Department of Chemistry

Course Title : Physical Chemistry I

Course No. : CH 101

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 Chemical Kinetics

Chemical Kinetics: It is the study of reaction

rates, how reaction rates change under
varying condition, and what molecular events
occur during the overall reaction.

Elementary reaction or elementary step: A

single molecular event, such as a collision of
molecules, resulting in a reaction is known as
elementary reaction.

Unimolecular reaction, O3*→ O2 + O

Bimolecular reaction, NO2 + NO2 → NO3 + NO
Termolecular reaction, Br + Br + Ar → Br2 + Ar

Complex Reaction: A reaction that takes

place in more than one step is known as
complex reaction.

Elementary reaction NO + NO→ N2O2

“ “ N2O2 + O2 → 2NO2
Complex reaction 2NO + O2 → 2NO2
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Reaction mechanism: The sequence of
elementary reactions (reaction steps) that
leads to product formation is called the
reaction mechanism. Or, a set of elementary
reactions written in a proper sequence leading
to the products formation is called reaction
mechanism.

Reaction intermediate: It is a species

produced in the reaction but does not appear
in the overall equation because it reacts in a
subsequent step in the mechanism. N2O2 is a
reaction intermediate in the following
reaction mechanism:

Elementary reaction NO + NO → N2O2

“ “ N2O2 + O2 → 2NO2
Overall reaction 2NO + O2 → 2NO2………1

Rate determining step: It is the slowest step

in the reaction mechanism. The 1st step of the
following is rate determining step.
NO2 + F2 → NO2F + F k1 slow step
F + NO2 → NO2F k2 fast step
2NO2 + F2 → 2NO2F overall reaction
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Rate of a reaction: It may be defined as the
increase of molar concentration of the
product of a reaction per unit time, or the
decrease in the molar concentration of a
reactant per unit time. So, the unit of reaction
rate is mol dm-3time-1(Ms-1 or Mmin.-1 or
Mday-1 and so on). The rate of the following
reactions can be written as:

2N2O5(g)→ 4NO2(g) + O2(g)………1

𝒅[𝑵𝟐𝑶𝟓] 𝒅[𝑵𝑶𝟐] 𝒅[𝑶𝟐]
Rate = - = =
𝟐𝒅𝒕 𝟒𝒅𝒕 𝒅𝒕

BrO3(aq)+5Br-(aq)+6H+(aq) → 3Br2(aq)+3H2O(l)…. 2

𝒅[𝑩𝒓𝑶𝟑] 𝒅[𝑩𝒓−] 𝒅[𝑯+] 𝒅 [𝑩𝒓𝟐] 𝒅[𝑯𝟐𝑶]

Rate = - =- =- = =
𝒅𝒕 𝟓𝒅𝒕 𝟔𝒅𝒕 𝟑𝒅𝒕 𝟑𝒅𝒕

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 Types of reaction rates
Initial rate of a reaction: The rate at the start of
a reaction when an infinitesimal amount of
reactant has been used up is known as initial rate
of a reaction. It is generally calculated from the
tangent drawn at t = 0 of the curves of the concn.
of the reactant or product vs. time plots.
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[P]

Concn.
0.5
[R]
0.25

Time

Average rate of reaction: If the rate of a reaction

is calculated by dividing the decrease of concn. of
the reactant (or increase in the concn. of the
product) in a definite interval of time by time is
called the average rate of reaction. If [O2] is the
increase in the concentration of oxygen of the
reaction-1 in the time interval, t, the average rate
of the reaction during the time is

Average rate = [O2] /t

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Instantaneous rate of reaction: The rate of
a reaction at a particular moment is called
instantaneous rate of reaction. It is calculated
by drawing tangent at desired time on the
curve of the concentration of reactant (or
product) vs. time of a reaction.
[P]

Concn.

[R]

5 10 15 20 25
Time/min
Rate law or rate equation: It is an equation
that relates the rate of a reaction to the
concentrations of the reactants raised to
various powers. Let us consider the reaction

2NO2(g)+F2(g)→2NO2F(g) ………3
𝒅[𝑵𝑶𝟐]
Rate equation is, Rate = - = k[NO2]m[ F2]n
𝟐𝒅𝒕

k-proportionality constant, known as rate

constant of the reaction, m-order with respect
to NO2 and n-order of the reaction with
respect to F2
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Rate constant or specific rate constant: It
is the proportionality constant of the rate
equation of a reaction. Its unit depends upon
the number of concn. terms and their powers
(exponents) in the rate equation.

For first order reaction, its unit is time-1, for

second order reaction mol-1dm3time-1, for
third order reaction-mol-2dm6 time-1 and so
on.

Order of a reaction: The order of a reaction

with respect to a given reactant species equals
the power (exponent) of concentration of that
species in the rate equation. It can’t be
determined by looking at the balanced
equation of the reaction and must be
determined experimentally.

For the reaction-3, the order of the reaction

with respect to both NO2 and F2 is 1, so the
rate equation will be

Rate = k[NO2][F2]……..4

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Overall order: The overall order of a
reaction is equal to the sum of the orders with
respect to all reactants shown in the rate
equation. So, overall order of the reaction-3
is 2 (from eq.-4).

Molecularity: It is the number of molecules

on the reactant side of an elementary reaction.
Unimolecular reaction, O3*→ O2 + O
Bimolecular reaction, NO2 + NO2 → NO3 + NO
Termolecular reaction, Br + Br + Ar → Br2 + Ar

Reactant concn. changes with time for

different order reactions:
(i) For a zero order reaction, it decreases linearly.
(ii)For a 1st order reaction, it decreases exponentially.
(iii)For a 2nd order reaction, it decreases rapidly
exponentiall
1.0

Zero order reaction

[Reactant] 0.5 1st order reaction

0.25

2nd order reaction

Time

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Variation of the rate of reaction of zero,
first and second order reaction with
concentration of the reactant:

(i) The rate of a zero-order reaction

doesn’t vary with the increase of the
concentration of the reactant.

(ii) The rate of a first order reaction

increases linearly with the increase of
concentration of the reactant.

(iii) The rate of a second order

(unimolecular) reaction increases
exponentially with the increase of concn.
of the reactant.

(iii) First order

Rate of
Reaction (i) Zero order

(ii) Second order

[Reactant]

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Exptl. Determination of Order of a Reaction:

Consider the Reaction, 2A + B → product

The rate eq. can be written as, Rate = k[A]m[B]n
Expt. [A]/mol dm-3 [B]/mol dm-3 Initial rate/mol dm-
3 -1
No. s
1 0.5 1.0 2.0
2 0.5 2.0 8.0
3 10 3.0 36.0
4 2.0 3.0 72.0
In expts.1 and 2, the concn. of A is const., so
𝑅𝑎𝑡𝑒(2) n 8 n
= {[B]2 /[B]1 } or = {2/1} or
𝑅𝑎𝑡𝑒(1) 2
4 = 2n, or 22 = 2n, therefore, n = 2
So, the reaction is first order w.r.t. A.

In expts. 3 and 4, concn. of B is constant, so

𝑅𝑎𝑡𝑒(4) m 72 m
= {[A] 4 / [A]3 } or = {2/ 1}
𝑅𝑎𝑡𝑒(3) 36
or 2 = 2m, therefore, m = 1
The rate equation is, Rate = k[A][B]2,
Overall order is 3,

So, the rate constant is given by

k = Rate/[A] [B]2
= 2/(0.5x1.02) mol-2dm6s-1
= 4.0 mol-2dm6s-1.
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First order reaction: A first order reaction is
a reaction whose rate depends on the reactant
concentration raised to first power. In a first
order reaction of the type
A → product
𝑑[𝐴]
The rate is Rate = - 𝑑𝑡
𝑑[𝐴]
Also, from the rate law, - = k[A]
𝑑𝑡
𝑑[𝐴]
or - [𝐴] = kdt………5
Let us suppose that, at the beginning of the
reaction the concn. of the reactant A is [A]0
and that of at the time t is [A], i.e. when, t=0,
[A]=[A]0, now integrating the equation-5
between [A]0 to [A] and time=0 to time=t we
have
[𝐴 ] 𝑑[𝐴] 𝑡
∫[𝐴]0 - [𝐴]
= ∫0 kdt

or, - ln[A] +ln [A]0 = kt

or, ln[A] = - kt +ln[A]0……..6

[𝐴] o [𝐴] o
or ln [𝐴]
= kt or 2.303 log [𝐴]
= kt

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 1 [𝐴] o
therefore, k = 𝑡 2.303log [𝐴] …….7
[𝐴] [𝐴]
or, ln = - kt or, = e-kt
[𝐴] o [𝐴] o

therefore, [A] = [A]0 e-kt ……8

From equation-6, it is clear that if the plot of

ln of concn. of reactant (i.e., ln[A]) against
time (t) gives a straight line with –ve slope,
then the reaction is first order, and from the
value of slope the rate constant, k, can be
calculated (slope = - k).
ln[A]0

ln[A] slope = - k

Time (t)

*If the concns. of the reactant at the

beginning of the reaction, [A]0, and at any
time, t, [A] are known, the value of the rate
constant, k, can be calculated by using the
equation-7.
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*If the reactant concn. at the beginning of the
reaction and the rate constant, k, are known,
then the concn. of the reactant at any time, t,
can be calculated by using the equation-8.

*The unit of rate constant, k, of the first order

reaction can determined from equation-7,
which will be time-1 (i.e. s-1, or min.-1 and so
on).
Half-life of a reaction: It is the time required
for the concn. of a reactant to decrease to half
of its initial value. It is represented by t1/2. The
half-life of a first order reaction can be
expressed as follows. From equation-7 we
write
1 [𝐴] o
t = 2.303log
𝑘 [𝐴]
by the definition, when t = t1/2 , [A] = [A]0/2
1 [𝐴] o
t1/2 = 𝑘 2.303log[𝐴]o/2
1
or, t1/2 = 𝑘2.303log2

0.693
therefore, t1/2 = …….9
𝑘

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Eq.-9 tells us that the half-life of a first order
reaction in independent of the initial concn.
of the reactant. Thus, it takes he same time for
the concn. of the reactant to decrease from
1.0M to 0.5M, say, it does for a decrease in
concn. from 0.1M to 0.05M. Measuring the
half-life of a reaction is one way to determine
the rate constant of a first order reaction and
vice versa.

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