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A Spotter's Guide to Dispersion in Surface-Confined Voltammetry Experiments

preprint
submitted on 27.11.2020, 14:04 and posted on 30.11.2020, 08:09 by Henry Lloyd-Laney, Martin Robinson, Alan Bond, Alison Parkin, David Gavaghan
This paper describes the effect of thermodynamic and kinetic dispersion on numerical simulations of three different surface-confined voltammetry experiments, ramped FTACV, Purely sinusoidal voltammetry (PSV) and direct current voltammetry (DCV), and the differences between the dispersed and non-dispersed cases.
Dispersion in this case refers to a range of observed values for the thermodynamic driving force and reaction rate of a redox reaction (thermodynamic and kinetic dispersion respectively) . This has been acknowledged as a complicating factor of voltammetry experiments for some time.
We demonstrate that thermodynamic dispersion has a far stronger effect than kinetic dispersion, and detail the ways in which kinetic dispersion can be resolved under such conditions. The work is novel in its comparison of three separate voltammetry techniques, and a focus on how to determine the presence of dispersion through computational analysis of experimental voltammetry data alone; previous work has required specific experiments designed to distinguish between dispersed and non-dispersed cases.

Funding

EPSRC and BBSRC Centre for Doctoral Training in Synthetic Biology

Engineering and Physical Sciences Research Council

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EPSRC CDT in Sustainable Approaches to Biomedical Science: Responsible and Reproducible Research - SABS:R^3

Engineering and Physical Sciences Research Council

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Dynamic electrochemistry with Bayesian inference

Australian Research Council

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History

Email Address of Submitting Author

henry.lloyd-laney@cs.ox.ac.uk

Institution

University of Oxford

Country

UK

ORCID For Submitting Author

0000-0003-4650-8937

Declaration of Conflict of Interest

none

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