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Kinetics of the reaction of OH with HI between 246 and 353 K

Journal Article · · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
DOI:https://doi.org/10.1021/jp984321x· OSTI ID:347660
;  [1]
  1. Max-Planck-Inst. fuer Chemie, Mainz (Germany). Div. of Atmospheric Chemistry

Iodine chemistry is believed to play a role in tropospheric, and, potentially, also stratospheric ozone loss. The laser-flash photolysis technique combined with resonance fluorescence detection of OH was used to investigate the kinetics of the title reaction at temperatures between 246 and 353 K and at a total pressure of 75 {+-} 1 Torr Ar. Under these conditions the rate coefficient shows a negative temperature dependence which is described by {kappa}{sub 4}(246--353 K) = 7.0{sub {minus}0.4}{sup +1.9} {times} 10{sup {minus}11}(T/298){sup 1.5{+-}0.5} cm{sup 3} s{sup {minus}1}. Both the large rate coefficient and trends in the reactivity of OH with HCl, HBr, and HI are suggestive of a reaction mechanism that proceeds without a significant activation barrier. The room temperature (294 K) rate constant is {kappa}{sub 4} = 6.5{sub {minus}0.4}{sup +2} {times} 10{sup {minus}11} cm{sup 3} s{sup {minus}1}, which is significantly larger than previous measurements. Reasons for this difference and the implications of the new rate coefficients for the lifetime of HI in the atmosphere are discussed.

OSTI ID:
347660
Journal Information:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 15 Vol. 103; ISSN 1089-5639; ISSN JPCAFH
Country of Publication:
United States
Language:
English

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