Page:Scientific Papers of Josiah Willard Gibbs.djvu/382

346 whence We cannot assign a precise value to $$\Delta W_{\text{P}}$$, since the quantity of chlorine which was evolved in the form of gas is not stated. But the value of $$-\Delta W_{\text{P}}$$ must lie between 290cal and 580cal, probably nearer to the former.

The great difference in the results of the two series of experiments relating to electrodes of zinc and platinum in hydrochloric acid is most naturally explained by supposing some difference in the conditions of the experiment, as in the concentration of the acid, or in the extent to which the substitution of zinc for hydrogen took place. That which it is important for us to observe in all these cases is that there are conditions under which heat is absorbed in a galvanic or electrolytic cell, so that the galvanic cell has a greater electromotive force than can be accounted for by the diminution of its energy, and the operation of electrolysis requires a less electromotive force than would be calculated from the increase of energy in the cell,—especially when the work done against the pressure of the atmosphere is taken into account.

It should be noticed that in all these experiments the quantity represented by $$\Delta Q$$ (which is the critical quantity with respect to the point at issue) was determined by direct measurement of the heat absorbed or evolved by the cell when placed alone in a calorimeter. The resistance of the circuit was made so great by a rheostat placed outside of the calorimeter that the resistance of the cell was regarded as insignificant in comparison, and no correction appears to have been made in any case for this resistance. With exception of the error due to this circumstance, which would in all cases diminish the heat absorbed in the cell (or increase the heat evolved), the probable error of $$\Delta Q$$ must be very small in comparison with that of $$(V' - V'')\Delta e$$, or with that of $$\Delta \epsilon$$, which were in general determined by the comparison of different calorimetrical measurements, involving very much greater quantities of heat.

In considering the numbers which have been cited, we should remember that when hydrogen is evolved as gas the process is in general very far from reversible. In a perfect electrochemical