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VLPP unimolecular rate theory
Author(s) -
Barker John R.
Publication year - 1975
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.550070613
Subject(s) - chemistry , gas phase , pyrolysis , thermal decomposition , decomposition , thermal , phase (matter) , thermodynamics , computational chemistry , rrkm theory , reaction rate constant , kinetics , classical mechanics , organic chemistry , physics
The exact theory is derived for the thermal unimolecular decomposition of gas‐phase molecules activated and deactivated exclusively through heterogeneous collisions with the walls of a spherical vessel. This theory is appropriate for the treatment of very‐low‐pressure pyrolysis (VLPP) experiments and other experiments carried out at very low pressures. It is shown, however, that the exact theory is closely approximated by ordinary gas‐phase unimolecular rate theory and that for practical application to experiments the results of both theories are indistinguishable.