why can we not use electrolytes in the solid form for electrolysis
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because in solid form there will be no formation of ions
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Electrolysis
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Electrolysis of molten compounds
The ions in the electrolyte must be free to move to the electrodes for electrolysis to work. They are free to move in aqueous solutions and in molten liquids. However, the ions are in fixed positions in solid ionic compounds - they cannot move around, so electrolysis does not work in solids.

Ions in ionic solids are arranged in a giant lattice and cannot move around
When a molten (melted) ionic compound is electrolysed:
the positive ions are discharged at the cathode
the negative ions are discharged at the anode
For example, during the electrolysis of molten lead bromide:
lead ions, Pb2+, move to the cathode and are discharged as lead
bromide ions, Br–, move to the anode and are discharged as bromine
Half equations
You should be able to write half equations for the reactions happening at the electrodes during the electrolysis of a molten electrolyte if you are given the formulae of the ions it contains.
Example
Molten mead bromide contains Pb2+ ions and Br–ions. Write half equations for the electrode processes when it is electrolysed.
At the cathode: Pb2+ + 2e- → Pb
At the anode: 2Br- - 2e- → Br2
Science
Electrolysis
Page
1
2
3
4
Back
Next
Electrolysis of molten compounds
The ions in the electrolyte must be free to move to the electrodes for electrolysis to work. They are free to move in aqueous solutions and in molten liquids. However, the ions are in fixed positions in solid ionic compounds - they cannot move around, so electrolysis does not work in solids.

Ions in ionic solids are arranged in a giant lattice and cannot move around
When a molten (melted) ionic compound is electrolysed:
the positive ions are discharged at the cathode
the negative ions are discharged at the anode
For example, during the electrolysis of molten lead bromide:
lead ions, Pb2+, move to the cathode and are discharged as lead
bromide ions, Br–, move to the anode and are discharged as bromine
Half equations
You should be able to write half equations for the reactions happening at the electrodes during the electrolysis of a molten electrolyte if you are given the formulae of the ions it contains.
Example
Molten mead bromide contains Pb2+ ions and Br–ions. Write half equations for the electrode processes when it is electrolysed.
At the cathode: Pb2+ + 2e- → Pb
At the anode: 2Br- - 2e- → Br2
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