Page:Scientific Papers of Josiah Willard Gibbs.djvu/370

334 a cell in which hydrogen acts as an ion between electrodes of palladium charged with hydrogen as another illustration of the same principle, but the solidity of the electrodes and the consequent resistance to the diffusion of the hydrogen within them (a process which cannot be assisted by convective currents as in a liquid mass) present considerable obstacles to the experimental verification of the relation.

(II.) Sometimes the ion is soluble (as an independently variable component) in the electrolytic fluid. Of course its condition in the fluid when thus dissolved must be entirely different from its condition when acting on an ion, in which case its quantity is not independently variable, as we have already seen. Its diffusion in the fluid in this state of solution is not necessarily connected with any electrical current, and in other relations its properties may be entirely changed. In any discussion of the internal properties of the fluid (with respect to its fundamental equation, for example), it would be necessary to treat it as a different substance. (See page 63.) But if the process by which the charge of electricity passes into the electrode, and the ion is dissolved in the electrolyte is reversible, we may evidently regard the potentials for the substance of the ion in (687) or (688) as relating to the substance thus dissolved in the electrolyte. In case of absolute equilibrium, the density of the substance thus dissolved would of course be uniform throughout the fluid (since it can move independently of any electrical current), so that by the strict application of our principle we only obtain the somewhat barren result that if any of the ions are soluble in the fluid without their electrical charges, the electromotive force must vanish in any case of absolute equilibrium not dependent upon passive resistances. Nevertheless, cases in which the ion is thus dissolved in the electrolytic fluid only to a very small extent, and its passage from one electrode to the other by ordinary diffusion is extremely slow, may be regarded as approximating to the case in which it is incapable of diffusion. In such cases, we may regard the relations (687), (688) as approximately valid, although the condition of equilibrium relating to the diffusion of the dissolved ion is not satisfied. This may be the case with hydrogen and oxygen as ions (or apparent ions) between electrodes of platinum in some of its forms.

(III.) The ion may appear in mass at the electrode. If it be a conductor of electricity, it may be regarded as forming an electrode, as soon as the deposit has become thick enough to have the properties of matter in mass. The case therefore will not be different from that first considered. When the ion is a non-conductor, a continuous thick deposit on the electrode would of course prevent the possibility of an