Chemical Kinetics

1
 Chemical Kinetics: Outline
1. Rate of Chemical Reaction
2. Reaction Rate and Reactants Concentrations
3. Rate Constant
4. Elementary Reaction and Molecularity of Reaction
5. Order of Reaction
6. Methods of Determining Reaction Order
7. Effect of Temperature on Reaction Rate
8. Types of Reactions
9. Theoretical Description of Elementary Reactions
10. Reaction in Solution
2
 Chemical Kinetics: Introduction
What is chemical kinetics?
Study of rates of chemical reactions, i.e. how the
concentration of reactants and products change
with time.

Why is chemical kinetics?

To determine experimentally rate of chemical reaction;
dependence on concentration, temperature etc.
To understand the mechanism of reaction, i.e. number
of steps involved, nature of intermediated involved etc.

3
 1. Reaction Rate
So,
dC
rate  
dt
Unit of rate 
  mol.L .s
-1 -1

time
 : refer to the product formation
 : refer to the reactantsconsuming
C : concentration of product or reactant
4
 A B

time

d[A]
rate =-
dt

d[B]
rate =
dt
5
2. Reaction Rate and Reactant (!!)
Concentration(reaction of molecular bromine and formic acid)

Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

time

393 nm Detector
light
[Br2] α Absorption 6
 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

d[Br2] [Br2]final – [Br2]initial

average rate = - =-
dt tfinal - tinitial
instantaneous rate = rate for specific instance in time 7
 rate α [Br2]
rate = k [Br2]
rate
k= = rate constant
[Br2]
= 3.50 x 10-3 s-1
8
 Reaction Rates and Stoichiometry
2A B

Two moles of A disappear for each mole of B that is formed.

1 d[A] d[B]
rate = - rate =
2 dt dt

aA + bB cC + dD

1 d[A] 1 d[B] 1 d[C] 1 d[D]

rate = - =- = =
a dt b dt c dt d dt

9
13.1
 3. Rate Constant
rate α [ reactant]

rate = k [reactant]

k = specific rate constant, i.e. depends

on the type of reaction order

10
 Rate Constant & Order of
Reaction
For 1st order rate reaction
 rate  k1 reactant
1

1
rate Ms 1
 k1    s
reactant M
1

For 2 nd order rate reaction

 rate  k 2 reactant
2

rate Ms1 1 1 1 1
 k2    M s  L.mol .s
reactant M
2 2

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 Rate Constant & Order of
Reaction
For zero order rate reaction
 rate  k0 reactant  k0
0

 k0  rate  Ms1  mol.L1.s 1

Thus, the rate of reaction is directly proportional to the
concentration of reactants each raised to the power
equal to the number of its molecules that participate to
form the activated complex.

(Power equal to the number of its molecules that participate

to form the activated complex = ORDER writ to that reactant)
[reactant]power = [reactant]order
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 Factors Affecting Rates
1. Concentration - molecules must collide to
react;
Rate α collision frequency α concentration
2.Physical state - molecules must mix to collide;
Smaller the particle size, greater the surface
area and more the collisions.
3.Temperature - molecules must collide with
enough energy to react;
Rate α collision frequency α concentration
4.The use of a catalyst.
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 Example 1
2H2 (g) + O2 (g) → 2H2O (g)
Write the rate equation in terms of reactants and
products. If [O2] is decreasing at 0.23 mol/L.s at
what rate is [H2O] increasing?
d[O2] 1 d[H2] 1 d[H2O]
rate = - =- =
dt 2 dt 2 dt
d[O2] 0.23 mol
rate = - =
dt L.S
d[H2O]
= 2 x rate = 2 x 0.23 = 0.46 mol/L.s
dt

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Example 2

15
Example 3

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Example 4 Determining Reaction Order from Initial Rate Data

PROBLEM: Many gaseous reactions occur in a car engine and exhaust

system. One of these is

NO2(g) + CO(g) NO(g) + CO2(g) rate = k[NO2]m[CO]n

Use the following data to determine the Rate constant, individual and
overall reaction orders.
Experiment Initial Rate(mol/L*s) Initial [NO2] (mol/L) Initial [CO] (mol/L)
1 0.0050 0.10 0.10
2 0.080 0.40 0.10
3 0.0050 0.10 0.20

PLAN: Solve for each reactant using the general rate law using the
method described previously.

SOLUTION: rate = k [NO2]m[CO]n

First, choose two experiments in which [CO] remains

constant and the [NO2] varies.
 rate 2 k [NO2]m2[CO]n2 [NO2] 2 m
= = The reaction is
rate 1 k [NO2]m1 [CO]n1 [NO2] 1 2nd order in NO2.

0.080 0.40 m
= ; 16 = 4m and m = 2
0.0050 0.10

rate 3 k [NO2]m3[CO]n3 [CO] 3 n

The reaction is
= =
rate 1 k [NO2]m1 [CO]n1 [CO] 1 zero order in CO.

0.0050 0.20 n
= ; 1 = 2n and n = 0
0.0050 0.10

rate = k [NO2]2[CO]0 = k [NO2]2

rate 0.0050
k= = [0.1]2 = 0.5 L.mol-1.S-1
[NO2 ]2
rate 0.080
k= = [0.4]2 = 0.5 L.mol-1.S-1
[NO2]2
 4. Elementary reaction &
Molecularity of reaction
Elementary reaction:
Many chemical reactions proceed through a
number of steps (or stages) between initial
reactants and final products, each of
individual step is called an elementary
reaction.

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 2NO (g) + O2 (g) 2NO2 (g)

N2O2 is detected during the reaction!

Elementary step: NO + NO N2O2 - Fast step

+ Elementary step: N2O2 + O2 2NO2 - (slow step,

rate-
Overall reaction: 2NO + O2 2NO2 determining)

Rate determining step is The

SLOWEST STEP
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 Example 5
The reaction 2 NO + Cl2  2NOCl is thought to
follow the mechanism:
NO + Cl2  NOCl2 (slow)
NOCl2 + NO  2NOCl (fast).

The Rate Law of the reaction is ______.

A) rate = k [NO]2
B) rate = k [NO] [Cl2]
C) rate = k [Cl2] 2
D) rate = k [NO] [NOCl2]

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 Molecularity of Reaction
Molecularity of reaction: It is the number of molecules of
reactants that are collide in order to allow the chemical
reaction to takes place.

How can we determine the molecularity of reaction?

(Theoretically) as follows:
Molecularity = sum of number of molecules
= stoichiometry of the balanced chemical equation
For a hypothetical reaction:
aA + bB → product
Molecularity = a + b

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Types of molecularity of reaction:
Unimolecular reaction→ one molecule used to describe
the reaction (one type of molecules collide)
A→ product……………….. Unimolecular

Bimolecular reaction → two molecules used to describe

the reaction (two types of molecules collide, or two
molecules of the same type collide)
A+B →product………………... Bimolecular
2A→ product…………………..Bimolecular

Trimolecular reaction→ three molecules used to

describe the reaction

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 Order of Reaction
Types of order of reaction:
Zero order reaction
First order reaction
Second order reaction
Third order reaction
Other, ½, or 3/2, or 5/2 …….. Order and so on.

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Rate law and order of reaction: rate law is an equation that
relates the rate of reaction to the rate constant, concentration
of reactants & the order of reaction.
For a hypothetical reaction:
aA + bB → product

Rate law: rate = k [A]x [B]y Note: x & y not a & b

x & y: are the order of reaction with respect to reactant A & B

respectively.

So, the reaction is xth order with respect to A

And the reaction is yth order with respect to B
Overall order of the reaction = x + y
Molecularity = a + b
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 How can we determine the order of reaction?
The order of the reaction can be determined experimentally.
(review ch13 Chang)

Relationship between order of reaction and molecularity

of reaction:
e.g. A → product
Rate law: could be (as the experiment concludes)
rate = k[A]………………..1st order
Rate = k …………………0th order
Where, the molecularity is always one

in some cases, the Molecularity equals the order of

reaction and in other cases they are totally different
quantities. 26
 Molecularity Order
Obtained theoretically Obtained experimentally
= ‫ العناصر المتفاعلة‬Stoichiometry can be determined experimentally only
chemical equation and cannot be calculated.
It is the number of atoms, ions or It is the number of molecules that their
molecules that must collide with one collision result in the formation of
another simultaneously to result into activated complex (effective collisions)
a chemical reaction. and thus affect the reaction rate.

It is always a whole number It need not be a whole number i.e. it can

be fraction as well as zero.

For elementary reaction: Molecularity = order

For complex reaction: Molecularity of the overall reaction has no meaning

regarding the rate. It is the molecularity of the slowest elementary step which
determine the rate of reaction
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 5. Order of Reaction
Now we will study the different orders of chemical
reactions. We are going to specify the following
properties for each order:
(0th,1st, 2nd, 3rd, pseudo 1st, & nth order reaction)
• General form?
• Integrated form?
• Half-life time?
• Graphical representation?

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 Half-life time (t1/2): it is the time required to
consume half (50%) of the initial concentration of
the reactants.
third-life time (t1/3): it is the time required to
consume third (33%) of the initial concentration
of the reactants.
quartet-life time (t1/4): it is the time required to
consume quartet (25%)of the initial concentration
of the reactants.
fifth-life time (t1/5): it is the time required to
consume fifth (20%) of the initial concentration of
the reactants.
……. and so on
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 5.1. First Order Reaction
Obtaining the integrated form of a first order reaction
(an equation gives the conc. vs. time)
1. Consider a unimolecular reaction
A → product
At t = 0 a 0
At t = t (a-x) x
a: is the initial concentration of reactant, i.e. concentration
at t = 0
(a-x): concentration of reactant at t = t
x: concentration of product
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2.
dx d (a  x)
Rate   
dt dt
Rate  a  x 

 a  x 
dx
dt
 k1 a  x 
dx General
dt form of a
first
 k1 a  x 
dx order
dt reaction
k1 : specific rate constant
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3. To obtain the integrated form of first order reaction, this
is done in two steps:
Separate the variables: (variables are: concentration &
time)
dx dx
 k1 (a  x)   k1dt
dt (a  x)

Integrate the equation: the integration limits are

at t = 0 → x = 0
at t = t → x = x
x x t t
1
x0 (a  x) dx  t 0k1dt
 ln( a  x)  k1t  constant
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4. To determine the constant: at the beginning of the
reaction(t = 0), i.e. no product has formed → x = 0 →
constant = -ln a
t = 0, x = 0
- ln(a) = const
- ln(a - x) = k1t - ln a
ln(a - x) = -k1t + ln a
(OR)
a
ln = k1t
(a - x)
Integrated form of first order
reaction 33
 Half-life time (t1/2): it is the time required to
consume half of the initial concentration of the
reactants.
Determination of t1/2 :
a
At t  t1/ 2  x  (a  x) 
2
a a
 ln  k1t  ln  k1t1/ 2
(a  x) a
( )
2
k1t1/ 2  ln 2
ln 2 0.693
t1/ 2  
k1 k1
 t1/ 2 is independent on the initial concentration of reactant
0.693 1
Unit of k1 : k1    s 1
t1/ 2 s
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 slope
Graphically: Intercept with y axis

 ln( a  x)  k1t  ln a
Concentration changes with time

Plot ln(a-x) vs. t give a straight line

intercept = lna

ln(a-x)

slope=-k

t
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 Example 6
What is the half-life for the reaction assuming first-order kinetics if 75%
of a reactant decomposes in 60 minutes?
A) 120 min
B) 15 min
C) 90 min
D) 30 min

Example 7
The slope of the plot of ln (a-x) vs. t of the reaction A  B is
– 6.18 x10–4 min–1. The half-life of the reaction is ______
minutes.
A) 6.12 x 10–2
B) 1.12 x 103
C) 4.15 x 10–3
D) 7.2 x 102
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 5.2. Zero Order Reaction
These reactions are not common, but they occur
in some heterogeneous systems.
Obtaining the integrated form of a zero order
reaction
1. Suppose:
A → product
At t = 0 a 0
At t = t (a - x) x

37
2.
dx d (a  x)
Rate   
dt dt
dx
 (a  x) 0

dt
dx
 k0 (a  x) ;
0
since, (a - x)  1
0

dt
dx
 k0
dt
General form of zero order
reaction 38
3. To obtain the integrated form of zero order reaction,
this is done in two steps:
Separate the variables: (variables are: concentration
& time)
dx
 k 0  dx  k 0 dt
dt
Integrate the equation: (integration limits are: x = 0 at
t = 0 & x = x at t = t)
x x t t

 dx   k dt
x 0 t 0
0

x  k 0 t  constant
39
4. To determine the constant: at the
beginning of the reaction, i.e. no product
has formed → x = 0 → constant = 0

 x  k 0t
Integrated form of zero order
reaction

40
 Example 8

The rate of the reaction 4PH3(g)  P4(g) + 6H2(g)

does not depend on the pressure of PH3. The rate
constant units of the reaction are

A) s–1
B) zero
C) Ms–1
D) M–1s–1

41
Determination of t1/2 :
a
At t  t1 / 2  x  (a  x) 
2
a
  k 0 t1 / 2
2
a
t1 / 2 
2k 0
 t1 / 2  a
 t1 / 2 is directely propotional to
the initial concentration of the reactant
a M
Unit of k 0 : k 0    Ms 1
2t1 / 2 s

42
Graphically: slope

x  k 0t
Concentration changes with time

Plot x vs. t give a straight line

x
slope=k

t 43
 5.3. Second Order Reaction
Obtaining the integrated form of a second order
reaction Case I: A = B
1. Consider a bimolecular reaction
A + B → product
i.e. 2A → product
At t = 0 a 0
At t = t (a-x) x

44
2.

dx d (a  x)
Rate   
dt dt
 a  x 
dx 2

dt
 k 2 a  x 
dx 2

dt General form
of a second
order reaction
where A=B 45
3. To obtain the integrated form of second order reaction,
this is done in two steps:
Separate the variables: (variables are: concentration &
time)
dx dx
 k 2 (a  x) 
2
 k 2 dt
dt (a  x) 2

Integrate the equation: the integration limits are at

t = 0 → x = 0 & x = x at t = t
x x t t
1
x0 (a  x) 2 dx  t 0k2 dt
1
 k 2t  constant
(a  x)
46
4. To determine the constant: at the
beginning of the reaction, i.e. no product
has formed → x = 0 → constant = 1/a
1 1
  k 2t 
(a  x) a
(OR)
Integrated forms of
1 1
  k 2t second order
(a  x) a
reaction when A=B
(OR)
x
 k 2t
a a  x 
47
Determination of t1/2 :

48
Graphically:
1 1
 k 2t 
(a  x) a
Concentration changes with time

Plot 1/(a-x) vs. t gives a straight line

slope=k

1/(a-x)

intercept = 1/a

t
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 Example 9
The rate constant of the reaction A  product is 0.54 M–1s–1. The time
taken for the concentration of A to decrease from 0.62 M to 0.28 M is
_____ seconds.
A) 6.3
B) 21
C) 3.6
D) 15

Example 10
The half-life of a second-order reaction when [A]0 = 0.072 M
was 25 minutes. The half-life when [A]0 = 0.036 M will be
_____ minutes.
A) 50
B) 25
C) 12.5
D) 6.25
50
 Obtaining the integrated form of a second order
reaction Case II: A ≠ B
1. Consider a bimolecular reaction
A + B → product
At t = 0 a b 0
At t = t (a-x) (b-x) x
where,
a: the initial concentration of reactant A (concentration at t = 0)
b: initial concentration of reactant B
(a-x): concentration of reactant A at any time
(b-x): concentration of reactant B at any time
x: concentration of product
51
2.

dx d (a  x) d (b  x)
Rate    
dt dt dt
 a  x b  x 
dx
dt
 k 2 a  x b  x 
dx
General form of
dt a second order
reaction where
A≠ B

52
3. To obtain the integrated form of second order reaction,
this is done in two steps:
Separate the variables: (variables are: concentration &
time)
 k 2 (a  x)b  x  
dx dx
 k 2 dt
dt (a  x)b  x 

Consider (b-x) = constant = B then the equation will be

dx
 k 2 Bdt
(a  x)
Integrate the equation: the integration limits are at t = 0
→ x = 0 & x = x at t = t
x x t t
1
x0 (a  x) dx  t 0k2 Bdt
53
 x x t t
1
x0 (a  x) dx  t 0k2 Bdt
 ln( a  x)  k 2 Bt  constant
To determine the constant: at the beginning of the reaction,
i.e. no product has formed → x = 0 → constant = -lna
 ln( a  x )  k 2 Bt  ln a
a
ln  k 2 Bt (1)
ax
Consider (a-x) = constant = A then the equation will be
dx
 k 2 Adt
(b  x)
54
 Integrate the equation: the integration limits are at t = 0
→ x = 0 & x = x at t = t
x x t t
1
x0 (b  x) dx  t 0k2 Adt
 ln(b  x)  k 2 At  constant
To determine the constant: at the beginning of the reaction,
i.e. no product has formed → x = 0 → constant = -lnb
 ln(b  x)  k 2 At  ln b
b
ln  k 2 At (2)
bx
If [A] > [B]
Subtract equation 1 from equation 2 we found 55
 b a
ln  ln  k 2 At  k 2 Bt
bx ax
b
ln b  x  k 2t ( A  B )
a
ax
ba  x 
ln  k 2t ( A  B )
ab  x 
1 ba  x 
ln  k 2t
( A  B ) ab  x 
1 ba  x 
ln  k 2t
(a  b) a b  x  56
 If [B] > [A]
Subtract equation 2 from equation 1 we found
a b
ln  ln  k 2 Bt  k 2 At
ax bx
a
ln a  x  k 2t ( B  A)
b
bx
ab  x 
ln  k 2t ( B  A)
ba  x 
1 ab  x 
ln  k 2t
( B  A) ba  x 
1 a b  x 
ln  k 2t
(b  a ) ba  x  57
4. The final equations are:
If [A] > [B]
1 b( a  x )
ln  k 2t
(a  b) a (b  x)
Integrated forms
If [B] > [A] of second order
reaction when A≠B
1 a (b  x)
ln  k 2t
(b  a) b(a  x)

58
 Example 11
The rate of the reaction A ® B when [A] = 0.35 M is 1.6 ´ 10–2 Ms–1. If the reaction is
–1 –1
second order in A, the rate constant is _____ M s .
A) 1.3
B) 2.6
C) 26
D) 0.13
The rate for the reaction A ® B is rate = k. The plot of rate vs. time for the reaction is a
______.
A) curve
B) straight line with a positive slope
C) straight line with a zero slope
D) straight line with a negative slope

The plot of concentration of reactant vs. time for a zero order reaction of the type A ®
B is ______.
A) Straight line with a positive slope
B) Straight line with a negative slope
C) Straight line with a zero slope
D) Straight line with an infinity slope
59
 5.4. Third Order Reaction
Third order reaction is quite rare, however, it is
theoretically uncommon because:
Since, the probability of collision involving three
molecules with sufficient energy and with the right
orientation (symmetry) is very small.
The simple case of the third order reaction is the
case where all the reactants are at the same
initial concentration.
i.e. 3A →product
(OR) A+ B+ C→ product; where, [A]=[B]=[C]
60
 Obtaining the integrated form of a third order
reaction
1. Consider a trimolecular reaction:
3A → product
At t = 0 a 0
At t = t (a-x) x

61
2.

dx d (a  x)
Rate   
dt dt
 a  x 
dx
Rate 
3

dt
Rate  k3 a  x 
3

 k3 a  x 
dx 3
General form
dt of a third
order reaction
where A=B=C 62
3. To obtain the integrated form of third order reaction, this
is done in two steps:
Separate the variables: (variables are: concentration &
time)
dx dx
 k3 ( a  x ) 
3
 k3dt
dt (a  x) 3

Integrate the equation: the integration limits are

at t = 0 → x = 0 & x = x at t = t
x x t t
1
x0 (a  x)3 dx  t 0k3dt
1
 k3t  constant
2( a  x ) 2

63
4. To determine the constant: at the beginning of
the reaction, i.e. no product has formed → x = 0
→ constant = 1/(2a2)

1 1 Integrated
  k 3t  2 forms of third
2( a  x ) 2
2a
order reaction
(OR) when
1 1 3A→product
 2  k 3t
2( a  x ) 2
2a
64
 Determination of t1/2 :
a
At t  t1/ 2  x  (a  x) 
2
1 1
   k3t
2( a  x ) 2
2a 2

1 1
 2
 2
 k3t1/ 2
a 2a
2 
2
4 1
  k3t1/ 2
2a 2 2a 2
3 3
 k t
3 1/ 2  t1/ 2 
2a 2 2k3 a 2
1
t1/ 2 
a2
 t1/ 2 is inversly propotional to the square of initial concentration of reactant
3 1  2 1  2 1
Unit of k3 : k3  2
 2
 M s  L2
.mol .s
2a t1/ 2 M s
65
Graphically:
1 1
  k 3t  2
2( a  x ) 2
2a
Concentration changes with time

Plot (1/(2(a-x)2) vs. t give a straight line

slope=k

(1/(2(a-x)2)

intercept = 1/2a2

t 66
 In case [A] ≠ [B] ≠ [C]
General form of third
 k3 a  x b  x c  x 
dx
order reaction where
dt [A] ≠ [B] ≠[C]

a  b ln c  x
ln
a  x
ln
b  x
c  b  c  a  c  a  b
 k3t
a  b b  c c  a 
Integrated form of third order reaction when
A+B+C→product
67
5.6. Pseudo First Order Reaction

There are reactions of various kinds which satisfy

the first order equation, but actually more than
one molecule is involved in the chemical reactions
such processes called:
Pseudo first order reactions
A B C
d[ X ]
 k[b  x][a  x]  k '[a  x] When [B] >> [A]
dt

68
 5.6. Pseudo First Order Reaction
In a pseudo-1st-order reaction. One of the reactants, B, for
example, would have a significantly high concentration, while the
other reactant, A, would have a significantly low
concentration. We can then assume that reactant B's concentration
remains constant during the reaction because its consumption is so
small that the change in concentration becomes negligible.
Because of this assumption, we can multiply the reaction
rate, , with the reactant with assumed constant concentration, B, to
create a new rate constant. k′ = k (b-x)

69
 5.6. Pseudo First Order Reaction
ln( a  x)  k t  ln a
intercept = lna

ln(a-x)
a
At t  t1/ 2  x  (a  x) 
2 slope=-k′
k1t1/ 2  ln 2
ln 2 0.693 t
t1/ 2  
k1 k1
 t1/ 2 is independent on the initial concentration of reactant
0.693 1
Unit of k1 : k1    s 1
t1/ 2 s
70
 5.7. nth Order Reaction
nA → product
At t = 0 a 0
At t = t (a-x) x

dx d (a  x)
Rate   
dt dt
 a  x 
dx
Rate 
n

dt
 k n a  x 
dx
Rate 
n

dt 71
 Separate the variables: (variables are: concentration &
time)
 k n a  x 
dx n

dt
Integrate the equation: the integration limits are at t = 0 →
x = 0 & x = x at t = t
x x t t
dx 1
x0 a  x n  kn t 0dt 
(n  1)a  x 
n 1
 k nt  constant

• To determine the constant: at the beginning of the reaction,

1
i.e. no product has formed ? x  0 ? constant 
(n  1)a 
n 1

1 1 1 1
 k nt     k nt
(n  1)a  x  (n  1)a  (n  1)a  x  (n  1)a 
n 1 n 1 n 1 n 1

1  1 1 
  n 1 
 k nt General form of nth
(n  1)  a  x n 1
a  
order reaction
72
Determination of t1/2 :
a
At t  t1/ 2  x  (a  x) 
2
1  1 1 
     k nt
(n  1)  a  x n 1 a n 1 
 
 
1  1 1 
  n 1  k n t

(n  1)  a  n 1
a  
  
  2  
2 n 1  1 2 n 1  1
 k n t1/ 2  t1/ 2 
(n  1)a n 1 (n  1)k n a n 1
2 n 1  1
kn 
(n  1)t1/ 2 a n 1
1
 Unit of k n   M n 1s 1  Ln 1.mol 1 n .s 1
M n 1s
73
6. Methods of Determining the
Reaction Order
1. Integration method
a. Numerically
b. Graphically
2. Half-life time
a. Alternative method (Relation between t1/2 and
initial concentration)
b. Direct equation method
3. Vant Hoff differential method
4. Ostwald’s isolation method
74
 6.1. Integration Method
a. Numerically:
The conc- time data are substituted into the integrated
rate equation for the different order to get the rate
constant (k).
The equation which give the most constant value of the
rate constant gives the correct order of reaction.
b. Graphically:
By plot the conc-time data according to each order
equation.
The graph which give straight line, thus its equation
gives the order of reaction.
75
 6.2. Half-Life Time Method
a. Alternative method:
If t1/2 = constant → The reaction is first order
If (t1/2 /a) = constant → The reaction is zero order
If (t1/2 .a) = constant → The reaction is second order
If (t1/2 .a2) = constant → The reaction is third order

b. Direct equation method:

 t1/ 2 1 
log  Since, n  order of reaction

 t1/ 2 2  a  initial concentration
n  1 t1/ 2  half - life time
 a2 
log  
 a1  76
 6.3. Vant Hoff Differential
Method
Vant Hoff differential equation relates the rate of
reaction (R) to the initial concentration (a):

n  log
 R1 / R2 
a1 / a2 
Since, n  order of reaction
77
6.4. Ostwald’s Isolation Method
Ostwald's isolation method: is the method used
to calculate the order of the reaction which
contains multiple reactants.

Consider the general equation:

aA + bB → cC+ dD
The reactants are isolated to determine the order
with respect to each reactant and then the total
order of the reaction is determined .

78
6.4. Ostwald’s Isolation Method

We isolate B by taking A in large excess

→ the determination of the order of reaction
will be from the concentration change of B
→ this will give the order of reaction with
respect to B reactant.
Suppose the order of reaction with respect
to B is y.

79
Similarly, we isolate A by taking B in large
excess.
→ the determination of the order of reaction
will be from the concentration change of A
→ this will give the order of reaction with
respect to A reactant.
Suppose the order of reaction with respect to
A is x.
→ the total order of reaction is the sum (x +
y).
80
 7. Effect of Temperature on Reaction Rate
How Reaction Rate Depends on Temperature?
Arrhenius in 1889 proposed an equation that represent the
dependence of rate constant (→ rate of reaction) on temperature.
Rates increases with temperature.
Approximately double rate for 10oC rise in temperature.
Ea

k  Ae RT
.............Arrhenius equation
k  rate constant
A  pre - exponential factor,or frequencyfactor
or collision factor,or probabilit y factor.
A has the same unit as the rate constant k
Ea  activation energy
R  gas constant T  absolute temperature 81
Potential Energy Activated Complex (AC)
Curve OR Transition State (TS)

Activation Energy = Energy Barrier

= Ea = E (TS) – E (Reactants)

Ea
Energy

Reactant

Reaction Energy = Product

E (Products) – E (Reactants) Reaction Coordinate 82
 Ea

k  Ae RT

Ea = 10 J/mol T1 = 20 K k1 = (0.89)

T2 = 80 K k2 = (0.99)
T = 40 K (Ea)1 = 10 J/mol k1 = (0.89)

(Ea)2 = 50 J/mol k2 = (0.86)

Ea↑ k↓
T↑ k↑
T↓ k↓ Ea↓ k↑
83
 Ea Ea
 ln k  ln A 

k  Ae RT

RT
1
Plot ln k vs.   should give a straight line
T 
 Ea 
The slope    
 R
The intercept  ln A

84
 Ea
ln k  ln A 
RT
Chemical Reaction At
Different Temperatures →
Different Rate Constants
Intercept = ln A But The Same Activation
Energy
→→→ Each Chemical
ln k Reaction Has A Specific
Activation Energy

Slope= (-Ea/R)

1/T

85
If we have twosets of data :
Ea
ln k1  ln A 
RT1
Ea
ln k 2  ln A 
RT2
Ea Ea
 ln k1  ln k 2  ln A   ln A 
RT1 RT2
k1 Ea  1 1 
 ln    
k 2 R  T2 T1  86
 1
t1/ 2 n 1
a There is a relation between
t½ & initial concentration.
k
t1/ 2 
a n 1
ln 2 0.693
st
1 order : t1/ 2    const.
k k
a
th
0 order : t1/ 2   const.  a
2k
1 1
nd
2 order : t1/ 2   const. 
ak a
3 1
ed
3 order : t1/ 2  2
 const.  2
2ka a 87
There is a relation between t1/ 2 and T.

since, t1/ 2 1  n 1 and t1/ 2 2

k1 k2
 n 1
a a
t1/ 2 1 k1
 
t1/ 2 2 k2
t1/ 2 1 Ea 1 1
ln    
t1/ 2 2 R  T2 T1 
88
Methods of Determining Ea?
1. Knowing k and T
a. One set of data
2. Knowing t1/2 and T
Ea
ln k  ln A  (two sets of data)
RT
b. Two sets of data t1/ 2 1 Ea 1 1
ln    
k1 Ea  1 1  t1/ 2 2 R  T2 T1 
ln    
k2 R  T2 T1 
c. Series of data →
graphically
89
 Example 12
The activation energy for the reaction CH3CO  CH3 + CO is 71 kJ/mol.
How many times greater is the rate constant for this reaction at 170C than
at 150C?

A. 0.40
B. 1.1
C. 2.5
D. 4.0
E. 5.0

Example 13
The isomerization of cyclopropane follows first order kinetics. The rate
constant at 700 K is 6.20  10-4 min-1, and the half-life at 760 K is 29.0 min.
Calculate the activation energy for this reaction.

A. 5.07 kJ/mol
B. 27.0 kJ/mol
C. 50.7 kJ/mol
D. 160. kJ/mol 90
E. 270. kJ/mol
Example 14
For the chemical reaction system described by the diagram below, which
statement is true?

If the Ea for the forward reaction is 25 kJ/mol and the enthalpy of reaction
is -95 kJ/mol, what is Ea for the reverse reaction?

A. 120 kJ/mol
B. 70 kJ/mol
C. 95 kJ/mol
D. 25 kJ/mol
E. -70 kJ/mol
91
 8. Types of Reactions
1. Consecutive Reactions: A 
k1
B 
k2
C

2. Parallel Reactions: A ¾k¾

1
®B
k2 C

3. Reversible (Opposing)Reactions: A 

k1
B

k 1

4. Series Reactions: (later in photochemistry)

92
 8.1. Consecutive Reaction
A  B  C
k1 k2

It often happen that the product of one reaction

become itself the reactant of another reaction.
Consecutive reactions are especially important in
polymerization and de- polymerization processes.
The simple consecutive reaction is irreversible
first order reaction.

93
The concentration of A falls exponentially with time.
The concentration of the intermediate B, rise to
maximum and ends to zero since all of it is finally
converted into C
The final product C rises gradually to the value of A0.

94
 since, ln( a  x)  kt  ln a
ln A  ln Ao  kt
[ A]  Ao e  kt .........Eq1

A  B  C
k1 k2

 k1 A........Eq2
dA
rate of consumingof A = rate of formation of B  
dt
 k 2 B .........Eq3
dC
rate of consumingof B = rate of formation of C 
dt
Net rate of formation of B  rate of its formation
- rate of its consuming
dB dA dC
   k1[ A]  k 2 [ B]........Eq4
dt dt dt
95
 Substitute Eq1 in Eq4
dB  k1t
  k1 Ao e  k 2 [ B ]
dt
dB  k1t
  k 2 [ B ]  k1 Ao e ......Eq5
dt
Multiply both sides by ek2t, the
integrating factor.

96
 dB
e k 2t
 k 2 [ B]e k 2t  k1 Ao e  k1t .e k 2t
dt
dB t ( K 2  k1 )
e k 2t
 k 2 [ B]e  k1 Ao e
k 2t

dt
e k 2t
dB
dt
 k 2 [ B]e 
k 2t d
dt

[ B ]e k 2t 
d
dt

[ B ]e  k1 Ao e
k 2t

t ( K 2  k1 )

   k A  e
[B] t
k 2t t ( K 2  k1 )
d [ B]e 1 o dt
0 0

 1 t ( K 2  k1 ) 
[ B]e k 2t
 k1 Ao  e   Constant
 K 2  k1  97
To determine the constant: at the beginning of the
reaction, t = 0 [B] = 0 →
k1 Ao
Constant  
K 2  k1
 1 t ( K 2  k1 )  k1 Ao
[ B ]e  k1 Ao 
k 2t
e 
 K 2  k1  K 2  k1
k 2t
divided both sides by e gives
k1 Ao  k1t k1 Ao  k 2 t
[ B]  e  e
K 2  k1 K 2  k1

[ B] 
k1 Ao
K 2  k1

e  k1t  e  k 2 t 
98
 Since, every time A disappear B appear, and every
time B disappear C appear (Conservation of mass)
Thus, Ao=[A]+[B]+[C] → [C]= Ao-[A]-[B]

[C ]  Ao  Ao e  k1t

k 2  k1

k1 Ao  k1t
e  e  k 2t 
 
 k1t
[C ]  Ao 1  e 
k1
k 2  k1

e  k1t  e  k2t  
 
 k 2  k1  k1t k1 k1  k 2t 
[C ]  Ao 1  e  e  k1t  e 
 k 2  k1 k 2  k1 k 2  k1 

99
  k2  k1t k1  k1t k1  k1t k1  k 2t 
[C ]  Ao 1  e  e  e  e 
 k 2  k1 k 2  k1 k 2  k1 k 2  k1 
 k2  k1t k1  k 2t 
[C ]  Ao 1  e  e 
 k 2  k1 k 2  k1 
 k2  k1t k1  k 2t 
[C ]  Ao 1  e  e 
 k1  k 2 k1  k 2 
  k 2t 
[C ]  Ao 1 
1

 k1t
k 2 e  k1e  
 k1  k 2 

100
8.2. Parallel Reaction A ¾k¾ ®B
1

k2 C
Suppose this is schematic pair of parallel first
order kinetics.

If Ao  initial concentration of A reactant

A  concentration of reactant A at any time
Since, Ao  A  B   C  at any time
 A  Ao  B   C 

101
 Rate of disapear of A A ¾k¾
1
®B
C
 k1 A  k 2 A  k1  k 2 A
dA
 k2
dt
A t t

A A  k1  k2 t 0dt
dA
0

ln A  k1  k 2 t  constant
To determine the constant: at the
beginning of the reaction, t = 0 , i.e. no
product has formed → A = [A]0 →
constant = ln [A]0

ln A  (k1  k 2 )t  ln[ A]0

102
  k1  k 2 t
A A ¾k¾
1
®B
ln
A0 k2 C

A  A0  e   k1  k 2 t

Rate of formation of B

 k1 A  k1 A0  e
dB   k1  k 2 t

dt B
   k  k t
t
0 dB  k 1 A0 
0
e 1
dt2

k1 A0  k  k t
B e 1
 constant
2

k1  k 2 103
To determine the constant: at t = 0 → B = 0 → constant =
K1[A0]/K1+K2
k1 A0  k1  k2 t k1 A0 
B e 
k1  k 2 k1  k 2
k1 A0 
B
k1  k 2
1 e  k1  k 2 t


Rate of formation of C

 k 2 A  k 2 A0  e
dC   k1  k 2 t

dt
104
  k 2 A0 e k1  k2 t
dC
dt
dC  k 2 A0 e k1  k 2 t dt
k 2 A0  k1  k 2 t
C e  constant
k1  k 2
k 2 A0 
To determine the constant: at t  0  C  0  constant 
k1  k 2
k 2 A0  k1  k 2 t k 2 A0 
C e 
k1  k 2 k1  k 2

 C  
k 2 Ao
k1  k2 

1  e k1  k 2 t 
105
8.3. Reversible Reaction A 
k 1
B

k 1

Consider first order reversible reaction

Assume Ao=[A]+[B] → [B] =Ao-[A]
Net rate of formation of A
 rate of its formation - rate of its consuming
dA
 k 1[ B ]  k 1[ A]
dt
Net rate of formation of B
 rate of its formation - rate of its disappearance
dB
 k 1[ A]  k 1[ B ]
dt 106
  k 1  Ao  A  k 1 A
dA

dt
 k 1 Ao  k 1 A  k 1 A
dA

dt
 k 1 Ao  Ak 1  k 1 ....Equation 1
dA

dt

dA
 k 1
k 1  k 1 
Ao  Ak 1  k 1 
dt k1  k1 
 
 k 1  k 1 A 
dA k 1
Ao 
dt  k 1  k 1 

107
 At EQUILIBRIUM:
Rate of forward reaction = Rate of backward reaction
dA
  0 and Ao  Aeq  Beq ..........Equation 2
dt
Substitute  dA  k 1 Ao  Ak 1  k 1 ....Equation 1
Eq 2 in Eq 1 dt
0  k 1 ( Aeq  Beq )  Aeq (k 1  k 1 )
0  k 1 Aeq  k 1 Beq  k 1 Aeq  k 1 Aeq
0  k 1 Beq  k 1 Aeq
k 1 Aeq  k 1 Beq
k 1 Beq
 .................Equation 3
k 1 Aeq
108
k 1 Aeq  k 1 Ao  k 1 Aeq
k 1 Aeq  k 1 Aeq  k 1 Ao
Aeq [k 1  k 1 ]  k 1 Ao
 k 1 
Aeq    Ao
 k 1  k 1  
109
  
 k 1  k 1 A 
dA k 1
Ao 
dt  k 1  k 1 
 k 1 
Aeq    Ao
 k 1  k 1  
 k 1  k 1 A  Aeq 
dA
dt
 A t t

 A  A  Aeq  k1  k1 t 0dt

dA
o

ln A  Aeq   k 1  k 1 t  constant 110

To determine the constant: at the beginning of the
reaction, t = 0 , i.e. no product has formed → A = [A]0 →
constant = ln ([A]0 - [A]eq)

ln A  Aeq   k 1  k 1 t  ln  A0  Aeq 

ln A  Aeq   ln A0  Aeq   k 1  k 1 t

A0  Aeq
ln  k 1  k 1 t
A  Aeq

111
 9. Theoretical Description of
Elementary Reactions
9.1 Transition State Theory ‫نظرية الحالة االنتقالية‬
9.1.1 Eyring Transition State ‘’for Bimolecular
Reactions ’’
9.1.2 Transition State theory in Thermodynamic
Terms
9.2 Collision Theory of Unimolecular
Reactions (Lindemann-Christiansen
Theory) ‫نظرية التصادم‬

112
 9.1 Transition State Theory:
How a Reaction Goes? Introduction
Collision frequency: Total number of collisions per
unit time
More collisions → faster reaction→ more
products
Activation energy: The minimum amount of energy
required to initiate a chemical reaction.
→ Combined KEs of the colliding molecules must
be equal or greater than the activation
energy

Orientation: The molecules must orientated on the

right way so when they hit each other to form the
product. 113
 Ea is 100J
A
10J

X A B
B 10J
114
 Ea is 100J
A
30J

√ A B
B 70J
115
Orientation!
N  N O  N  O
O=N
X
N N O √ N=O

N  N ON O
116
Transition State Theory:
N  N O  N  O 
activated complex

N  N O  N  O 
Bond formation

Bond breaking

TS: high-energy species (top-point on the PES) in which

a bond is breaking & a bond is forming

N  N ON O 117
 9.1 Transition State Theory
9.1.1 Eyring Transition State (For Bimolecular
Reactions): (1935)
Henry Eyring
Transition state theory postulates that molecules
must form an activated complex before undergoing
reaction. The activated complex is in equilibrium
with the reactants.

The rate of reaction is the number of activated

complexes passing per second over the top of the
potential energy barrier. (rate of disappearance of
activated complex to produce product)
This rate is equal to the concentration of the
activated complexes times the average frequency of
that complex moves across to the product side.
118
 The rate of reaction depends on two factors:
1. Concentration of activated complex
2. Rate to break up the activated complex to give
products

The calculation of the concentration of the activated

complex is greatly simplified if we assume that it is in
equilibrium with the reactants.

We will consider the activated complex (or transition state

T.S.) of simple bimolecular reaction.

119
120
A  B  AB  

 product
equilibriu m k

The activated complex [AB]≠ is in equilibrium with

reactants
The equilibrium constant K≠ for the formation of activated
complex is: 
[ AB]
K 
[ A][B]
 
[ AB]  K [ A][B]
121
 If K≠ is written in term of molecular
partition functions per unit volume:
 Ea
q 

K   e AB RT
q A .qB
 q 
 
Ea
[ AB]  [ A][B]
 AB
 
e RT
........Eq1
q q A B 

q AB  concentration of activated complex (TS)
q A  concentration of reactant A

q  concentration of reactant B
B
122
 A  B   AB  

 product
equilibriu m k

Rate of reaction = rate of bimolecular reaction to produce

product
= rate of disappearance of activated
complex to produce product

Rate of bimolecular reaction = k [A][B]

(there are an equilibrium between [A][B] and the activated
complex [AB]≠

Rate of disappearance of activated complex = [AB]≠Υ≠

(Because the rate is equal to the concentration of the
activated complex [AB]≠ times the frequency of the
activated complex)
123
 Rate  k[ A][B]  AB   ......Eq2


RT
since,  


Noh
 Eqs 1 and 2

 q  

Ea
 k[ A][B]  [ A][B] e
AB
 
RT

K≠  q q 
A B

 q AB

  RT
Ea
 RT 
 k     e  
 q A qB   Noh 
 RT 
k  K 

........ Eyring equation
 Noh 
K   Equilibriu m constant & k  Rate constant 124
 Eyring Equation vs.
Arrhenius Equation
Ea
  RT 

k  K  ........Eyring equation k  Ae RT
.............Arrhenius equation
 Noh 


Ea
 q 
 
Ea
 RT 
 Ae RT
  AB
 
e RT  
q q A B   Noh 
 q 
 RT 
 A   AB
 
 
q q A B  N o h  125
  q AB

 RT   q AB 
 KT 
 A            
 q A qB  N o h   q A qB  h 
RT KT
  6.0 x1012 s 1 at 27C
Noh h
since, A  vibrational energy needed
or absorbed , leading to the decomposition
of the activated complex togive products.

q AB  concentration of activated complex (T.S)
q A  concentration of reactant A
qB  concentration of reactant B
N o  Avogadro's number  6.02 x1023 mol 1
h  Blank' s constant  6.62 x1034 Js
T  Absolute temperature
126
 9.1 Transition State Theory
9.1.2 Transition State Theory in Thermodynamic Terms:
Means it is possible to evaluate the reaction rate
thermodynamically.
Before from Eyring!
(i.e. with doing
k  f T , conc.; A  f conc. experiment- Eyring
equation )
Rate of reaction from thermodynamic parameters!

   

k  f T , G , H , S ; A  f S  
 (i.e. without doing
experiment)

The transition state theory is often expressed in terms of

thermodynamic functions rather than in partition functions
127
Consider this reaction:
A  B  AB  

equilibriu m
 product
k

since, K  
 AB

AB
K   Equilibriu m constant

 RT  
since, k    K ......Eyring eq.
 Noh 
k  Rate constant 128
K≠ as any equilibrium constant depends on the
free energy, since the activated complex is in
thermodynamic equilibrium with the reactants

 
G   RT ln K
G 


K  e RT

G 
 RT  
k   .e RT

 Noh 
G   Gibbs free energy of activation 129
   
since, G  H  TS
 H  TS  
 RT   

 k   e  RT 

 Noh 
  H    S  
This is Eyring
 RT  
 RT
 
  R

 equation in
 k   e    
thermodynamic
 Noh  parameters


H  Enthalpy change of activation
S   Entropy change of activation
130
   
since, H  E  n RT 
E  Ea

n  number of moles of activated complex
 number of moles of reactants


n for first order reaction  1 - 1  0

 H  Ea

n for second order reaction  1  2  1

 H  Ea  RT 131
    This is Eyring
 a   S
E
 RT       
 equation in
k   e  RT   R 
thermodynamic
parameters
 o 
N h
Ea  Activation energy

S  Entropy changeof activation

132
 Eyring Equation vs.
Arrhenius Equation
S  Ea
 RT  E
 a
k  Ae

 k   e
RT
R
e RT
........Eyring equation ......Arrhenius equation
 Noh 

S 
 RT 
 A   e R

 Noh 
  ANo h 
 S  R ln  
 RT 
133
 k  f T , conc.; k  f T , H  , S  ;
A  f conc. A  f S 

Eyring equation in terms of Eyring equation in terms of
partition functions! thermodynamic parameters!

 H    S  
 q 
 RT  E
 a  RT    
  R


k   AB
 
 e RT k   e  RT   

q q A B  N o h   Noh 

S 
 q AB

 RT   RT  
A       A   e R

 q A qB  N o h   Noh  134
9.2 Collision Theory of Unimolecular Reactions
(Lindemann-Christiansen Theory)(1922)
Effect of Pressure on Gaseous Unimolecular Reaction

In unimolecular reaction the activated complex is a single

reactant molecule which gained the necessary energy of
activation by collision with other molecules
Unimolecular reactions are two types:
Isomerisation ‫تحول‬
H 3C  C  N ( g )  H 3C  N  C ( g )
methyl cyanide methylisosyanide

Decomposition

CH 3  CH 2  I ( g )  CH 2  CH 2 ( g )  HI ( g )
135
 Activation complex of unimolecular reaction
appeared that the activation by collision would
give rise to second order kinetics
no. of collision α [ ]2
Until, Lindemann-Christiansen showed how
activation by collision can rise to first order
kinetics under certain circumstances (conditions)
and to second order kinetics in different
condition→ (different PRESSUREs)

How the pressure changes the kinetics of unimolecular gaseous reaction?

(OR) what is the effect of pressure on the kinetics of a unimolecular
gaseous reaction?

136
 consider this unimolecular reaction:

A  A 
k1
A  A fast step
k-1

A  prod
k2
slow step
intermediate
where,
A  represent normal reactant molecule
A  represent an energized molecule or activated molecule

 d [ A ]
Net rate of formation A , rate 
dt
 Rate of its formation - Rate of its disappearance
d [ A ]
 k1[ A]2  k 1[ A ][ A]  k 2 [ A ]
dt
137
A representative of Lindemann-
Christiansen mechanism of
unimolecular reaction. The
species A is excited by collision
with A, and the excited A
molecule (A*) may either be
deactivated by a collision with A
or go on to decay by a
unimolecular process to form
products.

138
 
 d [ A ]
At steady state for A , 0
dt
 k1[ A]2  k 1[ A ][ A]  k 2 [ A ]  0
 k1[ A]2  k 1[ A ][ A]  k 2 [ A ]  [ A ]k 1[ A]  k 2 
2
 k [ A]
[ A ]  1
..........Eq1
k1[ A]  k2 
Steady state approximation (SSA):
when the reaction is proceeding with the intermediate at
constant concentration, the reaction is said to be reacting ‘’
in the steady state’’ i.e. the steady state → the
concentration of the intermediate is not changing.
139
 
Rate of formation of prod  k 2 [ A ]....... Eq2
substitute Eq1in Eq2 
2
k 2 k1[ A]
 rate 
k 1[ A]  k 2 
From this equation and as can be seen under
certain condition the order can change from 1st
order to 2nd order and vice versa.
Found by experiment :
at high pressure → this unimolecular reaction is 1st
order.
At low pressure → the reaction is 2nd order.
140
 since, the product volume > reactant
volume
¹
A + A ¬¾
k
®A + A
k1
At low pressure: k2>>k-1[A]
-1

A ¹ ¾k¾
2
® prod Rate 
k1k2 [ A]2 kk
 1 2 [ A]2 .........2nd order
k1[ A]  k2  k2
2
k2 k1[ A]
Rate 
k1[ A]  k2  since, the product volume <
reactant volume
• k2 represent the
At high pressure: k2<< k-1[A]
product formation
• k-1 represent the Rate 
k1k2 [ A]2

k1k2 [ A]2 k1k2
 [ A].........1st order
k1[ A]  k2  k1[ A] k1
reformation of
reactant
141
 Different PRESSURES vs.
Kinetics

Low pressure High pressure

2nd order kinetics 1nd order kinetics

142
 Example
78. The exact Rate Law for the reaction 2H2 + 2NO ® 2H2O + N2 is

The Rate Law expression at very high [H2] is ______.

2
A) rate = k [NO]
B) rate = k [H2]
C)

D)

143
 10. Reactions in Solutions
10.1 Theory of Absolute Reaction Rate in
Solutions or Reaction in gas phase and in
solution
10.2 Primary Kinetic Salt Effect of Ionic
Reactions

144
10.1 Theory of Absolute Reaction
Rate in Solutions
Eyring proposed:
transition state

¹
A+ B« x ® p
In gaseous phase or in solution phase
Rate constant
 RT  
since, k    K ........Eyring Eq
Equilibrium  N o h 
constant of 
TS  [x ]
since, K  ........in gaseous phase
[ A][B]
Conc units 145
But, for solution we use activity unit instead
of concentration unit.
since, a  C  a   .C
where,
a  activity of solution
  activity coefficient  1 for ideal & very dilute solution
C  concentration (mol/L)
a
C 


146
 
 [ x ]
K  ..........Eq1
[ A][B ]
a x
[x ]  ;.........Eq2
 
x

aA
[ A]  ;...........Eq3
A
aB
[ B]  ............Eq4
B
Substitute Eq2,3,4 in Eq1
 a x   A  B 

 K  

  
 a A aB   x  147
  RT  
 k    K .........Eyring Eq
 Noh 
 RT  a x   A  B 

 k      
 N o h  a A aB   x 

148
When γ = 1 In case of ideal & very dilute solution

 ax 
K  

o

 a AaB 
 RT  a x   RT  
k 0        K o
 N o h  a A a B   N o h 
 RT     A B 
 k    K o  
 
 N o h    x 
  A B 
 k  k o   
 x 
where, k  the rate constantin nonideal solution
k o  the rate constantin ideal solution, the rate
constant when all activity coefficient are unity
149
 10.2 Primary Kinetic Salt Effect of Ionic
Reactions
Effect of ionic strength on kinetics of
reaction in solution
It is generally observed that the rate of reaction can
be altered by the presence of non-reacting or inert
ionic species in the solution. This effect is especially
great for reactions between ions, where rate of
reaction is effected even at low concentrations. The
influence of a charged species on the rate of reaction
is known as salt effect.
150
 The effects are classified as primary and
secondary salt effects .

 In primary salt effect ,addition of an electrolyte

(salt) affects the activity coefficients and hence
the rate of reaction.

 the secondary salt effect is the actual change in

the concentration of the reacting ions resulting
from the addition of electrolytes.
 Both effects are important in the study of ionic
reactions in solutions.
151
The deviation from ideal behaviour can be
expressed in terms of Brönsted-Bjerrum equation.
Brønsted-Bjerrum equation find a relation
between the rate of reaction (rate constant) and
the ionic strength of ionic solution.
1
I   CZ 2 .........for ionic soultion (electrolyte solution)
2
where,
I  ionic strenght of solution
C  concentration
Z  charge on ion

152
Brønsted-Bjerrum equation relates k with I as:
log k = log ko + Z A Z B I
At infinite dilution, all activity coefficients are unity (i.e. = 1)
Infinite dilution Solution is diluted until Ionic Strength
reaches a value of zero
k
\log = Z A Z B I ........... Kinetic Salt Effect
ko

k
Plot logk / ko vs. I
log
ko

153
I
There are three cases depend on
ZAZB.
1. If Z A Z B  0  no effect of I on the rate constant.
e.g.[ Pt( NH 3 )Cl2 ]  OH  ...........Z A Z B  0
[C2 H 22O11 ]  OH  ...............Z A Z B  0

2 If Z A Z B = +ve ® the rate constant increases as I increases.

i.e. rate of reaction will increase on addition of electrolyte
e.g. PtCl4-2 + OH -...........Z A Z B = +2
(NO2 NCO2C2 H 5 )- + OH -...............Z A Z B = +1
2[CO(NH 3 )5 Br]+2 + Hg+2 ..............Z A Z B = +4
SO4-2 + 3I -..................Z A Z B = +2 154
If Z A Z B  ve  the rate constantdecreasesas I increases.
rate of reaction will decreaseon increasing
I, i.e. on adding salt in reaction mixture
e.g. Pt NH 3 Cl   NO3 ...........Z A Z B  1
H 2O2  OH 3  Br  ...............Z A Z B  1
[CO ( NH 3 ) 5 Br] 2  OH  ..............Z A Z B  2

155
 +2

2+ +1

1+ 1+
+1
+ve

k 0
or 0
log 0
+1 -1
ko
-ve -1
1+ 2- +1 1-

-2

I
156
Example:
A solusion is 0.5M in MgSO4,0.1M in AlCl3 and 0.2M
in (NH4)2SO4,
What is the ionic strength of the solution?

a)3.2

b)5.9

c) 0.04

d)2.3
157
 Example
What is the ratio of rate constants for the following ionic
reaction:

If the ionic strength changes from 0.001 M to 0.01 M?

æk ö
logçç ÷÷
è ko ø 0.001
Ratio= = 0.3 )
ækö
logçç ÷÷
è ko ø 0.01
158