scholarly journals 12C/13C kinetic isotope effects of the gas-phase reactions of isoprene, methacrolein, and methyl vinyl ketone with OH radicals

2009 ◽  
Vol 43 (19) ◽  
pp. 3103-3110 ◽  
Author(s):  
Richard Iannone ◽  
Ralf Koppmann ◽  
Jochen Rudolph
Keyword(s):  
Gas Phase ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Oh Radicals ◽  
Gas Phase Reactions ◽  
Methyl Vinyl ◽  
Kinetic Isotope

Activation of methane by gaseous platinum(II) ions PtX+ (X = H, Cl, Br, CHO)

2005 ◽  
Vol 83 (11) ◽  
pp. 1936-1940 ◽  
Author(s):  
Detlef Schröder ◽  
Helmut Schwarz
Keyword(s):  
Mass Spectrometry ◽  
Key Words ◽  
Electrospray Ionization ◽  
Gas Phase ◽  
Bond Activation ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Methane Activation ◽  
Gas Phase Reactions ◽  
Kinetic Isotope

The gas-phase reactions of methane with the platinum(II) ions PtX+ with X = H, Cl, Br, and CHO are studied by mass spectrometry. The PtX+ ions are generated by electrospray ionization of methanolic solutions of hexachloroplatinic acid and hexabromoplatinic acid, respectively. Small to moderate intramolecular kinetic isotope effects determined for the C—H(D) bond activation of CH2D2 suggest that the activation of methane by gaseous PtX+ cations is subject to thermochemical control by the product channels. In addition, the PtCl2+ cation is also able to activate methane, whereas PtCl3+ is unreactive under the conditions chosen. Key words: gas-phase reactions, mass spectrometry, methane activation, platinum bromide, platinum chloride.

scholarly journals Kinetic isotope effects in the gas phase reactions of OH and Cl with CH<sub>3</sub>Cl, CD<sub>3</sub>Cl, and <sup>13</sup>CH<sub>3</sub>Cl

2005 ◽  
Vol 5 (3) ◽  
pp. 3873-3898 ◽  
Author(s):  
A. A. Gola ◽  
B. D’Anna ◽  
K. L. Feilberg ◽  
S. R. Sellevåg ◽  
L. Bache-Andreassen ◽  
...  
Keyword(s):  
Cross Sections ◽  
Relative Rate ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Reaction Rates ◽  
Oh Radicals ◽  
Gas Phase Reactions ◽  
Global Emission ◽  
Kinetic Isotope ◽  
Fitting Method

Abstract. The kinetic isotope effects in the reactions of CH3Cl, 13CH3Cl and CD3Cl with OH radicals and Cl atoms were studied in relative rate experiments at 298±2K and 1013±10mbar. The reactions were carried out in a smog chamber using long path FTIR detection and the spectroscopic data analyzed employing a non-linear least squares spectral fitting method using measured high-resolution infrared spectra as well as absorption cross sections from the HITRAN database. The reaction rates of 13CH3Cl and CD3Cl with OH and Cl were determined relative to CH3Cl as: kOH + CH3Cl/kOH + 13CH3Cl=1.059±0.008, kOH + CH3Cl/kOH + CD3Cl=3.9±0.4, kCl + CH3Cl/kCl + 13CH3Cl=1.070±0.010 and kCl + CH3Cl/kCl + CD3Cl=4.91±0.07. The uncertainties given are 2σ from the statistical analyses and do not include possible systematic errors. The unusually large 13C kinetic isotope effect in the OH reaction of CH3Cl has important implications for the global emission inventory of CH3Cl.

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