Page:Scientific Papers of Josiah Willard Gibbs.djvu/86

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REPRESENTATION BY SURFACES OF THE

such as at the close of the processes are left in their initial condition. This has been called the available energy of the body. The initial state of the body is supposed to be such that the body can be made to pass from it to states of dissipated energy by reversible processes.

If the body is in a state represented by any point of the surface of dissipated energy, of course no work can be obtained from it under the given conditions. But even if the body is in a state of thermodynamic equilibrium, and therefore in one represented by a point in the thermodynamic surface, if this point is not in the surface of dissipated energy, because the equilibrium of the body is unstable in regard to discontinuous changes, a certain amount of energy will be available under the conditions for the production of work. Or, if the body is solid, even if it is uniform in state throughout, its pressure (or tension) may have different values in different directions, and in this way it may have a certain available energy. Or, if different parts of the body are in different states, this will in general be a source of available energy. Lastly, we need not exclude the case in which the body has sensible motion and its vis viva constitutes available energy. In any case, we must find the initial volume, entropy, and energy of the body, which will be equal to the sums of the initial volumes, entropies, and energies of its parts. ('Energy' is here used to include the vis viva of sensible motions.) These values of , and will determine the position of a certain point which we will speak of as representing the initial state.

Now the condition that no heat shall be allowed to pass to external bodies, requires that the final entropy of the body shall not be less than the initial, for it could only be made less by violating this condition. The problem, therefore, may be reduced to this,—to find the amount by which the energy of the body may be diminished without increasing its volume or diminishing its entropy. This quantity will be represented geometrically by the distance of the point representing the initial state from the surface of dissipated energy measured parallel to the axis of .

Let us consider a different problem. A certain initial state of the body is given as before. No work is allowed to be done upon or by external bodies. Heat is allowed to pass to and from them only on condition that the algebraic sum of all heat which thus passes shall be 0. From both these conditions any bodies may be excepted, which shall be left at the close of the processes in their initial state. Moreover, it is not allowed to increase the volume of the body. It is required to find the greatest amount by which it is possible under these conditions to diminish the entropy of an external system. This will be, evidently, the amount by which the entropy of the