Chemical Kinetics

Kinetics – Background
• To understand & predict behaviour of a chemical system one must consider certain factors of both
Thermodynamics & Kinetics to analyze the feasibility of a chemical change
Thermodynamics : does a reaction takes place ???
1. Gibbs Free Energy ΔG = (-)ve

2. Entropy Change ΔS = (+)ve

Kinetics : how fast does a reaction proceed ???

3. The RATE of the change Kinetics

The branch of chemistry, which deals with the study of reaction rates and their mechanisms,
called chemical kinetics.
• Kinetic studies not only help us to determine the speed or rate of a chemical reaction but also
describe the conditions by which the reaction rates can be altered.
• The factors such as concentration, temperature, pressure and catalyst affect the rate of a reaction.
Rate Of Reaction: Change in concentration (mol/L) of a reactant or product with time (s, min, hr);

Rate of Reaction =

Progress of a simple reaction

Reactant A Product B

• Concentration of Reactant A
(Black ) decreases with time time

• Concentration of Product B
(Red) increases with time The graph shows the change in
the number of A
and B molecules in the reaction
• Concentrations of A & B are as a function of time
measured at time t1 & t2
respectively A1 , A2 & B1 , B2
 Rate with respect to A

Change in concentration of A Conc. A2 – Conc. A1 Δ[A]

Rate = = - = - Δt
change in time t2 - t1

Rate with respect to B

Rate = Change in concentration of B Conc. B2 – Conc. B1 Δ[B]

= =
change in time t2 - t1 Δt

-Δ[A] Δ[B]
Rate = = ( - ve ) sign is used because the concentration of A is decreasing
Δt Δt
 aA+bB→cC+dD
where a, b, c,d are stoichiometric coefficients in the balanced
Chemical equation & A, B , C , D are Chemical Species

Rate of reaction = rate of disappearance of reactants = rate of appearance of products

1 Δ[A] Δ[B] 1 Δ[C] 1 Δ[D]
- =- 1 = =
a Δt b Δt c Δt d Δt
Unit Of Rate: mol L-1s-1 for reactants & products.

 Average rate depends upon the change in conc. of reactants or products and the time taken for that change to occur, rav.

 The rate of reaction at a particular moment of time is called as the instantaneous rate, rins.
Rate Law or Rate Expression and Rate Constant

The expression which relates of rate of reaction to concentration of the reactants is known as rate law. It is also
called as rate equation or rate expression.
• Consider a general reaction: aA + bB → cC + dD where a, b, c and d are the stoichiometric coefficients of
reactants and products.
The rate expression for this reaction is –
Acc. to the Law Of Mass Action
Rate of reaction = k [A]x[B]y where exponents x and y may or may not be equal to the stoichiometric coefficients
(a and b) of the reactants.
Thus, rate law is the expression in which reaction rate is given in terms of molar concentration of reactants with
each term raised to some power, which may or may not be same as the stoichiometric coefficient of the reacting
species in a balanced chemical equation.

k is Rate Constant & is a function of T & P ( P dependence is small & usually

ignored )
When [A] = [B] = 1 mol/L, than Rate of reaction = k, rate constant of a chemical reaction may be defined as the
reaction rate when the concentration of each reactant is unity. Depends on Temperature and independent of
concentration of reactant.
• The sum of powers of the concentration of the reactants in the rate law expression is called the order of that
chemical reaction.
• For a general reaction
aA + bB → cC + dD Let Rate of reaction = k [A]x[B]y Here ,

x = order of reaction w.r.t. A y = order of reaction w.r.t. B

Overall order of reaction(n) = x + y
 Order of a reactioncan be 0, 1, 2, 3 and even a fraction.

 Depending upon order of reaction, reactions are termed as zero, first or second order reactions.

 Order of reaction cannot be predicted by merely looking at the balanced chemical

equation, i.e., theoretically but must be determined experimentally.
For a nth order reaction- Rate = k [A]n

Rate concentration 1
k = = x
[A]n time (concentration)n
k = (concentration)1-n time-1
Molecularity of a Reaction
Molecularity of a reaction is simply the number of reacting species (atoms, ions or molecules)
involving is an elementary reaction which must collide simultaneously.

Why the reactions having molecularity greater than three is

rare ?
Since the chances of collision and reaction of more than
three molecules at a time are very less, the molecularity
greater than three is rare.

Molecularity of a complex reaction has no meaning.

Actually a complex reaction is the series of two
or more elementary reactions and thus, it completes in
several steps. The slowest step or slowest reaction
determines the rate of the reaction. Hence we
find out the molecularity of the slowest elementary
reaction of a complex reaction which is, in general,
similar to the overall order of the complex reaction.
 Integrated Rate Equations
Zero Order Reactions Zero order reaction means that the rate of the reaction is proportional to zero
power of the concentration of reactants. Consider the reaction,
R→P

Rate

Integrating both sides between proper limits

𝑹
Concentration
∫ 𝒅 [𝑹] = −𝒌 ∫ 𝒅𝒕
𝑹𝟎
𝟎

[R] ̶ [Ro] = ̶ kt

[Ro ] ̶ [R] = kt
 First Order Reactions
First order reaction means that the rate of the reaction is proportional to first power
of the concentration of reactants. Consider the reaction,
R→P
Rate constant unit:

Integrating both sides between proper limits

𝐭
𝐑 𝐝[𝐑]
𝟐.𝟑𝟎𝟑 [Ro]
∫
𝐑
= −𝐤 ∫ 𝐝𝐭 k= log10 [R]
𝐑𝟎 𝐭
𝟎
ln[R] ̶ ln [Ro] = ̶ kt
Or
ln [Ro ] ̶ ln[R] = kt

k =𝟏ln [Ro]
[R]
𝐭
 Second Order Reactions Half-Life of a Reaction
The half-life of a reaction is the time in which the
−d[A]/dt=k[A]2 concentration of a reactant is reduced to one half of its initial
concentration. It is represented as t1/2
The equation can then be rearranged:
t1/2 for a Zero Order Reactions
Half-Life of a First Order Reaction
t1/2 for a First Order Reactions Half-Life of a Second Order Reaction
Thus for a first order
reaction, half-
life period is constant, i.e.,
it is independent of initial
concentration of the
reacting species.

t1/ t1/ t1/

2 2 2

a a 1/a
zero first second
order order order
 Examples of observed
rate laws for some
reactions follow:

Pseudo - first order reaction

Reactions which are not truly of the first order but under certain conditions
reactions become that of first order are called pseudo unimolecular reaction.
For example: Hydrolysis of ester in presence of acid

CH3COOC2H5 + H2O  CH3COOH + C2H5OH therefore, r = k’ [ester]

From this reaction, the rate expression should be Where k’ = k[H2O].
r = k [ester] [H2O]
Since, hydrolysis takes place in the excess of H2O
and concentration change of H2O is negligible practically.
 Nature Of Reactants
FACTORS AFFECTING THE RATE
• Rate of “ Homogeneous Reactions” is higher than the
• Nature Of Reactants “Heterogeneous Reactions”
• Surface Area Of Reactants • Rate depends on the physical state of reactants , e.g.
• Concentration Of Reactants liquid /gaseous/solid
• Temperature • Rate depends on the number of collisions or
• Catalyst encounters between the reacting species
Concentration Of Reactants Temperature &Catalyst
• Surface Area Of Reactants
• Rate of reaction is directly proportional to conc. of reactants
•Heterogeneous reaction occurs at interface of two • Rate of reaction increases with increase in temperature.
phases of reactants • A catalyst alters the Rate of a reaction
•If one reactant is Solid , rate increases with increase in
surface area of solid phase reactant
•Surface area increases , area of contact between
reactants increases - rate of encounter between V = 1 m3 A = 6 V = 1 m3 A V = 1 m3 A
reactants increases - Rate increases m2 = 8 m2 = 12 m2
•Surface area of a solid can be increased by Sub-
division i.e. dividing the bigger particles in smaller
V= 1 V = 1 m3 A = V = 1 m3 A
m3 A 36 m2 = 20 m2
=
 Theories of chemical kinetics

1. Collision theory • The frequency of collisions

• The fraction of collisions with enough energy to react

• The orientation of colliding molecules (steric factor)

Energy barrier:
The minimum energy which the colliding particles possess in order to
bring about the chemical reaction is called threshold energy The energy
difference between threshold energy & average energy of reacting
molecules is called activation energy
Orientation barrier:
Colliding molecules should be in their proper orientation at the time of
collision.
Transition state theory In the activated complex theory, we
consider two reactants approaching and
their potential energy rising and reaching a
maximum.

Activation energy - the energy needed to form activated

complex is called energy of activation. It is very low for some
reactions and very high for others.
H  Ea  Ea` 1. Ea is always positive.

Effect of temperature on rate of chemical 2. The larger the value of Ea, the slower the rate
reaction of a reaction at a given temperature.
For a chemical reaction with rise in temperature by 10°, the
3. The larger the value of Ea, the steeper the
rate constant is nearly doubled slope of (ln k) vs (1/T). A high activation
k(T+10)/kT = 2 or 3 is called the temperature coefficient energy corresponds to a reaction rate that is
very sensitive to temperature.
Arrhenius equation

The temperature dependence of the rate of a chemical reaction can be

accurately explained by Arrhenius equation

Plot of ln k vs 1/T is a straight line & slope =Ea/R

Effect of temperature on rate of chemical reaction Catalysts
At temperature T1 A substance that changes the rate of a reaction without being
consumed in the reaction.
• catalysts are substances that affect the rate of a reaction
without being consumed
At temperature T2
• catalysts work by providing an alternative
k1 and k2 are the values of rate constants at mechanism for the reaction with a lower activation
energy, Ea
temperatures T1 and T2 respectively. Subtracting
equation (2) from (1), we obtain mechanism without catalyst
O3(g) + O(g)  2 O2(g)
mechanism with catalyst, Cl

Cl(g) + O3(g)  O2(g) + ClO(g) Fast

ClO(g) + O(g)  O2(g) + Cl(g) Slow

How catalyst change reaction rate

Catalysts

homogeneous catalysts are in the same phase as the reactant particles

Cl(g) in the destruction of O3(g)

• heterogeneous catalysts are in a different phase than the reactant

particles
 solid catalytic converter in a car’s exhaust system
 solid MnO2 catalyses liq H2O2
Sugar is fermented in a 1st order process (using an enzyme as a catalyst).

sugar + enzyme  products

Rate of disappear of sugar = k[sugar]

k = 3.3 x 10-4 sec-1

What is the half-life of this reaction?

Solution

[A]/[A]0 = fraction remaining

when t = t1/2, then fraction remaining = 1/2
Therefore, ln (1/2) = - k • t1/2
0.693 = k • t1/2
So, for sugar,
t1/2 = 0.693/3.3 10-4 s-1 = 2100 sec = 35 min