Fiftieth Anniversary: Diffusion and Convection in Electrolysis—A Theoretical Review

Tobias, Charles W.; Eisenberg, M.; Wilke, Charles R.

doi:10.1149/1.2779636

Cited by 168 publications

(78 citation statements)

References 11 publications

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“…the second term between square brackets), which we substitute in Eq. (12) to obtain [7,8,21,39,[48][49][50][51][52], (14) where D* = 2D c D a /(D c + D a ), which is the "ambipolar diffusivity" of the salt. Eq.…”

Section: Generalized Frumkin-butler-volmer Equationmentioning

confidence: 99%

Frumkin-Butler-Volmer theory and mass transfer in electrochemical cells

Soestbergen

2012

Russ J Electrochem

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Abstract-An accurate mathematical description of the charge transfer rate at electrodes due to an electro chemical reaction is an indispensable component of any electrochemical model. In the current work we use the generalized Frumkin Butler-Volmer (gFBV) equation to describe electrochemical reactions, an equa tion which, contrary to the classical Butler-Volmer approach, includes the effect of the double layer compo sition on the charge transfer rate. The gFBV theory is transparently coupled to the Poisson-Nernst-Planck ion transport theory to describe mass transfer in an electrochemical cell that consists of two parallel plate electrodes which sandwich a monovalent electrolyte. Based on this theoretical approach we present analytical relations that describe the complete transient response of the cell potential to a current step, from the first initial capacitive charging of the bulk electrolyte and the double layers all the way up to the steady state of the system. We show that the transient response is characterized by three distinct time scales, namely; the capac itive charging of the bulk electrolyte at the fastest Debye time scale, and the formation of the double layers and the subsequent redistribution of ions in the bulk electrolyte at the longer harmonic and diffusion time scales, respectively.

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Section: Generalized Frumkin-butler-volmer Equationmentioning

confidence: 99%

Frumkin-Butler-Volmer theory and mass transfer in electrochemical cells

Soestbergen

2012

Russ J Electrochem

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“…During that period, firstly C.S. Lin with his co-workers [2], and shortly afterwards Tobias, Eisenberg and Wilke [3] considered, both experimentally and theoretically, the mass transfer phenomenon of ions coming from the bulk electrolyte to the electrode surface by molecular diffusion, migration and convection. Their considerations resulted in the well-known equation connecting limiting current density with the other variables affecting it:…”

Section: Interconnection Between Chemical Engineering and Electrochemmentioning

confidence: 99%

Electrochemical Engineering - its appearance, evolution and present status. Approaching an anniversary.

Stanković¹

2012

J. Electrochem. Sci. Eng.

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“…Theoretical considerations of the limiting current conditions for a variety of electrochemical systems have been published in detail elsewhere. Among the most cited works analysing the use of the limiting current for mass transport are those published by Selman and Tobias [18] and Tobias et al [19], the latter involving a smooth rotating cylinder electrodes (RCE). Typically, the limiting current value is taken from the plateau region in a current vs. potential curve.…”

Section: Factors Affecting the Limiting Currentmentioning

confidence: 99%

Strategies for the determination of the convective-diffusion limiting current from steady state linear sweep voltammetry

et al. 2007

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The limiting current is an important parameter for the characterization of mass transport in electrochemical systems operating under convective-diffusion control. Four methods to determine the limiting current from current (I) vs. potential (E) plots are considered. Strategies to determine the limiting current values include: (1) direct measurement from I vs. E curves, (2) estimation from the current value at E L = DE/2 where DE is the length of the limiting current plateau, (3) evaluation of the first derivative dI/dE in the I vs. E curve and (4) À3NaOH at a 60 ppi reticulated vitreous carbon electrode (RVC).

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Fiftieth Anniversary: Diffusion and Convection in Electrolysis—A Theoretical Review

Abstract: not Available.

Cited by 168 publications

References 11 publications

Frumkin-Butler-Volmer theory and mass transfer in electrochemical cells

Frumkin-Butler-Volmer theory and mass transfer in electrochemical cells

Electrochemical Engineering - its appearance, evolution and present status. Approaching an anniversary.

Strategies for the determination of the convective-diffusion limiting current from steady state linear sweep voltammetry

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