The Phase Rule and Its Applications Part 30

The former method, which has been employed in several cases, need not be described here. The second method, however, is of considerable interest and importance, and calls for special reference.[405]

If two pieces, say, of zinc, connected together by a conducting wire, are placed in a solution of a zinc salt, _e.g._ zinc sulphate, the potential of the two electrodes will be the same, and no current will be produced in the connecting wire. If, however, the zinc electrodes are immersed in two solutions of _different_ concentration contained in separate vessels, but placed in connection with one another by means of a bent tube filled with a conducting solution, the potentials at the electrodes will no longer be the same, and a current will now flow through the connecting wire. The direction of this current _in the cell_ will be from the weaker to the more concentrated solution.

The greater the difference in the concentration of the solutions with respect to zinc, the greater will be the difference of the potential at the two electrodes, or the greater will be the E.M.F. of the cell. When the concentration of the two solutions becomes the same, the E.M.F. will become zero, and no current will pa.s.s.

It will be understood now how this method can be made use of {338} for determining the transition point of a salt, when we bear in mind that at the transition point the solubility of the two forms becomes identical.

Thus, for example, the transition point of zinc sulphate heptahydrate into hexahydrate could be determined in the following manner. Tube A (Fig. 134) contains, say, a saturated solution of the heptahydrate along with some of the solid salt; tube B, a saturated solution of the hexahydrate along with the solid salt. The tube C is a connecting tube bent downwards so as to prevent the mixing of the solutions by convection currents. ZZ are two zinc electrodes immersed in the solution; the cell is placed in a thermostat and the zinc electrodes connected with a galvanometer. Since, now, at temperatures below the transition point the solubility of the hexahydrate (the metastable form) is greater than that of the heptahydrate, a current will be produced, flowing in the cell from heptahydrate to hexahydrate. As the temperature is raised towards the transition point, the solubilities of the two hydrates also approach, and the current produced will therefore become weaker, because the E.M.F. of the cell becomes less; and when the transition point is attained, the E.M.F. becomes zero, and the current ceases. If the temperature is raised above this, the solubility of the heptahydrate becomes greater than that of the hexahydrate, and a current will again be produced, but in the opposite direction. By noting the temperature, therefore, at which the current ceases, or the E.M.F. becomes zero, the transition temperature can be ascertained.[406]

[Ill.u.s.tration: FIG. 134.]

In the case just described, the electrodes consisted of the same metal as was contained in the salt. But in some cases, _e.g._ sodium sulphate, electrodes of the metal contained in the salt cannot be employed.

Nevertheless, the above electrical method can be used {339} even in those cases, if a suitable non-polarizable mercury electrode is employed.[407]

Although, as we saw, no current was produced when two pieces of zinc were immersed in the same solution of zinc salt, a current will be obtained if two different metals, or even two different modifications of the same metal, are employed. Thus an E.M.F. will be established when electrodes of grey and of white tin are immersed in the same solution of zinc salt, but at the transition point this E.M.F. will become zero. By this method Cohen determined the transition point of grey and white tin (p. 42).