Reactivity trends in reactions of the nitrate radical (NO[sub 3]) with inorganic and organic cloudwater constituents

Journal Article · Mon Aug 01 04:00:00 EDT 1994 · Geochimica et Cosmochimica Acta; (United States)

DOI:https://doi.org/10.1016/0016-7037(94)90051-5· OSTI ID:6763907

Herrmann, H; Exner, M; Zellner, R ^[1]

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1. Universitaet GH, Essen (Germany)

NO[sub 3] radicals were produced by excimer laser photolysis of peroxodisulfate anions in the presence of excess nitrate. For the time-resolved detection of NO[sub 3], a sensitive laser long path absorption technique at 632.8 nm was applied. For the reaction of NO[sub 3] with H[sub 2]O[sub 2] the temperature dependent rate coefficient was found to be k[sub 1](T) = (4.0 [+-] 0.5)[center dot]10[sup 9] exp[-(2000 [+-] 850)/T] L mol[sup [minus]1] s[sup [minus]1], corresponding to k[sub 1] = (7.0 [+-] 1.2)[center dot]10[sup 6] L mol[sup [minus]1] s[sup [minus]1] at 298 K. The rate coefficients of the reactions of NO[sub 3] with acetone, tetrahydrofuran, and hydrated formaldehyde were determined at T = 298 K to be k[sub 2] = (4.4 [+-] 0.6)[center dot]10[sup 3] L mol[sup [minus]1] s[sup [minus]1], k[sub 3] = (2.1 [+-] 0.1)[center dot]10[sup 7] L mol[sup [minus]1] s[sup [minus]1], and k[sub 4] = (7.8 [+-] 1.2)[center dot]10[sup 5] L mol[sup [minus]1] s[sup [minus]1], respectively. For the reactions of NO[sub 3] with the alcohols methanol, ethanol, 1-propanol, 2-propanol, and 2-methyl-2-propanol the following rate constants at T = 298 K were obtained: k[sub 5] = (5.1 [+-] 0.3)[center dot]10[sup 5] L mol[sup [minus]1] s[sup [minus]1], k[sub 6] = (2.4 [+-] 0.5)[center dot]10[sup 6] L mol[sup [minus]1] s[sup [minus]1], k[sub 7] = (3.2 [+-] 0.1)[center dot]10[sup 6] L mol[sup [minus]1] s[sup [minus]1], k[sub 8] = (3.7 [+-] 0.9)[center dot]10[sup 6] L mol[sup [minus]1] s[sup [minus]1], and k[sub 9] = (6.6 [+-] 0.7)[center dot]10[sup 4] L mol[sup [minus]1] s[sup [minus]1], respectively. A linear relationship between the logarithm of the rate coefficients and C-H bond dissociation energies was found, which is described by the expression lg (k[sub NO[sub 3]][sup H]) = (44 [+-] 8) - (0.1 [+-] 0.02)[center dot]D[sub C-H]/kJ mol[sup [minus]1]. A comparison of aqueous phase and corresponding gas phase rate constants of NO[sub 3] provides a linear correlation.

• OSTI ID: 6763907
• Journal Information: Geochimica et Cosmochimica Acta; (United States), Journal Name: Geochimica et Cosmochimica Acta; (United States) Vol. 58:15; ISSN GCACAK; ISSN 0016-7037
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
540120* -- Environment
Atmospheric-- Chemicals Monitoring & Transport-- (1990-)
ACETONE
ALCOHOLS
ALDEHYDES
CHEMICAL REACTION KINETICS
CLOUDS
ETHANOL
FORMALDEHYDE
FURANS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROGEN PEROXIDE
HYDROXY COMPOUNDS
KETONES
KINETICS
METHANOL
NITRATES
NITROGEN COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
PROPANOLS
REACTION KINETICS
TETRAHYDROFURAN