Solution
ISC CHEMICAL KINETICS
Class 12 - Chemistry
Section A
1. (c) a1-n
Explanation: t1/2 ∝ (a)1-n
1 1
2. (d) Rate = -d [N2]/dt = − 3
d[H2]/dt = 2
d[NH3]/dt
Explanation: For, N2 + 3H2 = 2NH3
d[ N 2 ] d[ H2 ] d[ NH 3 ]
rate of reaction = dt
= −
1
3 dt
=
1
2 dt
d[ N 2 ]
where, − dt
is rate of consumption of N2 (-ve sign)
d[ H2 ]
−
dt
is rate of consumption of H2 (-ve sign)
+d[ NH 3 ]
dt
is rate of formation of NH3 (+ve sign)
Individual rates become equal when each of these is divided by their respective stoichiometric coefficient.
3. (c) Rate = k [B2]
Explanation: r = K [A]m [B2]n
1.6 × 10-4 = K [0.5]m [0.5]n ...(i)
3.2 × 10-4 = K [0.5]m [1.5]n ...(ii)
3.2 × 10-4 = K [1.0]m [1.0]n ...(ii)
By (i) and (ii) n = 1
By (ii) and (iii) m = 0
∴ r = K [A]0 [B2]1 = K [B2]
4. (c) O(g)
Explanation: The intermediate species is O(g). The intermediate species is one that is formed and used up during the course of
the reaction and is not formed as a product.
5. (c) 597
Explanation: y = -16653x + 30.88
−Ea 1
ln k = ( R
)(
T
) + ln A
−Ea
R
= -16653
Ea = 16653 × 8.314 = 138453 J/mol
k1 = 6.15 s-1; T1 = 573 K
k2 = 19.65 s-1; T2 = ?
k2 Ea
ln( k1
) =
R
(
1
T1
−
1
T2
)
ln( 19.65
6.15
) =
138453
8.314
(
1
573
−
1
T2
)
1.162 = 16653 (1.745 × 10-3 - 1
T2
)
6.978 × 10-5 - 1.745 × 10-3 = − 1
T2
-1.675 × 10-3 = − 1
T2
∴ T2 = 597 K
6. (c) all of these
Explanation: The higher threshold energy barrier prevents coal to bum spontaneously and provides kinetic stability to fuel.
V3 − V1
7. (c) Average rate upto 40 seconds is 40−20
V3 − V0
Explanation: Average rate (upto 40 s) = 40−0
1/4
V3 −0 V3
= 40
= 40
8. (d) A is false but R is true.
Explanation: Molecularity and order of reaction are identical if the reaction is elementary. They may become different when
the reaction is complex and has a mechanism.
9. (a) Both A and R are true and R is the correct explanation of A.
Explanation: Both A and R are true and R is the correct explanation of A.
10. (c) A is true but R is false.
Explanation: According to the Arrhenius equation (k = Ae-Ea/RT); it is found almost accurate for single as well as complex
reactions.
However, orientation is essential for the reactant molecules participating in the reaction.
Section B
11. Average rate of a reaction is defined as the change in concentration of a reactant or a product per unit time. It can be determined
by dividing the change in concentration of reactant or product by the time interval.
For the reaction: A → B
−Δ[A] Δ[B]
Rav =
Δt
=
Δt
where Rav is the average rate of reaction.
12. Rate of reaction is defined as change in concentration of reactants or products per unit time. For example, the reaction A→ B has
the rate expressed as:
−[dA] [dB]
rate of reaction = dx
dt
=
dt
=
dt
13. 2 H2(g) + O2(g) → 2 H2O(l)
This reaction does not take place at the room temperature because the activation energy of the reaction is very high.
14. i. Rate of growth of population, if there is no change of birth and death rates.
ii. Radioactive decay in which the number of nuclei disintegrating is proportional to the number of nuclei present.
15. Though the reacting large fraction of molecules may be having energy more than threshold energy, yet they may not be effective
due to lack of proper orientation.
16. First order reaction.
17. The units of rate of a reaction are mol L-1 s-1. In gaseous reaction the unit of rate of reaction is atm s-1.
18. In terms of pressures,
Unit of rate= bar min . −1
Rate
Unit of K = 3/2
.
[P C H3 OC H3 ]
−1
barmin
=
3/2
.
bar
= bar .
−1/2
min
−1
19. The rate law is experimentally determined. It cannot be predicted by merely looking at the balanced chemical equation.
20. Rate = k [NO]x [O2]y
order of a reaction = x + y
3
So order = + = 2, i.e., second order of reaction.
1
2 2
Section C
21. Rate of reaction increases with increase in temperature because kinetic energy of molecules increases. Thereby, the fraction of
molecules possessing activation energy increases, which in turn increases the number of effective collision.
22. When reaction is completed 99.9%, [R]n = [R]0 - 0.999[R]0 rate constant is
2.303 [R]0
k = log
t [R]
[R]
2.303 0 2.303 3
= log = log 10
t [R] −0.999[R] t
0 0
t = 6.909 / k
For half-life of the reaction
t1/2 = 0.693 / k
t 6.909 k
= × = 10
t1/2 k 0.693
23. It is believed that the catalyst provides an alternate pathway or reaction mechanism by reducing the activation energy between
reactants and products and hence lowering the potential energy barrier
2/4
24. Temperature coefficient is the ratio of two rate constants at two different temperature that differ by 100. If its value is two it means
the reaction rate gets almost doubled and so on.
25. The four factors that effect the rate of reaction are:
i. Nature of reactants
ii. Temperature
iii. Catalyst
iv. Physical state of reactant
Section D
26. Activation energy is the extra energy which must be supplied to the reactants so that they can change into products.
i. It is believed that the catalyst provides an alternate pathway or reaction mechanism by reducing the activation energy between
reactants and products and hence lowering the potential energy barrier.
ii. There is no effect on activation energy with rise in temperature but number of molecules possessing energy equal to or more
than activation energy will increase.
27. k = 2.0 × 10 −2
s
−1
T= 100 s
−1
[A]0 = 1.0 mol L
Since the unit of k is s −1
, the given reaction is a first order reaction.
[A]
Therefore, k = 2.303
t
log
0
[A]
−2 −1 2.303 1.0
2.0 × 10 s = log
100 [A]
−2 −1 2.303
2.0 × 10 s = (− log[A])
100
−2
2.0× 10 ×100
− log[A] =
2.303
−2
[A] = antilog (− 2.0× 10
2.303
×100
)
= 0.135 mol L-1 (approximately)
Hence, the remaining concentration of A is 0.135 mol L-1.
28. i. Slope = K
2.303
ii. As slope = 2 × 10 −4
s
−1
−4 −1
∴ K = 2.303 × 2 × 10 s
−4 −1
K = 4.606 × 10 s
[R]
iii. For a first order reaction t = 2.303
K
log
[R]
0
[R]
At t
1/2
[R] =
0
[2]
2.303
t1/2 = log 2
K
0.693
t1/2 =
K
k2 Ea T2 − T1
29. From Arrhenius equation, we obtain log k1
=
2.303R
(
T1 T2
)
It is given that, k 2 = 4k1
T1 = 293K ; T2 = 313K
4k1 Ea 313−293
Therefore, log k2
=
2.303×8.314
(
293×313
)
20×Ea
0.6021 =
2.303×8.314×293×313
0.6021×2.303×8.314×293×313
Ea =
20
−1 −1
= 52863.33 J mo l = 52.86 kJ mo l
Hence, the required energy of activation is 52.86 kJ mol −1
.
30. i. The chemical reaction which look like higher order reaction but in real they follow lower order kinetics.
For example,
+
H
CH3 COOC2 H5 + H2 O ⟶ CH5 COOH + C2 H5 OH
Rate = K[CH3COOC2H5]
Order = 1
Ea
ii. Slope =
2.303R
= −4250K
So, Ea = -2.303 × R × Slope
3/4
= -2.303 × 8.314 J K-1 mol-1 × 4250
= 81375.3 J mol-1
= 81.375 KJ mol-1
4/4