Oxidation studies. III. Oxidation of ketone by ceric ions in perchloric acid

Rangaswamy, M. ; Santappa, M. (1967) Oxidation studies. III. Oxidation of ketone by ceric ions in perchloric acid Proceedings of the Indian Academy of Sciences, Section A, 66 (3). pp. 174-183. ISSN 0370-0089

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Official URL: http://www.ias.ac.in/j_archive/proca/66/3/174-183/...

Related URL: http://dx.doi.org/10.1007/BF03049458


The oxidation of aliphatic unsymmetrical ketones-n-propyl methyl ketone and isobutyl methyl ketone and cyclic ketone-cyclohexanone by ceric perchlorate in perchloric acid (≈0.5-2.0 M) was studied in the temperature range 10°-30°C. The kinetics of the reactions were followed by measuring rate of Ce4+ disappearance effecting variations in [Ce4+], [Ketone], [HClO4], ionic strength μ, temperature, etc., and the reactions were found to be 2nd order-first order each with respect to [Ce4+] and [ketone]. No evidence for complex formation between Ce4+ and ketone was obtained from kinetics or by an independent absorptiometric method. Ce4+ (αq) and enol of the ketones were the active species for oxidation. Correlations between rates of enolisation of ketones and oxidation of the latter by Ce4+ were observed. The rate constants and their thermodynamic data were calculated and discussed. A mechanism based on the concept of oxidation as a process of successive hydroxylation of organic molecules is proposed.

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