Radiolytic reductions of Ag(I), Cu(II), Hg(II) and Pb(II) in aqueous-ethanol systems and the effect of colloidal sulfur |
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| Institution: | 1. Structural Materials Group, Institute of Nuclear Materials Science, SCK CEN, Mol 2400, Belgium;2. Department of Materials, Textiles and Chemical Engineering, Ghent University (UGent), Technologiepark 903, B-9052 Ghent, Belgium;3. Dutch Institute for Fundamental Energy Research, DIFFER, De Zaale 20, 5612 AJ Eindhoven, The Netherlands;4. Max-Planck-Institut für Plasmaphysik, 85748 Garching, Germany;5. V.N. Karazin Kharkiv National University, 4 Svobody Sq., Kharkiv 61022, Ukraine;6. Forschungszentrum Jülich GmbH, Institut für Energie- und Klimaforschung – Plasmaphysik, Partner of the Trilateral Euregio Cluster (TEC), 52425 Jülich, Germany;7. Peter the Great St. Petersburg Polytechnic University (SPbPU), 195251 St. Petersburg, Polytechnicheskaya, 29, Russia;1. College of Mechanics and Materials, Hohai University, Nanjing 211100, China;2. School of Chemistry and Materials Engineering, Changshu Institute of Technology, Changshu 215500, China;3. Suqian Institute, Hohai University, Suqian 223800, China |
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| Abstract: | Radiation-induced reductions in aqueous AgClO4, CuCl2, PbCl2 and HgCl2 systems have been measured in the presence of ethanol and for Ag(I) and Cu(II) with several other organic components. In dilute solutions and under deaerated conditions, the rates were consistent with known radical yields and rate constants. Approximately one-third of the radicals formed from ethanol under conditions of complete OH scavenging are ineffective in reducing Cu(II). In the presence of colloidal Cu or Ag, all of the radicals are effective in the reduction. In the presence of 0.4–2 × 10-3 g-atom 1-1 of colloidal sulfur, sulfur reduction competes with and augments that of Ag(I) and Cu(II). Ag2S and CuS are formed with a reaction chain occuring in the Ag system at 1.7 M ethanol. A mechanism is suggested that involves reaction of a radical-cation complex at the sulfur-aqueous interface in which the metal sulfide is formed. HgCl2 reduction is unaffected by colloidal sulfur and that of PbCl2 is depressed. |
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