Electrolysis

What is Electrolysis?

Electrolysis is the decomposition of a compound

by electricity. The compound is usually an ionic
compound in the molten or aqueous state.
 Uses:

 It is used to extract metals high in reactivity series.

 It is used to produce non metals such a chlorine.
 It is used to purify some metals.
 Electrolytic Cell:
The apparatus for electrolysis is called an electrolytic cell.
 Important Terms:
Electrode:
Rod of plate which conducts electricity through an electrolyte during
electrolysis. Usually carbon/ graphite or platinum.
There are two electrodes:
1) Cathode: Electrode connected to the negative terminal of a battery.
Any cations present will migrate to the cathode. Reduction occurs at
the cathode.
2) Anode: Electrode connected to the positive terminal of a battery. Any
anions presents will migrate to the anode. Oxidation occurs at the
anode.
Electrolyte:
 Conducts electricity through the movement of free-moving ions.

 Usually molten ionic compound or in aqueous form.

 Is decomposed in the process.

Battery:
Provides the source of electrical energy for electrolysis to take place.
 Process
Process involved in electrolysis:

 Electrons flow from positive terminal to negative terminal of power source.

 At the cathode (electrode connected to negative terminal), cations migrate
to the cathode, and are reduced when they accept electrons. The cation is
discharged.
 At the anode (electrode connected to positive terminal), anions migrate to
the anode, and are oxidized when they donate electrons. The anion is
discharged.
 The movement of ions in the electrolyte constitutes the flow of electric
current.
Electrolysis of Molten Ionic
Compounds:
 Binary compounds contain only two elements, usually a metal
cation and a non-metal anion. They are usually ionic compounds.
The cations and anions are discharged during electrolysis.
Electrolysis of Molten Sodium Chloride:
 Identify electrolyte: NaCl(l)
In solid state, the ions are held in fixed positions in the crystal lattice
by strong electrostatic forces of attraction

 Identify ions present: Na+(l) and Cl-(l)

When heated strongly, the electrostatic forces of attraction between the
cations and anions are broken, and the ions are free to move and no
longer held in fixed positions.
 Identify electrodes used: carbon
Carbon is an inert electrode. Inert electrodes do not react with the
products of electrolysis or the electrolyte, and are not involved in the
electrolysis process.
At the anode (electrode connected At the cathode (electrode
to the positive terminal of the connected to the negative terminal
battery) of the battery)
Cl- ions are attracted to the anode. Na+ ions are attracted to the cathode.

Each Cl- ion lose 1 electron to the Each Na+ ion gain 1 electron from the
anode to form a chloride atom. cathode to form a sodium atom

2 Cl atoms come together to form Cl2 Na+ ions are reduced.

gas

Cl- ions are oxidized. Na+ ions are discharged as sodium

metal.

Cl- ions are discharged as chlorine gas.

 Electrolysis of Aqueous
Solutions of Ionic Compounds:

When aqueous solutions are involved, ions compete to be discharged at

the electrodes.

 NaCl(l) gives only Na+(l) and Cl-(l)

 NaCl(aq) gives Na+(aq), Cl-(aq), H+(aq) and OH-(aq)
 The ions that are discharged in aqueous solutions depends on:
1) Cation – position in the reactivity series. The more reactive the metal, the less
reactive the ion formed, the less likely it is to be discharged.

2) Anion – ease of discharge follows the series below. The larger anions are more
stable and less likely to be discharged.
3) Concentration – higher concentrations can affect which ion is
preferentially discharged .
4) Electrodes – Reactive electrodes participate in the electrolysis reaction;
inert electrodes do not participate in the electrolysis reaction.
Electrolysis of Dilute Sodium Chloride:
Step 1: Identify the ions present in the electrolyte.

Step 2: Determine ion preferentially discharged at the cathode (electrode connected to

negative terminal of battery)
Positively charged ions will migrate to cathode: Na+(aq), H+(aq)

H+(aq) is more easily discharged over Na+(aq).

H+(aq) is preferentially discharged as hydrogen gas.

2H+(aq) + 2e- ® H2(g) [reduction]

Na+(aq) remains in solution
 Step 3: Determine ion preferentially discharged at the anode
(electrode connected to positive terminal of battery)

 Negatively charged ions will migrate to anode: Cl-(aq), OH-(aq)

 OH-(aq) is more easily discharged compared to Cl-(aq).

OH (aq) is preferentially discharged as water and oxygen gas.
-

4OH-(aq) ® 2H2O(l) + O2(g) + 4e-[oxidation]

 Cl-(aq) remains in solution.

Overall

 Equivalent to electrolysis of water.

 As electrolysis proceeds, concentration of sodium chloride will

increase. This would affect the products formed during electrolysis
after some time.
Electrolysis of Concentrated
Sodium Chloride:
 Step 1:

 Identify the ions present in the electrolyte.

 Step 2
 Determine ion preferentially discharged at the cathode (electrode
connected to negative terminal of battery)
 Positively charged ions will migrate to cathode: Na+(aq), H+(aq)

 H+(aq) is more easily discharged over Na+(aq).

 H+(aq) is preferentially discharged as hydrogen gas.
 2H+(aq) + 2e- H2(g) [reduction]
 Na+(aq) remains in solution.
 Step 3:
 Determine ion preferentially discharged at the anode (electrode
connected to positive terminal of battery)

 Negatively charged ions will migrate to anode: Cl-(aq), OH-(aq)

 OH-(aq) is more easily discharged compared to Cl-(aq) in dilute

solutions. However, in concentrated solutions, Cl-(aq) is
preferentially discharged instead. (Halide ions such as chloride,
bromide and iodide ions are only discharged during the
electrolysis of concentrated solutions.)
2Cl-(aq) Cl2(aq) + 2e- [oxidation]
 OH-(aq) remains in solution.
 Test Electrolysis
Time : 20 mins Marks: 10
Question # 1:
Electrolysis of Dilute Sulphuric Acid:
Draw the Diagram
a) Identify the ions present in the solution
b) Determine ion preferentially discharged at the cathode and mention
whether oxidation or reduction is occurring at cathode and also write
the half reaction.
c) Determine ion preferentially discharged at the anode and mention
whether oxidation or reduction is occurring at Anode and also write
the half reaction.
d) Write the overall Reaction.
Electrolysis of Dilute
Sulphuric Acid:
 Step 1:

 Identify the ions present in the electrolyte

 Step 2

 Determine ion preferentially discharged at the cathode (electrode

connected to negative terminal of battery)
 Only positively charged ion which migrates to cathode: H+(aq)

 H+(aq) is discharged as hydrogen gas.

2H+(aq) + 2e- H2(g) [reduction]

 Step 3
 Determine ion preferentially discharged at the anode (electrode
connected to positive terminal of battery)

 Negatively charged ions will migrate to anode: (aq), OH-(aq)

 OH-(aq) is more easily discharged compared to (aq).

 OH-(aq) is preferentially discharged as water and oxygen gas.

 Step 4

Overall Reaction:

Equivalent to electrolysis of water as only water decomposes

Electrolysis of Molten Lead
Bromide:
Electrolysis of Aqueous
Copper(II) Sulfate Using
Carbon Electrodes:
 Step 1:
 Identify the ions present in the electrolyte
 Step 2
Determine ion preferentially discharged at the cathode (electrode connected to
negative terminal of battery)

 Positively charged ions will migrate to cathode: (aq), (aq)

 (aq) is more easily discharged compared to (aq),

 (aq) is preferentially discharged as Cu(s).

(aq) + 2 ® Cu(s) [reduction]

 Step 3
 Determine ion preferentially discharged at the anode (electrode
connected to positive terminal of battery)
 Negatively charged ions will migrate to anode: (aq), (aq)

 (aq) is more easily discharged compared to (aq).

 (aq) is preferentially discharged as water and oxygen gas.

 4(aq) ® 2(l) + (g) + 4e- [oxidation]

 (aq) remains in solution.

 Overall:

 The copper metal discharged forms a layer around the cathode.

 The concentration of (aq) in the solution decreases as the reaction

proceeds.

 The intensity of the blue colour decreases.

Electrolysis of Aqueous
Copper(II) Sulfate Using
Copper Electrodes
 Step 1:

 Identify the ions present in the electrolyte

 Step 2
 Determine ion preferentially discharged at the cathode (electrode
connected to negative terminal of battery)
 Positively charged ions will migrate to cathode: (aq),) (aq
 (aq) is more easily discharged compared to (aq).
 (aq) is preferentially discharged as Cu(s).
 Step 3
 Determine ion preferentially discharged at the anode (electrode
connected to positive terminal of battery)
 Negatively charged ions will migrate to anode: (aq), (aq)

 However, the copper anode participates in the electrolysis process. It is

known as a reactive electrode.
 The copper electrode is oxidised into (aq) ions which enter into the
electrolyte solution.

 (aq) and (aq) remains in solution

 Overall
 The copper anode dissolves and decreases in mass.

 The concentration of (aq) in the solution remains unchanged as (aq)

deposited as Cu(s) at the cathode is continuously replenished by
the anode.

 The intensity of the blue colour remains unchanged until the anode
disappears
 Industrial Applications of
Electrolysis
1)Purification of Metals:
 During electrolysis of copper(II) sulfate solution with copper
electrodes, the anode dissolves.

 A piece of pure copper is used as the cathode.

 Impure copper is used as the anode.

 Pure copper from the anode is oxidised into Cu2+(aq) which enters the
electrolyte.

 Cu2+(aq) is then deposited on the cathode.

 Impurities fall off the anode and collect below.
 The mass of the cathode increases.
 Impure copper can be purified in this way.
2) Electroplating:
 Electroplating is the process of depositing a thin layer of metal on
another object by electrolysis.

 Allows coating of a metal object with another metal to give it an

attractive appearance, or to protect the metal below.
 The metal to be used for electroplating is made the anode.

 The object to be plated is made the cathode.

 For copper plating for example,

 Copper is used as the anode.

 The electrolyte is aqueous copper(II) sulfate.

 Copper from the electrolyte is deposited on the object, while copper
from the anode replaces the Cu2+(aq) in the electrolyte.

 Cathode:

 Anode:
 Extraction of Aluminum :
 Aluminium is the most abundant metal on Earth, but it is expensive,
largely because of the amount of electricity used in the extraction
process.

 Aluminium ore is called bauxite (Al2O3). The bauxite is purified to

yield a white powder – aluminium oxide (also known as alumina) –
from which aluminium can be extracted.
 The extraction is done by electrolysis, but first the aluminium
oxide must be melted so that electricity can pass through it.
However, aluminium oxide has a very high melting point (over
2,000°C) so it would be expensive to melt it.
 Instead, it is dissolved in molten cryolite – an aluminium
compound with a lower melting point than aluminium oxide. The
use of molten cryolite as a solvent reduces some of the energy
costs involved in extracting aluminium by allowing the ions in
aluminium oxide to move freely at a lower temperature.
 The diagram shows an aluminium oxide electrolysis cell. Both the
negative electrode (cathode) and positive electrode (anode) are
made of graphite, which is a form of carbon.
 Aluminium ions receive electrons at the negative electrode and
are reduced to aluminium atoms:
Al3+ + 3e– → Al (reduction – gain electrons)
 The molten aluminium sinks to the bottom of the cell, where it is
tapped off.
 The molten aluminium sinks to the bottom of the cell, where it is
tapped off.
Oxide ions lose electrons at the positive electrodes and are oxidised
to oxygen gas:
2O2– → O2 + 4e– (oxidation – lose electrons)
 This oxygen reacts with the carbon of the positive electrodes,
forming carbon dioxide, so they gradually burn away. As a result, the
positive electrodes have to be replaced frequently. This adds to the
cost of the process.
 Simple Electric Cells:
 Reverse of electrolysis – converts chemical energy to electrical
energy.
Zinc-Copper Cell with Dilute Sulfuric Acid
as Electrolyte
 Step 1

 Identify which electrode is oxidised. Reduction will occur at the

other electrode.

 The more reactive metal will be oxidised. In this case, Zn is more

reactive than Cu. Hence Zn is oxidised.
 Step 2

 Identify the flow of electrons.

 Electrons flow from the negative electrode to the positive

electrode.
 Aqueous
Zinc-Copper Cell with

Copper(II) Sulfate as Electrolyte

 Step 1

 Identify which electrode is oxidised. Reduction will occur at the

other electrode.

 The more reactive metal will be oxidised. In this case, Zn is more

reactive than Cu. Hence Zn is oxidised.
 Step 2

 Identify the flow of electrons.

 Electrons flow from the negative electrode to the positive

electrode.
 What Affects the Voltage
Reading for Simple Electric
Cells?

• The voltage reading on the voltmeter for zinc-copper

electrodes is 1.1v.
• The voltage reading depends on the difference in
reactivity between the two metals used for the
electrodes.

• The further apart the metals, the greater the

difference in reactivity, the larger the voltage reading
on the voltmeter