标题：Kinetic, Mechanistic and Thermodynamic Investigations on Iridium (III) catalyzed Oxidation of D-Mannitol by N-chloro-p-toluenesulfonamide in Perchloric Acid Medium
期刊名称：International Journal of Innovative Research in Science, Engineering and Technology
印刷版ISSN：2347-6710
电子版ISSN：2319-8753
出版年度：2017
卷号：6
期号：7
页码：14308
DOI：10.15680/IJIRSET.2017.0607237
出版社：S&S Publications
摘要：The present papers deals with the kinetics and mechanism of homogeneously Ir(III) chloride catalyzedoxidation 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 resultsshow first order kinetics with respect to the oxidant [CAT] and catalyst [Ir(III)] while zero order with respect tosubstrate, i.e., D-Mannitol was observed. The reaction shows negligible effect of [Hg(OAc)2], [H+] and ionic strengthof the medium. Chloride ion positively influence the rate of reaction. The reaction between chloramine-T and DMannitolin acid medium shows 2:1 stoichiometry. To calculate activation parameters, the reactions have been studiedat four different temperatures between 30 to 45ºC. A mechanism involving the complex formation between catalyst andoxidant has been proposed. Mannonic acid has been identified chromatographically and spectroscopically as the finalproduct of oxidation of D-Mannitol. Based on the kinetic data, reaction stoichiometry and product analysis, a reactionmechanism has been proposed and rate law has been derived.
关键词：Kinetics; mechanism; Ir(III) catalysis; D-Mannitol; chloramine-T; acidic medium
