OXIDATION-REDUCTION

REACTION
 INTRODUCTION
Redox is a type of chemical reaction in which the
oxidation states of atoms are changed. It is
characterized by transfer of electrons between
chemical species, most often with one species
undergoing oxidation while another species
undergoing reduction. Oxidation and
reduction are two complementary terms in
that both occur simultaneously.
 OXIDATION & REDUCTION
1. IN TERMS OF OXYGEN:
• Oxidation is the gain of oxygen.
• Reduction is the loss of oxygen.
The substance that donates oxygen is called
oxidizing agent while the one that accepts the
oxygen is a reducing agent.
 OXIDATION & REDUCTION
2. IN TERMS OF HYDROGEN: Oxidation a reaction
that involves removal of hydrogen from a
substance while reduction involves addition of
hydrogen to a substance. The substance that
donates the hydrogen is known as the reducing
agent (R.A) while the substance that accepts the
hydrogen is known as the oxidizing agent (O.A).
Example,
H2S(g) + Cl2(g) → 2HCl(g) + S(s)
R.A O.A Reduced Subst Oxidized S
OXIDATION –REDUCTION IN TERMS OF HYDROGEN
 OXIDATION & REDUCTION
3. IN TERMS OF ELECTRONEGATIVE ELEMENT: Oxidation
is the addition of electronegative elements and removal
of electropositive elements from a substance while
reduction is the removal of electronegative elements
from a substance as well as the addition of electropositive
elements to a substance. Electronegative elements are
those elements that ionize by electron gain while
electropositive elements are those elements that ionize
by electron loss. Example,
2Na(s) + Cl2(g)→ 2NaCl(s)
R.A O.A
H2S(g) + Br2(g)→ 2HBr(g) + S(s)
 ADDITION OF ELECTRONEGATIVE
ELEMENTS
In a reaction where two electronegative elements
are present, the more electronegative of the two is
regarded as the oxidizing agent.
Elements:
(Non-metals) F, O, Cl, N, Br, S, C, I, P
→ Electronegativity decreases
(Metals) K, Na, Ca, Mg, Al, Zn, Fe, Pb, Cu
→ Electropositivity decreases
 OXIDATION & REDUCTION
4. IN TERMS OF ELECTRON TRANSFER: Oxidation is a loss of
electron(s) while reduction is gain of electron(s). A substance is
reduced when it gains electrons and oxidized when it loses
electrons. During oxidation, a substance loses electron(s) and its
oxidation number increases in the positive direction and vice versa.
The substance that loses electron(s) is known as the reducing
agent (R.A).
 The substance that gains electron(s) is known as the oxidizing
agent (O.A). Example:
Iron (II) chloride reacts with chlorine to form iron (III) chloride.
2FeCl2(s) + Cl2(g)→ 2FeCl3(s)
R.A O.A
4FeO(s) + O2(g)→ 2Fe2O3(s)
R.A O.A
 ELECTRON TRANSFER

In the above reaction, magnesium reduces the

copper(II) ion by transferring electrons to the ion
and neutralizing its charge and therefore acts as a
reducing agent while the Cu2+ is the oxidizing
agent.
 OXIDIZING AGENT

This is a substance that;

 supplies oxygen to another substances
 can supply an electronegative element to another substance
 accepts electrons
Examples include:
1. Oxygen
2. Halogens eg chlorine, bromine, fluorine
3. Hydrogen peroxide
4. Sulphur (IV) oxide
5. Potassium tetraoxomanganate (VII) (KMnO4)
6. Potassium heptaoxodichromate (VI) (K2Cr2O7)
7. Concentrated H2SO4
8. Concentrated HNO3
9. Iron(III) salts eg FeCl3
 TESTS FOR OXIDIZING AGENTS
Action on iron(II) chloride
When an oxidizing agent is added to iron(II) ion
(Fe2+), the Fe2+ donates electron to the oxidizing
agent and the green colour of Fe2+ changes to
brown due to oxidation to Fe3+
Fe2+ → Fe3+
Green brown
Action on H2S
When H2S is passed through an oxidizing agent,
yellow deposit of sulphur is formed as the sulphide
ion donates 2 electrons to the oxidizing agent.
 REDUCING AGENT

This is a substance that:

 Removes oxygen from another substance
 Can remove electronegative elements from a substance or the
one that can add electropositive element.
 Can lose electrons. Examples are;
1. Hydrogen
2. Metals,
3. Carbon
4. Carbon (II) oxide (CO)
5. Hydrogen sulphide
6. Sulphur (IV) oxide (SO2)
7. Hydrogen peroxide (H2O2)
8. Iron(II) salts e.g FeCl2
9. Lithium aluminium hydride (LiAlH4)
 TESTS FO R REDUCING AGENTS
Action on acidified KMnO4
Reducing agents change the purple colour of
KMnO4 to colourless as the MnO4- (purple) is
reduced to Mn2+ which is colourless

Action on acidified K2Cr2O7

Reducing agents change the orange colour of
K2Cr2O7 to green as the Cr2O72-(orange) is
reduced to Cr3+.
 REDOX REACTION

Redox reaction is basically a reaction that

involves transfer of electrons from the reducing
agent to the oxidizing agent. Oxidation occurs at
the anode where the anions lose electrons. This
reaction at the anode is known as anodic half-
reaction. The cathodic half-reaction takes place
simultaneously at the cathode is a reduction
reaction since the cations gain electrons.
 REDOX REACTION
Reaction between potassium iodide solution and
iron(III) tetraoxosulphate (VI). The reaction
mixture turns brown due to the liberation of
iodine.
2KI(aq) + Fe2(SO4)3(aq) → I2(s) + K2SO4(aq) + 2FeSO4(aq)

Which is represented ionically as:

2I-(aq) + 2Fe3+(aq) → I2(s) + 2Fe2+(aq)

 OXIDATION NUMBER
Oxidation number or oxidation state is the total number of electrons
that an atom either gains or loses in order to form a chemical bond
with another atom.
[Link] elements in the free or uncombined state have an oxidation
number of zero. E.g Ko, Nao, Cl2o, P4o, S8o etc.
2. The oxidation number of a simple ion has the same size and sign as
the charge of the ion
3. When an ion consists of more than one element, its oxidation
number is the sum of the oxidation numbers of all the elements in
the ion..
4. The sum of all the oxidation numbers of elements in a compound is
zero
5. The oxidation number of hydrogen is +1 (except in metallic
hydrides where the oxidation number is -1
6. The oxidation number of oxygen is -2 (except in peroxides where
 OXIDATION NUMBER
1. Find the oxidation number of chromium atom in potassium
heptaoxodichromate (VI), K2Cr2O7
2[Oxidation number of K] + 2[Oxidation number of Cr] +
7[Oxidation number of O] = 0
2[+1] + 2[Cr] + 7[-2] = 0
+2 + 2Cr - 14 = 0
2Cr + 2 - 14 = 0
2Cr - 12 = 0
2Cr = 12
Cr = 12
2
Cr = +6
The oxidation number of chromium atom in potassium
heptaoxodichromate (VI) is + 6.
 OXIDATION NUMBERS
Determine the oxidation number of Mn in MnO4-
SOLUTION
Equate the oxidation number of elements to the net
charge in the compound.
MnO4- = -1
Mn + 4[-2] = -1
Mn + [-8] = -1
Mn - 8 = -1
Mn = -1 + 8
Mn = +7
Name : Tetraoxomanganate (VI) ion
 OXIDATION STATE OF CENTRAL ATOM
ANIONS CENTRAL ATOM OXIDATION STATE OF IUPAC NAME
CENTRAL ATOM

CO32- Carbon +4 Trioxocarbonate (IV) ion

SO32- Sulphur +4 Trioxosulphate(IV) ion

SO42- Sulphur +6 Tetraoxosulphate(VI)

ClO3- Chlorine +5 Trioxochlorate(V) ion

ClO- Chlorine +1 Oxochlorate(I) ion

NO2- Nitrogen +3 Dioxonitrate(III)

NO3- Nitrogen +5 Trioxonitrate (V)

 BALANCING REDOX EQUATION
Steps
1. Write down the oxidizing and reducing agents
and the products.
2. Write the half-equations for the oxidation and
reduction. Balance the atoms and charges.
[Link] the electron loss in the oxidation half-
equation and the ones gained in the reduction
half-equation.
[Link] the half- equations to eliminate the
electrons and get the overall redox equation.
 EXAMPLE 1

1. Balance the half reduction equation

MnO4- → Mn2+
 EXAMPLE 2
• Balance the ionic equation for the redox
reaction between acidified potassium
tetraoxomanganate(vii) and iron (ii)
tetraoxosulphate(vi)
(a)MnO4- →Mn2+
(b)Fe2+ →Fe3+
BALANCING OF REDOX REACTION IN ACIDIC MEDIUM
1. Write a balanced ionic equation for the redox reaction
between acidified heptaoxodichromate (VI) ion and
chloride ion.
Solution
(a). Heptaoxodichromate (VI) ion is the oxidizing agent, so
it is reduced to chromate (III) ion as shown below:
Cr2O72-(aq) → Cr3+(aq)
(b) Chloride ion is the reducing agent, so it is oxidized to
chlorine atom.
2Cl-(aq) → Cl2(g)
 BALANCING OF REDOX REACTION IN ACIDIC MEDIUM
(c). Balance the number of atoms and charges as shown below:
(i). Reduction half- cell reaction:
Add correct number H2O to balance oxygen atoms and of H+ to
balance hydrogen atoms on the appropriate and add
corresponding number of mole of electron to balance the
charge.
Cr2O72-(aq) + 14H+(aq) + 6e- → 2Cr3+(aq) + 7H2O(l)
Total number of charges on the left hand side = -2 + 14 -6 = +6
Total number of charges on the right hand side = +6

(b) Oxidation half – cell reaction:

2Cl-(aq) → Cl2(g) + 2e-
 BALANCING OF REDOX REACTION IN ACIDIC MEDIUM
STEP 4
Balance the number of electrons loss in oxidation
half – cell reaction to correspond to the number of
electron gain in reduction half – cell reaction.
Multiply the oxidation half cessll reaction by 3
6Cl-(aq) → 3Cl2(g) + 6e-
Therefore, the number of electron loss in oxidation
half cell equation is equal to the number of electron
gain in reduction half cell reaction.
BALANCING OF REDOX REACTION IN ACIDIC MEDIUM
STEP 5:
Add the two half cell reactions to eliminate the
number of electrons as shown below:
Cr2O72-(aq) + 14H+(aq) + 6e- → 2Cr3+(aq) + 7H2O(l)
And
6Cl-(aq) → 3Cl2(g) + 6e-
Overall net reaction:
Cr2O72-(aq) + 14H+(aq) + 6Cl-(aq) → 2Cr3+(aq) + 3Cl2(g)
+ 7H2O(l)
 HINT;
NOTE: H+ and H2O used to balance the number of
oxygen and hydrogen, since the reaction occurs
in the acidic medium, by adding both on the
appropriate sides.
However, to balance redox reaction that takes
place in alkaline solution is slightly different from
those that occur in acidic solution. All the steps
are the same, except the second step where OH-
is used instead of H+ to balance the oxygen and
hydrogen.
 BALANCING OF REDOX EQUATION IN ACIDIC
MEDIUM
2. Balance the following redox equation in acidic
solution with the smallest whole number
coefficients possible. What is the sum of all the
coefficients? (Do not forget coefficients of one.)
Cu + SO42- → Cu2+ + SO2 (in acidic solution)
3. When the following equation is balanced with the
smallest possible set of integers, what is the sum of
all the coefficients? (Do not forget coefficients of
one.)
Cr2O72- + H2S → Cr3+ + S (in acidic solution)
MnO4- + I- + H+ → I2 + Mn2+
 REDOX EQUATION IN ALKALINE MEDIUM

Balance the following in basic or alkaline

medium
1. Cr3+ → CrO42-
2. Ag(s)+Zn2+(aq)→Ag2O(aq)+Zn(s)
 REDOX EQUATION IN ALKALINE MEDIUM
1. Write a balanced ionic equation for the redox
reaction between tetraoxomanganate (VII) ion,
MnO4- and hydrazine, N2H4 in alkaline solution.
STEP 1:
Tetraoxomanganate (VII) ion (MnO4- ) is the oxidizing
agent, so it is reduced to manganese (IV) oxide as
shown below;
MnO4- → MnO2 (Reduction reaction)
Hydrazine, N2H4 is reducing agent, since it is oxidized
to Nitrogen as shown below;
N2H4 → N2 (Oxidation reaction)
 REDOX IN ALKALINE MEDIUM
STEP 2
(a). Reduction half-cell equation:
MnO4- → MnO2
(b) Oxidation half-cell equation:
N2H4→ N2
Balance the number of atoms and charges by adding the correct
number of OH- and H2O on the appropriate side:
(c)Reduction half – cell equation:
Balance the number of oxygen atom by adding H2O to the RHS
MnO4- → MnO2 + 2H2O
Balance the number hydrogen atom by addition of equal moles of
water to the LHS
MnO4- + 4H2O → MnO2 + 2H2O
 REDOX IN ALKALINE MEDIUM
(d) Balance the oxygen and hydrogen by adding equal
moles of OH- to the RHS
MnO4- + 4H2O → MnO2 + 2H2O + 4OH-
Balance the number of electron and collect like terms
MNO4- + 4H2O + 3e- → MnO2 + 2H2O + 4OH-
Combine H2O together;
MNO4- + 2H2O + 3e- → MnO2 + 4OH-
Oxidation half-equation
N2H4 + 4OH- → N2 + 4H2O
Balance the number of charges:
N2H4 + 4OH-→ N2 + 4H2O + 4e-
 REDOX IN ALKALINE MEDIUM
STEP 4
Balance the number of electron gain in reduction half – cell
reaction to correspond to the number of electrons loss in
oxidation half – cell reaction.
(a)Reduction half – cell equation:
MnO4- + 2H2O + 3e- → MnO2 + 4OH-
Multiply the equation by 4,
4MnO4- + 8H2O + 12e- → 4MnO2 + 16OH-
(b) Oxidation half – cell equation:
N2H4 + 4OH- → N2 + 4H2O + 4e-
Multiply the equation by 3,
3N2H4 + 12OH- → 3N2 + 12H2O + 12e-
-
 REDOX IN ALKALINE MEDIUM
STEP 5
Add the two half - cell equation together to eliminate the number of
electrons.
(a)Reduction half – cell equation:
4MnO4- + 8H2O + 12e-→ 4MnO2 + 16OH-
(b) Oxidation half – cell equation:
3N2H4 + 12OH-→ 3N2 + 12H2O + 12e-
Net Equation:
4MnO4- + 8H2O + 3N2H4 +12OH-→ 4MnO2 + 16OH- + 3N2 + 12H2O
Eliminate the excess OH- and H2O
4MnO4- + 3N2H4 → 4MnO2 + 3N2 ­+ 4OH- + 4H2O
 Class activity
[Link] the following half- reaction in alkaline
medium:
Cr3+ → CrO42-
[Link] the following redox equation:
Cr2O72- + C2O42- → Cr3+ CO2
 EXAMPLE 2
Balance the following equation in alkaline medium
Cr3+ → CrO42-
SOLUTION
Balance the oxidation no by adding 3e- to the RHS
Cr3+ + → CrO42- + 3e-
Balance the atoms of O and H by adding H2O
Cr3+ + 4H2O → CrO42- + 3e-
Balance the no of H atom by adding equal no of H2O and OH-
molecule required to balance hydrogen i.e 8H2O and 8OH- at the
RHS and LHS respectively.
Cr3+ + 4H2O + 8OH- → CrO42- + 3e- + 8H2O
Subtract duplication of H2O on both sides.
Cr3+ + 8OH- → CrO42- + 8H2O + 3e-
 EXAMPLE 3
(a).Write out the reaction between permanganate ion and
sulfite ion in basic solution and balance it.
MnO4- + SO32- → MnO2 + SO42-
(b). What is the sum of all the coefficients? (Do not forget
coefficients of one.)
MnO4- → MnO2 (reduction half eqn.)
MnO4- + 2H2O + 3e- → MnO2 + 4OH-
SO32- → SO42- (oxidation half eqn.)
SO32- + 2OH- → SO42- + H2O + 2e-
Combining the 2 equation when like terms are collected:
2MnO4- + H2O + 3SO32- → 2MnO2 + 2OH- + 3SO42-
Sum of the coefficient = 2 + 1 +3 + 2 + 2 + 3 = 13
 QUESTION
Write a balanced
equation for the redox
reaction between
trioxonitrate (V) acid and
hydrogen sulphide.
 SOLUTION
Unbalanced Equation:
HNO3(aq) + H2S(g)→ NO(g) + S(s) + H2O(l)
STEP 1
Determine the oxidation number of each element.
HNO3(aq) + H2S(g)→ NO(g) + S(s) + H2O(l)
I III
N = +5 S = -2 N = +2 S=0
 SOLUTION
STEP 2
The oxidation number of nitrogen
changes from +5 to +2 (a decrease in the
positive oxidation number by +3,
representing reduction) while that of
sulphur changes from -2 to 0 (an increase
in positive oxidation number by +2,
representing oxidation).
 SOLUTION
STEP 3
Since the increase in oxidation number of sulphur is not
equal to the decrease in the oxidation number of N. It
means that 3 atoms of sulphur must react with 2 atoms of
nitrogen as shown below:
2HNO3(aq) + 3H2S(g)→ 2NO(g) + 3S(s) + H2O(l)
The number of 8 hydrogen atoms on the reactant side has
to be balanced by adding 4 molecules of water on the
product side of the equation.
2HNO3(aq) + 3H2S(g) → 2NO(g) + 3S(s) +
4H2O(l)
 IONIC THEORY
1. Arrhenius Theory: Arrhenius proposed that
when a substance (acid, base or salt) is melted
or dissolved in water, some if not all of the
substance breaks up (dissociate) into freely
moving charged particles called ions. The
process of dissociation into ions is known as
ionization. Ionization occurs before the passage
of electric current into the electrolyte as the
atoms move about at random in all direction.
The number of electric charges carried by an ion
is equal to its valency.
 IONIC THEORY
2. Modern Ionic Theory: The modern ionic
theory proposes that an ionic compound
consists of oppositely charged ions even in
the solid-state.
This proposes that the ions in ionic solids are
pulled away from one another either as a result
of the heat energy applied when the solid
melts, or with the help of the solvent molecules
when the solid dissolve. Thus
Arrhenius Theory: NaCl(s) → Na+(aq) + Cl-(aq)
Modern theory: Na+Cl-(s) → Na+(aq) + Cl-(aq)
 DIFFERENCES BETWEEN ELECTROVALENT
COMPOUNDS AND COVALENT COMPOUNDS
ELECTROVALENT COMPOUNDS COVALENT COMPOUNDS
They do not contain molecules but They consist of molecules
ions
They are solids at room They are gases or volatile liquids at
temperature room temperature
They have high melting and boiling They have low melting and boiling
points points

They are soluble in water and They are usually soluble in no-
other polar solvents. polar solvent like benzene

They are good conductors of They do not conduct electricity

electricity when in molten state or
in solution
 ELECTROLYTES AND NON- ELECTROLYTES

An electrolyte is a compound in molten or

solution form that conducts electricity and gets
decomposed in the process. For a compound to
behave as an electrolyte, it must be in solution
or molten form. Electrolytes conduct electricity
by the movement of ions to the electrodes and
their subsequent reactions at the electrode.
Electrolytes are classified into two:
Strong electrolytes
Weak electrolytes
 STRONG ELECTROLYTES
A strong electrolyte dissociates completely to form ions
in the molten or aqueous state. They are good
conductors of electricity.
Examples :
Most soluble salt solutions e.g NaCl, CuSO4 e.t.c
Mineral acids like HCl, HNO3, H2SO4
Alkali solutions e.g NaOH, KOH.
NOTE: Sodium chloride dissociates completely in
aqueous solution to form sodium ions and chloride ions.
NaCl(aq) → Na+(aq) + Cl-(aq)
 WEAK ELECTROLYTES
Weak electrolytes dissociate incompletely or partially
to form ions in the molten or aqueous state. They do
not conduct electricity readily.
Examples:
Aqueous ammonia- Solution of ammonia in water
contains only a small proportion of ammonium and
hydroxide ions.
NH4OH(aq)↔ NH4+(aq) + OH-(aq)
Water
Most organic acids such as ethanoic acid, citric acid
and tartaric acid.
 NON- ELECTROLYTES
These are those substances which do not conduct
electricity under any condition since they do not
ionize. They are mostly covalent and organic
compounds.
Example:
Urea,
Benzene,
 Cane sugar
Trichloromethane,
Ether
Tetrachloromethane.
 DIFFERENCES BETWEEN CONDUCTOR AND
ELECTROLYTE
.
GET READY
 C.E 4

1(a). Define electrolyte. (4 mks)

(b). Classify electrolyte and give 2 examples of
each class. (10 mks)
2. Draw and label an electrolytic cell. (10 mks)
 ELECTROLYTIC CELL
This is an assemblage of two electrodes in an
electrolyte used for electrolysis. It is made up
of electrolyte, electrodes and the container.
 ELECTRODES
These are the poles through which current or electron enters
or leaves a solution. They include:
ANODE: The positive pole through which current enters into an
electrolyte or pole through which electrons leave an
electrolyte. Oxidation occurs at the anode.
CATHODE: The negative terminal through which current leaves
an electrolyte or through which electrons enter into an
electrolyte. Reduction occurs at the cathode during
electrolysis.
 ELECTROLYSIS
Electrolysis is the chemical decomposition of
a compound in solution or molten form by
the passage of current through it. This
process can be used to separate a substance
into its original components or elements.
In Electrolysis, an electric current is sent
through an electrode and into solution in
order to stimulate the flow of ions necessary
to run an otherwise non-spontaneous
reaction .
 STAGES IN ELECTROLYSIS
1. Ionization of the compound
2. Migration of ions to the electrodes
3. Discharge of ions at the electrodes
 MECHANISM OF ELECTROLYSIS
During electrolysis a electrolyte is decomposed into
positive and negative ions. Positive ions called
cations are migrated to the cathode (negative
electrode), and accept electron from cathode and
become neutral in charge. This is called reduction.
The negative ions called anions migrate towards the
anode (positive electrode),lose electron and become
neutral. This is called oxidation.
In case where are there are more than one positive
and negative ions, which will preferably gain or lose
electrons depends on their respective discharge
potential of the ions.
FACTORS THAT AFFECT THE DISCHARGE OF
IONS DURING ELECTROLYSIS
1. The position of ion in electrochemical series.
2. The concentration of ion.
3. The nature of electrode.
 POSITION OF IONS IN THE ELECTROCHEMICAL SERIES
Electrochemical series is the or arrangement of elements
in the order of their increasing or decreasing reactivity.
Ions lower in the electrochemical series are discharged
in preference to those higher up in the series. A cation
which is lower in the electrochemical series (less
electropositive) will show a greater tendency to be
discharged than another which is higher up (more
electropositive). The more electropositive a metal is,
the more it has the greater tendency to give up
electron(s). So, it is expected that it will have the least
tendency to accept electron(s) and remain in solution
as a positive ion while the less electropositive metal
becomes discharged as a neutral atom.
ELECTROCHEMICAL SERIES
 POSITION OF IONS IN THE ELECTROCHEMICAL
SERIES

In a solution containing Cu2+ and Na+, Cu2+ has higher

tendency of getting discharged at the cathode
than Na+ because Cu2+ is lower in the series.
 POSITION OF IONS IN THE ELECTROCHEMICAL
SERIES
H+ ion will be discharged in preference to Zn2+ ion in
solution where both are present in the same
concentration during electrolysis.
Therefore, the more electronegative an ion is, the
greater the tendency to accept electrons.
Conversely, it will be expected to have the least
tendency to donate or give up electrons to the
anode. In a solution containing SO42- and OH- ions,
the OH- will be discharged in preference to the SO42-
which is left behind as a negative ion.
REACTIVITY SERIES OF
METALS
 CONCENTRATION OF IONS
Increase in concentration of a given ion tends to
promote its discharge from solution. The influence of
concentration is effective only when the two competing
ions are closely positioned in the electrochemical series,
while it is minimal if the ions are widely spread in their
positions.

For instance in the electrolysis of brine (concentrated

sodium chloride solution), Cl- ions is discharged at the
anode in preference to OH- ion due to the higher
concentration of Cl- over OH- and the closeness in their
position in the series.
 NATURE OF ELECTRODE

Inert electrodes do not take part in electrolytic reaction.

Platinum and carbon (graphite) usually behave as inert
electrodes, though platinum is attacked by liberated
chlorine and carbon attacked by liberated oxygen. Some
electrodes however influence the discharge of ions because
they have strong affinity for certain ions. For example in the
electrolysis of aqueous sodium chloride using platinum
electrodes, H+ ions are preferentially discharged in
accordance with its position in the electrochemical series. If
on the other hand a mercury cathode is used, the mercury
will associate itself with the Na+ ions to form the sodium
amalgam (Na/Hg).
Na+(aq) + Hg(l) + e- → Na/Hg(l)
 NATURE OF ELECTRODE CONT’D
For example, the electrolysis of copper (II)
tetraoxosulphate(VI) using copper anode,
neither SO42- nor OH- is discharged. Instead,
copper (II) atoms from the anode go into
solution as Cu2+ ions because the copper
atoms will give up their electrons more
readily than SO42- or OH-. This principle is
applied in the extraction and purification of
some metals.
 ELECTROLYSIS
OF
SOME COMPOUNDS
 ELECTROLYSIS OF ACIDIFIED WATER OR DIL H2SO4
Acidified water is aqueous solution of H2SO4.
Ions present:
H2SO4 H 2O
Cations: 2H+(aq) H+(aq)
Anions: SO42-(aq) OH-(aq)
Position in e.c.s : OH- is lower than SO42-
At Cathode: H+ will migrate there and each accept electron to form neutron atom which
combine in pairs to form hydrogen gas.
2H+(aq) + 2e- → H2(g)
At Anode: Both SO42- and OH- migrate to the anode where OH- is preferentially discharged.
The OH- combine in pair to form water and oxygen. The oxygen atoms combine in
pairs to form oxygen gas.
4OH-(aq) → 2H2O + O2(g) + 4e-
Over all reaction: 4H+(aq) + 4OH-(aq) → 2H2O(l) + O2(g) + 2H2(g)
4H2O → 2H2O(l) + O2(g) + 2H2(g)
2H2O → O2(g) + 2H2(g
NOTE: If the carbon or graphite electrode is used as anode, it should be changed at
interval because the oxygen liberated attacks (burns) it.
 HOFMAN VOLTMETER

It is a convenient form of apparatus for collecting the

gases liberated during the electrolysis of various liquids.
 ELECTROLYSIS OF CuSO4 SOLUTION
1. USING AN INERT ELECTRODE(GRAPHITE OR PLATINUM)
CuSO4 solution contain CuSO4 and H2O
Ions present: CuSO4 H2O
Cations: Cu2+(aq) H +(aq)
Anions: SO42-(aq) OH -(aq)

Position of ions in e.c.s: Cu2+ is lower than H+ and OH- is lower than SO42-
At Cathode: Cu2+ and H+ ions will migrate to the cathode but Cu 2+ will be
preferentially discharged and each accept 2 electrons from the cathode to
form metallic copper.
Cu2+(aq) + 2e– → Cu(s)
At Anode: Both SO42- and OH- migrate to the anode where OH- is preferentially
discharged.
4OH-(aq) → 2H2O + O2(g) + 4e-

Overall reaction: 2Cu2+(aq) + 4OH-(aq) → 2Cu(s) + O2(g) + 2H2O(l)

NOTE: With time, the blue colour of the solution keeps fading away.
 ELECTROLYSIS OF CuSO4 SOLUTION
2. USING COPPER ELECTRODE:
CuSO4 solution contain CuSO4 and H2O
Ions present: CuSO4 H2O
Cations: Cu2+(aq) H+(aq)
Anions: SO42-(aq) OH-(aq)

Position of ions in e.c. s : H+ is higher than Cu2+ and OH- is lower than SO42-

At Copper Cathode: Cu2+ and H+ ions will migrate to the cathode but Cu2+ will be
preferentially discharged and each accept 2 electrons from the cathode to form
metallic copper.
Cu2+(aq) + 2e– → Cu(s)
At Copper Anode: The copper anode dissolves into the solution as Cu2+ leaving electrons
behind
Cu(s) → Cu2+ (aq) + 2e-
The gradual ionization of the copper anode into the solution keeps the solution blue
because the Cu2+ ions from the anode replace the ones deposited at the cathode from
the solution. The process leads to increase in the thickness of the cathode and
reduction in the size of the anode.
Overall reaction: Cu(s) + Cu 2+(aq) → Cu2+(aq) + Cu(s)
 ELECTROLYSIS OF CuSO4 SOLUTION

Before electrolysis After electrolysis

 ELECTROLYSIS OF DIL SOLUTION OF NaCl
3. USING INERT ELECTRODE:
NaCl solution contains NaCl and H2O
Ions present:
NaCl H 2O
Cations: Na+(aq) H+(aq)
Anions: Cl-(aq) OH-(aq)
Position of ions in e.c.s : Na+ is higher than H+ and OH- is lower than Cl-
At Cathode: Na+ and H+ ions will migrate to the cathode but H+ will be preferentially
discharged. The hydrogen atoms pair up to give hydrogen gas
2H+ + 2e- → H2(g)
At Anode: Both Cl- and OH- migrate to the anode where OH- is preferentially
discharged. The OH- combine in pair to form water and oxygen. The oxygen atoms
combine in pairs to form oxygen gas.
4OH-(aq) → 2H2O + O2(g) + 4e-
Overall reaction : 4H+(aq) + 4OH-(aq) → 2H2O(l) + O2(g) + 2H2(g)
4H2O → 2H2O(l) + O2(g) + 2H2(g)
2H2O → O2(g) + 2H2(g
This causes the solution to be more concentrated and at a point, chlorine gas starts
getting discharged at the anode.
 ELECTROLYSIS OF CONC NaCl (BRINE)

4. USING PLATINUM ELECTRODE:

NaCl solution contains NaCl and H2O
Ions present: NaCl H 2O
Cations: Na+(aq) H +(aq)
Anions: Cl-(aq) OH -(aq)
Position of ions in e.c.s : Na+ is higher than H+ and OH- is lower than Cl-
At Cathode: Na+ and H+ ions will migrate to the cathode but H+ will be
preferentially discharged. The hydrogen atoms pair up to give hydrogen gas
2H+ + 2e- → H2(g)
At Anode: Both Cl- and OH- migrate to the anode where Cl- is preferentially
discharged due to its high concentration to give chlorine gas.
2Cl-(aq) → Cl2(g) + 2e-
NOTE: Sodium ions Na+(aq) (from the dissolved sodium chloride) and
hydroxide ions OH– (aq) (from the water) stay behind and form sodium
hydroxide solution, NaOH(aq)
Over all reaction: 2HCl(g) → H2(g) + Cl2(g)
Platinum electrode should be changed at interval because the chlorine
produced attacks it.
 ELECTROLYSIS OF CONC NaCl
USING MERCURY ELECTRODES:
Na+ ions are discharged at the cathode because of the affinity of
mercury to sodium. The sodium metal will be coated on the
mercury cathode to form an alloy called sodium amalgam.
At the cathode: Na+(aq) + Hg(l) + e- → Na/Hg(l
The sodium amalgam is separated by reaction with water
where it decomposes into NaOH, H2 and Hg.
The mercury gotten is recycled.

At the Anode: 2Cl-(aq) → Cl2 + 2e-

Over all reaction:
2Na+ +2Hg + 2Cl- → 2Na/Hg + Cl2(g)
 ELECTROLYSIS OF MOLTEN NaCl
USING INERT ELECTRODE:
At the Cathode:
Sodium ions migrate to the cathode, where electrons enter the
melt and are reduced to sodium metal:
Na++ e−→ Na(s)
At the Anode:
Chloride ions migrate the other way, toward the anode. They give
up their electrons to the anode and are oxidized to chlorine
gas:
2Cl−→ Cl2 + 2e−
The overall reaction is the breakdown of sodium chloride into its
elements:
2Na+(aq) + 2Cl-(aq)→ 2Na(s) + Cl2(g)
 FARADAY’S LAWS OF ELECTROLYSIS
First law: The mass (m) of an element deposited
at the electrodes during electrolysis is directly
proportional to the quantity(Q) of electricity
passing through it.
Mα Q
Q = I x t where I = current, t= time in seconds, M=
mass
.
GRAPH OF FARADAY’S 1ST LAW
 FARADAY’S LAWS OF ELECTROLYSIS
Second law: It states that, when the same quantity of electricity
is passed through several electrolytes, the relative number of
moles of the elements discharged are inversely proportional
to the charges on the ions of the elements.
I Faraday = 1 mole of electrons and
2 Faradays = 2 moles of electrons etc.
 EXAMPLES 1
1. What mass of magnesium would be obtained by passing a current of
2 amperes for 2 hours 30 minutes, through molten magnesium
chloride?
[1 faraday = 96500C, Mg = 24]
Current (I) = 2A; Time (t) = 2 hours 30 minutes = 9000 secs
Q = It
= 2 x 9000 = 18000C
1 F = 96500C
x = 18000C
x = 18000/96500 = 0.19F
Mg2+ + 2e− → Mg
2F → 24g
0.19F → x
2x = 24 x 0.19
x = 24×0.19/2 = 2.28g
 EXAMPLE 2
Calculate the mass of silver deposited at the cathode
during the electrolysis of silver trioxonitrate(V) solution
if a current of 0.10 amps was used for 10 minutes.
(1F =96500 C, Ag = 108).
Solution
Q=Ixt
I= current in amps , t = time in seconds
Q= 0.10 x 10 x 60 = 60C
Equation for the reaction at the cathode:
Ag+ + e- → Ag(s)
1 mol of electrons gives 1 mol of silver( Ag),
96500 coulombs give 108 g of silver.
Then 60C will give: x 108 g = 0.067 g
 EXAMPLE 3
Calculate the volume of hydrogen produced (measured at room temperature
and pressure) during the electrolysis of dilute tetraoxosulphate (VI) acid if
current of 1.0 amp was used for 15 minutes.
[ 1F = 96500 C, molar volume of a gas at room temp = 24 dm3.]
SOLUTION
Q = current in amps x time in seconds
= 1.0 x 15 x 60 = 900C
Equation for the reaction at the cathode:
2H+ + 2e- → H2(g)
2 mol of electrons give 1 mol of hydrogen gas (H2), then two moles of electrons
require 2 faradays .
⇒2 x 96500 = 193000C
193000 give 24 dm3
The 90C will give

= 0.11 dm3
 EXAMPLE 4
How long would it take to deposit 0.635 g of copper at the cathode
during the electrolysis of copper(II) tetraoxosulphate (VI) solution
if you use a current of 0.200 amp. [1F= 96500 C, Cu = 63.5]
Equation at the cathode:
Cu2+(aq) + 2e- → Cu(s)
2 mol of electrons give 1 mol of copper requires 2F= 193000C
Then 193000C give 63.5 g of copper.
x will give 0.635g of Cu
X=

X = 1930C But Q = I x t
Q = current in amps x time in seconds
1930 = 0.200 x t
t = 1930/0.200 = 9650 seconds.
How long would it take to deposit 0.635 g of
copper at the cathode
during the electrolysis of copper(II)
tetraoxosulphate (VI) solution if you use a
current of 0.200 amp. [1F= 96500 C, Cu =
63.5]
How long would it take to deposit 0.635 g of
copper at the cathode
during the electrolysis of copper(II) sulphate
solution if you use a
current of 0.200 amp
 EXAMPLE 5
A given quantity of electricity was passed through 3 electrolytic cells connected in series containing solutions of
AgNO3, CUSO4 and NaCl respectively. If 10.5g of copper are deposited on the second cell. Calculate:
(a). The mass of silver deposited at the first cell.
(b). Vol of chlorine liberated at the third cell at stp.
[Ag = 108, Cu= 63.5, 1F = 96500C]
Solution
Cu2+(aq) + 2e- → Cu(s)
2F produced 63.5 g of Cu
Then 10.5g of Cu require 10.5 X 193000C/63.5 = 31913.4 C of electricity.
(a). Mass of silver deposited
Ag+(aq) + e- → Ag(s)
1 F will produce 108g of Ag
Then 31913C of electricity will produce

= 35.7g of Ag
(b). 2Cl- → Cl2 + 2e-
2F give mole of Cl2 gas = 2x 96500= 193000C
193000C liberate 22.4dm3, of chlorine gas (22.4 dm3= 22400cm3)
Then 31913.4C will liberate
= 3704cm3 of chlorine at s t p

+
++t.p
 EXAMPLE 4
In the electrolysis of copper sulphate solution using carbon electrodes, what
mass and volume of oxygen would be formed at the positive electrode if
254g of copper was deposited on the negative electrode? [Cu = 63.5, O =
16]
SOLUTION
Cu2+(aq) + 2e- → Cu(s) and 4OH-(aq) - 4e- → 2H2O(l) + O2(g)
It takes a transfer of 2 moles of electrons to form 1 mole of solid copper (63.5g)
from 1 mole of copper(II) ions, Cu2+
and a transfer of 4 moles of electrons to form 1 mole of oxygen from 4 moles of
hydroxide, OH- ions.
Therefore the expected mole ratio of Cu(s) : O2(g) from the electrolysis is 4: 2
which is 2 : 1 ( based on the no of mole of electron is inversely proportional
to the charge )
The moles of Cu deposited = 254/63.5 = 4 moles
so moles oxygen formed = 2 moles, since Mr(O2) = 2 x 16 = 32
• mass of oxygen formed = 2 x 32 = 64g
• and volume of oxygen = 2 x 24 = 48 dm3
1.2F of electricity are passed through three
electrodes of cells containing Na+, Cu2+ and Al3+ in
series. Calculate the mass of each of the metal
that would be formed at the cathode of each of
the cells.
[Na = 23, Cu =63.4, Al =27, 1F =96500C]
 USES OF ELECTROLYSIS
1. Electroplating. This is the process of coating the surface layer of metal
with another type of metal. Precious metal such as, gold, silver, nickel and
chromium are used to coat cutlery, jewelry and cheap metals.
Importance of electroplating
i. Protection of metals against corrosion.
ii. Giving shiny appearance to articles.
iii. Giving reflecting properties to reflectors.
For example, cutlery, statues, and jewelry made of cheaper metals are
coated with expensive metals like gold and silver to enhance their look.
2. Extraction of metals like sodium, potassium, aluminium from their ores.
3. Refining of Metals: During extraction of metals by electrolysis, the
anode is made of the extracted metal. Pure metal is deposited at the
cathode. The metal to be refined is made the anode
 ELECTRODE POTENTIAL MEASUREMENT
Electrode potential is the electromotive force (e.m.f) of a galvanic
cell built from a standard reference electrode called standard
hydrogen electrode (SHE). Standard hydrogen electrode is
defined to have a potential of zero volts.
 If the electrons flow from the hydrogen electrode to the metal
electrode, the value
is positive .
 If the electrons flow
From metal electrode
to the hydrogen
electrode, the value
is negative.
 ELECTRODE POTENTIAL MEASUREMENT
1. COPPER SYSTEM:
When copper plate is immersed in a solution of copper ion e.g CuSO 4
solution, each copper ion in the solution acquire two electrons from the
plate and gets deposited as metallic copper on the plate.
Cu2+(aq) + 2e- → Cu(s)
This makes the plate to become positively charged while the solution
becomes negatively charged. This creates the potential difference
between the solution and the plate called electrode potential of copper.
2. ZINC SYSTEM:
If zinc plate is immersed in a solution containing zinc ion e.g ZnSO 4 solution,
the zinc metal go into solution and the electrons remain on the plate.
Zn(s) → Zn2 (aq) + 2e-
This makes the zinc plate to become negatively charged while the solution
becomes positively charged. Then the potential difference between the
solution and the zinc plate is established.
 ELECTRODE POTENTIAL OF
COPPER AND ZINC

Copper Zinc
STANDARD ELECTRODE POTENTIAL
It is the potential difference set up between a
metal and a one-molar solution of its ions at
25oC. Electrode potentials differ from one
metal or ion to another. It is dependent on:
 Energy change
 Concentration of ions in the solution
 Temperature
ELECTRODE POTENTIAL OF COPPER
 C. E 1
1. Briefly explain the electrolysis of CuSO4
solution using copper electrode.
2. State 2 uses of electrolysis
3. What mass of sodium would be obtained by
passing a current of 0.2 amperes for 1hours 10
minutes, through molten magnesium chloride?
[1 faraday = 96500C, Na = 23]
 CALCULATING E.M.F OF A CELL
E.m.f cell = Eocathode – EoAnode
EXAMPLE 1:
Given that the electrode potential of copper to be +0.34V and
that of zinc to be -0.76V. Calculate the e.m.f of the cell.
Solution
E.m.f cell = Eocathode – EoAnode
EoCu = +0.34V, EoZn= -0.76V
Then E.m.f cell = +0.34 –(-0.76)
= +1.10V
This means that the system is spontaneous i.e. electricity can
be generated.
If the Eo is negative, it is non-spontaneous which means that
electricity cannot be generated in that cell.
 ELECTROCHEMICAL CELL
An electrochemical or voltaic or galvanic cell is a
device that converts chemical energy to electrical
energy.
It is made up of:
Anode: This is the negative electrode where oxidation
occurs.
Cathode: The positive electrode where reduction
occurs.
The electron flow from the anode to the cathode
while the current flow from the cathode to the
anode.
 ELECTROCHEMICAL CELL
.
ELECTROLYTIC AND ELECTROCHEMICAL
CELLS

Electrolytic cell
Electrochemical cell
 COMPARISON BETWEEN ELECTROLYTIC
AND ELECTROCHEMICAL CELLS
ELECTROLYTIC CELL ELECTROCHEMICAL CELL
1. They convert electrical energy to They convert chemical energy into
chemical energy. electrical energy

2. Anode is the positive electrode while Cathode is the positive electrode while
cathode is the negative one anode is the negative electrode

3. Electrons flow from the battery to Electron flow from the anode to the
the cathode and come out from the cathode
anode

4. Oxidation occurs at the anode while Oxidation occurs at the anode while
reduction occur at the cathode reduction occur at the cathode

5. External source of power is needed Electricity is generated within the cell

because the redox reaction is non- because the redox reaction is spontaneous
spontaneous
ELECTROCHEMICAL CELL
 SALT BRIDGE
A salt bridge laboratory device used to connect the
oxidation and reduction half-cells of a galvanic cell.
It may be made of filter paper soaked in sodium or
potassium chloride solution or ammonium
trioxonitrate (V) solution. The functions are;
1. To complete the electric circuit.
2. To enable the movement of ions from one half-cell
to the other or to maintain electrical neutrality in
the solutions when current flows.
Zn(s)|Zn2+(aq) || Cu2+(aq)|Cu(s)
Anode (left) Cathode (right)
|| means salt bridge
SALT BRIDGE

A B
 HOW SALT BRIDGE WORKS
In beaker A, the Cu2+ accepts electrons and gets
deposited as metallic copper at the cathode.
This makes the solution to be negatively charged.
The negatively charged solution is neutralized by
SO42- ions moving into the salt bridge and Na+ or K+
from the bridge into the solution.
In beaker B, the zinc atom give up electrons and go
into solution. This makes the solution to become
positively charged. The solution is neutralized by
migration of the Zn2+ into the bridge and
movement of Cl- from the bridge into the solution.
TYPES OF ELECTROCHEMICAL CELLS
They include;
1. Primary cells: These are the cells that cannot
be recharged when discharged. Examples
include: Daniel(wet cell), Leclanche (dry cell)
and mercury cells.
2. Secondary Cells: They are the cells that can
be recharged when discharged. They include
lead acid accumulator, alkaline, lithium-ion
battery (phone) cells.
 PRIMARY CELL
1. Leclanche cell: This is a dry cell whose anode is made of zinc
while the cathode is graphite (carbon) and the electrolyte is
ammonium chloride.
At the Anode: Each zinc atom loses 2 electrons (oxidation) and go
into the electrolyte as positively charged ion(Zn2+). This is
oxidation.
Zn(s) → Zn2+ + 2e-
The electrons pass through the circuit to generate electricity.
At the Cathode: Each NH4+ from the electrolyte accepts electron to
form NH3 and H2(reduction). The H2 gas formed is removed by
the manganese (IV) oxide which serves as a depolarizer.
2NH4+ + 2e- → 2NH3(g) + H2(g)
The formation of hydrogen gas at the cathode causes polarization
of the cell and when it accumulates, the cell stops working.
Alkaline cells
LECLANCHE CELL
LECLANCHE CELL
 PRIMARY CELLS CONT’D
2. Daniel cell: This is a wet cell containing copper and zinc
electrodes in CuSO4 and zinc in ZnSO4 electrolytes
respectively separated with a porous pot. It is not portable.
At the Anode: Zn electrode dissolve into the solution to form
Zn2+ and electrons.
Zn → Zn2+ + 2e– (oxidation)
At the cathode: Each Cu2+ from the solution accepts 2
electrons from the anode to form metallic copper.
Cu2+(aq) + 2e– → Cu(s) (reduction)
The net cell reaction is
Zn + Cu2+ → Zn2+ + Cu(s)
Cell is represented as
Zn/Zn2+ || Cu2+/Cu
DANIEL CELL
DANIEL CELL
 MERCURY CELL
In a mercury cell, mercury compound acts as a cathode where
reduction reaction occurs and the zinc compound acts as an
anode, where oxidation reaction takes place. Sodium hydroxide
or potassium hydroxide is used as an electrolyte and it ionizes
in a molten state to conduct electricity.
 SECONDARY CELLS
1. Lead Acid accumulator (Car battery)
Here the anode is metallic lead while the cathode is lead (IV) oxide (PbO 2)
and the electrolyte is dilute H2SO4.
At the Anode: During discharging process, the lead go into solution to form
Pb2+ which combine with SO42- ion in the electrolyte to form PbSO4. This
causes the released electrons to go through the circuit to generate
electricity.
Pb(s) → Pb2+ + 2e-, (Oxidation)
Pb2+ + SO42- → PbSO4(s)
At the Cathode: The electrons from the anode are accepted by the cathode
where the PbO2 and H+ from the electrolyte get reduced to form Pb 2+ and
H2O. The Pb2+ combine with SO42- ion from the electrolyte to form PbSO4
PbO2(s) + 4H+ + 2e- → Pb2+ + 2H2O (Reduction)
Pb2+ + SO42- → PbSO4(s)
When both electrodes are covered with PbSO4 deposits, the battery stops
working until it is recharged.
LEAD ACID ACCUMULATOR
CHARGING OF LEAD ACID CELL
 CHARGING OF LEAD ACID CELL
During recharging of lead acid accumulator, the
anode of the cell is connected to the cathode of
the external source and the cathode of the cell is
connected to the anode of the external source.
After the recharging, the density of the
electrolyte returns to 1.25g/dm3 and the emf
returns to 2.2V
 ALKALINE RECHARGEABLE CELL
The cathode is made of manganese (IV) oxide
while anode consists of zinc powder dispersed
in an electrolyte while the electrolyte is
potassium hydroxide.
LITHIUM-ION BATTERY
 ADVERSE EFFECTS OF ELECROCHEMICAL PROCESS
1. CORROSION: This is the deterioration of metals in the presence of
oxygen. Example include rusting of iron where iron corrodes in the
presence of oxygen and water or moisture to form brown
hydrated iron (III) oxide (Fe2O3.xH2O).
At the Anode: Iron oxidizes to give iron(II) ions.
Fe(s) → Fe2+(aq) + 2e-
At the Cathode: Oxygen from the air gets dissolved in the water
layer. Because of the high concentration of oxygen in water, the
oxygen is reduced by the electrons from the anode to give OH -.
O2(aq) + 2H2O(l) + 4e- → 4OH- (aq)
The Fe2+ from the anode combines with OH- from the cathode to
form iron (II) hydroxide (Fe(OH)2) which gets oxidized to rust
(Fe2O3.xH2O) in the presence of more oxygen.

4Fe2+(aq) + O2(g) + (2+4x)H2O → 2Fe2O3⋅xH2O + 4H+

 CATHODIC PROTECTION
This is the prevention of corrosion of a metal surface by
making it the cathode of an electrochemical cell. For
instance, zinc can be used to protect iron from
rusting by a process called galvanization. Zinc being
higher than iron in the electrochemical series serves
as anode in this case thereby undergoing oxidation
instead of iron. This implies that the iron will start
rusting only when the zinc has deteriorated
completely.
NOTE: Tinning (use of tin to coat iron) cannot be used
to protect iron because when scratched, iron is
higher in the series and therefore acts as anode
where oxidation occurs while the tin acts as cathode.
 SACRIFICAL PROTECTION
By this method, a more electropositive (or more
reactive) metal (e.g. Zn or Mg) is made the anode and
the iron, the cathode. A conducting wire is connected
between them.
Replacing the sacrificial electrodes is more cheaper
than replacing the iron objects they are protecting.
SACRIFICAL PROTECTION
 C.E. 2
1. In a tabular form, give 3 differences between
electrolytic and electrochemical cells.
2. Briefly explain electrochemical cells.
3. State 2 functions of salt bridge.