Atmosphere aromatics

Nutmagul W, Cronn DR. 1985. Determination of selected atmospheric aromatic hydrocarbons at remote continental and oceanic locations using photoionization/flame-ionization detection. J Atmos Chem 2 415-433. 

Stern, J. E., Flagan, R. C.. Grosjean, D., and Seinfeld, J. H. (1987) Aerosol formation and growth in atmospheric aromatic hydrocarbon photooxidation. Environ. Sci. TechnoL, 21, 1224-1231. 

Gattermann-Koch reaction Formylation of an aromatic hydrocarbon to yield the corresponding aldehyde by treatment with CO, HCl and AICI3 at atmospheric pressure CuCl is also required. The reaction resembles a Friedel-Crafts acylation since methanoyl chloride, HCOCl, is probably involved. 

SARA (Saturates, Aromatics, Resins, Asphaltenes) analysis is widely practiced on heavy fractions such as vacuum and atmospheric residues and vacuum distillates for two purposes ... 

Around 2000, the regulations should become more severe. In this area, a European limit of benzene of 3% appears very probable certain countries such as Germany are even looking at 1%. In Italy, it was decided towards the end of 1991, to limit benzene to 2.5% for leaded and unleaded fuels in the seven largest cities characterized by having heavy atmospheric pollution concurrently, in these same cities, the overall aromatic contents of gasolines should not exceed 33%. 

More precisely, the rate of ozone formation depends closely on the chemical nature of the hydrocarbons present in the atmosphere. A reactivity scale has been proposed by Lowi and Carter (1990) and is largely utilized today in ozone prediction models. Thus the values indicated in Table 5.26 express the potential ozone formation as O3 formed per gram of organic material initially present. The most reactive compounds are light olefins, cycloparaffins, substituted aromatic hydrocarbons notably the xylenes, formaldehyde and acetaldehyde. Inversely, normal or substituted paraffins. 

Donor substituents on the vinyl group further enhance reactivity towards electrophilic dienophiles. Equations 8.6 and 8.7 illustrate the use of such functionalized vinylpyrroles in indole synthesis[2,3]. In both of these examples, the use of acetyleneic dienophiles leads to fully aromatic products. Evidently this must occur as the result of oxidation by atmospheric oxygen. With vinylpyrrole 8.6A, adducts were also isolated from dienophiles such as methyl acrylate, dimethyl maleate, dimethyl fumarate, acrolein, acrylonitrile, maleic anhydride, W-methylmaleimide and naphthoquinone. These tetrahydroindole adducts could be aromatized with DDQ, although the overall yields were modest[3]. 

In a polluted or urban atmosphere, O formation by the CH oxidation mechanism is overshadowed by the oxidation of other VOCs. Seed OH can be produced from reactions 4 and 5, but the photodisassociation of carbonyls and nitrous acid [7782-77-6] HNO2, (formed from the reaction of OH + NO and other reactions) are also important sources of OH ia polluted environments. An imperfect, but useful, measure of the rate of O formation by VOC oxidation is the rate of the initial OH-VOC reaction, shown ia Table 4 relative to the OH-CH rate for some commonly occurring VOCs. Also given are the median VOC concentrations. Shown for comparison are the relative reaction rates for two VOC species that are emitted by vegetation isoprene and a-piuene. In general, internally bonded olefins are the most reactive, followed ia decreasiag order by terminally bonded olefins, multi alkyl aromatics, monoalkyl aromatics, C and higher paraffins, C2—C paraffins, benzene, acetylene, and ethane. 

G-9 Aromatic Petroleum Resins. Feedstocks typically used for aromatic petroleum resin synthesis boil in the approximate range of 100—300°C at atmospheric pressure, with most boiling in the 130—200°C range. The C-9 designation actually includes styrene (C-8) through C-10 hydrocarbons (eg, methylindene). Many of the polymerizable monomers identified in Table 1 for coumarone—indene type cmdes from coal tar are also present in aromatic fractions from cracked petroleum distillates. Therefore, the technology developed for the polymerization of coal-tar cmdes is also appHcable to petroleum-derived aromatic feedstocks. In addition to availabiHty, aromatic petroleum resins offer several advantages over coumarone—indene resins. These include improved color and odor, as weU as uv and thermal stabiHty (46). 

Polymerization and GycliZation. Acetylene polymerizes at elevated temperatures and pressures which do not exceed the explosive decomposition point. Beyond this point, acetylene explosively decomposes to carbon and hydrogen. At 600—700°C and atmospheric pressure, benzene and other aromatics are formed from acetylene on heavy-metal catalysts. 

Iron(III) bromide [10031-26-2], FeBr, is obtained by reaction of iron or inon(II) bromide with bromine at 170—200°C. The material is purified by sublimation ia a bromine atmosphere. The stmcture of inoa(III) bromide is analogous to that of inon(III) chloride. FeBr is less stable thermally than FeCl, as would be expected from the observation that Br is a stronger reductant than CF. Dissociation to inon(II) bromide and bromine is complete at ca 200°C. The hygroscopic, dark red, rhombic crystals of inon(III) bromide are readily soluble ia water, alcohol, ether, and acetic acid and are slightly soluble ia Hquid ammonia. Several hydrated species and a large number of adducts are known. Solutions of inon(III) bromide decompose to inon(II) bromide and bromine on boiling. Iron(III) bromide is used as a catalyst for the bromination of aromatic compounds. 

Most ionic nitrations are performed at 0—120°C. For nitrations of most aromatics, there are two Hquid phases an organic and an acid phase. Sufficient pressure, usually slightly above atmospheric, is provided to maintain the Hquid phases. A large interfacial area between the two phases is needed to expedite transfer of the reactants to the interface and of the products from the interface. The site of the main reactions is often at or close to the interface (2). To provide large interfacial areas, a mechanical agitator is frequently used. 

Environmental Impact of Ambient Ozone. Ozone can be toxic to plants, animals, and fish. The lethal dose, LD q, for albino mice is 3.8 ppmv for a 4-h exposure (156) the 96-h LC q for striped bass, channel catfish, and rainbow trout is 80, 30, and 9.3 ppb, respectively. Small, natural, and anthropogenic atmospheric ozone concentrations can increase the weathering and aging of materials such as plastics, paint, textiles, and mbber. For example, mbber is degraded by reaction of ozone with carbon—carbon double bonds of the mbber polymer, requiring the addition of aromatic amines as ozone scavengers (see Antioxidants Antiozonants). An ozone decomposing polymer (noXon) has been developed that destroys ozone in air or water (157). 

The Tatoray process, which was developed by Toray Industries, Inc., and is available for Hcense through UOP, can be appHed to the production of xylenes and benzene from feedstock that consists typically of toluene [108-88-3] either alone or blended with aromatics (particularly trimethylbenzenes and ethyl-toluenes). The main reactions are transalkylation (or disproportionation) of toluene to xylene and benzene or of toluene and trimethylbenzenes to xylenes in the vapor phase over a highly selective fixed-bed catalyst in a hydrogen atmosphere at 350—500°C and 1—5 MPa (10—50 atm). Ethyl groups are... 

Air Monitoring. The atmosphere in work areas is monitored for worker safety. Volatile amines and related compounds can be detected at low concentrations in the air by a number of methods. Suitable methods include chemical, chromatographic, and spectroscopic techniques. For example, the NIOSH Manual of Analytical Methods has methods based on gas chromatography which are suitable for common aromatic and aHphatic amines as well as ethanolamines (67). Aromatic amines which diazotize readily can also be detected photometrically using a treated paper which changes color (68). Other methods based on infrared spectroscopy (69) and mass spectroscopy (70) have also been reported. 

Low temperature tars contain 30—35 wt % non aromatic hydrocarbons, ca 30% of caustic-extractable phenols in the distillate oils, and 40—50% of aromatic hydrocarbons. The latter usually contain one or more alkyl substituent groups. On atmospheric distillation, coke-oven tars yield 55—60% pitch, whereas CVR tars give 40—50% pitch. The pitch yield from low temperature tars is in the 26—30% range. 

Butadiene is a noncorrosive, colorless, flammable gas at room temperature and atmospheric pressure. It has a mildly aromatic odor. It is sparingly soluble in water, slightly soluble in methanol and ethanol, and soluble in organic solvents like diethyl ether, ben2ene, and carbon tetrachloride. Its important physical properties are summarized in Table 1 (see also references 11, 12). 1,2-Butadiene is much less studied. It is a flammable gas at ambient conditions. Some of its properties are summarized in Table 2. 

Conventional nitrocellulose lacquer finishing leads to the emission of large quantities of solvents into the atmosphere. An ingeneous approach to reducing VOC emissions is the use of supercritical carbon dioxide as a component of the solvent mixture (172). The critical temperature and pressure of CO2 are 31.3°C and 7.4 MPa (72.9 atm), respectively. Below that temperature and above that pressure, CO2 is a supercritical fluid. It has been found that under these conditions, the solvency properties of CO2 ate similar to aromatic hydrocarbons (see Supercritical fluids). The coating is shipped in a concentrated form, then metered with supercritical CO2 into a proportioning airless spray gun system in such a ratio as to reduce the viscosity to the level needed for proper atomization. VOC emission reductions of 50% or more are projected. 

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