Page:Scientific Papers of Josiah Willard Gibbs.djvu/378

342 such a direction of the electromotive force would involve the possibility of obtaining an indefinite amount of electromotive work, and therefore of mechanical work, without other expenditure than that of heat at the constant temperature of the cell.

None of the cases which we have been considering involve combinations by definite proportions, and, except in the case of the cell with electrodes of mercury and zinc, the electromotive forces are quite small. It may perhaps be thought that with respect to those cells in which combinations take place by definite proportions the electromotive force may be calculated with substantial accuracy from the diminution of the energy, without regarding, the variation of entropy. But the phenomena of chemical combination do not in general seem to indicate any possibility of obtaining from the combination of substances by any process whatever an amount of mechanical work which is equivalent to the heat produced by the direct union of the substances.

A kilogramme of hydrogen, for example, combining by combustion under the pressure of the atmosphere with eight kilogrammes of oxygen to form liquid water, yields an amount of heat which may be represented in round numbers by 34000 calories. We may suppose that the gases are taken at the temperature of 0° C., and that the water is reduced to the same temperature. But this heat cannot be obtained at any temperature desired. A very high temperature has the effect of preventing to a greater or less extent, the combination of the elements. Thus, according to M. Sainte-Claire Deville, the temperature obtained by the combustion of hydrogen and oxygen cannot much if at all exceed 2500° C., which implies that less than one-half of the hydrogen and oxygen present combine at that temperature. This relates to combustion under the pressure of the atmosphere. According to the determinations of Professor Bunsen in regard to combustion in a confined space, only one-third of a mixture of hydrogen and oxygen will form a chemical compound at the temperature of 2850° C. and a pressure of ten atmospheres, and only a little more than one-half when the temperature is reduced by the addition of nitrogen to 2024° C., and the pressure to about three atmospheres exclusive of the part due to the nitrogen.

Now 10 calories at 2500° C. are to be regarded as reversibly convertible into one calorie at 4° C. together with the mechanical work representing the energy of 9 calories. If, therefore, all the 34000 calories obtainable from the union of hydrogen and oxygen under atmospheric pressure could be obtained at the temperature of