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A Gibbs energy minimization method for (吉布斯能量最小化的方法)
Pure Appl. Chem., Vol. 83, No. 6, pp. 1243–1254, 2011.
doi:10.1351/PAC-CON-10-09-36
© 2011 IUPAC, Publication date (Web): 4 May 2011
A Gibbs energy minimization method for
constrained and partial equilibria*
Pertti Koukkari‡ and Risto Pajarre
VTT Technical Research Centre of Finland, P.O. Box 1000, FI-02044 VTT, Finland
Abstract : The conventional Gibbs energy minimization methods apply elemental amounts of
system components as conservation constraints in the form of a stoichiometric conservation
matrix. The linear constraints designate the limitations set on the components described by
the system constituents. The equilibrium chemical potentials of the constituents are obtained
as a linear combination of the component-specific contributions, which are solved with the
Lagrange method of undetermined multipliers. When the Gibbs energy of a multiphase sys-
tem is also affected by conditions due to immaterial properties, the constraints must be
adjusted by the respective entities. The constrained free energy (CFE) minimization method
includes such conditions and incorporates every immaterial constraint accompanied with its
conjugate potential. The respective work or affinity-related condition is introduced to the
Gibbs energy calculation as an additional Lagrange multiplier. Thus, the minimization pro-
cedure can include systemic or external potential variables with their conjugate coefficients
as well as non-equilibrium affinities. Their implementation extends the scope of Gibbs
energy calculations to a number of new fields, including surface and interface systems, multi -
phase fiber suspensions with Donnan partitioning, kinetically controlled p
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