CHEMICAL KINETICS
Chemical Kinetics: (Study of reaction rates and their mechanisms. )
Rate of Reaction : The change in concentration of reactant or product per unit time .(SI unit molL1s1).
Let a reaction : aA + bB cC + dD.
Average rate of reaction:
The rate of reaction measured over a long period of time.
Rav =
Conc. of reactants
Temperature
Surface area of reactants
4.
1
Bond dissociati on energy of reactants
5.
6.
1 3
+ =2
2 2
Rate constant :
It is defined as the rate of reaction, when the conc. of each of the reactants is unity.
The unit of rate constant for nth order = (molL1)lns1
Reaction
n
Units of rate constant
zero order
0
mol L1s1
1st Order
1
s1
2nd Order
2
mol1L s1
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2
CHEMICAL KINETICS
Molecularity of a reaction :
The number of reacting species which collide simultaneously to bring about a chemical reaction.
Molecularity = a + b
eg.
NH4NO2 N2 + 2H2O
(Unimolecular reaction)
2HI H2 + I2
(Bimolecular reaction)
2NO + O2 2NO2 (Tri or termolecular)
Rate
Thus
k=
eg. 2NH3(g)
- d[R ]
= k [R ]o
dt
[R ]o -[R ]
t
Pt
1130 K
N2(g) + 3H2(g)
Rate = k[NH3] = k
First order reaction: R P
So.
Rate =
Thus k =
eg.1
eg.2
[R]o
2.303
log
t
[R ]
eg.3
- d[R]
= k [R ]
dt
22
42 He + 86
Rn
eg.
t1/2=
[R]o
2k
2.303
k
log2 =
0.693
k
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CHEMICAL KINETICS
3
Psendo First Order reaction :
A reaction which behaves as a first order reaction even when there is more than one concentration involved. It is
because the other concentration is in large excess or present as a catalyst for which the concentration does not
change.
eg.1 Hydrolysis of cane sugar.
C12H22O11 + H2O
H+
C6H12O6
(excess)
eg.2
t=0
t
Thus.
C6H12O6
Glucose
Fructose
Hydrolysis of ester
CH3COOC2H5 +
H2O
CH3COOH +
C2H5OH
0.01 mol
10 mol 0 mol
0 mol
0 mol
9.9 mol0.01 mol
0.01 mol
'
Rate = k [H2O][CH3COOC2H5]
[H2O] taken as constant as it does not altered much.
Rate = k[CH3COOC2H5]
I
+
H
H
I
+
I
P.E
A
H2 + I2
Reaction Co-ordinate
t
t +10
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4
* If rate constants of a reaction at T1 and T2 are K1 and K2,
log
CHEMICAL KINETICS
K2
1
Ea 1
=
K1 2.303R T1 T2
ZAB = Collision frequency : No. of collisions per second per unit volume of the reaction mixture.
Effective collistion :
The collisions in which molecules collide with suffcient K.E. (Called threshold energy) and proper orientation, so as
to facilitate breaking of bonds between reacting species and formation of new bonds to form products are called as
effective collisions.
Threshold Energy = Ea + energy possesed by reacting species.
*
To account for effective collisions another factor 'P' called steric factor was introduced.
Rate = PZAB eEa/RT .
H
Improper
H
H
_
C Br + OH
Orientation
_
C Br
H
Proper
HO
H
Orientation
OH
No products
H
C
H
Br
H
HO C H + Br
H
Solved Problems
Q.1
Sol.
For the reaction R P, the concentration of a reactant changes from 0.03 M to 0.02 M in 25 minutes.
Calculate the average rate of reaction using units of time both in minutes and seconds.
[R]
[R] - [R]
D
2
1
Average rate = Dt = - t - t = 2
1
0.02M - 0.030 M
25min
-0.01M
-4
-1
= 25 min = 4 10 Mmin
-0.01M
-6
-1
= 25 60 s = 6.66 10 M s
Q.2
Sol.
The decomposition of NH3 on platinum surface is zero order. What are the rates of production of N2 and
H2 if k = 2.5 104 mol1 Ls1 ?
2NH3(g) Pt N2(g) + 3H2(g)
Rate of reaction
dx - 1 d[NH3 ] d[N2 ] 1 d[H2 ]
=
=
=
dt
2
dt
dt
3 dt
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CHEMICAL KINETICS
Rate of production of N2 = Rate constant
Q [Rate = K [NH3 ] = K ]
In a Pseudo first order hydrolysis of ester in water, the following results were obtained.
t/s
Sol.
0
30
60
90
0.55 0.31 0.17 0.085
(i) Calculate the average rate of reaction between the time interval 30 to 60 seconds
(ii) Calculate the pseudo first order rate constant for the hydrolysis of ester.
(i) Average rate of reaction
=
= 4.67 103L1s1
(ii)
k=
[A ]
2.303
log 0
[A ]
t
Where [A0] = 0.55 M is initial concentration of ester ( t = 0 ) and [A] is the concentration of ester at time t.
At 30 sec :
k1 =
2.303
0.55
log
30
0.31
At 60 sec :
k2 =
2.303
0.55
log
60
0.17
At 90 sec :
k3 =
2.303
0.55
log
90
0.85
Thus, Average
k=
k1 + k 2 + k 3
3
Sol.
Q.5
In a reaction between A and B, the initial rate of reaction (r0) was measured for different initial
concentration of A and B as given below:
0.20
0.20
0.40
0.30
0.10
0.05
Rate(r0 ) / mol L-1S -1 5.07 10-5 5.07 10 -5 1.43 10- 4
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Sol.
CHEMICAL KINETICS
Let the rate of reaction, r = k [A]m [B]n
(r1) 5.07 105 = k [0.20]m [0.30]n
(r2) 5.07 105 = k [0.20]m [0.10]n
(r3) 1.43 104 = k [0.40]m [0.05]n
From experiment (i) and (ii)
r2 5.07 10 -5 Ms -1
=
5.07 -5 Ms -1
r1
......Exp (i)
......Exp (ii)
......Exp (iii)
k (0.20 )m (0.10 )n
k (0.20 )m (0.30 )n
0.10
0.30
=1
or
3n = 1
3n = 3
\
n=o
From experiment (i) and (iii)
r3 1.43 10 -4 Ms -1
=
-5
-1
r1 5.07 10 Ms
k (0.40 )m (0.05 )n
k (0.20 )m (0.10 )n
2.8 = (2)m or
m log2 = log 2.8
m 0.3010 = 0.4472
0.4472
= 1.49
0.3010
n=
Q.6
Sol.
Q.7
Sol.
Thus, order of reaction with respect to A is 1.49 and order with respect to B is zero. So rate law is, Rate k [A]1.49
[B]
Calculate the half-life of a first order reaction from their rate constants given below:
(a) 200 s1
(b) 2 min1
(c) 4 years1
(a)
t1/2 =
(b)
t1/2 =
0.693 0.693
=
k
200
0.693 0.693
=
k
2
(c)
t1/2 =
0.693 0.693
=
k
4
= 3.465 103 s
= 3.465 101 min
= 0.17325 years
The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing wood has
only 80% of the 14C found in a living tree. Estimate the age of the sample.
t1/2 = 5730 years
14
If R0 is the initial C activity in a living tree = 100
Activity in the dead wood R = 80
The nuclear radioactive decay follows the first order kinetics so
t=
[R ]
2.303
log 0
[R]
k
0.693
k= t
1/ 2
t=
2.303 t1/ 2
100
log
0.693
80
= 1845.4 years
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CHEMICAL KINETICS
7
1
Q.8 The rate constant for a first order reaction is 60 s . How much time will it take to reduce the initial
concentration of the reactant to its 1/16th value?
Sol.
k=
t=
[R ]
2.303
log 0
[R]
t
[R ]
2.303
log 0
[R]
k
1
2.303
log
1/ 16
60
= 0.0462 s1
During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If 1 mg of 90Sr was
absorbed in the bones of a newly born baby instead of calcium, how much of it will remain after 10 years
and 60 years if it is not lost metabolically?
0.693
0.693
,k=
T1/2 Sr90 = 28.1 years, k = t
28.1
1/ 2
Sol.
We know,
Now,
k=
t=
year1
[R ]
2.303
log 0
[R]
k
[R ]
2.303
log 0
[R]
k
At t = 10 year 10 =
[R ]
2.303 28.1
log 0
[R]
0.693
log
[R0 ]
[R] = 0.1070
[R0 ]
[R] = antilog (0.1070) = 1.279
So,
[R] =
At t = 60 year 60 =
1mg
1.279
= 0.7818 mg
[R ]
2.303 28.1
log 0
[R]
0.693
log
[R0 ]
[R] = antilog 0.9409
= 4.374
So,
Q.10
Sol.
[R] =
1mg
4.374
= 0.228 mg.
For a first order reaction, show that time required for 99% completion is twice the time required for the
completion of 90% of reaction.
t=
[R ]
2.303
log 0
[R]
k
2.303
100
log
k
l
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CHEMICAL KINETICS
=
2.303
k
log 102
2.303
k
[R ]
2.303
log 0
[R]
k
t90% =
Q.11
Sol.
2.303
k
log
100
10
2.303
k
log 10
2.303
k
t 99% 2.303 2
k
=
t 90%
k
2.303
or
t99% = 2 t90%
=2
A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
t1/2 =
k=
0.693
k
[R ]
2.303
log 0
[R]
t
2.303
k
2.303
0.1549
40
t1/2
0.693
k
log
100
70
0.693
8.918 10 -3
2.303
k
log
10
7
min1
= 77.7 min.
Q.12 The following data were obtained during the first order thermal decomposition of SO2Cl2 at constant
volume:
SO2Cl2(g)
SO2(g) + Cl2(g)
Experiment
1
2
Time / s-1
0
100
Calculate the rate of the reaction when total pressure is 0.65 atm.
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CHEMICAL KINETICS
Sol. Suppose initial pressure of SO2Cl2 is Pi and its pressure decreases by x atm after time t then
SO2Cl2(g)
SO2(g) +
Cl2(g)
Initial pressure (at t = 0) 0.5 atm
0
0
Pressure (at time = t) 0.05 x
x
x
Ptotal at time t = 0.5 x + x + x = 0.5 + x atm
i.e.,
0.6 = 0.5 x
or
x = 0.6 0.5 = 0.1 atm
Now, Pi = 0.5 atm and P(at time 100 sec) = 0.5 x = 0.5 0.1 = 0.4 atm
(a) Evaluation of k :
k100
(b)
Initial pressure
2.303
t
2.303
t
log
2.303
100
2.303
=
100
0.5
0.4
log 1.25
0.0969 = 2.23 103 s1
Sol.
179900 J mol -1
2.303 8.314 J k -1 mol -1 546 K
= 4.6184 + 17.21
log A
= 4.6184 + 17.21
= 12.5916
= antilog 12.5916
= 3.9 1012 s1.
Q.14 The decomposition of A into product has value of k as 4.5 103 s1 at 10C and energy of activation 60 kJ
mol1. At what temperature would k be 1.5 104 s1?
Sol.
k2
Ea
T2 - T1
1.5 10 4
4.5 10
T2 - 283
60000
T2 - 283
or
0.5228
3133 .62
T2 - 233
= 283 T
2
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CHEMICAL KINETICS
1.67 104 283 =
T2 - 283
T2
0.0472 T2 = T2 283
T2 0.0472 T2 = 283
0.9528 T2 = 283
Hence,
T2 =
283
0.9528
= 297.02 K .
Q.15 The time required for 10% completion of a first order reaction at 298 K is equal to that required for its
25% completion at 308. If the value of A is 4 1010s1, calculate k at 308 K and Ea.
Sol.
k298 =
Similarly,
[R ] 2.303 100
2.303
log 0 =
log
[R]
k
k
90
k308 =
..........(i)
100
2.303
log
75
t
..........(ii)
As time required for 10% completion = time required for 25% completion.
k 308 log100 / 75 0.1249
=
=
k 298 log100 / 90 0.0457
= 2.733
or
Ea =
=
Ea
308 - 298
2.303 8.314 308 298
1089 10- 4
= 76658 J mol1
Now,
or
k308
= A . e -Ea / RT
= 10.602
76658
2.303 8.314 308
k308
= antilog (2.396)
= 4.02 103 s1.
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CHEMICAL KINETICS
11
Q.16 The rate of reaction quadruples when the temperature changes from 298 K to 313 K. Calculate the
energy of activation of the reaction assuming that it does not change with temperature.
Sol.
T1 = 293 K ; T2 = 313 K
According to Arrhenius equation
Ea T2 - T1
k
log 2 =
k1 2.303 R T1T2
T1T2
k2
Ea = 2.303 R T - T log k
1
1
2
T1T2
T2 - T1
293 313
313 - 293
and
log
4
k2
= log = log 4 = 0.6021
1
k1
Ea
4
2.303 8314 JK -1mol-1 293 313
log
1
313 - 293
Ea
Now,
= 4585.45 K
Sol.
d[F ]
1 d[NO2 ]
- 1 d[NO2 ]
=- 2 =+
2
dt
dt
2 dt
[ ]
[ ]
- 1 d Br BrO3- 1 d H+
1 d[Br2 ]
= -d
=
=
dt
6 dt
3 dt
5 dt
Q.18 A first order reaction has specific rate constant 103 sec1. How muct time time will it take for 10 g to
reduce to half of the quantity?
Sol.
Half-life period for the first order reaction is given by the expression.
0.693
k
t 0 .5 =
Now,
\
k = 103 sec1
t0,5 =
0.693
10 -3
= 693 seconds.
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CHEMICAL KINETICS
Q.19 60 per cent of a first order reaction was completed in 60 minutes. When was it half completed?
Sol.
a
2.303
log
a-x
t
100
2.303
In first case:
in second case:
100
2.303
log
100 - 50
t
k=
..........(i)
..........(ii)
or
t=
60 log 2 60 0.3010
min
=
10
1 - 0.6020
log
4
= 45.4 min.
Q.20 A first orer reaction is 20% complete in 10 minutes. Calculates the time for 75% completion of the
reaction.
Sol.
k =
a
2.303
log
(a - x )
t
100
k = 10 min log 80
and, also
k=
2.303
100
log
t
25
............(ii)
Equating the two equation (i) and (ii) , we get
2.303
5 2.303
log =
log 4
10
4
t
10 log 4
or
t = log 5 / 4
or
t=
=
10 0.6020
0.6990 - 0.6020
6.020
6020
=
0.0970
97
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............(i)
CHEMICAL KINETICS
13
Q.21 The half-life of a chemical reaction at a particular concentration is 25 minutes. When the concentration
is doubled, the half-life becomes 50 minutes. Find the order of reaction.
Sol.
Suppose the initial concentration in the first case is a mol L1. Then
[A0]1 = a1(t1/2)1 = 25 minutes
and
Now,
(t1/ 2 )1
(t1/ 2 )2
[A ]
= 0 1
[A 0 ]2
n-1
n -1
So,
a1
2a1
1=n-1
n-1
1
=
2
n-1
or 2 = 2
n=2
Hence, the reaction is of second order
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CHEMICAL KINETICS
Exercise1
Q.1
The rate of decomposition of substance A becomes eight times when its concentration is doubled. What is the
order of the reaction?
Q.2
The following rate data were obtained at 300 K for the reaction
2A + B C + D
Exp.No.
[A](mol/L )
[B](mol/L )
0.1
0.1
0.3
0.2
7.2 10 -2
0.3
0.4
2.40 10 -1
0.4
0.1
2.40 10 -2
Rate of formation
of D(mol/L/min)
6 10 -3
Q.4
The rate of a particular reaction triples when temperature changes from 50C to 100C. Calculate the
activation energy of reaction.
Q.5
Q.6
From the rate expression for the following reactions determine the order of reaction and the dimensions of the rate
constants.
(i) 3NO(g) N2O(g) + NO2(g) ;
Rate = k[NO]2
Q.7
Rate = k[CH3CHO]3/2
Rate = k[C2H5Cl]
Q.8
A reaction is second order with respect to a reactant. How is the rate of reaction affected if the concentration of the
reactant is
(i) doubled
Q.9
Sucrose decomposes in acid solution into glucose and fructose according to the first order rate law, with t1/2 = 3.00
hours. What fraction of sample of sucrose remains after 8 hours.
Q.10
Show that in case of a first order reaction, the time required for 99.9% of the reaction take place is ten times that
required for half of the reaction.
Q.11
The half life of a reaction A B is 8 minutes. How long it takes [A] to reach 25% of the initial concentration?
Q.12
For a first order reaction, calculate the ratio between the time to complete three fourth of the reaction and the time
taken to complete half of the reaction.
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CHEMICAL KINETICS
15
Exercise2
Q.1
Q.2
Q.3
A first order decomposition reaction takes 40 minutes for 30% decomposition. Calculate its t1/2 value.
[C.B.S.E. 2008]
The decomposition of phosphine, 4 PH3(g) P4(g) + 6 H2(g) has the rate law, rate = k [PH3]. The rate contant is 6.0
104 s1 at 300 K and activation energy is 3.05 105 J mol1. Calculate the value of rate contant at 310 K. (Give,
R = 8.314 JKmol)
[C.B.S.E. 2008]
Define the following :
(i) Elementary step in a reaction
[C.B.S.E. 2008]
(ii) Rate of a reaction
Q.4
For a decomposition reaction the values of rate constant k at two different temperatures are given below:
k1 = 2.15 108 L mol1 s1 at 650 K , k2 = 2.39 107 L mol1 s1 at 700 K
[C.B.S.E. 2008]
Calculate the value of activation energy for this reaction (R = 8.314 J K1 mol1)
Q.5
Define the following :(i) Order of a reaction (ii) Activation energy of a reaction
Q.6
A first order reaction has a rate constant of 0.0051 min . If we begin with 0.10 M concentration of the reactant,
what concentration of the reactant will be left after 3 hours ?
[C.B.S.E. 2009]
Q.7
Q.8
Q.9
Q.10
The thermal decomposition of HCO2H is a first order reaction with a rate constant of 2.4 10 3 s1 at a certain
temperature. Calculate how long will it take for three-fourths of initial quantity of HCO2H to decompose. (log 0.25
= 0.6021)
[C.B.S.E. 2011]
Q.11
What do you understand by the rate law and rate constant of a reaction? Identify the order of a reaction if the units
of its rate constant are :
[C.B.S.E. 2011]
(i) L1 mol s1
(ii) L mol1 s1
The rate of a reaction increases four times when the temperature changes from 300 K to 320 K. Calculate the
energy of activation of the reaction, assuming that it does not change with temperature. (R = 8.314 JK1 mol1)
[C.B.S.E. 2012]
Q.12
Q.13
Q.14
[C.B.S.E. 2009]
[C.B.S.E. 2011]
(a) For a reaction A + B P, the rate law is given by, r = k[A]1/2 [B]2
What is the order of this reaction ?
(b) A first order reaction is found to have a rate constant k = 5.5 114 s1 . Find the half life of the reaction.
[C.B.S.E. 2013]
The rate of a reaction becomes four times when the temperature changes from 293 K to 313 K. Calculate the
energy of activation (E a) of the reaction assuming that it does not change with
temperature. [R = 8.314 J K1 mol1 , log 4 = 0.6021]
[C.B.S.E. 2013]
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16
CHEMICAL KINETICS
Answer Key
Q.1
Q.4
Q.8
Q.10
n=3
22.012 kJ/mole
(i) 4 times, (ii) 1/4 times
t99.9% = 10 t50%
Q.2
Q.7
Q.9
Q.11
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