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Two New Thermodynamic Constraints for a Solid/Supercritical Fluid System
Author(s) -
Esmaeilzadeh F.,
Bozorgi Y.
Publication year - 2008
Publication title -
chemical engineering and technology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.403
H-Index - 81
eISSN - 1521-4125
pISSN - 0930-7516
DOI - 10.1002/ceat.200800308
Subject(s) - supercritical fluid , crossover , thermodynamics , gibbs free energy , solubility , dilution , chemistry , constraint (computer aided design) , statistical physics , mathematics , physics , computer science , artificial intelligence , geometry
One of the phenomenological observations in any supercritical system is the common pressure where all the solubility isotherms intersect. Thus, this crossover pressure addresses a thermodynamic constraint or a key set of conditions for supercritical mixtures. In this paper, a phase stability analysis has been performed for the formulation and estimation of the crossover pressure. This absolute theoretical approach includes two subsequent steps. At the first step, it has been formulated in terms of an abstract quantity, i.e., Gibbs free energy. However, the system should be treated more quantitatively in order to estimate the crossover pressure. Therefore, at the second step, which is based on the solute behavior at the infinite dilution limit, the equations formerly used have been further manipulated, which ultimately leads to two equations that are given in terms of estimable properties. They are actually two thermodynamic constraints for solid/SCF mixtures. One of them has been used to predict the crossover pressure of certain mixtures. The other one has not been used for this task due to a theoretical restriction. However, the successfully prediction of the crossover pressure by using either of the equations confirms the other one since they are subsequent and related equations.