Influence of medium on the kinetics of oxidation of iron(II) ion with t-butyl hydroperoxide
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B. Mihaljević
und
D. Ražem
Abstract
The oxidation of iron(II) with tert-butyl hydroperoxide was investigated in the absence of oxygen in water, methanol, and the dichloromethane—methanol solvent mixture (φr = 2:1). The oxidation rate depends on solvent polarity; measured in the presence of SCN− at constant 0.8 mmol dm−3 HCl, the rate constant increases with the polarity decrease passing from water and methanol to the dichloromethane—methanol solvent mixture. Further, in non-aqueous solutions at this acid concentration the rate constant was higher than the rate constant in the presence of Cl− only. The oxidation rate measured in the [FeCl]2+ complex in dichloromethane—methanol was slow in acidic medium and increased by decreasing the acid concentration. Approaching the physiological pH conditions the rate constant attained the value of an order of magnitude of 103 dm3 mol−1 s−1, while very little alteration of stoichiometry of the oxidation reaction was observed. The rate constant measured in the presence of Cl− strongly depends on electrolyte concentration at concentrations less than 0.5 mmol dm−3 HCl, both in MeOH and the solvent mixture. Based on these results, a possible mechanism of the influence of solvent, acidity, and ligand type on the rate constant is discussed. We assume that the oxidation proceeds by an inner-sphere mechanism considering that the breakdown of the successor inner-sphere complex forming reactive alkoxyl radicals is probably the rate-limiting step.
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© 2006 Institute of Chemistry, Slovak Academy of Sciences
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Artikel in diesem Heft
- Influence of medium on the kinetics of oxidation of iron(II) ion with t-butyl hydroperoxide
- Synthesis of new thiazolo[2,3-b]pyrimidine derivatives of pharmaceutical interest
- Enthalpic analysis of the CaTiSiO5 system
- Kinetic, spectrophotometric determination of nanogram levels of manganese(II) using catalytic azo dye—potassium periodate—1,10-phenanthroline system
- Application of a ternary complex of tungsten(VI) with 4-nitrocatechol and thiazolyl blue for extraction-spectrophotometric determination of tungsten
- Determination of risperidone at picogram level in human urine by luminol—H2O2 chemiluminescence
- Electrochemical dissolution of chalcopyrite studied by voltammetry of immobilized microparticles
- Colon tissue concentrations of copper, iron, selenium, and zinc in colorectal carcinoma patients
- Structure of tetrakis(pyridinioacetate) neodymium(III) tetrahydrate perchlorate
- Thermally stable oligomer—Metal complexes based on oligo-ortho-aminophenol and oligophenylazomethinephenol
- Adsorption of SO2 on alumina
- One-pot, three-component synthesis of secondary amines and trisubstituted hydrazines from ketones
- Synthesis of α,α′-bis(R-benzylidene)cycloalkanones catalyzed by potassium hydrogen sulfate under solvent-free conditions
- Electrical conductivity of the molten KF—K2TaF7 system
- New substituted mono-and bis(imidazolyl)pyridines and their application in nitroaldolisation reaction
