Abstract
The kinetics of chromium(III) catalyzed oxidation of 1,10-phenanthroline by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically. The reaction between permanganate and 1,10-phenanthroline in alkaline medium exhibits 4:1 stoichiometry (KMnO4:1,10-phenanthroline). The reaction shows first order dependence on [permanganate] and [chromium(III)] and less than unit order dependence in 1,10-phenanthroline, zero order in alkali concentrations. The results suggest the formation of a complex between the 1,10-phenanthroline and the chromium(III) which reacts further with one mole of permanganate species in the rate-determining step, resulting in the formation of a free radical, which again reacts with three moles of permangante species in a subsequent fast step to yield the products. The reaction constants involved in the mechanism were evaluated. The activation parameters were computed with respect to the slow step of the mechanism.
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REFERENCES
R. Stewart, in K.B. Wiberg (Ed.): Oxidation in Organic Chemistry, Part A. Chapter 1. Academic Press, New York 1965.
F. Freeman: Rev. React. Species Chem. React., 1, 179 (1976).
D.G. Lee: The Oxidations of Organic Compounds by Permanganate Ion and Hexavalent Chromium, Open Court. La Salle, IL 1980.
D.G. Lee, in W. S. Trahanovsky (Ed.): Oxidation in Organic Chemistry, Part D, p. 147. Academic Press, New York 1982.
L.I. Simándi, in by S. Patai, Z. Rappoport (Eds.): The Chemistry of Functional Groups, Suppl. C., Chapter 13, Wiley Chichester, 1983.
D.G. Lee, E.J. Lee, K.C. Brown: Phase Transfer Catalysis, New Chemistry, Catalysts and Applications, ACS symposium series No. 326. p.82. American Chemical Society. Washington, DC. 1987.
A.J. Fatiadi: Synthesis, 106, 85 (1987).
J.F. Perez-Benito, D.G. Lee: J. Org. Chem., 52, 3239 (1987); L.I. Simándi, M. Jáky, C.R. Savage, Z.A. Schelly: J. Am. Chem. Soc. 107, 4220 (1985).
O.S. Fedorova, V.M. Berdinicov: Izv Akad Nauk SSSR Ser Khim., 6, 1226 (1979).
F.L. Wimmer, S. Wimmer: Org. Prep. Proc. Int., 15, 368 (1983).
R.G. Panari, A.L. Harihar, S.T. Nandibewoor: J. Phys.Org.Chem., 12, 340 (1999).
M.W. Rophael: Chem. Scr., 20, 171 (1982).
D. Rai, B.M. Sass, D.A. Moore: Inorg. Chem., 26, 345 (1987).
G.H. Jeffery, J. Bassett, J. Mendham, R.C. Denney: Vogel's Text Book of Quantitative Chemical Analysis, 5th edit., p. 371. Longman, Essex 1996.
A. Carrington, M.C.R. Symons: J. Chem. Soc., 3373 (1956).
S.M. Tuwar, S.T. Nandibewoor, J.R. Raju: Transition Met. Chem., 16, 335 (1991).
A.I. Vogel: A Text Book of Practical Organic Chemistry including Quantitative Organic Analysis, 3rd edn., p. 332. Longman, London 1973.
S.V. Rao, V. Jagannadham: React. Kinet. Catal. Lett., 26, 329 (1985).
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Pol, P.D., Mahesh, R.T. & Nandibewoor, S.T. Kinetics and mechanism of chromium(III) catalyzed oxidation of 1,10-phenanthroline by alkaline permanganate. Reaction Kinetics and Catalysis Letters 81, 113–119 (2004). https://doi.org/10.1023/B:REAC.0000016524.81337.e0
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DOI: https://doi.org/10.1023/B:REAC.0000016524.81337.e0