Electrolysis

What is meant by electrolysis?

When an electric current is passed through a molten ionic compound, the compound
decomposes or breaks down. The process also occurs for aqueous solutions of ionic compounds.
Covalent compounds cannot conduct electricity hence they do not undergo electrolysis. Ionic
compounds in the solid state cannot conduct electricity either since they have no free ions that
can move and carry the charge.

Molten = Melted form.

Aqeous = Dissolved in water

Particles in ionic compounds are in fixed position in the solid state but can move around when
molten or in solution

Key Terms
Cell is a source of electricity.

Battery is a collection of cells.

Conductor is a solid which allows electricity to pass through it due to free electrons.

Insulator is a solid which does not allows electricity to pass through it.

Electrode is a rod of metal or graphite through which an electric current flows into or out of an
electrolyte. (usually of less reactive metals such as Graphite and Copper.

Types of electrodes:
1) On the basis of charge: Anode (connected to positive charge of battery)
Cathode (connected to negative charge of battery)
2) On the basis of reactivity: Inert (which does not react with electrolytes)
Reactive (which reacts with electrolytes)
.Electrolyte is the ionic compound in molten or dissolved solution that conducts the electricity

Types of electrolyte:
1) Strong electrolyte: Liquid or an aqueous solution which contains a lot of free ions.
2) Weak electrolyte: Liquid or an aqueous solution which contains limited free ions.
3) Poor electrolyte: Liquid which does not allow electricity to pass through it due to lack of free ions.
Ions are charged atoms / polyatom.

Anode is the positive electrode of an electrolysis cell.

Anion is a negatively charged ion which is attracted to the anode.

Cathode is the negative electrode of an electrolysis cell.

Cation is a positively charged ion which is attracted to the cathode.

The basic set-up of an electrolysis cell

Electrolysis of molten compounds eg: Lead (II) Bromide:

Method:
1) Add lead (II) bromide into a beaker and heat so it will turn molten, allowing ions to be free to move and
conduct an electric charge

2) Add two graphite rods as the electrodes and connect this to a power pack or battery

3) Turn on power pack or battery and allow electrolysis to take place

4) Negative bromide ions move to the positive electrode (anode) and lose two electrons to form bromine
molecules.There is bubbling at the anode as brown bromine gas is given off.

5) Positive lead ions move to the negative electrode (cathode) and gain electrons to form a grey lead
metal which deposits on the surface of the electrode
Reaction at electrodes

General Principles of Electrolysis:

Rules:

1) Aqueous solutions will always have water (H2O)

2) H+ and OH– ions from the water are involved as well

Positive electrode (anode)

OH– ions and non-metal ions (anions) are attracted to the positive electrode

Either OH– or non-metal ions will lose electrons and oxygen gas or gas of non-
metal in question is released, eg. chlorine, bromine, nitrogen

The product formed depends on which ion loses electrons more readily, with the
more reactive ion remaining in solution.

A reactivity series of anions is shown below:

More reactive SO42- → NO3- → OH- → Cl- → Br- → I- Less reactive

Negative electrode (cathode)

H+ and metal ions attracted to the negative electrode but only one will gain electrons
Either hydrogen or metal will be produced
If the metal is above hydrogen in reactivity series, then hydrogen will be produced and
bubbling will be seen at the cathode
Concentrated and dilute solutions

Concentrated and dilute solutions of the same compound give different products
For anions, the more concentrated ion will tend to get discharged over a more dilute
ion

Electrolysis of binary molten compound

For a binary molten compound of a metal and a nonmetal, the cathode product will
always be the metal

The product formed at the anode will always be the non-metal

Electrolysis of Aqueous Solutions

Diagram showing the electrolysis of aqueous solutions

Method:
Add aqueous solution into a beaker
Add two Graphite rods as the electrodes and connect this to a power pack or
battery
Turn on power pack or battery and allow electrolysis to take place

Determining what gas is produced

If the gas produced at the cathode burns with a ‘pop’ when a sample is lit with a
lighted splint then the gas is hydrogen

If the gas produced at the anode relights a glowing splint dipped into a sample of
the gas then the gas is oxygen

The halogen gases all produce their own colours (bromine is red-brown, chlorine is
yellow-green and fluorine is pale yellow)
Reactions at the Electrodes
Products of Electrolysis & Charge Transfer

Copper refining

The electrolysis of CuSO2 using graphite rods produces oxygen and copper.

By changing the electrodes from graphite to pure and impure copper, the products can be changed
at each electrode.

Electrolysis can be used to purify metals by separating them from their impurities.

In the set-up, the impure metal is always the anode, in this case the impure copper.

The cathode is a thin sheet of pure copper.

The electrolyte used is an aqueous solution of a soluble salt of the pure metal at the anode, e.g:
CuSO4.

Copper atoms at the anode lose electrons, go into solution as ions and are attracted to the cathode
where they gain electrons and form now purified copper atoms.

The anode thus becomes thinner due to loss of atoms and the impurities fall to the bottom of the cell
as sludge.

The cathode gradually becomes thicker.

Electrolysis of halide solutions

We have seen that cations lower down on the reactivity series tend to be discharged in preference to
more reactive cations.

The same occurs for anions which can be arranged in order of ease of discharge:

More reactive SO42- → NO3- → OH- → Cl- → Br- → I- Less reactive

Eg. in a concentrated aqueous solution of barium chloride, the Cl– ions are discharged more readily
than the OH– ions, so chlorine gas is produced at the anode.

If the solution is dilute however only the OH– ion is discharged and so oxygen would be formed.
Transfer of Charge

During electrolysis the electrons move from the power supply towards the cathode.

Positive ions within the electrolyte move towards the negatively charged electrode which is the
cathode.

Here they accept electrons from the cathode and either a metal or hydrogen gas is produced.

Negative ions within the electrolyte move towards the positively charged electrode which is the
anode.

If the anode is inert (such as graphite or platinum), the ions lose electrons to the anode and form a
nonmetal or oxygen gas.

If the anode is a reactive metal, then the metal atoms of the anode lose electrons and go into
solution as ions, thinning the anode.

Diagram showing the direction of movement of electrons and ions in the electrolysis of NaCl
Ionic Half-Equations & Electrical Energy

Reduction occurs at the cathode as the positive ions gain electrons

Electrochemical cells

An electrochemical cell is a source of electrical energy.

The simplest design consists of two electrodes made from metals of different reactivity immersed in
an electrolyte and connected to an external circuit.

A common example is zinc and copper.

Zinc is the more reactive metal and forms ions more easily, releasing electrons as its atoms form
ions.

The electrons give the more reactive electrode a negative charge and they then flow around the
circuit to the copper electrode.

The difference in the ability of the electrodes to release electrons causes a voltage to be produced.

The greater the difference in the metal’s reactivity, the greater the voltage.
Electrochemical cell made with copper and magnesium. These metals are further apart
on the reactivity series than copper and zinc and would hence produce a greater voltage
Electroplating
Definition: When one metal object is coated by another metal by the process of
electrolysis.

Advantages:
1. Protection of metals against rusting.
2. To add value to cheap metals.
3. For decorative purposes
Purification of metals

Example: Purification of copper