Electrolysis

1. Electrolytic cell (consists of two electrodes and electrolyte)

When electricity is applied to the electrodes, the electrolyte provides ions that migrates to one of the
two electrodes based on the concept of opposite attract. Cations are attracted to the negative
electrode-cathode to accept electrons, undergoing reduction. Anions are attracted to the positive
electrode-anode to lose electrons, undergoing oxidation.
Summary:
Electrochemical cells: chemical energy → electricity
Electrolytic cell: electricity → chemical energy

In electrochemical cell:
Anode - lose(produce) electrons, oxidation occurs, negative polarity
Cathode - gain(consume) electrons, reduction occurs, positive polarity
 In electrolytic cell:
Anode - anions are attracted to,positive polarity, anions lose electrons, oxidation occurs.
Cathode - cations are attracted to, negative polarity, cations gain electrons, reduction occurs.

2. Selective discharge of ions in electrolyte

Discharge: take place redox reaction

Influenced by:
The electrode potential of the species
The relative concentrations of the species
The nature of the electrolyte
The nature of electrode.

A. The nature of the electrolyte (molten or aqueous)

Electrolyte Anode Cathode Reaction on cathode(reduction) Reaction on anode(oxidation)
NaCl(aq) Pt Pt Na+ H+ H2O Cl- OH- H2O
Na+ Cl-
H+ OH-
H2O

NaCl(molten) Pt Pt Na+ Cl-

Na+ Cl-

B. The nature of the electrode

Electrolyte Anode Cathode Reaction on cathode(reduction) Reaction on anode(oxidation)
CuSO4(aq) Graphite Graphite Cu2+ H2O SO42- H2O
Cu2+
SO42-
H2O

CuSO4(aq) Cu Cu Cu2+ H2O Cu SO42- H2O

Cu2+
SO42-
H2O
 C.The relative concentrations of the species
Electrolyte Anode Cathode Reaction on cathode(reduction) Reaction on anode(oxidation)
NaCl(aq) Graphite Graphite Na+ H2O Cl- OH- H2O
Na+ Cl-
H2O

NaCl(conc) Pt Pt Na+ H2O Cl- OH- H2O

Na+ Cl-
H2O

Practice
Electrolyte Anode Cathode Reaction on cathode Reaction on anode Overall reaction
MgCl2(l) Graphite Graphite

Al2O3(l) Pt Pt

FeCl3 pt pt

AgNO3 pt pt

PbBr2 pt pt

FeSO4 pt pt
3. Faraday’s Law of electrolysis
1st law: m or v is directly proportional to the amount of charge that passes through the cell.
2nd law: the amount of charge required to discharge one mole of an element depends on the charge z
on the ion.

Q = I×t
One faraday F is the charge carried by one mole of electrons: F = Le = 6.02 × 10 23 ×1.6 × 10-19 =
96,500c/mol

Amount of e- =

Eg.
Calculate the mass of Cu produced in the electrolytic cell of CuSO4. The current measured is 2.00A,
and the duration is 20min.
Electrolysis of Cr2(SO4)3 produced 1.0g Cr, and the current measured is 1.20A. calculate the time for
the whole process.