### Abstract

In addition, upper bounds on the amounts of products can be set, which then limit the maximum extents of selected spontaneous chemical reactions in terms of affinity. The range of Gibbs energy calculations can then be extended to new intricate systems. Example models based on free energy minimisation have been made e.g. for surface and interfacial systems, where the surface, interfacial or adsorbed atomic or molecular layers are modeled as separate phases. In an analogous fashion the partitioning effect of a semi-permeable membrane in a two-compartment aqueous system can be modeled. In such system the large ions, not permeable through the membrane, cause an uneven charge distribution of ionic species between the two compartments. In this case, the electrochemical potential difference between the two aqueous phases becomes calculated for the multi-component system. The calculated results are consistent with the Donnan equilibrium theory; however the multi-phase system may also include the gas phase and several precipitating phases, which extends the applicability of the new method. Finally, similar constraints can also be set to extents of reaction advancements, allowing usage of Gibbs energy calculations in dynamic reaction rate controlled systems.

Original language | English |
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Title of host publication | 18th European Symposium on Computer Aided Process Engineering |

Editors | Bertrand Braunschweig, Xavier Joulia |

Publisher | Elsevier |

Pages | 883-888 |

ISBN (Print) | 978-0-444-53227-5 |

DOIs | |

Publication status | Published - 2008 |

MoE publication type | A4 Article in a conference publication |

Event | 18th European Symposium on Computer Aided Process Engineering - Duration: 1 Jan 2008 → … |

### Publication series

Series | Computer Aided Chemical Engineering |
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Volume | 25 |

ISSN | 1570-7946 |

### Conference

Conference | 18th European Symposium on Computer Aided Process Engineering |
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Period | 1/01/08 → … |

### Fingerprint

### Keywords

- Gibbs energy calculation
- Gibbs energy minimization
- ion exchange
- multi-phase chemistry
- reaction rate
- surface tension

### Cite this

*18th European Symposium on Computer Aided Process Engineering*(pp. 883-888). Elsevier. Computer Aided Chemical Engineering, Vol.. 25 https://doi.org/10.1016/S1570-7946(08)80153-8

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*18th European Symposium on Computer Aided Process Engineering.*Elsevier, Computer Aided Chemical Engineering, vol. 25, pp. 883-888, 18th European Symposium on Computer Aided Process Engineering, 1/01/08. https://doi.org/10.1016/S1570-7946(08)80153-8

**Thermochemical multi-phase models applying the constrained gibbs energy method.** / Pajarre, Risto (Corresponding author); Blomberg, Peter; Koukkari, Pertti.

Research output: Chapter in Book/Report/Conference proceeding › Conference article in proceedings › Scientific › peer-review

TY - GEN

T1 - Thermochemical multi-phase models applying the constrained gibbs energy method

AU - Pajarre, Risto

AU - Blomberg, Peter

AU - Koukkari, Pertti

PY - 2008

Y1 - 2008

N2 - Computation of chemical equilibria in multiphase systems by Gibbs free energy minimization under constraints set by the material balance has increasing interest in many application fields, including materials technology, metallurgy and chemical engineering. The results are utilised in multi-phase equilibrium studies or as parts of equilibrium-based process simulation. Yet, there exist a number of practical problems where the chemical system is influenced by other constraining factors such as surface energy or electrochemical charge transport. For such systems, an extended Gibbs energy method has been applied. In the new method, the potential energy is introduced to the Gibbs energy calculation as a Legendre transformed work term divided into substance specific contributions. The additional constraint potential is then represented by a supplementary undertermined Lagrange multiplier.In addition, upper bounds on the amounts of products can be set, which then limit the maximum extents of selected spontaneous chemical reactions in terms of affinity. The range of Gibbs energy calculations can then be extended to new intricate systems. Example models based on free energy minimisation have been made e.g. for surface and interfacial systems, where the surface, interfacial or adsorbed atomic or molecular layers are modeled as separate phases. In an analogous fashion the partitioning effect of a semi-permeable membrane in a two-compartment aqueous system can be modeled. In such system the large ions, not permeable through the membrane, cause an uneven charge distribution of ionic species between the two compartments. In this case, the electrochemical potential difference between the two aqueous phases becomes calculated for the multi-component system. The calculated results are consistent with the Donnan equilibrium theory; however the multi-phase system may also include the gas phase and several precipitating phases, which extends the applicability of the new method. Finally, similar constraints can also be set to extents of reaction advancements, allowing usage of Gibbs energy calculations in dynamic reaction rate controlled systems.

AB - Computation of chemical equilibria in multiphase systems by Gibbs free energy minimization under constraints set by the material balance has increasing interest in many application fields, including materials technology, metallurgy and chemical engineering. The results are utilised in multi-phase equilibrium studies or as parts of equilibrium-based process simulation. Yet, there exist a number of practical problems where the chemical system is influenced by other constraining factors such as surface energy or electrochemical charge transport. For such systems, an extended Gibbs energy method has been applied. In the new method, the potential energy is introduced to the Gibbs energy calculation as a Legendre transformed work term divided into substance specific contributions. The additional constraint potential is then represented by a supplementary undertermined Lagrange multiplier.In addition, upper bounds on the amounts of products can be set, which then limit the maximum extents of selected spontaneous chemical reactions in terms of affinity. The range of Gibbs energy calculations can then be extended to new intricate systems. Example models based on free energy minimisation have been made e.g. for surface and interfacial systems, where the surface, interfacial or adsorbed atomic or molecular layers are modeled as separate phases. In an analogous fashion the partitioning effect of a semi-permeable membrane in a two-compartment aqueous system can be modeled. In such system the large ions, not permeable through the membrane, cause an uneven charge distribution of ionic species between the two compartments. In this case, the electrochemical potential difference between the two aqueous phases becomes calculated for the multi-component system. The calculated results are consistent with the Donnan equilibrium theory; however the multi-phase system may also include the gas phase and several precipitating phases, which extends the applicability of the new method. Finally, similar constraints can also be set to extents of reaction advancements, allowing usage of Gibbs energy calculations in dynamic reaction rate controlled systems.

KW - Gibbs energy calculation

KW - Gibbs energy minimization

KW - ion exchange

KW - multi-phase chemistry

KW - reaction rate

KW - surface tension

U2 - 10.1016/S1570-7946(08)80153-8

DO - 10.1016/S1570-7946(08)80153-8

M3 - Conference article in proceedings

SN - 978-0-444-53227-5

T3 - Computer Aided Chemical Engineering

SP - 883

EP - 888

BT - 18th European Symposium on Computer Aided Process Engineering

A2 - Braunschweig, Bertrand

A2 - Joulia, Xavier

PB - Elsevier

ER -