Hydrazine autoxidation in solution: catalysis by pentacyanoferrate(II)

Hydrazine is oxidized by dissolved oxygen in aqueous solutions containing [Fe(CN)5]3-, in slightly acidic or alkaline conditions. The reaction involves the oxidation of [FeII(CN)5(N2H4)]3- to [FeIII(CN)5(N2H4)]2- as the first step, and kinetic features suggest that this is followed by dimerization t...

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Autores principales: Funai, I.A., Blesa, M.A., Olabe, J.A.
Formato: JOUR
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_02775387_v8_n4_p419_Funai
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Sumario:Hydrazine is oxidized by dissolved oxygen in aqueous solutions containing [Fe(CN)5]3-, in slightly acidic or alkaline conditions. The reaction involves the oxidation of [FeII(CN)5(N2H4)]3- to [FeIII(CN)5(N2H4)]2- as the first step, and kinetic features suggest that this is followed by dimerization to [(NC)5FeIII(N2H4)FeII(CN)5]5-; FeIIIFeIll and FeIIFeII dimers are then originated by fast electron-transfer. The first of these evolves to [(NC)5FeII(N2H2 FeII(CN)5]6-; this diimide complex shows a strong MLCT band at 515 nm and is very stable in alkaline solutions (pH 8) free of O2 or H2O2. In the presence of these, or in more acidic media it evolves further to [Fe(CN)5(H2O)]3-+N2. © 1989.