Page:Scientific Papers of Josiah Willard Gibbs.djvu/77

From Wikisource
Jump to navigation Jump to search
This page has been proofread, but needs to be validated.
THERMODYNAMIC PROPERTIES OF SUBSTANCES.
41

It is evident that the sign of inequality holds in (e) if it holds in either (b) or (c), therefore, it holds in (e) if there are any differences of pressure or temperature between the different parts of the body or between the body and the medium, or if any part of the body has sensible motion. (In the latter case, there would be an increase of entropy due to the conversion of this motion into heat.) But even if the body is initially without sensible motion and has throughout the same pressure and temperature as the medium, the sign will still hold if different parts of the body are in states represented by points in the thermodynamic surface at different distances from the fixed plane representing and . For it certaintly holds if such initial circumstances are followed by differences of pressure or temperature, or by sensible velocities. Again, the sign of inequality would necessarily hold if one part of the body should pass, without producing changes of pressure or temperature or sensible velocities, into the state of another part represented by a point not at the same distance from the fixed plane representing and . But these are the only suppositions possible in the case, unless we suppose that equilibrium subsists, which would require that the points in question should have a common tangent plane (page 37), whereas by supposition the planes tangent at the different points are parallel but not identical.

The results of the preceding paragraph may summed up as follows:—Unless the body is initially without sensible motion, and its state, if homogeneous, is such as is represented by a point in the primitive surface where the tangent plane is parallel to the fixed plane representing and , or, if the body is not homogeneous in state, unless the points in the primitive surface representing the states of its parts have a common tangent plane parallel to the fixed plane representing and , such changes will ensue that the distance of the point representing the volume, entropy, and energy of the body from that fixed plane will be diminished (distances being considered negative if measured from points beneath the plane). Let us apply this result to the question of the stability of the body when surrounded, as supposed, by a medium of constant temperature.

The state of the body in equilibrium will be represented by a point in the thermodynamic surface, and as the pressure and temperature of the body are the same as those of the surrounding medium, we may take the tangent plane at that point as the fixed plane representing and . If the body is not homogeneous in state, although in equilibrium, we may, for the purposes of this discussion of stability, either take a point in the derived surface as representing its state, or we may take the points in the primitive surface which represent the states of the different parts of the body. These points, as we have