance hydrogen and oxygen by putting
H 2 O  molecules wherever needed.
to ensure that there are as many atoms of each
element on the right as they are on the left.
(2) Preparation of di hydrogen ( H 2 )
 Zn  H 2 SO4  ZnSO4  H 2
Fe2 O3 or Cr2O3
 CaH 2  2H 2O   Ca(OH )2  2 H 2 .
 Mg  2 HNO3  Mg ( NO3 ) 2  H 2
 2 Al  2 NaOH  2 H 2 O  2 NaAlO2  3H 2
       (Uyeno's method)
 3Fe  4 H 2 O  Fe3O4  4 H 2
 CO( g )  H 2 O( g )  CO2( g )  H 2( g )
(3) Chemical Properties of dihydrogen
 2 Na  H2  2NaH
 H 2  X 2  2 HX
 Reducing nature
 Chemistry Times March

Fe3O4  4 H 2  3Fe  4 H 2 O At cathode (Cu):  2 H   2e   H 2

Ni
Unsaturated fat   H 2    Saturated fat At anode (Pt):  2 HSO4  H 2 S 2 O8  2e 
(Oil)       (Vanaspati Ghee) H 2 S2 O8  2 H 2 O  H 2 O2  2 H 2 SO4
(4) Different forms of H2
(I) Nascent Hydrogen
(II)Adsorbed  Hydrogen
(III)Atomic Hydrogen    
(IV)Ortho and Para hydrogen
(i) Ortho hydrogen: Spin of protons or nucleii (II) Physical Properties
are in same direction ortho hydrogen
 Pure  H 2O2  is weak acidic in nature and exists
(ii) Para hydrogen: Spin of protons or nucleii
are in opposite direction. as associated liquid due to hydrogen bonding.
(5) Hydrides  Smell of  H 2O2  resembles like nitric acid.
(I) Ionic hydrides or Saline hydrides  It causes blisters on skin.
(II) Covalent hydrides or Molecular hydrides  A dilute solution of  H 2O2  is concentrated by
(III) Metallic or Interstitial hydrides
vacuum distillation or by distillation under
(IV) Polymeric hydrides pressure.
(6) Hydrogen Peroxide (III) Chemical Properties
(I) Methods of preparation 2 H 2 O2  2 H 2 O  O2
BaO2  CO2  H 2 O  H 2 O2  BaCO3
PbS  4 H 2 O2  PbSO4  4 H 2 O
Na2 O2  H 2 SO4  Na2 SO4  H 2 O2    2Cr2O7  H2 SO4  4H 2O2  2CrO5  K2 SO4  5H2O
K
By electrolysis of 50%  H 2 SO4  at 0°C using Pt     2 K3 [ Fe(CN )6 ]  2 KOH  H 2O2  2 K 4 [ Fe(CN )6 ]
electrode.
                                       2H 2 O  O2
2 H 2 SO4  2 H   2 HSO4

(7) Strength of H 2O2

           

(8) Structure of H 2O2 (9) Soft water and Hard water

 Water which gives foam easily with soap is known
as soft water. The other which gives with difficulty
is known as hard water.
 Hardness of water is of two types
(I) Temporary hardness
(i) Due to soluble bicarbonates of Ca and Mg
(ii) It can be removed by boiling or adding

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Chemistry Times March

calculated quantity of slaked lime. CaSO4  Na2 CO3  CaCO3  Na2 SO4


Ca ( HCO3 ) 2   CaCO3  H 2 O  CO2 (iii) Calgon’s method:
Clark’s method  Sodium hexametaphosphate
Ca( HCO3 ) 2  Ca(OH ) 2  2CaCO3  2 H 2 O M 2  Na4 P6O182  [ Na2 MP6O18 ]2  2 Na  (M  Mg , Ca)
(II) Permanent hardness (iv)Synthetic  resins  method:
 Due to soluble sulphates, chlorides, nitrates of 2 RNa ( s )  M 2  (aq )  R2 M ( s )  2 Na  (aq)
Ca and Mg.
 It can be removed  MR2 ( s)  2 H  (aq).
2 RH ( s)  M 2  (aq) 
(i) By Permutit Process:
 RNH 3 .OH  (s)
RNH 2 ( s)  H 2O(l ) 
(ii) By washing soda (Na2CO3):
MgCl2  Na2 CO3  MgCO3  2 NaCl  RNH3 .X  ( s)  OH  (aq)
    RNH3 .OH  (s)  X  (aq) 
H  (aq )  OH  (aq )  H 2 O (l )

10. S-BLOCK ELEMENTS (ALKALI & ALKALINE EARTH METALS)

(1) Alkali metals (2) Alkaline Earth Metals

 The elements lithium (Li), sodium (Na), potassium    The  elements  of  group  2  are  beryllium  (Be),
(K), rubidium (Rb), caesium (Cs) and francium (Fr), magnesium  (Mg),  calcium  (Ca),  strontium
constitute group 1 of the periodic table. (Sr),barium (Ba) and radium (Ra).
(3) Atomic and Physical properties of s - block elements

      

22

(4) Chemical properties of s-block elements
(5) Diagonal relationship between Lithium
and Magnesium
 The carbonates of lithium and magnesium
decompose easily on heating to form the oxides
and  CO2 .
 Both  LiCl  and  MgCl2  are soluble in ethanol
 Both  LiCl  and  MgCl2  are deliquescent and
crystallise from aqueous solution as hydrates,
LiCl.2 H 2 O  and  MgCl2 .8H 2 O
Chemistry Times March
(6) Diagonal relationship between Be and
Al
 Compounds of Be like those of Al undergo
hydrolysis.
BeCl2  2 H 2 O  Be(OH )2  2 HCl
AlCl3  3H 2 O  Al (OH )3  3HCl
 Be forms complex anions (beryllates like
aluminium forms aliminates, while other alkaline
earth metals do not form complex anions.
Be  2 NaOH  Na2 BeO2  H 2 
2 Al  2 NaOH  2 H 2 O  2 NaAlO2  3H 2 
 Beryllium and aluminium ions have strong
tendency to form complexes  BeF42  , AlF63 .
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Chemistry Times March 19

11. p-BLOCK ELEMENTS

(1) Group - 13 elements

  B, Al, Ga, In, and Tl belongs to group - 13 elements
 General electronic configuration is ns2np1
 Atomic radius increases suddenly from B  to Al
The atomic radii of Ga is less than Al. This is because of the poor shielding effect of d-electrons in Gallium.
 The order of ionization enthalpy is B  Tl  Ga  Al  In
 The common oxidation state of these elements is +3
 Amorphous boron and aluminium metal on heating in air form B2O3 and Al2O3 respectively.
2 Al( s )  6 HCl( aq ) 
 2 AlCl3( aq )  3H 2( g )
2 Al( s )  2 NaOH ( aq )  6 H 2 O( l )  2 Na[ Al (OH ) 4 ]( aq )
      Sodium tetrahydoxoaluminate(III)

3H 2( g )

           

(2) Carbon family  Common oxidation state of IV A group elements

Carbon, Silicon, Germanium, Tin and Lead are  IV are +2, +4.
A group elements.  When heated in oxygen form two types of oxides.
  The general outer electronic configuration of  IV A Monoxide (MO)             Dioxide (MO2)
group elements is ns2 np2. C, Si, Ge are unaffected by water.
 The number of electrons present in the penultimate  Sn reacts with steam to give SnO2 and H2.
shell of carbon is 2,  Si is 8 while Ge, Sn, Pb contain   Sn + 2H2O 

 SnO2 + 2H2(g)
18 electrons each. Pb is not affected by H2O due to an oxide layer
 Covalent radius increases considerably from C to onthe surface.
Si there after small increase is observed up to Pb  Reaction with acids and base:
due to completely filled d and f orbitals.
 4Sn + 10HNO3  4Sn  NO3 2 + NH4 NO3 + 3H 2O
 IP1 & IP2 order is C > Si > Ge > Pb > Sn
 The order of catenating power in IV A group 3Pb + 8HNO3  3Pb  NO3  2 + 2NO + 4H 2O
elements is  C >> Si > Ge > Sn > Pb . Si + 2NaOH + H 2 O  Na 2 SiO 3 + 2H 2
Sodium Silicate

24
 Chemistry Times March

  The thermal stability of tetrahalides decreases in
the order
CX4 > Si X 4 > Ge X4 > Sn X4 > Pb X4
Thermal stability order of hydrides :
CH 4 > SiH 4 > GeH 4 > SnH 4 > PbH 4
(3) Silicones
 Silicones are Organo Silicon polymers containing
Si – O – Si bonds.
Polymerisation of dialkyl silane diols yield linear
thermoplastic polymers.
 Cyclic or ring silicones are formed when water is
eliminated from terminal –OH groups of linear
silicones.
 Hydrolysis of RSiCl3 gives crosslinked silicones.
Commercial silicone polymers are usually methyl
derivatives  and  to  a  lesser  extent  phenyl
derivatives.
(4) Silicates
 Silicates are the metal derivatives of silicic acid
H4SiO4 or Si(OH)4.
 The basic structural unit in silicates is the SiO44,
a tetrahedron.
 Depending on the number of corners 0,1,2,3 or 4
of  SiO44-  shared  various  kinds  of  silicates  are
formed.

12. ORGANIC CHEMISTRY (SOME BASIC PRINCIPLES & TECHNIQUES)

(1) Classification of organic compounds

 A group of organic compounds which show similar properties but differ from the preceding or succeeding
member by one -CH2- (methylene) unit is known as Homologous series. The different members of a
homologous series are called homologues and the phenomenon is called homology.
(2) Nomenclature Of Organic Compounds
  IUPAC nomenclature
Nomenclature according to IUPAC system involves use of following terms
20 Prefix+10 Prefix+ Root Word +10Suffix+20Suffix

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Chemistry Times March

(I) Root Word (II) Suffix

The root word represents the number of C atoms
in parent chain.

    

(3) Isomerism

26
 Chemistry Times March 19

(4) Fission or breaking of a covalent bond (iv) Basicity of Amines :  (+I) groups (EDG)

The covalent bond is broken equally such that each increase the basic nature of amines,
of the bonded atoms retain their electron used in whereas (-I) groups (EWG) decrease the
bonding.  This  leads  to  the  formation  of  odd basic strength of amines.  
electron species known as free radical.
The covalent bond is broken unequally such that
only  one  of  the  bonded  atoms  gets  both  the
electrons resulting in the formation of positive and
negative charged  species.
(5) Attacking
Attackingreagents
r eagents
I. Electrophiles or Electrophilic reagents.
II. Nucleophiles or Nucleophilic reagents. (II) Electromeric effect:
     atom has unfilled d-sub shells. The electronic system of an unsaturated
displacement effects in organic
(6) Electron displacement molecule is deformed when the reagent
approaches close to it. When the reagent is
molecules
molecules
removed without allowing the reaction to takes
(I) Inductive effect:
place, the electronic system reverts to the
The polarization of a    bond due to electron
original state of the molecule.
withdrawing or electron donating effect of
This kind of polarisation of multiple bonds is
adjacent groups or atoms is called inductive
known as electromeric effect.
effect. The decreasing order of  -I effect :
(III) Mesomeric effect:
  NR 3 > NH3+ > NO2 > CN > SO3H > COOH > Permanent polarisation in a compound due to
F > Cl > Br > I > OR > NR2 > C6H5 > H delocalisation of   - e-s along the conjugated
(R = H, alkyl, aryl, acyl)  systems caused by an atom or group in
The decreasing order of +I effect : conjugation is called mesomeric effect
+M Effect atoms or groups
     >  C0 R3  CHR
0 2  C3 H7  C2 H5  CH3  H
3 2 10 10  NH 2 ,  NHR,  NR2 ,  OH ,  OR,
Applications of Inductive Effect:       
SR,  X ( X  Cl , Br , I )
(i) Stability of carbonium ions:
The order of stability of carbonium ions is (IV) Hyperconjugation or No bond resonance or
3o > 2o > 1o > Methyl Baker Nathan effect:
(ii)Stability of carbanions : The delocalization of  -electrons of C—H
Methyl > 1o > 2o > 3o bond of an alkyl group into adjacent empty (or
(iii) Acidic strength of Carboxylic acids: partially filled) non bonding p-orbital of carbon
EWG (-I) increases the acidic strength.  of a double bond or a carbocation or a free
  However, the EDG (+I) groups decrease the carbon radical is called hyperconjugation. 
  acidic strength.
(7) Reaction intermediates

             

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Chemistry Times March
(8) Purification of organic compounds
(I)  Sublimation
 The organic compounds such as benzoic acid,
naphthalene, anthracene, camphor, indigo,
anthraquinone etc., are purified by this process
(II)  Crystallisation
(i) Simple Crystallisation:
 It is based on the fact that all organic
compounds are more soluble in hot than in cold
solvents, so that solid gets dissolved on heating
and is obtained back on cooling.
E.g:
 Sugar having an impurity of common salt can
be crystallised from hot ethanol since sugar
dissolves in hot ethanol but common salt does
not.
(ii) Fractional Crystallisation:
 The process of separation of different
components of a mixture by repeated
crystallisation is called fractional crystallisation.
 Fractional crystallisation can be used to separate
a mixture of KClO3 (less soluble) and KCl (more
soluble).
(III) Simple  distillation:
 For example, chloroform (CHCl3) and aniline
(9) Characterisation Of The Organic Compound
Qualitative analysis (Detection of elements)
 Detection of Carbon and Hydrogen
 Detection of Phosphorus
28
can be separated by simple distillation because
of the large difference in their boiling points.
Boiling point of (CHCl3) is 60o and boiling
point of aniline is 189oC. Ether (B.P. 308K)
and toulene (B.P. 384K)  can be separated by
this method.
(IV)  Fractional  distillation
 This method may be used to separate a mixture
of acetone (b.p. 330K) and methyl alcohol
(b.p. 338. K).
(V) Distillation under reduced pressure
Certain liquids have a tendency to decompose
at a temperature below their boiling points.
Such liquids cannot be purified by ordinary
distillation.
E.g: glycerol boils with decomposition at
563K.
(VI)  Steam  distillation
Chromatography
 This technique is very useful for the separation,
isolation, purification, and identification of the
constituents of a mixture.
(i)  Adsorption  Chromatography
(A) Column Chromatography:
(B) Thin layer chromatography:
(ii)  Partition  chromatography
 Chemistry Times March

 Detection of N, S and Halogens

N, S, and halogens present in an organic compound are detected by “Lassaigne’s test”.

Equilibrium
1. The reaction quotient (Q) predicts
(a) The direction of equilibrium to be attained
(b) The ratio of activities at equilibrium, i.e.,  KC
(c) The ratio of activities at any time
(d) All of these
2. CH3COOH2+ is present in the solution of acetic acid
in
(a) NH3 (b) Water (c) Benzene (d) HCl
3.  When  CO2   is  bubbled  in  excess  of  water,  the
following equilibrium is established.
CO2  2 H 2 O  H 3O   HCO2
K a  3.8  107 , pH  6
What would be the value of   [ HCO3 ] / [CO2 ]?
(a) 6 (b) 0.0038 (c) 0.038 (d) 0.38
4. The values of  K p1 and  K p2 for the reactions
X  Y  Z ;   A  2 B  are in the ratio 9:1. The
total pressure at equilibrium are in the ratio, when
the degree of dissociation of X and A are equal is
(a) 36:1 (b) 1: 1 (c) 3:1 (d) 1:9
5. The pH of blood is 7.4. Assuming that the buffer in
blood is carbon dioxide, hydrogen carbonate ion,
what is the ratio of conjugate base to acid necessary
to maintain blood at its proper

29
Chemistry Times March 19

(10) Quantitative Analysis [Estimation of elements]

           

pH? ( Ka  4.5  10 7 ) if  a  copper  spoon  is  used  to  stir  a  solution  of
aluminium nitrate?
(a) 9 (b) 10 (c) 11 (d) 12
(a) The solution becomes blue
Redox Reactions
(b) There is no reaction
6. The reducing agent among the following is
(c) The spoon will get coated with aluminium
(a) HNO3 (b) SO3 (c) H2S (d) HNO2
(d) An alloy of aluminium and copper is formed
7. Which of the following is not intramolecular redox
9.
9. The oxides which can not act as reductant?
reaction?
(I)  CO2 (II)  SO3 (III)  P4 O10 (IV)  NO2
(a)  ( NH 4 ) 2 Cr2 O7 
 N 2  Cr2 O3  4 H 2 O
(a) (I), (II), (III) (b) (II), (III), (IV)
(b)  2 KClO3 
 2 KCl  3O2 (c) (I), (II), (IV) (d) (III), (IV)
(c)  2 Mn2 O7 
 4 MnO2  3O2 10. What is the equivalent weight of  C12 H 22 O11  in

the following reaction ?
2 OH
(d)  2ClO2  5 H 2 O2   2Cl   5O2  6 H 2 O      C12 H 22 O11  36 HNO3  6 H 2 C2 O4  36 NO2  23H 2 O
8. The position of some metals in the electrochemical
series  in  decreasing  electropositive  character  is 342 342 342 342
(a)  (b)  (c)  (d) 
given as Mg > Al > Zn > Cu > Ag. What will happen 36 12 22 3

30
 Chemistry Times March 19

(a) Ionic nature of  BeF2
Hydrogen
11. The  number  of    hydrogen-bonded  water (b) Greater hydration energy of  Be2  ion
molecule(s) are associated in CuSO4.5H2O is (c) Covalent nature of  BeF2
(a) 1 (b) 2 (c) 3 (d) 4
(d) None of the above
12. Which of the following is not true ?
(a) Hardness of water is shown by its behaviour 20. Mixture of  MgCl2  and MgO is called
towards  soap (a) Portland cement (b) Sorel’s cement
(b) The temporary hardness is due to the presence (c) Double salt (d) None
of Ca and Mg bicarbonates
(c) Permanent hardness is due to the presence of p-Block Elements
soluble Ca and Mg sulphates and chloride 21. AlCl3 is an electron deficient compund but AlF3 is
(d) Permanent hardness can be removed by boiling not. This is because
the water (a) Atomic size of F is smaller than Cl which  makes
13. The percentage of  H 2O2  in 1.5 N solution is AlF3 more covalent
(b) AlCl3 is a covalent compound while AlF3 is an
(a) 3.6 (b) 2.99 (c) 2.55 (d) 2.4
ionic compound
14. Correct order of occlusion property is
(c) AlCl3 exists as a dimer but AlF3 does not
(a) Pd > Pt > Au > Colloidal Pd > Pt
(d) Al in AlCl3 is in sp3 hybrid state but Al in AlF3
(b) Colloidal Pd > Pd > Pt > Au > Ni
is in sp2 state
(c) Ni < Au > Pt > Pd > Colloidal Pd
22. Which of the following halides is the most stable?
(d) Au > Pt > Pd > Ni > Colloidal Pd
(a)  CF4 (b)  CI4 (c)  CBr4 (d)  CCl4
15. 100 mL of tap water containing 
15. Ca( HCO3 ) 2  was
23. Different layers in graphite are held together by:
titrated  with  N/50  HCl  with  methyl  orange  as
(a) Ionic bonding (b) Metallic bonding
indicator.  If  30  mL  of  HCl  were  required,  the
(c) Covalent bonding (d) Vanderwaals forces
temporary hardness as  parts of  CaCO3  per  106 24.  Which  of  the  following  structures  correctly
24.
parts of water is represents the boron trifluoride molecule?
(a) 150 ppm (b) 300 ppm
(c) 450 ppm (d) 600 ppm
(a) 
S-Block Elements (Alkali & Alkaline Earth Metals)
16. Which of the alkaline earth metal sulphate is least
soluble ?
(b)  
(a)  BeSO4 (b)  CaSO4
(c)  SrSO4 (d)  BaSO4
17. Which  of  the  following  is  used  as  a  source  of
oxygen  in  space  capsules,  submarines  and (c) 
breathing masks?
(a)  Li 2 O (b)  Na 2 O2 (c)  KO2 (d)  K 2 O 2
18. A sodium salt of an unknown anion when treated (d) 
with  MgCl2  gives white precipitate only on boiling.
The anion is 25. When  SnCl2   reacts  with  HgCl2 ,   the  product
(a)  SO42  (b)  HCO3 (c)  CO32  (d)  NO3 formed are :
19. BeF2  is soluble in water, whereas, the fluorides of (a)  Sn  HgCl4 (b)  SnCl2  Hg 2 Cl2
other alkaline earth metals are insoluble because
of

31
 Chemistry Times March 19

(c)  SnCl4 and Hg 2 (d) None of these (b)  C4 H 9 COOH and CH 3OOC3 H 7

(c)  CH 3COOCH 3 and CH 3OOC3 H 7
Organic Chemistry (Some Basic Principles &
Techniques) (d)  CH 3COOC3 H 7 and C3 H 7 COOCH 3
26. Homolytic fission of C-C bond in ethane gives an 30. In column chromatography the MOVING PHASE
intermediate in which carbon is is  constituted  by
(a) sp3-hybridised (b)sp2-hybridised (a) A substance which have to be separated
(c)sp-hybridised (d)  sp2d-hybridised (b) Eluent
27. In triplet carbenes, the two electrons (c) Adsorbent
(a) are paired in one orbital (d) Mixture of eluent and substances to be
(b) are present in different orbitals separated
(c) have the same spin
(d) Both (b) and (c)
28. Liquid which decompose below their normal boiling
points can be distilled at lower temperature by
(a) Increasing the pressure 1.
1. d 2.
2. d 3.
3. d 4.
4. a 5.
5. c
(b) Decreasing the pressure 6.
6. c 7.
7. d 8. b
8. 9. a
9. 10. a
10.
(c) Heating in water bath 11.
11. a 12. d 13. c
13. 14. b
14. 15. b
15.
(d) Heating in sand bath 16.
16. d 17.
17. c 18. b
18. 19. b
19.  20.
20. b
29. Metamers of ethylpropionate are 21. b 22. a 23. d 24. a 25. c
(a)  C4 H 9 COOH and HCOOC4 H 9 26.
26. b 27.
27. d 28. b 29. d
29. 30. d

.
.
. 32
 Chemistry Times March 19

ALDEHYDES, KETONES & CARBOXYLIC ACIDS,

CHEMICAL KINETICS

Aldehydes, Ketones & Carboxylic Acids (c) Aromatic acid (d) Schiff base
1. Of the following which is the product formed when 3. Reaction of carbonyl compound with one of the
cyclohexanone undergoes aldol condensation following reagents involves nucleophilic addition
followed by heating? [2017] followed by elimination of water. The reagent is:
[2015]
(a) a Grignard reagent
(a) (b) hydrazine in presence of feebly acidic solution
(c) hydrocyanic acid
(d) sodium hydrogen sulphite
4. An organic compound ‘X’ having molecular formula
C5 H10 O yield phenylhydrazone and gives negative
(b) response to the iodoform test and Tollens’test. It
produces n-pentane on reduction. ‘X’ could be
[2015]
(a) pentanal (b) 2-pentanone
(c) 3-pentanone (d) n-amyl alcohol
(c)
5. Treatment of cyclopentanone with
methyllithium gives which of the following species?
[2015]
(a) Cyclopentanonyl anion
(b) Cyclopentanonyl cation
(d) (c) Cyclopentanonyl radical
(d) Cyclopentanonyl biradical
6. A single compound of the structure, [2015]
2. The product formed by the reaction of an aldehyde CH3COCH2CH(CH3)CH2CH3 is obtainable from
with a primary amine is: [2016] ozonolysis of which of the following cyclic
(a) Ketone (b) Carboxylic acid compounds?

33
Chemistry Times March 19

10. The correct order of decreasing acid strength of

trichloroacetic acid (A), trifluoroacetic acid (B),
(a) (b) acetic acid (C) and formic acid (D) is [2012]
(a) A > C > B > D (b) B > D > C > A
(c) A > B > C > D (d) B > A > D > C
11. Which of the following compounds will give a
(c) (d) yellow precipitate with iodine and alkali? [2012]
(a) Acetophenone (b) Methyl acetate
7. Which one is most reactive towards nucleophilic (c) Acetamide (d) 2- Hydroxypropane
addition reaction? [2014] 12. Consider the reaction:
RCHO  NH 2 NH 2  R  CH  N NH 2
What sort of reaction is it? [2012]
(a) Electrophilic substitution - elimination reaction
(b) Nucleophilic addition - elimination reaction
(c) Electrophilic addition - elimination reaction
(a) (b)
(d) Free radical addition - elimination reaction
13. Acetone is treated with excess of ethanol in the
presence of hydrochloric acid. The product
obtained is [2012]

(c) (d) (a)

8. Reaction by which Benzaldehyde cannot be

(b)
prepared? [2013]

(c)
(a)
(d)

14. CH 3CHO and C6 H 5CH 2 CHO can be

(b)
distinguished chemically by [2012]
(a) Benedict’s test
(b) Iodoform test
(c) (c) Tollen’s reagent test
(d) Fehling’s solution test
15. Predict the products in the given reaction. [2012]

(d)

9. Consider the following reaction: ?

The product ‘A’’

is [2012] (a)
(a) C6 H 5 COCH 3 (b) C6 H 5 CHO
(c) C6 H 5Cl (d) C6 H 5OH

34
 Chemistry Times March 19

of: [2010]
(a) acyl chloride > ester > acid anhydride > amide
(b) acyl chloride > acid anhydride > ester > amide
(b) (c) ester > acyl chloride > amide > acid anhydride
(d) acid anhydride > amide > ester > acyl chloride
20. Propionic acid with Br2 P yields a dibromo
product. Its structure would be [2009]

(c)

(a)

(d) (b)

16. In a set of reaction m-bromobenzoic acid gave a (c)

product D. Identify the product D [2011]
1]

(d)
21. Trichloroacetaldehyde, CCl3CHO reacts with
chlorobenzene in presence of sulphuric acid and
produces [2009]

(a)
(a) (b)

(c) (d)
(b)

17. Clemmensen reduction of a ketone is carried out in

the presence of which of the following? [2011] 1]
(a) Zn-Hg with HCl (b) LiAlH 4
(c) H 2 and Pt as catalyst (d) Glycol with KOH
18. Acetamide is treated with the following reagents (c)
separately. Which one of these would yield methyl
amine? [2010]
(a) Hot. conc. H 2 SO4 (b) NaOH  Br2
(d)
(c) PCl5 (d) Sodalime
19. The relative reactivities of acyl compounds
towards nucleophilic substitution are in the order

35
Chemistry Times March

22. Acetophenone when reacted with a base (b) a β -hydroxy aldehyde or a β -hydroxy ketone
C2 H 5 ONa , yields a stable compound which has
(c) an β -hydroxy acid
the structure: [2008]
(d) an α -hydroxy aldehyde or ketone
26. Which of the following on treatment with 50%
(a) aqueous NaOH gives alcohols and acid? [2007]
(a) CH 3COCH 3 (b) C6 H 5CH 2 CHO
(c) C6 H 5 CHO (d) CH 3CH 2 CH 2CHO
(b) 27. Reduction of aldehydes and ketones into
hydrocarbons using Zn - Hg + HCl conc. is called
[2007]
(a) Wolff-Kishner reduction
(b) Clemmensen reduction
(c) (c) Cope reaction
(d) Dow reaction

Chemical Kinetics
(d) 1. Mechanism of a hypothetical reaction
X 2  Y2  2XY is given below : [2017]
23. The correct decreasing order of their reactivity
(i) X2  X  X(fast)
towards hydrolysis is [2007]
(i) C6 H 5 COCl (ii) X  Y2  XY  Y(slow)
(iii) X  Y  XY(fast)
(ii) The overall order of the reaction will be :
(a) 2 (b) 0 (c) 1.5 (d) 1
2. A first order reaction has a specific reaction rate of
(iii) 102 sec1 . How much time it takes for 20 g of the
reactant to reduce to 5g? [2017]
(a) 138.6 sec (b) 346.5 sec
(iv) (c) 693.0 sec (d) 238.6 sec
3. The rate of a first-order reaction is 0.04 molL-1S-1 at
(a) (iv) > (ii) > (i) > (iii) (b) (ii) > (iv) > (iii) > (i) 10 seconds and 0.03 molL-1S-1 at 20 seconds after
(c) (i) > (ii) > (iii) > (iv) (d) (ii) > (iv) > (i) > (iii) initiation of the reaction. The half-life period of the
24. Which of the following orders is wrong with reaction is: [2016]
respect to property indicated? [2007] (a) 34.1 s (b) 44.1 s (c) 54.1 s (d) 24.1 s
(a) Benzoic acid > Phenol > Cyclohexanol(Acid 4. The addition of a catalyst during a chemical reaction
strength) alters which of the following quantities? [2016]
(b) Aniline > Cyclohexylamine > Benzamide (Base (a) Internal energy (b) Enthalpy
strength) (c) Activation energy (d) Entropy
(c) Formic acid > Acetic acid > Propionic acid (Acid 5. The rate constant of the reaction A  B is
strength)
0.6 103 mole per second. If the concentration of
(d) Fluoro acetic acid > Chloro acetic acid > Bromo
A is 5 M, then concentration of B after 20 minutes
acetic acid (Acid strength)
is: [2015]
25. The product formed in aldol condensation is
(a) 0.36 M (b) 1.08 M
[2007]
(c) 0.72 M (d) 3.60 M
(a) an α,β -unsaturated ester 6. When initial concentration of a reactant is doubled
in a reaction, its half-life period is not affected. The

36
 Chemistry Times March

order of the reaction is [2015] (c) Rate  k[ A]2 [ B ] (d) Rate  k[ A][ B ]
(a) Zero
(b) First 12. In a zero-order reaction for every 100 C rise of
(c) Second temperature, the rate is doubled. If the temperature
(d) More than zero but less than first is increased from 100 C to 1000 C , the rate of the
7. The activation energy of a reaction can be
reaction will become [2012]
determined from the slope of which of the following
(a) 265 times (b) 128 times
graphs? [2015]
(c) 64 times (d) 512 times
ln k 13. The rate of the reaction 2 N 2 O5  4 NO2  O2 can
(a) ln k vs.T (b) vs.T
T be written in three ways: [2011]
1]
1 T 1  d [ N 2 O5 ]
(c) ln k vs. (d) ln k vs. T  k[ N 2 O5 ]
T dt
8. A reaction having equal energies of activation for
forward and reverse reaction has [2013] d [ NO2 ]
 k '[ N 2 O5 ]
(a) H  G  S  0 (b) S  0 dt
d [O2 ]
(c) G  0 (d) H  0  k "[ N 2 O5 ]
dt
9. What is the activation energy for a reaction if its The relationship between k and k ' and k " are:
rate doubles when the temperature is raised from
1 1
(a) k '  2k ; k "  2k (b) k '  k ; k "  k
200 C to 350 C ? ( R  8.314 J mol K ) [2013]
(c) k '  2k ; k ''  k (d) k '  2k ; k "  k / 2
(a) 15.1kJ mol 1 (b) 342kJ mol 1 14. Which one of the following statements for the order
(c) 269kJ mol 1 (d) 34.7kJ mol 1 of a reaction is incorrect? [2011]
1]
(a) Order is not influenced by stoichiometric
10. Activation energy ( Ea ) and rate constants coefficient of the reactants.
( k 1 and k 2 ) of a chemical reaction at two different (b) Order of reaction is sum of power to the
concentration terms of reactants to express the
temperatures (T1 and T2 ) are related by [2012] rate of reaction.
(c) Order of reaction is always whole number.
k2 Ea  1 1
(a) ln k   R    (d) Order can be determined only experimentally.
1  T2 T1  15. During the kinetic study of the reaction
2A  B  C  D following results were obtained.
k2 Ea  1 1
(b) ln k   R    Initial rate of forma
1  T2 T1  Run[ A]in M [ B]in M
tion of D in ms 1
k2 Ea  1 1  I 0.1 0.1 6.0  103
(c) ln k   R  T  T  II 0.3 0.2 7.2 102
1  1 2 
III 0.3 0.4 2.88  101
k2 Ea  1 1  IV 0.4 0.1 2.40  102
(d) ln k   R  T  T 
1  2 1  On the basis of above data which one is correct?
[2010]
11. In a reaction, A  B  Product, rate is doubled
when the concentration of B is doubled, and rate (a) r  k[ A]2 [ B]2 (b) r  k[ A][ B]2
increases by a factor of 8 when the concentrations
(c) r  k[ A]2 [ B] (d) r  k [ A][ B ]
of both the reactants (A and B) are doubled, rate
law for the reaction can be written as [2012] 1
2 2 2
16. For the reaction N 2 O5  2 NO2  O2 , the rate of
(a) Rate  k[ A][ B] (b) Rate  k[ A] [ B ] 2
disappearance of N 2 O5 is 6.25 103 molL1s 1 .

37
Chemistry Times March 19

The rate of formation of NO2 and O2 will be (c) rate  k [ A][ B ] (d) rate  k[ A]2 [ B ]
respectively. [2010] 22. In the reaction
(a) 6.25  10 3 molL1 s 1and 3.125  103 molL1 s 1 BrO3 (aq)  5Br  (aq)  6H   3Br2 (l )  3H 2O(l )
(b) 1.25  10 3 molL1 s 1and 3.125  10 3 molL1 s 1 The rate of appearance of bromine ( Br2 ) is related
3 1 1
(c) 6.25  10 molL s and 6.25  10 molL s 3 1 1 to rate of disappearance of bromide ions as
following: [2009]
(d) 1.25  10 2 molL1 s 1and 3.125  10 3 molL1 s 1
d [ Br2 ] 3 d [ Br  ] d[ Br2 ] 3 d[ Br  ]
17. The rate of reaction: (a)  (b) 
dt 5 dt dt 5 dt
2 NO  Cl2  2 NOCl is given by the rate,
d [ Br2 ] 5 d [ Br  ] d [ Br2 ] 5 d [ Br  ]
equation rate  k [ NO ]2 [Cl2 ] . The value of the rate (c)  (d) 
dt 3 dt dt 3 dt
constant can be increased by [2010]
23. The bromination of acetone that occurs in acid
(a) Increasing the concentration of the Cl2 solution is represented by this equation.
(b) Increasing the concentration of NO
CH 3COCH 3 (aq)  Br2 (aq ) 
(c) Increasing the temperature
(d) Doing all of these CH 3COCH 2 Br ( aq )  H  ( aq )  Br  ( aq )
18. For an endothermic reaction energy of activation These kinetic data were obt ained for given reaction
is Ea and enthalpy of reaction is H (both in concentrations.
Initial concentrations, M
kJ mol 1 ). Minimum value of Ea will be [2010]
(a)  H (b)  0 (c)  H (d)  H [CH 3COCH 3 ] Br2 H Initial rate,
19. Half-life period of a first-order reaction is 1386 disappearance of Br2
seconds. The specific rate constant of the reaction
is [2009] 0.30 0.05 0.05 5.7  105
(a) 0.5 102 s 1 (b) 0.5 103 s 1 0.30 0.10 0.05 5.7  105
0.30 0.10 0.10 1.2  104
(c) 5.0 102 s 1 (d) 5.0 103 s 1
0.40 0.05 0.20 3.1  104
20. For the reaction, N 2  3H 2  2 NH 3 ,
d [ NH 3 ] Based on these data, the rate equation is [2008]
if  2  104 mol L1 s 1 , the value of (a) rate  k[CH 3COCH 3 ][ Br2 ][ H ] 
dt
d [ H 2 ] (b) rate  k [CH 3COCH 3 ][ H  ]
would be: [2009]
dt (c) rate  k [CH 3COCH 3 ][ Br2 ][ H  ]2
(a) 4  104 mol L1 s 1 (b) 6 104 mol L1 s 1 (d) rate  k[CH 3COCH 3 ][ Br2 ]
(c) 1  10 4 mol L1 s 1 (d) 3  10 4 mol L1 s 1 24. The rate constants k1 and k2 for two different
21. For the reaction A + B  products, it is observed reactions are 1016 e2000/T and 1015 e1000 /T
that: [2009]
(1) On doubling the initial concentration of A only, respectively. The temperature at which k1  k2 is
the rate of reaction is also doubled and [2008]
(2) On doubling the initial concentrations of both
1000
A and B, there is a change by a factor of 8 in the (a) K (b) 1000 K
rate of the reaction. 2.303
The rate law of this reaction is given by 2000
(c) K (d) 2000 K
(a) rate  [ A][ B ]2 (b) rate  k[ A]2 [ B ]2 2.303

38
 Chemistry Times March

25. If 60% of a first-order reaction was completed in

60 min, 50% of the same reaction would be
completed in approximately [2007] 2.Sol:
(a) 40 min (b) 50 min
(c) 45 min (d) 60 min
3.Sol: Reaction of carbonyl compounds with ammonia
26. In a first-order reaction A  B , if K is the rate
derivatives is an example of Nucleophilic addition
constant and initial concentration of the reactant elimination reaction.
is 0.5 M, then half-life is [2007]
4.Sol: Compound ‘X’ yields
log10 2 0.693
(a) (b)
k 0.5k phenyl hydrazone
ln 2 Negative iodoform test
ln 2
(c) (d)
k k 0.5

Negative Tollen’s test  ketone

hence, the compound is 3-pentanone.

Aldehydes, Ketones & Carboxylic Acids

1. a 2. d 3. b 4. c 5. a
6. a 7. b 8. a 9. b 10. d
11. a, d 12. b 13. d 14. b 15. c
16. b 17. a 18. b 19. b 20. c 5.Sol:
21. c 22. a 23. d 24. b 25. b
26. c 27. b

Chemical Kinetics
1. c 2. a 3. d 4. c 5. c
6. b 7. c 8. d 9. d 10. b,d
11. c 12. d 13. d 14. c 15. b
16. d 17. c 18. d 19. b 20. d
21. a 22. b 23. b 24. a 25. c
26. c

6..Sol:

Aldehydes, Ketones & Carboxylic Acids

1.Sol:

7.Sol: Any substituent in the carbonyl compound that

increases the positive charge on the carbonyl
carbon will increase reactivity towards nucleophilic
addition.

39
Chemistry Times March

 NO2 shows -M effect hence

Acetophenone

8.Sol: Zn/Hg and HCl reduce carbonyl group to

methylene group (Clemmensen reduction).

9.Sol: 12.Sol: Consider the reaction:

RCHO  NH 2 NH 2  RCH  N - NH 2
It is Rosenmund’s reaction (reduction)
The reaction is nucleophilic addition elimination
reaction.
10.Sol:

13.Sol:

The presence of electron withdrawing group. in
carboxylic acid increases acidic character. Also
electron withdrawing nature of F is more than Cl.
14. Sol: CH3 CHO will give positive iodoform test as
it has CH 3CO 
15.Sol: It is Cannizzaro’s reaction.

11.Sol: and give

iodoform test
It is iodoform reaction. Acetophenone and 2-
Hydroxy propane both give a yellow precipitate of 16.Sol:
CHI 3 (Iodoform) with iodine and alkali.

40
 Chemistry Times March

23.Sol: The ease of hydrolysis depends upon the

magnitude of the +ve charge on the carbonyl
group.
24.Sol: Cyclohexylamines are more basic than aniline;
the later shows resonance.
25.Sol: CH3CH2CHO  CH3CHO 

or

17.Sol: Clemmensen reduction involves Zn-Hg with

HCl to convert > C = O group to > CH 2 .
26.Sol: It is Cannizzaro’s reaction shown by aldehydes
18.Sol: This is Hoffmann’s bromamide reaction with
lacking with α -H atom.
stepping down of series.
27. Sol: It is called Clemmensen reduction.
19.Sol: Better is leaving group higher will be reactivity
of acyl compound towards nucleophilic acyl
Chemical Kinetics
substitution. Weaker is its acid and vice-versa.
1.Sol: According to law of mass action
20.Sol: CH 3CH 2 COOH  CH 3CHBr.COOH
r  k[X][Y2 ] ....(i)
from fast step - 1
[X]2
K eq 
[X 2 ]
This is Hell-Volhard-Zelinsky reaction. [X]2  K eq .[X2 ]
21.Sol: It is preparation of DDT.
1
22.Sol: It is condensation reaction. [X]  K eq [X 2 ] 2
...(ii)
From equation (i) & (ii)
1
r  k. K eq [X 2 ] 2 [Y2 ]
1
r  k '[X 2 ] 2 [Y2 ].
Overall order of reaction =1 + 0.5 = 1.5
0.693
2.Sol: Half life of first order reaction t1/ 2 
k
0.693
  69.3sec
102
Method - 1

Total time  2t1/ 2  2  69.3  138.6sec

Method - 2

41
Chemistry Times March 19

Hence, if ln k is plotted against 1/T, slope of the

2.303 [A]
t log line will be  Ea / RT
k [A]t
8.Sol:  H  ( Ea ) f  ( Ea ) b  0
2.303 20
t log  t  138.6sec
102 5 k2 Ea  1 1 
9.Sol: log    
2.303 ( a  x1 ) k1 2.303R  T1 T2 
3.Sol: k log
(t 2  t1 ) ( a  x2 ) Ea  1 1 
log 2  
2.303  0.04  2.303  8.314  293 308 
 log  
(20  10)  0.03  Ea 15
0.3  
2.303  0.1249 2.303  8.314 293  308

10 0.3  2.303  8.314  293  308
Ea 
2.303  log 2 2.303  0.1249 15

t1/ 2 10  34673J mol1  34.7 J mol1

0.3010  10 10.Sol: On integrating within limits k1 to k2 and T1 to

t1/ 2   24.1sec
0.1249 T2
4.Sol: Catalyst can affect only activation energy of k2 T2
the chemical reaction and cannot alter any Ea 1
thermodynamic parameters:  ln k  
k1
R T
T1

(i.e.H , G, S )
k 2 Ea  1 1  Ea  1 1 
ln       
k1 R  T2 T1  R  T1 T2 

k2 Ea  1 1 
or ln    
k1 R  T1 T2 
Options (b) and (d) both are one and the same and
are correct.
11.Sol: Let r  k [ A]m [ B ]n
r1  k [ A]m [2 B ]n
5.Sol: For zero order reaction:
r2  k [2 A]m [2 B ]n
x = kt  0.6 103  20  60
x  0.72 M r1 r
Also,  2 and 2  8 (Given)
6.Sol: Half-life period of a first-order reaction is r r
independant of initial concentration,
Therefore m  2 and n  1
0.693
t1/ 2   r  k [ A]2 [ B ]1
k
12.Sol: Rate or rate constant doubles for every 10o or
7.Sol: Accroding to Arrhenius equation,
10K rise in temperature
k  Ae  Ea / RT
r100
  (2)9  512
E r10
ln k  ln A  a
RT

42
 Chemistry Times March

13.Sol: Rate of disappearance of reactants = Rate of By (i) and (ii), m = 1

appearance of products By (ii) and (iii), n = 2
1 d [ N 2 O5 ] 1 d [ NO2 ] d [O2 ]  r  k[ A]1[ B]2
  
2 dt 4 dt dt
1 d [ Br2 ] 1 d [ Br  ]
22.Sol:   R.O.R
k k' k 3 dt 5 dt
  k " k  2k , k " 
2 4 2
23.Sol: r  k [CH 3 COCH 3 ]a [ Br2 ]b [ H  ]c
14.Sol: Order of reaction may be fractional.
15.Sol: r  K [ A]m [ B ]n 5.7  10 5  k [0.30]a [0.05]b [0.05]c ...(1)
5 a b c
5.7  10  k [0.30] [0.10] [0.05] ...(2)
d [ N 2 O5 ] 1 d [ N O5 ] 2d [O2 ]
16.Sol:     R.O.R
dt 2 dt dt 1.2  10 4  k [0.30]a [0.10]b [0.10]c ...(3)
17.Sol: 15k increases with increase in temperature 3.1  10 4  k [0.40]a [0.05]b [0.20]c ...(4)
18.Sol: By (1) and (2) b = 0
By (2) and (3) c = 1
By (3) and (4) a = 1
24.Sol: k1  1016 e 2000 / T ; k 2  1015 e 1000 / T
if k 1  k 2 then 1016 e 2000/T  1015 e 1000/T

2000 1000 1000

or log10   or T  K
T T 2.303
19.Sol: For first order:
2.303 100
0.693 0.693 25.Sol: 60  log
k   5  10 4 s 1 k 40
t1/ 2 13.86
2.303 100
1 d [ NH 3 ] 1 d [ H 2 ] t1/2  log
20.Sol:  k 50
2 dt 3 dt
60 0.40
d [ H 2 ] 3 d [ NH 3 ]  
   t 0.310
dt 2 dt  t = 45 minute
3 26.Sol: For Ist order reaction,
  2  104  3 104
2 2.303log10 2
k
m
21.Sol: r  k[ A] [ B ] n
...(i) t1/ 2

2r=k[2A]m [ B ]n ...(ii) t1/ 2 

0.693 ln 2

k k
8r  k [2 A]m [2 B ]n ...(iii)

43
Chemistry Times March 19

CHEMISTRY

1. A, B and C are hydroxy-compounds of the elements (a) K  , F  and H  (b) K  , F  and HF

X, Y and Z respectively. X, Y and Z are in the same
 
period of the periodic table. A gives an aqueous (c) K  and  HF2  (d)  KHF  and F2
solution of pH less than seven. B reacts with both
5. 1.75 L of a gas at 127C and 5 atm is converted to
strong acids and strong alkalies. C gives an
aqueous solution which is strongly alkaline 2.875 L at 85C and 1 atm. The percentage of gas
Which of the following statements is/are true: escaped is
I : The three elements are metals (a) 11.11% (b) 23.2% (c) 56.3% (d) 63.5%
II : The electronegativities decrease from X to Y to 6. A mixture of dihydrogen and dioxygen at one bar
Z. pressure contains 20% by weight of dihydrogen.
III : The atomic radius decreases in the order X, Y Calculate the partial pressure of dihydrogen.
and Z. (a) 0.2 (b) 0.4 (c) 0.6 (d) 0.8
IV : X, Y and Z could be phosphorus, aluminium 7. At 25C and 1 atm, N 2O4 dissociates by the
and sodium respectively : reaction,
(a) I, II, III only correct
(b) I, III only correct  2 NO2 ( g )
N 2O4 ( g ) 
(c) II, IV only correct If it is 35% dissociated at given condition, find the
(d) II, III, IV only correct volume of above mixture that will diffuse if 20 mL
2. Basic, acidic and amphoteric oxides among them of pure O2 diffuses in 10 min at same temperature
(a) A, B ,C (b) B, A, C
and pressure.
(c) A, C, B (d) B, C, A
(a) 13.7 mL (b) 13.7 L (c) 68 mL (d) 68 L
3. Molecular shapes of SCl4 , CCl4 and XeF4 are 8. For a first order reaction A  B the reaction rate
(a) Same with 2,0 and 1 lone pairs of electrons at which reactant concentration of 0.01 M is found
respectively to be 2.0  10 5 M sec 1 . The half -life period of the
(b) Same with 1,1 and 1 lone pairs of electrons
reaction is :
respectively
(a) 30 s (b) 300 s (c) 220 s (d) 347s.
(c) Different with 1,0 and 2 lone pairs of electrons
9. Which of the following statements regarding the
respectively
molecularity of reaction is wrong?
(d) Different with 1,1 and 1 lone pairs of electrons
(a) It is the number of molecules of the reactions
respectively
taking part in a single step chemical reaction.
4. KF combines with HF to form KHF2 . The (b) It is calculated from the reaction mechanism.
compound contains the species

44
 Chemistry Times March 19

(c) It may be either a whole number or fractional. 15. Geometrical isomerism shows
(d) It depends on the rate determining step in the
reaction.
10. The specific heat of a gas at constant volume is (a) (b)
0.075 cal/g-K. Predict the atomicity of the gas.
(Molar mass of gas is 40 g mol 1 .)
(a) 1 (b) 2
(c) 3 (d) None of these
(c) (d)
11. Two solutions marked as A and B are separated
through semipermeable membrane as below. The
phenomenon undergoing 16. Which of the following possesses highest melting
point ?
(a) Chlorobenzene (b) o-Dichlorobenzene
(c) m-Dichlorobenzene (d) p-Dichlorobenzene
17. The compound “A” when treated with ceric
ammonium nitrate solution gives yellow ppt. The
compound “A” is
(a) Alcohol (b) Alkane
(c) Aldehyde (d) Acid

OH
18. C6 H5COCOC6 H5  (C6 H5 )2 C(OH )COOH .

(a) Na moves from solution A to solution B The above reaction is known as
(b) Both Na  and Cl  moves from solution (A) to (a) Beckmann rearrangement
solution (B) (b) Benzilic acid rearrangement
(c) Benzoin condensation
(c) Both Na  and Cl  moves from solution (B) to (d) Aldol condensation
(A) 19. The pair of amphoteric hydroxides is
(d) Solvent molecules moves from solution (A) to
(a) Al (OH )3 , LiOH (b) Be(OH )2 , Mg (OH )2
(B)
12. A solution is obtained by mixing 300g of 25% (c) B(OH )3 , Be(OH ) 2 (d) Be(OH ) 2 , Zn(OH )2
solution and 400g of 40% solution by mass.The 20. Lithopone is a mixture of:
mass percentage of the resulting solution is: (a) Barium sulphate and zinc sulphide
(a) 66.66% (b) 3.36% (b) Barium sulphide and zinc sulphide
(c) 33.6% (d) 22.4% (c) Calcium sulphate and zinc sulphide
13. Molar conductance of 0.1 M acetic acid is (d) Calcium sulphide and zinc sulphide
7 ohm1 cm 2 mol 1 . If the molar conductance of 21. Acidified potassium dichromate oxidises
acetic acid at infinite dilution is I. Iodides to iodine
II. Sulphides to sulphur
380.8 ohm 1cm 2 mol 1 , the value of dissociation III. Tin (IV) to tin (II)
constant will be: IV. Iron (III) salts to iron (II) salts
(a) 3.38  10 5 mol dm 3 (b) 226  10 5 mol dm 3 The appropriate option with correct choices are
(a) I, II and III (b) II, III and IV
(c) 1.66  10 3 mol dm 1 (d) 1.66  102 mol dm 3 (c) I and IV (d) I and II
14. Which of the following is crotonic acid? 22. Gun metal contains
(a) CH 2  CH  COOH (a) Cu, Sn, Zn (b) Cu, Ni
(c) Cu, Ni, Fe (d) Cu, Sn, P
(b) C6 H 5  CH  CH  COOH 23. The total number of possible isomers of the
(c) CH 3  CH  CH  COOH complex compound [Cu ( NH 3 )4 ][ PtCl4 ] is
(a) 4 (b) 3 (c) 6 (d) 5
(d)

45
Chemistry Times March 19

24. The coagulation values of AlCl3 and NaCl are

0.093 and 52 respectively. Then coagulating power
of AlCl3 as compared to that of NaCl is 2.Sol: CaO, SO3, Al2O3
(a) 52  0.093 times (b) 52/0.093 times 3.Sol: In SCl4,
(c) 0.093/52 (d) 52-0.093 times number of bond pairs = 4
25. The number of Nucleotide pairs present in one turn number of lone pairs = 1
of DNA helix is In CCl4,
(a) 10 (b) 9 (c) 8 (d) 4 number of bond pairs = 4
26. The end product (B) formed in the reaction number of lone pairs = 0
sequence In XeF4,
HCN HI,P number of bond pairs = 4
Glucose 
H3 O+
 A 
Δ
B
number of lone pairs = 2
(a) Hexanoic acid (b) Hexane 4.Sol: F- forms H-bond with HF, therefore, the species
(c) Heptane (d) Heptanoic acid 
27. In the oxyacids of chlorine Cl - O bond contains  H ....F H  or HF2- exists.
(a) p  d  bonding PV
1 1 T2 5 1.75 360
(b) p  p bonding 5.Sol: V2  T  P  400  1  7.875L
1 2
(c) d   d  bonding Percentage escaped
(d) None of these
7.875  2.875
28. The term “fools gold” is used for a mineral which   100  63.5%
shines like gold. It is 7.875
(a) Iron pyrites (b) Copper pyrites 20 80
(c) Cinnabar (d) Cadmium sulphide 6.Sol: nH 2  nO2 
2 32
29. Which process of reduction of mineral to the metal
is suited for the extraction of copper from its ores nH 2
with low copper content ? pH 2  P.
nH 2  nO2
(a) Metal displacement
(b) Auto reduction
 2 NO2 ( g )
7.Sol: N 2 O4 ( g ) 
(c) Chemical reduction
(d) Electrolytic reduction 1 0
30. Which of the following layering pattern will have a 1 2
void fraction of 0.26?
(a) ABCCBABC (b) ABBAABBA   n  1 
(c) ABCABCABC (d) ABCAABCA 2
4 2 P 4  0.35 1
KP    0.56atm
1 2 1   0.35
2

1. c 2. c 3. c 4. c 5. d
1    MWMixture  Initial
 

MWN2O4 
6. d 7. a 8. d 9. c 10. a 1  MWMixture  Final  MWMixture Final
11. d 12. c 13. a 14. c 15. d
16. d 17. a 18. c 19. d 20. a 92
1  0.35 
21. d 22. c 23. d 24. b 25. a  MWMixture Final
26. c 27. a 28. b 29. b 30. c
MWMixture  68.15
Let, V(mL) be the volume of mixture diffused in.
From Graham’s law of diffusion,

46
 Chemistry Times March 19

21.Sol: Acidified potassium dichromate oxidises

rO2 MWMixture 20 / 10 68.15
  iodides to iodine, sulphides to sulphur, tin (II) to
rMixture MWO2 V / 10 32 tin(IV), iron (II) salts to iron (III).
23.Sol: The possible isomers of the complex are
V  13.70mL
1
[Cu ( NH 3 )3 Cl ][ PtCl3 NH 3 ] ,
8.Sol: rate = k  A  [Cu(NH3)2Cl2][Pt(NH3)2Cl2],
2.0  105 [Cu ( NH 3 )Cl3 ][ Pt ( NH 3 )3 Cl ]
k=  2.0  103
0.01 [CuCl4 ][ Pt ( NH 3 )4 ]
0.693 The total number of isomers is five.
 t 12 =  347 s
2.0  103 Coagulation power of AlCl3
24.Sol: Coagulation power of NaCl
9.Sol: Molecularity can never be fractional.
10.Sol: Cv  0.075  40  3 cal K 1 mol 1
C p  Cv  R Coagulation value of NaCl

Coagulation value of AlCl3
 C p  3  2  C p  5 cal K 1mol 1
26.Sol: Compound A is glucose cyanohydrin.
5 Cp Compound B is Heptane.
   1.66
Cv 3 27.Sol:
Thus, the gas is monoatomic.
12.Sol: Mass percentage of solute in the solution
Oxygen doesn’t have vacant “d” orbitals in the
2
 7 
2 5 valence shell and only p electron participates
13.Sol: K a  C  0.1    3.38  10
 380.8  and chlorine has vacant “d” orbital in valences
16.Sol: Due to symmetrical structure, p-dichloroben- shell thus only d  electron participates.
zene fits closely in the crystal lattice.
28.Sol: Copper pyrites or chalcopyrite  CuFeS2  is
17.Sol:
known as fools gold.
R  OH  ( NH4 )2 Ce( NO3 )6 
Ce( NO3 )6 ( ROH )9  N2 14NO3
alcohol cerric amine. nitrate yellow ppt.
29.Sol: Auto reduction is used for the extraction of
20.Sol: Lithopone is used as paint. copper from its ore with low copper content.

47
Chemistry Times March 19

COORDINATION COMPOUNDS

[ONLINE QUESTIONS] 4. When concentrated HCl is added to an aqueous

1. Identify the correct trend given below:
(Atomic No.: Ti  22, Cr  24 and Mo  42 )
2 2
(a)  of Cr(H 2 O)6    Mo(H 2 O) 6 
3 2
 of Ti(H 2 O)6    Ti(H 2 O)6 
2
(b)  of Cr(H 2 O)6    Mo(H 2 O) 6 
3 2
 of Ti(H 2 O)6    Ti(H 2 O)6 
2
(c)  of Cr(H 2 O)6    Mo(H 2 O) 6 
3
 of Ti(H 2 O)6    Ti(H 2 O)6 
2
2
(d)  of Cr(H 2 O)6    Mo(H 2 O) 6 
3 2
 of Ti(H 2 O)6    Ti(H 2 O)6 
2. Which one of the following complexes will
consume more equivalents of aqueous solution of
Ag(NO3) ? [2016]
(a) Na 3 [CrCl6 ] (b) [Cr(H 2 O)5 Cl]Cl 2
(c) [Cr(H 2 O)6 ]Cl3 (d) Na 2 [CrCl5 (H 2 O)]
3. Which of the following is an example of homoleptic
complex ? [2016]
(a) [Co(NH3 )4 Cl 2 ] (b) [Co(NH3 )6 ]Cl3
(c) [Co(NH3 )5 Cl]Cl 2 (d) [Pt(NH3 ) 2 Cl2 ]
[2016] solution of CoCl2 , its colour changes from reddish
pink to deep blue. Which complex ion gives blue
colour in this reaction? [2015]
and
(a) [CoCl6 ]3 (b) [CoCl6 ]4 
(c) [Co(H 2 O) 6 ]2  (d) [CoCl 4 ]2 
2
and 5. Which of the following complex ions has electrons
that are symmetrically filled in both t 2g and e g
orbitals? [2015]
2
and (a) [FeF3 ]3 (b) [CoF6 ]3
(c) [Co(NH 3 ) 6 ]2  (d) [Mn(CN) 6 ]4 
6. Nickel (Z = 28) combines with a uninegative
2
and monodentate ligand to form a diamagnetic complex
[NiL 4 ]2  . The hybridisation involved and the
number of unpaired electrons present in the
complex are respectively : [2014]
(a) sp3 , zero (b) sp 3 , two
(c) dsp 2 , one (d) dsp 2 , zero
7. An octahedral complex with molecular composition
M.5NH3 .Cl.SO 4 has two isomers, A and B. The
solution of A gives a white precipitate with AgNO3
solution and the solution of B gives white
precipitate with BaCl2 solution. The type of
isomerism exhibited by the complex is : [2014]

48
 Chemistry Times March 19

(a) Geometrical isomerism(b) Coordinate isomerism series is more than 3d series.

(c) Ionisation isomerism (d) Linkage isomerism 3 2
But  of  Ti(H 2 O)6    of  Ti(H 2 O)6 
8. Which of the following name formula combinations
is not correct ? [2014] 2. Sol: Complex [Cr(H 2 O)6 ]Cl3 will consume
Formula Name more equivalents of aqueous solution of
(a) K[Cr(NH3 ) 2 Cl4 ] Pottassium diamine Ag(NO3 ).
Tetrachlorochromate III 3.Sol: Complex having only 1 type of ligands are
(b) [CO(NH3 ) 4 (H 2 O)I]SO 4 Tetraamine examples of homoleptic complex.
aquaiodo cobalt (III) 4.Sol: Aqueous of solution of CoCl2
sulphate
contains [Co(H 2 O) 6 ]2  which is pinkish in colour
(c) [Mn(CN)5 ]2  Pentacynomagnate (II)
so option d is incorrect.
ion
Reduction potential of Co3  Co2  is high so
(d) K 2 [Pt(CN) 4 ] Potassium
option (b) is incorrect. Co 2 does not oxidise easily
tetracyanoplatinate (II)
9. Consider the coordination compound, to Co3 .
[Co(NH3 )6 ]Cl3 . In the formation of this complex, It a general case that symmetrial substituted
the species which acts as the Lewis acid is : octahedral complexes are less deeper in colour than
[2014] tetrahedral complexes. So [CoCl 4 ]2  is deep blue
(a) NH3 (b) CI 
in colour.
3
(c) [Co(NH 3 )] (d) Co3 5.Sol: Symmetrically filled t 2g and eg are those which
10. The correct statement about the magnetic contain equal distribution of electrons.
properties of [Fe(CN) 6 ]3 and [FeF6 ]3 is :
(Z = 26). [2014]
(a) [Fe(CN)6 ]3 is paramagnetic, [FeF6 ]3 is
diamagnetic.
(b) Both are diamagnetic
(c) [Fe(CN) 6 ]3 is diamagnetic, [FeF6 ]3 is
paramagnetic.
(d) Both are paramagnetic

1. a 2. c 3. b 4. d 5. a
6. d 7. c 8. c 9. d 10. d

8. Sol: Correct Name of [Mn(CN)5 ]2  is

Pentacynomagnate (III) ion.
9. Sol: Metalcation i.e., Ca 3 acts as a lewis acid which
1. Sol:   CFSE (Crystal field stabilisation energy) accept lone pair from ligands of NH3 .
2 2 10.Sol: In [FeF6 ]3 , 5 unpaired electron present.
 of Cr(H 2 O) 6    of  Mo(H 2 O) 6 
Because here  depends on Zeff & Zeff of 4d In [Fe(CN)6 ]3 1 unpaired electron present.

49
Chemistry Times March

By: A.N.S. SANKARA RAO (Hyderabad)

Some of the competitive exams are either based on only XII class syllabus or based on maximum questions
from XII class syllabus. You have enjoyed with XI class shortcuts, memory tips and chemistricks in
February 2019 issue, now you will get XII class in this issue.

SOLID STATE
1 1 1
 Contributuion of an atom at body centre =1, face centre  , edge  , corner 
2 4 8

THE TRY MONDAY. If she slaps TRYCLINIC

CHEMISTRICK for 7 crystal systems CUTE ORTHE YCLINIC

50
 Chemistry Times March

S = Simple cubic or primitive,  Edge length of NaCl (FCC)  2(rc  ra )  a

F = FCC, B = BCC, E = End centred
CHEMISTRICK for No. of Bravias lattices :  Edge length of CsCl (BCC)  2(rc  ra )  3  a
Reading 3 to (2) 4 is not enough, Read from  HCP = AB AB AB......
11 to (2) 1.  FCC or CCP = ABC ABC ABC ........
 Radius ratio  rcation / ranion

P-type: dope III (B, Al) with IV (Si, Ge)
n-type: dope V (P, As) with IV (Si, Ge)
( e  equilibrium group IV i.e. middle of III & V)
ZM
 Density (  )  a3  N
A

( Z  no. of atoms in unit cell, a  edge length)

 n atoms = n Octahedral Voids

 = 2n Tetrahedral voids 

 n  2d sin  (Bragg’s equation)

 Radius ratio of  F- Centres: gives colour when anionic site is
rVoid occupied by unpaired e 
Tetrahedral voids  r  0.225  NaCl + Na (excess) : Yellow
Sphere
 LiCl + Li (excess) : Pink
rVoid  KCl + K (excess) : Violet
Octahedral Voids  r  0.414
Sphere
CHEMISTRICK: K V Li P is So(sodium) Yellow.
 Each unit cell of NaCl consists 14Cl- ions & 13Na+ Why?
ions  Paramagnetic: (B > H)
 Nearest neighbour distance (d): eg: Cr 3 , Fe 2 & Fe 3 , Cu 2 , O2
3 1  Diamagnetic: (B < < < < < H)
Simple cubic : BCC : FCC  a : a: a
2 2 eg: H 2 O, C6 H 6 , ZnO, KCl , NaCl
 1 a : 0  86 a : 0  7a  Ferromagnetic: (B >>>>> H)
 Radii (r): eg: Fe, Co, Ni
1 3 1  Ferrimagnetic:
Simple cubic : BCC : FCC  a: a: a
2 4 2 2 eg: CuFe2 O4 , ZnFe2 O4 like Ferrites
 0  5 a : 0  43 a : 0  35a
 Anti Ferromagnetic:
 Packing fraction:
Simple cubic : BCC : FCC  0  52 : 0  68: 0  74 eg: V2 O3 , MnO2
 Packing efficiency: SOLUTIONS
Simple cubic : BCC : FCC  52% : 68% : 74% No. of parts of one component 6
 Vacant space:  ppm  No. of parts of all components  10
Simple cubic : BCC : FCC  48% : 32% : 26%

51
Chemistry Times March

 N  M  Basicity ( for acid ) eg: C6 H6  C6 H5  CH3 , n-Hexane + n-Heptane,

 N  M  Acidity ( for base) C2 H 5 Br  C2 H 5 Cl

M 1V1  M 2V2  +ve deviation: H  0, V  0

 M mix  V1  V2 eg: C2 H 5OH  CH 3COCH 3 ,

N1V1  N 2V2 C2 H 5OH  H 2 O, CHCl3  CCl4

 N mix  V1  V2  -ve deviation: H  0, V  0
 Neutralisation: eg: C6 H 5OH  C6 H 5 NH 2 , CHCl3  CH 3COCH 3
M aVa M bVb  Azeotropes: 95% C2 H 5OH  5% H 2O,
 N aVa  NbVb
na nb
68% HNO3  32% H 2 O
 Dilution:  No. of solute particles  B.P  L.V.P  Tb
M1V1  M 2V2 N1V1  N 2V2
1 1
 Vol. of Water added  V2  V1  Tf  
V . P F .P
 No. of Milli moles  M  V  Tb  Tb  T0  i  K b  m
M V  T f  T0  T f  i  K f  m
 No. of moles 
1000
  V  nTR (   Osmotic pressure)
 No. of Milli equivalents  N  V   of 1 lit. soln of 1M = 22.4 atm (at 00C)
N V   1   2 (Isotonic solution)
 No. of equivalents 
1000
i 1
n1  Degree of dissociation  
n 1
 Mole fraction of solvent ( X 1 ) 
n1  n2
1 i
 Degree of association  
n2 1
 Mole fraction of solute ( X 2 )  1
n1  n2 n
 Hypotonic solution: low  , Haemolysis,
 X1  X 2  1
 w
n2 [salt]  0  9%   , Water flow into cell & burst.
 For aqueous solutions X Solute  n  55  5  w
2
 Hypertonic solution: high  , plasmolysis,
1000 M
 molality (m)  1000d  M  M  w
[salt]  0  9%   , Water flow out of cell & shrink.
Solute
 w
1
 Pgas  K H  X gas KH  T ELECTRO CHEMISTRY
Solubility
 To prevent bends, scuba divers are filled with l
 Resistance R   (units : ohm)
mixture contains 11.7% He + 56.2% N2+ 32.1% O2 a
 Ptotal  X 1 P10  X 2 P20 1 1 a
 conductance C    (ohm1 or siemen)
0
P P n2 R  l
 0
 X2  (1=solvent, 2= solute)  Specific resistance or Resistivity
P n1  n2
 Ideal solution obeys Raoult’ss law, a
( )  R  ( ohm m )
Vmix  H mix  0 l

52
 Chemistry Times March

 Specific Conductance or Conductivity

0 0  059
1 l1 l  For cation electrode ECell  ECell  log C
( K )     C  (ohm 1 m1 ) n
 R a a
0 0  059
 Molar Conductivity  For Anion electrode ECell  ECell  log C
n
K  1000
( m )  (ohm 1 m2 mol 1 )  For Zn  2 Ag  (aq.)  Zn 2 ( aq.)  2 Ag
M
 Equivalent conductivity 2
 Ag  
0  059
K  1000 ECell  E 0
Cell  log  2
( eq )  (ohm 1 m 2 equivalent 1 ) n  Zn 
N
  c  0  b c  ECell  0.059 pH (for Hydrogen electrode at
(slope  b, intercept   0 )
  0m  V 0  V 0 (V  no. of ions) 250 C )
0 0 0 0
 G 0  2.303RT log K C
  CH3COOH  CH3COONa   HCl   NaCl
0
  nFE Cell
(  0  limiting molar conductance)
0 0  059
0 1 0 0  ECell  log K C
  ( BaCl2 )  Ba2  Cl 
eq n
2
0 0 0 Gm0
  m ( BaCl2 )  Ba 2  2Cl   Thermodynamic efficiency of fuel cell 
H m0
1 0  Products in electrolysis of aqueous electrolyte : If
  m ( NH 4 OH )  m ( NH 4 Cl )  m  Ba(OH ) 2 
0 0

2 Cu, Ag, Au, Pt, halogens are present we will get

them, if not H2 at cathode, O2 at anode will be
1
 m0 ( BaCl2 ) liberated.
2 eg: aq.K2SO4 on electrolysis gives H2 at cathode,
K Salt 1000 O2 at anode.
 Solubility ( S )  aq.CuSO4 gives Cu at cathode, O2 at anode with Pt
 m0
electrodes.

53
Chemistry Times March

E
 Faraday’s 1st law m  c  e  t e (TRICK: m = cet pronounce as EAMCET)
96500
 1F=96,500C = can deposit 1Equivalent
W1 E1
 Faraday’s 2nd law W  E
2 2

 CHEMISTRICK for Electro Chemical Series is

“ LipoBa Sir Call Naturally while MagisterAll Man are Zingy and Crossing
(Potassium) (Natrium)
(Kailum) (Sodium)

by Ferry (boat). Cadet Coach Nitin leads Highly Cupid, Ideal, mercy,
(Stannum) (Plumbum) (mercury)
(Hydrargyrum)

Silly Broad minded, Class Augumentative Fellows”

(Silver)
(Argentum)

 S .R.P.( E 0 )  oxidising power  Lead accumulator:

discharging
1 
Pb  PbO2  2 H 2 SO4   2 PbSO4  2 H 2 O
 Charging
reducing power
 ECell  ERight  Eleft CHEMICAL KINETICS
To calculate Ecell problems easily follow the table: For the reaction N 2  3H 2  2 NH 3

d  N2  1 d  H2  1 d  NH3 
 rate    
dt 3 dt 2 dt
 rate  k [ N 2 ][ H 2 ]3

54
 Chemistry Times March

 k  A  e  Ea RT
 H  ( Ea ) forward reaction  ( Ea )backward reaction

k2 Ea  1 1 
 log k  2  303R  T  T  SURFACE CHEMISTRY
1  1 2  1
x n
 Freundlich adsorption isotherm  K  P
1 m
 For zero order reaction k  [ A]0  [ A]
t
1
2  303 a ( can have values 0 to 1)
n
 For 1st order reaction k  log
t ax
1
 
(Slope  , intercept  log K )
[ A]0 n
 Half life  t 1  for zero order reaction 
 2  2k
x aP
 Langmuir adsorption isotherm 
0  693 m 1  bP
 For 1st order reaction t 1  k
2  Adsorption  TC

t '1  For adsorption H  ve, S  ve, G  ve

n 1
2  a ''   Amount of adsorption:

 t '' 1  a ' 
SO2  NH 3  CO2  CH 4  N 2  H 2
2
 Zeolites: good shape selective catalysts, water
 t50% : t75% : t87.5% : t93.75%  1: 2 : 3 : 4 softners
 t90% : t99% : t99.9% : t99.99%  1: 2 : 3 : 4  YEAST: source of Zymase, Invertase, Maltase
enzymes
 Specific rate k  P  z  e  Ea RT
TRICK: ZYM (ZIM) is in the EAST (YEAST)
(P= probability factor)

55
Chemistry Times March

 Lyophilic sol (Solvent loving): gum, gelatin, starch,
albumin
 Lyophobic sol(Solvent hating): gold sol, silver sol
 Multi molecular colloids: starch, cellulose,
proteins, polymers
 CMC for soap: 10 3 to 104 mol / lit
 +vely charged sols: hydrated metallic oxides, TiO2 ,
haemoglobin, Methylene blue, basic dye
 -vely charged sols: Metals, Metal sulphides, Acid
dyes, eosin, Congo red, starch, gum, gelatin, clay,
charcoal
 Coagulating power  Charge on the ion
 Gold Number: The minimum number of milli grams
of lyophilic colloid required to prevent the
coagulation of a standard gold sol on addition of 1
ml of 10% NaCl Solution.
1  Cupellation: Ag
protective power  gold number
 Cause of Artificial rain: AgI or electrified sand in
contact with cloud
1  Bronze: Cu (75 to 90%), Sn (25 to 10%)
 flocculation value  Charge on ion
56
eg: KCl  MgCl2  CrCl3  SnCl4
GENERALPRINCIPLES OF METALLURGY
 Froth Collectors: pine oil, sodium ethyl xanthate
 Froth stabilizers: Cresols, Aniline
 Depressant: NaCN (prevents ZnS from coming to
froth, but PbS comes with froth)
 Copper Matte: More Cu2 S  little FeS
 Metallurgical transformation:
G  ve, H  ve, S  ve
 Pig iron: obtained from blast furnace, contains
4% C
 2Cu2 O  Cu2 S  SO2  6Cu (Blister copper)
 Refining by distillation: Zn, Cd, Hg
 Liquation: Sn, Pb, Bi, Hg
 Poling: Cu
 Electrolytic refining: Cu, Ag, Au, Al, Pb, Zn
 Zone refining: Ge, Si, B, Ga, In
 Vapour phase refining: Ni (Mond’ss process),
Hf & Zr & Ti (Vanan Arkel Method)
 Brass: Cu (60 to 80%), Zn (40 to 20%)

 German silver: Cu (25 to 30%), Zn (25 to 30%),
Ni (40-50%)
 % of C: Pig iron (4%) > Cast iron(3%)>Steel(2.1%)
> Wrought iron(0.08%)
 Cryolite ( Na3 AlF6 ) : lowers M.P., increases
conductivity
Fluorspar(CaF2): Decreases Fusion temperature.
p- Block Elements
15 th group:
 Stability, Basic Nature, Bond Angle:
NH 3  PH 3  AsH 3  SbH 3  BiH 3
 M.P: NH 3  SbH 3  AsH 3  PH 3
 B.P: SbH 3  NH 3  AsH 3  PH 3
 Hydrolysis of P4 O6 or PCl3 gives H 3 PO3
 Hydrolysis of P4 O10 or PCl5 gives H 3 PO4
 Anhydride of H 3 PO4 is: P4 O10 & H 3 PO3 is : P4 O6
(TRICK : 4H3 PO4  6H2O  PO
4 10 )
(4 H 3 PO3  6 H 2 O  P4 O6 )
 Nessler’s reagent: K 2  HgI 4 
a mixture of KI , NaOH , HgCl2
 Brown ring:  Fe( H 2O)5 NO  SO4 Where oxi. state
of Fe = +1
 IUPAC name of brown ring: penta aqua
Nitrosonium Iron (I) Sulphate
 Aquaregia: conc HNO3 : con HCl in 1 : 3 ratio
 Nitrolim: CaCN 2 +graphite (used as fertilizer)
 Oxo Acids of S:
Chemistry Times March
 NH 3 dried over: CaO (quick lime)
 Heating of Pb( NO3 ) 2 gives O2 , NO2 , PbO;
NH4NO3 gives N 2O; NH4NO2 gives N 2 ;
N2O3 gives NO & NO2 .
 Smoke screens & Holme’s signals: combustion
of PH 3 (produced by CaC2 & CaS).
 dil.HNO3 reacts with Cu to give NO whereas
Zn gives N2O
 Con.HNO3 reacts with Cu, Zn, I 2 , C , S8 , P4 gives
NO2 along with Cu(NO3)2 , Zn(NO3)2, HIO3, CO2,
H2SO4, H3PO4.
 Meta phosphoric acid exists in polymeric form
( HPO3 ) n only
16 th group
 Electron gain enthalpy: S  Se  Te  Po  O
 Electronegativity: O  Se  S  Te  Po
 Thrust in rockets given by combustion of
Hydrazine in liquid O2
 Oxi.agent in the manufacture of KMnO4 is O3
 SO2 is Antichlor, disinfectant, preservative
 As impurities purified by gelatinous Fe2O3
 O3 oxidises NO2 to NO3 , SO32 to SO42 ,
NO to NO2, SO2 to SO3 ,
HX to X 2 (not HF ), PbS to PbSO4 , Moist
I 2 to HIO3 , Hg to Hg 2 O (tailing of Hg)
 For decomposition of O3 :
H  G  ve S  ve
57
Chemistry Times March

 Charring of sugar is dehydration reaction asthma patients

conc. H 2 SO4  Solubility & ease of liquifaction & enthalpy of
C12 H 22O11  12C  11H 2O
vaporisation : Xe  Kr  Ar  Ne  He
 Cyclic trimer of SO3 has 6S  0 & 3 S  O  S
 % of d character: XeF6  XeF4  XeF2
bonds
 Rn: used in the treatment of cancer
17th GROUP
 Ne: used in Beacon lights, decorative discharge
 Oxidising power: Cl2 O  ClO2  Cl2 O6  Cl2 O7 tubes
 Acidic Nature: Cl2 O7  Cl2 O6  ClO2  Cl2 O  Kr-85: used in electronic tubes
 Ar+Hg Vapour: used in fluoroscent tubes
 Bond angle: HClO2  HClO4  HClO3  HClO
 C p C v  1.66 for noble gases (Mono atomic)
0 0 0 0
(111 ) (109  5 ) (106 ) (90 )
 reducing power: I  Br  Cl
  

 Acid strength of oxyacid  No. of Oxygens

 Acid strength: H 2 Se  HI  HBr
 pseudohalide: CN 
 Tincture of Iodine: alcoholic Solution of I 2
 Iodised salt prepared from: KI & KIO3
 Spent Nuclear fuel PuF6 removed by: O2 F2
 Bleaching agent in paper industry: Cl O2
 CO can be estimated by: I 2 O5
 Bond disso. energy: Cl2  Br2  F2  I 2
 Litmus paper is decolourised by chlorine water
CHEMISTRICK:
due to bleaching action of HOCl.
G  ( No. of F  2  oxygens)
 X X3 ' are Bent T-shaped, X X5 ' are square No. of L.P.S 
2
pyramidal
No. of   No. of F  No. of oxygens
 Poisonous gases: phosgene (COCl2 ), tear gas
No. of = No. of oxygens
(CCl3 NO2 ), mustard gas (Cl CH 2 CH 2 ) 2 S
 reaction of Cl2 with cold, dil NaOH gives NaCl, d & f BLOCK ELEMENTS & CO-ORDINATION
COMPOUNDS
NaOCl, but hot, conc.NaOH gives NaCl & NaClO3.
CHEMISTRICK “ScanTii Vecro Man ICoNi
 enrichment of U235 is done by ClF3 or BrF3.
CuZim”
(Sc, Ti, V, Cr, Mn, I = Iron Ferrum, Co, Ni, Cu, Zn)
18th GROUP
 He can diffuses through rubber, glass, plastic    n(n  2) B.M.
 liquid He used in: Nuclear reactors, NMR, MRI.    n  0.7 or 0.8 or 0.9.
 X eF 2  2 H 2 O  4 H F  2 X e  O 2
n = no. of electrons    0.7 or 0.8 or 0.9
6 XeF4  12 H 2 O  24 HF  4 Xe  2 XeO3  O2  E.A.N.= Z - oxi.No. + 2 unidentate ligands
XeF6  1H 2 O  2 HF  XeOF4 4
 t  0
XeF6  2 H 2 O  4 HF  XeO2 F2 9
XeF6  3H 2 O  6 HF  XeO3  If  0  P (Weak field ligands) if 4e  are there
 Mixture of O2+He: used by deep sea divers &
t 24g e g0

58
 Chemistry Times March

 If  0  P (strong field ligands) if 4e  are there 4

eg:  Fe(CN )6   d 2 s1 p 3
t23g e1g  Spectro chemical series (order of  or CFSE):
 Weak field ligands: H 2O, halides, OH-, S-2, I   Br   S 2  SCN   Cl   N 3  F 
C2O4-2 can form outer orbital complex with formula  OH   C2O42  H2O  NCS   NH3
nsx npy ndz
 en  CN   CO
(Where x + y + z = coordination Number) (n =
principal quantum number)  Overall stability constant  n  K1  K 2  K n
3
eg: CoF6   s1 p 3 d 2 1
 Instability constant  
 Strong field ligands: NCS  , en, CN  , CO can n

form inner orbital complex with formula CHEMISTRICK for 14 Lanthanoids

“LaCe is Predominantly Needed to Promote
(n  1)d x ns y npz Same European God’s Terrible, Dynamic,
 Note: some times x could be zero Honourable Erratic TommYbLue”.
POLYMERS

59
Chemistry Times March

 Ziegler Natta catalyst: Low level of thyroxine: Leads to hypothyroidism

(C2 H5 )3 Al  TiCl4 used to get HDPE (lethargyness & obesity)
Characters of Addison’s disease: stress, weakness,
Mw hypoglycemia
 PDI   Hormone produced during stress: Adrenaline
Mn
BIOMOLECULES Sucrose =   D - glucopyranose +   D -
CHEMISTRICK: Mono remala weds Noresu fructotfuranose
Reducing sugars: maltose, lactose, all mono  Mutarotation: exhibited by reducing sugars (in
saccharides hemiacetal & hemiketal forms)
Non reducing sugars: sucrose  Chirality of DNA & RNA: due to D-sugar content
Anomers:   D glucose &   D glucose
Glycogen: structure is similar to amylopectin,
highly branched present in liver, brain, muscles, No of Chiral Carbons in   or   D  glucose: 5
yeast, fungi.
In DNA: A = T; G=C
 Essential Amino acids: obtained through diet
 Complimetary strand of TATGACTG of DNA is
(CHEMISTRICK TV FILM WHRK is
ATACTGAC; RNA is AUACUGAC
essential) they are Threonine, Valine, F-phenyl
CHEMISTRY IN EVERYDAY LIFE
alanine, Isoleucine, Methionine, W- trypophan,
 Deltol: Mixtrue of Terpineol & Chloroxylenol, used
Histidine, R-Arginine, K-Lysine
as antiseptic
 Proline has secondary amino (imino) group
 Antiseptic: Bithional, 0.2% phenol
 Except glycine all other natural amino acids are
 Stable artificial sweetener: Alitame
optically active.
 Antihistamines: Diphenyl hydramine,
 Peptide bonds are present in proteins & enzymes
promethazine, brompheniramine (Dimetapp),
 Insulin Contain 51 amino acids
terfenadine (seldane)
 Insulin, albumins, haemoglobin, enzymes are
 Tranquilisers: Valium, Equanil, noradrenaline,
globular proteins
Luminal, seconal
 20, 30 - structure of proteins: consists H-bonds,
 Aspirin: Acetylation product of O-hydroxy
- S - S - bonds, electrostatic forces of attraction
benzoic acid, it is antipyretic & analgesic
and Van der Waals forces.
 During denaturation of proteins only 20 & 30  Antacids: NaHCO3 , Al (OH )3 , Mg (OH ) 2 ,
structures are destroyed omeprazole, Lansoprazole, Ranitidine (zantac)
 expect B12 others B1 , B2 , B6 are excreted in urine  Analgesics:
 Non-Narcotic: Novalgin, Aspirin, Ibuprofen
CHEMISTRICK U R TireD
 Narcotic: Morphine, Heroin, Codeine
CAGU : RNA
 Antibiotics: (Salvarsan, Prontosil, Sulphanilamide,
CAGT : DNA
Azo dye)
Purine bases: Adenine (A), Guanine (G)
 Bactericidal: ofloxacin, pencillin
Pyramidine bases: Cytosine (C), Uracil (U),
 Bateriostatic: Tetracycline, chloramphenicol,
Thymine (T)
erythromycin
CHEMISTRICK: CUT the Pyramid
 Nucleoside: Base + Pentose sugar  Antiseptics: Dettol, SO2 , 0.2% phenol, Cl2 ,
 Nucleotide: Base + Pentose sugar + Phosphate Bithional, H 2 O2 , Boric acid, CH I 3
 Steroid hormones: estrogens, androgens
 Antifertility drugs: Norethindrone, Novestrol,
 Poly peptide hormones: glucagon, insulin,
Mifepristone
endorphins
 Amino acid derivative hormones: Thyroxine  Anti oxidants: BHT, BHA, SO2
[contains iodine], epinephrine, norepinephrine  Food preservatives: Sugar, Vegetable oils, NaCl,
 Insulin: decrease the glucose level (by converting C6 H 5COONa
glucose to glycogen)
 Order of Sweetness of Artificial Sweetners:
 Glucagon: increase the glucose level into glycogen
Alitame > Sucrolose > Saccharin > Aspartame

60
 Chemistry Times March

 Scum: Insoluble soap (C17 H 35COO)2 Ca or Mg (3) p- nitro phenol > o - nitrophenol > m-nitrophenol
> Phenol.
 Shaving Soap: glycerol + rosin
 Laundry Soap: sodium rosinate + sodium silicate + (4) C6 H 5COOH  C6 H 5CH 2 COOH 
Sodium carbonate + Borax CH 3COOH  C2 H 5COOH
 Anionic detergent: sodium lauryl sulphate
 Cationic detergent: Cetyltrimethyl Ammonium (5) CF3   NO2  CN   F  Cl   Br
bromide (present in hair conditioner)   I  C6 H 5
 Non ionic detergent: Liquid dish washing
detergent
 Biodegradable detergent: unbranched
hydrocarbons (6) p   o   m  >  m  p  o 
 Non biodegradable detergent: branched
hydrocarbons
ORGANIC CHEMISTRY (e  . W . D. groups (e  . Donating groups
Orders:
 Dipole moment: are substituted ) are substituted )
CH 3Cl  CH 3 F  CH 3 Br  CH 3 I Basic Nature:
(1) In gaseous state:
 B.P.: Phenol > Wa ater > alcohol
(CHEMISTRICK: The great eat pheno Waal like 30  NH 2  20  NH 2  10  NH 2  NH 3
the great china wall) (2) In aqueous state:
 B.P. of dichloro Benzene: o > p > m R2 NH  RNH 2  ArCH 2 NH 2  NH 3 
M.P. of dichloro Benzene: p > o > m
 SN 1: A rN H R  A rN H 2  A rN R 2
0 0 0 0
3 RX  2 n  butylX  2 isobutylX  1 RX (3) (CH 3 ) 2 NH  CH 3 NH 2  (CH 3 )3 N  NH 3
SN 2: (4) (C2 H 5 ) 2 NH  (C2 H 5 )3 N  C2 H 5 NH 2  NH 3
30 RX  20 n  butylX  20 isobutylX  10 RX
 SN 1:
Ar2 CRX  Ar2 CHX  ArRCHX  ArCH 2 X (5) p  o  m   m   p   o 
SN 2:
Ar2 CRX  Ar2 CHX  ArRCHX  ArCH 2 X
(e  . Donating groups (e . W .D. groups
(R = alkyl, Ar = (C6H5) Aryl, X = halide)
CHEMISTRICK Two In One (SN2- Inversion- are substituted ) are substituted )
One step)
 Order of dehydration of alcohols: 30  20  10 (6)
 Order of reactivity of alcohols with HX:
30 > 20 > 1 0
 Order of reactivity
(1) RCOCl  ( RCO) 2 O  RCOOR  RCOOH
R  CH 3 Ar  C6 H 5
 RCONH 2
(2) Alkene > alkyne > alkane  -Cl is o  & p  directing
(3) RCHO  RCOR But -NO2 group shows its effect only at o- and p-
 Acidic nature positions (though it is m-directing)
(1) picric acid > 3, 5 dinitro phenol > o - nitro phenol>  In coupling BDC reacts with PhenOl to give
m- nitro phenol > phenol > m - cresol > p- cresol Orange dye, whereas Aniline gives An yellow dye
> o - cresol  Ozonolysis: break = bond or  bond put oxygen
(2) 10  OH  20  OH  30  OH before & after the bond to get the products.

61
Chemistry Times March

 Names of series of Oxyacids in order:

CHEMISTRICK OMSGAP,
Oxalic acid, Malonic acid, Succinic acid, Glutaric Hydrolysis of NC:
acid, Adipic acid, Pimelic acid
Purpose of reagents:  Alkaline KMnO4 (Baeyer’s reagent ) : To detect
unsaturation & oxidation
 Hydration (  H 2 O ) : HgSO4  dil.H 2 SO4
 Red P4  conc HI : To reduce  CHO,  CO,
 Dehydration ( H 2 O ) : conc  HgSO4  Heating
COOH ,  CH 2 OH to  CH 3
at 1700 C(or) P4O10 (or ) Al2O3  Heating upto 3500 C
 ZnHg  conc.HCl : To reduce  CO to CH 2
 Dehydrohalogenation(-HX): alc.KOH
 Dehalogenation(-X): Zn dust  Removal of CO : Br2  KOH
 Reduction ( H 2 ) : Zn  Cu  C2 H 5OH (or ) Zn   Distinguish 10, 20, 30 Alcohols: ZnCl2+Conc.HCl
 Distinguish aldehydes from ketones:
Hg  conc.HCl (or ) H 2 N  NH 2 (or ) H 2 / Ni
 Tollen’s reagent (Ammonical AgNO3 )
(or ) Pt (or ) Pd ; HI / Red P4 ; LiAlH 4 ; NaBH 4
 Fehling’s solution(alk. CuSO4  sodium
 Partial reduction ( H 2 ) : H 2  Pd / BaSO4 in potassium tartarate)
quinoline  Schiff’s reagent: decolouration of rosaniline
 Oxidation (O or  H 2 ) : Alk .KMnO4 (or ) hydro chloride with SO2 .
acidified K 2 Cr2 O7 (or ) Cr2 O3 / H 2 SO4  Benedict’s Solution: alk CuSO4 + sodium
potassium citrate
 Partial reduction ( H 2 ) : PCC or PDC  To neutralise acid: pyridine
 Hydroboration oxidation: to convert alkene to Named reactions:
alcohol  Hydroboration-oxidation:
B 2 H 6  H 2 O2  aq.NaOH H 3C  CH  CH 2  1) B2 H 6
2) H 2 O , H 2 O2 , NaOH
 Decarboxylation: (CO2 ) : NaOH  CaO  Heat CH 3CH 2 CH 2 OH
 Halogenation ( X ) : X 2 / h.v. (sunlight) (or) TRICK:
(1) Addition of water
Cl2 / FeCl3 (or) Br2 in CH 3COOH (or) Br2 in
(2) Follow Anti Markovnikov rule
CS2 at 00C  Esterification: CH 3COOH  HOH 5 C2 
H 

   Halogenation ( +X at  carbon):
CH 3COOC2 H 5  H 2 O
Cl2  Red P4
 Kolbe’s:
 Nitration (substitution of  NO2 ): 1) NaOH
C6 H 5OH 
2) CO , H 
 C6 H 5 (OH ) COOH
2
Conc.HNO3  Conc.H 2 SO4 (or ) KNO2 / DMF
 Reimer - Tiemann:
Sulphonation (sub. of  HSO3 ) : 1) CHCl3
C6 H 5OH 
2) aq . NaOH
C6 H 5 (OH ) CHO
conc. H 2 S2O7 (oleum)
[Intermediate: Benzalchloride; Intermediate species:
 Alkylation (sub. of -R): RX & Anhyd . AlX 3 dichlorocarbene(:CCl2)]
 Williamson’s:
 Acylation(sub.of -COR): RCOX & Anhyd . AlX 3
C 2 H 5 Cl  C 2 H 5 ONa  C 2 H 5 OC 2 H 5  NaCl
 Aldol condensation: dil. NaOH
 Rosenmund’s:
 Ketol condensation: Ba (OH ) 2
Pd
 Cannizzaro condensation (For aldehydes does not C6 H 5COCl  H  H 
BaSO4
 C6 H 5CHO  HCl
contain   H ): KOH or NaOH 1) SnCl2 , HCl
 Stephen: CH 3CN 
2) H3O
 CH 3CHO  NH 3
 Etard:
 Hydrolysis of CN: 1) CrO2 Cl2 , CS2
C6 H 5CH 3 2) H O 
 C6 H 5CHO
3

62
 Chemistry Times March

 Gattermann-Koch:  Diazotisation:
1) CO , HCl NaNO2
C6 H 6  
2) Anhyd  AlCl3 / CuCl
 C6 H 5  CHO CH 3 NH 2  HNO2 
HCl
 CH 3 N 2Cl
 Clemmensen: H 2O
  CH 3OH  N 2  HCl
ZnHg
CH 3COCH 3 
 CH 3CH 2CH 3  H 2O
HCl  Sandmeyer:
 Wolff-Kishner: Cu2 Br2
C6 H 5 N 2Cl  HBr   C6 H 5 Br
NH 2 NH 2
CH 3COCH 3  (CH 3 ) 2 C  NNH 2
 H 2O  N 2  HCl
KOH , ethylene glycol
 CH 3CH 2CH 3  N 2
 Heat
 Gatterman:
Cu
 Cannizzaro: C6 H 5 N 2Cl  HCl   C6 H 5Cl
 N 2  CuCl
 Carbyl amine:
 H.V.Z.:
C6 H 5 NH 2  CHCl3  3KOH

  C6 H 5 NC  3 KCl  3 H 2 O
 Finkelstein:  Idoform:
dry ether
CH 3Cl  NaI 
 CH 3 I  NaBr CH 3CHO  4 KOH  3I 2  CHI 3
 Swarts: CH 3 Br  AgF  CH 3 F  AgBr  HCOOK  3KI  3H 2O
 Saytzeff:  Aldol Condensation:

 Wurtz:
dry ether
CH3 Br  2 Na  BrCH3   
CH3  CH3  2NaBr
 Fitting:
dry ether
C6 H5 Br  2 Na  BrC6 H5   
 Cross Aldol Condensation:
C6 H 5C6 H 5  2 NaBr 1) NaOH
 Wurtz Fitting:
CH 3CHO  C2 H 5CHO  2) 


dry ether
C6 H5 Br  2 Na  BrCH3    But  2  enal 
Pent  2  enal 
C6 H 5CH 3  2 NaBr
2  Methyl But  2  enal 
 Gabriel pthalimide:
i ) alc . KOH
2  Methyl pent  2  enal
C6 H 4 (CO ) 2 NH 
ii ) R X , 

iii ) aq . NaOH

C6 H 4 (COONa)2  RNH 2 (aliphatic) RANK EDGE AKADEMI OF CHEMISTRY

 Hoffmann bromamide degradation: Deepthisri nagar, Hyderabad.
RCONH 2  Br2  4 NaOH  RNH 2 Mobile No: 9848685179
Email: rasayanam.Jeeneet@gmail.Com
2 NaBr  Na2CO3  2 H 2O

63
Chemistry Times March 19

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