The reduction of Cr(III) in concentrated aqueous electrolytes at a DME: The influence of anions |
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| Affiliation: | 1. Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan;2. Japan Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Hyogo 679-5198, Japan;1. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan;2. Department of Energy and Environment, Research Institute of Electrochemical Energy, National Institute of Advanced Industrial Science and Technology, 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan;1. Università degli Studi di Milano – Department of Chemistry; INSTM Milano Unit, Via Golgi 19, 20133 Milano, Italy;2. C.N.R. – I.S.T.M., Via Golgi 19, 20133 Milano, Italy;3. Università di Pavia, Dipartimento di Chimica, Via Taramelli 16, 27100 Pavia, Italy;4. Ecole Polytechnique Fédérale de Lausanne, Institut des sciences et ingénierie chimiques, EPFL SB ISIC GGEC, CH J2 489 (Bât. CH) Station 6, CH-1015 Lausanne, Switzerland |
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| Abstract: | The reduction of Cr(III) at a dropping mercury electrode is studied in the presence of highly concentrated NaCl, NaI and Na2SO4 solutions. Thermodynamic analyses of the interface in the supporting electrolyte solutions are also performed in order to account for the double-layer contributions to the reaction rates. The results can be rationalized better fi the relative surface excesses are corrected for the amount of adsorbed water and if the discharge plane is situated outside the OHP. The reactivities in NaI solutions are higher than those in NaClO4 at the same concentration but they are equal when compared at the same water activity. Lower rate constants are observed in NaCl and Na2SO4 solutions, which are explained on the basis of ion-pair associations in the bulk of the solution. |
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