Page:Scientific Papers of Josiah Willard Gibbs.djvu/383

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EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.

347

apparatus, the same changes in the cell would yield a much greater amount of electromotive work, or absorb a much less amount. In either case, the value of $\Delta Q$ would be much greater than in the imperfect apparatus, the difference being measured perhaps by thousands of calories.^[1]

It often occurs in a galvanic or electrolytic cell that an ion which is set free at one of the electrodes appears in part as gas, and is in part absorbed by the electrolytic fluid, and in part absorbed by the electrode. In such cases, a slight variation in the circumstances, which would not sensibly affect the electromotive force, would cause all of the ion to be disposed of in one of the three ways mentioned, if the current were sufficiently weak. This would make a considerable difference in the variation of energy in the cell, and the electromotive force cannot certainly be calculated from the variation of energy alone in all these cases. The correction due to the work performed against the pressure of the atmosphere when the ion is set free as gas will not help us in reconciling these differences. It will appear on consideration that this correction will in general increase the discordance in the values of the electromotive force. Nor does it distinctly appear which of these cases is to be regarded

↑ Except in the case of the Grove's cell, in which the reactions are quite complicated, the absorption of heat is most marked in the electrolysis of hydrochloric acid. The latter case is interesting, since the experiments confirm the presumption afforded by the behavior of the substances in other circumstances. (See page 343.) In addition to the circumstances mentioned above tending to diminish the observed absorption of heat, the following, which are peculiar to this case, should be noticed.
The electrolysis was performed in a cell with a porous partition, in order to prevent the chlorine and hydrogen dissolved in the liquid from coming in contact with each other. It had appeared in a previous series of experiments (Mém. Savants Étrang., loc. cit., p. 131; or Comptes Rendus, t. lxvi, p. 1231), that a very considerable amount of heat might be produced by the chemical union of the gases in solution. In a cell without partition, instead of an absorption, an evolution of heat took place, which sometimes exceeded 5000 calories. If, therefore, the partition did not perfectly perform its office, this could only cause a diminution in the value of $\Delta Q$ .
A large part at least of the chlorine appears to have been absorbed by the electrolytic fluid. It is probable that a slight difference in the circumstances of the experiment—a diminution of pressure, for example,—might have caused the greater part of the chlorine to be evolved as gas, without essentially affecting the electromotive force. The solution of chlorine in water presents some anomalies, and may be attended with complex reactions, but it appears to be always attended with a very considerable evolution of heat. (See Berthelot, Comptes Rendus, t. lxxvi, p. 1514.) If we regard the evolution of the chlorine in the form of gas as the normal process, we may suppose that the absorption of heat in the cell was greatly diminished by the retention of the chlorine in solution.
Under certain circumstances, oxygen is evolved in the electrolysis of dilute hydrochloric acid. It does not appear that this took place to any considerable extent in the experiments which we are considering. But so far as it may have occurred, we may regard it as a case of the electrolysis of water. The significance of the fact of the absorption of heat is not thereby affected.

[1] Except in the case of the Grove's cell, in which the reactions are quite complicated, the absorption of heat is most marked in the electrolysis of hydrochloric acid. The latter case is interesting, since the experiments confirm the presumption afforded by the behavior of the substances in other circumstances. (See page 343.) In addition to the circumstances mentioned above tending to diminish the observed absorption of heat, the following, which are peculiar to this case, should be noticed.
The electrolysis was performed in a cell with a porous partition, in order to prevent the chlorine and hydrogen dissolved in the liquid from coming in contact with each other. It had appeared in a previous series of experiments (Mém. Savants Étrang., loc. cit., p. 131; or Comptes Rendus, t. lxvi, p. 1231), that a very considerable amount of heat might be produced by the chemical union of the gases in solution. In a cell without partition, instead of an absorption, an evolution of heat took place, which sometimes exceeded 5000 calories. If, therefore, the partition did not perfectly perform its office, this could only cause a diminution in the value of $\Delta Q$ .
A large part at least of the chlorine appears to have been absorbed by the electrolytic fluid. It is probable that a slight difference in the circumstances of the experiment—a diminution of pressure, for example,—might have caused the greater part of the chlorine to be evolved as gas, without essentially affecting the electromotive force. The solution of chlorine in water presents some anomalies, and may be attended with complex reactions, but it appears to be always attended with a very considerable evolution of heat. (See Berthelot, Comptes Rendus, t. lxxvi, p. 1514.) If we regard the evolution of the chlorine in the form of gas as the normal process, we may suppose that the absorption of heat in the cell was greatly diminished by the retention of the chlorine in solution.
Under certain circumstances, oxygen is evolved in the electrolysis of dilute hydrochloric acid. It does not appear that this took place to any considerable extent in the experiments which we are considering. But so far as it may have occurred, we may regard it as a case of the electrolysis of water. The significance of the fact of the absorption of heat is not thereby affected.

[1]