as a particular case of the general thermodynamic equation of available energy. This equation was obtained in different ways by J. Willard Gibbs and H. von Helmholtz.
It will be noticed that when dE/dT is zero, that is, when the electromotive force of the cell does not change with temperature, the electromotive force is measured by the heat of reaction per unit of electrochemical change. The earliest formulation of the subject, due to Lord Kelvin, assumed that this relation was true in all cases, and, calculated in this way, the electromotive force of Daniell’s cell, which happens to possess a very small temperature coefficient, was found to agree with observation.
When one gramme of zinc is dissolved in dilute sulphuric acid, 1670 thermal units or calories are evolved. Hence for the electrochemical unit of zinc or 0.003388 gramme, the thermal evolution is 5.66 calories. Similarly, the heat which accompanies the dissolution of one electrochemical unit of copper is 3.00 calories. Thus, the thermal equivalent of the unit of resultant electrochemical change in Daniell’s cell is 5.66 − 3.00 = 2.66 calories. The dynamical equivalent of the calorie is 4.18 × 107 ergs or C.G.S. units of work, and therefore the electromotive force of the cell should be 1.112 × 108 C.G.S. units or 1.112 volts—a close agreement with the experimental result of about 1.08 volts. For cells in which the electromotive force varies with temperature, the full equation given by Gibbs and Helmholtz has also been confirmed experimentally.
As stated above, an electromotive force is set up whenever there is a difference of any kind at two electrodes immersed in electrolytes. In ordinary cells the difference is secured by using two dissimilar metals, but an electromotive force exists if two plates of the same metal are placed in solutions of different substances, or of the same substance at different concentrations. In the latter case, the tendency of the metal to dissolve in the more dilute solution is greater than its tendency to dissolve in the more concentrated solution, and thus there is a decrease in available energy when metal dissolves in the dilute solution and separates in equivalent quantity from the concentrated solution. An electromotive force is therefore set up in this direction, and, if we can calculate the change in available energy due to the processes of the cell, we can foretell the value of the electromotive force. Now the effective change produced by the action of the current is the concentration of the more dilute solution by the dissolution of metal in it, and the dilution of the originally stronger solution by the separation of metal from it. We may imagine these changes reversed in two ways. We may evaporate some of the solvent from the solution which has become weaker and thus reconcentrate it, condensing the vapour on the solution which had become stronger. By this reasoning Helmholtz showed how to obtain an expression for the work done. On the other hand, we may imagine the processes due to the electrical transfer to be reversed by an osmotic operation. Solvent may be supposed to be squeezed out from the solution which has become more dilute through a semi-permeable wall, and through another such wall allowed to mix with the solution which in the electrical operation had become more concentrated. Again, we may calculate the osmotic work done, and, if the whole cycle of operations be supposed to occur at the same temperature, the osmotic work must be equal and opposite to the electrical work of the first operation.
The result of the investigation shows that the electrical work Ee is given by the equation
Ee = ∫p2p1 vdp,
where v is the volume of the solution used and p its osmotic pressure. When the solutions may be taken as effectively dilute, so that the gas laws apply to the osmotic pressure, this relation reduces to
| E = | nrRT | logε | c1 |
| ey | c2 |
where n is the number of ions given by one molecule of the salt, r the transport ratio of the anion, R the gas constant, T the absolute temperature, y the total valency of the anions obtained from one molecule, and c1 and c2 the concentrations of the two solutions.
If we take as an example a concentration cell in which silver plates are placed in solutions of silver nitrate, one of which is ten times as strong as the other, this equation gives