Chloride ion influencing potential oscillation generated by formaldehyde oxidation

Kikuchi, Mitsunobu; Mukouyama, Yoshiharu; Okamoto, Hiroshi

doi:10.1016/j.electacta.2008.05.056

Cited by 9 publications

(6 citation statements)

References 44 publications

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“…Parameter-plane diagrams can be constructed relating morphology and important features of the experiment such as concentrations and applied currents. Comparable diagrams have been also reported for the case of formic acid, and formaldehyde oxidation under the influence of chloride anions [57] , [58] .…”

Section: Resultsmentioning

confidence: 56%

Experimental Assessment of the Sensitiveness of an Electrochemical Oscillator towards Chemical Perturbations

2012

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In this study we address the problem of the response of a (electro)chemical oscillator towards chemical perturbations of different magnitudes. The chemical perturbation was achieved by addition of distinct amounts of trifluoromethanesulfonate (TFMSA), a rather stable and non-specifically adsorbing anion, and the system under investigation was the methanol electro-oxidation reaction under both stationary and oscillatory regimes. Increasing the anion concentration resulted in a decrease in the reaction rates of methanol oxidation and a general decrease in the parameter window where oscillations occurred. Furthermore, the addition of TFMSA was found to decrease the induction period and the total duration of oscillations. The mechanism underlying these observations was derived mathematically and revealed that inhibition in the methanol oxidation through blockage of active sites was found to further accelerate the intrinsic non-stationarity of the unperturbed system. Altogether, the presented results are among the few concerning the experimental assessment of the sensitiveness of an oscillator towards chemical perturbations. The universal nature of the complex chemical oscillator investigated here might be used for reference when studying the dynamics of other less accessible perturbed networks of (bio)chemical reactions.

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Section: Resultsmentioning

confidence: 56%

Experimental Assessment of the Sensitiveness of an Electrochemical Oscillator towards Chemical Perturbations

2012

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“…For formaldehyde, we have already reported 39 that the potential oscillation appeared in the current range of 15-0.35 mA for 0.1 M formaldehyde with sulfuric acid at 315 K. We, then, studied again potential oscillation during oxidation of 0.1 M formaldehyde in the current range between 10 and 0.05 mA but we could not find a ¦I (od). As an example, Fig.…”

Section: Comparison With Oscillation Behavior During Formic Acidmentioning

confidence: 90%

“…and formaldehyde oxidations Usually oscillation behavior has been studied at a comparatively high or medium current [31][32][33]38,39 and, therefore, oscillations with a very long induction period of the order of hours, the key oscillations to finding the ¦I (od), have not been studied. To know whether a ¦I (od) is present or not with formic acid or formaldehyde, we investigated oscillation behavior at a very low current.…”

Section: Comparison With Oscillation Behavior During Formic Acidmentioning

confidence: 99%

Separate Current Range for Appearance of Potential Oscillation during Methanol Oxidation on Platinum

et al. 2014

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We have found that the current range is divided into two parts for the appearance of potential oscillation during methanol oxidation on polycrystalline platinum at 315 K when the methanol concentration is between 10 and 0.03 mol dm −3 (M). The current range for oscillation disappearance, named ΔI (od), increases with a decrease in the methanol concentration. At currents below the ΔI (od), the oscillation waveform is always a large-amplitude and long-period (sometimes of the order of an hour) oscillation, named oscillation L. At currents immediately above the ΔI (od), a small-amplitude and short-period oscillation, named oscillation S, is observed for 0.03 to 0.1 M methanol and oscillation L is for 0.3 to 10 M methanol. For the latter methanol concentrations, oscillation S also becomes observed at higher currents. Such a ΔI (od) has not been found for potential oscillations during formic acid or formaldehyde oxidation and, thus, the existence of the ΔI (od) is distinctive to potential oscillations during methanol oxidation.

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“…33,34 As a result, a new chaotic oscillation, a very large-amplitude one and others have been found. As for methanol oxidation, this paper describes in detail and discusses potential oscillations, especially regeneration oscillation, in comparison with the oscillations observed during formic acid and formaldehyde oxidation in the presence of wide range of chloride ion concentrations from 10 ¹7 to 10 0 M.…”

Section: Introductionmentioning

confidence: 98%

Regeneration Oscillation Observed during Oxidation of Methanol, Formic Acid, and Formaldehyde with Chloride Ions

et al. 2014

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A new type of oscillation, which we name regeneration oscillation, is investigated in detail. The regeneration oscillation is the ordinary potential oscillation with the higher turning potential lower than 0.85 V appearing repeatedly after the potential stays at a value higher than 1.0 V for a long time, of the order of 10 min or an hour. The oscillation has been observed during the oxidation of methanol, formaldehyde, and formic acid at 315 K when their concentrations are high, 1 or 10 mol/L (M), in the presence of high chloride ion concentrations, such as 10 −2 M, at a current far lower than the maximum current for the appearance of ordinary oscillation. The reason for the appearance of regeneration oscillation has been found by voltammetry and surface-enhanced infrared absorption spectroscopy to be due to the presence of two potentials for oxidizing adsorbed CO, one shifting to a value higher than 1.0 V and the other remaining unchanged, with increasing chloride ion concentration.

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Chloride ion influencing potential oscillation generated by formaldehyde oxidation

Cited by 9 publications

References 44 publications

Experimental Assessment of the Sensitiveness of an Electrochemical Oscillator towards Chemical Perturbations

Experimental Assessment of the Sensitiveness of an Electrochemical Oscillator towards Chemical Perturbations

Separate Current Range for Appearance of Potential Oscillation during Methanol Oxidation on Platinum

Regeneration Oscillation Observed during Oxidation of Methanol, Formic Acid, and Formaldehyde with Chloride Ions

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