铁离子催化十二钨酸络钴酸钾氧化羟胺反应的动力学和机理 Ⅱ.在HCIO_4-NaClO_4介质中的反应

KINETICS AND MECHANISM OF IRON (Ⅲ) CATALYZED OXIDATION OF HYDROXYLAMINE BY 12-TUNGSTO-COBALT(Ⅲ)ATE

羟胺是典型的显影剂和防氧化剂,研究它的氧化反应机理是很有意义的。前文在HAc-NaAc(pH-3.9—5.0)介质中的研究发现,当Σ[Fe^(3+)]<3×10^(-6)mol·L^(-1)时,铁离子催化十二钨酸络钴酸钾K_5[CoW_(12)O_(40)](简记为Co^3+W)氧化羟胺的反应遵循(1)式:

Different from in HAc-NaAc (pH = 3.9-5.0), in HClO4-NaClO4 ([H+] - 0.1-0.4 mol/L) the reaction of the Fe (Ⅲ) catalyzed oxidation of hydroxylamine by 12-tungstocobalt (Ⅲ) ate obeys the following kinetic law:This paper gives a description of the mechanism of the synergetic electron-proton transfer between NH2OH and Fe3+(OH)1- through a pentagonal model, considering that the active form of Fe (Ⅲ) is Fe3+(OH)1-.