Abstract
The kinetics and mechanism of citric acid oxidation by CrVI; catalyzed by MnII, has been studied in H2O and in the presence of anionic and cationic surfactants. A linear correlation between k obs −1 and [MnII]−1 was found, satisfying the Michaelis–Menten kinetics. The rate-determining step is the decomposition of complex HCrO4–citric acid–MnII formed between citric acid–MnII and CrVI. Based on kinetic data, a one-step three-electron oxidation mechanism has been proposed. The rate decreased with increase in concentration of the cationic surfactants cetyltrimethylammonium bromide (CTAB) and cetylpyridinium bromide (CPB), while anionic sodium dodecyl sulphate (SDS) had no effect on the rate. The data have been interpreted in terms of reaction in the aqueous phase. The effect of added anions, such as chloride, bromide, nitrate, and sulphate, has been studied and discussed. The activation parameters (ΔH ‡ and ΔS ‡) were significantly affected by the presence of 10.0 × 10−4 mol dm−3 of CTAB or CPB.
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References
N.R. Dhar, J. Chem. Soc., 111, 707 (1917).
D.N. Chakravarty and S. Ghosh, J. Indian Chem. Soc., 34, 841 (1957).
T.J. Kemp and W.A. Waters, J. Chem. Soc., 3193 (1964).
C.F. Huber and G.P. Haight, Jr., J. Am. Chem. Soc., 98, 4128 (1976).
S.L. Oswal and G.V. Bakore, Indian J. Chem., 19A, 211 (1980)
P.V. Subba Rao, G.S.R. Krishna Rao, K. Ramkrishna and P.S.N. Murthy, Indian J. Chem., 30A, 239 (1991).
W. Watanabe and F.H. Westheimer, J. Chem. Phys., 17, 61 (1949).
K.B. Wiberg and T. Mill, J. Am. Chem. Soc., 80, 3022 (1958).
F.H. Westheimer, Chem. Rev., 45, 419 (1964).
J.F. Perez-Benito, C. Arias and D. Lamrhari, J. Chem. Soc., Chem. Commun., 472 (1992); (b) C. Arias and J.F. Perez-Benito, Collect. Czech. Chem. Commun., 57, 1821 (1992); (c) J.F. Perez-Benito and C. Arias, Can. J. Chem., 71, 649 (1993).
Z. Khan and Kabir-ud-Din, Indian J. Chem., in press.
G.P. Haight, Jr., T.J. Huang and B.Z. Shakhashiri, J. Inorg. Nucl. Chem., 33, 2169 (1971).
C. Srinivasan, A. Chellamani and S. Rajagopal, J. Org. Chem., 50, 1201 (1985).
G.V. Bakore and S. Narain, J. Chem. Soc., 3419 (1963).
K.K. Sen Gupta, A.K. Chatterjee and S.P. Moulik, Bull. Chem. Soc. Jpn., 43, 3841 (1970).
F. Hasan and J. Rocek, J. Org. Chem., 38, 3812 (1973); J. Am. Chem. Soc., 95, 4521 (1973); 97, 1444 (1975); (b) D. Ip and J. Rocek, J. Am. Chem. Soc., 101, 6311 (1979); J. Org. Chem., 44, 312 (1979); (c) P.C. Samal, B.B. Patnaik, S. Ch. Dharma Rao and S.N. Mahapatro, Tetrahedron, 39, 143 (1983).
G.P. Haight, G.M. Jursich, M.T. Kelso and P.J. Merrill, Inorg. Chem., 24, 2740 (1985).
Z. Khan, M. Akram and Kabir-ud-Din, Int. J. Chem. Kinet., submitted.
C.A. Bunton in J.B. Jones (Ed.), Application of Biomedical Systems in Chemistry, Part II, Wiley, NY, 1976, Ch. 4.
J.H. Fendler and E.J. Fendler, Catalysis in Micellar and Macro-molecular Systems, Academic Press, NY, 1975.
L.F. Sala, C. Palopoli, V. Alba and S. Signorella, Polyhedron, 12, 2227 (1993).
Z. Khan, M.Z.A. Rafiquee and Kabir-ud-Din, Transition Met. Chem., 22, 350 (1997).
Z. Khan and Kabir-ud-Din, Indian J. Chem., 38A, 361 (1999).
Z. Khan, Kabir-ud-Din and M. Akram, J. Chem. Res. (S), 460 (1998).
Z. Khan and Kabir-ud-Din, Int. J. Chem. Kinet., 31, 409 (1999).
S. Signorella, M. Rizzotto, V. Daier, M.I. Frascaroli, C. Palopoli, D. Martino, A. Boussekou and L.F. Sala, J. Chem. Soc., Dalton Trans., 1607 (1996).
R.E. Hamm, R.L. Johnson, R.H. Perkins and R.E. Davis, J. Am. Chem. Soc., 80, 4469 (1958).
L. Michaelis and M.L. Menten, Biochem. Z., 49, 333 (1973).
J.K. Beattie and J.P. Haight, Jr., Progr. Inorg. Chem., 17, 93 (1972).
C.A. Bunton and G. Savelli, Adv. Phys. Org. Chem., 22, 213 (1986); (b) H. Al-Lohedan and C.A. Bunton, J. Org. Chem., 47, 1160 (1982); (c) M.N. Khan and Z. Arifin, J. Chem. Res. (S), 132 (1995).
T.J. Broxton, J.R. Christie and A.J. Dole, J. Phys. Org. Chem., 7, 437 (1994).
F.M. Menger and C.A. Portnoy, J. Am. Chem. Soc., 89, 4968 (1967).
H. Morawetz, Adv. Catal., 20, 341 (1969); (b) E.M. Cordes and R.B. Dunlap, Acc. Chem. Res., 2, 329 (1969); (c) E.J. Fendler and J.H. Fendler, Adv. Phys. Org. Chem., 8, 271 (1970).
E.W. Anacker and H.M. Ghose, J. Am. Chem. Soc., 90, 3116 (1968).
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Kabir-ud-Din, Hartani, K. & Khan, Z. Unusual rate inhibition of manganese(II) assisted oxidation of citric acid by chromium(VI) in the presence of ionic micelles. Transition Metal Chemistry 25, 478–484 (2000). https://doi.org/10.1023/A:1007010306107
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DOI: https://doi.org/10.1023/A:1007010306107