Calculation of multiphase chemical equilibrium in electrolyte solutions with non-stoichiometric methods

Research output: Contribution to journalJournal article – Annual report year: 2019Researchpeer-review

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Calculation of multiphase chemical equilibrium in electrolyte solutions with non-stoichiometric methods. / Tsanas, Christos; Stenby, Erling Halfdan; Yan, Wei.

In: Fluid Phase Equilibria, Vol. 482, 2019, p. 81-98.

Research output: Contribution to journalJournal article – Annual report year: 2019Researchpeer-review

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@article{7c467bcfaab040b898897206320078e7,
title = "Calculation of multiphase chemical equilibrium in electrolyte solutions with non-stoichiometric methods",
abstract = "Electrolyte systems constitute an important class of chemical and phase equilibrium mixtures. They usually involve complex speciation in the aqueous solution and the formation of solids phases. For geochemical systems in particular, the number of species, solids and speciation reactions is often large. In this study, we extend the application of two recently developed non-stoichiometric methods to multiphase chemical equilibrium in electrolyte systems: the first-order Lagrange multipliers method and the second-order modified RAND method. The methods are based on the Gibbs energy minimization approach with Lagrange multipliers as elemental chemical potentials and they are suitable to systems with many reactions and many phases. We demonstrate that the overall electroneutrality condition is always satisfied as long as the material balance is met. Therefore, the two methods can be directly applied to electrolyte systems while special caution is needed for the different reference states used in the electrolyte models. In addition, the stability analysis for pure solid formation can be expressed in a compact form using the Lagrange multipliers. We present three examples with emphasis on geochemical reactions. The aqueous phase can be at equilibrium with a vapor phase consisting of the volatile components and multiple solid phases. Formation of vapor and solid phases does not impede convergence or affect the convergence rate. For the geochemical system with three solid phases, our methods are orders of magnitude faster than PHREEQC.",
keywords = "Chemical equlibrium, Phase equilibrium, Electrolytes, Geochemical reactions, Algorithm, Non-stoichiometruc methods",
author = "Christos Tsanas and Stenby, {Erling Halfdan} and Wei Yan",
year = "2019",
doi = "10.1016/j.fluid.2018.10.008",
language = "English",
volume = "482",
pages = "81--98",
journal = "Fluid Phase Equilibria",
issn = "0378-3812",
publisher = "Elsevier",

}

RIS

TY - JOUR

T1 - Calculation of multiphase chemical equilibrium in electrolyte solutions with non-stoichiometric methods

AU - Tsanas, Christos

AU - Stenby, Erling Halfdan

AU - Yan, Wei

PY - 2019

Y1 - 2019

N2 - Electrolyte systems constitute an important class of chemical and phase equilibrium mixtures. They usually involve complex speciation in the aqueous solution and the formation of solids phases. For geochemical systems in particular, the number of species, solids and speciation reactions is often large. In this study, we extend the application of two recently developed non-stoichiometric methods to multiphase chemical equilibrium in electrolyte systems: the first-order Lagrange multipliers method and the second-order modified RAND method. The methods are based on the Gibbs energy minimization approach with Lagrange multipliers as elemental chemical potentials and they are suitable to systems with many reactions and many phases. We demonstrate that the overall electroneutrality condition is always satisfied as long as the material balance is met. Therefore, the two methods can be directly applied to electrolyte systems while special caution is needed for the different reference states used in the electrolyte models. In addition, the stability analysis for pure solid formation can be expressed in a compact form using the Lagrange multipliers. We present three examples with emphasis on geochemical reactions. The aqueous phase can be at equilibrium with a vapor phase consisting of the volatile components and multiple solid phases. Formation of vapor and solid phases does not impede convergence or affect the convergence rate. For the geochemical system with three solid phases, our methods are orders of magnitude faster than PHREEQC.

AB - Electrolyte systems constitute an important class of chemical and phase equilibrium mixtures. They usually involve complex speciation in the aqueous solution and the formation of solids phases. For geochemical systems in particular, the number of species, solids and speciation reactions is often large. In this study, we extend the application of two recently developed non-stoichiometric methods to multiphase chemical equilibrium in electrolyte systems: the first-order Lagrange multipliers method and the second-order modified RAND method. The methods are based on the Gibbs energy minimization approach with Lagrange multipliers as elemental chemical potentials and they are suitable to systems with many reactions and many phases. We demonstrate that the overall electroneutrality condition is always satisfied as long as the material balance is met. Therefore, the two methods can be directly applied to electrolyte systems while special caution is needed for the different reference states used in the electrolyte models. In addition, the stability analysis for pure solid formation can be expressed in a compact form using the Lagrange multipliers. We present three examples with emphasis on geochemical reactions. The aqueous phase can be at equilibrium with a vapor phase consisting of the volatile components and multiple solid phases. Formation of vapor and solid phases does not impede convergence or affect the convergence rate. For the geochemical system with three solid phases, our methods are orders of magnitude faster than PHREEQC.

KW - Chemical equlibrium

KW - Phase equilibrium

KW - Electrolytes

KW - Geochemical reactions

KW - Algorithm

KW - Non-stoichiometruc methods

U2 - 10.1016/j.fluid.2018.10.008

DO - 10.1016/j.fluid.2018.10.008

M3 - Journal article

VL - 482

SP - 81

EP - 98

JO - Fluid Phase Equilibria

JF - Fluid Phase Equilibria

SN - 0378-3812

ER -