THE PHOTO-CE MECHANISM - THE OXIDATION OF TRIS-(PARA-TOLYL)AMINE IN ACETONITRILE AT AN ILLUMINATED PLATINUM-ELECTRODE
| العنوان: | THE PHOTO-CE MECHANISM - THE OXIDATION OF TRIS-(PARA-TOLYL)AMINE IN ACETONITRILE AT AN ILLUMINATED PLATINUM-ELECTRODE |
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| المؤلفون: | Donald Bethell, Barry A. Coles, Richard G. Compton, Adrian C. Fisher, Sadhana Tripathi |
| المصدر: | JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS. 86(21) |
| سنة النشر: | 1990 |
| مصطلحات موضوعية: | Photocurrent, Chemistry, Inorganic chemistry, chemistry.chemical_element, Disproportionation, Photochemistry, chemistry.chemical_compound, Radical ion, Electrode, Amine gas treating, Physical and Theoretical Chemistry, Platinum, Acetonitrile, Equilibrium constant |
| الوصف: | The oxidation of tris-(p-tolyl)amine (A) has been studied in acetonitrile solution using a channel electrode flow cell. In the dark a simple reversible one-electron oxidation to the corresponding (stable) radical cation is observed. However on irradiation with light of wavelength 300 nm a 'pre-wave' is additionally seen ca. 200 mV cathodic of the simple 'dark' process. Action spectrum measurements, preparative experiments and photocurrent/solution flow rate data are used to show that this process has the kinetic characteristics of a 'photo-CE' reaction in which the product of a photochemical pre-equilibrium involving A undergoes a disproportionation reaction forming an electroactive species. The nature of the species involved is deduced and a detailed mechanistic scheme presented. Rate and equilibrium constants are estimated. The 'photo-CE' reaction is shown to have the unusual property for an electrode reaction at a channel electrode that the photocurrents decrease with solution flow rate. |
| اللغة: | English |
| تدمد: | 1364-5455 0956-5000 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::6901976caccba53e3a5ded66a88b3dfe http://ora.ox.ac.uk/objects/uuid:b7ef674d-5bd4-44a0-9912-a5422090aa2d |
| Rights: | OPEN |
| رقم الانضمام: | edsair.doi.dedup.....6901976caccba53e3a5ded66a88b3dfe |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 13645455 09565000 |
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