JMS 5 PAPER 1

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PAPER-1
Maximum Marks: 80

Question paper format and Marking scheme:

1. In Section I ( Total Marks: 21), for each question you will be awarded 3 marks if you darken ONLY the
bubble corresponding to the correct answer and zero marks if no bubble is darkened. In all other cases,
minus one (1) mark will be awarded.

2. In Section II (Total Marks: 16), for each question you will be awarded 4 marks if you darken ALL the
bubble(s) corresponding to the correct answer(s) ONLY and zero marks other wise. There are no negative
marks in this section.

3. In Section III (Total Marks: 15), for each question you will be awarded 3 marks if you darken ONLY the
bubble corresponding to the correct answer and zero marks if no bubble is darkened. In all other cases,
minus one (1) mark will be awarded.

4. In Section IV (Total Marks: 28), for each question you will be awarded 4 marks if you darken ONLY the
bubble corresponding to the correct answer and zero marks otherwise. There are no negative marks in this
section.






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SECTION I (Total Marks : 21)
(Single Correct Answer Type)

This section contains 7 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out of
which ONLY ONE is correct.

1. Resonance energy of C
6
H
6
using Kekule formula for C
6
H
6
from the following data:
(1)
0
H for C
6
H
6
= 358.5 kJ mol
1

(2) Heat of atomisation of C = 716.8 kJ mol
1

(3) Bond energy of C
__
H, C-C, C = C, and H
__
H are 490, 340, 620 and 436.9 kJ mol
1
A) 140 kJ B) 150 kJ C) 160 kJ D) 170 kJ

Sol. (B)

6 6
2 6 6
tan
exp
6 ( ) 3 ( ) ; 358.5
[6 716.8 3 436.9] [3 340 3 620 6 490]
208.5
358.5 ( 208.5) 150
cal reac ts pro ucts
cal
cal
cal
ForC H
C s H g C H H kJ
H BE B
H x x x x x
H kJ
RE H H
kJ

+ =
=
= + + +
=
=
= =
d


2. Which of the following oxidation reactions incorrectly matched?

(A)
( ) Cr VI
CH -CH OH CH CHO
3 2 3 +
H O
3

(B)

( ) ( )
CrO , H SO
3 2 4
CH - CH C C CH CH CH CH C C C CH
3 2 3 3 2 3
propanone, 2 2

OH
O

(C)

(D)

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Sol. (A)
In aqueous medium, over oxidation takes place to give acid rather than aldehyde.
( )
O O
|| ||
Cr VI
CH -CH -OH CH - C-H CH - C-OH
3 2 3 3 +
H


3. Chromyl chloride test is employed for the detection of chloride ions. A similar test can be
employed for
(A) Br (B) I (C) Both (D) None of these

Sol. (D)
K
2
Cr
2
O
7
will oxidise Br

& I

into Br
2
and I
2
which give colourless solutions with NaOH

4. D fructose is a ketose, but it reduces Tollens reagent. It can be explained on the basis of
(A) Mutarotation (B) Reimer Tiemann reaction
(C) Amadori reararangement (D) Lobry de Bruyn Van Ekenstein rearrangement

Sol. (D)
Glucose with dil. NaOH solution gives a mixture of D-Glucose,D-Fructose and D-Mannose .This
mixture is obtained even when the starting material is either fructose or mannose.This is called Lobry-
debruyn- van-Ekenstein rearrangement. Due to this,though fructose is a ketose, it can reduce tollens test.

5. Chlorine evolved by the reaction of 45.31 g of pyrolusite (impure) and excess of HCl is found to
combine completely with the hydrogen produced by the reaction of 10 g of magnesium and excess
of dilute hydrochloric acid. Hence, the percentage purity pyrolusite sample is
A) 80.56% B) 60.56% C) 40.56% D) 90.56%

Sol. (C)

2 2
2 Mg HCl MgCl H + +
24g 73g 2g

2 2 2 2
4 MnO HCl MnCl Cl H O + + +
87g

2 2
2 H Cl HCl +
2g 71g

2g H obtained from 24 g of Mg will combine completely with
71 g of Cl
2
produces from 87 g of pure MnO
2
(Pyrolusite)

So, when 10 g of Mg are used, mass of pure MnO
2
needed =
10 87
36.25
24
x
=
Therefore, % purity =
36.25
100 80.04%
45.31
x =

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6. An optically pure compound X gave an [ ]
25
0
D
20.0 = . A mixture of (X) and its enantiomer (Y) gave
[ ]
25
0
D
10.0 = + . Select the True / False statements regarding this mixture.
(1) It has 50% dextrorotatory isomer
(2) It has 25% laevorotatory isomer
(3) It has 50% optical purity
(A) TTF (B) FFT (C) FTT (D) TFT

Sol. (C)
% optical purity of mixture =
[ ]
[ ]
obs
pure

100

10
100 50%
20
= =
So 50 d l =
100 d l + =
2 150 d =

75% d = and l = 25%

7. Match the following

ListI List II
(Crystal System) (axial distances)

1) Trigonal P)
c b a

2) Monoclinic Q)
c b a =

3) Rhombic R) a = b = c
4) Hexagonal


ListIII List IV
(axial angles) (unit cells possible)

a)
o
90 = =
i) P, F, E, B
b)
o
90 = = =
ii) Primitive
c)
o o
120 , 90 = =
iii) Primitive
d)
o o
120 , 90 = = =
iv) P, E



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A) 1 - P, a, iii; 2 - R, b, iv; 3 - P, d, i; 4 - Q, c, iii
B) 1 - R, b, i; 2 - P, c, ii; 3 - P, a, iii; 4 - Q, d, iv
C) 1 - Q, a, iii; 2 - P, b, iv; 3 - R, d, ii; 4 - P, c, i
D) 1 - R, a, ii; 2 - P, c, iv; 3 - P, b, i; 4- Q, d, iii

Sol. (D)
Crystal system
Axial
distances
Axial angles
Unit cells
possible
Cubic a b c = =
0
90 = = = PBF
Tetragonal a b c =
0
90 = = = PB
Orthorhombic (or)
Rhombic
a b c
0
90 = = = PBFE
Monoclinic

a b c
0
90 = = ,
0
120 PE
Triclinic a b c
0
90 P
Hexagonal a b c =
0 0
90 , 120 = = = P
Rhombohedral (or)
Triogonal
a b c = =
0
90 = = P

P =Primitive, B = Body centered, F = Face centred, E = end centred

SECTION II (Total Marks : 16)
(Multiple Correct Answers Type)

This section contains 4 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out of
which ONE OR MORE may be correct.

8.

Lucas test is used to distinguish 1
0
, 2
0
and 3
0
alcohols. Correct options regarding this are
2
.
2
ROH H O
conc
White turbidity
anhydrous ZnCl
HCl RCl + +
A) ROH behaves as a Lewis base

B) Greater the value of pK
a
(alcohol), greater is the reactivity with conc. HCl and thus faster the formation
of white turbidity.
C) Alcohol which readily reacts with Na metal, will give turbidity readily

D) Alcohol which gives red colour in Victor Meyer test, will give turbidity at slower rate than those giving
blue or white colour in Victor Meyer test.


Sol. (A,B,D)
In victor Meyer test, 1
0
, 2
0
and 3
0
alcohols give red , blue and white colours respectively

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9. The values of E
0
of some reactions are givenbelow.
I
2
+ 2e

2I

E
0
= 0.54 volts
Sn
+4
+ 2e

Sn
2+
E
0
= 0.152 volts
Cl
2
+ 2e

2Cl

E
0
= 1.36 volts
Fe
+3
+ e

Fe
2+
E
0
= 0.76 volts
Ce
+4
+ e

Ce
3+
E
0
= 1.6 volts
Hence
(A) Fe
3+
oxidizes Ce
+3
(B) Ce
4+
can oxidize Fe
2+

(C) Sn
2+
will reduce Fe
3+
to Fe
2+

(D) Cl
2
will be liberated from KCl by passing I
2
.

Sol. (B,C)
Greater the SRP, greater is the tendency to undergo reduction, greater is the tendency to act as oxidant
and vice cersa
B) As SRP is more for Ce
+4
/Ce
+3
, it undergoes reduction by oxidizing Fe
+2
C)
As SRP is less for Sn
+4
/Sn
+2
, it undergoes oxidation by reducing Fe
+3



10. Which of the following reactions generate tertiary alcohol function

(A)

CH
3
CH
3
O
CH O
3
CH OH
3

H O
2

(B)

CH
3
CH
3
CH O
2
Ag
+

CH
2
Cl


(C)

CH
3
Br
H O
2
+
Ag

(D)

CH
3
O
CH MgBr
3

CH
3
H
3
O
+

Sol. (A,B,C)


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(A)
CH
3
CH
3
O
CH O
3

H
+
CH C CH OCH
3 2 3

CH
3
OH

(B)
+
Ag

CH
2
Cl
CH
3
CH
3
CH
3
CH
3
CH
2
+


(C)
CH
3
Br
+
Ag

+
CH
3


CH
3
H O
2
+
-H

+
alkylic and 3
carbocation
0
CH
3
OH


(D)
CH
3
O
CH MgBr
3

H C
3
CH C C OCH
3 3

CH
3
+
O

HH
H


11. Which of the following on hydrolysis produces ammonia
(A) CaNCN (B)Borazine
(C) Li
3
N (D) NCl
3

Sol. (A,B,C,D)

2 3 3
CaNCN 3H O 2NH CaCO + +

3 3 6 2 3 3 3 2
B N H 9H O 3H BO 3NH 3H + + +

3 3
Li N 3H2O 3LiOH NH + +

3 2 3
NCl 3H O NH 3HOCl + +
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SECTION-III (Total Marls : 15)
(Paragraph Type)

This section contains 2 paragraphs. Based upon one of paragraphs 2 multiple choice questions and
based on the other paragraph 3 multiple choice questions have to be answered. Each of these questions
has four choices (A), (B), (C) and (D) out of which ONLY ONE is correct.

Paragraph for Question Nos. 12 to 13

Estimation of Carbon and Hydrogen in an organic compound can be carried out by
liebigs method and nitrogen by either Dumas method or by Kjeldahls method. Although
Kjeldahls method is easy to carry out in the laboratory, it is not of general applicability.

12. 0.50g of an organic compound was Kjeldahlised and the NH
3
evolved was absorbed in 50ml of 0.5
M H
2
SO
4
. The residual acid required 60ml of 0.5 M NaOH. The percentage of nitrogen in the
organic compound is
A) 14 B) 28 C) 56 D) 42

Sol. (C)
Moles of H
2
SO
4
reacting with
Ammonia = (moles of H
2
SO
4
absorbed ) (moles of NaOH solution required/2)
=
( )
3
3
60 0.5 10
50 0.5 10
2

| |

|
\
=20x0.5x10
-3

% of N can be calculated using the formula,

1.4volumeof acid Normality of acid
wt of organic compd taken



1.4 20 (2 0.5)
56
0.5
x x x
=
13. 0.46g of an organic compound containing carbon, hydrogen and oxygen was heated strongly in a
stream of N
2
gas. The gaseous mixture thus obtained was passed first over heated coke at 1373 K
and then through a warm solution of iodine pentoxide when 1.27 g of I
2
was liberated. The
percentage of oxygen present in the organic compound is
A) 87.4 B) 86.96 C) 47.38 D) 38.47

Sol. (B)
% of O can be calculated using the following formulae


2
wt of I formed 100
5 16
2 127 wt of org.compd

2
wt of CO formed 100
16
44 wt of org.compd


5x16 1.27
%' O' x 86.96%
2x127 0.46
= =
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Para. Q. Nos (14 - 16)

Addition of a non-volatile solute to a solvent lowers its vapour pressure. Therefore, the vapour
pressure of a solution (i.e., V.P. of solvent in a solution) is lower than that of pure solvent, at the
same temperature. A higher temperature is needed to raise the vapour pressure upto one
atmosphere pressure, when boiling point is attained. However increase in b.pt. is small. For
example 0.1 molal aqueous sucrose solution boils at 100.05oC. Sea water, an aqueous solution,
which is rich in Na+ and Cl ions, freezes about 1OC lower than frozen water. At the freezing
point of a pure solvent, the rates at which two molecules stick together to form the solid and leave
it to return to liquid state are equal when solute is present. Fewer solvent molecules are in contact
with surface of solid.
However, the rate at which the solvent molecules leave the surface of solid remains unchanged.
That is why temperature is lowered to restore the equilibrium. The freezing point depression in a
dilute solution is proportional to molality of the solute.

14. The freezing point of benzene solution was 5.4oC. The osmotic pressure of same solution at 10oC
is (boiling point of benzene = 5.5oC).Assume solution to be dilute.
K
f
for C
6
H
6
is 4.9K molality 1].
A) 0.274 atm B) 0.474 atm C) 0.674 atm D) 0.874 atm

Sol. (B)

0
f
f
5.5 5.4 0.1 C
0.1 k .m
0.1
m
4.9
CST
M m
0.1x0.0821x283
0.474atm
4.9
= =
=
=
=
=
= =


15. The amount of ice separated out on cooling a solution containing 50 g ethylene glycol in 200 g
water to 9.3
o
C is [K
f
for H
2
O = 1.86 K molality
1
]
A) 38.71g B) 61.29g C) 138.71g D) 161.29g

Sol. (A)
Ethylene glycol is CH
2
OH- CH
2
OH

.
0 ( 9.3) 1.86
50 1000
9.3 1.86
62
161.29
Ice seperated=200 -161.29 = 38.71
f f
T k m
xm
x
x
xW
W
=
=
=
=

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16. 2 g of benzoic acid dissolved in 25 g of C6H6 shows a depression in f.pt. equal to 1.62 K. Kf for
C6H6 is 4.9 K molality1. The percentage association of acid if it forms doubls molecules in
solution is
A) 0.8% B) 99.2% C) 90.2% D) 9.8%

Sol. (B)

6 5 6 5 2
2 ( ) C H COOH C H COOH
1 /2
i = 1- + /2 =1+ /2

. .
2 1000
1.62 (1 ).(4.9) .
2 122 25
(1 ) 0.504
2
( ) 0.495
2
0.9916 99.2%

f f
T i k m
x
x

=
=
=
=
= =

SECTION-IV (Total Marks : 28)
(Integer Answer Type)
This section contains 7 questions. The answer to each of the questions is a single digit integer, ranging
from 0 to 9. The bubble corresponding to the correct is to be darkened in the ORS.

17. Co-ordination number of Cr in CrCl
3
.5H
2
O is six. The volume of 0.1 N AgNO
3
needed to ppt. the
chlorine in outer sphere in 200 ml of 0.01 M solution of the complex is/are indicated .
(1) 140 ml (2) 40 ml (3) 80 ml (4) 20 ml
Sum of the correct options is

Sol. (6)
Case : 1
[ ]
2 5 2
Cr(H O) Cl Cl
0.01x200
0.002
1000
0.002x2 0.1xV(lit)
V(lit) 0.04
40ml
=
=
=
=
Case : 2
[ ]
2 4 2 2
Cr(H O) Cl Cl.H O
0.01x200
0.002
1000
0.002x1 0.1xV(lit)
V(lit) 0.02
20ml
=
=
=
=


18. The number of products obtained when propane is subjected to vapour-phase nitration is

Sol. (4)

|
CH CH CH NO , CH CH CH
3 2 2 2 3 3

NO
2

CH NO , CH CH NO
3 2 3 2 2

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19. A chemical reaction takes place in three steps having rate constant k
1
, k
2
, k
3
respectively. If
E ,E
a a
1 2
and E
a
3
are 50, 40 and 30 respectively in kJ and the overall rate constant,
1 3
2
k k
k=
k
.
The overall energy of activation is x x 10 kJ. x is


Sol. (4)
Arrhenius equation,

/
.
Ea RT
K Ae

=
1
/ /
/
3 2
; . ; .
1 1 2 2 3 3
Ea RT Ea RT
Ea RT
K A e K A e K A e

= = =
As
/
2
1 3 1 3 1 3
2 2
E E Ela RT
a a K K A A
K e
K A
| |
+
|
| | |
\
|
= =
|
\

50 30 40 40
1 3 2
E E E E KJ
a a a a
= + = + =

20. Green vitriol
O
300 C
anhydrous salt
high
temp
L M N + + . If oxidation state of the central atom in
L,M,N are X,Y,Z respectively (X<Y<Z). The value of Y Z X + is ___

Sol. (7)

O
300 C High
4 2 4 2 3 2 3 720 temp
FeSO .7H O 2FeSO Fe O SO SO

+ +
Oxidation state of Fe in Fe
2
O
3
= +3(X)
Oxidation state of S in SO
2
= +4(Y)
Oxidation state of S in SO
3
= +6(Z)
Y Z X + = 4 + 6 3 = 7

21.
24
11
Na (half-life = 15 hrs) is known to contain some radioactive impurity (half-life = 3 hrs) in a
sample. This sample has an initial activity of 1000 counts per minute, and after 30 hrs it shows an
activity of 200 counts per minute. Percent of the initial activity that was due to the impurity is Z x
10. Z is

Sol. (2)

n
0
1/ 2
1
N N ( )
2
t
n
t
=
=

where N
0
= Initial no of atoms, N = No. of atoms left after time t,
n= no of half lives, t = total time, t
1/2
= Half life

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Let the activity due to impurity be a cpm.
And that due to Na is (1000 a) cpm.
After 30 hrs a would be reduced to
10
1
a( )
2
cpm
and (1000 a) would be reduced to
1
(1000 a)
4
cpm
total activity after 30 hrs would be

10
1
a( )
2
+
1
(1000 a)
4
= 200 (given)
Solving, we get
250
1
a
4
= 200
a = 200
Hence 20% activity was due to impurity.

22. A hydrogen like species (atomic number Z) is present in a higher excited state of quantum
number n. this excited atom can make a transition to the first excited state by successive emission
of two photons of energies 10.20 eV and 17.0 eV respectively. Alternatively, the atom from the
same excited state can make transition to the second excited state by successive emission of two
photons of energy 4.25eV and 5.95 eV respectively. Value of Z is

Sol. (3)


2
2
2
1 1
17 13.6
3 2
eV Z
(
=
(



2
17 36
13.6 5
Z

=

9 =
3 Z =

23. There are 100 persons sitting at equal distance in a row XY . N
2
O (laughing gas) is released from
the side X and tear gas (molar mass = 176) from side Y at the same moment and at the same
temperature. The person who will have a tendency to laugh and weep simultaneously is at z
from side Y. Unit place of z is

Sol. (3)
Let 1 be N
2
O and 2 be tear gas
5
4
3
2
1
(1
st
excited
(2
nd
excited
4.25 eV
5.95 eV
10.20 eV
17 eV
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2
2 1
176
100 44
M
M
x
x
=
=

1
d
d
d is distance travelled, M is mol wt
From X = 67
From Y = 33