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Sökning: WFRF:(Joelsson J) > (2010-2014)

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  • Heimdal Nilsson, Elna, et al. (författare)
  • Re-evaluation of the reaction rate coefficient of CH3Br + OH with implications for the atmospheric budget of methyl bromide
  • 2013
  • Ingår i: Atmospheric Environment. - : Elsevier BV. - 1352-2310. ; 80, s. 70-74
  • Tidskriftsartikel (refereegranskat)abstract
    • The reaction rate coefficient k(CH3Br + OH) has been determined in the temperature range 298-373 K, using pulse radiolysis/UV kinetic spectroscopy, and at 298 K using a relative rate method. The Arrhenius expression obtained from a fit to the experimental results is (2.9 +/- 0.9) x 10(-12) exp(-(1230 +/- 125)/T) cm(3) molecule(-1) s(-1), which is greater than the expression currently recommended. The relative rate experiments give k(298 K) = (4.13 +/- 0.63) x 10(-14) cm(3) molecule(-1) s(-1). The results of the absolute and relative rate experiments indicate that the source budget of atmospheric CH3Br should be reinvestigated, as was recently done for CH3Cl. (C) 2013 Elsevier Ltd. All rights reserved.
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  • Joelsson, L. M. T., et al. (författare)
  • Relative rate study of the kinetic isotope effect in the (CH3D)-C-13 + Cl reaction
  • 2014
  • Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614. ; 605, s. 152-157
  • Tidskriftsartikel (refereegranskat)abstract
    • The (CH3D)-C-13/(CH4)-C-12 kinetic isotope effect, alpha((CH3D)-C-13), of CH4 + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. alpha((CH3D)-C-13) is found to be 1.60 +/- 0.04. In addition, a quantum chemistry/transition state theory model with tunneling correction is constructed and the primary cause for alpha((CH3D)-C-13) is found to be the substantially reduced reactivity of the D atom, which, in turn, can be explained by a significant increase in the reaction barrier due to changes in the vibrational zero point energy and to a lesser extent tunneling. (C) 2014 Elsevier B.V. All rights reserved.
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