A kinetic study of the homogeneous oxidation of hydroxylamine by manganese(III)-bis(salicylaldimine) complexes

✍ Scribed by Ibrahim A. Salem

• Publisher: Springer
• Year: 1995
• Tongue: English
• Weight: 329 KB
• Volume: 20
• Category: Article
• ISSN: 0340-4285
• DOI: 10.1007/bf00143500

✦ Synopsis

The kinetics of the oxidation of hydroxylamine by manganese(III)-bis(salicylaldimine) complexes have been studied over the 5.2-8.4 pH range. The reaction is first order in both hydroxylamine and oxidant, and inversely proportional to I-H+]. The [complex]: l-hydroxylamine] stoichiometric ratio is 1:1 in both acidic and neutral media, and 2:1 in an alkaline medium. The second-order rate constant increased in the sequence: [-Mnm(L2)OH2] -C104.2H20 > I-Mnln(L1)OH2]C104 > [Mnm(L1)OAc]-H20. The reactivity of unprotonated hydroxylamine is much higher than that of the protonated form. The reaction rate decreased significantly with addition of chloride ions. A plausible mechanism is proposed.