Ozone with aromatic hydrocarbons

As the reaction temperature is increased, chemiluminescence is observed in the reactions of ozone with aromatic hydrocarbons and even alkanes. Variation of temperature has been used to control the selectivity in a gas chromatography (GC) detector [35], At room temperature, only olefins are detected at a temperature of 150°C, aromatic compounds begin to exhibit a chemiluminescent response and at 250°C alkanes respond, giving the detector a nearly universal response similar to a flame ionization detector (FID). The mechanisms of these reactions are complex and unknown. However, it seems likely that oxygen atoms produced in the thermal decomposition of ozone may play a significant role, as may surface reactions with 03 and O atoms. 

The last general category—namely, the reaction of ozone with aromatic hydrocarbons, has received an enormous amount of attention by ozone chemists. Most of this attention has concerned rate and reactivity studies in an attempt to correlate these experimental quantities with some known parameters of the hydrocarbons. Several reactivity correlations have been proposed, including those with bond localization energy, atom localization energies, and oxidation-reduction potentials. This category is also represented by a paper in this section, in which a possible correlation between ozone reactivity and carcinogenicity of some polycyclic aromatic compounds is explored. 

Polycyclic hydrocarbons are extremely reactive with ozone. For example, naphthalene reacted with ozone at a rate about 1500 times faster than benzene (Hoigne and Bader, 1983b), and higher polycyclic hydrocarbons such as phenanthrene, pyrene, and benzo[a]pyrene were also extremely reactive (Butkovic et al., 1983). The experiments of Hoigne and Bader also indicate that the rate constants for reaction of ozone with aromatic hydrocarbons in water were about 100 times greater than in nonpolar solvents such as CCI4. However, aliphatic compounds did not show such a profound solvent effect. 

Another nitration procedure uses ozone and nitrogen dioxide.11 With aromatic hydrocarbons and activated derivatives, this nitration is believed to involve the radical cation of the aromatic reactant. 

FIGURE 3 12 Possible initial steps for ozone, atomic oxygen, nitrogen dioxide, and hydroxyl-radical reaction with aromatic hydrocarbons. 

In 2003, urban air pollution was monitored at 76 stations (44 and 32 operated by the Ministry of Health and the Ministry of the Environment, respectively) located in 27 cities involved in the Monitoring System (SZU, 2004). In 2003, sulphur dioxide (SO2), nitrogen oxides (NO/N02/NOx), particulate matter (TSP and/or suspended PMio fractions), and mass concentrations of selected metals (arsenic, chromium, cadmium, manganese, nickel and lead) in particulate matter samples were monitored in all the cities of the Monitoring System except for Melnik. The SO2 measurements in the Public Health Service network were terminated at all the manual stations in the cities with CHMI stations in the cities without a CHMI station, measurements are made during the heating season only). Concentrations of carbon oxide, ozone, polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs) continue to be monitored selectively in a number of the monitored cities. 

Butkovic, V., Klasinc, L., Orhanovic, Turk, J., Glisten, H. (1983) Reaction rates of polynuclear aromatic hydrocarbons with ozone in water. Environ. Sci. Technol. 17, 546-548. 

For soybean-based biodiesel at this concentration, the estimated emission impacts for percent change in emissions of NO,, particular matter (PM), HC, and CO were +20%, -10.1%, -21.1%, and -11.0%, respectively (EPA, 2002). The use of blends of biodiesel and diesel oil are preferred in engines in order to avoid some problems related to the decrease of power and torque, and to the increase of NO, emissions (a contributing factor in the localized formation of smog and ozone) that occurs with an increase in the content of pure biodiesel in a blend. Emissions of all pollutants except NO appear to decrease when biodiesel is used. The use of biodiesel in a conventional diesel engine dramatically reduces the emissions of unbumed hydrocarbons, carbon dioxide, carbon monoxide, sulfates, polycyclic aromatic hydrocarbons, nitrated polycyclic aromatic hydrocarbons, ozone-forming hydrocarbons, and particulate matter. The net contribution of carbon dioxide from biomass combustion is small. 

Alebic-Juretic, A., T. Cvita, and L. Klasinc, Heterogeneous Polycyclic Aromatic Hydrocarbon Degradation with Ozone on Silica Gel Carrier, Environ. Sci. Technol., 24, 62-66(1990). 

Pitts, J. N., Jr., H.-R. Paur, B. Zielinska, J. Arey, A. M. Winer, T. Ramdahl, and V. Mejia, Factors Influencing the Reactivity of Polycyclic Aromatic Hydrocarbons Adsorbed on Filters and Ambient POM with Ozone, Chemosphere, 15, 675-685 (1986). 

The reaction does not have preparative significance. However, it has been surmised that polycyclic aromatic hydrocarbons adsorbed on atmospheric particulate matter can become activated as a result of atmospheric oxidation. Samples of such materials could display a degree of mutagenicity not associated with inactivated hydrocarbons. Although in many cases the precise nature of the oxidant is not clear, Pitts et al.60 have been able to show that ozone can convert benzo[a] pyrene, adsorbed on a glass filter, to its 4,5-oxide (28). 

On the other hand, the indirect type of ozonation is due to the reactions of free radical species, especially the hydroxyl radical, with the organic matter present in water. These free radicals come from reaction mechanisms of ozone decomposition in water that can be initiated by the hydroxyl ion or, to be more precise, by the hydroperoxide ion as shown in reactions (4) and (5). Ozone reacts very selectively through direct reactions with compounds with specific functional groups in their molecules. Examples are unsaturated and aromatic hydrocarbons with substituents such as hydroxyl, methyl, amine groups, etc. [45,46],... 

Beltran FJ, Ovejero G, Rivas J. Oxidation of polynuclear aromatic hydrocarbons in water. 4. Ozone combined with hydrogen peroxide. Ind Eng Chem Res 1996 35 891-898. 

Physical properties such as adhesion to metals tear resistance, abrasion resistance, resistance to diffusion of gas as well as resistance to dilute and concentrated acids, aliphatic and aromatic hydrocarbons, ketones, oil and gasoline, water absorption, oxidation, ozone, sunlight, heat aging, low temperature and flame of the common elastomers are documented in the literature.114 Rating of elastomers with respect to resistance to the factors cited above are in terms of outstanding, excellent, very good, good, fair and poor. 

Oxidizer Chemical substance that causes oxygen to combine with another chemical substance examples include oxygen and hydrogen peroxide Ozone depletion Destruction of the stratospheric ozone layer that protects the Earth from harmful effects of ultraviolet radiation. Depletion of ozone layer is due to the breakdown of certain chlorine- and/or bromine-containing compounds (chlorofluorocarbons or halons), which break down when they reach the stratosphere and then catalytically destroy ozone molecules Ozone layer Protective layer in the atmosphere, about 15 miles above the ground. The ozone layer absorbs some of the sun s ultraviolet rays, thereby reducing the amount of potentially harmful radiation that reaches the Earth s surface PAHs Polycyclic aromatic hydrocarbons... 

The largest sink for alkanes in the atmosphere is reaction with OH and NO3 radicals. The formation of photochemical smog is described in detail in (Chapter 9.11, Sillman). Mono-aromatic hydrocarbons react only slowly with O3 and NO3 radicals in the troposphere. The only important atmospheric processes for mono-aromatic hydrocarbons, and naphthalene and dinaphthalenes are reactions with OH radicals (Atkinson, 1990). The products of these reactions include aldehydes, cresols, and, in the presence of NO, benzylnitrates. Methane can be an important contributor to ozone formation, especially in the remote troposphere, as described in (Chapter 9.11, Sillman). 

When a stream of ozonized oxygen or air, usually under 6% ozone, is passed through a solution of an olefin, such as 2,4,4-trimethyl-2-pentene, absorption occurs as fast as the ozone is introduced and no ozone escapes through the solution until all the olefin has been converted to ozonide. If an aromatic hydrocarbon such as benzene is ozonized rather than an aliphatic olefin, absorption of ozone is not complete and several times the theoretical amount of ozone must be used to effect complete ozoniza-tion. When a molecule has both an aromatic system and an aliphatic double bond, the aliphatic bond may react selectively, with little or no reaction with the aromatic system. Anethole will absorb a mole of ozone and produce, on hydrolysis of the ozonide, a very good yield of anise aldehyde. Complete saturation of the molecule requires almost 10 moles of ozone, however. 

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