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http://dx.doi.org/10.5012/jkcs.2013.57.6.703

Selection of Suitable Micellar Catalyst for 1,10-Phenanthroline Promoted Chromic Acid Oxidation of Formic Acid in Aqueous Media at Room Temperature  

Ghosh, Aniruddha (Homogeneous Catalysis Laboratory, Department of Chemistry, The University of Burdwan)
Saha, Rumpa (Homogeneous Catalysis Laboratory, Department of Chemistry, The University of Burdwan)
Ghosh, Sumanta K. (Homogeneous Catalysis Laboratory, Department of Chemistry, The University of Burdwan)
Mukherjee, Kakali (Homogeneous Catalysis Laboratory, Department of Chemistry, The University of Burdwan)
Saha, Bidyut (Homogeneous Catalysis Laboratory, Department of Chemistry, The University of Burdwan)
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Abstract
In the present investigation, kinetic studies of oxidation of formic acid with and without catalyst and promoter in aqueous acid media were studied under the pseudo-first order conditions [formic acid]T ${\gg}[Cr(VI)]_T$ at room temperature. In the 1,10-phenanthroline (phen) promoted path, the cationic Cr(VI) phen complex is the main active oxidant species undergoes a nucleophilic attack by the substrate to form a ternary complex which subsequently experiences a redox decomposition through several steps leading to the products $CO_2$ and $H_2$ along with the Cr(III) phen complex. The anionic surfactant (i.e., sodium dodecyl sulfate, SDS) and neutral surfactant (i.e., Triton X-100, TX-100) act as catalyst and the reaction undergo simultaneously in both aqueous and micellar phase with an enhanced rate of oxidation in the micellar phase. Whereas the cationic surfactant (i.e., N-cetyl pyridinium chloride, CPC) acts as an inhibitor restricts the reaction to aqueous phase. The observed net enhancement of rate effects has been explained by considering the hydrophobic and electrostatic interaction between the surfactants and reactants. The neutral surfactant TX-100 has been observed as the suitable micellar catalyst for the phen promoted chromic acid oxidation of formic acid.
Keywords
Formic acid; $[Cr(VI)]_T$; Cr(VI)-phen; TX-100; SDS;
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