A Ring−Disk Study of the Competition between Anodic Oxygen-Transfer and Dioxygen-Evolution Reactions

Voltammetric data obtained at a rotated ring−disk electrode for oxidation of dimethyl sulfoxide (DMSO) to dimethyl sulfone support the conclusion that anodic O-transfer and O2(aq)-evolution reactions are in competition for a common reaction precursor. That species is concluded to be the adsorbed OH...

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Veröffentlicht in:	Analytical chemistry (Washington) 1998-02, Vol.70 (3), p.468-472
Hauptverfasser:	Popović, Nataša D, Johnson, Dennis C
Format:	Artikel
Sprache:	eng
Schlagworte:	Chemistry Electrochemistry Exact sciences and technology General and physical chemistry Kinetics and mechanism of reactions
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container_title	Analytical chemistry (Washington)
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creator	Popović, Nataša D Johnson, Dennis C
description	Voltammetric data obtained at a rotated ring−disk electrode for oxidation of dimethyl sulfoxide (DMSO) to dimethyl sulfone support the conclusion that anodic O-transfer and O2(aq)-evolution reactions are in competition for a common reaction precursor. That species is concluded to be the adsorbed OH radical generated by anodic discharge of H2O. Because of this competition, an increase in the flux of the reactant in the O-transfer reaction causes a decrease in the rate of O2(aq) evolution. Therefore, difference voltammetry and hydrodynamically modulated voltammetry cannot be considered reliable for accurate deconvolution of the total electrode current resulting from these concomitant processes. A simple mathematical model is developed to describe the total current resulting from these simultaneous processes, and results of preliminary tests of this model are in good agreement with experimental data for DMSO oxidation.
doi_str_mv	10.1021/ac9707803
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That species is concluded to be the adsorbed OH radical generated by anodic discharge of H2O. Because of this competition, an increase in the flux of the reactant in the O-transfer reaction causes a decrease in the rate of O2(aq) evolution. Therefore, difference voltammetry and hydrodynamically modulated voltammetry cannot be considered reliable for accurate deconvolution of the total electrode current resulting from these concomitant processes. 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A simple mathematical model is developed to describe the total current resulting from these simultaneous processes, and results of preliminary tests of this model are in good agreement with experimental data for DMSO oxidation.</description><subject>Chemistry</subject><subject>Electrochemistry</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Kinetics and mechanism of reactions</subject><issn>0003-2700</issn><issn>1520-6882</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1998</creationdate><recordtype>article</recordtype><recordid>eNpt0M9u0zAcwHELgVgZHHgB5AMT4hD42fnj5Fi1GzAqDbZy4WI5zs_DWxoXO2HrG3DeI-5J5pJSceBg2bI_tqwvIS8ZvGPA2XulKwGihPQRmbCcQ1KUJX9MJgCQJlwAHJBnIVwBMAaseEoOOCuyTGT5hJgpPbfd5f3vu7kN1_SiH5oNdYb2P5DO3GqNve2t62iN_Q1iR6eda6ymZ7ebS-ySpVddMOip6ho6t27cPf7l2uHPrXNUersIz8kTo9qAL3bzIfl2crycfUwWZx8-zaaLRKWi6hMhSl00lckgDmVM0YgcQDes0sh4XmZc1UZXwCrASkOmGhOVMQpZXWNm0kPyZnx37d3PAUMvVzZobFvVoRuCLAXbVihYlG9Hqb0LwaORa29Xym8kA7mtKvdVo321e3WoV9js5d-MEbzeARW0ak3Mom34x_GSiyKyZGQ29Hi7P1b-WhYiFblcfrmQ3_l8kfHTz_Jr9EejVzrIKzf4Lrb7z_8eAJ-sm8M</recordid><startdate>19980201</startdate><enddate>19980201</enddate><creator>Popović, Nataša D</creator><creator>Johnson, Dennis C</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>19980201</creationdate><title>A Ring−Disk Study of the Competition between Anodic Oxygen-Transfer and Dioxygen-Evolution Reactions</title><author>Popović, Nataša D ; Johnson, Dennis C</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a379t-778c6d9f409f4aff6d7500cd19ce125842abfc90190e9c04adfaffffae1bbe4f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1998</creationdate><topic>Chemistry</topic><topic>Electrochemistry</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>Kinetics and mechanism of reactions</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Popović, Nataša D</creatorcontrib><creatorcontrib>Johnson, Dennis C</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Analytical chemistry (Washington)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Popović, Nataša D</au><au>Johnson, Dennis C</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Ring−Disk Study of the Competition between Anodic Oxygen-Transfer and Dioxygen-Evolution Reactions</atitle><jtitle>Analytical chemistry (Washington)</jtitle><addtitle>Anal. 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title	A Ring−Disk Study of the Competition between Anodic Oxygen-Transfer and Dioxygen-Evolution Reactions
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