Page:Scientific Papers of Josiah Willard Gibbs.djvu/23

Rh illustrations, which he employed as symbols and aids to the imagination, rather than the mechanical models which have served so many great investigators; such models are seldom in complete correspondence with the phenomena they represent, and Professor Gibbs's tendency toward rigorous logic was such that the discrepancies apparently destroyed for him the usefulness of the model. Accordingly he usually had recourse to the geometrical representation of his equations, and this method he used with great ease and power. With this inclination, it is probable that he made much use, in his study of thermodynamics, of the volume-pressure diagram, the only one which, up to that time, had been used extensively. To those who are acquainted with the completeness of his investigation of any subject which interested him, it is not surprising that his first published paper should have been a careful study of all the different diagrams which seemed to have any chance of being useful. Of the new diagrams which he first described in this paper, the simplest, in some respects, is that in which entropy and temperature are taken as coordinates; in this, as in the familiar volume-pressure diagram, the work or heat of any cycle is proportional to its area in any part of the plane; for many purposes it is far more perspicuous than the older diagram, and it has found most important practical applications in the study of the steam engine. The diagram, however, to which Professor Gibbs gave most attention was the volume-entropy diagram, which presents many advantages when the properties of bodies are to be studied, rather than the work they do or the heat they give out. The chief reason for this superiority is that volume and entropy are both proportional to the quantitty of substance, while pressure and temperature are not; the representation of coexistent states is thus especially clear, and for many purposes the gain in this direction more than counter-balances the loss due to the variability of the scale of work and heat. No diagram of constant scale can, for example, adequately represent the triple state where solid, liquid and vapor are all present; nor, without confusion, can it represent the states of a substance which, like water, has a maximum density; in these and in many other cases the volume-entropy diagram is superior in distinctness and convenience.

In the second paper the consideration of graphical methods in thermodynamics was extended to diagrams in three dimensions. James Thomson had already made this extension to the volume-pressure diagram by erecting the temperature as the third coordinate, these three immediately cognizable quantities giving a sufrace whose interpretation is most simple from elementary considerations, but which for several reasons, is far less convenient and fertile of results tan one in which the coordinates are thermodynamic quantities less directly known. In fact, if the general relation between the volume, entropy