JEE Advanced 2014 Solved Paper 2014-1

JEE ADVANCED 2014 CHEMISTRY

PAPER - 1
SECTION - I 7. For the reaction
This section contains 10 multiple choice questions. Each question I- + ClO3- + H 2SO4 Cl- + HSO 4- + I 2
has 4 choices (a), (b), (c) and (d) out of which ONLY ONE or
The correct statement(s) in the balanced equation is/are
MORE THAN ONE are correct.
(a) Stoichiometric coefficient of HSO-4 is 6
1. Upon heating with Cu2S, the reagent(s) that give copper
metal is/are (b) Iodide is oxidized
(a) CuFeS2 (b) CuO (c) Sulphur is reduced
(c) Cu2O (d) CuSO4 (d) H2O is one of the products
2. In a galvanic cell, the salt bridge 8. In the reaction shown below, the major product(s) formed is/
(a) Does not participate chemically in the cell reaction are
(b) Stops the diffusion of ions from one electrode to
another NH2
(c) Is necessary for the occurrence of the cell reaction acetic anhydride
(d) Ensures mixing of the two electrolytic solutions Product(s)
NH2 CH2Cl2
3. Hydrogen bonding plays a central role in the following
phenomena Z O
(a) Ice floats in water
(b) Higher Lewis basicity of primary amines than tertiary H
N CH3
amines in aqueous solutions
(c) Formic acid is more acidic than acetic acid O
(d) Dimerisation of acetic acid in benzene (a) + CH3COOH
4. The correct combination of names for isomeric alcohols with NH2
molecular formula C4H10O is/are O
(a) Tert-butanol and 2-methylpropan-2-ol
(b) Tert-butanol and 1, 1-dimethylethan-1-ol NH2
(c) n-butanol and butan-1-ol
(d) Isobutyl alcohol and 2-methylpropan-1-ol H + CH3COOH
5. The reactivity of compound Z with different halogens under (b) N CH3
appropriate conditions is given below: O O

OH mono halo substituted

derivative when X2 = I2 H
N CH3
X2 di halo substituted O
derivative when X2 = Br2
Z C(CH3)3 (c) H + H2O
N CH3
tri halo substituted
derivative when X2 = Cl2 O O

The observed pattern of electrophilic substitution can be

+
explained by NH3CH3COO
(a) The steric effect of the halogen
(b) The steric effect of the tert-butyl group
(c) The electronic effect of the phenolic group (d) H
N CH3
(d) The electronic effect of the tert-butyl group
6. The pair(s) of reagents that yield paramagnetic species is/are O O
(a) Na and excess of NH3
9. An ideal gas in a thermally insulated vessel at internal pressure
(b) K and excess of O2 = P1, volume = V1 and absolute temperature = T1 expands
(c) Cu and dilute HNO3 irreversibly against zero external pressure, as shown in the
(d) O2 and 2-ethylanthraquinol
2-2014 Chemistry
diagram. The final internal pressure, volume and absolute (a) q = 0 (b) T2 = T1
temperature of the gas are P2, V2 and T2, respectively. For (c) P2V2 = P1V1 (d) P2V2g = P1V1g
this expansion,
10. The correct statement(s) for orthoboric acid is/are
(a) It behaves as a weak acid in water due to self ionization.
Pext = 0 (b) Acidity of its aqueous solution increases upon addition
of ethylene glycol
Pext = 0 Irreversible (c) It has a three dimensional structure due to hydrogen
P2, V2, T2 bonding
P1, V1, T1 (d) It is a weak electrolyte in water

Thermal insulation

SECTION - II
This section contains 10 questions. Each question, when worked out will result in one integer from 0 to 9 (both inclusive).
11. The total number of distinct naturally occurring amino acids obtained by complete acidic hydrolysis of the peptide shown
below is
O

O O O H
O H H N
N N N
N N N
N O
CH2 O H O H CH2
H
O

12. MX2 dissociates into M2+ and X ions in an aqueous solution, with a degree of dissociation (a) of 0.5. The ratio of the observed
depression of freezing point of the aqueous solution to the value of the depression of freezing point in the absence of ionic
dissociation is
13. If the value of Avogadro number is 6.023 1023 mol1 and the value of Boltzmann constant is 1.380 1023 J K1, then the number
of significant digits in the calculated value of the universal gas constant is
14. A compound H2X with molar weight of 80g is dissolved in a solvent having density of 0.4 g ml1. Assuming no change in volume
upon dissolution, the molality of a 3.2 molar solution is
1
15. In an atom, the total number of electrons having quantum numbers n = 4, | ml | = 1 and ms = - is
2
16. Consider the following list of reagents:
Acidified K2Cr2O7, alkaline KMnO4, CuSO4, H2O2, Cl2, O3, FeCl3, HNO3 and Na2S2O3.
The total number of reagents that can oxidise aqueous iodide to iodine is
17. A list of species having the formula XZ4 is given below.
XeF4, SF4, SiF4, BF4, BrF4, [Cu(NH3)4]2+, [FeCl4]2, [CoCl4]2 and [PtCl4]2.
Defining shape on the basis of the location of X and Z atoms, the total number of species having a square planar shape is
18. Consider all possible isomeric ketones, including stereoisomers of MW = 100. All these isomers are independently reacted with
NaBH4 (NOTE: stereoisomers are also reacted separately). The total number of ketones that give a racemic product(s) is/are
19. The total number(s) of stable conformers with non-zero dipole moment for the following compound is (are)
Cl
Br CH3

Br Cl
CH3
20. Among PbS, CuS, HgS, MnS, Ag2S, NiS, CoS, Bi2S3 and SnS2, the total number of BLACK coloured sulphides is
JEE Advanced 2014 Solved Paper 2014-3

PAPER - 2
SECTION - I 6. The major product in the following reaction is
This section contains 10 multiple choice questions. Each question O 1. CH3MgBr, dry ether, 0C
has four choices (a), (b), (c) and (d) out of which ONLY ONE Cl 2. aq. acid
option is correct. CH3
1. For the identification of b-naphthol using dye test, it is O
necessary to use
(a) Dichloromethane solution of b-naphthol (a) H3C
(b) Acidic solution of b-naphthol CH3
(c) Neutral solution of b-naphthol
(d) Alkaline solution of b-naphthol OH
2. Assuming 2s-2p mixing is NOT operative, the paramagnetic
species among the following is (b)
(a) Be2 (b) B2 H2C CH3
(c) C2 (d) N2 CH3
3. For the elementary reaction M N, the rate of disappearance
of M increases by a factor of 8 upon doubling the
concentration of M. The order of the reaction with respect to (c)
M is CH2
O
(a) 4 (b) 3
(c) 2 (d) 1
CH3
4. Isomers of hexane, based on their branching, can be divided
into three distinct classes as shown in the figure. (d)
O CH3
and and 7. Hydrogen peroxide in its reaction with KIO4 and NH2OH
respectively, is acting as a
(a) Reducing agent, oxidising agent
(I) (II)
(b) Reducing agent, reducing agent
(c) Oxidising agent, oxidising agent
(d) Oxidising agent, reducing agent
8. The product formed in the reaction of SOCl2 with white
phosphorous is
(III) (a) PCl3 (b) SO2Cl2
The correct order of their boiling point is (c) SCl2 (d) POCl3
(a) I > II > III (b) III > II > I 9. Under ambient conditions, the total number of gases released
(c) II > III > I (d) III > I > II as products in the final step of the reaction scheme shown
5. The acidic hydrolysis of ether (X) shown below is fastest below is
when
Complete
Hydrolysis
XeF6 P + Other product

Acid
OH /H2O
OR OH + ROH

Slow disproportionation
in OH/H2O
(a) One phenyl group is replaced by a methyl group
(b) One phenyl group is replaced by a para-methoxyphenyl
group Products
(c) Two phenyl groups are replaced by two para-
methoxyphenyl groups (a) 0 (b) 1
(d) No structural change is made to X (c) 2 (d) 3
4-2014 Chemistry
10. For the process 13. The product X is
H2O(l) H2O(g) H3CO
at T = 100C and 1 atmosphere pressure, the correct choice is
(a) DSsystem > 0 and DSsurroundings > 0
(b) DSsystem > 0 and DSsurroundings < 0 (a)
(c) DSsystem < 0 and DSsurroundings > 0 H
(d) DSsystem < 0 and DSsurroundings < 0 H
H
SECTION - II
This section contains 3 paragraphs, each describing theory, H
(b)
experiments, data etc. 6 questions related to the three paragraphs
with two questions on each paragraph. Each question has only H3CO
one correct answer among the four given options (a), (b), (c) and CH3CH2O
(d).
Paragraph for Questions 11 and 12 (c)
X and Y are two volatile liquids with molar weights of 10 g mol1
and 40 g mol1 respectively. Two cotton plugs, one soaked in X H H
and the other soaked in Y, are simultaneously placed at the ends H
of a tube of length L = 24 cm, as shown in the figure. The tube is
filled with an inert gas at 1 atmosphere pressure and a temperature
of 300 K. Vapours of X and Y react to form a product which is first (d) H
observed at a distance d cm from the plug soaked in X. Take X and
CH3CH2O
Y to have equal molecular diameters and assume ideal behaviour
for the inert gas and the two vapours. 14. The correct statement with respect to product Y is
(a) It gives a positive Tollens test and is a functional isomer
L = 24 cm of X
(b) It gives a positive Tollens test and is a geometrical
isomer of X
Cotton wool Cotton wool (c) It gives a positive iodoform test and is a functional
soaked in X d Initial formation soaked in Y
of the product isomer of X
(d) It gives a positive iodoform test and is a geometrical
11. The value of d in cm (shown in the figure), as estimated from isomer of X
Grahams law, is
(a) 8 (b) 12 Paragraph For Questions 15 and 16
(c) 16 (d) 20 An aqueous solution of metal ion M1 reacts separately with
12. The experimental value of d is found to be smaller than the reagents Q and R in excess to give tetrahedral and square planar
estimate obtained using Grahams law. This is due to complexes, respectively. An aqueous solution of another metal
(a) Larger mean free path for X as compared to that of Y ion M2 always forms tetrahedral complexes with these reagents.
(b) Larger mean free path for Y as compared to that of X Aqueous solution of M2 on reaction with reagent S gives white
(c) Increased collision frequency of Y with the inert gas as precipitate which dissolves in excess of S. The reactions are
compared to that of X with the inert gas summarized in the scheme given below:
(d) Increased collision frequency of X with the inert gas as Scheme:
compared to that of Y with the inert gas
Q R
Tetrahedral M1 Square planar
Paragraph For Questions 13 and 14 Excess Excess
Schemes 1 and 2 describe sequential transformation of alkynes M
and N. Consider only the major products formed in each step for Q R
both the schemes. Tetrahedral Excess
M2 Excess
Tetrahedral

1. NaNH 2 (excess)
2. CH3CH 2I (1 equivalent) S, stoichiometric amount
H X Scheme-1
3. CH3I (1 equivalent)
R
HO M 4. H2, Lindlars catalyst White precipitate Precipitate
Excess
dissolves
1. NaNH 2 (2 equivalent)
OH 15. M1, Q and R, respectively are
2. Br (a) Zn2+, KCN and HCl (b) Ni2+, HCl and KCN
Y Scheme-2 (c) Cd2+, KCN and HCl (d) Co2+, HCl and KCN
H + 16. Reagent S is
3. H 3O, (mild)
N 4. H2, Pd/C (a) K4[Fe(CN)6] (b) Na2HPO4
5. CrO3 (c) K2CrO4 (d) KOH
JEE Advanced 2014 Solved Paper 2014-5

SECTION - III
This section contains 4 questions, each having two matching lists. Choice for the correct combination of elements from List-I and List-
II are given as options (a), (b), (c) and (d), out of which one is correct.
17. Match each coordination compound in List-I with an appropriate pair of characteristics from List- II and select the correct answer
using the code given below the lists.
{en = H2NCH2CH2NH2; atomic numbers : Ti = 22; Cr = 24; Co = 27; Pt = 78}
List-I List-II
P. [Cr(NH3)4Cl2]Cl 1. Paramagnetic and exhibits ionisation isomerism
Q. [Ti(H2O)5Cl](NO3)2 2. Diamagnetic and exhibits cis-trans isomerism
R. [Pt(en)(NH3)Cl]NO3 3. Paramagnetic and exhibits cis-trans isomerism
S. [Co(NH3)4(NO3)2]NO3 4. Diamagnetic and exhibits ionisation isomerism
Code:
P Q R S
(a) 4 2 3 1
(b) 3 1 4 2
(c) 2 1 3 4
(d) 1 3 4 2
18. Match the orbital overlap figures shown in List-I with the description given in List-II and select the correct answer using the code
given below the lists.
List-I List-II

P. 1. p d p antibonding

Q. 2. d d s bonding

R. 3. p d p bonding

S. 4. d d s antibonding

Code:
P Q R S
(a) 2 1 3 4
(b) 4 3 1 2
(c) 2 3 1 4
(d) 4 1 3 2
19. Different possible thermal decomposition pathways for peroxyesters are shown below. Match each pathway from List-I with an
appropriate structure from List-II and select the correct answer using the code given below the lists.
P
R + RO
CO 2
O
O Q
R + RO R + X + carbonyl compound
R O R
CO 2
(Peroxyester)
R
RCO2 + RO R + X + carbonyl compound
CO 2

S
RCO2 + RO R + R O
CO 2
6-2014 Chemistry
List-I List-II
O
O
P. Pathway 1. C 6H 5CH 2 O CH3

O
O
Q. Pathway 2. C6H5 O CH3

O
O CH3
R. Pathway 3. C6H5CH2 O CH3
CH2C6H5

O
O CH3
S. Pathway 4. C6H5 O CH3
C6H5
Code:
P Q R S
(a) 1 3 4 2
(b) 2 4 3 1
(c) 4 1 2 3
(d) 3 2 1 4
20. Match the four starting materials (P, Q, R, S) given in List-I with the corresponding reaction schemes (I, II, III, IV) provided in
List-II and select the correct answer using the code given below the lists.
List - I List - II
P. H H 1. Scheme I

(i) KMnO4, HO , heat (ii) H, H2O
OH (iii) SOCl2 (iv) NH3
? C7H6N2O3

Q. 2. Scheme II
OH (ii) Sn/HCl (ii) CH3COCl (iii) conc. H2SO4

(iv) HNO3 (v) dil. H2SO4, heat (vi) HO
NO2
? C6H6N2O2

R. 3. Scheme III
(i) red hot iron, 873 K (ii) fuming HNO3, H2SO4, heat
(iii) H2S.NH3 (iv) NaNO2, H2SO4 (v) hydrolysis
NO2
? C6H5NO3

S. 4. Scheme IV
(i) conc. H2SO4, 60C
CH3 (ii) conc. HNO3, conc. H2SO4 (iii) dil. H2SO4, heat
? C6H5NO4

Code:
P Q R S
(a) 1 4 2 3
(b) 3 1 4 2
(c) 3 4 2 1
(d) 4 1 3 2
JEE Advanced 2014 Solved Paper 2014-7

SOLUTIONS
Paper - 1
1. (b, c, d) Cu2S + 2Cu2O 6Cu + SO2 smallest electrophile (Cl2) can attack all the three sites,
Cu2S + 2CuO 4Cu + SO2 viz., a, b and c (most sterically hindered site).
Cu2S + CuSO4 3Cu + 2SO2 OH
2. (a, b) Salt bridge is introduced to keep the solutions of two
electrodes separate, so that the ions in electrodes do a c
not mix freely with each other. Salt bridge stops the
diffusion of ions from one electrode to another. It is C(CH3)3
b
not necessary for occurrence of cell reaction, as we
know that there is no salt bridge in lead accumulator, 6. (a, b, c) Na + NH3 (excess) Dilute solution of Na in liq.
but still reactions take place. NH3 Paramagnetic
3. (a, b, d) In ice, water molecules are excessively H-bonded K + O2 (excess) KO2 (O2 is paramagnetic)
giving a cage-like structure which is lighter than water. Cu + HNO3 (dil.) Cu(NO3)2 + NO
Primary amines are more basic than tertiary amine, (NO is paramagnetic)
because the protonated 1 amines are extensively
2-Ethylanthraquinol + O2
H-bonded and hence more stable than the
corresponding protonated 3 amines. 2-Ethylanthraquinone + H2O2
(H2O2 is diamagnetic)
+ +
gg H+ gg H+
R NH 2
R NH3 ; R 3 N
R 3 NH 7. (a, b, d) Balanced chemical equation is
-1 0
H OH 2 6 I + ClO3- + 6H 2SO 4 Cl - + 6HSO4 - + 3I 2 + 3H 2O
-
+
R N+ H OH 2 > R3NH OH2 gg
8. (a) NH 2 group is acetylated by acetic anhydride in
H OH 2
methylene chloride (solvent). Note that CONH2
More stable Less stable
group does not undergo acetylation because here lone
Acetic acid undergoes dimerisation in benzene. pair of electrons is delocalised.
O H O COCH3
H3C C C CH3 CH 2Cl2
O H O CH2 NH2 + (CH3CO)2O CH2 NH + CH3COOH
4. (a, c, d) Isomeric alcohols with molecular formula C4H10O
are O O
+
C NH2 C NH2
OH
9. (a, b, c) Since the vessel is thermally insulated, q = 0
n-Butanol OH Further since, Pext = 0, so w = 0, hence DU = 0
(Buta-1-ol)
Butan-2-ol
Since DT = 0, T2 = T1, and P2V2 = P1V1
OH However, the process is adiabatic irreversible, so we
OH cant apply P2V2g = P1V1g.
lsobutyl alcohol tert-Butanol 10. (b, d)H3BO3 does not undergo self ionization. However, it
(2-methylpropan-1-ol) (2-methylpropan-2-ol) acts as a weak acid in water (hence it is a weak
electrolyte in water).
5. (a, b, c) OH group is strongly activating and o, p-directing
due to +M effect. Thus positions a, b and c are the H3 BO3 + H 2 O B(OH)4- + H +
sites for attack by an electrophile. However, sites b
Addition of cis-diols (e.g., ethylene glycol) to aqueous
and c are not preferred by bulky electrophile due to
solution of orthoboric acid leads to complex formation,
steric crowding. Thus more bulky electrophile (like I2)
thus acidity of aqueous solution of orthoboric acid is
can attack only site a, which is least sterically hindered,
increased.
a bit smaller electrophile (Br2) can attack at sites a and
also b (relatively less sterically hindered site) and the
8-2014 Chemistry

CH2 OH CH2 O O CH2 F

B(OH)4 + 2 B + 4H2O F
CH2 OH CH2 O O CH2 SiF4 = Si Tetrahedral (sp3)
It arranges to planner sheets due to H-bonding. F F
11. (1) On hydrolysis, the given peptide gives only one
naturally occurring amino acid (glycine). F
F
2+ - BF4 = B Tetrahedral (sp3)
12. (2) MX2 M + 2X
F F
1- a a 2a

obser. depression in f.pt of aq. solution
i= F F
depression of f.p.t. in absence of ionic dissociation
BrF4 = Br Square planar (sp3d2)
1 - a + a + 2a
F F
= = 1 + 2a = 1 + 2 0.5 = 2
1
13. (4) R = NA k 2+
= 6.023 1023 1.380 1023 H3N NH3
[Cu(NH3)4]2+ = Cu
= 8.312 which has 4 significant figures NH3
H3N
14. (8)
Square planar (dsp2)
wt. of solute in 1 L of solution 1000
Molality = wt. of solvent in 1 L of solution mol. wt. of solute 2
Cl
Cl
Calculation of wt. of solvent [FeCl4]2 = Fe Tetrahedral (sp3)
1 mL of solvent = 0.4 g Cl Cl
1000 mL of solvent = 400 g
2
Calculation of wt. of solute Cl
1000 mL of solution contain = 3.2 80 g solute = 256 g Cl
[CoCl4]2 = Co Tetrahedral (sp3)
256 1000
\ Molality = =8 Cl Cl
400 80
2
15. (6) ml = 1 means ml can be +1 and 1. Cl Cl
[PtCl4]2 = Pt Square planar (dsp2)
So, for n = 4, six orbitals are possible and each has 1 Cl Cl
1 18. (5) General molecular formula for ketones is CnH2nO
electron with s = - . So total number of electrons = 6.
2 \ CnH2nO = 100 or 12n + 2n + 16 = 100, n = 6
16. (7) K2Cr2O7 + KI + H2SO4 K2SO4 + Cr2(SO4)3 Possible isomeric ketones with 6 carbon atoms are
+ I2 + H2O O O
2CuSO4 + KI 2CuI + I2 + 2K2SO4 CH3CH2CH2CH2CCH3 CH3CH2CH2CCH2CH3
H2O2 + 2KI 2KOH + I2
Cl2 + 2KI 2KCl + I2 (I) (II)
O
O3 + H2O + 2KI 2KOH + O2 + I2
FeCl3 + 2KI 2KCl + FeCl2 + I2 CH3 O CH3CHCH2CCH3
HNO3 + KI KNO3 + I2 + NO *
CH3CH2CHCCH3 CH3
(III) (IV)
F F CH3 O
17. (4) XeF4 = Xe Square planar (sp3d2)
F F CH3 O CH3C CCH3
CH3CHCCH2CH3 CH3

F (V) (VI)
F Note that only isomer III has a chiral carbon so on
SF4 = S See-saw (sp3d) reduction with NaBH4 it will give diastereomeric
F alcohols, while all other five isomers will give racemic
F mixture.
JEE Advanced 2014 Solved Paper 2014-9

19. (3) Cl CH3

Br CH3 Cl Br

Br Cl Br Cl
CH3 CH3

Following three conformers (with m 0) are possible

CH3 CH3 CH3

Br Cl Br Cl CH3
CH3

Br Cl Br Cl Br Cl
CH3 Cl Br

20. (7) All except MnS (buff coloured) and SnS2 (yellow) are black in colour.

Paper - 2
1. (d) In dye test, phenolic OH group is converted to 7. (a) KIO4 + H2O2 KIO3 + H2O + O2
O which activates the ring towards electrophilic Thus H2O2 is acting as a reducing agent
aromatic substitution 2NH2OH + H2O2 N2 + 4H2O
2. (c) Be2 = s1s2 s* 1s2 s2s2 s*2s2 Here H2O2 is acting as an oxidising agent
B2 = s1s2 s* 1s2 s2s2 s* 2s2 s2pz2
8. (a) P4 + 8SOCl 2 4PCl3 + 4SO 2 + 2S2 Cl 2
C2 = s1s2 s*1s2 s2s2 s* 2s2 s2pz2 p2px1 p2py1 white phosphorus
N2 = s1s2 s*1s2 s2s2 s*2s2 s2pz2 p2px2 p2py2
9. (c)
Thus only C2 will be paramagnetic
3. (b) M N Complete
XeF6 XeO3 + H2F2
r = k [M]x Hydrolysis
(P)
when M = 2M; r = 8r, thus OH /H2O
8r = k[2M]x OH /H2O
HXeO4 XeO64 + Xe(g)
(Slow disproportionat
8 = (2)x (Q)
ion) + H2O + O2(g)
x= 3
4. (b) Greater the extent of branching, lesser is the boiling 10. (b) Given conditions are boiling conditions for water due
point of the hydrocarbon, so order of b.p is III > II > I. to which
5. (c) The given reaction proceeds through SN1 mechanism DStotal = 0
which involves carbocation as intermediate. DSsystem + DSsurroundings = 0
DSsystem = DSsurroundings
H+ +
For process, DSsystem > 0


Ph 3C O R Ph3 C+ + ROH
Ph3 C O R
H DSsurroundings < 0
Thus, higher the stability of the carbocation, greater 11. (c) According to Grahams law of diffusion, if all conditions
will be reactivity. Presence of electron releasing group are identical,
(e.g., OCH3) in p-position of the phenyl group will
disperse the positive charge of the carbocation by +M 1
r=
effect, hence stabilizes the carbocation. M
6. (d) As in this question, all conditions are identical for X
(i) CH 3 MgBr and Y, then
(ii) aq. acid
O My
Cl O Cl O rx
=
ry Mx
10-2014 Chemistry
(d = diameter of molecule, p = pressure inside the vessel)
d 40
= =2 Since d and p are same for both gases, ideally their l
24 - d 10
are same. Hence it must be the higher drift speed of X
d = 48 2d due to which it is facing more collisions per second
3d = 48 with the inert gas in comparison to gas Y. Hence X
d = 16 cm faces more resistance from inert gas than Y and hence
covers lesser distance than that predicted by Grahams
12. (d) The general formula of mean free path (l) is
law.
RT
l=
2 pd 2 N A p

CH 3CH2 I
NaNH2 + C Na+
H Na O (1 eq.)
13. (a) HO

CH3 I C H2
+ C H3CO H3CO
(1 eq.) Lindlar
Na O
catalyst
H H
(X), C7H14O

OH
NaNH2 Br
14. (c) H CNa+

ONa+ (i) H + OH CrO3

C O
(ii) H2 , pd/C

(Y), C7H17O

15. (b) Ni 2 + + 4HCl

[NiCl 4 ]2 -
(M1) (Q) Tetrahedral

Ni 2+ + 4KCN
[Ni(CN) 4 ]2 -
(M1) (R) Square planar

[Note: Co2 + + 6CN -

[Co(CN)6 ]4 - ]
Octahedral

OH -
16. (d) Zn 2+ + 2OH - [Zn(OH) 4 ]2-
Zn(OH)2
(M2) (S) excess
white ppt. so lub le

17. (b) Complex Magnetic character Isomerism

P, [Cr(NH 3 ) 4 Cl2 ]Cl Cr 3+ is d 3 , hence paramagnetic cis-trans
3+ 1
Q, [Ti(H 2 O)5Cl](NO 3 ) 2 Ti is d , hence paramagnetic. ionization

R, [Pt(en)(NH3 )Cl]NO3 Pt 2 + is d 8 , complex is square planar, ionization

all electrons are paired, hence diamagnetic
3+ 6
S, [Co(NH3 ) 4 (NO3 ) 2 ]NO3 Co is d , all electrons are paired cis-trans
due to strong ligands, hence diamagnetic
JEE Advanced 2014 Solved Paper 2014-11

18. (c) P. d d (s bonding)

Q. p d( p bonding)

R. p d (p antibonding)

S. d d (s antibonding

19. (a)
O O
(1) C6H5CH2CO CH3 C 6H 5CH 2 + CO 2 + CH 3 O

O O CH3 CH3
(3) C6H5CH2CO C CH3 CO2 + C6H5CH2 + CH3CO
CH2 C6H5 CH2C6H5

O
C O CH3 O CH3
(4) C6H5 O CCH3 C6H5 C O + O C CH3
CH3 CH3

O O
C O C
(2) C 6H5 O CH3 C 6H 5 O + CH 3 O

NO2

red hot Nitration NH4HS

20. (c) Scheme (III) : H H Fe, 873 K
Acetylene, P
NO2

NO2 NO2 NO2

NaNO2 H 2O
+ N2 + H +
H+ + boil
NH2 N2 OH
(C6H5NO3)
12-2014 Chemistry

OH OH OH OH

Conc. H2SO4 Conc. HNO3

O2N O2N
dil. H2SO4
Scheme (IV) :
60C Conc. H2 SO4 heat
OH OH OH OH
Q (C6 H5NO4 )
SO3H SO3H

NO2 NH2 NHCOCH3 NHCOCH3

Sn/HCl CH 3COCl Conc.

Scheme (II) :
H2SO4

R
SO3H

NHCOCH3 NHCOCH3 NH2

NO2 NO2 NO2
Conc. HNO3 dil. OH
H2SO4 , heat

(C6H6N2O2)
SO3H

NO2 NO2 NO2 NO2

(i) KMnO4, OH , heat SOCl2 NH3
Scheme (I) : +
(ii) H , H2O

CH3 COOH COCl CONH2

S (C7H6N2O3)