5.

CHEMICAL KINETICS
1)

Consider the reaction 2A + B

2C. 2)
Suppose that at a particular moment
during the reaction, rate of
disappearance of A is 0.076 M/s,
i) What is the rate of formation of C ?
ii) What is the rate of consumption of B ?
iii)What is the rate of the reaction ?
Given :
Rate of disappearance = 0.076 M/s
i)
To Find :
i) Rate of formation of C
ii) Rate of consumption of B
ii)
iii) Rate of reaction
Solution :
d[A]
dt
= 0.076 M/s.

Rate of disappearance of A =

i) Rate of formation of C

+d[C]
dt

Rate of disappearance of A
= Rate of formation C
= 0.076 M/s.
ii) Rate of consumption of B =
d[A]
dt

d[B]
= 2
=
dt
d[B]
dt

d[B ]
dt

d[I ]
dt

d[S2 O82 ]
?
dt

d[SO 2
4 ]
= 2.2 102 M/S
dt
To Find :

d[I ] d[S 2 O 2
8 ] d[I 3 ]
,
,
dt
dt
dt
Solution :

d[SO 2
4 ]
= 2.2 102 M/s
dt

2[SO24] =

1 d[SO 2
4 ]
2
dt

Rate of formation of SO 2
4
1
2.2 102
2
= 1.1 102 M/s

1 d[A]
2 dt

1 d[C]
2 dt

d[I3 ]
at the same time ?
dt
Given :

= 0.038

d[B]
=
dt

d[SO2
4 ]
= 2.2 102 M/s.
dt
What are the values of

iii)

1 d[A]
2 dt

0.076
=
2

iii) Rate of reaction =

d[B]
dt

Consider the reaction

3I(aq) + S2O2
I3(aq) + 2SO2
8(aq)
4(aq)
At a particular time t,

i)

Rate of disappearance =

1 d[I ]
3 dt

1 d[S2O2
8 ]
2
dt

1
[0.076] = 0.038
2
Chemical Kinetics

.. 2

Rate of disappearance of [I]

2 ( 0.12 )

ii)

1 d[ I ]
3 dt

= 1.1 102M/s

d[I ]
= 3.3 102M/s
dt
]
Rate of disappearance of [S2O2
8

2
2

1
d[SO 4 ]
d[S 2 O 8 ]
=
=
2
dt
dt
Rate of disappearance

d[S 2 O 2
8 ]
= 1.1 102M/s
dt
Rate of formation of [I3]

iii)

3)

d[I 3 ]
dt

d[I3 ]
dt

1 d[SO 2
4 ]
2
dt

= 1.1 102M/s

0.160

0.24

0.244

0.160

0.06

0.244

0.320

0.12

( 0.12 )
( 0.06 )

2 ( 0.06 )

4)

k2 ( 0.244 ) 2 ( 0.320 )

k2 ( 0.244 ) 2 ( 0.160 )

( 0.320 ) y
( 0.160 ) y

2 = 2y
y = 1
Thus the order of reaction with respect
to B is first order
Dividing equation (i) by (ii)
2 ( 0.24 )

Consider the reaction

2C + D. From the
2A + 2B
following data, calculate the order and

rate constant of the reaction.

[B]0 /M
r0 /Ms
[A]0 /M
0.488

2 ( 0.06 )

k2 ( 0.488 ) 2 ( 0.160 )

k2 ( 0.244 ) 2 ( 0.160 )

4 = 2x
x = 2
Thus the order of reaction with respect
to A is second order
Rate = k [A]2 [B]
Order of reaction :
A is second order and B is first order
Over all order of reaction is third order
R
= k[A]2 [B]
0.24
= k[0.488]2 [0.160]
0.24
= k[0.238] [0.160]
k
= 6.30 M2s1

For the reaction

2A + 2B
products. Find the rate
law from the following data

[B] /M
ra te/Ms1
[A] /M
Write the rate law of reaction.
0.3
0.05
0.15
Solution :
Let the rate of the reaction be given by
0.6
0.05
0.30
R = k[A]x[B]y
0.6
0.20
1.20
When the concentration of A and B is
What is the rate constant and order of
doubled the rate is doubled
the reaction ?

2R = k[2[A]x][2[B]y]
Thus, the rate law for the three cases can Solution :
Let the rate law of the reaction be given
be written as
x
y
by
2(0.24) = k 2(0.488) 2(0.160) ......(i)
x
y
R = k[A]x[B]y
2(0.06) = k 2(0.244) 2(0.160) ......(ii)
When the concentration of A is doubled
2(0.12) = k 2(0.244)x 2(0.320)y ......(iii)
rate is doubled
Dividing equation (iii) by (ii)
Chemical Kinetics

.. 3

2R = k[A]x [B]y
Thus, the rate law for three cases can be
written as
2(0.15) = k 2(0.3)x 2(0.05)y
......(i)
......(ii)
2(0.30) = k 2(0.6)x 2(0.05)y
x
y
2(1.20) = k 2(0.6) 2(0.20) ......(iii)
Dividing equation (iii) by (ii)
2 ( 1.20 )
2 ( 0.30 )

5)

k 2 ( 0.6 ) 2 ( 0.05 )

4 = 4
y = 1
Thus the order of reaction with respect
to B is first order
Dividing equation (ii) by (i)

2 ( 0.15 )

k 2 ( 0.6 ) 2 ( 0.20 )

2 ( 0.30 )

k 2 ( 0.6 ) 2 ( 0.05 )

k 2 ( 0.3 ) 2 ( 0.05 )

To Find :
Rate constant (k)
Solution :
Rate of Reaction

1.1 104 M/s =

1.1 104 M/s =

0.0216M 2
1.1 104 /s
2.16 102 M

= k[C2 H4Br2][I ]
k[0.12M][0.18M]
k[0.0216M2 ]

= k

= k

k =

2 = 2x
x = 1
Thus the order of reaction with respect
to A is first order
Over all order of reaction is second order
Rate
= k[A] [B]

Substituting the values

0.15
= k[0.3] [0.05]
6)
0.15
= k[0.015]
k
= 10 M1s1

The rate law for the reaction

C2H4 + 2B
C2H4Br2 + 3I

r + I3 is the rate = k[C2H4Br2][I ]. The

rate of the reaction is found to be
1.1 104 M/s when the concentrations

of C2H4Br2 and I are 0.12 M and 0.18 M

respectively. Calculate the rate constant
of the reaction.
Given :
Rate of reaction (R) = 1.1 104 M/s
Concentration of C2H4Br = 0.12 M

Concentration of I = 0.18

Rate = k[C2H4Br2][I ]

1.1 104 M /s

=?

1.1 104 / s
2.16 102 M

= Al log 1.1 = 0.04139

2
log 2.16 = 0.3344 10

1.7070

= Al 1.7070 102
1

= 5.09 10 102
= 5.09 103 M1 s1
k = 5.1 103 M1 s1

Consider the reaction.

A2 + B
products. If the
concentration of A2 and B are halved,
the rate of the reaction decreases by the
factor of 8. If the concentration of A is
increased by a factor of 2.5, the rate
increases by the factor of 2.5. What is
the order of the reaction ? Write the rate
law.
Solution :
A2 + B
products
Let the rate of reaction be
x
y
Rate1 = k[A2] [B]
If the concentration of A 2 and B are
halved the new rate of reaction is
x

A B
Rate2 = k 2
2 2

Also, Rate2 =

Rate 1
8

Chemical Kinetics

.. 4

7)

Rate 2
Rate 1

Rate 2
Rate 1

A B
k 2
2 2
=
y
k[A 2 ]x [ B ]

1
8
x

x
y
1 1
k [A 2 ] [ B]
2 2
=
y
k[A 2 ]x [ B]

1
=
2

1
8
3

x+ y

Rate 3
Rate 1

= 2.5

Rate 3
Rate 1

y
x
k ( 2.5 )( A 2 ) [ B]

=
x
y
k [A 2 ] [ B]

x
k2 [ C ] D y
rate 2

Hence,
=
x
y
rate1
k [ C] [D]

x+ y

1
1
=

2
2
x+y
= 3
... (i)
Also, Rate3 = k[(2.5)(A2)x][B]y
Rate3
= 2.5 [Rate1]

Consider the reaction

C+D
products. The rate of the
reaction increases by a factor of 4 when
concentration of C is doubled. The rate
of the reaction is tripled when
concentration of D is tripled. What is
the order of the reaction ? Write the rate
law.
Solution :
C+D
products
The rate law of the reaction is of the form
x
y
Rate1 = k[C] [D]
i)
If the concentration of [C] is doubled the
x
y
new rate of law is rate2 = k2[C] [D]

ii)

k ( 2.5 ) [A 2 ] [ B ]
x

k [A 2 ] [ B ]

2.5 = (2.5)x
x = 1
A is first order reaction
Substituting the value of x in (i)

1+y = 3
y = 31
y = 2.

B is second order reaction The overall

reaction is third order. Rate = k[A2][B]2

Chemical Kinetics

rate 2
= 2x
rate1

But when C is doubled the reaction rate

increases four times of rate1 is
rate2 = 4(rate1)
4 = 2x
x = 2
Hence C is of second order.
If the concentration of D is tripled the
new rate law is
x
y
rate3 = k[C] [3[D] ]
rate 3 = 3[Rate1]
rate 3
kC x 3y D y
Therefore rate =
1
kC x D y

rate3
rate1

= 3

3rate 1
rate 1

= 3

y = 1
Hence D is first order reaction.
Order of Reaction is third order.
And Rate of reaction = k[C]2[D]

.. 5
8)

The reaction
F2(g) + 2ClO2(g)
2FClO2(g) is first
order in each of the reactants. The rate
of the reaction is 4.88 104 M/s when
[F2] = 0.015 M and [ClO2 ] = 0.025 M.
Calculate the rate constant of the
reaction.
Given :
Rate of reaction = 4.88 104 M/s
Concentration of F2 = 0.015 M
Concentration of ClO2 = 0.025 M
To Find :
Rate constant (k)
Formula :
Rate of reaction = k[F2][ClO2 ]
Solution :
Rate of reaction = k[F2][ClO2 ]

4.88 104 M/s = k[0.015M][0.025 M]

4.88 104 M/s = k 0.000375 M2

4.88 104 M/s = k 3.75 104 M2

k =

k =

4.88 10 4 M /s
3.75 10 4 M 2
4.88 104
3.75 10 4

= AL log 4.88 = 0.68842

log 3.75 = 0.57403

0.11439

= AL(0.11439)
k = 1.3 M1 S1

9)

Concentration of NO = 0.025 M
Rate constant (k)
= 0.42 M2 s1
To Find :
Rate (R)
Formula :
Rate = k[H][NO]2
Solution :
Rate = k[H][NO]2
Rate = 0.42 M2 s1 [0.015 M][0.025 M]2

Rate = 0.42 0.015 (0.025)2

= 42 102 15 103 (25 103)2
= 42 15 (25)2
[102 103 106]
= 42 15 (25)2 1011

=
1.6232
Al log 42
+log 15 =
1.1760

1011
+2 log 25 = 1.13979 2

5.5950

=
=
=
Rate =

Al(5.5950) 1011
3.935 105 1011
3.935 106
3.97 106 M/s

10)

In acidic solution sucrose is converted

to a mixture of glucose and fructose in
pseudo first order reaction. It has been
found that the concentration of sucrose
decreased from 20 mmol L 1 to
8 mmol L1 in 38 minutes. What is the
half life of the reaction ?
Given :

The reaction
2H2(g) + 2NO(g)
2H2O(g) + N2(g) is first
+H2O
C6H12O6 + C6H12O6
C12H22O11
order in H2 and second order in NO.
The rate constant of the reaction at a
Sucrose
Glucose Fructose
certain temperature is 0.42 M 2 s 1 .
t = 38 minutes
Calculate the rate when [H2] = 0.015 M
[A]0 = 20 mmol L1
and [NO] = 0.25 M.
[A]t = 8 mmol L1
Given :
To Find :
H2 is first order
= [H]
Half life (t1/2)
NO is second order = [NO]2
Concentration of H2 = 0.015 M

Chemical Kinetics

.. 6
Solution :

Formula :
i)

k =

0.693
t

ii)

k =

[A ]0
2.303
log 10
t
[A ]t

i)

k =

0.693
t1 / 2

0.693
102

Solution :
i)

= 0.0068.

[A ]0
2.303
log 10
t
[A ]t

[A ]0
2.303
log 10
t
[A ]t

ii)

k =

2.303
20
log 10
38
8

0.0068

[ 100]
2.303
log 10
t
[ 80]

2.303
log 10 2.5
k =
38
k = 0.06 log 2.5
k = 0.024278 min1

0.0068

2.303
log 10 1.25
t

0.0068

2.303
0.0969
t

2.303 0.0969
0.0068

k =

k =

ii)

0.693
Now, k = t
1/2

0.693
0.024 = t
1/2

0.693
0.024
t1/2 = 28.87 min.

t1/2 =

11)

The half life of a first order reaction is

1.7 hours. How long will it take for 20%
of the reactant to disappear ?
Given :
t1/2
= 1.7 hours = 102 min

[A]0 = 100
[A] t = 100 20 = 80
12)
To Find :
time (t)
Formula :
i)

k =

0.693
t1 / 2

ii)

k =

[A ]0
2.303
log 10
t
[A ]t

Chemical Kinetics

2.303 969 10 4
68 10 4

= Al log 2.303 =
+log 969 =

log 68 =

0.3622
2.9869
3.3485

1.8325

1.5160

= Al(1.5160)
= 32.809 min
t = 32.809 min

The gaseous reaction A2

2A is first
order in A2. After 12.3 minutes 65% of
A2 remains undecomposed. How long
will it take to decompose 90% of A2 ?
What is the half life of the reaction ?
Given :
t
= 12.3 min
At
= 65
= 100
A0

.. 7
To Find :
half life (t1/2)
Formula :
i)

ii)

k =

k =

[A]0
2.303
log 10
t
[A]t

0.693
t 1/2

Solution :
k =

[A]0
2.303
log 10
t
[A]t

k =

2.303
100
log 10
12.3
65

k =

2.303
log101.538
12.3

0.693
0.035

t1 2

t1 2

= 19.8 min

= 19.8 min

13)

The rate constant of a first order reaction

is 6.8 104s1. If the initial concentration
of the reactant is 0.04 M, what is its
molarity after 20 minutes ? How long
will it take for 25% of the reactant to
react ?
Given :
k
= 6.8 104s1
[A0 ] = 0.04 M
t
= 20 min
= 20 60 = 1200 sec.
To Find :
Molarity (M)
time (t)
Formula :

2.303
0.187
12.3
[A]0
2.303
k = 0.035
log
k =
t
[A]t
Time required for decomposition of
90%of A2 is
Solution :
A0 = 100
A t = 100 90 = 10
=
i)
6.8 104
[A]0
2.303
log 10
k
=
t
[A]t
6.8 10 4 1200

=
2.303
2.303
[100]
log 10
0.035 =
t
[10]

0.3545 =
2.303
log10 10
0.035 =
t

Antilog (0.3545) =
2.303
0.035 =
1
t

2.261
=
2.303
t =
0.035
t = 65.8

At
=

ii)

i)

k =

0.035 =

0.693
t1 2
0.693
t1 2

A t = 0.0177 M

ii)

6.8 104

2.303
[0.04]
log 10
1200
[A t ]

log

[0.04]
[A t ]

[0.04]
log [A ]
t
0.04
[A t ]
0.04
[A t ]

0.04
2.261

2.303
0.04
log 10
t
0.03
[25% of 0.04 = 0.01]
Chemical Kinetics

.. 8

6.8 104

t
t

=
=

2.303
log10 1.3333
t
[ 0.04 0.01 = 0.03]

2.303
6.8 104

k =

[A]0
2.303
log
t
[A]t

Solution :

log10 1.333

2.303 0.124
2.303 124 103
6.8 104

= AL(1.6231) 10
= 41.98 101
= 420 sec

[A]0
2.303
log
t
[A]t

i)

k =

3.12 103 =

2.303
[0.045]
log 10
t
[0.02]

3.12 103 =

2.303
log10[2.25]
t

3.12 103 =

2.303
0.3521
t

6.8 10 4
101

= Al log 10 2.303 = 0.3622

+ log 124 = 2.0934
10

2.4556 10 1

= 0.8325
log 10 6.8

1.6231

Formula :

420
=
60
= 7 min
= 7 min.

14)

The rate constant of a certain first order

reaction is 3.12 103 min1
i)
How many minute does it take for the
reactant concentration to drop to 0.02 M
if the initial concentration of the
reactant is 0.045 M ?
ii)
What is the molarity of the reactant after
1.5 h ?
Given :
k
= 3.12 103 min1

A0
= 0.045 M
At
= 0.02 M
ii)
To Find :
i)
t
ii)
[At]

3.12 103
2.303 0.3521
3.12 10 3
2.303 3521 104
3.12 10 3
2.303 3521
101
3.12

= Al log 10 2.303 = 0.3622

+log 3521 = 3.5466
10

3.9088 101

log 10 3.12 = 0.4941

3.4147

=
=
=
=

Al (3.4147) 101
2598.364
259.836 min
259.839 min.

= 1.5 hrs
= 1.5 60
= 90 min
k =

Chemical Kinetics

2.303 0.3521

[A]0
2.303
log 10
t
[A]t

MAHESH TUTORIALS SCIENCE

k2
k1

k2
k2
k2

18)

.. 11
=
=
=
=

= Al (0.30081)
=
=
=
=

1.9989
k1 1.9989
3.7 105 1.9989
7.4 105

Al (4.7394)
54878.21
54.878 103 kJ/mol
54.878 J/mol

19)

The activation energy for a certain

reaction is 334.kJ mol1. How many times
larger is the rate constant at 610 K than
the rate constant at 600 K ?
Given :
Ea = 334.4 kJ/mol = 334.4 103 J/mol
T1 = 600 K, T2 = 610 K
To Find :
k1
Formula :

What is the activation energy for a

reaction whose rate constant doubles
when temperature changes from 300C to
400 C ?
Given :
T1 = 300C = 303 K,T2 = 400C = 313 K
Rate constant doubles when temperature
changes from 300C to 400C.
Ea T2 T1
k

k2 = 2k1
log10 2
=

2.303R T1 T2
k1
To Find :
Activation energy Ea
Solution :
Formula :
k2
log10
=
Ea T2 T1
k2
k1
log10
=

2.303R T1 T2
k1
334.4 103 610 600
Solution :

2.303 8.314 610 600

E a 313 303
2k 1
log10
=
2.303R 313 303
334.4 103
k1
=
2.73 105
2.303

8.314
Ea
1.05 10 4
log102
=
k2
2.303 8.314
334.4 103 2.73 105
log
=
k1
2.303 8.314
0.3010 2.303 8.314

Ea
=
4
1.05 10
= Al log 334.4 = 2.5242
4
+log 2.73 = 0.4361
3010 10 2.303 8.314

Ea
=

1.05 10 4
2.9603

102
log
2.303
=
0.3622

+log 8.314 = 0.9198

= Al log 3010 = 3.4785

+log 2.303 = 0.3622

= 1.2820

+log 8.314 = 0.9198

4.7605

= Al 2.9603
log 1.05 = 0.0211

1.2820 10

4.7394
1.6783

Chemical Kinetics

MAHESH TUTORIALS SCIENCE

.. 13

The rate law for the reaction

2H2(g)+ 2NO(g)
N2(g)+ 2H2O(g) is
given by rate = k[H2] [NO]2. The reaction
occurs in the following steps :

N 2O + H 2O
i)
H2 + 2NO

ii)
N 2O + H 2
N 2 + H 2O
What is the role of N 2 O in the

mechanism ? Identify the slow step.

Solution :
2H2(g) + 2NO(g)
N2(g)+2H2O(g)
Rate = k[H2][NO]2
25)
H2 + 2NO
N2O + H2O

23)

i)

ii)

N2O + H2
N2 + H2O
N 2 O is formed in the first step and
consumed in the second step. Hence, it
is the reaction intermediate.
H2 + 2NO
step.

N2 O + H 2O is a slow

24)

log10 7.5 105

Ea
8.333 10 4
2.303 8.314
log10 7.5 + 5 log10 = Ea 0.4352 104
log10 7.5 + 5 1 = Ea 0.4352 104

5.875061
0.4352 10 4

Ea = 134.99 103 J/mol

= 135 kJ/mol.

The rate constant of a first order reaction

at 25 0 C is 0.24 s 1 . If the energy of
activation of the reaction is 88 kJ mol1 ,
at what temperature would this reaction
have rate constant of 4 102 s1 ?
Given :
k2 = 0.24 s1
T2 = 250 C = 25 + 273.15 = 298 K
Ea = 88 kJ mol1 = 88 103 J mol1
k1 = 4 102 s1
To Find :
Temperature (T2 )
Formula :

The rate of a reaction at 600 K is

7.5 10 5 times the rate of the same
reaction at 400 K. Calculate the energy
of activation for the reaction.
Given :
Rate1 = 8.314 Jk1 mol1,
Rate2 = 7.5 105 (Rate1),
log10
T1 = 600 k, T2 = 400 k.
Solution :
To Find :
Ea
log10
Formula :

log10

Ea T2 T1
k2
=

2.303R T1 T2
k1

Solution :

log10

Ea T2 T1
k2
=

2.303R T1 T2
k1

log10

7.5 10 5 k 1
k1
=

Ea
600 400
2.303 8.314 600 400

= Ea

log10

k2
=
k1

Ea T2 T1

2.303R T1 T2

k2
=
k1

Ea T2 T1

2.303R T1 T2

0.24
0.04

88 103 298 T1

=
19.147 T1 .298

log10 6

0.7782

88 103 298 T1

2.303 8.314 T1 .298

88 103
=
19.147

0.7782 19.147
88 10

298 T1

T1 .298

298 T1
=

T1 .298
Chemical Kinetics

MAHESH TUTORIALS SCIENCE

.. 14

298 T1
7782 19.147 104 103

=
88
T1 .298

log 7782 = 3.8910

+log 19.147 = 1.2821

298 T1
5.1731 107 =
Al

T1 .298

log
88
=
1.9444

3.2287

1.693 104

298 T1
=
T1 .298

T1

T1
298 T1
298 T1
298
298

= log10A

Ea
2.303RT

A
Ea
= log10
K
2.303RT
Solution :
Ea
A
= log10
2.303RT
k

56 103 Jmol 1

2.303 8.314 Jk mol

298 T1
Al (3.2287) 107 =

T1 .298

1.693 104 298

=
0.0504 T1
=
0.050 T1
=
1.0504 T1
=

log10 k

log10

298
1.0504

) 773.15K
A

1.6 103 M 1s1

= 4.7481
log 56
log 2.303 = 0.3622

Al
103
+log 8.314 = 0.9198

+log 773.151 = 2.8882

4.1702

= log10

1.6 103

26)

Chemical Kinetics

56000
A
= log10
2.303 8.314 773.151
1.6 103

T1 = 283.7 K
The rate constant for a reaction at 5000 C
is 1.6 103 M1 s1. What is the frequency
factor of the reaction if its energy of
activation is 56 kJ mol1.

Given :
T = 5000 C = 500 + 273.15 = 773 K,
k = 1.6 103 M1 s1,
Ea = 56 kJ mol1

= 56 103 J mol1
To Find :
Frequency Factor (A)

Formula :
k = AeEa / RT

E
log10 k = log10A a
RT

Al

4.7481
4.1702
A
103 = log10
=
1.6 103
0.5779

3.783 = log10

3.783 = log10

A
1.6 103
A
1.6 103 M 1s1

Antilog (3.783)

1.6 103 M 1s1

6067.363 1.6 10 M1 s1 = A
A
= 9707780.8 M1 s1
= 9.71 106 M1 s1
3

MAHESH TUTORIALS SCIENCE

.. 15

27)

A first order gas-phase reaction has an

energy of activation of 240 kJ mol1. If
the frequency factor of the reaction is
1.6 1013 s1, calculate its rate constant
at 600 K.
Given :
E a = 240 kJ mol1 = 240 103 J mol1,
A = 1.6 1013 s1,
T = 600 K
To Find :
Rate constant (k)
Formula :
A
Ea
= log10
K
2.303RT
Solution :
Ea
A
= log10
2.303RT
k

240 103 J mol 1

2.303 8.314 Jk 1mol 1 600K

log10
2400
2.303 8.314 6

log 2400

Al log 2.303
+log 8.314

+log 6

1.6 10 13 s 1
k

= log10

1.6 1013
k

= 3.3802
13
= 0.3622 = log 1.6 10
10
k
= 0.9198

= 0.7781

240 103
11488.285

= log10

20.8908

= log10

7.7768 1020

1.6 10 13 s 1
k

1.6 10 13 s 1
k

1.6 10 13 s 1

7.7768 10 20
= 2.057 108s1

28)

The half life of a first order reaction is

900 min at 820 K. Estimate its half life
at 720 K if the energy of activation of
the reaction is 250 kJ mol1 .
Given :
(t1/2) = 900 min
T1
= 820 K
T2
= 720 K
= 250 kJ mol1
Ea
= 250 103 J mol1
To Find :

k2
k1
Formula :

i)

log

ii)

i)

k2
k1

Ea T2 T1

2.303R T1 T2

k2
k1

( t 1 / 2 )1
( t 1 / 2 )2

1.6 10 s
k

log

k2
k1

250 103 J mol 1

720 820

1
1
720 820
2.303 8.314 Jk mol

1.6 10 13 s 1
k
13 1

Antilog (20.8908)

Solution :

3.3802
2.0601
1.6 1013
= log
Al
10
k
1.3201

k2
log10
=
k1

250 103 100

19.147 590, 400
Chemical Kinetics

MAHESH TUTORIALS SCIENCE

.. 16

k2
log10
= 13056.876 [ 1.6938 104]
k1

k1
k1

= 3.838 103 0.1458

= 5.595 104 s1

k2
log10
= 2.2116
k1

ii)

k2

[A 0 ]
2.303
log10
[A t ]
t

k2
= Antilog ( 2.2116)
k1

[A0 ] = 0.624
[At] = 0.318
t
= 1200 s

k2
= 6.1433 103
k1

k2

k2
k2
k2

= 1.919 103 log [1.962]

= 1.919 103 0.2927
= 5.616 104 s1

iii)

k3

ii)

k2
k1

( t 1 / 2 )1
( t 1 / 2 )2
900

29)

6.1433 10

( t 1 / 2 )2

6.1433 103
(t1/2) 2 = 146.50 103
(t1/2) 2 = 1.465 105min

From the following data for the liquid

phase reaction A
B, determine the
order of the reaction and calculate its
rate constant.
0

t/s
[A]/mol L

600

1200

0.624 0.446 0.318 0.226

k1

[A 0 ]
2.303
log10
[A t ]
t

[A0 ] = 0.624
[At] = 0.446
t
= 600 s

[0.624]
2.303
log
[0.446]
600

k1

k1

= 3.838 103 log [1.399]

Chemical Kinetics

[0.624]
2.303
log
[0.226]
1200

k3

k3
k3
k3

= 1.279 103 log [2.7615]

= 1.279 103 0.4411
= 5.641 104 s1

All the k values calculated at different

time intervals are the same. This implies
that the reaction obeys the integrated rate
equation of first order reaction. Hence,
the reaction is a first order reaction.

1800

Solution :
We require to calculate the rate constant
at different time intervals.

i)

[A 0 ]
2.303
log
[A t ]
t

[A0 ] = 0.624
[At] = 0.226
t
= 1800 s

900

(t1/2) 2 =

[0.624]
2.303
log
[0.318]
1200

30)

The following results were obtained in

the decomposition of H 2 O 2 in KI
solution at 300C
t/s

100

200

300

Volume of O2
collected/cm3

7.3

13.9 19.6 65.0

Show that the reaction is first order.

Calculate the rate constant of the
reaction.
To Find :
Rate constant k

MAHESH TUTORIALS SCIENCE

.. 17

Formula :

k =

2.303
a
log10
t
ax

Solution :

2H2O2 KI 2H2O(l)+ O2(g)

V = Volume of O 2 liberated after the
completion of reaction
= a = 65.0 cm3
V t = Volume of O2 liberated at time t
= amount of H 2O 2 decomposed at
time t
= x.
Hence, (a x) = V Vt

k =

2.303
a
log10
t
ax

k =

V
2.303
log10 V V
t

i)
Given :
V t = 7.3 cm3, t
Solution :
k1 =

k2 = 1.2 103 s1
iii)
Given :
V t = 19.6 cm3, t = 300s
Solution :
k3 =

Show that the time required for 99.9 %

completion of a first order reaction is
three times the time required for 90 %
completion.
Solution :
For a first order reaction,

i)

2.303
65.0
log10
100
57.7
k1 = 0.02303 log10 1.1265
k1 = 0.02303 0.05173
k1 = 1.2 103 s1

k1 =

ii)
Given :
V t = 13.9 cm3 t = 200s
Solution :
k2 =

65.0
k2 = 0.011515 log10

51.1

k2 = 0.011515 log10 1.2720

k2 = 0.011515 0.10449

[A 0 ]
2.303
log10
[A t ]
k

Time taken for 99.9% completion

Let the time taken for 99.9% completion
of the reaction t99.9%
Let initial concentration,
[A0 ] = a
Then final concentration,
[At] = a 99.9% of a
99.9
a
100
= 0.001 a

= a

t99.9% =

2.303
65.0cm 3
log10
200
( 65.0 13.9 ) cm 3

31)

= 100s

k = 1.2 103 s1
Since all the k values are constant, it is a
first order reaction.
k = 1.2 103 s1

65.0cm 3
2.303
log10
100
( 65.0 7.3 ) cm 3

2.303
65.0cm 3
log10
300
65 19.6 cm 3

a
2.303
log10
0.001a
k

2.303
log 1000 ... (i)
k
Time taken for 90% completion
Let the time taken for 90% completion of
the reaction be t90%
Let initial concentration,
[A0 ] = a
Chemical Kinetics

ii)

[A 0 ]
2.303
log10
k
[A t ]

MAHESH TUTORIALS SCIENCE

.. 18
Then final concentration,
[At] = a 90% of a
90
a
100
= 0.1 a

= a

t90%

2.303
[A 0 ]
log10
k
[A t ]

k =

2.303
a
log10
k
0.1a

2.303
log 10
k
Dividing (i) by (ii), we get

... (ii)

t 99.9% log 1000 3

=
=
1
log 10
t 90%
t 99.9%
= 3
t 90%

32)

0.65

200

1.0

k =

p0
2.303
log10
2p
200
0 pt

k =

2.303
0.65
log10
200
2 0.65 1

k =

2.303
0.65
log10
200
1.3 1

k =

2.303
0.65
log10
200
0.3

k =

2.303
log 102.1667
200

k =

2.303
0.3358
200

Given :
Pt
=
0.75 atm
Po
=
0.65 atm
To find :
Rate of reaction k
Solution :
( C H 3)2 (HN = NCH(CH 3)2
At t = 0
At t = t

Chemical Kinetics

p0
p0 p

N 2 +C 6H 14
0
p

0
p

p0
2.303
log10
2p0 p t
t

From the following data for the

decomposition of azoisopropane,
(CH3)2CHN = NCH(CH3)2(g)

N2(g) + C6H14(g)
estimate the rate of the reaction when
total pressure is 0.75 atm.

Total pressure/atm

p0
2.303
log10
t
p0 pt

when t = 200 s1 , p0 = 0.65, pt = 1

t99.9% = 3 t90%
Therefore, for a first order reaction, the
time required for 99.9% completion is 3
times that required for 90% completion.

Times/s

After time, t, total pressure,

pt = (p0 p) + p + p
pt = p0 + p
p = pt p0
p0 p
= p0 (pt p0)
= 2p0 pt
For first order reaction,

2.303 0.3358
200
k = 3.87 103 s1
When
pt
= 0.75 atm
p0 + p = 0.75
p
= 0.75 p0
p
= 0.75 0.65
p
= 0.1 atm
p0 p
= 0.65 0.1 = 0.55 atm
Rate of the reactions is
Rate
= k [Reactant]
= k [p of reactant]
= 3.87 103 s1 0.55 atm
= 2.13 103 atm s1

k =