Periodic Table: This shows the arrangement or grouping of elements in order of increasing

atomic number.

Periodic Law: Is the basic assumption behind the modern periodic table; it states that the
properties of the elements are the periodic function of their atomic number.

ELECTRONIC CONFIGURATION OF THE FIRST THIRTY ELEMENTS

The lectronic configuration of an atom is the representation of the arrangement of the

electrons distributed among the orbital shells and subshells. Commonly, the electronic
configuration is used to describe the orbitals of an atom in its ground state

MEANING OF ATOMIC ORBITAL

Orbital is the region of space around the nucleus where there is a high probability of finding
electron. The four different types of orbitals are s, p, d, and f. These orbitals have different
shapes and one orbital can hold a maximum of two electrons. The p-orbital has three
degenerate orbitals, with a maximum of six electrons, d has five sub orbitals with a maximum of
ten electrons and the f-orbital has seven sub-orbitals with maximum of fourteen electrons.

Orbitals Number of sub-ortals [Link]. electrons Shape

S - 2 Spherical

P 3 6 Dumb-bell

D 5 10 Double dumb-bell

F 7 14 Complex

RULES AND PRINCIPLES FOR FILLING IN ELECTRONS

1. Aufbau Principle: states that electrons are filled in their orbital in order of increasing energy
level. The order is as follows:
1s < 2s < 2p< 3s < 3p <4s < 3d <4p etc.

2. Pauli’s Exclusion Principle: states that two electrons in the same orbital of an atom cannot
have same values for all quantum numbers. Usually the first electron in an orbital is assumed to
enter with up-spin (clockwise ),↑ while the second electron enters the same orbital but with a
down-spin (anti-clockwise ), ↓.

3. Hund’s Rule of maximum Multiplicity: This rule states that electrons occupy each orbital
singly first before pairing takes place in a degenerate orbital. Hence, no pairing in degenerate
orbital until each orbital is singly occupied with parallel spin.
EVALUATION:

1. Draw a periodic table showing the 1st 20 elements

2. Define periodic law

3. Define periodic table.

4. Write the electronic configuration of the following elements: Cu, Na, Al, and Cl
PERIOD 3: BLOCKS OF ELEMENTS (IUPAC) CO2 ------Carbondioxide, CARBON(IV)OXIDE

From the position of the various elements on the periodic table and the electrons arrangements
or configuration seem to stand out. Elements that have one and two electron(s) in their last s-
orbital i.e. group 1 and 2 elements are called s-block elements. P-block elements have their
last electron (s) in the p-orbital are called P block elements.

Elements that have their last electrons in the d orbital are called d blocks elements while f
block elements have their last electrons in the f- orbital.
Moving across a particular period on the periodic table, two elements are present in the S
block, six elements in the P block, ten elements in the d- block and fourteen elements in the f-
block. This corresponds with the maximum number of electrons in the s, p, d, and f orbitals
respectively. Also, S block elements are metals, P block elements are mostly non-metals d-
block elements are transition metals while f-block elements are lanthanides (rare earth metals)
and actinides (heavy rare earth metals).

There is therefore a diagonal division of the elements into metals and non-metals as shown
below. Metals are found on the left side of the thick boundary line and the non-metals on the
right with metalloids occurring along the boundary line.

CHARACTERISTICS PROPERTIES OF TRANSITION ELEMENTS

1. Paramagnetism: Transition elements exhibit paramagnetism because of the presence of

unpair elecrons in the d-orbital. Paramagnetism is the ability of an element to align to the poles
of a magent.

2. Variable oxidation states: Transition elements exhibit variable oxidation states because they
can lose electrons from both 4s and 3d orbitals for bond formation e.g we have Fe 2+ and Fe3+

3. Complex ion formation: Transition elements form complex ions due to the presence of
vacant or empty d- orbitals in their ions.

4. Catalytic ability: The catalytic ability of transition metals is due to the fact that they exist in
different oxidations states, hence they are used as catalyst. The partially filled d-orbital allows
the exchange of electrons to and from molecules which enable them to act as catalyst.

EVALUATION:

1. State the blocks of the following elements: H, F, Na, Ca, Fe and Mn

2. State three properties of transition elements and explain any two of the properties.
PERIOD 4: FAMILIES OF ELEMENTS.

Elements are arranged into groups or families and periods. Each group has been given a name
to allow proper understanding during discussions on the periodic table.

Names of the different group (1-8) on the periodic table are shown below.

Group (i) i.e. Li, Na, K etc. -------- alkaline metals

Group (ii) i.e. Be, Mg, Ca, etc. ------ Alkaline earth metals

Group (iii) i.e. B, Al, Ga, etc. ------- Boron family

Group (iv) i.e. C, Si, Ge, etc. --------- Carbon family

Group (v) i.e. N, P, As, etc. ---------- Nitrogen family

Group (vi) i.e. O, S, Se, etc. --------- Oxygen family or Chalcogens

Group (vii) i.e. Fl, Cl, Br, etc. ------ Halogens

Group (viii) or group O i.e. He, Ne, Ar, etc. ------ Rare, inert, noble gases.

Transition Elements: These are between groups 2 and 3 on periods 4 and 5.

Lanthanides (Rare- earth elements): these are fifteen elements La- Lu.

Actinides: These are found on the seventh period AC –Lr.

Artificial Elements: These are elements with atomic numbers 93 to 103. They are products
formed during chemical reactions. They are unstable and disintegrate in a short time e.g.
Plutonium (Pu) and curium (Cm)

EVALUATION:

1. Four elements P, Q, R and S, have 1, 2, 3 and 7 electrons in their outermost shell respectively.
What is the element that is unlikely to be a metal?

2. The elements listed below belong to the same group in the periodic table; 9F, 17Cl, 35Br, 53I
 (i) What is the electronic structure of the first-member?
(ii) What is the family name of the elements?
(iii) Which of the elements has the strongest oxidizing ability?

GENERAL EVALUATION

OBJECTIVE TEST;

1. The period table is an arrangement of elements in order of their. (a) Relative molecular mass
(b) mass numbers (c) molecular masses (d) atomic numbers.

2. Four elements T, X, Y, Z have 1, 2, 3 and 6 electrons in their outmost shells respectively. The
element that is likely to be a non-metal is. (a) X (b)T (c) Z (d) Y

3. An atom with the electronic configuration: Is2, 2s2, 2p6, 3S2, 3d1, 4s2 is that of:

(a) an alkali metal (b) an alkali earth metal (c) a transition metal (d) a halogen

4. An element whose atomic number is 19 is

(a) a noble gas (b) an alkali earth metal (c) An alkali metal (d) a transition metal

5. Group 0 or 8 elements are called. (a) Active elements (b) lanthanides (c) noble gas (d) alkali
earth metals.

ESSAY QUESTIONS

1. A shortened form of the periodic table is shown below. Use it to answer questions a and b.

I II III IV V VI VII O

1. A

2. B
C
3.
 4. D E

(a) Which of the elements represented as A to E in the table above is

(i) A transition metal; (ii) an alkaline earth metal

(iii) The least reactive (iv) the most electronegative

2. State the four properties of transition elements (d-block)

3. Name one element in each case which

(a) forms an amphoteric oxide;

(b) Liberates hydrogen from cold water;

(c) Exists as a liquid at room

4. Give the names of the members of the alkaline earth metal family.
WEEK 2

TOPIC: PERIODIC TABLE

CONTENT:

1. Periodic properties

2. Periodic gradation of the element in the third period

3. Diagonal relationships

PERIOD 1 AND 2 : PERIODIC PROPERTIES. Some properties of the atom change along a group or
across a period on the periodic table. Atomic radius which is measured of the size is one of such
properties. The orbiting electrons in an atom are best represented by an electron cloud which
has no distinct limit as the size of an action cannot be defined easily.

1. Atomic radius: This has been defined as the distance of closest approach to another identical
atom in a given bonding situation. There are two types of atomic radii. Covalent radius and Van
der Waals radius. Covalent radius is half the distance between two identical atoms which are
not chemically bonded. For the two types of atomic radius two variations are noticeable:

(i) The atom radius increases down a group

(ii) The atomic radius decreases along a period.

This is because going down any group on the periodic table the number of valence electrons
remains constant while the shells increase in size (radius) despite increase in nuclear charge.
The atomic radius of potassium is greater than that of Sodium. The atomic radius of caesium is
greater than that of rubidium.

Across a period, electrons are added to orbitals in the same shell, all the valence electrons are
therefore at the same energy level. As atomic number increase the positive charge of the
nucleus increases giving rise to greater attraction between the positive nucleus and negative
electrons. This is turn result in contraction of the electrons cloud resulting in a smaller atom.
Atomic radii therefore decrease across a given period on the periodic table.

2. Ionic Radius: Ions are formed by a loss or gain of electrons by an atom. A positive ion (cation)
is smaller than the original metal atom because electrons are pulled in due to increase in
effective nuclear charge.

A negative ion (anion) is bigger than the corresponding non- metal atom because the
effective nuclear charge is reduced.
As we move across the second short period, the cationic radii decrease from sodium to
aluminium while the anionic radii increase from phosphorous to chlorine.

3. Ionization energy: Ionization occurs when gaseous atom loses electrons from its outer most
shell to become positively charged

−¿¿ +¿ ¿
K e K
The energy required to do this is called ionization energy or ionization potential.
First ionization energy of an element is the energy needed to remove one mole of
electron(s) from one mole of atoms in the gaseous state. It is expressed in kilo- joules per
mole of atoms ionized.
First ionization energy increase across the period with noble gases having the highest. As
we go down he the group, the value of first ionization energy decreases.
FIRST IONIZATION ENERGIES OF ALKALI METALS

Element LI Na K Rb Cs

First 520 500 420 400 380

ionization
energy
KJMOL-1
 FIRST IONIZATION ENERGIES OF THE ELEMENTS IN THE THIRD PERIOD OF THE PERIODIC
TABLE

Element Na Mg Al Si P S Cl Ar

First 496 737 577 786 1012 999 1255 1521

ionization
energy
KJMOL-1

Three factors that affect the ionization potential of an atom

Ionization potential of an atom is affected by.
(i) Distance of the outer most electrons from the nucleus.
(ii) Size of the positive or effective nuclear change.
(iii) Screening effect of the inner electrons.

Moving from left to right across a period, there is a general rise in the first ionization energy.
This is due to the fact that the nuclear charge is increasing across the period. This in turn causes
a decrease in atomic radius that is a decrease in the distance of the outermost electrons from
the nucleus. The screening effect is almost the same across the period. Down a group of the
periodic table, ionization energy decreases because the nuclear charge on the outermost
electron is reduced. The outermost electron are properly shielded from the effect of nuclear
charge

4. Electron Affinity: is the energy released when an electron is added to gaseous atom in its
lowest energy state. Its unit is kJmol -1 or electron volts (ev). Electron affinity increase across a
period from left to right and decrease down the group on the periodic table.

Group 1 elements, alkali metals have the least tendency to add electrons to their neutral
atoms.
Elements in groups VI and VII have greatest tendency to accept electron. Noble gases (group 8
or 0) have stable electronic configuration

5. Electronegativity: Electronegativity is the ability or power of that atom in a molecule to

attract shared pair of electrons. It is more pronounced in heteronuclear molecules where two
dissimilar atoms share one or more pairs of electrons.

Electronegativity increases across the period, i.e. going from left to right of the Periodic Table
but decreases down the group i.e. going down the Periodic Table. The steady increase as one
goes across the period is due to a steady increase in nuclear charge and decrease in atomic size.
Consequently, the halogen atom, Fluorine, has the highest electronegativity in the period, due
to the strong affinity for electrons. But down the group, the increase in atomic size due to
screening effect of the inner shells of electrons decreases the nuclear attraction for shared
electrons. The noble gases of group O are not assigned electronegativity values since they have
completed shells of electrons.

EVALUATION

1. List three periodic properties of elements that generally increase the across the period
of the Periodic Table.
2. Explain the term electron affinity and discuss how it varies across the period and down
the group of the Periodic Table.

PERIOD 3: PERIODIC GRADATION OF THE ELEMENTS IN THE THIRD PERIOD (Na-Ar)

Gradation in properties is not confined only to the elements, but it is also found in their
compounds with increasing atomic number.

The extent of hydrolysis of the chlorides changes across the third period. Sodium chloride is not
hydrolyzed at all in aqueous solution. The same applies to magnesium chloride although
hydrated crystals undergo hydrolysis when heated given off HCl and leaving a basic salt. An
aqueous solution of aluminium chloride shows appreciable hydrolysis and turns blue litmus red.
The chlorides of silicon, phosphorus and Sulphur hydrolyze completely in water.
The general conclusion from the above is therefore as follows: From left hand side to right hand
side across any period of representative elements, the metallic character, i.e. tendency to lose
electron(s) decreases, and the non-metallic character, i.e. tendency to gain electron(s)
increases. Also, as one goes across the period, ionic property decreases while covalent property
increases.

PERIOD 4: DIAGONAL RELATIONSHIP

Because metallic character increases down a group and decreases from left to right along a
period, there exists a diagonal relationship between the chemical properties of the first
member of a group and that of the second member of the next group as in the cases of lithium
and magnesium on one hand, and beryllium and aluminium on the other (see the periodic
table)

EVALUATION

1. The atoms of four elements are represented as Q,

20 R,
16 S and 8T. Which of the
10

elements would be unreactive?

2. Explain the meaning of the diagonal relationship the periods 2 and 3 of elements in the
Periodic Table.

GENERAL EVALUATION
 OBJECTIVE TEST:

1. An element which has atomic number 11, is likely to have similar chemical properties with
another element having atomic number. (a) 7 (b) 9 (c) 18 (d) 19

2. If the electronic configuration of an element X is 1s 2, 2S2, 2P5, which of the following

statements about X is false? It (a) Have five electrons in its valence shell. (b) Has atomic
number 9 (c) Is a halogen (d) Is a non-metal

3. The electronic configuration of an element X is 1s 2, 2s2, 2p6 , 3s2,3P4. It can be deduced that X
(a) Belongs to group 6 of the periodic table.(b) Belongs to period IV of the periodic table.(c) Has
3 unpaid electrons in its atom. (d) belongs to group 4

4. Which of the properties of the atom increases across the period and down the group in the
periodic table? (a) Atomic radius (b) electronegativity (c) electropositivity (d) Ionic radius

5. Which of the following group 1 elements has the highest Ionization energy? (a) LI (b) Na (c) K
(d) Rb

ESSAY QUESTIONS

1. (a) What are isoelectronic ions? (b) Give two examples, one each of a cation and an anion,
which are isoelectronic with neon.

2. (a) Which of the following elements: calcium fluorine, iodine, neon, magnesium and helium
are: (a) Halogens (b) noble gas (c) alkaline earth metal

3. List three periodic properties of elements that generally increase across the periodic table.

4. Arrange the following elements in order of decreasing electro negativity.

S, 13Al, 11Na, 15P

16

5. State the periodic law.

WEEK 3

TOPIC: CHEMICAL REACTIONS

CONTENTS:

1. Basic concept (Activation energy) and

2. Introduction to collision theory.
3. Factors affecting rate of chemical reactions.
4. Types of chemical reactions – Endothermic and Exothermic.

PERIOD 1: BASIC CONCEPTS: REACTANTS AND PRODUCTS

Chemical reactions can be represented simply on paper by chemical equations involving only
formula and symbols e.g.

4NH3(g) + O2(g) →
4NO(g) + 6H2O(g)

Reactants Products

Reaction time: The total time taken for a particular reaction to take place.

Reaction rate: is the number of moles of reactions converted or product formed per unit time.
Unit is moldm-3s-1

In all chemical reactions, existing bonds in the reactants particles must be broken first before
new bonds can be formed to form products. The breakings of bonds require energy. An initial
energy input is required to activate the reactant particles. This energy is the activation energy
of the reaction. The activation energy of a reaction is equivalent to that energy barrier that
must be overcome before bonds are broken to enable the reaction to occur. Hence, activation
energy can be defined as the minimum amount of energy required for a reaction can occur.
When this activation is acquired by the reactant particles, they form complex particles of high
energy content. This complex particle is known as the activated complex. Therefore activated
complex is an unstable molecule with high energy contents which gives the product It is
unstable because of its high energy content and so will readily decompose to give the products
or the reactants, depending on the nature if the reaction.
EVALUATION
Define activation energy.

PERIOD 2: INTRODUCTION TO COLLISION THEORY

The collision theory was developed from the kinetic theory of gases to account for the kinetic
theory of gases to account for the influence of concentration and temperature on reaction
rates. The theory is based on the following postulates:

i. Reactions occur as a result of the collision of reactant particles.

ii. A reaction results only if collision attains certain minimum energy. This minimum energy is
called activation energy.

iii. Collision will not give rise to a reaction unless the colliding particles are correctly oriented to
one another.

iv. The rate of reaction is proportional to the number of effective collisions. A collision is said to
be effective if the energy of the colliding molecules is greater than or equal to the activation
and the molecules are correctly oriented to one another.

The collision theory assumes that for a chemical reaction to occur there must be collisions
between reactant particles.

EVALUATION

Explain the collision theory.

PERIOD 3: FACTORS AFFECTING THE RATE OF CHEMICAL REACTION

The rate at which reaction takes place will be affected by the following factors:

1. Nature of reactant: The chemical nature of the reactants taking part in the reaction
influences the rate of reaction. For instance if iron, zinc and gold metals are placed in different
beaker continually Hydro chloric acid, there will be rapid evolution in the beaker containing the
acid and zinc metal wherein the beaker containing Iron metal and the acid there will be slower
evolution of hydrogen gas and in the beaker containing gold metal and the acid solution there
will be no reaction.

2. Effect of concentration / pressure (gases) of reactants: If reactant particles are crowded in a

particular place, their frequency of collision will be faster than if the particles are far from one
another. Thus, the more the concentration of reactant particles the higher the rate of reaction.

Pressure affects the concentration of gaseous reactant, the higher the pressure of gaseous
reactants, the higher the frequency of collision of the particles the higher the rate of reaction.

3. Effect of surface area of the reactants: the more exposed the area of contact of reacting
particles to each other the faster the rate of reaction. For solid reactants the exposed surface
area must be increased by subdividing or breaking the solid into smaller pieces.

Where the reactants are gases, liquids or solids dissolved in solution, the thoroughness of
mixing is of vital importance so as to ensure maximum contact between the reactants.

4. Effect of temperature of reaction mixture: The higher the temperature the higher the rate of
reaction of most reactions. When the temperature of a chemical reaction is increased, the
number of particles with energies equal to or greater than the activation energy increases. Also
the kinetic energy of the reactant particles increase which implies increase in frequency of
effective collision and increase in the rate of reaction.

5. Effect of the presence of light: Reactions whose rates are affected by light are called
photochemical reactions. They are thus able to overcome the activation energy barrier and
react rapidly by a chain reaction.

Examples: i. The decomposition of hydrogen peroxide

ii. The reactions between methane and chlorine Photosynthesis
iii. The conversion of silver halides to grey metallic silver
iv. The halogenations of alkanes
 6. Effect of catalyst: catalyst will alter the rate of a chemical reaction but itself does not
undergo any permanent change at the end of the reaction.

Catalysts that speed up the rate of a chemical reaction are called positive catalyst. They lower
the activation energies of the reactant particles by providing alternative pathway so more
reactant particles are able to collide effectively to produce more products. E.g. Manganese(IV)
oxide, MnO2 catalysts is used in the production of oxygen thermal decomposition of KClO3

EVALUATION

List and explain 5 factors that affect the rate of chemical reaction.

PERIOD 3: TYPES OF CHEMICAL REACTIONS: ENDOTHERMIC AND EXOTHERMIC REACTIONS

An endothermic reaction is one during which heat is absorbed from the surrounding. Most
decomposition processes are endothermic reaction. Dissolution of ammonium chloride,
ammonium tetraoxosulphate(vi) etc are endothermic process. In endothermic reaction, the
enthalpy of product(s) is greater than that of reactant(s). change in enthalpy is equal to the
sum of heat of product minus the sum of heat of reactant i.e △H = ∑ HP - ∑ H R . Where
∑ HP is sum of heat of products and ∑ H R is sum of heat of reactants. Enthalpy change in
this regard is positive. i.e △H = +ve

Examples of Endothermic reaction

(a) N2(g) + O2(g) →

2NO(g) ∆H= +180.6KJmol -1
Exothermic reaction is one during which heat is released to the surrounding. Examples of
exothermic reaction is combustion reaction. Dissolution of H2SO4, NaOH, KOH, neutralization
and AlCl3 are exothermic process. In exothermic reaction, the enthalpy of product(s) is less
than that of reactant(s). change in enthalpy is equal to the sum of heat of product minus the
sum of heat of reactant i.e △H = ∑ HP - ∑ HR . Where ∑ HP is sum of heat of products
and ∑ H R is sum of heat of reactants. Enthalpy change in this regard is negative. i.e △H = -ve

(b) Example of exothermic reaction.

C(s) + O2(g) →
CO2(g)

∆H = - 408KJmol –1

Note: The negative and the positive signs indicated in the above figures indicate exothermic
and endothermic reactions respectively

Heat of formation: Heat of formatiom of a compound is the heat change that occurs when one
mole of a compound is formed from its elements in their standard states. The standard
condition are 25Oc and 1 atm. The heat of formation of water is -286kJmol -1. The equation is
given below: H2(g) + ½O2(g0 → H2O(l) ΔHf = -286kJmol-1

Heat of combustion: This is the heat evolved when one mole of a substance is completely burnt
in oxygen under state condition. The heat of combustion of carbon is -393kJmol -1

Example:

Calculate the heat of reaction in the equation below given that the heat of combustion of
carbon and hydrogen are -393kJmol -1 and -286kJmol-1 respectively and heat of formation of
butane is -125kJmol-1.

13
C4H10(l) + O 4CO2 + 5H2O(l)
2 2(g) →

Solution

△H = ∑ HP - ∑ HR
= [-393+(-286)] - (-125+0)

= -2877kJmol-1

NOTE: The enthalpy of formation of an element is zero

EVALUATION

1. Differentiate between exothermic and endothermic reaction.

GENERAL EVALUATION

OBJECTIVE TEST:

1. Endothermic reaction may be defined as except

(a) Reaction in which heat is absorbed

(b) Reaction in which heat is released’
(c) Reaction in which H is positive
(d) Reactant than energy of the reactant.
2. Rate of chemical reaction depends on the following factors except.

(a) Rate at which gas is evolved

(b) Rate at which products are formed
(c) Rate at which colour of reactions change.
(d) Rate at which the reactants diminish.

3. The unit of rate of chemical reaction is (a) Moldm-3S-1 (b) Mol-1S-1 (c) Mol-1 (d) Smol-1

4. The rate of a reaction is proportional to the number of effective collisions occurring per
second between the reactants. This statement is associated with the.

(a) Kinetic theory (b) rate law (c) atomic theory (d) collision theory

5. Which of the following statement is not true about the reaction between dilute hydrochloric
acid and marble chips calcium trioxocarbonate(IV)?

(a) It is faster after three seconds than it is after ten seconds.

(b) It slows down with time.
(c) It eventually stops.
(d) It proceeds at a constant rate
ESSAY QUESTIONS

1. Use the arguments of the collision theory to explain how the following factors affect the rate
of a chemical reaction. (i) concentration (ii) surface area

2. (a) State in three short sentences the main ideas of the collision theory.

3. State how the rate of a chemical reaction is affected by the following factors.

(a) Concentration (b) surface area

4. (i) What is a catalyst?

(iii) Write a relevant equation to show the industrial process in which V 2O5 was used
as a catalysts.

5. Explain briefly how temperature affects the rate of a chemical reaction.

WEEK 4

TOPIC: CHEMICAL REACTIONS

CONTENTS:

1. CHEMICAL EQUILIBRIUM:

2. CHARACTERISTICS OF A CHEMICAL SYSTEM AT EQUILIBRIUM,

3. LE CHATELIER’S PRINCIPLE AND FACTORS AFFECTING EQUILIBRIUM OF CHEMICAL REACTION

4. EQUILIBRIUM CONSTANT, KC

PERIOD 1: CHEMICAL EQUILIBRIUM

Studies have shown that some reactions are such that all the reactants are never completely
converted into products. In such reactions, the products are converted into the reactant as they
are been formed.

A reaction is said to be reversible, if it can be made to proceed forward and backward, under a
given set of conditions.

For a chemical reaction involving a gas to be reversible, it must be carried out in a closed vessel,
i.e. an isolated or closed system. Two opposing arrows in a chemical equation represent a
reversible reaction:

a) H2O(l) H2O(g)

b) N2(g) + 3H2(g) 2NH3(g)

c) CaCO3(s) CaO(s) + CO2(g)

Such reactions usually have relatively low activation energies for the reverse reactions.

A reaction in which the products cannot readily be combined to give the reactants is said to be
irreversible. In such a reaction, a single arrow is used pointing to the product(s), e.g.
combustion reactions
a) C(s) + O2(g) →
CO2(g)

b) 2Mg(s) + O2(g) → 2MgO(s)

Such reactions usually have relatively high activation energies for the reverse reaction.

REACTIONS AT EQUILIBRIUM
Dynamic Equilibrium
When the rates of forward and backward reactions in a reversible reaction are equal, the
reaction is said to be at equilibrium. At equilibrium, both the forward and backward reactions
are still going on, but because there rates are the same, the concentrations of the reactants and
products do no longer change with time. Hence, chemical equilibrium is dynamic and not
static.
How to Identify a Reaction at Equilibrium
At equilibrium, certain observable properties become constant depending on the type of
reaction. Such properties include;
 Concentrations of the reactants and products;
 Pressure of gases;
 Density or intensity of colour of a solution;
 Temperature of the system.
EVALUATION
1. When is a reaction said to be reversible?
2. Describe a natural process that is reversible.

PERIOD 2: CHARACTERISTICS PROPERTIES OF A SYSTEM AT EQUILIBRIUM

1. Equilibrium is dynamic; that is,
 The reactants and products are present at equilibrium, i.e. equilibrium can be achieved
from either direction:

H2(g) + I2(g) 2HI(g)

 2HI(g) H2(g) + I2(g)
2. The concentrations of the reactants and the products, pressure, density or intensity of
colour, and the temperature of the system are constant- depending on the type of the reaction.
3. The rate of forward and backward reactions are equal.
4. The equilibrium position is not affected by the presence of the catalyst, it only quickens the
rate at which equilibrium is achieved.
5. At equilibrium, the free energy change, ∆G, of the reaction is zero.
6. A system at equilibrium will resist a change.

Information Obtained from an Equilibrium Equation

Consider a typical reversible reaction:

N2(g) + 3H2(g) 2NH3(g) ∆H = - 92kJ

The following information can be obtained:
1. The two opposing reactions are occurring at the same time – as indicated by the opposing
double arrow.
2. The two opposing reactions are at equilibrium.
3. The amounts, in moles, of the reactants and products at equilibrium are proportional to the
stoichiometry in the balanced equation.
4. The forward reaction is exothermic (∆H is negative; hence, the backward (or reverse)
reaction will be endothermic (∆H is positive), i.e.

2NH3(g) N2(g) + 3H2(g) ∆H = + 92kJ

EVALUATION
1. What is meant by an equilibrium system?
2. Give three properties of a chemical system at equilibrium.

LE CHATELIER’S PRINCIPLE
Le Chatelier’s principle stares that if an external constraint such as a change to temperature,
pressure or concentration is imposed on a chemical system in equilibrium, the equilibrium will
shift so as to annul or neutralize the constraint.

FACTORS AFFECTING EQUILIBIUM OF A CHEMICAL REACTION

1. EFFECT OF A CHANGE IN TEMPERATURE e.g. For the following systems at equilibrium

(a) 2SO2(g) + O2(g) ⇌ 2SO3(g) H = - 395.7 KJmol –1

The forward equation is exothermic i.e. it involves increase in temperature whereas the
backward equation is endothermic or it involves decrease in temperature.

If the temperature of the system is increased:

Increase in the temperature of the system will shift the equilibrium position o backward
reaction, that is, reactant formation is favoured.

Increasing the temperature of the system will shift the equilibrium position to the left,
favouring the backward reaction i.e. reactants formation (i.e. SO2 and O2).

If the temperature of the system is decreased:

Decrease in the temperature of the system will cause the equilibrium position to shift to the
right favouring the forward reaction, that is, product formation.

(b) N2(g) + O2 ⇌ 2NO(g) ΔH = +90.4KJmol –1

When the system is at equilibrium, the forward reaction is endothermic and the backward
reaction is exothermic.

If the temperature of the system is increased:

Increase in the temperature of the system will cause the equilibrium position to shift to the
right favouring forward reaction. i.e. product formation.

If the temperature of the system is decreased:

Decrease in the temperature of the system will cause the equilibrium position to shift to the left
favouring the backward reaction.

2. EFFECT OF A CHANGE IN PRESSURE:

For a change in pressure to affect a chemical system in equilibrium.

(a) One of the reactants in the or products in the reversible reaction must be gaseous.
(b) The total number of gaseous molecules on the left side of the equation must be
different from the total number of moles of gaseous molecules on the right side.

For the following systems at equilibrium

(a) 3H2(g) + N2(g) ⇌ 2NH3(g)

The forward reaction is from high pressure to low pressure and the backward reaction is from
low pressure to high pressure.

Increase in pressure of the system:

When the pressure of the system is increased the equilibrium position will shift to the right
favouring the forward reaction that is, the product formation.

Decrease in the pressure of the system:

When the pressure of the system is decreased the equilibrium position will shift to the left
favouring the backward reaction that is reactant formation.

(b) N2O4(g) ⇌ 2NO2(g)

When the system is at equilibrium, the forward reaction involves an increase in the pressure of
the system and the backward reaction involved a decrease in the pressure of the system.

If the pressure of the system is decreased:

A decrease in the pressure of the system will cause the equilibrium position to shift to the right
favouring the forward reaction that is, product formation.
If the pressure of the system is increased:

An increase in the pressure of the system will cause the equilibrium position to shift to the left
favouring the backward reaction that is, reactant formation

(c) H2(g) + I2(g) ⇌ 2HI(g)

A change in pressure will not affect this system at equilibrium because the number of moles of
the reactants is the same as the number of moles of the product.

(d) 3Fe(s) + 4H2O(g) ⇌ Fe3O4(s) +4H2(g)

A change in pressure will not affect this system at equilibrium because the number of moles of
gaseous reactant and product is the same.

3. EFFECT OF A CHANGE IN CONCENTRAION

E.g. 3Fe(s) + 4H2O (g) ⇌ Fe3O4(s) + 4H2(g)

If the concentration of any of the reactants is increased the equilibrium position will shift to the
right but if it is decreased it will shift to the left.

Also removal of any of the reactant or product will also cause the equilibrium position to shift.
E.g. removal of hydrogen gas from the system will cause the equilibrium position to shift to the
right.

4. EFFECT OF A CATALYST

Addition of a catalyst to a system in equilibrium will not affect the equilibrium position. Instead,
addition of catalysts will only make equilibrium state to be reached attained faster.

EQUILIBRIUM CONSTANT, KC

In a reversible reaction, there is a fixed relationship, at constant temperature, between the

concentrations in moldm-3 of the products and the reactants. This relationship is accounted for
in the study carried out by Guldberg and Waage. This law, known as the Law of Mass Action
states that at constant temperature, the rate of reaction is proportional to the active masses
(concentration raise to the power of its coefficient) of each of the reactants.

EXPRESSION OF EQUILIBRIUM CONSTANT, KC

In a reaction: aA + bB ⇌ cC +dD

The equilibrium constant KC is expressed as follows:

c d
[C] [D]
KC = a B . In the cause of a chemical reaction, it the concentration of gases and aqueous
[ A] [B]
species the normally change. The concentrations of solid and pure liquid are always constant,
hence, thay cannot appear in equilibrium constant expression.

Note: The species must be written in a square bracket as shown above e.g. in the reaction:

(a) 2SO2(g) + O2(g) ⇌ 2SO3(g)

The equilibrium expression

KC = ¿ ¿ ¿

(b) N2(g) +3H2(g) ⇌ 2NH3(g)

2
KC = [ NH 3]
¿¿

(c). CaCO3(s) ⇌ CaO(s) + CO2(g)

KC = ¿ ¿ ]

IMPORTANCE OF KC

KC determines the yield of chemical reaction at equilibrium. If Kc is greater than one, it more
product is formed 1.e forward reaction is favoured. But if Kc is less than one, it less product is
formed (poor yield) i.e backward reaction is favoured. Kc is temperature dependent and change
with change in temperature.
RELATIONSHIP BETWEEN KC AND △G

Free energy (G) is the energy for doing useful work. Gibb’s free energy cannot be measured
directly but the change in free energy is usually measured. Change in free energy determines
the spontaneity of a given reaction. For a spontaneous reaction, △G is negative.

△G = -RTInKc. Where n = no of mole of specie, R = gas constant (8.314Jmol -1K-1 and T =

temperature in Kelvin

EVALUATION:

1. Write the expression for the equilibrium constant KC for the following

(a) 2H2(g) + O2(g) ⇌ 2H2O(g)

(b) 2CO(g) + O2(g) ⇌ 2CO2(g)

GENERAL EVALUATION:

OBJECTIVE TEST:

1. Two boys balanced in a sea-saw game is an example of

(a) Static equilibrium (b) dynamic equilibrium (c) homogenous equilibrium (d) mutual
equilibrium

2. In the reaction, 2SO2(g) + O2(g) ⇌ 2SO3(g)

(a) The reaction is in physical equilibrium

(b) Contact process

(c) The reaction is the rate determining step

3. In the decomposition of CaCO3(s) ⇌ CaO(s) + CO2(g)

The reaction will attain dynamic equilibrium

 (a) When the reaction is in open system
(b) When the reaction is heated strongly
(c) When the reaction is in a closed system
(d) When the reaction is catalysed

4. Factors affecting equilibrium reaction include the following except.

(a) Pressure (for solid system)

(b) Concentration

(c) Temperature

(d) Pressure (for gaseous system)

5. All except one is not a condition for considering pressure in an equilibrium system.

(a) There must be concentration gradient between the reactants and the products.

(b) The reactants could be gas while the products may be solids

(c) Both products and reactants must be gaseous.

(d) The reaction takes place in a closed system

ESSAY QUESTIONS

1. What is the effect of each of the following on the equilibrium position of the system
indicated below?

A(s) + B(g) ⇌ C(g) Δ H = - xKLmol-1

(a) Cooling the system
(b) Removing
(c) As soon as it is formed

2. Write the expression of equilibrium constant for

 2AB2(g) + B2(g) ⇌ 2AB3(g)

3. Consider the reaction represented by the equation

N2O4(g) ⇌ 2NO2(g) △H = +57.2KJmol-1

(a) When is the reaction said to be at equilibrium
(b) Mention two conditions that can favour the forward reaction.
(c) Name the principle involved in (b) above
(d) Addition of catalyst.