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Chemical equilibrium algorithm for highly non-ideal multiphase systems: free energy minimization

Journal Article · · Geochim. Cosmochim. Acta; (United States)
A method is presented for calculating equilibrium phase assemblages in very nonideal systems. It may be applied to any system for which a thermodynamically consistent model of the free energy which satisfies the usual Maxwell relations and convexity criterion is available. The algorithm minimizes the Gibbs free energy by independently choosing stable reaction directions. The procedure is described in detail and various numerical problems encountered and strategies for dealing with them are discussed. It will be shown that the necessary and sufficient conditions for solution phase selection may be derived from the values of the Lagrange multipliers corresponding to constraints on phases that are not present in the system. The method for evaluating the solution phase Lagrangian multipliers and choosing the optimum composition with which to bring the new solution phase into the system involves a separate constrained minimization problem. This method is sufficiently general so that the correct phase assemblage is chosen free from external control. Special procedures for adding and removing phases including solution phases are also described.
Research Organization:
Univ. of California, San Diego, La Jolla (USA)
DOE Contract Number:
AC03-85SF15522
OSTI ID:
6992563
Journal Information:
Geochim. Cosmochim. Acta; (United States), Journal Name: Geochim. Cosmochim. Acta; (United States) Vol. 51:5; ISSN GCACA
Country of Publication:
United States
Language:
English