Document Type : Research note


1 Department of Applied Chemistry, BBAU, Lucknow-226025, U.P., India

2 Chemical laboratories, Feroze Gandhi College, Raebareli-229001, U.P., India


The present paper deals with the kinetics and mechanism of homogeneously Ir(III) chloride catalyzed oxidation of D-mannitol by chloramine-T [CAT] in perchloric acid medium in the temperature range of 30 to 45 0C. The reaction is carried out in the presence of mercuric acetate as a scavenger for chloride ion. The experimental results show first order kinetics with respect to the oxidant [CAT] and catalyst [Ir(III)] while zero order with respect to substrate, i.e., D-Mannitol was observed. The reaction shows negligible effect of [Hg(OAc)2], [H+] and ionic strength of the medium. Chloride ion positively influence the rate of reaction. The reaction between chloramine-T and D-Mannitol in acid medium shows 2:1 stoichiometry. To calculate activation parameters, the reactions have been studied at four different temperatures between 30 to 45ºC. A mechanism involving the complex formation between catalyst and oxidant has been proposed. Mannonic acid has been identified chromatographically and spectroscopically as the final product of oxidation of D-Mannitol. Based on the kinetic data, reaction stoichiometry and product analysis, a reaction mechanism has been proposed and rate law has been derived.


Main Subjects

[1]      Puttaswmy, J. P., Shubha, R. V. and Jagadeesh., “Ruthenium(III)-catalyzed oxidative cleavage of p-aminoazobenzene by chloramine-B in alkaline medium and uncatalyzed reaction in acid medium: Spectrophotometric kinetic and mechanistic study”, Trans. Met. Chem., 32, 991 (2007).
[2]      Jennings, V. J.,“Analytical applications of chloramine-T”, Critical Rev. Anal-Chem., 3 (4), 407(1974).
[3]      Kolvari, A., Choghamarani, A. G.,  Salehi, P.,  Shirini, F. and Zolfigol, M. A., “Applications of N- halo reagents in organic synthesis”, J. Iran. Chem. Soc., 4 (2), 126 (2007).
[4]      Umemoto, T., Fukami, S., Tomizava, G., Harasava, K., Kavada, K. and Tomita, K., “Formal electrophillic reactions of fluorine presumably involve alternative Mechanisms”, J. Am. Chem. Soc., 112, 8563 (1990).
[5]      Ramananda, M. G. and Ananda, S., “Kinetics and mechanism of oxidation of o-toluidine by sodium-N-chloro benzene sulphonamide in acid medium”, Asian J. Chem., 11 (4), 1348 (1999).
[6]      Singh, A. K., Negi, R., Jain, B., Katre, Y., Singh, S. P. and Sharma, V. K., “Kinetics and mechanism of Ru(III)-catalyzed oxidation of paracetamol by chloramine-T in aqueous acidic medium”, Catal. Lett.,132, 285 (2009).
[7]      Campbell, M. M. and Johnson, G., “Chloramine-T and related N-halogeno-N-metallo reagents”, Chem. Rev.,8, 65 (1978).
[8]      Singh, A. K., Negi, R., Katre, Y. and Singh, S. P., “Mechanistic study of novel oxidation of paracetamol by chloramine-T using micro-amount of chloro-complex of Ir(III) as a homogeneous catalyst in acidic medium”, J. Mol. Catal A: Chem., 302, 36 (2009).
[9]      Puttaswamy, Jagadeesh, R.V. and Vaz, N., “Ru(III)-catalyzed oxidation of some N-heterocycles by chloramine-T in hydrochloric acid medium: A kinetic and mechanistic study”, J. Mol. Catal. A., 229, 211 (2009).
[10]  Filler, R., “Oxidations and dehydrogenations with N-bromosuccinimide and related N-   haloimides”, Che. Rev., 63, 21 (1963).
[11]  Wadhwani, M. and Jain, S., “Kinetic study of oxidation of some monosaccharides by     chloramine-T inded by visible light source”, Res. J. Chem. Sci., 4 (7), 61 (2014).
[12]  Veena, M. S., Prashanth, M. K., Kumar, K. Y., Muarlidhara, H. B. and Nayaka, Y. A., “Kinetics and mechanistic study of oxidation of amoxicillin by chloramine-T in acid medium”, J. Chil. Chem. Soc., 60 (3), 3063 (2015).
[13]  Wadhwani, M. and Jain, S., “Ultraviolet light induced oxidation of malonic acid by chloramine-T in an aqueous acidic medium: A kinetic study”, Ind. J. Adv. Chem. Sci., 40 (1), 36 (2016).
[14]  Singh, A. K., Negi, R., Jain, B.,  Katre, Y., Singh, S. P. and Sharma, V. K., “Pd (II) catalyzed oxidative degradation of paracetamol by chloramine-T in acidic and alkaline media”, Ind. Eng. Chem. Res., 50, 8407 (2011).
[15]  Rajeswari, V., Hosahalli, A. P., Savanur Sharanappat, N. and Shivamrti, A., “Ru(III) mediated oxidation of D-Mannitol by cerium (IV) inaqueous sulphuric acid medium: A kinetic & mechanistic approach”, Wiley Inter. Science, 10 (J), 1002 (2010).
[16]  Srivastava, S. and  Srivastava, P., “Kinetics and mechanism of oxidation of D-Mannitol by  potassium bromate in aqueous acidic medium”, Pelg. Res. Lib., 1 (1), 13 (2010).
[17]  Singh, B., Singh, D., Singh, S. and Kumar, A., “Kinetics and mechanism of Ru(III) catalysis in the oxidation of erythritol and dulcitol by NBS”, Trans. Met. Chem., 16, 610 (1991).
[18]  Agarwal, A., Sharma,G., Khandelwal,C. L. and SharmaP. D., “Kinetics and mechanism of oxidation of mannitol by sulphato-cerium(IV) species in aqueous acid medium”, Inorg. React. Mech., 4 (3), 233 (2002).
[19]  Aparna, R. and Das, A. K., “Studies on kinetics and mechanism of iridium(III) catalysed cerium(IV) oxidation of D-mannitol and D-glucose in aqueous acid media”, Indian J. Chem., 41 (A), 2468 (2002).
[20]  Srivastava, S. and Singh, A. L., “Mechanistic studies of oxidation of D-sorbitol and D-mannitol by an alkaline solution of potassium bromate in the presence of chloro complex of Ru(III) as homogeneous catalyst”, Oxid. Communi., 36 (1), 41 (2013).
[21]  Puttaswamy and Vaz, N., “Ruthenium(III) and osmium(VIII)-catalyzed oxidation of 2-thiouracil by bromamine-B in acid and alkaline media: A kinetic and mechanistic study”, Trans. Met. Chem., 28, 409 (2003).
[22]  Hiremath, C. V., Kiran, T.,S. and Nandibewoor, S.,T., “Os(VIII)/Ru(III) catalysed oxidation of aspirin drug by a new oxidant, diperiodatoargentate(III) in aqueous alkaline medium: A comparative kinetic study”, J. Mol. Catal A. Chem., 248, 163 (2006).
[23]  Uma, V.,  Sethuram, B. and Rao, T. N., “Kinetics of oxidation of isopropanol by IO4− catalyzed by metal ion”, React. Kinet. Catal .Lett., 18, 283 (1981).
[24]  Song, W., Zhao, R. and  Jiang, Q., “Catalyzed oxidation of tetrahydrofurfuryl alcohol by cerium(iv) in aqueous sulphuric acid medium.”, Acta. Phys. Chim. Sin., 21 (8), 929 (2005).
[25]  Singh, A. K., Rahmani, S., Singh, B., Singh, R. K. and Singh, M., “Mechanism of Ir(III)-catalysed and Hg(II)-co-catalysed oxidation of reducing sugars by N-bromoacetamide in acidic medium”, J. Phys.Org. Chem, 17 (3), 249 (2004).
[26]  Bai, W., Zhai, Y., Liu, H., Lu, H. and Song, W., “Kinetics and mechanism of iridium(III) catalyzed oxidation of ethylene glycol by cerium(IV) in sulfuric acid media”,  Ind. J. Chem., 47 (A), 1194 (2008).
[27]  Singh, A. K., Sachdev, N., Srivastava, A., Jain, B. and Khtre, Y., “Oxidation of d-glucose by N-bromophthalimide in the presence of chlorocomplex of iridium (III): A kinetic and mechanistic study”, Res. Chem. Intermed.,38, 507 (2012).
[28]  Venkatasubramanian, N.  and Thiagarajan, V., “The mechanism of oxidation of alcohols by bromine”,  Tetra. Lett. 9, 1711 (1968).
[29]  Grover, N., Kambo, N. and Upadhyay, S. K., “Kinetics and mechanism of palladium(II) catalysed oxidation of some alpha-aminoacids by chloramine-T in perchloric acid”, Ind. J. Chem.,  41 (A), 2482 (2012).
[30]  Lewis, E. S., Investigation of rates and mechanism of reactions in techniques of chemistry: Aweissberger, 3rd ed., Wiley, New York, p. 421 (1974).
[31]  Onkar, A. S.,  Naik, P. N., Gunagi, S. D., Nandibewoor, S. T. and Chimatadar, A. S., “Kinetics and mechanism of oxidati of  tyrosine by vanadium(V) in aqueous hydrochloric and ethanoic acid medium”, Ind. J. Chem., 51 (A), 1574 (2012).
[32]  Gopalakrishanan, G., Pai, B. R. and Venkatasubramaniam, N., “Oxidation of alcohols by N-Bromosuccinimide-A curious dependence on initial concentration of the oxidant”, Ind.  J. Chem, 19 (B), 293 (1998).
[33]  Chang, J. C. and Garner, G. S. “Kinetics of aquation of aquopentachloroiridate(III) and chloride anation of diaquotetrachloroiridate(III) anions”, Inorg. Chem., 4 (2), 209 (1965).