Page:Scientific Papers of Josiah Willard Gibbs.djvu/72

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36
REPRESENTATION BY SURFACES OF THE


the thermodynamic surface, for many substances at least, can be divided into two parts, of which one represents the homogeneous states, the other those which are not so. We shall see that, when the former part of the surface is given, the latter can readily be formed, as indeed we might expect. We may therefore call teh former part the primitive surface, and the latter the derived surface.

To ascertain the nature of the derived surface and its relations to the primitive surface sufficiently to construct it when the latter is given, it is only necessary to use the principle that the volume, entropy, and energy of the whole body are equal to the sums of the volumes, entropyes, and energies respectively of the parts, while the pressure and temperature of the whole are the same as those of each of the parts. Let us commence with the case in which the body is in part solid, in part liquid, and in part vapor. The position of the point determined by the volume, entropy, and energy of such a compound will be that of the center of gravity of masses proportioned to the masses of solid, liquid, and vapor placed at the three points of the primitive surface which represent respectively the states of complete solidity, complete liquidity, and complete vaporization, each at the temperature and pressure of the compound. Hence, the parte of the surface which represents a compound of solid, liquid, and vapor is a plane triangle, having its vertices at the points mentioned. The fact that the surface is here plane indicates that the pressure and temperature are here constant, the inclination of the plane indicating the value of these quantities. Moreover, as these values are the same for the compound as for the three different homogeneous states corresponding to its different portions, the plane of the triangle is tangent at each of its vertices to the primitive surface, viz: at one vertex to that part of the primitive surface which represents solid, at another to the part representing liquid, and at the third to the part representing vapor.

When the body consists of a compound of two different homogeneous states, the point which represents the compound state will be at the center of gravity of masses proportioned to the masses of the parts of the body in the two different states and placed at the points of the primitive surface which represent these two states (i.e., which represent the volume, entropy, and energy of the body, if its whole mass were supposed succesively in the two homogeneous states which occur in its parts.) It will therefore be found upon the straight line

    so that the results are in general strictly valid only in cases in which the influence of these particulars may be neglected. When, therefore, two states of the substance are spoken of as in contact, it must be understood that the surface dividing them is plane. To consider the subject in a more general form, it would be necessary to introduce considerations which belong to the theories of capillarity and crystallization.