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Title: Concentration and density changes at an electrode surface and the principle of unchanging total concentration

In this study, the principle of unchanging total concentration as described by Oldham and Feldberg [J. Phys. Chem. B, 103, 1699 (1999)] is invoked to analyze systems comprising a redox pair (X z1 1 and X z2 2) plus one or more non-electroactive species (X z3 3,X z4 4...X zjmax jmax) where X zj j is the j th species with charge z j and concentration; c j. The principle states that if the diffusion coefficients for all species are identical and mass transport is governed by the Nernst-Planck expression, the total concentration does not change during any electrochemical perturbation, i.e.: Σ jmax j=1[X zj j]=Σ jmax j=1 c j = S P With this principle we deduce the electrochemically induced difference between the surface and bulk concentrations for each species. Those concentration differences are translated into density differences which are a function of the density of the solvent and of the concentration differences, molecular masses and the standard partial molar volumes of all species. Those density differences in turn can induce convection that will ultimately modify the observed current. However, we did not attempt to quantify details of the natural convection and current modification produced by those density differences.
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  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Report Number(s):
Journal ID: ISSN 0013-4651; R&D Project: 2016-BNL-EE630EECA-Budg; KP1701000
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 163; Journal Issue: 4; Journal ID: ISSN 0013-4651
The Electrochemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Country of Publication:
United States
54 ENVIRONMENTAL SCIENCES; electrode surfaces
OSTI Identifier: