Hydrocarbons atmospheric importance

The chapter on Dalton may correct some perennial errors, e.g. that he was an inaccurate worker, and did nothing after his proposal of the atomic theory. His early work on the physical properties of gases was recognised by his election to the Paris Institut, and if he had done nothing else it would give him a claim to be an outstanding figure of his times. His later work on the combustion of hydrocarbons is important. His explanation of the constancy of composition of the atmosphere, and of the aurora borealis, were both proposed by others (the second by Faraday) who were unaware of Dalton s publications. 

The photodecomposition of the various oxidation products of the alkanes, alkenes, and the aromatic hydrocarbons play important roles in the chemistry of the urban, mral, and remote atmospheres. These processes provide radical and other reachve products that help drive the chemistry that leads to ozone generation and other important chemistty in the troposphere. In this chapter, we have reviewed the evidence for the nature of the primary processes that occur in the aldehydes, ketones, alkyl nitrites, nittoalkanes, alkyl nitrates, peroxyacyl nitrates, alkyl peroxides, and some representative, ttopospheric, sunlight-absorbing aromatic compounds. Where sufficient data exist, estimates have been made of the rate of the photolytic processes that occur in these molecules by calculation of the photolysis frequencies ory-values. These rate coefficients allow estimation of the photochemical lifetimes of the various compounds in the atmosphere as well as the rates at which various reactive products are formed through photolysis. 

Irradiation of ethyleneimine (341,342) with light of short wavelength ia the gas phase has been carried out direcdy and with sensitization (343—349). Photolysis products found were hydrogen, nitrogen, ethylene, ammonium, saturated hydrocarbons (methane, ethane, propane, / -butane), and the dimer of the ethyleneimino radical. The nature and the amount of the reaction products is highly dependent on the conditions used. For example, the photoproducts identified ia a fast flow photoreactor iacluded hydrocyanic acid and acetonitrile (345), ia addition to those found ia a steady state system. The reaction of hydrogen radicals with ethyleneimine results ia the formation of hydrocyanic acid ia addition to methane (350). Important processes ia the photolysis of ethyleneimine are nitrene extmsion and homolysis of the N—H bond, as suggested and simulated by ab initio SCF calculations (351). The occurrence of ethyleneimine as an iatermediate ia the photolytic formation of hydrocyanic acid from acetylene and ammonia ia the atmosphere of the planet Jupiter has been postulated (352), but is disputed (353). 

Uranium hexafluoride [7783-81-5], UF, is an extremely corrosive, colorless, crystalline soHd, which sublimes with ease at room temperature and atmospheric pressure. The complex can be obtained by multiple routes, ie, fluorination of UF [10049-14-6] with F2, oxidation of UF with O2, or fluorination of UO [1344-58-7] by F2. The hexafluoride is monomeric in nature having an octahedral geometry. UF is soluble in H2O, CCl and other chlorinated hydrocarbons, is insoluble in CS2, and decomposes in alcohols and ethers. The importance of UF in isotopic enrichment and the subsequent apphcations of uranium metal cannot be overstated. The U.S. government has approximately 500,000 t of UF stockpiled for enrichment or quick conversion into nuclear weapons had the need arisen (57). With the change in pohtical tides and the downsizing of the nation s nuclear arsenal, debates over releasing the stockpiles for use in the production of fuel for civiUan nuclear reactors continue. 

Forests can act as sources of some of the trace gases in the atmosphere, such as hydrocarbons, hydrogen sulfide, NO, and NH3. Forests have been identified as emitters of terpene hydrocarbons. In 1960, Went (10) estimated that hydrocarbon releases to the atmosphere were on the order of 108 tons per year. Later work by Rasmussen (11) suggested that the release of terpenes from forest systems is 2 x 10 tons of reactive materials per year on a global basis. This is several times the anthropogenic input. Yet, it is important to remember that forest emissions are much more widely dispersed and less concentrated than anthropogenic emissions. Table 8-2 shows terpene emissions from different types of forest systems in the United States. 

Equation (12-17) is called the photostationary state expression for ozone. Upon examination, one sees that the concentration of ozone is dependent on the ratio NO2/NO for any value of k. The maximum value of k is dependent on the latitude, time of year, and time of day. In the United States, the range of k is from 0 to 0.55 min T Table 12-5 illustrates the importance of the NO2/NO ratio with respect to how much ozone is required for the photostationary state to exist. The conclusion to be drawn from this table is that most of the NO must be converted to NO2 before O3 will build up in the atmosphere. This is also seen in the diurnal ambient air patterns shown in Fig. 12-2 and the smog chamber simulations shown in Fig. 12-3. It is apparent that without hydrocarbons, the NO is not converted to NO2 efficiently enough to permit the buildup of O3 to levels observed in urban areas. 

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... 

Table 1 lA presents tabulations of the safety of important refrigerants, but this list does not include aU available refrigerants. Table 11-5 summarizes a limited list of comparative hazards to life of refrigerant gas and vapor. The current more applicable refrigerants from the m or manufacturers of the CFC and HCFC refrigerants and their azeotropes/ blends/mrxtures are included, but the list excludes the pure hydrocarbons such as propane, chlorinated hydrocarbons such as methyl chloride and others, inorganics, ammonia, carbon dioxide, etc. See Table 11-6. The CFC compounds have a longer and more serious ozone depletion potential than the HCFC compounds, because these decompose at a much lower atmospheric level and have relatively short atmospheric lifetimes therefore, they do less damage to the ozone layer. Table 11-7 summarizes alternate refrigerants of the same classes as discussed previously. Table 11-8 correlates DuPont s SUVA refrigerant numbers to the corresponding ASHRAE numbers.

No information was found on the transformation of diisopropyl methylphosphonate in the atmosphere. Based on the results of environmental fate studies of diisopropyl methylphosphonate in distilled water and natural water, photolysis (either direct or indirect) is not important in the transformation of diisopropyl methylphosphonate in aquatic systems (Spanggord et al. 1979). The ultraviolet and infrared laser-induced photodegradation of diisopropyl methylphosphonate in both the vapor or liquid phase has been demonstrated (Radziemski 1981). Light hydrocarbon gases were the principal decomposition products. Hydrogen, carbon monoxide (CO), carbon dioxide (C02), and water were also detected. 

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