Dynamic Simulation of Cyclic Voltammogram on the Electrochemical Reduction of VO<SUP>2+</SUP> Ions

Moon JK; Byun KH; Park SY; Oh WZ

Korean Journal of Chemical Engineering, Vol.14, No.6, 521-527, November, 1997

Dynamic Simulation of Cyclic Voltammogram on the Electrochemical Reduction of VO²⁺ Ions

An electrochemical reduction of VO²⁺ ions in a formic acid electrolyte was analyzed by cyclic voltammetry. A new four step reaction mechanism, EECE, was proposed to derive the mass transfer equation, and then it was solved by numerical method, which enabled us to obtain theoretical cyclic voltammograms. Kinetic parameters such as diffusion coefficients, rate constants and transfer coefficients, describing the VO²⁺ ion reduction system, were estimated by fitting the theoretical curve with the experimental data. The parameters obtained were then evaluated on their extended applicability in various concentrations and scan rates. It was shown that the theoretical voltammograms obtained using the above parameters fitted well with the experimental curves for the scan rate variation from 2 to 20 V/sec, while the deviation increased in proportion to the VO²⁺ ion concentration.

Keywords:Cyclic Voltammogram;Electrochemical Reduction;Decontamination;Dynamic Simulation;Vanadous Picolinate

[References]

Bard AJ, Faulkner RL, "Electrochemical Methods," John Wiley & Sons, New York, USA (1980)
Bradbury D, Segal MG, Sellers RM, Swan T, Wood CJ, "Development of LOMI Chemical Decontamination Technology," EPRI/NP-3177 (1983)
DeSesa MA, Hume DN, Glamm AC, Deford DD, Anal. Chem., 25, 983 (1953)
Finlayson BA, "Nonlinear Analysis in Chemical Engineering," McGraw-Hill Inc. (1980)
Jung KS, "Studies on the Electrode Reaction of Polyamino-carboxylate Complexes of Vanadium and Uranium at Mercury Electrode in Aqueous Solution," Ph.D. Thesis, Dept. Chem., Chungnam National Univ. (1989)
Lingane JJ, J. Am. Chem. Soc., 67, 182 (1945)
Lingane JJ, Meites L, J. Am. Chem. Soc., 70, 2525 (1948)
Nicholson RS, Shain I, Anal. Chem., 36, 706 (1964)
Nicholson RS, Shain I, Anal. Chem., 37, 178 (1965)
Nicholson RS, Anal. Chem., 37, 1351 (1965)
Polcyn DS, Shain I, Anal. Chem., 38, 376 (1966)
Oh WZ, Moon JK, Jung CH, Park SY, Shim JB, Choi WK, "Decontamination and Restoration Technology Development," KAERI-NEMAC/RR-109/93 46-69 (1993)
Wood CJ, "Reformulation of the LOMI Chemical Decontamination Reagent," EPRI NP-7276 (1991)

[Referenced By]

[1] Bard AJ, Faulkner RL, "Electrochemical Methods," John Wiley & Sons, New York, USA (1980)

[2] Bradbury D, Segal MG, Sellers RM, Swan T, Wood CJ, "Development of LOMI Chemical Decontamination Technology," EPRI/NP-3177 (1983)

[3] DeSesa MA, Hume DN, Glamm AC, Deford DD, Anal. Chem., 25, 983 (1953)

[4] Finlayson BA, "Nonlinear Analysis in Chemical Engineering," McGraw-Hill Inc. (1980)

[5] Jung KS, "Studies on the Electrode Reaction of Polyamino-carboxylate Complexes of Vanadium and Uranium at Mercury Electrode in Aqueous Solution," Ph.D. Thesis, Dept. Chem., Chungnam National Univ. (1989)

[6] Lingane JJ, J. Am. Chem. Soc., 67, 182 (1945)

[7] Lingane JJ, Meites L, J. Am. Chem. Soc., 70, 2525 (1948)

[8] Nicholson RS, Shain I, Anal. Chem., 36, 706 (1964)

[9] Nicholson RS, Shain I, Anal. Chem., 37, 178 (1965)

[10] Nicholson RS, Anal. Chem., 37, 1351 (1965)

[11] Polcyn DS, Shain I, Anal. Chem., 38, 376 (1966)

[12] Oh WZ, Moon JK, Jung CH, Park SY, Shim JB, Choi WK, "Decontamination and Restoration Technology Development," KAERI-NEMAC/RR-109/93 46-69 (1993)

[13] Wood CJ, "Reformulation of the LOMI Chemical Decontamination Reagent," EPRI NP-7276 (1991)