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

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

Aug 1994

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1994gecoa..58.3239h&link_type=abstract

Geochimica et Cosmochimica Acta, vol. 58, Issue 15, pp.3239-3244

Computer Science

1

Scientific paper

In an extended study on the reactivity of the nitrate radical in aqueous solution, NO 3 radicals were produced by excimer laser photolysis of peroxodisulfate anions in the presence of excess nitrate. For the time-resolved detection of NO 3 , a sensitive laser long path absorption technique at 632.8 nm was applied. For the reaction of NO 3 with H 2 O 2 (reaction 1 ) the temperature dependent rate coefficient was found to be k 1 ( T ) = (4.0 ± 0.5) · 10 9 exp[-(2000 ± 850)/ T ] mol -1 s -1 , corresponding to k 1 = (7.0 ± 1.2) · 10 6 L mol -1 s -1 at 298 K . The rate coefficients of the reactions of NO 3 with acetone (reaction 2), tetrahydrofuran (reaction 3), and hydrated formaldehyde (reaction 4) were determined at T = 298 K to be k 2 = (4.4 ± 0.6)· 10 3 L mol -1 s -1 , k 3 = (2.1 ± 0.1 )· 10 7 L mol -1 s -1 , and k 4 = (7.8 ± 1.2)· 10 5 L mol -1 s -1 , respectively. For the reactions of NO 3 with the alcohols methanol (reaction 5), ethanol (reaction 6 ), 1-propanol (reaction 7), 2-propanol (reaction 8), and 2-methyl-2-propanol (reaction 9 ) the following rate constants at T = 298 K were obtained: k 5 = (5.1 ± 0.3)·10 5 L mol -1 s -1 , k 6 = (2.4 ±0.5)·10 6 L mol -1 s -1 , k 7 = (3.2 ± 0.1)· 10 6 L mol -1 s -1 , k 8 = (3.7 ± 0.9)·10 6 L mol -1 s -1 , and k 9 = (6.6 ± 0.7)·10 4 L mol -1 s -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 No 3 H ) = (44 ±8) - (0.1 ± 0.02)· D C - H / kJ mol -1 . A comparison of aqueous phase and corresponding gas phase rate constants of NO 3 provides a linear correlation, which is expressed by Ig ( kNO 3( g ) + X ) = (0.58 ± 0.15) + (0.79 ± 0.2)·lg( k NO 3( aq ) + X ).

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