Title: Journal of the Electrochemical Society

Title: Journal of the Electrochemical Society

ISO Abbreviated Title: J. Electrochem. Soc.

JCR Abbreviated Title: J Electrochem Soc

ISSN: 0013-4651

Issues/Year: 12

Journal Country/Territory: United States

Language: English

Publisher: Electrochemical Soc Inc

Publisher Address: 65 South Main Street, Pennington, NJ 08534

Subject Categories:

Electrochemistry: Impact Factor 2.293, 2/16 (2000)

Materials Science, Coatings & Films: Impact Factor 2.293, 1/16 (2000)

Frumkin, A.N. (1959), Adsorption of ions at the metal solution interface and its influence on electrode kinetics. Journal of the Electrochemical Society, 106 (3), C70.

Full Text: J Ele Soc106, C70.pdf

Harvey, W.W. and Gatos, H.C. (1960), The reaction of germanium with aqueous solutions. II. Dissolution kinetics in electrolytes and the role of specific adsorption. Journal of the Electrochemical Society, 107 (2), 65-72.

Full Text: 1960-80\J Ele Soc107, 65.pdf

Abstract: The corrosion products developed by steel when reacting with water of varying oxygen content at room temperature and at 316°C are described. The reaction was carried out in sealed steel capsules and followed by pH measurement of the solution and by microscopic, x-ray, and electron diffraction analysis of the corrosion product films. Data on the transformation behavior of the corrosion products involved and a summary of some of their physical properties are included.

Beck, T.R. (1962), Anion adsorption and anode kinetics. Journal of the Electrochemical Society, 109 (3), C87.

Full Text: J Ele Soc109, C87.pdf

Conway, B.E., Gileadi, E. and Dzieciuch, M. (1963), Determination of real surface areas and Temkin isotherm parameters from analysis of adsorption pseudocapacity curves. Journal of the Electrochemical Society, 110 (3), C68.

Full Text: J Ele Soc110, C68.pdf

Breiter, M.W. (1963), Anodic oxidation of methanol on platinum. III. Adsorption kinetics in acidic solution. Journal of the Electrochemical Society, 110 (5), 449-452.

Full Text: 1960-80\J Ele Soc110, 449.pdf

Abstract: The rate of methanol adsorption during low-speed, periodic potential sweeps was computed on the basis of the measured current density and the methanol coverage in the potential region of the prewave during the anodic sweep and of the shoulder of the wave during the cathodic sweep. The rate of adsorption was analyzed as a function of free surface area, potential, and methanol bulk concentration. The found dependence suggests that each methanol molecule covers two platinum atoms on the average. The rate of adsorption is potential- dependent. It decreases with potential on both sides of 0.65v. The rate constant of the discharge step of adsorbed methanol molecules is smaller during the anodic sweep than during the cathodic sweep while the rate constant of the adsorption step shows the opposite behavior. This effect is interpreted by the concept that the heat of adsorption of methanol molecules on a surface whose oxygen coverage has just been reduced has a lower value initially than some time later.

Bockris, J.O’M. and Swinkels, D.A.J. (1964), Adsorption of n-decylamine on solid metal electrodes. Journal of the Electrochemical Society, 111 (6), 736-743.

Full Text: 1960-80\J Ele Soc111, 736.pdf

Abstract: The adsorption from solution of n-decylamine on five metals has been measured using a new method, which consists of adsorbing radioactively labeled organic compounds on a metal tape electrode and measuring the reulting radioactivity from the tape. After calibration of the counters and determination of the roughness factor of the tapes by the B.E.T. method using krypton, the amount adsorbed per actual square centimeter is calculated. The coverage has been determined as a function of potential and bulk concentration, and the free energy of adsorption has been calculated for each system. A consideration of thermodynamic cycles for water and for the organic absorbate leads to a relationship between the free energy of adsorption and the solubility and vapor pressure of the organic compound. The adsorption arises largely from metal-adsorbate dispersion interaction differences between water and the organic. These vary little with the metal. The potential dependence arises primarily from the field dependence of the metal-water interaction.

Conway, B.E., Gileadi, E. and Angerste, H. (1965), Significance of nonsteady-state A-C and D-C measurements in electrochemical adsorption kinetics: Applications to galvanostatic and voltage sweep methods. Journal of the Electrochemical Society, 112 (3), 341-349.

Full Text: 1960-80\J Ele Soc112, 341.pdf

Abstract: Information obtainable from nonsteady-state electrochemical studies is examined with particular reference to the determination and significance of capacitance associated with adsorbed intermediates in consecutive reactions. The frequency dependence of the capacity in a-c measurements is related to the rise-time dependence in d-c charging transients and the concept of an equivalent frequency in d-c measurements is proposed. The nonsteady-state kinetics for a galvanostatic charging process is examined for a reaction sequence involving adsorbed intermediates, and it is shown how the capacitance behavior depends on the charging current density. Applications to the triangular voltage sweep method are made, and it is shown that for this case where neither steady-current nor steady-state kinetics apply, care must be exercised in interpretation of results derived from this method. The nonsteady-state kinetics for this case are derived and the dependence of the capacity on sweep-rate is deduced. The differential galvanostatic method leads to results which can be much more explicitly analyzed in a rigorous kinetic manner, for irreversible charging processes. Applications to experimental results which support the treatment given are discussed.

Kelly, E.J. (1965), Specific adsorption of an organic inhibitor and effects thereof on kinetics and mechanistics of active iron electrode. Journal of the Electrochemical Society, 112 (8), C178.

Full Text: J Ele Soc112, C178.pdf

Cairns, E.J. and Breitens, A.M. (1966), Adsorption kinetics for propane on platinum in hydrofluoric acid. Journal of the Electrochemical Society, 113 (3), C76.

Full Text: J Ele Soc113, C76.pdf

Cairns, E.J., Breitens, A.M. and Scarpell, A.J. (1966), Kinetics of adsorption and surface reaction of propane on platinum in hydrofluoric acid. Journal of the Electrochemical Society, 113 (8), C196.

Full Text: J Ele Soc113, C196.pdf

Brummer, S.B. (1966), Panel discussion on adsorption at solid electrodes. II. Structure and composition of organic adsorption layers on Pt electrodes-relation to reaction kinetics. Journal of the Electrochemical Society, 113 (10), 1041-1043.

Full Text: 1960-80\J Ele Soc113, 1041.pdf

Locker, L.D. (1967), Adsorption processes in semiconductor dissolution kinetics. Journal of the Electrochemical Society, 114 (8), C213.

Full Text: J Ele Soc114, C213.pdf

Cairns, E.J. and Breitens, A.M. (1967), Kinetics of propane adsorption on platinum in hydrofluoric acid. Journal of the Electrochemical Society, 114 (8), 764-672.

Full Text: 1960-80\J Ele Soc114, 764.pdf

Abstract: As a first stage in the investigation of the electrochemical oxidation of saturated hydrocarbons on platinum in acid electrolytes, the rate of adsorption of propane on a smooth platinum electrode was studied at 90°C in 37 mole % HF. Using an all-PTFE apparatus and single linear voltage sweep techniques, the surface coverage by hydrocarbon species was measured as a function of adsorption time and potential. The steady-state coverage resulting from propane adsorption shows a sharp maximum at 0.2v (vs. rhe). The amount of the most electrochemically active species is highest at 0.3v. The adsorption rate follows Langmuir kinetics with a third-order dependence on free surface. The rate constant has been measured for 0.2 and 0.3v at 90°C.

Cairns, E.J., Breitens, A.M. and Scarpell, A.J. (1968), The kinetics of adsorption, surface reaction, and electrochemical oxidation of propane on platinum in hydrofluoric acid. Journal of the Electrochemical Society, 115 (6), 569-576.

Full Text: 1960-80\J Ele Soc115, 569.pdf

Abstract: The rate of adsorption of propane on platinum in 37 m/o HF at 30°C has been measured using single linear voltage sweep techniques as a complement to earlier studies at 90°C. The surface coverage by hydrocarbon species was measured as a function of adsorption time and potential. The rate of adsorption follows Langmuir kinetics with a third-order dependence on free surface. The rate of reaction of the initial adsorbate at 90°C to form a highly electro-active species (type I) was also measured, and found to be proportional to the surface coverage of the initial adsorbate (type II) and the square of the fraction free surface. The subsequent rate of electrochemical oxidation of type I was proportional to the surface coverage of type I and to free surface. Values for the kinetic parameters are reported, and the results are discussed in terms of a proposed mechanism for the over-all oxidation process.

Lai, T.T. and Wen, C.S. (1970), Polarography of uranyl-diethylenetriaminepentaacetate complexes and adsorption kinetics at dropping mercury electrode. Journal of the Electrochemical Society, 117 (9), 1122-1126.

Full Text: 1960-80\J Ele Soc117, 1122.pdf

Abstract: The chelation of uranium(VI) with diethylenetriaminepentaacetate was investigated polarographically over the pH range 3.7–8.4 and ligand concentration range 0.005–0.1M. The predominant chelate species was found to be UO2(OH)H2A2− with the logarithmic formation constant of 2.96 at pH 6.4–7.5 and ionic strength 0.25. In the presence of Triton X-100 <0.003%, a single irreversible and diffusion-controlled wave was obtained. The kinetic parameters were determined (ks is the order of 10−3 cm/sec and = 0.42 ±0.02). When the concentration of Triton X-100 is greater than 0.003%, the single wave splits into two irreversible waves, due to the adsorption of surface active substance.

? DiMasi, G.J. and Williams, D. (1964), Kinetics of propane adsorption. Journal of the Electrochemical Society, 118 (8), C205.

Full Text: J Ele Soc118, C205.pdf

Notes: highly cited

? Etsell, T.H. and Flengas, S.N. (1971), Overpotential behavior of stabilized zirconia solid electrolyte fuel cells. Journal of the Electrochemical Society, 118 (12), 1890-1900.

Full Text: 1960-80\J Ele Soc118, 1890.pdf

Charpin, J.E. and Rasneur, B. (1973), Isothermograph: Automatic apparatus for surface-area measurement and pore size analysis of porous materials or fine powders from nitrogen adsorption isotherm. Journal of the Electrochemical Society, 120 (8), C250.

Full Text: J Ele Soc120, C250.pdf

Mayanna, S.M. (1975), Adsorption isotherm of iodide-ions on copper single-crystal planes in sulfuric-acid. Journal of the Electrochemical Society, 122 (2), 251-252.

Full Text: 1960-80\J Ele Soc122, 251.pdf

Schultze, J.W. (1979), Kinetics of adsorption processes. Journal of the Electrochemical Society, 126 (3), C145.

Full Text: J Ele Soc126, C145.pdf

? Heyrovska, R. (1979), Yessin-Markov shifts, E1/2 shifts of complexes, and the Langmuir isotherm. Journal of the Electrochemical Society, 126 (3), C147

Full Text: J Ele Soc126, C147.pdf

Notes: highly cited (> 1000)

? Springer, T.E., Zawodzinski, T.A. and Gottesfeld, S. (1991), Polymer electrolyte fuel cell model. Journal of the Electrochemical Society, 138 (8), 2334-2342.

Full Text: 1991\J Ele Soc138, 2334.pdf

Abstract: We present here an isothermal, one-dimensional, steady-state model for a complete polymer electrolyte fuel cell (PEFC) with a 117 Nafion(R) membrane. In this model we employ water diffusion coefficients electro-osmotic drag coefficients, water sorption isotherms, and membrane conductivities, all measured in our laboratory as functions of membrane water content. The model predicts a net-water-per-proton flux ratio of 0.2 H₂O/H⁺ under typical operating conditions, which is much less than the measured electro-osmotic drag coefficient for a fully hydrated membrane. It also predicts an increase in membrane resistance with increased current density and demonstrates the great advantage of a thinner membrane in alleviating this resistance problem. Both of these predictions were verified experimentally under certain conditions.

Keywords: Diffusion, Flux, Fuel Cell, Isotherms, Membrane, Model, Polymer, Predictions, Resistance, SCI, Sorption, Steady State, Water

El-Awady, A.A., Abd-El-Nabey, B.A. and Aziz, S.G. (1992), Kinetic-thermodynamic and adsorption-isotherms analyses for the inhibition of the acid corrosion of steel by cyclic and open-chain amines. Journal of the Electrochemical Society, 139 (8), 2149-2154.

Full Text: 1992\J Ele Soc139, 2149.pdf

Abstract: The corrosion inhibition characteristics of the quadridentate macrocycle 1, 4, 8, 11 tetra-azacyclotetradecane (cyclam) on steel in sulfuric acid media are investigated at 25, 35, 45, and 55C, and the thermodynamic energy parameters calculated. In addition the inhibition characteristics of the open-chain polydentate amines, ethylenediamine (en), diethylenetriamine (dien), triethylenetetraamine (trien), and tetraethylenepentamine (tetren) were investigated at 25C. Activation-free energies, enthalpies, and entropies for the inhibition process of both cyclam and tetren were determined from the rate constants data measured at four temperatures viz., 25, 35, 45, and 55C at one or two fixed inhibitor concentrations. All data were compared and fitted to a previously published kinetic-thermoydnamic model in terms of an active site occupancy parameter y and a binding constant K of the inhibitor to the active site. The results obtained are compared with fits obtained from the application of Fumkin and Flory-Huggins adsorption isotherms. The first isotherm attempts to treat the deviations from the ideal Langmuir isotherm by the use of a lateral interaction parameter a while the second uses a relative-size parameter x which is a measure of the relative size of the inhibitor molecule to the surface-adsorbed water molecule. Good agreement was obtained between the kinetic-thermodynamic and Flory-Huggins models. The Frumkin isotherm model, however, agreed only in cases where the active site occupancy, or the relative-size parameters were equal to or close to unity. A discussion of the strengths and weaknesses of each treatment is given. In addition, the results obtained are correlated to the chemical structure of the inhibitors, the number of donor atoms, and the macrocyclic effect.

Keywords: Ligands

Notes: highly cited

? Mukerjee, S., Srinivasan, S., Soriaga, M.P. and Mcbreen, J. (1998), Role of structural and electronic-properties of Pt and Pt alloys on electrocatalysis of oxygen reduction - An in-situ xanes and exafs investigation. Journal of the Electrochemical Society, 142 (5), 1409-1422.

Full Text: 1998\J Ele Soc142, 1409.pdf

Abstract: The electrocatalysis of the oxygen reduction reaction (ORR) on five binary Pt alloys (PtCr/C, PtMn/C, PtFe/C, PtCo/C, and PtNi/C) supported on high surface area carbon in a proton exchange membrane fuel cell was investigated. All the alloy electrocatalysts exhibited a high degree of crystallinity with the primary phase of the type Pt(3)M (LI(2) structure with fcc type lattice) and a secondary phase (only minor contribution from this phase) being of the type PtM (LI(0) structure with tetragonal lattice) as evidenced from x-ray powder diffraction (XRD) analysis. The electrode kinetic studies on the Pt alloys at 95°C and 5 atm pressure showed a two- to threefold increase in the exchange current densities and the current density at 900 mV as well as a decrease in the overvoltage at 10 mA cm^-2 relative to Pt/C electrocatalyst. The PtCr/C alloy exhibited the best performance. In situ EXAFS and XANES analysis at potentials in the double-layer region [0.54 V vs. reversible hydrogen electrode (RHE)] revealed (i) all the alloys possess higher Pt d-band vacancies per atom (with the exception of PtMn/C alloy) relative to Pt/C electrocatalyst and (II) contractions in the Pt-Pt bond distances which confirmed the results from err situ XRD analysis. A potential excursion to 0.84 V vs. RHE showed that, in contrast to the Pt alloys, the Pt/C electrocatalyst exhibits a significant increase in the Pt d-band vacancies per atom. This increase, in Pt/C has been rationalized as being due to adsorption of OH species from the electrolyte following a Temkin isotherm behavior, which does not occur on the Pt alloys. Correlation of the electronic (Pt d-band vacancies) and geometric (Pt-Pt bond distance) with the electrochemical performance characteristics exhibits a volcano type behavior with the PtCr/C alloy being at the top of the curve. The enhanced electrocatalysis by the alloys therefore can be rationalized on the basis of the interplay between the electronic and geometric factors on one hand and their effect on the chemisorption behavior of OH species from the electrolyte.

Keywords: X-Ray Absorption, Platinum Loading Electrodes, Membrane Fuel-Cells, Fine-Structure, Synchrotron Radiation, Monochromator, Spectroscopy, Kinetics, Clusters, Spectra

Winder, E.J., Kuech, T.F. and Ellis, A.B. (1998), Photoluminescence studies of cadmium selenide crystals in contact with group III trialkyl derivatives. Journal of the Electrochemical Society, 145 (7), 2475-2479.

Full Text: 1998\J Ele Soc145, 2475.pdf

Abstract: Upon exposure to several group III trialkyls: trimethylaluminum, trimethylgallium, triethylgallium, and trimethylindium, the bandedge photoluminescence intensity of etched single-crystal n-CdSe samples exhibits a large and irreversible enhancement relative to a vacuum reference ambient. From X-ray photoelectron spectroscopy, this photoluminescence enhancement, which ranges from factors of similar to 3 to 100, appears to correspond to irreversible binding of a group III metal-bearing species to the surface. Subsequent exposure of the sample to butylamine, C4H11N, isomers can partially reverse this enhancement by similar to 10 to 80%, depending upon the amine and group III trialkyl precursor combination, presumably through adduct formation with a group III atom-derived, surface-confined species. The magnitude of the amine interaction appears to be the greatest for combinations of less bulky amines with trimethylaluminum- and trimethylgallium-derived species. Reversible photoluminescence enhancements could be obtained through use of volatile discrete 1: 1 trimethylamine adducts of trimethylaluminum and trimethylgallium. These adducts bind to the CdSe surface with an equilibrium constant of similar to 10⁴ atm^-1, based on the Langmuir adsorption isotherm model. Implications for the use of these effects in sensing chemical vapor deposition precursor molecules are discussed.

Keywords: Trimethylgallium Decomposition, Gaas(100), Surfaces, Binding, Sulfide, Probe

Loewenstein, L.M. and Mertens, W. (1998), Adsorption of metal ions onto hydrophilic silicon surfaces from aqueous solution: Effect of pH. Journal of the Electrochemical Society, 145 (8), 2841-2847.

Full Text: 1998\J Ele Soc145, 2841.pdf

Abstract: This work examines the pH and time dependence of metal deposition onto hydrophilic silicon surfaces. We find that the surface concentration of metalspecies is proportional to the pH. Time dependence is seen for only a few metals, notably Cr and Fein this study, especially at high pH. Si surfaces with wet chemical oxides were exposed to a dilute solution of ten metals: Al, Ba, Ca, Cr, Cu, Fe, K, Ni, Sr, and Zn, in dilute nitric acid solution, from pH 3 to 5.6, for different periods of time, from about 1 to 1000 s. At equilibrium the surface concentration of metals is approximately proportional to the ratio of ionic charge to ionic radius of the metal ions for many of the metal ions which exist as hydrated cations at that particular pH. We observe this proportionality over the pH range under study, although the surface concentration varies over several orders of magnitude. Cations which form amphoteric species, such as Al³⁺ which forms Al₂O₃ and Al(OH)₄^-at high pH, and several other cations that do not exist as simple cations at some pHs (e.g., Fe³⁺, Zn²⁺, and Ni²⁺ at high pH), do not show this dependence on ionic charge and radius.

Loewenstein, L.M., Charpin, F. and Mertens, P.W. (1999), Competitive adsorption of metal ions onto hydrophilic silicon surfaces from aqueous solution. Journal of the Electrochemical Society, 146 (2), 719-727.

Full Text: 1999\J Ele Soc146, 719.pdf

Abstract: Si surfaces prepared using the IMEC-clean were exposed to a dilute solution of ten metals, Ba, Ca, Co, Cr, Cu, Fe, K, Ni, Sr, and Zn, in dilute nitric acid solution. The metal deposition onto hydrophilic silicon surfaces was found to be dependent on the metal concentration, pH, and adsorption time, the power-dependence of metalsurface concentrations, as expressed in [M⁺] (n’), ranged from 0.27 for K⁺ to 0.73 for Cr³⁺, With an average value of 0.54. The [H⁺] power dependence of metalsurface concentrations, as [H⁺] (m’), ranged from -0.07 for K to -0.56 for Sr, with an average value of -0.30. We interpret these results to be consequences of all cations, in solution, including H⁺, competing for a limited number of adsorption sites. Using the Langmuir assumptions for adsorption behavior, we derive mathematical relationships for such behavior, with the key result being sigma (i) = sigma K-i[M-i (+)]/l + Sigma (i)K (i)[M-i (+)].sigma (i) is the surface concentration of the metal, [M-i (+)] the solution concentration of the metal cation, and K-i is the equilibrium constant governing its attachment to the surface, for the ith species. sigma is the areal density of adsorption sites on the surface. Summation proceeds over all cations, including H⁺, in solution. Consequences of this relationship include the observed fractional power dependencies of H⁺ and the metal cations, and the reduced adsorption onto the surface of any given metal cation when in the presence of other cations, including H⁺. (C) 1999 The Electrochemical Society. S0013-4651 (98)04-082-8. All rights reserved.

Keywords: Wafer, Water, Spectroscopy, Interface, Removal