ELECTROLYSIS

Electrolysis is the passage of a direct electric current through an ionic substance that is either molten or
dissolved in a suitable solvent, resulting in chemical reactions at the electrodes and separation of
materials (electrolyte). But before we start to explain electrolysis, there is one important idea that needs
to be understood; if an electric current is to be passed between 2 points, there must be a movement of
charge particles between the points. In a metal the particles are the free electrons. If a voltage is applied
across the ends of a metal wire, free electrons will begin to move along the wire and we could measure
the current. However, if a current is to pass through a liquid, there must be ions that are free to move.

Pure water does not conduct electricity well because it is only slightly dissociated into hydrogen
and hydroxide ions. However if we dissolve NaCl in water, the large number of free sodium and
chloride ions allows the solution to conduct very easily because the crystal structure is broken
down freeing the ions to move about

The main components required to achieve electrolysis are :

 An electrolyte : a substance containing free ions which are the carriers of electric
current. In the electrolyte. If the ions are not mobile, as in a solid salt then electrolysis
cannot occur. An electrolyte is such a chemical whose atoms are normally closely bonded
together but when it is dissolved in water, its molecules split up into positive and negative
ions. The positively charged ions is referred as cations whereas negatively charged ions
are referred as anions. Both cations and anions move freely in the solution.
 A direct current (DC) 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 : an electrical conductor which provides the physical interface between
the electrical circuit providing the energy and the electrolyte

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

Principle of Electrolysis
As discussed in the definition of electrolyte whenever any electrolyte dissolved in water its molecules
split into cations and anions moving freely in the electrolytic solution. Now two metal rods (electrodes)
are immersed in the solution and a potential difference applied between the rods externally preferably by
a battery. The electrode connected with negative terminal of the battery is known as cathode and the
electrode connected with positive terminal of the battery is known as anode. The freely moving positively
charged cations are attracted by cathode and negatively charged anions are attracted by anode. In cathode
the positive cations take electrons from negative cathode and in anode negative anions give electrons to
the positive anode. For continually taking and giving electrons in cathode and anode respectively there
must be flow of electrons in the external circuit of the electrolytic. That means electric current continuous
to circulate around the closed loop created by battery, electrolyte and electrodes. This is the most basic
principle of electrolysis. 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 melted (fused) by heating

Those atoms that gain or lose electrons to become charged ions pass into the electrolyte. Those
ions that gain or lose electrons to become uncharged atoms separate from the electrolyte. The
formation of uncharged atoms from ions is called discharging.

The energy required to cause the ions to migrate to the electrodes, and the energy to cause the
change in ionic state, is provided by the external source of electrical potential.

Oxidation and reduction at the electrodes

Oxidation of ions or neutral molecules occurs at the anode, and the reduction of ions or neutral
molecules occurs at the cathode. For example, it is possible to oxidize ferrous ions to ferric ions
at the anode:

Fe 2+aq → Fe3+aq + e–

It is also possible to reduce ferricyanide ions to ferrocyanide ions at the cathode:

Fe(CN) 63- + e– → Fe(CN)64-

Neutral molecules can also react at either of the electrodes. For example: p-Benzoquinone can be
reduced to hydroquinone at the cathode:

+ 2 e– + 2 H+ →

In the last example, H+ ions (hydrogen ions) also take part in the reaction, and are provided by an
acid in the solution, or the solvent itself (water, methanol etc.). Electrolysis reactions involving
H+ ions are fairly common in acidic solutions. In alkaline water solutions, reactions involving
OH- (hydroxide ions) are common.

The substances oxidised or reduced can also be the solvent (usually water) or the electrodes. It is
possible to have electrolysis involving gases. (Such as when using a Gas diffusion electrode)
Factors affecting products of Electrolysis
There are TWO considerations:

A. If the electrolyte is molten (and carbon/graphite inert electrodes are used

the electrolytic reactions are simple and straightforward.
During electrolysis,
M+ positive ions migrate to Cathode: M + (l) + e ==> M (l)

X - negative ions migrate to Anode: 2X - (l) - 2e ==> X2 (g)

B. If the electrolyte is aqueous the electrolytic reaction becomes more complicated. Water
comes into the picture as water ionizes to form H + and OH – ions. Thus, selection of
ions for preferential discharge is based on the following three factors:

1. Position of the ion in the Electrochemical Series:

Cations K Na Ca Mg Al Zn Fe Sn Pb H Cu Ag

Anions SO4 NO3 CO3 Cl Br I OH

Increasing ease of discharge

Note:
*If two or more positive ions migrate to the cathode, it is the ion lowest in the ECS
(i.e. of the least electropositive metal) that is discharged preferentially.
Examples Copper ions are discharged in preference to Hydrogen ions; Hydrogen ions are
discharged in preference to Sodium ions.
It will be recalled that the reactivity series gives the order of the tendency of metals to form ions.
Metals at the top of the series have the greatest tendency to form ions and are therefore the most
difficult to discharge at the cathode.
* If two or more negative ions migrate to the anode, the ion lower in the ECS is discharged
preferentially.

2. Concentration of the ions in the electrolyte:

A very dilute solution of any electrolyte on electrolysis liberates oxygen at the anode
However, if the concentration of a particular ion is high, then this can alter the preferential
discharge.
For example, if dilute hydrochloric acid is electrolysed, hydrogen gas is produced at the cathode
and oxygen gas at the anode. However, when concentrated hydrochloric acid is electrolysed,
hydrogen gas is still liberated at the cathode, but chlorine gas (and NOT oxygen gas) is now
 produced at the anode instead. The higher concentration of the chloride ions favor their
discharge over the hydroxide ions.
NOTE: Ions of Sodium, Potassium, Sulphate and Nitrate ions are NOT discharged even if the
are high in concentrations.

3. Electrode material used:

Inert electrodes (made of graphite or platinum) do not affect the products of electrolysis ; only
Reactive / Active electrodes do affect.
Example
Electrodes Electrolyte At Cathode At Anode
Carbon (inert) aqueous copper(II) sulfate copper metal deposited oxygen liberated
Copper aqueous copper(II) sulfate copper metal deposited copper electrode dissolves
(active)

Examples of Electrolysis

A. Electrolysis of water:

At the anode: 2H2O(l) — 4e- → 4H+aq + O2(g)

At the cathode: 4H2O(l) + 4e- → 4OH-aq + 2H2(g)

From the equation the release of 1 mole of oxygen needs 4 moles of electrons therefore in
the elerolysis equal number of electrons lost from the cathode is gained at the anode. Thus
4 mole of electrons must be picked up from the water molecules at the cathode. 2 moles of
hydrogen gas will be given off for every 1 mole of oxygen. A reflection of the ratio of the
elements in the formula of water.
B. Electroysis of Copper (II) Sulphate solution:

There are two ways of carrying out the electrolysis

i. The use of two inert electrodes, platinum or carbon.

ii. The use of electrode made from copper

In both cases we have the same set of ions and molecules present.

From water----------- H2O molecules

From CuSO4--------- Cu2+ and SO42-

With Inert Electrodes

H2O molecules and Cu2+ ions are preferentially discharged.

At the anode 2H2O – 4e- → 4H+(aq) + O2(g)

At the cathode Cu2+ + 2e- → Cu(s)

This perhaps the simplest example of the basis of electroplating. Copper metal is liberated
at the cathode. If the conditions are right the copper will cling to the cathode, thereby
plating it. In industries electroplating is very important. Cutlery can be silver plated and
many of the shiny decorative parts of cars and bicycles are chromium plated. Usually the
object to be plated is made the cathode in an electrolysis bath. The length of time they
spend in the electrolyte and the current flowing determines the thickness of the plating.

With Copper electrodes

It is easier for copper metal to lose electrons (be oxidized) than it is for water molecules to
lose them. Instead of oxygen being given off, the copper from the anode changes into
copper (II) ions.
At the anode Cu – 2e- → Cu2+(aq)

At the cathode Cu2+(aq) + 2e- → Cu(s)

From these 2 equations it can be seen that the anode will gradually be worn away while the
cathode becomes coated with copper. The cathode will gain a mass of copper equal to that
lost from the anode.

How to calculate the mass of a substance liberated in electrolysis

Example 1: If silver nitrate is electrolysed, the following reactions take place at the
electrodes:

At the anode 2H2O(l) - 4e- → 4H+(aq) + O2(g)

At the cathode Ag+ + e- → Ag(s)

Calculate the amount of silver in grams deposited at the cathode if a current of 0.2A is
passed for 30mins through the electrolytic cell.

Solution: First calculate the number of Coulombs of charge transferred by the current.

No of Coloumbs = Current (A) x Time of current flow (secs)

0.2A x 60 x 60(s) = 720C

No of moles of electrons = = 7.46 x 10-3 mol

From the equation: 7.46 x 10-3mol of electrons → 7.46 x 10-3 of silver

Thus the mass of silver is 7.46 x 10-3 x 108gmol-1 = 0.81g

Faraday's laws of electrolysis

In 1832, Michael Faraday was the first person to investigate electrolysis systematically and came
up with the following laws;

Faraday’s first law: It states that the quantity (mass) of a substance liberated in an electrolysis
is proportional to the quantity of electricity passed.

Faraday’s second law: When the same amount of electricity is passed through different
electrolytes/elements connected in series, the mass of substance liberated/deposited at the
electrodes is directly proportional to their equivalent weights (or inversely proportional to the
charges on the ions).

Faraday's laws can be summarized by m

where:

 m is the mass of the substance liberated at an electrode in grams

 Q is the total electric charge passed through the substance
 F = 96485 C mol−1 is the Faraday constant
 M is the molar mass of the substance
 z is the valency number of ions of the substance (electrons transferred per ion).

Note that M/z is the same as the equivalent weight of the substance altered.

For Faraday's first law, M, F, and z are constants, so that the larger the value of Q the larger m
will be.

For Faraday's second law, Q, F, and z are constants, so that the larger the value of M/z
(equivalent weight) the larger m will be.

Difference between Electrochemical Cell and Electrolytic Cells.

Electrochemical Cell Electrolytic Cell

It converts chemical energy into It converts electrical energy

electrical energy. into chemical energy.

It is based upon the redox The redox reactions are non-

reactions which are spontaneous. spontaneous and take place
only when energy is supplied.

The chemical changes occurring Only one chemical compound

in the two beakers are different. undergoes decomposition.

Anode (-ve) - Oxidation takes Anode (+ve) - Oxidation

 Electrochemical Cell Electrolytic Cell

place. takes place.

Cathode (+ve) - Reduction takes Cathode (-ve) - Reduction

place. takes place.

Uses of Electrolysis

Industrial uses

 Production of aluminium, lithium, sodium, potassium, magnesium, calcium. Coulometric

techniques can be used to determine the amount of matter transformed during electrolysis
by measuring the amount of electricity required to perform the electrolysis
 Production of chlorine and sodium hydroxide
 Production of sodium chlorate and potassium chlorate
 Production of perfluorinated organic compounds such as trifluoroacetic acid
 Production of electrolytic copper as a cathode, from refined copper of lower purity as an
anode.

Electrolysis has many other uses:

 Electrometallurgy is the process of reduction of metals from metallic compounds to

obtain the pure form of metal using electrolysis. For example, sodium hydroxide in its
molten form is separated by electrolysis into sodium and oxygen, both of which have
important chemical uses. (Water is produced at the same time.)
 Anodization is an electrolytic process that makes the surface of metals resistant to
corrosion. For example, ships are saved from being corroded by oxygen in the water by
this process. The process is also used to decorate surfaces.
 Production of oxygen for spacecraft and nuclear submarines.
 Electroplating is used in layering metals to fortify them. Electroplating is used in many
industries for functional or decorative purposes, as in vehicle bodies and nickel coins.
 Production of hydrogen for fuel, using a cheap source of electrical energy.
 Electrolytic Etching of metal surfaces like tools or knives with a permanent mark or logo.
 Electrolysis is also used in the cleaning and preservation of old artifacts. Because the
process separates the non-metallic particles from the metallic ones, it is very useful for
cleaning old coins and even larger objects.