The purpose of this paper is to make a critical study of some of the basic assumptions involved in considerations of thermodynamic equilibrium as applied to physico-chemical states. We shall be concerned principally with the law of mass-action and the equation of state.
A chemical reaction in a single phase may be represented by the following stoichiometric equation:
The mass-action law will be expressed in the form
where CA, Cm''', CM, CN,''" are the concentrations, and K(p, T) is a function of the pressure p and temperature T. Consider a closed gaseous system which contains the above reactants, and write for this system
where v is the specific volume. If it is known that (I) applies to this closed system, we may conclude from Eqs. ( ) and (3) that F (cA, cB, โข โข., cu, c~r, โข โข .) and v are completely determ!ned by p and T.
Let us consider the agreement between theory and experience. We find that Eq. ( ) agrees with experimental data for simple, gaseous systems at low pressures and relatively high temperatures, and also for very dilute solutions. (There are, however, exceptions as will be pointed out below). It is not necessary to go to very high pressures or very low temperatures, or to slightly increased concentrations of solutions 4Ix