Page:Scientific Papers of Josiah Willard Gibbs.djvu/174

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138
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.

We shall see hereafter, when we come to consider the properties of gases, that these equations may be verified experimentally in a very large class of cases, so that we have considerable reason for believing that they express a general law in regard to the limiting values of potentials.[1]


On Certain Points relating to the Molecular Constitution of Bodies.

It not unfrequently occurs that the number of proximate components which it is necessary to recognize as independently variable in a body exceeds the number of components which would be sufficient to express its ultimate composition. Such is the case, for example, as has been remarked on page 63, in regard to a mixture at ordinary temperatures of vapor of water and free hydrogen and oxygen. This case is explained by the existence of three sorts of molecules in the gaseous mass, viz., molecules of hydrogen, of oxygen, and of hydrogen and oxygen combined. In other cases, which are essentially the same in principle, we suppose a greater number of different sorts of molecules, which differ in composition, and the relations between these may be more complicated. Other cases are explained by molecules which differ in the quantity of matter which they contain, but not in the kind of matter, nor in the proportion of the different kinds. In still other cases, there appear to be different sorts of molecules, which differ neither in the kind nor in the quantity of matter which they contain, but only in the manner in which they are constituted. What is essential in the cases referred to is that a certain number of some sort or sorts of molecules shall be equivalent to a certain number of some other sort or sorts in respect to the kinds and quantities of matter which they collectively contain, and yet the former shall never be transformed into the latter within the body considered, nor the latter into the former, however the proportion of the numbers of the different sorts of molecules may be varied, or the composition of the body in other respects, or its thermodynamic state as represented by temperature and pressure or any other two suitable variables, provided, it may be, that these variations do not exceed certain limits. Thus, in the

  1. The reader will not fail to remark that, if we could assume the universality of this law, the statement of the conditions necessary for equilibrium between different masses in contact would be much simplified. For, as the potential for a substance which is only a possible component (see page 64) would always have the value the case could not occur that the potential for any substance would have a greater value in a mass in which that substance is only a possible component, than in another mass in which it is an actual component; and the conditions (22) and (51) might be expressed with the sign of equality without exception for the case of possible components.