Overview[edit]

Electrolysis is the passing of a direct electric current through an ionic substance that is either
molten or dissolved in a suitable solvent, producing chemical reactions at the electrodes and
separation of materials.
The main components required to achieve electrolysis are:

An electrolyte: a substance, frequently an ion-conducting polymer that contains free ions,

which carry electric current in the electrolyte. If the ions are not mobile, as in a solid salt
then electrolysis cannot occur.

A direct current (DC) electrical supply: provides the energy necessary to create or
discharge the ions in the electrolyte. Electric current is carried by electrons in the external
circuit.

Two electrodes: electrical conductors that provide the physical interface between the
electrolyte and the electrical circuit that provides the energy.

Electrodes of metal, graphite and semiconductor material are widely used. Choice of suitable
electrode depends on chemical reactivity between the electrode and electrolyte and
manufacturing cost.

Process of electrolysis[edit]
The key process of electrolysis is the interchange of atoms and ions by the removal or addition of
electrons from the external circuit. The desired products of electrolysis are often in a different
physical state from the electrolyte and can be removed by some physical processes. For example,
in the electrolysis of brine to produce hydrogen and chlorine, the products are gaseous. These
gaseous products bubble from the electrolyte and are collected.[3]
2 NaCl + 2 H2O 2 NaOH + H2 + Cl2
A liquid containing mobile ions (electrolyte) is produced by:

Solvation or reaction of an ionic compound with a solvent (such as water) to produce

mobile ions

An ionic compound is fused by heating

An electrical potential is applied across a pair of electrodes immersed in the electrolyte.

Each electrode attracts ions that are of the opposite charge. Positively charged ions (cations)
move towards the electron-providing (negative) cathode. Negatively charged ions (anions) move
towards the electron-extracting (positive) anode.
In this process electrons are either absorbed or released. Neutral atoms gain or lose electrons and
become charged ions that then pass into the electrolyte. The formation of uncharged atoms from
ions is called discharging. When an ion gains or loses enough electrons to become uncharged
(neutral) atoms, the newly formed atoms separate from the electrolyte. Positive metal ions like
Cu++ deposit onto the cathode in a layer. The terms for this are electroplating, electrowinning, and
electrorefining. When an ion gains or loses electrons without becoming neutral, its electronic
charge is altered in the process. In chemistry, the loss of electrons is called Oxidation, while
electron gain is called reduction.

3. The electrolysis of sodium chloride solution (brine)

Aqueous solutions with inert electrodes (carbon or platinum)
The products of electrolysing aqueous sodium chloride solution are hydrogen
gas, chlorine gas and sodium hydroxide solution
The simple apparatus illustrated on the right can be used in simple school or college
experiments for the electrolysis of sodium chloride solution (often referred to as 'brine' in
the chemical industry). The graphite (carbon) electrodes are, through a large rubber
bung, 'upwardly' dipped into an solution of the sodium chloride solution (the electrolyte).
The cell can be made from plastic pipe and a big rubber bung with two holes in it. In the
simple apparatus the gaseous products (hydrogen and chlorine) are collected in small
test tubes inverted over the carbon electrodes and chemical tests performed on them.
You have to fill the little test tubes with the electrolyte (sodium chloride solution), hold
the liquid in with your finger and carefully invert them over the nearly full electrolysis
cell.
A more elaborate format is to use a Hoffman Voltammeter (left diagram) using
platinum electrodes and accurately calibrated collecting tubes like burettes. The
Hofmann voltameter is filled with the electrolyte (aqueous sodium chloride solution) by
opening the taps at the top of the outer tubes to allow any gas to escape. The gases
formed on the electrolysis of the dilute 'brine' solution can be collected via the same
taps. The students should note that nothing happens until you switch on the electricity
supply (see simple animation above!). The platinum or carbon electrodes are inert.
The industrial electrodes must be made of an inert material like platinum/titanium which
is not attacked by chlorine or alkali, but in the school /college laboratory, the Hofmann
voltameter is a good demonstration (platinum electrodes) and the 'simple cell' for
students uses carbon/graphite electrodes which are reasonably inert.

However a simple cell using carbon electrodes can be used by students/pupils to

demonstrate the industrial process in the laboratory.
The electrolysis will only take place when electricity is passed through the sodium
chloride solution.

The electrode reactions and products of the electrolysis of sodium chloride

solution (brine) are illustrated by the theory diagram above
The electrolyte sodium chloride solution (brine), provides a high concentration of
sodium ions Na+ and chloride ions Cl to carry the current during the electrolysis
process. Initially there are only traces of hydrogen ions H+ and hydroxide ions OH from
the self-ionisation of water.
Brine is moderately concentrated sodium chloride solution (brine) with carbon (graphite)
gives equal volumes of hydrogen gas (hydrogen ions H+ discharged at the ve
cathode) and green chlorine gas (chloride ions Cl discharged at the +ve anode) with
sodium hydroxide left in solution. The electrolysis will only take place when electricity
is passed through the sodium chloride solution.
The electrode equations and the theory of what happens in the electrolysis of
aqueous sodium chloride

The half-equations for the electrolysis of sodium chloride solution (the electrolyte brine).

(a) The negative cathode electrode reaction for the electrolysis of brine (sodium
chloride solution)
The negative () cathode attracts the Na+ (from sodium chloride) and H+ ions (from
water). Only the hydrogen ions are discharged at the cathode. The more reactive a
metal, the less readily its ion is reduced on the electrode surface.
The hydrogen ions are reduced by electron (e) gain to form hydrogen molecules at the
negative electrode which attracts positive ions.
2H+(aq) + 2e ==> H2(g)
positive ion reduction by electron gain
other equations
2H2O(l) + 2e ==> H2(g) + 2OH-(aq)
or 2H3O+(aq) + 2e ==> H2(g) + 2H2O(l)
Nothing happens to the sodium ion, but it is still important (see after the anode
reaction has been described).
In fact, if sodium was released (which it isn't), it would immediately react with water to
give hydrogen, the same product you get from the reduction of the hydrogen ion.
Test for the cathode gas - colourless gas gives a squeaky pop with a lit splint
hydrogen

(b) The positive anode electrode reaction for the electrolysis of brine (sodium
chloride solution)
The positive anode attracts the negative hydroxide OH ions (from water) and chloride
Cl ions (from sodium chloride). Only the chloride ion is discharged in appreciable
quantities i.e. it is preferentially oxidised to chlorine.
The chloride ions are oxidised by electron loss to give chlorine molecules at the positive
electrode which attracts negative ions.
an oxidation electrode reaction

2Cl(aq) 2e ==> Cl2(g)

or 2Cl ==> Cl2(g) + 2e
negative ion oxidation by electron loss
Note that you can write these anode oxidation reactions either way round
The chloride ion is oxidised to chlorine gas molecules in any chloride salt solution
electrolysed, hydrochloric acid and in any electrolysis of a molten chloride salt.
Test for the anode gas - pale green gas turns damp blue litmus red and then bleaches
it white chlorine (test 2 gas 2)

Usually nothing happens to the hydroxide ion BUT it is important, because, the
hydroxide ion, with the unchanged sodium ion, the residual solution contains sodium
hydroxide. In fact this is how sodium hydroxide is manufactured in the chemical
industry.
Na+ + OH = NaOH
The chloralkali process (also chlor-alkali and chlor alkali) is an industrial process for the
electrolysis of NaCl. It is the technology used to produce chlorine and sodium hydroxide (caustic
soda), which are commodity chemicals required by industry. 35 million tons of chlorine were
prepared by this process in 1987.[1] Industrial scale production began in 1892.
Usually the process is conducted on a brine (an aqueous solution of NaCl), in which case NaOH,
hydrogen, and chlorine result.