Current response for a single redox moiety trapped in a closed generator-collector system: the role of capacitive coupling

Analytical Chemistry
Stephen W Feldberg, Martin A Edwards

Abstract

A theoretical model is proposed to describe the steady-state average limiting current associated with a single redox moiety (ox or red) trapped in a closed generator-collector system along with excess supporting electrolyte. By "closed" we mean that neither solvent nor solutes can enter or leave the system. The potential difference, EOE - ERE, between the oxidizing electrode (OE) and the reducing electrode (RE) is maintained constant with the values of EOE and ERE chosen so that the operative faradaic electrode processes are very fast, i.e., red = ox + nETe(-) (kox = ∞) at the OE and ox + nETe(-) = red (kred = ∞) at the RE. Because there is only a single redox moiety the faradaic process occurs at only one electrode at a time while current at the other electrode is purely capacitive (we refer to this as capacitive coupling). We propose that a two-step process is required to transfer nETqe coulombs (qe is the absolute value of the elemental electronic charge). The first step is associated with diffusion (approximated as a random walk) of a single red moiety to the OE where it is oxidized to ox with a concomitant transfer of qstep1 (= nETqe/(1 + AOECOE/ARECRE)) coulombs; the second step is associated with the diffusion (random wa...Continue Reading

References

Feb 1, 1983·Molecular and Cellular Biology·H Okayama, P Berg
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Feb 10, 1995·Science·F R Fan, A J Bard
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Citations

Dec 3, 2015·Analytical Chemistry·Stephen M OjaBo Zhang
Sep 24, 2015·Analytical Chemistry·Joshua C ByersPatrick R Unwin
Oct 27, 2020·Current Opinion in Electrochemistry·Hang Ren, Martin A Edwards

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