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Grade 11 Note Unit 4

Chemical kinetics studies the rates of chemical reactions and their mechanisms, focusing on how reactant concentrations change over time. The rate of a reaction can be determined qualitatively and quantitatively, influenced by factors such as the nature of reactants, surface area, concentration, temperature, and the presence of catalysts. For a reaction to occur, reactants must collide with proper orientation and sufficient energy, known as activation energy.

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35 views

Grade 11 Note Unit 4

Chemical kinetics studies the rates of chemical reactions and their mechanisms, focusing on how reactant concentrations change over time. The rate of a reaction can be determined qualitatively and quantitatively, influenced by factors such as the nature of reactants, surface area, concentration, temperature, and the presence of catalysts. For a reaction to occur, reactants must collide with proper orientation and sufficient energy, known as activation energy.

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Unit 4

Chemical Kinetics

Chemical kinetics is the branch of chemistry, which deals with the study of reaction
rates and their mechanisms, The word kinetics is derived from the Greek word
‘kinesis’ meaning movement or change.

The Rate of a Reaction


It is 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 (Rate of
disappearance of

Reactants) or
(ii) the rate of increase in concentration of any one of the products (Rate of
appearance of Products) .
It measures the how fast the concentration of a reactant or product
changes with time.
For example, for a general reaction:
Reactants → Products

During the course of a reaction, reactant molecules are consumed while


product molecules are formed. As a result, we can follow the progress of a
reaction by monitoring either the decrease in concentration of the reactants
or the increase in concentration of the products.
Consider the progress of a simple reaction in which A molecules are
converted to B molecules:
A→B
The decrease in the number of A molecules and the increase in the number
of B molecules with time
In general, it is more convenient to express the rate in terms of change in
concentration with time.
Note that  denotes the difference between the final and initial state. Thus, for the
preceding reaction we can express the rate as: in which, ∆[A] and ∆[B] are
the changes in concentration (mol L-1) over a period ∆t
Because the concentration of A decreases during the time interval, ∆[A] is a
negative quantity. The rate of a reaction is a positive quantity, so a minus
sign is needed in the rate expression to make the rate positive. The rate of
product formation does not require a minus sign because ∆[B] is a positive
quantity (the concentration of B increases with time).
Where r is the rate of reaction, A and B are reactants, C and D are products, and a,
b, c, d are stoichiometric coefficients.
Determination of Rate of Reaction

The rate of reaction can be determined both quantitatively and qualitatively. Qualitatively, an
idea about the rate of reaction can be obtained by observing either the speed of disappearance of
the reactants or the speed of appearance (formation) of the products.
Average rate depends upon the change in concentration of reactants or products
and the time taken for that change to occur. Instantaneous rate of reaction is defined as
the rate of a reaction for a given instant of time and it is calculated by drawing a tangent to the
graph at that instant of time.
Conditions needed for a chemical reaction

01. Collisions between reactants


The fundamental concept of the collision theory of rate of reaction is that, in order for a
reaction to occur between reacting species (atoms, ions or molecules), they must first collide
(come in contact). The rate of reaction is directly proportional to the number of collisions per
second (the frequency of collision).
According to collision theory, the more collisions there are, the faster the rate of reaction
would be. However, not all collisions between reacting species result in a reaction. This
is because collisions between reactants can be either effective or ineffective.
Effective collisions are collisions that result in a reaction to form the desired products.
Ineffective collisions are collisions that do not result in a reaction to form the desired products.

2. Proper Orientation

In order for a collision between reactants to be effective, the reacting species must be
in proper orientation to each other at the time of collision.

3. Activation energy
If the collisions between the reactant molecules do not have sufcient
energy, then
no reaction will occur. Therefore, for the reaction to take place collision
must always
occur with sufcient energy to break the bonds in the reactants and form
new bonds
in the product. Thus, minimum amount of energy needed for the reaction
is known
as activation energy, Ea.
Generally , according to postulates of collision theory, for a reaction to occur between
reactants:
1. The particles of the reacting substances must collide.
2. The particles of the reacting species must have proper orientation.
3. The particles of the reactants must collide with energy greater than or equal to
the energy of activation.

Factors Affecting the Rates of Chemical Reaction


The collision theory assumes that the rate of a reaction depends on the number (frequency) of
collisions of particles and those factors which affect the frequency of collisions will also affect
the rate of a reaction.

i. Nature of the reactants


The rate of a reaction depends on the chemical nature of the substances
in the reaction.
The combination of two oppositely charged ions usually occurs very
rapidly. For example, the reaction of an acid with a
base is:

The acid-base reaction of HCl and NaOH is much faster than the
decomposition of hydrogen peroxide, which involves the reorganization of
molecules.

Even similar reactions may have different rates under the same conditions, due to the
nature of the reactants.
Forexample, the following reactions have different rates due to the nature of the
reactants, Mg, Fe and Cu.

ii.Surface Area of Reactants


Reactions can be classifed as homogeneous (same phase) and
heterogeneous (different
phases).
A reaction between substances that are in different physical phases (solid, liquid, gas) is called a
heterogeneous reaction. The reaction occurs only at the interface (boundary)
between two phases. The area of contact between the phases determines the rate of
reaction in heterogenous reaction. When the size of particles is minimized, contact between the

atoms, ions, or molecules in the solid state maximizes with those in a different phase.
For example, the reaction between steam and red hot iron, proceeds very slowly if the iron is in
one large block, but it goes rapidly if the metal is powdered.

A reaction of substances when both are in the gaseous or liquid phase, (a reaction occurs
only in one phase) is called homogeneous reaction. Because of the molecules and ions are
free to move and collisions are frequent, the surface area of contact between them do not affect
the rate a reaction.
For example:

iii. Concentration of Reactants


At a fixed temperature, the rate of a given reaction depends on the
concentration of the reactants. When the concentration of one or more reactants
increases, rate of reaction increases. This is because increasing the concentration produces
more contacts between the reacting particles, which results in increasing the rate of reaction.
For those reactions that involve gaseous reactants, an increase in pressure increases the
concentration of the gases which leads to an increase in the rate of reaction. However,
pressure change has no effect on the rate of reaction if the reactants are either solids or
liquids.

iv.Temperature of Reactants
Temperature usually has a major effect on the rate of reaction. Molecules at higher
temperatures have more thermal energy. An increase in the temperature of a reaction mixture
increases the rate of reaction of chemical reactions. This is because as the temperature of the
reaction mixture raises, the average kinetic energy of the reacting particles increases. So, they
collide more frequently and with greater energy.
In many homogeneous system , the rate of a reaction is approximately
doubled by an increase in temperature of only 10 °C.
Temperature not only affects the rate of reaction but can even change the course of a
reaction. For example,
At 200°C ,

At even higher temperature,

v. Presence of a Catalyst
A catalyst is a substance that changes reaction rate by providing an alternate pathway or
reaction mechanism by reducing the activation energy between reactants
and products and hence lowering the potential energy barrier.
A catalyst may undergo physical changes and it may even form temporary chemical bonds with
the reactants but it is recovered unchanged in original form at the end of the reaction. Although a
catalyst speeds up the reaction, it does not alter the position of equilibrium.

FigFig 4.9. : Effect of catalyst on activation energy

Chemical catalysts can be either positive or negative. Positive catalysts


increase the
rate of reaction by lowering the Ea.

Negative catalysts or inhibitors decrease the rate of reaction by increasing

the value of Ea.


A substance that catalyzes one reaction may have no effect on another reaction,
even if that reaction is very similar. For examples , highly specific catalysts
are enzymes.

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