Abstract
AbstractThe oxidation of N-(2-hydroxyethyl)phthalimide with cerium(IV) with a small amount of ruthenium(III) present as a catalyst has been studied by spectrophotometric means. The spectroscopic study has been carried out in aqueous H2SO4 and SO42- media at constant ionic strength of I = 1.60 mol dm−3. Stoichiometric analysis shows that one mole of NHEP reacts with two moles of cerium(IV). The oxidation products were identified by IR and GC–MS. Orders with respect to substrate, oxidant, ruthenium(III) and acid concentrations were determined. Increase in sulphuric acid concentration increases the rate. Effect of ionic strength and solvent polarity of the medium on the rate of the reaction was studied. The added product, cerium(III), has no significant effect on the rate of reaction. The active species of oxidant in sulphate medium and catalyst are CeSO42+ and [Ru(H2O)6]3+. Based on the experimental results a suitable mechanism is proposed. The activation parameters and the thermodynamic quantities are also...
Highlights
Cerium is the most abundant of the rare earths
This paper demonstrates the kinetic study of oxidation of ruthenium(III)-catalysed oxidation of N-(2-hydroxyethyl)phthalimide(NHEP) by cerium(IV) in aqueous H2SO4 and SO24− media spectrophotometrically
The results indicated that two moles of cerium(IV) reacted with one mole of NHEP as given in Equation (1)
Summary
Cerium is the most abundant of the rare earths. The cerous state closely resembles the other trivalent rare earths. The ceric state is the only non-trivalent rare earth ion stable at high acid concentration. Cerium (IV) is a well-known oxidant in acid media (Byadagi, Naik, Savanur, Nandibewoor, & Chimatadar, 2010; Thabaj, Chimatadar, & Nandibewoor, 2006), having the reduction potential (Day & Selbin, 1964) of the couple Ce(IV)/ Ce(III) is 1.70 V. In sulphuric acid and sulphate media, several sulphate complexes of cerium(IV) form (Bugaenko & Kuam-lin, 1963; Kharzeoua & Serebrennikou, 1967; Thabaj et al, 2006) but these have not been studied in-depth so far
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