147794-12-5Relevant articles and documents
Henry's law constants of some β-, γ-, and δ-hydroxy alkyl nitrates of atmospheric interest
Rudich,Treves,Shragina
, p. 1197 - 1203 (2007/10/03)
Novel synthetic methods to produce β,γ, and σ-hydroxy nitrates, which are formed via the atmospheric reaction of alkanes and alkenes, were developed using NMR and IR spectroscopies. Henry's law coefficients of C4 and C5 hydroxy nitrates at 291 ± 2 K were measured using a dynamic equilibrium system. The solubility decreased with the organic chain length and increased with increasing distance between the nitrooxy and hydroxy groups. These species divided into droplets in the presence of clouds and fogs. Appropriate parameters of hydroxy nitrates photochemical reactions, such as rate coefficients, absorption cross sections, and quantum yields were necessary to determine the atmospheric lifetime of the species. The estimated lifetime (> 2 days) implied that hydroxy nitrates are important NOx reservoir species and can survive long range transport in the troposphere, especially in dry environments.
Determination of the hydroxy nitrate yields from the reaction of C2-C6 alkenes with OH in the presence of NO
O'Brien, Jason M.,Czuba, Eva,Hastie, Donald R.,Francisco, Joseph S.,Shepson, Paul B.
, p. 8903 - 8908 (2007/10/03)
The yields of hydroxy nitrates from the reaction of selected C2-C6 alkenes with OH in the presence of NO were measured at 296 ± 3 K in a 9600 L photochemical smog chamber. Hydroxyl radicals were produced from the photolysis of isopropyl nitrite in the presence of NO. The loss of the alkene was followed using gas chromatography. The hydroxy nitrate products were determined using a combination of capillary chromatography and an organic nitrate specific chemiluminescence detector. The yield of hydroxy nitrates was observed to increase with the size of the precursor alkene as follows: ethene (0.86%), propene (1.5%), 1-butene (25%), cis-2-butene (3.4%), and 1-hexene (5.5%). Previous studies involving the production of alkyl nitrates from alkanes show a similar trend, but the yields reported here are a factor of 2-3 lower than for the corresponding simple alkylperoxy radical. The impact of a β-hydroxy group on the nitrate yield is examined using an ab initio molecular orbital study. It indicates that a hydrogen-bonded peroxy nitrite intermediate is formed, which results in a decrease in D0(O-O) for the peroxy linkage of about 8 kJ/mol. This would be expected to effectively decrease the organic nitrate yield. The implications of these findings for the organic nitrate path as an atmospheric NOx removal mechanism are discussed.
