CHAPTER 3

CHEMICAL KINETICS

Rate of a reaction
 Rate of a reaction can be expressed in two ways:
i) Rate of disappearance of= Decrease in concentration of R = -∆[R]
Time taken ∆t

ii) Rate of appearance of P = Increase in concentration of P = +∆[P]

Time taken ∆t
Instantaneous and average rate of a reaction
 Average rate is the change in the concentration of a reactant or product per
unit time.
 The instantaneous rate of a reaction is the reaction rate at any given point of
time. It is obtained when we consider the average rate at the smallest time
interval, say dt.

Consider a reaction,

Factors affecting rate of a reaction

 Rate of a reaction depends on concentration of reactants, temperature surface
area and catalyst.
Rate law or Rate equation or Rate expression
 The representation of rate of a reaction in terms of concentration of the
reactants is known as rate law.
 Consider a reaction aA + bB → cC + dD, where a, b, c and d are the
stoichiometric coefficients of reactants and products.
Rate equation for this reaction is Rate ∞ [A]x [B]y or Rate = k [A]x [B]y

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Order of a reaction
 Consider a rate equation Rate = k [A]x [B]y.
 The sum of these exponents, that is, x + y is known as order of the reaction.
 Hence, the sum of powers of the concentration of the reactants in the rate
law expression is called the order of the chemical reaction.
 The reactions taking place in one step are called elementary reactions.
 When a sequence of elementary reactions (called mechanism) gives us the
products, the reactions are called complex reactions.
Units of rate constants
 Consider a rate equation Rate = k [A]x [B]y.
 Order of the reaction, n = x + y
 k= Rate .
[A]x [B]y
k = concentration x 1 .
n
Time (concentration)
-1 -1
Unit = mol L s
(molL-1)n

Molecularity of a Reaction
 The number of reacting species (atoms, ions or molecules) taking part in an
elementary reaction, which must collide simultaneously in order to bring
about a chemical reaction is called molecularity of a reaction.
 The overall rate of the reaction is controlled by the slowest step in a reaction
called the rate determining step.
They are of three different types.
 The reaction is said to be unimolecular when only one reacting species is
involved. Eg:- NH4NO2 → N2 + 2H2O
 The reaction is said to be bimolecular when two reacting species are involved.
Eg:- 2HI → H2 + I2
 The reaction is said to be trimolecular when three reacting species are
involved. Eg:- 2NO + O2 → 2NO2
 The probability that more than 3 molecules can collide and react
simultaneously is very small. Hence, molecularity greater than 3 is not
observed.
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Qn. How order of reaction and molecularity differ towards a complex reaction?
For a complex reaction, order of reaction is applicable while molecularity has no
meaning.
Integrated rate equations
Zero Order Reactions

 Consider the reaction, R → P

 Rate = -d[R] = k[R]0 (because of zero order reaction)
dt
 Rate = -d[R] = k
dt
d[R] = -k dt

 Integrating both sides

[R] = - kt + I ................... (1), where I is the constant of integration.

 At t=0, R = [R]0, where [R]0 is initial concentration of the reactant.

 [R]0 = -k x 0 + I
[R]0 = I .........................(2)

 Substituting (2) in (1),

[R] = - kt + [R]0 ..................(3)
 Comparing (3) with equation of a straight line, the slope would be –k and the
intercept would be [R]0
 Equation (3) on rearranging, k = [R]0 - [R]
t
 An example for a zero order reaction is decomposition of gaseous ammonia on
a hot Pt surface at high pressure.

 In this reaction, platinum metal acts as a catalyst. At high pressure, the metal
surface gets saturated with gas molecules.

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 First Order Reactions

 Consider the reaction, R → P

 Rate = -d[R] = k[R] (because of first order reaction)

dt

d[R] = -kdt
[R]
 Integrating on both sides,

ln [R] = -kt + I ...................... (1) where, I is the constant of integration.

 At t=0, R = [R]0, where [R]0 is initial concentration of the reactant.

 ln [R]0 = -k x 0 + I

ln [R]0 = I .........................(2)

 Substituting (2) in (1),

ln [R] = - kt + ln[R]0 ..................(3)

 Comparing (3) with equation of a straight line, the slope would be –k and the
intercept would be ln[R]0

 Equation (3) on rearranging, kt = ln[R]0 - ln[R]

1
Or, k = ln [R]0 / [R]
t

Eg:- All natural and artificial radioactive decay.

226 4 222
88Ra → 2He + 86Rn

First Order Reactions in Gas Phase

Let pi be the initial pressure of A and pt the total pressure at time ‘t’.

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Half-Life of a Reaction
 Half- life of a reaction is the time in which the concentration of a reactant is
reduced to one half of its initial concentration.
 It is represented as t ½
Half-life of a zero order reaction

t ½ = [R]0
2k
Half life of a first order reaction

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 t ½ = 0.693
k

Pseudo First Order Reaction

 A Pseudo first order reaction can be defined as a reaction that appears to
be of higher order but follows first-order kinetics. This occurs when one
reacting material is present in large excess.

t=0 0.01 mol 10 mol 0 mol 0

mol
0 mol 9.99 mol 0.01 mol
0.01 mol

 Eg:- Rate = k′ [CH3COOC2H5] [H2O]

the term [H2O] can be taken as constant. The equation, thus, becomes
Rate = k [CH3COOC2H5] where k = k′ [H2O]
Account for the following:
(a) The rate of a reaction does not remain constant throughout the course of
reaction.
 Rate of a reaction depends on concentration of reactants and since
concentration becomes less and less as the reaction progresses, the rate also
goes on decreasing.
(b) The boiling of an egg or cooking rice in an open vessel takes more time in hilly
areas.
 At hilly areas, atmospheric pressure is low as a result of which water boils at
lower temperature.
TEMPERATURE DEPENDENCE OF THE RATE OF A REACTION
 As temperature increases rate of reaction also increases because there are more
particles with energy greater than activation energy at a higher temperature.
ARRHENIUS EQUATION

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where A is the Arrhenius factor or frequency factor or pre-exponential factor. R is gas
constant and Ea is activation energy measured in Jmol-1

 The plot of ln k vs 1/T gives a straight line according to the above equation.

EFFECT OF CATALYST
 A catalyst is a substance which increases the rate of a reaction without itself
undergoing any permanent chemical change.

 A catalyst provides an alternate pathway by reducing the activation energy

between reactants and products and hence lowering the potential energy
barrier.

COLLISION THEORY OF CHEMICAL REACTIONS

 According to collision theory, the reactant molecules are assumed to be hard

spheres and reaction is postulated to occur when molecules collide with each
other.
 The number of collisions per second per unit volume of the reaction mixture is
known as collision frequency (Z).
 For a bimolecular elementary reaction, A + B → Products

where ZAB represents the collision frequency of reactants, A and B.

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  All collisions do not lead to the formation of products. The collisions in which
molecules collide with sufficient kinetic energy (called threshold energy) and
proper orientation are called as effective collisions.
 To account for effective collisions, another factor P, called the probability or
steric factor is introduced.

 Thus, in collision theory, activation energy and proper orientation of the

molecules together determine the criteria for an effective collision.

 Collision theory also has certain drawbacks as it considers atoms/ molecules to

be hard spheres and ignores their structural aspect.

Q. Write two conditions for the collisions to be effective collisions.

 Proper orientation.

 Energy of colliding particles should be equal to or greater than threshold

energy.

Q. State one condition in which a bimolecular reaction may be kinetically of 1st order.
When one of the reactants is in excess.
Q. Define activation energy.
The energy required to form activated complex / The minimum amount of extra
energy required by reacting molecules to get converted into a product.

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 EQUATIONS
1. Rate of a reaction = Change in concentration of reactants / products
Time
2. mol L−1 s−1
Unit of Rate constant, k = where n is the order of reaction
(mol L−1)n
3. Rate equation,

4. Integrated rate equation - for ZERO order reaction,

5. For FIRST order reaction,

6. For FIRST order reactions in GAS PHASE,

k=

7. Half-Life of a Reaction for ZERO order reaction,

8. Half-Life of a Reaction for FIRST order reaction,

GRAPHICAL REPRESENTATIONS
FOR ZERO ORDER REACTIONS
FOR THE EQUATION RATE
EQUATION

UNIT OF k

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FOR FIRST ORDER REACTIONS

FOR THE EQUATION FOR THE EQUATION

RATE EQUATION
UNIT OF k

HALF LIFE OF A REACTION

FOR ZERO ORDER REACTIONS FOR FIRST ORDER REACTIONS

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