Process of the catalytic reduction of Ti(IV) in oxalate–chlorate media

Krulic, Denise; Larabi, Nathalie; Fatouros, Nicolas

doi:10.1016/j.jelechem.2005.02.011

Cited by 6 publications

(7 citation statements)

References 9 publications

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“…Of these, the so-called "voltammetric enzymatic biosensors" are probably the most important [27][28][29]. Although the EC' electrode mechanism is one of the most thoroughly studied under voltammetric conditions [1,8,[16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34], we give in this work some new insights that are not elaborated so far in detail. The main focus of this theoretical work is on the features of the square-wave (SW) voltammograms of a quasireversible electrode reaction coupled with a chemical catalytic reaction.…”

Section: Introductionmentioning

confidence: 99%

New aspects of the electrochemical-catalytic (EC’) mechanism in square-wave voltammetry

Gulaboski

Mirčeski

2015

Electrochimica Acta

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Keywords:EC' catalytic mechanism electrode reaction kinetics standard rate constant enzymatic biosensors protein-film voltammetry A B S T R A C T Several new theoretical aspects of the electrocatalytic (regenerative) EC' mechanism under conditions of square-wave (SWV) and staircase cyclic voltammetry (SCV) are presented. Elaborating the effect of the rate of the catalytic reaction in the diffusion-controlled catalytic mechanism (diffusional EC' mechanism) and surface catalytic mechanism (surface EC' mechanism), we refer to several phenomena related to the shift of the position and the half-peak width of the net peak in square-wave voltammetry (SWV). If the rate of the catalytic reaction is much higher than the kinetics of the electrode reaction, a linear dependence between the peak potential of the simulated net SWV peaks and the logarithm of the catalytic parameter can be observed. The intercept of that linear dependence is a function of the kinetics of the electrode reaction. Based on this finding, we propose a new methodology to determine the electrode kinetics rate constant. The proposed approach relies on the variation of the concentration of the regenerative reagent. To the best of our knowledge, this is one of very few voltammetric approaches for electrode kinetic measurements not based on the time or potential variation in the experimental analyzes. In addition, we present a brief analysis of the catalytic mechanism under conditions of staircase cyclic voltammetry in order to emphasize the main differences between SCV and SWV.

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Section: Introductionmentioning

confidence: 99%

New aspects of the electrochemical-catalytic (EC’) mechanism in square-wave voltammetry

Gulaboski

Mirčeski

2015

Electrochimica Acta

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“…It is worth noting that Krulic et al [23] analyzed the catalytic reduction of Ti(IV) in an oxalate-chlorate medium, which proceeds according to a reaction scheme similar to that for a catalytic mechanism of the second kind. In their brief theoretical treatment only solutions for steady-state conditions are suggested.…”

Section: Introductionmentioning

confidence: 99%

Electrocatalysis of the first and second kind: Theoretical and experimental study in conditions of square-wave voltammetry

Mirčeski¹,

Bobrowski

Zarębski

et al. 2010

Electrochimica Acta

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“…[8]. In acid oxalate medium the catalytic effect of chlorate ion is significant for H + concentrations in the range 0.02-0.5 M. In more acid media, ClO À 3 reacts with C 2 O 2À 4 so as to generate chlorine.…”

Section: Oxalate-chlorate Acid Mediummentioning

confidence: 99%

“…Well-formed voltammograms and accurate current readings are obtained only with the mercury drop electrode [2][3][4]. The investigation of the electrochemical kinetics of the Ti(IV)/Ti(III) couple in sulfuric acid and in acid oxalate media [5][6][7][8], enabled us to define and validate the experimental conditions for determining Ti(IV) at minor or trace levels by DC polarography, square wave voltammetry (SWV) and differential pulse voltammetry (DPV) at the static mercury drop electrode (SMDE).…”

Section: Introductionmentioning

confidence: 99%