UNIT-7

CHEMICAL KINETICS

I. ANSWER THE FOLLOWING QUESTIONS

1. Define average rate and instantaneous rate.

Average rate Instantaneous rate

It is the rate between the intervals of time It is the rate at a particular time.

Average rate becomes instantaneous rate when t→ 0

2. Define rate law and rate constant.

Rate Law

aA + bB ⎯⎯
→ products
rate [A]x [B]y

rate = k [A]x [B]y

Rate is given in terms of molar concentration of reactants raised to the power which may or

may not equal to stoichiometric coefficient.

Rate constant

Rate constant is same as rate of reaction when concentration of all the reactants is unity.

3. Derive integrated rate law for a zero order reaction A ⎯⎯

→ product.
Rate is independent of the concentration of reactant is called zero order reaction.

Consider a general zero order reaction.A ⎯⎯

→ Product
At t = 0 concentration of reactant = [A0]

At time t, concentration of reactant left = [A]

rate = k[A]0

d[A]
− = k
dt
– d[A] = k dt

Integrate between limits of [A0] at t = 0 and [A] at time 't'.

[A] t
−  d[A] = k  dt
[A0 ] 0
 − ([A])[A
[A]
= k(t)0t
0]

[A0] – [A] = k

[A]0 − [A]
k=
t

4. Define half life of a reaction. Show that for a first order reaction half life is independent

of initial concentration.

Time required for the reactant concentration to reach one half its of initial value is called

half life of a reaction.

First order reaction half-life

2.303 [A ]
k= log 0
t [A]

[A 0 ]
when t = t1/2 then [A] =
2

2.303 [A ]
k= log 0
t1/2 [A0 ]
2

2.303
t1/2 = log 2
k

2.303
t1/2 =  0.3010
k

0.693
t1/2 =
k

No concentration terms involved, so half life is independent on initial concentration of reactant.

5. What is an elementary reaction? Give the differences between order and molecularity

of a reaction.

Each and every single step in a reaction mechanism is called an elementary reaction.
 No Order of a reaction Molecularity of a reaction

1. It is the sum of the powers of concentration It is the total number of reactant species
terms involved in the experimentally
determined rate law. that are involved in an elementary step.

2. It can be zero (or) fraction (or) Integer It is always whole number, cannot be

zero or fraction.

3. It is assigned for a overall reaction It is assigned for each elementary step

of mechanism.

6. Explain the rate determining step with an example.

I−
Consider a reaction 2H 2O2 ⎯⎯→ 2H 2O + O2

This reaction takes place in two steps

H2O2(aq)+ I –(aq) ⎯⎯⎯

→ H2O(l) + OI –(aq)
slow
Step – 1
RDS

Step – 2 H2O2(aq)+ OI –(aq) ⎯⎯

→ H2O(l) + I –(aq) + O2(g)

Overall reaction 2H2O2(aq) ⎯⎯

→ 2H2O(l) + O2(g)

Step – 1 is a slow step and rate determining step. In this step H2O2 and I– are involved,

hence it is bimolecular reaction.

7. Describe the graphical representation of first order reaction.

1 [A ]
k = ln 0 Intercept =ln [A0]
t [A]
slope = – k
kt = ln [A0] – ln[A] ln [A]

ln [A] = – kt + ln [A0]

y = – mx + C t
Plot of ln [A] Vs t gives straight line with negative slope.

Slope equal to –k and intercept equals to ln[A].

8. Write the rate law for the following reactions.

(a) A reaction that is 3/2 order in x and zero order in y.

 (b) A reaction that is second order in NO and first order in Br2.

(a) rate = k [X]3/2 [Y]0

rate = k [X]3/2

(b) rate = k [NO]2 [Br2]1

9. Explain the effect of catalyst on reaction rate with an example.

1. A catalyst is a substance which alters the rate of a reaction without itself undergoing

any permanent chemical change.

2. It may participate in a reaction but regenerated at the end of reaction.

3. A catalyst increases rate of reaction by lowering the activation energy.

Example : 2KClO3 ⎯⎯⎯→

MnO2
2KCl +3O2

MnO2 acts as catalyst. Potential Ea

Without
Energy Ea
catalyst With

Reactant catalyst Product

s Reaction progress
→
10. The rate law for a reaction of A, B and L has been found to be rate = k [A]2 [B] [L]3/2.

How would the rate of reaction change when

(i) Concentration of [L] is quadrupled

(ii) Concentration of both [A] and [B] are doubled

(iii) Concentration of [A] is halved

(iv) Concentration of [A] is reduced to (1/3) and concentration of [L] is quadrupled.

(i) rate = k [A]2 [B] [L]3/2 ⎯⎯

→ (1) (ii) (ii) x rate = k [2A]2 [2B] [ L]3/2 ⎯⎯
→ (3)

x rate = k [A]2 [B] [4L]3/2 ⎯⎯

→ (2)
2
(3) x rate k [2 A] [2 B] [L]3/2
 =
(1) rate k [A]2 [B] [L]3/2
(2) x rate k [A]2 [B][4 L ]3/2
 = 3/2
(1) rate k [A]2 [B] [L] x = (2)2 (2)

x=8
1
3 Rate increase by 8 times
x=4 3/2
x = (4) 2
 1
x=8x = (64) 2

Rate increase by 8 times

(iii) 2 (iv) 2
A A
x rate = k   [B][L]
3/ 2
⎯⎯
→(4) x rate = k   [B][4L]
3/ 2
⎯⎯
→(5)
2 3
2 2
A A
k   [ B ][ L]3/2 k   [ B ][ 4L]3/2
=  
3
=  
(4) x rate 2 (5) x rate
 
(1) rate k [ A ]2[ B ][ L]3/2
(1) rate k [ A ]2[ B ][ L]3/2

2
1
2 1
x =  x =   (4)3/2
2 3

1 1
x= x =  (8)
4 9

1 8
Rate decrease by times Rate decrease by times
4 9

11. The rate of formation of a dimer in a second order reaction is 7.5 × 10 – 3 mol L – 1 s – 1

at 0.05 mol L – 1 monomer concentration. Calculate the rate constant.

rate = k [monomer]2

7.5 10−3 = k  (0.05)2

7.5  10−3 7.5  10−3 7.5  10 −3 7.5  10

1
75
k= = −2 2
= −4
= = = 3 molL−1s −1
(0.05) 2
(5  10 ) 25  10 25 25

12. For a reaction X + Y + Z ⎯⎯

→ products the rate law is given by rate = k [X3/2 [Y]1/2 .

What is the overall order of the reaction and what is the order of the reactionwith respect to z.

X + Y + Z ⎯⎯
→ product

rate = k [X]3/2 [Y]1/2

order w.r.to Z = 0

3 1
overall order = + =2
2 2
 − Ea
13.Explain briefly the collision theory of bimolecular reactions. (or) Derive k = pz e RT

Consider a bimolecular reaction between A2 and B2 proceeds through collision betweenthem

which is proportional to number of collision per second

Rate Collision rate

Collision rate [A2] [B2]

Collision rate =Z [A2] [B2] Z is the collision Frequency

Collision rate in gas phase reaction is calculated from kinetic theory of gas and its value is

109collision per seconds at 298K and 1 atm pressure.

All these collisions are not effective and in order for reaction to takes place, the colliding

molecules must possess activation energy.

Ea
−
Fraction of effective collision (f) is given by f =e RT

In addition to activation energy, orientation factor(p) also necessary for reaction to take place.

rate = p  f  collision rate

Ea
−
rate = p  e RT  Z [A2] [B2] ⎯⎯
→ (1)

As per rate lawrate = k [A2] [B2] ⎯⎯

→ (2)

comparing (1) and (2)

Ea
−
k = pze RT

14. Write Arrhenius equation and explains the terms involved.

Ea
−
Arrhenius equation k = Ae RT

k is rate constant

A is Frequency factor

Ea is Activation energy( Jmol-1)

T is Temperature in Kelvin

R is gas constant (8.314 JK–1 mol–1)

15. The decomposition of Cl2O7 at 500 K in the gas phase to Cl2 and O2 is a first order reaction.
After 1 minute at 500K, the pressure of Cl2O7 falls from 0.08 to 0.04 atm.

Calculate the rate constant in s – 1.

2.303 [A ]
k= log 0
t [A]

2.303 0.08 2.303 2.303 0.6932

k= log = log 2 =  0.3010 = = 0.011553 s – 1
60 0.04 60 60 60

k = 1.153 10 – 2 s –1

17. Explain pseudo first order reaction with an example.

A second order reaction can be altered to a first order reaction by taking one of the reactants in

large excess, such reaction is called pseudo first order reaction.

Example : Acid hydrolysis of ester

+
CH3COOCH3 + H2O ⎯⎯→
H
CH3COOH + CH3OH

18. Identify the order for the following reactions

(i) Rusting of Iron

(ii) Radioactive disintegration of 92U238

(iii) 2A + 3B ⎯⎯
→ products ; rate = [A]1/2 [B]2

(i) First order

(ii) First order

1 1+ 4 5
(iii) +2 = =
2 2 2
19. A gas phase reaction has energy of activation 200 kJ mol – 1. If the frequency factor of the

−40.09
reaction is 1.6 × 1013 s – 1. Calculate the rate constant at 600 K. ( e = 3.8 × 10 – 18)

Ea = 200 kJ mol – 1

A = 1.6  1013 s – 1

T = 600 K andR = 8.314 J K –1 mol–1

k=?
 Ea
log k = log A −
2.303RT

2000 0 0
= log1.6 1013 −
2.303  8.314  6 0 0

2000
= log1.6  1013 −
2.303  8.314  6

2000
= log1.6  1013 −
114.88

= log1.6 1013 − 17.409

= log 1.6 + 13 – 17.409

= 0.2041 + 13 – 17.409

= 13.2041 – 17.409

log k = – 4.2049

= – 4 – 0.2049 + 1 – 1

= – 5 + 0.7951

= = 5.7951

k = Antilog 5.7951

k = 6.238 10−5 s−1

20. For the reaction 2x + y ⎯⎯

→ L. Find the rate law from the following data.

[x] [y] rate

(min) (min) (M s – 1)

0.2 0.02 0.15

0.4 0.02 0.30

04 0.08 1.20

rate = k [X]a [Y]b

0.15 = k (0.2)a (0.02)b ⎯⎯

→ (1)

0.30 = k (0.4)a (0.02)b ⎯⎯

→ (2)
 1.20 = k (0.4)a (0.08)b ⎯⎯
→ (3)

(2) 0.30 k(0.4)a (0.02) b

 =
(1) 0.15 k(0.2)a (0.02) b

2 = 2a
order w.r.to X = 1

(3) 1.20 k(0.4)a (0.08) b

 =
(2) 0.30 k(0.4)a (0.02) b

4 = 4b

b=1

order w.r.to y = 1

rate law is rate = k [X]1 [Y]1

21. How do concentrations of the reactant influence the rate of reaction?

Rate of reaction increases with increases of concentration of reactant.

rate[Reactant]

As reactant concentration is more, which leads to more collision of reactant molecules which

increases the rate of reaction.

22. How do nature of the reactant influence rate of reaction. (or)

Titration between potassium per mangate and oxalic acid is carried out at 60C where as

titration between potassium per manganate and ferrous ammonium sulphate at room

temperature. Give reason.

Chemical reaction involves bond breaking and bond formation. The net energy involved in

this process depends on nature of reactants and hence rate differs for different reactants.

For example, titration between KMnO4 vs FAS takes place at room temperature whereas

titration between KMnO4 vs Oxalic acid is heated to 60C. This is because oxidation of oxalate ion

by KMnO4 is slow compared to reaction between KMnO4 and Fe2+.

23. The rate constant for a first order reaction is 1.54 × 10 – 3 s – 1. Calculate its half life time.

k = 1.54  10–3 s–1

t1/2 = ?
 0.693 0.693 0.693  103 693
t1/2 = = = =
k 1.54 10−3 1.54 1.54

t1/2 = 450 sec

24. The half life of the homogeneous gaseous reaction SO2Cl2 ⎯⎯

→ SO2 + Cl2 which obeys first
orderkinetics is 8.0 minutes. How long will it take for the concentration of SO2Cl2 to be

reduced to 1% of the initial value?

t1/2 = 8 min t=?

[A0] = 100

[A] = 1% of initial value

1
[A] =  100 = 1
100

0.693
k=
t1/2

0.693
k= min −1
8

2.303 [A ]
k= log 0
t [A]

0.693 2.303 100

= log
8 t 1

0.693 2.303
= 2
8 t

0.693 4.606
=
8 t

4.606  8 36.848
t= =
0.693 0.693

t = 53.17 min
25. The time for half change in a first order decomposition of a substance A is 60 seconds.

Calculate the rate constant. How much of A will be left after 180 seconds.

(i) t1/2 = 60sec k=?

(ii)t = 180 sec [A] = ?

[A0] = 100

0.693
(i) t1/2 =
k

0.693 0.693
k= = = 0.01155 sec−1
t t1/2 60

0.693 [A ]
(ii) k = log 0
t t1/2 [A]

2.303 [A ]
0.01155 = log 0
180 [A]

100 0.01155 180

log =
[A] 2.303

100 2.079
log =
[A] 2.303

100
log = 0.9027
[A]

100
= Anti log 0.9027
[A]

100
= 7.993
[A]

100
[A] =
7.993
[A] = 12.5%

26. A zero order reaction is 20% complete in 20 minutes. Calculate the value of the rate constant.

In what time will the reaction be 80% complete?

(i) [A0] = 100 [A] = 80

t = 20 min k=?
 (ii) t = ? [A] = 20

[A 0 ] − [A] 100 − 80 20
(i) k = = =
t 20 20

k = 1 mol L– 1min – 1

[A 0 ] − [A]
(ii) k =
t

100 − 20
1=
t

t = 80 min

27. The activation energy of a reaction is 225 k cal mol – 1 and the value of rate constant at 40C

is1.8 × 10 – 5 s – 1. Calculate the frequency factor A.

E a = 225 k cal.mol−1 = 225000 cal .mol–1

k = 1.8  10–5 s–1

R = 1.987 cal K –1 mol –1

T = 40C = 40 + 273 = 313 K

A=?

Ea
log k = log A –
2.303RT

22500
log 1.8  10 – 5 = log A –
2.303  1.987  313

22500
log 1.8  10 – 5 = log A –
1432

log 1.8  10 – 5= log A – 15.7089

log 1.8  10 – 5= log A – 15.7089

log 1.8 – 5 = log A – 15.7089

0.2553 – 5 = log A – 15.7089

 log A = 15.7089 + 0.2553 – 5

log A = 10.9642

A = Antilog 10.9642

A = 9.208 1010 collisons s –1

28. Benzene diazonium chloride in aqueous solution decomposes according to the equation

C6H5N2Cl ⎯⎯
→ C6H5Cl + N2. Starting with an initial concentration of 10 g L – 1,

the volume of N2 gas obtained at 50C at different intervals of time was found to be as under:

t (min) : 6 12 18 24 30 

Vol. of N2 (ml ): 19.3 32.6 41.3 46.5 50.4 58.3

Show that the above reaction follows the first order kinetics. What is the value of the rate constant?

2.303 V
k= log
t V − Vt

2.303 58.3 2.303 58.3 2.303 2.303

(i) k = log = log = log1.495 =  0.1746 = 0.067 min −1
6 58.3 − 19.3 6 39 6 6

2.303 58.3 2.303 58.3 2.303 2.303

(ii) k = log = log = log 2.268 =  0.3556 = 0.0682 min −1
12 58.3 − 32.6 12 25.7 12 12

2.303 58.3 2.303 58.3 2.303 2.303

(iii) k = log = log = log 3.429 =  0.5351 = 0.0685min −1
18 58.3 − 41.3 18 17 18 18

2.303 58.3 2.303 58.3 2.303 2.303

(iv) k = log = log = log 4.9407 =  0.6938 = 0.666 min −1
24 58.3 − 46.5 24 11.8 24 24
Average k = 0.0676 min –1 and as follows first order kinetics.

29. From the following data, show that the decomposition of hydrogen peroxide is a reaction of the

first order :

t (min) 0 10 20

V (ml ) 46.1 29.8 19.3

Where t is the time in minutes and V is the volume of standard KMnO4 solution required

for titrating the same volume of the reaction mixture.

 2.303 V
k= log 0
t Vt

2.303 46.1 2.303 2.303

(i) k = log = log1.5469 =  0.1895 = 0.0436 min −1
10 29.8 10 10

2.303 46.1 2.303 2.303

(ii) k = log = log 2.3886 =  0.3781 = 0.0435min −1
20 19.3 20 20
Average k = 0.04355min –1 and as follows first order kinetics.

30. A first order reaction is 40% complete in 50 minutes. Calculate the value of the rate

constant.In what time will the reaction be 80% complete?

(i) t = 50 min [A0] = 100 [A] = 60 k=?

(ii) [A] = 20 t=?

2.303 [A ] 2.303 100 2.303 2.303

(i) k = log 0 = log = log1.667 =  0.2219 =
t [A] 50 60 50 50
0.01022 min – 1

2.303 [A ]
(ii) k = log 0
t [A]

2.303 100 2.303

0.01022 = log 0.01022 = log 5
t 20 t

2.303
0.01022 =  0.6990
t

2.303 1.61
t=  0.6990 = t = 157.51 min
k 0.01022

II. EXAMPLES
Example-1 (Page 211)

Consider the oxidation of nitric oxide to form NO2

2NO(g) + O2(g) ⎯⎯
→ 2NO2 (g)

(a) Express the rate of the reaction in terms of changes in the concentration of NO, O2 and NO2.

(b) At a particular instant, when [O2] is decreasing at 0.2 mol L–1 s–1 at what rate is [NO2]

increasing at that instant?

 1 d[NO] d[O 2 ] 1 d[NO 2 ]
(a) − =− =
2 dt dt 2 dt

d[O 2 ] 1 d[NO 2 ]
(b) − =
dt 2 dt

1 d[NO 2 ]
0.2 =
2 dt

d[NO 2 ]
= 0.2  2 = 0.4 mol  L−1s −1
dt
Example-2 (Page 211)

What is the order with respect to each of the reactant and overall order of the following reaction?

− − +
(a) 5Br (aq) + BrO3 (aq) + 6H (aq) ⎯⎯
→ 3Br2(l) + 3H2O(l)

The experimental rate law is Rate = k [Br–] [BrO3] [H+]2


(b) CH 3CHO(g) ⎯⎯
→ CH 4 (g) + CO(g) the experimental rate law is Rate = k[CH3CHO]3/2

(a)Order w.t.to Br – is 1

−
Order w.t.to BrO 3 is 1

Order w.t.to H+ is 2

Overall order is 1 + 1 + 2 = 4

(b)order = 3/2

Example-3 (Page 211)

The rate of the reaction x + 2y → product is 4  10 –3 mol L –1 s –1, if [x] = [y] = 0.2 M and

rate constant at 400 K is 2  10 –2 s –1, What is the overall order of the reaction.

rate = k [X]9 [Y]6

4  10 –3 = 2  10 –2 (0.2)a (0.2)b

4 10−3
−2
= (0.2)a + b
2 10

2 10−1 = (0.2)a + b

0.22 = (0.2)a + b
Comparing the powers a + b = 1

Overall order = a + b = 1

Example-4 (Page 216)

A first order reaction takes 8 hours for 90% completion. Calculate the time required for

80% completion. (log 5 = 0.6989 ; log 10 = 1)

t = 8 hr

[A0] = 100

[A] = 10

t = ?for [A] = 20 (80% completion)

2.303 [A ] 2.303 100 2.303

k= log 0 = log = log10
t [A] 8 10 8

2.303 −1
k= hr
8

2.303 [A ]
k= log 0
t [A]

2.303 2.303 100

= log
8 t 20

2.303 2.303
= log 5
8 t

2.303 2.303
=  0.6989
8 t

2.303 1.6096
=
8 t

1.6096 12.876
t= =
2.303 2.303

t = 5.59 hr

Example-5 (Page 216)

The half life of a first order reaction x → products is 6.932  104 s at 500 K. What
percentage

of x would be decomposed on heating at 500 K for 100 min. (e0.06 = 1.06)

t1/2 = 6.932  104 s

t = 100 min = 100  60 = 6000 s

0.693
t1/ 2 =
k

0.693 0.693 0.693 10−1 0.693 10−1

k= = = = = 10−5 s −1
t1/ 2 6.932  10 4
6.932 10 4
6.932 10 4

2.303 [A ]
k= log 0
t [A]

2.303 [A ]
10−5 = log 0
6000 [A]

[A 0 ] 6000 10−5 6  103  10 −5 6 10−2

log = = = = 2.605  10 –2
[A] 2.303 2.303 2.303

[A 0 ]
log = 0.02605
[A]

[A0 ]
= Anti log(0.02605)
[A]

[A 0 ]
= 1.0618
[A]

100
= 1.0618
[A]

100
[A] =
1.0618

[A] = 94179

Left out concentration of reactant x = 94.179 mol .L –1. Reacted amount = 5.82%

Example-6 (Page 217)

Show that in case of first order reaction, the time required for 99.9% completion is nearly

ten times the time required for half completion of the reaction.

t99.9%

2.303 [A ]
k= log 0
t [A]
 2.303 100
t99.9% = log
k 0.1

2.303
t99.9% = log 1000
k

2.303
t99.9% = ×3
k

6.909
t 99.9% = ⎯⎯
→ (1)
k

0.693
t 50% = ⎯⎯
→ (2)
k

(1) t 99.9% 6.909 k

From , = ×
(2) t 50% k 0.693

t 99.9%
= 10
t 50%

t 99.9% = 10 t 50%

Hence proved.

Example-7 (Page 221)

The rate constant of a reaction of a reaction at 400 and 200 K are 0.04 and 0.02 s –1
respectively. Calculate the value of activation energy.

T1 = 200 K k1 = 0.02 s –1

T2 = 400 K k1 = 0.04 s –1

R = 8.314 JK –1mol –1

E a= ?

k2 Ea  T2 − T1 
log =  
k1 2.303 R  T1T2 

0.04 Ea  400 − 200 

log =  
0.02 2.303  8.314  400  200 

Ea 20 0
log 2 = 
2.303  8.314 800 0 0
 Ea 2
0.3010 = 
2.303  8.314 800

Ea 1
0.3010 = 
2.303  8.314 400

Ea = 2.303  8.314  400  0.3010

E a = 2.305 J mol−1

Example-8 (Page 221)

Rate constant k of a reaction varies with temperature T according to the following

Arrhenius equation

Ea  1 
log k = log A  
2.303R  T 

1
Where Ea is the activation energy. When a graph is plotted for log k Vs astraight line
T

with a slope of –4000 K is obtained. Calculate the activation energy

Slope = –4000 K

E a= ?

Ea
slope = −
2.303R

Ea
− 4000K = −
2.303  8.314 JK −1mol−1

Ea = 2.303  8.314 J K −1 mol−1  4000 K

E a = 76589 J mol−1

Solved Problem in page 209

For the reaction 2NO(g) + O 2(g) ⎯⎯

→ 2NO(g) the following data were obtained.

Expt. [NO]  10 –2 (mol [O2]  10 –2 (mol Initial rate  10 –2 (mol L –

L –1) L –1) 1 –1
s )

1. 1.3 1.1 19.26

 2. 1.3 2.2 38.40

3. 2.6 1.1 76.80

Determine order with respect to NO, O2 and overall order.

rate = k[NO]x [O 2 ]y

19.26  10−2 = k(1.3  10−2 ) x (1.1 10−2 ) y ⎯⎯

→ (1)

38.40  10−2 = k(1.3  10−2 ) x (2.2  10−2 ) y ⎯⎯

→ (2)

76.80  10−2 = k(2.6  10−2 ) x (1.1 10−2 ) y ⎯⎯

→ (3)

y
(2) 38.40  10 −2 k (1.3  10−2 ) x (2.2  10−2 )
 =
19.26  10−2
(1) y
k (1.3  10−2 ) x (1.1 10−2 )

2 = 2x

x=1

order w.r.to NO = 1

y
(3) 76.80  10−2 k (2.6  10−2 ) x (1.1 10−2 )
 =
−2 y
(1) 19.26  10 k (1.3  10−2 ) x (2.1 10−2 )

4 = 2x

x=2

order w.r.to O2 = 2

rate = k [NO]1 [O2]2

Overall order = 1 + 2 = 3

III EVALUATE YOURSELF

Evaluate Yourself-1 (Page 211)

(1) Write the rate expression for the following reactions, assuming them as elementary

reactions.

(i) 3A + 5B2 ⎯⎯
→ 4CD (ii) X2 + Y2 ⎯⎯
→ 2XY
(2) Consider the decomposition of N2O5(g) to form NO2(g) and O2(g). At a particular

instant N2O5 disappears at a rate of 2.5  10 –2 mol dm –3 s –1. At what rate are NO2

and O2 formed? What is the rate of the reaction?

(1) (i) rate = k [A]3 [B2]5

(ii)rate = k [X2]1 [Y2]1

(2) 2N2O5 ⎯⎯
→ 4NO2 + O2

1 d[N 2O5 ] 1 d[NO 2 ]

− =
2 dt 4 dt

1 1 d[NO 2 ]
 2.5  10−2 =
2 4 dt

d[NO 2 ] 4
=  2.5  10−2 = 2  2.5  10 –2 = 5  10 –2 mol L –1 s –1
dt 2

1 d[N 2O5 ] d[O 2 ]

− =
2 dt dt

1 d[O 2 ]
 2.5  10−2 =
2 dt

d[O2 ]
= 1.25  10−2 mol L−1s −1
dt

Evaluate Yourself-2 (Page 212)

(1) For a reaction, X + Y ⎯⎯

→ product ; quadrupling [x], increases the rate by a factor of 8.

Quadrupling both [x] and [y], increases the rate by a factor 16. Find the order of the

reaction with respect to x and y. What is the overall order of the reaction?

(2) Find the individual and overall order of the following reaction using the given date

2NO(g) + Cl2(g) ⎯⎯
→ 2NOCl(g) .

Expt. [NO] [Cl2] Initial

rate

1. 0.1 0.1 7.8  10 –

5
2. 0.2 0.1
 3. 0.2 0.3 3.12  10
–4

9.36  10
–4

(1)rate = k [X]a [Y]b ⎯⎯

→ (1)

8 rate = k [4X]a [Y]b ⎯⎯

→ (2)

16 rate = k [4X]a [Y]b ⎯⎯

→ (3)

a b
(2) 8 rate k [4 X ] [ Y]
 =
(1) rate k [ X ]a [ Y]b

8 = 4a
23 = 22a

3 = 2a

a = 3/2

order w.r.to X = 3/2

a b
(3) 16 rate k [ 4X ] [ 4Y]
 =
(2) 8rate k [ 4X ]a [ Y]b

2 = 4b
b = 1/2

order w.r.to Y = 1/2

(2) rate = k[NO] [Cl2 ]

x y

7.8  10−5 = k(0.1) x (0.1) y ⎯⎯

→ (1)

3.12  10−4 = k(0.2) x (0.1) y ⎯⎯

→ (2)

9.36  10−4 = k(0.2) x (0.3) y ⎯⎯

→ (3)

y
3.12 10−4 k (0.2) ( 0.1)
x
(2)
 =
(1) 7.8 10−5 k (0.1) x ( 0.1)
y

4 = 2x
 x=2

order w.r.to NO = 2

9.36  10−4 k (0.2) (0.1)

x y
(3)
 =
(2) 3.12  10−4 k (0.2) x (0.3) y

y
1
3= 
3

3 = (3−1 ) y

3=3

Equating the powers

1 = –y

y = –1

order w.r.to O2 = 1

rate = k [NO]2 [O2]–1

overall order = 2 – 1 = 1

Evaluate Yourself-3 (Page 217)

(1) In a first order reaction A→ products 60% of the given sample of A decomposes in 40 min.

What is the half life of the reaction?

(2) The rate constant for a first order reaction is 2.3  10 –4 s –1. If the initial concentration

of the reactant is 0.01 M. What concentration will remain after 1 hour?

(3) Hydrolysis of an ester in an aqueous solution was studied by titrating the liberated

carboxylic acid against sodium hydroxide solution. The concentrations of the ester at

different time intervals are given below.

Time (min) 0 30 60 90

Ester concentration mol L –1 0.85 0.80 0.754 0.71

Show that, the reaction follows first order kinetics.

(1) t = 40 min

[A0] = 100

[A] = 40

t1/2 = ?

2.303 [A ] 2.303 100 2.303 2.303 0.9163

k= log 0 = log = log 2.5 =  0.3979 =
t [A] 40 40 40 40 40

k = 0.0229 min −1

0.693 0.693
t1/2 = =
k 0.0229

t1/2 = 3.026 min

t1/2 = 3min

(2) k = 2.3  10 –4 s –1

[A0] = 0.01 M

t = 1 hour = 3600 s

[A] = ?

2.303 [A ]
k= log 0
t [A]

2.303 0.01
2.3 10−4 = log
3600 [A]

0.01 2.3 10−4  3600

log = = 3600  10 –4 = 36  10210 –4 = 36  10 –2
[A] 2.303

0.01
log = 0.36
[A]

0.01
= Anti log 0.36
[A]

0.01
= 2.29
[A]

0.01
[A] = = 0.0044 M = 4.4  10 –3 M
2.29
 2.303 V 2.303 0.85 2.303 2.303 0.0606
(3) k = log 0 = log = log1.0625 =  0.0263 = = 0.002019 min –
t Vt 30 0.80 30 30 30
1

k = 2.019  10−3 min −1

2.303 0.85 2.303 2.303 0.05918

k= log = log1.061 =  0.0257 =
60 0.754 60 60 30

= 0.001972

k = 1.972 10−3 min −1

2.303 0.85 2.303 2.303 0.18009

k= log = log1.1972 =  0.782 = = 0.002001min −1
90 0.71 90 90 90

k = 2.00110−3 min −1

As all k values are nearly same, ester hydrolyzing follows first order kinetics.

Evaluate Yourself-4(Page 221)

For a first order reaction the rate constant at 500 K is 8  10 –4 s –1. Calculate the frequency
factor, if the energy of activation for the reaction is 190 kJ mol –1.

T = 500 K

k = 8  10 –4 s –1

A=?

Ea = 190 kJ mol –1 = 190000 J mol –1

R = 8.314 JK–1 mol –1

Ea
log k = log A −
2.303 RT

1900 0 0
log8 10−4 = log A −
2.303  8.314  5 0 0

1900
log 8 10−4 = log A −
95.735

log 8  10 –4 = log A – 19.846

log 8 + log 10 –4 = log A – 19.846

log 8 – 4 = log A – 19.846

 0.9031 – 4 = log A – 19.846

log A = 0.9031 – 4 + 19.846

= 20.7491 – 4

log A = 16.7491

A = Antilog 16.7491

A = 5.6117 1016 collision s −1

IV ADDITIONAL QUESTIONS WITH ANSWERS

1. Define rate of a reaction.

Rate is defined as change in concentration of reactant or product with respect to time.

2. Give the unit of rate of reaction for (i) aqueous reaction (ii) Gaseous reaction

(i) mol L–1 s–1 (ii) atm s–1

3. How to determine rate of a reaction.

Draw a plot of concentration vs time graph. The slope of the curve between the interval of time
gives the average rate.
Instantaneous rate is the rate at a particular time which is calculated by drawing a tangent at that
point on the concentration vs time graph. The slope of the tangent gives the instantaneous rate.

0.5
0.5
0.4
Slope 0.4 Slope
Conc 0.3
0.2 Average Rate Conc 0.3 Instantaneous Rate
0.2
0.1
0.1
0 5 10 15 20 25
0 5 10 15 20 25
Time
0
Time
0
4. Differentiate rate and rate constant.
S

No Rate of a reaction Rate constant of a reaction

1. It represents the speed at which the It is a proportionality

reactants are converted intoproducts at any constant
instant.

2. It is measured as decrease in the It is equal to the rate of

concentration of the reactants or increase in reaction,
the concentration of
when the concentration of
 products. each

of the reactants in unity.

3. It depends on the initial on the It does not depend on the

concentrations of reactants. initial

concentration of reactants.

5. Define molecularity.

It is the total number of reactant speciesthat are involved in an elementary step.

6. Define order of a reaction.

aA + bB ⎯⎯
→ products
rate = k [A]x [B]y

overall order = x + y

It is the sum of the powers of concentration terms involved in the experimentally determined rate law.

7. Derive an expression of half life of a zero order reaction.

[A 0 ] − [A]
k=
t

[A 0 ]
t = t1/2 then [A] =
2

[A 0 ]
[A 0 ] −
k= 2
t1/2

2[A 0 ] − [A 0 ] [A0 ]
t1/2 = t1/2 =
2k 2k

8. Give general expression for half life of nth order reaction.

2n −1 − 1
Half life of nth order reaction is t1/2 =
(n − 1)k[A 0 ]n −1

9. Draw a plot of concentration vs time for zero order reaction.

Intercept = [A0]
[A 0 ] − [A] slope = – k
k=
t [A]

[A] = −kt + [A0 ]

t
 y = – mx + C

Plot of [A] Vs t gives straight line with negative slope.

Slope equal to –k and intercept equals to [A].

10. Give examples of first order reaction.

1
(i) N 2O5 (g) ⎯⎯
→ 2NO 2 (g) + O 2 (g)
2

(ii) SO2Cl2 (l ) ⎯⎯
→SO2 (g) + Cl2 (g)

1
(iii) H 2O 2 (aq) ⎯⎯
→ H 2O(l ) + O 2 (g)
2
(iv) All radioactive decay

(v) Isomerisation of cyclopropane to propene

11. Give two examples of zero order reaction.

h
(i) H2 (g) + Cl2 (g) ⎯⎯→ 2HCl(g)

⎯⎯
→ N 2 (g) + 1
(ii) N 2O(g) ⎯
⎯ O 2 (g)
2
12. Give units of rate constant of

(a) first order reaction (b) zero order reaction

(a) sec–1 (b) mol L–1s–1

13. What is collision frequency?

Number of collisions per second per unit volume is called collision frequency.

14. Why molecularity can never be more than 3?

Probability of simultaneous collision of more than three reactants is rare.

So molecularity can never be more than three.

15. Define activation energy?

In order to react, the colliding molecules must possess a minimum energy called activation energy.

16. What is the usefulness of Arrhenius equation.

With the help of Arrhenius equation, we can calculate activation energy of the reaction provided

rate constants at two different temperatures are given.

17. Mention the factors affecting rate of reaction.

 1. Nature and state of reactant 2. Concentration of reactant.

3. Surface area of reactant. 4. Temperature of reaction.

5. Presence of catalyst.

18. What does the slope represent in the following graphs.

[R] log[R]

t t
Slope = -k Slope = -k/2.303

19. Which of the following reaction is fast. Give reason.

(i) 2Na (s) + I2(s) ⎯⎯

→ 2NaI(s)

(ii) 2Na (s) + I2(g) ⎯⎯

→ 2NaI(s)

Second reaction is fast because the state of reactant is gas. Gaseous reaction is faster than

solid state reactants.

20. Which of the two reacts faster? Why?

(i) Powdered CaCO3 with dil. HCl

(ii) Lump of CaCO3 as marble with dil. HCl

First reaction is faster because powdered form of reactant has more surface area.

21. Derive integrated rate law for a first order reaction A ⎯⎯

→ product.

Rate is directly proportional to the concentration of one reactant is called first order reaction.

Consider a general first order reactionA ⎯⎯

→ Product

At t = 0 concentration of reactant = [A0]

At time t, concentration of reactant left = [A]

rate = k[A]1

d[A]
− = k[A]
dt

d[A]
− = k dt
[A]
 Integrate between limits of [A0] at t = 0 and [A] at time 't'.

[A] t
d[A]
−  = k  dt
[A ]
[A] 0
0

− ( l n [A])[A
[A]
= k(t) 0t
0]

–ln [A] – (–ln [A0] ) = k (t – 0)

–ln [A] + ln [A0] = kt

 [A ] 
ln  0  = kt
 [A] 

1 [A ]
k = ln 0
t [A]

2.303 [A ]
k= log 0
t [A]

*** Page 219 Computing e–40 = 4  10–18

f = e −40
1
f = e 40
Let x = e40

Take log(ln) on both sides

ln x = ln e40
ln x = 40 ln e ( ( l n e = 1)

ln x = 40
2.303 log x = 40

40
log x =
2.303
log x = 17.3686

x = Antilog 17.3686

x = 2.34  1017

1
f= = 0.4  10 –17 = 4  10−18
2.34 10 17