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Abstract
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.
Supplementary materials
Title
Dispersion paper supporting information(1)
Description
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