Extents of reaction as supplementary constraints for Gibbs energy minimization

Pertti Koukkari* (Corresponding Author), Peter Blomberg

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

Abstract

The stoichiometric conservation matrix C used in Gibbs energy minimization calculations conserves the molar amounts of the chemical elements of the multi-phase system. Supplementary reaction kinetic constraints can be included in min(G) by using additional massless components in the conservation matrix. A systematic method to incorporate such reaction constraints is based on row operations by which a coupled identity matrix I and a reaction matrix R is transformed into the augmented conservation matrix, C′. The reaction constraints then appear as well-defined components, based on measurable extents of slow reactions in the complex system, the incorporation of which allows for the calculation of the dynamical time evolution of the irreversible thermodynamic system. The non-zero affinities of the slow reactions are obtained as constraint potentials. The systematic I,R approach is explained by working through a few illustrative examples, showcasing the mechanics of applying it and the thermodynamic reasoning that accompanies it.

Original languageEnglish
Article number120112
Number of pages8
JournalChemical Engineering Science
Volume295
DOIs
Publication statusPublished - 5 Aug 2024
MoE publication typeA1 Journal article-refereed

Keywords

  • Extent of reaction
  • Gibbs energy minimization
  • Massless constraint
  • Reaction component
  • Stoichiometric conservation matrix
  • Thermodynamic affinity

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