A systematic method to create reaction constraints for stoichiometric matrices

Peter Blomberg (Corresponding Author), Pertti Koukkari

Research output: Contribution to journalArticleScientificpeer-review

9 Citations (Scopus)

Abstract

Modeling rate-controlled chemically reactive systems in biocatalysis, fuel combustion, material science, and chemical process engineering involves the quantification and exploitation of interactions between many chemical species. These dynamic chemical systems, having relatively few limiting reactions, can be conceived as a series of snapshots where reactions have fixed extents but otherwise idle. Since the reactions affect the stoichiometric matrix of the internal constraints, such constrained equilibrium states cannot be defined in terms of conventional atomic mass balances.

A systematic method for obtaining generalized equilibrium constraints for reaction mechanisms of arbitrary complexity is presented. Reaction matrices are converted into entity conservation matrices using row operations. The simultaneously introduced virtual components enable Gibbs energy calculations for complex reaction schemes including organic systems and enzyme-catalyzed biochemical transformations having multiple limiting reactions. Classical Gibbs energy minimization, which would otherwise readily model phase transformations and solvent interactions, is thereby made accessible to these emerging application fields.
Original languageEnglish
Pages (from-to)1238-1250
Number of pages13
JournalComputers and Chemical Engineering
Volume35
Issue number7
DOIs
Publication statusPublished - 2011
MoE publication typeA1 Journal article-refereed

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Gibbs free energy
Process engineering
Chemical engineering
Materials science
Conservation
Enzymes
Phase transitions
Biocatalysis

Keywords

  • Entity conservation matrix
  • Gibbs energy minimization
  • Rate-controlled constrained equilibrium
  • Reaction constraint
  • Virtual component

Cite this

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title = "A systematic method to create reaction constraints for stoichiometric matrices",
abstract = "Modeling rate-controlled chemically reactive systems in biocatalysis, fuel combustion, material science, and chemical process engineering involves the quantification and exploitation of interactions between many chemical species. These dynamic chemical systems, having relatively few limiting reactions, can be conceived as a series of snapshots where reactions have fixed extents but otherwise idle. Since the reactions affect the stoichiometric matrix of the internal constraints, such constrained equilibrium states cannot be defined in terms of conventional atomic mass balances.A systematic method for obtaining generalized equilibrium constraints for reaction mechanisms of arbitrary complexity is presented. Reaction matrices are converted into entity conservation matrices using row operations. The simultaneously introduced virtual components enable Gibbs energy calculations for complex reaction schemes including organic systems and enzyme-catalyzed biochemical transformations having multiple limiting reactions. Classical Gibbs energy minimization, which would otherwise readily model phase transformations and solvent interactions, is thereby made accessible to these emerging application fields.",
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A systematic method to create reaction constraints for stoichiometric matrices. / Blomberg, Peter (Corresponding Author); Koukkari, Pertti.

In: Computers and Chemical Engineering, Vol. 35, No. 7, 2011, p. 1238-1250.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

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AU - Blomberg, Peter

AU - Koukkari, Pertti

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AB - Modeling rate-controlled chemically reactive systems in biocatalysis, fuel combustion, material science, and chemical process engineering involves the quantification and exploitation of interactions between many chemical species. These dynamic chemical systems, having relatively few limiting reactions, can be conceived as a series of snapshots where reactions have fixed extents but otherwise idle. Since the reactions affect the stoichiometric matrix of the internal constraints, such constrained equilibrium states cannot be defined in terms of conventional atomic mass balances.A systematic method for obtaining generalized equilibrium constraints for reaction mechanisms of arbitrary complexity is presented. Reaction matrices are converted into entity conservation matrices using row operations. The simultaneously introduced virtual components enable Gibbs energy calculations for complex reaction schemes including organic systems and enzyme-catalyzed biochemical transformations having multiple limiting reactions. Classical Gibbs energy minimization, which would otherwise readily model phase transformations and solvent interactions, is thereby made accessible to these emerging application fields.

KW - Entity conservation matrix

KW - Gibbs energy minimization

KW - Rate-controlled constrained equilibrium

KW - Reaction constraint

KW - Virtual component

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