1, (b): Aromatic halides are less reactive thar alkyl or
aralkyl halides. Hence, CHsCH,Cl is the most reactive
towards aqueous NaOH.
2 @
1
3 @i5A —+ 2B
1 ala) 1a
W/2 dt
a 2d
1a) _, ~ BaSO,! + 2cr
‘White ppt.
xe cr
7. (b): NaNO HCI ‘CuCN
Oo — O — é
COOH
Ho
%
8 (c) A cell is reversible if the cell reaction can be
reversed by applying opposite voltage greater than that of
the cell, ¢.g., Daniell cell.
% @
10. (b) : Aromatic aldehydes and ketones are less reactive
than the corresponding aliphatic analogues. towards
nucleophilic addition reactions due to the +R effect of
benzene ring. Further, aldchydes are more reactive than
ketones due to +/ effect and steric effect of alkyl group.
‘Therefore, the ease of nucleophilic addition will follow the
order:
1H
i i ee
cu, ——H> cry —E- cn >
1 m 1
11. (a) : Lowering of E, raises the value of k.
Bae
12, (a) Structure (a) will be reducing sugar as both
monasaccharide units are not linked through their reducing
centres. In structure (b), the two monosaccharide unity
ae linked through their reducing centres hence, it will be
non-reducing,
13. @
14, (c): The two strands in a DNA molecule are not
cxactly similar but are complementary to each other.
1s. (@):
oxa spliting in an
‘ctbedralerytl fld
+. Inhigh spin situation, A, < P, in d° configuration, 4" and
‘St*electron are added to e rather than t,,. So, configuration
of dion will bet, 2,
16. (a) : 0 Substituted benzoic acids are generally stronger
acids than benzoic acid. This is regardless of the nature
(+1 or ~ of the substituent. This is called ortho-effect and
is probably due to a combination of steric and electronic
factors.
7% @) Sas (il) CH,CH.NC
CH, CH,
OR
(Boiling point increases with increase in molecular
mass. It also depends on the size and number of halogen
atoms. Therefore, the arrangement of the given compounds
in order of increasing boiling points is as follows :
CH,Cl < CH,Br< CH,Br, < CHBr,
(i) For the same halogen, boiling point increases with
increase in size of the alkyl group. Further the boiling
point decreases as the branching increases. Therefore,
the arrangement of the given compounds in the order of
increasing boiling points is as follows :
(CH,),CHCI < CICH,CH,CH, < CICH,CH,CH;CH)
18, (i) : Thisis due to lanthanide contraction.
(ii) Zinc (2 = 30) has completely filled d-orbital (34).
4 -orbitals do not take part in inter-atomic bonding. Hence,
metallic bonding is weak. This is why it has very low
enthalpy of atomization (126 kJ mol-?),
19. (i) First order
In [R] = - kt + In [R), =-k
(i) lnfR}=- + Inf}, ape
Comparing this equation with
aoe hate eens
we get a straight line with slc
= and intercept = In[R]y pa?
Class 12 20. (a) HNO, reacts with C,H,,N to give an alcohol
means the compound is primary amine. C,HysN means
CyH,,NH, (primary amine),
Optically active alcohol means CyH,,OH segment contain
a chiral carbon.
4
5S 4 3) af
CH, — CH, — CH, —C —NH,,
‘on,
Pestan-2 amine
(b) Asthebond polarity increases, dipole momentincreases
and hence, order is
(CH,CH,CH, 4H,O1n + 4e°
Net reaction:
2Hyg + Ox 7 2H,0y
(0) x (Conductivity) = XG (Cell constant)
R(Resistance)
(g) If the protective tin coating over an iron bucket is
broken in some places then iron corrodes faster as oxidation
potential of Fe is higher than that of Sn
32, (a) Since the compound forms 2, 4-DNP derivative
and reduces Tollens' reagent, it must be an aldehyde.
Since the compound undergoes Cannizzaro reaction, Le,
there is no a-hydrogen as —CHO group is directly attached
to the benzene ring.
‘These observations suggest that the compound is
o-Ethylbenzaldehyde.
(b) Since compound (A) liberates CO, on reaction with
NaHCO, it is carboxylic acid.
As it undergoes hydrogenation, it should contain double
bond. Therefore, A can be
HCN COOH CSc,
H7 4) SCH, ~ SCOOH
(a) rw
On hydrogenation of (A) it wll form
H
HCY COOH a
DcH-CHT or CH,—CH,~C—CooH
W cH I
cH,
@ @
(B) has asymmetric carbon and therefore, will exist in two
‘enantiomeric forms.
OR
Element | Percentage] Relative | Simplest
ofatoms | numberratio | ratio
c 68.32 5.69 8
H 64 64 9
cl 25.26 O71 1
‘Therefore, empirical formula of compound (A) = CJH,Cl.
‘Empirical weight = 12 x 8 + 1x9 + 35.5 = 140.5
Molecular weight (given) = 140.5
As empirical formula weight and molecular weight are
same,
Molecular formula = CHCl
Since (C) reacts with phenyl hydrazine, therefore, it is a
carbonyl compound. Since (C) gives positive odoform test,
ithas — COCH, group.
1-Chloro--penplethane 1-Phenylethanol
“ iO}
CH,Cl yy
HC cocH,
J CAHGNHNH
oY %
o CHO
33. (a) These complexes can ionise in solution as :
[Co(NH,),Cly| - does not ionise.
[Co(NH,),Cl,]c1—> {Coot hl (ato)
[Co(NH, J, —+ [Co(NH,),)* + 3Cr (ions)
[Co(NH,),ClICl—+ [Co(NH),CIP* + 2CIr (3 ions)
‘Asthe number of ions in solution increases, their conductivity
also increases. Therefore, conductivity follows the order
[Co(NH,),Cl] < (Co(NH,),ChJCl < [Co(NH,),C1}Cl,
< [Co(NH,)1Ch,
(b) The compounds having similar geometry may have
different number of unpaired electrons due to the presence
of weak and strong field ligands in complexes. If CFSE
is high, the complex will show low value of magnetic
‘moment and if CFSE is low, the complex will show high
value of magnetic moment. For example, the [CoF,) is
paramagnetic but [Co(NH)4]°* is diamagnetic.
(©) In CuSOy5H,O, water acts as ligand. As a result it
causes crystal field splitting. Hence, d-d transition i possible
in CuSO,5H,O and shows colour. In the anhydrous CuSO,
due to the absence of water (ligand), crystal field splitting is
not possible and hence, no d-d transition occurs and shows
no colour.
OR
(2) Lower wavelength is absorbed in octahedral complex
than tetrahedral complex for the same metal and ligand. In
tetrahedral coordination entity, formation ofthe d-orbital
splitting is inverted and is smaller as compared to the
‘octahedral field splitting. Thus, the energy of tetrahedral
‘complex is smaller than compared to octahedral complex.
4,= 4/9),
(b) When white light falls on the comples, some part of itis
absorbed. Higher the crystal field splitting. lower will be the
wavelength absorbed by the complex. The observed colour of
complex isthe colour generated from the wavelength lft over.
(©) CoSO,CLSNH, :
(i) Isomer A reacts with AgNO, but not with BaCl,, it
shows it has CI ion outside the coordination sphere.
Hence, A = [Co(NH,),S0,]CI
Isomer B reacts with BaCl, but not with AgNO, it shows it
thas SO} outside the coordination sphere.
Hence, B = [Co(NH,),Cl]SO,
(ii) Tonisation isomerism
(ii) is Pentaamminesulphatocobalt(III) chloride and
Bis Pentaamminechloridocobalt(II1) sulphate.
990
Chemistry 1. _(€) The boiling points of isomeric amines vary inthe
order of primary > secondary > tertiary
oH
ato ‘coon
I wa, | NN yo
2 @e (EHO, ASS (enon, HE CHO
cH,OH con (Gaon,
«
cHOH
Goort a
Gry
cH,
@
(Mepuboicacd
3. (+ Let rate of reaction R= k{X]" 0)
27R = k{ax]" - (i)
or 27=3" [Dividing (ii) by ()] or 3°=3" or
4, (b): The third ionisation energy of Mn required to
change Mn?*(d*) to Mn™*(d*) is much larger due to stable
half-filled electronic configuration,
5. (6): CH,cH=CHCHO “++ cHcH=cHCHOH
6. (a): In the first step, ether gets protonated to form:
oxonium ion CgHs— 6 —CHy. I” prefers to combine with
H
‘smaller group in order to reduce steric hindrance.
7. (b): Basic strength decreases from La(OH), to
Lu(OH),, Hence, (1) is incorrect.
Ce= [Xe] 4f! 5d! “= [Xe]
Yb = [Xe] 4f" 6:2; yb?* = [Xe] 4f*
La = [Ke] 4" Sd! 6:2; Lu* = [Xe] 4f'*
‘The given ions contain no unpaired electrons and therefore,
are diamagnetic.
8. (6): Atcathode : Ag’ +e > Ag; E = +0.80 V
At anode : Pb > Pb** + 2¢°; E = -0.13 V
Feat = Feathode ~ Eanode = 0-80 ~ (-0.13) = 0.93 V.
‘Hence, the reaction will be 2Ag* + Pb > Pb** + 2Ag.
a (ads
e i
i
H—C— 4 nr, —cH0 4» en, eH cH
on [we
Ciy= cui EH COOH FS HC! CH= CH— CHO
2 a
on
o
10. (a)
LL. (@): CH,Br + KCN —9 CH,CN + KBr
Due to ionic nature, the attack by CN occurs through
Catom and alkyl cyanide is formed.
12. (b): * K{X] (For a first order reaction)
0.00352=kx001 => k= 0.352
yg = 8 9 2.969 min
1B. © 14. (@)
18, (©): o-Nitrophenol is steam volatile due to
intramolecular hydrogen bonding while p-nitrophenol is
less volatile due to intermolecular hydrogen bonding.
16. (a)
17. On oxidation with nitric acid, glucose yields a
dicarboxylic acid, saccharic acid. This indicates presence of
‘one primary (~OH) alcoholic group in glucose because only
1°(-OH) groups ae oxidised to (COOH) group with mild
oxidising agents such as HNO, while 2°(-OH) groups need
drastic conditions to oxidise. Thus, rest four (-OH) groups
in ghicose are 2*(-OH) groups.
GHO, OH
(Guo, 2, (CHOM),
CH,OH coon
Ghcose Sacchi acid
18. (i) (a) Brat vinylic position: CH,CH = CHBr and
ong '=CH,
Br
(b)_ Brat allylic position : CH, = CHCH,Br
(i) R—OH + SOCl, — R—Cl+S0,7 +HCIT
SO, and HCl in the gaseous form escape from the reaction
‘mizture hence R— Clis isolated in pure form
19. Vapour pressure of heptane = 105.2 kPa
‘Vapour pressure of octane = 46.8 kPa
Mass of heptane = 25.0 g
‘Molar mass of heptane = 100 g/mol
Mass of octane = 35.0 g
‘Molar mass of octane = 114 g/mol
25.0 g
100 g/mol
350g
114 g/mol
Mole fraction of heptane,
_ 025 mol
0.25 mol +031 mol ~
So, moles of heptane, n, = =0.25 mol
males of octane, n, =
%, 0.446,
Class 12 Mole fraction of octane,
0.31 mol
0.25 mol + 0.31 mol
‘Now, vapour pressure of the mixture,
P= 34% Py + %5% Py = 0446 x 105.2 kPa + 054 x 46.8 KPa
P= 46.9 kPa + 25.9 kPa = 72.8 kPs 728 bar
20. (i) The reaction is of zero order,
xe = 0554
(ii) Slope = -k a
(ii) INF TEGO Nag + 3Hayy
OR
(8) Order of reaction is sum of powers of concentration
terms of reacting species in the rate law equation.
+. order of reaction = 1 +2
2303, [Rly
(in k= tos et
where (Rg = Initial concentration
[R= Concentration at time ¢
Unit of rate constant for ist order reaction is
ect
21. cHcHO MES 5) cH, CHC
"2. cHy GHA Gils Gis > CHCH=CHCH,
Daze
‘a
{pereosie
HyC~EH-G-cH,
HBr
a
22. Let the rate law forthe reaction be
Rate = k[NO}(CL)"
From Expt. (1), 1.2 x 10 = k{0.010}(0.010P (i)
From Expt. (2), 2.4 10° = k{0.010}[0.0207 Ci)
Dividing Eq. (ii) by Eq. (i),
24x10~ _ (0.020)”
12x10 [0.010
From Expt. (2), 2.4 x 10“ = k{0.010}"{0.0207
From Expt. (3),9.6 x 10 = k{0.020}"(0.0207
Dividing Eq, (iv) by Ea. (ti),
4
9.6x10~ _ {0.020 _,
24x10 [0.010/"
Order of reaction =x+y=2+1=3
Rate law for the reaction is Rate = k{NO}?{Ch}]
Considering Eq. (i) again, 1.2 x 10°*= k(0.010}"(0.010),
2x10
3 2=QV syst
flv)
==
= 1.2x10?mol litre? sec“
23, (a) In aqueous solution carboxylic group loses a proton
and amino group accepts proton to form zwitter ion.
RCH é-on= R—GH-CHO-
NH, MH
(Zier on)
‘Galt
(6) As glucose forms a six-membered ring in which
—CHO group combines with —OH group at C-5,
pentaacetate of glucose does not react with hydroxylamine
due to the absence of free —CHO group.
(©). Two nucleic acid chains are wound around each other
and held together by hydrogen bonds between pairs of
bases. The two strands are complementary to each other
because the hydrogen bonds are formed between specific
pairs of bases. Adenine forms hydrogen bonds with thymine
whereas cytosine forms hydrogen bonds with guanine.
24. (a) Wolff-Kishner reduction : The carbonyl group
of aldehydes and ketones is reduced to >CH, group
on treatment with hydrazine followed by heating with
potassium hydroxide in a high boiling solvent such as
ethylene glycol.
NH,NE,
CH, CHy:
cH >CZ0 He? cH, >C= NNT
CEN,
(CHI, | + CH,CH,CH,COONa
yellow ppt
CH CH C-cH,CH, 2S No yellow pptof CH,
25. ‘A’ gives precipitate with AgNO,, so in it Clis present
‘outside the coordination sphere. ‘B’ gives precipitate with
BaCl,, so in it SO,?" is present outside the coordination
sphere.
()_A~[Co(NH,),S0,]C1. B- [CoH ,ClISO, (ii) Tonisation isomerism
(ii) A : Pentaamminesulphatocobalt(III chloride
2B: Pentaamminechloridocobali({Il) sulphate
26, (a) CHOH HS cry i>
‘CHjMgt —OHCHO_, cH.CH,OH
Hone
eh oo
to cone. 1,80,
©) cy patton SPH c= cH,
CH; CH,
a orga iow, cut,
OH
tert Butyl alcohol
© ¢,H,0H# 21, cx,cHo—l2L, c,coon
Bihanol
NH,
> CH,COONH, Ht CH,CONH,
‘Aeamide
27. (a) Allyl chloride shows high reactivity as the
carbocation formed by hydrolysis is stabilised by resonance
while no such stabilisation of carbocation exists inthe case
‘of n-propyl chloride.
(b) Grignard reagents are highly reactive and react with
even traces of water to give corresponding hydrocarbons.
RMgX + H,O—+ RH + Mg(OH)X
(©) Forahaloalkane to dissolve in water, energy is required
to overcome the attractions between the haloalkane
molecules and break the hydrogen bonds between water
molecules. Less energy is released when new attractions are
set up between the haloalkane and the water molecules as
these are not as strong as the original hydrogen bonds in
water, As a result, the solubility ofhaloalkanes in waters low.
28, Au + 3e°—> Au
197 g of Au required 3F charge
So,L.2.gof Au required 21.2 = 0.0183 F charge
(2) For the evolution of O,,
2H,0 0, + 4H + 4"
4F charge is required for evolution of 1 mol O,,
0.0183 F charge is required for evolution of
410188% 1 mol 0, = 0.00457 mol O,
Number of coulombs of electricity passed
(b)
= 96,500 x 0.0183 = 1.76 x 10°C
(© Qeit
Q_176x10°C _ 5510s
‘Therefore, t= t= 3.52 x10"
29, In [Ni(CO)
(@) In [Ni(CO),) as 4p
Ni-3d 45° [H]HTOTATT 0
Ground state
PR,
Since CO is strong feld ligand, hence 4s electrons are shite
to 3d orbital.
3d
NiO) in TATN TTS) |) fo
excited state
onccoy, [FTN TTT) bx) bx pox
3d co cococo
Sincecomplex has no unpaired electron, so, it is diamagnetic,
“Hybridisation is sp, hence structure is tetrahedral.
OR
In (Mn(CN),]**, Mn is in +3 state so, it has configuration
of 3,
‘Since CN" isa strong field ligand hence pairing of electrons
in 3d-orbital takes place.
‘
ttat ee
Fremeulion \O tt,
a te
G4) In strong octahedral
Tigand field
So, [Mn(CN).|* has two unpaired electrons. But in
[MnCl], CI" is a weak field ligand, so no pairing takes
place and it has 4 unpaired electrons.
(b) For tetrahedral complexes crystal field splitting
energy A, is always less than pairing energy. So, tetrahedral
complexes are always high spin.
(©) In[CoF,)*",Coisin +3 state and has 3° configuration.
i 3d ds dp
Co ~ 30° fF 70 TD]
Ground state
‘Since F is a weak field ligand, so, outer d-orbitals will be
used.
GEITH & Ee) GT
Six par of electrons
from F ions (sp'd?)
Since, outer d-orbital is used for hybridisation, so, itis outer
orbital complex.
In [Co(NH,),}** Co is in +3 state,
3d 4s 4p
1) 1) CI
tilt
Co¥ - 34 [TT
Ground state
Since NH, is strong field ligand pairing of electrons in
3-orbital takes place to make two 3d orbitals vacant.
ad
p° bybridised (DTH IN]
orbital of Co™*
int 1%
Since it uses inner d-orbital for its hybridisation, so it is
inner orbital complex.
30. (a) Given: Ey) = 2.71 V
For the reaction,
Mein + Cie —> Mey + Cuy
Class 12 nH2AG=?
Using formula, A,G° = ~ nFE*
b,G? =-2 x 96500 Cmol"!x2.71V
or ae ~~ 523.03 kJ mol"!
(b) Bey == 044 - (0.74) = 030
0.0591
fog CO
Bagi" 030-6 Bar
= 0.30 + 0.00985 = 0.31 V
(0) Nig) +248 (ag) Nay + 2A B= 1.05
Here, n= 2
Using formula, log K, = = ca
0.059
= 35.5932
21.05
log K.=
oF 1B Ke 0.059
K, = antilog 35.5932 or K, = 3.92 x 10°
‘Again, AG® = FE?
AG? = -2 x 96500 x 1.05 = - 202650}
AG" = -202.65 kJ
OR
‘The electrode reaction is
Zn** +26 —» Zn (n=2)
Applying Nernst equation, we get,
[ean Ferma
AS 0.1 M ZnSO, solution is 95% dissociated, this means that
in the solution,
0.0591
Pan =~ 0.76 - 29? hig 1
ata OS aps
.76 — 0.02955 (log 1000 - log 95)
76 — 0.0295 (3 ~ 1.9777) = - 0.79021 V
31. (a) Aniline reacts with conc. H,SO, to give sulphanilic
NH, XH,HSO,
oO 36, Oo sOK DK
Ailine Aniiniamykogen
sulphate R
NH, NH,
O o
So So;
Suiphanicncid ——Zwiter on
(b) Due to strong activation of amino group halogenation
of aniline occurs very fast and the halogenation occurs at
Para and both ortho positions and 2,4,6-tribromoaniline is,
produced.
Chemistry
So
xa
of = Oe On
o
@) iniiiidiahibucinieel Ueshantog NH,
group by acetylation reaction with acetic anhydride
a by the nitration and hydrolysis.
NHCOCH,
oe00, HNO, HO,
288K
NHCOCH,
oO ak 6
NO, i Ma
(©) In alkyl diazonium salts, the C - eee
So, alkyl diazonium salts are unstable.
(f) Aniline being a 1° amine gives carbylamine test
‘whereas N-methylaniline being a 2° amine does not give
carbylamine test.
NH, Ne
ean, oH cand Oo +3KCI+3H,0
Paming Phenyl carylamine
NHcH,
+ KOH No reaction
2 eine
(@) Lower aliphatic amines are soluble in water because
they can form hydrogen bonds with water molecules. Effect
of small hydrophobic alkyl part is negligible.
RONAH- 0-H
HOR
32, (a) Preparation of potassium permanganate: Potassium
‘permanganate is prepared by the fusion of MnO, (pyrolusite)
with potassium hydroxide and an oxidising agent like KNO,
to form potassium manganate which disproportionates in a
neutral or acidic solution to form permanganate.
2MnO, + 4KOH + 0, > 2K,MnO, +2H,0
3MnOj; + 4H” — 2MnO; + MnO, + 2H,0
of, 3K,MnO, + 4HCl— 2KMnO, + MnO, + 2H,O
+4KCL
2MnO}+ I6H* + 5C,O% — 2Mn** + 10CO, + 3H,O
(©) (TH has highest oxidation state among the given
ions. Ti** has stable inert gas configuration and hence, most
stable in aqueous solution. ‘On the other hand, V?*, Mn®*, Cr* have unstable electronic
configuration and hence, are less stable.
(ii) Due to stable half-filled d* configuration in Mn,
Mn’ readily accepts one electron, hence behaves as
strongest oxidsing agent among the given ions,
(iii) Due to absence of unpaired electron in Ti, itis a
colourless ion.
EC. of Ti** = [Ar]3d%4s?
OR
(a) Oxoanion of chromium in which it shows + 6
oxidation state equal to its group number is Cr,0,?-
(dichromate ion).
(b) i) In presence of strong field ligand, Co(II) has electronic
configuration f3,¢),
eas,
It can easly lose one electron present in e, orbital to give
stable 44, configuration. This is why Co** is easily oxidised
to Co™ in the presence of strong field ligand.
(ii) Electrode potential (E*) value is the sum of three
factors:
= Enthalpy of atomisation 4H for Cu) —> Cay,
= Tonisation enthalpy 4, for Cu —> Cuiy;
- Hydration enthalpy 4,,,4H for Cuts — Cuf,,
In case of copper the sum of enthalpy of atomisation and
ionisation enthalpy is greater than enthalpy of hydration,
This is why Ey; for Cu is positive.
(©) (i) MnO; +5Fe* + 8H* —> Mn®* + 5Fe™ +4H,0
(ii), 2MnO; +5C,O% + 16H*—9 2Mn* + 8H,0 + 10CO,,
33. (a) The depression in freezing points are in the order:
A>
a F
cH,-coon< ci ¢—coon< F Sc—coon
av Fr
pewicucd _—_‘Toichlorosei serio id
Fluorine being most electronegative, has the highest
dlectron withdrawing inductive effect. Consequently,
trifluoroacetic acid is the strongest acid while acetic acid
is the weakest acid. Hence, trifluoroacetic acid ionises to
the largest extent while acetic acid ionises to the minimum
extent to give ions in their solutions in water. Greater the
ions produced, greater is the depression in freezing point.
Hence, the depression in freezing point is maximum for
trifluoroacetic acid and minimum for acetic acid.
(©). Given mass of CH,CH,CHCICOOH = 20 g
Molar mass of CH,CH,CHCICOOH
12x44 1x7 +3551 + 16x 2= 122.5 g mol"
‘Number of moles of CH;CH;CHCICOOH
20g
122.5 g mol
0.1632
0.1632 mol
X 1000 = 0.3264 m
Mollity of the solution (m)
If ex be the degree of dissociation of CH,CH,CHCICOOH
then CH,CH,CHCICOOH == CH,CH,CHCICOO™ + 11"
Inti cone ox ou
Atequliiam: ox ou
x, 02x08 ca?
2 ca =a)
v K,=Co?
3
ae [Re = ft”. Jor008289 = 0.065
c 03268
c= 0065
To calculate vant Hof factor:
CH,CH,CHCICOOH = CHCH,CHCIOO + H"
tntidmel: o °
Moeateg: I-a @ «
Total number of moles =1-a+a+a=1+a
+0.065 = 1,065
i
1.065) (1.86)(0.3264) = 0.65 K
Hence, depression in freezing point of water = 0.65 K
OR
(2), Molecular mass of Glauber’ salt Na,SO,,10H,0
=[2x23432+ 16x 4+ 10x (2x1 +16)
= (46 + 32 + 64 + 180) g mol"! = 322 g mol"!
Na,S0,-10H,0 ionises as :
Na,S0,10H,0 = 2Na* + $07" + 10,0
= IS
i Ws 6.00 g
Mg X Wacinkgy) 322 g mol x0.1 kg.
X 1.86 kg m~ x 0.186 m = 1.04 K
= Ty= Ty -ATy = (273 ~1.04) K = 271.96 K
(b)_ Here, n=2 because phenol forms dimer on association.
W, = 208, W, kg= 1000 g, AT,= 0.69 K, Kp= 5.1 Km
Ky xW, x1000
pare
My XW,
Ky Wy X1000 _5.1520%1000
My = 2 = 314201000 147 99 g mol”!
‘aT; xW, 069x100
47.82 g mol"
x12+6%1+16=94g mol
Malcaictated) _
Malobsered)
2C,H,OH = (C,H,0H),
a y felt
n 2
©0o
Class 12 1, (a) : In hypotonic solution, the wateris drawn in and the
grape swells while in hypertonic solution the water is drawn
‘out and the grape shrinks,
Ma a“ ®
2 WIC0C:0))” AEE] | ELE
3. (b): La(OH), is most basic among hydroxides of
lanthanides. Hence, (I) is wrong. (II) is correct due to
lanthanoid contraction. (II) is correct because Ce" tends
to change to stable Ce™.
4. (©): More the number of methyl groups (electron
releasing) lesser will be the acidity. Hence the reactivity
towards sodium metal will be tert. < sec. < pri.
5. (@)
6. (a): 2H,0 > H,O* + OF
0.0591
Fee = log K
tog = FSX 08277 yg ge
0.0591 00591
7. (©:
oO =o a= OO)
8 @):
g
Hy—C=CH + H,0 22488, cH,—C—cH,,
Propyne Propane
9% (b): NaOBr is used to convert acetamide to
‘methanamine by Hoffmann bromamide reaction.
CH,CONH, [25> CH,NH, + NaBe
‘NaOBr serves as the attacking species.
fut
10. (b): Arrhenius equation, k
Given equation is, k= (4.5 x 10's"
Comparing both the equations, we get ~
E,= 28000 Kx R
= 28000 K x 8.314] K'mol*
= 232,79 kj mol"!
- (a): Oren > Q
‘CH; ‘CH;
2etylyeicunl eto
cH,cH,cH,cH,on YS cH,-ch=cH-cH,
Butan-I-ol But-2-ene
Chemistry
12, (@): la [FeFg)? oxidation state of Fe = +3
Fe" = 3d, configuration = 13 ¢?
ATA
ATTA)
13. )
14. (6) The vapour pressure of solution is found to be
lower than the vapour pressure of pure solvent. In the
solution, the surface has both solute and solvent molecules,
thereby the number of solvent molecules gets reduced at
the surface, consequently, the number of solvent molecules
escaping from the surface is correspondingly reduced and
this results in the decrease of vapour pressure of the solvent.
15. (c) : The reaction occurs by Syy1 mechanism.
CH, CHy
ery fen, > on, -¢ 13 cn, >
cH, CH, H
os os
cue + CHOW > cH, -C-1+ CHO
cH, cH,
Ifthe reaction have been occurred by $2 mechanism, methyl
iodide and tert-butyl alcohol would have been produced.
16. (a)
F “ocr, OCH,
~ocH, .
“a?
7 @
No, NO,
(i) CH,CH,Br + AgCN a.) —> miawae 2c
18, Mol. wt. of HCl = 36.5,
Wt of HClin 1 litre of M/2 HCI = 36.5 x 1/2.g = 18.25 g
‘Weight of HCI lost on heating = 2.675 g
Weight of HCl eft in solution = 18.25 - 2.675 g
5.575 g
36.5 gof HCl = 1 mole
1
3.5 =SoxI5:
15575 gof HCl = 55 x15.575 mole,
Volume ofthe estan solution = 750 mL = 22 1 =34L mole of solute
vol. of solution in L
2 15.575/365
3/4
Molarity of solution =
=057M
19. (i)
CH.NH, cH,-NcHyr
cen CBC)
Beneylamine
(i) Primary amine and formic acd are formed.
R-X + AgCN 25 rnc HOH
lees Allyl isocyanide
RNH, + HCOOH <—J
Amine Formicacid
20. (i) The reaction between H, and O, does not take
place at room temperature because activation energy for the
reaction is very high at room temperature.
(ii) According to Arrhenius equation, k= Ae™®!*7,
at higher temperature, average energy of the reactant
‘molecules is greater. Hence, large fraction of coliding particles
‘can cross the energy barrier which leads to a faster rate.
21. (a) [CuCl]? has the square planar geometry.
a sw
Cu: [NINN] |
oe: RNTNINT
(cuc,?:[N TN]
(©) [Ag(NH,),]C1 is colourless because there is no unpaired
clectron in its d-orbitals hence, no d—d transition is possible.
“ Pas
NINTNTNIN) [1
Ast: [NINININIA
AB:
[agovtt).1: [AN]
‘OR
‘On mixing FeSO, and (NH,),SO, in 1:1 molar ratio, a double
salt, FeSO,,(NH,);SO,.6H,0 (Mohr’s salt) is formed which
‘on jonisation gives all constituent ions. Thus, it gives the
test of Fe** ions.
When CuSO, solution and aqueous ammonia are mixed in
1:4 molar ratio, a complex salt, {oun S04 nies
This complex compound on ionisation gives at?
‘and SO?" ions and not Cu" ions. Due to absence of free Cu?
ions, it does not give the test of Cu” ions.
Seem
22, (i) The formation of cyanohydrin involves the
nucleophilic attack by CN" fon on the carbonyl carbon. The
presence of three methyl groups in trimethylcyclohexanone
Jowers the positive charge on the carbonyl carbon, leading
to the decreased nucleophilic attack.
(ii) Ketones are less reactive than aldehydes towards
nucleophilic addition reactions because the two electron
releasing alkyl groups increase the electron density on
the carbonyl carbon and make it less susceptible to
‘nucleophilic attack. a
R
Sexo *c=0
RY sone A idehyde
‘Also, the two bulkier alkyl groups hinder the approach of the
nucleophile to the carbonyl carbon.
9
I
(ii) Benzamide, ©re '— NH, and methyl benzoate,
9
Op E-oct,canberpesenedy general formal
as follows.
oe
eA
‘The ease of nucleophilic attack (as by H,O during hydrolysis)
‘on the carbonyl carbon depends upon the electronegativity of
the group G. The — OCH, group is more electronegative than
the -NH, group. So, the nucleophilic attack on the carbonyl
carbon becomes more favourable in methyl benzoate than
in benzamide. As a result, methyl benzoate undergoes
hydrolysis more easly than benzamide.
23, (a i) Reimer-Tiemann reaction :
(ii) Friedel-Crafts alkylation
OH
OH OH
-CH;
O scr, ME, A Os 5
cea
CH; (Minor)
pees
ae
H (Major)
ob) w) eed db
Class 12 OH
COOH
w +
ococH,
COOH + CH,COOH
‘CH,CON Ht
cH,cCo~
Aspirin
(©) i) The solubility of alcohols in water is due to their
ability to form hydrogen bonds with water molecules.
Hydrocarbons cannot form such hydrogen bonds, hence
they are insoluble in water.
(i) Weknow that the electron withdrawing groups enhance
the acidic character of phenols because they help in the
stabilisation of phenoxide ion by dispersing negative charge.
Nitro group is an electron withdrawing group whereas
methoxy group is electron donating group, thus destabilises
the phenoxide ion by intensifying the negative charge. Thus,
o-nitrophenol is more acidic than o-methoxyphenol.
HH 1H
NO, OCH,
>
e-Nitrophenol o-Matborypenol
24. (i) The first compound is a 2° alkyl halide while all
others are 3° alkyl halide. Since 3° alkyl halides are more
reactive than 2° alkyl halides in Sy1 reaction, therefore, first
compound is the least reactive. Further reactivity increases in
the order: chloride < bromide < iodide. Thus, the increasing
order of reactivity in Sy reactions is
@ ) (i) The given reaction is
Cu + 26 Cu
mle 2a
1 2moles of electrons are needed for reduction of 1 mole
of Cu to Cu,
2 moles of electrons = 2 Faraday = 2 x 96500 coulombs
= 1.93 x 10° coulombs
(i) “The given reaction is
Mai 8H" +5 Mal 484,09 z+ Simole electrons are needed for reduction of | mole of
MnO,” toMn?*,
5 mole of electrons = 5 Faradays
= 5 x 96500 coulombs
= 4.825 x 108 coulombs
29, (a) todo testis given by the organic compounds
OH
q i
having CHy—C— or CH,—CH— group.
Gua GH + Isopropyl alcohol
CH,
CH,CH,CHO : Propionaldehyde
‘Therefore, isopropyl alcohol will give positive iodoform test.
OR
Given reagents indicate the presence of -COCH, group in
the starting compound A. Further, since the COOH group
introduced in B due to iodoform reaction is absent in the
final product, B should be a B-keto acid.
RSP
0 ‘COOH ont
ss "ale compat CHO) undergoes iodoform test,
it must be CH,COCH, (propanone). Further, the compound
‘B’ obtained from ‘A’ has three times more the number of
‘carbon atoms as in ‘A’ (propanone), ‘B’ must be phorone,
ie, 2, 6-dimethyl-2, 5-heptadien-4-one.
(CH,),C=0 + H,CCOCH, + O=C(CH,),
‘A. propanone (3 molecules)
HD, (cH,),c=cHCOCH=C(CH,),
a eT
9
b
© ‘OH 288s bin SoH
Brketo Acid
wasted +CHl;
© @
30, (a) Fora first order reaction :
(b) For a first order reaction,
ti = RAIS = . Thus ty +
is independent of initial tun
concentration. Hence plot of ty.
¥%s[A]p will be a horizontal line,
Tale
ey
(c). Halflife(t,.) ofa first order reaction is given as:
typ x23 20693. 9995
eR “70x10
OR
Let the concentrations of the reactant after 10 min and
20min be C, and C, respectively.
2s Rateafter 10 min = kC, = 0.04
and rate after 20 min = kC, = 0.03
G4
qQ3
Let the reaction starts after 10 minutes.
2303) 4
k 2a 2
8.0 85
4 0.6932 _ 0.6932
Ete
= 24.086 min
0.02878
31. (a) As amino acids have both acidic (carboxy! group)
and basic groups (amino group) in the same molecule, they
react with both acids and bases. Hence, they show amphoteric
behaviour.
(b) Vitamin Cis soluble in water and regularly excreted in
urine and hence cannot be stored in body.
(©). Sucrose isa disaccharide and its two monosaccharides,
are held together by a glycosidic linkage. Since the reducing
sroups of glucose and fructose are involved in glycosidic
bond formation, therefore, sucrose is a non-reducing sugar.
(@) Deficiency of Vitamin C causes bleeding of gums.
(©). Starchisapolymer ofa-glucose that has two components,
namely amylose and amylopectin.
(6) Glucose and fructose are the products of hydrolysis of
sucrose as follows:
Cahn + Hy OES CgH,,0 + CgHy20,
Glucose” Fructose
(8) Mahtoseis disaccharide as it consists of two oL-D-glucose
units,
32. (a) (i) Zn** ion has completely filled d-subshell and nod-d
transition is possible. So zinc salts are white.
Configuration of Cu’* is [Ar]3d’. It has partly filled
d-subshell and hence itis coloured due to d-d transition,
(ii) As the atomic number increases each succeeding.
clement contains one more electron in the 4f-orbital and
‘one extra proton in the nucleus. The 4f-clectrons are rather
ineffective in screening the outer electrons from the charge
‘of nucleus. As a result there is a gradual increase in the
‘nuclear attraction for the outer electrons. Consequently the
atomic size gradually decreases. This is called lanthanoid
contraction
Class 12
— (&) (i) Sc** has d° configuration, no d-d transitions
are possible. So, all scandium salts are white.
(ii) The bivalent ion Mn?* ((Ar] 3c°) has stable half filled
configuration. So, the third ionisation energy of manganese
is unexpectedly high.
(©) Compounds having ligand capable of n-acceptor
character in addition to the o-bonding show very low
oxidation state, e.g., CO, NO.
OR
(a) All transition elements except the first and the last
member in each series show a large number of variable
oxidation states. This is because difference of energy in the
(n-1) and ns-orbitals is very litle, Hence electrons from
both the energy levels can be used for bond formation.
(b) Transition metals form a number of interstitial
compounds in which small atoms such as H, C, B and N
‘occupy the empty spaces in their latices. These compounds
are hard and rigid eg. steel and cast iron, the interstitial
compounds of iron and carbon are hard and extensively used
in industry.
(©) Ce (II) has outer configuration 4f15°6s?. It easily
loses an electron to acquire the configuration 4f° and forms
‘Ce(IV). In fact, this isthe only (+1V) lanthanoid which exists
in solution.
(@) (i) Electronic configuration of ,.Mn?* is [Ar] 34° 4s
whereas that of »;Mn°* is [Ar] 3d* 4s°. As half filled orbital
‘are more stable, Mn?* compounds are more stable than Mn**.
The electronic configuration of ygFe"*is [Ar] 3d® 4s and that
of agFe™* is [Ar] 3 4°
So, Fe°* is more stable than Fe** due to stable configuration.
(i) When the pH of the solution of potassium dichromate is
decreased, the colour of the solution changes from yellow to
‘orange due to the conversion of CrO}- ions into Cr,03" ions.
2CrOy + 2H" = CO} +H,0
Yalow! one,
33. (a) (i) CaCl, — Ca + 2c
on, CaP +26 —> Ca
40 g of calcium needs 2 mole of electrons =2F
20 g of calcium needs = 1F
(ui) A1,0,—+ 2AP* + 307°
on APT+3e —> Al
3mole 1 mole (27 —)
27 gof aluminium needs 3 moles of electrons = 3F
3x 40.0
-, 40.0 of aluminium needs Fo444F
(b) (The charge carried by one mole of electrons is called
‘one Faraday. (1 F = 96500 coulombs)
(ii) Given, pH = 10, B=?
Using Nernst equation for hydrogen electrode
or =~ 0.0591 x 10 = ~0.591 volt
OR
(a) The given cell may be represented as :
Cay] Cu?* |] CL,
Ecq=E°, -E°g = (+1.36V)-(+0.34V) = L02V
(0) AG°=-nFE*=-2x96500Cx1.02V =~ 196.86 k}
0.0591 6k
”
21.02
0.0591
Fa
K =antilog = antilog (34.51)
K=3.236x 10
(©) The given cell may be represented as
PtH, (1 atm) | H* (pH = 2) || H* (pH = 1) | H, (1 atm)
(HY
‘sing formula, Eaag = 295" fg! ke
i,
of 0.16 V = 0.0591 [log [H"], ~ log (H*},}
of, 0.16 V = 0.0591 [pH - pH,J or,
0.16 V = 0.0591 [pH ~ 1]
of, pH, =2.70+1=3.70
00
Chemistry =
1. Ws cH,cHO EAE cy coon
CH,COCH, « (CHjCOO),Ca
2 (€): More the number of methyl groups (electron
releasing groups) lesser will be the acidity. Hence, the
reactivity towards sodium metal will be 3° < 2° < 1°
3% @)
40
5. (@): For isotonic solution, m, =m,
cor C, = C; (At same temperature)
Concentration of glucose solution (C;) = 005M
cxor,
Concentration of another solution (C;) =
Ww, = mass of compound = 6 g
1m, = molecular mass of compound = x
cy
2 Molecular formula = (CH,O) x 4= C,H,0,
cH,
CyiFecty Nwether,
+ -O™O esr
7. (+ 24-DNP test is ca by both stipes and
ketones
Fehling’s, Tollens’ and Cannizzaro reactior
aldehydes only.
8 (a): The number of reacting species (atoms, ions or
molecules) taking part in an elementary reaction is called
molecularity and it has no influence on the rate of reaction.
9. (©): CHyNH) on reaction with nitrous acid releases
N; gas, not NO; gas.
10. (a): ATy= iKjx m= 2 x 1.86 x 0.5 = 186°C
T=T-a 1.86°C
11. (6) : Thetwo.cyclichemiacetal forms of monosaccharide
‘which differ only in the configuration of the hydroxyl group
at C-1 are anomers.
E,
rina
Equating the above equation with straight line graph,
yemxte
(i) Intercept
(i) Slope = =
shown by
12. (€): Ink
13. (€): Thetwo strands are complementary to each other
because hydrogen bonds are formed between specific pairs
ofbases
14, (a): Corrosion is the process of change of metal surface
{nto sats ike oxides, sulphides, carbonates, etc. due to attack
cof atmospheric gases
18. (@)
16, (a): [Se(H,0)¢]°* has no unpaired electron in its
dd subshell and thus d - d transition is not possible whereas
(TI(H,0),]°* has one unpaired electron in its d-subshell
‘hich gives rise to dd transition to impart colour.
17. Glucose was assigned the structure on the basis of
following evidences
(@) On prolonged heating with HI, it forms n-hexane
suggesting that all the six carbon atoms are linked in a straight
hain,
(b)_ Glucose reacts with hydroxylamine to form an oximeand
adds a molecule of hydrogen cyanide to give cyanohydrin. It
confirms the presence of a >C=O group in glucose.
(©) Glucose gets oxidised to six carbon carboxylic acid
(gluconicacid) on reaction with a mild oxidising agent which
shows ithas aldehyde group.
(@)_ Formation of pentaacetate confirms presence of five
~OH groups on different carbon atoms.
CONH,
Gud
Benzamide
osc
NaNO,+ HCE
‘dai
I N3cl-
© ®
Todobenzene Benzene diazonium
chloride
(ii) ‘The more electron donating group present in coupling
compound, the faster will be coupling.
‘As electron donating power isin the order :
—CH,>—G>—No,
So, order of reactivity towards coupling reaction :
I> I>
5 Bi
19. (i) 2CH,MgBr 4h, (CH,),cd+ 2Mg7
cy Sel
(CHiy),C4 + 2CgHsCOCI > 2¢4H1,COCH, + CdCl,
) (B)
Class 12 (ji). The reaction is an example of Rosenmund reduction
in which an acid chloride is reduced into an aldehyde.
‘Therefore, X is CgHsCH,COCL.
CH,COC|
Cf ma?
0
20, (a) ELOH/H,O being more polar than EtOH facilitates
ionization of (CH,),CBr and hence reaction (I) occurs faster
than reaction (11).
(b) (CHs),CHS" being bigger in size than CHS” causes
steric hindrance and hence reaction (I) proceeds faster than
reaction (II).
CH,CHO
+H
OR
‘Thionyl chloride is preferred because other two products are
cescapable gases. Hence, the reaction gives pure alkyl halide.
R—OH + SOC —> R—C1+ 50,1 + HAT
: 98
21. Given: p= (= |p
ven: ps= (2p
1m
Paps) m4 Pm Ps te
PP’ Ps "a Ps my
Paps Wa Ma M1099, Ma
Ps | Mg Wy MyxWq, 1000
‘P°—(98/100) p° 18
Coanooyg® = MMY™ Toop
+ Molality = —22°__ 1000 1.133 mot kg!
10x 28 pe 18
100°
22, (i) Phenoxide ion has the following resonating
structures:
ey © 9 o fo
Badge OL
9 ay am wo
Carboxylate ion has the following resonance structures.
Bare af a]
‘o- So ~
(ii) Phenoxide ion is a resonance hybrid of structures
Tito V, where each structure has a contribution of 20% in
the resonance hybrid. On the other hand, each of the two
Contributing structures of carboxylate ion contribute 50%
towards the resonance hybrid, Therefore, the carboxylate ion
Chomistry
tends to be more stable than the phenoxide ion and hence
has higher acidity.
(iil) The negative charge rests on the electronegative O
atom in carboxylate ion. The presence of negative charge on
an electronegative atom makes the ion more stable. For the
same reason RCOO™ is more stable than the phenoxide ion
where the carbon has negative charge on it. For the above
two reasons carboxylate ion is mote stable and has higher
acidity than phenol.
23, (a) The driving force of osmosis is known as osmotic
pressure. It is the difference in the pressure between the
solution and the solvent system or it is the excess pressure
which must be applied to a solution in order to prevent
flow of solvent into the solution through semi permeable
membrane.
‘Osmotic pressure (m) = par '=CRT
(b) Osmotic pressure, x = (500/76) atm
Temperature, T'= (27 + 273) = 300K
Mass of solute, w = 4 g
‘Volume of solution, V = 100.cm? = 0.1 L
R= 0.0821 Latm K* mol
We know, nV = RT
M
pra 4%0.0821x 300
mv (500/76) 0.1
24, (a) Aromatic 1° amines cannot be prepared by
Gabriel phthalimide reaction because aryl halides do not
undergo nucleophilic substitution reactions with potassium
phthalimide under mild conditions.
(b) (CH;),NH is most basic amongst the given amines.
‘Thus, its most reactive amine towards HCl.
g/mol = 149.7 g/mol
25. (i) Zo platy
Heirons low fom Zn -+ Ag
(ii) Agacts as cathode, because at Ag plate reduction of Ag*
fons takes place,
(til) Cell will stop functioning since the movement of ions
is stopped.
(iv) The cell will stop functioning when Ey = 0.
(¥) As the reaction proceeds concentration of Zn*
increases and concentration of Ag* decreases.
(vi) The concentration of Zn** and Ag* will not change after
the reaction ceases,
26. (a) Actually, glucose exists in the cyclic hemiacetal
form with only a small amount (< 0,05%) of the open chain
form. Since, the concentration of the open chain form is, ow and its reaction with 2,4-DNP is reversible, therefore,
formation of 2,4-DNP derivative cannot disturb the
‘equilibrium to regenerate more ofthe open chain form from
the cyclic hemiacetal form and hence, doesnot give this test.
(b)_ The two strands in DNA molecule are held together
by the hydrogen bonds between purine base of one strand
and pyrimidine base of the other and vice versa, Because of
different sizes and geometries of the bases, the only possible
pairing in DNA are G (guanine) and C (cytosine) through
three H-bonds, ie, (C = G) and between A (adenine) and
T (thymine) through two H-bonds (ie, A =T). Due to this
base-pairing principle, the sequence of bases in one strand
automatically fies the sequence of bases inthe other strand,
‘Thus, the two strands are complementary and not identical
(©) The basic structural difference between starch and
cellulose is of linkage between the glucose units. In starch,
there is a-D-glycosidic linkage. Both the components,
of starch-amylose and amylopectin are polymers of
D-glucose.
On the other hand, cellulose is a linear polymer of
B-D-glucose in which C, of one glucose unit is connected to
C, of the other through B-D-glycosidic linkage.
27, (a) Allare derivatives of p-xylene. (II) has maximum
melting point since itis symmetrical and it fits into crystal
lattice more easily than others and force of attraction is larger,
thus maximum melting point.
(@) As benzyl carbocation, Oa, is resonance
stabilised thus, II undergoes faster Sy1 reaction.
28. (a) The configuration 4f'5d'6s? corresponds to
CelZ = 58).
It exhibits oxidation states Ce”* (4f?), Ce?"(4f!) and Ce
of)
‘The configuration 4f75d°6s" corresponds to Eu (Z = 63).
exhibits oxidation states Eu’*(4f7) and Eu* (4f*).
(b) In the begining when electrons start occupying 5f
orbitals, they will penetrate less into the inner core of
electrons. 5f electrons will be more effectively shielded
from nuclear charge than 4f electrons of corresponding,
lanthanoids, Therefore, outer electrons are less firmly held
and they are available for bonding in actinoids. Hence Th,
a and U have lower ionisation enthalpies.
(© In the first row of transition elements the higher
oxidation state increases with increase in atomic number,
reaches a maximum in the middle and then starts decreasing,
For example, manganese shows the oxidation state of +7. In
general the minimum oxidation state shown by any transition
element is equal to the number of ns-electrons, For the first
five members of transition series the highest oxidation state is
equal to the sum of ns and (n ~ 1)d electrons, For remaining
e162
five elements the maximum oxidation state is not related
to the electronic configuration. Except scandium, the most
‘common oxidation state is +2. The most common oxidation
states of transition elements differ from each other by unity,
29, (a) Fey) + 20Hjaq) —P FeOyy + HzOq + 2e™ (anode)
OR
Exar = Engh ~ Beg = 0.40 -(-0.87) = 1.27 V
(b)_ It does not depend on concentration of OH" ions,
(©). Electrical energy, AG* = ~nFE%qy = ~2 x 96500 x 1.27
= -2.45 x 108 J mol”! = -245 kJ mol"!
30, (a) Europium (Eu) is well known to exhibit +2 oxidation
state due to its half-filed f orbital in +2 oxidation state,
(0) Ce has the tendency of attaining +3 oxidation stateby
accepting one electron and hence it is used as an oxidising
agent in volumetric analysis.
(© (Lanthanum and all the lanthanoids predominantly
show +3 oxidation state. However, some of the lanthanoids
also show +2 and +4 oxidation states in solution or in solid
‘compounds. This irregularity arises mainly due to attainment
of stable empty (4/°), half-filled (4f7) and fully filled (4f")
‘sub shell.
eg, Cel: 4f°, Butt: 4f7
Tosa? Oe ag
ii) Lanthanoids showing +4 oxidation state are sgCe, s9Pr,
@sTband geDy.
OR
(OAs the size decreases covalent character increases.
‘Therefore La,0s is more ionic and Lu,O, is more covalent.
(i) Radii of 4d and Sd elements will be almost same. Itis
associated with intervention of the 4f orbitals which must
be filled before 5d series of elements begins. The filling off
before Sd results in lanthanoids contraction hence 4d and 54
series have almost same size.
31. (a) Starting material used in industrial preparation of
pheno is isopropyl benzene or cumene.
so
CH;CH CH,;-C-0-O-H OH
6,
1 BY,
nk ae +CH,COCH,
Cone Phenol
(&) Bromination of phenol
(@) Inaqueous medium,
‘OH OH
Be
+38 5544)
Br.
24,6 -Tibromophenol (ii) In non-aqueous medium,
(©) Inbromination of benzene, Lewis acd is used to polarise
Bry to form electrophile Br*, Lewis acid is not required for
bromination of phenol. In case of phenol polarisation of
bromine takes place even in absence of Lewis acid as the
(O-atom of phenol itself polarises Br, molecule to form Br*.
Also, +R-effect of —OH group makes phenol highly activated
towards electrophilic substitution reaction.
(4) Ethanol has higher boiling point because of strong
intermolecular hydrogen bonding whereas in methaxymethane,
molecules are held by dipole-dipole interaction.
(e) When one alkyl group is a tertiary group, the halide
formed is tertiary halide.
In step II, the departure of leaving group (CH,—OH) creates
a more stable carbocation (3*) and the reaction follows Sy1
mechanism.
CH; oe
ca ¢ bc, ciy-¢ + CHOH
Gat oH,
Gas 5
cae +r Bs cen
CH, cH,
(£) Mechanism : The formation of ether is nucleophilic
bimolecular reaction.
Hq
Step: CHy—CH,— Q-H + H'—>CHy~ cH, SH
a
Step IL Cry cH Qn $A
canary lcs,
H
Step I: CHy—CH,—4Y— CH) — Cs >
(CHs—CH,—O- CH) — CH +H"
(®) Acid dehydration of 2° and 3* alcohols give alkenes
rather than ethers,
Due to steric hindrance the nucleophilic attackby the alcohol
‘molecule on the protonated alcohol molecule does not occur
‘The protonated 2° and 3° alcohols lose water molecules to
form stable 2° and 3° carbocations.
32, (a) k= Ae EAT
In the absence of catalyst, ky = e752"
In the presence of catalyst, k= Ae 7"
Chemistry
ky _ T5207
-2506/RT
ae 28008
ky ear
k
log = 43920 = p= 240
‘Thus, rate of reaction increases by 24660 times.
(b) (Change in concentration of reactants or products
per unit time is known as rate of reaction.
(ii) The minimum extra energy which must be supplied to
the reactants to enable them to cross over the energy barrier
between reactants and products is called activation energy.
‘Activation energy = (Threshold energy-average energy of
‘Teactant).
(©) Given: Rate = K{PHs], fy = 379
6) t= Pwhen (R}=21Rly
Using formula BG)
4
Jutta
Again ¢= mx yp = 2379827588
w #605(1 mind). RE
is =2:203 jog, lo
sing formula k=—— logie Tet
209
379s 60s {R]
(a) Time required for the completion of a zero order
racine
(b) Rate constant is independent of the concentration of
the reactants,
(©) Fora first order reaction, rate of reaction is directly
Proportional tothe concentration of the reactant.
Rate=kC Hence, graph between rate of reaction (b)_ Structure of cis-[Co(NHy),Cl]”
and change in concentration will acl a cl +
be straight line passing through the dr BN A
arigia. Co.
(@) Given: Rate = k[A}*1B] S of AS
Unit of rate = mol L*! 5"! aw LON
,
Unit of rate constant, k= —Rate— iybrdiation 2p")
{Cone.}? OR
mols gayagt (4) [Berg s Feb adh
or k=
(mol 174 aitle
33. (@) [CHCO)sI”: stele
aTtT tT ty
Number of unpaired electrons = 5
‘Magnetic moment = ./5(5+2) = 5.92 B.M.
UFe(H,0)¢]** : Fe** = 3°
us [s alt
wATA 4,
Number of unpaired electrons = 4
‘Magnetic moment = /4(4+2) = 4.9 BM.
(>) Complexes in which metal is bound to only one kind
of donor groups are known as homoleptic complexes. eg.
[Co(H,)*.
‘Complexes in which metal is bound to more than one kind
of donor groups is called heteroleptic complexes.
eg. [Co(NH,) Ch”
©60
Ea) Class 12
/ 1, (d) :In [Cu(NH;),]SOq, primary valency is 2 and
secondary valency is 4.
2, (b): (ili) and (jv) will form ideal solutions hence do
not form azcotropes. Azeotropes have same composition in
liquid and vapour form when distilled.
@
5. (b)
6. (d): Electrode M is inert electrode like Pt metal with
coating of fine powder of Pt metal,
7. (d): The number of moles of ions produced by 1 mol
of ionic compound = i
x Kym
0.00732 = i x 1.86 x 0.002
8 (b): When the transition metals are in their highest
oxidation state, they no longer have tendency to give away
electrons, thus they are not basic but show acidic character
and form anionic complexes.
isomeric forms and one of the geometrical isomers exhibit
enantiomers.
Beet
WE cy ee asa
_Conc HNO ,
Cone oa?
NO;
(2.4 6 initropbenod)
Chemistry
13, (4): In strongly acidic medium, aniline gets protonated
and so the lone pair of electrons is not available to produce
++Bor +M effects, On the other hand, the- NH, group exerts
strong -I effect and thus it causes the deactivation of the ring
iu
oO:
14. 0)
15. (6): Nitro group is an electron withdrawing group
which leads to weakening of C— Cl bond, hence making it
‘easier to replace the -Cl group.
16. (@)
ak KMn0,
17, (a) CH;—CH,—CH,OH +>
pel Cy CH,COOH + H,0
Propanoie acid
OH ONa
CHO
(b) + CHCl, 22 MOH,
Phenol {= ya
OH
CHO
Salicylaldehyde
OR
Williamson's synthesis cannot be employed for tertiary alky
halides as they yield alkenes instead of ethers. The reaction of
(CH;ONa with (CH,)sCBr gives exclusively 2-methylpropene.
s
CH;—¢—Br + Na $-CH,—> CH C=CH, +NaBr
cH, cH,
Aryl halides and vinyl halides cannot be used as substrates
because of their low reactivity in nucleophilic substitution
reactions.
18, Ligands which can coordinate with the central metal
atom or ion through two donor atoms are known as bidentate
ligands. Examples of bidentate ligands are =
eee o=c—o" yr
1 o=cl
HN Ny o=C-0- No
en die uals ance Caras on
19. Molar mass of heptane (CjHy.) = 100 g mol"?
Molar mass of octane (CyHy,) = 114 g mol” Number of moles of heptane = —7©98 _ - 9.26mot
100g mol”
Number of moles of octane = 3598 «9 5) mol
114g mol
0.26
0.26 + 0.31
x (octane) = 1 - 0.456 = 0.544
p(heptane) = 0.456 x 105.2 kPa = 47.97 kPa
ploctane) = 0.544 x 46.8 kPs 15.46 kPa
Pyoaat = 47.97 + 25.46 = 73.43 kPa
20, Since the molecular formula of D is CHO», thus, Dis
HCOOH (formic acid). Dis obtained by the acidification of
C, 80, Cis sodium formate (HCOONa).
Thus, A must be formaldehyde (as it undergoes Cannizzaro
reaction with a strong base),
HCHO", cHOH +
x (heptane) = 456
HCOONa
) @)
Formaldehyde Methanol
lca
——
HCHO.
Formaldehyde
a ©)
‘Thus, A = Formaldehyde (HCHO), B= Methanol (CH,OH)
(C= Sodium formate (HCOONa), D = Formic acid (HCOOH)
21. CH,—CH,—CH=CH, + HA»
Sec at
a
2-Chlorobitane
(b)_ The structure of 4-chloropentan-2-one is
aa al
5
x, cut, c-tu,
22. (a) Stepheris method:
‘An alkyl cyanide is dissolved in ether, or better, in ethyl
formate or ethyl acetate and reduced with stannous chloride
and hydrochloric acid, and then steam distiled.
RCN + SnCl, + HC1—+ RCH=NH ——> RCHO
() ().CH,CHO EONS 5 cH.cH, + H,0
This reaction is known as Clemmensen reduction reaction,
(ii) GHCHO + 4NH, > (CH,)
Actaldchyée :
cx,coon SEH
[0] Ca(OH),
w cacno—>cricoon >
‘Acetaldchyde t
Dry dition yy Hh
(CH,COO),Ca rarer ‘C-CH,
gS OMEBr ] ot
Mab te,
or iO |CH-CH—CH,
HH oO
ol
I cu I
CH=CH CH, 37g CH-C- CH,
‘Acetone
23, (a) Given: xy = 2.71 V
For the reaction, Mg) + Cufzg) > MB) + Cu
n=2,A,6°
Using formula, 3,G° = ~ nFEZa,
A,G* =-2 x 96500 Cmol"' «2.71 V
or A,G* = -523030} mol” = -523.03 kJ mol”
(&) Alternating current is used to prevent electrolysis
so that concentration of ions in the solution rem:
constant,
CHy CH;
Kou
i |
4 () CECH, “_ Cryer
Br OH
(a) 2-Meth 1-2-0
2-Bromo-2-methylpropane epeoren
Compound (A) being a tertiary halide, undergoes Sy1
substitution hence, the rate of reaction depends on
concentration of one reactant only.
KOH
GucHc—cHy a“ cHCHEH—cH
Br
@).
2-Bromobutane
Compound (B) undergoes Sy2 nucleophilic substitution
which is bimolecular and rate depends upon the
‘concentration of both reactants.
(i) Compound (B) will be converted to product with
inverted configuration.
25. (a) The order of a reaction is the sum of the powers to
‘which the concentration (or pressure) terms are raised in the
rate law expression.
(b)_ The given data is
Sin
05 mol L* "40,25 mol Lt 0,125 moll"
Halflife period is independent of initial concentration of the
reactant, hence reaction is of first order.
For first order reaction
j= 2:68 _ 0.693
a Smin
26, (a) (i) NaBr + conc. H,S0,—» NaHSO, + HBr
(CH CH,CH,OH + HBr—> CH,CH,CH,Br + H;0
(Gi) Phenol is acidic in nature hence it does not react with HB
(b) Bronsted acids are proton donors. Since, alcohols and
phenols can donate protons, hence, they are Bronsted acids.
Acids are converted to conjugate bases,
27. (a) ATy= Kym =k,
fs XW, (in kg)
Let molar masses of benzoic acids be My and M'g in acetone
and benzene respectively.
Class 12 41.71.22 1000
‘My x10
2.6%1.22%1000
‘M x10
2.6X1.22%1000 2 344 5 mot!
013x100
(b) Calculated molar mass of benzoic acid (C,H,COOH)
= 72454 12+3241= 122g mol!
In acetone : 0.17 = => My=122 gor!
In benzene : 0.13 =
Ms
vvar't Hoff factor, 1 = Calculated molar mass
Observed molar mass
Inacetone, i = 122/122 = 1
‘Thus, benzoic acid remains as such in acetone.
(i) The virus isa single helix DNA virus.
(Gli) The bases pairs are ATGC and not AUGC 0 itis not a
RNA.
OR
“According to Chargaff's rule, all double helix DNA will
ieee cmceot ofA thd T aswel as G wl be of
same amount as G. If the ratio of A and T or G and C is not
‘maintained then, helix is single stranded.
sn+HCl
BI. (a) CgHsNO, => CoHsNH,
a
Hor &22 conser
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