Page:Scientific Papers of Josiah Willard Gibbs.djvu/24

xvi and energy of any body is known, the relation between the volume, pressure and temperature may be immediately deduced by differentiation; but the converse is not true, and thus a knowledge of the former relation gives more complete information of the properties of a substance than a knowledge of the latter. Accordingly Gibbs chooses as the three coordinates the volume, entropy and energy and, in a masterly manner, proceeds to develop the properties of the resulting surface, the geometrical conditions for equilibrium, the criteria for its stability or instability, the conditions for coexistent states and for the critical state; and he points out, in several examples, the great power of this method for the solution of thermodynamic problems. The exceptional importance and beauty of this work by a hitherto unknown writer was immediately recognized by Maxwell, who, in the last years of his life, spent considerable time in carefully constructing, with his own hands, a model of this surface, a cast of which, very shortly before his death, he sent to Professor Gibbs.

One property of this three dimensional diagram (analogous to that mentioned in the case of the plane volume-entropy diagram) proved to be of capital importance in the development of Gibbs's future work in thermodynamics; the volume, entropy and energy of a mixture of portions of a substance in different states (whether in equilibrium or not), are the sums of the volumes, entropies and energies of the separate parts, and, in the diagram, the mixture is represented by a single point which may be found from the separate points, representing the different portions, by a process like that of finding centers of gravity. In general this point is not in the surface representing the stable states of the substance, but within the solid bounded by this surface, and its distance from the surface, taken parallel to the axis of energy, represents the available energy of the mixture. This possibility of representing the properties of mixtures of different states of the same substance immediately suggested that mixtures of substances differing in chemical composition, as well as in physical state, might be treated in a similar manner; in a note at the end of the second paper the author clearly indicates the possibility of doing so, and there can be little doubt that this was the path by which he approached the task of investigating the conditions of chemical equilibrium, a task which he was destined to achieve in such a magnificent manner and with such advantage to physical science.

In the discussion of chemically homogeneous substances in the first two papers, frequent use had been made of the principle that such a substance will be in equilibrium if, when its energy is kept constant, its entropy cannot increase; at the head of the third paper the author puts the famoust statement of Clausius: "Die Energie der Welt ist constant. Die Entropie der Welt strebt einem Maximum zu." He