[1]

PHYSICAL CHEMISTRY
TIME : 2 HOUR SITTING -1 MARKS :112
Single correct [18 3 = 54]
Q.1 During study of a liquid phase reaction A (aq) B (aq) + C (aq) the variation in concentration of B
with time is given
t/min 0 10 20 30 .......
conc. (B) mole/L 0 0.1 0.19 0.271 ....... 1
The initial rate of reaction was?
(A) 1.76 10
4
M sec
1
(B) 2.76 10
4
M sec
1
(C) 3.86 10
4
M sec
1
(D) 2 10
3
M sec
1
Q.2 Consider this gas phase reaction.
Cl
2
(g) + CHCl
3
(g) HCl(g) + CCl
4
(g)
The reaction is found experimentally to follow this rate law.
rate = k[CHCl
3
][Cl
2
]
1/2
Based on this information, what conclusions can be drawn about this proposed mechanism?
Step 1. Cl
2
(g) 2Cl (g)
Step 2. Cl(g) + CHCl
3
(g) HCl (g) + CCl
3
(g)
Step 3. Cl(g) + CCl
3
(g) CCl
4
(g)
(A) Step 1 is the rate-determining step (B) Step 2 is rate-determining step
(C) Step 3 is the rate-determining step (D) The rate-determining step cannot be identified
Q.3 The mechanism of esterification in presence of acid catalyst(H
2
SO
4
) is proposed as follows
) I (
COH CH
||
O
3

) II (
H CO CH
|
H O
3

) III (
H C O H
|
H O C CH
|
H O
5 2
3

) IV (
H C O
|
OH C CH
|
H O H
5 2
3

) IV (
H C O
|
OH C CH
|
H O H
5 2
3

) V (
H C O
|
OH C CH
5 2
3

Which of the following potential energy vs reaction coordinate diagram is consistant with given mechanism.
(Use basic bond energy consideration, and information given in reaction mechanism)
(A) (B) (C) (D)
[2]
Q.4 Reaction A + B C + D follow's following rate law : rate =
2
1
2
1
] B [ ] A [ k
+
= . Starting with initial
conc. of one mole of A and B each, what is the time taken for amount of A of become 0.25 mole. Given
k = 2.31 10
3
sec
1
.
(A) 300 sec. (B) 600 sec. (C) 900 sec. (D) none of these
Q.5 Consider the reaction . The rate constant for two parallel reactions were found to be
10
2
dm
3
mol
1
s
1
(k
1
) and 4 10
2
dm
3
mol
1
s
1
(k
2
). If the corresponding energies of activation of the
parallel reactions are 80 and 100 kJ respectively. What is the apparent (net) overall energy of activation
of given reaction.
(A) 96 kJ/mole (B) 120 kJ/mole (C) 100 kJ/mole (D) none
Q.6 At a certain temperature the following data were collected for the reaction
HCl 2 I H ICl 2
2 2
+ +
Initial Concentrations(M) Initial Rate of formation of I
2
(Ms
1
)
[ICl] [H
2
]
0.10 0.10 0.0015
0.20 0.10 0.0030
0.10 0.05 0.00075
Determine overall order of reaction
(A) 0 (B) 1 (C) 2 (D) 3
Q.7 The rate law of a reaction between the substances A and B is given by rate = k[A]
n
[B]
m
. On doubling
the concentration of A and halving the conc. of B, the ratio of the new rate to the earlier rate of reaction
will be
(A)
n m
2
1
+
(B) m + n (C) n m (D) 2
(n m)
Q.8 The activation energies of two reactions I and II are E
a
and 2E
a
respectively. If the temperature of the
reacting systems is increased from T to T', predict which of the following alternative is correct?(k represent
rate constant)
(A)
II
'
II I
'
I
k / k k / k = (B)
II
'
II I
'
I
k / k k / k > (C)
II
'
II I
'
I
k / k k / k < (D)
II
'
II I
'
I
k / k 2 k / k =
Q.9 A first order reaction is 50% completed in 20 minutes at 27C and in 5 min at 47C. The energy of
activation of the reaction is
(A) 43.85 kJ/mol (B) 55.14 kJ/mol (C) 11.97 kJ/mol (D) 6.65 kJ/mol
Q.10 The decomposition of N
2
O
5
in chloroform was followed by measuring the volume of O
2
gas evolved :
2N
2
O
5
(CCl
4
) 2N
2
O
4
(CCl
4
) + O
2
(g). The maximum volume of O
2
gas obtained was 100 cm
3
. In
500 minutes, 90 cm
3
of O
2
were evolved. The first order rate constant (in min
1
) for the rate of
disappearance of N
2
O
5
is
(A)
500
303 . 2
(B)
500
303 . 2
log
90
100
(C)
500
303 . 2
log
100
90
(D)
500 10
100

[3]
Q.11 For the reaction
CH
3
COCH
3
+ Br
2

+
H
CH
3
COCH
2
Br + H
+
+ Br
the following data was collected
[Acetone] [Br
2
] [H
+
] Rate of reaction (Ms
1
)
0.15 0.025 0.025 6 10
4
0.15 0.050 0.025 6 10
4
0.15 0.025 0.050 12 10
4
0.20 0.025 0.025 8.0 10
4
The order of the reaction w.r.t. CH
3
COCH
3
and Br
2
respectively are :
(A) 0,1 (B) 1,0 (C) 1,1 (D) 1,2
Q.12 For any reaction,
A + B C + D
Rate law obtained is : Rate = k [A] [B]
Select the correct option :
(A) Reaction must be elementary (B) Reaction must be complex
(C) Reaction may be elementary or complex (D) None of these
Q.13 For a two step reaction.
A R + B R + C

2
k
P
(Where, R is a reactive intermediate whose concentration is maintained at some low steady state throughout
the reaction). If the concentration of C is very high then the order of reaction for formation of "P" is
(A) 2 (B) 0 (C) 1 (D) 1/2 (E) 3
Q.14 The dependence of rate constant of a reaction on temperature may be given as
2
a
RT
E
dT
) K n ( d
=
l
where E
a
is activation energy for the reaction. For a reaction, the dependence of rate constant on
temperature is given as
ln K = 10
T
2500
+ 3 ln T
The activation energy of reaction is
(A) 2500 + 3T (B) 2500 R (C) (2500 + 3T)R (D) (2500 3ln T)R
Q.15 For the reaction,
2SO
2
+ O
2
2SO
3
if rate of disappearance of O
2
is 8 gm /sec., then rate of appearance of SO
3
will be
(A) 16 gm/sec. (B) 4 gm/sec. (C) 40 gm/sec. (D) 10 gm/sec.
Q.16 If binding energy per nucleon of
1
H
2
is "x" while that of
2
He
4
is "7x". Then ratio of energy liberated in
following reaction & binding energy per nucleon of
1
H
2
is
1
H
2
+
1
H
2

2
He
4
(A) 6 (B) 24 (C) 26 (D) 5
[4]
Q.17
35
X
88
is an unstable isotope, decays in two successive steps to produce stable isotope
32
Z
84
as
35
X
88

I
Y
II

32
Z
84
The correct statement is (possible emission are o , | , positron, neutron,
1
H
1
and K-e

capture)
(A) I may involve a |-emission. (B) II may involve a neutron emission.
(C) Y and Z may be isodiaphers (D) X and Z may be isodiaphers
Assertion Reason
Q.18 Statement-1:
238
UF
6
and
238
U both have same specific activity.
Statement-2:
238
U has same half life whether in free state or bonded state.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
More than one may be correct [3 4 = 12 ]
Q.19 For the reaction A B, the rate law expression is
t d
] A [ d

= k [A]
1/2
. If initial concentration of [A] is
[A]
0
, then
(A) The integerated rate expression is k =
) A A (
t
2
2 / 1 2 / 1
0

(B) The graph of A Vs t will be
(C) The half life period
2 / 1
t =
2 / 1
0
] A [ 2
K
(D) The time taken for 75% completion of reaction
4 / 3
t =
k
] A [
0
Q.20 o-maltose (C
12
H
22
O
11
) can be hydrolysed to glucose (C
6
H
12
O
6
) according to the following reaction:
C
12
H
22
O
11
(aq) + H
2
O () 2 C
6
H
12
O
6
(aq)
Given:
Standard enthalpies of formation of C
12
H
22
O
11
(aq) = 2238 kJ / mol
Standard enthalpies of formation of H
2
O () = 285 kJ / mol
Standard enthalpies of formation of C
6
H
12
O
6
(aq)= 1263 kJ / mol
25 . 0 0 . 1 0 . 4 ) M ( maltose of . Conc
100 50 0 .) (min Time
o
Which of the following statement(s) is / are true?
(A) The hydrolysis of o-maltose is exothermic
(B) Heat liberated in combustion of 1.0 mol of o-maltose is greater than the heat liberated in combustion
of 2.0 mol of glucose.
(C) Increasing temperature will increase the degree of hydrolysis of o-maltose.
(D) The hydrolysis of o-maltose follow 1
st
order kinetics.
[5]
Q.21 The polarimeter readings in a experiment to measure the rate of inversion of cane sugar (1
st
order
reaction) were as follows:
Time ( min.) 0 30
Rotation due to solution (degree) 30 20 15
Identify the true statements:
[Given : log2 = 0.3, log3 = 0.48, log7 = 0.84, (log
e
10) = 2.3]
(A) The half life of the reaction is 75 min. (B) The solution is optically inactive at 120 min
(C) The half life of the reaction is 60 min. (D) The solution is optically inactive at 90 min
Match the column [6]
Q.22 For the first order consecutive reactions.
A
1
k
B
2
k
C
the reaction is started with some amount of A . Match the given observation (column I) with the time
(column II) related with the above reaction.
Column I Column II
(Observation) (Time)
(A) Rate of formation of C is maximum (P) At time 't' = t
1/2
of A (Given k
2
= 2k
1
)
(B) [B]
t
= [C]
t
(Q) At time 't' =
|
|
.
|

\
|

1
2
1 2
k
k
n
) k k (
1
l
(R) At time 't' when rate of formation of B is maximum
Subjective [8 5 = 40]
Q.23 The reaction A(g) 2B(g) + C(g) is a first order reaction with respect to A, with rate constant 1.386
10
3
sec
1
. Starting with 0.1 mole/L of gas A, find the concentration of A after 500 sec. from the
start of reaction when the reaction is allowed to take place at constant total pressure at 300 K.
Q.24 10 gm mixture of two gases A
2
(Mol. wt. = 20) and B
2
(Mol. wt. = 30), which decompose by first order
kinetics, was taken in a vessel. The half life for decomposition of A
2
and B
2
are

2 and 3 hours respectively.
After 6 hours, weight of the gases A
2
and B
2
is found to be 2 gm. Find the weight (in mg) of remaining
A
2
& B
2
gases after 12 hours.
Q.25 N-chloroacetanilide isomerises into p-chloroacetanilide in presence of HCl.
+ HCl
The kinetics of reaction in monitored by taking a definite volume of reaction mixture containing
N-chloroacetanilide and excess of HCl at different time intervals. Now excess of KI is added and
liberated iodine is titrated with standard thiosulphate solution (KI reacts only with N-chloroacetanilide).
From the given data find the rate constant in (mole/litre)
1n
sec
1
unit.
0 5 . 40 45 50 ) ml ( te Thiosulpha of . Vol
60 30 0 .) (min Time
Usefuel Data : log3 = 0.48,
X log
X n l
= 2.3
[6]
Q.26 Kinetic data for hydrolysis of a 0.3 M solution of ethyl acetate in presence of HCl as catalyst is given in
the following table. A constant volume of reaction mixture is taken at different time and titrated against
standard alkali solution at different time.
00 . 40 00 . 28 00 . 25 ml / Alkali of . Vol
t 10 0 min / Time =
If the rate law is given by rate = k[Ester]
1
[H
+
]
1
, where H
+
is a catalyst ,find the rate (in M/min) of ester
hydrolysis in a solution which is 0.1 M each in ester and acid HCl (M/min)
Use: ln
|
.
|

\
|
4
5
= 0.225
Q.27 For the reaction
A + B product
rate law is
rate = k[A]
2
[B]
where k = 5 10
5
(mol/lit)
2
min
1
Determine the time (in minutes) in which concentration of 'A' becomes half of its initial concentration.
If initial concentration of A and B are 0.2 M and 2 10
3
M respectively.
Q.28 A man weighing 80 kg was injected with 5 ml of water containing tritium giving 1.08 10
11
dpm. When
the sample is distributed uniformly within the body water of patient, a 1.0 ml sample of water showed an
activity of 3.0 10
4
dps. Estimate the weight percentage of water in the human body. Neglect any
change in volume of water in the human body during the observation period and take the density of water
as 1000 kg/m
3
. (Half life of
1
H
3
is 12.3 years).
[If answer is 82.45 % then fill OMR as 8245]
Q.29 For a zero order chemical reaction,
2NH
3
(g) N
2
(g) + 3H
2
(g)
rate of reaction = 0.1 atm / sec. Initially only NH
3
is present & its pressure = 3 atm. Calculate total
pressure at t = 10 sec.
Q.30 0.01 moles of sulphuryl chloride SO
2
Cl
2
(g) is taken in a sealed tube & heated to 400 K. It decomposes
following 1
st
order kinetics according to reaction :
SO
2
Cl
2
(g) SO
2
(g) + Cl
2
(g)
The tube is broken after 4 hours & gas passed through a 25 ml of an acidified 1 N iodine solution where
all SO
2
is oxidised to SO
4
2
. The resulting solution required 10 ml of 1M Hypo solution. What is half life
in hours.
[7]
PHYSICAL CHEMISTRY
TIME : 1 HOUR SITTING -2 MARKS :65
Single correct [13 3 = 39]
Q.1 Two liquid A and B form an ideal solution. The ratio of vapour pressures of pure liquids A and B are 3 :
5. if the mole- fraction of A in the liquid solution at equilibrium with vapours, is 0.4, then the mole-fraction
of B in the vapour is
(A)
5
3
(B)
7
5
(C)
7
2
(D)
5
2
Q.2 Consider the following arrangement.
I II
100ml
NaCl 0.1M
100ml
Pure H O
2
Volume of liquid in container I and II at equilibrium are
(A) I = 100 ml, II = 100 ml (B) I = 200 ml, II = 0 ml
(C) I = 0 ml, II = 200 ml (D) I = 110 ml, II = 90 ml
Q.3 The vapour pressure of A, B & C are 75 torr , 22 torr and 10 torr at 20C which of the following is not
possible value of vapour pressure of an equimolar binary / ternary solution of these at 20C.
Assume all solution are ideal in nature.
(A)
2
107
(B)
3
107
(C)
2
97
(D) 16
Q.4 Two liquids A and B form an ideal solution. The solution has a vapour pressure of 700 torr at 90 C. It
is distilled till 2/3
rd
of the solution is collected as condensate. The composition of the condensate is
'
A
X
=0.75 and that of the residue is
"
A
X
= 0.3. If the vapour pressure of the residue at 90 is 600 torr,,
which of the following option is incorrect.
(A) The composition of the original liquid was X
A
= 0.6.
(B) The composition of the original liquid was X
A
= 0.4.
(C)
3
2500
P
0
A
=
torr
(D)
0
B
P
= 500 torr
(E) The composition of the original liquid was X
B
= 0.4
[8]
Q.5 Using the following information determine the boiling point of a mixture contains 1560 gm benzene and
1125 gm chlorobenzene, when the external pressure is 1000 torr. Assume the solution is ideal.
Given :Molar mass of benzene = 78
Molar mass of chlorobenzene = 112.5
Temperature (0C) Vapour pressure Vapour pressure of
of benzene (torr) chlorobenzene (torr)
80 750 120
90 1000 200
100 1350 300
110 1800 400
120 2200 540
(A) 120 C (B) 110 C (C) 100 C (D) 90 C (E) 80C
Q.6 A cylinder fitted with a movable piston contains liquid water in equilibrium with water vapour at 25C.
Which of the following operation results in a decrease in the equilibrium vapour pressure at 25C?
(A) Moving the piston downward a short distance (B) Removing a small amount of vapour
(C) Removing a small amount of liquid water (D) Dissolving some salt in the water.
Q.7 The solubility of common salt is 36.0 gm in 100 gm of water at 20C. If systems I, II and III contain
20.0, 18.0 and 15.0 g of the salt added to 50.0 gm of water in each case, the vapour pressures would
be in the order.
(A) I < II < III (B) I > II > III (C) I = II > III (D) I = II < III
Comprehension
Paragraph for question nos. 8 to 10
10 mole of liquid 'A' and 20 mole of liquid 'B' is mixed in a cylindrical vessel containing a piston arrangement.
Initially a pressure of 2 atm is maintained on the solution. Now, the piston is raised slowly and isothermally.
Assume ideal behaviour of solution and A and B are completely miscible.
atm 9 . 0 P and atm 6 . 0 P
o
B
o
A
= =
Q.8 The pressure below which the evaporation of liquid solution will start, is
(A) 0.6 atm (B) 0.8 atm (C) 0.77 atm (D) 0.9 atm
Q.9 The pressure at which
3
1
th of the total amount (by mol) of liquid solution taken initially, will be present in
the vapour form, is [Given : 57 = 7.55 ]
(A) 0.783 (B) 0.800 (C) 0.600 (D) 0.652
Q.10 The minimum pressure for the existence of liquid solution is
(A) 0.6 atm (B) 0.8 atm (C) 0.77 atm (D) 0.9 atm
Assertion Reason
Q.11 Statement-1: If a solute is mixed in a solvent to form a homogenous mixture then its vapour pressure
must decrease.
Statement-2: Relative lowering of vapour pressure is the colligative property of solution.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
[9]
Q.12 Statement-1: Addition of HgI
2
to aqueous solution of KI increases the freezing point.
Statement-2: A complex K
2
[HgI
4
] is formed.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
Q.13 Statement-1 : The freezing of water is an endothermic process.
Statement-2 : Heat must be removed from the water to make it freeze.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
More than one may be correct [4]
Q.14 Which of the following is correct for a non-ideal solution of liquids A and B, showing negative deviation?
(A) AH
mix
= ve (B) AV
mix
= ve (C) AS
mix
= +ve (D) AG
mix
= ve
Match the column [12]
Q.15 Column I Column II
(Colligative properties) (Aqueous solution)
(Assume m = M)
(A) AT
f
= 0.3 K
f
(P) 0.1 m Ca(NO
3
)
2
(B) AT
b
= 0.28 K
b
(Q) 0.14 m NaBr
(C) t= 0.19 RT (R) 0.1 m MgCl
2
(o = 0.9)
(D)
|
|
.
|

\
| A
+
|
.
|

\
|
|
|
.
|

\
| A
=

f
f
f
f
0
0
K
T
18
1000
K
T
P
P P
(S) 0.28 m Urea
(T) 0.1 m HA (monobasic acid , K
a
= 0.81)
Subjective [2 5 = 10]
Q.16 How many gm of glucose should be dissolved in 500 gm of water in order to produce a solution with
105C difference between the freezing point and the boiling point ? For water, K
f
= 1.9 K-Kg/mol and
K
b
= 0.6 K-Kg / mol.
Q.17 The Henry law constant for O
2
(g) and N
2
(g) in water at 0C are 2.5 10
4
bar and 5.0 10
4
bar
respectively. Calculate AT
f
of solution made by dissolving air at 1 bar pressure.
Given : mole % of O
2
in air = 20 & mole % of N
2
in air = 80
K
f
of H
2
O = 1.86 K kg mol
1
[Write your answer by multiplying with 10
5
]
[10]
PHYSICAL CHEMISTRY
TIME : 2 HOUR SITTING -3 MARKS :93
Single correct [15 3 = 45]
Q.1 What is the value of compressibility factor of a vander waal gas at its Boyle temperature?
(A) 1.0 at all pressure
(B) 1.0 at low pressure and greater than 1.0 at very high pressure
(C) 1.0 at low pressure and less than 1.0 at very high pressure
(D) 1.0 at high pressure and less than 1.0 at low pressure
Q.2 For 1 mole of a vander Waal gas at high pressure the slope at constant volume in P (Pressure) v/s T
(Temperature) curve is
(A)
m
V
R
(B)
b
R
(C)
) b V (
R
m

(D) Can not be predicted
Q.3 A mixture of equal mass of O
2
and O
3
gases are allowed to effuse through an orifice, the rate of effusion
of O
3
to O
2
is
(A)
3
2
(B)
2
3
(C)
3 3
2 2
(D) None of these
Q.4 The ratio of fraction of molecules present in the range 450 m/s to (450 + 0.01) m/s for O
2
at 100 K &
SO
2
present at 200 K is
(A) 2 (B)
2
1
(C) 4 (D) 1
Q.5 1 mole each of He, H
2
, O
2
& N
2
with Vander waal constant (atm L
2
mol
2
) 1.2, 1.6, 4, 3.2 respectively
are kept separately in four different vessels of equal volume at same temperature. Their pressures are
observed to P
1
, P
2
, P
3
, P
4
respectively. On the basis of this data alone, select the correct option (Assuming
the effect of b to be same).
(A) P
1
> P
2
> P
3
> P
4
(B) P
3
> P
4
> P
2
> P
1
(C) P
3
> P
4
> P
1
> P
2
(D) P
1
> P
2
> P
4
> P
3
Q.6 Two gases of molecular mass M
A
and M
B
are taken in a container of volume 'V' at temperature. 'T'. If
M
A
> M
B
then momentum change per collision of gases are such that
(A) AP
A
>AP
B
(B) AP
B
< AP
A
(C) AP
B
= AP
A
(D) data insufficient
Q.7 At 273 K temp. and 9 atm pressure, the compressibility for a gas is 0.9. The volume of 1 millimoles of
gas at this temperature & pressure is
(A) 2.24 litre (B) 0.020 ml (C) 2.24 ml (D) None
Q.8 Two vessel of equal volume are connected to each other by a value of negligible volume. One container
(I) has 2.8 gm of N
2
gas and 12.7 gm of I
2
(s) at temperature T
0
K. The other container (II) is completely
evacuated. The evacuated container is now maintained at
3
T
K, and valve is opened. The mass of N
2
in
container (II) after long time will be (V.P. of I
2
(s) = 3 torr at
3
T
K)
(A) 2.1 gm (B) 0.75 gm (C) 0.65 gm (D) 0.70 gm
Q.9 If Pd v/s P (where P denotes pressure in atm and d denotes density in gm/L) is plotted for H
2
gas (ideal
gas) at a particular temperature. If
atm 21 . 8 P
) Pd (
dP
d
=
(

= 10, then the temperature will be

(A) 40 K (B) 400 K (C) 20 K (D) none
Q.10 Equation of Boyle's Law is
(A)
P
dP
=
V
dV
(B)
P
dP
=
V
dV
(C)
P
P d
2
=
dT
dV
(D)
P
P d
2
=
dT
V d
2
[11]
Q.11 In two different vessels X and Y containing H
2
O(l) at the same temperature, the vacant space left over
the surface of H
2
O(l) is V and 3V. What is the weight ratio ( ) Y in W / X in W
O H O H
2 2
of vapours in
two vessels?
(A) 1 : 3 (B) 3 : 1 (C) 1 : 4 (D) 1 : 1
Comprehension
Question No. 12 & 13 (2 questions)
According to kinetic theory of gases, the rate at which molecule strike an area per unit time per unit area
(the collision flux z) is given by z = (1/4) c N
c = Average velocity
N = no. of particles per unit volume
Rate of effusion of gas is directly proportional to z
rate of effusion = z A; A = area of orifice
Q.12 A 1m
3
vessel containing 10
23
particles have an orifice of area 10
2
mm
2
. If the average velocity of
particle is 10
3
m/sec, the time taken when initial pressure in the container drop to half of initial value is
(A) 2772 sec (B) 277200 sec (C) 477200 sec (D) 27720 sec
Q.13 How much time it will take for a gas with molecular weight one fourth of gas in previous part for the
pressure to drop to half of initial value(conditions identical as in previous problem)
(A) 1386 sec (B) 55440 sec (C) 238600 sec (D) 138600 sec
Read the comprehension carefully & answer the questions (Q.14 & Q.15) that follow.
Analysis of distribution of molecular speeds of an ideal gas can be mathematically represented by the
equation
N
N A
=
du u e
RT 2
M
4
2 RT 2 / Mu
2 / 3
2

|
.
|

\
|
t
t
where
N
N A
is fraction of molecule having speed between u to u + du M molecular mass, T is absolute
temperature.
The graph of 'fraction of molecules' vs 'speed' when plotted was found to be 'unsymmetrical' with very
few molecules with very high or low speed & mostly molecules possesssing speeds in the range of
270-330 m/s.
The plotting of the graph & the variation of fraction of molecules with mass of the gas & temperature of
the gas can be compared by identifying the 'influencing' terms. At higher speeds the nature of graph is
influenced by the exponential term ] e [
RT 2
Mu
2

& at lower speed it is influenced by the parabolic term

2
2 / 3
u
RT 2
M
|
.
|

\
|
t
. Using the above expression values of U
mps
, U
avg
and U
rms
can also be established.
Q.14 Mark the correct statement
(A) Number of molecules having speed around 300 m/s will be greater than number of molecules
possessing either very low speed or very high speed.
(B) The speed possessed by most of the molecules & average speed has the same value.
(C) At lower speed the fraction of the molecules decrease with increasing speed.
(D) At higher speed the fraction of molecules increases with increasing speed.
[12]
Q.15 For a sample containing O
2
and SO
2
mark out the incorrect statement
(A) At same temperature average speed of O
2
is greater than that of SO
2
.
(B) If absolute temperature of O
2
is half to that of SO
2
gas than the speed distribution curves will be
different.
(C) At same temperature & at lower speed, fraction of molecules of SO
2
will be greater.
(D) At same temperature & at higher speed, fraction of molecules of O
2
will be greater than that of SO
2
.
More than one may be correct [4 4 = 16]
Q.16 Two flasks A and B have equal volume V. Flask A is maintained at 400 K and B at 800 K. Flask A
contains H
2
gas, B has an equal mass of 'He' gas. Assuming ideal behaviour of both gases &
He H
2
o = o ,
select the incorrect option:
(A) (U
rms
)
A
> (U
rms
)
B
(B) Total translational kinetic energy in flask B < total translational kinetic energy in flask A
(C) Z
1
in flask A > Z
1
in flask B
(D) Total number of bimolecular collisions in container A is equal to
2
1
t
2
H
) (
2
o U
avg

2
V
N
|
.
|

\
|
,
where N represents number of molecules of H
2
present in the container.
Q.17 At 27 C a container contains O
2
, N
2
and H
2
O(g)

only in such a way that total pressure of container is
1.025 atm. Under these condition the partial pressure of H
2
O is equal to the aqueous tension of the H
2
O
at 27. Aqueous Tension at 300 K = 19 torr then at constant (T), select the correct option(s).
(A) If volume of container is reduced half to its original value then final total pressure is 2.05 atm.
(B) If volume of container is reduced half to its original value then final total pressure is less than 2.05 atm.
(C) If volume of container is doubled then the final total pressure becomes 0.5125 atm.
(D) If volume of container is doubled then the final total pressure becomes 0.525 atm.
Q.18 A gas is characterised by Vander Waals equation then select the correct option(s).
(A) Volume of 1 mole gas at critical point is 12 times of the volume of 1 mol gaseous molecules.
(B) Boyles temperature of a gas is 3.375 times of its critical temperature.
(C) At critical temperature substance presnt in only gaseous state.
(D) At Boyles temperature & in a low pressure range
dP
) PV ( d
= 0.
Q.19 Select correct statement for a real gas.
(A) Larger the value of
c
c
P
T
of gas, larger would be the excluded volume.
(B) Critical temperature (T
c
) of a gas is greater than Boyle's temperature (T
b
)
(C) At critical point in the Vander Waal's gas isotherm
0
V
P
c
T
=
|
.
|

\
|
c
c
(D) For a real gas T
c
= 30C then it is gas at 25 C & vapour at 35C always.
Match the column [12]
Q.20 Consider gas to be characterised by Vander Waals equation.
Column - I Column - II
(A) Free volume (P) Depends upon nature of gas
(B) Critical temperature (Q) Constant quantity for a particular gas
(C) Boyles temperature (R) Depends upon pressure for a particular gas
(D) Compressibility factor (S) Depends upon the radius of gas molecule
[13]
Subjective [4 5 = 20]
Q.21 The compressibility factor (Z) vs P for one mole of a real gas is shown in following diagram. The graph
is plotted at constant temperature 300 K. If the slope of the graph at very high pressure is
10
1
atm
1
. Find
the volume (V) of one mole gaseous molecules (in litre).
Given R = 0.08 atm litre/mol K.
[Fill your answer by multiplying it with 10
3
]
Z
P
dz
dP
dz
dP
is ve
is 0
behaviour of most
real gases
Q.22 For 2 moles of a real gas, curves are plotted under different condition at same temperature as shown in
diagrams:
Slope = 0.2
32.84
PV
m
(atm lit.)
1 V
m
(lit. )
1
Curve I
Slope = 0.02
Z
u
P(atm)
Curve II
Curve I is plotted at low pressure conditions
Curve II is plotted at very high pressure conditions.
Calculate Vander waals constant b (in litre) for the gas, using above graphs.
[Fill your answer by multiplying by 10
4
]
Q.23 From the given equation for a gas at 300 K,
P
d
= 4 + 0.02 P + 0.001 P
2
................
Calculate the molecular weight of gas (in gm/mole)
[where P (Pressure) is in atm & d (density) is in gm/lit.]
[Given R = 0.08 atm lit. mol
1
K
1
].
Q.24 A mixture of NH
3
(g) & N
2
H
4
(g) is placed in a sealed container at 300 K. The total pressure is 0.5 atm.
The container is heated to 1200 K at which time both substances decompose completely according to
the equations
2NH
3
(g) N
2
(g) + 3H
2
(g) and N
2
H
4
(g) N
2
(g) + 2H
2
(g)
After decomposition is complete, the total pressure at 1200 K is found to be 4.5 atm. Find the mole %
of NH
3
in the original mixture.