Title: Journal of Educational Administration

Title: Journal of Electroanalytical Chemistry

ISO Abbreviated Title: J. Electroanal. Chem.

JCR Abbreviated Title: J Electroanal Chem

ISSN: 0022-0728

Issues/Year: 24

Journal Country/Territory: Switzerland

Language: English

Publisher: Elsevier Science SA

Publisher Address: PO Box 564, 1001 Lausanne, Switzerland

Subject Categories:

Chemistry, Analytical: Impact Factor

Electrochemistry: Impact Factor

Wroblowa, H., Rao, M.L.B., Damjanov, A. and Bockris, J.O. (1967), Adsorption and kinetics at platinum electrodes in presence of oxygen at zero net current. Journal of Electroanalytical Chemistry, 15 (2-3), 139-150.

Full Text: J\J Ele Che15, 139.pdf

Abstract: The rest potentials at Pt electrodes were determined in 1 N₂SO₄. Solutions saturated at 0°, 20°, 50° and 80° with various partial pressures of oxygen ranging from 0.005 to 1 atm. Oxygen adsorption isotherms were obtained by cathodic reduction transient technique. The nature of the rest potentials is analyzed. The behavior of the Pt-O₂-H₂O system under open circuit conditions, appears to be best interpreted in terms of the following model. Oxide-free Pt electrodes immersed in an aqueous solution of H₂SO₄ acquire a mixed potential due to cathodic reduction of oxygen and oxidation of impurities as the anodic component. The value of this potential is simply dependent upon the oxygen pressure. The potential in turn determines the coverage of oxygen atoms, which arises from an equilibrium of the water discharge reaction with the Pt surface. According to this model, this reaction, and not the dissociative adsorption of oxygen, is the origin of oxygen coverage at the surface. The lack of reversibility of the O₂ electrode would therefore result from the presence of impurities. Further analysis of the Behavior of noble metal electrodes In O₂-saturated solutions is in progress.

Armstron, R.D., Race, W.P. and Thirsk, H.R. (1968), The kinetics of adsorption of neutral organic compounds at a mercury electrode. Journal of Electroanalytical Chemistry, 16 (4), 517-529.

Full Text: J\J Ele Che16, 517.pdf

Abstract: It is shown theoretically, and illustrated experimentally, that an entirely diffusion-controlled adsorption process leads to a frequency-dependence of an electrode impedance which is analogous to that produced by a dielectric relaxation process with a particular spread of relaxation times. The possibility of detecting a finite adsorption rate from impedance measurements is examined experimentally for the adsorption of n-butyric acid, and cyclohexanol on a mercury electrode, and it is concluded that the relaxation time of the adsorption step lies between 10⁻⁶ and 10⁻¹⁰ sec in these cases.

Frumkin, A.N., Damaskin, B.B. and Survila, A.A. (1968), The congruence of the adsorption isotherm with respect to the electrode potential or charge and the choice of an independent electric variable. Journal of Electroanalytical Chemistry, 16 (4), 493-503.

Full Text: J\J Ele Che16, 493.pdf

Abstract: In a strictly thermodynamic approach to the investigation of the adsorption isotherm, the choice of an electric variable is of no fundamental importance and is determined by considerations of expediency or convenience. This is not the case, however, when the thermodynamic approach to the investigation of adsorption is supplemented by the assumption of the congruence of the adsorption isotherm with respect to the electrode potential or charge. These assumptions are only compatible provided the double-layer capacity in the supporting electrolyte solution, C_o, does differ from the capacity, C’, at complete surface coverage with adsorbed substance. If C_o markedly exceeds C’ as, for example, in the case of adsorption of aliphatic compounds on mercury, the assumption of the congruence of the adsorption isotherm with respect to the elctrode potential is in better agreement with the experimental data. Moreover, this assumption corresponds to a clear and consistent physical picture of the surface layer in the presence of adsorbed molecules of organic substance (the model of two parallel capacitors).

Trasatti, S. and Formaro, L. (1968), Kinetics and mechanism of the adsorption of glycolaldehyde on a smooth platinum electrode. Journal of Electroanalytical Chemistry, 17 (3-4), 343-364.

Full Text: J\J Ele Che17, 243.pdf

Abstract: The adsorption of glycolcaldehyde from 1 M HClO₄ solutions on smooth platinum electrodes was studied by means of galvanostatic pulses at high current densities. The methods used for the graphical calculation of q_ox and q_H are presented and discussed. q_ox is the charge expended in adsorbate oxidation, as determined by an anodic pulse, and q_H is the charge consumed in depositing a hydrogen atom on every available surface site, the charge being determined by a cathodic pulse.

At 0.4 V (RHE), glycolaldehyde adsorbs on to the platinum surface following the kinetics of activated adsorption described by the Elovich equation. Up to a coverage of 70%, glycolaldehyde adsorbs on to the electrode, losing three hydrogen atoms and occupying three surface sites. Above this coverage, adsorption proceeds on two surface sites; the organic molecule losing two hydrogen atoms. Adsorption activation energy, increases linearly with increasing surface coverage from 12.80 ±0.05 kcal/mole at =0 to 15.95±0.05 kcal/mole at =1.

The effect of the electrode potential on the structure of the ad-layer is presented. Adsorption conforms well to the Temkin logarithmic isotherm; nevertheless, no desorption phenomenon can be detected experimentally. Difficulties arising from this apparent contradiction, which is one of the fundamental problems in the study of adsorption of organic substances on platinum, are discussed.

Möllers, F. and Jaenicke, W. (1968), Determinability and instationary electrochemical processes for studying adsorption and adsorption kinetics of reactants and reaction products. Journal of Electroanalytical Chemistry, 18 (1-2), 61-80.

Full Text: J\J Ele Che18, 61.pdf

Abstract: The adsorption of hydroquinone and of quinone, both as reactant and as product in an electrochemical process was investigated at a stationary mercury electrode. This was done galvanostatically, with a single current pulse and with a double pulse with current reversal, as well as potentiostatically with a single potential jump.

In order to evaluate the measurements with single pulses, the model set up by Lorenz for the relation between adsorbed amount and concentration during the pulse, was used in part. For the double pulse measurements, four further models were discussed.

The adsorption calculated from the different models for the single pulse depends on the current density in the pulse. This dependence indicates a kinetic hindrance to the adsorption. An attempt was made to explain this hindrance quantitatively in terms of a relaxation time. This made it possible to determine the adsorption isotherm quite accurately. A kinetic law considering the adsorption displacement allowed the derivation of rate constants for adsorption and desorption from the relaxation times for quinone and hydroquinone. The methods used are also suitable for the investigation of the adsorption of intermediates or reaction products at the electrode, although here the choice of the model considerably affects the results.

Holub, K. and Němec, L. (1968), The analog method for solution of problems involving diffusion to the electrode. II. Kinetics of adsorption controlled by diffusion to the plane spherical and dropping electrodes for an arbitrary adsorption isotherm. Journal of Electroanalytical Chemistry, 18 (3), 209-214.

Full Text: J\J Ele Che18, 209.pdf

Abstract: Kinetics of adsorption controlled by diffusion can be solved on an analog computer with the functional element, s^0.5+constant, previously proposed¹. The method covers the plane, spherical, and dropping electrodes and any kind of adsorption isotherm.

The general formulation for these cases has been given. Examples of solution for the Frumkin isotherm (plane and spherical electrodes) and for the linear isotherm (dropping electrode) are shown.

Kooijman, D.J. (1968), Kinetics of Hg(I)/Hg electrode with consideration of specific adsorption. Journal of Electroanalytical Chemistry, 19 (4), 365-371.

Full Text: J\J Ele Che19, 365.pdf

Abstract: The kinetics of the Hg(I)/Hg electrode reaction in 1 M HClO₄ are re-examined with the galvanostatic and coulostatic pulse methods. Results are interpreted on the basis of coupling between double-layer charging and faradaic charge transfer. Such a coupling is clearly established. Adsorption of mercurous ions is tentatively explained by a linear adsorption isotherm.

Loučka, T. and Weber, J. (1969), Adsorption and oxidation of formaldehyde at the platinum electrode in acid solutions. Journal of Electroanalytical Chemistry, 21 (2), 329-344.

Full Text: J\J Ele Che21, 329.pdf

Abstract: The adsorption of formaldehyde on a smooth platinum electrode was studied in 1 N H₂SO₄ at 40°. The kinetics of adsorption follow the Elovich equation and the dependence of the equilibrium coverage on the bulk concentration of formaldehyde can be described by the Temkin isotherm. The maximum coverage of the electrode is attained at the potential, E = +0.2 V vs. HE.

The mechanisms of adsorption and of electro-oxidation of formaldehyde were deduced from the adsorption measurements. The chemisorbed species formed by the dehydrogenation of formaldehyde molecules are relatively less active. They act as inhibitors in the anodic oxidation of formaldehyde in the region of potentials, E < +0.6 V.

Armstron, R.D. (1969), Kinetics of adsorption of pyridine at a mercury electrode. Journal of Electroanalytical Chemistry, 20 (1), 168-170.

Full Text: J\J Ele Che20, 168.pdf

Brummer, S.B. and Cahill, K. (1969), Kinetics of reductive adsorption of CO₂ on smooth Pt electrodes. Journal of Electroanalytical Chemistry, 21 (3), 463-482.

Full Text: J\J Ele Che21, 463.pdf

Sathyana, S. and Baikerik, K.G. (1970), Kinetics of adsorption of camphor, camphene, pinene and nonylic acid at mercury-solution interface. Journal of Electroanalytical Chemistry, 25 (2), 209-218.

Full Text: J\J Ele Che25, 209.pdf

Abstract: Adsorption kinetic measurements have been made for substances such as camphor, camphene, -pinene and nonylic acid which undergo a two-dimensional condensation at an ideally polarised mercury-solution interface. The results have been correlated theoretically with the way capacitance changes with time when the adsorption process is controlled by diffusion and satisfies any arbitrary adsorption isotherm. For the special case of Frumkin’s isotherm, explicit equations have been derived relating the non-equilibrium capacitance with the time of adsorption. The interaction parameter for the adsorption of camphor at the mercury-solution interface has been evaluated by comparing theory with experimental data.

Armstron, R.D., Race, W.P. and Thirsk, H.R. (1970), The kinetics of adsorption of sulphide ions at a mercury electrode. Journal of Electroanalytical Chemistry, 27 (1), 21-29.

Full Text: J\J Ele Che27, 21.pdf

Abstract: The kinetics of adsorption of S²⁻ ions at a mercury electrode have been studied by the a.c. impedance method, using the concept of relaxation times. A single relaxation time will explain most of the impedance—frequency spectrum. The relaxation time is shown to be due to a slow heterogeneous adsorption step.

Trasatti, S. and Olivieri, G. (1970), The congruence of the adsorption isotherm and the model of the double layer new results regarding ethyl bromide. Journal of Electroanalytical Chemistry, 27 (2), A7-A9.

Full Text: J\J Ele Che27, A7.pdf

Formaro, L. and Castelli, G. (1970), Glyoxal adsorption on smooth platinum electrodes: II. Kinetics and mechanism. Journal of Electroanalytical Chemistry, 28 (2), 363-374.

Full Text: J\J Ele Che28, 363.pdf

Abstract: The kinetics and mechanism of glyoxal adsorption on platinum from 1 M HClO₄ aqueous solutions have been investigated by means of fast cathodic and anodic charging curves. Glyoxal has been found to adsorb, via a dehydrogenation reaction, according to the kinetics of activated adsorption (Elovich). Up to about 50% coverage, glyoxal adsorbs onto platinum lying flat on the surface and blocking four surface sites per molecule. For higher coverages, glyoxal adsorbs perpendicularly to the surface, losing only one hydrogen atom and blocking two surface sites. No adsorption isotherm could be observed, since the maximum coverage seems to be independent of the concentration owing to competitive adsorption of polymeric forms of glyoxal present in the solution.

Whitehou, D.R. (1971), Analysis and interpretation of interfacial impedance in adsorption kinetics. Journal of Electroanalytical Chemistry, 32 (2), 265-270.

Full Text: J\J Ele Che32, 265.pdf

Abstract: The interfacial impedance associated with adsorption kinetics is discussed. A series circuit obtained after separating the infinite frequency capacitance is suggested by analogy with electrode kinetics. It is shown that this simplifies the equations involved and the physical interpretation of the various components of the impedance, and leads to more satisfactory methods of analysing the data. The ideas are illustrated using data for n-amyl alcohol and the sulphide ion available in the literature

Ridgway, T.H., Reilley, C.N. and Vanduyne, R.P. (1972), Double potential step chronocoulometry. Part I. Reexamination of EC kinetic theory including effects of electrode reactant and product adsorption. Journal of Electroanalytical Chemistry, 34 (2), 267-282.

Full Text: J\J Ele Che21, 267.pdf

Abstract: Calculation of the theoretical double potential step chronocoulometry working curve (|Q_b/Q_f| vs. (k)^0.5) for an irreversible pseudo first-order chemical reaction coupled to a heterogeneous charge transfer process (EC mechanism) by finite difference methods revealed an error in the previously published working curve for this situation. The analytical solution to the mass transport equations for the EC mechanism with double potential step boundary conditions is rederived. The working curve, calculated from this new analytical solution, was in close agreement with the finite difference results. In addition, a theoretical treatment is presented for double potential step chronocoulometry where the effect of electrode reactant and product adsorption on the charge ratio, |Q_b/Q_f|, both with and without EC kinetic complications, is incorporated. A procedure whereby experimentally determined charge ratios can be corrected for the effects of reactant and product adsorption has been developed.

Bŕezina, M., Loučka, T., Koryta, J., Maršíková, D. and Pradac, J. (1972), Adsorption and kinetics of oxidation of ascorbic acid at platinum electrodes. Journal of Electroanalytical Chemistry, 40 (1), 13-17.

Full Text: J\J Ele Che40, 13.pdf

Abstract: As shown by cyclic voltammetry and by polarography with a rotating disc electrode, ascorbic acid is oxidized at platinum electrodes in a two-electron process. There are two reaction paths of the oxidation, one corresponding to an irreversible electrode reaction of the substance without appreciable adsorption with an n₂≈0.4, the other being the oxidation of the adsorbed substance in the potential range of Pt surface oxide formation. The adsorption of ascorbic acid is reversible and non-destructive, attaining its maximum value (68 % of sites of hydrogen adsorption) even at low concentrations of ascorbic acid. The process is controlled by kinetics of adsorption proper together with diffusion. One molecule of ascorbic acid occupies two hydrogen adsorption sites.

Laviron, E. (1973), Influence of adsorption of depolarizer or of a product of electrochemical reaction on polarographic currents. XIX. Study of kinetics of benzidine rearrangement on surface of a mercury electrode. Journal of Electroanalytical Chemistry, 42 (3), 415-422.

Full Text: J\J Ele Che42, 415.pdf

Abstract: A study has been made of the kinetics of the benzidine rearrangement on the surface of a mercury electrode by using linear potential sweep voltammetry. The reaction is first order in hydrazobenzene and second order in acid. The surface reaction has been compared with the volume reaction, which has been investigated in a purely aqueous acidic medium, by following polarographically the decrease of the oxidation wave of hydrazobenzene. The surface rate constant is much smaller than the volume rate constant. This result can be explained by the influence of the adsorption of the hydrazobenzene molecule on the activation energy of the reaction.

Whitehou, D.R. (1973), Method for study of asymmetry in adsorption kinetics at an electrode surface. I. Theory. Journal of Electroanalytical Chemistry, 43 (3), 415-424.

Full Text: J\J Ele Che43, 415.pdf

Abstract: The theory of a method for studying adsorption kinetics at an electrode/solution interface is described. The method is based on measurement of the phase and amplitude of the second harmonic current arising when the potential of the electrode is varied sinusoidally at a fundamental frequency. The theory is first developed in a completely general way, which is independent of any particular rate equation or isotherm. The resulting equations are also given for the case of a Frumkin isotherm and a rate equation similar to the one proposed by Delahay and Mohilner⁴. The method can be employed to test the rate equation and to determine the parameters  and , designated by Delahay and Mohilner⁴ as the charge and coverage parameters, respectively.

Cachet, C., Cachet, H., Epelboin, I. and Lestrade, J.C. (1973), Surface tension measurements at mercury-solution interface and adsorption kinetics of organic substances. Journal of Electroanalytical Chemistry,