MODULE - 5 Chemical Kinetics

Chemical Dynamics

14
Notes

CHEMICAL KINETICS

You know that a knowledge of Gibbs energy change in a given process can tell
you whether the process is feasible or not. However, the Gibbs energy decrease
does not indicate anything about the speed of a reaction. For example, the reaction
between hydrogen and oxygen to give water is accompanied by a large decrease
in Gibbs energy. However, you would not be able to observe the formation of
water, even if hydrogen and oxygen are kept in contact with each other for ever.
On the other hand, there are reactions which take place instantaneously. For
example, when HCl is added to AgNO3, white precipitate of AgCl is formed
instantaneously. In this lesson we shall study the speed or rate of reactions which
are neither very slow nor very fast. We shall also study the factors that control the
rate of a reaction.

OBJECTIVES
After reading this lesson you will be able to :
z explain the rate of a chemical reaction;
z differentiate between average rate and instantaneous rate;
z correlate the average and instantaneous rates with changes in concentrations
of various reactants and products;
z explain the factors that affect the rate of a reaction;
z define rate law and rate constant;
z define order and molecularity of a reaction;
z distinguish between order and molecularity;
z derive rate law for first order reaction and define half life period for first
order reaction;

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z derive a relationship between half life and rate constant for first order reaction;
z solve numericals on the relationships;
z explain collision theory of reaction rates.
z explain the effect of temperature on reaction rate, and
z explain Arrhenius equation and activation energy.
Notes
14.1 RATE OF A CHEMICAL REACTION
When the reactants are mixed to perform a reaction, there are no products present
initially. As time passes, the concentration of the products increases and that of
the reactants decreases. The rate of any chemical reaction can be expressed as
the rate of the change in concentration of a reactant (or a product).

Rate of a chemical reaction = Change in concentration of a reactant or a product

Time taken
mol litre −1
=
second
Let us consider the following chemical reaction :

2NO(g) + Br2(g) ⎯⎯
→ 2NOBr(g)

The rate for this reaction can be determined by measuring the increase in the
molar concentration of NOBr at different time intervals.
Let us see how we can express the rate of this reaction. You know that molar
concentration of a substance is expressed by enclosing the formula of the substance
in square bracket.
For example, [NOBr] represents the molar concentration of NOBr.
Let us suppose that [NOBr]1 is the molar concentration at time t1 and [NOBr]2 is
the molar concentration at time t2.
Then, change in molar concentration = [NOBr]2 – [NOBr]1 = Δ[NOBr]
Time required for the change = t2 – t1 = Δt
Here, Δ means change in the respective quantity.
Δ[NOBr]
Therefore, the rate of formation of NOBr =
Δt
This expression gives the rate of reaction in terms of NOBr.
If the decrease in the molar concentration of NO or Br2 is measured we can write
the rate of the reaction with respect to NO as
−Δ[NO]
=
Δt

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−Δ[Br2 ]
and w.r.t. Br2 as =
Δt
Thus, the rate of a reaction can be expressed either in terms of reactants or
products. We find in the reaction mentioned above that two moles of NO react
with one mole of Br2. Therefore, the change in concentration of NO in a given
time Δt will be double than that for Br2. Thus, in order to make the rates with
Notes respect to different reactants or products equal, the rate expression is divided by
the storichrometric coefficient in the balanced chemical equation.
For example, in the equation,

2NO(g) + Br2(g) ⎯⎯
→ 2NOBr(g)

The rate of reaction with respect to reactants and products is expressed as

1 Δ[NOBr] 1 Δ[NOBr] −Δ[Br2 ]
rate of reaction = + =– =
2 Δt 2 Δt Δt

14.2 AVERAGE RATE AND INSTANTANEOUS RATE

The rate of a reaction depends on the concentration of reactants. As the reaction
proceeds the reactants get consumed and their concentration decreases with time.
Therefore, the rate of reaction does not remain constant during the entire reaction.

Δ[concentration]
The rate of a reaction given as gives an average rate.
Δt

Δ[NOBr]
For example, gives the average rate of reaction. Instantaneous rate of
Δt
a reaction is the rate of reaction at any particular instant of time, we express
instantaneous rate by making Δt very small φ

lim [NOBr] d[NOBr]

Δt → 0 =
Δt dt
When concentration of any of the reactants or products is plotted against time,
the graph obtained is as given below :

Product
Concentration

Reactant

Time

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For the reaction,

2N2O5(g) ⎯⎯
→ 2NO2(g) + O2(g)

Average rate of reaction

1 Δ[N 2O5 ] 1 Δ[NO 2 ] Δ[O2 ]

=– = =
2 Δt 2 Δt Δt
Notes
1 d [N 2 O5 ] 1 d [NO2 ] d [O 2 ]
and instantaneous rate = − = =
2 dt 2 dt dt

14.3 FACTORS AFFECTING RATE OF A REACTION

The rate of a chemical reaction is affected by the following factors :
1. The concentration of reactants : Generally the rate of a reaction increases
as the concentration of the reactants is increased.
2. Temperature – A reaction is faster when the reaction temperature is
increased.
3. Presence of a catalyst – A catalyst alters the reaction rate without being
consumed by the reaction.
For example :
(i) Reaction between hydrogen and oxygen to form water is extremely slow. It
occurs very fast in the presence of platinum as catalyst.
You would study these effects in more detail in the following sections of this
lesson.

Example 14.1 : Express the average and instantaneous rate of the following
reaction
N2(g) + 3H2(g) 2NH3(g)
in terms of (i) rate of formation of NH3,
(ii) rate of disappearance N2, and
(iii) rate of disappearance of H2.
Write the different expressions for the rate of reactions.
Solution : The expression for the three rates are :
Δ[NH 3 ]
Average rate of formation of NH3 =
Δt

Δ[N 2 ]
Average rate of disappearance of N2 = –
Δt

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Δ[H 2 ]
Average rate of disappearance of H2 =
Δt
d[NH3 ]
Instantaneous rate of formation of NH3 =
dt
d[N 2 ]
Instantaneous rate of disappearance of N2 = –
Notes dt
d[H 2 ]
Instantaneous rate of disappearance of H2 =
dt
To equate the three rates, divide each rate by the coefficient of the corresponding
substances in the balanced equation.
1 Δ[NH3 ] Δ[N 2 ] 1 Δ[H 2 ]
Average rate = + =– =–
2 Δt Δt 3 Δt
1 d[NH3 ] d[N 2 ] 1 d[H 2 ]
Instantaneous rate = =– =–
2 dt dt 3 dt

INTEXT QUESTIONS 14.1

1. Which of the following units could be used to express the rate of reaction
between magnesium and hydrochloric acid?
(a) cm–3 s
(b) cm3 min–1
(c) cm3 s–1
(d) mol dm–3 min–1
2. For the following reaction,

2NO2(g) + F2(g) ⎯⎯
→ 2NO2F(g)

Write the expression for the average, rate of reaction in terms of :

(a) rate of formation of NO2F
(b) rate of disappearance of NO2
(c) rate of disappearance of F2
(d) equivalent rate of formation of product and disappearance of reactants.
3. Express the instantaneous rates of formation of product and disappearance
of reactants for the above reaction.
4. Explain why the reaction CO(g) + NO2(g) → CO2(g) + NO(g) occurs more
slowly when the volume of the system is increased.

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14.4 DEPENDENCE OF REACTION RATE UPON
CONCENTRATION
Rate law : If we follow a chemical reaction over a period of time, we find that its
rate slowly decreases as the reactants are consumed. We can say that the rate is
related to the concentration of the reactants. Rate is directly proportional to the
concentration of the reactants raised to some power.
Notes
For example, consider the reaction
xA (g) + yB(g) → Products ...(i)
where a and b are coefficients of A and B respectively in the balanced equation.
We can express the rate as
Rate α [A]x [B]y
or Rate = k [A]x [B]y
where k is the constant of proportionality.
The above equation is known as the rate law for the reaction.
Rate law is defined as the mathematical relationship between rate of a
reaction and the concentration of the reactants.
It is important to note that x and y are not necessarily equal to the stoichiometric
coefficient of A and B in the reaction. The constant k in the rate law is called the
rate constant. It is numerically equal to the rate of the reaction if all the
concentrations were set equal to unity.
rate = k [1]x [1]y
∴ rate = k
It means that large values of k indicate fast reaction and small values of k indicate
slow reactions. Each reaction is characterised by its own rate constant, whose
value is dependent on the temperature, but independent of concentration of the
reactants.

14.5 ORDER AND MOLECULARITY OF A REACTION

Order and molecularity are two properties of a chemical reaction. In this section
we shall learn about these.

14.5.1 Order of a Reaction

The powers to which the concentration terms are raised in the rate expression
describes the order of the reaction with respect to that particular reactant
In the rate law,
rate = k [A]x [B]y

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the values of x and y are order of the reaction with respect to the reactants A and
B respectively. The sum of the powers x + y represents the overall order of the
reaction.
For example in the reaction 2NO(g) + O2(g) 2NO2(g)
The rate law as found by experiment is
rate = k [NO]2 [O2]1
Notes
Here the order of reaction with respect to NO is 2 and with respect to O2 is 1. The
sum of the powers is termed as overall order of reaction. In the above example it
is 2 + 1 = 3.
It must be remembered that order of a reaction must be determined experimentally
and cannot be deduced from the coefficients in the balanced equation
2N2O5(g) 4NO2(g) + O2(g)
The overall order is 1 and it is termed as first order reaction.
The order of reaction can be 0, 1, 2, 3 called as zero order, first order, second
order and third order respectively. The order of a reaction can be a fraction as
well; for example the decomposition of ethanal to methane and carbon monoxide,
723 K
CH3 CHO (g) CH4(g) + CO(g)
is experimentally found to the following rate law :
rate = k [CH3CHO]3/2

14.5.2 Difference between Rate of Reaction and Rate Constant

Rate of reaction Rate constant
1. It is the speed at which the reactants It is the proportionality constant
are converted into products. It is in the rate law and is defined as
measured as the rate of decrease the rate of the reaction when
of concentration of reactant or the concentration of each of the
rate of increrase in the concentration reactant is unity.
of the products.
2. It depends upon the initial It is independent of the initial
concentration of the reactant. concentration of reactant.

14.5.3 Molecularity of a Reaction

A reaction occurs when its reactants are mixed. At molecular level, this ‘mixing’
occurs through molecular collisions. The balanced chemical equation does not
always gives the correct picture of how a reaction is occurring at molecular level.
For the following reaction to occur

MnO −4 + 5Fe 2+ + 8H + → Mn 2+ + 5Fe3+ + 4H 2O

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apparently 14 ionic species must collide. However, the probability of a collision
involving more than 3 particles is practically zero. Therefore, this reaction must
be occurring in many steps, each step involving collision of not more than 3
species. Such reactions are called complex reactions and each step is called an
elementary reaction step. Some reactions occur in a single step and such
reactions are called simple reactions.
Molecularity is the number of molecules, atoms or ions taking part in an Notes
elementary reaction step, which must collide simultaneously in order to
bring about the chemical reaction.
Molecularity of a reactions is its characteristic property and reactions are
classified according the their molecularity.
(i) Unimolecular reactions
These are reactions whose molecularity is one. For example
NH 4 NO 2 → N 2 + 2H 2O
2N 2O5 → 2N 2O4 + O 2
(ii) Bimolecular reactions
These are the reactions with molecularity equal to two, for example:
2HI → H 2 + I 2

[H + ]
CH 3COOC 2 H 5 + H 2O ⎯⎯⎯
→ CH 3COOH + C 2 H 5OH.
(iii) Termolecular or trimolecular reactions
These reactions have molecularity equal to three, for example
2NO + O 2 → 2NO 2

2NO + Cl2 → 2NOCl

Termolecular reactions are rare because the probability of three molecules
colliding simultaneously is very small. Most of the reactions are unimolecular
or bimolecular.
Molecularity of a reaction can only be a whole number, 1, 2 or 3. It is never
zero, fractional or more than 3.

14.6 UNITS OF RATE CONSTANT

For zero order
Rate = k [A]º
Rate = k

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The unit for rate of a reaction is mol L–1 s–1. The unit of k for zero order is same
as that for rate.
For a first order reaction
Rate = k [A]1

mol L−1
= k mol L–1
s
Notes
k = s–1
For a first order reaction, the unit for rate constant is time–1.
For second order reaction
Rate = k [A]2

mol L−1
= k (mol L–1)2
s
Therefore k = mol–1 L s–1
In general for any order n the unit for rate constant k is given as
k = (mol L–1)1-n s–1

14.6.1 Zero Order Reactions

Zero order reactions are those whose rate is proportional to zeroth power of
concentration, that is, the rate is independent of concentration of the reactant.
Table: Compession of Order and molecularity

Order Molecularity
1. It is the sum of powers of concentration It is the number of molecules, atoms
terms in the experimentally determined or ions which must collide simultaneo-
rate equation usly in order to bring about the chem-
cal reaction.
2. Order of a reaction can be 1, 2, 3, zero Molecularity can be 1, 2 or 3 only. It
or fractional. cannot be zero or fractional.
3. It is an experimental quantity. It is a theoretical quantity and depen-
ds on the mechanism of the reaction.
4. It is applicable to elementary as well It is applicable to only elementary
as complex reaction. reaction.
5. For complex reactions, order is deter- For complex reactions, molecularity
mined by the slovest step and the order has no meaning.
and molecularity of the slowest step
are the same.

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Examples of Zero Order Reactions
Some reactions show zero order under certain conditions.
(1) Decomposition of HI on the surface of gold catalyst when the pressure of
HI is high.
(2) Photochemical combination of H2 and Cl2 to form HCl when carried out
over water. Notes
(3) Enzyme reactions when the substrate concentration is high in comparison
to the enzyme concentration.
Consider the reaction:
A → Products.
Since the order of the reaction is zero, its differential rate equation is
d[A]
Rate = − = k [A]0
dt
Since anything raised to the power zero is equal to 1,

d[A]
Rate = − =k (1)
dt
Separating the variables, we get
d [A] = − kdt
Integrating both sides

∫ d [A] = −k ∫ dt
[A] = − kt + I (2)

Where [A] is the concentration of A at time t and I is the constant of integration.

It can be evaluated from the initial conditions. When t = 0, [A] = [A]0, where
[A]0 is the initial concentration of the reactant. Substituting in equation (2)
[A]0 = − k × 0 + I = 0 + I

∴ [A]0 = I (3)
Substituting for I in equation (2)
[A] = –kt + [A]0 (4)
This equation is the integrated rate equation for a zero order reaction. This
equation is an equation of a straight line and is of the form
y = mx + c

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It [A] is plotted as a function of t, the plot is a straight line graph with intercept
equal to [A]0 and slope equal to –k.

[A]o

Slope = –k
Notes [A]

t®

Fig. Concentration versus time plot for a zero order reaction.

Units of k
Equation (4) can be rearranged as
kt = [A]0 – [A]

[A]0 − [A] concentration

or k= = (5)
t time

= Concentration time–1 = mol L–1s–1

Half-Life Period, t1/2
It is the time during which one-half of the initial amount of the reactant reacts.
It is denoted by t1/2 or t0.5. It is also called half-change period. It can be
obtained from equation (4). Rearranging it, we get

[A]0 − [A]
t= (6)
k

1
when t = t1/2, [A] = [A]0
2
that is after half-life period, one-half of the reactant is consumed. Also, one-
1
half reactant is left unreacted or [A] = [A]0 .
2
Putting in equation (6)

1
[A]0 − [A]0
t1/2 = 2
k

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[A]0
t1/2 = (7)
2k
Thus, the half-life period of a zero order reaction depends upon the initial
concentration of the reactant [A]0 and from the above equation

t1/2 ∝ [A]0
Notes
the half-life period is directly proportional to the initial concentration of the
reactant.
Example: The rate constant of a zero order reaction is 2.4 × 10–3 mol L–1s–1.
What would be the half-life of the reaction if the initial concentration of the
reactant is 1.2 × 10–2 mol L–1?
Solution
For a zero order reaction

[A]0
t1/2 =
2k

Given: initial concentration of the reactant, [A]0 = 1.2 × 10–2 mol L–1 and
k = 2.4 × 10−3 mol L−1s −1.

1.2 ×10−2 mol L−1

∴ t1/2 = .
2 × 2.4 ×10−3 mol L−1s −1

= 2.5 s.

14.6.2 First Order Reaction

We will now discuss how to determine the rate constant for a first order reaction.
For the first order reaction, this equation would tell us how does the concentration
vary with time. The predicted variations can then be compared with the
experimental data to obtain the order of the reaction.
Let us consider for the reaction A Product.
For first order reaction.

−d[A]
rate = = k1[A]
dt
where k1 is the rate constant,

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Rearranging the rate expression, we have :

− d[A]
[A]
= k1dt

Integrating the two sides we get :

–1n [A] = k1t + constant ...(i)
Notes where the constant can be determined from the initial conditions.
Let [A]0 be concentration of [A] when t = 0 i.e., at the beginning of the reaction,
then –1n [A] = –1n [A]0, when t = 0
or constant = –1n [A]0
Putting the value of the constant in equation
–1n [A] = k1t –1n[A]0
or –1n [A] + 1n [A]0 = k1t
1n[A]0
or [A]
= k1t

1 0 [A]
Rate constant, k1 = t .1n [A]

We can convert it in to log to the base 10

2.303 [A]0
k1 = log
t [A]

k1t
= log [A]0 – log [A]
2.303
k1t
− = log [A] – log [A]0
2.303

⎛ k1 ⎞
log [A] = – ⎜⎝ ⎟ t + log [A]0
2.303 ⎠
The unit of k1 = time–1
This equation has the same form as the equation of a straight line.
y = mx + c
where m is the slope and c is the intercept. If we plot log10 [A] vs t, it would give
k1
a straight line with a slope equal to – . The rate constant, k1 can then be
2.303
calculated from the slope as shown in Fig. 14.1.

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log10 (concentration)
k1
Slope = –
2.303

Slope
Notes
Time
Fig. 14.1 : A graph of log10 (concentration) against time for a first-order reaction.

14.6.3 Half-Life Period

The time taken for a reaction to reach the half-way stage i.e. when half of the
starting material has reacted is called half-life period of the reaction. It is denoted
by t1/2 or t0.5. Let us now see how the half-life period of a first order reaction is
calculated.
You know that
ln[A] = 1n[A]0 – k1t

1
when [A] = [A]0 (reactant reduces to half of the initial concentration)
2
then t = t1/2 (half life period)
Therefore, we have
⎧[A]0 ⎫
1n ⎨ ⎬ = 1n[A]0 – k1t1/2
⎩ 2 ⎭

⎧[A]0 ⎫
or 1n ⎨ ⎬ – 1n [A]0 = –k1t1/2
⎩ 2 ⎭
1
or 1n = – k1t1/2
2
1n2 0.693
or t1/2 = k = k
1 1

You would notice that half-life period is independent of the initial concentration.

Example 14.2 : The decomposition of hydrogen peroxide to water and oxygen.

2H2O2(l) ⎯⎯
→ 2H2O (l) + O2(g)

is a first order reaction with a rate constant of 0.0410 min–1. If we start with 0.20
M solution of H2O2, what will be concentration after 10 minutes?

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Solution : We have equation for first order reaction as

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

converting it into log10 base

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

If [A] = x, after 10 minutes then subsituting the values of k and t, we have

2.303 0.20
0.0410 (min–1) = 10(min) log x

0.20 10(min) (0.0410 min −1 )

or log = = 0.178
x 2.303
Taking antilog
0.20
= antilog 0.178 = 1.51
x
0.20
Solving x = = 0.132 mol litre–1.
1.51

Example 14.3 : In example 14.2 if we start with initial concentration of 0.50 how
long will it take for this concentration to drop to 0.10 M.
Solution : We have to find the time taken by the reaction starting from
concentration of H2O2 of 0.5M to concentration of 0.1 M.
We have the equation,

2.303 [A]0
k = log [A]
t
Substituting the values of k, [A]0 and [A] we have
2.303 0.50
0.0410 min–1 = log
t 0.10

2.303 0.699 × 2.303

t = log 5 × −1
= min
0.0410 min 0.041

or t = 39 minutes
Example 14.4 : In example 14.2, how long will it take for the sample to decompose
to 50%.
Solution : When half the sample has decomposed, we have

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0.693
t1/2 =
k
Putting the value of k = 0.0414 min–1 we have
0.693
t= min = 16.9 minutes
0.0414

Notes
INTEXT QUESTIONS 14.2
1. The rate of a certain reaction, A ⎯⎯→ Product is 1.0 × 10–3 mol/litre.
When conc. A = 0.020M, what is rate constant k, if the reaction is :
(a) zero order
(b) first order
2. For the following reaction
C2H4 (g) + I2(g) C2H4I2(g)
the rate equation is
rate = k [C2H4(g)] [I2(g)]3/2
(a) What is the order of reaction with respect to each reactant?
(b) What is the overall order of reaction?
(c) What is the unit of k, if concentrations are measured in mol dm–3?
3. The first order rate constant for the decomposition of C2H5Cl at 700K is 2.5
× 10–3 min–1. If the initial concentration is 0.01 mol L–1, calculate the time
required for the concentration of C2H5Cl to drop to half of its original value.

14.7 COLLISION THEORY OF REACTION RATES

Collision theory was proposed to explain the rates of reactions occurring in gas
phase. It is largely based on kinetic molecular theory of gases. According to
this theory:
1. A reaction would occur only when the reactant molecules collide with one
another. Thus, the rate of a reaction would depend upon the collision
frequency, ZAB which is the number of collisions involving one molecule each
of two reactants A and B occurring in unit volume of the gaseous reaction
mixture and in unit time.
2. Not all molecular collisions result in chemical reaction. Only effective
collisions can bring about chemical reaction. An effective collision is the one

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in which the combined kinetic energy of colliding moleculas is equal to or
more than the activation energy of the reaction Ea. The fraction of molecules
possessing a minimum of activation energy Ea at a particular temperature
E
− a
T is given by e RT .
3. For a reaction to occur not only the collision should be energetically
effective, the orientation of the colliding molecules should be such which
Notes would permit the formation of new bonds. Consider, for example, the
decomposition reaction of HI
2HI(g) → H 2 (g) + I 2 (g)
The product would be formed only if during the collision the two H atoms are
near each other and so are the two I atoms. (Fig 14.3(a)). This would permit
the formation of bond between two H atoms and another bond between two
I atoms. If orientation is not proper (Fig 14.3(b), it is not possible as two I atoms
are too far apart for the bond formation. After the collision, the two HI molecules
rebound back without any reaction. Only a certain fraction of energetically
effective collisions would have proper orientation and would result in a chemical
reaction. This fraction is represented in terms of probability P, that molecules
during a given collision would have proper orientation. P is called probability
factor or steric factor.
H—I H—I
H—I I—H
(a) (b)

Fig. 14.3 (a) Proper orientation of two HI molecules (b) Improper orientation.

Taking these three factors into account, the rate of the reaction is given by the
relation
E
− a
Rate = Z AB ⋅e RT ⋅P

14.7 DEPENDENCE OF REACTION RATE ON

TEMPERATURE
You have learnt earlier that an increase in temperature causes an increase in the
rate of reaction. The rate is about doubled, for many reactions, by a 10 degree
rise in temperature. How can we explain this behaviour?
In order for a chemical reaction to occur, the reacting molecules must collide
with each other. Only fast moving molecules i.e. the molecules having high energy
are able to react. There must be some minimum energy possessed by the reacting
molecules during the collision. This is called the threshold energy. All molecules

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having energy higher than the threshold energy are therefore, capable of reacting.
What would happen if we increase the number of molecules having higher energy?
More molecules will react. In other words rate of reaction would increase. Thus,
if we increase the temperature, we increase the rate of reaction. Let us see if we
can express it quantitatively.

The change in energy that takes place during the course of a reaction is shown in
Fig. 14.2. The horizontal axis denotes the progress of the reaction and it indicates Notes
the extent to which the reaction has progressed towards completion. The graph
indicates that the reactant molecules A and B must possess enough energy. This is
known as Activation energy, to climb the potential energy hill to form the activated
complex. All the reacting molecules do not possess energy equal to threshold
energy in their normal energy state. Therefore a certain extra energy needs to be
supplied so that their energy equals the threshold energy. The potential energy of
activated complex is maximum. The reaction thereafter proceeds to completion
(i.e. formation AB). Ea indicates the activation energy of forward reaction and
Ea′ is the activation energy of the backward reaction.

energy of the Activated complex

Ea Ea¢
Energy

A+B
A + B
Reactants

AB Products

Progress of reaction

Fig. 14.2 Energy diagram for a reaction

You know that rate of reaction = k [concentration]. If we have value of

concentration as unity, then rate of reaction is equal to the rate constant, k. The
rate constant k depends on the magnitude of the activation energy, Ea, and also
on the absolute temperature (T), k is small when Ea is very large or the temperature
is low.
We can express this relationship by a mathematical equation known as Arrhenius
equation after its discoverer, S. Arrhenius as follows :
k = Ae–Ea/RT
Where A is a proportionality constant and is also known as frequency factor, R is
the gas constant. How can we utilise this relationship between k, Ea and T? We

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can calculate activation energy, if we measure the rate constant at two different
temperatures.
Taking natural logarithm of equation, we get
Ea
ln k = lnA –
RT
We can compare this equation with that of a straight line y = mx + c as follow :
Notes
–E a ⎛ 1 ⎞
ln k = ⎜ ⎟ + lnA
R ⎝T⎠
The plot of in k vs 1/T gives a straight line whose slope is equal to –Ea/R and
whose intercept is In A (in Fig. 14.3).

lnk

1
T
Fig. 14.3 Graphical determination of Ea.

We can also obtain Ea from k at two temperatures by direct computation.

At T1, the equation becomes
k1 = Ae − Ea / RT1
At T2, we can write
k2 = Ae − Ea / RT2
k1 Ae – Ea / RT1
Dividing k1 by k2 we get k2 = Ae – Ea / RT2

k
1 –E a ⎛1 1 ⎞
taking natural logarithm ln k = ⎜ – ⎟
2 R ⎝ T1 T2 ⎠
Converting into logarithm (base 10)
k1 –E ⎛ T2 – T1 ⎞
log k = a
⎜ ⎟
2 2.303R ⎝ T1 . T2 ⎠
Multiply by –1 on both sides and inverting the fraction
k2 E ⎛ T2 – T1 ⎞
log k = a
⎜ ⎟
1 2.303R ⎝ T1 . T2 ⎠

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This equation can also be used to calculate the rate constant at some specific
temperature if Ea and k at some other temperature are known.
Example 14.5 : What must be the value of Ea if the rate constant for a reaction is
doubled when the temperature increases from 300K to 310K?
k2
Solution : Given k = 2, R = 8.31 JK–1
1

T2 = 310 K Notes
T1 = 300 K
Ea = ?
We have equation :

k2 Ea ⎛ T2 – T1 ⎞
log k = 2.303 R ⎜ T . T ⎟
1 ⎝ 1 2 ⎠
substituting the values we have
Ea (310 – 300)K
log 2 = 2.303 × 8.31 JK –1 (310K × 300K)

solving, we have
Ea = 53.5 kJ

INTEXT QUESTIONS 14.3

1. As a rough rule of thumb, the rates of many reactions double for every 10ºC
rise in temperature? Explain.
2. The rate constant of a reaction at 288 K is 1.3 × 10–5 litre/mol. While at 323K
its rate constant is 8.0 × 10–3 lit./mol. What is the Ea for the reaction.
3. The rate of the reaction triples when temperature changes from 293 K to 323
K. Calculate the energy of activation for such a reaction.
4. H2(g) and O2(g) combine to form H2O(l) by an exothermic reaction. Why do
they not combine when kept together for any period of time.
5. What is an effective collision?

WHAT YOU HAVE LEARNT

z The rate of a chemical reaction can be expressed as the rate of change in
concentration of a reactant or product.

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z The factors that affect the rate of a chemical reaction are : the concentration
of the reactants, temperature and catalyst.
z Rate law is defined as the mathematical relationship between rate of a reaction
with the concentration of the reactant.
z The constant k in the rate law is called the rate constant. It is numerically
Notes equal to the rate of the reaction if all the concentrations were set equal to
unity.
z The sum of the powers to which the concentration terms are raised in the rate
expression describe the order of the reaction.
z The rate constant of a first order reaction, k1, is given by

1 [A]0
k1 = In [A]
t
z The time taken for a reaction to reach the half way stage, i.e., when half of the
starting material has reacted is called half-life period of a reaction.
z According to the collision theory, a reaction occurs only when the reactant
molecules collide provided they have sufficient energy and proper orientation.
z The dependence of the rate constant on the magnitude of the activation energy,
Ea, and the absolute temperature, T, is given by the Arrhenius equation, k =
Ae–Ea/RT.
z The activation energy for the decomposition of a compound corresponds to
the difference between the energy of the reactants and the maximum on the
energy curve.

TERMINAL EXERCISE
1. Sketch an energy vs progress of reaction diagram for a reaction. Indicate the
activation energy for both forward (Ea) and reverse reaction (E′a).
2. For the reaction 2N2O5(g) → 4NO2(g) + O2(g), it is found that N2O5 is
decomposing at the rate of 0.02 mol/litre sec. Calculate to rate of reaction
Δ [NO 2 ]
defined as with Δt in seconds.
Δt
3. The rate constant for a certain first order decomposition reaction is 0.23 s–1
at 673K. Calculate the half-change period for this reaction.

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4. The rate constant for a certain first order reaction is 1.00 × 10–3 s–1 at 298K.
The rate constant for the reaction is 1.4 × 10–2 s–1 at 323K. Calculate the
activation energy for this reaction.
5. The rate of a reaction was found to be 3.0 × 10–4 mol/litre second. What will
be the rate if it were expressed in the units mol/litre minute.
6. List the three factors that affect the rate of a chemical reaction. Notes
7. For a certain first order reaction the concentration of the reactant decreases
from 2.00 mol/litre to 1.50 mol/litre in 64 minutes. Calculate the rate constant
for this reaction.
8. The rate constant for a certain first order reaction is 1.0 × 10–3 min–1 at 298K.
If the activation energy is 10.0 k cal, calculate the rate constant at 323K.
9. The reaction
A2 + B ⎯⎯
→ C+D
Occurs in the following steps
(i) A2 ⎯⎯
→ 2A

(ii) A + B ⎯⎯
→ X

(iii) A + X ⎯⎯
→ C+D

The order of this reaction is one. What is its molecularity. What one of the
three steps is the slowest or rate determining step?

ANSWERS TO INTEXT QUESTIONS

14.1
1. d
Δ [NO2 F] – Δ [NO2 ]
2. (i) (ii)
Δt Δt

– Δ [F2 ] 1 Δ [NO2 F] 1 Δ [NO2 ] – Δ [F2 ]

(iii) (iv) =– =
Δt 2 Δt 2 Δt Δt

1 d [NO 2 F] 1 d [NO2 ] d [F2 ]

3. =– =
2 dt 2 dt dt
4. Increase in volume would decrease the pressure which would decrease the
rate of reaction.

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14.2
1. (a) 1.0 × 10–3 mol litre–1 s–1
(b) 5.0 × 10–2 s–1
2. (a) First order with respect to C2H4 and 1.5 with respect to I2.
(b) The over all order of reaction is 2.5
Notes sec –1
(c) k = (mol dm –3 )3 / 2

= mol–3/2 dm9/2 s–1.

2.303 0.01 mol L–1

3. (a) 2.5 × 10 (min ) = 10 min log10
–3 –1
x
(b) When half of the sample is decomposed

0.693
t1/2 = min = 0.277 × 103 min = 2.77 × 102 min
2.5 × 10 –3

14.3
1. 10
2. 34.0 K cal mol–1
3. 28.82 kJ
4. Molecules do not have enough energy to be equal to threshold energy.

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