Regression analysis of electrochemical data with expanding space grid digital simulation at spherical electrodes

Arena, James V.; Rusling, James F.

doi:10.1021/ac00298a047

Cited by 24 publications

(7 citation statements)

References 29 publications

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“…This particular implementation of the box method exhibits therefore the same flux properties as the box 2 method but only when simulating a planar electrode with sufficiently large values of the grid parameter a. However, this equivalence is lost if Feldberg's approach is extended to non-planar electrode geometries (as described, for instance in [15]) because the factor q k ðDY Þ ¼ OðDY 2 Þ establishing the proportionality of the integral approximations in the kth volume element is no longer independent of k if P > 0.…”

Section: Cylindrical Electrodementioning

confidence: 94%

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Digital simulations on unequally spaced grids. Part 3. Attaining exponential convergence for the discretisation error of the flux as a new strategy in digital simulations of electrochemical experiments

Rudolph

2004

Journal of Electroanalytical Chemistry

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Section: Cylindrical Electrodementioning

confidence: 94%

“…The above findings can be readily applied now to Feldberg's implementation of the box method [14][15][16]. In the limiting case of planar diffusion it is characterized by the following discretisation scheme DC k DT X k ð À X kÀ1 Þ ¼ c C kþ1 À C k X kþ1 À X k À c C k À C kÀ1 X k À X kÀ1…”

Section: Cylindrical Electrodementioning

confidence: 99%

Digital simulations on unequally spaced grids. Part 3. Attaining exponential convergence for the discretisation error of the flux as a new strategy in digital simulations of electrochemical experiments

Rudolph

2004

Journal of Electroanalytical Chemistry

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“…Apparent standard heterogeneous rate constants (k°) were estimated from anodic-cathodic peak potential differences (27,22) of CVs over a range of scan rates where these differences exceeded about 65 mV, assuming equal diffusion coefficients of reduced and oxidized forms of the redox couple and electrochemical transfer coefficients of 0.5. Simulations of cyclic voltammograms were done by a previously described (23) expanding space grid explicit digital simulation program compiled in Turbo Basic on a PC-AT type microcomputer. Simulations assumed equal diffusion coefficients of both halves of the redox couples and electrochemical transfer coefficients of 0.5.…”

mentioning

confidence: 99%

Bicontinuous microemulsions as media for electrochemical studies

Iwunze¹,

Sucheta²,

Rusling³

1990

Anal. Chem.

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Biocontinuous microemulsions of didodecyldimethylammonium bromide (DDAB)/dodecane/water were explored as media for voltammetric reductions and oxidations of ruthenium(III) hexaammine, ferrocyanide, ferrocene, cob(II)alamin, and several polycyclic aromatic hydrocarbons (PAHs). These clear microemulsions are conductive and are believed to contain a dynamic extended network of interconnected water tubules. Agreement of simulated and experimental voltammetric data shows that electrochemical theory for homogeneous media is followed to a good approximation in DDAB microemulsions. Diffusion of electroactive solutes did not reflect the high bulk viscosities of the microemulsions. Non-polar molecules and ions diffuse as if they were in neat oil or aqueous media, respectively, and voltammograms with good signal to noise ratio are obtained. Reductions of PAHs in the microemulsions occurred by an ECE-type pathway, with nearly reversible one-electron reductions achieved at high scan rates.

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“…Electrochemical instrumentation, three-electrode cells, and procedures were the same as those reported previously. 10 The working electrode was a spherical hanging-drop mercury electrode (A = 0.0183 cm2), the counter electrode was a platinum wire, and the reference was a Ag/AgI wire. Ohmic distortion of voltammograms was negligible after compensation of about 70% of the IR drop of the cell.…”

Section: Methodsmentioning

confidence: 99%

“…Thus, in simulating the homogeneous kinetics of Scheme I, eq [9][10][11][12] can be used with eq 8 to compute the concentration of each diffusing species in each space element. However, when the simulation is coupled to nonlinear regression analysis, under conditions where eq 2 is the rds, no unique value of k2 can be computed upon convergence since for any value of k2 » /c_,C*A, k^W^il^w ill be approximately zero.…”

Section: Introductionmentioning

confidence: 99%

Kinetic control in two-electron homogeneous redox electrocatalysis: reduction of monohalobiphenyls

Arena¹,

Rusling²

1987

J. Phys. Chem.

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Kinetic control of the two-electron electrocatalytic dehalogenation of monohalobiphenyls to biphenyl was elucidated by analyzing voltammetric data with expanded-grid digital simulation/nonlinear regression. The method involves comparing goodness of fit of limiting and mixed kinetic simulation models to the data and is applicable to second-order conditions. The rate-determining step in the dehalogenations was confirmed as electron transfer between the electrochemically generated phenanthridine anion radical and 4-chloro-(4-CB) and 4-bromobiphenyl (4-BB), rather than decomposition of the halobiphenyl anion radical. Rate constants for this step of (1.42 ± 0.12) X 103 M-1 s-1 for 4-CB and (5.1 ± 1.8) X 104 M-1 s-1 for 4-BB showed considerably improved precision (and accuracy in the latter case) over rate constants obtained under pseudo-first-order conditions, where the catalytic current had to be extracted from large currents for direct reduction of excess substrate. The simulation/regression method is general for two-electron homogeneous electrocatalytic reactions following similar mechanisms. Synthetic data were used to show that, for systems under mixed kinetic control, rate constants for both homogeneous electron transfer and decomposition of the haloaromatic anion radical can be estimated simultaneously.

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Regression analysis of electrochemical data with expanding space grid digital simulation at spherical electrodes

Cited by 24 publications

References 29 publications

Digital simulations on unequally spaced grids. Part 3. Attaining exponential convergence for the discretisation error of the flux as a new strategy in digital simulations of electrochemical experiments

Digital simulations on unequally spaced grids. Part 3. Attaining exponential convergence for the discretisation error of the flux as a new strategy in digital simulations of electrochemical experiments

Bicontinuous microemulsions as media for electrochemical studies

Kinetic control in two-electron homogeneous redox electrocatalysis: reduction of monohalobiphenyls

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