Time resolved impedance spectroscopy as a probe of electrochemical kinetics: The ferro/ferricyanide redox reaction in the presence of anion adsorption on thin film gold
In this work, we use the time resolved technique of Fourier transform electrochemical impedance spectroscopy (FT-EIS) for quantitative kinetic analyses of Faradaic and nonfardaic, as well as heterogeneous and adsorption reactions. As a model system, we investigate the Fe(CN) 6 3−/4− redox reaction o...
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| Veröffentlicht in: | Electrochimica acta 2005-09, Vol.50 (28), p.5659-5672 |
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| container_title | Electrochimica acta |
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| creator | Emery, Samuel B. Hubbley, Jennifer L. Roy, Dipankar |
| description | In this work, we use the time resolved technique of Fourier transform electrochemical impedance spectroscopy (FT-EIS) for quantitative kinetic analyses of Faradaic and nonfardaic, as well as heterogeneous and adsorption reactions. As a model system, we investigate the Fe(CN)
6
3−/4− redox reaction on a thin film Au electrode in the presence of nonfaradaically adsorbing ClO
4
− or Cl
− in neutral electrolytes. The redox process indicates a predominantly Faradaic outer sphere reaction, with nearly negligible adsorption of reactants on Au. dc voltage dependent kinetic parameters for both the anion and redox reactions are obtained by FT-EIS in real time during cyclic voltammetry. Equilibrium values of reaction rate constants, adsorption resistances and pseudocapacitances for the redox couple are also obtained. The theoretical background and working principles of these measurements are discussed, and the experimental findings are compared with previously published data. |
| doi_str_mv | 10.1016/j.electacta.2005.03.043 |
| format | Article |
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6
3−/4− redox reaction on a thin film Au electrode in the presence of nonfaradaically adsorbing ClO
4
− or Cl
− in neutral electrolytes. The redox process indicates a predominantly Faradaic outer sphere reaction, with nearly negligible adsorption of reactants on Au. dc voltage dependent kinetic parameters for both the anion and redox reactions are obtained by FT-EIS in real time during cyclic voltammetry. Equilibrium values of reaction rate constants, adsorption resistances and pseudocapacitances for the redox couple are also obtained. The theoretical background and working principles of these measurements are discussed, and the experimental findings are compared with previously published data.</description><identifier>ISSN: 0013-4686</identifier><identifier>EISSN: 1873-3859</identifier><identifier>DOI: 10.1016/j.electacta.2005.03.043</identifier><identifier>CODEN: ELCAAV</identifier><language>eng</language><publisher>Oxford: Elsevier Ltd</publisher><subject>Chemistry ; Cyclic voltammetry ; Electrochemistry ; Exact sciences and technology ; Fourier transform ; General and physical chemistry ; Impedance spectroscopy ; Kinetics and mechanism of reactions ; Redox reaction ; Time resolved</subject><ispartof>Electrochimica acta, 2005-09, Vol.50 (28), p.5659-5672</ispartof><rights>2005 Elsevier Ltd</rights><rights>2006 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c376t-940f947591c91ef064f832988f20f0c29fc230ea7679d3de8ef178d23ee1d9c43</citedby><cites>FETCH-LOGICAL-c376t-940f947591c91ef064f832988f20f0c29fc230ea7679d3de8ef178d23ee1d9c43</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.electacta.2005.03.043$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,780,784,3550,27924,27925,45995</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=17123491$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Emery, Samuel B.</creatorcontrib><creatorcontrib>Hubbley, Jennifer L.</creatorcontrib><creatorcontrib>Roy, Dipankar</creatorcontrib><title>Time resolved impedance spectroscopy as a probe of electrochemical kinetics: The ferro/ferricyanide redox reaction in the presence of anion adsorption on thin film gold</title><title>Electrochimica acta</title><description>In this work, we use the time resolved technique of Fourier transform electrochemical impedance spectroscopy (FT-EIS) for quantitative kinetic analyses of Faradaic and nonfardaic, as well as heterogeneous and adsorption reactions. As a model system, we investigate the Fe(CN)
6
3−/4− redox reaction on a thin film Au electrode in the presence of nonfaradaically adsorbing ClO
4
− or Cl
− in neutral electrolytes. The redox process indicates a predominantly Faradaic outer sphere reaction, with nearly negligible adsorption of reactants on Au. dc voltage dependent kinetic parameters for both the anion and redox reactions are obtained by FT-EIS in real time during cyclic voltammetry. Equilibrium values of reaction rate constants, adsorption resistances and pseudocapacitances for the redox couple are also obtained. The theoretical background and working principles of these measurements are discussed, and the experimental findings are compared with previously published data.</description><subject>Chemistry</subject><subject>Cyclic voltammetry</subject><subject>Electrochemistry</subject><subject>Exact sciences and technology</subject><subject>Fourier transform</subject><subject>General and physical chemistry</subject><subject>Impedance spectroscopy</subject><subject>Kinetics and mechanism of reactions</subject><subject>Redox reaction</subject><subject>Time resolved</subject><issn>0013-4686</issn><issn>1873-3859</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><recordid>eNqFkc9u1DAQxi0EEkvhGfAFbknHcTa2uVUV_6RKXJazZewx9ZLEwU4r9o14TCbdCo5I1vjg33yf5xvGXgtoBYjh8tjiiH51dNoOYN-CbKGXT9hOaCUbqffmKdsBCNn0gx6esxe1HgFADQp27PchTcgL1jzeY-BpWjC42SOvC4mWXH1eTtxV7vhS8jfkOfIHv5L9LU7Ju5H_SDOuydd3_HCLPGIp-XKryZ_cnMImH_IvqvTHlGeeZr4SuJArblYkSRw9uFBzWR6YvDEExjRO_Hsew0v2LLqx4qvH-4J9_fD-cP2pufny8fP11U3jpRrWxvQQTa_2RngjMMLQRy07o3XsIILvTPSdBHQ0vQkyoMYolA6dRBTB-F5esLdnXRr35x3W1U6pehxHN2O-q7YzoHuQikB1Bj2lVAtGu5Q0uXKyAuy2GXu0fzdjt81YkJY2Q51vHi1cpfxiocBT_deuRCd7I4i7OnNI894nLLb6tCUWUiFdG3L6r9cfEbascQ</recordid><startdate>20050930</startdate><enddate>20050930</enddate><creator>Emery, Samuel B.</creator><creator>Hubbley, Jennifer L.</creator><creator>Roy, Dipankar</creator><general>Elsevier Ltd</general><general>Elsevier</general><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20050930</creationdate><title>Time resolved impedance spectroscopy as a probe of electrochemical kinetics: The ferro/ferricyanide redox reaction in the presence of anion adsorption on thin film gold</title><author>Emery, Samuel B. ; Hubbley, Jennifer L. ; Roy, Dipankar</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c376t-940f947591c91ef064f832988f20f0c29fc230ea7679d3de8ef178d23ee1d9c43</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><topic>Chemistry</topic><topic>Cyclic voltammetry</topic><topic>Electrochemistry</topic><topic>Exact sciences and technology</topic><topic>Fourier transform</topic><topic>General and physical chemistry</topic><topic>Impedance spectroscopy</topic><topic>Kinetics and mechanism of reactions</topic><topic>Redox reaction</topic><topic>Time resolved</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Emery, Samuel B.</creatorcontrib><creatorcontrib>Hubbley, Jennifer L.</creatorcontrib><creatorcontrib>Roy, Dipankar</creatorcontrib><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Electrochimica acta</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Emery, Samuel B.</au><au>Hubbley, Jennifer L.</au><au>Roy, Dipankar</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Time resolved impedance spectroscopy as a probe of electrochemical kinetics: The ferro/ferricyanide redox reaction in the presence of anion adsorption on thin film gold</atitle><jtitle>Electrochimica acta</jtitle><date>2005-09-30</date><risdate>2005</risdate><volume>50</volume><issue>28</issue><spage>5659</spage><epage>5672</epage><pages>5659-5672</pages><issn>0013-4686</issn><eissn>1873-3859</eissn><coden>ELCAAV</coden><abstract>In this work, we use the time resolved technique of Fourier transform electrochemical impedance spectroscopy (FT-EIS) for quantitative kinetic analyses of Faradaic and nonfardaic, as well as heterogeneous and adsorption reactions. As a model system, we investigate the Fe(CN)
6
3−/4− redox reaction on a thin film Au electrode in the presence of nonfaradaically adsorbing ClO
4
− or Cl
− in neutral electrolytes. The redox process indicates a predominantly Faradaic outer sphere reaction, with nearly negligible adsorption of reactants on Au. dc voltage dependent kinetic parameters for both the anion and redox reactions are obtained by FT-EIS in real time during cyclic voltammetry. Equilibrium values of reaction rate constants, adsorption resistances and pseudocapacitances for the redox couple are also obtained. The theoretical background and working principles of these measurements are discussed, and the experimental findings are compared with previously published data.</abstract><cop>Oxford</cop><pub>Elsevier Ltd</pub><doi>10.1016/j.electacta.2005.03.043</doi><tpages>14</tpages></addata></record> |
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| ispartof | Electrochimica acta, 2005-09, Vol.50 (28), p.5659-5672 |
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| language | eng |
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| source | Access via ScienceDirect (Elsevier) |
| subjects | Chemistry Cyclic voltammetry Electrochemistry Exact sciences and technology Fourier transform General and physical chemistry Impedance spectroscopy Kinetics and mechanism of reactions Redox reaction Time resolved |
| title | Time resolved impedance spectroscopy as a probe of electrochemical kinetics: The ferro/ferricyanide redox reaction in the presence of anion adsorption on thin film gold |
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