Hydrocarbons photochemical reactions

Ozone, known for its beneficial role as a protective screen against ultraviolet radiation in the stratosphere, is a major pollutant at low altitudes (from 0 to 2000 m) affecting plants, animals and human beings. Ozone can be formed by a succession of photochemical reactions that preferentially involve hydrocarbons and nitrogen oxides emitted by the different combustion systems such as engines and furnaces. 

Methanol substitution strategies do not appear to cause an increase in exposure to ambient formaldehyde even though the direct emissions of formaldehyde have been somewhat higher than those of comparable gasoline cars. Most ambient formaldehyde is in fact secondary formaldehyde formed by photochemical reactions of hydrocarbons emitted from gasoline vehicles and other sources. The effects of slightly higher direct formaldehyde emissions from methanol cars are offset by reduced hydrocarbon emissions (68). 

Since ground-level ozone is formed by the photochemical reaction of nitrogen oxides and certain hydrocarbons, abatement strategies should focus not only on... 

Area sources of either a selected chemical or a precursor present a common problem for modeling. In particular, the rich and complex patterns of hydrocarbon emissions from general urban and industrial sources either include or might produce through atmospheric photochemical reactions some of the species on the analysis list. The treatment of such species in photochemical airshed modeling is difficult (8, 9). The effort required for any one such exercise is substantial, and the effort required for a comprehensive analysis of all urban regions relevant to this program would be prohibitive. 

Hashimoto, S. and Akimoto, H. (1989). UV absorption spectra and photochemical reactions of simple aromatic hydrocarbons in the cryogenic oxygen matrix. J. Phys. 

Scheme 2 Photochemical reaction of sulfur dioxide with hydrocarbons...

Primary pollutants are those emitted directly to the atmosphere while secondary pollutants are those formed by chemical or photochemical reactions of primary pollutants after they have been admitted to the atmosphere and exposed to sunlight. Unbumed hydrocarbons, NO, particulates, and the oxides of sulfur are examples of primary pollutants. The particulates may be lead oxide from the oxidation of tetraethyllead in automobiles, fly ash, and various types of carbon formation. Peroxyacyl nitrate and ozone are examples of secondary pollutants. 

The chemical problem here involves the photochemical and catalytic oxidation of S02 and its mixtures with the hydrocarbons and NO however the primary concern is the photochemical reactions, both gas-phase and aerosol-forming. 

Some work [5] has been performed on the photochemical reaction between sulfur dioxide and hydrocarbons, both paraffins and olefins. In all cases, mists were found, and these mists settled out in the reaction vessels as oils with the characteristics of sulfuric acids. Because of the small amounts of materials formed, great problems arise in elucidating particular steps. When NO and 02 are added to this system, the situation is most complex. Bulfalini [3] sums up the status in this way The aerosol formed from mixtures of the lower hydrocarbons with NO and S02 is predominantly sulfuric acid, whereas the higher olefin hydrocarbons appear to produce carbonaceous aerosols also, possibly organic acids, sulfonic or sulfuric acids, nitrate-esters, etc. ... 

As a last example of a molecular system exhibiting nonadiabatic dynamics caused by a conical intersection, we consider a model that recently has been proposed by Seidner and Domcke to describe ultrafast cis-trans isomerization processes in unsaturated hydrocarbons [172]. Photochemical reactions of this type are known to involve large-amplitode motion on coupled potential-energy surfaces [169], thus representing another stringent test for a mixed quantum-classical description that is complementary to Models 1 and II. A number of theoretical investigations, including quantum wave-packet studies [163, 164, 172], time-resolved pump-probe spectra [164, 181], and various mixed... 

Particular attention has been focused on the toxic effects of aromatic hydrocarbons because these chemicals have proven highly carcinogenic to humans and marine life. Of greatest concern are the PAHs, which are toxic to the benthos at the ppb level. The most common compounds are shown in Figure 28.20 their structures are based on fused aromatic rings. These high-molecular-weight compoimds are very nonpolar and, hence, have low solubilities. Once in seawater, they tend to adsorb onto particles and become incorporated in the sediments. The toxicity of PAHs is enhanced by photochemical reaction with UV radiation. Photo-activated toxicity is especially problematic in shallow-water sediments, such as found in estuaries. 

Organic aerosols formed by gas-phase photochemical reactions of hydrocarbons, ozone, and nitrogen oxides have been identified recently in both urban and rural atmospheres. Aliphatic organic nitrates, such dicarboxylic acids as adipic and glutaric acids, carboxylic acids derived from aromatic hydrocarbons (benzoic and phenylacetic acids) and from terpenes emitted by vegetation, such as pinonic acid from a pinene, have been identified. The most important contribution in this held has been that of Schuetzle et al., who used computer-controlled... 

Chemical radicals—such as hydroxyl, peroxyhydroxyl, and various alkyl and aryl species—have either been observed in laboratory studies or have been postulated as photochemical reaction intermediates. Atmospheric photochemical reactions also result in the formation of finely divided suspended particles (secondary aerosols), which create atmospheric haze. Their chemical content is enriched with sulfates (from sulfur dioxide), nitrates (from nitrogen dioxide, nitric oxide, and peroxyacylnitrates), ammonium (from ammonia), chloride (from sea salt), water, and oxygenated, sulfiirated, and nitrated organic compounds (from chemical combination of ozone and oxygen with hydrocarbon, sulfur oxide, and nitrogen oxide fragments). ... 

Eye irritation has been a common complaint of people exposed to phohx hemical air poUution. Attempts to investigate this experimentally have encountered problems, because of the subjective nature of the human response and the multiphasic photochemical reactions involved. Human studies conducted until 1970 on eye irritation were cataloged and discussed in Air Quality Criteria for Hydrocarbons. 

Kanno, S. and Nojima, K. Studies on photochemistry of aromatic hydrocarbons. V. Photochemical reaction of chlorobenzene with nitrogen oxides in air, Chemosphere, 8(4) 225-232, 1979. 

Nojima. K. and Karmo, S. Stndies on photochenristry of aromaUc hydrocarbons. Vll. Photochemical reaction of p-dichlorobenzene with nitrogen oxides in air, Chemosphere, 9(7/8) 437-440, 1980. 

Ghe, T. Mutagenicity of photochemical reaction products of polycyclic aromatic hydrocarbons with nitrite, Sci. Total Environ., 39(1/2) 161-175, 1984. 

Chlorination of Alkanes. Free-radical chlorination is the most commonly used method for the chlorination of a saturated hydrocarbon.31 106-108 111 112 Both thermal and photochemical processes may be carried out in the liquid or vapor phase. The liquid-phase photochemical procedure is preferred for polychlorination gas-phase photochemical reactions can yield either mono- or polychlorinated product. 

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