Rate constants for reactions between atmospheric reservoir species. 2. H sub 2 O

Journal Article · Thu Jul 27 04:00:00 EDT 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100352a027· OSTI ID:7171059

Hatakeyama, Shiro; Leu, Mingtaun ^[1]

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1. California Institute of Technology, Pasadena (USA)

The kinetics of the reactions of H{sub 2}O with ClONO{sub 2}, N{sub 2}O{sub 5}, O{sub 3}, and COCl{sub 2} have been investigated by using a large-volume static cell and a Fourier transform infrared spectrometer at 296 K. Upper limits for the homogeneous gas-phase reaction rate constants of the ClONO{sub 2} + H{sub 2}O, N{sub 2}O{sub 5} + H{sub 2}O, O{sub 3} + H{sub 2}O, and COCl{sub 2} + H{sub 2}O reactions were found to be 3.4 {times} 10{sup {minus}21}, 2.8 {times} 10{sup {minus}21}, 1.1 {times} 10{sup {minus}22}, and 1.2 {times} 10{sup {minus}23}, respectively (all in units of cm{sup 3} s{sup {minus}1}), based on the observed decay rates of ClONO{sub 2}, N{sub 2}O{sub 5}, O{sub 3}, and COCl{sub 2}. Product analyses gave 0.82 {plus minus} 0.07 for the yield of HNO{sub 3} in the ClONO{sub 2} + H{sub 2}O {yields} HOCl + HNO{sub 3} reaction and 1.1 {plus minus} 0.3 for the yield of HNO{sub 3} from the N{sub 2}O{sub 5} + H{sub 2}O {yields} 2HNO{sub 3} reaction. The quoted error represents one standard deviation of the measurement. An attempt was also made to monitor possible reaction products such as H{sub 2}O{sub 2} for the O{sub 3} + H{sub 2}O reaction, and CO{sub 2} or HCl for the COCl{sub 2} + H{sub 2}O reaction. These results may be important in the elucidation of the springtime Antarctic ozone depletion over the past decade. The implication for NO{sub x} chemistry in the nighttime troposphere based on their results of the N{sub 2}O{sub 5} + H{sub 2}O reaction will be discussed.

• OSTI ID: 7171059
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:15; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400000* -- Chemistry
400500 -- Photochemistry
54 ENVIRONMENTAL SCIENCES
540110
ATMOSPHERIC CHEMISTRY
CHEMICAL REACTION KINETICS
CHEMISTRY
CHLORINE
DATA
DATA ANALYSIS
ELEMENTS
EXPERIMENTAL DATA
FLUIDS
GASES
HALOGENS
HYDROGEN COMPOUNDS
INFORMATION
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
NITROGEN COMPOUNDS
NONMETALS
NUMERICAL DATA
OXYGEN COMPOUNDS
OZONE
REACTION KINETICS
WATER