Chemistry Handout 13 REF #: 013

Electrochemistry
An electric current is the flow of charged particles (electrons or ions)

Conductors and Insulators

A conductor of electricity is any substance which will allow the passage of an electric current through itself. Conduction
can either be

- Metallic Conduction
 Involves the movement of mobile (free) electrons through metals
 The metal remains chemically unchanged (only physical changes occur)
 It does not involve the transfer of matter
 Conductivity decreases with increase in temperature- due to the resistance offered to the moving
electrons by the vibration of atoms.

Metal atoms have outer electrons which are not tied to any one atom. These electrons can move freely
within the structure of a metal when an electric current is applied.

Electrons have a negative charge.

- Electrolytic Conduction
 Involves the movement of mobile (free ions) in a molten substance or a solution
 The molten substance or the solution decomposes (changes chemically and physically)
 It involves the transfer of matter in the form of ions
 Conduction increases with rise in temperature due to increase in the mobility of ions and to increase in
the degree of ionization of the electrolyte.
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An insulator of electricity is any substance which will not allow the passage of an electric current through itself.
Electrons are localized and held in fixed position. They cannot move- so they cannot conduct electricity. There
are no such free electrons in covalent or ionic solids, so electrons can't flow through them - they are non-
conductors.

Electrolyte- a molten substance or a solution that contains free ions and so allows electricity to pass through, e.g molten
salts, aqueous solutions of acids, alkalis and salts.

In the solid state of ionic substances, the ions are rigidly held together in the crystal lattice by strong electrostatic forces
and therefore cannot move around. This is why ionic solids cannot conduct electricity. In molten state or in a solution,
they are free to move around.

Non- Electrolyte- A molten substance or a solution that does not allow electricity to pass through because it does not
contain any free ions. E.g organic solvents, aqueous solutions of organic substances such as glucose, molten covalent
substances such as wax.

Strong and Weak Electrolytes

- Strong electrolytes are substances that are fully ionized and as such contain a large number of ions. E.g strong
acids, strong alkalis, solution of salts, molten salts.
- Acids: HCL, H2SO4, HNO3, HCLO4, HBR, HI, etc. 
Bases: NaOH, KOH, Ca(OH)2, Mg(OH)2, etc. 
Salts: Practically all salts are strong electrolytes like NaCL, CaCL2, KCL, etc.
-  The equations for the ionization or dissociation reactions of reactions of strong electrolytes are written with only
single headed arrow (----> ) directed to the right. For example,
- HCL + Water --------->  H+(aq) + Cl-(aq)
- Na+Cl- + Water --------->  Na+(aq) + Cl-(aq

- Weak electrolytes are substances that are partially ionized and as such contains a fewer number of ions. E.g
weak acids, weak alkalis, pure water

Acids: H2SO3, H2CO3, all organic acids such as phenol, oxalic acid, acetic acid, etc. 
Bases: NH4OH
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Note: Pure water is an extremely weak electrolyte. Approximately one molecule in every 560 000 000 molecules is
ionized:

H2O (l)   H+ (aq) + OH- (aq)

Strong electrolytes can be distinguished from weak electrolytes by testing how easily an electric current can pass
through them.

The solution in beaker A contains dilute hydrochloric acid which is a strong electrolyte. The bulb glows brightly.

The solution in beaker B contains ethanoic acid which is a weak electrolyte. The bulb glows dimly because there are few
ions to carry the electric current.

The solution in beaker c is sugar solution which is a non-electrolyte. The bulb does not glow at all because there are no
ions to carry the electric current.

Electrolysis is defined as the chemical change that occurs when an electric current is passes through an electrolyte.

Electrolysis is the passage of an electric current through an electrolyte causing it to decompose.

To understand electrolysis, you need to know what an ionic substance is.

Ionic substances form when a metal reacts with a non-metal. They contain charged particles called ions. For
example, sodium chloride forms when sodium reacts with chlorine. It contains positively charged sodium ions
and negatively charged chloride ions. Ionic substances can be broken down by electricity.

Electrode- an electrode is a conductor through which electricity enters or leaves an object or substance. Electrolysis
involves the use of electrodes connected to a battery. The electrodes carry current into and out of the electrolyte.
Electrodes are usually made of inert (unreactive) materials e.g graphite (carbon), platinum.
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Anode- the positive electrode connected to the positive terminal of the battery.

Cathode- the negative electrode connected to the negative terminal of the battery.

Anion- An atom which has gained electrons and has acquired a net negative charge or extra negative charge

Cation- An atom which has lost electrons and has acquired a net positive charge or less negative charge.

The Process of Electrolysis

The key process of electrolysis is the interchange of atoms and ions by the removal or addition of electrons to the
external circuit. The required products of electrolysis are in a different physical from the electrolyte (solid and gas) and
are deposited at the electrodes which can then be removed by some physical process.

Each electrode attracts ions that are of the opposite charge.

1. Anions (-) are attracted to the anode (+). These anions lose electrons to form neural atoms. The formation of
uncharged atoms from ions is called discharging.
An- - ne-  A
Oxidation therefore occurs at the anode.
2. The battery is an ‘electron pump’, which sucks the electrons out of the solution at the anode and pushes them
to the cathode.
3. Electrons lost at the anode are sucked along to the positive terminal of the battery and pushed out of the
negative terminal the cathode.
4. Cations (+) are attracted to the cathode (-) where they gain electrons lost from the anode to form neutral atoms
i.e they are discharged.
Cn+ + ne-  C
Reduction therefore occurs at the cathode.
5. As the ions move they carry the electric charge through the electrolyte and a current flows around the circuit.
This means that electrolysis is taking place and an electrochemical reaction is happening.
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Ions Present in the Electrolyte

Molten Electrolytes

Molten electrolytes contain only two kinds of ion. Both are discharged during electrolysis.

Example: Electrolysis of molten lead (II) bromide using inert electrodes.

Ions present: Cation Pb2+ (l) Anion Br- (l)

At anode:

Br- ions are attracted to the anode and discharged, i.e, they lose electrons to form bromide atoms:

Br- (l) - e-  Br

Pairs of bromine atoms immediately join to form bromine molecules:

Br + Br  Br2 (g)

Overall reaction: 2Br- (l) -2e-  Br2 (g)

At the temperature required to melt lead (II) bromide (370 oC), brown bromine vapour is released.

At cathode:

Pb2+ ions are attracted to the cathode and are discharged, i.e they gain electrons to form lead atoms.

Pb2+ + 2e-  Pb (l)

Molten lead drips off the cathode.

Electrolysis of molten potassium iodide using inert electrodes.

Ions present: Cation K+ (l) Anion I- (l)

At anode:

I- ions are attracted to the anode and discharged, i.e, they lose electrons to form iodine atoms:

I- (l) - e-  I

Pairs of bromine atoms immediately join to form bromine molecules:

I + I  I2 (g)

Overall reaction: 2I- (l) -2e-  I2 (g)

At the temperature required to melt potassium iodide (685 oC), purple iodine vapour is released.

At cathode:

K+ ions are attracted to the cathode and are discharged, i.e they gain electrons to form potassium atoms.

2K+ + 2e-  2K (l)

Molten potassium drips off the cathode.

Aqueous Solutions
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An aqueous solution usually contains at least two different cations and two different anions, owing to the presence of H +
and OH- ions from the water. Only one type of ion of each charge is usually discharged at each electrode.

The three factors which affects which ions are discharged:

1. Position of the ion in the electrochemical series.

The electrochemical series is the arrangement of chemical elements based on their standard electrode potential.
A hydrogen electrode is taken as having zero electrode potential. Elements that have a greater tendency than
hydrogen to lose electrons to their solution are taken as electropositive; those that gain electrons from their
solution are below hydrogen in the series and are called electronegative.

The lower an ion in the electrochemical series, the more likely it is to be discharged from solution.

Cation Anion
K+ SO42-
Ca2+ NO3-
Na+ Cl-
Mg2+ Br-
Al3+ I-
Zn2+ OH-
Fe2+
Pb2+
H+
Cu2+
Ag+

2. Relative concentration of the ions

The greater the concentration of an ion, the more likely it is to be discharged. Irrespective of the position of the
ions in the electrochemical series, there is a tendency to promote the discharge of the most concentrated ion
present. For example, in concentrated sodium chloride solution (i.e. brine) , the two anions present are the
chlorine ion and the hydroxyl ion. Although the hydroxyl ion is more easily oxidised than the chlorine ion, it is
the chlorine ion which will be discharged because its concentration is much greater than that of the hydroxyl.

3. Nature of the electrode

Usually, inert electrodes such as graphite or platinum are used for electrolysis. These electrodes do not interfere
with the reactions occuring at the surface of the electrode, they simply act as a point of connection between the
electrical circuit and the solution.
An electrode which is not inert can take part in a reaction. If an active electrode is used, then the reaction
occurring is the one that requires the least energy. Example: if metal electrodes are used in metal ion solutions
they can get involved in the reactions by dissolving as ions, leaving their electrons behind (this can only happen
when the metal takes the place of the anode, the positive electrode) - this is called electrode participation

Electrolysis of dilute H2SO4 (aq)

Ions Present:

From H2O: H+ (aq) OH- (aq)

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+ 2-
From H2SO4: H (aq) SO (aq)4

Cation: H+ (aq) Anions: OH- (aq), SO42- (aq)

Electrodes: Inert- platinum or carbon

Electrode reactions and products:

At the Anode: OH- discharged, lower in electrochemical series than SO 42- (there is a competition between the two ions)

4OH- (aq) – 4e-  2H2O (l) + O2 (g)

Oxygen gas evolved.

At the Cathode: 4H+ (aq) + 4e-  2H2(g)

Hydrogen gas evolved.

Volume of gases: 1 volume O2 : 2 volume H2

(for every 4 moles of e-, 1 volume O2 and 2 volumes H2 are produced)

Changes in electrolytes: Acid becomes more concentrated: H+ (aq) and OH- (aq) are removed leaving H+ (aq) and SO42-
(aq)

Electrolysis of concentrated HCl (aq)

Ions Present:

From H2O: H+ (aq) OH- (aq)

From HCl: H+ (aq) Cl- (aq)

Cation: H+ (aq) Anions: OH- (aq), Cl- (aq)

Electrodes: Inert- carbon at anode to resist attack by Cl 2 platinum or carbon at cathode

Electrode reactions and products:

At the Anode: Cl- discharged, higher concentration than OH -

2Cl- (aq) – 2e-  Cl2(g)

Chlorine gas evolved.

At the Cathode: 2H+ (aq) + 2e-  H2(g)

Hydrogen gas evolved.

Volume of gases: 1 volume Cl2 : 1 volume H2

Changes in electrolytes: Acid becomes more dilute: H+ (aq) and Cl- (aq) are removed leaving H+ (aq) and OH- (aq)

Electrolysis of very dilute NaCl (aq)

Ions Present:
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+ -
From H2O: H (aq) OH (aq)

From NaCl: Na+ (aq) Cl- (aq)

Cations: H+ (aq) Na+ (aq) Anions: OH- (aq), SO42- (aq)

Electrodes: Inert- platinum or carbon

Electrode reactions and products:

At the Anode: OH- discharged, lower in electrochemical series than Cl -

4OH- (aq) – 4e-  2H2O (l) + O2 (g)

Oxygen gas evolved.

At the Cathode: H+ discharged, lower in electrochemical series than Na +

4H+ (aq) + 4e-  2H2(g)

Hydrogen gas evolved.

Volume of gases: 1 volume O2 : 2 volume H2

Changes in electrolytes: solution becomes more concentrated: H+ (aq) and OH- (aq) are removed leaving Na+ (aq) and Cl-
(aq)

Electrolysis of concentrated NaCl (aq)

Ions Present:

From H2O: H+ (aq) OH- (aq)

From NaCl: Na+ (aq) Cl- (aq)

Cations: H+ (aq) Na+ (aq) Anions: OH- (aq), Cl- (aq)

Electrodes: Inert- carbon at anode to resist attack by Cl 2 platinum or carbon at cathode

Electrode reactions and products:

At the Anode: Cl- discharged, higher concentration than OH -

2Cl- (aq) – 2e-  Cl2(g)

Chlorine gas evolved.

At the Cathode: H+ discharged, lower in electrochemical series than Na +

2H+ (aq) + 2e-  H2(g)

Hydrogen gas evolved.

If sodium ion was discharged instead of hydrogen ion, then The sodium metal would have reacted with water, and
hydrogen gas will still be given off. This however requires more energy.

Volume of gases: 1 volume Cl2 : 1 volume H2

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Changes in electrolytes: solution becomes alkaline: H (aq) and Cl (aq) are removed leaving Na+ (aq) and OH- (aq)
+ -

Electrolysis of CuSO4 (aq)

Ions Present:

From H2O: H+ (aq) OH- (aq)

From CuSO4 : Cu2+ (aq) SO42- (aq)

Cations: H+ (aq) Cu2+ (aq) Anions: OH- (aq), SO4 2- (aq)

Electrodes: Inert- platinum or carbon

Electrode reactions and products:

At the Anode: OH- discharged, lower in electrochemical series than SO 42-

4OH- (aq) – 4e-  2H2O (l) + O2 (g)

Oxygen gas evolved.

At the Cathode: Cu+ discharged, lower in electrochemical series than H +

Cu2+ (aq)+ 2e-  Cu (s)

Pink-brown copper deposited, cathode gets thicker.

Changes in electrolytes: solution becomes acidic: Cu2+ (aq) and OH- (aq) are removed leaving H+ (aq) and SO42- (aq)

Solution becomes paler blue: Cu2+ (aq) removed

Electrolysis of CuSO4 (aq)

Ions Present:

From H2O: H+ (aq) OH- (aq)

From CuSO4 : Cu2+ (aq) SO42- (aq)

Cations: H+ (aq) Cu2+ (aq) Anions: OH- (aq), SO4 2- (aq)

Electrodes: Anode: copper (active), Cathode: platinum, carbon or copper

Electrode reactions and products:

At the Anode: Cu (s) from electrode converted to Cu 2+, requires less energy than the discharge of OH -

Cu (s) - 2e-  Cu2+ (aq)

Anode gets thinner

At the Cathode: Cu+ discharged, lower in electrochemical series than H +

Cu2+ (aq)+ 2e-  Cu (s)

Copper deposited, cathode gets thicker.

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Changes in electrolytes: No change, copper is transferred from anode to cathode.

Solution becomes paler blue: Cu2+ (aq) removed

Quantitative Electrolysis

Faraday’s laws of electrolysis are concerned with the quantity of an element, measured in moles, formed during
electrolysis.

First Law

States that the mass of a substance produced at, or dissolved from an electrode during electrolysis is directly
proportional to the quantity of electricity passing through the electrolyte.

The quantity of electricity is measured in Coulombs (C) and depends on:

- The length of time, measured in seconds, that a steady current is flowing through the electrolyte.
- The size of that steady current- measured in Amperes (A).

Q= It

1 C = 1As

And 96,500 C = 1 faraday

1 mole of electrons (6.02 x 1023) = 1 faraday

96, 500 C mol-1 is called the Faraday constant.

When a faraday of electricity or 96500 C of electricity have flowed through a circuit, one mole of electrons or 6.02 x 10 23
electrons have flowed through that circuit.

A- - e-  A C+ + e-  C

1 mole 1 mole 1 mole 1 mole 1 mole 1 mole

One mole of electrons is needed to discharge one mole of an ion with a single charge, hence, one faraday is the quantity
of electricity required to discharge one mole of an ion with a single charge.

1. What quantity of charged in C, is transferred when 0.5 A of current flows for 5 seconds?
2. How much current is needed to transfer 96500 C of electricity in 2 minutes?
3. How long would it take for 50000 C of electricity to flow past a certain point at a current of 1200 A?

4. Calculate the quantity of electricity in C obtained from 2 moles of electrons.

1 moles of electrons = 1 faraday

2 moles of electrons = 2 faradays

1 faraday = 96, 500 C

2 faradays = 96, 500 C x 2 = 193, 000 C

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5. Calculate the number of moles of electrons obtained from 250 C of electricity.

96500 C = 1 faraday

1 C = 1/ 96500 faraday

250 C = 1/96500 x 250 = 2.59 x 10 -3 faraday

1 faraday = 1 mole of electrons

2.59 x 10-3 faraday = 2.59 x 10-3 moles of electrons

Second Law

The number of faradays required to discharge one mole of an ion at an electrode is equal to the size of the charge on the
ion.

Therefore:

- 1 faraday is required to discharge one mole of an ion with a single charge. E.g Na +
Na+ + e-  Na
1 mole ions 1 mole electrons 1 mole atoms

- 2 faradays are required to discharge one mole of an ion with a double charge. E.g Cu 2+
Cu2+ + 2e-  Cu
1 mole ions 2 mole electrons 1 mole atoms

- 3 faradays are required to discharge one mole of an ion with a triple charge. E.g Al 3+
Al3+ + 3e-  Al
1 mole ions 3 mole electrons 1 mole atoms

Number of faradays used = number of moles of atoms of the element formed x charge on the ion.

Eg. Cu2+ + 2e-  Cu

1 mole ions 2 mole electrons 1 mole atoms

1 mole x charge of 2 = 2 faradays

1. Four faradays of electricity are passed through molten sodium chloride. How much chlorine gas (mass and volume) at
r.t.p will be formed at the anode?

Equation: (at anode: oxidation) 2Cl- - 2e-  Cl2

2 moles 2 moles 1 mole

Number of faradays used = 1 mole x 2 (charge of 1) = 2 faradays.

Therefore, 2 faradays will discharge 2 moles of Cl - ions producing one mole Cl2

2 faradays produce 1 mole Cl2

2/2 faraday produce ½ mole Cl2

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1 faraday produce ½ mole Cl2

1 x 4 faradays produce ½ x 4 moles Cl2

4 faradays produce 2 moles Cl2

Mass of Cl2 formed = # of moles x molar mass = 2 moles x 71 = 142 g Cl 2

2. During the electrolysis of copper (II) sulphate solution, if 0.5 faraday is used, what mass of copper will be deposited at
the cathode?

Equation: (at cathode: reduction) Cu2+ + 2e-  Cu

1 moles 2 moles  1 mole

Number of faradays used = 1 mole x charge of 2 = 2 faradays.

Therefore, 2 faradays will discharge 1 mole of Cu 2+ ions producing one mole Cu

2 faradays produce 1 mole Cu

2/2 faraday produce ½ mole Cu

1 faraday produce ½ mole Cu

1 x 0.5 faradays produce ½ x 0.5 moles Cu

0.5 faradays produce 0.25 moles Cu

Mass of Cu formed = # of moles x molar mass = 0.25 moles x 64 = 16 g Cu

3. Calculate the number of moles of copper metal that can be produced by electrolysis of molten copper sulphate using
500 C of electricity.

96500 C = 1 faraday

1 C = 1/96500 faraday

500 C = 1/ 96500 x 500 = 5.18 x 10 -3

Equation: (at cathode) Cu2+ + 2e-  Cu

1 mole 2 moles 1 mole

Number of faradays used = 1 mole x charge of 2 = 2 faradays

2 faradays discharge 1 mole Cu2+ ions producing 1 mole Cu

2 faradays produce 1 mole Cu

1 faraday produce ½ mole Cu

5.18 x 10-3 faraday produce ½ x 5.18 x 10-3 mole Cu

500 C produce 2.59 x 10-3 mole Cu

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4. What quantity of electricity is required to produce 5.4 g of aluminum during electrolysis of molten aluminum oxide?

Equation: (at cathode: reduction) Al3+ + 3e-  Al

1 mole 3 moles 1 mole

Number of faradays used = 1 mole x charge of 3 = 3 faradays

3 faradays discharge 1 mole Al3+ ions producing 1 mole Al

3 faradays produce 1 mole Al

# of moles of Al = mass/ molar mass = 5.4 g/ 27 g/mol = 0.2 mol Al

3 x 0.2 faraday produce 1 x 0.2 mol Al

0.6 faraday produce 0.2 mol Al

0.6 faraday produce 5.4 g of Al

Quantity of electricity required: 0.6 faraday

5. What quantity of electricity is required to produce 9.6 g of oxygen during electrolysis of molten aluminum oxide?

Equation: (at anode: oxidation) 2O2- - 4e-  O2

2 moles 4 moles 1 mole

Number of faradays used = 1 mole x 2 (charge of 2) = 4 faradays

4 faradays discharge 2 mole O2- ions producing 1 mole O2

4 faradays produce 1 mole O2

# of moles of O2 = mass/ molar mass = 9.6 g/ 32 g/mol = 0.3 mol O2

4 x 0.3 faradays produce 1 x 0.3 mol O 2

1.2 faradays produce 0.3 mol O2

1.2 faradays produce 9.6 g of O2

Quantity of electricity required: 1.2 faradays

6. During the electrolysis of molten sodium chloride, if 5 A of current flows for 32 minutes and 10 s, what mass of
chlorine will be produced?

t = (32 x 60) + 10 = 1930 s

Q = It = 5 x 1930 = 9650 C

96500 C = 1 faraday

1 C = 1/ 96500 faraday

9650 C = 1/ 96500 x 9650 = 0.1 faraday

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Equation: (At anode) -
2Cl - 2e 
-
Cl2 (g)

2 moles 2 moles 1 mole

2 faradays are required to discharge 2 moles Cl - to produce 1 mole Cl2

2 faradays produce 1 mole Cl2

1 faraday produce ½ mole Cl2

1.1 faraday produce ½ x 0.1 mole Cl2

1.1 faraday produce 0.05 mole Cl2

Mass of Cl2 produced = # of moles x molar mass = 0.05 mol x 71 g/mol = 3.55 g Cl 2

7. A current of 10 A is allowed to flow through molten aluminum oxide for 5 hours. What mass of aluminum is deposited
at the cathode? Ans: 16.79 g of Al

8. A current of 13.4 A was used for 0.5 hours. Calculate the mass of bromine produced. 1 F = 96,500 C. Ar of Br2 = 160.

Remember: charge = current × time

Charge = 13.4 × 1,800 = 24,120 C

Remember: One faraday represents one mole of electrons. It is equal to 96,500 coulombs.

Number of moles of electrons = 24,120 ÷ 96,500 = 0.25 mol

Amount of bromine produced = 0.25 ÷ 2 = 0.125 mol

Mass of bromine produced = Ar × mol = 0.125 × 160 = 20 g

9. Dilute sulphuric acid is electrolyzed using platinum electrodes. If a current of 2.5 A flows for 35 minutes and 44 s, what
mass and volume of oxygen, measured at s.t.p will be formed at the anode.

t = (25 x 60) + 44 = 1544 s

Q = It = 2.5 x 1544 = 3860 C

96500 C = 1 faraday

1 C = 1/ 96500 faraday

3860 C = 1/ 96500 x 3860 = 0.04 faraday

Equation: (At anode: oxidation) 4OH- - 4e-  2H2O (l) + O2 (g)

4 moles 4 moles 2 mole 1 mole

Number of faradays used = 1 mole x 4(charge of 1) = 4 faradays

4 faradays are required to discharge 4 moles OH - to produce 1 mole O2

4 faradays produce 1 mole O2

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2 faraday produce ¼ mole O2

0.04 faraday produce ¼ x 0.04 mole O 2

0.04 faraday produce 0.01 mole O2

Mass of O2 produced = # of moles x molar mass = 0.01 mol x 32 g/mol = 0.32 g O 2

Volume of O2 produced = # of moles x 22.4 dm3 = 0.01 x 22.4 dm3 = 0.224 dm3

10. Some dilute sulphuric is electrolyzed using platinum electrodes. At the cathode 8 g of hydrogen are formed. How
much oxygen will be released at the anode?

Equation: (at the cathode: reduction) 2H+ + 2e-  H2 (g)

2 moles 2 moles 1 mole

3 of moles of H2 formed = mass / molar mass = 8 g / 2 g/mol = 4 mol

Number of faradays used = 1 mole x charge of 2 = 2 faradays

2 faradays are required to produce 1 mole H 2

2 x 4 faradays are required to produce 4 x 1 mol H 2

8 faradays are required to produce 4 moles H 2

Equation: (At anode: oxidation) 4OH- - 4e-  2H2O (l) + O2 (g)

4 moles 4 moles 2 moles 1 mole

Number of faradays used = 1 mole x 4(charge of 1) = 4 faradays

4 faradays are required to produce 1 mole O 2

1 faraday is required to produce ¼ mole O 2

8 faradays of electricity have passed through the liquid

1 x 8 faradays are required to produce ¼ x 8 moles O 2

8 faradays are required to produce 2 moles O 2

Mass of oxygen produced = # of moles x molar mass = 2 x 32 = 64 g of O 2

Applications of Electrolysis

1. Extraction of Reactive metals

2. Purification of metals
3. Electroplating
4. Anodizing
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