Heterogeneous interactions of NO{sub 2} with aqueous surfaces

Journal Article · Thu Mar 30 04:00:00 EST 2000 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp992929f· OSTI ID:20023372

Cheung, J L; Li, Y Q; Boniface, J; Shi, Q; Davidovits, P; Worsnop, D R; Jayne, J T; Kolb, C E

Uptake of gas-phase NO{sub 2} by water was studied in both the droplet train and bubble train flow reactors. Aqueous surface reaction of NO{sub 2}(g), reported previously in the literature, is not substantiated by these studies. The uptake of NO{sub 2}(g) is a function of Henry's law coefficient (H{sub NO{sub 2}}) and the second-order NO{sub 2}(aq)-NO{sub 2}-(aq) hydrolysis reaction rate coefficient (k{sub 2}), in the form H{sub NO{sub 2}}(k{sub 2}){sup 1/2}. The NO{sub 2}(aq)-NO{sub 2}(aq) hydrolysis rate coefficient is defined by: {minus}d[NO{sub 2}(aq)]/dt = 2k{sub 2}[NO{sub 2}(aq)]{sup 2}. The coupled nature of the uptake makes it difficult to obtain reliable separate values for the two parameters H and k{sub 2}. Literature values for these parameters vary by as much as a factor of 5. With the bubble train apparatus it was possible to separate clearly the effects of solubility and reaction on NO{sub 2} gas uptake. From these measurements and analysis of literature values, recommended values of these parameters at 293 K are H{sub NO{sub 2}} = (1.4 {+-} 0.2) x 10{sup {minus}2} M atm{sup {minus}1} and k{sub 2} = (3.0 {+-} 0.9) x 10{sup 7} M{sup {minus}1} s{sup {minus}1}. At 276 K, the best estimates are H{sub NO{sub 2}} = 2.3 (+0.3--0.9) x 10{sup {minus}2} M atm{sup {minus}1} and k{sub 2} = (2.2 {+-} 0.6) x 10{sup 7} M{sup {minus}1} s{sup {minus}1}.

• Research Organization: Boston Coll., Chestnut Hill, MA (US)
• Sponsoring Organization: National Science Foundation; Environmental Protection Agency; US Department of Energy
• DOE Contract Number: FG02-91ER61208; FG02-98ER62581
• OSTI ID: 20023372
• 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: 12 Vol. 104; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
ATMOSPHERIC CHEMISTRY
DROPLETS
HYDROLYSIS
NITROGEN DIOXIDE
SOLUBILITY