The Effect of Concentration on Cell Potentials

Altering the concentrations of the ions in the half cells of a

galvanic cell affects the cell potential in a logarithmic fashion.
When all the concentrations of the ions in a cell are 1.00 M the cell
potential is equal to the standard potential. When the
concentrations change, so does the potential of the cell. For
example in a battery, the potential of the cell decreases as the
reactants are consumed. When the cell reaches equilibrium, the
potential will drop to zero. The advent of rechargeable batteries
has brought the idea that a galvanic cell can be recharged so long
as an external source of electrons reverses the reaction and creates
a condition where the reactants are present again.
The effect of concentration on the cell potential can be
calculated from the Nernst equation : Ecell = Ecell (2.303 RT / n
F) log Q
But since we normally work at SATP this appears as:

Ecell = Ecell (0.0592 / n )log Q where Ecell is the

actual cell potential
Ecell is the standard cell potential
N is the number of moles of electrons
transferred
Q is the [product ion]y / [reactant ion] x

Example: What is the potential of a copper-silver cell if the

concentration of Ag+ is 1.0 x 10-3 M and the Cu+2 is 1.0 x 10-5 M?
The standard cell potential is +0.46 V.

Step 1) Write out the balanced reaction 2 Ag+ (aq) + Cu(s)

Cu+2 (aq) + 2 Ag (s)
Step 2) Determine the Nernst equation Ecell = 0.46 V (0.0592
V/ 2) log (1.0 x 10-5)/(1.0 x 10-3 )2
Step 3) Solve the equation E cell = 0.46 V 0.0296 V
(log 10)
E cell = 0.46 V (0.0296)
Ecell = 0.43 V
This shows how the potential of a cell can decrease if the
concentrations are less than 1.00 M.

Work: 1) In a given zinc copper cell, the ion

concentrations are [Cu+2] = 0.0100M and
the [Zn+2] = 1.0 M, what is the cell potential if the
standard cell potential is 1.10V?
2) A cell was constructed with the following reaction:
Cd+2 (aq) + Mg (s) Mg+2 (aq) + Cd (s) Ecell =
1.97 V
If the [MgSO4] = 1.00M and [Cd+2] is unknown, what is
the concentration if the measured cell potential is
1.67V?
3) The cell rxn NiO2 (s) + 4 H+ (aq) + 2 Ag (s) Ni+2 (aq)
+ 2H2O (l) + 2Ag+(s) has Ecell of 2.48 V. What is the
cell potential if concentrations of Ni+2 and Ag+ are 0.10
M and the pH is 6.00?

Answers: 1) 1.04 V
2) 7.2 x 10 11 M
3) 1.86 V