Electricity and Chemistry:
Electrolysis
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.
What Is Electrolysis?
Electrolysis is a way of separating a compound by passing an
electric current through it; the products are the compound’s
component ions.
• 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.
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 that provides the
physical interface between the electrical circuit providing the
energy and the electrolyte.
• Electrode is a rod of metal or graphite through
which an electric current flows into or out of an
electrolyte.
• Electrolyte is the ionic compound in molten or
dissolved solution that conducts the electricity.
• 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.
Selective Discharge of Ions in Electrolytic Cells.
• In an aqueous solution, more than one type of
cation and anion are present in the electrolyte.
However, only one cation and one anion are
preferentially or selectively being discharged
during the process of electrolysis.
• If the electrodes used during electrolysis
are inert, the ions being preferentially
discharged will depend on three factors:
1) Selective Discharge of Cations
2) Selective Discharge of Anions
3) Effect of Concentration on the Selective Discharge of
Anions
1. Selective Discharge of Cations
• This is linked to the topic of Metals & Reactivity Series.
• The ease of discharge of cations will depend on the position of the metals in
the reactivity series.
• You learnt that the more reactive a metal, the greater its tendency to react and
form ions.
• This simply means that in electrolysis, the more reactive the metal, the
least tendency for the metal ions to be preferentially discharged at
the cathode.
• Ions of reactive metals like potassium and sodium will remain in the electrolyte
solution and will not be discharged.
• Hydrogen ion and ions of less reactive metals like copper and silver will be
preferentially discharged.
• In aqueous solution, hydrogen ions will be preferentially discharged over the
ions of the metals above hydrogen in the reactivity series. Hydrogen gas will be
liberated.
• Likewise, if the cations come from a metal which is below hydrogen in the
reactivity series, then the metal ions will be preferentially discharged. A metal
2. Selective Discharge of Anions
• Ease of discharge of anions increases down the list:
• Sulfate ion, SO42-
• Nitrate ion, NO3–
• Chloride ion, Cl–
• Bromide ion, Br–
• Iodide ion, I–
• Hydroxide ion, OH–
• Note that sulfate and nitrate ions will remain in the electrolyte
solution. They are not electrolysed during electrolysis.
• Hydroxide ions has the highest ease of discharge because it gives out
electrons most readily (easy to be oxidised) during electrolysis.
Oxygen gas will be produced.
• Half equation for the discharge of hydroxide ions: 4OH–(aq) => 2H2O(l)
–
3. Effect of Concentration on the Selective Discharge of Anions
• It is important to note that an anion in higher concentration is always being
preferentially discharged, regardless of the ease of discharge of anions (factor 2).
• Let me give you a simple example to discuss the effect of concentration on the
selective discharge of anions.
• In the electrolysis of concentrated sodium chloride solution, the ions available in the
electrolyte are:
• Sodium ion, Na+
• Chloride ion, Cl–
• Hydrogen ion, H+ (due to partial dissociation of water)
• Hydroxide ion, OH– (due to partial dissociation of water)
• Both chloride and hydroxide ions are attracted to the positive anode.
• Based on the ease of discharge of anions (factor 2), hydroxide ions should be
preferentially discharged.
• However, in concentrated solution, there are a lot more chloride ions than hydroxide
ions.
• Therefore, chloride ions are preferentially being discharged over the hydroxide ions at
Faraday’s First Law of Electrolysis states that the
Faraday’s
chemical deposition First Law
due to the flow of
of current through an
Electrolysis
electrolyte is directly proportional to the quantity of
electricity (coulombs) passed through it.
i.e. mass of chemical deposition:
Where, Z is a constant of proportionality and is known as
electro-chemical equivalent of the substance.
If we put Q = 1 coulombs in the above equation, we will get
Z = m which implies that electrochemical equivalent of any
substance is the amount of the substance deposited on the
passing of 1 coulomb through its solution. This constant of
the passing of electrochemical equivalent is generally
expressed in terms of milligrams per coulomb or kilogram
per coulomb.
