Introducing mechanistic kinetics to the Lagrangian Gibbs energy calculation

被引：59

作者：

Koukkari, P ^{[1
]}

Pajarre, R ^{[1
]}

机构：

[1] VTT Proc, FI-02044 Espoo, Finland

来源：

COMPUTERS & CHEMICAL ENGINEERING | 2006年 / 30卷 / 6-7期

关键词：

Gibbs energy minimization; lagrange multipliers; kinetic constraints; reaction rate; process modeling;

D O I：

10.1016/j.compchemeng.2006.03.001

中图分类号：

TP39 [计算机的应用];

学科分类号：

081203 ; 0835 ;

摘要：

The Gibbs free energy minimum is usually calculated with the method of Lagrangian multipliers with the mass balance conditions as the necessary subsidiary conditions. Solution of the partial derivatives of the Lagrangian function provides the equilibrium condition of zero affinity for all stoichiometric equilibrium reactions in the multi-phase system. By extension of the stoichiometric matrix, reaction rate constraints can be included in the Gibbsian calculation. Zero affinity remains as the condition for equilibrium reactions, while kinetic reactions receive a non-zero affinity value, defined by an additional Lagrange multiplier. This can be algorithmically connected to a known reaction rate for each kinetically constrained species in the system. The presented method allows for several kinetically controlled reactions in the multi-phase Gibbs energy calculation. (c) 2006 Elsevier Ltd. All rights reserved.

引用

页码：1189 / 1196

页数：8

共 27 条

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