Nernst Equation (Cambridge (CIE) A Level Chemistry): Revision Note
The Nernst Equation
Under non-standard conditions, the cell potential of the half-cells is shown by the symbol Ecell
The effect of changes in temperature and ion concentration on the Ecell can be deduced using the Nernst equation
E = electrode potential under nonstandard conditions
Eθ = standard electrode potential
R = gas constant (8.31 J K-1 mol-1)
T = temperature (kelvin, K)
z = number of electrons transferred in the reaction
F = Faraday constant (96 500 C mol-1)
ln = natural logarithm
This equation can be simplified to
At standard temperature, R, T and F are constant
ln x = 2.303 log10 x
The Nernst equation only depends on aqueous ions and not solids or gases
The concentrations of solids and gases are therefore set to 1.0 mol dm-3
Worked Example
Calculating the electrode potential of a Fe3+ / Fe2+ half-cell
Calculate the electrode potential at 298K of a Fe3+ / Fe2+ half-cell.
Fe3+ (aq) + e– Fe2+ (aq)
[Fe3+] = 0.034 mol dm-3
[Fe2+] = 0.64 mol dm-3
Eθ = +0.77 V
Answer
From the question, the relevant values for the Fe3+ / Fe2+ half-cell are:
[Fe3+] = 0.034 mol dm-3
[Fe2+] = 0.64 mol dm-3
EΘ = + 0.77 V
The oxidised species is Fe3+ as it has a higher oxidation number (+3)
The reduced species is Fe2+ as it has a lower oxidation number (+2)
z is 1 as only one electron is transferred in this reaction
The Nernst equation for this half-reaction is, therefore:
E = (+0.77) + (-0.075)
E = +0.69 V
Worked Example
Calculating the electrode potential of a Cu2+ / Cu half-cell
Calculate the electrode potential at 298K of a Cu2+ / Cu half-cell.
Cu2+ (aq) + 2e– Cu (s)
[Cu2+] = 0.001 mol dm-3
Eθ = +0.34 V
Answer
From the question, the relevant values for the Cu2+ / Cu half-cell are:
[Cu2+] = 0.0010 mol dm-3
EΘ = + 0.34 V
The oxidised species is Cu2+ as it has a higher oxidation number (+2)
The reduced species is Cu as it has a lower oxidation number (0)
Cu is solid which means that it is not included in the Nernst equation
Its concentration does not change and is, therefore, fixed at 1.0
z is 2 as 2 electrons are transferred in this reaction
The Nernst equation for this half-reaction is, therefore:
E = (+ 0.34) + (– 0.089)
E = + 0.25 V
Examiner Tips and Tricks
You need to know the Nernst equation, so make sure you learn it
CIE specifically ask students to learn use this version:
Make sure you always check what the temperature is
If the temperature is not 298 K (or 25 oC) the full Nernst equation should be used
You don’t need to know how to simplify the Nernst equation
You are only expected to use the equation when the temperature is 298 K (or 25 oC)
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