Studies of the metal ion-catalysed oxidation of heterocyclic sulfur compounds.

Chemical oxidation by hydrogen peroxide is used for the treatment of hazardous organic materials present at low concentrations in contaminated soil and water. A knowledge of the oxidation of thiophene and its derivatives, with particular reference to oxidative destruction and the identification of intermediate oxidation products would be useful for a deeper understanding of reaction mechanisms in waste treatment and the optimization of conditions. In this thesis, the oxidation of thiophenes, namely thiophene and 2- and 3-methylthiophene, with hydrogen peroxide and catalyst systems, e.g. Fenton's reagent, Gif systems and titanium dioxide-assisted photocatalytic oxidations, all of which may involve the formation of free radicals, e.g. the hydroxyl radical (HO-), has been studied. Fenton-related catalyst systems, mixtures of iron salts (and sometimes also with copper salts) and hydrogen peroxide, have been suggested in the literature and their reactions with thiophenes have been investigated. Additionally, other catalytic systems that have also been suggested in the literature as having potential have been studied. The oxidation of thiophene derivatives with Fenton-like reagents involving a combinations of hydrogen peroxide with other metal salts including vanadium(IV), titanium(III), copper(I) and copper(II) have been explored, since all of these systems appear to form hydroxyl radicals. Further Fenton-related oxidations of reaction intermediates have been carried out in order to help understand whether the oxidation products described are derived directly from the original compound or from further oxidation of a reaction intermediate. The progress of the oxidation reactions was followed by chromatographic analysis, using Gas Chromatography-Mass Spectrometry and High Performance Liquid Chromatography, so as to establish the nature of the oxidation products and the possible reaction pathways. Components of the mixtures were identified by comparison with commercially available products or synthetic standards. Oxidation reactions were monitored over set time intervals and the amounts of residual thiophenes were determined. In all of the oxidation reactions investigated, Fenton-related and Fenton-like, heteroaromatic ring destruction was observed, together with the formation of small amounts of hydroxylated ring products and dimeric structures. The oxidative destruction of thiophenes was successfully achieved with the above catalyst systems in the presence of excess hydrogen peroxide.Recent literature has questioned the formation of hydroxyl radicals in Fenton-related systems, and in order to contribute to the debate regarding the oxidizing species responsible for the destruction of each of the thiophenes, the oxidation reactions have been carried out in the presence of a complexing agent such as ethylenediaminetetraacetic acid (EDTA), and a radical trapping reagent 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), respectively. Evidence of radical trapping was observed. Gif chemistry may involve the formation of high oxidation state iron complexes rather than free radicals. The oxidation of thiophenes was carried out using Fenton's reagent under Gif conditions and the results were compared with those from conventional Fenton and related conditions, to determine whether free radical species are involved in the latter. Radical derived products were again observed.Titanium-catalysed photooxidation has also formed part of this study to determine the nature of intermediate products which might be similar to those from Fenton-catalysed systems. For these reasons, the photocatalytic oxidation of 2-methylthiophene was studied in aqueous solution and the reaction was conducted in the presence and absence of titanium dioxide under an oxygen atmosphere. A similar range of radical derived products was found as in the conventional Fenton and related systems.