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Thermal decomposition of CH 3 I using I‐atom absorption
Author(s) -
Kumaran S. S.,
Su M.C.,
Michael J. V.
Publication year - 1997
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/(sici)1097-4601(1997)29:7<535::aid-kin8>3.0.co;2-v
Subject(s) - chemistry , reaction rate constant , thermal decomposition , dissociation (chemistry) , torr , atmospheric temperature range , atom (system on chip) , decomposition , kinetics , molecule , computational chemistry , analytical chemistry (journal) , thermodynamics , organic chemistry , physics , computer science , embedded system , quantum mechanics
The recently developed I‐atom atomic resonance absorption spectrometric(ARAS) technique has been used to study the thermal decomposition kineticsof CH 3 I over the temperature range, 1052–1820 K. Measured rateconstants for CH 3 I(+Kr)→CH 3 +I(+Kr) between 1052 and 1616 K are bestexpressed by k (±36%)=4.36×10 −9 exp(−19858 K/T) cm 3 molecule −1 s −1 . Two unimolecular theoretical approaches were used torationalize the data. The more extensive method, RRKM analysis, indicatesthat the dissociation rates are effectively second‐order, i.e., themagnitude is 61–82% of the low‐pressure‐limit rate constantsover 1052–1616 K and 102–828 torr. With the knownE 0 =ΔH 0 0 =55.5 kcal mole −1 , theoptimized RRKM fit to the ARAS data requires (ΔE) down =590 cm −1 . © 1997 John Wiley & Sons,Inc. Int J Chem Kinet 29: 535–543, 1997.