CHEMICAL KINETICS

INTRODUCTION
Rate is a measure of how fast or slow
a reaction occurs
Rate is the change in concentration
per unit time.
Units of rate are mol dm-3 s-1 mol dm-3
min-1 and mol dm-3 h-1

FACTORS AFFECTING RATES OF

REACTIONS
According to collision theory, a chemical reaction takes
place only by collision between the reacting molecules.
TEMPERATURE: The rate increases as temperature
increases
CONCENTRATION: The rate increases as concentration
increases.
PRESSURE: The rate increases as pressure increases
CATALYST: Catalysts change the rate reaction by creating
an alternative pathway of lower activation energy
the nature of the reacting species the nature of the
reacting species

The Decomposition of Nitrogen Dioxide

Types of Rates

Initial Rates
Rates measured at the beginning of the reaction,
which is dependent on the initial concentrations of
reactants.

Instantaneous Rates
Rates measured at any point during the reaction.

Average Rates
An overall rate measured over a period or time
interval.
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Instantaneous Rate
Value of the rate
at a particular
time.
Can be obtained
by computing the
slope of a line
tangent to the
curve at that point.
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REACTION RATE

The rate of a chemical reaction is

defined
as
the
change
in
concentration of a reactant in a
particular time interval.

The Decomposition of Nitrogen Dioxide

Reaction Rates and Stoichiometric Relationships

Consider
the reaction:

2N2O5 4NO2 + O2

Rate of disappearance of N2O5 =

Rate of formation of NO2 =
Rate of formation of O2 =
Stoichiometric relationships of these rates

In general

For a reaction

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Rate law

An expression which shows how the reaction rate is related to concentration of

reactants (catalyst) is called the rate law or rate equation.
For a reaction
The rate law generally has the form
: rate constant,
proportionality constant
temperature dependent
Value and unit obtained from the rate law

and are small whole numbers called the order of reaction

Rate law is determined from experimental data

The reaction rate with respect to A or B is determined by varying

concentration of one reactant, keeping that of the other constant.

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Rate law
The
date below is for the experiment

Compare Experiments 1 and 2:

[NH4+] doubles, the initial rate doubles.
when

12

Rate law

Likewise, compare Experiments 5 and 6:

when [NO2 ] doubles, the initial rate doubles.

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Rate

This equation is called the rate law,

and k is the rate constant.

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Rate law
Other Examples of rate law:
1.

2N2O5 4NO2 + O2

2.

H2 + I2 2HI

Rate = k[H2][I2]

3.

2NO2 2NO + O2

Rate = k[NO2]2

Rate = k[N2O5]

4. 2NO + 2H2 N2 + 2H2O

Rate = k[H2]
2
In these
[NO]rate
laws where the quotient or concentration is not
shown, it is understood to be 1. That is [H2]1 = [H2].
the powers of concentration in the rate law are different
from coefficient of the respective reactant in the
equation.

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RATE LAWS
It is apparent that the rate law for a reaction must
be determined by experiment.
It cannot be written by merely looking at the
equation with a background of our knowledge of
Law of mass action.
However, for some elementary reactions the
powers in the rate law may correspond to
coefficient in the chemical equation.
But usually the powers of concentration in
the rate law are different from coefficient.
Thus for the reaction (4) above, the rate is found
to be proportional to [H2] although the quotient of
H2 in the equation is 2.
For NO the rate is proportional to [NO]2 and power

Order of a reaction
called rate order
Also

It is the powers/exponents of the concentration terms in the

rate equation (law)
Consider the rate law
The reaction order with respect to a given reactant species
equals the exponent of the concentration of that species in
the rate law, as determined experimentally.
and are reaction orders with respect to A and B respectively
The overall order of a reaction equals the sum of the orders
of the reactant species in the rate law
is the overall order
Can have integral or half integral values
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Order of a reaction

Reaction

Observed Rate
law

Order
with
respect
to
Reactant
1

Order
Overall
with
order
respect
to
Reactant
2

1
2

3
4
5
6
7

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ORDER OF A REACTION
Reactions may be classified
according to the order. If in the rate
law
Rate = k[A]m[B]n
m + n = 1, It is first order reaction
m + n = 2, It is second order
reaction
m + n = 3, It is third order reaction

ZERO ORDER REACTION

A reactant whose concentration does not affect the
reaction rate is not included in the rate equation (law).
In effect, the concentration of such a reactant has the
power 0. Thus [A]0 = 1.
A zero order reaction is one whose rate is
independent of concentration. For example
NO2 + CO NO + CO2
At 200C , its rate equation is
Rate = k[NO2]2
Hence the rate does not depend on [CO], so this is not
included in the rate law and the power of [CO] is
understood to be zero.
The reaction is zeroth order with respect to CO.
The reaction is second order with respect to [NO 2].
The overall reaction order is 2 + 0 = 2

The Rate Constant and the Rate

For all orders, except zero order, the rate of
reaction varies with concentration and is used as a
means of either quantifying reactions or comparing
them.
In contrast, the rate constant is a constant at a
given temperature and is independent of
concentration.
It can be used to quantify reactions and to compare
them.
Also, if the rate constant and the order are known,
then it is easy to calculate the rate for any
concentration.

MOLECULARITY OF A REACTION
Chemical reactions may be classed
into two types
Elementary reactions
Complex reactions
An elementary reaction is a simple
reaction which occurs in a single step.
A complex reaction is that which
occurs in two or more steps.

Molecularity of an elementary reaction

The molecularity of an elementary reaction is
defined as:
The number of reactant molecules involved in
the reaction.
Thus the molecularity of an elementary reaction
is 1, 2, 3, etc, according as one, two or three
reactant molecules are participating in the
reaction.
The elementary reactions having molecularity
1,2 and 3 are called unimolecular, bimolecular
and termolecular respectively.

Molecularity of an elementary reaction

Thus we have
(a) Unimolecular Reactions: (Molecularity = 1)
AProducts
Example : Br2 2Br
(b) Bimolecular Reactions: (Molecularity = 2)
A + B Products
A + A Products
Examples are:
(i) CH3COOC2H5 + H2O CH3COOH + C2H5OH

Ethyl acetateacetic acid

ethyl alcohol
(ii) 2HI H2 + I2
(c) Termolecular Reactions: (Molecularity = 3)
A + B + C Products
Examples are:
(i) 2NO + O2 2NO2
(ii) 2NO + Cl2 2NOCl

Complex Reaction
A complex reaction is that which occurs in two or
more steps.
For example, the overall reaction:
2A + B C + D
may involve the following elementary steps in its mechanism:
Step-1:
A + B X;
Step-2:
Step-3:

X + A Y;

YC+ D

Overall reaction: 2A + B C + D;
X and Y are called reactive intermediates

Complex reactions
The mechanism for the reaction between CO and NO2 is proposed
to be
Step 1

NO2 + NO2 NO3 + NO (an elementary reaction)

Step 2

NO3 + CO NO2 + CO2

(an elementary reaction)

Add these two equations led to the overall reaction

NO2 + CO = NO + CO2
(overall reaction)
and a two-step mechanism is proposed:
i
NO2 (g) + F2 (g) NO2F (g) + F (g)
(an
elementary reaction)
ii
NO2 (g) + F (g) NO2F (g)
(an elementary
reaction)
Overall reaction 2 NO2 (g) + F2 (g) 2 NO2F (g),
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Multistep Mechanisms
In a multistep process, one of the steps will be
slower than all others.
The overall reaction cannot occur faster than this
slowest,
It is the rate-determining step.

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Slow Initial Step

NO2

(g)

+ CO

(g)

NO

(g)

+ CO2

(g)

The rate law for this reaction is found

experimentally to be
Rate = k [NO2]2
CO is necessary for this reaction to occur, but
the rate of the reaction does not depend on its
concentration.
This suggests the reaction occurs in two steps.

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Slow Initial Step

A proposed mechanism for this reaction is

Step 1: NO2 + NO2
NO3 + NO (slow)
Step 2: NO3 + CO

NO2 + CO2 (fast)

The NO3 intermediate is consumed in the second step.

As CO is not involved in the slow, rate-determining

step, it does not appear in the rate law.

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Fast Initial Step

The rate law for this reaction is found

(experimentally) to be

Because termolecular (= trimolecular)

processes are rare, this rate law
suggests a two-step mechanism.

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Fast Initial Step

A proposed mechanism is

Step 1 is an equilibriumit includes the forward and reverse reactions.

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Fast Initial Step

The rate of the overall reaction

depends upon the rate of the slow
step.
The rate law for that step would be

But how can we find [NOBr2]?

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Fast Initial Step

NOBr2 can react two ways:
With NO to form NOBr
By decomposition to reform NO and Br2

The reactants and products of the

first step are in equilibrium with each
other.
Therefore,
Ratef = Rater
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Fast Initial Step

Because Ratef = Rater ,

k1 [NO] [Br2] = k1 [NOBr2]
Solving for [NOBr2] gives us
k1
[NO] [Br2] = [NOBr2]
k1

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Fast Initial Step

Substituting this expression for
[NOBr2] in the rate law for the
rate-determining step gives

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Meaning of the Rate Expression

Example: It has been determined experimentally that
the sequence of steps for a chemical reaction is as
follows:
A + B C (slow)
C + B D (fast)
What is the rate equation and the overall chemical
equation?
Solution: The overall chemical equation will be
obtained by adding the above equations i.e.
A + B C (slow)
C + B D (fast)
A + 2B D (slow)
Since the rate of reaction is controlled by the slow
step, the rate equation will be
Rate = k[A][B]

MOLECULARITY VERSUS ORDER OF REACTION

The term molecularity is not the same as

order of reaction.
The total number of molecules or atoms
which take part in a reaction as
represented by the chemical equation is
known as the molecularity of reaction.
The sum of the powers to which the
concentrations are raised in the rate law
is known as the order of reaction.

DIFFERENCES BETWEEN ORDER AND

MOLECULARITY

DETERMINATION OF ORDER OF REACTION

The rate equation of a reaction with a multi-step
mechanism cannot, in general, be deduced from the
stoichiometric coefficients of the overall reaction;
it must be determined experimentally.
The equation may involve fractional exponential
coefficients, or it may depend on the concentration
of an intermediate species.
The rate equation is a differential equation, and it
can be integrated to obtain an integrated rate
equation that links concentrations of reactants or
products with time.

DETERMINATION OF ORDER OF REACTION

Differential Rate Law (Rate law) - expresses how
the rate depends on concentration.
Integrated rate law - expresses how the
concentration depends on time.
We can work backwards from the rate law to infer
the steps by which their reaction occurs.
Most chemical reactions do not take place in a single
step but result from a series of sequential steps.
To understand a chemical reaction, we must learn
what these steps are.

CONCEPT CHECK
QUESTION: The following tabulated data
refer to the hypothetical reaction
A + 2B C
At a specific temp.

(a) Write the rate expression for the reaction

(b) Calculate the rate constant for the
reaction

Example: The following tabulated data refer to

the hypothetical reaction
A + 2B C
At a specific temp.

(a) Write the rate expression for the reaction

(b) Calculate the rate constant for the reaction

42

The general expression for a rate law is

From 1 & 2 changed by a factor of

Dividing 2 by 1

Thus
In a similar fashion

Will yield
Thus the rate law is

43

(b)
To calculate the rate constant, ,
substitute any of the three sets of
data into the rate law expression

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For the reaction: S2O82-(aq) + 3I- (aq) 2SO42- (aq) +

I3- (aq)
The data below were obtained.

(a) Determine the order of the reaction w.r.t. each reactant. Write the rate law
for the above reaction.
(b) Calculate the rate constant, k, and give its appropriate units.
(c) Calculate the reaction rate when each reactant concentration is 0.20 M
Expt. [S2O82-]
#
(mol/L)

[I-]
(mol/L)

Initial
Rate,
(mol/L.s)

0.036

0.060

1.5 x 10-5

0.072

0.060

2.9 x 10-5

0.036

0.120

2.9 x 10-5

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 Solution: The rate law has the form Rate = k[S2O82-]x[I-]y,

here x and y are rate orders.

(a) Calculation of rate order, x: we nee to use the equations with varying concentration of [S 2O82-]

Dividing gives

similarly

This reaction is first order w.r.t. [S2O82-] and [I-]

Rate = k[S2O82-][I-]

If
, and

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Types of Rate Laws

Differential Rate Law (rate law) shows
how the rate of a reaction depends on
concentrations.
This is what we have been discussing so far
Integrated Rate Law shows how the
concentrations of species in the reaction
depend on time.
Graphical method to derive the rate law of
a reaction
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Zero order
If the reaction A Products is a zero
order reaction, then
which yields
And a plot ofversuswill yield a straight line
with slope =

48

First order

If the reaction A Products is a first

order reaction, then
which yields
or
And a plot of versuswill yield a straight line
with slope = and y-intercept =

49

Second order
If the reaction A Products is a second
order reaction, then

which yields
A plot of versuswill yield a straight line with
slope = k and y-intercept =
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INTEGRATED RATE FOR VARIOUS

REACTION ORDERS

Example:
The
hydrolysis
of
ethyl
nitrobenzoate by aqeous sodium hydroxide
was followed at 250C by titration of the
hydroxide against standard acid at different
stages in the reaction. From the given data,
show that the reaction is second order

Solution: For the second order reaction

The
alternative
method
A plot of 1/
[A]t versus t
will give a
straight line
with
Slope = +k

HALF-LIFE

Half life of a reaction, t1/2 is the time

required for the concentration of a
reactant to drop to one half of its initial
value.
i.e. when
Half-life is a convenient way to describe
how fast a reaction occurs, especially if it
is a first-order process. A fast reaction has
a short half-life.
Substituting this for [A]t in the integrated
rate equation for any of the order gives
the half life expression.

54

Half-Life

For a first-order process, set [A] t=0.5 [A]0 in

integrated rate equation:

NOTE: For a first-order

process, the half-life
does not depend on [A]0.

55

Half-Life- 2nd order

For a second-order process, set
[A]t=0.5 [A]0 in 2nd order equation.

56

COLLISION THEORY OF REACTION RATES

According to this theory, a chemical reaction
takes place only by collision between the
reacting molecules.
But not all collisions are effective. Only a small
fraction of collisions produce a reaction.
The two main conditions for a collision
between reacting molecules to be productive
are
The colliding molecules must posses sufficient
kinetic energy to cause a reaction.
The reacting molecules must collide with
proper orientation

COLLISION THEORY OF REACTION RATES

Activation Energy

the rearrangement:
For

59

Reaction Coordinate
Diagrams

It shows the energy

of the reactants and
products (and,
therefore, E).
The high point on the
diagram is the
The species
present
at the
transition
state.
transition state is called the
activated complex.
The energy gap between the
reactants and the activated
complex is the activation energy
barrier.
60

the collision theory

For
the reaction:

61

62

EFFECT OF TEMPERATURE OF REACTION

VELOCITY
The temperature has a significant
effect
on the rate of the reaction.
It has been observed experimentally
that increase in temperature leads to
a remarkable increase in the rate of a
chemical reaction and hence in rate
constants.
A relationship between the energy
barrier to the reactions known as
ACTIVATION ENERGY, Ea and rate
constant k is
Where R is the gas constant and T is
the absolute temperature and A is the
frequency factor

EFFECT OF TEMPERATURE OF REACTION

VELOCITY

The
constant k and Ea are

related to A and B. The

factor A is known as
frequency factor.
Rewriting the equation as
a plot of log k versus 1/T
should be a straight line
with a slope Ea/2.303RT
and intercept log A .

EFFECT OF TEMPERATURE
Knowing the slope, the value of constant E a which is
characteristic of the reaction can be calculated e.g.
for the decomposition of N2O5, the slope is -5400.
Hence Ea is given by
Ea = -(-5400)(2.303)(1.987) = 24,700 cals/mol
Ea can also be determined if the specific rate
constants are known at two different temperatures.
If k1 is the specific rate constant at temperature T 1
and k2 at another temperature T2 then from the last
equation

EFFECT OF TEMPERATURE OF REACTION

VELOCITY

The effect of catalyst

The catalyst does not alter the value
of equilibrium constant for any
reversible reaction.
It simply helps in approaching the
equilibrium at an earlier stage by
catalyzing equally both the forward
and backward reaction.

Catalysts
One way a
catalyst can
speed up a
reaction is by
holding the
reactants
together and
helping bonds
to break.
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