Abstract
An improved mass transport model for numerical electrochemical simulation
S. Van Damme*, J. Deconinck
Computational Electrochemistry Group, ETEC, Faculty of Engineering,
Vrije Universiteit Brussel, Pleinlaan 2, 1040 Brussels
*Corresponding author: [email protected]
Numerical simulation of electrochemical systems has known a rapid evolution over the past decade and is developing into a powerful tool in electroanalytical chemistry [1] and industrial reactor design [2,3]. In many systems the current density distribution is influenced by mass transport, which is nowadays modeled by the transport laws for infinitely diluted solutions. At finite concentrations the diffusion constants are treated as adjustable parameters.
Within the framework of the mean spherical approximation it is, in principle, possible to compute all the thermodynamic and transport properties of electrolyte solutions, the only adjustable parameters being the effective diameters of the ions. Analytical expressions for the ion activity coefficients [4] and the electrophoretic effect on the Onsager coefficients [5] have in recent years been proposed. Now an analytical expression for the relaxation effect on the Onsager coefficients is derived from the Fuoss-Onsager equation. The predicted quantities are in good agreement with experiment up to a total concentration of 1M.
The linear phenomenological laws of irreversible thermodynamics combined with the mean spherical approximation constitute a new and promising mass transport model for numerical electrochemical simulation software. A theoretical comparative study on a rotating disc electrode between the new model and the classical model to determine the magnitude of the deviation in predicted limiting current densities for different types of electrochemical systems will be presented. Both models will also be tested on real electrochemical systems.
[1] L. Pauwels, A. Hubin, B. Van Den Bossche, L. Bortels, J. Deconinck Electrochim. Acta 51 (2006) 1505.
[2] S. Goldbach, B. Van Den Bossche, T. Daenen, J. Deconinck, F. Lapicque, J. Appl. Electrochem. 30 (2000) 1.
[3] B. Van Den Bossche, G. Floridor, J. Deconinck, P. Van Den Winkel, A. Hubin, J. Electroanal. Chem. 531 (2002) 61.
[4] J.-P. Simonin, L. Blum, P. Turq J. Phys. Chem. 100 (1996) 7704.
[5] J.-F. Dufrêche, O. Bernard, P. Turq J. Chem. Phys. 116 (2002) 2085.
S. Van Damme*, J. Deconinck
Computational Electrochemistry Group, ETEC, Faculty of Engineering,
Vrije Universiteit Brussel, Pleinlaan 2, 1040 Brussels
*Corresponding author: [email protected]
Numerical simulation of electrochemical systems has known a rapid evolution over the past decade and is developing into a powerful tool in electroanalytical chemistry [1] and industrial reactor design [2,3]. In many systems the current density distribution is influenced by mass transport, which is nowadays modeled by the transport laws for infinitely diluted solutions. At finite concentrations the diffusion constants are treated as adjustable parameters.
Within the framework of the mean spherical approximation it is, in principle, possible to compute all the thermodynamic and transport properties of electrolyte solutions, the only adjustable parameters being the effective diameters of the ions. Analytical expressions for the ion activity coefficients [4] and the electrophoretic effect on the Onsager coefficients [5] have in recent years been proposed. Now an analytical expression for the relaxation effect on the Onsager coefficients is derived from the Fuoss-Onsager equation. The predicted quantities are in good agreement with experiment up to a total concentration of 1M.
The linear phenomenological laws of irreversible thermodynamics combined with the mean spherical approximation constitute a new and promising mass transport model for numerical electrochemical simulation software. A theoretical comparative study on a rotating disc electrode between the new model and the classical model to determine the magnitude of the deviation in predicted limiting current densities for different types of electrochemical systems will be presented. Both models will also be tested on real electrochemical systems.
[1] L. Pauwels, A. Hubin, B. Van Den Bossche, L. Bortels, J. Deconinck Electrochim. Acta 51 (2006) 1505.
[2] S. Goldbach, B. Van Den Bossche, T. Daenen, J. Deconinck, F. Lapicque, J. Appl. Electrochem. 30 (2000) 1.
[3] B. Van Den Bossche, G. Floridor, J. Deconinck, P. Van Den Winkel, A. Hubin, J. Electroanal. Chem. 531 (2002) 61.
[4] J.-P. Simonin, L. Blum, P. Turq J. Phys. Chem. 100 (1996) 7704.
[5] J.-F. Dufrêche, O. Bernard, P. Turq J. Chem. Phys. 116 (2002) 2085.
| Original language | English |
|---|---|
| Title of host publication | The 58th Annual Meeting of the International Society of Electrochemistry |
| Publication status | Published - 9 Sept 2007 |
| Event | Finds and Results from the Swedish Cyprus Expedition: A Gender Perspective at the Medelhavsmuseet - Stockholm, Sweden Duration: 21 Sept 2009 → 25 Sept 2009 |
Conference
| Conference | Finds and Results from the Swedish Cyprus Expedition: A Gender Perspective at the Medelhavsmuseet |
|---|---|
| Country/Territory | Sweden |
| City | Stockholm |
| Period | 21/09/09 → 25/09/09 |
Keywords
- mean spherical approximation
- ion transport
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The 58th Annual Meeting of the International Society of Electrochemistry
De Wilde, D. (Speaker)
9 Sept 2007 → 15 Sept 2007Activity: Talk or presentation › Talk or presentation at a conference
-
The 58th Annual Meeting of the International Society of Electrochemistry
Van Damme, S. (Speaker)
9 Sept 2007 → 15 Sept 2007Activity: Talk or presentation › Talk or presentation at a conference
-
The 58th Annual Meeting of the International Society of Electrochemistry
Smets, N. (Participant)
9 Sept 2007 → 15 Sept 2007Activity: Participating in or organising an event › Participation in conference
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