13C, 18O, and D Fractionation Effects in the Reactions of CH3OH Isotopologues with Cl andOH Radicals

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Standard

13C, 18O, and D Fractionation Effects in the Reactions of CH3OH Isotopologues with Cl andOH Radicals. / Feilberg, Karen; Gruber-Stadler, Margaret; Johnson, Matthew Stanley; Muhlhauser, Max; Nielsen, Claus Jørgen.

I: Journal of Physical Chemistry A, Bind 112, Nr. 44, 2008, s. 11099-11114.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt

Harvard

Feilberg, K, Gruber-Stadler, M, Johnson, MS, Muhlhauser, M & Nielsen, CJ 2008, '13C, 18O, and D Fractionation Effects in the Reactions of CH3OH Isotopologues with Cl andOH Radicals', Journal of Physical Chemistry A, bind 112, nr. 44, s. 11099-11114.

APA

Feilberg, K., Gruber-Stadler, M., Johnson, M. S., Muhlhauser, M., & Nielsen, C. J. (2008). 13C, 18O, and D Fractionation Effects in the Reactions of CH3OH Isotopologues with Cl andOH Radicals. Journal of Physical Chemistry A, 112(44), 11099-11114.

Vancouver

Feilberg K, Gruber-Stadler M, Johnson MS, Muhlhauser M, Nielsen CJ. 13C, 18O, and D Fractionation Effects in the Reactions of CH3OH Isotopologues with Cl andOH Radicals. Journal of Physical Chemistry A. 2008;112(44):11099-11114.

Author

Feilberg, Karen ; Gruber-Stadler, Margaret ; Johnson, Matthew Stanley ; Muhlhauser, Max ; Nielsen, Claus Jørgen. / 13C, 18O, and D Fractionation Effects in the Reactions of CH3OH Isotopologues with Cl andOH Radicals. I: Journal of Physical Chemistry A. 2008 ; Bind 112, Nr. 44. s. 11099-11114.

Bibtex

@article{3ce88e20bf9c11dd8e02000ea68e967b,
title = "13C, 18O, and D Fractionation Effects in the Reactions of CH3OH Isotopologues with Cl andOH Radicals",
abstract = "A relative rate experiment is carried out for six isotopologues of methanol and their reactions with OH and Clradicals. The reaction rates of CH2DOH, CHD2OH, CD3OH, 13CH3OH, and CH318OH with Cl and OH radicalsare measured by long-path FTIR spectroscopy relative to CH3OH at 298 ( 2 K and 1013 ( 10 mbar. The OHsource in the reaction chamber is photolysis of ozone to produce O(1D) in the presence of a large excess of molecularhydrogen: O(1D) + H2 f OH + H. Cl is produced by the photolysis of Cl2. The FTIR spectra are fitted using anonlinear least-squares spectral fitting method with measured high-resolution infrared spectra as references. Therelative reaction rates defined as R ) klight/kheavy are determined to be: kOH + CH3OH/kOH + 13CH3OH ) 1.031 ( 0.020,kOH + CH3OH/kOH + CH318OH ) 1.017 ( 0.012, kOH + CH3OH/kOH + CH2DOH ) 1.119 ( 0.045, kOH + CH3OH/kOH + CHD2OH )1.326 ( 0.021 and kOH + CH3OH/kOH + CD3OH ) 2.566 ( 0.042, kCl + CH3OH/kCl + 13CH3OH ) 1.055 ( 0.016, kCl + CH3OH/kCl + CH318OH ) 1.025 ( 0.022, kCl + CH3OH/kCl + CH2DOH ) 1.162 ( 0.022 and kCl + CH3OH/kCl + CHD2OH ) 1.536 (0.060, and kCl + CH3OH/kCl + CD3OH ) 3.011 ( 0.059. The errors represent 2s from the statistical analyses and do notinclude possible systematic errors. Ground-state potential energy hypersurfaces of the reactions were investigatedin quantum chemistry calculations at the CCSD(T) level of theory with an extrapolated basis set. The 2H, 13C, and18O kinetic isotope effects of the OH and Cl reactions with CH3OH were further investigated using canonicalvariational transition state theory with small curvature tunneling and compared to experimental measurements aswell as to those observed in CH4 and several other substituted methane species. Udgivelsesdato: 16 August 2008",
author = "Karen Feilberg and Margaret Gruber-Stadler and Johnson, {Matthew Stanley} and Max Muhlhauser and Nielsen, {Claus J{\o}rgen}",
note = "Paper id:: doi:10.1021/jp805643x",
year = "2008",
language = "English",
volume = "112",
pages = "11099--11114",
journal = "Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "44",

}

RIS

TY - JOUR

T1 - 13C, 18O, and D Fractionation Effects in the Reactions of CH3OH Isotopologues with Cl andOH Radicals

AU - Feilberg, Karen

AU - Gruber-Stadler, Margaret

AU - Johnson, Matthew Stanley

AU - Muhlhauser, Max

AU - Nielsen, Claus Jørgen

N1 - Paper id:: doi:10.1021/jp805643x

PY - 2008

Y1 - 2008

N2 - A relative rate experiment is carried out for six isotopologues of methanol and their reactions with OH and Clradicals. The reaction rates of CH2DOH, CHD2OH, CD3OH, 13CH3OH, and CH318OH with Cl and OH radicalsare measured by long-path FTIR spectroscopy relative to CH3OH at 298 ( 2 K and 1013 ( 10 mbar. The OHsource in the reaction chamber is photolysis of ozone to produce O(1D) in the presence of a large excess of molecularhydrogen: O(1D) + H2 f OH + H. Cl is produced by the photolysis of Cl2. The FTIR spectra are fitted using anonlinear least-squares spectral fitting method with measured high-resolution infrared spectra as references. Therelative reaction rates defined as R ) klight/kheavy are determined to be: kOH + CH3OH/kOH + 13CH3OH ) 1.031 ( 0.020,kOH + CH3OH/kOH + CH318OH ) 1.017 ( 0.012, kOH + CH3OH/kOH + CH2DOH ) 1.119 ( 0.045, kOH + CH3OH/kOH + CHD2OH )1.326 ( 0.021 and kOH + CH3OH/kOH + CD3OH ) 2.566 ( 0.042, kCl + CH3OH/kCl + 13CH3OH ) 1.055 ( 0.016, kCl + CH3OH/kCl + CH318OH ) 1.025 ( 0.022, kCl + CH3OH/kCl + CH2DOH ) 1.162 ( 0.022 and kCl + CH3OH/kCl + CHD2OH ) 1.536 (0.060, and kCl + CH3OH/kCl + CD3OH ) 3.011 ( 0.059. The errors represent 2s from the statistical analyses and do notinclude possible systematic errors. Ground-state potential energy hypersurfaces of the reactions were investigatedin quantum chemistry calculations at the CCSD(T) level of theory with an extrapolated basis set. The 2H, 13C, and18O kinetic isotope effects of the OH and Cl reactions with CH3OH were further investigated using canonicalvariational transition state theory with small curvature tunneling and compared to experimental measurements aswell as to those observed in CH4 and several other substituted methane species. Udgivelsesdato: 16 August 2008

AB - A relative rate experiment is carried out for six isotopologues of methanol and their reactions with OH and Clradicals. The reaction rates of CH2DOH, CHD2OH, CD3OH, 13CH3OH, and CH318OH with Cl and OH radicalsare measured by long-path FTIR spectroscopy relative to CH3OH at 298 ( 2 K and 1013 ( 10 mbar. The OHsource in the reaction chamber is photolysis of ozone to produce O(1D) in the presence of a large excess of molecularhydrogen: O(1D) + H2 f OH + H. Cl is produced by the photolysis of Cl2. The FTIR spectra are fitted using anonlinear least-squares spectral fitting method with measured high-resolution infrared spectra as references. Therelative reaction rates defined as R ) klight/kheavy are determined to be: kOH + CH3OH/kOH + 13CH3OH ) 1.031 ( 0.020,kOH + CH3OH/kOH + CH318OH ) 1.017 ( 0.012, kOH + CH3OH/kOH + CH2DOH ) 1.119 ( 0.045, kOH + CH3OH/kOH + CHD2OH )1.326 ( 0.021 and kOH + CH3OH/kOH + CD3OH ) 2.566 ( 0.042, kCl + CH3OH/kCl + 13CH3OH ) 1.055 ( 0.016, kCl + CH3OH/kCl + CH318OH ) 1.025 ( 0.022, kCl + CH3OH/kCl + CH2DOH ) 1.162 ( 0.022 and kCl + CH3OH/kCl + CHD2OH ) 1.536 (0.060, and kCl + CH3OH/kCl + CD3OH ) 3.011 ( 0.059. The errors represent 2s from the statistical analyses and do notinclude possible systematic errors. Ground-state potential energy hypersurfaces of the reactions were investigatedin quantum chemistry calculations at the CCSD(T) level of theory with an extrapolated basis set. The 2H, 13C, and18O kinetic isotope effects of the OH and Cl reactions with CH3OH were further investigated using canonicalvariational transition state theory with small curvature tunneling and compared to experimental measurements aswell as to those observed in CH4 and several other substituted methane species. Udgivelsesdato: 16 August 2008

M3 - Journal article

VL - 112

SP - 11099

EP - 11114

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

SN - 1089-5639

IS - 44

ER -

ID: 8804933