INOR 369 |
| James H. Espenson and Yang Cai. Department of Chemistry, Iowa State University, 25 Spedding Hall, Ames, IA 50011 |
| The reactions cited in the title do not occur in practice, even over long time periods, despite their being spontaneous. The oxidations with perchlorate have ΔE° = 1.61 V (ΔG° = –155 kJ / mol of ClO4 –) and those with H3O+ have ΔE° = 0.42 V (ΔG° = –40 kJ mol-1). The oxidations with perchlorate ions are catalyzed by MeReO3 (MTO). MTO also catalyzes the oxidation of Eu2+ by H3O+, whereas Cr2+, with the same value of E°, does not evolve H2 in the presence of MTO. The reaction stoichiometries are cleanly 8 M2+ + 8 H+ + ClO4 – = 8 M3+ + Cl– + 4 H2O and 2 Eu2+ + 2 H3O+ = 2 Eu3+ + H2. The kinetics and mechanisms will be reported. |
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Homogeneous and Heterogeneous Oxidation Catalysis
8:30 AM-12:05 PM, Tuesday, August 24, 2004 Pennsylvania Convention Center -- 108A, Oral
Division of Inorganic Chemistry |