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The chemical changes that involve the flow of electric current are called
electrochemical changes. There are two types of electrochemical changes.
Electrolytic Cells:
These cells constitute the electrochemical reactions in which electrical energy is
converted into chemical energy.
In these cells electric energy is used to drive redox reactions, which are non-
spontaneous and have positive free energy (∆G)
Two metallic rods are suspended in the electrolytic solution. These plates are
connected to the terminals of a battery with the help of connecting wires. These
plates or rods are called electrodes and allow the passage of current.
The electrode, which is connected to the positive terminal of the battery, is called
anode while that connected to the negative terminal is called cathode.
When electrolyte is dissolved in water it splits up into positive ion (cation) and
negative ion (anion).
When electric current is allowed to pass through the solution then oppositely
charged electrodes attract the ions. As a result cation move towards cathode and
anion moves towards anode. This movement of ions in the solution is called ionic
conduction and constitutes flow of current through the solution.
When anions reach at cathode they give up their electrons and these electrons
flow out of the solution while cations gain the electrons from the cathode and get
converted into neutral particles.
Example:
Now the resulting solution contains only Na+ and OH- ions. At cathode both Na+
and H+ ions try to get reduced but the reaction having higher value of reduction
potential ( Eo) is preferred. Therefore at cathode the reaction occurring is
So the reaction at cathode is
Since we have added Sulphuric acid in the water for electrolysis so, SO42- ions
are also present in the electrolyte. And these are also formed at the anode.
In this case both OH- and SO42- ions move towards anode .But SO2-4 ions will not
be released at because of their high discharge potential as compared to OH-
ions.
The gases H2 and O2 are collected at anode and cathode respectively. The
volume of the gases collected is in the ratio of 2:1 respectively, thus the formula
of the compound is H2O.
3) Electrolysis of aqueous Copper Sulphate solution:
It may be noted that in the above example, the electrode used should be of other
non reactive metal i.e. Pt (platinum) so that it should not be attacked by the
copper ions.
5) Electrolysis of aqueous copper sulfate using copper electrode:
At anode: In this type of electrolysis no ions are produced. On the other hand,
anode itself undergoes loss of electron to form Cu2+ ions, which go to solution.
So, the net result of electrolysis is that copper is deposited at the cathode from
the solution and an equivalent amount of copper from the anode dissolves in the
solution as Cu 2+.
Electrolysis of Sulphuric acid: During electrolysis, Sulphuric acid is dissociated
into H+ ions and SO42- ions.
For dilute solutions, reaction (i) is preferred and O2 liberates at anode. But at
higher concentration of sulfuric acid, reaction (ii) is preferred and solution of
H2S2O8 (per oxo disulphuric acid) is obtained.
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