Overvoltage and the Structure of the Electrical Double Layer at a Hydrogen Electrode

Kimball, George E.; Glasstone, Samuel; Glassner, Alvin

doi:10.1063/1.1750831

Cited by 16 publications

(5 citation statements)

References 3 publications

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“…Consideration of (67) shows that the first requirement would be expected for any mechanism, however, and it has in any case been shown in an earlier section of this paper that a sufficiently accurate ex-perimental determination of B is prohibitively difficult [see also Butler (19)]. In order that the prototropic transfer theory can yield a satisfactory theory of pH effects and of reversible electrode potentials an unusual structure of the double layer has to be assumed (20). Forecasts made upon this basis of similarities between hydrogen and oxygen overpotentials have also not been confirmed (27).…”

Section: Summary Of Some Recent Advancesmentioning

confidence: 95%

The Mechanism of the Cathodic Hydrogen Evolution Reaction

Bockris

Potter

1952

J. Electrochem. Soc.

489

285

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Some of the outstanding problems of concept and mechanism in the field of cathodic hydrogen evolution kinetics are discussed and clarified. A full derivation and correlation of kinetic equations which assume no mechanism reveals expressions for several parameters which take values specific to one or more mechanisms. The use of statistical methods of treatment of data proves indispensable in estimating the values of these parameters. A further method of ascertaining the mechanism of the hydrogen evolution reaction is to examine the kinetics of the individual reaction paths, so that the expected values of parameters common to all paths may be deduced. A number of mechanisms important in acid and alkaline solutions are thus treated, and are shown to be distinguishable experimentally. Using already published data, the actual conditions under which various reaction paths take place at mercury, silver, nickel, and smooth platinum cathodes are calculated. It is not only possible to compare these deduced data with observation, and thereby verify the occurrence of a particular reaction path, but also to demonstrate the impossibility of some mechanisms in specific cases. The recent advances which the foregoing methods have made possible are discussed in relation to data which have recently become available.

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Section: Summary Of Some Recent Advancesmentioning

confidence: 95%

The Mechanism of the Cathodic Hydrogen Evolution Reaction

Bockris

Potter

1952

J. Electrochem. Soc.

489

285

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“…s A model very similar to the model given here, and leading to Eq. [13], was used by Kimball, et al (12) in their discussion of hydrogen evolution on metals.…”

Section: ~2 = Eo Ls Lymentioning

confidence: 99%

“…was used by Kimball, et al(12) in their discussion of hydrogen evolution on metals. bine these equations to obtain V, as a function of O.…”

mentioning

confidence: 99%

The Reduction of Oxygen on Passive Zirconium

Meyer¹

1963

J. Electrochem. Soc.

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The reduction of oxygen on film-covered zirconium was investigated by the measurement of the rate as a function of potential and concentration. The amount of hydrogen peroxide produced was measured and compared to the theoretical amount. The results showed two distinct polarization regions, a very low-current region with a Tafel slope of about 1.4 (2.3 RT/F) and an oxygen order of unity, and a higher current region with a much larger Tafel slope and a fractional oxygen order. Equations accounting for the general features of the data are derived based on a model which considers the separate potential drops across the film and the solution double layer.Zirconium is known to form a film, presumably of ZrO2, when in contact with 02 in aqueous solution. The standard potential (1) for the half-reactionZr + 2H20 = ZrO2-b 4H + ~-4e-is--l.43v. It is evident from this potential that ZrO2 is thermodynamically stable under potentials at which such oxidizing agents as 02, H202, and H + are easily reduced. Furthermore, measurements made in 02-saturated 0.1M NaeSO4 (pH ~ 4) showed that the rate of formation of ZrO2 at potentials in the vicinity of S.C.E. falls off to values on the order of 10 -s to 10 -9 amp/cm 2 after a few days (2). Therefore it should be possible to study reduction processes on film-covered zirconium without significant interference from the film-forming reactions. It is found, in practice, that determinations of reduction rates are reasonably reproducible on a given sample, and therefore it is safe to conclude that the effect of reduction experiments on the surface of the electrode is slight.In a previous paper (3), experiments were described concerning the reduction on zirconium of several oxidizing agents including oxygen. Because the primary purpose of that paper was to present and illustrate kinetic equations resulting from consideration of a two-barrier model for film-covered electrodes, specific mechanisms were not discussed. In the present paper, additional experiments concerning the reduction of oxygen on zirconium are described, and the mechanism of this reaction is discussed. This reaction was chosen because of its importance for the film-formation process in oxygenated aqueous solutions.The reduction of oxygen on metals has not received a great deal of attention. On mercury in acid solutions, Iofa et al.

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“…The silver-platinum electrode pair has been used by Lingane and Small (5) as the basis for an electrolytic coulometer in which the hydroxide generated is titrated with standard acid.…”

Section: In Strum Entationmentioning

confidence: 99%