The Rate of Solution of Metals in Acids as a Function of Overvoltage I. The Diffusion Potential

Kimball, George E.; Glassner, Alvin

doi:10.1063/1.1750585

Cited by 6 publications

(5 citation statements)

References 3 publications

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“…Lyklema et al (20) demonstrated several aspects of nonequilibrium behavior at glass electrodes. In view of the success of kinetic theories in treating corrosion processes, it seems that the relationships developed for mixed potentials at zero current by various workers (21)(22)(23) could be fruitfully applied to ion-selective membrane electrodes. We have demonstrated that relationships originally developed for metal electrodes are approximately valid for ion-selective membrane electrodes as well.…”

Section: Discussionmentioning

confidence: 99%

Exchange kinetics at ion-selective membrane electrodes

Cammann¹,

Rechnitz²

1976

Anal. Chem.

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Section: Discussionmentioning

confidence: 99%

Exchange kinetics at ion-selective membrane electrodes

Cammann¹,

Rechnitz²

1976

Anal. Chem.

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“…Once the "characteristics", i.e., the straight lines associated with the critical points, have been found, it is an easy matter, knowing equation (III), to give the main features of a transient corresponding to any values of E and R. 5 Under similar circumstances, the potential drop across the diffusion layer has been deduced to be negligible. See reference (9).…”

Section: Prediction Of General Features Of a Make Transient-mentioning

confidence: 99%

Anodic Behavior of Copper in HCl

Stephenson

Bartlett

1954

J. Electrochem. Soc.

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Anodic behavior of copper in 2N HC1 has been studied by both electrical and optical methods The temporal behavior of current and voltage have been found, as well as the current vs. voltage characteristics. The anode surface has been observed both visually and photographically with the aid of conventional microscopes, and the anolyte has been photographed cinematographically using a sehlieren microscope.When the current is turned on, a layer, probably CuC1, starts to form at random nucleation spots on the anode. This grows until the whole anode is covered, at which time the current drops abruptly. Up until this time the anolyte becomes less concentrated, but the concentration may increase again after the current has become low.The anode-calomel voltage may be written as V = e(i) + it, where e(i) becomes constant at high current densities. The values of e(i) have been found by both the interruption and the direct method, and there appear to be at least four of physical significance These values are --0.35, --0.27, -0.05, and +0.11 v.In general, the current drops twice before reaching its minimum value. If t I is the time from the make to the first drop, and if Q = ]to1 i dt, and if io is the "initial" current after the make, then empirically Q = 24(io -0.70) -0 53, where io is in ma.The anode layer is about 3 ~ thick in the steady state. When the circuit is broken, r and e change rather rapidly (in about 0.1 sec), but the layer dissolves off slowly.

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“…Kozlowski (32) already successfully applied the mixed potential theory (25,26) used in corrosion research to amalgam electrodes which can be viewed as standing between metal electrodes and ion-selective electrodes. It is therefore justified to describe ion-selective electrodes also from this point of view.…”

Section: Concerning the Selectivity Coefficient Defined In An Extendedmentioning

confidence: 99%

“…For this the theory predicts a mixed potential located in between both the equilibrium potentials. In this model (25,26), the location of the mixed potential depends on the thermodynamic parameters (equilibrium potentials) as well as on the kinetic parameters (exchange current densities) according to Equation 11.27 of (27). The establishment of a thermodynamic equilibrium may be prevented for one or both reactions, depending on the course of the interacting current-voltage curves.…”

mentioning

confidence: 99%

Exchange kinetics at potassium-selective liquid membrane electrodes

Cammann¹

1978

Anal. Chem.

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dependent current recorded in the blank buffer solution.Similar behavior was observed with both ac-treated glassy carbon and carbon film electrodes. Pretreatment appears to renew the electroactive surface and the PRV technique permits separation of the transport-dependent current signal from background current transients. The procedure appears to be a workable approach to overcoming a surface fouling problem. The oxidation of NADH appears to have a significantly greater over-potential on the carbon film, but the very broad, well-defined plateau indicates considerable analytical promise for the carbon film electrode. CONCLUSIONSAn adherent, shiny, black carbon film can be formed on quartz surfaces simply, inexpensively, and in a variety of shapes. As yet, no attempt has been made to study the structure of the film, but electrochemical experiments indicate that it compares moderately well with glassy carbon as an electrode material. It appears to be a practical tool for electrochemical studies. Well-defined, reproducible current-voltage curves can be obtained by conditioning the surface with an ac-treatment of ±4 V at ~70 Hz before the current measurement. ACKNOWLEDGMENTThe authors appreciate the assistance of glass technicians W. J. Wheeler and C, M. Amling in developing the carbon coating process.

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The Rate of Solution of Metals in Acids as a Function of Overvoltage I. The Diffusion Potential

Cited by 6 publications

References 3 publications

Exchange kinetics at ion-selective membrane electrodes

Exchange kinetics at ion-selective membrane electrodes

Anodic Behavior of Copper in HCl

Exchange kinetics at potassium-selective liquid membrane electrodes

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