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Perturbation theory and one‐fluid corresponding states theories for fluid mixtures
Author(s) -
Smith William R.
Publication year - 1972
Publication title -
the canadian journal of chemical engineering
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.404
H-Index - 67
eISSN - 1939-019X
pISSN - 0008-4034
DOI - 10.1002/cjce.5450500223
Subject(s) - zeroth law of thermodynamics , perturbation theory (quantum mechanics) , conformal map , perturbation (astronomy) , first order , physics , classical mechanics , mathematics , order (exchange) , theoretical physics , mathematical analysis , quantum mechanics , finance , economics
A family of perturbation theories is defined which gives rise rationally, in zeroth order, to an infinite number of sets of corresponding states theories of the one‐fluid type, for solutions of molecules whose potentials are conformal. It is argued that the optimum zeroth order member of this family yields the highly successful one‐fluid van der Waals (vdWl) theory. This places that theory on a firm theoretical foundation and enables it to be systematically extended. The theory is derived to the second‐order terms and preliminary numerical results are presented for the case of hard‐sphere mixtures. Suggestions are made for empirical evaluation of some of the exact expressions.