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Title: Estimating parameters from rotating ring disc electrode measurements

Abstract

Rotating ring disc electrode (RRDE) experiments are a classic tool for investigating kinetics of electrochemical reactions. Several standardized methods exist for extracting transport parameters and reaction rate constants using RRDE measurements. Here in this work, we compare some approximate solutions to the convective diffusion used popularly in the literature to a rigorous numerical solution of the Nernst-Planck equations coupled to the three dimensional flow problem. In light of these computational advancements, we explore design aspects of the RRDE that will help improve sensitivity of our parameter estimation procedure to experimental data. We use the oxygen reduction in acidic media involving three charge transfer reactions and a chemical reaction as an example, and identify ways to isolate reaction currents for the individual processes in order to accurately estimate the exchange current densities.

Authors:
 [1];  [2]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States). Transportation and Hydrogen Systems Center
  2. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1407467
Report Number(s):
NREL/JA-5400-68209
Journal ID: ISSN 1023-1935
Grant/Contract Number:
AC36-08GO28308
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Russian Journal of Electrochemistry
Additional Journal Information:
Journal Volume: 53; Journal Issue: 10; Journal ID: ISSN 1023-1935
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION; rotating ring disc electrodes; hydrodynamics; simultaneous reactions; sensitivity analysis

Citation Formats

Santhanagopalan, Shriram, and White, Ralph E. Estimating parameters from rotating ring disc electrode measurements. United States: N. p., 2017. Web. doi:10.1134/S1023193517100111.
Santhanagopalan, Shriram, & White, Ralph E. Estimating parameters from rotating ring disc electrode measurements. United States. doi:10.1134/S1023193517100111.
Santhanagopalan, Shriram, and White, Ralph E. 2017. "Estimating parameters from rotating ring disc electrode measurements". United States. doi:10.1134/S1023193517100111.
@article{osti_1407467,
title = {Estimating parameters from rotating ring disc electrode measurements},
author = {Santhanagopalan, Shriram and White, Ralph E.},
abstractNote = {Rotating ring disc electrode (RRDE) experiments are a classic tool for investigating kinetics of electrochemical reactions. Several standardized methods exist for extracting transport parameters and reaction rate constants using RRDE measurements. Here in this work, we compare some approximate solutions to the convective diffusion used popularly in the literature to a rigorous numerical solution of the Nernst-Planck equations coupled to the three dimensional flow problem. In light of these computational advancements, we explore design aspects of the RRDE that will help improve sensitivity of our parameter estimation procedure to experimental data. We use the oxygen reduction in acidic media involving three charge transfer reactions and a chemical reaction as an example, and identify ways to isolate reaction currents for the individual processes in order to accurately estimate the exchange current densities.},
doi = {10.1134/S1023193517100111},
journal = {Russian Journal of Electrochemistry},
number = 10,
volume = 53,
place = {United States},
year = 2017,
month =
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on October 21, 2018
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  • The aim of this report is to scrutinize the thin-film rotating disc electrode (TF-RDE) method for investigating the electrocatalytic activity of high surface area catalysts. Special emphasis is given to the oxygen reduction reaction (ORR) on carbon-supported platinum catalysts. On the basis of measurements on four different Pt catalyst samples with various average particle sizes, it is demonstrated in detail how the intrinsic properties of the catalyst, i.e., the mass activity (A/g{sub Pt}) and the specific activity (A/m{sub Pt}{sup 2}), are evaluated. The potential sources of error are critically discussed and guidelines for the measurements are given. Furthermore, the specificmore » ORR activities determined for the different catalyst samples are analyzed and compared to polycrystalline Pt. The previously reported effect of the particle size on the specific activity for the ORR is interpreted on the basis of the shift in the potential of zero total charge and the concomitant alteration of the adsorption properties.« less
  • Coastal and marine waters receive strong oxidants, such as ozone and chlorine, from several natural and anthropogenic sources. These oxidants react rapidly with Br/sup -/ and I/sup -/ in seawater to produce Br/sub 2/, I/sub 2/ and various hydrolysis products. The fate of these halogen products is of geochemical and biological interest. The rotating ring disc electrode (RRDE) was used to study the rapid decay of these oxidants in natural waters. Copper-plated disc experiments address the hypothesis that Cu catalyzes the decomposition of oxidant. Pseudo first-order and second-order reaction kinetics of model compounds and field samples were also studied, viamore » in situ generation of Br/sub 3/. Pseudo first-order behavior is observed for ammonia and glycine, and the rate constants obtained from the RRDE method compare favorably with the literature (8.1 x 10/sup 7/ and 8.5 x 10/sup 7/ L/mol-sec, respectively). Second-order behavior is observed in natural water samples collected from the Patuxent River. Calculations suggest that the observed fast demand has a rate constant in excess of 10/sup 7/ L/mol-sec, and that the substrate responsible for the demand approaches concentrations of 1 x 10/sup -5/ M. The ubiquitous distribution of rapid demand, as measured in the Patuxent estuary, suggests that proteinaceous organosulfur may contribute to the observed rapid demand.« less