Journal of Physical Chemistry A, Vol.112, No.44, 11099-11114, 2008
13C, O-18, and D Fractionation Effects in the Reactions of CH3OH Isotopologues with Cl and OH Radicals
A relative rate experiment is carried out for six isotopologues of methanol and their reactions with OH and Cl radicals. The reaction rates of CH2DOH, CHD2OH, CD3OH, (CH3OH)-C-13, and (CH3OH)-O-18 with Cl and OH radicals are measured by long-path FTIR spectroscopy relative to CH3OH at 298 +/- 2 K and 1013 +/- 10 mbar. The OH source in the reaction chamber is photolysis of ozone to produce O(D-1) in the presence of a large excess of molecular hydrogen: O(D-1) + H-2 -> OH + H. Cl is produced by the photolysis of Cl-2. The FTIR spectra are fitted using a nonlinear least-squares spectral fitting method with measured high-resolution infrared spectra as references. The relative reaction rates defined as alpha = k(light)/k(heavy) are determined to be: k(OH + CH3OH)/k(OH) + (CH3OH)-C-13 = 1.031 +/- 0.020, k(OH) + CH3OH/k(OH) + (CH3OH)-O-18 = 1.017 +/- 0.012, k(OH + CH3OH)/k(OH + CH2DOH) = 1.119 +/- 0.045, k(OH + CH3OH)/k(OH + CHD2OH) = 1.326 +/-0.021 and k(OH + CH3,OH)/k(OH + CD3OH) = 2.566 +/- 0.042, k(Cl + CH3OH)/k(Cl + 13CH3OH) = 1.055 +/- 0.016, k(Cl + CH3OH/) k(Cl + CH318OH) = 1.025 +/- 0.022, k(Cl + CH3OH)/k(Cl + CH2DOH) = 1. 162 +/-0.022 and k(Cl + CH3OH)/k(Cl + CHD2OH) = 1.536 +/- 0.060, and k(Cl + CH3OH)/k(Cl + CD3OH) = 3.011 +/- 0.059. The errors represent 2 sigma from the statistical analyses and do not include possible systematic errors. Ground-state potential energy hypersurfaces of the reactions were investigated in quantum chemistry calculations at the CCSD(T) level of theory with an extrapolated basis set. The H-2, C-13, and O-18 kinetic isotope effects of the OH and Cl reactions with CH3OH were further investigated using canonical variational transition state theory with small curvature tunneling and compared to experimental measurements as well as to those observed in CH4 and several other substituted methane species.