Chemical Kinetics and Nuclear Chemistry

Chapter 12
Chemical Kinetics and Nuclear Chemistry
Solutions
SECTION - A
Objective Type Questions (One option is correct)
[Order and Molecularity]
1
1. For a reaction N2O5  2NO2  O2
2
Given :
d (N2O5 )
  k1[N2O5 ]
dt
d (NO2 )
 k 2 [N2O5 ]
dt
d (O 2 )
 k 3 [N2O5 ]
dt
The relation between k1, k2 and k3 are
(1) 2k1 = k2 = 4k3 (2) k1 = k2 = k3 (3) 2k1 = 4k2 = k3 (4) ½k1 = k2 = ¼k3
Sol. Answer (1)
For the reaction,
1
N2O5  2NO2  O2
2
We can express the rate as,
d N2 O5  1 d NO2  1 d [O2 ]

= . = 1/2  .
dt 2 dt dt
1
 K1 [N2O5] = K [N O ] = 2K3 [N2O5]
2 2 2 5
Hence, we can write
K2
K1 = = 2K3
2
 2K1 = K2 = 4K3.
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Solutions of Assignment Chemical Kinetics and Nuclear Chemistry 129
2. The reaction: A2 + B2  2AB, is bound to obey the following mechanism
k

A 2
1

A+A (fast)
k –1
k
A + B2 
2
AB + B (slow)
A + B  AB (fast)
The order of overall reaction is

(1) 3 (2) 2 (3) 2.5 (4) 1.5
Sol. Answer (4)
k1 [A]2 k1
 ⇒ [A]  [A 2 ]
k 1 [A 2 ] k 1
Rate = k2[A] [B] (r.d.s.)
k1
= k2  [A 2 ]  [B2 ]
k 1
k1
= k2   [A 2 ]1/2 [B2 ]
k 1
1
 Order of reaction =  1  1.5
2
3. The rate law for the reaction

AB + CD (aq) 
 AD + CB
is given by R = k[AB]. The rate of reaction will be
(1) Unaffected by increasing temperature of the reaction
(2) Halved on reducing the concentration of CD to one-half
(3) Increasing on increasing the concentration of CD
(4) Halved on reducing the concentration of AB to one-half
Sol. Answer (4)
The rate law is given
R = K[AB]
 When concentration of [AB] is reduced to half, the rate also becomes half .
4. The concentration of a reactant in a solution falls from 0.2 M to 0.1 M in 2 hours and to 0.05 M in 4 hours.
The order of reaction is
(1) Zero (2) Two (3) One (4) Half
Sol. Answer (3)
Same % decay in same time. So, it indicates that reaction is of first order.
[Integrated Rate Equation and Rate Law]
5. Rate constant of a first order reaction is 6.93 × 10–3 min–1. If we start with 10 mol/L. It is reduced to 1.25 mol/L
in
(1) 100 minute (2) 200 minute (3) 30 minute (4) 300 minute
130 Chemical Kinetics and Nuclear Chemistry Solutions of Assignment
Sol. Answer (4)

Given, k = 6.93 × 10–3 min–1
[A]0 = 10 M; [A]t = 1.25 M
st
Hence, for 1 order reaction we can write
1 [A]0 1 ⎛ 10 ⎞
ln ⎜ ⎟
 6.93  10 
t= ln =
k [A]t –3
⎝ 1.25 ⎠
103 3ln2  103

 t= × ln (8) =
6.93 6.93
3  0.693  10 3  103 693

 t= = × ×100
6.93 1000 693
 t = 300 minutes
6. The reaction A + 2B + C  2D + E is found to be 1, 2 and zero order with respect to A, B and C respectively.
What will be the final rate, if concentration of each reactant is doubled?
(1) 2 times (2) 4 times (3) 8 times (4) 16 times
Sol. Answer (3)
The given reaction is
A + 2B + C  2D + E
Order = 1 w.r.t. A; 2 w.r.t. B and zero w.r.t. C
dx 2
Initially = k [A] [B]
dt
Now when concentration is doubled

⎛ dx ⎞ 2 2
⎜ dt ⎟ = k(2) [A] (2) [B]
⎝ ⎠
 
⎛ dx ⎞ ⎛ dx ⎞
 ⎛⎜ ⎞⎟ = 8 ⎜ ⎟
2 dx
⎜ dt ⎟ = 8k [A] [B]
⎝ ⎠ ⎝ dt ⎠ ⎝ dt ⎠
The rate of reaction increases by 8 times.
7. A substance having initial concentration 'a' mole/L reacts according to zero order reaction. The time taken for
completion of reaction is
2a a a k
(1) (2) (3) (4)
k k 2k a
Sol. Answer (2)
Initial concentration is [A]0 = a M
Reaction follows zero-order kinetics
x = kt
x a
Here, x = a  t = =
k k
8. Which of the following is an incorrect statement?
(1) Half life of second order reaction decreases with increase in concentration of reactant
(2) Half life of first order is independent of concentration of the reactant
(3) The unit of rate constant of zero order is equal to unit of rate
(4) The unit of frequency factor 'A' in Arrhenius equation is the unit of half life of the reaction
Sol. Answer (4)
1
For second order reactions t1/2 =
K  A 0
 Half life decrease with increase in concentration of reactants.
st ln 2
For 1 order, t1/2 = and is independent of concentration.
k
For zero order
dx
= K (both are same)
dt
5/2 –1/2
9. For a hypothetical reaction x + y = A + B, Rate = k [x] [y] on doubling the concentration of x and y the
rate will become
(1) 2 times (2) 4 times (3) 8 times (4) Remains same
Sol. Answer (2)
Rate given is
Rate = K [x]5/2 [y]–1/2
On doubling the concentration of x and y
5 1

= K  (2) 2
5/2 –1/2 5/2 –1/2 2 5/2 –1/2 2 5/2 –1/2 5/2 –1/2
Rate = K(2) (2) [x] [y] [x] [y] = K.(2) [x] [y] = 4 K [x] [y]
Hence, rate becomes 4 times.
10. A reaction : aA  product. Follows zero order the concentration of A with respect to time(t) is given as
kt
(1) [A]0 = [A] – kt (2) [A] = [A]0 – kt (3) [A] = [A]0 + kt (4) [A] = [A]0 
a
Sol. Answer (2)
aA  product
1 d[A]
R  k (zero order)
a dt
Integrating, we get: (A)t = (A)0 – akt
11. The half life period of a radioactive substance is 69.3 minutes. In how much time will it be disintegrated 80% of
its original amount?
(1) 80 minutes (2) 100 minutes (3) 140 minutes (4) 161 minutes
Sol. Answer (4)

For radioactive disintegration
20 N0
t1/2 = 69.3 min. Nt = N0 =
100 5
ln 2 0.693
 =
–1
= = 0.01 min .
t1/2 69.3
Applying I–order reaction
1 ⎛ 5N0 ⎞ ln 5
t= ln ⎜ ⎟ =
  ⎝ 0 ⎠
0.01 N (0.01)
2.303  0.7
 Time taken (t) =
(0.01)
 t = 161 minutes
12. For a reaction 2N2O 5  4NO 2 ( g)  O 2 ( g) , the rate and rate constant are 1.02 × 10–4 mol L–1 s–1 and
–5 –1
3.4 × 10 s respectively. The concentration of N2O5 at this time will be
(1) 1.732 mol/L (2) 3 mol/L (3) 1.02 × 10–4 mol/L (4) 3.2 × 105 mol/L
Sol. Answer (2)
The given reaction is 2N2O5  4NO2 + O2
–4 –5 –1
R = 1.02×10 m/s; K = 3.4×10 s .
Reactions follows I-order kinetics as units of K is s–1
Rate = K [N2O5]
 1.02 × 10
–4 –5
= (3.4 × 10 ) [N2O5]
1.02  10 –4 1.02  10
 [N2O5] = = =3M
 3.4  10 –5 3.4
13. A gas phase reaction R  A + B + C + D is of first order. The initial pressure was x0 where pressure after 10
minutes was y. The correct expression for rate constant k is
2.303 4x0 2.303 2x 0

(1) k  log (2) k  log
10 3x0  y 10 3x0  y
2.303 3x 0 2.303 4x0

(3) k  log (4) k  log
10 4x 0  y 10 4x0  y
Sol. Answer (3)

The gas phase reaction is
R  A + B + C + D
t=0 x0 0 0 0 0
t = t x0–P P P P P
 x0 – P + 4P = y  x0 + 3P = y
⎛ y– x 0 ⎞
 3P = (y – x0)  P = ⎜ ⎟
⎝ 3 ⎠
Applying I-order kinetics equation
1 x0
K= ln x  P
10 0
2.303 x0
 K= log
10 ⎛ y – x0 ⎞
x0 – ⎜ ⎟
⎝ 3 ⎠
2.303 3 x0
 K= log
10 3 x 0  y  x0
2.303 3 x0
 K= log
10 4 x0  y
14. For the reaction 2NO  Br2  2NOBr , the following mechanism has been given
NO + Br2 NOBr2
Slow
NOBr2 + NO  2NOBr
Hence rate law is
2 2
(1) K[NO] [Br2] (2) K[NO] [Br2] (3) K[NOBr2] [NO] (4) K[NO] [Br2]
Sol. Answer (1)
Mechanism given is
Kc

NO  Br2
NOBr2
K
NOBr2  NO   2NOBr
slow
dx
From II- reaction, = K [NOBr2] [NO] …(i)
dt
NOBr2 
Kc =
[NO][Br2 ]
[NOBr2] = Kc [NO][Br2] …(ii)
Substituting eq. (ii) in eq. (i), we get,
dx dx
= KKc [NO]2 [Br2] or = K’ [NO]2 [Br2]
dt dt
15. For a reaction

A+B 
 C + D
the rate = k[A]–1/2 [B]3/2. On doubling the concentration of A and B. The rate will be
(1) 4 times (2) 2 times (3) 3 times (4) Same
Sol. Answer (2)

The rate law for the reaction
A + B  C + D is given by
–1/2 3/2
Rate = K [A] [B]
When [A] and [B] becomes twice
1 1 3 3
– –
R = K(2)– K(2) 2
[A] 2
2 2 [B] 2
1 3
– 
= K (2) 2 2
[A]–1/2 [B]3/2
2/2 –1/2 3/2
= K (2) [A] [B]
R = 2K [A]–1/2 [B]3/2
 R = 2 (rate)
Hence, the rate becomes 2 times.
[Numericals on 1st Order]
16. Half life of a chemical reaction at a particular concentration is 50 minutes. When the concentration of the reactant
is doubled, the half life becomes 100 minutes, then the order of reaction is
(1) Zero (2) First (3) Second (4) Third
Sol. Answer (1)
Half life for zero order reaction is given by the expression
a
t1/2 =
2K
When ‘a’ was doubled, Half-life also doubles. Hence, the reaction follows zero order kinetics.
17. In the first order reaction t99.9% is 60 minute. t50% of the reaction would be nearly
(1) 360 minute (2) 600 minute (3) 6 minute (4) 60 minute
Sol. Answer (3)
Let the initial concentration = a
Reaction follows I-order kinetics
1 ⎧ a ⎫ 1 ⎛ 100a ⎞
K= ln ⎪ ⎪ = in ⎜ ⎟
(60) ⎨ 99.9 ⎬ (60) ⎝ 100a–99.9a ⎠
⎪⎩ a– 100 a ⎪⎭
1 ⎛ 100a ⎞
= ln ⎜ ⎟
(60) ⎝ 0.1a ⎠
1 ⎧1000a ⎫ ln(1000)
= ln ⎨ ⎬ =
(60) ⎩ a ⎭ 60
 For 50% decomposition we can write
ln2 60(ln2)
t= =
K ln(1000)
 t = (60) (0.3)
60log 2 60log2
 t= =
log (1000) log(103 )
60log2
 t= = 20 log2
3
 t = 20 × 0.3 = 6 minute
18. For a first order reaction t0.75 is 138.6 seconds. Its specific rate constant (in s–1) is
(1) 10–2 (2) 10–4 (3) 10–5 (4) 10–6
Sol. Answer (1)
T = 138.6 s
For 75% decomposition we can write
1 ⎧ a ⎫ 1 ⎛ 100a ⎞
⎪ ⎪
K=
t
ln ⎨ 75 a ⎬ = t ln ⎜⎝ 100a–75a ⎟⎠
⎪⎩ a – 100 ⎪⎭
1 ⎧100 a ⎫ ⎧ ln 4 ⎫
 K= ln ⎨ ⎬ = ⎨ ⎬
t ⎩ 25 a ⎭ ⎩138.6 ⎭
2.303  2  0.3010
 K= = 0.01 = 10–2s–1
138.6
19. For the following reaction

A(g) 
 B(g) + C(g)
The initial pressure was P0 while pressure after time ‘t’ was Pt. The rate constant k will be given by
2.303 P 2.303 P0
(1) k  log 0 (2) k  log
t Pt t P0  2Pt
2.303 P0 2.303 P0
(3) k  log (4) k  log
t 2P0  Pt t P0  Pt
Sol. Answer (3)

The given reaction is
A(g)  B(g) + C(g)
At t = 0 P0 0 0
t = t P0–P P P
 Pt = P0 – P + P + P = P0 + P
 P = (Pt – P0)
Hence, applying I-order kinetics equation
1 ⎧ P0 ⎫ 1 ⎧ P0 ⎫
K = ln ⎨ ⎬ = ln ⎨ ⎬
t ⎩ P0  P ⎭ t ⎩ P0  (Pt –P0 ) ⎭
1 ⎧ P0 ⎫ 2.303 P0
 ln ⎨ ⎬ = log
t ⎩ 2P0 –Pt ⎭ t 2P0 – Pt
20. In the first order reaction, x 

 y; the concentration of ‘x’ changes from 0.1 M to 0.025 M in 40 minutes. The
rate of reaction (mol/L/min) when concentration of x is 0.01 M, would be
(1) 3.47 × 10–5 (2) 3.47 × 10–4 (3) 5.8 × 10–4 (4) 5.8 × 10–6
Sol. Answer (2)
[X]0 = 0.1 M; [X]t = 0.025 M
t = 40 minute.
1 ⎛ 0.1 ⎞ ln 4
 K= ln ⎜ ⎟ =
40 ⎝ 0.025 ⎠ 40
Rate of reaction = K[X]
⎧ ln 4 ⎫ 2ln 2
= ⎨ ⎬ × (0.01) ⇒ × (0.01)
⎩ 40 ⎭ 40
2  0.693  0.01
= = 3.47 × 10–4 m/s
40
21. The gaseous reaction A (g)  2B (g) + C (g) obeys first order kinetics. If the initial P = 90 mm and pressure
after 10 minutes = 180 mm. The velocity constant k of the reaction is
(1) 1.15 × 10+3 s–1 (2) 2.30 × 10+3 s–1 (3) 3.45 × 10–3 s–1 (4) 1.15 × 10–3 s–1
Sol. Answer (4)
A(g)  2B(g) + C(g)
t =0 P0 0 0
t = t P0–P 2P P
 Pt = 0; = P0 ; Pt = P0 – P + P + 2P
Pt = P0 + 2P
After 10 min; Pt = 180 mm Hg
180 = 90 + 2P  90 = 2P
P = 45 mmHg
 Applying I-order kinetics:
1 ⎧ 90 ⎫ ln 2
 K= ln ⎨ ⎬ =
10 ⎩ 90 – 45 ⎭ 10
0.693 0.693 –3 –1
K= = = 1.15 × 10 s
60  10 600
[Arrhenius Equation]
22. Select the correct statement regarding activation energy

(1) Activation energy may be greater than heat of reaction
(2) Activation energy is less than threshold energy
(3) Rate of reaction is inversely proportional to the activation energy
(4) All of these
Sol. Answer (4)
According to Arrhenius equation
–Ea
K = A.e Rt
The rate constant is inversely related to activation energy. It is energy required to make it equal to threshold
level and it can be greater than H for the reaction.
23. The temperature coefficient of most of the reactions lie between

(1) 2 and 4 (2) 3 and 4 (3) 1 and 2 (4) 2 and 3
Sol. Answer (4)
Temperature coefficient for the reaction is given by
K T  10
Tc = KT = 2 and 3
1
24. The plot of log k versus of a first order is linear with a
T
(1) Positive slope and zero intercept
(2) Positive slope and non-zero intercept
(3) Negative slope and non-zero intercept
(4) Negative slope and zero intercept
Sol. Answer (3)
According to Arrhenius logarithmic form,
Ea
log K = log A –
2.303 RT
1
Log K versus graph gives straight line having intercept = log A
T
–Ea
And slope (m) =
2.303R
Since Ea > 0; m < 0
 Slope is negative having non-zero intercept.
25. The rate constant, the activation energy and Arrhenius parameter of a chemical reaction at 25°C are K, Ea
and A respectively. The value of rate constant as T is
(1) Ea (2) Ea × A (3) A – Ea (4) A
Sol. Answer (4)
–Ea
K = A.e RT
A
When T  , K = =A
e0
 as T; K = A.
26. When the activation energies of forward and backward reactions are equal, then
(1) H = 0, S = 0 (2) H = , S = 0 (3) G = 0, H = 0 (4) Only H = 0
Sol. Answer (4)
For (Ea)f = (Ea)b, H = 0
But S  0 R P
 G  0 also
[Nuclear Chemistry]
27. The position of element RaC in the periodic table is
226     
88Ra   86Rn
 
 RaA  
RaB   RaC
th th th rd
(1) 13 group & 6 period (2) 16 group & 3 period
(3) 15th group & 7th period (4) 15th group & 6th period
Sol. Answer (4)
Ra  2He +
226 4 222
88 86 Rn
Rn 
222 218 4
86 84 RaA + 2He
RaA  –1
218 218 0
84 85 RaB +
RaB  2He +
218 4 214
85 83 RaC
Element RaC will be lying in 15th group and 6th in period.
28. The radiation from a naturally occurring radioactive substance as seen after deflection by a magnetic field in
one direction are
(1)  rays (2)  rays
(3) Both (1) & (2) (4) Either  or -rays
Sol. Answer (4)
Since  and -rays are +vely and –vely charged particles, hence, they will be deflected by magnetic field in
one direction.
29. When 92U235 is converted to 82Pb

207
, 'x' number of -particles and 'y' number of -particles are released. Then
'x' and 'y' respectively are
(1) 7, 4 (2) 4, 7 (3) 7, 5 (4) 5, 7
Sol. Answer (1)
(i) 92 U235 82 Pb207  7 2 He 4  4 –1 e0
30. One gram atom of 79Au198 (t1/2 = 65 hours) decays by -emission to produce stable nuclide of Hg. How much
Hg will be present after 260 hours?
1 1 15 16
(1) g atom (2) g atom (3) g atom (4) g atom
16 32 16 15
Sol. Answer (3)
No. grams atom, t = 0 of Au is equal to 1
After 260 hours (t1/2 = 65 hours)
ln 2
=
65
ln 2 1 ⎧ 1⎫
  = ln ⎨ ⎬
65 260 ⎩ x ⎭
260 ln 2 ⎛ 1⎞
= ln ⎜ ⎟
65 ⎝x⎠
⎛ 1⎞ 1
 4 ln2 = ln ⎜ ⎟  ln24 = ln
⎝x⎠ x
1 1 1

4
= 2 or x = 4 = g atoms
x 2 16
1 15
 No. of gram atoms after 260 hrs = 1 – =
16 16
31. 1.0 g atom of an -emitting isotope (t1/2 = 10 days) is sealed in a container. The volume of gas accumulated in the
container at STP after 10 days would be
(1) 1.0 L (2) 44.8 L (3) 11.2 L (4) 22.4 L
Sol. Answer (3)
[N0] = 1 g atoms
 since it is a-emitting
Isotope it produces 2He4 (1/2 mole)
1
 Volume of gas liberated at STP = 22.4 × = 11.2 L
2
32. There are two radio nuclei A and B. A is -emitter and B is a -emitter, their decay constant are in the ratio
of 1 : 2. What should be the number of atoms of A & B at time t = 0, so that probability of getting  and
-particles are same at time t = 0?
(1) 2 : 1 (2) 1 : 2 (3) 1 : 4 (4) 4 : 1
Sol. Answer (1)
Rate1 = 1N1 …(i)
Rate2 = 2N2 …(ii)
According to question,
Rate1 = Rate2
1N1 = 2N2
N1 2 2
N2 = 1 = 1
33. The activity of a radioactive sample reduced from 20 Ci to 1.25 Ci in 2000 years. The half life of the sample
and its decay constant are respectively
–3 –1 –2 –1
(1) 4000 years and 1.1 × 10 y (2) 500 years and 1.1 × 10 y
–3 –1 –3 –1
(3) 500 years and 1.386 × 10 y (4) 1000 years and 1.386 × 10 y
Sol. Answer (3)

The activity of radioactive sample decreases from 20 to 1.25
t = 2000 yrs.
1 ⎛ 20 ⎞ ln16
= ln ⎜ ⎟ =
2000 ⎝ 1.25 ⎠ 2000
  = 1.386 ×10–3 y–1

 Half life is
ln 2 ln 2
t1/2 = × 2000 = × 2000 = 500 years.
ln16 4ln 2
34. The amount of U-235 required per day to run a power house of capacity 15 MW (efficiency of nuclear reactor
75%. Assume energy liberated by fission of 1 U-235 atom is 200 MeV) is
(1) 15.8 g (2) 28.1 g (3) 21.1 g (4) None of these
Sol. Answer (3)
1 watt = 1 J s–1
Capacity of power house = 15 × 106 J s–1
1 day = 86400 s
 For 1 day (86400 sec) energy required
= 86400 × 15 × 106 J
12
= 1.296 × 10 J
6 –19 –11
200 MeV = 200 × 10 × 1.6 × 10 = 3.2 × 10 J
–11
∵ 3.2 × 10 J energy produced by 1 atom of U-235.
1.296  1012  1
 1.296 × 10
12 22
J energy will be produced = = 4.05 × 10 atoms
3.2  10 –11
⎛ 4.05  1022 ⎞
Mass of 4.05 × 1022 atoms = ⎜ 6.023  1023 ⎟ × 235 = 15.80 g
⎝ ⎠
100
Since efficiency is 75% hence actual mass required = 15.8 × = 21.06 g
75
35. The half life for decay of a radio active isotope is 14 hrs. Determine the fraction of radio isotope remaining
undecayed after 30 hours
(1) 4.456 (2) 0.227 (3) 0.256 (4) 0.358
Sol. Answer (2)
ln 2 ln 2
 
t1/2 14
⎛ ln 2 ⎞
Nt ⎜ ⎟  30
 et  e ⎝ 14 ⎠  0.227
N0
23
36. A positron is emitted from 11 Na . The ratio of the atomic mass and atomic number of the resulting nuclide is
[IIT-JEE 2007]
22 22 23 23
(1) (2) (3) (4)
10 11 10 12
Sol. Answer (3)

23
11 Na  10
23
X  01e
37. Consider a reaction aG + bH  Products. When concentration of both the reactants G and H is doubled, the
rate increases by eight times. However, when concentration of G is doubled keeping the concentration of H fixed,
the rate is doubled. The overall order of the reaction is [IIT-JEE 2007]
(1) 0 (2) 1 (3) 2 (4) 3
Sol. Answer (4)
 
r = K[G] [H]
8r = K[2G] [2H]
 
2r = K[2G] [H]
 =1=2
 order of reaction = 3
38. Under the same reaction conditions, initial concentration of 1.386 mol dm–3 of a substance becomes half in
⎛ k1 ⎞
40 seconds and 20 seconds through first order and zero order kinetics, respectively. Ratio ⎜⎜ k ⎟⎟ of the rate
⎝ 0⎠
constants for first order (k1) and zero order (k0) of the reactions is [IIT-JEE 2008]
(1) 0.5 mol–1 dm3 (2) 1.0 mol dm–3 (3) 1.5 mol dm–3 (4) 2.0 mol–1 dm3
Sol. Answer (1)
0.693
k1 = t1/2
0.693
k1 = (first order kinetics) …(1)
40
1.386
k0 = (zero order kinetics) …(2)
2  20
k1 –1 3
k 0 = 0.5 mol dm .
39. For a first order reaction A  P, the temperature (T) dependent rate constant (k) was found to follow the equation
1
log k = – (2000) + 6.0. The pre-exponential factor A and the activation energy Ea, respectively, are
T
[IIT-JEE 2009]
(1) 1.0 × 106 s–1 and 9.2 kJ mol–1 (2) 6.0 s–1 and 16.6 kJ mol–1
(3) 1.0 × 106 s–1 and 16.6 kJ mol–1 (4) 1.0 × 106 s–1 and 38.3 kJ mol–1
Sol. Answer (4)
1 Ea
log k = – (2000) + 6.0; comparing this equation with log k = log A – 2.303 RT
7
We get log A = 6  A = 106 s–1
Ea 2000
and – 2.303 RT = –
T
Ea = 2000 × 2.303 × 8.314
–1
Ea = 38.3 kJ mol
40. Plots showing the variation of the rate constant (k) with temperature (T) are given below. The plot that follows
Arrhenius equation is [IIT-JEE 2010]
(1) k (2) k (3) k (4) k
T T T T
Sol. Answer (1)

Ea

k  A e RT
Ea
ln k = ln A –
RT
41. Bombardment of aluminium by -particle leads to its artificial disintegration in two ways, (i) and (ii) as shown.
Products X, Y and Z respectively are [IIT-JEE 2011]
(ii)
27 30
13Al 15P +Y
(i)
30 30
14 Si +X 14Si +Z
(1) Proton, neutron, positron (2) Neutron, positron, proton
(3) Proton, positron, neutron (4) Positron, proton, neutron
Sol. Answer (1)
He4
27
13 Al 
2
 30
14 Si  1H1
(X)
He4
27
13 Al 
2
 30
15 P  10 n
(Y)
30
14 Si  01 e
(Z)
42. In the reaction,
P+Q R+S
The time taken for 75% reaction of P is twice the time taken for 50% reaction of P. The concentration of Q varies
with reaction time as shown in the figure. The overall order of the reaction is [JEE(Advanced)-2013]
[Q]0
[Q]
Time
(1) 2 (2) 3 (3) 0 (4) 1
Sol. Answer (4)
The order of reaction with respect to P is one since t3/4 is twice of t1/2. From the given graph the order of
reaction with respect to Q is zero. Therefore, overall order of reaction is one.
43. For the elementary reaction M  N, the rate of disappearance of M increases by a factor of 8 upon doubling
the concentration of M. The order of the reaction with respect to M is [JEE(Advanced)-2014]
(1) 4 (2) 3 (3) 2 (4) 1
Sol. Answer (2)

r2 ⎛ [M]2 ⎞
⎜ ⎟
r1 ⎝ [M]1 ⎠

8 = (2)
=3
So, order of reaction is 3.
SECTION - B
Objective Type Questions (More than one options are correct)
1. For the reaction A + B 

 2C + D. Which of the following statement is/are correct?
1
(1) Rate of disappearance of B  × rate of appearance of C
2
(2) Rate of disappearance of B = 2 × rate of appearance of C
(3) Rate of disappearance of A = rate of appearance of D
(4) Rate of disappearance of A = rate of disappearance of B
Sol. Answer (1, 3, 4)
We can relate rate for the reaction
A + B  2 C + D as :
– [A] – [B] 1 [C] [D]

= = =
t t 2 t t
We can conclude that (1), (3) & (4) are correct answer. (2) is not correct because
[B] 1 [C]
=
t 2 t
2.

In the formation of sulphur trioxide by the contact process, 2SO2 + O2
2SO3, the rate of reaction was
d(SO 2 )
measured as = 6.0 × 10–4 mol L–1s–1. Select correct statements
dt
(1) The rate of reaction expressed in terms of SO3 will be 6.0 × 10–4 mole L–1s–1
(2) The rate of reaction expressed in terms of O2 will be 6.0 × 10–4 mole L–1s–1
–4 –1 –1
(3) The rate of reaction expressed in terms of O2 will be 3.0 × 10 mole L s
–4 –1 –1
(4) The rate of reaction expressed in terms of O2 will be 12 × 10 mole L s
Sol. Answer (3)
3. The rate law for the reaction, RCl + NaOH 

 ROH + NaCl is given by Rate = K[RCl]. The rate of the
reaction is
(1) Doubled by doubling the concentration of NaOH
(2) Halved by reducing the concentration of RCl by one half
(3) Increased by increasing the temperature of the reaction
(4) Unaffected by change in temperature
Sol. Answer (2, 3)
The rate law is given by
Rate = K [RCl]
For reaction, RCl + NaOH  ROH + NaCl .
The rate  [RCl] hence when [RCl] reduces to half, rate also becomes half and is not affected by [NaOH].
The rate always increases with the increase in temperature.
4. Which of the following statements for order of a reaction are correct?

(1) Order can be determined experimentally
(2) Order of reaction is equal to sum of the power of concentration terms in differential rate law
(3) It is not affected by the stoichiometric coefficient of the reactants
(4) Order can be fractional
Sol. Answer (1, 2, 3, 4)
For any reaction we can write the rate law
dx
= K[A] [B]
dt
Order is purely an experimental quantity which cannot be determined by stoichiometry of reaction. It can be
+ve, –ve, fractional or zero and order = ( + ).
5. In a hypothetical reaction,
A2 + B2 
 2AB
follows the mechanism as given below
A2 A + A(fast reaction)
A + B2 
 AB + B (slow reaction)
A+B 
 AB (fast reaction)
Select the correct statement
3
(1) R = k[A]2 [B2] (2) Order of reaction is
2
(3) Molecularity is 2 (4) Both molecularity and order = 2

Sol. Answer (2, 3)
The reaction given is

A 2  B2
2AB
Mechanism

A  A (fast)
A 2
A + B2  AB + B (Slow reaction)
A + B  AB (Fast reaction)
Applying the rate equation w.r.t. slow reaction
dx
= k [A] [B2] …(i)
dt
and we can also write
[A]2
Kc =
[A 2 ]
 [A] = {Kc[A2]}1/2 …(ii)

Substituting eq. (ii) in eq. (i)
dx 1/2
= K {Kc[A2]} [B2]
dt
dx
 = K’ [A2]1/2 [B2]
dt
1/2
Here K’ = K.Kc
 According to above rate law
1
Order = 1  = 3/2
2
And since two reactants are involved hence molecularity is equal to 2.
6. Which of the following are unimolecular?

CH2
(1) O3  O2 + [O] (2)  CH3 – CH = CH2
CH2 CH2
(3) NO + O3  NO2 + O2 (4) O + NO + N2  NO2 + N2
Sol. Answer (1, 2)
Fact.
7. For the reaction A 

 B, the rate law is R = k[A]2, which of the following statements are correct?
(1) The reaction follows first order kinetics
(2) The t1/2 of the reaction depends upon initial concentration of reactant
(3) The unit of rate constant litre mole–1 s–1
(4) K is constant for the reaction at all temperature
Sol. Answer (2, 3)
The given reaction is A  B. Rate law is given as
dx
= K[A]2
dt
It indicates that reaction follows II order kinetics.
1
t1/2 = K[A] hence half life is inversely related to concentration,
0
M 1
K has units = 2 ⇒
s.M M.s
1 litre
= litre mol–1s–1
moles  s
and it depends upon temperature.
8. The plot given is not possible for
Y
1
(1) 2nd order reaction  vs. time (2) 1st order reaction  t1/2 vs. concentration
[A]
(3) Zero order reaction  t1/2 vs. concentration (4) n order reaction  rate vs. concentration
th
9. Incorrect statement(s) among the following is/are
(1) An autocatalytic reaction is catalysed by one of the reactants
(2) A catalyst never enters into chemical reactions
(3) An elementary exothermic reaction (step) can have zero activation energy
(4) An elementary endothermic reaction can have zero activation energy
Sol. Answer (1, 2, 3, 4)
Fact.
10. Which of the following is/are correctly matched for an elementary reaction?
Column-I Column-II
RateTº  10º C
(1) 2 Endothermic reaction
RateT C
RateTº  10º C 1
(2)  Exothermic reaction
RateT C 2
RateTº  20º C
(3) 4 Exothermic reaction
RateT C
RateTº  20º C 1
(4)  Endothermic reaction
RateT C 4
Sol. Answer (1, 2)

It is defined as the temperature coefficient of the reaction
k T 10ºC
as = 2 (Endothermic)
kT
k T  20ºC
and k = 4 (Exothermic)
TºC
11. Which of the following statements is/are correct regarding catalyst?

(1) Increases the average kinetic energy of reacting molecules
(2) Decreases or increases the activation energy
(3) Alters the reaction mechanism
(4) Increases the frequency of collisions of reacting molecules
Sol. Answer (2, 3)
A catalyst alters the mechanism and consequently decreases or increases the activation energy.
It does not increase the frequency of collisions, since it depends upon temperature.
12. For a first order reaction

–kt
(1) The degree of dissociation is equal to 1 – e
(2) The pre-exponential factor in the Arrhenius equation has the dimension of time, T–1
(3) The time taken for completion of 75% reaction is twice the t1/2 of the reaction
(4) A plot of reciprocal of concentration of the reactant versus time gives a straight line

For I-order reaction we can write
1 ⎛ 1 ⎞
K= ln ⎜ ⎟
t ⎝1– x ⎠
–Kt = ln (1 – x)
e–Kt = (1 –x) ⇒ x = 1–e–Kt
 Degree of dissociation is (1 – e
–Kt
)
–Ea
In the equation K = A.e RT

–1
‘K’ has same dimensions as ‘A’ as [time] .
For t1/2 of I-order
ln2
(t1/2)I =
K
For 75% completion
1 ⎛ a ⎞ ln 4
t= ln ⎜ =
K 75 a ⎟ K
⎜a – ⎟
⎝ 100 ⎠
2ln2
 t= = 2t1/2
K
1
versus t graph gives a straight line for II-order and not for I-order.
[A]t
13. Which of the following statement(s) is/are correct?
1
(1) A plot of log kp versus is linear
T
(2) A plot of log [x] versus time is linear for zero order reaction
1
(3) A plot of P versus is linear at constant volume
T
1
(4) A plot of P versus is linear at constant temperature and number of moles
V
Sol. Answer (1, 4)
According to Boyle’s law
1 K
P (at constant T and no. of moles)  P =
V V
⎛ 1⎞
Between P and ⎜ ⎟ the graph will be straight line
⎝V⎠
P versus T graph will be straight line. For zero order x = kt
i.e., x versus t graph gives straight line and not log x versus t.
⎛ K2 ⎞ H ⎛ T2  T1 ⎞
log ⎜ K ⎟ = ⎜ ⎟
⎝ 1⎠ 2.303 K ⎝ T1T2 ⎠
1
Hence the graph between log Kp versus will be linear.
T
14. Two reactions A products and B  products have rate constant kA and kB at temperature T and activation
energies EA and EB respectively. If kA > kB and EA < EB and assuming ‘A’ is same for both the reactions, then
(1) At higher temperature kA will be greater than kB
(2) At lower temperature kA and kB will be close to each other in magnitude
(3) As temperature rises, kA and kB will be close to each other in magnitude
(4) At lower temperature kB > kA
Sol. Answer (1, 3)
It can be concluded from the Arrhenius equation.
that KA > KB at higher temperature.
And they will approach each other as we increase the temperature
(i.e. K A  K B )
15. A catalyst lowers the activation energy of forward reaction . It also changes the activation energy of backward
reaction by an amount
(1) Equal to that of forward reaction
(2) Twice to that of forward reaction
(3) Determined only by average energy of products
(4) Determined by average energy of products relative that of reactants
Sol. Answer (1)
(E)af
Potential (E)ab Reaction path without catalyst
Energy
R Reaction path with catalyst
Collision number
16. Correct statement(s) among the following is/are

(1) A plot of number of neutrons vs. number of protons is linear when number of protons are very low
(2) Plot is increasing for log[A] vs. time for first order reaction
(3) Decreasing plot for t1/2 vs. concentration for zero order reaction
(4) Constant rate for zero order
Sol. Answer (1, 4)
17. Nuclear reactions accompanied with the emission of neutron(s) are
12
(1) 27
13 Al  4
2He  15P
30 (2) 6 C  1H1  7N13
241
(3) 30
15 P
30
 14 Si (4) 95 Am  2He 4  244
97 Bk
Sol. Answer (1, 4)

Applying mass and charge balance
⎛ q  13  2  15  0 ⎞
27
Al  24He  30
P  0n1 ⎜ ⎟
13 15
⎝ m  27  4  30  1⎠
⎛ 12  1  13  1⎞
12
C  1H1  0n1  7N13 ⎜ ⎟
6
⎝6 1 7  0 ⎠
⎛ m  30  30  1⎞
30
P 30
Si  e0  0n1 ⎜ ⎟
15 14 1
⎝ q  15  14  1 ⎠
⎛ 241  4  244  1⎞
241
Am  24He  244
Bk  0 n1 ⎜ ⎟
95 97
⎝ 95  2  97 ⎠
18. A radioactive element decays as
 decay (–2 )  decay

X Y Z
t1/2 = 30 minute t1/2 = 2 days
Which of the following statements about this decay process is/are correct?
(1) After two hours, less than 10% of the initial X is left
(2) Maximum amount of Y present at any time before 30 minute is less than 50% of the initial amount of X
(3) Atomic number of X and Y are same
(4) Mass number of X and Y are same

Sol. Answer (1, 2)
 –decay
(X)   (Y) 
–2
 (Z)
t1/2 = 30 minute t1/2 = 2 days

When above decays take place
–
– 2
A
Z X  A–4
Z–2 Y   A–4
Z Z
After 2 hrs
4
x
⎛ 1⎞ ⎛ N0 ⎞
Nt = N0 ⎛⎜ 1 ⎞⎟ = N0 ⎜ ⎟ = ⎜ ⎟ < 10%
⎝2⎠ ⎝2⎠ ⎝ 16 ⎠
Hence (Y) amount at any time before 30 minute is less than 50% as (Y) disintegrate to give Z also.
19. Which of the following statements is/are correct?
(1) Nuclear isomers contain same number of protons and neutrons
(2) The decay constant is independent of the amount of substance taken
(3) The decay constant is independent of temperature and pressure
(4) The value of decay constant generally increases with temperature since radioactive reaction obeys first order
kinetics
For radioactivity, which follows first order kinetics
ln2
= t hence, it is independent of the amount of substance taken. And  (or radioactivity) is independent
1/2
of external factors like temperature and pressure.

Nuclear isomers contains same number of protons and neutrons.
20. For the first order reaction,
2N2O5 (g)  4NO2 (g)  O2 (g) [IIT-JEE 2011]
(1) The concentration of the reactant decreases exponentially with time

(2) The half life of the reaction decreases with increasing temperature
(3) The half life of the reaction depends on the initial concentration of the reactant
(4) The reaction proceeds to 99.6% completion in eight half-life duration
2.303 A
t log
m 0.4  102  Α
8  0.693 2.303 103
  log250 = 2.303log = 2.303  (3  2  0.3010)
k k 4
21. In the nuclear transmutation 94 Be  X  84Be  Y (X, Y) is(are) [JEE(Advanced)-2013]
(1) (, n) (2) (p, D) (3) (n, D) (4) (, p)

Sol. Answer (1, 2)
9
4 Be    84Be  10 n
9
4 Be  1
1H  84Be  12H
22. The % yield of ammonia as a function of time in the reaction N 2  g + 3H 2 (g) 2NH 3 (g), H < 0 at (P, T1)
is given below
T1
%yield
time
If this reaction is conducted at (P, T2), with T2 > T1, the %yield of ammonia as a function of time is represented
by [JEE(Advanced)-2015]
T2
T2 T1 T1
T1 T1
%yield
%yield
T2
%yield
%yield
T2
(1) (2) (3) (4)
time time time time
Sol. Answer (2)

On increasing temperature forward as well as backward reaction rate increases due to which initially %yield
of NH3 is higher at T2 K but equilibrium attain at lower time at T2 K hence its yield at equilibrium is low at
T2 K.
23. According to the Arrhenius equation, [JEE(Advanced)-2016]

(1) A high activation energy usually implies a fast reaction
(2) Rate constant increases with increase in temperature. This is due to a greater number of collisions whose
energy exceeds the activation energy
(3) Higher the magnitude of activation energy, stronger is the temperature dependence of the rate constant
(4) The pre-exponential factor is a measure of the rate at which collisions occur, irrespective of their energy
 A high activation energy usually implies a slow reaction.
 Rate constant of a reaction increases with increasing temperature due to the increase in greater number
of collisions whose energy exceeds the activation energy.
 k  P  Z  e–Ea /RT
So, pre-exponential factor (A) = P × Z and it is independent of activation energy or energy of molecules.
24. A plot of the number of neutrons (N) against the number of protons (P) of stable nuclei exhibits upward deviation
from linearity for atomic number, Z > 20. For an unstable nucleus having N/P ratio less than 1, the possible
mode(s) of decay is/are [JEE(Advanced)-2016]
(1)  -decay ( emission)

–
(2) Orbital or K-electron capture
(3) Neutron emission
(4) +-decay (positron emission)
Sol. Answer (2, 4)

When N/P ratio is less than one, then proton changes into neutron.
Positron emission : 11 H  10n  01 
Capture : 11 H  0
1 e  10 n  X-rays
25. In a bimolecular reaction, the steric factor P was experimentally determined to be 4.5. The correct option(s)
among the following is(are) [JEE(Advanced)-2017]
(1) The activation energy of the reaction is unaffected by the value of the steric factor
(2) Since P = 4.5, the reaction will not proceed unless an effective catalyst is used
(3) The value of frequency factor predicted by Arrhenius equation is higher than that determined experimentally
(4) Experimentally determined value of frequency factor is higher than that predicted by Arrhenius equation
Sol. Answer (1, 4)
A exp erimental
Steric factor 
A calculated
Steric factor = 4.5

It means Aexperimental > Acalculated
[This seems that reaction occurs more quickly than particles collide, thus concept of steric factor was
introduced]
26. For a first order reaction A(g)  2B(g) + C(g) at constant volume and 300 K, the total pressure at the
beginning (t = 0) and at time t are P0 and Pt, respectively. Initially, only A is present with concentration [A]0,
and t1/3 is the time required for the partial pressure of A to reach 1/3rd of its initial value. The correct option(s)
is (are) (Assume that all these gases behave as ideal gases) [JEE(Advanced)-2018]
Rate constant
In(P0 – Pt)
In(3P0–Pt)
t1/3
(1) (2) (3) (4)
Time [A]0 Time [A]0
Sol. Answer (1, 4)

A  2B + C
P0 – –
P0 – P 2P P
Pt = P0 + 2P
ln (3P0 – Pt)
Pt  P0
P=
2
⎡ P0 ⎤ 2P0
Kt  ln ⎢ ⎥  ln
P  P0 3P0  Pt Time
⎢ P0  ⎛⎜ t ⎞⎥
⎟
⎢⎣ ⎝ 2 ⎠⎦⎥
Kt  ln 2P0  ln(3P0  Pt )
Rate constant of reaction is independent of initial concentration.
SECTION - C
Linked Comprehension Type Questions
Comprehension-I
The following data are for the reaction A + B  Products
Concentration Concentration Initial rate
[A] (M) [B] (M) (mol L–1s1)
0.1 0.1 4.0 × 10–4
0.2 0.2 1.6 × 10–3

–2
0.5 0.5 1.0 × 10
–2
0.5 0.2 1.0 × 10
1. What is the order with respect to A and B for the reaction respectively?
(1) 0, 0 (2) 2, 2 (3) 2, 0 (4) 0, 2
Sol. Answer (3)
2. Calculate the rate constant (mole L–1 s–1)
(1) 4 × 10–2 (2) 4 × 10–4 (3) 1.6 × 10–3 (4) 1 × 10–2
Sol. Answer (1)
3. Determine the reaction rate when [A] and [B] are 0.2 M and 0.35 M, respectively.
–2 –3 –4 –4
(1) 1 × 10 (2) 1.6 × 10 (3) 4 × 10 (4) 1 × 10
Sol. Answer (2)
Comprehension-II
According to Soddy Fajan Law
“When an -particle is emitted, the daughter element has atomic number 2 units less than that of parent element.
It is consequently displaced two places (groups) to the left in the periodic table. When a -particle is emitted, the
daughter element has an atomic number 1 unit higher than that of parent element. It is consequently displaced one
place (group) to the right in the periodic table”.
226
1. Radioactive disintegration of 88Ra takes place in the following sequence
   
 A 
Ra  B  C  D
The atomic number and group of D will be respectively
(1) 82, 14 (2) 83, 14 (3) 83, 15 (4) 84, 16

Sol. Answer (3)
222
88Ra
226
 2He4 + 86 A
222
86 A  2He 4  218
84 B
218
84 B  2He 4  214
82 C
214
82 C 214
83 D  01B
 Atomic number of D will be 83 and will be lying in group 15.
. The number of  and -particle emitted in this process will be respectively

234 206
2. 90Th disintegrates to give 82Pb
(1) 7, 6 (2) 6, 7 (3) 8, 8 (4) 6, 4
Sol. Answer (1)

234 206
90Th  82Pb
Since atomic mass decreases from 234 to 206 the difference is 28 and per -particle emission the mass
decreases by 4 units.
28
 Number of -particles emitted = =7
4
Atomic no. decreases by 7 × 2 = 14 or it becomes 76.

In the product no. of protons is 82 hence 6 particles are emitted
 No. of -particles emitted = 7
No. of -particles emitted = 6
3. Number of neutrons and group number after emission of an -particle from 92U
238
group III
(1) N =146, group III (2) N = 144, group I
(3) N = 144, group III (4) None of these
Sol. Answer (3)
The given radioactive element is 92U

238
 2He4 + 234
90 X
 Number of neutrons in X = 234 – 90 = 144
Comprehension-III
Hydrolysis of sucrose (C12H22O11), a first order reaction gives glucose (C6H12O6) and fructose (C6H12O6).
HO
S 
2
 G + F
(Dextro) (Dextro) (Laevo)
The rotation of plane polarised light at different angles by S, G and F is directly proportional to their concentration.
Given
Time 0 t 
Rotation (S + G + F) r0 rt r
a = Initial concentration of sucrose.
r0
1. If combined rotation of glucose and fructose is equal to the value of initial rotation, then is equal to
r
(1) 0 (2) 1 (3)  (4) a
Sol. Answer (2)
r10  r20  r30
r0 a r10
 1
r a(r20  r30 )
r
2. If amount of rotation of glucose (per mole) is equal to amount of rotation of fructose (per mole), then is equal
r0
to
(1) 0 (2) 1 (3)  (4) a
Sol. Answer (1)
r20  r30
r a(r20  r30 )
  0.(∵ r  0)
r0 ar10
3. In previous question, after 30 seconds total rotation is equal to half of initial rotation. Then value of rate constant
is (in s–1)
30 ln2 –2
(1) ln2 (2) (3) (4) 10
ln2 30
Sol. Answer (3)
1 ⎛ r  r0 ⎞
k ln ⎜ ⎟
30 ⎝ r  rt ⎠
1 ⎛ r0 ⎞ 1 ⎛ 1 ⎞
ln ⎜ ⎟ ln 2 ⎜∵ rt r0 ⎟
30 ⎝ rt ⎠ 30 ⎝ 2 ⎠
SECTION - D
Assertion-Reason Type Questions
1. STATEMENT-1 : Rate of Radioactive decay is independent of external factors (like pressure, temperature).
and
STATEMENT-2 : Radioactive decay follows second order kinetics.
Sol. Answer (3)
Radioactivity is a nuclear phenomenon and is independent of external factors like temperature, pressure etc.
Radioactivity follows first order kinetics and number of nuclei at any time ‘t’ is given by
Nt = N0 e–t
 Statement (1) is correct but statement (2) is false.
2. STATEMENT-1 : Acidic hydrolysis of ester is an example of pseudounimolecular reaction.

and
STATEMENT-2 : Molecularity of acidic hydrolysis of ester is one.
Sol. Answer (3)
For acidic hydrolysis the reaction is
CH3COOCH2CH3 + H2O  CH3CH2OH + CH3COOH
dx
= K[CH3COOCH2CH3]
dt
but two species are involved in the reaction. Hence, it is bimolecular. These reactions are pseudo-unimolecular
reactions.
 Statement (1) is true but statement (2) is false.
3. STATEMENT-1 : Half life of first order reaction is independent of initial concentration of reactants.
and
STATEMENT-2 : Half life of first order reaction is inversely proportional to the rate constant.
Sol. Answer (2)
Half life for I-order reaction is given as
ln2
t1/2 = (independent of initial concentration & inversely proportional to K)
K
 Statement (1) & (2) both are correct but statement (2) is not the correct explanation of statement (1).
4. STATEMENT-1 : Activation energy of forward reaction (Eaf) is greater than activation energy of backward reaction
(Eab) for an endothermic reaction.
and
STATEMENT-2 : Rate constant for a first order reaction is dependent on temperature.
Sol. Answer (2)
H for the reversible reaction is given by
(H) = (Ea)f – (Ea)b
For endothermic reaction H > 0  (Ea)f – (Ea)b > 0 or (Ea)f > (Ea)b
The rate constant for the first order reaction is given by
–E /RT
K = A.e a
Hence, statement (2) is not the correct explanation.
5. STATEMENT-1 : Positive catalysts lowers the activation energy of the reaction.

and
STATEMENT-2 : Heat of reaction is equal to the difference between activation energies for forward and backward
reactions.
Sol. Answer (2)
Only a positive catalyst lowers the activation energy and increases the rate of reaction.
And (H) = (EA)f – (EA)b
 Statement (2) is not the correct explanation because the catalyst provides an alternate mechanism for the
conversion of reactants to products.
6. STATEMENT-1 : The rate of reaction always depends on the concentration of reactants.
and
STATEMENT-2 : Order of reaction of a component can be negative with respect to reaction.
Sol. Answer (4)
The rate of reaction also depends upon temperature and order of the reaction can be positive, negative, zero
or even fractional.
7. STATEMENT-1 : The rate of reaction increases generally by 2 to 3 times for every 10°C rise in temperature.
and
STATEMENT-2 : Increase in temperature increases the collision frequency.
Sol. Answer (2)
The rate of reaction generally increases the rate by 2 times to 3 times. We also define
K T 10
= TC (Temp. coefficient)
KT
and with the increase in temperature collision frequency increases as more molecules cross the energy barrier
and acquire activation energy.
8. STATEMENT-1 : For a first order reaction, rate of the reaction doubles as concentration of reactant gets doubled.
and
STATEMENT-2 : Rate is directly proportional to concentration of reactant.
Sol. Answer (1)
Rate = k [reactant].

H
9.

STATEMENT-1 : The pseudo order of reaction CH3COOC2H5 + H2O
CH3COOH + C2H5OH is 2.
and
STATEMENT-2 : The molecularity of given reaction is two.
Sol. Answer (4)
Order of reaction is 1 (pseudo-order)
10. STATEMENT-1 : If activation energy is zero, then temperature will have no effect on rate constant.
and
STATEMENT-2 : Lower the activation energy, faster is the reaction.
Sol. Answer (2)
k  Ae Ea /RT
For Ea = 0  k = A
11. STATEMENT-1 : The plot of atomic number (y-axis versus number of neutrons (x-axis) for stable nuclei shows
a curvature towards x-axis from the line of 45° slope as the atomic number is increased.
and
STATEMENT-2 : Proton-proton electrostatic repulsions begin to overcome attractive forces involving protons and
neutrons in heavier nuclides. [IIT-JEE 2008]
Sol. Answer (2)
Elements with higher atomic number are more stable if they have slight excess of neutron as this increase
the attractive force and also reduces repulsion between protons.
SECTION - E
Matrix-Match Type Questions
1. Match the following :

Column-I Column-II
(A) 4Be + 2He 

9 4 12 4
6C + .......... (p) 2He
(B) 6C12 +............ 

 5B10 + 2He4 (q) 0n
1
+ ........... 
 8O17 + 1H1
14 2
(C) 7N (r) 1D
(D) 20Ca
40
+ ........ 
 19K37 + 2He4 (s) 1H
1
Sol. Answer A(q), B(r), C(p), D(s)

Applying the mass –balance and charge balance
The reactions can be written as
⎛ mass  13 ⎞
(A) 4Be9 + 2He4  6C12 + 0n1 ⎜ ⎟
⎝ charge  6 ⎠
⎛ mass  12  2  10  4 ⎞
(B) 6C12 + 1D2  5B10 + 2He4 ⎜ ⎟
⎝ charge  6  1  5  2 ⎠
⎛ mass  14  4  17  1⎞
(C) 7N + 2He  8O
14 4 17 1
+ 1H ⎜ ⎟
⎝ charge  7  2  8  1 ⎠
⎛ mass  40  1  4  37 ⎞
+ 1H 
40 1 37 4
(D) 20Ca 19K + 2He ⎜ ⎟
⎝ charge  20  1  19  2 ⎠

Column-I Column-II
1
(A) Half life of zero order reaction (p) k.a
(B) Half life of first order reaction (q) 2 – 3
0.693
(C) Temperature coefficient (r)
k
a
(D) Half life of second order reaction (s)
2k
Sol. Answer A(s), B(r), C(q), D(p)
Half life for the reaction is inversely related to (a)n–1 where ‘n’ is the order of the reaction
ln2 0.693
 For I-order; t1/2 = =
k k
a
for zero order; t1/2 =
2k
for II-order reaction
1
t1/2 =
k.a
The temperature coefficient of reaction is the ratio of rate constants differing by a temperature of 10ºC.

Column-I Column-II
Concentration
(A) (A) (p) 3
Rate
(B) (q) 2
Concentration
(C) 1 (r) 1
A
t
Rate
(D) (s) 0
(Conc)3
Sol. Answer A(s), B(r), C(q), D(p)
For III-order reaction we can write
dx
= k (a – x)3
dt
⎛ dx ⎞
The graph will be straight line between ⎜ ⎟ and
⎝ dt ⎠
3
(a – x) passing through the origin.
For II order, the equation is,
1 1
[A]t = [A]0 + kt
1
The graph between [A] versus t is a straight line
t
1
1 [A]
having +ve slope and intercept = [A] .
0
t
 The graph is for II-order reaction
For I-order reaction the equation can be written as
dx
= k (a – x)
dt
⎛ dx ⎞
Hence ⎜ ⎟  (a – x)
⎝ dt ⎠
 The graph for I-order is

Rate
For zero-order reaction, the concentration decreases
as time progresses at constant rate
 Graph will be
(conc.)
Column I Column II
K T  10
(A) (p) Arrhenius equation
KT
(B) e Ea /RT (q) Temperature coefficient
(C) Rate = K [Reactant]n (r) Boltzmann factor
(D) k  Ae Ea /RT (s) Rate law expression
Sol. Answer A(q), B(r), C(s), D(p)

Column I Column II
[D]
Concentration
[C]
(A) A  B  C  D (p)
[B] [A]
time
[B]
Concentration
[D]
(B) A  B  D (q)

C [C] [A]
time
Concentration
[D]
B
(C) A (r) [B]
C D
[C] [A]
time
[D]
Concentration
[C]
B C
(D) A (s)
D
[B] [A]
time
Note : Assume that all reactions are moderately fast reactions.
Sol. Answer A(r), B(p), C(q), D(s)
SECTION - F
Integer Answer Type Questions
1. Two radioactive elements X and Y have half lives of 100 and 50 minutes respectively. Initial sample of both the
elements have same number of atoms. Find the ratio of remaining no. of atoms of X and Y after 200 minutes.
Sol. Answer (4)
After 200 minutes,
a
Remaining about of X 
22
a
Remaining about of Y 
24
24
 Ratio = =4
22
2. H2O and O atom react in upper atmosphere bimolecularly to form two OH radicals. H for the reaction is 72 kJ
at 500 K and energy of activation is 77 kJ / mol. Estimate Ea (kJ/mol) for bimolecular recombination of two
OH radicals to form H2O & O atom.
Sol. Answer (5)
Ea
H2 O  O  2OH H  72 kJ
Eb
2OH  H2 O  O H  72 kJ
Also, Ea – Eb = H
 Eb = 5 kJ/mol
3. For the reaction given below, the rate expression is given as : RX  OH  ROH  X
5
4.7  10 RX  OH

  0.24

10
5
RX

rate =
SN 2 SN 1
–
What percentage of RX reacts by the SN2 mechanism when [OH ] = 0.001M?
Sol. Answer (2)
4.7  10 5 RX OH 

 100 2.1∵ OH   0.001M
⎡ rSN 2 ⎤ 
% rate of SN 2  ⎢ ⎥  100 = 5
   

4.7  10 RX OH  0.24  10 RX 5
 
⎣⎢ rSN 1  rSN 2 ⎦⎥
4. The rate of a certain reaction depends on concentration according to the equation :
dC K1C
 
dt 1  K 2 C
What will be the order of reaction, when concentration C is very low?
Sol. Answer (1)
∵ C is low, then 1  k 2 C  1
dC
   k1C
dt
st
Hence, reaction is of 1 order.
5. For a first order reaction
t99.99% = y  t90%
Find the value of y.
Sol. Answer (4)
2.303 1 2.303
t 99.99%  log10 4  4 
k 10 k
2.303 1 2.303
t 90%  log10 1 
k 10 k
238 214
6. The total number of  and  particles emitted in the nuclear reaction 92 U  82 Pb is [IIT-JEE 2009]
Sol. Answer (8)
238 214
92 U 
 82 Pb  X24He  y01e
24 = 4x; x = 6
10 = 2x – y
y=2
 x+y=8
7. The concentration of R in the reaction R  P was measured as a function of time and the following data is
obtained [IIT-JEE 2010]
[R] (molar) 1.0 0.75 0.40 0.10
t(min.) 0.0 0.05 0.12 0.18
The order of the reaction is
Sol. Answer (0)

For zero order reaction
dx
k
dt
from 1 to 0.75 (M) from 0.75 to 0.40 from 0.40 to 0.10
0.25 0.35 0.30

5 5 5
0.05 0.07 0.06
It mean order of this reaction is zero.

8. The periodic table consists of 18 groups. An isotope of copper, on bombardment with protons, undergoes a nuclear
reaction yielding element X as shown below. To which group, element X belongs in the periodic table?
63
29 Cu  11H  610 n    211H  X [IIT-JEE 2012]
Sol. Answer (8)
63
29 Cu  11H  610 n  ( 24 He)  211H  X(52
26 Fe)
Fe belongs to group-8.
1 1
9. An organic compound undergoes first-order decomposition. The time taken for its decomposition to and
8 10
⎡ ⎤
⎢t 1 ⎥
t1 t1 ⎣ 8 ⎦  10 ?
of its initial concentration are and respectively. What is the value of (take log102 = 0.3)
8 10 ⎡ ⎤
⎢t 1 ⎥
⎣ 10 ⎦
[IIT-JEE 2012]
Sol. Answer (9)
2.303 1
t1/8  log10 …(i)
k 18
2.303 1
t1/10  log10 …(ii)
k 1 10
[t1/8 ] log8
 10   10  3  0.3  10  9
[t1/10 ] log10
238
10. A closed vessel with rigid walls contains 1 mol of 92 U and 1 mol of air at 298 K. Considering complete decay
238 206
of 92 U to 82 Pb, the ratio of the final pressure to the initial pressure of the system at 298 K is
[JEE(Advanced)-2015]
Sol. Answer (9)
238 206 4 0
92 U  82 Pb  8 2He  6 – 
Now number of moles in gas phase = 1 + 8 = 9 mole

at constant temperature and pressure
PF nF 9
  9
Pin nin 1
11. Consider the following reversible reaction,
A(g)  B(g) AB(g) .
The activation energy of the backward reaction exceeds that of the forward reaction by 2RT
(in J mol–1). If the pre-exponential factor of the forward reaction is 4 times that of the reverse reaction, the
absolute value of G (in J mol–1) for the reaction at 300 K is __________. [JEE(Advanced)-2018]
–1
(Given; ln(2) = 0.7, RT = 2500 J mol at 300 K and G is the Gibbs energy)
Sol. Answer (8500.00)
A(g) + B(g) AB(g)
Eab – Eaf  2RT
Af
4
Ab
Kf
K
Kb
–Eaf /RT
Kf  Af e
K b  A b e –Eab /RT
Kf A (E –E )/RT
 f e ab af
Kb Ab
 K = 4e2RT/RT
K = 4e2
G° = – RT In K
= – RT (2 + ln 4)
= – 2500 (2 + 2 × 0.7)
= – 8500 J mol–1
Absolute value is 8500.00
SECTION - G
Multiple True-False Type Questions
1. STATEMENT-1 : Helium present in uranium mineral is formed from -particles.

STATEMENT-2 : If helium and uranium contents of a mineral are known, the age of the mineral can be
estimated.
STATEMENT-3 : Most of the rocks contain lead / uranium ratio much less than unity indicating that the age
238
of rocks may be more than half life period of U92 .
(1) T T F (2) TFT (3) FFT (4) FTF
Sol. Answer (1)
Facts about age of minerals and rocks.
2. STATEMENT-1 : The rate of a reaction sometimes does not depends on concentration.

STATEMENT-2 : Lower the activation energy, faster is the reaction
STATEMENT-3 : Increase in temperature decreases collision frequency.
(1) FFT (2) TTF (3) FFF (4) TTT
Sol. Answer (2)
For zero order reaction, rate is independent of concentration
 Rate = k [reactant] and k = Ae Ea /RT

n
 Increasing the temperature increases collision frequency.
SECTION - H
Aakash Challengers Questions
1. From the following data for the reaction between A and B
–1 –1
[A] [B] Initial rate (mole L sec ) at
–1 –1
(mole L ) (mole L ) 300 K 320 K
–4 –5 –4 –3
2.5 10 3.0 10 5.0 10 2.0 10
–4 –5 –3
5.0 10 6.0 10 4.0 10 ________
–3 –5 –2
1.0 10 6.0 10 1.6 10 ________
Calculate:
(i) Order of reaction w.r.t. A and w.r.t. B
(ii) Rate constant at 300 K
(iii) Pre-exponential factor
Sol. (i) Order w.r.t. A = 2
Order w.r.t. B = 1
8 2 –2 –1
(ii) K300 = 2.66 × 10 L mol s .
(iii) A = 1.15 × 1018 L2 mol–2 s–1.
From data at 300 K,
5 × 10–4 = k[2.5 × 10–4]m [3.0 × 10–5]n …(i)
–3 –4 m –2 n
4 × 10 = k[5.0 × 10 ] [1.6 × 10 ] …(ii)
–2 –3 m –2 n
1.6 × 10 = k[1.0 × 10 ] [6.0 × 10 ] …(iii)
 m  2, n  1
Rate law  rate =k[A] [B]

2
5.0  104
K300 =
(2.5  104 )2 (3.0  105 )
 K 300  2.66  108 L2mol2 s1
2.0  103
 K320 =
[2.5  104 ]2 [3.0  105 ]
 K320 = 1.07 × 109 L2 mol–2 s–1
K 320 Ea ⎡ 1 1 ⎤
log10  
K 300 2.303  8.314 ⎣ 300 320 ⎥⎦
⎢
 Ea = 55.34 × 103 joule

Ea 55.34103
 
∵ k  Ae RT ⇒ 2.66  10  Ae 8 8.314300
A  1.15  1018 L2 mol2 s1
2. The rate of a first order reaction is 0.04 mole L–1 sec–1 at 10 minutes and 0.03 mole L–1 sec–1 at 20 minutes,
respectively after initiation. Find the half life of the reaction
–1 –1
Sol. Rate at (t = 10 min) = 0.04 mol L sec = kC10 = R10
–1 –1
Rate at (t = 20 min) = 0.03 mol L sec = kC20 = R20
C10 R10 4
So, C  R  3
20 20
2.303 C 2.303 4
K log 10 min1  log min1
(20  10) C20 10 3
0.693 0.693  10 3 3
t1/2     min = 24.19 min
K ⎛ 4⎞ 4 0.124
2.303 ⎜ log ⎟ log
⎝ 3⎠ 3
3. 2X(g) 3Y(g) + 2Z(g)
Time(in minute) 0 100 200

Partial pressure of X [in mm of Hg] 800 400 200
Assuming ideal gas condition, calculate
(i) Order of reaction (ii) Rate constant
(iii) Time taken for 75% completion of reaction (iv) Total pressure when Px = 700 mm of Hg
Sol. (i) First order
(ii) k = 6.93 × 10–3 min–1
(iii) t = 200 min
(iv) Ptotal = 950 mm Hg
2X(g)  3Y(g)  2Z(g)

t=0 800 mm 0 0
t = 100 minute 400 mm 600 mm 400 mm
t = 200 minute 200 mm 900 mm 600 mm
K100 = K200  above reaction is first order
2.303 800
K log10 ⇒ k  6.93  10 3 min1
100 400
2.303 1
t 75%  3
log ⇒ t75%  200min
6.93  10 0.25
2X(g)  3Y (g) + 2Z(g)

800  2 x 3x 2x
800 – 2x = 700  x = 50 mm Hg
Ptotal = 800 – 2x + 3x + 2x = 800 + 3 × 50
 Ptotal = 950 mm Hg
4.

The progress of a reaction A
nB with time is presented in the figure determine
0.7
0.6
Concentration (mol/lt)
0.5
0.4
0.3
0.2
0.1
1 2 3 4 5 6 7
Time (hour)
(i) The value of n
(ii) The equilibrium constant K
(iii) The initial rate of conversion of A
Sol. (i) n = 2, (ii) k = 1.2 mol L1, (iii) Rate = 0.1 mol L1 hour 1
0.6  0.5
Loss in [A] in 1 hour =  0.1
1
0.2  0
Gain in [B] in 1 hour =  0.2
1
0.1 mole of A forms 0.2 mole of B in 1 hour

 n=2
[B]2
Equilibrium constant, k =
[A]
Equilibrium is attained after 5 hours, where

[B] = 0.6, [A] = 0.3
(0.6)2
 k ⇒ k  1.2 mol L–1
(0.3)
– d[A]
Initial rate of conversion of A =
dt
[0.5  0.6]
=
(1  0)
= 0.1 mol L–1 hour–1
227
5. Ac has a half life of 22.0 years with respect to radioactive decay. The decay follows two parallel paths, one
222 223 222
leading to Th and the other to Fr. The percentage yield of Th is 2%. What are the decay constant() for
each of the separate paths?
Sol. 1(for Th)  0.00063 yr –1,  2 (for Fr)  0.03087 yr 1
0.693 0.693 1
overall decay constant,    yr .
t1/2 22
If 1 and 2 are decay constants of the reactions leading to

222 223
Th and Fr respectively, we have
0.693
1   2 
22
1
% Yield of 222
Th = 2% =  100
1   2
2
% Yield of 223
Fr = 98% =  100
1   2
 1 = 0.00063 yr , 2 = 0.03087 yr
–1 –1
6. On analysis, a sample of uranium was found to contain 0.277 gram of 82Pb206 and 1.667 gram of 92U238. The half
life period of 92U
238
is 4.51  109 years. If all the lead was assumed to come from decay of 92U
238
, what is the
age of earth?
9
Sol. Age = 1.1 × 10 years
7. The energy profile diagram for the following reaction is given
Energy
R y
P
z
Reaction path

CO(g)  NO2 (g)
CO2 (g)  NO(g)
(i) What are the activation energies of forward and backward reactions?
(ii) What is the heat of reaction?
(iii) What is the threshold energy of reaction?
(iv) What are the enthalpies of reactants and products?
Sol. (i) x, x + y
(ii) y I
(iii) x + y + z
(iv) y + z, z (E)af (E)ab
ETh
Energy R
H
HR P
HP
Reaction path
8. Rate constant for the decomposition of ethylene oxide into CH4 and CO may be described by the equation
–1 1.25  104
log10k (sec ) = 14.34 –
T
(i) What is the energy of activation of this reaction?
(ii) What is the value of k at 670 K?
Sol. (i) Ea = 234.339 kJ/mol, (ii) 4.82 × 10 –5 s –1
E0
 log0 k  log10 A 
2.303 RT
Ea
  1.25  104
2.303 R
 Ea = 2.303 × 8.314 × 10–3 × 1.25 × 104
 Ea = 234.339 kJ/mol
1.25  104
Also, log10 k  14.394   4.3167
670
 k = 4.82 × 10–5 s–1
9. The energy of activation for a reaction is 100 kJ mol–1. Presence of a catalyst lowers the energy of activation by
75%. What will be effect on rate of reaction at 20°C (other things being equal) in presence of catalyst?
13
Sol. Rate increases by 2.34 × 10 times
k  Ae Ea /RT
In absence of catalyst, k1 = Ae–100/RT
In presence of catalyst, k2 = Ae–25/RT
r2 Rate in presence of catalyst k

  2
r1 Rate in absence of catalyst k1
k2 k 75
  e75/RT ⇒ 2.303log 2 
k1 k1 8.314  103  293
k2
  2.34  1013
k1
r2
  2.34  1013
r1
stable atom along with -particles If 'm' gram

m m–12
10. A radioactive isotope zA (t1/2 = 10 days) decays to give z – 6B
of A are taken and kept in a sealed tube, how much He will accumulate in 20 days at S.T.P. (in litre)?
Sol. 50.4 litre
zA
m
z 6 Bm12  32 He4
m
Moles of A  1
m
20
Number of half lives = 2
10
2
⎛ 1⎞ 3
Moles of A decayed = 1  ⎜ ⎟ 
⎝2⎠ 4
3 9
Moles of He formed = 3  
4 4
9
Volume of Heat STP = 22.4 
4
VHe = 50.4 liters
11. A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in the presence of a
catalyst at the same rate, the temperature required is 400 K. Calculate the activation energy of the reaction, if
the catalyst lowers the activation barrier by 20 kJ/mol.
Sol. According to Arrhenius equation we have
–E /RT
K = A.e a
At T = T1 = 500 K
– (Ea )1
R  500
K1 = A.e
At T = T2 = 400 K
– (Ea )2
R  400
K2 = A.e
According to problem
Reactions are having same rate at 400 K and 500 K
Therefore,
K1 = K2
– (Ea )1 – (Ea )2
R  400
 A.e R  500 = A.e
Ea1 Ea2 500
 = , Ea1 = Ea
R  500 R  400 400 2
5
 Ea1 = Ea2
4
and Ea1 – Ea2 = 20 kJ/mol
 (Ea)500k = 100 kJ/mol
12. The mean lives of a radioactive substance are 1620 years and 405 years for -emission and -emission
respectively. Find out the time during which three fourth of a sample will decay if it is decaying both by
-emission and -emission simultaneously.
⎡ 1 1 ⎤
Sol. K = K1 + K2 = ⎢  ⎥ = 3.09 × 10
–3
⎣ 1620 405 ⎦
⎛ a ⎞
kt = ln ⎜ ⎟
⎝a/ 4⎠
2 ln 2
t= = 448.7 yrs.
3.09  10 –3
13. The rate constant for an isomerisation reaction.
X 
 Y is 4.5 × 10–3 min–1. If the initial concentration of X is 1 M, calculate rate of reaction after 1 hour.
Sol. X  Y K = 4.5 × 10–3 min–1
rate = K [X]
⎛ [X]0 ⎞
Kt = ln ⎜ ⎟
⎝ [X] ⎠
1
4.5 × 10–3 × 60 = ln
[X]

–3 –3
[X] = 0.763 M Rate = 4.5 × 10 × 0.763 = 3.43 × 10 M min
14. A counter rate meter is used to measure the activity of a radioactive sample. At a certain instant, the count rate
was recorded as 475 counters per minute. Five minutes later, the count rate recorded was 270 counts per
minute. Calculate the decay constant and half life period of the sample.
N0
Sol. t = ln
N
⎛ 475 ⎞
 × 5 = ln ⎜ ⎟
⎝ 270 ⎠
 = 0.113 min–1
0.693
t1/2 = = 6.134 min

15. For the following reaction, the rate law has been determined as
2 –6 –2 2 –1
Rate = k[A] [B] with k = 2 × 10 mol L s .
2A + B + C 
 A2B + C
For this reaction the initial of the various species
[A] = 0.1 mol L–1, [B] = 0.2 mol L–1, [C] = 0.8 mol L–1. Determine the rate after 0.04 mol L–1 of A has reacted.
2
Sol. Rate = K [A] [B]
–6 –2 2 –1
K = 2×10 mol Ls
Reaction is 2A + B + C  A2B + C
t=0 0.1 0.2 0.8 0 0
t = t (0.1 – 0.04) (0.2 – 0.02) (0.02) (0.02)
dx dx
 = (2 × 10–6) (0.1 – 0.04) (0.2 – 0.02)2  = 0.00388 × 10–6
dt dt
Hence, rate is 3.89 × 10–9 mol L–1 s–1.
16. If for the first order reaction, rate constant varies with temperature according to the graph given below. At 27°C,
1.5 × 10–4 percent of the reactant molecules are able to crossover the potential barriers. At 52°C, the slope of
this graph is equal to 0.2 K–1 s–1. Calculate the value of rate constant at 52°C, assuming that activation energy
does not change in this temperature range.
Rate constant
Temperature (t)
– Ea/RT
Sol. K = A . e …(i)
dK Ea
0.2 = = A . e– Ea/RT at T = 325 K …(ii)
dT RT 2
At T = 300 K, e– Ea/RT = 1.5 × 10–4 × 10–2 (Given)
Ea
 = 4023 …(iii)
R
Putting (iii) in (ii), we get,
4023
0.2 = K52ºC  K52ºC = 5.251 sec–1
3252
–3 –1
17. The reaction given below, involving the gases is observed to be first order with rate constant 7.48 × 10 s .
Calculate the time required for the total pressure in a system containing A at an initial pressure of 0.1 atm to
rise to 0.145 atm and also find the total pressure after 100 s.
2A(g) 
 4B(g) + C(g)
Sol. Reaction involves 1st order Kinetics 2 A  4 B + C
K = 7.48 × 10–3 s–1
2A  4B + C
P0 0 0
P0–2P 4P P
 Pt = P0 – 2P + P + 4P = P0 + 3P
P0 = 1 atm; Pt = 0.145 atm
0.145 = 0.1 + 3P  3P = 0.145 – 0.1
3P = 0.045
P = 0.015 atm
1 0.1
t= ln  t = 47.8 s
7.48  10 –3 0.1– (2  0.015)
1 ⎛ 0.1 ⎞
 7.48 × 10–3 = ln ⎜ ⎟  P = 0.026 atm
100 ⎝ 0.1 – 2P ⎠
Now, Pt = P0 + 3P = 0.1 + 3 (0.026) = 0.18 atm
18. At 380°C, the half life period for the first order decomposition of H2O2 is 360 minutes. The energy of activation of
the reaction is 200 kJ mol–1. Calculate the time required for 75% decomposition at 450°C.
Sol. 20.39 minutes
0.693
k1  at 380 C
360
⎛k ⎞ Ea ⎡1 1⎤
log10 ⎜ 2 ⎟  ⎢  ⎥
⎝ k1 ⎠ 2.303 R ⎣ T1 T2 ⎦
Putting Ea = 200 kJ mol–1, R = 8.314 × 10–3
T1 = 653 K, T2 = 723 K
We get, k2 = 6.81 × 10–2 min–1.
2.303 100
t 2
log ⇒ t  20.39 minutes
6.81 10 25
k 35ºC
19. Temperature coefficient µ = of a reaction is 1.82. Calculate the energy of activation in calories.
k 25ºC
Sol. Ea = 10.924 kcal/mol
k  Ae Ea /RT
Ea ⎛ 1 1 ⎞
k 35 C k 308 k ⎜  ⎟
R ⎝ 298 308 ⎠
 e  1.82
k 25C k 298 k
Ea 10
 3
  ln(1.62)
2  10 298  308
 Ra = 10.924 kcal/mol
20. The following data were obtained for a given reaction at 300 K
Reaction Energy of activation (kJ/mol)
(1) Uncatalysed 76
(2) Catalysed 57
By what factor the rate of catalysed reaction is increased?
kp (Ea Ep )/RT 3

Sol. e  e(76 57)/8.31410 300
= 2033
ka


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Chapter 12

Chemical Kinetics and Nuclear Chemistry

[Order and Molecularity]

d N2 O5  1 d NO2  1 d [O2 ]

The order of overall reaction is

Rate = k2[A] [B] (r.d.s.)

3. The rate law for the reaction

[Integrated Rate Equation and Rate Law]

Sol. Answer (4)

103 3ln2  103

3  0.693  10 3  103 693

 Half life decrease with increase in concentration of reactants.

For zero order

Hence, rate becomes 4 times.

Integrating, we get: (A)t = (A)0 – akt

Sol. Answer (4)

Applying I–order reaction

2.303 4x0 2.303 2x 0

2.303 3x 0 2.303 4x0

Sol. Answer (3)

15. For a reaction

Sol. Answer (2)

[Numericals on 1st Order]

 For 50% decomposition we can write

19. For the following reaction

Sol. Answer (3)

20. In the first order reaction, x 

Rate of reaction = K[X]

22. Select the correct statement regarding activation energy

23. The temperature coefficient of most of the reactions lie between

(1) H = 0, S = 0 (2) H = , S = 0 (3) G = 0, H = 0 (4) Only H = 0

Sol. Answer (4)

For (Ea)f = (Ea)b, H = 0

27. The position of element RaC in the periodic table is

Element RaC will be lying in 15th group and 6th in period.

29. When 92U235 is converted to 82Pb

(i) 92 U235 82 Pb207  7 2 He 4  4 –1 e0

Sol. Answer (3)

  = 1.386 ×10–3 y–1

Sol. Answer (3)

(1) k (2) k (3) k (4) k

Sol. Answer (1)

1. For the reaction A + B 

– [A] – [B] 1 [C] [D]

3. The rate law for the reaction, RCl + NaOH 

4. Which of the following statements for order of a reaction are correct?

(3) Molecularity is 2 (4) Both molecularity and order = 2

and we can also write

 [A] = {Kc[A2]}1/2 …(ii)

6. Which of the following are unimolecular?

7. For the reaction A 

8. The plot given is not possible for

Sol. Answer (1, 2, 4)

Sol. Answer (1, 2)

11. Which of the following statements is/are correct regarding catalyst?

12. For a first order reaction

Sol. Answer (1, 2, 3)

In the equation K = A.e RT

13. Which of the following statement(s) is/are correct?

16. Correct statement(s) among the following is/are