THERMODYNAMICS OF EQUILIBRIUM AND STABILITY

The dependence of the entropy of a homogeneous system on the composition is investigated with the help of a reversible adiabatic process which allows the change of composition by means of a semipermeable wall. The conditions of equilibrinm for phase transition and for homogeneous chemical reaction are derived in a new way. Next the criterion of minimum energy for constant entropy and volume is derived from the principle of increase of entropy. This criterion is then applied to obtain the conditions of equilibrium and stability with the help of Lagrange's multipliers. The conditions of stability are expressed in several alternative forms. Next the equilibrium properties of a binary system arc considered, and some types of phase diagram are explained by means of equations. The theory is extended to the general heterogeneous equilibrium of a system consisting of any number of independent components. A system of equations for the change of temperature, pressure, and composition are obtained and are solved by means of determinants. Next Planck's theory of a binary solution is extended to a solution consisting of several solnte components, with the same conclusion regarding the lowering of freezing point as for a binary solution. Finally Planck's theory on the number of coexisting phases for aone-component system is extended to a system consisting of k components with the result that a state with, σ coexisting phases is more stable than one with σ-1 phases: where σ is an integer not greater than k + 2.