Reaction Kinetics

Rate of Reaction:
The rate of reaction is defined as the change in
concentration of reactant or product per unit time.

units: mol dm–3 s–1 (or mol dm–3 min–1 or mol dm–3 h–1)
The rate of reaction is a positive quantity that expresses
• how the concentration of a reactant decreases with time,
or
• how the concentration of a product increases with time.

Note:
Rate of reaction is always a positive value.
Since the [reactant] is decreasing, d[reactant] is a negative
value. The minus sign ensures
that rate of reaction is a positive value.
(A) Instantaneous Rate
It is the rate at a particular time i.e. the rate at a
particular instant during the reaction.

(B) Initial Rate

• It is the instantaneous rate at time, t = 0. It is the
instantaneous rate at the start of the reaction, when an
infinitely small amount of the reactant has been used up.
Rate Equation
Consider a reaction represented by the following equation,
aA + bB → cC + dD

Experimentally, it can be shown that the rate of the

reaction can be related to the concentrations of individual
reactants by a rate equation (or rate law),
rate = k[A]m[B]n
where, [A] = concentration of reactant A
in mol dm−3
[B] = concentration of reactant B
in mol dm−3
k = rate constant
m = order of reaction with respect
to [A]
n = order of reaction with respect
to [B]
m + n = overall order of reaction

Term Definition and

remarks
rate Definition
equation The rate equation is a mathematical
(or rate law) expression that is experimentally
determined to show the exact dependence of
the rate of reaction on the
concentrations of all the reactants.
The rate equation
• can only be obtained experimentally;
 • cannot be deduced from the stoichiometric
equation (unless the reaction
is an elementary reaction);
• may not include all the reactants (but may
include catalyst) in the
chemical equation.

rate Definition
constant, k The rate constant, k, of a reaction is the
constant of proportionality in the
experimentally determined rate equation.

• k is constant for a given reaction at a

particular temperature.
• The larger the rate constant, the faster the
reaction.
• Its units depend on the overall order of the
reaction.
overall zero order reaction : mol dm–3 s–1
overall first order reaction : s-1
overall second order reaction : mol-1dm3s-1
In general, units of k is (mol dm−3)1−n
time−1, where n is the overall order of the
reaction.
rate Rate constant, k can be represented in the
constant, k Arrhenius equation

Where, A = Arrhenius constant or pre-

exponential factor
Ea = activation energy
R = molar gas constant
T = temperature in Kelvin
Increasing the temperature or decreasing the
Ea (through the use of
catalyst) will increase the value of k and hence
increases the rate of reaction.
order of Definition
reaction The order of reaction with respect to a given
 reactant is the power to
which the concentration of that reactant is
raised to in the experimentally
determined rate equation.

Example: rate = k[B]2

order of reaction with respect to [B] = 2

Example: rate = k, order of reaction with

respect to [B] = 0
• It shows the exact dependence of rate on the
concentration of a given
reactant.
• It must be found experimentally.
It can be a whole number or a fraction, positive
or negative (only 0, 1 and
2 are required in the syllabus).
overall order Definition
of a reaction The overall order of a reaction is the sum of
the powers of the
concentration terms in the experimentally
determined rate equation.

Examples: rate = k [P] [Q]2

Overall order of reaction = 1 + 2 = 3

rate = k [P] [Q]2[R]

Overall order of reaction = 1 + 2 + 1 = 4

Zero Order Reaction

A zero-order reaction is one in which the reaction rate is
independent of the concentration of the reactant, i.e. the
rate is unaffected by changes in the concentration of the
reactant, i.e. rate.

Consider a zero-order reaction,

 A → products

The rate equation is

rate = k[A]0 = k
(where k is the rate
constant)

In this case, the reaction proceeds at a constant rate, k, at

a constant temperature.
For example, when [A] is doubled, the rate of the reaction
remains the same.
The units of rate constant, k = mol dm–3 s–1 (or mol dm–
3 min–1 or mol dm–3 h–1)
The graphs associated with a zero-order reaction are shown
below.

First Order Reaction

A first-order reaction is one in which the reaction rate is
directly proportional to the concentration of a single
reactant.

Consider a first-order reaction,

A → products

The rate equation is

rate = k[A]
(where k is the rate
constant)
For example, when [A] is doubled, the rate of the reaction
is doubled.
The units of rate constant, k = s–1 (or min–1 or h–1)
First-order reaction has a constant half-life, t ½. (Half-life is
the time taken for the concentration of a reactant to
decrease to half its initial value).
The graphs associated with a first-order reaction are shown
below.
Second Order Reaction
A second-order reaction is one in which the reaction rate is
proportional to the product of the concentrations of two
reactants (e.g. rate  [A][B], where A and B are reactants)
or to the concentration of a single reactant raised to the
power of two.

Consider a second-order reaction,

A → products
The rate equation is
rate = k[A]2
(where k is the rate
constant)
For example,
When [A] is doubled, the rate of the reaction increases by,
2 = 4 times.
When [A] is tripled, the rate of the reaction increases by, 3
= 9 times.
The units of rate constant, k = mol–1 dm3 s–1 (or mol–1
dm3 min–1 or mol–1 dm3 h–1)
For a second-order reaction, the half-life of the reaction is
not constant. In fact, the half-life gets larger as the reaction
proceeds.
The graphs associated with a second-order reaction are
shown below.

Half-Life
The half-life, t ½ , of a reaction is the time taken for the
concentration of a reactant to decrease to half its initial
value.
For a first-order reaction, the half-life is constant (at
constant temperature).
• t ½ is independent of the initial concentration of the
reactant.
• For all other orders of reaction, the half-life is not
constant. It changes throughout the reaction.
• Hence, if the half-life is NOT a constant, you cannot
conclude that the order of a reaction is 2nd order!
To determine whether a reaction is a first order reaction,
plot a graph of [reactant] against time and determine the
successive half-life from the graph.
If it is a first order reaction, its successive half-life is a
constant.
* Half-life can only be used for first order reaction.
Initial Rate Method
The order of a reaction with respect to a reactant can be
found by comparing the initial rates of the reaction at
different known initial concentrations.
There are two approaches: inspection and mathematical
methods.
Graphical Method
The order of reaction with respect to each reactant can be
determined by studying the
• concentration against time graphs or
• rate against concentration graph.
Based on the graphs obtained, the order of reaction with
respect to a particular reactant can be deduced.
For the reaction: aA → products
Experimental studies of kinetics
Two types of kinetics experiments can be performed to
monitor the rate of a reaction:
• continuous method
• non-continuous method (or initial rate method)

Continuous Rate Method

The continuous rate method entails performing one set of
experiment and monitoring
concentration changes over a period of time.
The rate of a reaction can be studied by analysing the
reaction mixture at suitable regular time intervals as
it is possible to determine how the concentration of a
reactant and/or product changes at these time intervals.
Any changes in a physical property (for example, pressure
for gases, colour intensity etc.) proportional to
concentration of reactant or product can also be measured
to determine the reaction rate.
Non-continuous Rate Method (Initial Rate Method)
The non-continuous rate method entails performing
separate sets of the same experiment by using different
starting concentrations of the reactants.
In studying kinetics using the non-continuous rate method,
the determination of the initial rate involves measuring the
change in concentration of one of the reactants or
products, which occurs in the first small time interval after
the reagents are mixed.
In practice, the reaction rate of reacting a fixed
concentration of a reactant or forming a fixed
concentration of product is usually measured using the
“clock” method.
Rate of reaction is also inversely proportional to the time
taken for a fixed concentration of product to be formed or
fixed concentration of reactant to be used.

Certain reactions are accompanied by prominent visual

changes such as the formation of a precipitate or an
obvious change in colour.
The rate of reaction may be studied by measuring the time
taken for a prescribed visual change to occur. Reactions
that are studied this way are called ‘clock’ reactions.
Why is there a need to vary the volume of water in each
experiment?
• The volume of water is varied in each experiment to keep
the total volume of the reaction mixture constant for the
different experiments.
In this way, the initial concentration of each reactant in the
reaction mixture is directly
proportional to its volume used.

Since the same stock Na2S2O3 solution is used for all the
experiment, the concentration of
Na2S2O3 solution is constant. The total volume of the
reaction mixture is also kept constant for all the
experiments by adding appropriate volume of water to
each reaction mixture.
• Hence, initial [Na2S2O3]  volume of Na2S2O3 added.
Similarly, initial volume of H+ added.
The Collision Theory
The collision theory is important in explaining the rate of
reaction in terms of particle collisions and energy profile of
a chemical reaction.
The theory states that chemical reactions occur only if
• reactant particles undergo collisions;
• collisions take place with the minimum amount of energy
known as activation energy, Ea; and
• collisions have the correct geometry/orientation (i.e.
reactant particles are correctly oriented with respect to
each other)
The rate of reaction is proportional to the frequency of
effective collisions leading to a chemical reaction.
Activation Energy
The activation energy, Ea, of a reaction is the minimum
amount of energy that the reactant particles must possess
before they can collide to result in a reaction.
Activation energy is used to break existing bonds within the
reactant particles or to overcome repulsive forces between
reactant particles in close proximity before forming new
bonds in the products.
The lower the activation energy, the larger the value of the
rate constant, k, the faster is the rate of the reaction.
The energy profile diagrams below show the energy
changes for an exothermic and an endothermic reaction. In
both diagrams, Ea is represented as the energy barrier that
needs to be overcome. The source of activation energy
comes from the kinetic energy of the particles.
Maxwell-Boltzmann Distribution Curve
The Maxwell-Boltzmann Distribution Curve shows how the
kinetic energy of the particles of a sample of gas varies at
a given temperature.

The area under the curve represents the number of

gaseous particles within a certain energy range. The total
area under the curve, represents the total number of
gaseous particles present.
Only the particles represented by the shaded region have
the minimum amount of energy for the reaction to occur,
as these particles have energy greater than or equal to the
activation energy. The rest of the particles will not
participate in the reaction.
Factors affecting the rate
Physical State of the Reactants
Reactant particles must mix in order to collide and react.
Thus, the frequency of collisions between reactant particles
also depends on the physical states of the reactants.
(1) CaCO3 (marble chips) + 2HCl(aq) → CaCl2(aq) +
H2O(l) + CO2(g) slower
(2) CaCO3 (powder) + 2HCl(aq) → CaCl2(aq) + H2O(l) +
CO2(g) faster

The rate of a reaction involving a solid is affected by the

available surface area of the solid. Reactions involving a
solid take place faster when the solid is in a finely divided
state.
• The more finely divided a solid reactant, the greater its
surface area per unit volume.
• The number of sites of collisions increase and the
frequency of effective collisions increases.
• Frequency of effective collisions taking place in the
reaction increases, thus, the rate of reaction increases.
Concentration of the Reactants
In general, the rate of a reaction increases as the
concentration of a reactant is increased, provided that
the order of reaction with respect to that reactant is not
zero.
The rate of reaction increases when the concentration
of reactant is increased.
• When concentration increases, the number of reactant
particles per unit volume increases, frequency of
collisions increases. Hence, the frequency of effective
collisions also increases.
• The increased frequency of effective collisions leads to
an increase in reaction rate.

For a gaseous reaction mixture, the concentration of

the gaseous reactants can be increased by increasing
their partial pressures.
The rate of reaction increases when the pressure
exerted on the gaseous reactants increases.
• When pressure increases, the number of gaseous
reactant particles per unit volume increases.
• Frequency of collision increases. Hence frequency of
effective collisions between reactant particles also
increases.
• The increased frequency of effective collisions leads to an
increase in reaction rate.
Note: If the pressure is increased due to a decrease in
volume, it is as though there is an increase in
“concentration” as there are more moles of gas per
volume. Hence, rate of reaction will increase.
Temperature
In general, increasing the temperature increases the rate of
a reaction significantly.
[For many reactions, the rate is approximately doubled for
every 10 K rise in temperature.]
Maxwell-Boltzmann distribution of kinetic energies at two
different temperatures

When the temperature is increased from T1 to T2,

• The average kinetic energy of the particles increases.
• There is an increase in the fraction of particles with
energy equal to or greater than the activation energy,
Ea (this is as shown by the larger shaded area at a higher
temperature in the above diagram).
• This result in an increase in the frequency of
effective collisions, hence in a larger rate constant k and
an increase in reaction rate.

Note: Essential features of the Maxwell Boltzmann curve

when temperature increases:
1. As temperature increases from T1 to T2,
• the maximum of the curve is displaced to the right,
• there is a greater spread of kinetic energies i.e. the
distribution curve broadens, and
• the area under the curve at T1 is the same as that at T2
since the total number of particles in the system remains
the same.
2. Shaded area is larger when curve is “flattened” at higher
temperature.
• fraction of reactant particles with energy at least Ea,
activation energy increases.
Catalyst
Maxwell-Boltzmann distribution of kinetic energies for
catalysed and uncatalyzed reaction

• Catalyst provides an alternative reaction pathway which

lowers the activation energy of reaction.
• Thus, the fraction of particles with energy equal to or
greater than the activation energy of the catalysed
reaction Ea(cat) increases (this is as shown by the
larger shaded area for the catalysed reaction in the
above diagram).
• This results in an increase in frequency of effective
collisions, a larger rate constant, k, and hence an increase
in the reaction rate.

Catalysis
Catalysis is the process of increasing the rate of a reaction
by a catalyst.
There are a few types of catalysis:
(A) homogeneous catalysis – catalyst and the reactants are
in the same phase;
(B) heterogeneous catalysis – catalyst and the reactants
are in different phases;
(C) auto-catalysis – the product of a chemical reaction acts
as its own catalyst; and
(D) enzymes – proteins which catalyse the chemical
reaction in living systems.

A catalyst increases the rate of a reaction by providing an

alternative reaction pathway with a lower activation
energy.
The features of a catalyst are
• A catalyst is usually unchanged in quantity but may
change physically at the end of reaction.
For example, pellets may become powder.
• A small amount of catalyst is usually sufficient to bring
about a rapid increase in reaction rate. Increasing the
amount of catalyst indefinitely does not mean that the rate
will keep increasing indefinitely.
• Each catalyst is specific in character. One may catalyse a
class of reactions but not for all other reactions.
• A catalyst generally increases the rate constant, k, for a
reaction.
• A catalyst alters the reaction mechanism and hence the
order and rate equation
Note:
Although catalysts are not present in the stoichiometric
equation, they take part in the reaction. If they take
part in the rate determining step, they would appear
in the rate equation.
Homogeneous Catalysis
In homogeneous catalysis, the catalyst and the
reactants are in the same phase, either liquid or
gaseous.
Consider a reaction, A + B → AB
hReaction Mechanism
Some terms and definitions
elementar An elementary step is the simplest step
y step which cannot be further broken down into
simpler steps.
molecular The molecularity of an elementary step in a
ity of an reaction mechanism is the number of
elementar reactant particles (e.g. atoms, molecules or
y step ions) taking part in that step.
• A unimolecular step involves one reactant
particle in that step.
(for example, A → 2B)
• A bimolecular step involves two reactant
particles in that step.
(for example, A + B → AB)
• A termolecular step involves three reactant
particles in that step.
(for example, A + 2B → AB2)
intermedi An intermediate is a species that is formed
ate in one step of a reaction
mechanism and consumed in a subsequent
step.
reaction A collection of elementary steps which gives
mechanis a complete description of how reactants are
m converted to product.
rate- The slowest step in the reaction, usually
determini indicated by the word “slow”
ng
step
(r.d.s)

• Termolecular elementary steps are extremely rare,

although some do occur, as the probability of three
particles colliding simultaneously with the required
activation energy and the correct orientation is very small.
• An intermediate is not represented in the stoichiometric
equation, does not appear in the rate equation for the
overall reaction and may be isolated for a very short
duration during the reaction.

Single-Step Reactions (Elementary Reactions)

A reaction that takes place in a single step (i.e. a single-
step or one-step reaction) is termed an elementary
reaction.
For a single–step reaction,
• the reaction mechanism consists of one elementary step,
• the reaction mechanism is identical to the stoichiometric
equation for the reaction,
• the rate equation can be deduced directly from the
stoichiometric equation.

Multiple-Steps Reactions (Non-Elementary Reactions)

A multi-step reaction takes place by two or more steps. For
such a reaction, the different steps are likely to proceed at
different rates.
For a multi-steps reaction,
• the reaction mechanism consists of two or more
elementary steps,
• the rate equation cannot be deduced directly from the
stoichiometric equation, but is derived from the rate
determining step,
The rate-determining step is the slowest step in the
reaction mechanism of a multi-step reaction and it
determines the overall reaction rate. It is the step with the
highest activation energy.
In a proposed reaction mechanism for a multi-step reaction,
the rate-determining step is stated as the slow step while
all other steps are referred to as fast steps.

Deduction of Rate Equation from Reaction Mechanism

Rate equation can be deduced from the reaction
mechanism by taking the following steps.
• The rate equation for the overall reaction is deduced from
the rate-determining step (slow step).
• The reactants that participate in the slow step are those
reactants that appear in the rate
equation.
• The order of reaction with respect to a reactant X is the
number of X particles that
participates in the slow step.
• For elementary reaction, the overall reaction is the rate
determining step since it is a one
step process.
For non-elementary reactions, there are 2 main situations
to be considered when deducing the rate equation.
(A) Reaction
mechanism with Step 1 as the slow step
Proposal of Reaction Mechanism from Rate Equation
A proposed reaction mechanism must meet the
following criteria:
• It must agree with the balanced stoichiometric
equation.
The elementary steps in the proposed reaction
mechanism must sum to give the overall balanced
equation.
• It must be consistent with the observed kinetics i.e.
it must agree with the rate equation obtained.
Rate equation is derived from rate-determining step.
reactants in the rate equation = reactants of the rate-
determining step order of reaction = coefficient of the
reactant in the rate-determining step
• It must include intermediates that are detected
during the reaction but intermediates do not appear in
rate equation.
Energy Profile Diagram
Energy profile diagram depicts the changing energy of
the chemical system as it progresses from reactants
through transition state(s) to products.
When drawing an energy profile diagram,
• The products have lower energy level than the
reactants in an exothermic reaction. Likewise, the
products have higher energy level than the reactants
in an endothermic reaction.
• The number of steps in the reaction corresponds to
the number of humps in the diagram.
• The slow step (rate determining step) has higher
activation energy, Ea, than the fast step(s).
• The intermediate, which has an energy minimum, is
positioned in between the humps.
For a one-step reaction,

reactants → products

• there is only one transition state, and

• no intermediate.
For a two-step reaction,

reactants ⎯→ intermediate

intermediate ⎯→ products
(slow)

(fast)

• two transition states (one for each step),

• one intermediate, and
• 1st Ea > 2nd Ea since the first step is the slow
step/rate-determining step.