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JEE ADVANCED 2015 CHEMISTRY (PAPER 2)

SECTION - I
This section contains 8 questions. Each question, when worked
out will result in one integer from 0 to 9 (both inclusive).
1. Three moles of B2H6 are completely reacted with methanol.
The number of moles of boron containing product formed is
2. The molar conductivity of a solution of a weak acid HX (0.01
M) is 10 times smaller than the molar conductivity of a solution
of a weak acid HY (0.10 M). If
the difference in
l 0x l0y

II.

III.

their pKa values, pKa(HX) pKa (HY), is (consider degree of

ionization of both acids to be <<1)
3.

A closed vessel with rigid walls contains 1 mol of

238
92 U

1 mol of air at 298 K. Considering complete decay of

206
82 Pb,

4.

5.

and

238
92 U

7.

to

the ratio of the final pressure to the initial pressure of

the system at 298 K is

In dilute aqueous H2 SO 4 , the complex diaquodioxalatoferrate(II) is oxidized by MnO4 . For this reaction, the
ratio of the rate of change of [H+] to the rate of change of
[MnO4] is
The number of hydroxyl group(s) in Q is
H+

IV.

aqueous dilute KMnO (excess)

P
Q
heat
0 C

8.

H O

100C

H2

Pd - BaSO
4

DIBAL H

Toluene,78C
H 2O

In
the
complex
acetylbromidodicarbonylbis
(triethylphosphine) iron (II), the number of FeC bond(s) is
Among the complex ions, [Co(NH2CH2CH2NH2)2Cl2]+,
[CrCl2(C2O4)2]3, [Fe(H2O)4(OH)2]+, [Fe(NH3)2(CN)4],
[Co(NH2CH2CH2NH2)2(NH3)Cl]2+ and
[Co(NH3)4(H2O)Cl]2+, the number of complex ion(s) that
show(s) cis-trans isomerism is
SECTION - II

This section contains 8 multiple choice questions. Each question

has 4 choices (a), (b), (c) and (d) out of which ONE or MORE
THAN ONE are correct.
9.

The major product U in the following reactions is

CH =CHCH , H+

6.

Among the following, the number of reaction(s) that

produce(s) benzaldehyde is

I.

radical, initiator, O

2
3
2

T
high pressure, heat

CO, HCl

Anhydrous AlCl / CuCl

3

(a)

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(b)

(b)

The number of lone pairs of electrons on Cl in (ii) and

(iii) together is three

(c)

The hybridization of Cl in (iv) is sp3

(d)

Amongst (i) to (iv), the strongest acid is (i)

12. The pair(s) of ions where BOTH the ions are precipitated
upon passing H2S gas in presence of dilute HCl, is(are)
Ba2+, Zn2+

(b) Bi3+, Fe3+

(c)

Cu2+, Pb2+

(d) Hg2+, Bi3+

13. Under hydrolytic conditions, the compounds used for

preparation of linear polymer and for chain termination,
respectively, are

(c)

(d)
10. In the following reactions, the major product W is

NaNO2 , HCl

N=N

(a)

CH3SiCl3 and Si(CH3)4

(b)

(CH3)2SiCl2 and (CH3)3SiCl

(c)

(CH3)2SiCl2 and CH3SiCl3

(d)

SiCl4 and (CH3)3SiCl

14. When O2 is adsorbed on a metallic surface, electron transfer

occurs from the metal to O2. The true statement(s) regarding
this adsorption is(are)

OH

(a)

O2 is physisorbed

, NaOH

(b)

Heat is released

(c)

*
Occupancy of p2r of O2 is increased

(d)

Bond length of O2 is increased

0C

(a)

(a)

15. One mole of a monoatomic real gas satisfies the equation

p(V b) = RT where b is a constant. The relationship of
interatomic potential V(r) and interatomic distance r for the
gas is given by

OH

OH

(b)

N=N

(a)

OH

(c)

N=N

(b)

(d)

N=N

11. The correct statement(s) regarding, (i) HClO, (ii) HClO2,

(iii) HClO3 and (iv) HClO4, is(are)
(a)

(c)

The number of Cl=O bonds in (ii) and (iii) together is

two
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3
17. Enthalpy of dissociation (in
from the Expt.2 is
(a) 1.0
(c) 24.5

kJ mol1) of acetic acid obtained

(b) 10.0
(d) 51.4

18. The pH of the solution after Expt. 2 is

(d)

(a)

2.8

(b) 4.7

(c)

5.0

(d) 7.0

16. In the following reactions, the product S is

PARAGRAPH 2
In the following reactions
C8 H6

Pd - BaSO 4
H2

C8 H8

(i) B2 H6

X
(ii)H 2 O 2 , NaOH, H 2 O

H2O

(a)

HgSO 4 ,H 2SO 4
C8 H 8 O

(b)

(i) EtMgBr, H2 O

Y
(ii) H + , heat

19. Compound X is

(a)

(b)

(c)

(d)

(c)

20. The major compound Y is

(d)
SECTION - III

(a)

This section contains 2 paragraphs, each describing theory,

experiments, data etc. four questions related to the two paragraphs
with two questions on each paragraph. Each question has one or
more than one correct answer(s) among the four given options
(a), (b), (c) and (d).

(b)

PARAGRAPH 1

(c)

When 100 mL of 1.0 M HCl was mixed with 100 mL of 1.0 M NaOH
in an insulated beaker at constant pressure, a temperature increase
of 5.7 C was measured for the beaker and its contents (Expt.1).
Because the enthalpy of neutralization of a strong acid with a
strong base is a constant (57.0 kJ mol1), this experiment could
be used to measure the calorimeter constant. In a second
experiment (Expt. 2), 100 mL of 2.0 M acetic acid (Ka = 2.0 105)
was mixed with 100 mL of 1.0 M NaOH (under identical conditions
to Expt. 1) where a temperature rise of 5.6 C was measured.

(d)

(Consider heat capacity of all solutions as 4.2 J g1 K1 and density

of all solutions as 1.0 g mL1)
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1.
2.

SOLUTIONS
(6)
(3)

3B2H6 + 18CH3OH 6B(OCH3)3 + 18H2

1 HX
2 HY
a1 =

( l m )HX

a2 =

lm

K a1 = C1a12

(
= 0.01

K a1
Ka 2

( )

0.01( l m ) HX
0.1( l m )HY
2

= 0.1

PF
n
9
= F = =9
Pin n in 1

( lm ) 2 HY

(lm )

( l m ) HX
= 0.1

( l m ) HY

Number of moles in gas phase, at start (ni) = 1

Now number of moles in gas phase, after decomposition (n F)

= 1 + 8 = 9 mole
at constant temperature and pressure

l m

2
l m HX
2
lm

(9)

206
4
0
238
92 U 82 Pb + 82 He + 6 b

( l m )HY

K a 2 = C2a 22

3.

4.

(8)

8H+ + 5[Fe(H2O)2(OX)2]2 + MnO4 Mn2+ +

+ 5 [Fe(H2O)2(OX)2] + 4H2O

d[MnO 4 ]
1 d[H + ]
=
dt
8 dt

Rate =

1
= 0.1 = 103
10

Hence,

K a1
pKa(HX) pKa(HY) = log K
= log103 = 3

rate of [H + ]decay
rate of [MnO 4 ] decay

=8

a2

5.

(4)

H2O

1, 2 Methyl Shift

OH CH CH
3
3
aq. dilute
KMnO4excess

0C

OH
OH
OH
CHO

6.

(4)

CO, HCl
Anhyd AlCl3 /CuCl

OH

(Gatterman Koch Reaction)

OH

CHCl 2

CHO

CH
H2O

OH

100C

COCl
H2
PdBaSO 4

COOMe

H 2O

CHO
(Rosenmund Reduction)

CHO
DIBALH
Toluene, 78C H2O

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5
CO

Et3P
O
7.

(3)

CH3 C

Fe

+2

Et3P
8.

(6)

Br
CO

All the complexes given show cis-trans isomerism

[Co (NH2 CH2 CH2 NH2) Cl2] +

[CrCl2(C2O4)2]3

Cl

en

Cl

ox

en Co

en en Co

ox Cr

ox ox Cr

Cl

Cl

Cl

Cl
[Fe(H2O)4(OH)2]+
HO
2
HO
2

OH
Fe
OH

OH2
OH2

[Fe(NH3)2(CN)4]
OH

HO
2

OH

HN
3

Fe

HO
2

OH2

OH2

HN
3

[Co(NH2CH2CH2NH2)2(NH3)Cl]2+
en
en Co
Cl

9.

HO
2
en

Cl

Cl

,H

(b)

en Co

CN
Fe
CN

CN NC
CN

NC

NH3
Fe
NH3

CN
CN

(Co(NH3)4(H2O)Cl]2+

NH3
NH3

Cl

NH3
Co
NH3

NH3 H3N
NH3 H3N

OH2
Co
Cl

NH3
NH3

Radical, initiator, O 2

High Pressure, heat

Cumene, T

Cumene hydroperoxide, U

NH 2

10. (a)

O
11.

(b, c)

Cl

ClOH
O
(i)

Cl

Cl
OH

(ii)

O OH
(iii)

OH

(iv)

Number of Cl = O bonds in (ii) and (iii) together is 3

Number of lone pairs on Cl in (ii) and (iii) together is 3
Hybridisation of Cl in all the four is sp3
Strongest acid is HClO4 (iv)
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6
12. (c, d) Only group II cations precipitate as sulphide with H2S
in acidic medium that is (Cu2+, Pb2+) and (Hg2+, Bi3+)
13. (b) (CH3)2SiCl2 form linear polymer on hydrolysis and
(CH3)3SiCl is a chain terminator.
14. (b, c, d) Reaction on metal surface
+

M + e
M

15.

(c) P(Vb) = RT
PV Pb = RT

Pb
RT
Hence Z > 1 at all pressures.
This means , repulsive tendencies will be dominant
when interatomic distance are small.
This means, interatomic potential is never negative
but becomes positive at small interatomic distances.

O2
O2 + e

This is an example of chemisorption.

16. (a)

PV Pb
=
+1
RT RT
Z =1+

NH 3

(i) O3
(ii) Zn, H 2O

2H2O

17.

(a) Let the heat capacity of insulated beaker be C.

Mass of aqueous content in expt. 1 = (100 + 100) 1
= 200 g
Total heat capacity = (C + 200 4.2) J/K
Moles of acid, base neutralised in expt.
1 = 0.1 1 = 0.1
Heat released in expt. 1 = 0.1 57 = 5.7 KJ
= 5.7 1000 J
5.7 1000 = (C + 200 4.2) DT.
5.7 1000 = (C + 200 + 4.2) 5.7
(C + 200 4.2) = 1000
In second experiment,
nCH COOH = 0.2, nNaOH = 0.1
3

18.

Total mass of aqueous content = 200 g

Total heat capacity = (C + 200 4.2) = 1000
Heat released = 1000 5.6 = 5600 J.
Overall, only 0.1 mol of CH3COOH undergo
neutralization.
5600
DHneutralization of CH3COOH =
0.1
= 56000 J/mol
= 56 KJ/mol.
DHneutralization of CH3COOH = 57 56 = 1 KJ/mol
(b) Final solution contain 0.1 mole of CH3COOH and
CH3COONa each.
Hence it is a buffer solution.
pH = pKa log

19. (c)

OH
i. B 2H6
ii. H2 O2 , NaOH, H2O

Pd-BaSO4
C8 H 6
H2

20. (d)

C8H6

H2O
HgSO4 ,
H2SO4

i. Et MgBr, H2O
ii. H+, Heat

[CH3COO- ]
[CH3COOH]

= 5log 2 + log

0.1
= 4.7
0.1

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