Oxidation of 4-methylanisole by aqueous cerium(IV) in a two-phase immiscible liquid/liquid system: Interfacial versus homogeneous control
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. ISSN 1520-6106Full text not available from this repository.
Official URL: http://dx.doi.org/10.1021/jp013818v
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|
|Subjects:||Q Science > QD Chemistry|
|Journal or Publication Title:||JOURNAL OF PHYSICAL CHEMISTRY B|
|Publisher:||AMER CHEMICAL SOC|
|Official Date:||21 March 2002|
|Number of Pages:||7|
|Page Range:||pp. 3019-3025|
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