ELECTROLYSIS
Electrolysis: is a process of decomposition of a substance using electricity or the process
of decomposing a substance using electrical energy. The substance should
contain some ions i.e. In solution or molten state.
Electrolyte: are compounds which conduct electricity when molten or dissolved in water
and are decomposed by it.
Electrolytes are made up of ions. This ion are free to move when the electrolytes
is dissolved in water or molten.
Example of electrolytes
Ionic compound Acids
Lead (ii) Bromide Hydrochloric acid
Copper (ii) Sulphate Sulphuric acid
Sodium Chloride
Non electrolyte: a solution or a molten compound that can not decompose by electricity.
Example of non electrolyte
Ethanol
Paraffin
Strong electrolyte: completely ionize in water. E.g. CuSO4, H2SO4, NaCl
Weak electrolyte: will ionize partially in water. E.g H2O, CH3COOH
Electrode: two poles carbon or metal at which current enter or leave an electrolyte
Anode: is the positive (+) electrode which is electron deficient it attracts negatively
charged ions, because unlike charges attract. Anions from electrolyte lose
electrons and become atoms. Oxidation take place
Cathode: negative (-) electrode which has excess electrons and attracts a cations. Cations
from the electrolytes gain electrons and become atoms. Reduction takes place
Anion: negative ion (atom with extra electrons)
Cation: positive ion (atom in short of electrons)
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Ionic theory
Electrolytes are made up of ions. When molten or dissolve in water the ions are free to
move there by conduct electrolyte.
Solid electrolytes
No free movement of ions. Only vibrations
Molten or solution electrolytes
Free movement of ions
THE PROCESS OF ELECTROLYSIS
THE ELECTROLYTIC CELL
Anion are attracted to the anode. Extra electrons of anion are removed at the
anode and the anion become atom.
Cation are attracted to the cathode. At the cathode they gain electron and become
atoms
The electron are sucked into the battery
The overall effect is that electrons are continually entering the circuit at the anode
and are moved at the cathode.
Electrons do not pass through the liquid they are carried by ions.
ELECTROLYSIS OF SOLUTION
Water is s very weak electrolyte, meaning it will ionize partially in water. Water is
electrolyte when dissolve in it are being electrolyte
H2O → H+ +OH-
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FACTORS INFLUENCING PREFERENTIAL DISCHANGE OF IONS AT THE
ELECTRODES
1. Position of the ion in the electrochemical serie
Na+
Mg2+ SO42-
Al3+ NO3-
Zn2+ Increase in ease
Fe2+ Increase in ease of discharge at Cl- of discharge
Pb2+ cathode Br- at the anode
H+ I-
Cu2+ OH-
Hg+
Ag+
Au+
Electrochemical series
When two or more ions similar change are present under similar condition
in a solution one is preferentially selected for discharge
A less stable ion is preferred for discharge than a more stable ion.
At the cathode: Hydrogen ion (H+) are discharged to the more reactive
metals producing hydrogen gas and ions of less reactive metals are
discharged in preference to the hydrogen ions. This is because more reactive
metals prefer staying in the ionic form than the less reactive ones
Example 1: sodium chloride solution (Na+, Cl- and H+, OH- from water)
2H+(aq) + 2e- ==> H2(g)
Example 2: Copper (II) Sulphate solution ( Cu2+, SO42- and H+, OH- from water)
Cu2+(aq) + 2es ==> Cu (s)
At the anode: If ions of the halogens and OH - ions are present in the
electrolyte the halogen ion will ready dive up its electrons (discharge) than
the OH- ions will do and molecules of the halogen will be formed. If no
halogen ions are present, the OH - ion will give up its electrons (discharge)
than other non metals ions will do and oxygen and water will be formed
Example 1: sodium chloride solution (Na+, Cl- and H+, OH- from water)
2Cl-(aq) ==> Cl2(g) + 2e-
Example 2: Copper (II) Sulphate solution ( Cu2+, SO42- and H+, OH- from water)
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4OH- - 4es ==> 2H2O + O2
2. Concentration of the ion
Increase in concentration of the ion tend to promote its discharge e.g. in
concentrated hydrochloric acid which contains OH- ions as the anions CI-
will be discharged in preference but if the acid is very dilute the discharge
of the OH- ion is preferred
3. Nature of the electrode
The electrode used also influence the ion to the discharged from the
electrolyte
Example: Electrolysis of Copper (II) Sulphate solution using carbon or
copper electrodes
Carbon electrodes: Carbon is inert therefore do not take part in the
chemical changes that take place hence according to the electrochemical
series Cu2+ ions are discharged at the cathode and OH- ions at the anode
Copper electrodes: The copper anode take part in the chemical changes as
copper atoms lose electrons to replace the Cu 2+ ions that are discharge at the
cathode hence the concentration of copper (II) Sulphate does not change
and the mass of the anode decreases will that of the cathode increases
Electrolysis of water
Pure water is a very poor conductor of electricity because there are so few ions in it.
However, it can be made to decompose if an electric current is passed through it in a
Hofmann voltammeter.
To enable water to conduct electricity better some sulphuric acid is added. When an
electric current flow through this solution gases can be seen to be produced at the two
electrodes
Electrolysis of concentrated sodium chloride
Electrodes: Platinum/Carbon
Ions present: from NaCl: Na+Cl-.
From H2O : H+; OH-
Anode
Chloride ion and hydroxide ion migrate to the anode
Chloride ions discharged
2Cl-(aq) ==> Cl2(g) + 2e-
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Chlorine gas produced at the anode
Cathode
Sodium ion and hydrogen ion migrate to the cathode
Hydrogen ions discharge
2H+(aq) + 2e- ==> H2(g)
Hydrogen gas produced at the cathode.
Sodium ion gain electrons (reduction) to form sodium atoms and chloride ion lose
electrons (oxidation) to form chlorine atoms.
Na+ and OH- ion are left behind forming an alkaline solution of sodium hydroxide
Electrolysis of dilute sulphuric acid
Electrodes: carbon
Ions present: From H2SO4, H+; SO42-
From H2O: H+; OH-
Anode
Hydroxide ion and Sulphate ion migrate to the anode
OH- ions discharged
4OH → 2H2O + O2
Oxygen and water produced at the anode
Cathode
Sulphate ion and hydroxide migrate to the cathode
Hydrogen ion discharged
2H+(aq) + 2e- ==> H2(g)
Hydrogen gas produced at the cathode
H+ and SO42+ ions are left behind forming an acids called sulphuric acid
Electrolysis of dilute sulphuric acid is referred to as electrolysis of water because only the
ions from water are discharged
Electrolysis of hydrochloric acid
Electrode: Carbon
Ions present: From HCl: H+; Cl-
From H2O: H+; OH-
Anode
Hydroxide ion and Chloride ion migrate to the anode
Chloride ions discharged
2Cl-(aq) ==> Cl2(g) + 2e-
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Chlorine gas produced at the anode
Cathode
Hydrogen ion and Chloride ion migrate to the cathode
Hydrogen ions discharged
2H+(aq) + 2e- ==> H2(g)
Hydrogen gas produced at the cathode
H+ and OH- ions are left behind forming an neutral solution which is water (H2O)
ELECTROLYSIS OF MOLTEN COMPOUNDS
Electrolysis of molten lead (ii) Bromide
Ions present: Pb2+, Br-
Anode
Br- ion migrate to the anode
The bromine ions move through the melt until they reach the anode. Once they
get there, they give up their two extra electrons to become bromine atoms.
2Br- → Br2 + 2e-
Bromide is produced at the anode
Cathode
Pb2+ Migrate to the anode
Pb2+ + 2e- → Pb
Molten lead collects at the at the cathode
ACTIVE AND INERT ELECTRODES
Inert electrodes: do not take part in electrolysis e.g. Carbon, Platinum
Active electrodes: take part in electrolysis e.g. Copper electrodes in a solution containing
Copper ions
Electrolysis of copper (ii) Sulphate using inert electrode
Electrodes: carbon/platinum
Ions present: CuSO4: Cu2+, SO42-
H2O 2H+, OH-
Anode
Hydroxide ion and Sulphate ion migrate to the anode
Hydroxide ions discharged
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4OH- - 4es ==> 2H2O + O2
Water and oxygen gas produced at the anode
The anode remains the same
Cathode
Copper ions and Hydrogen ion migrate to the anode
Copper ions discharged
Cu2+(aq) + 2es ==> Cu (s)
Copper deposited at the cathode (cathode increase in mass)
The blue color of copper (ii) will fade as copper ion removed from the solution at the
cathode
Electrolysis of aqueous copper (ii) Sulphate using active electrodes
Electrodes: Copper
Copper electrode is going to be active because they are copper ions in the solution
Ion present:
Anode ( made of copper)
Copper atoms making up the anode are turned to copper (ii) ions to replace ion
removed from at the cathode
Cu(s) ==> Cu2+(aq) + 2es
Anode is eaten up and it decreases in mass
Cathode (made up of Copper)
Copper ions are removed from the solution and deposited on the cathode as
cathode increase in mass
Cu2+(aq) + 2e s ==> Cu (s)
N:B decreases in mass at the anode equals to increase in mass at the cathode
The colour of copper (ii) Sulphate will remain the same as copper ion are always
replaced by the anode.
PURIFICATION/ REFINING OF METALS USING ELECTRICITY
The process of electrolysis can be used to purity metals.
Anode: made up of impure metals
Cathode: strips of pure metal
Electrolyte: Must contain ions of the metal which is purified
Metal atoms in the impure anode are oxidized of metal ions (anode dissolves). The impurities fall
to the bottom of the container
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Metal ions are reduced to atoms at the cathode. Atoms are deposited on the pure cathode.
Example: purification of copper
The half equations are:
Cu (s) Cu2+(aq) + 2e-
Cu2+(aq) + 2e- Cu (s
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ELECTROPLATING
Electroplating: is the coating an object with a thin layer of metal using electricity.
Reasons for electroplating
To make the object to be attractive or to enhance their appearance
Protect it from corrosion and wear
Example of metal used for electroplating
Gold
Copper
Silver
Nickel
Tin
Chromium
Platinum
Procedure
a) Clean the object
b) Use the object to be electroplated as the cathode of the cell
c) The metal used to electroplate must be used as the anode
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d) The electrolyte must contain ions of the metal used for electroplating.
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