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The conditions of pressure, temperature and composition under which liquid and vapour mixtures are in equilibrium must generally be determined by direct experiment. The thermodynamical relationships connecting them are applicable only when an accurate equation of state is known for the mixture in both phases, or when special circumstances permit the equations to be simplified, such as when the vapour phase may be considered as a perfect gas, or when the laws of perfect solutions may be expected to hold. At sufficiently low pressures and temperatures some such simplification may frequently be made, but at higher pressures and temperatures, more especially near or above the critical point of one of the components, the data needed to calculate the equilibrium conditions are usually unknown and difficult to ascertain. This can be made clear by deriving, as shortly as possible, the principal thermodynamical relationships for a two-phase binary system.

Two-phase equilibrium in binary and ternary systems. I. The system methane-ethane