CPE 312

CHEM/PET AKSU
Dr Rasheed BABALOLA
 INTRODUCTION TO CHEMICAL
KINETICS
The rate of chemical reactions differs based on the
type of reaction.
Some of these reactions are slow while others a fast.
There are also some reactions that occur at average
speed.
Examples
• A white precipitate of silver chloride forms almost
immediately when silver trioxonitrate (V) solution is
added to hydrochloric acid.
•The rusting of an iron in air is a slow process that can
take several days if not months.
The rate of chemical reactions and their control
are important in industry as they are, often,
the deciding factor that determines whether a
reaction may be used economically or not.
MEANING OF THE RATE OF REACTION
Zinc reacts with dilute hydrochloric acid in the
following way
Zn(s) + 2HCl(aq) ZnCl2 (s) + H2(g)
as the reaction proceeds, zinc and the acid , i. e. the
reactants, are used up while zinc chloride and
hydrogen, i. e. the products, are formed.
The rate of reaction is the speed at which reactants
are used up or products are formed.
The rate of a chemical reaction is the number
of moles of reactant converted or product
formed per unit time.
The rate of the reaction can be measured by
 Taking a given mass of zinc
Adding an excess of hydrochloric acid to it
Noting the time taken for all the zinc to react.
Mathematically the rate of reaction can be
written as
Rate of reaction = Amount of zinc (mol dm-3)
Time taken (min)
Most of the reaction involves the change in concentration
of one of the components of the reaction with time.
The reaction rate can therefore be written as
Reaction rate=Change in concentration of reactant/product
Time taken for the change
The concentration of the reactant or product is expressed in
mol dm-3 or g dm-3. The time taken to undergo the
reaction can be in seconds, minutes, days, or even years
for very slow reactions.
Example:
When 0.5 g of calcium trioxocarbonate (IV) was added to
excess dilute hydrochloric acid, carbon (IV) oxide was
produced. The entire reaction took 5 minutes. What is
the rate of reaction?
Solution
Rate of reaction = Mass of reactant (CaCO3)
Time taken for the change
= 0.5g = 0.1 g min-1
5 min
Ways of Measuring Reaction Rates
The rate of reaction can be determined by
• the rate at which the mass or concentration of
a reactant is decreasing or
• the rate at which the mass or concentration
the product is increasing.
• The decrease in the mass of the reaction
system
• Volume of the gaseous product released
• Amount of the precipitate formed
• Time taken for the reaction
• Changes in the intensity of colour
• Changes in pH
• Changes in the total gas pressure
How the Rate of Reaction Varies
The variability of the rate of reaction can be
describe by the use of a rate curve. The curve
passes through the origin due to the fact that no
mass is lost at the beginning of the reaction.
• The gradient of the curve is steep at first because
the rate of the reaction is fast
• The gradient of the curve becomes less steep as
the rate of reaction slows down
• Finally the curve becomes horizontal which
indicates the end of the reaction
The rate curve describes the following
• Average rate of reaction
• Rate at a particular instant during the reaction
Average rate
of the whole reaction = Total time of the mass
Total reaction time
= x grams
t3 minutes
= x g min-1 of CO2 produced
t3
Rate of reaction at t1 = gradient of tangent at A
= x
y
Rate of reaction at t2 = gradient of tangent at B
= x1
y1
The rate of the tangent at any point on the rate curve
represents the rate of loss of carbon (IV) oxide, and
therefore the rate of the reaction at that given
instant.
From the rate curve, it can be seen that a larger
gradient indicates a faster reaction rate while a
smaller gradient indicates a slower one.
This can be summarized by stating that,
Rate of reaction is directly proportional to the
[concentration of A ]
Where is
(i) Amount in moles of products
(ii) Amount in moles of disappeared reactants
(iii) Volume of gas/es evolved
Therefore,
Rate of reaction = K [concentration of A]
K is the rate constant.
FACTORS AFFECTING RATES OF REACTION
The factors which influences the rate of reaction are
as follows:
• Nature of reactants.
• Concentration/Pressure of reactants.
• Temperature of reaction mixture.
• Presence of light.
• Presence of a catalyst.
Effect of the Nature of Reactants
When a piece of iron is placed in dilute
hydrochloric acid, there is a slow evolution of
hydrogen gas; with a piece of zinc, hydrogen is
evolved rapidly; and with a piece of gold,
there is no evidence of a reaction. Thus, the
rate of a chemical reaction is determined by
the chemical nature of the reactants as
different substances have different energy
contents.
Effect of Concentration of Reactants
An increase (or decrease) in the concentration
of the reactants will result in a corresponding
increase (or decrease) in effective collisions of
the reactants and hence in the reaction rate.
Pressure affects the concentration of gaseous
reactants. For example, a mixture of hydrogen
and chlorine gases will react twice as fast if
the partial pressure of hydrogen or chlorine is
increased from 0.5 to 1.0 atm. The
concentration of solid and liquid reactant is
unaffected by changes in pressure.
 Rate of α 1
reaction Time taken for cross to disappear
Effect of Surface Area of Contact
To bring about greater contact between the
reacting particles, the exposed surface area of
the solid reactant must be increased by
subdividing or breaking the solid into smaller
pieces. The greater the surface area of the
reactant, the higher is the rate of reaction.
In a reaction where the reactants are gases, liquids
or solids dissolved in solution, the thoroughness
of mixing is important to ensure maximum
contact between the reactant particles.
Effect of Temperature
Reactions are faster at high temperatures and
slower at low temperatures. In general, the
reaction rate doubles for each rise of 10oC. The
reverse effect of cooling a reaction in order to
slow it down is true. Increasing the temperature
of a system can lead to an increase in reaction
rate in a way. When the temperature is raised,
energy in the form of heat is supplied to the
reactant particles,
• The average speed of all the reactant particles
increases due to the greater kinetics energy,
leading to a higher frequency of collision.
The average kinetic energy of a collection of
molecules is proportional to the absolute
temperature. At a particular temperature, T1, a
definite fraction of the reactant molecules have
sufficient kinetic energy greater than the activation
energy, Ea, needed to react to form product
molecules on collision. At a higher temperature, T2,
a greater fraction of the molecules possess the
necessary activation energy, and the reaction
proceeds at a faster rate. This is illustrated in the
following slide. From experimental
observations, Arrhenius developed a
relationship between Ea, the absolute
temperature, and the rate constant of a
reaction, k, at that temperature. The
relationship,
Effect of Light
Some reactions are influenced by light. The reaction
between hydrogen and chlorine is negligible in the
absence of light, moderate in daylight and explosive
in bright sunlight. Such reactions are known as
photochemical reactions.
Other examples includes:
• the decomposition of hydrogen peroxide
• The reaction between methane and chlorine
• Photosynthesis of silver halides to grey metallic
silver (used in photography)
The reactant molecule become activated on
absorbing light energy, and react rapidly together in
a series of chain reactions.
Effect of Catalyst
A catalyst is a substance which alters the rate of
a reaction but itself does not undergo any
permanent change at the end of the reaction.
A positive catalyst usually acts by lowering the
energy barrier of a chemical reaction. Thus, in
the presence of a catalyst, more reactant
particles are able to react when they collide.