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Gas/wall collision efficiencies in very low pressure pyrolysis experiments
Author(s) -
Dick Paul G.,
Gilbert Robert G.,
King Keith D.
Publication year - 1984
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550160908
Subject(s) - chemistry , pyrolysis , dipole , excited state , collision , molecule , energy transfer , quartz , atomic physics , moment (physics) , activation energy , analytical chemistry (journal) , molecular physics , organic chemistry , classical mechanics , paleontology , physics , computer security , computer science , biology
A readily applicable empirical formula is obtained for the collisional efficiency for energy transfer between a highly vibrationally excited reactant and a seasoned (usually quartz) wall, in terms of the molecular weight, potential well depth and dipole moment of the reactant. This expression is used to examine corrections due to nonunit wall collision efficiency in the high‐pressure rate parameters obtained from very low‐pressure pyrolysis experiments. It is found that these corrections are up to ca. ±5 kJ/mol in the high‐pressure activation energy and a factor of ca. 2 in the high‐pressure frequency factor, for molecules with molecular weight less than ca. 100 and where experiments are carried out at temperatures exceeding 1000 K.