ELECTROLYSIS

Electrolysis is a process of decomposing a substance using electrical energy.

.i.e Some ions are Discharged during electrolysis.
To Discharge-is to remove charge..ie. Ions change into atoms.

e.g Cu2+ + 2e- Cu (s) (reduction)

4OH- 2H2O + O2 + 4e- (oxidation)

Substance / materials which conduct electricity are;

✓ Metals-Conduct by movement of free/delocalized electrons (metallic bonding).

✓ Graphite (which is carbon)-It has delocalized electrons which carry electric current.

✓ Ionic compounds- conduct by movement of ions. They can only conduct in molten
state (liquid) or when dissolved in water (aqueous) because ions are free to move.

NB; ionic compounds do not conduct in solid state unlike metals and graphite
because their ions are strongly attracted to each other in a giant lattice structure.

An electrolytic cell is used to demonstrate conduction by electrolytes.

An Electrolytic cell.
+ - Cell

Bulb

Anode Cathode

--- ----
Electrolyte

Electrodes

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PARTS OF ELECTROLYSIS CELL

✓ An electrolyte is a compound in solution or molten state which can conduct an

electric current.

✓ Electrodes are electric conducting materials like copper, platinum and carbon
rods. They are classified as;

Anode-it is connected to the positive terminal of a cell/battery.

It attracts anions during electrolysis.

Cathode- It is connected to the negative terminal of a cell/battery.

It attracts cations during electrolysis.

Types of electrodes

i) Inert electrodes-they are unreactive. .eg. Carbon and Platinum electrodes.

ii) Active/reactive electrodes-They react or are corroded during electrolysis. .eg.
Copper metal electrodes ionize during electrolysis forming Copper (ii) ions in
solution. This causes copper anode to reduce in size.
e.g. Cu (s) Cu2+ + 2e-

ELECTROLYSIS OF MOLTEN LEAD BROMIDE,PbBr2(l)

It is a liquid hence during electrolysis the following occurs;

Lead ions (Pb2+) migrate to the cathode. They are discharged forming lead atoms.

Bromide ions (Br-) migrate to the anode. They are discharged forming bromine
atoms/ (diatomic hence forms bromine gas)

IONS IN LIQUID LEAD (II) BROMIDE

PbBr2 (s) Pb2+ ( ) + 2Br- ( )

Cathode and Anode reactions

a) At the cathode (-ve)

Pb2+ ions are attracted and discharged;

Pb2+ + 2e- Pb (s) [Reduction]

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b) At the anode (+ve)

Br- ions are attracted and discharged.

2Br- Br2 + 2e- [oxidation]

OBSERVATIONS

Bubbles are produced and a brown gas is seen at the anode because bromine gas is
produced.

OVERALL ELECTROLYSIS EQUATION

Redox reaction; reduction + oxidation

[Cathode + Anode]

Pb2+ + 2e- Pb(s)

Br- Br2 + 2e-
．．．． ． ．．．． ．．．．． ．．．
Pb2+ + 2Br- Pb(s) + Br．2

Question
Show the ions in liquid, reaction at the cathode and anode for electrolysis of
molten (liquid) sodium chloride.

Soln
a. At the anode (+ve )

Cl- ions are attracted and discharged.

2Cl- Cl2 + 2e- [oxidation]

b. At the cathode (-ve)

Na+ ions are attracted and discharged.

Na+ + 1e- Na(s) [reduction]

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 Overall equation

2Na+ + 2e- 2Na(s)

2Cl- Cl2 + 2e-

2Na + 2Cl- 2Na + Cl2

Observation
Bubbles of a yellow gas (Cl2) are produced at the anode.

ELECTROLYSIS OF AQUEOUS SOLUTIONS

Aqueous means dissolves in water. Water takes part during electrolysis of salt
solutions, salts, acids and alkalis influence water molecules to separate into hydroxide
(OH-) and hydrogen ions (H+).

.eg. H2O (l) H+ (aq) + OH- (aq)

H+ and OH- ions can also be discharged at the electrodes during electrolysis.

Copper (ii) sulphate solution has the following ions;

✓ Cu2+ and SO42- from copper (ii) sulphate.

✓ H+ and OH- ions from water.

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RULES OF SELECTIVE DISCHARGE

a) CATHODE RULES (-ve)

During electrolysis, ions of least reactive metals are selected and discharged first.
e.g

discharged Cu2+ e.g [Cu2+ + 2e- Cu(s) ]

first

H+ eg. [2H+ + 2e- H2 ]

Na+ [Ion of more reactive metal very difficult to discharge]

The above summary is obtained from the electrochemical series which is shown on
the next page.

ELECTROCHEMICAL SERIES may also be used

ATOM IONS
K K+
Na Na+
Ca Ca2+
Mg Mg2+
Al Al3+
Zn Zn2+
Fe Fe2+/3+
H H+
Pb Pb2+
Cu Cu2+

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 b) ANODE (+ve)

Halides first (I-, Br-, Cl-, F-,), -for concentrated solutions.

e.g [2Cl- Cl2 + 2e- ]

Hydroxides (OH-) eg. [4OH- 2H2O + O2 + 4e- ]

Others (NO 3-, SO42-etc, difficult to discharge)

✓ NB .For dilute solutions, hydroxide ions are discharged first. This is because
concentration can also influence discharge of ions. Ions in high
concentration are always discharged first.
✓ Type of electrode used can also influence discharge of ions. Reactive electrodes always
form ions in solution during electrolysis.

ELECTROLYSIS OF COPPER (II) SULPHATE SOLUTION using inert

electrodes

Inert electrodes: carbon or platinum

Ions in solution

a. From CuSO4 we have Cu2+ and SO 42-

b. From water we have H+ and OH-

At the Anode (+ve)

SO42- and OH- ions migrate to the anode. OH- ions are selectively discharged forming
water and oxygen gas.

4OH- (aq) 2H2O (l) + O2(g) + 4e-

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Observation

Bubbles of oxygen gas were produced.

Cathode (-ve)

Cu2+ and H+ ions migrates to the cathode, Cu2+ ions are selectively discharged forming
red-brown copper metal.

Cu2+ (aq) + 2e- Cu(s) [red-brown]

Observations

The cathode is coated by red brown colour of copper. The solution gradually charges
from blue to colorless.

NB; The solution becomes acidic because H+ and SO 42- ions remain in solution.

OVERALL ELECTROLYSIS REACTION EQUATION

4OH- 2H2O + O2 +4e-

[Cu2+ +2e- Cu (s)] × 2 (multiply by two to cancel electrons)

4OH- 2H2O + O2 + 4e -
2Cu2+ + 4e -
2Cu (s)

2Cu2+ + 4OH- 2H2O + 2Cu(s) + O2

ELECTROLYSIS OF COPPER SULPHATE SOLUTION using copper electrodes

NB; copper electrodes are reactive

Ion in solution-

From CuSO4 we have Cu2+ and SO42-

From water we have H+ and OH-

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 ANODE (+ve)

SO42- and OH- ions are attracted to the anode.

• the ions remains undischarged
• instead the copper anode is corroded forming copper(ii) ions

.ie. Cu(s) Cu2+ + 2e-

More Cu2+ are formed by the anode hence the solution remains blue.

CATHODE (-ve)

Cu2+ and H+ ions are attracted to the cathode. Cu2+ ions are selectively discharged
forming copper.

.ie. Cu2+ + 2e- Cu (s)

OBSERVATION

✓ Anode is corroded
✓ Cathode is coated with red-brown copper.
✓ The solution remains blue or the intensity of the blue colour increases because for every
Cu2+ ions discharged at the cathode, a new Cu2+ is formed at the anode.

NB: Loss in mass by the anode equal to gain in mass by the cathode

ELECTROLYSIS OF DILUTE SULPHURIC ACID OR WATER.

IONS IN SOLUTION;

a) For H2SO4 = 2H+ and SO 42-

b) For H2O = H+ and OH-

AT THE ANODE (+ve)

SO42- and OH- ions migrate to the anode. OH- ions are selectively discharged forming
water and Oxygen gas.

4OH- 2H2O + O2 + 4e-

OBSERVATION

Bubbles of oxygen gas produced. More gas is produced at the cathode than anode
(Why?).

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AT THE CATHODE (-ve)

H+ ions migrate to the cathode and are discharged forming hydrogen gas.

2H+ + 2e- H2 (g)

OBSERVATION
Bubbles of hydrogen gas produced.

OVERALL ELECTROLYSIS EQUATION

4OH- 2H2O + O2 + 4e-

[2H+ + 2e- H2 ] × 2

4OH- 2H2O + O2 + 4e-

4H+ + 4e- 2H2

………………………………………………………………..
4OH- + 4H+ 2H2O + O2 + 2H2

NB; The volume of hydrogen gas produced is twice that of oxygen gas. The mole ratio is
2H2: 1O2.
The two gases can be collected using the Hoffmann voltameter.

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Hofmann Voltameter.

- +

RE ; concentration can also determine ions to be discharged. .i.e. ions in high

concentration are always preferred than those at low concentration.

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 ELECTROLYSIS OF CONCENTRATED AQUEOUS SODIUM CHLORIDE
(INERT ELECTRODES)

Ions in solution;

From NaCl = Na+ and Cl-

From H2O = H+ and OH-

ANODE (+ve)

Cl- and OH- ions migrate to the anode. Cl- ions are selected and discharged forming
chlorine gas (solution is concentrated hence there are more Cl- ions than OH-.

Observation

Bubbles of a yellow gas produced.

CATHODE
Na+ and H+ ions are attracted. H+ ions are selectively discharged forming hydrogen gas.

2H+ + 2e- H2

QUESTION 1
1. Show all the process that occurs during electrolysis of dilute aqueous HCl
between inert electrolysis.
2. Show all the process that occurs during electrolysis of concentrated HCl between
inert electrolysis.

FACTORS AFFECTING PREFERENTIAL DISCHARGE OF IONS

a) CONCENTRATION

Ions in high concentration are always discharged first than those at low concentration.

SOLUTION Ions in Anode reaction Cathode reaction

solution
Dilute HCl H+ , Cl- 4OH- 2H2O + O2 + 2H+ + 2e- H2
H+ , OH- 4e-

Conc. HCl H+ , Cl- 2Cl- Cl2 + 2e- 2H+ + 2e- H2

H+ ,OH-

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b) The ease with which ion of metals gain electrodes to form stable atom. i.e.
Electrochemical series is used.
.e.g. Ions of less reactive metals are discharged first. For mixture of Cu2+, H+ , Cu2+ ions
are Selectively discharged. .eg.
Cu2+ + 2e- Cu

c) Types of electrodes used

Reactive electrodes (anode) are corroded during electrolysis.
Example
Solution Ions in sol Electrodes Anode Cathode
2+ 2-
CuSO4 Cu ,SO 4 Platinum 4OH- 2H2 + O2 Cu2+ + 2e- Cu
H+ ,OH- (inert) +4e-
CuSO4 Cu2+ SO42- Copper Cu Cu2+ + 2e- Cu2+ + 2e- Cu
+ -
H , OH

USES OF ELECTROLYSIS

1. ELECTROPLATING- It is the coating of a metal with a thin layer of another

metal.

REASONS
• to make a metal more attractive
• to prevent rusting/ corrosion of the original metal

Metals commonly used are; silver, copper, gold

STEPS FOR ELECTROPLATING

✓ Make the object ( eg. Ear ring) to be electroplated cathode

✓ Anode should be the same metal you want to electroplate with.
✓ Electrolyte should be a salt solution of a metal used for electroplating.

Example
Copper plating; the ring becomes the ........................ , Copper wire
becomes ................... the electrolyte is made up of a solution
of………………………………………………………..

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Experimental set up
+ -

Bulb

Anode Cathode (ring)

---
Electrolyte ( aq. CuSO4)

Electrodes
2. REFINING/ Purification of metals

EXAMPLE
Refining of copper and gold.

STEPS
✓ Anode should be impure metal.
✓ cathode should be pure metal (e.g copper)
✓ electrolyte should be a salt solution of a metal to be purified (e.g CuSO4 (aq)

Experimental set up.

+ -

Bulb

Anode Cathode ( pure copper)

---
Electrolyte

Electrodes

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Reaction equations:
Anode

Cu Cu2+ + 2e-;

Cathode

Cu2+ + 2e- Cu (s)

NB; Loss in mass of the anode is equal to the gain in mass by the cathode.

3. Extraction of more reactive metals.

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