Atmosphere photochemical smog

Effect of Initial NO2 Concentration. In laboratory studies conducted to simulate atmospheric photochemical smog, a serious effort is usually made to start the experiment with low initial concentrations of NO2. In the data of Altshuller et al. studied here [N02]o was 0.05 ppm in other studies [N02]o had lower values (15, 16, 17, 18, 19, 20), and in most of the studies reported [N02]o was not even specified. The effect of reduc-... 

Reduction of metal oxides with hydrogen is of interest in the metals refining industry (94,95) (see Metallurgy). Hydrogen is also used to reduce sulfites to sulfides in one step in the removal of SO2 pollutants (see Airpollution) (96). Hydrogen reacts directiy with SO2 under catalytic conditions to produce elemental sulfur and H2S (97—98). Under certain conditions, hydrogen reacts with nitric oxide, an atmospheric poUutant and contributor to photochemical smog, to produce N2 ... 

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). 

Nitrogen Oxides. From the combustion of fuels containing only C, H, and O, the usual ak pollutants or emissions of interest are carbon monoxide, unbumed hydrocarbons, and oxides of nitrogen (NO ). The interaction of the last two in the atmosphere produces photochemical smog. NO, the sum of NO and NO2, is formed almost entkely as NO in the products of flames typically 5 or 10% of it is subsequently converted to NO2 at low temperatures. Occasionally, conditions in a combustion system may lead to a much larger fraction of NO2 and the undeskable visibiUty thereof, ie, a very large exhaust plume. 

The important hydrocarbon classes are alkanes, alkenes, aromatics, and oxygenates. The first three classes are generally released to the atmosphere, whereas the fourth class, the oxygenates, is generally formed in the atmosphere. Propene will be used to illustrate the types of reactions that take place with alkenes. Propene reactions are initiated by a chemical reaction of OH or O3 with the carbon-carbon double bond. The chemical steps that follow result in the formation of free radicals of several different types which can undergo reaction with O2, NO, SO2, and NO2 to promote the formation of photochemical smog products. 

Combustion processes are the most important source of air pollutants. Normal products of complete combustion of fossil fuel, e.g. coal, oil or natural gas, are carbon dioxide, water vapour and nitrogen. However, traces of sulphur and incomplete combustion result in emissions of carbon monoxide, sulphur oxides, oxides of nitrogen, unburned hydrocarbons and particulates. These are primary pollutants . Some may take part in reactions in the atmosphere producing secondary pollutants , e.g. photochemical smogs and acid mists. Escaping gas, or vapour, may... 

Consider the air pollutants NO and N02, contributors to photochemical smog. Both can be formed by the reaction between atmospheric nitrogen and oxygen. At 25°C,... 

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. 

A reaction of ozone provides an example of concentration effects. Ozone in the atmosphere near the Earth s surface is a serious pollutant that damages soft tissues such as the lungs. In major urban areas, smog alerts are issued whenever there are elevated concentrations of ozone in the lower atmosphere. Nitmgen oxide, another component of photochemical smog, is a colorless gas produced in a side reaction in automobile engines. One reaction that links these species is the reaction of NO and O3 to produce O2 and NO2 ... 

A second important class of pollutant compounds resulting from combustion processes is the general class of the oxides of nitrogen (NO, NO2, NO3, N2O4, and so forth), typically denoted as NO . These NO molecules are key intermediates in the atmospheric conversion of VOCs into photochemical smog and ozone. There are three identified sources of NO molecules in combustion systems. 

VOCs - A VOC is any compound of carbon, excluding carbon monoxide, carbon dioxide, carbonic acid, metal carbides or carbonates and ammonium carbonate, which participate in atmospheric photochemical reactions1. VOCs are precursors to ground-level ozone production and various photochemical pollutants and are major components in the formation of smog through photochemical reactions2,3. There are many sources of VOCs, as will be discussed later. 

In the early 1950 s, it was reported by Haagen-Smit that many of the characteristics of photochemical smog could be explained by the presence of ozone and other photochemical oxidants. These substances, he believed, were formed in the atmosphere as a result of chemical reactions involving nitrogen oxides and hydrocarbons present in automobile exhaust. Significant quantities of nitrogen oxides were also emitted by power plants. 

Calvert, J. G., and R. D. McQuigg. The computer simulation of the rates and mechanisms of photochemical smog formation. Int. J. Chem. Kinet. Symp. 1 (Chemical Kinetics Data for the Lower and Upper Atmosphere) 113-154, 1975. 

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