Page:Scientific Papers of Josiah Willard Gibbs.djvu/94

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58
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.

second of the above terms of the condition of equilibrium, which will then become

(9)

, etc., denoting the entropies of the various parts between which there is no communication of heat. When the condition of equilibrium is thus expressed, the limitation in respect to the conduction of heat will need no farther consideration.

In order to apply to any system the criteria of equilibrium which have been been given, a knowledge is requisite of its passive forces or resistances to change, in so far, at least, as they are capable of preventing change. (Those passive forces which only retard change, like viscosity, need not be considered.) Such properties of a system are in general easily recognized upon the most superficial knowledge of its nature. As examples, we may instance the passive force of friction which prevents sliding when two surfaces of solids are pressed together,—that which prevents the different components of a solid, and sometimes of a fluid, from having different motions one from another,—that resistance to change which sometimes prevents either of two forms of the same substance (simple or compound), which are capable of existing, from passing in to the other,—that which prevents the changes in solids which imply plasticity, (in other words, changes of the form to which the solid tends to return,) when the deformation does not exceed certain limits.

It is a characteristic of all these passive resistances that they prevent a certain kind of motion or change, however the initial state of the system may be modified, and to whatever external agencies of force and heat it may be subjected, whitin limits, it may be, but yet within limits which allow finite variations in the values of all the quantities which express the initial state of the system or the mechanical or thermal influences acting on it, without producing the change in question. The equilibrium which is due to such passive properties is thus widely distinguished from that caused by the balance of the active tendencies of the system, where an external influence, or a change in the initial state, infinitesimal in amount, is sufficient to produce change either in the positive or negative direction. Hence the ease with which these passive resistances are recognized. Only in the case that the state of the system lies so near the limit at which the resistances cease to be operative to prevent change, as to create a doubt whether the case falls within or without the limit, will a more accurate knowledge of these resistances be necessary.

To establish the validity of the criterion of equilibrium we will consider first the sufficiency, and afterwards the necessity, of the condition as expressed in either of the two equivalent forms.

In the first place, if the system is in a state in which the entropy is