Mechanism of the chlorine electrode reaction on platinum, iridium and rhodium in aqueous hydrochloric acid

Yokoyama, Takamitsu; Enyo, M.

doi:10.1016/0013-4686(70)85029-0

Cited by 45 publications

(15 citation statements)

References 15 publications

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“…20 Notably, there are large oxidation waves at 1−2 V of Fe(III/II)-IL/DMF (Figure 2 peaks 4 and 5), which are due to the oxidation of the chlorine element on platinum electrode: Cl − → Cl(a) + e − , 2Cl(a) ↔ Cl 2 , where Cl(a) is a chlorine adatom. 26 This result can be attributed to the solvation effect by polar and Lewis basic DMF on Fe−Cl in Fe(III/II)-IL, which may decrease the stability of the Fe−Cl bond and produce free chlorine easily in the electric field. In addition, the redox peak current of Fe(III/II)-IL/DMF is clearly higher than that of Fe(III/II)-IL, which indicates that the addition of DMF is beneficial to the regeneration of the Fe(III/II)-IL desulfurizer using the electrochemical method.…”

Section: Resultsmentioning

confidence: 99%

Nonaqueous System of Iron-Based Ionic Liquid and DMF for the Oxidation of Hydrogen Sulfide and Regeneration by Electrolysis

Guo

Zhang

Liu

et al. 2015

Environ. Sci. Technol.

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To improve the hydrogen sulfide removal efficiency with the application of an iron-based imidazolium chloride ionic liquid (Fe(III)-IL) as desulfurizer, Fe(II) and N,N-dimethylformamide (DMF) are introduced to Fe(III)-IL to construct a new nonaqueous desulfurization system (Fe(III/II)-IL/DMF). Following desulfurization, the system can be regenerated using the controlled-potential electrolysis method. The addition of Fe(II) in Fe(III)-IL is beneficial for the hydrogen sulfide removal and the electrochemical regeneration of the desulfurizer. The addition of DMF in Fe(III/II)-IL does not change the structure of Fe(III/II)-IL but clearly decreases the acidity, increases the electrolytic current, and decreases the stability of the Fe-Cl bond in Fe(III/II)-IL. Fe(III/II)-IL/DMF can remove hydrogen sulfide and can be regenerated through an electrochemical method more efficiently than can Fe(III/II)-IL. After six cycles, the desulfurization efficiency remains higher than 98%, and the average conversion rate of Fe(II) is essentially unchanged. No sulfur peroxidation occurs, and the system remains stable. Therefore, this new nonaqueous system has considerable potential for removing H2S in pollution control applications.

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Section: Resultsmentioning

confidence: 99%

Nonaqueous System of Iron-Based Ionic Liquid and DMF for the Oxidation of Hydrogen Sulfide and Regeneration by Electrolysis

Guo

Zhang

Liu

et al. 2015

Environ. Sci. Technol.

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“…Such a changeover of the RDS was actually found [5] to take place within the potential range of about 0.2 volt.…”

Section: Application To Electrode Processesmentioning

confidence: 93%

“…For example, it has been concluded that the mechanism of the chlorine electrode reaction on noble metals [5] changes with the electrode potential in a fixed reaction route (hence the case of the coupled control is involved). I t was considered, based on a qualitative discussion on the variation of activity of the reaction intermediate with electrode potential, that the ratedetermining step (RDS) in a consecutive reaction scheme shifts with the change of affinity of the reaction, and further that there may exist a rule on the direction of the shift.…”

Section: Introductionmentioning

confidence: 99%

Shift of the rate‐determining step in a consecutive chemical reaction with variation of the reaction affinity

Enyo

1975

Int J of Chemical Kinetics

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“…Yokoyama et al (22) have reasonably used a similar range to avoid significant hypochlorate formation. Operating with a 95-99% efficiency for chlorine reaction, the interface is typically more acidic than the bulk anolyte due to the 1% to 5% current efficiency in oxygen evolution from,water.…”

Section: Experimental Methodsmentioning

confidence: 99%

Measurements of the Steady‐State Activation Overpotential of Chlorine Evolving Electrodes

Kadija

1984

J. Electrochem. Soc.

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Detailed measurements of interfacial concentration and concentration overpotential of chlorine evolving platinized platinum electrodes were performed in 4.9M NaC], at 25~ and 1 atm chlorine or 1 arm nitrogen in the cell. Based on these and electrode polarization measurements, steady-state activation overpotential curves were obtained. The applied method enabled for the first time in this field, development of true steady-state activation overpotential curves. Our findings indicated that 30-40 mV/decade slopes typically obtained in nitrogen atmosphere were essentially a sequence of quasi equilibria at the electrode interface. Also, micropolarization data obtained near the open circuit with chlorine atmosphere in the cell were found to be a concentration overpotential phenomenon. The true activation overpotential was found to become a significant part of the electrode polarization only after it exceeded several millivolts in chlorine saturated brine. In nitrogen saturated brine, where the open circuit was undefined, the activation overpotential became significant for polarizations that exceeded two decades of steady-state low current density polarization. In this case, the activation overpotential was observable as a departure from a 32 mV/decade slope. The obtained activation overpotential curves can be used as a base for developing kinetic parameters, however, a considerably greater emphasis than in the past must be given to the corresponding interfacial conditions. ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 138.251.14.35 Downloaded on 2015-03-29 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 138.251.14.35 Downloaded on 2015-03-29 to IP

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Mechanism of the chlorine electrode reaction on platinum, iridium and rhodium in aqueous hydrochloric acid

Cited by 45 publications

References 15 publications

Nonaqueous System of Iron-Based Ionic Liquid and DMF for the Oxidation of Hydrogen Sulfide and Regeneration by Electrolysis

Nonaqueous System of Iron-Based Ionic Liquid and DMF for the Oxidation of Hydrogen Sulfide and Regeneration by Electrolysis

Shift of the rate‐determining step in a consecutive chemical reaction with variation of the reaction affinity

Measurements of the Steady‐State Activation Overpotential of Chlorine Evolving Electrodes

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