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The Benzylphenylether thermolysis mechanism: Insights from phase behavior
Author(s) -
Wu Benjamin C.,
Klein Michael T.,
Sandler Stanley I.
Publication year - 1990
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690360802
Subject(s) - chemistry , supercritical fluid , hydrogen atom abstraction , toluene , methanol , thermal decomposition , phenol , pyrolysis , photochemistry , hydrogen , reaction mechanism , decomposition , selectivity , organic chemistry , catalysis
The thermolysis of benzylphenylether (BPE) was examined at 320°C in liquid, vapor, and supercritical methanol phases as a probe of the reaction mechanism. Toluene and phenol were the major products in all cases, but observed selectivities were dependent upon the reaction phase. Isotopic labeling experiments demonstrated that methanol participated in the reaction network as a hydrogen donor through a free‐radical mechanism. These results are consistent with free‐radical steps for neat BPE primary pyrolysis that include BPE fission followed by hydrogen abstraction and radical recombination reactions. A detailed set of 21 free‐radical steps quantitatively explains the dependence of the selectivity and conversion on the phase behavior.