[ 1 ]

JEE ADVANCED 2014_25-05-14 (PAPER-I)_CODE-8 (CHEMISTRY) [ 1 ]

Mentors Eduserv: Plot No.-136/137, Parus Lok Complex, Boring Road Crossing,
Patna-1, Ph. No. : 0612-3223701/02
PART-II : CHEMISTRY
SECTION I
(Multiple Correct Answer(s) Type)
This section contains 10 multiple choice questions. Each question has four choices (A), (B), (C) and (D), out of
which ONE OR MORE are correct.
21. For the reaction :
3 2 4 4 2
I CIO H SO CI HSO I

+ + + +
The correct statement(s) in the balanced equation is/are:
(A) Stoichiometric coefficient of
4
HSO

is 6.
(B) Iodine is oxidized.
(C) Sulphur is reduced.
(D) H
2
O is one of the products.
Ans. (A,B,D)
Sol.
3 2 4 4 2 2
6I CIO 6H SO CI 6HSO 3I 3H O

+ + + + +
(A). Stoichiometric coefficient of
4
HSO

is 6.
(B). Iodine is oxidized, as oxidation number of iodine increases from -1 to 0.
(C). Oxidation number of sulphur does not changed, so sulphur is not oxidized or reduced.
(D). H
2
O is one of the products.
22. The pair(s) of reagents that yield paramagnetic species is/are
(A) Na and excess of NH
3
. (B) K and excess of O
2
.
(C) Cu and dilute HNO
3
. (D) O
2
and 2-ethylanthraquinol
Ans. (A,B,C)
Sol. (A). ( ) ( ) ( )
3 3 3
x y
paramagnetic
Na x y NH Na NH e NH
+
+ + +
(B).
2 2
paramagnetic
K O KO +
(C).
( ) ( )
3 3 2
2
paramagnetic
3Cu 8HNO dil. 3Cu NO 2NO 4H O + + +
(D).
2 2 2
no paramagnetic species
2 ethylanthraquinol O 2 ethylanthraquinone H O + +
[ 2 ] (CHEMISTRY) JEE ADVANCED 2014_25-05-14 (PAPER-I)_CODE-8
Mentors Eduserv: Plot No.-136/137, Parus Lok Complex, Boring Road Crossing,
Patna-1, Ph. No. : 0612-3223701/02
23. In the reaction shown below, the major product(s) formed is/are
NH
2
NH
2
acetic anhydride
product(s)
CH CI
2 2
O
(A)
N
H
NH
2
CH
3
CH
3
COOH +
O
O
(B)
N
H
NH
2
CH
3
CH
3
COOH +
O O
(C)
N
N
H
H
CH
3
CH
3
H
2
O +
O
O
O
(D)
N
H
O O
2 3
NH CH COO

O
3
CH
Ans. (A)
Sol.
O
N
H
H
NH
2
O O
2
NH
2 2
CH Cl
3 3
CH C O C CH +
O O
3
N C CH
H
24. In a Galvanic cell, the salt bridge
(A) does not participate chemically in the cell reaction.
(B) stops the diffusion of ions from one electrode to another.
(C) is necessary for the occurrence of the cell reaction.
(D) ensures mixing of the two electrolytic solutions.
Ans. (A,B)
Sol. In Galvanic cell, salt bridge does not involve in cell reaction. Also salt bridge stops the diffusion of ions from one
electrode to another. There are many Galvanic cell in which there is no salt bridge.
25. Upon heating with Cu
2
S, the reagent(s) that give copper metal is/are
(A) CuFeS
2
(B) CuO (C) Cu
2
O (D) CuSO
4
Ans. (B, C, D)
Sol.
2 2 2
Cu O Cu S Cu SO + +
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JEE ADVANCED 2014_25-05-14 (PAPER-I)_CODE-8 (CHEMISTRY) [ 3 ]
Mentors Eduserv: Plot No.-136/137, Parus Lok Complex, Boring Road Crossing,
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26. Hydrogen bonding plays a central role in the following phenomena:
(A) Ice floats in water
(B) Higher Lewis basicity of primary amines than tertiary amines in aqueous solutions.
(C) Formic acid is more acidic than acetic acid.
(D) Dimerisation of acetic acid in benzene.
Ans. (A,B,D)
Sol. (A). Ice has lower density than water because it has cage like structure due to intermolecular H-bonding.
(B).
2
R NH H
+
+
R---N
I
H
+
---H
H
I
(3 H-bonds)
( )
3 3
R N H R N H one H bond
+
+
+
(C). Formic acid is more acidic than acetic acid due to inductive effect.
(D). Acetic acid dimerises in benzene due to formation of intermolecular H-bonding.
CH
3
CH
3 C
C
H
O H
O
O
O
27. The reactivity of compound Z with different halogens under appropriate conditions is given below:
OH
X
2
mono halo substitued derivative when X = I
2 2
di halo substitued derivative when X = Br
2 2
tri halo substitued derivative X = CI
2 2
C(CH )
3 3
Z
The observed pattern of electrophilic substitution can be explained by
(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) the electronic effect of the tert-butyl group
Ans. (A,B,C)
Sol. - OH is stronger activating group than t-butyl group.
[ 4 ] (CHEMISTRY) JEE ADVANCED 2014_25-05-14 (PAPER-I)_CODE-8
Mentors Eduserv: Plot No.-136/137, Parus Lok Complex, Boring Road Crossing,
Patna-1, Ph. No. : 0612-3223701/02
28. The correct combination of names is for alcohols with molecular formula C
4
H
10
O is/are
(A) tert-butanol and 2-methylpropan-2-ol (B) tert-butanol and 1, 1-dimethylethan-1-ol
(C) n-butanol and butan-1-ol (D) isobutyl alcohol and 2-methylpropan-1-ol
Ans. (A, C, D)
Sol. All the four isomers are
3 2
CH CH CH
3
CH
OH
(I)
3 2 3
CH CH CH CH
OH
(II)
3 2 2 2
(III)
CH CH CH CH OH
3
CH C OH
3
CH
3
CH
(IV)
Names : IV : tert-butanol and 2-methylpropan-2-ol
III : n-butanol and butan-1-ol
I : isobutuyl alcohol and 2-methyl propan-1-ol
29. An ideal gas in thermally insulated vessel at internal pressure = P
1
, volume = V
1
and absolute temperature = T
1
expands irreversibly against zero external pressure, as shown in the diagram. The final internal pressure, volume
and absolute temperature of the gas are P
2
, V
2
and T
2
, respectively. For this expasnsion
ext
P 0 =
2 2 2
P .V .T
1 1 1
P, V ,T
ext
P 0 =
irreversible
Thermal insulation
(A) q = 0 (B) T
2
= T
1
(C) P
2
V
2
= P
1
V
1
(D)
2 1 2 1
P V P V

=
Ans. (A, B, C)
Sol. q 0, w 0 = =
U q w 0 A = + =
1 2
T T =
1 1 2 2
PV P V =
Note:-
2 1
2 1
P V P V

=
is for reversible adiabatic process
[ 5 ]
JEE ADVANCED 2014_25-05-14 (PAPER-I)_CODE-8 (CHEMISTRY) [ 5 ]
Mentors Eduserv: Plot No.-136/137, Parus Lok Complex, Boring Road Crossing,
Patna-1, Ph. No. : 0612-3223701/02
30. The correct statement(s) for orthoboric acid is/are
(A) It behaves as a weak acid in water due of self ionization.
(B) Acidity of its aqueous solution increases upon addition of ethylene glycol.
(C) It has a three dimensional structure due to hydrogen bonding.
(D) It is weak electrolyte in water.
Ans. (B, D)
Sol.
4 3 3 2 2
H BO H O B(OH) H (H Oionises)
+
+ +
....(i)
4 2
B(OH) CH OH

+
2
CH OH
2
CH
2
CH
2
H O +
2
CH
2
CH
B
O
O
O
O
....(ii)
2nd step drag more first step hence acidity increases
2D sheet
[ 6 ] (CHEMISTRY) JEE ADVANCED 2014_25-05-14 (PAPER-I)_CODE-8
Mentors Eduserv: Plot No.-136/137, Parus Lok Complex, Boring Road Crossing,
Patna-1, Ph. No. : 0612-3223701/02
SECTION 2 (One Integer Value Correct Type Type)
This section contains 10 questions. Each question, when worked out will result in one integer from 0 to 9 (both
inclusive).
31. In an atom, the number of electrons having quantum number n 4,| m | 1 = =

and
s
m 1/ 2 = is
Ans. (6)
Sol. For n 4 l 0 m 1
l 1 m 1
2 electron
m 1
l 2 m 1
2 electron
m 1
l 3 m 1
2 electron
m 1
Total 6 electron
= = =
= = +
`
=
)
= = +
`
=
)
= = +
`
=
)
=
32. The total number of distinct naturally occuring amino acids obtained by complete acidic hydrolysis of the peptide
shown is
2
CH
2
CH
N
N
N
N
N N
N N
H H
H H
O O
O
O
O
O O
O O
H
H
Ans. (1)
Sol.
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
CH
2
CH
OH
O O O
O
O
O
+
+
+
+ +
+ +
+
O
O
HO
O
HO
HO HO
HO
OH
H
HO
O
N
H
Only Glycine H
2
N CH
2
COOH is prepared as distinct naturally occuring amino acid
[ 7 ]
JEE ADVANCED 2014_25-05-14 (PAPER-I)_CODE-8 (CHEMISTRY) [ 7 ]
Mentors Eduserv: Plot No.-136/137, Parus Lok Complex, Boring Road Crossing,
Patna-1, Ph. No. : 0612-3223701/02
33. If the value of Avogadro number is 6.023 10
23
mol
1
and the value of Boltzaman constant is 1.380 10
23
J K
1
,
then the number of significant digits in the calculated value of the universal gas constant is
Ans. (4)
Sol.
23
23
23 23
N 6.023 10 (4 significant digits)
K 1.380 10 (4 significant digits)
R
K
N
R (6.023 10 ) (1.380 10 ) 8.31174

=
=
=
= =
But answer should contain significant figure equal least significant digit of multipling data
hence R should be = 8.312
34. A compound H
2
X with molar weight of 80 g is dissolved in a solvent having density 0.4 g ml
1
. Assuming no change
in volume upon dissolution, the molality of a 3.2 molar solution is
Ans. (8)
Sol. 3.2 M solution
1000 ml solution contains 3.2 mole since volume does not change hence volume of solvent is 1000 ml and mass
of solvent = 1000 0.4 = 400 g
Now m =
3.2 1000
8
400

=
35. MX
2
dissociates into M
2+
and X

ions in an aqueous solution, with a degree of dissociation (o) of 0.5. The ratio of
the observed depression of freezing point of the aqueous solution of the value to the depression of freezing point in
the absence ionic dissociation is
Ans. (2)
Sol.
2
2
MX M 2X
+
+
( ) i 1 3 1 = + o =
1 2 + o
= 1+ 2 0.5 = 2
observed depression in freezing point
i
depression in freezing point(without ionic dissociation)
=
36. Consider the following list of reagents :
Acidified K
2
Cr
2
O
7
, alkaline KMnO
4
, CuSO
4
, H
2
O
2
, Cl
2
, O
3
, FeCl
3
, HNO
3
and Na
2
S
2
O
3
. The total number of reagents
that can oxidise aqueous iodide to iodine is
Ans. (7)
Sol.
3
2 2 7 2 2
K Cr O 6KI 14H 3I 2Cr 8K 7H O
+ + +
+ + + + +
alkaline KMnO
4
on rection with I

gives iodate
_
2 3 2
4
2MnO I H O IO 2MnO 2OH

+ + + +
4 2 2 2 2 4
2CuSO 4KI Cu I I 2K SO + + +
2 2 2
H O 2I 2H I 2HO
+
+ + +
2 2
Cl 2I 2Cl I

+ +
3 2 2
3O I I 3O

+ +
3 2 2
2FeCl 2Kl 2FeCl 2KCl I + + +
3 3 2 2
8HNO 6KI 6KNO 2NO 3I 4H O + + + +
2 2 3 2 2 4 6
Reduction
Na S O I NaI Na S O + +
[ 8 ] (CHEMISTRY) JEE ADVANCED 2014_25-05-14 (PAPER-I)_CODE-8
Mentors Eduserv: Plot No.-136/137, Parus Lok Complex, Boring Road Crossing,
Patna-1, Ph. No. : 0612-3223701/02
37. The total number(s) of stable conformers with non-zero dipole moment for the following compound is (are)
3
CH Br
Br Br Cl
Cl
Cl
Ans. (3)
Sol.
3
CH
3
CH
3
CH
60

120

120

3
CH
3
CH
3
CH
3
CH
3
CH
Cl Cl Cl Cl
Cl Cl
Br
Br
Br Br Br Br
Br
Br
Cl
Cl
(I) (II) (III) (IV)
Only II, III and IV are stable conformer having non-zero dipole moment.
38. Among PbS, CuS, HgS, MnS, Ag
2
S, NiS, CoS, Bi
2
S
3
and SnS
2
, the total number of BLACK coloured sulphides
is
Ans. (7)
Sol. PbS: black HgS : black
CuS : black MnS : Light Pink
Ag
2
S : black CoS : black
Bi
2
S
3
: black SnS
2
: yellow
NiS : black
39. Consider all possible isomeric ketones, including stereoisomers of MW = 100. All these isomers are idependently
reacted with NaBH
4
(Note: stereoisomers are also reacted separately). The total number of ketones that give a
racemic product(s) is/are
Ans. (5)
Sol. M.F. of Ketone :
x 2x
C H O
12x 2x 16 100, 14x 84 x 6 + + = = =
4
NaBH
3 2 2 2 3
CH C CH CH CH CH
O
( )
( )
3 2 2 2 3
I
OH
R and S
Racemicmix
CH CH CH CH CH CH
-

( )
( )
4
O
II
NaBH
3 2 2 2 3 3 2 2 2 3
I
OH
R and S
Racemicmix
CH CH C CH CH CH CH CH CH CH CH CH
-

( )
( ) ( )
4
3 3
NaBH
3 2 3 3 2 2 3
II I I I
R form
O CH OH CH
Rand S onlyR
(Diastereomers)
CH C CH CH CH CH CH CH CH CH CH
- - -

[ 9 ]
JEE ADVANCED 2014_25-05-14 (PAPER-I)_CODE-8 (CHEMISTRY) [ 9 ]
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Patna-1, Ph. No. : 0612-3223701/02
( )
( ) ( )
4
3 3
NaBH
3 2 3 3 2 3
II I I I
O OH CH CH
Rand S only S
S form
(Diastereomers)
CH C CH CH CH CH CH CH CH CH
- - -

( )
( )
3 3
4
CH CH
I I
NaBH
3 2 3 3 2 3
II I
O OH
RandS
Racemicmixture
CH CH C CH CH CH CH CH CH CH
-

( )
( )
4
3 3
NaBH
3 2 3 3 2 3
II I I I
O CH OH CH
RandS
Racemicmixture
CH C CH CH CH CH CH CH CH CH
-

( )
( )
3 3
4
3 3
Racemic mixture
CH CH O OH
I II I I
NaBH
3 3 3 3
I I
RandS
CH CH
CH C C CH CH C CH CH
40. A list of species having the formula XZ
4
is given below.
2 2 2 2
4 4 4 4 4 3 4 4 4 4
XeF ,SF ,SiF ,BF ,BrF ,[Cu(NH ) ] ,[FeCl ] ,[CoCl ] and[PtCl ] .
+
Defining shape on the basis of the location of X and Z atoms, the total number of species having a square planar
shape is
Ans. (4)
Sol.
4
XeF : Square planar
4
SF : See Saw
4
SiF : tetrahedral
4
BF : tetrahedral

4
BrF : square planar

2
3 4
[Cu(NH ) ] : square planar
+
2
4
[FeCl ] : tetrahedral
2
4
[CoCl ] : tetrahedral

2
4
[PtCl ] : square planar