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) (log 10)

Solve the equation

E cell = 0.46 V 0.0296 V

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)
2)

3)

1.04 V 7.2 x 10 11 M 1.86 V