BAHRIA COLLEGE KARACHI

Chapter # 8: Introduction To Chemical Kinetics

Chemical Kinetics:
It is the branch of physical chemistry which deals with:
i. Rate of chemical reaction
ii. Factors affecting rate
iii. Mechanism through which reaction proceed
iv. Optimum conditions to get maximum yield

Rate Of Chemical Reaction:

Consider a chemical reaction:
A B

Rate of reaction = Increase in concentration of product or decrease in concentration of reactant

Time
It is defined as:
“The quantity of reactant consumed or quantity of product formed per unit
time.” Overall rate of reaction is called average rate of reaction.

Velocity Of Reaction:
“The rate of chemical reaction at particular given moment that is at specific
time is called velocity of reaction or instantaneous rate of reaction.”
If we consider a very small interval of time (dt) in which change in concentration
(dx) is taken to be nearly constant then velocity of reaction is given by the
expression: dx
dt
Unit Of Rate Of Reaction:
The concentration is usually expressed in moles/dm3 and time in seconds (s).
Rate of reaction = Change in concentration
Time taken for change
= moles/dm3 = moles = moles.dm3.s-1
s dm3.s
= M.s-1
Rate Constant Or Velocity Constant:
Consider a hypothetical reaction:
A + B Product
According to law of mass action:
“Rate or velocity of the reaction is directly proportional to active mass or
molar concentration of reactant.”
Velocity of reaction α [A]. [B]
dx α [A] . [B]
dt
dx = K [A] . [B] …………. (i)
dt
The expression (i) is called rate expression. Where K is rate constant or velocity
constant, and it has fixed value for a chemical reaction at particular temperature.

Specific Rate Constant:

If molar concentration of all reactants is unity that is 1 mole/dm3, under such
conditions rate constant becomes equal to rate of chemical reaction so it is known
as specific rate constant.
dx = K [A] . [B]
dt
dx = K [1] . [1]
dt
dx = K
dt
Characteristics Of Rate Constant (K):
Following are the characteristics of K:
1. It has fixed value for a chemical reaction at a particular temperature.
2. Its value varies with temperature.
 3. The value of K is independent of concentration of reactants.

Significance Of Sign:
A B

- dA= Represents the rate of reaction in terms of decrease in concentration of reactant A.

dt
+dA= Represents the rate of reaction in terms of increase in concentration of product B.
dt

Types Of Reaction Based On Reaction Velocity:

On the basis of their rates, chemical reactions are classified as:
i. Fast reaction
ii. Slow reaction
iii. Moderate reaction

Fast Reaction:
“The reactions which proceed very fast are called instantaneous or fast
reactions.”
They are so fast that they are completed in very small time of the order of 10-6 s.
All ionic reactions are of this type. The rate of such reactions can not be
determined.
Examples:
NaCl + AgNO3 AgCl + NaNO3
NaOH + HCl NaCl + H2O
Slow Reaction:
“The reactions which proceed at extremely slow speed and take very long
time for completion are called slow reactions.”
The rate of such reactions can not be determined.
Examples:
i. Rusting of iron.
ii. Radioactive decay of elements.
iii. Formation of diamond from carbon in earth crust.
iv. Decomposition of Hydrogen fluorine.
Moderate Reactions:
“The reactions which proceed in measurable time interval are called
moderate reactions.”
They have limited speed and are completed in few minutes or in few hours. The
rate of such reactions can be determined. Generally reactions of organic and
covalent compounds are of such type.
Examples:
CaCO3 + HCl CaCl2 + CO2 + H2O
PCl5 PCl3 + Cl2
H2 + I2 2HI

Activation Energy:
“Minimum amount of energy, in addition to the average kinetic energy
which the particles must have for effective collision is called activation energy.”
OR
“The excess energy that the reactant molecule having average internal
energy less than the threshold energy, must acquire in order to react and change
into products is called activation energy.”
OR
“The energy required by the reactant molecules in order to form activated
complex is called activation energy.”

Explanation:
For a chemical reaction to occur the particles of reactant must collide with
each other. These collisions are of two types:
i. Effective collision
ii. Ineffective collision

Effective Collisions:
“Collisions which led to the formation of products are called effective
collisions.”
Ineffective Collisions:
“Collisions which do not lead to the formation of products are called
ineffective collisions.”
For effective collisions, molecules must possess sufficient amount of energy
(threshold energy) and must have proper orientation.
If all collisions among the particles are effective then reaction will complete
immediately.
If all the collisions are not effective the reaction will be slow and it will take long
time to complete.
Threshold Energy:
“Minimum amount of energy of molecules required for effective collisions
is called threshold energy.”
Let us explain it with the help of example. Consider the reaction between A2 and
B2 to form the product AB.
A2 + B2 2AB
If A2 and B2 molecules have energy equal to or greater than activation energy, then
upon collisions the bonds will break and new bonds will form and the reaction will
complete via activated complex.
A A A………A A A
+
B B B………B B B
Reactants Activated Complex Products

Activated Complex:
“It is an unstable combination of all atoms involved in chemical reactions
for which maximum energy is required. It is short lived specie and decomposes
into product immediately. It has transient existence that is why it is also called
transition state.”
When the molecules are just near to collide, they slow down in order to
decrease their kinetic energy and to increase their potential energy for the effective
collision (Threshold energy).
The excess energy that the reactant molecules having average energy less
than the threshold energy must acquire in order to react and change into product is
called activation energy.
Activation energy = Threshold energy – Average internal energy of molecules
The reactant particles collide and form the activated complex which have
high energy. Ea is activation energy and appears as a potential energy hill between
reactants and the products. Only colliding molecules with the proper activation
energy will be able to climb up the hill and give products. If the combined initial
kinetic energy of reactants is less than Ea, they will be unable to reach to the top of
the hill and fall back chemically unchanged.
Determination Of Rate Of Reaction:
Two methods are employed for the determination of rate of chemical
reaction. These are:
i. Physical method
ii. Chemical method
i. Physical Method:
In these methods, the reaction is followed by measuring the change in
some physical property of reactant and product. Following methods
are employed
1. Spectrometry
2. Electrical conductivity
3. Dilatometric method
4. Refractrometric method
5. Optical rotation method
6. Calorimetric method
7. pH method
1. Spectrometry:
This method is applicable when the reactants or products are able to
absorb ultraviolet radiations. The rate of reaction can be measured by
measuring the amount of UV radiations absorbed.
2. Electrical Conductivity:
This method is applicable when the reaction mixture involves ions.
The conductivity of such solution depends upon the rate of change of
concentration of the reacting ions or the ions formed during reaction.
The conductivity will be proportional to the rate of change in
concentration of such ions.
3. Dilatometric Method:
This method is useful for those reactions which involves small
changes in solution. The volume changes are directly proportional to
extent of reaction.
4. Refractrometric Method:
This method is applicable to reactions in solution where there are
changes in refractive indices of the substances taking part in chemical
reactions.
5. Optical Rotation Method:
In this method, the angle through which plane polarized light is
rotated by the reacting mixture is measured by polarimeter. The extent
of rotation determines the concentration of optically active substance.
If any of the specie in the reaction mixture is optically active, then this
method can be followed to find out the rate of reaction.
6. Colorimetric Method:
In physical and analytical chemistry, colorimetry is a technique used
to determine the concentration of colored compound in solution.
7. pH Method:
This method is used when there is a change in pH throughout the
reaction.
i. Chemical Method:
When physical methods are not available or suitable then a proper
chemical method is used.
In a chemical method generally samples are drawn from the reacting
vessel at regular intervals of time. Reaction is stopped at that
particular moment by suddenly chilling the sample adding it to a
suitable chemical. The amount of a reactant or product present at that
time is generally found by titrating the sample against a proper
reagent.
Example:
An example is the hydrolysis of methyl acetate (CH3COOCH3)
in acidic medium.
CH3COOCH3 + H2O CH3COOH + CH3OH
Reaction is followed by measuring the amount of acetic acid
(CH3COOH) formed at regular interval by titrating the chilled
samples against standard alkali (NaOH) with the passage of time more
and more acetic acid is formed till reaction goes to completion.
 The results are plotted as a graph and rate curve is obtained.
The slope of rate curve at different times gives the rate of reaction
(dx/dt) at that moment.
Why some reactions are fast and some are slow?
The speed of the reaction depends upon the activation energy.
Fast reactions have low activation energy and slow reaction have very high value
of activation energy.
Fast reactions can be slow down and slow reactions can be speed up by controlling
activation energy.
Factors Affecting Rate Of Chemical Reaction:
Following are the factors on which rate of reaction depends:
i. Nature of reactants
ii. Surface Area
iii. Light (Radiation)
iv. Concentration of reactants
v. Temperature
vi. Catalyst
i. Nature of Reactants:
Rate of reaction depends upon nature of reactants. Ionic substances
react much more rapidly as compared to covalent substances. Redox
reactions involve transfer of electrons and are slower than ionic
reactions.
The natures of reactants have their effect because activation energy
for effective collision is different for different reacting substances.
Consider the following reactions in which the collision probabilities
are same but even then, their rates are not equal.
2NO + O2 2NO2 (fast)
2CO + O2 2CO2 (slow)
Reaction between NO and O2 is fast while reaction between CO and
O2 is slow. This is because activation energy of CO is higher than that
of NO.
ii. Surface Area:
In case of heterogeneous reaction where reactants are in different
physical states, surface area of the solid substance plays an important
role with respect to the rate of reaction. The rate of chemical reaction
is directly proportional to the surface area of solid substances.
Example:
A piece of marble reacts very slowly with dilute HCl but powdered
calcium carbonate (CaCO3) reacts very fast with dilute HCl. It is
because powdered CaCO3 offers greater surface area for HCl to react
that is why rate of reaction is fast.
CaCO3 + 2HCl CaCl2 + H2O + CO2
Crystalline forms have specific geometry so reaction with it is slow as
compared to amorphous solid because atoms in it are spread and
consumed.
iii. Light (Radiations):
Some chemical reactions proceed under the influence of light such
chemical reactions are called photochemical reactions.
In photochemical reaction, concentration of reactant does not depend
on its rate of reaction and such reactions are of zero order. This factor
affect only if the reactants are sensitive to light when the reactants are
irradiated so as the radiation or light consist of photons so photons
strike the reactant molecules and provides the necessary activation
energy to the reactant molecules to react.
Example:
Reaction between H2 and Cl2:
H2 + Cl2 bright sunlight 2HCl
Reaction between CH4 and Cl2:
CH4 + Cl2 bright sunlight CH3Cl + HCl
iv. Concentration Of Reactant:
Concentration:
“Number of moles or molecules of a substance per unit volume is
called concentration.”
 Explanation:
Rate of reaction varies with concentration of reactants. According
to the law of mass action:
“Rate of chemical reaction is directly proportional to the
concentration of reactants.”
The greater the concentration of reactants the greater will be the rate of
reaction. This is because with the increase in concentration, the number
of molecules of reactants also increases. There is now more crowding of
molecules so frequency of collisions between them increases resulting in
the increase in rate of formation of product. Let’s suppose an equation:
2A + B Product
dx/dt α [A]2[B]
dx/dt = K[A]2[B]
If the concentration of reactant B is doubled, then rate will also doubled.
Concentration of reactant B = [x] [2x] = 2x
Rate (dx/dt) = Its value gets twice
If the concentration of reactant A is doubled, then rate will increase four
times.
Concentration of reactant A = [x] = [2x]
[A]2 = [2x]2 = 4x2
Rate (dx/dt) = Its value will increase four times.

v. Temperature:
The rate of reaction are greatly influenced by the temperature at which
reaction is carried out
As a general rate of thumb, “the rate of reaction doubles for every
10° rise in temperature.” The reasons are:
i. As temperature increases, the velocity of molecules also
increases. This results in increase in frequency of collisions.
ii. The rise in temperature raises the kinetic energy of each
molecule. It has been found by rising the temperature by 10°,
refraction of molecules possessing threshold energy or
activation energy becomes double as a result number of
effective collision also doubled. Hence the rate is doubled.
i. Catalyst:
“The substance which alters the rate of chemical reaction without
itself being consumed during a chemical reaction is known as
catalyst.”
Types of Catalyst:
1. Positive Catalyst:
It increases the rate of chemical reaction by decreasing the
activation energy. It provides an alternative path to the
reactions. The activation energy of this alternative route is
lower as a result more reactant molecules have the energy
required for successive collision. The total number of effective
collisions per unit time increases thus the rate of chemical
reaction increases.
Example:
MnO
2H2O2 2 2H2O + O2
 2. Negative Catalyst:
It decreases the rate of chemical reaction. They are also called
inhibitors. They do not lower the activation energy but they
combine with reactant molecules and decrease the number of
collisions between them. That’s why rate of reaction becomes
slow.
Example:
Glycerin
2H2O2 2H2O + O2

3. Biocatalyst:
Enzymes are complex protein molecules which catalyzed the
chemical reaction in living system such as digestion, respiration
and muscle contraction. These enzymes are known as
biocatalyst.
Example:
Glucose is converted into ethanol by enzyme zymase
present in yeast.
Zymase (in yeast)
C6H12O6 2C2H5OH + 2CO2

4. Autocatalsyt:
Sometimes one of the products of the reaction act as a catalyst.
This phenomenon is known as autocatalysis. Initial rate of such
reaction is slow but later on increases as the product concerned
is formed.
Example:
CH3COOCH3 + H2O CH3COOH + CH3OH
Autocatalyst
Here the reaction is catalyzed by acetic acid which is named as
autocatalyst.
Catalysis:
“The process which takes place in presence of catalyst is called
catalysis.”
Types of Catalysis:
There are two types of catalysis:
 i. Homogeneous catalysis
ii. Heterogeneous catalysis

Promoters Or Activators:
“Such substances which promote the activity of catalyst are called
promoters or activators.”
Example:
Hydrogenation of vegetable oil is accelerated by Nickel (Ni) catalyst
activity of nickel can be increased using copper.

Order Of Reaction:
Consider a reaction:
aA + bB cC + dD
Rate of reaction can be given as:
Rate [A]m [B]n
¿
Rate = K [A]m [B]n
The exponents of the concentration term that is m and n are known as order of
reaction with respect to A and B.
“The sum of all exponents of the concentration involved in the rate equation
of the reaction is known as overall rate of reaction.”
Order of reaction = m + n

Determination of Order of Reaction:

Order of reaction with respect to reactants that is m and n may or may not be
equal to corresponding coefficients a and b of the reactants given in a balanced
chemical equation. This is why numerical values of exponents m and n can not be
deduced from the balanced chemical equation. These are always determined
experimentally. These are found to be 0, 1, 2, 3, or fraction. The value of overall
order of reaction can not be greater than 3 for a reaction.
With the help of given formula, order of reaction can be calculated:
Formula:
(Conc. Of A in exp 2, 3_m x (Conc. Of B in exp 2, 3)n = Rate of reaction of exp 2,3
(Conc. Of A in exp 1)m x (Conc. Of B in exp 1)n Rate of reaction of exp 1
Molecularity Of Chemical Reaction:
The number of reactant molecules taking part in rate determination of
chemical reaction is called molecularity of a reaction.
It is calculated by balanced chemical equation.
Rate Law:
The rate expression on the basis of experimental data is called rate law.

Differences Between Molecularity and Order of Reaction:

Molecularity Order Of Reaction

It is a theoretical quantity. It is an experimental quantity.
It is the number of species undergoing It is the sum of the power to which the
simultaneous collision in the reaction. concentration terms are raised in the
rate law equation.
It has only whole number value. It may have fractional value.
It can not be zero. It can be zero.