WEEK ONE DATE: _________

TOPIC: RATE OF REACTION

MEANING OF RATE OF REACTION

The rate of a chemical reaction is the number of moles of reactants converted or products formed
per unit time.

Usually, rate of reaction is determined experimentally by measuring change in concentration of one

of the components in the reaction with time.

Thus,

Rate of reaction = change in concentration of reactant or product (mol/dm3)

Time taken for the change (seconds)

The unit of the rate of reaction is mol/dm-3s-1 or g dm-3s –1.

Rate of reaction can also be expressed as:

Rate of reaction = change in number of mole or mass of reactant or product

Time taken for the change

Then the unit of rate is mols-1 or gs-1

EXAMPLE: When 0.5g of calcium trioxocarbonate (IV) was added to excess dilute hydrochloric acid,
carbon (IV) oxide was evolved. The complete reaction took 5 minutes. What was the rate of reaction?

SOLUTION:

Rate of reaction = change in mass of reactant

Time taken for the change

= (0.5 – 0)g = 0.5

5 x 60 300

= 1.67 x 10-3 gs-1

WAYS OF MEASURING REACTION RATE

Concentration is one of the properties of a reaction that can change with time.

The following properties can also change with time and can thus be used to measure rate of reaction.

VAM ∆ in PPC

1. Volume of gaseous product

2. Amount of precipitate formed
3. Decrease in mass of reaction system
4. Change in pH
5. Change in total gas pressure
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6. Change in colour intensity

RATE CURVE

The rate curve is a graphical illustration of the rate of a reaction.

The following graph illustrate rate curve

FEATURES OF RATE CURVE

1. It passes through the origin. This is because there is no change in concentration or mass at
the start of reaction.
2. It steeps at first, this because the rate is fast at the beginning.
3. It becomes less steep later. This is because the rate slows down.
4. It finally becomes horizontally. This is because the reaction has reached the end points.

When the rate of reaction has direct variation with concentration, then

Rate of reaction α[Concentration of A]

R α [A]

R = k[A]

Where k is called Rate constant

COLLISION THEORY

The collision theory states that for a chemical reaction to occur the reactant particles must collide
and they must collide with a certain minimum amount of energy known as activation

energy.

Not all collisions result into chemical reaction. Collisions, which result into chemical reaction, are
called EFFECTIVE COLLISIONS. Minimum amount of energy required by reacting particles for chemical
reaction to occur is called ACTIVATION ENERGY. Activation energy is the ENERGY BARRIER the
reactants must overcome for reaction to occur. It is the minimum energy required for bond breaking
for chemical reaction to occur.

Chemical reaction occur only when the energy of the colliding reactant particles is equal to or more
than the activation energy. Activation energy must be equal to energy barriers also for chemical
reaction to occur.

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Every reaction has its own energy of activation. Reactions with low activation energy have high rate
of reaction and occur spontaneously. Reaction with high activation energy have low rate of reaction
and are not spontaneous.

The graph below illustrates the concepts of the activation energy for endothermic and exothermic
reactions.

EXOTHERMIC REACTIONENDOTHERMIC REACTION

From graph, it can be seen that

1. Both exothermic and endothermic reactions generally require an initial input of energy to
overcome the activation energy barriers.

2. Exothermic reaction once started proceed without any further external energy supply e.g
burning of kerosene

3. Endothermic reaction proceeds with continuous supply of external energy e.g cooking of rice.

FACTORS AFFECTING RATE OF REACTION

From the collision theory, it can be seen that rates of reaction depends on the following features.

1. The energy of the particle.

2. The frequency of collision of the reaction.
3. The activation energy of the reaction.

These features of a chemical reaction are in turn affected by some factors, which can make them to
change and consequently affect the rate of reaction. These are factors that affect the rate of
reactions. Some important ones are:

1. Nature of reactants.
2. Concentration / pressure (for gases) of reactants.
3. Surface area of reactants
4. Temperature of reaction mixture
5. Presence of light
6. Presence of catalysts

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To study the effect of any one of these factors on rate of reaction all other factors must be kept
constant.

EFFECT OF NATURE OF REACTANTS

The difference in rate of reaction is due to the chemical nature of the elements as they naturally
posses different amount of energy content.

EFFECT OF CONCENTRATION OF REACTANTS

The frequency of collision among particles is high when the particles are crowded in a small space, i.e
high concentration. This leads to high effective collision and thus high rate of reaction. An increase or
decrease in the concentration of the reactants will result in corresponding increase or decrease in
effective collisions of the reactants and hence the reaction rate.

EFFECT OF SURFACE AREA OF REACTANTS

This is a very important factor to be considered when a solid is involved in a chemical reaction.
Lumped solids offer small surface area of contact for reaction while powdered solids offer large
surface area for reaction. Rate of reaction is slow with lumped solid but high with powdered solids.

EFFECT OF TEMPERATURE

Increasing the temperature of a system can lead to an increase in reaction rate in two ways. When
heat is raised, energy in form of heat is supplied to the reactant particles, so that

1. The number of particles with energy equal to or greater than the activation energy increases.
2. The velocity of all the reactant particles increases due to the greater kinetic energy, leading to
a higher frequency of collision.
As a result, the number of effective collisions increases and the reaction proceeds at a faster rate and
vice versa.

EFFECT OF LIGHT

Some reactions are influenced by light. The rate of reaction is high when the lights intensity is high,
low when the intensity is low and does not proceed at all in the absence of light. Such reactions are
known as photochemical reaction. Examples of photochemical reactions include.

1. Reaction between hydrogen and chlorine and

2. Decomposition of hydrogen peroxide
3. Reactions between methane and chlorine
4. Photosynthesis in plant
5. Conversion of silver halides to grey metallic silver.

EFFECT OF CATALYST

A Catalyst is a substance, which alters the rate of a reaction, but itself does not undergo any change
at the end of the reaction.

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A positive catalyst increases the rate of reaction by lowering the activation energy of the reaction
whereas, the one which increases the activation energy is known as a negative catalyst or an
inhibitor.

The diagram below illustrates the energy profile for catalyzed and uncatalyzed exothermic and
endothermic reactions

Assignment

List factors affecting the rate of chemical reaction

List 5 ways of measuring chemical reaction

WEEK TWO DATE: _________

TOPIC: EXOTHERMIC AND ENDOTHERMIC REACTIONS

ENERGY

Energy is defined as the ability to do work. It exists in different forms like: heat, light, sound,
electrical, potentials (stored), kinetic etc.

LAWS OF CONSERVATION OF ENERGY

Energy can be changed from one form to another. The total amount of energy before and after the
change remains the same. This observation is stated in the law of conservation of energy which
states that energy can neither be created nor destroyed but can be changed from one form to
another.

There are types of energy such as chemical energy, heat energy, and light energy.

HEAT CONTENT (ENTHALPY) OF A SUBSTANCE

Heat content or Enthalpy of a substance is the characteristic internal energy possess by the
substance, which is due to the structure and physical state of a substance. The potential
energy is due to the structure while the kinetic energy is due to the physical state. Enthalpy
of one substance is different from another. Total enthalpy cannot be measured but only
enthalpy change. Generally, an enthalpy change (∆H) is the heat that would be exchanged
with the surrounding, that is, it is the amount of energy involved in a reaction.

Thus,
Enthalpy change = Heat of products – Heat of reactants

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That is, ∆H = Hproducts - Hreactants

The enthalpy change of a given reaction is always written side by side with the given equation and it
may be either a positive or negative value.

Example: HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) ∆H = -57.3kJ

Unit of enthalpy change(∆H) is Joules(J) or kilojoules(kJ)

EXOTHERMIC REACTION
A chemical reaction in which heat is given off to the surrounding is known as exothermic
reaction.

Examples of exothermic reactions include:

1. Reaction between calcium oxide and water
2. Reaction between an acid and a base.
3. Combustion of fuel
4. Corrosion of metals
5. Respiration
In exothermic reaction, enthalpy change is negative since the heat content of the products is
less than the heat content of the reactants.

ENDOTHERMIC REACTION
An Endothermic reaction is a type of reaction in which heat is absorbed from the
surroundings.

Examples of endothermic reactions are:

1. Thermal decomposition of calcium trioxocarbonate (IV)
2. Thermal dissociation of ammonium chloride
3. Action of light on silver bromide in photographic film
4. Photosynthesis in plants
In endothermic reaction, the heat content of the product is more than the heat content of
the reactant; hence the enthalpy change is positive.

ENERGY LEVEL DIAGRAMS

Energy changes can be presented by diagrams, which shows at once whether reactions are
exothermic or endothermic.

2ND TERM/CHEMISTRY/SS2 PAGE 6

HEAT OF REACTION AND CHEMICAL BONDS
During chemical reactions, chemical bonds are broken, atoms are regrouped and new bonds
are formed. Bond breaking requires energy and bond forming evolves energy. The minimum
amount of energy required for bond breaking is called activation energy. While bond
breaking is endothermic, bond forming is exothermic. Thus, heat of reaction is positive
[endothermic] when bond-breaking energy is more than bond forming energy and vice
versa.

TYPES OF HEAT CHANGES IN CHEMICAL REACTIONS

HEAT OF FORMATION
The amount of heat evolved or absorbed when one mole of a substance is formed from its
elements under standard conditions. It is known as heat of formation [or enthalpy of
formation].

HEAT OF NEUTRALIZATION
Neutralization is an exothermic reaction. The amount of heat evolved when 1 mole of
hydrogen ions, H+, from an acid reacts with 1 mole of hydroxide ions, OH-, from an alkali to
form 1 mole of water under standard conditions. L
H+(aq) + OH-(aq) → H2O(l) ∆Hnθ = – 57.4kJmol-1

HEAT OF COMBUSTION
Combustion reaction is always exothermic. The amount of heat evolved when one mole of a
substance is burned completely in oxygen under standard conditions.

A bomb calorimeter is usually used for accurate determination of heat of combustion.

Heat of combustion can be determined from the relation below:
Heat of combustion = Heat energy produced x molar mass
Mass burnt 1
But heat energy produced (Q) = mC∆θ
Heat of combustion = mC∆θ x molar mass
Mass burnt 1
Where m = mass of water
C = Specific heat capacity of water
∆θ = change in temperature, that is, θ2 – θ1

HEAT OF SOLUTION
Heat of solution can be exothermic or endothermic. Heat of solution, ∆Hsθ , is the amount of
heat evolved or absorbed when 1 mole of substance is dissolved in so much water that
further dilution results in no detectable heat change at standard conditions.

THERMODYNAMICS
Thermodynamics is the study of relationship between heat and other forms of energy.

System in thermodynamics is any part of the universe chosen for thermodynamics consideration, i.e.
the physical and chemical phenomenon or process occurring in a given

environment. A system can be isolated, closed or open.

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Surrounding is the environment in which a phenomenon or a process occurs.

The first law of thermodynamics states that energy can neither be created nor destroyed but may be
converted from one form to another.

In thermodynamics, heat is represented by q and other forms of energy are referred to as work
denoted by w. The conditions or state of a chemical system is changed when:

i. Heat is evolved or absorbed, and / or

ii. Work is done on or by the system

In any case, the internal energy, U, of the system is affected and it is changed.

From first law, heat is changed into internal energy of the system it may be represented by

change in internal energy = Heat absorbed by the system + Work done by the system

i.e. U = q + w

Work done by the system is negative since this lead to decrease in internal energy, therefore:

U = q - w

For a gaseous system, w = P∆V

U = q - P∆V

U = H - P V

H = U + P V

SECOND LAW OF THERMODYNAMIC

The second law of thermodynamic states that a spontaneous process occurs only if there is an
increase in the entropy of a system and its surroundings

Factors which determines the spontaneously of a process are:

i. enthalpy, H: The heat content of the substances involved

ii. entropy, S: The measure of degree of disorderliness or randomness of a substance
iii. free energy G: The energy which is available for doing work.

ENTROPY (S)

Entropy is the measure of degree of disorderliness or randomness of a system. The standard entropy
change (∆Sθ) is a state function because it depends on the initial and final state of the system. That is:

∆Sθ = Sθproducts - Sθreactants

The S.Iunit of is JK-1mol-1

Entropy increases from solid to liquid to gaseous state because as you go from solid to liquid to
gaseous state, randomness increases, that is; ∆Sθ tends to positive.

For a reversible process at constant temperature,

S = H/T

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When ∆S is positive, there is increase in entropy. When ∆S is negative there is decrease in the
entropy of a system.

GIBB’S FREE ENERGY

The free energy of a system is the energy which is available for doing work in the system; that is, the
driving force that brings about a chemical change.

The standard free energy change (∆Gθ) is a state function because it depends on the initial and final
state of the system. That is:

∆Gθ = Gθproducts - Gθreactants

Free energy takes into account the effect of the enthalpy and entropy factors as represented in the
equation below:

G = H-TS

For a change at constant temperature,

G= H- T S

NOTE:

1. When ∆G is negative, the reaction is spontaneous or feasible.

2. When ∆G is positive, the reaction is not spontaneous or feasible.

3. When ∆G is zero, the system is in equilibrium

Example: The reaction: C(s) + O2(g) → CO2(g) is carried out at a temperature of 57oC. If the enthalpy
change is -5000J and the entropy change is +15J.Calculate the free energy change

Solution:

G= ∆H - T∆S

= -5000 - (57 + 273) x (+15)

= -5000 - 330 x 15

= -5000 - (+4950)

= -5000 - 4950

= -9950J or -9.950kJ

WEEK THREE DATE: _________

EQUILIBRIUM

Equilibrium can be defined as the state of a system where there is no observable or detectable
change in the properties of the system with respect to time. Examples of system in equilibrium

a. a balanced see – saw

b. a saturated solution of NaCl

2ND TERM/CHEMISTRY/SS2 PAGE 9

STATIC AND DYNAMIC EQUILIBRIUM

Static equilibrium is attained when a system in equilibrium is in a state of rest or stationary state.

Example of this is balanced see – saw

Dynamic equilibrium can occur during a physical change or a chemical change that is reversible.
Dynamic equilibrium involving a physical change is referred to as physical equilibrium while that
involving a chemical change is a chemical equilibrium.

A system is said to be in a state of dynamic equilibrium when both the forward and backward
reactions take place at the same rate. Example

N2O4(g) ⇌ 2NO2(g)

EQUILIBRIUM IN REVERSIBLE REACTION

A reversible reaction is one which proceeds in both forward and backward directions under suitable
conditions.

For example: NH4Cl(s) NH3(g) + HCl(g)

A reversible reaction is said to be in dynamic equilibrium when both the forward and backward
reaction are occurring at the same rate, thereby producing no net change in concentrations of the
reactants or products.

Properties of system in equilibrium

1. A chemical reaction at equilibrium is in dynamic state with the rates of the forward and
backward reactions are equal.

2. The equilibrium position can be reached from reactants alone or form product alone

3. For equilibrium to be established, the system must be close

FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

The position of equilibrium depends on the following set of condition

i. Temperature
ii. Concentration
iii. Pressure (for gases)
Variation in any of these factors will upset the balance of the system and results in a shift in the
position of the equilibrium. These factors and their effect on chemical systems in equilibrium were
studied by Le Chatelier’s who formed the Le Chatelier’s principle.

Le Chatelier’s principle states that if a chemical system is in equilibrium and one of the factors
involved in the equilibrium is altered, the equilibrium position will shift so as to neutralize the effect
of the change.

Importance of Le Chatelier’s principle in chemical industry: It helps to

2ND TERM/CHEMISTRY/SS2 PAGE 10

i. Define optimum conditions for chemical process
ii. Reduce undesirable reversibility
iii. Predict the effect of an altered factors on the equilibrium

EFFECT OF TEMPERATURE

For an endothermic reaction, increase in temperature shifts the position of equilibrium to the right.
That is, the forward reaction is favoured while a decrease in temperature favours the backward
reaction. The reverse is the case for exothermic reactions.

EFFECT OF CONCENTRATION

In a system of equilibrium, if the concentration of reactants is increased or product decreased, the

forward reaction will be favoured, that is; equilibrium position shifts to the right. Also, if the
concentration of the products is increased or reactant decreased, the backward reaction will be
favoured, equilibrium position shifts to the left.

EFFECT OF PRESSURE

Pressure of gas is proportional to the number of moles. Increase in number of moles implies
increase in pressure and vice visa. If the forward reaction proceeds by decreases in number of moles
(pressure), an imposed increase pressure will favour forward reaction. Reverse is the case if it
proceeds by increase in number of moles (pressure). In other words, when high pressure is applied,
equilibrium will shift to the side with less number of moles while when low pressure is applied,
equilibrium will shift to the side with greater number of moles.

N2(g) + 3H2(g) ⇌ 2NH3(g)

1 mole 3 moles 2 moles

Increase in pressure favours forward reaction while decrease in pressure favours backward reaction

EFFECT OF CATALYST

A catalyst does not change (affect) the position of equilibrium. Addition of catalyst, however
increase the rate of both forward and backward reaction by lowering the activation of energy of the
reaction.

Equilibrium position is attained at faster rate when a catalyst is present.

ASSIGNMENT

1. State Le Chatelier’s principle

2. Explain the effect of

i. Increase in temperature

ii. decrease in pressure

on the following reaction

2SO2(g) + O2(g) 2SO3(g) ∆H= -3957KJmol-1

2ND TERM/CHEMISTRY/SS2 PAGE 11
HABER PROCESS

Haber process is an industrial process for the manufacture of ammonia.

Ammonia, NH3, is an important chemical for the manufacture of fertilizers. During the process, the
following equilibrium is established

N2(g) + 3H2(g) ⇌ 2NH3(g) ∆H =-96KJmol-1

1 mole 3 moles 2 moles

CHOICE OF TEMPERATURE

Since forward reaction is exothermic, Le Chatelier’s principle shows that the greatest yield of
ammonia, NH3, would be obtained at low temperature. However, if the temperature is too low, time
taken to reach equilibrium would be much. A temperature of 500 0C gives reasonable yield of
ammonia.

CHOICE OF PRESSURE

Since forward reaction leads to decrease in number of moles (pressure), Le Chatelier’s principle
shows that high yield of ammonia would be obtained at high pressure. The pressure of 25atm gives
a satisfactory yield.

CHOICE OF CATALYST

Iron is used as catalyst in Haber process. Iron is found to be effective in speeding up the rate of
which equilibrium is reached. It is used in form of small pellets which increased the surface area
available for contact.

EQUILIBRIUM CONSTANT (K) AND LAW OF MASS ACTION

The law of mass action states that at constant temperature, the rate of reaction is proportional to the
active masses of each of the reactants;

The active mass of the reactants is the concentration of the substance raised to the power of
coefficient (number of mole) of that substance in the equation of reaction under study.

NOTE: Active mass = molar concentration x activity coefficient

In most reactions, the active masses of the reactant may be taken as their molar concentrations.

Example:

aA + bB products

Thus, r α [A]a and r α [B]b

where [ ] represents concentration in moldm-3

r α [A]a x [B]b

2ND TERM/CHEMISTRY/SS2 PAGE 12

 r = k [A]a [B]b

where k is called equilibrium constants

Applying the law to the reversible reaction represented by the equation below:

aA(aq) + bB(aq) ⇌ cC(aq) + dD(aq)

Kc= [C]c [D]d

[A]a [B]b
Where Kc is called equilibrium constant

For reactions involving gases, the equilibrium constant is expressed in terms of the partial pressures
of the gases involved in the reaction.

Therefore, for the general gaseous reaction:

aA(g) + bB(g) ⇌ cC(g) + dD(g)

Kp = PCc x PDd

PAa x PBb

Where Kp is equilibrium constant for the gaseous reaction, P A, PB, PC and PD are partial pressures of
gases A, B, C and D respectively.

NOTE: For a given reaction, concentrations of solids are ignored. A Kc or Kp value greater than one
tells you that product formation is favoured at equilibrium; while a Kc or Kp value less than one tells
you that reactants formation is favoured at equilibrium. A system in equilibrium has Kc or Kp value
equal to one.

GENERAL EVALUATION/REVISION

1. State the conditions for the optimum yield of ammonia in Haber process.
2. State Le Chatelier’s principle
3. State Le Chatelier’s principle
4. Explain the effect of
i. Increase in temperature
ii. decrease in pressure
on the following reaction

2SO2(g) + O2(g) ⇌ 2SO3(g) ∆H= -3957KJmol-1

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