The reaction mechanism of the oxidative degradation of polyvinyl alcohol (PVA) by the photochemically enhanced Fenton reaction was studied using a homogeneous (Fe2+aq + H2O2) and a heterogeneous reaction system (iron(III)-exchanged zeolite Y+ H2O2). In the homogeneous Fenton system, efficient degradation was observed in a batch reactor, equipped with a medium pressure mercury arc in a Pyrex envelope and employing 80% of the stoichiometric amount of H2O2 required for the total oxidation of PVA and a concentration ratio as low as 1 mole of iron(II) sulfate per 20 moles of PVA sub-units (C2H4O). Model PVA polymers of three different molecular weights (15,000, 49,000 and 100,000 g mol-1) were found to follow identical degradation patterns. Strong experimental evidence supports the formation of super-macromolecules (MW: 1 - 5 × 106 g/mol) consisting of oxidized PVA and trapped iron(III) at an early reaction stage. Low molecular weight intermediates, such as oxalic acid, formic acid or formaldehyde were not found during PVA degradation in the homogeneous Fenton system, and we may deduce that the manifold of degradation reactions is mainly taking place within the super-macromolecules from which CO2 is directly released. However, in the heterogeneous Fenton system, the reaction behavior was found to be distinctly different: a decrease of the molecular weights of all three tested monodisperse PVA samples was observed by the broadening of the GPC-traces during irradiation, and oxalic acid was formed. The results lead to the mechanistic hypothesis that during the heterogeneous Fenton process, the cleavage of the PVA-chains may occur at random positions, the reactive centres being located inside the iron(III)-doped zeolite Y photocatalysts.

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