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Notes on electrolysis

ELECTROLYSIS

Electrolysis is the chemical decomposition of a substance by the passage of an electric current.

Electrolytes are substances that carry an electric current in the molten and/or aqueous form. Aqueous
means dissolved in water. Electrolytes can be strong or weak. Strong electrolytes have a high
concentration of ions as they dissociate completely. Weak electrolytes have a low concentration of ions.

An electrode is the point at which current enter or leaves the electrolyte.

The cathode is the negative electrode where electrons enter the electrolyte. Cations go to the cathode.

The anode is the positive electrodes where electrons enter the electrolyte. Anions go to the anode.

Metallic conduction involves the conduction by mobile electrons and no decomposition occurs.

Electrolytic conduction involves conduction by ions and decomposition occurs.

The ions present in an electrolyte depend on the nature of the electrolyte. An electrolyte which is
molten or fused contains the ions present in the formula. The ions present in the aqueous form contain
the ions as well as H+ and OH- from the water.

E.g. NaCl (l) = Na+ and Cl-

NaCl (aq) = Na+, Cl- , H+ and OH- .

© Alrick Moodie March 2008 Page 1


Examples of reactions at electrodes

At cathode: Cu2+ + 2e → Cu Ag+ + e → Ag 2H+ + 2e → H2

At anode: 2Cl- - 2e → Cl2 4OH- - 4e → 2H2O + O2

Therefore reduction occurs at the cathode. Electrons are gained.

Oxidation occurs at the anode. Electrons are lost.

At the electrodes the ions are converted to their elements.

At the anode the products are usually diatomic gases or liquids. O 2 (g), F2 (g), Cl2 (g), Br2 (l), I2 (l),

While at the cathode they are usually metal solids, except for hydrogen.

Factors which affect electrolysis

i) Concentration of electrolyte

ii) Position of ions in the electrochemical series

iii) Type of electrode

iv) Size and duration of current

When an electrolyte contains more than one ion with the same type of charge, positive or negative,
there will be competition for which ion will be preferentially discharged. The position of the ion in the
electrochemical series determines this.



Using the charts above, an ion will be discharged in preference to anyone above it.

In a mixture containing Al3+ and Pb2+ the lead would be discharged first. If it was Cl - and I – the iodide
would be discharged first.

If we had CuCl2 (l), the ions present are Cu2+ and Cl- .

However in CuCl2 (aq) the ions are Cu2+, H+, Cl- and OH- . Remember the H+ and OH- comes from the
water. This affects the products.

How?

The more concentrated the ions the more likely it would be discharged. Therefore a concentrated
solution of sodium chloride NaCl would discharge Na + and Cl- . While a dilute solution would discharge H +
and OH- .

There are two types of electrodes, inert and active. Inert electrodes do not take part in the reaction and
are usually graphite or platinum. Active electrodes interfere with the process. One common active
electrode is a copper anode. During electrolysis involving metal ions above copper in the series the
copper anode will dissolve in the solution to form Cu 2+ ions and copper metal will be deposited at the
cathode.

The size and duration of the current only affects the amount of products. The larger the current and the
longer it flows the larger the mass and volume of the products.

Description of solutions during electrolysis

For the typical electrolyte in which a metal and a gas are produced during electrolysis we would observe
a deposit at the cathode and effervescence at the anode.

However there are some solutions that we must be aware of:

Electrolysis of dilute sulphuric acid

During this process hydrogen is given off at the cathode and oxygen at the anode. The solution becomes
more acidic as effectively we are removing water.

We would observe bubbles of gases forming at both electrodes with the rate of effervescence and
volume of gas at the cathode twice that at the anode.



At cathode: 4H+ + 4e  2H2 (g)

At anode: 4OH- - 4e → 2H2O + O2 (g)

Electrolysis of brine (concentrated sodium chloride)

The products formed are sodium metal and chlorine gas. There will be a metal deposit at the cathode
and bubbles of a greenish gas at the anode. In the industrial preparation the cathode is made of mercury
and the sodium formed will form an amalgam. The amalgam is added to water and sodium hydroxide
and hydrogen gas is produced. The mercury is recovered and can be re-used.

Electrolysis of copper sulphate using inert electrodes

The products formed are copper and oxygen gas. The oxygen is formed by the decomposition of the
hydroxide ions. The solution will get acidic as we are removing Cu 2+ ions leaving H+ as the only positive
ions.

We would observe a metal deposit at the cathode and effervescence at the anode. The blue colour of
the solution will fade.



Electrolysis of copper sulphate using copper electrodes

During this electrolysis the anode would get smaller and the cathode would get larger the blue colour of
the solution would remain constant.

This because the copper anode is involved in the reaction. The copper there forms Cu 2+ ions and enter
the solution. The Cu2+ ions drift to the cathode and is deposited as a metal. The blue colour remains
constant as the Cu2+ concentration does not change.

At Cathode: Cu2+ + 2e → Cu

At anode: Cu – 2e → Cu2+

Amount of Substance liberated during electrolysis

The faraday constant is the quantity of charge needed to liberate one mole of electrons during
electrolysis. The amount required for a reaction can be determined from the reaction at the electrode.

Cu2+ + 2e → Cu requires two faradays

Ag+ + e → Ag requires 1 faraday

2H+ + 2e → H2 requires 2 faradays

4OH- - 4e → 2H2O + O2 requires 4 faradays.

The value of a faraday is 96,500 Coulombs.

The coulomb is the charge produced when 1 ampere flows for one second.

Q = It

Therefore the charge when 10Amperes flow for 30 seconds is 10 x 30 = 300 C

The number of Faradays = coulombs / 96,500

Therefore 40,000 coulombs is 40,000/96,500 = 0.415 F.

TIME MUST BE CALCULATED IN SECONDS

Calculate the charge when:


i) 2 A flows for 10 minutes

ii) 6 A flows for 45 seconds

iii) 2.5 A flows for 1 hour

iv) 12 A flows for 30 minutes

v) 3 A flows for 1 ½ hours.

Calculate the number of Faradays in:

i) 28,000 C

ii) 50,000 C

iii) 125,000 C

Calculate the number of Coulombs in:

i) O.2 F ii) 0.05 F iii) 1.67 F iv) 1.4 F

Calculate the current needed when:

i) A charge of 100 C is produced after 20 seconds

ii) A charge of 0.5 F is produced after 40 minutes

iii) A charge of 47,000 coulombs is produced after 1 hour

We can calculate the mass of substance ( or volume ) liberated during electrolysis using the Faraday.

Cu2+ + 2e → Cu

This is saying that 2F = 64g of copper.



Calculations

When we are calculating the mass deposited or volume liberated during electrolysis

1. We write the electrode reaction

2. From the reaction we determine how many moles of electrons / faraday that is used

3. We then determine the number of faradays needed for 1 mole

4. Calculate the charge by Q = It

5. Calculate the faraday used by F = Q / 96,500

6. We can calculate the mass or volume using the equation(s)

Mass = molar mass x faraday used / faraday needed

Volume = molar volume x faraday used / faraday needed

Examples

What is the mass of copper deposited from a solution of Cu 2+ when 10 Amperes flow for 30 minutes?

i) Cu2+ + 2e → Cu

ii) 2F = Cu

iii) 2F = 64g

iv) Q = 10A x(30 x 60)s = 18,000C

v) F = 18,000/96,500 = 0.187F

vi) Mass = 64 x 0.187 / 2= 5.98g



What is the mass of silver that could be deposited from Ag + ions when a current of 30 Amperes flows for
40 minutes?

i) Ag+ + e → Ag

ii) 1F = Ag

iii) 1F = 108g

iv) Q = 30A x (40 x 60)s = 72,000C

v) F = 72,000/96,500 = 0.746F

vi) Mass = 108 x 0.746 / 1 = 80.57g

What mass of oxygen gas at r.t.p. would be liberated at the anode when a current of 200 Amperes flows
for 20 minutes through O2- ions?

i) 2O2- - 4e → O2

ii) 4F = O2

iii) 4F = 24 dm3

iv) Q = 200A x (20 x 60)s = 240,000

v) F = 240,000 / 96,500 = 2.49

vi) Volume = 24 x 2.49 / 4 = 14.94 dm3

Calculate the following

a) The mass of chromium that could be liberated from a solution of Cr 3+ when 18.125 Amperes
flows for 1 hour . Cr = 52g

b) The volume of oxygen at r.t.p. that will be liberated from OH - ions when a current of 9.65
Amperes flows for 5 ½ minutes .

c) The volume of chlorine gas at r.t.p. that will be liberated when a current of 3A flows for 40
seconds through molten lead chloride.


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