[1]

PHYSICAL CHEMISTRY
TIME : 1 HOUR 30 MIN. SITTING -1 MARKS :78
Single correct [16 3 = 48]
Q.1 500 ml of sample of AgNO
3
is treated with 49.8 gm of pure KI in excess. The resulting ppt. was filtered
off and filterate including washing made upto 2 L. 20 ml of this filterate required 10 ml of M/10 KIO
3
in
presence of HCl till all iodine converts into ICl. The molarity of AgNO
3
solution used is
(A) 0.2 (B) 0.1 (C) 0.05 (D) none of these
Q.2 One litre of a sample of hard water contain 2.22 mg CaCl
2
and 1.9 mg of MgCl
2
in 1 L H
2
O. What is the
total hardness in terms of ppm of CaCO
3
. [Ca = 40; Mg = 24, Cl = 35.5]
(A) 2 ppm (B) 3 ppm (C) 4 ppm (D) 4.12 ppm
Q.3 What volume of O
2
(g) measured at STP will be formed by action of 100 mL of 0.5 N KMnO
4
on
hydrogen peroxide in an acid solution? The Skeleton equation for the reaction is
KMnO
4
+ H
2
SO
4
+ H
2
O
2
K
2
SO
4
+ MnSO
4
+ O
2
+ H
2
O
(A) 0.12 litre (B) 0.028 litre (C) 0.56 litre (D) 1.12 litre
Q.4 What per cent of CO
2
in air is just sufficient to prevent loss in weight when CaCO
3
is heated at 100C.
Equilibrium constant K
p
for
CaCO
3
(s) CaO (s) + CO
2
(g) is 0.0095 atm at 100C.
(A) 0.95 % (B) 0.29 % (C) 0.05 % (D) 0.71 %
Q.5 Assuming that petrol is octane (C
8
H
18
) and has density 0.8 g/ml. 1.425 litre of petrol on complete
combustion will consume
(A) 80 mole of O
2
(B) 170 mole of O
2
(C) 200 mole of O
2
(D) 125 mole of O
2
Q.6 11.6 gm of an organic compound having formula C
n
H
2n+2
is burnt in excess of O
2
(g) initially taken in a
22.4 litre steel vessel. Before reaction the gaseous mixture was at 273 K with pressure reading 2 atm.
After complete combustion and loss of considerable amount of heat, the mixture of product and excess
of O
2
had a temperature of 546 K and 4.6 atm pressure. The formula of organic compound is
(A) C
2
H
6
(B) C
3
H
8
(C) C
5
H
12
(D) C
4
H
10
Q.7 6 10
3
mole K
2
Cr
2
O
7
reacts completely with 9 10
3
mole X
n+
to give

3
XO and Cr
3+
. The value of
n is
(A) 1 (B) 2 (C) 3 (D) None of these
Q.8 A mixture of NaHC
2
O
4
and KHC
2
O
4
H
2
C
2
O
4
required equal volumes of 0.2 N KMnO
4
and
0.12 N NaOH separately. What is the molar ratio of NaHC
2
O
4
and KHC
2
O
4
H
2
C
2
O
4
in the mixture?
(A) 6 : 1 (B) 1 : 6 (C) 1 : 3 (D) none
Q.9 In iodometric estimation of Cu
2+
ion, the following reaction took place.
2Cu
2+
+ 4I

Cu
2
I
2
+ I
2
I
2
+ 2Na
2
S
2
O
3
2NaI + Na
2
S
4
O
6
If 100 ml of CuSO
4
solution added to excess KI requires 50 ml of 0.2 M Na
2
S
2
O
3
, the molarity of
CuSO
4
solution is
(A) 0.05 M (B) 0.1 M (C) 0.2 (D) 0.25
[2]
Q.10 A
2
O
x
is oxidised to AO
3
by MnO
4
in acidic medium. If 1.5 10
3
mole of A
2
O
x
requires 40 ml of
0.03 M-KMnO
4
solution in acidic medium. Which of the following statement(s) is/are correct?
(A) The value of "x" = 1
(B) The value of "x" = 3
(C) Empirical formula of oxide is AO
3
.
(D) Empirical formula of oxide is A
2
O.
Q.11 Calculate the millimoles of
2
3
SeO in solution on the basis of following data:
70 ml of
60
M
solution of KBrO
3
was added to
2
3
SeO solution. The bromine evolved was removed by
boiling and excess of KBrO
3
was back titrated with 12.5 ml of
25
M
solution of NaAsO
2
.
The reactions are given below.
(a)
2
3
SeO +

3
BrO + H
+

2
4
SeO
+ Br
2
+ H
2
O (b)

3
BrO +

2
AsO
+ H
2
O Br +
3
4
AsO
+ H
+
(A) 1.6 10
3
(B) 1.25 (C) 2.5 (D) None of these
Q.12 The % of Fe
+2
in Fe
.93
O
1.00
is
(A) 15 % (B) 85 % (C) 93% (D) 7%
Q.13 A mixture of hydrocarbon C
2
H
2
, C
2
H
4
& CH
4
in mole ratio of 2 : 1 : 2 is burnt completely in the
presence of air containing 80% N
2
& 20% O
2
by volume. The mass of air required for the complete
combustion of the one gm of mixture is
(A)
112
1728
(B)
73
1528
(C)
120
1920
(D)
1728
112
Q.14 A hydrate of magnesium iodide has a formula MgI
2
x H
2
O. A 1.055 g sample is heated to a constant
weight of 0.695 g. What is the value of x?
(A) 2 (B) 4 (C) 6 (D) 8
Q.15 Concentration of NaOH solution 3.0 Molal and it's density is 1.1 gm/ml. What is the Molarity of the
solution?
(A) 1.48 M (B) 2.43 M (C) 2.94 M (D) 3.14 M
Q.16 The pH values 0.1 M solution of CH
3
COONa (I), CH
3
COOH (II), CH
3
COONH
4
(III), NaOH (IV),
HCl (V), will be in the order
(A) IV > III > I > II > V (B) IV > I > III > II > V
(C) II > III > I > IV > V (D) V > II > III > I > IV
Subjective [6 5 = 30]
Q.17 Chlorine gas can be produced by the reaction of HCl (aq) with MnO
2
(s). Only MnCl
2
(s) and H
2
O()
are the by products. What volume of Cl
2
(g) (in litre) of density 2.84 g/L will be produced from the
reaction of 400 mL of 0.1 M HCl(aq) with an excess of MnO
2
?
[3]
Q.18 A mixture of FeO and Fe
2
O
3
is reacted with acidified KMnO
4
solution having a concentration of
0.25 M, 100 ml of which was used. The solution was then titrated with Zn dust which converted Fe
3+
of
the solution to Fe
2+
. The Fe
2+
required 1000 ml of 0.10M K
2
Cr
2
O
7
solution.
Find out the weight % of FeO and Fe
2
O
3

in the mixture.
Q.19 224 ml of Dry CO
2
(g) at STP was passed in IL of NaOH solution of unknown molarity. 10 ml of
resulting solution when titrated with 0.01 M HCl required 30 ml for phenolphthalein end point. Find the
molarity of original NaOH solution.
Q.20 The aluminium in a 0.2 gm sample was precipitated with 8-hydroxyquinoline and the ppt was filtered and
dissolved in acid. To this solution was added 25.00 ml of 0.05 M KBrO
3
and 2 gm of KBr. After
reaction of Br
2
with 8-hydroxyquinoline, 2 gm of KI was added and the liberated I
2
titrated with 25 ml
of 0.1 N Na
2
S
2
O
3
. Calculate the % of Al
2
O
3
in the sample.
The relevent reactions are :
Al
3+
+
. Ppt
3
) HOQL ( Al + 3H
+
....(1)
(HOQL) = 8-hydroxyquinoline
HOQL 3 Al ) HOQL ( Al
3 H
ppt
3
+
+
+
....(2)
O H 3 Br 3 H 6 Br 5 BrO
2 2 3
+ + +
+
....(3)
....(4)
2

2
I Br 2 I 2 Br + +

....(5)

6 4 2 3 2 2 2
I O S Na O S Na 2 I + + ....(6)
Q.21 A 1.0 gm impure sample containing [Zn(NH
3
)
4
]Cl
2
and some inert impurity was treated with 12 ml of
1.0 M NaOH solution, where all the complex was converted into Na
2
[Zn(OH)
4
]. Ammonia formed is
first boiled off and then the excess of base required 4 ml of 1.0 M HCl solution for complete neutralisation.
After the neutralisation the solution is reacted with excess of AgNO
3
solution. Calculate the mass of
AgCl produced (in mg).
Q.22 Thermal decomposition of H
2
O
2
follows first order kinetics. Three flask, each containing 20 mL of
2.8 V H
2
O
2
were taken for kinetic study. Into the first flask, 20 mL of a KI solution was added after
1.0 hour, heated gently to expel-off liberated iodine and finally titrated against 0.5 M chromic acid
solution, 10 mL of chromic acid was required to reach end point. After three hour from beginning,
20 mL of KI solution of same strength was added to the second flask, heated gently and finally titrated
against chromic acid solution of same strength. After a very long time, similar experiment was repeated
with the third flask and required 40 mL of 0.5 N chromic acid solution. What was the volume of chromic
acid required for second experiment? Given ln2= 0.693
[4]
PHYSICAL CHEMISTRY
TIME : 2 HOUR SITTING -2 MARKS :119
Single correct [16 3 = 48]
Q.1 A certain weak acid has K
a
= 10
4
, then the equilibrium constant for its reaction with a strong base is
(K
w
= 10
14
)
(A) 10
18
(B) 10
10
(C) 10
4
(D) 10
18
Q.2 The indicator constant for an acidic indicator, HIn is 5 10
6
M. This indicator appears only in the
colour of acidic form when
20
1
] HIn [
] In [
s
and it appears only in the colour of basic form when
40
] HIn [
] In [
>

.
The pH range of indicator is
Given : [log 5 = 0.7]
(A) 4.3 6.3 (B) 4.0 6.6 (C) 4.0 6.9 (D) 3.7 6.6
Q.3 Isohydric solutions are the solutions having the same concentration of hydronium ion. If 0.2 M HA
(monobasic acid) solution is isohydric with 410
4
M HCl solution, then K
b
for A is
(A) 8 10
7
(B) 1.25 10
8
(B) 1.25 10
6
(D) 8 10
7
Q.4 The remaining molar concentration of Ag
+
ion if 100 ml of 0.1 M AgNO
3
solution is mixed with 400 ml
of 0.2 M K
2
Cr
2
O
4
solution is,
[Given: K
sp
(Ag
2
CrO
4
) = 1.5 10
11
M
3
]
(A) 10
10
(B) 2.5 10
3
(C) 5 10
3
(D) 10
5
Q.5 An ammonia - ammonium chloride buffer has a pH value of 9 with [NH
3
] = 0.25. What will be the new
pH if 500 ml 0.1 M KOH is added to 200 ml buffer solution (K
b
= 2 10
5
)
[log 2 = 0.3]
(A) 8.4 (B) 9.6 (C) 5.6 (D) 4.4
Q.6 pH of a saturated solution of silver salt of monobasic acid HA is found to be 9.
Find the K
sp
of sparingly soluble salt Ag A(s).
Given : K
a
(HA) = 10
10
(A) 1.1 10
9
(B) 1.1 10
10
(C) 1.1 10
11
(D) 10
12
Q.7 When glycinium hydrochloride (NH
2
CH
2
COOH . HCl) is titrated against NaOH, pH at the first half equivalence
point is 2.34 and at second half equivalence point it is 9.60. The pH at first equivalence point is
(A) 5.97 (B) 6.17 (C) 6.23 (D) 4.8
Q.8 Calculate the pH of a solution containing 0.2 M HCO
3

and 0.1 M CO
3
2
[K
1
(H
2
CO
3
) = 4 10
7
; K
2
(HCO
3

) = 4 10
11
]
(A) 10.4 (B) 10.1 (C) 6.1 (D) 10.7
Q.9 What is [Ag
+
] in a solution made by dissolving both Ag
2
CrO
4
and Ag
2
C
2
O
4
until saturation is reached
with respect to both salts. K
SP
(Ag
2
C
2
O
4
) = 2 10
11
, K
SP
(Ag
2
CrO
4
) = 2 10
12
(A) 2.80 10
4
(B) 7.6 10
5
(C) 6.63 10
6
(D) 3.52 10
4
[5]
Q.10 Consider the following statements
I K
sp
of Fe(OH)
3
in aqueous solution is 3.8 10
38
at 298K. The concentration of Fe
3+
will
increase when [H
+
] ion concentration decreases
II In a mixture of NH
4
Cl and NH
4
OH in water, a further amount of NH
4
Cl is added. The pH
of the mixture will decreases.
III An aqueous solution of each of the following salts(NH
4
I, Cr(NO
3
)
3
9H
2
O, KCN) will be
basic, basic, acidic respectively.
Choose the correct alternative.
(A) only I is correct (B) only II is correct
(C) II and III are correct (D) All are incorrect
Q.11 At same temperature N
2
O
4
is dissociated to 40% & 50% at total pressure P
1
& P
2
atm respectively in
NO
2
. Then the ratio of P
1
& P
2
is
(A)
5
4
(B)
4
7
(C)
7
4
(D) None of these
Q.12 If K
P
for a reaction is
2 2
atm 10
9
1

at 500 K. Magnitude of K
C
will be [Take R = 0.08]
(A) 3 10
1
(B)
2
10
9
1

(C)
9
16
(D) Data insufficient
Q.13 For the reaction N
2
(g) + 3H
2
(g) 2NH
3
(g)
AH = 24 kJ/mole
The percentage yield of the reaction against pressure is plotted at three
different temperature T
1
, T
2
, T
3
as shown in the adjacent figure. Pick
out the correct statement among the following.
(A) T
1
> T
2
> T
3
(B) T
3
> T
2
> T
1
(C) T
2
> T
1
> T
3
(D) None of these
Comprehension
Paragraph for question nos. 14 to 15
Following reaction is at equilibrium in basic medium at 300 K.
I
2
(s) I

(aq.) + IO

3
(aq.)
Equilibrium concentration at 300 K are , [ I

] = 0.1 M, [IO

3
] = 0.1 M
Given AG
f
(I

, aq) = 50 kJ/ mol

AG
f
(IO

3
, aq) = 123.5 kJ/ mol
AG
f
(H
2
O, l ) = 233 kJ/ mol
AG
f
(OH

, aq ) = 150 kJ/ mol
R =
3
25
J mol
1
K
1
log
10
e = 2.3
Q.14 AG of the reaction in KJ mol


is
(A) 150.7 (B) 172.5 (C) 172.5 (D) 150.7
Q.15 Value of equilibrium constant is
(A) 10
25
(B) 10
35
(C) 10
30
(D) 10
27
[6]
Q.16 pH value at equilibrium is
(A) 8 (B) 6 (C) 9 (D) 5
More than one may be correct [4]
Q.17 Select the incorrect statement(s).
(A) At equilibrium concentration of reactants become equal to concentration of products.
(B) In presence of catalyst, rate of forward reaction increases & rate of backward reaction decreases
by same amount.
(C) K
eq
constant may have zero or ve value.
(D) As pressure increases K
eq
increases, for the reaction, N
2
(g) + 3H
2
(g) 2 NH
3
(g), at given
temperature.
Match the column [12]
Q.18 For the given endothermic reaction
A(g) 2 B(g)
The variation in concentration due to different changes is plotted. In column II various changes are given
and you are supposed to match the entries in column-I with possible changes the system have undergone.
Neglect the slope of change in concentration when system approaches equilibrium.
Assume that changes are carried out very fast.
effect-I effect-II effect-III effect-IV
C
o
n
c
e
n
t
r
a
t
i
o
n

Time
Column I Column II
(The effect is )
(A) Effect-I (P) Addition of inert gas at constant pressure
(B) Effect-II (Q) Decrease in total equilibrium pressure by changing
volume.
(C) Effect-III (R) Decreases in temperature at constant volume
(D) Effect-IV (S) Addition of B only at constant volume
(T) Addition of inert gas at constant volume
[7]
Subjective [11 5= 55]
Q.19 At 27C, the rate of the forward reaction at a time 't' between reactants 'A' and 'B' to form the product
'P' is 12 times greater than the reverse rate. Calculate the magnitude of free energy change involved at
same time in J/mole? [Given : R = 8.3 J / mol / K, ln 12 = 2.5]
Q.20 Equimolar mixture of two gases A
2
and B
2
is taken in a rigid vessel at temperature 300 K. The gases
reacts according to given equations:
A
2
(g) 2A (g) ? K
1
P
=
B
2
(g) 2B (g) ? K
2
P
=
A
2
(g) + B
2
(g) 2AB (g)
2 K
3
P
=
If the initial pressure in the container was 2 atm and final pressure developed at equilibrium is 2.75 atm
in which equilibrium partial pressure of gas AB was 0.5 atm, calculate the ratio of
1
2
P
P
K
K
.
[Given : Degree of dissociation of B
2
is greater than A
2
].
Q.21 A flask containing 0.5 atm of A
2
(g) contains some solid AB which undergoes dissociation according to
2AB (s) A
2
(g) + B
2
(g). K
p
= 0.06 atm
2
Calculate the total pressure (in atm) at equilibrium.
Q.22 For the gas phase reaction SO
3
(g) SO
2
(g) + O
2
(g)if the gaseous mixture in a closed container is
allowed to come at equilibrium and the degree of dissociation (o) at equilibrium is found to be 2/3 at 400
K and 1 atm pressure then calculate the vapour density of the equilibrium mixture.
Q.23 At certain temperature (T) for the gas phase reaction.
) g ( O ) g ( O H 2 ) g ( NO 4
2 2 2
+ + 4HNO
3
(g), K
p
= 10
12
atm
3
If NO
2
, HNO
3
& O
2
each at partial pressure of 1 atm & H
2
O at 0.25 atm are mixed & the mixture is
brought into contact with excess of liquid water. What would be approximate partial pressure of NO
2
(in atm) when equilibrium is attained at temperature T.
[Given : Vapour pressure of water is 380 Hg at temperature T]
Fill your answer by multiplying (3 10
12
)
1/4
.
Q.24 H
3
A is a weak triprotic acid (
1
a
K
= 10
5
,
2
a
K
=10
9
,
3
a
K
=10
13
).
Calculate the value of pX of 0.1 M H
3
A (aq) solution where pX = log X & X =
] HA [
] A [
2
3

.
Q.25 pH of a lemon water bottle is 3, and that of orange juice is 4. Calculate the pH of final solution obtained
by mixing above solutions in volume ratio 1 : 2 respectively. (Assuming there is no chemical reaction.)
(Given log 2 = 0.30)
[8]
Q.26 A solution contains 0.1 M Mg
2+
and 0.1 M Sr
2+
. The concentration of H
2
CO
3
in solution is adjusted to
0.05 M. Determine the pH range which would permit the precipitation of SrCO
3
without any precipitation
of MgCO
3
.
Given : K
sp
(MgCO
3
) = 4 10
8
M
2
K
sp
(SrCO
3
) = 9 10
10
M
2
respectively.
The overall dissociation constant for H
2
CO
3
is 5 10
17
.
[Hint: H
+
ion concentration is controlled by external means]
[log 2 = 0.3, log 3 = 0.5 & log 5 = 0.7]
(If pH range is 2.5 to 4.8, then answer as 2548)
Q.27 A 1.025 gm sample containing a weak acid HX (M
w
= 82) is dissolved in 60 ml water & titrated with
0.25 M NaOH. When half of the acid was neutralised, the pH was found to be 5 & at equivalence point
pH is 9. What is weight % of HX in sample.
Q.28 In Mohr's method, solution of Cl is titrated against standard AgNO
3
. During the titration, a small
quantity of K
2
CrO
4
solution is added as an indicator. As AgCl is less soluble than Ag
2
CrO
4
, the added
Ag
+
reacts first with Cl than with CrO
4
2
. At the equivalence point, when Cl is precipitated quantitatively
as AgCl, the slight excess of Ag
+
reacts with CrO
4
2
to give intensely red precipitate of Ag
2
CrO
4
.50.0
mL of 0.1 M Cl solution is titrated against 0.1 M standard AgNO
3
. What must be the theoretical molar
concentration of CrO
4
2
in the solution so that Ag
2
CrO
4
will start precipitating at the equivalence-point.
Given : K
sp
(AgCl) = 10
10
M
2
; K
sp
(Ag
2
CrO
4
) = 4 10
12
M
3
[Fill your answer by multiplying it with 10
4
.]
Q.29 Calculate the ratio of pH values of a 1M CH
3
COOH solution and a solution containing equimolar
mixture of CH
3
COOH and CH
3
COONa. [K
a
(CH
3
COOH) = 10
5
M]
[If the ratio is 1 : 5, then answer as 0105]
[9]
PHYSICAL CHEMISTRY
TIME : 1 HOUR 30 MIN. SITTING -3 MARKS :89
Single correct [18 3 =54 ]
Q.1 An ideal gas undergoes expansion from A (10 atm, 1l ) to B (1 atm, 10 l) either by
(I) Infinite stage expansion or by
(II) First against 5 atm and then against 1 atm isothermally
Calculate
II
I
q
q
(A)
303 . 2 13
1

(B) 13 2.303 (C)

03 . 23
13
(D)
13
03 . 23
Q.2 Which of the following statement(s) is/are correct?
(A) The quantities E, H and G have the same dimension
(B) Gibbs free energy of 10 gm ice at 0C and 1.0 atm is less than the Gibbs free energy of 10 gm
water at 0C and 1 atm.
(C) AS
sys
= 0 for every adiabatic process in a closed system.
(D) For every reversible process, in a closed system, AS
sys
=
T
H
sys
A
Q.3 Calculate the heat capacity of the monoatomic gas undergoing the process, as shown in the P-V graph:
V(ltr.)
P
(
a
t
m
)
45
4
2
(A)
2
3
R (B)
2
5
R (C)
2
7
R (D)
6
8
R
Q.4 The temperature of a definite amount of an ideal monoatomic gas becomes four times in an isoentropic
process. Which of the following is correct relation between the final and initial parameters of gas?
(A) V
f
= 8V
i
(B) V
f
= 16 V
i
(C) P
f
= 32 P
i
(D) P
f
=
16
1
P
i
Q.5 A diatomic ideal gas initially at 273 K is given 100 cal heat due to which system did 209 J work.
Molar heat capacity (C
m
) of gas for the process is :
(A)
2
3
R (B)
2
5
R (C)
4
5
R (D) 5 R
Q.6 If AH
vaporisation
of substance X (l) (molar mass : 30 g/mol) is 300 J/g at it's boiling point 300 K, then
molar entropy change for reversible condensation process is
(A) 30 J/mol.K (B) 300 J/mol.K (C) 30 J/mol.K (D) None of these
[10]
Q.7 What is the AU for the system, if system absorbs 500 kJ of heat and does 350 kJ of work on the
surroundings.
(A) 850 kJ (B) 150 kJ (C) 150kJ (D) None of these
Q.8 Calculate A
r
G (in kJ / mol) for reaction at 300 K
N
2
(g) + O
2
(g) 2NO(g)
the partial pressure of N
2
, O
2
& NO are 10
4
bar, 10
2
bar and 10
5
bar respectively when mixed
together at 300 K.
Given : 2.303 RT = 5750 J/mol
g) NO, ( H
300

A
f
= 90.5 kJ/mol ; g) , N ( S
2 300

= 190 J/K-mol
g) NO, ( S
300

= 210 J/K-mol ; g) , O ( S
2 300

= 205 J/K-mol
(A) 150.5 kJ/mol (B) 173.5 kJ/mol (C) 196 kJ/mol (D) None of these
Q.9 For the hypothetical reaction
A
2
(g) + B
2
(g) 2AB(g)
A
r
G and A
r
S

are 20 kJ/mol & 20 JK
1
mol
1
respectively at 200 K.
If A
r
C
p
is 20 JK
1
mol
1
then A
r
H at 400 K is
(A) 20 kJ / mol (B) 7.98 kJ/mol (C) 28 kJ / mol (D) None
Q.10 When two equal sized pieces of the same metal at different temperatures T
h
(hot piece) and
T
c
(cold piece) are brought into contact into thermal contact and isolated from it's surrounding. The total
change in entropy of system is given by
(A) C
v
ln
c
h c
T 2
T T +
(B) C
v
ln
1
2
T
T
(C) C
v
ln
c h
2
h c
T . T 2
) T T ( +
(D) C
v
ln
c h
2
h c
T . T 4
) T T ( +
Q.11 For the reaction at 300 K
A(g) + B(g) C (g)
AE = 3.0 kcal ; AS = 10.0 cal/K
value of AG is
(A) 600 cal (B) 6600 cal (C) 6000 cal (D) None
Q.12 An exothermic reaction is represented by the graph :
(A) (B) (C) (D)
Q.13 When 1 gm equivalent of strong acid reacts with strong base heat released is 13.5 Kcal, when 1 gm
equivalent H
2
A is completely neutralised against strong base 13 Kcal is released, when 1 gm equivalent
B(OH)
2
is completely neutralised against strong acid 10 Kcal heat is released. Calculate enthalpy
change when 1 gm mole H
2
A is completely neutralised by B(OH)
2
.
(A) 27 Kcal (B) 10 Kcal (C) 20 Kcal (D) 19 Kcal
Q.14 1 mole of NH
4
CN is added to a large amount of solution of NH
4
CN, calculate the differential enthalpy
of solution if enthalpy of ionisation of NH
4
OH and HCN are 7 kJ/mol and 8 kJ/mol. also,
) O H ( f
2
H A
= 57.3 kJ/mol.
(A) 15 kJ/mol (B) 42.3 kJ/mol (C) +1 kJ/mol (D) 42.3 kJ/mol
Q.15 Select the option in which heat evolved is maximum.
Given : A
f
H (CO
2
,g) = 75 kcal/mol ; A
f
H (CO,g) = 25 kcal/mol
The product will be CO if excess amount of carbon is present and CO
2
if excess O
2
is present
(A) 10 moles of carbon and 4.5 moles of O
2
(B) 24 gm of carbon and 64 gm of O
2
(C) 4 moles of carbon and 3.5 moles of O
2
(D) 30 gm of carbon and 80 gm of O
2
Q.16 The difference between heat of reaction at constant volume and constant pressure for the reaction
C
2
H
2
(g) +
2
5
O
2
(g) 2CO
2
(g) + H
2
O (l)
at 300 K in Kcal is: [Given : R = 2 cal / mol. K]
(A) 0.3 Kcal (B) + 0.3 Kcal (C) 0.9 Kcal (D) None of these
Q.17 Calculate the resonance energy of C
6
H
6
(g) using Kekule formula for benzene from the following data.

A
f
H
for C
6
H
6
(g) = 358 kJ/mol
Heat of atomization of carbon = 716 kJ/mol
Bond energy of CH, CC, C=C and HH bonds are 490, 340, 620, 436 kJ/mol respectively.
(A) 150 kJ/mol (B) 142 kJ/mol (C) 158 kJ/mol (D) none of these
Q.18 A 500 gm sample of water is reacted with an equimolar amount of CaO (both at an initial temp of 25C).
What is the final temperature of the product? [Assume that the product absorbs all of the heat released
in the reaction] Heat produced per mol of Ca(OH)
2
is 65.2 kJ and specific heat Ca(OH)
2
is 1.2 J/gC.
(A)
~
735C (B)
~
760C (C)
~
746C (D)
~
789C
More than one may be correct [2 4 = 8]
Q.19 The normal boiling point of a liquid 'A' is 300 K. Which of the following statement is true about the
process A(l) A(g)
(A) at 300 K and 1 atm pressure AG = 0 (B) at 300 K and 2 atm pressure AG = +ve
(C) at 300 K and 0.1 atm pressure AG = ve (D) at 310 K and 1 atm pressure AG = +ve
Q.20 From the following data, mark the option (s) where AH is correctly written for the given reaction. Given:
H
+
(aq) + OH

(aq) H
2
O (l) AH = 57.3 kJ
AH
solution
of HA (g) = 70.7 kJ/mol
AH
solution
of BOH(g) = 20 kJ/mol
AH
ionization
of HA = 15 kJ/mol & BOH is a strong base
Reaction H
R
(kJ/mole)
(A) HA(aq) + BOH(aq) BA(aq) + H
2
O 42.3
(B) HA(g) + BOH(g) BA(aq) + H
2
O 93
(C) HA(g) H
+
(aq) + A

(aq) 55.7
(D) B
+
(aq) + OH

(aq) BOH(aq) 20
[12]
Match the column [12]
Q.21 Match the Column :
Column I Column II
(A) Isothermal vaporisation of (P) AT = 0
water at 100C & 1 atm
(B) Isothermal reversible expansion (Q) AE = 0
of an ideal gas
(R) AH = 0
(C) Adiabatic free expansion of
ideal gas (S) q = 0
Subjective [3 5 = 15]
Q.22 Calcium oxide (CaO) prepared by reaction
CaCO
3
(s) CaO (s) + CO
2
(g)
Calculate free energy change for the reaction (A
r
G) in kJ/mole at 300 K
Given: A
f
H(CaO, s) = 635 kJ/mole ; A
f
H(CO
2
, g) = 394 kJ/mole
A
f
H(CaCO
3
, s) = 1207 kJ/mole
S(CO
2
, g) = 214 J/K-mole ; S(CaO, s) = 40 J/K-mole
S(CaCO
3
, s) = 94 J/K-mole; all given data at 300 K
Q.23 Two mole of an ideal gas is expanded irreversibly & isothermally at 27C untill its volume is doubled and
3.3 kJ heat is absorbed from surrounding. Determine AS
system
& AS
surrounding
.
Q.24 In solid NH
3
, each NH
3
molecule has six other NH
3
molecules as nearest neighbours. The enthalpy of
sublimation of NH
3
(s) at its melting point is 30.4 kJ mol
1
and the estimated value of enthalpy of
sublimation of NH
3
(s), when there were no hydrogen bonds, is 15.4 kJ mol
1
. What is the average
strength of hydrogen bonds in solid NH
3
in kJ mol
1
?
Answer Key and Solution will be uploaded on
17
th
January after 11:00 AM. Analysis key will
be uploaded on 21
st
January. Use Analysis key
to identify weak areas for improvement.