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Title: Laser flash photolysis studies of radical-radical reaction kinetics: The HO{sub 2} + IO reaction

Journal Article · · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
DOI:https://doi.org/10.1021/jp990135v· OSTI ID:355555
; ; ;  [1]
  1. Georgia Inst. of Tech., Atlanta, GA (United States)

Reactive iodine as a potential tropospheric O{sub 3} sink has received considerable attention recently. Laser flash photolysis of Cl{sub 2}/CH{sub 3}OH/O{sub 2}/I{sub 2}/NO{sub 2}/SF{sub 6}N{sub 2} mixtures at 308 nm has been coupled with simultaneous time-resolved detection of HO{sub 2} (by infrared tunable diode laser absorption spectroscopy) and IO (by visible absorption spectroscopy) to investigate the kinetics of the atmospherically important reaction HO{sub 2} + IO {r_arrow} products over the temperature range 274--373 K in N{sub 2} buffer gas at pressures of 12 and 25 Torr. All experiments were performed under near pseudo-first-order conditions with HO{sub 2} in excess over IO. At 298 K, the rate coefficient was determined to be (9.7 {+-} 2.9) {times} 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1}s{sup {minus}1}, with the primary source of uncertainty being knowledge of the infrared line strength(s) required to convert measured HO{sub 2} absorbances to absolute concentrations. The temperature dependence of the HO{sub 2} + IO rate coefficient was found to be adequately described by the Arrhenius expression k = 9.3 {times} 10{sup {minus}12} exp(680/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The results reported in this study are compared with other recent studies of HO{sub 2} + IO kinetics, and the potential roles of this reaction in atmospheric chemistry are discussed.

OSTI ID:
355555
Journal Information:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Vol. 103, Issue 17; Other Information: PBD: 29 Apr 1999
Country of Publication:
United States
Language:
English