CHEMISTRY - CHEMICAL KINETICS - 2

13 Feb 2021

A
1) 4 2) 4 3) 1 4) 1 5) 3 6) 3 7) 1, 2, 4 8) 4 9) 1 10) 3 11) 2 12) 3

13) 4 14) 1 15) 2 16) 1, 2, 3, 4 17) 4 18) 2 19) 3 20) 4 21) 4 22) 4 23) 2 24) 1

25) 2 26) 2 27) 4 28) 3 29) 2 30) 1 31) 1 32) 1 33) 2 34) 1 35) 4 36) 4

37) 3 38) 4 39) 1 40) 1 41) 2 42) 4 43) 1 44) 3 45) 3 46) 1 47) 2 48) 1

49) 4 50) 2 51) 3 52) 3 53) 1 54) 4 55) 1 56) 1 57) 2 58) 3 59) 4 60) 4

Solution :-
1) Increase in the rate of reaction is determined by the increase in the number of effective collisions.
2) 1
Rate = k [A] [B]; when volume is reduced to th, concentration will become 4 times:
4
Therefore, new rate = k [4A] [4B] = 16 k [A] [B]
= 16 times
3) 2N 2O 5 → 4NO 2 + O2
(50 − 2p) 4p p
total pressure = (50 - 2p) + 4p + p
= 50 + 3p = 87.5
p = 12.5
p 0 = 50
2.303 a
R= log
t (a − x)

2.303 50
= log
30 (50 − 2 × 12.5)

= 0.023 at 30 min
the same k s valid throughout the reaction

()
2.307 50
0.023 = log
60 x

x = 12.5 = 50 - 29
p = 18.75
total pressure = 50 + 3p = 106.25 mm
4) A→B
∵ r = k[A] 0 or r = k
This is a zero order reaction
a
∴ t1 / 2 =
2k

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5) r = K[CH 3COCH 3] x [Br 2] y [H + ] z
5.7 × 10 − 5 = K[0.3] x [0.05] y [0.05] z → (1)
5.7 × 10 − 5 = K[0.3] x [0.1] y [0.05] z → (2)
1.2 × 10 − 4 = K[0.3] x [0.1] y [0.1] z → (3)
3.1 × 10 − 4 = K[0.4] x [0.05] y [0.2] z → (4)
(1) (2) (1)
From , , Then
(2) (3) (4)

[
Rate = k CH 3COCH 3 ] [H + ]
6) rate=K[CH 3OCH 3] 3 / 2
3
Here n = (order)
2
∴ units of 'K' are
= bar 1 − 3 / 2. min − 1
= bar − 1 / 2. min − 1
8)

()
K2 Ea (T 2 − T 1)
log =
K1 2.303 R T 1T 2

()
2.303R T 1T 2 K2
Ea = × log
(T 2 − T 1) K1

( )
2.303 × 8.314 × 400 × 500 2.60 × 10 − 3
= log
(500 − 400) 2.60 × 10 − 5

= 76, 588 J
= 76.588 kJ / mol
9) The reactive intermediate formed for I has a lower E a and (I) is formed fast. Lower E a corresponds to a faster reactio
controlled reaction, the preferred direction is formation of faster product.

10) r = K[R] 1

[]
n 1
r1 = K
v

[ ]
n 1
r1 = K
v/3

r 1 = 3 × K[n / v]
= 3 × r, (3 times)

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11) T 1(A) = 300 K T 2(B) = 310 K
T b(1) = 300 K Eb = 2 × A
we have to find T 2(B)

( ) ( )
1 1 1 1
Ea × − = Eb × −
T 1(A) T 2(A) T 1(B) T 2(B)

Eb = 2 × Ea
so we get T B(2) = 304.92 K
temperature increase = 4.92 K
12) 0.693
K= (For first order reactions)
tH
2

0.693
K1 = (At T 1 = 300 K)
50

0.693
K2 = (At T 2 = 400 K)
10

K2 0.693 50
= × =5
K1 10 0.693

()
K2 E0 (T 2 − T 1)
log =
K1 2.303 R T 1. T 2

()
2.303 R T 1 × T 2 K2
Ea = log
(T 2 − T 1) K1

2.303 × 8.314 × 300 × 400

= log5
(400 − 300)

= 16.10 kJ mol − 1
13) K1 = K2
10 10e − 500 / T = 10 12e − 1000 / T
e − 500 / T
= 10 2
e − 1000 / T

e 500 / T = 10 2
lne 500 / T = ln 10 2
500
ln ee = 2ln e10
T

500
× 1 = 2 × 2.303 × log 1010
T

500
= 4.606 × 1
T

500
∴ K=T
4.606

14) − d(N 2) 1 d(H 2) 1 d(NH 3) 3

= − = = × 40 × 10 − 3 = 60 × 10 − 3.
dt 3 dt 2 dt 2
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15) 1 1 1
1−n 1−0
t ∝a t ∝a =t ∝ a1
2 2 2

So zero order is constant rate through and the rate of reaction is equal to rate constant & rate constant is called spec
dependent of the concentration of reactant R = K[A] is rate of reaction
R R
K= K=
[A] [A]

R = mole L − 1 time − 1
[A] = mole L − 1
mole L − 1time − 1
K=
mole L − 1

1
K= = time − 1
time

K=R
17) 32 = 2 × t 50%
32
t 50% = = 16 min
2

18) [O 2][O]
For the equilibrium step, K eq =
[O 3]

K eq [O 3]
[O] =
[O 2]

The species preent in the slowest step appear in the rate law equation
[O 3] [O 3] K[O 3] 2
Rate=K 1[O 3][O] = K 1 K eq =
[O 2] [O 2]

19)
[
− d N 2O 5 ] −d 1 1 d d

dt
= k 1 N 2O 5 [ ] dt 2 [NO2 ] = k2 2 [N2O5 ] dt 2 [O2 ] = 2k3 dt [O2 ]2k1 = k2 = 4k3

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20) From Question data
0.693
K=
t1 / 2

0.693
K= = 0.01sec − 1
69.3

2.303 0.4
K= log
t 0.4 − x

2.303 0.4
0.01 = log
t 0.4 − x

0.01 0.4
= log
0.01 0.4 − x

0.4
10 = ; x = 0.36
0.4 − x

For given reaction

A (g) → P (g) + Q (g) + R (g)
initial 0.4 0 0 0
final 0.4 − x x x x
0.4 − 0.36 0.36 0.36 0.36
Total pressure = 0.4 − 0.36 + 3 × 0.36
= 1.12 atm
21) Pi + x = 100 ∴ x = 10
∴ Partial pressure of A = Pi − x = 90 − 10 = 80 mm
22) Rate of reaction depends on the
(1) Temperature (2) Concentration of reactant (3) Physical state (or) nature of reactants (4) Size of the vessel (5) Cat
23) 1 d [SO 3]
−4
2 × 10 =
2 dt

d [SO 3]
∴ = 4 × 10 − 4
dt

24) 2.303 a
t= log
k a−x

2.303 5
or t = log = 34.07 s
15 × 10 − 3 3

25) As the slowest step is the rate determining step, hence from step 2

[ ]
r = k O 3 [O]. . . . . (i)

[O2 ][O] K eq [O 3 ]
From step 1, K eq = or [O] = . . . . (ii)
[O3 ] [O 2 ]
from eq (i) and (ii)
[O3 ] 2 ′
r = k K eq = k [O 3 ] 2 [O 2 ] − 1 [ ∵ k ′ = kK eq ]
[O 2 ]
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26) From the rate law, order of the reaction is 1. From the reaction equation, molecularity is 2
Th rate law shows first dependence of concentration. There are two moleculas of reactant
27) 1 1
1−1
t ∝a t ∝ a0
2 2

[]
28)
1 d ¯ 1 d
−
5 dt
Br = −
6 dt
[H ] +

[]
d ¯ 5 d

dt
Br =
6 dt
[H ] +

29)

( )
K2 Ea 1 1
= − =6
K1 2.303 K 350 400

this given E a = 41.7 KJ mol − 1

30) 0.693 0.693
t1 / 2 = = = 1117.7 sec
k 6.2 × 10 − 4

31) Slower reaction rate indicates higher energy of activation

32) x x 2E 1E 2
− Ea / RT − Ea 1 / RT − Ea 2 / RT − Ea 1 / T − 2Ea 1 / T
K = A. e K 1 = xK 2 = K 1 + K 2 = KA . e + A. e x+ = A. e + A. e (or)E = E=
2 2 E1 + E2

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33) 0.693 0.693
k= = sec − 1
t1 / 2 14.26 × 60

2.303 a
k= log (For first order reaction)
t a−x

0.693 2.303 a
= log
14.26 × 60 50 a−x

a 0.693 × 50
log = = 0.0175
a−x 14.26 × 60 × 2.303

a
= 1.041
a−x

a−x x
or = 0.96 or 1 − = 0.96
a a

x
= 0.04 = 4%
a

34) R = k[A] m[B] n → (i)

2R = k[2A] m[B] n → (ii)
8R = k[2A] m[2B] n → (iii)
From (i), (ii) and (iii), m = 1, n = 2
So rate = k[A][B] 2
35) R ∝ [A] 1[B] 210 − 2R = K[A] 1[B] 2 → (1)
If 1 mole of each A & B are introduced so it has 0.5 mole of A & 0.5 mole B

()
1 1 2 8
2 2 −2 −3 3 −2
R = K[A][B] R = K[0.5][0.5] K = 10 mol L R = 10 × × R= = 1.25 × 10 − 3 = 1.25 × 10 − 3 mole / lit / sec
2 2 10 − 2

36) K = K1 × K2
K = 5.2 × 10 9 × 2.6 × 10 10
K = 1.352 × 10 20
K = 1.4 × 10 20
37)
r = K[A] B 2 [ ]
[A][A]
and K c = or
[ ] A2

[ ]1 / 2
[A] = K 1c / 2 A 2

Thus r = K. K 1c / 2 [A 2 ] 1 / 2 [B 2 ]

= K ′ [A 2 ] 1 / 2 [ B 2 ]

39) Activation energy = Threshold energy of the molecule - energy of reactant molecule
40) X = NO, Y = O 2, Z = NO 2
X, Y are products & backward reaction
Z is forward reaction and reactant
X is NO as NO is formed two times than O 2.

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41) At pH = 5, the half-life is 500 for all concentration of sugar, i.e t 1 / 2 ∝ [sugar] 0. Thus, the reaction is I order with respec
Now,
rate = k[sugar] 1[H + ] m
also for { [{H^ + }]}
{t_{1/2}} \propto {\left[ {{H^ + }} \right]^{1 - m}}
500 \propto {\left[ {{{10}^{ - 5}}} \right]^{1 - m}}
50 \propto {\left[ {{{10}^{ - 6}}} \right]^{1 - m}}
\therefore 10 = {\left( {10} \right)^{\left( {1 - m} \right)}}
or
\left( {1 - m} \right) = 1
\therefore m = 0
\therefore rate = K{\left[ {sugar} \right]^1}{\left[ {{H^ + }} \right]^0}
42) Number of collision depend upon pressure, concentration and temperature.
43) A \to B
K= n.t
Zero order reacts rate is independent.
44) r = K{\left[ X \right]^m}{\left[ Y \right]^n} \\
{2^1} = {2^m}\,\,\,\left( {m = 1} \right) \\
{2^0} = {2^n}\,\,\,\left( {n = 0} \right) \\
r = K{\left[ X \right]^1}{\left[ Y \right]^0}
45) Given {k_1} = {k_2}
Is {x_2} \rightleftharpoons 2X
{k_3} < < {k_1} = {k_2}
X + Z \to \,XZ (Slow step)
Rate =k\left[ X \right]\left[ Z \right] \to \left( 1 \right)
But {k_c} = \cfrac{{{{\left[ X \right]}^2}}}{{\left[ {{X_2}} \right]}}
\Rightarrow \,{\left[ X \right]^2} = \left[ {{X_2}} \right]
\Rightarrow \,\left[ X \right] = {\left[ {{X_2}} \right]^{1/2}}
From (1)
\therefore rate = k{\left[ {{X_2}} \right]^{1/2}}\left[ Z \right]
\therefore order=1+1/2=1.5
46) The minimum amount of energy absorbed by the reactants so that their energy becomes equal to threshold energy is
energy.
For the products activation energy will be
40+18=58=kJ
\Delta H = \mathop {{E_a}}\limits_{(F.R)} - \mathop {{E_a}}\limits_{(B.R)}

47) In first phase, K = \cfrac{{2.303}}{{20}}\,\,\log \cfrac{{90}}{{100}} .....(i)

In second phase K = \cfrac{{2.303}}{t}\,\,\log \cfrac{{81}}{{100}}.....(ii)
From eq. (i) \cfrac{{2.303}}{{20}}\,\,\log \cfrac{{90}}{{100}} = \cfrac{{2.303}}{t}\,\,\log \cfrac{{81}}{{100}}
t = \cfrac{{20(\log 81 - \log 100)}}{{(\log 90 - \log 100)}}
= \cfrac{{20(1.908 - 2)}}{{(1.954 - 2)}} = \cfrac{{20 \times ( - 0.092)}}{{( - 0.046)}} = 40 minutes

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48) A+B\to Products
Rate = k{\left[ A \right]^\alpha }{\left[ B \right]^\beta }
From exper No 1
2 = k{\left[ {0.2} \right]^\alpha }{\left[ {0.2} \right]^\beta }.....\left( 1 \right)
from exper No 2
4 = k{\left[ {0.2} \right]^\alpha }{\left[ {0.4} \right]^\beta }.....\left( 2 \right)
Dividing eq (1) by (2) we get
\cfrac{{2 = k{{\left[ {0.2} \right]}^\alpha }{{\left[ {0.2} \right]}^\beta }}}{{4 = k{{\left[ {0.2} \right]}^\alpha }{{\left[ {0.4} \right]
}}\cfrac{1}{2} = {\left[ {\cfrac{1}{2}} \right]^\beta } \Rightarrow \beta = 1
From exper No 3
{36 = k{{\left[ {0.6} \right]}^\alpha }{{\left[ {0.4} \right]}^\beta }}
Dividing eqn (2) by (3) we get
\cfrac{4}{{36}} = \cfrac{{k{{\left[ {0.2} \right]}^\alpha }{{\left[ {0.4} \right]}^\beta }}}{{k{{\left[ {0.6} \right]}^\alpha }{{\left[ {0
{\text{ or }}\cfrac{1}{9} = {\left[ {\cfrac{1}{3}} \right]^\alpha } \Rightarrow \alpha = 2
Rate law for the given reaction is
r = k{\left[ A \right]^2}\left[ B \right]^1
49) k = A{e^{ - \frac{{{E_a}}}{{RT}}}} k depends on frequency factor A, activation energy E_a and temperature T.
50) The arrhenius equation is k = A{e^{ - {E_a}/RT}}. Higher the activation energy, higher the minimum excess energy re
Hence k_2>k_1.

51) K = \cfrac{{2.303}}{t}\log \cfrac{{{P_0}}}{P}

\quad = \cfrac{{2.303}}{{1000}}\log \cfrac{2}{{0.1}}
\quad = \cfrac{{2.303}}{{1000}}\log 20
\quad = 3 \times {10^{ - 3}}{\min ^{ - 1}}
52) {t_{1/2}} = \cfrac{{2.303}}{K} \times \log \left( {\cfrac{{0.5}}{{0.25}}} \right)
= \cfrac{{2.303}}{K}\log (2)
{t_{1/2}} = \cfrac{{ln\,(2)}}{K}\,\,\,\,\,\,\,\,[ln\, = \,2.303\,\log ]
53) [{R_o}] = a,\,[R] = 0\, (for completion of the reaction)
t = \cfrac{{a - 0}}{K}
t = \cfrac{a}{K}
54) 1.\underbrace {0\,M\xrightarrow{{{t_{1/2}}}}0.5M\xrightarrow{{{t_{1/2}}}}0.2}_{T = 40\,{\text{minutes}}}5\,M
T = n \times {t_{1/2}}
{t_{1/2}} = \cfrac{T}{n} = \cfrac{{40\,\min }}{2} = 20\min
K = \cfrac{{0.693}}{{{t_{1/2}}}} = \cfrac{{0.693}}{{20}}{\min ^{ - 1}}
r = K\left[ X \right] (first order reaction)
\quad = \cfrac{{0.693}}{{20}} \times 0.1
\quad = 3.45 \times {10^{ - 3}}mol.{L^{ - 1}}.{\min ^{ - 1}}

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55) - \cfrac{1}{2}\,\,\,\cfrac{d}{{dt}}\left[ {S{O_2}} \right] = - \cfrac{d}{{dt}}\left[ {{O_2}} \right]
-\cfrac{d}{{dt}}\left[ {S{O_2}} \right] = - 2\cfrac{d}{{dt}}\left[ {{O_2}} \right]
= 2 \times 2.5 \times {10^{ - 4}}
=5 \times {10^{ - 4}}\,mol\,li{t^{ - 1}}{s^{ - 1}}
56) Given, Rate constant of the first order reaction (K) = 3 \times {10^{ - 6}} per sec and initial concentration [A] = 0.10 M
rate constant
K[A] = 3 \times {10^{ - 6}} \times 0.10 = 3 \times {10^{ - 7}}m{s^{ - 1}}.
57) \log \cfrac{{{K_2}}}{{{K_1}}} = \cfrac{{{E_a}}}{{2.303\,R}}\,\,\,\,\,\,\left[ {\cfrac{{{T_2} - {T_1}}}{{{T_1}\,{T_2}}}} \right] \\
\log \cfrac{{10}}{1} = \cfrac{{{E_a}}}{{2.303 \times R}}\,\,\,\left[ {\cfrac{{400 - 200}}{{80000}}} \right] \\
\log 10 = \cfrac{{{E_a}}}{{2.303 \times R}}\,\,\,\left[ {\cfrac{{200}}{{80000}}} \right] \\
{E_a} = 921.2\,R
58) Rate of reaction = \cfrac{{dx}}{{dt}} = \left[ {\cfrac{{0.2 - 0.1}}{{10}}} \right] = \cfrac{{0.1}}{{10}}
= 0.01\,\,mol\,\,d{m^{ - 3}}\,mi{n^{ - 1}}
59) {K_t} = \ln {K_0} + \cfrac{{\left( {\ln 3} \right)t}}{{10}} \\
\cfrac{{{R_{t + 10}}{}^0C}}{{{R_t}}} \simeq 2\,\,(or)\,\,3
60) Refer the figure.

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