Author/Editor		Vončina, Ernest; Šolmajer, Tomaž
Title		Termoliza 2-klorofenola kot primer površinsko katalizirane reakcije pri nastanku predhodnikov polikloriranih dibenzodioksinov in dibenzofuranov
Type		članek
Source		In: Glavič P, Brodnjak-Vončina D, editors. Zbornik referatov s posvetovanja Slovenski kemijski dnevi 1998; 1998 sep 17-18; Maribor. Maribor: FKTT,
Publication year		1998
Volume		str. 319-26
Language		slo
Abstract		The purpose of this work was to elucidate the mechanism of the thermolysis of 2-chlorophenol chemisorbed on the surface of aluminum oxide as an example of the surface mediated catalysis reaction where mono and dichloro-hydroxy-diphenylether and derivates of dichloro-dihydroxydiphenyls are formed as the main therniolytic products. In this work some electronic and structural properties of aluminum-2-chlorophenolate intermediates are discussed. The influence of Al atom as catalyst is explicitly provided for in the computational model. The transfer of chlorine or hydrogen generates a carbocation structure which is further rearranged into 2-oxocyclohexa-3,5-dienylidene derivative or takes part in the nucleophylic attack by the leaving chloro-phenoxyde anion. The latter intermediate, aluminum bonded ortho-hydroxy-diphenylether is further thermochemically rearranged into Smiles like dibenzo dioxin structure. Results of ab initio computations with inclusion of aluminum ion in the model show that the energetic barrier for transfer of ortho-clilorine in a favourable spatial position to aluminum ion is by 7.4 Kcal/mol higher than the barrier for its hydrogen substituted counterpart at position 6.
Descriptors		CHLOROPHENOLS ALUMINUM OXIDE CATALYSIS DIOXINS BENZOFURANS INCINERATION