Chemical Kinetics

For any chemical reaction, chemists try to

find out
 (a) the feasibility of a chemical reaction which
can be predicted by thermodynamics ( as you
know that a reaction with ∆G < 0, at constant
temperature and pressure is feasible);
 (b)extent to which a reaction will proceed can
be determined from chemical equilibrium;
 (c)speed of a reaction i.e., time taken by a
reaction to reach equilibrium.
It is important to know the rate and the
factors controlling the rate of a chemical
reaction for its complete understanding

For example,
 Which parameters determine as to how
rapidly food gets spoiled?
 How to design a rapidly setting material for
dental filling?
 Or what controls the rate at which fuel
burns in an auto engine?
Chemical Kinetics
The branch of chemistry, which deals with the study of
reaction rates and their mechanisms, called chemical
kinetics.
Greek word ‘kinesis’ meaning movement.
Thermodynamics tells only about the feasibility of a
reaction whereas chemical kinetics tells about the rate
of a reaction.
For example, thermodynamic data indicate that diamond
shall convert to graphite but in reality, the conversion
rate is so slow that the change is not perceptible at all.
Kinetic studies 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.
• At the macroscopic level, we are interested in
amounts reacted or formed and the rates of
their consumption or formation.
• At the molecular level, the reaction
mechanisms involving orientation and energy
of molecules undergoing collisions.
Rate of a Chemical Reaction
 Some reactions such as ionic reactions occur
very fast, for example, precipitation of silver
chloride occurs instantaneously by mixing of
aqueous solutions of silver nitrate and sodium
chloride.
 Some reactions are very slow, for example,
rusting of iron in the presence of air and
moisture.
 There are reactions like inversion of cane sugar
and hydrolysis of starch, which proceed with a
Rate of the reaction
The speed of a reaction or the rate of a
reaction can be defined as the change in
concentration of a reactant or product in
unit time.
It can be expressed in terms of: (i) the rate
of decrease in concentration of any one of
the reactants, or (ii) the rate of increase in
concentration of any one of the products.
 Consider a hypothetical reaction, assuming that
the volume of the system remains constant.
 R → P ,One mole of the reactant R produces one
mole of the product P.
 If[R]1 and [P]1 are the concentrations of R and P
respectively at time t1 and [R]2 and [P]2 are their
concentrations at time t2 then,
 ∆t = t2 – t1
• The square brackets in the
above
 ∆[R] = [R]2 – [R]1 expressions are used to
 ∆ [P] = [P] – [P] express molar concentration.
2 1
Since ∆[R] is a negative quantity (as
concentration of reactants is decreasing), it is
multiplied with –1 to make the rate of the
reaction a positive quantity.
Average rate of a reaction, rav
 Averagerate depends upon the change in
concentration of reactants or products and the
time taken for that change to occur.

• Average rate cannot be used to predict the

rate of a reaction at a particular instant as it
would be constant for the time interval for
which it is calculated.
 Instantaneous rate

To express the rate at a particular

moment of time we determine the
instantaneous rate.
 It is obtained when we consider the
average rate at the smallest time interval
say dt ( i.e., when ∆t approaches zero).
 Hence, mathematically for an infinitesimally small
dt instantaneous rate is given by

• It can be determined graphically by

drawing a tangent at time t on either of
the curves for concentration of R and P
vs time t and calculating its slope (Fig.
 Units of rate of a
reaction
• Units of rate are concentration time–1.
• For example, if concentration is in mol L–1 and
time is in seconds then the units will be mol L-
s .
1 –1

• However, in gaseous reactions, when the

concentration of gases is expressed in terms
of their partial pressures, then the units of
the rate equation will be atm s–1 .
In problem 4.1, rinst at 600s, can be calculated by
plotting concentration of butyl chloride as a function
of time.
• A tangent is drawn that touches the curve at t =
600 s (Fig. 4.2). The slope of this tangent gives
the instantaneous rate.
4.2 Factors Influencing Rate of a
Reaction
Rate of reaction depends upon the
experimental conditions such as
concentration of reactants (pressure in
case of gases) and temperature and
catalyst.
4.2.1 Dependence of Rate on
Concentration
 The rate of a chemical reaction at a given
temperature may depend on the concentration
of one or more reactants and products.
 The representation of rate of reaction in terms of
concentration of the reactants is known as rate
law.
 Itis also called as rate equation or rate
expression.
4.2.2 Rate Expression and Rate
Constant
 Rate of a reaction decreases with the passage of
time as the concentration of reactants decrease.
 Conversely, rates generally increase when
reactant concentrations increase.
 So, rate of a reaction depends upon the
concentration of reactants.
This form of equation (4.4 b) is known as differential rate
equation, where k is a proportionality constant called rate
constant. The equation like (4.4), which relates the rate of a
reaction to concentration of reactants is called rate law or
• 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.
4.2.3 Order of a Reaction
In the rate equation (4.4) Rate = k
[A]x[B]y x and y indicate how sensitive
the rate is to the change in
concentration of A and B.
 Sum of these exponents, i.e., x + y in
(4.4) gives the overall order of a reaction
whereas x and y represent the order
with respect to the reactants A and B
• Hence, the sum of powers of the
concentration of the reactants in the rate
law expression is called the order of that
chemical reaction.
• Order of a reaction can be 0, 1, 2, 3 and
even a fraction.
• A zero order reaction means that the rate
of reaction is independent of the
concentration of reactants.
• A balanced chemical equation never gives us
a true picture of how a reaction takes place
since rarely a reaction gets completed in one
step.
• 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.
• These may be consecutive reactions
(e.g., oxidation of ethane to CO2 and
H2O passes through a series of
intermediate steps in which alcohol,
aldehyde and acid are formed),
reverse reactions and side reactions
(e.g., nitration of phenol yields o-
nitrophenol and p-nitrophenol).
 4.2.4 Molecularity of a Reaction

 Another property of a reaction called molecularity

helps in understanding its mechanism.
 Thenumber 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 reaction can be unimolecular when one
reacting species is involved, for example,
decomposition of ammonium nitrite.
NH4NO2 → N2 + 2H2O
• Bimolecular reactions involve simultaneous
collision between two species, for example,
dissociation of hydrogen iodide.
2HI → H2 + I2
• Trimolecular or termolecular reactions involve
simultaneous collision between three reacting
species, for example, 2NO + O2 → 2NO2
• The probability that more than three molecules
can collide and react simultaneously is very
small. Hence, reactions with the molecularity
three are very rare and slow to proceed.
• It is, therefore, evident that complex reactions
involving more than three molecules in the
stoichiometric equation must take place in
more than one step.
KClO3 + 6FeSO4 + 3H2SO4 → KCl + 3Fe2(SO4)3 +
3H2O
 KClO3 + 6FeSO4 + 3H2SO4 → KCl + 3Fe2(SO4)3
+ 3H2O
• This reaction which apparently seems to be of
tenth order is actually a second order reaction.
• This shows that this reaction takes place in
several steps.
• The overall rate of the reaction is controlled by
the slowest step in a reaction called the rate
determining step.
Consider the decomposition of hydrogen
peroxide which is catalysed by iodide ion in an
alkaline medium.
(1)H2O2 + I – → H2O + IO–
(2)H2O2 + IO– → H2O + I – + O2
• Both the steps are bimolecular elementary
reactions.
• Species IO- is called as an intermediate since it is
formed during the course of the reaction but not in
the overall balanced equation.
• The first step, being slow, is the rate determining
step.
• Thus, the rate of formation of intermediate will
determine the rate of this reaction.
Differentiate between order and molecularity
(i) Order of a reaction is an experimental quantity.
It can be zero and even a fraction but
molecularity cannot be zero or a non integer.
(ii) Order is applicable to elementary as well as
complex reactions whereas molecularity is
applicable only for elementary reactions. For
complex reaction molecularity has no meaning.
(iii) For complex reaction, order is given by the
slowest step and molecularity of the slowest step is
same as the order of the overall reaction.
3. For a reaction, A + B Product; the rate law is
given by, r = K[A]1/2[B]2. What is the order of
the reaction?

Ans. The order of the reaction= ½ + 2

=2.5
 4. The conversion of molecules X to Y follows
second order kinetics. If concentration of X is
increased to three times how will it affect the rate
ofThe
Ans: formation
reaction of
X→ Y?Y follows second order kinetics.
The rate equation for this reaction will be:
Rate = k[X]2 ..............(1)
Let [X] = a mol L -1 , then equation (1) can be written as:
Rate = k[X]2 = ka2
If the concentration of X is increased to three times, then
[X] = 3a mol L -1 Now, the rate equation will be:
Rate = k(3a)2 = 9(ka 2 ) Hence, the rate of
formation will increase by 9 times.
 Integrated Rate Equations
 Itis not always convenient to determine the
instantaneous rate.
 Inorder to avoid this difficulty, we can integrate
the differential rate equation to give a relation
between directly measured experimental data, i.e.,
concentrations at different times and rate
constant.
 The integrated rate equations are different for the
reactions of different reaction orders.
Zero Order Reactions
 Consider the reaction
• Zero order reactions are relatively uncommon
but they occur under special conditions.
• Some enzyme catalysed reactions and reactions
which occur on metal surfaces are a few
examples of zero order reactions.
• The decomposition of gaseous ammonia on a
hot platinum surface is a zero order reaction at
high pressure.
• In this reaction, platinum metal acts as a catalyst.
• At high pressure, the metal surface gets saturated
with gas molecules.
• So, a further change in reaction conditions is unable
to alter the amount of ammonia on the surface of
the catalyst making rate of the reaction
independent of its concentration.
• The thermal decomposition of HI on gold surface is
another example of zero order reaction
First Order Reactions
Let us consider a typical first order gas phase
reaction A(g) → B(g) + C(g)
Let pi be the initial pressure of A and pt the total
pressure at time ‘t’.
Integrated rate equation for such a reaction can be
derived as
Total pressure pt = pA + pB + pC (pressure units)
pA , pB and pC are the partial pressures of A,
B and C, respectively.
Pseudo order reaction
 Theorder of a reaction is sometimes altered by
conditions.
 Thereare many reactions which obey first order rate law
although they are higher order reactions.
 Consider the hydrolysis of ethyl acetate.
 Butwater is taken in large excess for hydrolysis,
therefore, concentration of water is not altered much
during the reaction. Thus, the rate of reaction is affected
by concentration of ethyl acetate only.
 Temperature Dependence of the Rate of a
Reaction
• Most of the chemical reactions are accelerated by
increase in temperature.
• For example, in decomposition of N2O5 , the time
taken for half of the original amount of material to
decompose is 12 min at 50oC, 5 h at 25oC and 10
days at 0oC.
• You also know that in a mixture of potassium
permanganate (KMnO4 ) and oxalic acid (H2C2O4),
potassium permanganate gets decolourised faster
at a higher temperature than that at a lower
temperature.
• It has been found that for a chemical
reaction with rise in temperature by 10°, the
rate constant is nearly doubled.
• The temperature dependence of the rate of
a chemical reaction can be accurately
explained by Arrhenius equation (4.18).
• It was first proposed by Dutch chemist, J.H.
van’t Hoff but Swedish chemist, Arrhenius
provided its physical justification and
interpretation.
where A is the Arrhenius factor or the frequency
factor. It is also called pre-exponential factor. It
is a constant specific to a particular reaction.
R is gas constant and Ea is activation energy
measured in joules/mole (J mol–1).
• It can be understood clearly using the
following simple reaction

• According to Arrhenius, this reaction can take place

only when a molecule of hydrogen and a molecule of
iodine collide to form an unstable intermediate (Fig.
4.6).
• It exists for a very short time and then breaks up to
form two molecules of hydrogen iodide.
• The energy required to form this intermediate,
called activated complex (C), is known as activation
energy(Ea ).
• Fig. 4.7 is obtained by plotting potential energy vs
reaction coordinate.
• Reaction coordinate represents the profile of energy
change when reactants change into products.
Some energy
is released
when the
complex
decomposes
to form
products. So,
the final
enthalpy of
the reaction
depends upon
the nature of
• All the molecules in the reacting species do not
have the same kinetic energy.
• Since it is difficult to predict the behaviour of any
one molecule with precision, Ludwig Boltzmann
and James Clark Maxwell used statistics to predict
the behaviour of large number of molecules.
• According to them, the distribution of kinetic
energy may be described by plotting the
fraction of molecules (NE /NT ) with a given
kinetic energy (E) vs kinetic energy (Fig. 4.8).
• Here, NE is the number of molecules with
energy E and NT is total number of molecules.
• The peak of the
curve corresponds
to the most
probable kinetic
energy, i.e., kinetic
energy of
maximum fraction
of molecules.
• There are
decreasing number
of molecules with
energies higher or
lower than this
value.
When the
temperature is
raised, the
maximum of the
curve moves to the
higher energy value
(Fig. 4.9) and the
curve broadens out,
i.e., spreads to the
right such that there
is a greater
proportion of
molecules with much
• The area under
the curve must
be constant
since total
probability must
be one at all
times.
• We can mark the
position of Ea on
Maxwell
Boltzmann
distribution
curve (Fig. 4.9).
Maxwell Boltzmann distribution
curve
As temperature increases,
1. Maximum of curve shifted to higher kinetic energy
value.
2. Greater proportion of molecules possess higher
kinetic energy.
3. Fraction of molecules having energy greater than
Ea get doubled hence rate of reaction doubled.
• Increasing the temperature of the substance
increases the fraction of molecules, which collide
with energies greater than Ea .
• It is clear from the diagram that in the curve at (t
+ 10), the area showing the fraction of molecules
having energy equal to or greater than activation
energy gets doubled leading to doubling the rate
of a reaction.
• In the Arrhenius equation (4.18) the factor e -Ea /RT
corresponds to the fraction of molecules that have
kinetic energy greater than Ea .
• Thus, it has been found from Arrhenius equation (4.18) that
increasing the temperature or decreasing the activation
energy will result in an increase in the rate of the reaction
and an exponential increase in the rate constant.
 Effect of Catalyst

• A catalyst is a substance which increases

the rate of a reaction without itself
undergoing any permanent chemical
change.
• For example, MnO2 catalyses the
following reaction so as to increase its
rate considerably
• The word catalyst should not be used when the
added substance reduces the rate of raction. The
substance is then called inhibitor.
• The action of the catalyst can be explained by
intermediate complex theory.
• According to this theory, a catalyst participates
in a chemical reaction by forming temporary
bonds with the reactants resulting in an
intermediate complex. This has a transitory
existence and decomposes to yield products and
the catalyst.
• It is believed that the catalyst provides an
alternate pathway or reaction mechanism by
reducing the activation energy between
reactants and products and hence lowering
the potential energy barrier.
• It is clear from Arrhenius equation (4.18) that
lower the value of activation energy faster
will be the rate of a reaction.
• A small amount of the catalyst can catalyse a
large amount of reactants.
• A catalyst does not alter Gibbs energy, ∆G of a
reaction.
• It catalyses the spontaneous reactions but does
not catalyse non-spontaneous reactions.
• It is also found that a catalyst does not change the
equilibrium constant of a reaction rather, it helps
in attaining the equilibrium faster, that is, it
catalyses the forward as well as the backward
reactions to the same extent so that the
equilibrium state remains same but is reached
 Collision Theory of Chemical Reactions
• Though Arrhenius equation is applicable under a
wide range of circumstances, collision theory,
which was developed by Max Trautz and William
Lewis in 1916 -18, provides a greater insight into
the energetic and mechanistic aspects of
reactions.
• It is based on kinetic theory of gases.
• According to this 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).
• Another factor which affects the rate of
chemical reactions is activation energy (as
we have already studied). For a
bimolecular elementary reaction
where ZAB represents the collision frequency of reactants,
A and B and e-Ea /RT represents the fraction of molecules
with energies equal to or greater than Ea . Comparing
(4.23) with Arrhenius equation, we can say that A is
related to collision frequency.
• Equation (4.23) predicts the value of rate constants
fairly accurately for the reactions that involve
atomic species or simple molecules but for complex
molecules significant deviations are observed.
• The reason could be that 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, so as to facilitate breaking
of bonds between reacting species and formation of
new bonds to form products are called as effective
collisions.
• For example, formation of methanol from
bromoethane depends upon the orientation of
reactant molecules as shown in Fig. 4.12.
• The proper orientation of reactant molecules
lead to bond formation whereas improper
orientation makes them simply bounce back
and no products are formed
To account for effective collisions, another factor P,
called the probability or steric factor is introduced. It
takes into account the fact that in a collision,
molecules must be properly oriented i.e.,
• Thus, in collision theory activation energy
and proper orientation of the molecules
together determine the criteria for an
effective collision and hence the rate of a
chemical reaction.
• Collision theory also has certain drawbacks
as it considers atoms/ molecules to be hard
spheres and ignores their structural aspect.