Chemical Kinetics

Raju Bhattarai (RB)

Chemistry
 Chemical Kinetics
Course outline

• Concept of Rate of reaction

• Average rate of reaction and instantaneous rate of reaction
• Factor that influence the rate of reaction
• Rate law equation ,rate constant and its units
• Molecularity and Order of reaction
• Zero, first, second and third order reaction
• Integrated rate law equation for first order reaction
• Half life of a reaction (1st order)
• Concept of activation energy, threshold energy, activated complex, Arrhenius
equation
• Theories of reaction rate( only collision theory)
• Related numerical
 Introduction

The branch of Physical chemistry which deals with the rate of reactions is called Chemical
Kinetics.
The study of Chemical Kinetics includes :
(1) The rate of the reactions and rate laws.
(2) The factors as temperature, pressure, concentration and catalyst, that influence the rate of a
reaction.
(3) The mechanism or the sequence of steps by which a reaction occurs.
The knowledge of the rate of reactions is very valuable to understand the chemical of reactions.
It is also of great importance in selecting optimum conditions for an industrial process so that it
proceeds at a rate to give maximum yield.
 Reaction rate
The rate of a reaction tells as to what speed the reaction occurs.
The rate of reactions is defined as the change in concentration of any of reactant or
products per unit time. ie,
change in concentration of any of reactant or products
rate of reactions =
per unit time
Let us consider a simple reaction
A ⎯⎯→ B
The concentration of the reactant A decreases and that of B increases as time passes.
Thus rate of reaction = rate of disappearance of A = rate of appearance of B
𝑑[𝐴] 𝑑[𝐵]
or rate = – =+
𝑑𝑡 𝑑𝑡
where [ ] represents the concentration in moles per litre whereas ‘d’ represents infinitesimally
small change in concentration. Negative sign shows the concentration of the reactant A decreases
whereas the positive sign indicates the increase in concentration of the product B.
 UNITS OF RATE

Rate of Reactions has the units of concentration divided by time. ie,

mole per litre
rate of reactions =
time
We express concentrations in moles per litre (mol/litre )but time may be given in any convenient
unit second (s), minutes (min), hours (h), days (d) or possible years.
Therefore, the units of reaction rates may be
mol L–1 s -1
mol L–1 min–1
mol L–1 h–1 and, so on
 Type of Reaction rate

1. Average rate of reaction

2. Instantaneous rate of reaction
1. Average rate of reaction
The average rate of reactions is defined as the change in concentration of any of
reactant or products over certain time period. ie,
change in concentration of any of reactant or products
Average rate of reactions =
certain time

Let us consider a general reaction.

A B
Let, the initial concentration of reactant at time t1 , be [A1] and final concentration be [A2]
So, Average rate (R) = (change in concentration) / (Change in time)
[A ]−[A1] −Δ[A]
= 2 =
t2−t1 Δt
For the given reaction the rate of reaction may be equal to the rate of
disappearance of A which is equal to the rate of appearance of B.
Thus rate of reaction = rate of disappearance of A = rate of appearance of B
Δ[𝐴] Δ𝑑[𝐵]
or rate = – = +
𝑑𝑡 𝑑𝑡
whereas ‘Δ’ represents overall change in concentration.

2. Instantaneous Rate of Reaction

The instantaneous rate of reaction is define as the change in concentration of
reactant or product at instant time period during the course of reaction.
If time interval be small the rate is referred to as instantaneous rate and is written
as:

For a reaction
R P
𝑑[𝑅] 𝑑[𝑃]
Instantaneous Rate = – = +
𝑑𝑡 𝑑𝑡
 Factors affecting rate of reaction
The factors that influence the rate of reaction are given below:
(i) Concentration:
Rate depends on concentration of reaction. Initially reaction occurs fast due to high
concentration of reactant. As time passes, concentration of reactant goes on decreasing
which results decrease in reaction rate. Effect of concentration on reaction rate is shown
in the figure.
(ii) Temperature
According to kinetic theory, average kinetic energy is directly proportional to absolute
temperature. The rate of reaction increases with increase in temperature. It is because
average kinetic energy of reactant molecule increases as the temperature is increased. The
velocity of molecules increases with increase in temperature .This result in increases K.E.
Thus, rate increases with the increase in temperature. For a gaseous reaction, every 10°C
rise in the temperature, rate is increased by 2 – 3 folds.
(iii) Surface area:
The larger the surface area of the reaction the faster is the rate of reaction. This fact is
supported by the general observation that freely divided solids reacts faster than massive
substance. For eg. the powder calcium carbonate react faster than solid marble .
CaCO3 + dil. HCl CaCl2 + CO2 + H2O (Fast)
(Powder )
CaCO3 + dil. HCl CaCl2 + CO2 + H2O (Slow)
(Marble )
(IV) Catalyst
Catalyst is a substance which accelerates or retards the rate of reaction. In general the catalyst
increases the rate of reaction. Positive catalyst increases the rate by providing a new path and
lowering the activation energy while negative catalyst decrease the rate of reaction. i,e
1.positive catalyst
MnO
2KClO3 2 2KCl +3O2
2. Negative catalyst
Glycerol
2H2O2 2H2O + O2
The effect of catalyst is shown in figure.

Fig. energy profile diagram showing catalyzed and uncatalyzed reaction

(V) Nature of reactant
The rate of reaction depends upon nature of reactant . In a chemical reaction old bond are broken
and new bond are formed, so different amount of energy is required for breaking and formation
of bonds .in this context ionic reaction are faster than molecular reaction.
(VI) Light /Radiation
In certain types of reaction ,the presence of light alter the rate of reaction and takes place only in
presence of light ,such reaction are called photochemical reaction. In such reaction faster will be
the reaction in presence of light and sloe in absence of light. For eg,
hv
1. H2 +Cl2 2HCl
hv
2. 6CO2+6H2O C6H12O6 + 6O2
 RATE LAWS
The exact relation between concentration and rate is determined by measuring the
reaction rate with different initial reactant concentrations. An expression which
shows how the reaction rate is related to concentrations of reactant is called
the rate law or rate equation.
For a reaction, For a reaction , aA + bB ⎯⎯→ products
according to law of mass action
rate ∝ [A]a [B]b
But, experimentally,
rate = k [A]m [B]n
or rate = rate = k [A]m [B]n ...(1)
where k=rate constant m and n are the order with respect to A and B.
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. This equation (1) is known as rate law
equation.
 Rate constant(K)
For a reaction
A product
The rate law equation is written as.
rate = k [A]n …...(1) where k=rate constant
When the concentration of reactant be unity then equation (1) become
rate= k
Therefore rate constant may be define as the rate of reaction when the
concentration of reactant is unity. Different order of reaction have different unit of
rate constant.

Characteristics of rate constant

1.It measure the rate of reaction . Higher the value of rate constant faster will be the rate
of reaction and vice-versa.
2. The unit of rate constant depends upon the order of rection.
3. Each reaction has fixed value of rate constant at fixed temperature.
 Unit of rate constant for different order of rection
For a reaction
A product
The rate law equation is written as.
rate = k [A]n …...(1) where n denotes order of reaction.
1. For zero order reaction
n=o Then, rate = k [A]0
rate = k , therefore k= mol L–1 S -1
For zero order reaction, the unit of rate constant is mol L–1 S -1
2. For 1st order reaction
n=1 Then, rate = k [A]1
mol L–1 S -1 = k [mol L–1 ]1
K= S -1
For 1st order reaction, the unit of rate constant is S -1
3. For 2nd order reaction
n=2
Then, rate = k [A]2
mol L–1 S -1 = k [mol L–1 ]2
K= Lmol-1S -1
For 2nd order reaction, the unit of rate constant is Lmol-1S -1

4.. For 3rd order reaction

n=3
Then, rate = k [A]3
mol L–1 S -1 = k [mol L–1 ]3
K= L2mol-2S -1
For 3rd order reaction, the unit of rate constant is L2mol-2S -1
 ORDER OF A REACTION
The order of a reaction is defined as the sum of the powers of concentrations
term appear in the rate law equation.
For a reaction 2A + B ⎯⎯→ products
The rate law equation for above expression is given as
rate = k [A]m [B]n ...(1)
order= m + n
where m=order with respect A and n= order with respect to n. these term m and
n are experimentally determined term.
Depending on the value of m+n ,order of reaction may be of different type.
1. If m+n=o, zero order reaction
2. If m+n=1, 1st order reaction
3. If m+n=2, 2nd order reaction
4. If m+n=3, 3rd order reaction and so on.
 MOLECULARITY OF A REACTION
Chemical reactions may be classed into two types :
(a) Elementary reactions : An elementary reaction is a simple reaction which occurs in a
single step.
(b) Complex reactions : A complex reaction is that which occurs in two or more steps.

For a reaction a A +b B ⎯⎯→ products

molecularity= a +b
The molecularity of a reaction is defined as the number of reactant molecules involved
in a chemical reaction to form a product.
Thus the molecularity of an reaction can be 1, 2, 3, etc., according as one, two or three
reactant molecules are participating in the reaction to give product.
1. If a+b=1, unimolecular reaction
2. If a+b=2, bimolecular reaction
3. If a+b=3, termolecular reaction and so on.
Differences Between Order and Molecularity
 Types of order of reaction
Zero order reaction: A chemical reaction in which rate of reaction is independent of
concentration of the reactant is called zero order reaction.
• Unit of zero order reaction: mol-1 L-1 S-1
Example of zero order reaction
1. Decomposition of ammonia on platinum surface

First order of reaction: A chemical reaction in which the rate of reaction depends upon one
concentration is known as first order reaction.
• Units of first order reaction = min-1 or sec-1.
For example
1. Decomposition of N2O5
1
N2 O5 ⎯⎯→ 2NO2 + O2
2
2. NH4NO2 N2 +2H2O
rate= K[NH4NO2]1
 Half life period
The time required to decompose exactly the half of the initial concentration of reactant
is known as half life period. It is denoted by t1/2.
0.693
t1/2 =
K
Second order reaction:
A chemical reaction in which the rate depends upon second power of initial concentration of
reactant is called second order reaction.
• Unit of second order reaction:= mol-1 L sec-1.
Example
1. Hydrolysis of an Ester by NaOH.
CH3COOC2H5 + NaOH ⎯⎯→ CH3COONa + C2H5OH
ethyl acetate ethyl alcohol
2. H2 +I2 2HI

Third order reaction:

A Chemical reaction in which rate depends upon third power of initial concentration of the
reactant is called third order reaction.
• Unit of third order reaction = mol-2 L2 sec-1.
Example
1. 2FeCl3(aq) + SnCl2(aq) ⎯⎯→ 2FeCl2 + SnCl4
2. 2NO(g) + O2(g) ⎯⎯→ 2NO2(g)
3. 2NO(g) + Cl2(g) ⎯⎯→ 2NOCl(g
 Pseudo-first order reaction
A reaction in which one of the reactants is present in a large excess shows an order different
from the actual order. The experimental order which is not the actual one is referred to as the
pseudo order.
Let us consider a reaction
A + B ⎯⎯→ products
in which the reactant B is present in a large excess. Since it is an elementary reaction, its rate
law can be written as
rate = k [A] [B]
As B is present in large excess, its concentration remains practically constant in the course of
reaction. Thus the rate law can be written as
rate = k′ [A]
where the new rate constant k′ = k [B].
Thus the actual order of the reaction is second-order but in practice it will be first-order.
Therefore, the reaction is said to have a pseudo-first order.
Example
(1) Hydrolysis of an ester.
CH3 COOC2 H5 + H2O ⎯⎯→ CH3 COOH + C2H5 OH
ethyl acetate (excess) acetic acid ethyl alcohol
Here a large excess of water is used and the rate law can be written as
rate = k [CH3 COOH] [H2 O]
= k′ [CH3 COOH]
The reaction is actually second-order but in practice it is found to be first-order.
Thus it is a pseudo-first order reaction.
(2) Hydrolysis of sucrose.
C12H22O11 + H2O ⎯⎯→ C6H12O6 + C6H12O6
Sucrose (excess) glucose fructose
Activation energy [Ea]:
The minimum additional amount of energy required to cross the energy barrier is
called activation energy [Ea]. Thus, activation energy is the additional amount of
energy supplied to reactant to cause a chemical change. Thus activation energy is
the difference of threshold energy (Eth) and average (Ea).
So, Ea = Eth - Eav
Threshold energy (Eth)
The minimum amount of energy associated with activated complex that can cause a
chemical change is called threshold energy (Eth). In other words, it is the highest
point of energy barrier. Therefore, threshold energy is the sum of average (Ea) and
activation energy (Eav).
So, Eth = Eav + Ea
Activated complex : The short life molecular complex that is formed in the
midway between reactant and product at the top of energy barrier is called activated
complex. For eg,
A+B +C [A…..B….C] AB +C
reactant activated complex product
Temperature coefficient:
It is defined as the ratio of rate constant of reaction at two different temperature
differing by 10o C. thus
𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑎𝑡 (𝑇+10)
Temperature coefficient =
𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑎𝑡 𝑇
Arrhenius equation :
Arrhenius prosed a mathematical relationship to relate rate of reaction with
activation energy and temperature. Which is known as Arrhenius equation.
Mathematically, K = A e-(Ea /RT)
Theory of rate of reaction
1. Collision theory
According to this theory all molecules must collide with each other to occurs a chemical
reaction. All the collision are not effective. only a fraction of molecules colliding with
sufficient kinetic energy and proper orientation can leads to the formation of product,
which is known as called effective collision.
The molecules collision occurring with insufficient K.E. and improper orientation is
called ineffective collision. The main points of this theory are:
1. The colliding molecule must posses sufficient kinetic energy to cause reaction.
2. The reacting molecule must collide with proper orientation.
Consider the reaction
A2 + B2 2AB
This can be diagrammatically represented as:
Every substance has definite amount of energy called average energy [Eav]. In order to
cause a chemical change, reacting species should cross over energy barrier as shown in
energy profile diagram.
Similarly orientation of reacting molecules plays the significant role for product formation.
reacting molecules should be properly orientated for effective collision and to give product. The
proper orientation of reacting molecule is shown in fig below
Fig: orientation of reacting species showing effective and ineffective collision