Reaction rates as virtual constraints in Gibbs energy minimization

Research output: Contribution to journalArticleScientificpeer-review

10 Citations (Scopus)

Abstract

The constrained Gibbs energy method has been developed for the use of immaterial entities in the formula conservation matrix of the Gibbs energy minimization problem. The new method enables the association of the conservation matrix with structural, physical, chemical, and energetic properties, and thus the scope of free energy calculations can be extended beyond the conventional studies of global chemical equilibria and phase diagrams. The use of immaterial constraints enables thermochemical calculations in partial equilibrium systems as well as in systems controlled by work factors. In addition, they allow the introduction of mechanistic reaction kinetics to the Gibbsian multiphase analysis. The constrained advancements of reactions are incorporated into the Gibbs energy calculation by using additional virtual phases in the conservation matrix. The virtual components are then utilized to meet the incremental consumption of reactants or the formation of products in the kinetically slow reactions. The respective thermodynamic properties for the intermediate states can be used in reaction rate formulations, e.g., by applying the reaction quotients.
Original languageEnglish
Pages (from-to)1063-1074
Number of pages12
JournalPure and Applied Chemistry
Volume83
Issue number5
DOIs
Publication statusPublished - 2011
MoE publication typeA1 Journal article-refereed

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Gibbs free energy
Reaction rates
Conservation
Reaction kinetics
Free energy
Phase diagrams
Thermodynamic properties
Association reactions

Keywords

  • constrained Gibbs energy minimization
  • reaction quotients
  • reaction rates
  • virtual components
  • virtual species

Cite this

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title = "Reaction rates as virtual constraints in Gibbs energy minimization",
abstract = "The constrained Gibbs energy method has been developed for the use of immaterial entities in the formula conservation matrix of the Gibbs energy minimization problem. The new method enables the association of the conservation matrix with structural, physical, chemical, and energetic properties, and thus the scope of free energy calculations can be extended beyond the conventional studies of global chemical equilibria and phase diagrams. The use of immaterial constraints enables thermochemical calculations in partial equilibrium systems as well as in systems controlled by work factors. In addition, they allow the introduction of mechanistic reaction kinetics to the Gibbsian multiphase analysis. The constrained advancements of reactions are incorporated into the Gibbs energy calculation by using additional virtual phases in the conservation matrix. The virtual components are then utilized to meet the incremental consumption of reactants or the formation of products in the kinetically slow reactions. The respective thermodynamic properties for the intermediate states can be used in reaction rate formulations, e.g., by applying the reaction quotients.",
keywords = "constrained Gibbs energy minimization, reaction quotients, reaction rates, virtual components, virtual species",
author = "Pertti Koukkari and Risto Pajarre and Peter Blomberg",
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Reaction rates as virtual constraints in Gibbs energy minimization. / Koukkari, Pertti; Pajarre, Risto; Blomberg, Peter.

In: Pure and Applied Chemistry, Vol. 83, No. 5, 2011, p. 1063-1074.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Reaction rates as virtual constraints in Gibbs energy minimization

AU - Koukkari, Pertti

AU - Pajarre, Risto

AU - Blomberg, Peter

PY - 2011

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N2 - The constrained Gibbs energy method has been developed for the use of immaterial entities in the formula conservation matrix of the Gibbs energy minimization problem. The new method enables the association of the conservation matrix with structural, physical, chemical, and energetic properties, and thus the scope of free energy calculations can be extended beyond the conventional studies of global chemical equilibria and phase diagrams. The use of immaterial constraints enables thermochemical calculations in partial equilibrium systems as well as in systems controlled by work factors. In addition, they allow the introduction of mechanistic reaction kinetics to the Gibbsian multiphase analysis. The constrained advancements of reactions are incorporated into the Gibbs energy calculation by using additional virtual phases in the conservation matrix. The virtual components are then utilized to meet the incremental consumption of reactants or the formation of products in the kinetically slow reactions. The respective thermodynamic properties for the intermediate states can be used in reaction rate formulations, e.g., by applying the reaction quotients.

AB - The constrained Gibbs energy method has been developed for the use of immaterial entities in the formula conservation matrix of the Gibbs energy minimization problem. The new method enables the association of the conservation matrix with structural, physical, chemical, and energetic properties, and thus the scope of free energy calculations can be extended beyond the conventional studies of global chemical equilibria and phase diagrams. The use of immaterial constraints enables thermochemical calculations in partial equilibrium systems as well as in systems controlled by work factors. In addition, they allow the introduction of mechanistic reaction kinetics to the Gibbsian multiphase analysis. The constrained advancements of reactions are incorporated into the Gibbs energy calculation by using additional virtual phases in the conservation matrix. The virtual components are then utilized to meet the incremental consumption of reactants or the formation of products in the kinetically slow reactions. The respective thermodynamic properties for the intermediate states can be used in reaction rate formulations, e.g., by applying the reaction quotients.

KW - constrained Gibbs energy minimization

KW - reaction quotients

KW - reaction rates

KW - virtual components

KW - virtual species

U2 - 10.1351/PAC-CON-10-09-09

DO - 10.1351/PAC-CON-10-09-09

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JO - Pure and Applied Chemistry

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