The 13C and D kinetic isotope effects in the reaction of CH4 with Cl

✍ Scribed by Karen L. Feilberg; David W. T. Griffith; Matthew S. Johnson; Claus J. Nielsen

• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: English
• Weight: 134 KB
• Volume: 37
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.20058

✦ Synopsis

Abstract

The kinetic isotope effects in the reaction of methane (CH~4~) with Cl atoms are studied in a relative rate experiment at 298 ± 2 K and 1013 ± 10 mbar. The reaction rates of ^13^CH~4~, ^12^CH~3~D, ^12^CH~2~D~2~, ^12^CHD~3~, and ^12^CD~4~ with Cl radicals are measured relative to ^12^CH~4~ in a smog chamber using long path FTIR detection. The experimental data are analyzed with a nonlinear least squares spectral fitting method using measured high‐resolution spectra as well as cross sections from the HITRAN database. The relative reaction rates of ^12^CH~4~, ^13^CH~4~, ^12^CH~3~D, ^12^CH~2~D~2~, ^12^CHD~3~, and ^12^CD~4~ with Cl are determined as k/k = 1.06 ± 0.01, k/k = 1.47 ± 0.03, k/k = 2.45 ± 0.05, k/k = 4.7 ± 0.1, k/k = 14.7 ± 0.3. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 37: 110–118, 2005