Global kinetic analysis of cyclic voltammograms at a spherical electrode

Zoski, Cynthia G.; Oldham, Keith B.; Mahon, Peter J.; Henderson, T. L.; Bond, Alan M.

doi:10.1016/0022-0728(91)85355-s

Cited by 37 publications

(13 citation statements)

References 39 publications

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“…The theory of Global Analysis has been previously reported [2,4] and so only a brief summary of the important equations will be Table 1 A list of important polynomial coefficients. presented to demonstrate how the procedure can be easily implemented.…”

Section: General Theorymentioning

confidence: 99%

“…Global Analysis has been successfully demonstrated for planar [2] and spherical [4,5] electrode geometries with the acknowledged advantages being the use of all data obtained from a single cyclic voltammogram and not being reliant on an explicit functional dependence of the electron transfer rate with potential [2]. Due to these features it has been employed to explore the nature of this relationship [3,5].…”

Section: Introductionmentioning

confidence: 99%

“…The procedure known as Global Analysis [2][3][4][5][6] is an example of the third approach and relies on the existence of a unique surface in (E(t), I(t), c s (t)) space that is independent of the experimental technique with the three time dependent parameters being the electrode potential, the current and the surface concentration of the electroactive species, respectively. Access to the surface concentration is obtained from a convolution involving the measured current with a time dependent function derived for the specific electrode geometry that is used in the experiment.…”

Section: Introductionmentioning

confidence: 99%

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Application of Global Analysis for the measurement of electrochemical parameters with disk electrodes

Mahon

2010

Electrochimica Acta

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Section: General Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Application of Global Analysis for the measurement of electrochemical parameters with disk electrodes

Mahon

2010

Electrochimica Acta

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“…The electrochemical parameters calculated from experimental data were tested and confirmed by matching the experimental cyclic voltammograms with the simulated data. It was found that convolutive voltammetry provided higher sensitivity, better resolution and more accurate method for determination of the electrochemical parameters than ordinary cyclic voltammetry.convolutive voltammetry, cyclic voltammetry, chronopotentiometry, electrochemical parameters, digital simulation Convolutive voltammetry was introduced in the early 1970s to simplify the treatment of voltammetric data for analytical [1][2][3][4][5][6] and kinetic applications [7][8][9][10] . Convolutive procedure was proposed to convert a nearly steady state voltammogram to a steady state voltammogram [11] .…”

mentioning

confidence: 99%

“…Convolutive voltammetry was introduced in the early 1970s to simplify the treatment of voltammetric data for analytical [1][2][3][4][5][6] and kinetic applications [7][8][9][10] . Convolutive procedure was proposed to convert a nearly steady state voltammogram to a steady state voltammogram [11] .…”

mentioning

confidence: 99%

Cyclic voltammetry, convolutive voltammetry, chronopotentiometry and digital simulation studies of [Pt(C≡C tol)2(dppm)2Ir(CO)2]+PF− 6 complex

Ibrahim

2009

Chin. Sci. Bull.

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Citation: El-Hallag S I. Cyclic voltammetry, convolutive voltammetry, chrono-potentiometry and digital simulation studies of [Pt(C C ≡ tol) 2 (dppm) 2 Ir(CO) 2 ] + PF − 6 complex.The electrochemical behaviour of the heterobimetallic complex [Pt(C≡C tol) 2 (dppm) 2 -Ir(CO) 2 ] + PF − 6 was studied via cyclic voltammetry, convolutive voltammetry and chronopotentiometry at glassy carbon electrode in dichloromethane solution. The electrochemical parameters calculated from experimental data were tested and confirmed by matching the experimental cyclic voltammograms with the simulated data. It was found that convolutive voltammetry provided higher sensitivity, better resolution and more accurate method for determination of the electrochemical parameters than ordinary cyclic voltammetry.convolutive voltammetry, cyclic voltammetry, chronopotentiometry, electrochemical parameters, digital simulation Convolutive voltammetry was introduced in the early 1970s to simplify the treatment of voltammetric data for analytical [1][2][3][4][5][6] and kinetic applications [7][8][9][10] . Convolutive procedure was proposed to convert a nearly steady state voltammogram to a steady state voltammogram [11] . True steady state voltammogram is characterized by a current versus potential plot having a sigmoidal shape in which the current during the backward scan exactly retraces that during the forward scan. The interest in generating such voltammograms lies in the desire to determine heterogeneous electrode parameters [12,13] . With near steady-state voltammogram, the current waves during the forward and reverse potential scans are not coincident. This disagreement increases with increasing sweep rate. Thus convolutive voltammetry is more powerful in determining the electrochemical parameters as well as identifying the nature of electrode mechanism. The electrochemistry of organometallic metal-metal bonded complexes has been the object of many studies [14][15][16] . There has been much interest in the electrochemistry of tertiary phosphine substituted group 6 metal carbonyl complexes [17,18] , which further developed organometallic electrochemistry [19] . In addition to that phosphines may stabilize isolated compounds or intermediates in homogeneous catalysis and in chemotherapy agents [20][21][22] .In this work, we reported the electrochemical behaviour of the heterobimetallic complex [Pt(C≡C tol) 2 (dppm) 2 Ir-(CO) 2 ] + PF − 6 , where dppm is ph 2 pCH 2 pph 2 (bis-(diphenylphosphine methane), using cyclic voltammetry, convolu tive voltammetry and chronopotentiometry techniques at glassy carbon electrode (GCE). Verification of the electrochemical parameters determined experimentally via digital simulation method was also considered and discussed. Based on the electrochemical behavior of the complex under consideration, the mechanistic electrode pathway was suggested.

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Electrochemical Oxidation of Diethyl 1,4-Dihydro-2,4,6-trimethyl-3,5-pyridinedicarboxylate on a Glassy Carbon Electrode as Model Compound of NADH

et al. 1999

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The electrooxodation of diethyl 1,4-dihydro-2,4,6-trimethyl-3,5-pyridinedicarboxylate (DTP) in ethanolywater solutions on a glassy carbon electrode has been studied by linear-sweep cyclic voltammetry. Convolution voltammetry was used to analyze the I À À E curves. From the experimental results it was concluded that in acidic media, the rate-determining step, r.d.s., was the deprotonation of the radical cation formed after the ®rst one-electron transfer. In basic media, the mechanism consisted of a DISP1 scheme in which r.d.s. is the uptake of an H ion by both the OH À ion and the basic components of the buffer. The relative rate constant of the carbonate ion with respect to the OH À is calculated.

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Global kinetic analysis of cyclic voltammograms at a spherical electrode

Cited by 37 publications

References 39 publications

Application of Global Analysis for the measurement of electrochemical parameters with disk electrodes

Application of Global Analysis for the measurement of electrochemical parameters with disk electrodes

Cyclic voltammetry, convolutive voltammetry, chronopotentiometry and digital simulation studies of [Pt(C≡C tol)2(dppm)2Ir(CO)2]+PF− 6 complex

Electrochemical Oxidation of Diethyl 1,4-Dihydro-2,4,6-trimethyl-3,5-pyridinedicarboxylate on a Glassy Carbon Electrode as Model Compound of NADH

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