Premium
Weak collision effects: Non‐steady‐state thermal unimolecular reactions
Author(s) -
Malins R. J.,
Tardy D. C.
Publication year - 1979
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.550110907
Subject(s) - chemistry , cyclopropane , steady state (chemistry) , isomerization , thermodynamics , thermal , non equilibrium thermodynamics , shock tube , pulse (music) , collision , atomic physics , mechanics , physics , shock wave , quantum mechanics , ring (chemistry) , biochemistry , computer security , organic chemistry , voltage , computer science , catalysis
Abstract Bench‐mark calculations for non‐steady‐state thermal systems are presented. Although the equations and calculations were modeled for the isomerization of cyclopropane in the single‐pulse shock tube, the results are qualitatively and semiquantitatively correct for any experimental technique in which a finite time is required to energize the reactant to the reaction temperature. A useful parameter in describing this nonequilibrium behavior is the induction time τ 95 ; the log of τ 95 is linearly related to the collision frequency ω. For the model cyclopropane system a steady state is reached in ∼1 msec when ω ≈ 10 8 sec −1 and T ≈ 1500 K.