Nitrogen atmospheric chemistry

Nitrogen forms several oxides, with oxidation numbers ranging from - -l to +5. All nitrogen oxides are acidic oxides and some are the acid anhydrides of the nitrogen oxoacids (Table 15.2). In atmospheric chemistry, where the oxides play an important two-edged role in both maintaining and polluting the atmosphere, the) are referred to collectively as NO (read nox ). 

NOx An oxide, or mixture of oxides, of nitrogen, typically in atmospheric chemistry, noble gas A member of Group 18/VIlI of the periodic table (the helium family). 

The atmospheric chemistry of nitrogen is quite complex and involves literally hundreds or thousands of chemical reactions. Although the fluxes are much smaller than the biological fluxes, these processes are important for a variety of reasons, including impacts on climate, stratospheric ozone, and photochemical smog. In this section we present an overview of the most important processes. 

Photochemistry plays a significant role in nitrogen s atmospheric chemistry by producing reactive species (such as OH radicals). These radicals are primarily responsible for all atmospheric oxidations. However, since the photochemistry of the atmosphere is quite complex, it will not be dealt with in detail here. For an in-depth review on tropospheric photochemistry, the reader is referred to Logan et al. (1981), Finlayson-Pitts and Pitts (1986), Crutzen and Gidel (1983) or Crutzen (1988). 

Until recently the atmospheric chemistry of nitrogen-containing compounds such as the hydrazines, which are widely used as fuels in military and space vehicles, has received comparatively little attention. N,N-dimethyIhydrazine (also UDMH = unsymmetrical dimethylhydrazine) is used in liquid-fueled rockets, and thus there Is a possibility that its use, storage, and handling could result in its release in the atmosphere. 

Historically, the sulfur oxides have long been known to have a deleterious effect on the atmosphere, and sulfuric acid mist and other sulfate particulate matter are well established as important sources of atmospheric contamination. However, the atmospheric chemistry is probably not as well understood as the gas-phase photoxidation reactions of the nitrogen oxides-hydrocarbon system. The pollutants form originally from the S02 emitted to the air. Just as mobile and stationary combustion sources emit some small quantities of N02 as well as NO, so do they emit some small quantities of S03 when they bum sulfur-containing fuels. Leighton [2] also discusses the oxidation of S02 in polluted atmospheres and an excellent review by Bulfalini [3] has appeared. This section draws heavily from these sources. 

Grosjean et al. (1996) investigated the atmospheric chemistry of cyclohexene with ozone and an ozone-nitrogen oxide mixture under ambient conditions. The reaction of cyclohexene and ozone in the dark yielded pentanal and cyclohexanone. The sunlight irradiation of cyclohexene with ozone-nitrogen oxide yielded the following carbonyls formaldehyde, acetaldehyde, acetone, propanal, butanal, pentanal, and a C4 carbonyl. 

Oxides of nitrogen play a central role in essentially all facets of atmospheric chemistry. As we have seen, N02 is key to the formation of tropospheric ozone, contributing to acid deposition (some are toxic to humans and plants), and forming other atmospheric oxidants such as the nitrate radical. In addition, in the stratosphere their chemistry and that of halogens interact closely to control the chain length of ozone-destroying reactions. 

E. ATMOSPHERIC CHEMISTRY OF HNO, TABLE 7.3 Oxidized Nitrogen Distribution at Selected Locations" (Percentage of Total) 285... 

Barbara J. Finlayson-Pitts is Professor of Chemistry at the University of California, Irvine. Her research program focuses on laboratory studies of the kinetics and mechanisms of reactions in the atmosphere, especially those involving gases with liquids or solids of relevance in the troposphere. Reactions of sea salt particles to produce photochemically active halogen compounds and the subsequent fates of halogen atoms in the troposphere are particular areas of interest, as are reactions of oxides of nitrogen at aqueous and solid interfaces. Her research is currently supported by the National Science Foundation, the Department of Energy, the California Air Resources Board, the Dreyfus Foundation, and NATO. She has authored or coauthored more than 80 publications in this area, as well as a previous book, Atmospheric Chemistry Fundamentals and Experimental Techniques. 

The well known thermally induced isomerization of an isoimide to an imide was the chemistry selected to test the concept. A series of high molecular weight polyisoimides was prepared based on PMDA and pendent aromatic diamines that on thermal treatment would exhibit the required geometry for reinforcement. Polymerizations of the diamines with PMDA were carried out in DMAC (10% by weight) at room temperature in a dry nitrogen atmosphere. Subsequent cyclodehydration of the polyamic acid to the corresponding polyisoimide was... 

In this chapter we discuss the detailed chemistry of selected high-temperature processes where gas-phase reactions are important. Most research on gas-phase reactions has been motivated by environmental issues in atmospheric chemistry or in combustion. Significant advances in the detailed understanding of fuel-oxidation chemistry, as well as nitrogen, sulphur, and chlorine chemistry, have allowed development of modeling tools that can be used for design purposes for a number of combustion and industrial processes. 

Society is facing several crucial issues involving atmospheric chemistry, Species containing nitrogen are major players in each. In the troposphere, nitrogen species are catalysts in the photochemical cycles that form ozone, a major urban and rural pollutant, as well as other oxidants (references 1 and 2, and references cited therein), and they are involved in acid precipitation, both as one of the two major acids (nitric acid) and as a base (ammonia) (3, 4). In the stratosphere, where ozone acts as a shield for the... 

The nitrogen species enter the atmosphere from a variety of natural and anthropogenic sources (7). The largest sources are concentrated in urban and industrialized areas. The levels of the species in the atmosphere vary from hundreds of parts per billion by volume (ppbv, that is, 10 9 mole fraction) in these source regions to below one part per trillion by volume (pptrv, 10"12 mole fraction) in remote areas. Even at the pptrv level, these species can play significant roles in atmospheric chemistry, and measurements of species at the sub-pptrv level can yield useful information concerning atmospheric photochemistry. 

Li, and Cal profiles ai altitudes of Xrt to I00 km. The method also has been useful lor studying ihe hydroxyl free radical (OH), This radical is of principal inlerest because or ihe cataly tic role which it exerts in atmospheric chemistry. The OH radical, along with chlorine and nitrogen oxides, is involved in the ozone destruction cycle. 

Milne, P. J., and R. G. Zita. 1993. Amino acid nitrogen in atmospheric aerosols Occurrence, sources and photochemical modification. Journal of Atmospheric Chemistry 16 361-398. 

Studies of nitrogen oxide radicals in various condensed media by means of the EPR technique started about 45 years ago. Initial results were collected in [88, 28]. NxOy radicals are of interest first of all because of their toxicity and a key role in atmospheric chemistry. From this point of view, formation, stability and reactivity of these species adsorbed on the surface of nanosized metal-oxide semiconductor particles, which are photoactive and widely presented in atmosphere, are of essential importance. Principal values of g- and A-tensors for some cases are picked up in the following Table 8.4. 

Nitrogen dioxide photolysis is a key driver of tropospheric atmospheric chemistry since it leads directly to the production and eventual consumption of ozone during the daytime as follows ... 

In this chapter we will examine the atmospheric degradation mechanisms of the following important classes of anthropogenic molecules alkanes, alkenes, aromatics, nitrogen oxides, S()2, CFCs and Halons, and finally HFCs and HCFCs. Our intent is not to give an exhaustive account of the photochemical oxidation of every man-made chemical species but rather to present examples of the degradation mechanisms of a few representative members of each class of pollutant. First, we need to consider the general features of atmospheric chemistry. 

Gas-phase, solution-phase, and heterogeneous reactions all play important roles in atmospheric chemistry. The mean atmospheric composition is given in Table 1. N2, O2, and Ar comprise 99.9% of the atmosphere and, for all practical purposes, the relative proportion of these gases is constant in the lower 100 km of the atmosphere. We are concerned here with the fate of pollutants such as CO, volatile organic compounds, halocarbons, sulfur compounds, and nitrogen oxides, which are present in trace amounts and whose concentrations vary significantly both spatially and temporally. 

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