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Mechanism of isotope exchange reaction between methane and deuterium
Author(s) -
Gardiner W. C.,
Herrmann J. M.,
Mallard W. G.,
Owen J. H.
Publication year - 1976
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.550080112
Subject(s) - chemistry , deuterium , dissociation (chemistry) , methane , analytical chemistry (journal) , hydrocarbon , kinetic isotope effect , shock tube , pyrolysis , argon , atmospheric temperature range , photochemistry , shock wave , organic chemistry , thermodynamics , atomic physics , physics
The rate of CH 4 disappearance in a shock‐heated CH 4 :D 2 :Ar = 9.70:9.86:80.44 mixture was monitored by coincidence absorption of the 2948 cm −1 He‐Ne laser line over the shockfront temperature range of 1900–2300K. Comparison with CH 4 pyrolysis results by means of computer simulations suggested that atom and free radical chains are responsible for the homogeneous D/H exchange reaction on CH 4 . Additional simulations for the experimental conditions of previous single‐pulse shock tube experiments led to the recognition of a high sensitivity of the exchange rate to trace amounts of hydrocarbon impurity and to the dissociation rate of CH 4 .
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