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Quasi-Chemical Treatment of the Hole Theory for r-Mers. I. Pure Liquids

The quasi-chemical or first approximation proposed by Guggenheim was applied to the hole theory with fixed cell volume (the lattice fluid theory), in order to investigate effects of the nonrandom distribution of free volume in a liquid. These effects consisted in the differences between the first and zeroth approximations. The partition function for a pure liquid of an r-mer was derived, and the equation of state, saturated vapor pressures and orthobaric densities were calculated numerically for various values of r so as to investigate the effect of nonrandomness on these quantities. We also discuss the differences between the lattice fluid theory, the zeroth and first approximations.