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The kinetics of the reduction of protons at polycrystalline and monocrystalline gold electrodes

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In this paper, the reduction of H+ from 1 M FICiO, and 1 IV NaCIO, solurions at polycrystalline and single crystal faces of very pure gold electrode, was studied by determining the forward rate constant kr as a funcrion of porential and of H' concentration.
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This article is published in Journal of Electroanalytical Chemistry.The article was published on 1984-12-24 and is currently open access. It has received 84 citations till now. The article focuses on the topics: Single crystal.

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On the electrical capacitance of interfaces exhibiting constant phase element behaviour

TL;DR: In this paper, it was shown that an electrode with a double layer of CPE character can never be an ''ideally polarizable electrode'' and the conclusions can be qualitatively applied to all systems with an interface revealing CPE behaviour.
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ac Impedance of Faradaic reactions involving electrosorbed intermediates—I. Kinetic theory

TL;DR: In this paper, it was shown that interpretation of ac impedance measurements directly in terms of the components of an intuitively assumed equivalent circuit is rarely correct; only in the case of underpotential-deposition of an ad-species, where no continuous Faradaic currents pass, in such an approach satisfactory.
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Behavior of overpotential—deposited species in Faradaic reactions—II. ac Impedance measurements on H2 evolution kinetics at activated and unactivated Pt cathodes

TL;DR: In this article, the behavior of the opd H species in the H 2 evolution reaction (h.r) proceeding with appreciable net cathodic current at activated and unactivated rotated Pt electrodes is investigated by means of impedance spectrum measurements.
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Modeling of uniform CO2 corrosion of mild steel in gas transportation systems: A review

TL;DR: The state of the art with regards to mechanistic understanding of uniform carbon dioxide corrosion of mild steel is reviewed and corresponding mathematical models are presented in this article, where existing predictive models are categorized into three groups, termed: empirical/semi-empirical, elementary mechanistic, and comprehensive mechanistic.
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Hydrogen Evolution Reaction on Gold Single-Crystal Electrodes in Acid Solutions

TL;DR: In this paper, the hydrogen evolution reaction on the low index planes of single-crystal Au electrodes has been studied in HClO4 solutions with the aim of ascertaining the extent of the sensitivity of the reaction rate to the surface crystallographic structure.
References
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The analysis of electrode impedances complicated by the presence of a constant phase element

TL;DR: In this article, it was shown that the electrical double-layer at a solid electrode does not in general behave as a pure capacitance but rather as an impedance displaying a frequency-independent phase angle different from 90°.
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Work function, electronegativity, and electrochemical behaviour of metals: III. Electrolytic hydrogen evolution in acid solutions

TL;DR: In this paper, the dependence of the exchange current for the electrolytic evolution of hydrogen on metals (i 0,H ) on the work function is analyzed on the basic of a new list of polycrystalline surfaces.
Journal ArticleDOI

Eine methode zum ausschluss von randeffekten bei elektrochemischen messungen an einkristallen: Test anhand der adsorptionssysteme Ag/Pb2+ und Au/Cu2+

TL;DR: Ausschluss von Randeffekten wird anhand der Adsorptions systeme Ag/Pb 2+ und Au/Cu 2+ gezeigt, bei der aufgrund der Oberflachenspannung des Electrolyten nur die orientierte Flache benetzt wird.
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Frequently Asked Questions (9)
Q1. What are the contributions in "The kinetics of the reduction of protons at polycrystalline and monocrystalline gold e.lectrodes" ?

The reduction of H+ from 1 M FICiO, and 1 IV NaCIO., solurions at polycrystalline and single crystal faces of very pure gold electrode ; is studied by determining the forward rate constant kr as a funcrion of porential and of H ’ concentration. The slight differences in the rate constants observed, al single crystal faces of the same purity but wirh different crystallographic orientation are discussed. And dc current measurements with a continuous potential variation. In k, vs. potential are curved and exhibit limiting slopes corresponding to values for the operational transfer coefficient o = 1 at positive and a = 0. 5 at negative potentials. 

At sufficiently high frequeitcies the second term in eqn. (10) will become infinitely small, so that apparently a “charge transfer resistance” R, remains. 

In the, review given by Kuhn and Byrne [7] it can be seen that usually only one Tafel slope is reported, but a variety of values between 0.12 V (a = 0.5) to 0.03 V (a = 2j was found. 

the slopes of the ln k, vs. E curves from the sweep experiments appear to be 11:s~ steep, especially at the lower current densities. 

Depending on the reaction mechanism251and the extent of adsorption of the hydrogen atom, the reaction order in c*u+ can be second, first or zero order, but also in between these-values according to the ~‘u+ values in Table 1. 

The impedance measurements were analyzed using the procedure developed in a separate paper [25] to obtain the value of the charge transfer resistance R,, as a function of dc potential. 

the results for the phctogenerated atomic hydrogen appear to depend on the crystallographic orientation of the surface of the gold ejectrode [32] so another mechanism might be operative in this case. 

As eqn. (12) is obeyed by their results down to 9 = 0, it is easily realized that for any possible third term, e.g. exp(lS+)/f., or exp(2@)/L,, the value of L, should be larger than ca. 30 ,times Lz. 

Hz + site (R3’)The idea behind this scheme is to suppose the presence of “sites” (presumably foreign atoms) on the surface where H-atoms are adsorbed more strongly than at the gold atoms L;: zl that the recombination reaction promds at these sites preferably.