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Oxidation of 4-methylanisole by aqueous cerium(IV) in a two-phase immiscible liquid/liquid system: Interfacial versus homogeneous control
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UNSPECIFIED (2002) Oxidation of 4-methylanisole by aqueous cerium(IV) in a two-phase immiscible liquid/liquid system: Interfacial versus homogeneous control. JOURNAL OF PHYSICAL CHEMISTRY B, 106 (11). pp. 3019-3025. doi:10.1021/jp013818v ISSN 1520-6106.
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Official URL: http://dx.doi.org/10.1021/jp013818v
Abstract
The kinetics of the oxidation of 4-methylanisole (MA) by Ce(IV) have been measured in both two-phase (MA/aqueous sulfuric acid) and single-phase (aqueous sulfuric acid) arrangements by using microelectrochemical measurements at expanding droplets (MEMED) and UV-visible spectrophotometry, respectively. In the two-phase arrangement, the electron transfer (ET) reaction appeared to occur interfacially, rather than by dissolution of MA followed by reaction in solution as previously considered. The effective first-order rate constant for the consumption of Ce(IV) at the interface is 2.0 x 10(-4) cm s(-1). The homogeneous reaction is first-order in both Ce(IV) and MA, with a rate constant for the loss of Ce(IV) of 1.0 mol(-1) dm(3) s(-1). The lifetime of the 4-methylanisole radical cation in aqueous sulfuric acid, formed in the first step of the oxidation process, has been measured independently as similar to10 ins using steady-state ultramicroelectrode voltammetry. The factors leading to the different energetics of the one phase and interfacial reaction are discussed, and the implications of the observed kinetics on scale-up are highlighted.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Journal or Publication Title: | JOURNAL OF PHYSICAL CHEMISTRY B | ||||
Publisher: | AMER CHEMICAL SOC | ||||
ISSN: | 1520-6106 | ||||
Official Date: | 21 March 2002 | ||||
Dates: |
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Volume: | 106 | ||||
Number: | 11 | ||||
Number of Pages: | 7 | ||||
Page Range: | pp. 3019-3025 | ||||
DOI: | 10.1021/jp013818v | ||||
Publication Status: | Published |
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