Atmosphere, chemistry

Gas-phase reactions play a fundamental role in nature, for example atmospheric chemistry [1, 2, 3, 4 and 5] and interstellar chemistry [6], as well as in many teclmical processes, for example combustion and exliaust fiime cleansing [7, 8 and 9], Apart from such practical aspects the study of gas-phase reactions has provided the basis for our understanding of chemical reaction mechanisms on a microscopic level. The typically small particle densities in the gas phase mean that reactions occur in well defined elementary steps, usually not involving more than three particles. 

Squires R R 1997 Atmospheric chemistry and the flowing afterglow technique J. Mass Spectrum. 32 1271-72... 

Optical metiiods, in both bulb and beam expermrents, have been employed to detemiine tlie relative populations of individual internal quantum states of products of chemical reactions. Most connnonly, such methods employ a transition to an excited electronic, rather than vibrational, level of tlie molecule. Molecular electronic transitions occur in the visible and ultraviolet, and detection of emission in these spectral regions can be accomplished much more sensitively than in the infrared, where vibrational transitions occur. In addition to their use in the study of collisional reaction dynamics, laser spectroscopic methods have been widely applied for the measurement of temperature and species concentrations in many different kinds of reaction media, including combustion media [31] and atmospheric chemistry [32]. 

References 4, 5, 6, 7, 8, 11, 12, 45, 56, 61, 64, and 70 and the foUowiag books and reports constitute an excellent Hst for additional study. Reference 7 is an especially useful resource for global atmospheric chemistry. 

J. H. Seiafeld, Atmospheric Chemistry and Physics of Air Pollution, John Wiley Sons, Inc., New York, 1986. 

Representation of Atmospheric Chemistry Through Chemical Mechanisms. A complete description of atmospheric chemistry within an air quaUty model would require tracking the kinetics of many hundreds of compounds through thousands of chemical reactions. Fortunately, in modeling the dynamics of reactive compounds such as peroxyacetyl nitrate [2278-22-0] (PAN), C2H2NO, O, and NO2, it is not necessary to foUow every compound. Instead, a compact representation of the atmospheric chemistry is used. Chemical mechanisms represent a compromise between an exhaustive description of the chemistry and computational tractabiUty. The level of chemical detail is balanced against computational time, which increases as the number of species and reactions increases. Instead of the hundreds of species present in the atmosphere, chemical mechanisms include on the order of 50 species and 100 reactions. 

Three different types of chemical mechanisms have evolved as attempts to simplify organic atmospheric chemistry surrogate (58,59), lumped (60—63), and carbon bond (64—66). These mechanisms were developed primarily to study the formation of and NO2 in photochemical smog, but can be extended to compute the concentrations of other pollutants, such as those leading to acid deposition (40,42). 

The mechanisms by which a jurisdiction develops its air pollution control strategies and episode control tactics are outlined in Fig. 5-1. Most of the boxes in the figure have already been discussed—sources, pollutant emitted, transport and diffusion, atmospheric chemistry, pollutant half-life, air quality, and air pollution effects. To complete an analysis of the elements of the air pollution system, it is necessary to explain the several boxes not vet discussed. 

Sloane, C. S., and Tesche, T. W., "Atmospheric Chemistry Models and Predictions for Climate and Air Quality." Lewis Publishers, Chelsea, Ml, 1991. 

Atmospheric chemistry influences human health, climate, food production, and through its impact on visibility, our view of the world. Chemicals in the air affect us with each breath we take. Suspended particulate matter that form from gas-phase reactions affect the amount of solar energy reaching the earth s surface. 

P. Crutzen (Max Planck Institute for Chemistry, Mainz), M. Molina (Massachusetts Institute of Technology) andF. S. Rowland (Irvine, California) work in atmospheric chemistry, particularly concerning the formation and decomposition of ozone. 

Self-Test 2.9A Write a Lewis structure for the hydrogenperoxyl radical, HOO-, which plays an important role in atmospheric chemistry and which, in the body, has been implicated in the degeneration of neurons. 

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 ). 

Sulfur forms several oxides that in atmospheric chemistry are referred to collectively as SOx (read sox ). The most important oxides and oxoacids of sulfur are the dioxide and trioxide and the corresponding sulfurous and sulfuric acids. Sulfur burns in air to form sulfur dioxide, S02 (11), a colorless, choking, poisonous gas (recall Fig. C.1). About 7 X 1010 kg of sulfur dioxide is produced annually from the decomposition of vegetation and from volcanic emissions. In addition, approximately 1 X 1011 kg of naturally occurring hydrogen sulfide is oxidized each year to the dioxide by atmospheric oxygen ... 

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 choice of a particular type of gas discharge for quantitative studies of ion-molecule reactions is essential if useful information is to be obtained from ion abundance measurements. Generally, two types of systems have been used to study ion-molecule reactions. The pulsed afterglow technique has been used successfully by Fite et al. (3) and Sayers et al. (1) to obtain information on several exothermic reactions including simple charge transfer processes important in upper atmosphere chemistry. The use of a continuous d.c. discharge was initiated in our laboratories and has been successful in both exothermic and endothermic ion-molecule reactions which occur widely within these systems. 

Clean and Polluted Air. In the development of atmospheric chemistry, there has been an historic separation between those studying processes in the natural or unpolluted atmosphere, and those more concerned with air pollution chemistry. As the field has matured, these distinctions have begun to disappear, and with this disappearance has come the realization that few regions of the troposphere are completely unaffected by anthropogenic emissions. An operational definition of clean air could be based upon either the NMHC concentration, or upon the NOjj concentration. 

---