Ketones emissions

Martin, R. S., Villanueva, I., Zhang, J., and Popp, C. J., Nonmethane hydrocarbon, monocarboxylic acid, and low molecular weight aldehyde and ketone emissions from vegetation in central New Mexico, Environ. Sci. TechnoL, 33, 2186-2192, 1999. 

Xia and Advincula have prepared copolymers 146 containing holetransporting carbazole units by Yamamoto copolymerisation (Scheme 68) [247]. Cyclic voltammetry showed that the HOMO energy level increased from 5.8 eV to 5.6 eV with 10 mol % carbazole and to 5.5 eV with 30 mol % carbazole. They also found that films of these copolymers showed stabler blue PL than the homopolymer 89 with the green ketone emission band appearing only slowly upon aimealing at 200 °C. 

Ketones are emitted directly to the atmosphere, and their sources were discussed in detail in chapter I. In the U.K. acetone and butanone comprise about 1% and 5%, respectively, of the total anthropogenic emissions of oxygenated compounds, and 1.6% and 1.1%, respectively, of the total anthropogenic emissions of nonmethane volatile organic compounds. Ketone emissions from solvents (both industrial and personal) are substantial emissions from both gasoline- and diesel-fueled vehicles also contribute. Ketones are also formed extensively in the atmosphere in the oxidation of other compounds. Acetone, for example is formed in the OH-initiated oxidation of propane, iio-butane, iso-pentane, and neopentane and from a number of higher hydrocarbons. It is also formed in the oxidation of terpenes. The distribution, sources, and sinks of acetone in the atmosphere have been analyzed by Simpson et al. (1994). Methyl vinyl ketone is an important first generation product in the OH-initiated oxidation of isoprene. 

The 1990 Clean Air Act Amendments Hst 189 hazardous air pollutants (HAPs) that the EPA must regulate to enforce maximum achievable control technology (MACT) to standards which are to be set by the year 2000. The 33/50 project calls for reduction of emissions of 17 specified solvents to predetermined levels by 1995. The SARA statute provides a mechanism by which the community can be informed of the existence, quantities, and releases of toxic chemicals, and requires that anyone releasing specific toxic chemicals above a threshold level to annually submit a toxic chemical release form to the EPA. The status of various ketones under these regulations is shown in Table 4. 

The impact of the regulations in Table 4 is to require users and producers of VOC ketones to limit release by either reformulating to new solvent systems, to install environmental control systems which recover and recycle solvents, or reduce emissions with carbon absorption beds or incineration equipment. The use of some individual ketones will decline further, but the overall short-term use of ketones is forecast to remain stable (10). 

Reformulating to reduce HAP solvents frequently means that solvent blend costs increase. The newer blends are generally not be as effective. For example, many coatings were usually formulated using ketones as the active solvents with aromatic hydrocarbons as diluents. This combination produced the most cost-effective formulations. However, when MEK, MIBK, toluene, and xylene became HAP compounds, less-effective solvents had to be used for reformulation. Esters are the most common ketone replacements, and aUphatic diluents would replace the aromatic hydrocarbons. In this situation, more strong solvent is required compared to the ketone/aromatic formulation and costs increase. The combination of reduced VOC emissions and composition constraints in the form of HAP restrictions have compHcated the formulator s task. 

Sources. Methyl ethyl ketone (MEK) is used in some r neries as a solvent in lube oil dewaxing. Its extremely volatile characteristic makes fugitive emissions its primary source of releases to the environment. 

Adsorption, which utilizes the ability of a solid adsorbent to adsorb specific components from a gaseous or a liquid solution onto its surface. Examples of adsorption include the use of granular activated carbon for the removal of ben-zene/toluene/xylene mixtures from underground water, the separation of ketones from aqueous wastes of an oil refinery, aad the recovery of organic solvents from the exhaust gases of polymer manufacturing facilities. Other examples include the use of activated alumina to adsorb fluorides and arsenic from metal-finishing emissions. 

A singlet precursor has, however, been proposed for 4,4,4-triohloro-2-methyl-1-butene (17) produced in the photolysis of isomesityl oxide (18) in carbon tetrachloride solution on the basis of its all-emission spectrum (DoMinh, 1971). There remains some ambiguity, however, about the detailed route by which 17 is formed. Moreover there is other evidence suggesting that ketone photolysis in carbon tetrachloride is different CI3C. CHaCiMe) CHa CH3. CO. CHa. C(Me) CHa... 

Norrish Type I cleavage of cyclic ketones necessarily yields biradicals, and in certain cases (e.g., cycloheptanone, camphor) strong emissions due to T i S mixing have been reported (Gloss and Doubleday, 1972). 

Aromatic ketones Acetophone Auto plant emissions — No data... 

Since the phosphorescence emission from (6) (68.8 kcal/mole) is very similar in energy and vibrational structure to benzophenone, and has a short lifetime (0.5 msec), it was proposed that the photorearrangement takes place via the triplet state. A Zimmerman-like mechanism is as follows for the formation of the cyclopropyl ketone (7) from dienone (6) ... 

Scheme 6 The light emission from excited triplet ketones and singlet oxygen.

Beside the phosphorescence of the carbonyl compounds produced in autoxidation reactions, there is some additional luminescence by singlet oxygen 14,43) it js sometimes difficult to differentiate between emission and the longer-wavelength part of the ketone phosphorescence 38>. 

The yellow-green chemiluminescence of firefly luciferin is evidently dependent on the enol form of the thiazolinone 109a, for 5.5-dimethyl-luciferin 116a which does not yield an enolizable ketone does not exhibit a yellow-greenish emission on addition of excess base only red emission is observed. 

N-methylcarbamate and N,N -dimethylcarbamates have been determined in soil samples by hydrolyses with sodium bicarbonate and the resulting amines reacted with 4-chloro-7-nitrobenzo-2,l,3-Oxadiazole in isobutyl methyl ketone solution to produce fluorescent derivatives [81]. These derivatives were separated by thin layer chromatography on silica gel G or alumina with tetrahydrofuran-chloroform (1 49) as solvent. The fluorescence is then measured in situ (excitation at 436 nm, emission at 528 and 537nm for the derivatives of methylamine and dimethylamine respectively). The... 

Wanatabe et al. [57] have described a method for the separation and determination of siloxanes in sediment, using inductively coupled plasma emission spectrometry. The organosilicon extract with petroleum ether is evaporated to dryness. The damp residue is dissolved in methyl isobutyl ketone, aspirated into the plasma. The detection limit is O.Olmg kg-1. Recoveries are about 50% with a coefficient of variation of about 11%. 

A method with LOQ at ppt levels was developed based on LLE followed by GC-AFID for the determination of trace concentrations of nitrobenzene, l-chloro-2-nitrobenzene and synthetic fragrances such as musk xylene (223) and musk ketone (224). The method was applied to study the distribution of these compounds in environmental samples of North Sea waters460. GC with atomic emission detection (AED) has been successfully applied to the determination of nitro musks in human adipose tissues, at ppb concentration levels. A clean-up procedure for nonpolar substances and element-specific detection with AED enabled for the first time target screening analysis for lipophilic nitro aromatic compounds. The lack of sensitivity of AED was compensated by higher concentrations of the extracts... 

Lastly, photochemically unstable ligands should be avoided. Re(bpy)(CO)3Cl shows a moderately efficient MLCT emission at room temperature (R. M. Ballew, unpublished results from our laboratory). However, the apparently closely related Re(dpk)(CO)3Cl (dpk = 2,2 -dipyridyl ketone) shows a benzophenone like phosphorescence at 77K indicating that the n-n excited state of the ketone in complex is the lowest state of the complex. No luminescence is seen at room temperature, and even at 77K the dpk triplet state is such a powerful hydrogen atom extractor that it removes protons from alcohol glasses as seen by the formation of the intense blue color of the keto free radical. The absence of an MLCT emission is caused by the greater difficulty of reducing dpk relative to bpy, which pushes the MLCT states above the dpk ligand states. 

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