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Chemical Kinetics
Solutions
SECTION - A
Objective Type Questions
1. The unit of rate constant and rate of reaction are same for
(1) First order (2) Zero order (3) Second order (4) Third order
Rate = K [concentration]n
Rate = K
−d[A]
2. For a reaction of the type aA + bB ⎯→ products; is equal to
dt
−d[B] b d[B] a d[B] b d[B]
(1) (2) − (3) − × (4) − ×
dt d dt b dt a dt
aA + bB → products.
1 Δ [A] Δ [B]
Rate = − =−
a Δt Δt
3. For a gaseous reaction, the rate of reaction may be expressed in the units
Δ(pressure) atm
rate = K[atm]order = =
Δt sec.
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186 Chemical Kinetics Solutions of Assignment (Set-2)
1
4. A gaseous reaction, A 2 (g) ⎯⎯→ B(g) + C(g) , shows increase in pressure from 100 mm to 120 mm in 5
2
minutes. The rate of disappearance of A2 is
(1) 4 mm min–1 (2) 8 mm min–1 (3) 16 mm min–1 (4) 2 mm min–1
Sol. Answer (2)
1
A 2 (g) → B(g) + C(g)
2
t=0 100 mm 0 0
(Pinitial = 100, let x pressure dissociated)
x
t = 5 min 100 − x x
2
x
At equilibrium 100 − x + x + = 120
2
∴ x = 40
40mm
∴ Rate of disappearance of A2 =
5mm
= 8 mm min–1
5. Which of the following will react at the highest rate?
(1) 1 mol of A and 1 mol of B in a 1 L vessel (2) 2 mol of A and 2 mol of B in a 2 L vessel
(3) 3 mol of A and 3 mol of B in a 3 L vessel (4) All would react at the same rate
Sol. Answer (4)
1. r = K[A][B]
⎡1⎤ ⎡1⎤
=K⎢ ⎥⎢ ⎥ ⇒K
⎣1⎦ ⎣1⎦
⎡2⎤ ⎡2⎤
2. r =K⎢ ⎥⎢ ⎥ =K
⎣2⎦ ⎣2⎦
⎡3 ⎤ ⎡3 ⎤
3. r =K⎢ ⎥⎢ ⎥ =K
⎣3 ⎦ ⎣3 ⎦
⎡ mole ⎤
∵ ⎢conc. = volume ⎥
⎣ ⎦
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Solutions of Assignment (Set-2) Chemical Kinetics 187
7. In a reaction, 2X + Y ⎯→ X2Y, the X disappears at
(1) Half the rate as that of disappearance of Y (2) The same rate as that of disappearance of Y
(3) The same rate as that of appearance of X2Y (4) Twice the rate as that of appearance of X2Y
d(X) 2d(Y)
Rate of disappearance of (X) = − ⇒−
dt dt
2d(X2 Y)
⇒ ⊕
dt
⇒ Twice the rate as that of appearance of X2Y.
(3) Decreases as the reaction proceeds (4) First increases followed by a decrease
As during the course of reaction conc. of reactants decreases so, rate of reaction also decreases.
10. For the hypothetical reaction 2A → 3C, the reaction rate ‘r’ in terms of the rate of change of the concentration
is given by
1 d(A) 1 d(C)
r=− =+
2 dt 3 dt
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188 Chemical Kinetics Solutions of Assignment (Set-2)
−2 1 d(B)
⇒ −2.6 × 10 ⇒ −
2 dt
d(B)
so, ⇒ 2 × 2.6 × 10 –2
dt
= 5.2 × 10–2 Ms–1
12. For the reaction N2 + 3H2 → 2NH3, the rate of change of concentration for hydrogen is –0.3 × 10–4 Ms–1. The rate of
change of concentration of ammonia is
(1) –0.2 × 104 (2) 0.2 × 10–4 (3) 0.1 × 10–4 (4) 0.3 × 10–4
Sol. Answer (2)
N2 + 3H2 → 2NH3
d(N2 ) 1 d(H2 ) 1 d(NH3 )
r=− =− =+
dt 3 dt 2 dt
d(H2 )
Given, − = 0.3 × 10 –4 Ms –1
dt
1 –4 1 d(NH3 )
So, r ⇒ − × 0.3 × 10 = +
3 2 dt
d[NH3 ] 2
∴ ⇒ × 0.3 × 10 –4 ⇒ 0.2 × 10 –4
dt 3
C1
Conc.
C2
t1 t2 Time
d[C2 − C1 ]
(1) It gives rate of disappearance of reactant (2) Rate = −
t 2 − t1
(3) Both (1) & (2) (4) It predicts the order of reaction
Sol. Answer (3)
− d(C2 − C1)
In given graph concentration decreases with time r=
t2 − t 1
which shows that it is the graph of reactant because
concentration of reactant decreases as time Disappearance of reactant
increases. So,
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Solutions of Assignment (Set-2) Chemical Kinetics 189
14. For reaction, 2B + A 2C
Which of the following is correct ?
(1) Rate of disappearance of B is twice that of rate of disappearance of C
(2) Rate of disappearance of A is twice that of rate of disappearance of C
(3) Rate of appearance of C is twice that of rate of disappearance of A
(4) All of these
Sol. Answer (3)
16. The rate law of a reaction between the substance A and B is given by, rate = k[A]n [B]m. On doubling the
concentration of A and making the volume of B half the ratio of new rate to the earlier rate of reaction will be
1
(1) n +m
(2) m + n (3) 2n + m (4) 2n – m
2
Sol. Answer (3)
moles
r1 = K[A]n[B]m conc. ⇒
volume
r2 = K[2A]n[2B]m So, if volume becomes half then concentration becomes double
r2 K[2A]n [2B]m
= B′ = 2B
r1 K[A]n [B]m
⇒ (2)n(2)m = 2n + m
17. Consider the reaction, 2A + B C + D. If the rate expression is r = [A]2 [B]0 and if volume is reduced to
1
, the rate of reaction will increase
3
(1) 27 times (2) 9 times
(3) 8 times (4) Rate will not get affected
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190 Chemical Kinetics Solutions of Assignment (Set-2)
18. The rate constant is numerically the same for three reaction of first, second and third order respectively. Which
one is true for rate of three reaction, if concentration of reactant is greater than 1M?
(1) r1 = r2 = r3 (2) r1 > r2 > r3 (3) r1 < r2 < r3 (4) All of these
Sol. Answer (3)
r1 = K[A]1 given (A) > 1 m then, r1 = K[2A]1
r2 = K[A]2 Suppose (A) = 2 r2 = K[2A]2
r3 = K[A]3 r3 = K[3A]3
19. Assuming an elementry reaction H2O2 + 3I– + 2H+ –→ 2H2O + I3–. The effect on the rate of this reaction brought
about by doubling the concentration of I– without changing the order
(1) The rate would increase by a factor of 3 (2) The rate would increase by a factor of 8
(3) The rate would decrease by a factor of 1/3 (4) The rate would increase by a factor of 9
Sol. Answer (2)
r = K[H2O2][I–]3[H+]2
given [I–]1 = 2I–
r2 = K[H2O2][2I–]3[H+]2
⇒ 8K[H2O2][I–]3[H+] 2= 8r1
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Solutions of Assignment (Set-2) Chemical Kinetics 191
Sol. Answer (2)
r = K[RCl] → (r) doesn't depend on [NaOH]
r ∝ [RCl]
⎛ RCl ⎞ r
i.e., if [RCl]′ = ⎜
2 ⎟ then r′ =
⎝ ⎠ 2
On temperature increases ⇒ r increases
22. The rate constant for the forward and backward reactions of hydrolysis of ester are 1.1×10–2 and 1.5×10–3 min–1
respectively. The equilibrium constant of the reaction is
(1) 7.33 (2) 0.733 (3) 73.3 (4) 733
Sol. Answer (1)
23. For a reaction A + B → products, the rate of reaction was doubled when concentration of A was doubled. When
concentration of A and B both was doubled, the rate was again doubled, order of reaction w.r.t. A and B are
(1) 1, 1 (2) 2, 0 (3) 1, 0 (4) 0, 1
Sol. Answer (3)
r1 = K[A]x[B]y
r2 = 2r1
A′ = 2A
2r1 = K[2A]x[B]y ...(1)
2r1 = K[2A]x[2B]y ...(2)
It means (r) ∝ conc. of (A)
So order w.r.t. [A] = 1 and rate of reaction does not change on concentration of (B). So, w.r.t. (B) order = 0.
24. The overall order of reaction between X & Y is 3. Which of the following rate equation must be correct, if on
doubling the concentration of X, the rate of reaction gets doubled ?
(1) r = K [X]2 [Y]0 (2) r = K [X]1 [Y]2 (3) r = K [X]1 [Y]3 (4) r = K [X]2 [Y]1
Sol. Answer (2)
If concentration of (X) doubles rate of reaction also doubles means (r) ∝ concentration of (X).
So, order w.r.t. (x) = 1.
Hence, over all order = 3 so, w.r.t. (Y) order = 2
r = K[X]1[Y]2
(Integrated Rate Equations, Pseudo First Order Reaction)
25. For a zero order reaction, K = 1 × 10–3 mol L–1 s–1. If initial concentration of the reactant is 1.0 mol L–1, the
concentration after 10 minutes would be
(1) 1 × 10–2 mol L–1 (2) 0.6 mol L–1 (3) 0.4 mol L–1 (4) 1.0 mol L–1
Sol. Answer (3)
For zero order reaction, [R]0 – [R]t = Kt
1 – (R)t = 1 × 10–3 × 60 × 10
(R)t ⇒ 1 – 0.6 = 0.4 mol L–1
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192 Chemical Kinetics Solutions of Assignment (Set-2)
26. A sample of a radioactive substance undergoes 80% decomposition in 345 minutes. Its half life is _____ minutes.
ln 2 ln5 ln5 ln 4
(1) × 345 (2) × 345 (3) × 345 (4) × 345
ln5 ln 2 ln 4 ln5
0.693 2.303
= log5
t1/2 345
27. 99% of a first order reaction, was completed in 32 minute. When will 99.9% of the reaction complete?
(1) 50 minute (2) 46 minute (3) 49 minute (4) 48 minute
Sol. Answer (4)
2.303 100
K= log
2.303 100 (i) / (ii) 32 1
K= log 2.303 100
t 100 − x K= log
t 0.1
2.303 100 1 1
K= log ...(i) (log1000) = (log100)
32 100 − 99 t 32
2.303 100 1 1
K= log ...(ii) (log103 ) = (log102 )
t 100 − 99.9 t 32
1 1
× 3log10 = 2 × log10
t 32
∴ log10 = 1
3 × 32
t⇒ ⇒ 48 minute
2
28. For a reaction, A ⎯→ B, it has been found that the order of the reaction is zero with respect to A. Which of
the following expressions correctly describes the reaction?
2.303 [A 0 ] 0.693 1
(1) K = log (2) [A]0 − [A] = Kt (3) t1/2 = (4) t1/2 ∝
t [A] K [A]0
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Solutions of Assignment (Set-2) Chemical Kinetics 193
29. A substance (initial concentration 'a') reacts according to zero order kinetics. The time it takes for the
completion of the reaction is
a a k 2k
(1) (2) (3) (4)
k 2k a a
Sol. Answer (1)
[R]0 – [R]t = Kt
On completion [R]0 = 0 ⇒ (R)t = (R)0 = [a = x]
∴ (R)0 – (R)t = Kt
a – a + x = Kt
x = Kt
x a
∴ t= = on completion.
K K
or
r = K[A]0
d(A) a
− =k⇒
dt t
⎛ a⎞
∴ ⎜t = K ⎟
⎝ ⎠
30. For a Ist order reaction, a straight line is obtained if you plot
(1) log conc. vs. time
(2) Conc. vs. time
(3) 1/conc. vs. time
(4) log conc. vs. 1/time
Sol. Answer (1)
log(A)t
time
⎛ K ⎞
log(A)t = log(A)0 − ⎜ ⎟t
⎝ 2.303 ⎠
31. Consider the following in respect of zero order reaction
I. t1/2 is directly proportional to the initial concentration
II. Time taken for the completion of the reaction is twice its t1/2
III. Concentration of the reactant decreases linearly with time
Which of the statements given above are correct?
(1) I & II only (2) I & III only (3) II & III only (4) I, II & III
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194 Chemical Kinetics Solutions of Assignment (Set-2)
a
(i) t1/2 = t1/2 ∝ a
2K
(ii) x = Kt
x a
K= → t1/2 =
t x
2×
t
a×t
t1/2 ⇒
2x
2t1/2
∴ t⇒ ×x
a
(iii) concentration decreases with time.
32. If initial concentration is reduced to 1/4th in a zero order reaction, the time taken for half the reaction to complete
(1) Remains same (2) Becomes 4 times (3) Becomes one-fourth (4) Doubles
Sol. Answer (3)
r = K[A]0
a 1 a
t1/2 = ⇒ ⇒ becomes one fourth of initial half life.
2K 4 2K
1
∴ a′ ⇒
a
4
33. The inversion of cane sugar represented by C12H22O11 + H2O → C6H12O6 + C2H12O6 is a _____ reaction.
(1) Unimolecular (2) Second order (3) Zero order (4) First order
Sol. Answer (4)
Inversion of cane sugar is pseudo first order reaction because conc. of H2O remain constant. So, rate of reaction
doesn't depend on concentration of H2O.
r = K′[C12H22O11]
34. If initial concentration of the reactants is doubled, the time for half reaction is also doubled, the order of the
reaction is
(1) Zero (2) One (3) Two (4) Three
Sol. Answer (1)
Initial concentration → doubled → t1/2 also doubled when t1/2 ∝ a and it is in zero order reaction.
t1/2 ∝ a1−n
if n = 0 t1/2 ∝ a′
if n = 1 t1/2 ∝ a0
1
if n = 2 t1/2 ∝ a1–2 → t1/2 ∝ a–1 → t1/2 ∝
a
t1/2
a
(1) First order (2) Second order (3) Zero order (4) Can’t predict
Sol. Answer (1)
Graph shows that t1/2 does not depend on initial concentration which is property of first order reaction.
t1/2 ∝ a0
37. The half life period of a substance is 50 minutes at a certain initial concentration. When concentration is reduced
to one-half, half life is found to 25 minutes. Order of reaction is
(1) Zero (2) First (3) Second (4) Third
Sol. Answer (1)
t1/2 ∝ a1–n
1−n 1−n
(t1/2 )1 ⎛ a1 ⎞ ⎛ 50 ⎞ ⎛ a ⎞
=⎜ ⎟ →⎜ ⎟=⎜ ⎟
(t1/2 )2 ⎝ a2 ⎠ ⎝ 25 ⎠ ⎜ 1 a ⎟
⎝2 ⎠
(2) ⇒ (2)1–n
∴ n=0
(2) = (2)1–0
38. A first order reaction completes 60% in 20 minutes. The time required for the completion of 90% of the reaction
is approx
(1) 30 minutes (2) 40 minutes (3) 50 minutes (4) 60 minutes
Sol. Answer (3)
2.303 100
K= log
t 100 − x
2.303 100
K= log ...(i)
20 100 − 60
2.303 100
K= log ...(ii)
t 100 − 90
(i)/(ii)
2.303 100
K= log
20 40 → 1log10 = 1 [log10 − log 4]
2.303 100 t 20
K= log
t 10
1 1
⇒ ×1 = [1 − 0.6020]
t 20
∴ t = 50 minutes
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196 Chemical Kinetics Solutions of Assignment (Set-2)
40. At particular concentration, the half life of the reaction is 100 minutes. When the concentration of the reactant
become double half life becomes, 25 minutes, then what will be the order of the reaction?
(1) 1 (2) 2 (3) 0 (4) 3
Sol. Answer (4)
1−n
(t1/2 )1 ⎛ a1 ⎞
t1/2 ∝ a1−n =⎜ ⎟
(t1/2 )2 ⎝ a2 ⎠
1−n
⎛ 100 ⎞ ⎛ a1 ⎞
(a2 = 2a1 ) ⎜ 25 ⎟ = ⎜ 2a ⎟
⎝ ⎠ ⎝ 1⎠
1−n
⎛ 1⎞
(4) = ⎜ ⎟
⎝2⎠
1−3 −2
⎛ 1⎞ ⎛ 1⎞
If n = 3, then 4 = ⎜ ⎟ →4=⎜ ⎟ ⇒ 4 = (22 )
⎝2⎠ ⎝2⎠
T2 > T1
Fraction
of molecules
T2
T1
T→
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Solutions of Assignment (Set-2) Chemical Kinetics 197
42. Arrhenius parameter (A) depends on
(1) Steric factor (2) Collision frequency (3) Both (1) & (2) (4) Neither (1) nor (2)
Sol. Answer (3)
K = Ae–Ea/RT
∴ A = P.Z.
∴ P = steric factor
Z = collision frequency
43. The chemical reactions in which the reactants require high amount of activation energy are generally
(1) Slow
(2) Fast
(3) Instantaneous
(4) Spontaneous
Sol. Answer (1)
Activation energy (Ea) is the required energy to achieve threshold energy so, if (Ea) ↑ ⇒ reaction is slow.
44. For an exothermic chemical process occurring in two steps as
(i) A + B → X (slow) ; (ii) X → AB (fast)
The progress of the reaction can be best described by (X is considered as intermediate)
A + B → X(slow) X → AB(fast)
(Ea) (Ea)
45. A chemical process occurring in two steps, is plotted as
x
Energy
A+B AB
Progress of Reaction
The correct statement is
(1) Endothermic, A + B X (slow), (2) Exothermic, A+B X (slow)
X AB (fast) X AB (fast)
(3) Exothermic, A+B X (fast) (4) Endothermic, A + B X (fast)
X AB (slow) X AB (slow)
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198 Chemical Kinetics Solutions of Assignment (Set-2)
(Ea)f x
(Ea)b
A+ B AB
A + B → X → (Ea) ↑ → slow
X → AB (Ea) ↓ → fast
ΔH = (Ea)f – (Ea)b ↓
⇒ (–)ve → Exothermic
c
d
e
a
b
Progress of reaction
Which of the following is correct ?
(1) It is the exothermic reaction, ΔH = b – a (2) Threshold energy, e = a + c
(3) (Ea)f < (Ea)b (4) All of these
Sol. Answer (4)
ΔH ⇒ (Ea)f – (Ea)b or ΔH = b – a
(Ea)b (Ea)f a>b
⇒c–d
Energy
c
d (activation energy) Δ H ⇒ –ve
e
d>c Exothermic
a
b
Progress of reaction →
47. The rate of a reaction becomes 2 times for every 10°C rise in temperature. How many times rate of reaction
will be increased when temperature is increased from 30°C to 80°C?
(1) 16 (2) 32 (3) 64 (4) 128
Sol. Answer (2)
T2 − T1 80 −30 50
K= 2 10 = 2 10 ⇒ 2 10 = 25 = 32 times
48. The rate of a reaction increases by 2.5 times when the temperature is raised from 300 K to 310 K. If K is
the rate constant at 300 K, then the rate constant at 310 K will be equal to
(1) K (2) 2K (3) 2.5K (4) 3K
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Solutions of Assignment (Set-2) Chemical Kinetics 199
Sol. Answer (3)
Rate of reaction ∝ rate constant
or, rate constant ∝ rate of reaction
if (r)′ = 2.5r
K′ = 2.5K
49. The minimum amount of energy that the reacting molecules must possess at the time of collisions in order
to produce effective collision is called
(1) Activation energy (2) Threshold energy (3) Internal energy (4) Free energy
Sol. Answer (2)
Threshold energy (defination)
50. The rate constant, the activation energy and Arrhenius parameter of a chemical reaction at 25°C are x, 10x
kJ/mol and 2x s–1. Value of rate constant as T → ∞ is
(1) x s–1 (2) 2x s–1 (3) ∞ (4) 10x s–1
Sol. Answer (2)
K = Ae–Ea/RT
−10x
K = (2x).e RT ...(i)
−10X
R(8)
(T = 8) → K 2 = (2X)e ...(ii)
K2 = 2X.e0
K 2 = 2X
SECTION - B
Objective Type Questions
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200 Chemical Kinetics Solutions of Assignment (Set-2)
K 2 [N2O5 ]
r ⇒ K1[N2O5 ] = = 2 × K 3 [N2O5 ]
2
∴ 2K1 = K2 = 4K3
K1
2. For the reaction, N2O4 (g) 2NO2(g), the rate of disappearance of NO2 will be
K2
K2
for disappearance of NO2 → 2NO2
N2O4 K1
rf ⇒ K2[NO2]2
rb = K1[N2O4]
r = K2[NO2]2 – K1[N2O4]
1 d(NO2 )
For disappearance of NO2 r = (−)
2 dt
⎡ −d(NO2 ) ⎤ −d(NO2 )
⎢ ⎥ 2r =
⎣ dt ⎦ dt
−d(NO2 )
= 2[K 2 [NO2 ]2 − K1[N2 O 4 ]]
dt
= 2K 2 [NO2 ]2 − 2K1[N2 O 4 ]
3. For the reaction A + B → products, it is found that order of A is 2 and the order of B is 3 in the rate expression.
When the concentrations of both A and B are doubled the rate will increase by a factor
(1) 10 (2) 16 (3) 32 (4) 28
Sol. Answer (3)
r1 = K[A]2[B]3
r2 = K[2A]2[2B]3
= 32K[A]2[B]3
= 32r1
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Solutions of Assignment (Set-2) Chemical Kinetics 201
4. Nitric oxide (NO) reacts with oxygen to produce nitrogen dioxide
K
NO + O2 NO3 (fast)
K1
NO3+ NO NO2 + NO2 (slow)
(1) Rate = K′ [NO][O2] (2) Rate = K′ [NO][O2]2 (3) Rate = K′ [NO]2[O2] (4) Rate = K′ [NO]3[O2]
[NO3 ]
(i) K= → (NO3 ) = K[NO][O2 ]
[NO][O2 ]
(ii) r = K[NO3][NO]
= K[K[NO][O2][NO]
∴ K × K ⇒ K′ (new constant)
r = K′[NO]2 [O2 ]
5. If the volume of closed vessel in which the following simple reaction is carried out is reduced to one-third of
original volume, the rate of reaction becomes
2NO (g) + O2 (g) ⎯→ 2NO2 (g)
(1) One-third (2) Three times (3) Nine times (4) Twenty seven times
Sol. Answer (4)
V1 ⎛ 1 ⎞
V2 = → C2 = 3C1 ⎜ conc. ∝ volume ⎟
3 ⎝ ⎠
r1 = K[NO]2[O2]
r2 ⇒ K[3NO]2(3O2)
⇒ 27K[NO]2[O2] = 27r1
6. For a gaseous phase reaction 2A + B2 → 2AB, the following rate data was obtained at 300K
Rate of disappearance Concentration
of B2 (mole/litre min) [A] [B2]
(i) 1.8 × 10–3 0.015 0.15
(ii) 1.08 × 10–2 0.09 0.15
(iii) 5.4 × 10–3 0.015 0.45
The rate constant for the reaction is
(1) 0.5 mol–1 min–1 litre (2) 0.8 mol–1 min–1 litre (3) 1.5 mole–1 min–1 litre (4) 2 mol–1 min–1 litre
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202 Chemical Kinetics Solutions of Assignment (Set-2)
−d(B)2
r= = 1.8 × 10 −3 = K[A]x [B2 ]y
dt
1.8 × 10–3 = K[0.015]x[0.15]y ...(i)
1.08 × 10–2 = K[0.09]x[0.15]y ...(ii)
5.4 × 10–3 = K[0.015]x[0.45]y ...(iii)
(i)/(ii) divide
∴ i.e., y = 1
1.8 × 10−3
K⇒ ⇒ 0.8 mol−1 min−1 litre
0.00225
(Integrated Rate Equations, Pseudo First Order Reaction)
1
7. For a first order reaction, the time taken to reduce the initial concentration to a factor of is 10 minute If the
4
1
reduction in concentration is carried out to a factor of , then time required will be
16
(1) 10 minutes (2) 20 minutes (3) 40 minutes (4) 60 minutes
Sol. Answer (2)
2.303 a
K= log ...(i)
10 1
a
4
2.303 a
K= log ...(ii)
t 1
a
16
1 1
log16 = log 4
t 10
1 1
log(4)2 = log 4
t 10
1 1
× 2log 4 = × log 4
t 10
t = 20 minute
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Solutions of Assignment (Set-2) Chemical Kinetics 203
8. Consider the data below for a reaction A → B
Time
(sec)
0 10 20 30
9. For a homogeneous gaseous reaction A → B + C + D, the initial pressure was P0 while pressure after time ‘t’ was
P if (P > P0). The expression for the rate constant K is
A → B +C + D
t=0 P0 0 0 0
t=t P0 − X X X X
Total pressure P0 – X + X + X + X = P
P − P0
P = P0 + 2X → P − P0 = 2X → X =
2
2.303 p0 2.303 p0 2.303 ⎛ p0 ⎞
K= log ⇒ log = log ⎜ ⎟
t P0 − X t ⎛ P − P0 ⎞ t ⎝ 3P0 − P ⎠
p0 − ⎜ ⎟
⎝ 2 ⎠
10. Inversion of a sugar follows first order rate equation which can be followed by noting the change in rotation of
the plane of polarization of light in the polarimeter. If r ∞ , r t and r 0 are the rotations at
t = ∞, t = t and t = 0 then, first order reaction can be written as
1 r1 – r∞ 1 r0 – r∞ 1 r∞ – r0 1 r∞ – rt
(1) K = loge r – r (2) K = ln r – r (3) K = ln r – r (4) K = ln r – r
t 0 ∞ t t ∞ t t ∞ t ∞ 0
⎡ 2.303 r −r ⎤
⎢K = log 0 8 ⎥
⎣ t rt − r8 ⎦
Δ
11. The rate constant of the production of 2B(g) by the reaction, A(g) ⎯⎯ → 2B(g) is 2.48×10–4 s–1
A 1 : 1 molar ratio of A to B in the reaction mixture is attained after
(1) 26.25 minute (2) 27.25 minute (3) 28.25 minute (4) 0 minute
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204 Chemical Kinetics Solutions of Assignment (Set-2)
Δ 1− x 1
A(g) ⎯⎯ → 2B(g) Given = –4 –1
2x 1 K = 2.48 × 10 S
t=0 1 0
1 − x = 2x
t=t 1− x 2x First order
1
x=
3
2.303 1 2.303 1
K= log = log = 2.48 × 10 −4
t 1− x t 1
1−
3
2.303 3
2.48 × 10−4 = log
t 2
2.303 2.303 [0.4770 − 0.30]
t= –4
(log3 − log2) =
2.48 × 10 2.48 × 10 –4 × 60
t = 27.25 minutes
12. Two substances A and B are present such that [A]0 = 4[B]0 and half life of A is 5 minute and that of B is 15
minute. If they start decaying at the same time following first order kinetics how much time will the
concentration of both of them would be the same?
(1) 15 minute (2) 10 minute (3) 5 minute (4) 12 minute
Sol. Answer (1)
[A]0 = 4[B]0 → [A]t½ = 5 min. → fast
[B]t½ = 15 min. → slow
Half life for first order reaction doesn't depend on initial concentration, so, rate of reaction calculated by slow
reaction concentration of [A] = [B]) at same initial time = 15 min.
or
[A]t = [A]0 e −K1t ∴ (A)0 = 4[B]0
[B]t = [B]0 e –K 2 t [A]t = [B]t
e −K1t 1 1
−K 2 t
= ⎯⎯→ eK 2 t −K1t =
e 4 4
or eK1t −K 2 t = 4
K1t = K2t = loge4 = 2.303log104
0.693 0.693
t− t = 2.303 × 0.3010 × 2
(t1/2 )1 (t1/2 )2
0.693 0.693
t− t = 2.303 × 0.3010 × 2
5 15
0.693 ⎡ 1 ⎤
t ⎢1 − ⎥ = 2.303 × 0.3010 × 2
5 ⎣ 3⎦
t 2
× =2 t = 15 minute
5 3
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Solutions of Assignment (Set-2) Chemical Kinetics 205
13. The reaction A ⎯→ B follows first order kinetics. The time taken for 0.80 mole of A to produce 0.60 mole of
B is 1 hour. What is the time taken for conversion of 0.90 mole of A to produce 0.675 mole of B?
(1) 1 hour (2) 30 min (3) 15 min (4) 5 min
Sol. Answer (1)
A B A B
t=0 0.80 0 t=0 0.90 0
t = 1 hr 0.80 – x 0.60 t=? 0.90 – x 0.675
divide
2.303 0.80
k= log
1 0.20 ⇒ 1log 4 = log 4
2.303 0.90 t
k= log
t 0.225
t ⇒ 1 hr
3 –1
K1 = 2 × 10 s
B
14. If, A
3 –1
K2 = 6 × 10 s
C
find B%
(1) 25% (2) 50% (3) 75% (4) 80%
Sol. Answer (1)
k1 2 × 103 2 × 103
Percentage B = = = = 25%
k1 + k 2 2 × 103 + 6 × 103 8 × 103
⎛ Ea ⎞ 1
logK = log A − ⎜ ⎟
⎝ 2.303R ⎠ T
y = c – mx
1
∴ x=
T
Ea
m=− = slope
2.303R
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206 Chemical Kinetics Solutions of Assignment (Set-2)
16. The temperature coefficient for most of the reaction lies between
(1) 1 & 3 (2) 2 & 3 (3) 1 & 4 (4) 2 & 4
Sol. Answer (2)
When temperature rises by 10°C then rate of reaction becomes double / triple (2/3) known as temperature
coefficient.
17. Which of the following is correct?
K2 E a ⎡ ΔT ⎤
(1) log = ⎢ ⎥
K 1 2.303 ⎣ T1T2 ⎦
(2) For zero order t1/2 is inversely proportional to initial concentration
(3) Catalyst decreases the activation energy
(4) All of these
Sol. Answer (3)
K2 Ea ⎡ ΔT ⎤
1. log = ⎢ ⎥
K1 2.303R ⎣ T1T2 ⎦
2. for zero order t1/2 ∝ a
3. catalyst → Ea ↓ = r ↑
18. The rate constant of a reaction is 1.5 × 107 s–1 at 50°C and 4.5 × 107 s–1 at 100°C. What is the value of
activation energy?
(1) 2.2 × 103 J mol–1 (2) 2300 J mol–1 (3) 2.2 × 104 J mol–1 (4) 220 J mol–1
Sol. Answer (3)
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Solutions of Assignment (Set-2) Chemical Kinetics 207
−Ea
2. T = 8 K = Ae R×8
K = Ae° → (K = A)
3. Fraction of molecule crossing over the energy barrier becomes unity (100%) → (Ea = 0).
So, again (K = A)
−E /RT
4. At very low temperature K = Ae a
K≠A
20. If the rate of reaction increases by 27 times, when temperature is increased by 30 K, then temperature
coefficient of the reaction is
(1) 3 (2) 2 (3) 1 (4) 2.5
Sol. Answer (1)
T2 − T1 30 −0
=2 10 =2 10 ⇒ 23 ⇒ 8
T2 − T1 30 −0
= 3 10 =3 10 ⇒ 33 ⇒ 27 → i.e., temperature coefficient is 3.
SECTION - C
Previous Year Questions
1. A first order reaction has a specific reaction rate of 10–2 s–1. How much time will it take for 20 g of the reactant
to reduce to 5 g? [NEET-2017]
(1) 238.6 second (2) 138.6 second (3) 346.5 second (4) 693.0 second
Sol. Answer (2)
0.693
t1/2 = second
10–2
For the reduction of 20 g of reactant to 5 g, two t1/2 is required.
0.693
∴ t = 2× second = 138.6 second
10–2
2. Mechanism of a hypothetical reaction X2 + Y2 → 2XY is given below :
(i) X2 → X + X (fast)
(ii) X + Y2
XY + Y (slow)
(iii) X + Y → XY (fast)
The overall order of the reaction will be [NEET-2017]
(1) 1 (2) 2 (3) 0 (4) 1.5
Sol. Answer (4)
The solution of this question is given by assuming step (i) to be reversible which is not given in question
Overall rate = Rate of slowest step (ii)
= k[X] [Y2] ...(1)
k = rate constant of step (ii)
Assuming step (i) to be reversible, its equilibrium constant,
1 1
[X]2
k eq = ⇒ [X] = k eq 2 [X2 ] 2 ...(2)
[X2 ]
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208 Chemical Kinetics Solutions of Assignment (Set-2)
1 3
Overall order = +1=
2 2
3. The decomposition of phosphine (PH3) on tungsten at low pressure is a first-order reaction. It is because the
[NEET-Phase-2-2016]
(1) Rate is proportional to the surface coverage
(2) Rate is inversely proportional to the surface coverage
(3) Rate is independent of the surface coverage
(4) Rate of decomposition is very slow
Sol. Answer (1)
Rate is proportion to the surface coverage
4. The addition of a catalyst during a chemical reaction alters which of the following quantities? [NEET-2016]
(1) Activation energy (2) Entropy (3) Internal energy (4) Enthalpy
Sol. Answer (1)
Catalyst decreases the activation energy and thus increases the rate of reaction.
5. The rate of a first-order reaction is 0.04 mol l–1 s–1 at 10 seconds and 0.03 mol l–1 s–1 at 20 seconds after
initiation of the reaction. The half-life period of the reaction is [NEET-2016]
2.303 × 0.301× 10
∴ t1/2 =
2.303 × 0.124
= 24.27 s
∴ t1/2 ≈ 24.1 s
6. The rate constant of the reaction A ⎯→ B is 0.6 × 10–3 mole per second. If the concentration of A is 5 M,
then concentration of B after 20 minutes is [Re-AIPMT-2015]
(1) 0.36 M (2) 0.72 M (3) 1.08 M (4) 3.60 M
Sol. Answer (2)
Order of reaction is zero as unit of rate constant is mole per second.
[A]0 − [A]
∴ K=
t
5 − [A]
⇒ 0.6 × 10–3 =
20 × 60
∴ [A] = 5 – 0.72
∴ Concentration of B after 20 minutes is 0.72 M.
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Solutions of Assignment (Set-2) Chemical Kinetics 209
7. The activation energy of a reaction can be determined from the slope of which of the following graphs?
[AIPMT-2015]
T 1 In K 1
(1) vs (2) In K vs T (3) vs T (4) In K vs
In K T T T
Sol. Answer (4)
∵ K = Ae−Ea RT
Ea 1
i.e. lnK = ln A − ×
R T
8. When initial concentration of a reactant is doubled in a reaction, its half-life period is not affected. The order
of the reaction is [AIPMT-2015]
(1) More than zero but less than first (2) Zero
(3) First (4) Second
Sol. Answer (3)
1
t1/ 2 ∝ ; where n is order of reaction.
(a0 )n −1
9. A reaction having equal energies of activation for forward and reverse reactions has [NEET-2013]
(1) ΔG = 0 (2) ΔH = 0 (3) ΔH = ΔG = ΔS = 0 (4) ΔS = 0
Sol. Answer (2)
ΔH = (Ea)f – (Ea)b
∴ (Ea)f = (Ea)b → [ΔH = 0]
10. What is the activation energy for a reaction if its rate doubles when the temperature is raised from 20°C to
35°C? (R = 8.314 J mol–1K–1) [NEET-2013]
(1) 269 kJ mol–1 (2) 34.7 kJ mol–1 (3) 15.1 kJ mol–1 (4) 342 kJ mol–1
Sol. Answer (2)
K2 Ea ⎡ 1 1⎤
log = ⎢ − ⎥
K1 2.303R ⎣ T1 T2 ⎦
∵ K2 = 2K1
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210 Chemical Kinetics Solutions of Assignment (Set-2)
r1 = k[A]x[B]y
r = k[2A]2[2]1
⇒ 8k[A]2B = 8r1
13. Which one of the following statements for the order of a reaction is incorrect? [AIPMT (Prelims)-2011]
(1) Order of reaction is always whole number
(4) Order of reaction is sum of power to the concentration terms of reactants to express the rate of reaction
14. The unit of rate constant for a zero order reaction is [AIPMT (Mains)-2011]
(1) L2 mol–2 s–1 (2) s–1 (3) mol L –1 s –1 (4) L mol–1 s–1
Sol. Answer (3)
15. The half life of a substance in a certain enzyme- catalysed reaction is 138 s. The time required for the
concentration of the substance to fall from 1.28 mg L–1 to 0.04 mg L–1 is [AIPMT (Mains)-2011]
(1) 690 s (2) 276 s (3) 414 s (4) 552 s
16. For the reaction, N2O5(g) → 2NO2(g) + 1/2 O2(g), the value of rate of disappearance of N2O5 is given as
6.25×10–3 mol L–1s–1. The rate of formation of NO2 and O2 is given respectively as [AIPMT (Prelims)-2010]
(1) 6.25 × 10–3 mol L–1s–1 & 6.25 × 10–3 mol L–1s–1 (2) 1.25 × 10–2 mol L–1s–1 & 3.125 × 10–3 mol L–1s–1
(3) 6.25 × 10–3 mol L–1s–1 & 3.125 × 10–3 mol L–1s–1 (4) 1.25 × 10–2 mol L–1s–1 & 6.25 × 10–3 mol L–1s–1
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Solutions of Assignment (Set-2) Chemical Kinetics 211
Sol. Answer (2)
–3 1 d[NO 2 ]
⇒ 6.25 × 10 =
2 dt
d(NO2 )
rate of formation of (NO2), = 2 × 6.25 × 10 –3 = 1.25 × 10–2 mol L–1 s–1
dt
d[O2 ] 6.25 × 10 –3
rate of formation of (O2), = = 3.125 × 10 –3 molL−1 s−1
dt 2
17. For an endothermic reaction, energy of activation is Ea and enthalpy of reaction is ΔH (both of these in kJ/
mol). Minimum value of Ea will be [AIPMT (Prelims)-2010]
(1) Less than ΔH (2) Equal to ΔH (3) More than ΔH (4) Equal to zero
Sol. Answer (3)
For endothermic reaction,
(Ea) forward
P.E
ΔH
18. During the kinetic study of the reaction, 2A+B→C+D, following results were obtained
Run [A]/mol L–1 [B]/mol L–1 Initial rate of formation of
D/mol L–1 min–1
I. 0.1 0.1 6.0×10–3
II 0.3 0.2 7.2×10–2
III 0.3 0.4 2.88×10–1
IV 0.4 0.1 2.40×10–2
Based on the above data which one of the following is correct ? [AIPMT (Prelims)-2010]
2 2 2
(1) Rate = K[A] [B] (2) Rate = K[A][B] (3) Rate = K[A] [B] (4) Rate = K[A][B]2
Sol. Answer (4)
According to table When concentration of (A) = constant (II, III)
then (B) = doubles, r = four times.
i.e., order w.r.t. (B) = 2
When concentration of (B) = constant (I & IV)
(A) = four times, r = four times.
i.e., order w.r.t. (A) = 1
r = k[A]1[B]2
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212 Chemical Kinetics Solutions of Assignment (Set-2)
19. The rate of the reaction, 2NO + Cl2 ⎯→ 2NOCl is given by the rate equation rate = k[NO]2[Cl2]
The value of the rate constant can be increased by [AIPMT (Mains)-2010]
(1) Increasing the temperature (2) Increasing the concentration of NO
(3) Increasing the concentration of the Cl2 (4) Doing all of these
Sol. Answer (1)
r = K[NO]2[Cl2]
d[NH3 ] −d[H2 ]
if = 2 × 10−4 mol L–1 s–1, the value of would be [AIPMT (Prelims)-2009]
dt dt
(1) 4×10–4 mol L–1 s–1 (2) 6×10–4 mol L–1 s–1 (3) 1×10–4 mol L–1 s–1 (4) 3×10–4 mol L–1 s–1
Sol. Answer (4)
d[N2 ] ( − )d[H2 ] +1d[NH3 ]
r=− = =
dt 3 dt 2 dt
− 1 d[H2 ] 2 × 10 –4
=
3 dt 2
− d[H2 ]
= 3 × 10 –4 mol L–1 s –1
dt
21. In the reaction,
BrO3− (aq) + 5Br − (aq) + 6H+ → 3Br2 (l) + 3H2O(l)
The rate of appearance of bromine (Br2) is related to rate of disappearance of bromide ions as following
[AIPMT (Prelims)-2009]
d(Br2 ) 5 d(Br − ) d(Br2 ) 5 d(Br − ) d(Br2 ) 3 d(Br − ) d(Br2 ) 3 d(Br − )
(1) =− (2) = (3) = (4) =−
dt 3 dt dt 3 dt dt 5 dt dt 5 dt
Sol. Answer (4)
−d[BrO3 ]− −1 d[Br – ] −1 d[H+ ] 1 d[Br2 ]
r= = = =+
dt 5 dt 6 dt 3 dt
d[Br2 ] 3 d[Br – ]
∴ =−
dt 5 dt
22. Half life period of a first-order reaction is 1386 seconds. The specific rate constant of the reaction is
[AIPMT (Prelims)-2009]
(1) 0.5 × 10–2 s–1 (2) 0.5 × 10–3 s–1 (3) 5.0 × 10–2 s–1 (4) 5.0 × 10–3 s–1
Sol. Answer (2)
0.693 0.693
K= = = 0.5 × 10–3 s−1
t1/2 1386
23. For the reaction A + B ⎯→ Products, it is observed that
(a) On doubling the initial concentration of A only, the rate of reaction is also doubled and
(b) On doubling the initial concentrations of both A and B, there is a change by a factor of 8 in the rate of
the reaction.
The rate of this reaction is given by [AIPMT (Prelims)-2009]
2 2 2
(1) Rate = k [A] [B] (2) Rate = k [A] [B] (3) Rate = k [A] [B] (4) Rate = k[A]2[B]
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Solutions of Assignment (Set-2) Chemical Kinetics 213
Sol. Answer (1)
r1 = k[A]x[B]y
= k[2A]1[2B]2 = 8r1
r = k[A][B]2
24. The rate constants k1 and k2 for two different reactions are 1016 e–2000/T and 1015 e–1000/T respectively. The
temperature at which k1 = k2 is [AIPMT (Prelims)-2008]
1000 2000
(1) K (2) 1000 K (3) K (4) 2000 K
2.303 2.303
Sol. Answer (1)
∵ k = Ae −Ea /RT ;
−2000 −1000
∴ k1 = 1016.e T & k 2 = 1015.e T
∴ k1 = k2
−2000 −1000
∴ 1016
.e T = 1015
.e T
−1000
e T
⇒ 10 = −2000
e T
−1000 2000
+ 1000
⇒ 10 = e T T ⇒ loge 10 = loge e
T
1000
1000
⇒ 10 = e T ⇒ 2.303log10 10 =
T
1000 1000
⇒ loge 10 = loge e T T= kelvin
2.303
25. The bromination of acetone that occurs in acid solution is represented by this equation
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214 Chemical Kinetics Solutions of Assignment (Set-2)
So, r = K[CH3COCH3][H+]
26. In a first-order reaction A ⎯→ B, if K is rate constant and initial concentration of the reactant A is 0.5M then
the half-life is [AIPMT (Prelims)-2007]
1 1
⇒ × 0.3010 = [log10 − log 4]
t 60
1 1
⇒ × 0.3010 = [1 − 0.60]
t 60
0.3010 × 60
∴ t= = 45.15 45 min.
0.40
29. For the reaction, 2A + B → 3C + D. Which of the following does not express the reaction rate?
[AIPMT (Prelims)-2006]
d [ C] d [B] d[D] d[ A ]
(1) – (2) – (3) (4) –
3 dt dt dt 2dt
Sol. Answer (1)
1 d[A] −d[B] 1 d[C] d[D]
r=− = = =
2 dt dt 3 dt dt
d [NH3 ] d [H2 ]
30. Consider the reaction, N2(g) + 3H2(g) → 2NH3(g). The equality relationship between and – is
dt dt
[AIPMT (Prelims)-2006]
d [NH3 ] 1 d [H2 ] d [NH3 ] 2 d [H2 ]
(1) =− (2) + =−
dt 3 dt dt 3 dt
d [NH3 ] 3 d [H2 ] d [NH3 ] d [H2 ]
(3) + =− (4) =−
dt 2 dt dt dt
Sol. Answer (2)
− d[N2 ] − d[H2 ] 1 d[NH3 ]
r= = =+
dt 3dt 2 dt
d[NH3 ] 2 d[H2 ]
=−
dt 3 dt
31. For a first order reaction A ⎯→ B, the reaction rate at reactant concentration of 0.01 M is found to be 2.0 ×
10–5 mol L–1 s–1. The half life period of the reaction is [AIPMT (Prelims)-2005]
(1) 220 s (2) 30 s (3) 300 s (4) 347 s
Sol. Answer (4)
0.693 0.693
r = K[A]1 t1/2 = =
K 2 × 10 –3
2 × 10 –5
K= = 2 × 10−3 s−1
0.01
32. A nuclide of an alkaline earth metal undergoes radioactive decay by emission of three α-particles in succession.
The group of the periodic table to which the resulting daughter element would belong is
[AIPMT (Prelims)-2005]
(1) Group 14 (2) Group 16 (3) Group 4 (4) Group 6
Sol. Answer (1)
Release of one α-particle decreases the atomic number by two of the resulting elements.
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216 Chemical Kinetics Solutions of Assignment (Set-2)
33. The rate of reaction between two reactants A and B decreases by a factor of 4, if the concentration of reactant
B is doubled. The order of this reaction with respect to reactant B is [AIPMT (Prelims)-2005]
(1) –1 (2) –2 (3) 1 (4) 2
Sol. Answer (2)
r2 = K[A]x[B]y
1
r1 = K[A]x [2B]y
4
So, order w.r.t. (B) → (–2)
1
r1 = K[2B]–2
4
34. A reaction is 50% complete in 2 hours and 75% complete in 4 hours. The order of reaction is
(1) 0 (2) 1 (3) 2 (4) 3
Sol. Answer (2)
[A]0 − [A]
For zero order reaction, K =
t
∴ 50 = K × 2 & 75 = K × 4
75
K = 25 ...(i) K= = 18.75 ...(ii)
4
K is not constant
2.303 100 ⎫
K= log = 1.15log2 = 0.34 ⎪
2 100 − 50 ⎪
⎬ constant
2.303 100
K= log = 0.57log 4 = 0.34 ⎪
4 100 − 75 ⎪⎭
35. Activation energy (Ea) and rate constants (k1 and k2) of a chemical reaction at two different temperatures (T1
and T2) are related by
k2 Ea ⎛ 1 1⎞ k2 E ⎛ 1 1⎞
(1) ln k = − R ⎜ − ⎟ (2) ln =− a⎜ − ⎟
1 ⎝ T1 T2 ⎠ k1 R ⎝ T2 T1 ⎠
k2 E ⎛ 1 1⎞ k 2 Ea ⎛ 1 1⎞
(3) ln =− a ⎜ + ⎟ (4) ln = ⎜ − ⎟
k1 R ⎝ T2 T1 ⎠ k1 R ⎝ T1 T2 ⎠
k 2 Ea ⎛ 1 1⎞
loge = ⎜ − ⎟
k1 R ⎝ T1 T2 ⎠
k2 E ⎛ 1 1⎞
or loge =− a⎜ − ⎟
k1 R ⎝ T2 T1 ⎠
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Solutions of Assignment (Set-2) Chemical Kinetics 217
36. The half life time of 2g sample of radioactive nuclide ‘X’ is 15 min. The half life time of 1g sample of X is
(1) 7.5 min (2) 15 min (3) 22.5 min (4) 30 min
Sol. Answer (2)
Radioactive nuclide follows first order kinetics and for Ist order reaction t1/2 is independent of initial mole/
concentration that is why t1/2 remains constant i.e., 15 min.
37. The rate of the reaction : 2N2O5 ⎯→ 4NO2 + O2 can be written in three ways :
−d[N2 O5 ]
= k[N2O5 ]
dt
d[NO2 ]
= k′[N2 O5 ]
dt
d[O2 ]
= k ″[N2 O5 ]
dt
The relationship between k and k′ and between k and k″ are
k
(1) k′ = 2k; k″ = 2k (2) k′ = k; k″ = k (3) k′ = 2k; k″ = k (4) k′ = 2k; k″ =
2
Sol. Answer (4)
k[N2O5 ] +1
⇒ = k′[N2O5 ] = k′′[N2O5 ]
2 4
i.e., k′ = 2K
K
k′′ =
2
38. For the following reaction C6H12O6(aq) + H2(g) C6H14O6(aq). Which one of the following is not affected by
the addition of catalyst?
(1) Rate of forward reaction (2) Rate of backward reaction
(3) Time required to reach the equilibrium (4) Spontaneity
Sol. Answer (4)
⎧ decreases Ea
Catalyst ⎨
⎩rate of reaction increases
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218 Chemical Kinetics Solutions of Assignment (Set-2)
[X]
(i) kC = 2
⇒ [X] = k C [A]2
[A]
(ii) slow rate law r = k[X][B] = k × kc[A]2 × [B]
41. Half-life for radioactive 14C is 5760 years. In how many years 200 mg of 14C will be reduced to 25 mg?
(1) 17280 years (2) 23040 years (3) 5760 years (4) 11520 years
0.693
Radioactive decay follows 1st order kinetics; t1/2 =
K
2.303 200
K= log
t 25
0.693 2.303
⇒ = log8
t1/2 t
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Solutions of Assignment (Set-2) Chemical Kinetics 219
42. A chemical reaction is catalyzed by a catalyst X. Hence X
(1) Reduces enthalpy of the reaction (2) Does not affect equilibrium constant of reaction
(3) Decreases rate constant of the reaction (4) Increases activation energy of the reaction
Sol. Answer (2)
A catalyst does not affect the equilibrium constant of the reaction
43. The given reaction 2 FeCl3 + SnCl2 → 2 FeCl2 + SnCl4 is an example of
(1) Third order reaction (2) First order reaction
(3) Second order reaction (4) None of these
Sol. Answer (1)
2FeCl3 + SnCl2 → 2FeCl2 + SnCl4
For elementary chemical reaction, the order of the reaction is the sum of the coefficients of the reactants.
(1) rate = k [A]2 [B]2 (2) rate = k [A]2 [B] (3) rate = k [B2] (4) rate = k [B2]2
Sol. Answer (3)
From exp-I & exp-II, when [A] is constant and [B] doubles, rate becomes twice.
∴ Order w.r.t. [B] is I
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220 Chemical Kinetics Solutions of Assignment (Set-2)
K2 Ea ⎡ 1 1⎤
log = ⎢ − ⎥
K1 2.303R ⎣ T1 T2 ⎦
0.693
t1/2 = = 3 × 103 years
2.31× 10 –4
50. A 300 gram radioactive sample has a half life 3 hours. After 18 hours remaining quantity
(1) 4.68 gram (2) 2.34 gram (3) 3.34 gram (4) 9.37 gram
Sol. Answer (1)
[R]0 18
[R]t = n
n= =6
2 3
300
⇒ = 4.68 gram
26
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Solutions of Assignment (Set-2) Chemical Kinetics 221
Sol. Answer (2)
2N2O5 → 4NO2 + O2
Experimentally it is a 1st order reaction.
r = K[N2O5]1
1.02 × 10–4 = 3.4 × 10–5 [N2O5]
1.02 × 10 –4
N2 O 5 = =3
3.4 × 10 –5
53. A human body required 0.01 m activity of radioactive substance after 24 hours. Half life of radioactive substance
is 6 hours. Then injection of maximum activity of radioactive substance that can be injected
(1) 0.08 (2) 0.04 (3) 0.16 (4) 0.32
Sol. Answer (3)
[R]0 24
[R]t = n
n= =4
2 6
[R]0
0.01 = [R]0 = 0.01 × 16 = 0.16
24
54. When a biochemical reaction is carried out in laboratory, outside the human body in absence of enzyme, then rate
of reaction obtained is 10–6 times, the activation energy of reaction in the presence of enzyme is
6
(1) (2) P is required
RT
(3) Different from Ea obtained in laboratory (4) Can’t say anything
Sol. Answer (3)
In the presence of enzyme → rate of reaction increases by decreasing activation energy because it acts as
a catalyst.
i.e., different Ea
+ d(B)
55. 3A → 2B, rate of reaction is equal to
dt
3 d(A) 2 d(A) 1 d(A) d(A)
(1) − (2) − (3) − (4) + 2
2 dt 3 dt 3 dt dt
Sol. Answer (2)
3A → 2B
1 d(A) +1 d(B)
r=− =
3 dt 2 dt
d(B) 2d(A)
⇒−
dt 3 dt
56. 2A → B + C
It would be a zero order reaction when
(1) The rate of reaction is proportional to square of conc. of A
(2) The rate of reaction remains same at any conc. of A
(3) The rate remains unchanged at any conc. of B and C
(4) The rate of reaction doubles if conc. of B is increased to double
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222 Chemical Kinetics Solutions of Assignment (Set-2)
2.303 0.8
K= log ...(i)
1 0.6
2.303 0.8
K= log
1 0.6 1 0.9 0.8
2.303 0.9 log = log
K= log t 0.675 0.6
t 0.675
1
log1.33 = log1.33
t
t = 1 hr
59. If the rate of the reaction is equal to the rate constant, the order of the reaction is
(1) 0 (2) 1 (3) 2 (4) 3
Sol. Answer (1)
r = K[A]0 ← for zero order.
r =K
60. The temperature dependence of rate constant (k) of a chemical reaction is written in terms of Arrhenius equation,
*
k = A . e −E /RT . Activation energy (E*) of the reaction can be calculated by plotting
1 1
(1) k Vs T (2) k Vs logT (3) log k Vs (4) log k Vs T
T
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Solutions of Assignment (Set-2) Chemical Kinetics 223
Sol. Answer (3)
⎡ −E ⎤
*
K = Ae−E /RT log K ⎢slope = 2.303R ⎥
⎣ ⎦
E
logK = log A −
2.303RT ⎛ 1⎞
⎜ ⎟
⎝T⎠
61. The radioisotope, tritium (13 H) has a half-life of 12.3 years. If the initial amount of tritium is 32 mg, how many
milligrams of it would remain after 49.2 years?
(1) 1 mg (2) 2 mg (3) 4 mg (4) 8 mg
Sol. Answer (2)
(R)0 49.2
(R)t = n= =4
2n 12.3
32 32
(R)t = n
=
2 24
32
=
16
= 2 mg
62. The rate of a first order reaction is 1.5 × 10–2 mol L–1 min–1 at 0.5 M concentration of the reactant. The half-
life of the reaction is
(1) 0.383 min (2) 23.1 min (3) 8.73 min (4) 7.53 min
0.693 0.693
r = K[A]1 t1/2 = =
K 3 × 10 –2
1.5 × 10 –2
K= = 3 × 10−2
0.5
SECTION - D
R : The order of reaction can be negative with respect to a substance present in the reaction.
dC
Rate = − ∝C
dt
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224 Chemical Kinetics Solutions of Assignment (Set-2)
slow
2. A : NO2 + CO ⎯⎯⎯
→ CO2 + NO
Rate = K[NO2]2
R : Rate does not depend upon [CO] because it is involved in the first step.
R = K[NO2][CO]
All reactant concentration term (in slow state) must be included in Rate law.
4. A : The rate constant of first order reaction is used to calculate population if growth rate is given.
dC
R=− = KC
dt
2.303 ⎡A ⎤
or K = log ⎢ 0 ⎥
t ⎣ At ⎦
⎛ 0.693 ⎞
and ⎜⎜ K = t ⎟⎟
⎝ ½ ⎠
k
R : The plot of log of its partial pressure versus time is linear with slope, − and having intercept equal
2.303
to P.
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Solutions of Assignment (Set-2) Chemical Kinetics 225
Sol. Answer (1)
2.303 P
K= log 0
t Pt
⎛ K ⎞
t⎜ ⎟ = logP0 − logPt
⎝ 2.303 ⎠
⎛ K ⎞
logPt = − ⎜ ⎟ t + logP0
y ⎝ 2.303 ⎠ x interecept
m
11. A : The rate constant for zero order reaction is equal to rate of reaction.
R : t1/2 for zero order reaction is directly proportional to initial concentration.
Sol. Answer (2)
Rate = KC°
Rate = K
⎡ C0 ⎤
⎢ t½ = 2K ⎥
⎣ ⎦
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226 Chemical Kinetics Solutions of Assignment (Set-2)
14. A : In presence of +ve catalyst, activation energy & threshold energy decreases.
R : Minimum energy required to permit a reaction is known as threshold energy.
Sol. Answer (2)
Positive catalyst favours rate of reaction by decreasing activation energy and threshold energy.
2nd statement is a definition of threshold energy.
15. A : When temperature becomes ∞ infinite then the value of rate constant is maximum.
R : A is also known as maximum rate constant.
Sol. Answer (2)
K = Ae −Ea /RT
T→∞
Ea/RT → 0
e0 = 1
K=A
[∵ K increases as temperature increases.]
[Kmax = A = maximum rate constant]
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