Chemical Kinetics

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Chemical Kinetics

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CHEMICAL KINETICS

25-05-2015

Contact:

Phone: +92-303-7807073

E-mail: masif33pk@yahoo.com

4.1

4.2

4.3

4.4

4.5

4.6

4.7

4.8

4.9

4.10

4.11

4.12

4.13

4.14

Lecturer (Physical Chemistry)

Govt. College Sahiwal, Pakistan

Introduction

Rate of reaction ...

Rate equation and rate constant..

Order and molecularity of reactions ...

Pseudo order reactions

Zero order reactions ...

First order reactions ...

Second order reactions ...

Third order reactions ..

Elementary and complex reactions

4.10.1 Opposing reactions .

4.10.2 Consecutive reactions .

4.10.3 Parallel reactions ....

4.10.4 Chain reactions

Thermal reactions ....

Photochemical reactions ..

Effect of temperature on rate of reaction ....

Theories of reaction rates

4.14.1 Collision theory ...

4.14.2 Transition state theory .

02

02

03

04

05

06

07

09

13

23

23

34

36

37

37

40

44

48

48

52

2

4.1

INTRODUCTION

Chemical kinetics is the branch of chemistry that deals with the rates of chemical

reactions. The chemical reactions can broadly be divided into three classes:

1. Fast reactions e.g., the reaction between aqueous sodium chloride and silver nitrate.

2. Moderate reactions e.g., hydrolysis of an ester.

3. Slow reactions e.g., rusting of iron.

However, the chemical reactions can occur at a variety of rates from very fast to very slow.

For example, the paper on which this book is printed reacts extremely slowly with the

atmosphere oxygen, whereas explosion is extremely fast reaction. The two extreme classes of

reactions cannot be studied conveniently. Reactions which proceed with measureable rates

are the subjects of study by physical chemists.

In 1864 C. M. Guldberg and P. Waage pioneered the development of chemical

kinetics by formulating the law of mass action, which states that the speed of a chemical

reaction is proportional to the quantity of the reacting substances.

Experimentally it has been found that the rate of a chemical reaction depends on the

nature of the reacting species, the temperature, the pressure, the concentration of the reacting

species and the presence of catalyst.

The reactions may be classified kinetically as being either homogenous, if they take

place in one phase only, or heterogeneous if two or more phases are involved in the

processes. The reactions may be elementary or complex. An elementary reaction occurs in a

single step while a complex reaction occurs in two or more steps.

4.2

RATE OF REACTION

The rate of a chemical reaction is the change in the concentration of reactants or

Rate

Change in concentration c

t

This equation gives the average velocity of the reaction during the time of observation. By

shortening the time of observation the average velocity approaches more and more closely to

the actual velocity of the reaction. So in chemical kinetics the rate of reaction is not

represented by the average velocity but by the instantaneously velocity of the reaction that is

when the time of observation approaches zero then,

Rate

d[c]

dt

3

The brackets [ ] represent the concentration in moles per decimeter cube. Thus rate of

reaction is expressed in units of moles per decimeter cube per second ( mol dm3 sec1 ). For

gas phase reactions, pressure units are used in place of molar concentration.

Consider the following general reaction,

A+B

C+D

The rate at which reaction proceeds can be measured in terms of the rate at which one of the

reactants disappears or one of the products appears.

dx

d[A]

d[B] d[C] d[D]

dt

dt

dt

dt

dt

Where [A], [B], [C] and [D] represent the concentrations of A, B, C and D in moles per

decimeter cube at time t. The negative sign indicates that the concentrations of A and B

decreases with increasing time. The plus sign indicates that the concentrations of C and D

increase with increasing time.

4.3

According to law of mass action, the rate of a chemical reaction is proportional to the

product of the molar concentrations of the reactants raised to the power equal to the number

of molecules of each species taking part in the reaction. Consider the reaction,

aA + bB

cC + dD

dx

[A]a [B]b

dt

dx

= k[A]a [B]b

dt

specific rate constant. This expression shows how the reaction rate is related to

concentration and is known as rate equation, rate expression or rate law.

If the concentration of A and B are kept unity, then

dx

= k[1]a [1]b = k

dt

Thus rate constant may be defined as the rate of reaction when molar concentration of

each of the reactants is unity (1 mol dm3). The value of k varies from reaction to reaction

and also varies with temperature for a given reaction. The value of k for a reaction does not

change with time. The units of k depend on the order of reaction.

4

Anyhow it is not essential that the powers in the rate equation are always equal to the

coefficients of balance chemical equations. So we can say that the rate equation of above

reaction may be,

dx

= k[A]m [B]n

dt

The power or exponent of a concentration term, m or n in the rate equation is usually in small

whole number integers (0, 1, 2, 3) or may be fractional. Here n is called the order of reaction

with respect to A, and m is the order of the reaction with respect to B. The sum (n + m) is

called the overall order of the reaction.

Rate equation for an elementary reaction can be predicted from balanced chemical

equation but it cannot be predicted for complex reactions (involving more than one steps).

Therefore it is written from experimental facts for complex reactions. Actually rate equation

is an experimental expression. The order of the reaction is completely independent of the

reaction stoichiometry.

4.4

The order of a reaction is defined as the total number of atoms, ions or molecules

experimentally determined rate equation. It is the sum of exponents of all the

concentration terms in the differential form of rate equation. A reactant whose

concentration does not affect the rate of reaction is not included in the rate equation. The

concentration of such a reactant has the power 0 e.g., [A]0 =1. For a reaction maximum order

is three and the minimum is zero. However, the order of reaction may be in minus with

respect to a particular species in the reaction; such a species acts as an inhibitor and rate of

reaction is inversely proportional to its concentration. The reactions may be classified

according to the order. If (m + n) in the rate equation is:

m+n=0

m+n=1

m+n=2

The order of reaction provides valuable information about the mechanism of a reaction and

the knowledge of mechanism of a given reaction allows us to control that reaction.

The order of reaction should not be confused with molecularity which is defined as

the total number of atoms, ions or molecules which take part in a reaction as given by

the balanced chemical equation. Molecularity and order are identical for elementary

reactions. Most chemical reactions are complex reactions which occur in a series of steps.

5

Each step is an elementary reaction. The stepwise sequence of elementary reactions that

convert reactants to products is called mechanism of the reaction. In any mechanism, some

of the steps will be fast, others will be slow. The rate of the reaction is determined by the

slowest step known as the rate determining step. Hence, molecularity of a reaction can

also be defined as the total number of atoms, ions or molecules taking part in the rate

determining step. The term unimolecular, bimolecular and termolecular (or trimolecular)

indicate the number of particles reacting in a single elementary process.

No

1

2

3

4

5

6

7

4.5

Order of Reaction

It may be equal to zero.

It can be in fractions.

It is at most equal to three.

It can only be determined

experimentally.

It is the sum of all the

exponents of the concentration

terms in the rate equation.

It helps in determining the

mechanism of a reaction.

In case of complex reactions

order is determined by the

slowest step of the reaction.

Molecularity

It can never be equal to zero.

It can never be in fractions.

It can be more than three.

It can be obtained from a simple balanced

chemical equation.

It is the sum of number of molecules of the

reactants taking part in a single step chemical

reaction.

It gives no idea about the mechanism of a reaction.

In case of complex reactions each step of the

reaction has its own molecularity i.e., molecularity

has no significance for complex reactions.

A reaction in which one of the reactants is present in large excess shows an order

different from the actual order. The experimental order which is not the actual one is

referred as the pseudo order. Since for elementary reactions molecularity and order are

identical, pseudo reactions may also be called pseudo molecular reactions.

Let us consider a reaction,

A+B

Products

In which the reactant B is present in a large excess. Since it is an elementary reaction, its rate

equation can be written as;

Rate = k [A] [B]

As B is present in large excess its concentration remains practically constant in the course of

reaction. Thus the rate law can be written as;

Rate = k [A]

6

Where the new rate constant k = k [B]. Thus the actual order of the reaction is second order

but in practice it will be first order. Therefore, the reaction is said to have a pseudo first order.

Examples:

1. Hydrolysis of an ester: methyl acetate upon hydrolysis in aqueous solution using a

mineral acid as a catalyst forms acetic acid and methyl alcohol.

H

CH3COOCH3 + H2O

CH3COOH + CH3OH

Here a large excess of water is used and the rate law can be written as

Rate = k [CH3COOCH3] [H2O]

Rate = k [CH3COOCH3]

The reaction is actually second order but in practice it is found to be first order. Thus

it is a pseudo first order reaction.

2. Hydrolysis of sucrose: sucrose upon hydrolysis in the presence of a dilute mineral

gives glucose and fructose.

4.6

The reaction in which rate is independent of the concentration of the reactants is

called zero order. Let us take a substance A which decomposes into products. Its initial

concentration is a moles dm3. Let after time t seconds the amount left behind is (a-x)

moles dm3 and that converted into product is x moles dm3. Then

A

When t = 0

a

When t = teq

(a-x)

Hence, the rate of reaction is given by,

Products

0

x

dx

k(a x)

dt

dx

k

dt

dx kdt

Integrating,

dx k dt

x kt C

The value of integration constant C can be found by applying the initial conditions of the

reaction when t = 0, x = 0. That is

x kt

(1)

7

This equation (1) is similar to the equation for a straight line. Thus, if we plot a graph

between x on y-axis and t on x-axis, we should get a straight line passing through the origin

with slope k.

k

x

t

(2)

This equation (2) gives the rate constant for zero order reaction. The units of k are mole

dm3sec1.

Half-Life

It is defined as the time required to reduce the concentration of reactants to half of its

original value. Therefore, when t = t1/2 then x = a/2. Substitute this value in equation (2),

t1/2

a

2

a

2k

Examples

1. Thermal decomposition of HI on gold surface,

2HI

Gold Surface

H2 + I2

2NH3

Tungston

N2 + 3H2

4. The reactions which are catalyzed by enzymes are also zero order.

4.7

The reaction in which the concentration of only one molecule is changed is called

a first order reaction. Let us take a substance A which decomposes into products. Its initial

8

concentration is a moles dm3. Let after time t seconds the amount left behind is (a-x)

moles dm3 and that converted into product is x moles dm3. Then

When t = 0

When t = teq

A

a

(a-x)

Products

0

x

dx

k(a x)

dt

dx

kdt

(a x)

dx

(a x) k dt

ln(a x) kt C

(1)

The value of integration constant C can be found by applying the initial conditions of the

reaction when t = 0, x = 0. That is

ln(a 0) k(0) C

ln a C

Therefore Eq.(1) becomes,

ln(a x) kt ln a

ln a ln(a x) kt

kt

a

log

a x 2.303

(2)

This equation is similar to the equation for a straight line. Thus, if we plot a graph between

log

a

on y-axis and t on x-axis, we should get a straight line passing through the origin

(a x)

Rearranging Equation (2) for k,

k

2.303

a

log

t

ax

(3)

This equation (3) gives the rate constant k of first order reaction. The units of k are sec1.

Half-Life

When t = t1/2 then x = a/2. Substitute this value in equation (3),

a

2.303

log

a

k

a (2)

2.303

0.693

log2

k

k

t1/2

t1/2

Examples

1. Thermal decomposition of hydrogen peroxide is a first order reaction,

H2O2

H2O + O

2NO2 + 1/ 2 O2

N2O5

CH3COOC2H5 + H2O

4.8

CH3COOH + C2H5OH

The reaction in which two molecules undergo a chemical change is called a

second order reaction. Let us consider two substances A and B which react to give the

products. The reaction can be carried out by;

a) By taking equal concentrations of A and B

b) By taking different concentrations of A and B

a) Second order reaction with equal concentrations of reactants

Let the initial concentrations in moles dm3 are a moles dm3 and after time t the

concentrations left behind are (a-x) for both A and B. Then

A+B

a + a

(a-x) + (a-x)

When t = 0

When t = teq

dx

k(a x)(a x)

dt

dx

k(a x) 2

dt

dx

kdt

(a x) 2

dx

(a x)

(a x)

k dt

dx k dt

Products

0

x

10

(a x)21 (1)

kt C

2 1

1

kt C

(a x)

(1)

The value of integration constant C can be found by applying the initial conditions of the

reaction when t = 0, x = 0. That is

1

1

k0 C

C

(a 0)

a

Therefore equation (1) becomes,

1

1

kt

(a x)

a

1

1

kt

(a x) a

x

kt

a(a x)

x

akt

(a x)

(2)

This equation is similar to the equation for a straight line. Thus, if we plot a graph between

x

on y-axis and t on x-axis, we should get a straight line passing through the origin

(a x)

with slope ak.

Rearranging Equation (2) for k,

1

x

k

t a(a x)

(3)

This equation gives the rate constant k for second order reaction with same initial

concentrations of the reactants. The units of k are dm3 mol1 sec1.

Half-Life

When t = t1/2 then x = a/2. Substitute this value in equation (3),

t1/2

a

1

1

2

a

k a(a 2 ) ka

Examples

Saponification of an ester with a strong base is a second order reaction in solution,

CH3COOC2H5 + NaOH

CH3COONa + C2H5OH

11

b) Second order reaction with different concentrations of reactants

Let the initial concentrations of reactants A and B are a and b moles dm3 respectively,

and x moles dm3 of the reactants are disappeared in time t. Then

A+B

a + b

(a-x) + (b-x)

When t = 0

When t = teq

Products

0

x

dx

k(a x)(b x)

dt

dx

kdt

(a x)(b x)

dx

(a x)(b x) k dt

(1)

In order to integrate the L.H.S., we have to do the partial fractions first by using partial

fraction method,

1

A

B

(a x)(b x) (a x) (b x)

(2)

1 A(b x) B(a x)

(3)

1 A(b a)

1

1

b a (a b)

1 B(a b)

1

(a b)

1

1

1

Now substituting this value in equation (1),

1

dx

1

dx

k dt

(a b) (a x) (a b) (b x)

12

1

1

[ ln(a x)]

[ ln(b x)] kt C

(a b)

(a b)

1

1

ln(a x)

ln(b x) kt C

(a b)

(a b)

1

ln(a x) ln(b x) kt C

(a b)

1

(a x)

ln

kt C

(a b) (b x)

(4)

The value of integration constant C can be found by applying the initial conditions of the

reaction when t = 0, x = 0. That is

1

(a 0)

ln

k0 C

(a b) (b 0)

1

a

ln C

(a b) b

Therefore equation (4) becomes,

1

(a x)

1

a

ln

kt

ln

(a b) (b x)

(a b) b

1

(a x)

1

a

ln

ln kt

(a b) (b x) (a b) b

1 (a x)

a

ln

ln kt

(a b) (b x)

b

1

b(a x)

ln

kt

(a b)

a(b x)

2.303

b(a x)

log

kt

(a b)

a(b x)

log

b(a x) (a b)k

t

a(b x)

2.303

(5)

This equation is similar to the equation for a straight line. Thus, if we plot a graph between

L.H.S. of this equation (5) on y-axis and time t on x-axis, we should get a straight line

passing through the origin with slope

(a b)k

.

2.303

2.303

b(a x)

log

t(a b)

a(b x)

(6)

13

This equation (6) gives the rate constant k for a second order reaction when the initial

concentrations of the reactants are different. The dimensions of k are again dm3 mol1 sec1.

Half-Life

The half-life method cannot be used for reactions where the concentrations of A and B are

different, since A and B will have different times for half reaction.

Examples

1. H2 + I2

2HI

2. 2HI

H2 + I2

3. 2O3

3O2

4. 2NO2

4.9

N2 + 2O2

The reaction in which only three molecules undergo a chemical change is called a

third order reaction. Four different cases of 3rd order reaction are discussed here.

Case (I): when the initial concentration of all the reactants is same

Consider the following reaction in which A, B and C reactants are converting into

products in an elementary reaction. All reactants have same initial concentration (a). After

time (t) the concentration of each reactant becomes equal to a x as given below;

A + B + C

Products

When t = 0

When t = t

ax

ax

ax

dx

k[A][B][C]

dt

dx

k(a x)(a x)(a x)

dt

dx

k(a x)3

dt

This is the differential form of rate law for a third order reaction in which concentration of

all the reactants is same.

Integrating the above equation after separating variables,

dx

(a x)

(a x)

k dt

dx k dt

14

(a x) 31

kt c

(3 1)(1)

(a x) 2

kt c

2

1

kt c

2(a x) 2

(1)

When t = 0, x = 0, putting these values in equation (1), the value of c can be calculated

c

1

2a 2

1

1

kt 2

2

2(a x)

2a

1

1

2kt 2

2

(a x)

a

(2)

This is the integrated form of rate law for third order reaction with same initial

concentrations of reactants. This equation is similar to the equation for a straight line.

Therefore if we plot a graph between

1

on y-axis and t on x-axis, we should get a

(a x) 2

Also from equation (2),

kt

1

1

2

2

2(a x) 2a

kt

a 2 (a x) 2

2(a x) 2 a 2

a 2 (a 2 x 2 2ax)

kt

2(a x)2 a 2

kt

a 2 a 2 x 2 2ax

2(a x)2 a 2

2ax x 2

kt

2(a x) 2 a 2

kt

x(2a x)

2(a x) 2 a 2

1 x(2a x)

2a 2 t (a x) 2

(3)

15

This equation (3) gives the rate constant k. Units of k can be determined as follows,

1

(mol dm3 )(mol dm3 )

(mol dm3 ) 2

k mol2dm6 sec1

Half-Life

When t = t1/2 then x = a/2 = 0.5a. Substitute this value in equation (3),

1 x(2a x)

2a 2 k (a x) 2

t1/2

1 0.5a(2a 0.5a)

3

1.5

2

2

2

2

2a k

(a 0.5a)

2ka

ka

(4)

It is evident from the above equation that the half-life period is inversely proportional to the

square of the initial concentration of the reactant.

In general for a reaction of nth order, the half-life is found to be,

t1/2

1

a n 1

Thus, half-life period of any order reaction is inversely proportional to the initial

concentration raised to the power one less than the order of that reaction.

Examples:

The reaction between NO and H2 to give N2 and H2O follows the third order reaction

kinetics. The reaction is,

2NO + 2H2

N2 + 2H2O

Rate = k [H2][NO]2

Case (II): when the initial concentration of two reactants is same and that of the third

one is different

Consider the following reaction in which the reactants A and B have the same initial

concentrations equal to a but reactant C has different concentration equal to c as given

below,

A + B + C

Products

When t = 0

When t = t

ax

ax

cx

16

dx

k[A][B][C]

dt

dx

k(a x)(a x)(c x)

dt

dx

k(a x) 2 (c x)

dt

This is the differential rate equation for a third order reaction in which concentration of two

reactants are same and that of the third one is different.

Integrating the above equation after separating variables,

dx

(a x) (c x) k dt

(1)

1

A

B

C

2

2

(a x) (c x) (a x) (a x) (c x)

(2)

(3)

1 B(c a)

or

1

(c a)

1 C(a c)2

or

1

(a c) 2

1 A(ac ax cx x 2 ) B(c x) C(a 2 x 2 2ax)

1 Aac Aax Acx Ax 2 Bc Bx Ca 2 Cx 2 2Cax

0 AC

A C

or

1

(a c) 2

17

1

1

1

1

2

2

2

(a x) (c x)

(a c) (a x) (c a)(a x) (a c) 2 (c x)

Hence equation (1) becomes

(a c) (a x) (c a)(a x)

2

1

dx k dt

2

(a c) (c x)

1

dx

1

dx

1

dx

k dt

2

2

2

(a c) (a x) (c a) (a x) (a c) (c x)

1 ln(a x)

1

(a x) 21

1 ln(c x)

kt c

2

(a c)

1

(c a) (2 1)(1) (a c) 2

1

1

1

1

1

ln(a x)

ln(c x) kt c

2

(a c)

(c a) (a x) (a c) 2

1

1

1

ln(a x) ln(c x)

kt c

2

(a c)

(c a) (a x)

1

(a x)

1

1

ln

kt c

2

(a c)

(c x) (c a) (a x)

(4)

When t =0, x = 0, putting these values in above equation, the value of c can be calculated,

1

(a 0)

1

1

ln

k0 c

2

(a c)

(c 0) (c a) (a 0)

1

a

1

ln

c

2

(a c)

c a(c a)

Putting the value of c in equation (4),

1

(a x)

1

1

1

a

1

ln

kt

ln

2

2

(a c)

(c x) (c a) (a x)

(a c)

c a(c a)

1

(a x)

1

1

1

a

1

ln

ln

kt

2

2

(a c)

(c x) (c a) (a x) (a c)

c a(c a)

1

(a c)2

(a x)

a

1

1

1

ln (c x) ln c (c a) (a x) a(c a) kt

1

(a c)2

c(a x)

a (a x)

ln a(c x) a(a x)(c a) kt

1

(a c)2

c(a x)

a a x

ln a(c x) a(a x)(c a) kt

1

(a c)2

c(a x)

x

ln a(c x) a(a x)(c a) kt

18

1

(a c)2

ln

c(a x)

x

ln a(c x) a(a c)(a x) kt

c(a x) x(a c)

(a c)2 kt

a(c x) a(a x)

(5)

This is the integrated rate equation for a third order reaction in which concentration of two

reactants are same and that of the third one is different. This equation is similar to the

equation for a straight line passing through the origin, from the slope of which k can be

calculated if initial concentrations are known that is,

Slope (a c)2 k

Slope

(a c) 2

Left hand side of equation (5) is a dimensionless quantity. Hence units of k comes out to be,

1

mol / dm k sec

3 2

1 mol2dm6 sec k

k mol2dm6 sec1

Case (III): when the initial concentration of all the reactants is different

Consider the following reaction in which the initial concentration of reactants A, B

and C are a, b and c respectively.

A + B + C

Products

When t = 0

When t = t

ax

bx

cx

dx

k[A][B][C]

dt

dx

k(a x)(b x)(c x)

dt

dx

(a x)(b x)(c x) k dt

(1)

1

A

B

C

(a x)(b x)(c x) (a x) (b x) (c x)

(2)

19

1 A(b x)(c x) B(a x)(c x) C(a x)(b x)

1 A(b a)(c a) B(a a)(c a) C(a a)(b a)

1 A(b a)(c a)

1

1

(b a)(c a)

(a b)(c a)

1 A(b b)(c b) B(a b)(c b) C(a b)(b b)

1 B(a b)(c b)

1

1

(a b)(c b)

(a b)(b c)

1 A(b c)(c c) B(a c)(c c) C(a c)(b c)

1 C(a c)(b c)

1

1

(a c)(b c)

(c a)(b c)

1

1

1

1

(a x)(b x)(c x)

(a b)(c a)(a x) (a b)(b c)(b x) (c a)(b c)(c x)

Hence equation (1) becomes

1

dx

1

dx

1

dx

k dt

1

1

1

ln(a x)

ln(b x)

ln(c x) kt c

(a b)(c a)

(a b)(b c)

(c a)(b c)

1

(b c) ln(a x) (c a) ln(b x) (a b) ln(c x) kt c

(a b)(b c)(c a)

(a b)(b c)(c a)

(3)

When t =0, x = 0, putting these values in above equation, the value of c can be calculated,

(a b)(b c)(c a)

20

(b c) ln a (c a) ln b (a b) ln c c

(a b)(b c)(c a)

(a b)(b c)(c a)

(a b)(b c)(c a)

(b c) ln(a x) (c a) ln(b x) (a b) ln(c x) (b c) ln a (c a) ln b (a b) ln c kt

(a b)(b c)(c a)

(a b)(b c)(c a)

(a b)(b c)(c a)

(b c) ln

(a x)

(b x)

(c x)

(c a) ln

(a b) ln

(a b)(b c)(c a)kt

a

b

c

(4)

This is the integrated rate equation for a third order reaction in which the concentrations of all

the reactants are different. This is the equation of a straight line passing through the origin,

where the left hand side of the equation represents the dependent variable and t is the

independent variable. The plot will give a straight line whose slope is given by

Slope (a b)(b c)(c a)k

Slope

(a b)(b c)(c a)

Hence, the value of k can be determined if the initial concentrations of the three reactants are

known. Units of k can be determined by rearranging the equation (4),

k

(b c) ln

(a x)

(b x)

(c x)

(c a) ln

(a b) ln

a

b

c

(a b)(b c)(c a)t

mol dm 3

mol dm

3 3

sec

Sometime the rate of a reaction has more dependence on the concentration of one

reactant than that of the other. For example, 3rd order reactions, rate of reaction may be

directly proportional to the square of concentration of one reactant and concentration of the

other reactants. Consider a third order reaction of the type in which two moles of reactant A

are reacting with one mole of reactant B to give products. The initial concentration of reactant

A is a and that of B is b as given below,

21

2A + B

Products

When t = 0

When t = t

a2x

bx

dx

k[A]2 [B]

dt

dx

k(a 2x) 2 (b x)

dt

dx

(a 2x) (b x) k dt

2

(1)

1

A

B

C

2

2

(a 2x) (b x) (a 2x) (a 2x) (b x)

(2)

(3)

1 C(a 2b)2

C

1

(a 2b) 2

a

a

a

a

1 A(a 2 )(b ) B(b ) C(a 2 ) 2

2

2

2

2

a

2b a

1 B(b ) B(

)

2

2

2

2

(2b a)

(a 2b)

1 A(ab ax 2bx 2x 2 ) B(b x) C(a 2 4x 2 4ax)

1 Aab Aax 2Abx 2Ax 2 Bb Bx Ca 2 4Cx 2 4Cax)

Comparing coefficients of x2, we get

1 2A 4C

22

2A 4C

A 2C

2

(a 2b) 2

1

A

B

C

2

2

(a 2x) (b x) (a 2x) (a 2x) (b x)

1

2

2

1

2

2

2

(a 2x) (b x)

(a 2b) (a 2x) (a 2b)(a 2x) (a 2b) 2 (b x)

Hence equation (1) becomes

2

1

dx k dt

2

(a 2b) (b x)

1

2dx

1

2dx

1

dx

k dt

2

2

2

1

1

2 (a 2x) 21

ln(a

2x)

ln(b

x)

k dt

(a 2b)2

(a 2b)2

(a 2b) (2 1)(2)

(a 2x)

1

1

ln

kt c

2

(a 2b) (b x) (a 2b)(a 2x)

1

(a 2b) 2

(a 2x) (a 2b)

ln (b x) (a 2x) kt c

(4)

When t =0, x = 0, putting these values in above equation, the value of c can be calculated,

1

(a 2b) 2

(a 2 0) (a 2b)

ln (b 0) (a 2 0) k0 c

1

(a 2b) 2

a (a 2b)

c

ln b

a

1

(a 2b) 2

(a 2x) (a 2b)

1

ln (b x) (a 2x) (a 2b) 2

1

(a 2b)2

(a 2x) (a 2b)

a (a 2b)

kt

ln (b x) (a 2x) ln b

a

a (a 2b)

kt

ln b

a

ln

(a 2b) 2 kt

a(b x) (a 2x)

a

ln

1

b(a 2x)

1

(a 2b)

(a 2b) 2 kt

a(b x)

(a 2x) a

23

ln

a (a 2x)

b(a 2x)

(a 2b)

(a 2b) 2 kt

a(b x)

a(a 2x)

ln

2x

b(a 2x)

(a 2b)

(a 2b) 2 kt

a(b x)

a(a 2x)

ln

(a 2b)2 kt

a(b x)

a(a 2x)

(5)

This is the equation of straight line passing through the origin. The value of k can be found

from the slope if the initial concentrations are known.

Slope (a 2b)2 k

Slope

(a 2b) 2

Units of k

mole1n

time1

litre1n

4.10

An elementary reaction is a simple reaction which occurs in a single step. A complex

reaction is that reaction which occurs in two or more steps. Chemistry is comprised of

billions of reactions. The majority of reactions with which the chemist deals are not

elementary instead they involve two or more elementary steps and are complex. The complex

reactions are also known as composite reactions. There are various types of complex

reactions which may involve:

1. Reversible or opposing reactions

2. Consecutive reactions

3. Simultaneous or parallel or side reactions

4. Chain reactions

4.10.1 REVERSIBLE OR OPPOSING REACTIONS

These reactions may be of the following types:

a) First order opposed by first order reaction

b) First order opposed by second order reaction

c) Second order opposed by first order reaction

d) Second order opposed by second order reaction

24

a) First order opposed by first order reaction

In such reactions, the forward as well as the backward reaction is first order. This is

the simplest case of opposing reactions. Consider the following reaction

k1

A

B

k-1

When t = 0

When t = t

ax

When t = teq

axe

xe

dx

k1 (a x) k 1x

dt

(1)

Rf = Rb

and

x = xe

k1 (a x e ) k 1x e

k 1

k1 (a x e )

xe

(2)

k (a x e )

dx

k1 (a x) 1

x

dt

xe

(a x e )x

dx

k1 (a x)

dt

xe

x (a x) (a x e )x

dx

k1 e

dt

xe

ax xx e ax x e x

dx

k1 e

dt

xe

a(x e x)

dx

k1

dt

xe

dx k1a

(x e x)

dt

xe

(x

ka

dx

1 dt

xe

e x)

25

ln(x e x)

k1a

tc

xe

(3)

When t =0, x = 0, putting these values in above equation, the value of c comes out to be,

c ln x e

Putting the value of c in equation (3),

ln(x e x)

k1a

t ln x e

xe

ln x e ln(x e x)

ln

k1a

t

xe

xe

ka

1 t

(x e x) x e

k1

xe

xe

ln

at (x e x)

(4)

This is the integrated rate equation for opposing reaction of the type first order opposed by

first order.

b) First order opposed by Second order reaction

In such reactions, the forward reaction is first order and backward reaction is second

order. Consider the following reaction,

k1

A

k-1

When t = 0

When t = t

ax

When t = teq

axe

xe

xe

dx

k1 (a x) k 1x 2

dt

(1)

Rf = Rb

and

x = xe

k1 (a x e ) k 1 (x e )2

k 1

k1 (a x e )

(x e ) 2

(2)

26

k (a x e ) 2

dx

k1 (a x) 1

x

dt

(x e ) 2

k (a x e ) 2

dx

k1 (a x) 1

x

dt

(x e ) 2

dx k1 (a x)x e2 k1 (a x e )x 2

dt

x e2

x e2

dx

k1 (a x)x e2 k1 (a x e )x 2

dt

x e2

dx

k1ax e2 k1xx e2 k1ax 2 k1x e x 2

dt

x e2

dx

k1ax e2 k1ax 2 k1x e x 2 k1xx e2

dt

x e2

dx

k1a(x e2 x 2 ) k1xx e (x e x)

dt

x e2

dx

k1a(x e x)(x e x) k1xx e (x e x)

dt

x e2

dx

k1 (x e x) a(x e x) xx e

dt

x e2

dx

k1 (x e x) ax e ax xx e

dt

k dt

dx

12

(x e x)(ax e ax xx e )

xe

(x

k

dx

12 dt

xe

e x)(ax e ax xx e )

(3)

1

(x e x)(ax e ax xx e )

A

B

(x e x) (ax e ax xx e )

1 A(ax e ax xx e ) B(x e x)

For calculating the value of A, put (xe x) = 0 or x = xe that is

1 A(ax e ax e x e x e ) B(x e x e )

1 A(2ax e x e2 )

1 A x e (2a x e )

(4)

(5)

27

A

1

x e (2a x e )

1 A(ax e ax xx e ) B(x e x)

1 Aax e Aax Axx e Bx e Bx

Comparing coefficients of x, we get

0 Aa Ax e B

B Aa Ax e

B A(a x e )

Putting the value of A,

(a x e )

x e (2a x e )

1

(x e x)(ax e ax xx e )

(a x e )

1

dx

x (2a x )(x

e

x)

(a x e )dx

k

12 dt

x e (2a x e )(ax e ax xx e ) x e

(a x e )dx k1

1

dx

dt

x e (2a x e ) (x e x)

(ax e ax xx e ) x e2

k

1

ln(x e x) ln(ax e ax xx e ) 12 t c

x e (2a x e )

xe

(ax e ax xx e ) k1

1

ln

2 t c

x e (2a x e )

(x e x)

xe

(6)

When t =0, x = 0, putting these values in above equation, the value of c comes out to be,

(ax e a0 0x e ) k1

1

ln

2 0c

x e (2a x e )

(x e 0)

xe

c

1

ln a

x e (2a x e )

(ax e ax xx e ) k1

1

1

ln a

ln

2 t

x e (2a x e )

(x e x)

x e (2a x e )

xe

28

(ax e ax xx e )

k

1

1

ln a 12 t

ln

x e (2a x e )

(x e x)

xe

x e (2a x e )

(ax e ax xx e ) k1

1

ln

t

x e (2a x e )

(x e x)a x e2

k1

xe

ax x(a x e )

ln e

t(2a x e )

(x e x)a

(7)

This is the integrated rate equation for opposing reaction of the type first order opposed by

second order.

c) Second order opposed by first order reaction

In such reactions, the forward reaction is second order and backward reaction is first

order. Consider the following reaction,

k1

k-1

When t = 0

When t = t

ax

ax

When t = teq

axe

axe

xe

dx

k1 (a x) 2 k 1x

dt

(1)

Rf = Rb

and

x = xe

k1 (a x e )2 k 1x e

k 1

k1 (a x e ) 2

xe

(2)

k (a x e )2

dx

k1 (a x)2 1

x

dt

xe

dx k1 (a x) 2 x e k1 (a x e ) 2 x

dt

xe

dx k1

(a x)2 x e (a x e ) 2 x

dt x e

dx k1

(a 2 x 2 2ax)x e (a 2 x e2 2ax e )x

dt x e

29

dx k1 2

a x e x 2 x e 2axx e (a 2 x x e2 x 2ax e x)

dt x e

dx k1 2

a x e x 2 x e 2axx e a 2 x x e2 x 2ax e x

dt x e

dx k1 2

a x e x 2 x e a 2 x x e2 x

dt x e

dx k1 2

a x e a 2 x x 2 x e x e2 x

dt x e

dx k1 2

a (x e x) xx e (x x e )

dt x e

dx k1 2

a (x e x) xx e (x e x)

dt x e

dx k1

(x e x)(a 2 xx e )

dt x e

k dt

dx

1

2

(x e x)(a xx e )

xe

(x

k

dx

1 dt

2

xe

e x)(a xx e )

(3)

1

A

B

2

2

(x e x)(a xx e ) (x e x) (a xx e )

(4)

1 A(a 2 xx e ) B(x e x)

(5)

1 A(a 2 x e x e ) B(x e x e )

1 A(a 2 x e2 )

1

(a x e2 )

2

1 A(a 2 xx e ) B(x e x)

1 Aa 2 Axx e Bx e Bx

30

0 Ax e B

B Ax e

Putting the value of A,

x e

(a x e2 )

x e

1

1

2

2

2

2

2

(x e x)(a xx e ) (a x e )(x e x) (a x e )(a 2 xx e )

(a

x e dx

k

dx

2

1 dt

2

2

x )(x e x)

(a x e )(a xx e ) x e

2

e

x e dx k1

1

dx

dt

(a 2 x e2 ) (x e x) (a 2 xx e ) x e

k

1

ln(x e x) ln(a 2 xx e ) 1 t c

2

(a x e )

xe

2

(a 2 xx e ) k1

1

ln

t c

(a 2 x e2 )

(x e x)

xe

(6)

(a 2 0x e ) k1

1

ln

0c

(a 2 x e2 )

(x e 0)

xe

1

a2

ln

c

(a 2 x e2 ) x e

Putting the value of c in equation (6),

(a 2 xx e ) k1

1

1

a2

ln

ln

(a 2 x e2 )

(x e x)

xe

(a 2 x e2 ) x e

(a 2 xx e )

1

1

a 2 k1

ln

ln

t

(a 2 x e2 )

(x e x) (a 2 x e2 ) x e x e

(a 2 xx e )x e k1

1

ln

t

(a 2 x e2 ) (x e x)a 2 x e

k1

xe

(a 2 xx e )x e

ln

t(a 2 x e2 )

(x e x)a 2

(7)

31

This is the integrated rate equation for opposing reaction of the type second order opposed by

first order.

d) Second order opposed by second order reaction

In such reactions, the forward reaction is second order and backward reaction is also

second order. Consider the following reaction,

A

k1

k-1

When t = 0

When t = t

ax

ax

When t = teq

axe

axe

xe

xe

dx

k1 (a x) 2 k 1x 2

dt

(1)

Rf = Rb

and

x = xe

k1 (a x e )2 k 1x e2

k1 (a x e ) 2

k 1

x e2

(2)

k1 (a x e ) 2 2

dx

2

k1 (a x)

x

dt

x e2

dx k1 (a x) 2 x e2 k1 (a x e ) 2 x 2

dt

x e2

dx k1

2 (a x)2 x e2 (a x e ) 2 x 2

dt x e

dx k1

2 (a 2 x 2 2ax)x e2 (a 2 x e2 2ax e )x 2

dt x e

dx k1 2 2

a x e x 2 x e2 2axx e2 a 2 x 2 x e2 x 2 2ax e x 2

dt x e2

dx k1 2 2

a x e 2axx e2 a 2 x 2 2ax e x 2

dt x e2

dx k1 2 2

2 a x e a 2 x 2 2axx e2 2ax e x 2

dt x e

32

dx k1 2 2

2 a (x e x 2 ) 2axx e (x e x)

dt x e

dx k1 2

a (x e x)(x e x) 2axx e (x e x)

dt x e2

dx k1

2 (x e x) a 2 (x e x) 2axx e

dt x e

k

dx

12 dt

(x e x) a (x e x) 2axx e x e

2

(x

k

dx

12 dt

xe

e x) a (x e x) 2axx e

2

(3)

1

A

B

2

(x e x) a (x e x) 2axx e (x e x) a (x e x) 2axx e

(4)

1 A a 2 (x e x) 2axx e B(x e x)

(5)

1 A a 2 (x e x e ) 2ax e x e B(x e x e )

1 A(2a 2 x e 2ax e2 )

1

2ax e (a x e )

1 A a 2 (x e x) 2axx e B(x e x)

1 Aa 2 x e Aa 2 x 2Aaxx e Bx e Bx

0 Aa 2 2Aax e B

B A(a 2 2ax e )

(a 2 2ax e )

2ax e (a x e )

33

(a 2 2ax e )

1

1

2

(x e x) a 2 (x e x) 2axx e 2ax e (a x e )(x e x) [2ax e (a x e )][a (x e x) 2axx e ]

Hence equation (3) becomes

(a 2 2ax e )dx k1

1

dx

dt

2ax e (a x e ) (x e x) a 2 x e a 2 x 2axx e x e2

k

1

ln(x e x) ln(a 2 x e a 2 x 2axx e ) 12 t c

2ax e (a x e )

xe

(a 2 x e a 2 x 2axx e ) k1

1

ln

2 tc

2ax e (a x e )

(x e x)

xe

(6)

(a 2 x e a 2 0 2a0x e ) k1

1

ln

2 0c

2ax e (a x e )

(x e 0)

xe

a 2xe

1

ln

c

2ax e (a x e ) x e

c

1

ln a 2

2ax e (a x e )

(a 2 x e a 2 x 2axx e ) k1

1

1

ln a 2

ln

2 t

2ax e (a x e )

(x e x)

2ax e (a x e )

xe

(a 2 x e a 2 x 2axx e )

k

1

1

ln a 2 12 t

ln

2ax e (a x e )

(x e x)

xe

2ax e (a x e )

(a 2 x e a 2 x 2axx e ) k1

1

ln

2 t

2ax e (a x e )

(x e x)a 2

xe

k1

a(ax e ax 2xx e )

x e2

ln

2atx e (a x e )

(x e x)a 2

k1

ax e ax 2xx e

xe

ln

2at(a x e )

(x e x)a

k1

x(a 2x e ) ax e

xe

ln

2at(a x e )

(x e x)a

(7)

This is the integrated rate equation for opposing reaction of the type second order opposed by

second order.

34

4.10.2 CONSECUTIVE OR SEQUENTIAL REACTIONS

The reactions which proceed from reactants to products in one or more steps

through intermediates are known as consecutive reactions. Each step involved here has its

own rate constant. Consider the simplest consecutive reaction as follows,

k1

k2

When t = 0

When t = t

[A]

[B]

[C]

d[A]

k1[A]

dt

d[A]

k1 dt

[A]

ln[A] k1t c

(1)

ln a k1 0 c

ln a c

Putting the value of c in equation (1),

ln[A] k1t ln a

ln[A] ln a k1t

ln

[A]

k1 t

a

[A]

e k1t

a

[A] ae k1t

(2)

d[B]

k1[A] k 2 [B]

dt

d[B]

k 2 [B] k1[A]

dt

d[B]

k 2 [B] k1ae k1t

dt

35

Multiplying both sides by e k 2 t

d[B]

dt

d[B] k 2 t

e [B]k 2ek 2 t k1ae(k 2 k1 )t

dt

d

[B]ek 2 t k1ae(k 2 k1 )t

dt

d [B]ek2 t k1ae(k 2 k1 )t dt

d [B]e k a e

k2t

(k 2 k1 )t

[B]e

k2t

dt

e(k 2 k1 )t

k1a

D

k 2 k1

(3)

[0]e

k2 0

e(k 2 k1 )0

k1a

D

k 2 k1

k1a

D

k 2 k1

[B]e

k2t

ka

e(k 2 k1 )t

k1a

1

k 2 k1 k 2 k1

[B]ek 2 t

k1a

e(k2 k1 )t 1

k 2 k1

[B]ek 2 t

k1a

ek2t ek1t 1

k 2 k1

[B]

k1a ek 2 t k1t 1

e k2t

k 2 k1 e k 2 t

e

[B]

k1a

e k1t e k 2 t

k 2 k1

a [A] [B] [C]

[C] a ae k1t

k1a

e k1t e k 2 t

k 2 k1

(4)

36

[C] a ae

k1t

k 2 k1

[C]

k 2 k1

[C]

k 2 k1

[C]

k 2 k1

(k e k1t k1e k 2 t )

[C] a 1 2

k 2 k1

(5)

processes such as polymerization, thermal cracking and chlorination of hydrocarbons.

4.10.3 SIMULTANEOUS OR PARALLEL OR SIDE REACTIONS

The reactions in which reactants undergo two or more independent reactions

simultaneously are called as parallel reactions. These are also known as side reactions.

The reaction in which maximum yield of the product is obtained is called main or major

reaction while the others are called side reactions. Consider a general parallel reaction,

k1

A

a

a-x

when t = 0

when t = t

k2

B

0

x

at t = 0

at t = t

C

0

x

at t = 0

at t = t

dx

k1 (a x) k 2 (a x)

dt

dx

(k1 k 2 )(a x)

dt

dx

(a x) (k

k 2 ) dt

ln(a x) (k1 k 2 )t c

(1)

ln(a 0) (k1 k 2 )0 c

37

ln a c

Putting the value of c in equation (1),

ln(a x) (k1 k 2 )t ln a

(k1 k 2 )t ln a ln(a x)

1

a

(k1 k 2 ) ln

t ax

(2)

The equation (2) is the rate constant expression for a parallel reaction. It is similar to the

equation of a first order reaction, (k1 + k2) being the sum of the specific rates of the two

simultaneous reactions. If k1 > k2 then AB is main reaction and AC is side reaction.

Graphically this can be represented as shown in figure (4.1). For example, nitration of

phenols gives ortho-nitrophenol and para-nitrophenol in two simultaneous side reactions

Figure (4.2).

The chemical reactions which take place in a series of successive processes

involving the formation of free atoms and radicals are known as chain reactions. The

kinetic laws for such reactions are considerably complex. A well-known example of these

types of reactions is the hydrogenbromine reaction. Chain reactions usually proceed very

rapidly. Many explosive reactions occur by a chain mechanism; atomic fission and atomic

fusion are of this type of reactions.

4.11

THERMAL REACTIONS

A well known example of a thermal reaction is the hydrogen bromine reaction. The

H2

Br2

2HBr

d[HBr]

k[H 2 ][Br2 ]

dt

38

It follows the following empirical rate equation given by Bodenstein and Lind in 1906:

[HBr]

dt

1 k

[Br2 ]

The complexity of this equation could not be explained until 1919 when Christiansen,

Herzfeld and Polanyi independently and almost simultaneously solved the problem. They

proposed a chain of reactions with the following steps,

k1

(1)

Br2

(2)

Br + H2

(3)

H + Br2

(4)

(5)

2 Br

k2

k3

+ HBr

k5

Chain initiation

2 Br

k4

HBr + H

Chain propagation

HBr + Br

Chain propagation

H2

Chain inhibition

+ Br

Br2

Chain termination

According to this mechanism HBr is formed in reactions (2) and (3) and removed in reaction

(4). Consequently, the rate of formation of HBr is given by

d[HBr]

k 2 [Br ][H 2 ] k 3[H ][Br2 ] k 4[H ][HBr]

dt

d[HBr]

k 2 [Br ][H 2 ] k 3[Br2 ] k 4 [HBr][H ]

dt

(1)

The concentration of [Br ] and [H ] can be determined using steady state approximation.

The steady state approximation is also occasionally called stationary state approximation.

This approximation assumes that the concentration of reaction intermediates remains constant

throughout the reaction after an initial buildup. This approximation can only be applied to

short lived or very reactive species. Therefore mathematically we can write,

d[Br ]

k1[Br2 ] k 2 [Br ][H 2 ] k 3[H ][Br2 ] k 4[H ][HBr] k 5[Br ]2 0 (2)

dt

d[H ]

k 2 [Br ][H 2 ] k 3[H ][Br2 ] k 4[H ][HBr] 0

dt

Solving equation (3),

k 2 [Br ][H2 ] k 3[H ][Br2 ] k 4 [H ][HBr] 0

(3)

39

k 2 [Br ][H2 ] k 3[Br2 ] k 4 [HBr][H ] 0

[H ]

k 2 [Br ][H 2 ]

k 3[Br2 ] k 4 [HBr]

(4)

(5)

k1[Br2 ] k 2 [Br ][H2 ] k 3[H ][Br2 ] k 4[H ][HBr] k 5[Br ]2 0

k1[Br2 ] k 2 [Br ][H2 ] k 3[Br2 ] k 4[HBr][H ] k 5[Br ]2 0

k1[Br2 ] k 5[Br ]2 0

k 5 [Br ]2 k1[Br2 ]

1/2

k [Br ]

[Br ] 1 2

k5

(6)

Now putting the value of [Br ] from equation (6) in equation (5),

1/2

k [Br ]

k 2 1 2 [H 2 ]

k5

[H ]

k 3[Br2 ] k 4 [HBr]

(7)

Putting the values of [Br ] and [H ] from Eq.(6) and Eq.(7) in Eq.(1) we get

d[HBr]

k 2 [Br ][H 2 ] k 3[Br2 ] k 4 [HBr][H ]

dt

1/2

k [Br ]

k 2 1 2 [H 2 ]

1/2

k5

k [Br ]

d[HBr]

k 2 1 2 [H 2 ] k 3[Br2 ] k 4 [HBr]

dt

k 3[Br2 ] k 4 [HBr]

k5

1/2

k [Br ]

k [Br ] k 4 [HBr]

d[HBr]

k 2 1 2 [H 2 ] 1 3 2

dt

k5

k 3[Br2 ] k 4 [HBr]

1/2

k [Br ]

k [Br ] k 4 [HBr] k 3[Br2 ] k 4 [HBr]

d[HBr]

k 2 1 2 [H 2 ] 3 2

dt

k 3[Br2 ] k 4 [HBr]

k5

d[HBr] k 2

dt

k1

k5

[Br2 ]

1/2

[H 2 ]2k 3[Br2 ]

k 3[Br2 ] k 4 [HBr]

40

1/2

k1

1/2

d[HBr] 2k 2 k5 [Br2 ] [H 2 ]

k [HBr]

dt

1 4

k 3[Br2 ]

[HBr]

dt

1 k

[Br2 ]

Where k 2k 2

and k

k1

k5

k4

k3

(8)

equation given by Bodenstein and Lind. The appearance of the term [HBr] in the

denominator implies that the velocity of the reaction is decreased by the product HBr and this

product acts an inhibitor of the reaction. This is an example of self-inhibition.

4.12

PHOTOCHEMICAL REACTIONS

Photochemical reaction is a chemical reaction initiated by the absorption of

energy in the form of light. In photochemical reactions free radicals are produced which

initiate the chain reactions. An example is the photosynthesis of HCl gas. All photochemical

reactions are of zero order. These reactions are independent of concentration of reactants.

Change in concentration of reactants has no effect on rate of photochemical reactions.

a) HydrogenBromine Reaction

Consider the following photochemical reaction in which H2 and Br2 are going to

produce HBr,

H2

Br2

2HBr

(1)

Br2

(2)

Br + H2

(3)

H + Br2

(4)

(5)

2 Br

k1

k2

k3

+ HBr

k5

k4

2 Br

Chain initiation

HBr + H

Chain propagation

HBr + Br

Chain propagation

H2

Chain inhibition

+ Br

Br2

Chain termination

According to this mechanism HBr is formed in reactions (2) and (3) and removed in reaction

(4). Consequently, the rate of formation of HBr is given by

41

d[HBr]

k 2 [Br ][H 2 ] k 3[H ][Br2 ] k 4[H ][HBr]

dt

d[HBr]

k 2 [Br ][H 2 ] k 3[Br2 ] k 4 [HBr][H ]

dt

(1)

The concentration of [Br ] and [H ] can be determined using steady state approximation. This

approximation assumed that at steady state the rate of formation of reaction intermediates can

be considered to be equal to their rate of disappearance. Mathematically we can write,

d[Br ]

k1Ia k 2 [Br ][H 2 ] k 3[H ][Br2 ] k 4 [H ][HBr] k 5[Br ]2 0

dt

(2)

d[H ]

k 2 [Br ][H 2 ] k 3[H ][Br2 ] k 4[H ][HBr] 0

dt

(3)

k 2 [Br ][H2 ] k 3[H ][Br2 ] k 4 [H ][HBr] 0

k 2 [Br ][H2 ] k 3[Br2 ] k 4 [HBr][H ] 0

[H ]

k 2 [Br ][H 2 ]

k 3[Br2 ] k 4 [HBr]

(4)

(5)

k1Ia k 2 [Br ][H2 ] k 3[H ][Br2 ] k 4[H ][HBr] k 5[Br ]2 0

k1Ia k 2 [Br ][H2 ] k 3[Br2 ] k 4[HBr][H ] k 5[Br ]2 0

k1Ia k 5[Br ]2 0

k 5[Br ]2 k1Ia

1/2

k

[Br ] 1 Ia

k5

(6)

Now putting the value of [Br ] from equation (6) in equation (5),

1/2

k

k 2 1 Ia [H 2 ]

k5

[H ]

k 3[Br2 ] k 4 [HBr]

(7)

Putting the values of [Br ] and [H ] from Eq.(6) and Eq.(7) in Eq.(1) we get

42

d[HBr]

k 2 [Br ][H 2 ] k 3[Br2 ] k 4 [HBr][H ]

dt

1/2

k

k 2 1 Ia [H 2 ]

1/2

k

k

d[HBr]

k 2 1 Ia [H 2 ] k 3[Br2 ] k 4 [HBr] 5

dt

k 3[Br2 ] k 4 [HBr]

k5

1/2

k

k [Br ] k 4 [HBr]

d[HBr]

k 2 1 Ia [H 2 ] 1 3 2

dt

k5

k 3[Br2 ] k 4 [HBr]

1/2

k

k [Br ] k 4 [HBr] k 3[Br2 ] k 4 [HBr]

d[HBr]

k 2 1 Ia [H 2 ] 3 2

dt

k 3[Br2 ] k 4 [HBr]

k5

1/2

k1

d[HBr] k 2 k5 Ia [H 2 ]2k 3[Br2 ]

dt

k 3[Br2 ] k 4 [HBr]

1/2

k1

Ia1/2 [H 2 ]

d[HBr] 2k 2 k5

k [HBr]

dt

1 4

k 3[Br2 ]

kIa1/2 [H 2 ]

d[HBr]

[HBr]

dt

1 k

[Br2 ]

Where k 2k 2

and k

k1

k5

k4

k3

(8)

b) HydrogenChlorine Reaction

The chemical reaction between hydrogen and chlorine in the presence of light

produces hydrogen chloride with explosion. In 1930 Bodenstein and Hanger investigated the

kinetics of this photochemical reaction. The rate law expression for the reaction on the basis

of their experimental observations is given below,

H2

Cl2

2HCl

d[HCl]

kIa [H 2 ]

dt

Where k is constant and Ia is the intensity of absorbed light (expressed in Einstein dm-3 sec-1).

They proposed the following mechanism for the reaction,

(1)

Cl2

k1

2 Cl

Initiation step

43

(2)

Cl + H2

(3)

H + Cl2

(4)

Cl

k4

k2

k3

HCl + H

Propagation step

HCl + Cl

Propagation step

Termination step

1/2 Cl2

HCl is more stable than HBr. Bond between HCl is strong so [H ] radical do not react with

HCl molecule as in case of HBr. The net rate of reaction in terms of rate of formation of HCl

according to above mechanism can be written as,

d[HCl]

k 2 [Cl ][H 2 ] k 3[H ][Cl2 ]

dt

(1)

The concentration of [Cl ] and [H ] can be determined applying steady state approximation.

This approximation assumed that at steady state the net change in concentration of reaction

intermediates is zero. Mathematically,

d[Cl ]

k1Ia k 2 [Cl ][H 2 ] k 3[H ][Cl2 ] k 4 [Cl ] 0

dt

(2)

d[H ]

k 2 [Cl ][H 2 ] k 3[H ][Cl2 ] 0

dt

(3)

k 2 [Cl ][H2 ] k 3[H ][Cl2 ] 0

k 2 [Cl ][H2 ] k 3[H ][Cl2 ]

(4)

k 2 [Cl ][H 2 ]

k 3[Cl2 ]

(5)

[H ]

k1Ia k 2 [Cl ][H2 ] k 3[H ][Cl2 ] k 4[Cl ] 0

k1Ia k3[H ][Cl2 ] k 3[H ][Cl2 ] k 4 [Cl ] 0

k1Ia k 4 [Cl ] 0

[Cl ]

k 1I a

k4

(6)

Now putting the value of [Cl ] from equation (6) in equation (5),

[H ]

k 2 k1Ia [H 2 ]

k 3k 4 [Cl2 ]

(7)

44

Putting the values of [Cl ] and [H ] from Eq.(6) and Eq.(7) in Eq.(1) we get

d[HCl]

k 2 [Cl ][H 2 ] k 3[H ][Cl2 ]

dt

kI

k k I [H ]

d[HCl]

k 2 1 a [H 2 ] k 3 2 1 a 2 [Cl2 ]

dt

k4

k 3k 4 [Cl2 ]

k k I [H ]

d[HCl] k 2 k1Ia

[H 2 ] 2 1 a 2

dt

k4

k4

d[HCl] 2k 2 k1

Ia [H 2 ]

dt

k4

d[HCl]

kIa [H 2 ]

dt

(8)

and Hanger.

4.13

It is well established that the rate of reaction increases to an appreciable extent with

the rise in temperature. Experimentally, it has been found that for a 10 C rise in temperature,

the velocity of the reaction is doubled or trebled.

The first empirical equation to show the variation of rate constant k of a reaction with

temperature T was suggested by Hood. His equation is,

log k A

B

T

(1)

Where A and B are positive empirical constants and T is the absolute temperature. The

verification of this equation lies in the fact that a plot of log k versus 1/T is nearly a straight

line with negative slope for most of the reactions. This equation was theoretically justified by

Vant Hoff in 1884. His arguments were based on the variation of equilibrium constant with

temperature.

Svante Arrhenius extended his idea and suggested a similar equation to show the

variation of rate constant with temperature in the year 1889. The differential form of

Arrhenius equation is given by,

E

d ln k

a2

dT

RT

(2)

Integrating equation (2) we get,

45

d ln k

E a dT

R T2

Ea

ln A(constant)

RT

ln k

ln k ln A

Ea

RT

ln k ln A

ln

(3)

Ea

RT

E

k

a

A

RT

E

a

k

e RT

A

k Ae

Ea

RT

(4)

The constants A and Ea are related to A and B in equation (1). The factor A is known as

Arrhenius pre-exponential factor, also called frequency factor, have same units as that of

specific rate constant. The frequency factor is related to collision frequency and steric factor.

The steric (or orientation) effect, also called probability factor, is the fraction of collisions in

which the molecules have proper orientation favourable for reaction. Equation (3) and

equation (4) are the alternate forms of the Arrhenius equation. Arrhenius equation shows that

the value of k for a reaction is directly related to A. The value of A increases if collision

frequency or steric factor increases.

The second factor in Arrhenius equation Ea/RT depends on the value of Ea. This term

usually has a positive value because Ea is usually positive. Since this term is subtracted from

lnA in equation (3), we see that the value of k decreases as the value of Ea/RT increases. In

other words, an increase in the value of Ea decreases the rate of the reaction. Conversely, an

increase in temperature (which is in the denominator) reduces the value of the term Ea/RT

and thus increases the value of k. This increase is consistent with the observation that the

rates of almost all reactions increase as the temperature rises at the same concentration.

Rewriting equation (3) as follows,

log k

Ea

log A

2.303RT

(5)

This equation is identical with the empirical equation (1). To test the validity of this equation;

a plot of log k against 1/T should be a straight line having slope Ea/2.303R and intercept logA

46

as shown in figure. Knowing the slope, the value of constant Ea which is the characteristic

of the reaction can be calculated.

Alternatively, Ea can also be determined if the rate constants are known at two

different temperatures. For this purpose Arrhenius equation (2) can be integrated between the

limits k1 (the rate constant at T1) and k2 (the rate constant at T2),

k2

d ln k

k1

ln k k 2

k

Ea

R

T2

dT

T1

E a 1 T2

R T T1

ln k 2 ln k1

Ea

R

1 1

T2 T1

ln

k 2 E a T2 T1

k1 R T1T2

ln

E a T2 T1

k2

k1 2.303R T1T2

(6)

Equation (6) is another form of Arrhenius equation that is useful for calculating the value of

activation energy of a reaction when the value of rate constant at two different temperatures

is known for that reaction. The Arrhenius equation correlates rate constant with temperature.

It gives the idea of energy of activation.

Energy of Activation and Activated Complex

The concept of energy of activation was developed by Arrhenius in 1888 which

constitute the backbone of all the modern theories. According to Arrhenius, the molecules

must acquire a discrete minimum amount of energy before the end products are formed.

These activated molecules will then collide and lead to the reaction. Collisions between

molecules which are not activated will be of no use and no reaction will take place. Thus the

reactants must pass through an energy rich or activated state before they can react. The

47

minimum amount of energy required by the molecules to overcome the activated state

or energy barrier before the reaction takes place is known as energy of activation.

It follows from the concept of activation that the reactants are not directly converted

into products. The molecules first acquire the energy to form an activated complex and this

activated complex is then decomposed into products.

Activated Complex

Reactants

Products

In other words, there exists an energy barrier between the reactants and the products. If the

reactant molecules can cross this energy barrier, they will be converted into products.

The energy of activation is usually expressed in J mol-1 and kJ mol-1 and is denoted by

the symbol Ea. The relationship between enthalpy of reaction and energy of activation for an

exothermic reaction and an endothermic reaction is shown in figure (4.3) and (4.4).

In an exothermic reaction products are at lower energy level than the reactants and in

an endothermic reaction the products are at higher energy level than the reactants. With both

types of reactions the activation energy is an energy barrier which must be overcome before

products are formed. Surmounting this barrier is similar to carrying a ball to the top of a hill

and then rolling down the either side. But if the ball cannot be carried to the top, it will roll

back. Similarly if Ea is not supplied, the reaction will not start and the reactants will never get

converted into the products.

According to the arguments given above, a general reaction of the type A2 + B2

2AB

It must be kept in mind that the energy of activation is always positive whether the reaction is

exothermic or endothermic.

48

4.14

1) Collision theory

2) Transition state theory or activated complex theory

4.14.1 Collision Theory

This theory is based upon the kinetic theory of gases according to which the

molecules of a gas are continuously moving and hence colliding with each other. Since for a

collision to takes place, at least two molecules must be involved, therefore the simple case to

consider is that of bimolecular reactions. Hence in discussion that follows, we shall first

discuss the collision theory for bimolecular reactions and then for unimolecular reactions.

1) Collision Theory for Bimolecular Reactions

Bimolecular collision theory for the reactions consisting of two reactant molecules

was proposed independently by Max Trautz in 1916 and William Lewis in 1918. This

theory is based on following assumptions:

1. For a chemical reaction to takes place reactants must collide with each other.

2. Not all the collisions occurring lead to reaction but only those which form activated

molecules.

3. The molecules must be suitably oriented at the time of collisions.

Consider a gasphase bimolecular elementary reaction,

A+A

Products

e.g.,

2HI

A+B

Products

e.g.,

H2 + I2

H2 + I2

2HI

Rate k[A]2 kn A2

(1)

Rate k[A][B] kn A n B

(2)

Where nA and nB are the number of molecules per dm3 of the reactants.

The rate of reaction can also be written according to collision theory as follows,

Rate Z q

(3)

Where Z is number of binary collisions per second per dm3 of the reaction mixture and q is

fraction of activated molecules.

From kinetic theory of gases, number of collisions per second per dm3 between like

molecules of a gas in the reaction mixture is given by,

ZAA

1

A2 n 2A u

2

(4)

49

Where A is the collision diameter of the reactant molecules, nA is the number of molecules

per dm3 of reactants, u is the average velocity of molecules. Now the value of u is equal to,

8RT

M

Where R is the general gas constant, T is absolute temperature and M is the molar mass.

Putting this value in equation (4),

ZAA

1

8RT

A2 n A2

M

2

ZAA 22A n 2A

RT

M

(5)

When the two molecules are not alike then collision frequency (collision number) is given by,

8RT

ZAB n A n B2AB

(6)

MA MB

B

Where AB A

is the

is the mean collision diameter of the molecules;

2

MA MB

reduced mass; nA and nB are the number of molecules per dm3 of the reactants; MA and MB

are the molecular weights of two gaseous reactants.

The fraction of molecules q having the necessary energy of activation is given by

Boltzmann law as follows,

n

q

e Ea /RT

n

(7)

Where n is the number of activated molecules having energy equal to or greater than the

energy of activation Ea, and n is the total number of molecules per dm3.

Thus the expression for the rate of reaction involving identical molecules is given by,

RT Ea /RT

e

M

(8)

(9)

2

Rate ZAB q n A n BAB

8RT Ea /RT

e

Hence the rate constant expressions for bimolecular reactions comes out to be,

For like molecules, from equation (1) and (8)

kn 2A 22A n 2A

RT Ea /RT

e

M

50

RT Ea /RT

e

M

k 22A

(10)

2

kn A n B n A n BAB

8RT Ea /RT

e

8RT Ea /RT

e

k 2AB

(11)

k Ae

Ea

RT

(12)

Comparing Eq.(10) and Eq.(11) with Eq.(12) we find that the frequency factor A in

Arrhenius equation is proportional to ZAA or ZAB and depends on the square root of

temperature. Hence the expression for the rate constant becomes,

k Ze

Ea

RT

Where Z 22A RT / M

(13)

(for like molecules) and Z 2AB 8RT /

(for unlike

molecules). It has been found experimentally that for reactions between simple molecules Z

agrees well with the Arrhenius factor A. Therefore, collision theory successfully accounts for

the rates of simple reactions but in many cases the rates differ considerably. For this reason

the equation is further modified as

k PZe

Ea

RT

(14)

Where, P is called the probability factor or steric factor. The factor P is a measure of the

geometrical requirements that must be met when activated colliding molecules are

interacting. This factor, the steric factor, limits the successful collisions to the ones in which

molecules are favourably oriented. In other words, P is the fraction of collisions in which the

molecules have an orientation favourable for reaction. Equation (14) is the equation of the

collision theory.

Limitations of Collision theory

The collision theory in the form of equation (14) is not applicable to the following cases,

1. When the complex molecules are involved in the chemical reactions.

2. When the chain mechanism is to be obeyed by the chemical reactions.

3. When the reaction is surface catalyzed.

It is applicable only to gas phase reactions and cannot be applied to kinetic studies in

solutions. It does not give any explanation for abnormally high rates of reactions.

51

2) Collision Theory for Unimolecular Reactions (Lindemanns Mechanism)

In unimolecular reactions, only one molecule takes part in the reaction so

consequently the question arises: How do molecules in unimolecular reactions attain their

energy of activation? If the energy of activation is attained in a bimolecular collision, then the

reaction should be of second order. But the fact is that the unimolecular reactions are first

order except in gas phase at low pressure. Explanation of how a bimolecular collision can

give rise to first order kinetics was given by F. A. Lindemann in 1922.

Lindemann pointed out that the reacting molecules acquire activation energy through

collisions with other molecules and as a result some molecules are activated. Further he

postulated that the activated molecules do not decompose immediately, but remain in the

activated form for a definite period. Meanwhile the added excess energy may increase the

amplitude of vibration and thus can lead to rupture the bond, or may be robbed by a less

energetic molecule in the ensuing collision. These possibilities can be represented by a

mechanism consisting of following series of elementary steps,

(1)

A + A

(2)

A* + A

A*

(3)

k1

k2

k3

A + A*

(Activation)

A + A

(Dectivation)

Products

(Decomposition)

Where, A represents a normal molecule and A* an activated molecule. k1, k2 and k3 are the

rate constants of three steps. According to this mechanism rate of formation of product is

given by,

dx

k 3[A* ]

dt

(1)

The concentration of A*, the reaction intermediate, can be determined by using steady state

approximation. That is

d[A* ]

k1[A]2 k 2 [A* ][A] k 3[A* ] 0

dt

k 2 [A* ][A] k 3[A* ] k1[A]2

[A* ](k 2 [A] k 3 ) k1[A]2

k1[A]2

[A ]

k 2 [A] k 3

*

(2)

52

Purring the value of A* from equation (2) in equation (1), we get

k k [A]2

dx

3 1

dt k 2 [A] k 3

(3)

Case (1): At high pressure the concentration of reacting molecules is relatively high. The

activated molecules will have a greater chance of colliding with inactive molecules and thus

become deactivated. Under such conditions, the rate of bimolecular deactivation will be much

faster than that of unimolecular decomposition then k2 [A] >> k3 and equation (3) reduces to

dx k 3k1[A]2 k 3k1[A]

k[A]

dt

k 2 [A]

k2

Where, k k 3k1 / k 2 . The equation predicts a first order reaction.

Case (2): At low pressure the concentration of A decreases and hence the number of

collisions decreases. Consequently, the rate of decomposition will be much faster than its rate

of deactivation. Under such conditions k3 >> k2 [A] and equation (3) reduces to

dx k 3k1[A]2

k1[A]2

dt

k3

i.e., the reaction should be second order. Therefore it is the pressure which governs the order

of reaction. This conclusion was experimentally verified by Hinshelwood.

Examples:

Such changes from first order kinetics in gaseous reactions at higher pressures to

second order at lower pressures actually have been observed in many gaseous reactions. For

example, the thermal decomposition of nitrogen pentoxide and of azomethane at high

pressure are the first order reactions,

N2O5

N2O4 + 1/2 O2

(CH3)2N2

C2H6 + N2

whereas at very low pressures these reactions become second order. Such observations

confirm the Lindemanns mechanism.

4.14.2 Transition State Theory

This theory was first formulated in 1935 by Henry Eyring who was awarded Nobel

prize for this valuable work. This theory is also known as absolute rate theory because with

the help of it is possible to get the absolute value of the rate constant. The main postulates of

this theory are:

53

1. All reactions proceed through an activated or transition state which is higher in energy

than both reactants and products.

2. In the transition state the reactants are combined in a species called the activated

complex.

3. In activated complex the bonds between the atoms are in the process of being formed

and broken.

4. A true thermodynamic equilibrium exists between the reactant molecules and the

activated complex species even though the overall chemical reaction is irreversible.

5. The rate of the reaction is equal to the concentration of activated complex species

times the frequency at which the complex intermediates dissociate into products.

In the light of above mentioned postulates, the reaction between two reactants A and B can be

represented as follows

[AB]*

A + B

Products

On the basis of these ideas, Eyring derived an equation for the rate constant k of any reaction,

given by

k

RT *

K

NA h

(1)

Kelvin temperature and K* is equilibrium constant for the formation of activated complex

from the reactants.

Now from thermodynamics equilibrium constant for the first step reversible process is related

with the change in Gibbs free energy according to following expression,

G* RT ln K*

ln K*

K e

*

G*

RT

G*

RT

(2)

Where G* is the change in free energy of activation and is obtained by subtracting the free

energy of the activated complex from that of reactants.

Putting this value of K* from equation (2) in equation (1) we get

G

RT RT

k

e

NA h

(3)

54

Also from fundamental relations of thermodynamics we know that

G* H* TS*

Where G*, H* and S* represents the free energy, enthalpy and entropy of activation

respectively and T is the absolute temperature. Putting this value of G* equation (3)

becomes,

TS )

RT ( H RT

k

e

NA h

*

H

RT RS RT

k

e e

NA h

*

RT RS RTa

k

e e

NA h

*

(4)

( H* = Ea)

Equation (4) is the equation of transition state theory and is known as Eyring equation. This

equation gives valuable information about the reaction.

A comparison of equation (4) with Arrhenius equation shows that the pre-exponential

factor A is related to the entropy of activation by the expression,

RT RS

A

e

NA h

The entropy of activation introduced by the transition state theory is analogous to the steric

factor from collision theory.

Transition state theory is applicable to all types of reactions. This is due to the

presence of S* factor in the theory. It has been found that the value of S* is negative. The

negative value of S* indicates that the formation of activated complex (which is more

ordered than the molecules of the reactants) from the reactants is accompanied by a large

decrease of entropy. Larger the complexity of the reacting molecules, greater will be the

decrease in the value of entropy. This results in the smaller value of the quantity eS /R and

*

since RT / NA h is same for all reactions at same temperature, therefore, PZ value in collision

theory would be much less than the interpreted value.

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