Affiliation:
1. Department of Chemistry, Visva-Bharati University, Santiniketan 731235, India
Abstract
The kinetics and mechanism of the chromic acid oxidation of D-galactose in the presence and absence of picolinic acid (PA) in aqueous acid media have been determined under the conditions, [D — galactose]T≥ [CrVI]Tat different temperatures. Under the kinetic conditions, HCrO4-has been found kinetically active in the absence of PA while in the PA catalysed path, a CrVI- PA complex has been established as the active oxidant. In the PA-catalysed path, the CrVI- PA complex receives a nucleophilic attack by the substrate to form a ternary complex which subsequently undergoes a redox decomposition through a two-electron transfer leading to a lactone (oxidised product) and a CrIV- PA complex. Then the CrIV-PA complex participates further in the oxidation of D-galactose and ultimately is converted into a CrIII- PA complex. In the uncatalysed path, a CrVI- substrate ester experiences an acid catalysed redox decomposition (2e-transfer) at the rate-determining step. The uncatalysed path shows a second-order dependence on [H+]. Under the experimental conditions, both paths show first-order dependences on [D-galactose]Tand [CrVI]T. The PA-catalysed path is first-order in [PA]T. These observations remain unaltered in the presence of externally added surfactants. The effect of surfactants like N-cetylpyridinium chloride (CPC, a cationic surfactant) and sodium dodecyl sulfate (SDS, an anionic surfactant), on both the uncatalysed and PA-catalysed paths have been studied. CPC retards both the uncatalysed and PA-catalysed path, while SDS accelerates the reactions. The observed micellar effects have been explained by considering the hydrophobic and electrostatic interactions between the reactants and surfactants.
Subject
Physical and Theoretical Chemistry
Cited by
3 articles.
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