Activities per year
Abstract
Computational electrochemistry deals with the computation of the current and potential distribution in electrolyte solutions for electroanalytical chemistry [1] and industrial reactor design [2,3]. To achieve high throughput, the operating conditions are often close to mass transport control, which is nowadays modeled by the transport laws for ideal solutions. Sometimes, the limiting diffusion constants are replaced by apparent diffusion constants, such that the conductivity matches the experimental value. However, this procedure does not capture all the consequences of the nonideality of electrolyte solutions.
The mean spherical approximation (MSA) provides a means to calculate the thermodynamic and transport properties of electrolyte solutions up to a total ion concentration of about 2M. Analytical expressions for the ion activity coefficients [4], the electrophoretic effect on the Onsager coefficients [5] and the relaxation effect on the Onsager coefficients [6] have been derived.
The linear phenomenological laws of irreversible thermodynamics supplemented with the MSA expressions constitute a new mass transport model for computational electrochemistry. This MSA mass transport model is shown to predict the limiting current density of copper deposition from aqueous CuSO4 solutions on a rotating disc electrode, as measured by Hsueh and Newman [7], far better than the ideal mass transport model with apparent diffusion constants. The experimental and predicted limiting current densities are summarized in table 1. Both models will also be compared for electrochemical pattern replication (ECPR) applications.
Table 1: Limiting current density (A/m2) of copper deposition from aqueous CuSO4 solutions (mol/L) at 25 °C and 300 rpm.
Concentration Experiment MSA Ideal
0.02 160.3 174.6 120.4
0.05 394.6 425.5 262.7
0.10 788.1 834.6 473.9
0.30 2135.5 2433.8 1192.5
[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.
[6] S. Van Damme, J. Deconinck J. Phys. Chem. B 111 (2007) 5308.
[7] L. Hsueh, J. Newman Electrochim. Acta 12 (1967) 429.
The mean spherical approximation (MSA) provides a means to calculate the thermodynamic and transport properties of electrolyte solutions up to a total ion concentration of about 2M. Analytical expressions for the ion activity coefficients [4], the electrophoretic effect on the Onsager coefficients [5] and the relaxation effect on the Onsager coefficients [6] have been derived.
The linear phenomenological laws of irreversible thermodynamics supplemented with the MSA expressions constitute a new mass transport model for computational electrochemistry. This MSA mass transport model is shown to predict the limiting current density of copper deposition from aqueous CuSO4 solutions on a rotating disc electrode, as measured by Hsueh and Newman [7], far better than the ideal mass transport model with apparent diffusion constants. The experimental and predicted limiting current densities are summarized in table 1. Both models will also be compared for electrochemical pattern replication (ECPR) applications.
Table 1: Limiting current density (A/m2) of copper deposition from aqueous CuSO4 solutions (mol/L) at 25 °C and 300 rpm.
Concentration Experiment MSA Ideal
0.02 160.3 174.6 120.4
0.05 394.6 425.5 262.7
0.10 788.1 834.6 473.9
0.30 2135.5 2433.8 1192.5
[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.
[6] S. Van Damme, J. Deconinck J. Phys. Chem. B 111 (2007) 5308.
[7] L. Hsueh, J. Newman Electrochim. Acta 12 (1967) 429.
Original language  English 

Title of host publication  The 214th ECS Meeting. PRiME 2008 
Publication status  Published  2008 
Event  Finds and Results from the Swedish Cyprus Expedition: A Gender Perspective at the Medelhavsmuseet  Stockholm, Sweden Duration: 21 Sep 2009 → 25 Sep 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
 electrodeposition
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The 214th ECS Meeting. PRiME 2008
Steven Van Damme (Speaker)
13 Oct 2008 → 17 Oct 2008Activity: Talk or presentation › Talk or presentation at a conference

The 214th ECS Meeting. PRiME 2008
Nico Smets (Participant)
13 Oct 2008 → 17 Oct 2008Activity: Participating in or organising an event › Participation in conference