Demystifying an Electrochemical Oscillator

Rudolph, Manfred; Hromadová, Magdaléna; Levie, Robert de

doi:10.1021/jp981351r

Cited by 13 publications

(6 citation statements)

References 26 publications

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“…The simplest explanation, which is being made in some theoretical models of the oscillations in this process, can assume the noncatalytic electroreduction of In(III) ions, characterized with large cathodic overpotential, as suggested earlier. However, as de Levie et al indicate [38], in the absence of SCN À ions (or, more generally, in noncomplexing solutions), and in acidic solution at pH 3.5, In(III) is not polarographically reduced, until the potential is reached where hydrogen ions are reduced and, in consequence, . Two-electrode system was employed, with dropping mercury electrode as the working one, and Ag-AgSCN as the reference electrode.…”

Section: Oscillatormentioning

confidence: 98%

“…We shall only mention here that quite a good concordance was found between theory and dynamical instabilities observed for the Cu/H 3 PO 4 system, including the existence of MMOs and Farey sequences, extensively studied earlier by Albahadily and Schell, whose works are described in Sect. 6.1.3.3. oscillator, it is useful to confront the above approaches with recent comments by de Levie et al, included in the paper of intriguing title "Demystifying an Electrochemical Oscillator" [38]. In this work, the oscillations during polarographic reduction of In(III)-SCN À were carefully reproduced using the digital simulation technique.…”

Section: Application Of This Model To the In(iii)-scnmentioning

confidence: 99%

“…Quite a good concordance between the experimental and simulated oscillations shows the advantages of such an approach (long ago established in classical electrochemistry) which in this case also minimizes the number of simplifications of the models involving ODEs, if applied to nonstationary conditions. Furthermore, to cite de Levie et al [38]: "there is nothing strange, mysterious, or unexpected in such oscillations: they simply follow the generally accepted formalism given these particular rate parameters." And further: "To understand oscillatory processes, each system must be understood in terms of its individual chemistry and physics and preferably be amenable to reconstitution from its independently determined rate parameters."…”

Section: Application Of This Model To the In(iii)-scnmentioning

confidence: 99%

“…In this paper also conditions for the oscillations are summarized and several polarographic . Reprinted with permission from [38]. Copyright 1998 American Chemical Society À system, the author emphasizes that its oscillatory behavior was understood, in terms of its principles, three decades before recent digital simulations were made, which only confirmed the early mechanism.…”

Section: Application Of This Model To the In(iii)-scnmentioning

confidence: 99%

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Temporal Instabilities in Cathodic Processes at Liquid and Solid Electrodes

Orlik

2012

Monographs in Electrochemistry

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In this chapter, examples of temporal instabilities (oscillations and multistability) reported for cathodic processes carried out at both liquid and solid electrodes are described. With respect to liquid ones, the oscillations of the current associated with the electrode processes occurring at mercury have been quite intensively studied for several decades, especially when classical polarography was still the most popular experimental technique in electrochemistry. Therefore, studies of polarographic oscillations greatly contributed to the understanding of the mechanisms of electrochemical oscillations. A big advantage of mercury electrode is its smooth, uniform, and easily renewable surface and a high overvoltage for hydrogen evolution at negative potentials. The structure of the mercury-liquid electrolyte solution is thus much easier to define than, e.g., the structure of the passive layer on corroding solid electrodes. Hence, not only the general source of instability, but also a more detailed (electro)chemical mechanism of oscillations or multistability can be suggested. Based on the characteristics of the polarographic systems one can excellently show the different origins of the negative differential resistance in electrode processes: the potential-dependent repulsion of charged reactant particles from the reaction site in the double layer, the adsorption of an inhibitor of a charge-transfer process, or the desorption of a catalyst of this process (see Sect. 2.1.4). Such studies were later extended for solid electrodes, provided that the region of potential corresponding to instabilities was positive enough to avoid hydrogen evolution. One of the model electrode reactions that served for numerous studies of mechanisms and bifurcation scenarios of dynamic instabilities was the electroreduction of S 2 O 8 2À ions in which the negative differential resistance (N-NDR region) was caused by repulsive interaction of these anions with negatively charged electrode surface. This Frumkin effect was first reported as early as 1933 [1]. In order to understand the detailed origin of this effect, one has to take into account the spatial distribution of the electric potential in the double M. Orlik, Self-Organization in Electrochemical Systems I, Monographs in Electrochemistry,

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Section: Oscillatormentioning

confidence: 98%

Section: Application Of This Model To the In(iii)-scnmentioning

confidence: 99%

Section: Application Of This Model To the In(iii)-scnmentioning

confidence: 99%

Section: Application Of This Model To the In(iii)-scnmentioning

confidence: 99%

See 2 more Smart Citations

Temporal Instabilities in Cathodic Processes at Liquid and Solid Electrodes

Orlik

2012

Monographs in Electrochemistry

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“…A common feature of electrochemical oscillators is the negative differential resistance − in the electrochemical impedance spectrum (EIS). In such a case the addition of an external resistor to the electrochemical cell can evoke and control the current oscillations. − Electrochemical systems may show a change from stability to periodicity, periodicity with the frequency doubling, or transfer to the deterministic chaos. Extensive literature deals with data analysis based on pioneering theories developed by Henry Poincaré, Mitchell Feigenbaum, and Alexander M. Ljapunov .…”

Section: Introductionmentioning

confidence: 99%

Stochastic Resonance in Electron Transfer Oscillations of Extended Viologen

et al. 2014

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Selective generation of only odd harmonics and the absence of even harmonics were never described for electrochemical oscillators though this phenomenon is known in special fields of physics and in biological systems. The heterogeneous electron transfer to the extended viologen with four repetitive viologen units yields electrochemical current oscillations. Small perturbation of the applied voltage by only a few millivolts sine wave results in current oscillations, which selectively enhance only the odd harmonic higher frequencies. The effect is explained in terms of the theory of stochastic resonance occurring in driven oscillating reactions. The described interplay of heterogeneous and homogeneous coupled electron transfers complies with the behavior of a nonlinear potential-symmetric system.

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