Transients in convective systems

Hale, J.M.

doi:10.1016/0022-0728(64)80067-x

Cited by 41 publications

(8 citation statements)

References 8 publications

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“…2B -V A + D (10) would present a working curve identical in form with the Aeq = » curve of Figure 2, but shifted right on the abscissa by 0.3 (= log 2). The reasoning is quite simple : when Aeq = =°four molecules of species B per reaction 6 are consumed, while only two molecules of species B per reaction 10 are consumed.…”

mentioning

confidence: 86%

Dimerization of triphenylamine cation radicals. Evaluation of kinetics using the rotating disk electrode

Marcoux¹,

Adams²,

Feldberg³

1969

J. Phys. Chem.

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The rotated disk electrode (RDE) has unique advantages for studying chemical reactions interposed between successive electron transfers (so-called ECE reactions). A simple modification of previously described digital simulation techniques allows various chemical kinetic complications to be introduced into the basic RDE hydrodynamic equations. These calculations have been applied experimentally to the important class of ECE reactions involving dimerization of cation radicals. The anodic oxidation of several substituted triphenylamines and their subsequent dimerization to tetraphenylbenzidines was studied at a platinum RDE. Second-order rate constants for dimerization in the range 103-104 1. mol-1 sec-1 were readily uncovered.

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mentioning

confidence: 86%

Dimerization of triphenylamine cation radicals. Evaluation of kinetics using the rotating disk electrode

Marcoux¹,

Adams²,

Feldberg³

1969

J. Phys. Chem.

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“…The diffusion layer thickness that is created by the motion of the RDE is predicted by the following equation: A coordinate transform, based on the Hale transformation, ,, was also used to improve the efficiency of the simulation. The same boundary conditions apply as for the nonconvective simulation, and the mass transport equations are solved in a similar fashion.…”

Section: Simulation Theorymentioning

confidence: 99%

Differential Pulse and Chronoamperometric Studies of Insonated Systems: Acoustic Streaming and Cavitational Effects

et al. 2000

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Chronoamperometry has been undertaken at insonated electrodes of both micro and macro dimensions, for a range of simple, well-defined redox couples in water (298 K), DMF (298 and 218 K), and ammonia (218 K) as solvents. These are analyzed to assess the relative contributions of acoustic streaming and cavitational activity to the observed currents: both contribute significantly under the usual conditions adopted for sonovoltammetry. Differential pulse voltammetry (DPV) was then used to explore the nature of the diffusion layer prevailing under steady-state electrolysis of insonated macroelectrodes. Simulations showed that pure convection within a diffusion layer enhances the DPV currents for simple redox systems as compared to silent conditions. The experimentally observed decrease was attributed to cavitational disruption of the diffusion layer leading to a physical model of an insonated electrode which may be described as a steady diffusion layer a few microns thick brought about by acoustic streaming which is occasionally and randomly punctuated by a cavitational event. The frequency and violence of the event is dependent on the solvent and ultrasound power, except at very short electrode-to-horn separation where the cavitational contribution becomes substantial.

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“…We now introduce th e ^-coordinate in place o f w, according to th e H ale transform ation (Hale 1963(Hale , 1964: rw exp( -\wz)dw…”

Section: T He General Approachmentioning

confidence: 99%

Rotating disc electrodes: the theory of chronoamperometry and its use in mechanistic investigations

1988

Proc. R. Soc. Lond. A

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A general computational strategy is presented for the calculation of the chronoamperometric responses arising from potential-step experiments at rotating disc electrodes. The method is applicable to a wide range of electrode reaction mechanisms and theoretical results are given for single- and double-potential-step experiments for ECE, DISP1, DISP2, EC' and CE reactions. For the last, the treatment is extended to cover the case where reactants have grossly unequal diffusion coefficients. Steadystate behaviour is also deduced. The extent to which the various mechanistic pathways can be distinguished is identified and the necessary experiments defined.

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Transients in convective systems

Cited by 41 publications

References 8 publications

Dimerization of triphenylamine cation radicals. Evaluation of kinetics using the rotating disk electrode

Dimerization of triphenylamine cation radicals. Evaluation of kinetics using the rotating disk electrode

Differential Pulse and Chronoamperometric Studies of Insonated Systems: Acoustic Streaming and Cavitational Effects

Rotating disc electrodes: the theory of chronoamperometry and its use in mechanistic investigations

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