ELECTROLYSIS

WHY THINGS CONDUCT ELECTRICITY

For anything to conduct electricity, there must be charged particles present
and these charged particles must be free to move.

The charged particles will be either electrons or ions.

Metals conduct electricity because the delocalised electrons are free to move.

Ionic compounds don’t conduct electricity when they are solid because the
ions are held tightly in position in the lattice – they are not free to move
around (they can only vibrate).

They do, however, conduct electricity when they are molten (have melted) or
if they are dissolved in water (in aqueous solution).

This happens because the ions then become free to move around.

Remember that ionic compounds are made up of

◾◾ anions are negative ions

◾◾ cations are positive ions.

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Covalent molecular compounds are substances like methane (CH4) and carbon
dioxide (CO2), do not conduct electricity in any state or in solution.

Covalent molecular compounds consist of individual molecules.

They have no charged particles to move around. Also, all the electrons are
held tightly in the atoms or in covalent bonds and are not able to move from
molecule to molecule.

There are some exceptions of covalent compounds that form ions as they react
with water,

Example ammonia:

Ammonia conducts electricity because there are ions which are free to move.

Hydrogen chloride gas dissolves in water to form hydrochloric acid (HCl(aq)).

Hydrogen chloride ionises in water:

HCl(aq) → H+(aq) + Cl–(aq)

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What is Electrolysis

Electrolysis is a chemical change caused by passing an electric current

through a compound which is either molten or in solution.

An electrolyte is a liquid or solution that undergoes electrolysis.

Electrolytes all contain ions. The movement of the ions is responsible for both
the conduction of electricity and the chemical changes that take place.

The electricity is passed into and out of the electrolyte through two

electrodes.

Carbon (graphite) is frequently used for electrodes because it conducts

electricity and is chemically inert. Platinum is also inert and can be used
instead of carbon.

The positive electrode is called the anode. The negative electrode is called
the cathode.

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THE ELECTROLYSIS OF MOLTEN COMPOUNDS

ELECTROLYSING MOLTEN LEAD(II) BROMIDE, PbBr2

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◾ the bulb lights up, showing that electrons are flowing through it.

◾there is bubbling around the (the anode) connected to the

positive terminal of the power source as brown bromine gas is given off.

◾at (the cathode) connected to the negative terminal of the power source,

metallic lead is found underneath it.

Explanation:

Lead(II) bromide is an ionic compound that consists of lead(II) ions (Pb2+) and
bromide ions (Br–) packed regularly in a crystal lattice.

The ions are not free to move and doesn’t conduct electricity.

As it melts, the ions become free to move around.

As the power source is connected, mobile electrons move towards the right-
hand electrode and as there are extra electrons at the right-hand electrode, so
it is negative.

The left-hand electrode is positive because some of the electrons have been
removed from it.

The positive lead(II) ions in the molten lead(II) bromide are attracted to the
negative electrode, the cathode (negative electrode).

When they get there, each lead(II) ion picks up two electrons from the
electrode and forms neutral lead atoms. These fall to the bottom of the
container as molten lead.

Pb2+ + 2e– → Pb

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The power source pumps new electrons along the wire to replace the electrons

that have been removed from the cathode.

Bromide ions are attracted to the positive electrode, the anode, the extra
electron which makes the bromide ion negatively charged moves onto the
electrode.

2Br– → Br2 + 2e–

Thus, ions being discharged at the electrodes.

ELECTROLYSIS AND REDOX

◾ Oxidation occurs when something loses electrons.

◾ Reduction occurs when something gains electrons.

As the lead(II) ions gain electrons at the cathode:

Pb2+ + 2e– → Pb

Gain of electrons is reduction. The lead(II) ions are reduced to lead atoms.

The bromide ions lose electrons at the anode:

2Br– → Br2 + 2e–

Loss of electrons is oxidation. Bromide ions are oxidised to bromine

molecules.

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Electrolysis of molten NaCl

If we carry out electrolysis of molten sodium chloride, we get sodium at the

cathode (negative electrode) and chlorine at the anode (positive electrode).

The ionic half-equations are:

cathode: Na+ + e– → Na reduction

Sodium ions are reduced to sodium atoms.

anode: 2Cl– → Cl2 + 2e– oxidation

Chloride ions are oxidised to chlorine molecules.

Electrolysis of molten aluminium oxide (Al2O3)

We get aluminium at the cathode and oxygen at the anode. Aluminium

is in Group 3 in the Periodic Table and so an aluminium atom has 3 electrons

in its outer shell. This means that Al forms a 3+ ion.

This 3+ ion will be attracted to the negative electrode in electrolysis

Al3+ + 3e– → Al
The half-equation for the reaction at the anode is:
2O2– → O2 + 4e–

Electrolysis of molten zinc(II) chloride

zinc is obtained at the cathode and chlorine at the anode:

cathode: Zn2+ + 2e– → Zn reduction

anode: 2Cl– → Cl2 + 2e– oxidation

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THE ELECTROLYSIS OF AQUEOUS SOLUTIONS

PRACTICAL: INVESTIGATING THE ELECTROLYSIS OF AQUEOUS SOLUTIONS

The electrolysis of an aqueous solution of sodium chloride solution.

◾ Set up the apparatus as shown in Figure. The glass tube, rubber

bung and electrodes together are sometimes called an electrolytic cel

◾Pour concentrated sodium chloride solution into the glass tube.

◾Place a test-tube containing sodium chloride solution over each

electrode. The test-tubes must not completely cover the electrodes or

ions will be unable to flow and there will be no current.

◾Connect the battery/powerpack to the electrodes.

◾The experiment should be done in a fume cupboard (fume hood) or

well-ventilated room because chlorine gas is poisonous.

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Observe if something is happening by looking for bubbles of gas or a

metal forming at the electrodes. Any gases can be tested.

The tests for gases are covered in a later chapter.

Observations bubbles of gas at both electrodes.

When the gases are tested we find that hydrogen forms at the negative
electrode (cathode) and chlorine forms at the positive electrode (anode).

THE ELECTROLYSIS OF SODIUM CHLORIDE SOLUTION

Chlorine is formed at the anode, hydrogen is produced at the cathode.

The hydrogen at the cathode comes from the water.

Water is called a weak electrolyte. It ionises very slightly to give hydrogen ions

and hydroxide ions: H2O(l) ⇌ H+(aq) + OH–(aq)

During electrolysis:

The solution contains Na+(aq) and H+ (aq), and these are both attracted to

the negative electrode (cathode). However, sodium is a very reactive metal.

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Hydrogen is less reactive than sodium so it is easier to add an electron to a
hydrogen ion to form a hydrogen atom.

2H+(aq) + 2e– → H2(g)

Cl–(aq) and OH–(aq) are both attracted by the positive anode.

There are, however, many, many more chloride ions present in the solution,
and so it is mainly these that are oxidised at the anode:

2Cl–(aq) → Cl2(g) + 2e–

• hydrogen ions H+(aq) (from the water) are discharged at the negative
electrode as hydrogen gas, H2(g).
• chloride ions Cl– (aq) (from the dissolved sodium chloride) are discharged
at the positive electrode as chlorine gas, Cl2(g).
• sodium ions Na+(aq) (from the dissolved sodium chloride) and hydroxide
ions OH–(aq) (from the water) stay behind - they form sodium hydroxide
solution, NaOH(aq).

THE ELECTROLYSIS OF COPPER(II) SULFATE SOLUTION USING INERT

ELECTRODES

The copper(II) ions and hydrogen ions (from the water) will be attracted to the

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cathode. Copper is below hydrogen in the reactivity series, which means that

it is easier to add electrons to its ion in order to form an atom. The cathode will

get coated with pink-brown copper:

Cu2+(aq) + 2e– → Cu(s) reduction

Sulfate ions and hydroxide ions (from the water) will be attracted to the
anode. Sulfate ions aren’t easy to oxidise. Instead, you get oxygen from the
oxidation of hydroxide ions from the water:

4OH–(aq) → 2H2O(l) + O2 (g) + 4e– oxidation

You can see more easily why the solution becomes acidic using this
half equation: H+(aq) ions are produced.

If the electrolysis is continued the colour of the solution will fade from blue to

colourless.

What is left in the solution?

from CuSO4: SO42–

from water: H+

The solution turns into dilute sulfuric acid (H2SO4).

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THE ELECTROLYSIS OF DILUTE SULFURIC ACID USING INERT ELECTRODES

In this case, the only positive ions arriving at the cathode are hydrogen ions

(from the acid and the water).

These are discharged to give hydrogen gas:

2H+ (aq) + 2e– → H2(g)

At the anode – as with copper(II) sulfate solution – sulfate ions and hydroxide

ions (from the water) arrive.

Oxygen is obtained from the oxidation of hydroxide ions from the water:

4OH–(aq) → 2H2O(l) + O2(g) + 4e–

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Twice as much hydrogen is produced as oxygen.

The amount of hydrogen we obtain is more than twice as much as the oxygen.
This is because oxygen is more soluble in water than hydrogen.

THE ELECTROLYSIS OF SOME OTHER SOLUTIONS USING INERT ELECTRODES

◾ If the metal is high in the reactivity

series, you get hydrogen produced

at the cathode instead of the metal.

◾If the metal is below hydrogen in

the reactivity series, you obtain the

metal at the cathode.

◾If you have solutions of halides

(chlorides, bromides or iodides),

you obtain the halogen (chlorine,

bromine or iodine) at the anode.

With other common negative ions

(sulfate, nitrate, hydroxide), you
obtain oxygen at the anode

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The table shows some simple examples of these rules.

END OF UNIT

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