Polynuclear aromatic hydrocarbons reduction

More recently it has become apparent that proton equilibria and hence pH can be equally important in aprotic and other non-aqueous solvents. For example, the addition of a proton donor, such as phenol or water, to dimethylformamide has a marked effect on the i-E curve for the reduction of a polynuclear aromatic hydrocarbon (Peover, 1967). In the absence of a proton donor the curve shows two one-electron reduction waves. The first electron addition is reversible and leads to the formation of the anion radical while the second wave is irreversible owing to rapid abstraction of protons from the solvent by the dicarbanion. 

Composition of Parent Pitch. Once the chemical composition of the carbonizing system moves away from the comparative simplicity of polynuclear aromatic hydrocarbons to that of industrial pitches, then the pyrolysis chemistry incorporates effects caused by the presence of heteroatoms (0, N and S) and alkyl and naphthenic groups. In general terms, the system becomes more Reactive creating higher concentrations of radicals detectable by ESR. This in turn, leads to enhanced cross-linkages and polymerization of molecular constituents of any mesophase which is formed, and this causes enhanced viscosity and a reduction in size of optical texture. 

The synthesis of quinones from arenes is an area which demands further research, despite the number of reagents presently available for this transformation. This is highlighted by the synthesis of the naphthoquinone (3). Direct oxidation of the dibromoarene (1) was unsatisfactory, and therefore Bruce and coworkers had to resort to a multistep sequence involving nitration, reduction, diazotization, displacement by hydroxide and finally oxidation of the phenol (2) with Fremy s salt (Scheme 1). Although there are examples of the oxidation of polynuclear aromatic hydrocarbons to quinones, the direct oxidation of an arene to a quinone is a process not encountered in the synthesis of more complex mt ecules. 

Rappaport, S.M. Jin, Z.L. Xu, X.B. High-performance liquid chromatography with reductive electrochemical detection of mutagenic nitro-substituted polynuclear aromatic hydrocarbons in diesel exhausts. J. Chromatogr. 1982, 240, 145-154. 

A simpler way to achieve a considerable reduction in the mass of particulates emitted, is the use of special diesel oxidation catalysts (Section 1.4). They offer advantages over filtering devices as they are simple, cost effective and can also reduce the emissions of CO, gaseous hydrocarbons, aldehydes and polynuclear aromatic hydrocarbons. Their main disadvantage is that their particulate mass reduction efficiency is only about half that achieved by filtering devices. 

Themes linking polynuclear aromatic hydrocarbons to solid carbonaceous materials, including fossil fuels and graphite, are explored. X-ray diffraction proves that one may intercalate metaanthracite coal and calcined petroleum coke in the same sense that graphite may be intercalated. The chemistry of reductive protonation of large aromatic crystallites is investigated. 

An alternative starting point in chemically reacting fossil fuels is to treat them as if they were graphite. As noted earlier, graphite and larger polynuclear aromatic hydrocarbons are far from inert with respect to electron-transfer reactions, and thus the use of chemistry known to work for graphite may be of possible use in the investigation of coal, petroleum, and their derivatives. In the next two sections, we will discuss aspects of reduction and oxidation of carbonaceous solids and thereby parallel the chapters in this book on the reduction and oxidation of polynuclear aromatic hydrocarbon molecules. 

Rathkamp, G., D. Hoffmann, and E.L. Wynder Experiments on the reduction of polynuclear aromatic hydrocarbons in cigarette smoke 20th Tobacco Chemists Research Conference, Program Booklet and Abstracts, Vol. 20, Paper No. 19, 1966, p. 23. 

The process did not achieve the developer s claim of 90% overall removal of the semivolatiles present in the feedwater (on the average, a 74% reduction was achieved). However, the process does effectively remove polynuclear aromatic hydrocarbons from the feedwater and place them in the craicentrate. Overall, removal... 

Reductive Remediation of Nonhalogenated Molecules. Na/NHa treatments can also destroy nonhalogenated hazardous conqraunds. Three classes pollutants will be mentioned here polynuclear aromatic hydrocarbons (PNAs), nitro- and nitrate-type explosive wastes and chemical warfare agents. The treatment of neat sanq>les of PNAs leads to destmction efficiencies of 99.99% for many of these conq)ounds including such examples as acenaphthene, benzo[a]anthracene, benzo[b]fluoranthene, benzo[g,h,l]perylene, chrysene, fluorandiene, fluorine, naphdialene and phenanthrene. With the exception of naphthalene and anthracene, conq)lex product mixtures are formed. Radical anion formation followed by protonation occurs sequentially leading to dihydro, tetrahydro and further reduced products (see Scheme 3). Depending on the reaction conditions, dimerization of intermediate radicals can occur to give dimers in various states of reduction. 

Inhalation exposures of workers in the metals industries frequently involve a range of other chemicals. For example, in the potrooms conducting electrolytic reduction of aluminum, workers are exposed to sulfur dioxide, polynuclear aromatic hydrocarbons, coal tar pitch volatiles, CO and CO2 from the consumable petroleum coke and pitch anode to fluoride compounds from the cryolite... 

Rubbers. Plasticizers have been used in mbber processing and formulations for many years (8), although phthaHc and adipic esters have found Htde use since cheaper alternatives, eg, heavy petroleum oils, coal tars, and other predominandy hydrocarbon products, are available for many types of mbber. Esters, eg, DOA, DOP, and DOS, can be used with latex mbber to produce large reductions in T. It has been noted (9) that the more polar elastomers such as nitrile mbber and chloroprene are insufficiendy compatible with hydrocarbons and requite a more specialized type of plasticizer, eg, a phthalate or adipate ester. Approximately 50% of nitrile mbber used in Western Europe is plasticized at 10—15 phr (a total of 5000—6000 t/yr), and 25% of chloroprene at ca 10 phr (ca 2000 t/yr) is plasticized. Usage in other elastomers is very low although may increase due to toxicological concerns over polynuclear aromatic compounds (9). 

Hydriodic acid is a reagent of choice for reduction of alcohols [225], some phenols [225], some ketones [227, 228], quinones [222], halogen derivatives [22S, 229], sulfonyl chlorides [230], diazo ketones [231], azides [232], and even some carbon-carbon double bonds [233]. Under very drastic conditions at high temperatmes even polynuclear aromatics and carboxylic acids can be reduced to saturated hydrocarbons but such reactions are hardly ever used nowadays. 

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