CHEMICAL REACTIONS OCCURRING DURING THE ELECTROLYSIS.
In the paper of 1887, M. Moissan adopted the view that the first action of the electric current was to effect the decomposition of the potassium fluoride contained in solution in the hydrofluoric acid, fluorine being liberated at the positive pole and potassium at the negative terminal. This liberated potassium would at once regenerate potassium fluoride in presence of hydrofluoric acid, and liberate its equivalent of hydrogen:
KF = K + F.
K + HF = KF + H.
But when the progress of the electrolysis is carefully followed, by consulting the indications of the amperemeter placed in circuit, it is found to be by no means as regular as the preceding formulæ would indicate. With the new apparatus, the decomposition is quite irregular at first, and does not attain regularity until it has been proceeding for upward of two hours. Upon stopping the current and unmounting the apparatus, the platinum rod upon which the fluorine was liberated is found to be largely corroded, and at the bottom of the U-tube a quantity of a black, finely divided substance is observed. This black substance, which was taken at first to be metallic platinum, is a complex compound containing one equivalent of potassium to one equivalent of platinum, together with a considerable proportion of fluorine.
Moreover, the hydrofluoric acid is found to contain a small quantity of platinum fluoride in solution. The electrolytic reaction is probably therefore much more complicated than was at first considered to be the case. The mixture of acid and alkaline fluoride furnishes fluorine at the positive terminal rod, but this intensely active gas, in its nascent state, attacks the platinum and produces platinum tetrafluoride, PtF4; this probably unites with the potassium fluoride to form a double salt, possibly 2Kl.PtF4, analogous to the well known platinochloride 2KCl.PtCl4; and it is only when the liquid contains this double salt that the electrolysis proceeds in a regular manner, yielding free fluorine at the positive pole, and hydrogen and the complex black compound at the negative pole.