Heterogeneous reaction HOCl + HBr {r_arrow} BrCl + H{sub 2}O on ice films

Journal Article · Thu Feb 11 04:00:00 EST 1999 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp983407n· OSTI ID:332707

Chu, L; Chu, L T ^[1]

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1. State Univ. of New York, Albany, NY (United States). Dept. of Environmental Health and Toxicology

Heterogeneous reactions on the surface of polar stratospheric clouds (PSCs) are critical to an understanding of the annual appearance of the Antarctic ozone hole. The heterogeneous reaction HOCl + HBr(s) {r_arrow} BrCl + H{sub 2}O(s) on the ice surface at 189 and 220 K has been investigated in a flow reactor interfaced with a differentially pumped quadrupole mass spectrometer. Pseudo first-order decay of HOCl over the HBr-treated ice surfaces has been determined under the condition of P{sub HOCl} < P{sub HBr}. For the HBr partial pressure in the range of 1.1 {times} 10{sup {minus}7} to 6.6 {times} 10{sup {minus}5} Torr, the reaction probability ({gamma}{sub g}) was determined in the range of 0.06 to 0.38 at 189 K. The reaction probability is in the range of 0.01 to 0.07 at 220 K for HBr partial pressure from 7.2 {times} 10{sup {minus}7} to 1.3 {times} 10{sup {minus}5} Torr. The reaction probability was found to be strongly dependent on the ice surface temperature. The reaction probability is higher at the lower temperature than that at the warmer temperature and a mechanistic explanation is provided. The true reaction probabilities ({gamma}{sub t}) of the reaction were calculated using a pore diffusion model. The kinetic analysis indicates that the heterogeneous reaction of HOCl + HBr may follow the Eley-Rideal type of mechanism. Also, the heat of uptake of HOCl on ice was determined to be about {minus}8.5 {+-} 2 kcal/mol.

• OSTI ID: 332707
• 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: 6 Vol. 103; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
AIR POLLUTION
ATMOSPHERIC CHEMISTRY
BROMIC ACID
HYPOCHLOROUS ACID
ICE
MATHEMATICAL MODELS
OZONE LAYER