Chronoamperometric behaviour of a CE process with fast chemical reactions at spherical electrodes and microelectrodes. Comparison with a catalytic reaction

Molina, Á.; Morales, Isabel; López‐Tenés, Manuela

doi:10.1016/j.elecom.2006.04.011

Cited by 49 publications

(58 citation statements)

References 11 publications

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“…Expressions (17)- (19) could be used for a general good description of the system instead of those deduced under kss conditions [28,37] and are very helpful to estimate the values of E 1=2 , K and/or…”

Section: Cuðclþ Mmentioning

confidence: 99%

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Advances in Copper Electrodeposition in Chloride Excess. A Theoretical and Experimental Approach

Sebastián

Torralba

Vallés

et al. 2015

Electrochimica Acta

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A B S T R A C TThis is an in depth study in the knowledge of the nucleation and growth mechanism that governs copper electrodeposition in excess chloride media. In these conditions copper electro-reduction takes place via two well-separated steps, since the Cu(I) intermediate is stabilized through chloride complexation. The process was studied in two media, a deep eutectic solvent (DES) based on a mixture of urea and choline chloride, and in excess chloride aqueous solution, in order to also analyse solvent influence on the early stages of the deposition process. In both media, copper electrodeposition follows a nucleation and a diffusion controlled three-dimensional growth mechanism. In line with a previous work a double potentiostatic step signal was employed to record j-t transients associated to both nucleation and growth stages, and from them, the whole mechanistic analysis of the copper electrodeposition was performed. This analysis involved the calculation of the surface concentrations of Cu(II), free Cu(I) and complexed Cu (I) for any time and potential required and the application of Sharifker-Hills model, j m 2 t m products and rising part analysis including the calculated parameters, which are strengthened as valuable tools for complete copper electrodeposition analysis in these media.

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Section: Cuðclþ Mmentioning

confidence: 99%

“…assuming kinetic steady state conditions (kss)) [28,37] the following expression for the j/E/t response is derived…”

Section: Cuðclþ Mmentioning

confidence: 99%

Advances in Copper Electrodeposition in Chloride Excess. A Theoretical and Experimental Approach

Sebastián

Torralba

Vallés

et al. 2015

Electrochimica Acta

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“…The mathematical procedure used is initially based on Koutecký 's dimensionless parameter method [14,15] and it provides us with an explicit solution for current-potential curve as a series of two dimensionless variables referred to the homogeneous chemical kinetics (v = (k 1 + k 2 )t) and to the electrode sphericity (n ¼ 2 ffiffiffiffiffi ffi Dt p =r 0 ). This solution has been proved to converge for values of v 6 35 and n 6 15, which are high enough since for greater values the kinetic steady state approximation [8][9][10] is well valid. Moreover, we show in an appendix the total concordance between rigorous analytical and numerical solutions.…”

Section: Introductionmentioning

confidence: 98%

“…In the literature, simple approximated solutions have been deduced for CE mechanism in planar and spherical diffusion fields, by assuming kinetic steady state [8][9][10], diffusive steady state [9,10] or total steady state [6,11,12]. Although these approximated solutions are useful, simple and easily manipulated, their applicability is limited.…”

Section: Introductionmentioning

confidence: 99%

Rigorous analytical solution for a preceding chemical reaction in Normal Pulse Voltammetry at spherical electrodes and microelectrodes

Molina

Martı́nez-Ortiz

Laborda

et al. 2009

Journal of Electroanalytical Chemistry

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“…The kinetics of this homogeneous step can in principle be studied by observing how the limiting current responds to changes in electrode size. It must be mentioned here that the physical situation as well as the boundary conditions employed herein represent the simplest possible description whereas, in several recent investigations, more complicated but realistic problems [28][29][30] have been explored. Further, based on the outcome of this work it is possible to calculate the concentration and current for the CE mechanism for all microelectrodes for various complex boundary conditions.…”

Section: Discussionmentioning

confidence: 99%

Analytical expression of non steady-state concentration for the CE mechanism at a planar electrode

Indira

Rajendran

2012

J Math Chem

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The analytical solutions of the non-steady-state concentrations of species at a planar microelectrode are discussed. The analytical expression of the kinetics of CE mechanism under first or pseudo-first order conditions with equal diffusion coefficients at planar electrode under non-steady-state conditions are obtained by using Homotopy perturbation method. These simple new approximate expressions are valid for all values of time and possible values of rate constants. Analytical equations are given to describe the current when the homogeneous equilibrium position lies heavily in favour of the electroinactive species. Working surfaces are presented for the variation of limiting current with a homogeneous kinetic parameter and equilibrium constant. In this work we employ the Homotopy perturbation method to solve the boundary value problem. Furthermore, in this work the numerical simulation of the problem is also reported using Scilab program. The analytical results are found to be in excellent agreement with the numerical results.

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Chronoamperometric behaviour of a CE process with fast chemical reactions at spherical electrodes and microelectrodes. Comparison with a catalytic reaction

Cited by 49 publications

References 11 publications

Advances in Copper Electrodeposition in Chloride Excess. A Theoretical and Experimental Approach

Advances in Copper Electrodeposition in Chloride Excess. A Theoretical and Experimental Approach

Rigorous analytical solution for a preceding chemical reaction in Normal Pulse Voltammetry at spherical electrodes and microelectrodes

Analytical expression of non steady-state concentration for the CE mechanism at a planar electrode

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