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ELECTROCHEMISTRY
ELECTROLYSIS
Electrical conductors – can be divided into two groups
(i) Metals and graphite NB: Plastics, glass, rubber are non-conductors
(ii) Electrolytes

(i) Metals conduct in the solid and liquid states. Their electrical conduction is due to the presence of
mobile electrons. Graphite also contains mobile electrons.
NB: No chemical changes occur when metals or graphite conduct an electric current.

In the absence of an When an electrical field is applied, electrons move

electrical field, the net towards the positive end of the applied field.
movement of electrons in Simultaneously, electrons leave the negative end of
any one direction is zero, the field from the battery or DC supply and enter the
and no current flows metal. Hence the number of free electrons in the
metal remains constant. Conduction takes place at
the speed of light

(ii) Electrolytes are either (i) aqueous solution of (or molten) ionic compounds or (ii) aqueous
solution of certain polar covalent compounds e.g. ethanoic acid. Based on their extent of
ionisation, electrolytes can be divided into:-

(a) Strong electrolytes - these are completely ionised in aqueous solution e.g. ionic
compounds, strong acids e.g. H2SO4 and strong alkalis e.g. NaOH.
NaCl (aq) → Na+ (aq) + Cl-(aq)
H2SO4 (aq) → 2H+ (aq) +SO42-
NaOH (aq) → Na+ (aq) + OH-(aq)

(b) Weak electrolytes these are partially ionised in aqueous solution

e.g. Weak acids e.g. CH3COOH and weak alkalis e.g. NH3 (aq)
CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)
NH3(aq) + H2O(ℓ) ⇌ NH4+(aq) + OH−(aq)

NB: Solid ionic compounds do not conduct electricity because the ions are rigidly and tightly
held in a crystal lattice by strong bonds. However, ions are freed when the solid melts or when
it is dissolved in water.
It is these mobile ions which are responsible for conduction in electrolytes.

NB: Acid anhydrides e.g. SO3, CO2, HCl are non-conductors (covalent compounds) but form
electrolytes in aqueous solution
e.g. CO2 (g) + H2O (ℓ) ⇌ H2CO3 (aq)
Non-conductor weak electrolyte

Non-electrolytes are substances which do not conduct electricity when molten or in aqueous solution
e.g. sugar, carbon (iv) chloride (CCl4)/ carbon tetrachloride.
 Electrolysis is the process by which an electrolyte is decomposed by the passage of an electric
current through it.

NB: Electrolysis is a chemical change

The apparatus in which electrolysis is carried out is called an electrolytic cell.
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Electrodes are the points at which current enters and leaves the electrolytic cell and are made of either
graphite or a metal. The electrodes may be: Inert i.e. not taking part in the chemical changes occurring
in electrolysis, or Active i.e. taking part in the chemical changes.
The anode is the positive electrode by which current leaves the electrolyte. (It is connected to the
positive terminal of the power supply or battery.)
The cathode is the negative electrode by which current enters the electrolyte. (It is connected to the
negative terminal of the power supply or battery.)

Discharge of ions during electrolysis

When a current is passed through an electrolyte, the anions move towards the anode and the cations
move towards the cathode.

(a) Before the passage of a current through the electrolyte, there is random
motion of the ions. (b) When a current is being passed through the
electrolyte the ions move towards the electrode of opposite charge

At the anode, the anions lose electrons and form neutral atoms or molecules,
e.g. 2Cl- (aq) - 2e- → Cl2 (g). Hence oxidation occurs at the anode.
At the cathode, the cations gain electrons and form neutral atoms or molecules,
e.g. Cu2+(aq) + 2e- → Cu(s). Hence reduction occurs at the cathode.
The electrons lost at the anode enter the external circuit and re-enter the electrolytic cell at the cathode
via the battery (electron pump). Hence the number of electrons lost at the anode is equal to the number
of electrons gained at the cathode.
NB: The electric current can produce the following types of chemical changes
(1) Deposition of metals at cathode
(2) Evolution of hydrogen at the cathode
(3) Liberation of non-metals at the anode
(4) Metal atoms leaving the anode and entering the electrolyte as metal ions (soluble anode).
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Applications of electrolysis

1. Electrolysis of molten halides.

NB: Silver and lead halides are all insoluble in water
E.g. Electrolysis of molten lead (ii) bromide using graphite electrodes (NB: the electrolyte is
decomposed into its elements).

Crocodile clip

3 Carbon anode
The reddish-brown vapour 4 Carbon cathode. After cooling,
of bromine appears lead can be seen on the cathode

1 Lead (II) bromide. While

2 The crucible is heated. When the
the salt is solid, no current salt melts, the bulb lights, showing
flows through the cell. that an electric current is flowing.
Molten lead (II) bromide is a
conductor
Pipeclay triangle

Electrode reaction at cathode Electrode reaction at anode

Pb2+(ℓ) + 2e- → Pb(ℓ) 2Br−(ℓ) - 2e- → Br2(g)
Shiny bead of red-brown gas
molten lead

Preferential discharge of ions in aqueous solution

(i) In general, if two ions are competing at a given electrode, relative positions in the
electrochemical (reactivity) series determine which ion is preferentially discharged

Cations K+ Na+ Ca2+ Mg2+ Zn2+ Fe2+ Pb2+ H+ Cu2+ Ag+

Most easily discharged
Anions F- SO42- NO3- Cl- Br- I- OH-
Most easily discharged

(ii) Concentration effect – An anion present in a high concentration is more easily discharged than
the same anion in a lower concentration e.g. Cl- ions are not discharged from dilute HCl (aq) acid
but are discharged from concentrated HCl (aq) acid.
(iii) Nature of the electrode – If the anode is made from an unreactive metal such as copper, nickel
or silver, then the anode itself will lose electrons and dissolve in the electrolyte (soluble anode),
as this process is less energetic than the loss of electron from the anions in solution.

2. Electrolysis of dilute sulphuric acid (using platinum or graphite electrodes)

NB: Pure water is not a good conductor of electricity, because it ionises only to a small extent.
H2O (ℓ) ⇌ H+ (aq) + OH- (aq)
For pure water to conduct, a strong electrolyte must be added to it. e.g. H2SO4, NaOH, NaCl.
Cathode (-)/Pt or C H2SO4 Anode (+)/Pt or C
H+ ions discharged ↓ OH- selectively discharged
2H+ (aq) + 2e- → H2 (g) 2H+ SO42- (position in electrochemical series)
2H+ (aq) + 2e- → H2 (g) H+ OH- 4OH- (aq) - 4e- → 2H2O (ℓ) + O2 (g)
(colourless bubbles) ⥮ (colourless
H2O bubbles)

Results: (i) 2 volumes of H2 at cathode: 1 volume of oxygen at anode.

(ii) The electrolyte becomes more concentrated with sulphuric acid as the reaction
proceeds as only water is decomposed.
NB: The electrolysis of dilute sulphuric acid is equivalent to the electrolysis of water.
2H2O (ℓ) → 2H2 (g) + O2 (g)
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Oxygen Hydrogen

Dilute sulphuric acid

Graduated tube

Glass tube

Carbon anode (positive Carbon cathode (negative electrode)

electrode)

Rubber bung

Source of direct current

The electrolysis of dilute sulphuric acid

3. Electrolysis of dilute sodium hydroxide

Cathode/Pt or C Anode (+)/Pt or C

H+ selectively discharged NaOH
(position in E.S) ↓ OH−discharged
2H+(aq) + 2e− → H2(g) +
Na OH −

2H+ (aq) + 2e− → H2(g) H+ OH− 4OH− (aq) − 4e− → 2H2O(ℓ) + O2(g)
(colourless) (colourless)
⥮
H2O
Results:(i) 2 volume of H2 at cathode: 1 volume O2 at anode
(ii) Electrolyte becomes concentrated with sodium hydroxide.

4. Electrolysis of concentrated hydrochloric acid

Cathode (-)/Pt or C HCl Anode/C

H+ ions discharged ↓ Cl− selectively discharged (concentration effect)
2H+(aq) + 2e− → H2 (g) H Cl−
+

(colourless)
H+ OH− 2Cl−(aq) − 2e− → Cl2(g)
(greenish-yellow)
⥮
H2O

Results:(i) 1 volume of H2 at cathode: 1 volume Cl2 at anode

(ii) Electrolyte becomes less concentrated with HCl acid as it is the acid that is being
decomposed.

NB: In practice, less than 1 volume of Cl2 may be obtained as Cl2 is fairly soluble and some of
the gas will dissolve in the electrolyte.

NB: If Cl2 is being liberated at the anode, then the anode must be made of graphite and not a
metal, as chlorine oxidises metals.
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5. Electrolysis of dilute sodium chloride solution

Cathode/Pt or C NaCl Anode (+)/Pt or C
H+ selectively discharged ↓ OH- ions selectively
(due to position in EC. Series) Na Cl-
+
discharged (position in EC. series)
← →
2H+ (aq) + 2e- → H2 (g) H OH-
+

2H+(aq) + 2e- → H2 (g) ⥮ 4OH- (aq) - 4e- → 2H2O (ℓ) + O2

(colourless bubbles) (colourless)
H2O
bubbles)

Discharge of H+ ions from water creates Discharge of OH- ions from

an excess of OH-, hence solution water creates as excess of H+ ions
becomes alkaline (turns litmus blue) around anode. Hence, solution
around cathode becomes acidic (turns litmus red)
around anode

Results:(i) 2 mols of H2 at cathode: 1 mol O2 at anode

(ii) Solution becomes acidic around the anode and alkaline around the cathode.
NB: Process is ≡ to electrolysis of water.

6. Electrolysis of conc. sodium chloride solution (brine)

Cathode (-)/Pt or C NaCl Anode (+)/C
H+ selectively discharged ↓ Cl- ions selectively
(due to position in EC. Series) Na+ Cl- discharged (due to conc. effect)
2H+(aq) + 2e- → H2 (g)(colourless) ← →
H+ OH- 2Cl- (aq) - 2e- → Cl2 (g)green-yellow
Discharge of H+ ions from ⥮
water creates an excess of H2O
OH- ions which along with
the Na+ ions is ≡ to NaOH
being produced around the
cathode
Results:(i) 1 volume of H2 at cathode: 1 volume Cl2 at anode
(ii) NaOH is produced around cathode as a valuable by-product of the process.

7. Electrolysis of copper (ii) sulphate solution – using platinum electrodes

Cathode/Pt CuSO4 (aq) Anode/Pt
Cu2+ selectively discharged ↓ OH- ions selectively
(Position in E.S) ←Cu2+ SO42−→ (Position in E.S)
H+ OH− 4OH−(aq) - 4e− → 2H2O (ℓ) + O2 (g)
Cu2+(aq) + 2e− → Cu(s) ⥮ (colourless
(brown or pink deposit) bubbles)
H2O(ℓ)

Discharge of OH- ions from water

creates an excess of H+ ions which
along with the undischarged SO42-
ions is ≡ the formation of H2SO4
acid around the anode.

Results:(i) Brown deposit of copper on cathode : 1 volume of O2 at anode

(ii) Blue colour of solution gradually fades due to discharge of Cu2+ ions
NB: Cu2+ (aq) ions are blue
(iii) Solution becomes acidic with H2SO4 around anode (turns blue litmus red)
(iv) The electrolyte eventually converts to sulphuric acid with 2 volume H2 evolving at
cathode to 1 volume of O2 evolving at anode
NB: electrolysis stops when there are not enough ions in the electrolyte to conduct an
electric current.
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8. Electrolysis of copper (ii) sulphate solution – using copper electrodes

Cathode/Pt CuSO4 (aq) Anode/Cu
Cu2+ selectively discharged ↓ The copper anode dissolves
(Position in E.S) Cu SO42-
2+
to form Cu2+ ions which enter
H+ OH- the electrolyte (soluble anode)
Cu2+ (aq) + 2e- → Cu (s) ⥮ Cu (s) - 2e- → Cu2+ (aq)
(brown deposit (mass of anode decreases)
H2O(ℓ)

Results:(i) The electrolyte remains constant in mass and colour.

(ii) The mass of copper dissolved from the anode is equal to the mass of copper
deposited on the cathode
NB: The electrolytic process merely transfers copper from the anode to the cathode

ELECTROLYSIS IN INDUSTRY
Electrolysis is used commercially for
(i) The extraction of reactive metals e.g. Na, Al, from their ores
(ii) The extraction of active non-metals e.g. Halogens
(iii) Electroplating e.g. chrome-plating or nickel-plating
(iv) Anodising Aluminium sheets (to make corrosion-resistant articles)
(v) Electrorefining e.g. obtaining pure copper from impure copper

ELECTROPLATING
The purpose of electroplating is to coat objects with a layer of another metal by electrolysis e.g. knives
and forks with silver, and iron knobs with nickel or chromium. The plating prevents rusting and
improves the appearance of the object. Electroplating also avoids the use of expensive metals for
making the articles e.g. gold plated articles are less expensive than those made of pure gold.
Nickel plating - The object to be plated is cleaned and if it is a non-conductor e.g., plastic, painted with
a suspension of graphite in oil. The object is then made the cathode in a nickel (ii) sulphate cell, with a
strip of nickel as the anode. Nickel from the anode deposits on the object

Electrode reaction at anode Electrode reaction at cathode

Ni (s) - 2e- → Ni2+ (aq) Ni2+ (aq) + 2e- → Ni (s)

Object to be plated

Nickel anode

Nickel (II) sulphate solution

Silver, gold, copper or chromium can all be plated on to other metals in a similar way.
Satisfactory results are obtained with electroplates if:- (i) the surface to be plated is cleaned and (ii) a
small current is used so as to prevent the deposit flaking off.
Electrorefining e.g. purification of copper
The copper extracted by reducing the ore is not pure enough to use as an electrical conductor. The
impure copper is purified using electrolysis.
The impure copper is made the anode in a copper (ii) sulphate cell with a thin strip of pure copper as the
cathode. Copper from the anode deposits on the copper cathode which therefore increases in mass.
Impurities of metals higher than copper in the reactivity series e.g. Fe go into solution as their ions but
will not be discharged since they are in a lower concentration than the Cu 2+ ions. Impurities of metals
lower than copper in the reactivity series e.g. Ag, Au drop to the bottom of the anode as ‘anode slime’.

Reaction and anode Reaction at cathode

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Cu (s) - 2e- → Cu2+ (aq) Cu2+ (aq) + 2e- → Cu (s)

Uses of copper
(1) Electrical wiring – good conductor and easily drawn into wires.
(2) To make alloys e.g. brass (Cu and Zn), bronze (Cu and Sn), ‘Silver’ coins (Cu and Ni)
NB: Alloys are harder and stronger than the individual metals.

The manufacture of sodium from sodium chloride – The Down’s process

The raw material for this process is a 3:2 mixture of NaCl and CaCl2 kept at a temperature of 600ºC.
The CaCl2 is deliberately added to keep the temperature of the electrolyte well below the boiling point
of sodium (883 ºC). During electrolysis, both Na+ and Ca2+ ions move towards the cathode, where Na+
ions are preferentially discharged (due to concentration effect).

Cathode/Fe NaCl Anode/C

Na+ selectively discharged ↓ 2Cl- (ℓ) - 2e → Cl2 (g)
(conc. Effect) Na Cl-
+

Na+ (ℓ) + e- → Na (ℓ) Ca2+ Cl-

↑
CaCl2

Since sodium and chlorine react rapidly with each other, the Down’s cell is constructed to keep them apart.
NB: Chlorine is a valuable by-product of the process

Molten mixture in Chlorine gas

Molten sodium

Circular iron cathode

NaCl(ℓ)/CaCl2(ℓ)

+
Graphite anode
EXTRACTION OF ALUMINIUM FROM BAUXITE
Bauxite is hydrated aluminium oxide, Al2O3.2H2O

The mined bauxite is first treated with caustic soda solution to remove impurities of silica (SiO2) and
haematite (Fe2O3). Aluminium oxide is amphoteric and therefore dissolves in the alkaline solution
leaving behind the solid impurities (SiO2, Fe2O3) which are then filtered off (red mud). The filtrate
(sodium aluminate) is allowed to crystallise, then the crystals heated at high temperatures to drive off the
water of crystallisation. The product is anhydrous aluminium oxide (alumina).

ELECTROLYSIS OF ALUMINA
Pure alumina is dissolved in molten cryolite (sodium aluminium fluoride, Na3AlF6) which lowers the
melting point of the electrolyte from 2050ºC to 950ºC. Oxygen is evolved at the carbon anodes which
slowly burn away to form CO2. The molten aluminium collects on the floor of the cell which is lined
with a graphite cathode. It is run off at intervals. Cryolite is not decomposed during the process, so
alumina is added continuously.

Cathode/C Al2O3 (ℓ)/Na3AlF6 (ℓ) Anode/C

Al (ℓ) + 3e- → Al (ℓ)
3+
↓ 2O2- (ℓ) - 4e- → O2 (g)
Al O2-
3+

A large amount of energy is required to keep the electrolyte molten, as well as to decompose the electrolyte;
hence the process is only economical in countries with relatively cheap energy sources e.g. Hydroelectric
power. A significant part of the cost of the process is the replacement of the anodes every 24 hours.
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NB: The exhaust gases from this process contains fluorides which seem to affect trees and any that land
on grass enter the food chain, affecting the teeth and bones of grazing animals (pollution problem).
Graphite anode (+)
Molten ore

Steel outside

Bubbles of
oxygen

Al(ℓ)
Molten aluminium graphite
cathode (−)

Uses Of Aluminium
1. In alloys e.g. Duralumin (Al + 4% Cu) – because of its high tensile strength and low density is
used to make aircrafts and kitchen utensils.
2. For over-head cables – low density and good conductor
3. Cooking utensils – good conductor of heat, low density, attractive appearance, non-toxic
4. Aluminium foil – easily worked, non-toxic

ANODISING ALUMINIUM
Anodising is a method of producing corrosion-resistant articles. Aluminium readily forms a
protective oxide coating of Al2O3, and when anodised, this coating is thicker and tougher.
Aluminium is made the anode of a cell containing H2SO4 (aq) (sulphuric acid) as the electrolyte
(any electrolyte which releases O2 at the anode can be used).
The anode reaction is 4OH- (aq) - 4e- → 2H2O (ℓ) + O2 (g)
The liberated oxygen attacks the aluminium anode to form a thick, adhesive oxide coating which can
readily absorb dyes e.g. brightly coloured aluminium kettles. The dyes are permanently fixed by
treatment with boiling water.
NB: Iron is not a suitable metal for anodising as the iron (iii) oxide layer formed (rust) flakes off
easily exposing the metal to further corrosion.

Differences between
Electroplating Anodising
(1) Article to be plated is made cathode Article to be anodised is made the anode
(2) Article is plated with a layer of another Article anodised is coated with a
metal non-metallic (oxide) layer

EXTRACTION OF METALS FROM THEIR ORES

The method used to reduce the ore to the metal depends on
(i) the nature of the ore and
(ii) the reactivity of the metal.
Some of the most common methods of metal extraction
Energy needed for extraction decreases

Metal Most common ore Method of extraction Comments

Potassium Chlorides
Sodium Electrolysis of the These elements are high
Calcium Chlorides and molten chloride or in the Reactivity Series
Magnesium Carbonates oxide
Aluminium Oxide
Zinc Chemical reduction of
Iron the oxide with carbon, Moderately high in the
Tin Oxide carbon monoxide or Reactivity Series
Lead and hydrogen -------------------------
sulphides low in the Reactivity
Copper Series
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The more reactive metals e.g. Na, Al are extracted from their ores by electrolysis because it takes a lot of
energy to breakdown the strong bonds present in the ores. It takes less energy to extract the less reactive
metals since they form weaker bonds, hence the method used is chemical reduction.
Silver and gold are found uncombined in nature so all that is required is crushing and washing

CHEMICAL CELLS
There are two kinds of cells
Electrolytic cells – Electric current flows into the cell and decomposes an electrolyte (chemical reaction
occurs).
Chemical cells – A chemical reaction takes place in the cell resulting in an electric current flow through
the external circuit.
In the chemical cell shown below, the chemical reaction that takes place is
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s). As a result of this reaction an electric current flows through
the external circuit registers on the voltmeter.

VOLTMETER

2 Electrons travel through

2 the external circuit from
e- e-
zinc to copper

3 Copper rod receives

electrons from zinc 3
rod

1 Zinc rod. Zinc atoms

1
dissolve to form zinc ions:
4 Copper ions accept Electrons are released.
electrons from the rod Zn(s) – 2e- → Zn2+(aq)
to become copper atoms
4
Cu2+(aq) + 2e- → Cu(s)
Copper deposits on the
copper rod.

Copper (II) sulphate solution

Many metals can be paired up to make chemical cells. The more the metals differ in reactivity (e.g. Mg
and Cu) the greater the voltage supplied by the cell.
NB: If dilute H2SO4 was added to the cell instead of CuSO4(aq), bubbles of H2 gas would form around
the copper strip [Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)]
Use is made of this in the sacrificial protection of iron. Magnesium or zinc is coupled with iron.
The more reactive metal loses electrons (is oxidised) in preference to the iron, hence the iron is
protected from rusting.

FARADAY’S LAWS OF ELECTRICITY

1ST Law states that the mass of a substance liberated at (or dissolved from) an electrode during
electrolysis is proportional to the quantity of electricity passed.
Quantity of electricity (Coulombs) = Current (amperes) x time (seconds)
or Q = It
Calculate: the quantity of electricity produced by
(a) A current of 0.5A flowing for 10 minutes.
(b) A current of 10A flowing for 2 hrs.
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2nd Law states that one mole of an element is liberated by one or more mols of electrons,
depending on its valency.
The least quantity of electricity needed to liberate one mole of a monovalent element is 96500 coulombs
or 1 faraday.
But one mole of electrons is needed to liberate one mole of a monovalent element
e.g. Ag+(aq) + e- → Ag(s)
Hence 96500C = 1 Faraday = 1 mol of electrons.
Examples: Ag+(aq) + e- → Ag(s) [Ag = 108]
1mol electrons → 1 mol of silver (108g)
1Faraday → 1 mol Silver
1 x 96500C → 1 mol Ag

Mg2+(aq) + 2e- → Mg(s) [Mg = 24]

2 mol electrons → 1 mol magnesium (24g)
2F → 1 mol magnesium
2 x 96500C → 1 mol Mg

Al3+(ℓ) + 3e- → Al(ℓ) [Al = 27]

3 mol electrons → 1 mol Al (27g)
3F → 1 mol Al
3 x 96500C → 1 mol Al

2 Cl-(aq) - 2e- → Cl2(g) [Cl = 35.5]

2 mol electrons → 1 mol Cl2 (71g)
2F → 1 mol Cl2
2 x 96500C → 1 mol Cl2

2O2-(ℓ) - 4e- → O2(g)

4 mol electrons → 22.4 dm3 O2 (at s.t.p)
4F → 22.4dm3 O2
4 x 96500C → 22.4dm3 O2

QUESTIONS

1. How many Faradays are needed to produce

(a) 2.7g Al (b) 6.0g Mg (c) 10g H2 [Al = 27, Mg = 24, H = 1]
2. Calculate the mass of magnesium that will be liberated during the electrolysis of fused (molten)
magnesium chloride, if a current of 1.93A is passed for 16 mins. 40 sec. [Mg = 24]

3. Calculate the mass of silver and the volume of Oxygen (at s.t.p) liberated during electrolysis by
9650C [Ag = 108, 1 mol of gas at s.t.p = 22.4 dm3]

4. The same current is passed for the same time through a silver voltameter and a voltameter
containing dilute sulphuric acid. If 0.108g of Ag is deposited on the ‘silver’ cathode, what
volume of hydrogen at r.t.p is liberated at the other cathode?
[Ag = 108, 1 mol of gas at r.t.p = 24 dm3]

5. When a current of 0.156A is passed through lead (ii) nitrate solution, lead is deposited on the
cathode. How long will it take to deposit 0.1 g lead? [Pb = 207]

6. An element X has a relative atomic mass of 88. When a current of 0.5A is passed through the
fused (molten) chloride of X for 32 mins. 10 sec., 0.44g of X is deposited on the cathode.
Calculate the number of Faradays needed to liberate one mole of X (b) write the symbol for the
X ion (e) write the formula for the hydroxide of X.