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Rate constants and Arrhenius parameters for the reactions of Cl atoms with the halogenated ethers: CF 3 CH 2 OCHF 2 , CF 3 CHClOCHF 2 , and CF 3 CH 2 OCClF 2
Author(s) -
Hickson Kevin M.,
Smith Ian W. M.
Publication year - 2001
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 - 10.1002/1097-4601(200103)33:3<165::aid-kin1010>3.0.co;2-m
Subject(s) - chemistry , arrhenius equation , reaction rate constant , ether , infrared , molecule , atmospheric temperature range , infrared spectroscopy , analytical chemistry (journal) , kinetics , activation energy , organic chemistry , thermodynamics , optics , physics , quantum mechanics
Rate constants have been determined for the reactions of Cl atoms with the halogenated ethers CF 3 CH 2 OCHF 2 , CF 3 CHClOCHF 2 , and CF 3 CH 2 OCClF 2 using a relative‐rate technique. Chlorine atoms were generated by continuous photolysis of Cl 2 in a mixture containing the ether and CD 4 . Changes in the concentrations of these two species were measured via changes in their infrared absorption spectra observed with a Fourier transform infrared (FTIR) spectrometer. Relative‐rate constants were converted to absolute values using the previously measured rate constants for the reaction, Cl + CD 4 → DCl + CD 3 . Experiments were carried out at 295, 323, and 363 K, yielding the following Arrhenius expressions for the rate constants within this range of temperature: Cl + CF 3 CH 2 OCHF 2 : k = (5.1 5 ± 0.7) × 10 −12 exp(−1830 ± 410 K/ T ) cm 3 molecule −1 s −1 Cl + CF 3 CHClOCHF 2 : k = (1.6 ± 0.2) × 10 −11 exp(−2450 ± 250 K/ T ) cm 3 molecule −1 s −1 Cl + CF 3 CH 2 OCClF 2 : k = (9.6 ± 0.4) × 10 −12 exp(−2390 ± 190 K/ T ) cm 3 molecule −1 s −1 The results are compared with those obtained previously for the reactions of Cl atoms with other halogenated methyl ethyl ethers. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 165–172, 2001