Measuring standard electrode potentials

There are three main types of half-cell whose E —O value can be obtained when connected to a

standard hydrogen electrode:

 metal/metal ion half-cell

 non-metal/non-metal ion half-cell

 Ion/ion half-cell.

Half-cells containing metals and metal ions

 An example of a metal/metal ion half-cell is the Ag+/ Ag half-cell

o Ag is the metal
o Ag+ is the metal ion
This half-cell is connected to a standard hydrogen electrode and the two half-equations are:
Ag+ (aq) + e- ⇌ Ag (s) Eꝋ = + 0.80 V

2H+ (aq) + 2e- ⇌ H2 (g) Eꝋ = 0.00 V

 Since the Ag+/ Ag half-cell has a more positive Eꝋ value, this is the positive pole and the
H+/H2 half-cell is the negative pole

 The standard cell potential (Ecellꝋ) is Ecellꝋ = (+ 0.80) - (0.00) = + 0.80 V

 The Ag+ ions are more likely to get reduced than the H+ ions as it has a greater Eꝋ value
o Reduction occurs at the positive pole
o Oxidation occurs at the negative pole

Zn2+/Zn half-cell

Non-metal/non-metal ion half-cell

In a non-metal/non-metal ion half-cell platinum wire or foil is used as an electrode to make

electrical contact with the solution

o Like graphite, platinum is inert and does not take part in the reaction
o The redox equilibrium is established on the platinum surface
 An example of a non-metal/non-metal ion is the Br2/Br- half-cell
o Br is the non-metal
o Br- is the non-metal ion
 The half-cell is connected to a standard hydrogen electrode and the two half-equations are:

Br2 (l) + 2e- ⇌ 2Br- (aq) Eꝋ = +1.09 V

2H+ (aq) + 2e- ⇌ H2 (g) Eꝋ = 0.00 V

 The Br2/Br- half-cell is the positive pole and the H+/H2 is the negative pole
 The Ecellꝋ is: Ecellꝋ = (+ 1.09) - (0.00) = + 1.09 V
 The Br2 molecules are more likely to get reduced than H+ as they have a greater Eꝋ value
 Half-cells containing ions of the same element in different oxidation states

 A platinum electrode is again used to form a half-cell of ions that are in different oxidation
states.
 An example of such a half-cell is the Fe3+/Fe2+ half-cell
o Fe3+ is an ion containing Fe with oxidation state +3
o The Fe2+ ion contains Fe with oxidation state +2
 This half-cell is connected to a standard hydrogen electrode and the two half-equations are:

2H+ (aq) + 2e- ⇌ H2 (g) Eꝋ = 0.00 V

 The Fe3+/Fe2+ - half-cell is the positive pole and the H+/H2 is the negative pole

 The Ecellꝋ = (+ 0.77) - (0.00) = + 0.77 V

 MnO (aq) + 8H+ (aq) + 5e- ⇌ Mn2+ (aq) + 4H2O (l)
4
-

Eꝋ = +1.52 V

MnO4-/Mn2+ half-
cell