Page:Elementary Principles in Statistical Mechanics (1902).djvu/188

164 Yet while we exclude the kind of action which we call thermal between the fluid and the containing vessel, we allow the kind which we call work in the narrower sense, which takes place when the volume of the fluid is changed by the motion of a piston. This agrees with what we have supposed in regard to the external coördinates, which we may vary in any arbitrary manner, and are in this entirely unlike the coördinates of the second ensemble with which we bring the first into connection.

When heat passes in any thermodynamic experiment between the fluid principally considered and some other body, it is actually absorbed and given out by the walls of the vessel, which will retain a varying quantity. This is, however, a disturbing circumstance, which we suppose in some way made negligible, and actually neglect in a theoretical discussion. In our case, we suppose the walls incapable of absorbing energy, except through the motion of the external coördinates, but that they allow the systems which they contain to act directly on one another. Properties of this kind are mathematically expressed by supposing that in the vicinity of a certain surface, the position of which is determined by certain (external) coördinates, particles belonging to the system in question experience a repulsion from the surface increasing so rapidly with nearness to the surface that an infinite expenditure of energy would be required to carry them through it. It is evident that two systems might be separated by a surface or surfaces exerting the proper forces, and yet approach each other closely enough to exert mechanical action on each other.