Multiple Choice Questions:

1. A 5L vessel contains 2.8 g of N2 . When heated to 1800 K , 30% molecules are dissociated into atoms.
(A*) Total no. of moles in the container will be 0.13
(B*) Total no. of molecules in the container will be close to 0.421 × 1023.
(C) Total no. of moles in the container will be 0.098.
(D) All of these are correct.
Sol. (A) and (B) Explanation : 30% of molecule dissociated N2  2N
2 .8 70
Amount of N2 left = × = 0.1 × 0.7 = 0.07
28 100
(in moles)
30
No. of moles of N atoms formed = 2 × × 0.1 = 0.06
100
(A) Total no . of moles = 0.07 + 0.06 = 0.13
(B) Total number of molecules = 0.07 ×6.023 × 1023 = 4.2 × 1022 molecule = 0.421 × 1023
Q We have to calculate molecule of nitrogen not atoms.
2. Which of the following is / are heterocyclic compound (s)

(A) (B)
H2N OH

•(C) •(D)

N
H
3. Which of the following of compounds are position isomers

•(A) and •(B) and

(C) and (D) and

4. Consider the decay of P to A and B by two parallel first order reactions as shown in Fig. Given

Reaction H Rate constant Energy of activation

PA HA kA EA

PB HB kB EB

Which of the following is(are) true?

(A*) a = EB (B*) b = EA (C*) HA = b  d (D) HB = c  a

Sol. For the given curve
(A) a = EB (B) b = EA (C) HA = b – d and HB = a – c

5. The polarimeter readings in an experiment to measure the rate of inversion of cane suger (1st order
reaction) were as follows
time (min) : 0 30 
angle (degree) : 30 20 – 15
Identify the true statement (s) log 2 = 0.3, log 3 = 0.48, log 7 = 0.84
(A*) the half life of the reaction is 75 min.
(B*) the solution is optically inactive at 120 min.
(C) The equimolar mixture of the products is dextrorotatory.
(D*) The angle would be 7.5° at half time.
Sol. Moderate
0 30 
30 20 –15
1 30  ( 15)
k= 2.0303 log
30 20  ( 15)

1 45
= ln min–1
30 35

30 ln 2
 t1/2 = = 15 min
9
ln
7

1 45 1 45
ln min–1 = ln
30 35 t 0  ( 15)
t = 120 min
30  ( 15)
= 2 at half time
x  ( 15)

45 45
 =2  x + 15 =
x  15 2
 x = 22.5 – 15 = 7.5°
6. Decomposition of 3 A(g)  2 B(g) + 2C(g) follows first order kinetics. Initially only A is present in the
container. Pressure developed after 20 min. and infinite time are 3.5 and 4 atm respectively. Which of the
following is true.
(A*) t50% = 20 min (B*) t75% = 40 min (C) t99% = 64/3 min (D*) t87.5% = 60 min
Sol. 3 A(g)   2 B(g) + 2C (g)
t=0 P0
2x 2x
t = 20 P0 – x
3 3
2P0 2P0
t=
3 3
4P0
 =4
3
P0 = 3 atm.
x
P0 + = 3.5  t50% = 20 is the half life.
3
x = 1.5 t75% = 2 × 20 = 40 min.
 t87.5% = 3 × t50% = 3 × 20 = 60 min
2 2 400
t99% = × t99.9% = × 10 × t50% =
3 3 3
7. A reaction takes place in three steps. The rate constant of the three steps are K1, K2 and K3 respectively.
K1K 3
The overall rate constant K = K .
2
The energy of activation for the three steps are 40, 30 and 20 KJ respectively. Therefore :
(A) Overall energy of activation is 10 KJ
(B*) Overall energy of activation is 30 KJ
K1
(C*) The reaction mechanism is 2A A* + A ; A * product and overall order is one.
K2
K1
(D) The reaction mechanism is A  K2 K3
 B ; B  C ; C  product and overall order is one
K1K 3
Sol. K= K2

E E3
 1 
A1e RT  A 3e RT
(Ea )overall
Ae = E
RT – 2
A 2e RT

(Ea )overall  A1A 3  [E1E3 E2 ]

Ae RT
=  A   RT
 2  e

(Ea)overall = E1 + E3 – E2 = 30 KJ/mole

2A A* + A [Fast]

K1 [ A *][ A ] K1
K2 = 2 or [A*] = K 2 [A]
[A]

K1K 3
rate = K3[A*] = K 2 [A]

Single Choice Questions:

1. For the follwing parallel chain reaction the overall half life of A is 12 hours If

rate of formation of C is 60% of a rate of decomposition of A then what will be half life of A while it is
converting into B ?
(A) 40 hours (B) 60 hours (C) 50 hours (D*) 30 hours
2. Inversion of sucrose (C12H22O11) is first-order reaction and is studied by measuring angle of rotation at
different instant of time
 +
H
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose Glucose Fructose
d d l
If (r – r0)  a and (r – rt)  (a – x) (where r, rt and r are the angle of rotation at the start, at the time t and
at the end of the reaction respectively, then there is 50% inversion when :
(A*) r0 = 2rt – r (B) r0 = rt – r (C) r0 = rt – 2r (D) r0 = rt + r

Sol. Given (r – r0) = a , (r – rt) = (a – x)

At 50% Inversion
a
= (a – x)
2

r – r0  = (r – r0 )
2
(r – r0 ) = 2r – 2rt
r0 = 2rt – r

3. 5.85 g of NaCl is dissolved in 1 L of pure water. The number of ions in 1 mL of this solution is
(A) 6.02 × 1019 (B) 1.2 × 1022 (C*) 1.2 × 1020 (D) 6.02 × 1020
5.85
Sol. Mole of NaCl = = 0.1
58.5
0.1
Molarity = = 0.1 M
1
Moles in 1 ml of solution = MV = 0.1 × 10–3 = 10–4 mole.
Number of ions in 1 ml = 2 × 10–4 × 6.023 × 1023 = 1.204 × 1020.
4. Stability order of following carbocations is :
CH3 CH3
|  |
(I) CH3 – O – CH2 CH2  CH  CH2 (II) CH3 – O – CH2 CH2  C  CH3


CH3 CH3
 |  |
(III) CH3 – O – CH2 CH  CH  CH3 (IV) CH3 – O – C H CH2  CH  CH3
Ans. •(A) IV > III > II > I

– OCH3

This carbocation is stabilize by +M effect of H3CO- group and resonance with benzene ring.

5. Two beakers, one containing 20 ml of a 0.05 M aqueous solution of a non volatile, non electrolyte and the
other, the same volume of 0.03 M aqueous solution of NaCl, are placed side by side in a closed enclose.
What are the volumes in the two beakers when equation is attached ? Volume of the solution in the first and
second beaker are respectively.
(A) 21.8 ml and 18.2 mL (B*) 18.2 mL and 21.8 mL
(C) 20 mL and 20 mL (D) 17.1 mL and 22.9 mL
0.05  20
Sol. Mole of solute in first beaker = = 0.001
1000
 2  0.03  20
mole of solute (Na+ & Cl–) in other beaker = = 0.0012
1000
conc. of IInd beaker is higher then Ist beaker so water flowes from Ist beaker to IInd beaker till both beaker
achieved equal conc. let v volume of water flows from Ist to IInd beaker
0.001 0.0012
so 
20  v 20  v
v = 1.8 ml
volume of Ist beaker = 20 – 1.8 = 18.2 ml
volume of IInd beaker = 20 + 1.8 = 21.8 ml.

6. x mole of KCI and y mole of BaCl2 are both dissolved in 1 kg of water. Given that x + y = 0.1 and Kf for water
is 1.85 K/molal, what is the observed range of Tf, if the ratio of x to y is varied ?
(A*) 0.370 to 0.505º (B) 0.1850 to 0.930 (C) 0.560 to 0.930 (D) 0.370 to 0.930
Sol. x + y = 0.1
x / y = 0.37
x  x  y  2y
Tf = × 1000 × 1.85
1000

0. 2  y
Tf = × 1000 × 1.85
1000
Tf = (0.2 + 0.0729927) × 1.85 = 0.505
7. Given P-x curve for a non-ideal liquid mixture (Fig.). Identify the correct T-x curve for the same mixture.

(A) (B*)

(C) (D)
 Integer Type Questions:
1. A piece of Al weighing 27 g is reacted with 200 ml of H2SO4 (specific gravity = 1.8 and 54.5 % by weight)
After the metal is completely dissolved 73 gm HCl is added and solution is further diluted to 500 ml solution
then find the concentration of H+ ion in mol/litre.
Ans. 6M
1.8  54.5  10
Sol. Molarity of H2SO4 = = 10
98
2Al + 3H2SO4  Al2 (SO4)3 + 3H2
1 moles 2 moles
(limiting)
Moles of H2SO4 left = 2 – 1.5 = 0.5 moles
moles of HCl added = 2 moles
final volume of the solution = 500 ml
moles of H+ ion = 3
concentration of H+ ion = 6 M
2. Find the total number of the position where positive charge can be delocalized by true resonance

(Excluding the given position)

Ans. 10 Structures

3. Find the molecule which are Aromatic, Antiaromatic or nonaromatic in nature.

+ +

(a) (b) (c) (d)

+
H H
Cyclopropenyl Cyclobutenyl
cation di-cation

(e) (f) (g) Tropylium cation (h)

(Cycloheptatrienyl
cation)
 H
H H
(i) (j) (k) H
H
H

[18] Annulene
Ans. Aromatic – a, c, g, h, i, j, k ; Antiaromatic – b, d, e ; Nonaromatic – f

4. How many of the given molecules have all carbon atoms in one plane :

Ans. 7 [1, 2, 3, 4, 6, 7 and 9. have all carbon atoms in one plane.]

5. 1 g of a monobasic acid dissolved in 200 g of water lowers the freezing point by 0.186ºC. On the other hand
when 1 g of the same acid is dissolved in water so as to make the solution 200 mL, this solution requires
K  kg
125 mL of 0.1 N NaOH for complete neutralization. Calculate % dissociation of acid ? (Kf = 1.86 )
mol
Ans. 60
1 125
Sol. Macid = 1000 × 0.1  Macid = 80 g mol–1

 1 
 80 
0.186 = (1 + ) × 1.86 ×     = 0.6  60 percent
 0 .2 
 
6. The rate constant for the II order neutralization of 2-nitropropane by aqueous alkali obeys the equation
3163
log10 K = + 12
T
T is temperature in Kelvin.
Time and concentration were in minute and mol litre–1 respectively. Calculate half life at 43.3°C and for an
initial concentration of 0.001 mol litre–1 for each of the reactant.
Ans. 10–19 minute
3163
Sol. log10K = + 12
T
at T = (273 + 43.3) = 316.3 K
3163
log10K = + 12
316.3
log10K = (10+12) = 22
K = 1022
Then half life period
 1  1 1
t1 / 2 =  K  a  = = 19 = 10–19
  1022  .001 10
t1 / 2 = 10–19 min Ans. 10–19 minute.
7. The rate of decomposition of a substance increases by a factor 2.25 for 1.5 times increase in concentration
of substance at same temperature. Find out order of reaction.
Ans. 2
Sol. We know
Rate = K [conc]n for nth order Rxn.
n
Rate2  conc 2 
Then,  
Rate1 =  conc1 

given, Rate2 = Rate1 , conc2 = (conc1 × 1.5)

2.25 = (1.5)n
n = 2 second order Rxn
Comprehension # 1
Answer the questions (given below) which are based on the
following diagram.

Consider some facts about the above phase diagram :

Vapour pressure diagram for real solutions of two liquids A and B

that exhibit a positive deviation from Raoult’s law. The vapour
pressure of both A and B are greater than predicted by Raoult’s
law. The dashed lines represented the plots for ideal solutions.

1. A : This is observed when A...B attractions are greater than average of A...B and B...B attraction:
B : Hmix = +ve, Vmix = +ve
C : Boiling point is smaller than expected such that vaporisation is increased
D : Mixture is called azeotropic mixture
Select correct facts
(A) A, B, C (B*) B, C, D (C) A, C, D (D) A, B, C, D
Sol. B , C and D are the conditions and facts for positive deviation from Raoult’s law.
(A) is incorrect.
Because A – B attractive force should be weaker than A – A and B – B attractive forces.

2. Total vapour pressure of mixture of 1 mol of volatile component A (p°A = 100 mmHg) and 3 mol of volatile
component B (p°B = 60 mmHg) is 75 mm. For such case :
(A) There is positive deviation from Raoult’s law
(B) Boiling point has been lowered
(C) Force of attraction between A and B is smaller than that between A and A or between B and B.
(D*) All the above statements are correct.
1 3
Sol. XAPA0 + XBPB0 = × 100 + × 60 = 70 mm of Hg
4 0 4
Now PA + PB > XAPA + XBPB0
i.e., positive deviation from Raoult’s law.
for positive deviation,
B.P. < expected value
FA...B < FA...A
FA...B < FB...B
Comprehension # 2
A(g)  2B(g) + C(g)
Initially at t = 0 gas A was present along with some amount of gas (C). At t = 0 mole fraction of gas C is
1/3. After some time t = t1, total pressure is half of the final total pressure at t = tx (a very long time).
Assume this decomposition is a first order, at a constant temperature. It is also given at t = tx, final total
pressure is 35 bar.
1. Rate constant (k) = (log 64 – log 49) s–1. Value of t1 in seconds is :
(A) 2.15 s (B) 1.5 s (C) 2.3 s (D*) 1.15 s

2. Ratio of rate constant at t = 0 to t = t1 to t = tx is :

(A) 2 : 3 : 4 (B*) 1 : 1 : 1 (C) 1 : 3 : 5 (D) 1 : 3 : 5
Comprehension # 3
Study the following experiment and answer the questions at the end of it.
The following reactions was studied at 250C in benzene solution containing 0.10 M pyridine

CH3OH + (C6H5)3 CCl  (C6H5)3 C . OCH3 + HCl

A B C
The following sets of data were observed :

Set Initial concentration time difference Final concentration [C]

[A] 0 [B] 0
I 0.10 M 0.05 M 25 min 0.0033 M
II 0.10 M 0.10 M 15 min 0.0039 M
III 0.20 M 0.10 M 7.5 min 0.0077 M

d [C ]
51. Rates in sets I , II and III are respectively (in M min–1) :
dt
I II III
(A*) 1.30 × 10–4 2.6 × 10–4 1.02 × 10–3
(B) 0.033 0.0039 0.0077
(C) 0.02 × 10–4 0.04 × 10–4 0.017
(D) None of above

52. Rate law of the above experiment is :

(A) r = k [A] [B] (B*) r = k [A]3 [B] (C) r = k [A] [B]2 (D) r = k [A]2 [B]0

53. Rate constant of the above experiment is :

(A) 1.3 × 10–1 (B) 2.6 × 10–2 (C*) 2.6 × 10–1 (D) 1.3 × 10–2

Sol.
dc  c  .0033
51. (I) Rate (nj) = =  t  = = 1.32 × 10–4
dt   25

dc  c  .0039
(II) Rate (nj) = =  t  = = 2.6 × 10–4
dt   15

 c  .0077
(III) Rate (nj) =  t  = = 1.02 × 10–3
  15

52. (II) Rate of Rxn = Rate of formation of C.

Then we say by I data.
Suppose [Rate = k [A]a [B]b] ....(i)
1.32 × 10–4 = k [.10]a [.05]b ....(ii)
2.6 × 10–4 = k [.10]a [.10]b ....(iii)
1.02 × 10–3 = k [.20]a [.10]b ....(iv)
By equation (ii) and (iii) we find b = 1
By (iii) and (iv) we find a = 2.97  3.
Then Rate = k [A]2 [B]1

53. (III) Rate (nj) 1.32 × 10–4 = k [.10]2 [.05]

k = 2.6 × 10–1