Oxidation of pinacyanol chloride by H2O2catalyzed by FeIIIcomplexed to tetraamidomacrocyclic ligand: unusual kinetics and product identification

Autor:	Arani Chanda, Alexander D. Ryabov, Terrence J. Collins, Soumen Kundu, Douglas A. Mitchell
Rok vydání:	2010
Předmět:	Chemistry Kinetics Inorganic chemistry Medicinal chemistry Oxalate Catalysis Reaction rate chemistry.chemical_compound Nitrate Materials Chemistry Formate Physical and Theoretical Chemistry Nitrite Hydrogen peroxide
Zdroj:	Journal of Coordination Chemistry. 63:2605-2618
ISSN:	1029-0389 0095-8972
DOI:	10.1080/00958972.2010.492426
Popis:	Oxidative degradation of pinacyanol chloride (PNC) dye by H2O2, as catalyzed by the 1 FeIII-TAML activator (TAML = tetraamidomacrocyclic ligand), occurs rapidly in water, goes to completion, and exhibits noticeably complex kinetics at pH 11. The reaction achieves a carbon mineralization of 51%. The detected products are acetate, formate, oxalate, maleate, 2-nitrobenzoate, nitrite, and nitrate. The catalytic reaction is a first-order process in 1 and the reaction rate has a Michaelis dependence in hydrogen peroxide (H2O2). The reaction rate increases sharply with increasing PNC concentration, reaches a maximal value, and then declines as the PNC concentration is further increased. The initial rate (v) versus [PNC] profile has been quantified in terms of the equation: v = (c 1[PNC] + c 2[PNC]2)/(c 3 + c 4[PNC] + [PNC]2) which accounts for the maximum and further rate decline. Kinetic analysis at a more acidic pH (9 vs. 11) revealed that there is no initial rate increase and only the hyperbolic retardation b...
Databáze:	OpenAIRE
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