Automatic Recording of Polarographic Data Obtained with Platinum Electrodes

Rogers, L. B.; Miller, Harry H.; Goodrich, R. B.; Stehney, A.F.

doi:10.1021/ac60031a006

Cited by 37 publications

(22 citation statements)

References 10 publications

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“…The appearance of maxima on the polarographic curves obtained with the rotating platinum electrode has been reported. 19 In the preliminary investigations into the best set of operating conditions, we also observed maxima. In general these were found to be due to (i) incomplete cleaning of the cathode, (ii) too great a rate of voltage scanning, (iii) too small an anode.…”

Section: Maximamentioning

confidence: 64%

Studies in polarography. Part 1.—The rotating platinum electrode

Ferrett¹,

Phillips²

1955

Trans. Faraday Soc.

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The paper describes a series of experiments with the rotating platinum electrode. It has been found that by use of a platinum anode, cathodic pre-polarization, and the use of only the leading edge of the cathode, well-defined reproducible polarograms for mercury, gold, silver, copper, lead, thallium and cadmium can be obtained. The reversibility of the electrode reductions and the relationship between the diffusion currents and the rate of rotation of the electrode have been investigated for these metals and for oxygen.

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Section: Maximamentioning

confidence: 64%

Studies in polarography. Part 1.—The rotating platinum electrode

Ferrett¹,

Phillips²

1955

Trans. Faraday Soc.

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“…On the basis of the earlier findings of Rogers and co-workers (9)(10)(11)(12)(13)(14)(15)(16)(17), the adsorption of metal ions on foreign substrates was studied experimentally and theoretically in many systems by Schmidt and co-workers in the last decade . They develc>ped new experimental techniques in order to determine exactly the thermodynamics of metal ion adsorption processes and the formation of metal films.…”

Section: Eiectrochem Soc: Electrochemical Science and Technologymentioning

confidence: 99%

The Formation of Monolayer Metal Films on Electrodes

Lorenz¹,

Hermann²,

Wüthrich³

et al. 1974

J. Electrochem. Soc.

170

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The two-and three-dimensional nucleation and the metal ion adsorption process are discussed as initial steps for electrocrystallization on the same or on a foreign substrate. The metal ion adsorption takes place in the underpotential range, which is more positive than the equilibrium potential of the nucleated metal/metal ion electrode. Thermodynamic considerations show that an overlapping of disturbing processes in the underpotential range can be characterized by a factor ZE, which is called charge-coverage coefficient or electrosorption valency. It is a function of different independent variables. The metal monolayer model is satisfied only in the simplest case for ZE :-Z (valency of metal ions in solution).The different experimental methods for determining the thermodynamics, kinetics, and structure of metal ion adsorbates are critically discussed. The most reliable thermodynamic results are obtained by the twin-electrode thinlayer technique. Kinetic data can be obtained by pulse measurements under potentiostatic-galvanostatic conditions. The structure of metal films can be determined by combining different methods including optical investigations.Results are given for different systems. In the systems Au/Ag +, Au/T1 +, and Au/Pb + + the metal monolayer model is practically valid. In the case of Cu + + ion adsorption on Au the redox reaction forming Cu + ions acts as a disturbing process. A cosorption of anions takes place in the system Ag/Pb + +. The formation of alloys in the underpotential range was observed in the systems Pt/Pb + + and Bi/Pb + + The structure of metal ion adsorbates must be in correlation with the nucleation phenomena at more negative potentials. In many systems no three-dimensional nucleation overvoltage is observed by using a quasi-steadystate experimental technique. The density of the crystal imperfections and the crystallographic orientation of the surface planes influence the metal ion adsorption process and the structure of films. The results obtained in the systems Ag (poly-and monocrystalline)/T1 + can be explained by assuming the formation of superlattices on the electrode surface.Kinetic investigations in the systems Au/Ag +, Au/T1 +, and Au/Pb § + show relatively high exchange current densities for the metal ion adsorption process. In these cases the experimental results can be explained by assuming surface diffusion of adions as the rate determining step in the adsorption process. In the system Au/Cu + +, a charge transfer step is rate determining, which probably forms precedingly Cu + ions.Crystallization phenomena play an important role in the case of cathodic metal deposition. They include different steps after the metal ion has passed through the electrochemical double layer and is still partially solvated. The final state can be described as the in-* Electrochemical Society Active Member. ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 205.208.120.206 Downloaded on 2014-12-26 to IP ) unless CC L...

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“…It was only relatively recently that it was found that certain amounts of metal are being deposited at potentials well anoxic to the reversible potential [10][11][12][13][14][15][16][17][18][19][20][21][22][23]. The earliest explanation [11] of this phenomenon argued that the small number of lattice sites on the electrode have adsorption energies for metal atom deposition so high as to be equal to the substrate work function, the rest of the sites available being associated with adsorption energies smaller than this.…”

Section: Introductionmentioning

confidence: 99%