Autocatalytic Chemiluminescence Sheds New Light on the Classic Permanganate鈥揙xalate Reaction

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• 作者：Christopher M. Hindson ; Zoe M. Smith ; Neil W. Barnett ; Graeme R. Hanson ; Kieran F. Lim ; Paul S. Francis
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：May 16, 2013
• 年：2013
• 卷：117
• 期：19
• 页码：3918-3924
• 全文大小：394K
• 年卷期：v.117,no.19(May 16, 2013)
• ISSN：1520-5215

文摘

The emission of light from the permanganate鈥搊xalate reaction enables monitoring of intermediates not accessible through traditional spectrophotometric interrogation. Despite the inherent complexity of the underlying chemical reactions and equilibria, the emission intensity鈥搕ime profile was characterized by a simple model combining previously independent minimalistic descriptions of chemiluminescence and autocatalysis. The generation of the electronically excited [Mn^II]* emitter and the acceleration of the reaction even in the presence of high initial concentrations of Mn^II (under conditions that preclude accumulation of colloidal Mn^IV) provide new evidence for the reduction of manganese species by a reactive radical intermediate as a supplementary positive feedback loop to the formation of Mn^II.