Formaldehyde, photochemical

Benefits depend upon location. There is reason to beheve that the ratio of hydrocarbon emissions to NO has an influence on the degree of benefit from methanol substitution in reducing the formation of photochemical smog (69). Additionally, continued testing on methanol vehicles, particularly on vehicles which have accumulated a considerable number of miles, may show that some of the assumptions made in the Carnegie Mellon assessment are not vahd. Air quaUty benefits of methanol also depend on good catalyst performance, especially in controlling formaldehyde, over the entire useful life of the vehicle. 

Methanol substitution strategies do not appear to cause an increase in exposure to ambient formaldehyde even though the direct emissions of formaldehyde have been somewhat higher than those of comparable gasoline cars. Most ambient formaldehyde is in fact secondary formaldehyde formed by photochemical reactions of hydrocarbons emitted from gasoline vehicles and other sources. The effects of slightly higher direct formaldehyde emissions from methanol cars are offset by reduced hydrocarbon emissions (68). 

Methyl Isopropenyl Ketone. Methyl isopropenyl ketone [814-78-8] (3-methyl-3-buten-2-one) is a colorless, lachrymatory Hquid, which like methyl vinyl ketone readily polymerizes on exposure to heat and light. Methyl isopropenyl ketone is produced by the condensation of methyl ethyl ketone and formaldehyde over an acid cation-exchange resin at 130°C and 1.5 MPa (218 psi) (274). Other methods are possible (275—280). Methyl isopropenyl ketone can be used as a comonomer which promotes photochemical degradation in polymeric materials. It is commercially available in North America (281). 

In addition to these principal commercial uses of molybdenum catalysts, there is great research interest in molybdenum oxides, often supported on siHca, ie, MoO —Si02, as partial oxidation catalysts for such processes as methane-to-methanol or methane-to-formaldehyde (80). Both O2 and N2O have been used as oxidants, and photochemical activation of the MoO catalyst has been reported (81). The research is driven by the increased use of natural gas as a feedstock for Hquid fuels and chemicals (82). Various heteropolymolybdates (83), MoO.-containing ultrastable Y-zeoHtes (84), and certain mixed metal molybdates, eg, MnMoO Ee2(MoO)2, photoactivated CuMoO, and ZnMoO, have also been studied as partial oxidation catalysts for methane conversion to methanol or formaldehyde (80) and for the oxidation of C-4-hydrocarbons to maleic anhydride (85). Heteropolymolybdates have also been shown to effect ethylene (qv) conversion to acetaldehyde (qv) in a possible replacement for the Wacker process. 

It has also been found that there can be interactions between hydrolytic degradation and photochemical degradation. Especially in the case of melamine-formaldehyde cross-linked systems, photochemical effects on hydrolysis have been observed. 

Chemical Reactions. It burns with a luminous flame and is readily expld (Ref 2). It is reduced with Zn dust and Na hydroxide to dimethyl hydrazine (Ref 2). Action of coned HC1 forms methylhydrazine and formaldehyde (Ref 2). Treatment in anhyd eth with Na metal forms a solid adduct which gives dimethylhydrazine on addn of w (Ref 4). For a review of thermal and photochem reactions see Ref 8 Explosive Limits. In mixts with air the crit press at which exp] occurs varies inversely with temp betw 350 and 380° (Ref 6)... 

One attractive approach to photochemical conversion and storage of solar energy is photofixation of carbon dioxide to C-1 organic compounds (formic acid, formaldehyde, methanol, and methane). Photoreduction of CO2 to formic acid and formaldehyde has been demonstrated by using n-type Bi2S3 and CdS semiconductor powders (particle size 300 00 mesh) as photoelectrocatalysts in emulsions... 

The effects of transition metals on the photochemical reduction of C02 to formaldehyde (0.1 %), formaldehyde to methanol (6-8%), and methanol to methane (ca. 10 5%) were examined172 in aqueous solutions, but the yields were very low as shown in parentheses for each reaction. 

One of the considerations regarding the use of methanol as a fuel is that it emits higher amounts of formaldehyde, which is a contributor to ozone formation and a suspected carcinogen, compared to gasoline. Proponents of methanol dispute this, saying that one-third of the formaldehyde from vehicle emissions actually comes from the tailpipe, with the other two-thirds forming photochemically, once the emissions have escaped. They state that pure methanol vehicles produce only one tenth as much of the hydrocarbons that are photochemically converted to formaldehyde as do gasoline automobiles. 

Aldehydes may also be thought of as photochemical oxidants. The definition here becomes a bit hazy, because aldehydes in themselves are photooxidative reactants, as well as secondary pollutants that have adverse health effects. Referring to Figure 4-4, we note that aldehyde concentration throughout the day in Rome, Italy, seems to decay at roughly the same rate as the nitric oxide concentration. It would be expected to track the reactive fraction of the hydrocarbons, and this is also borne out approximately by the Rome data. A maximal formaldehyde concen-... 

Dodge, M. C., Formaldehyde Production in Photochemical Smog As Predicted by Three State-of-the-Science Chemical Oxidant Mechanisms, J. Geophys. Res., 95, 3635-3648 (1990). 

The development of new models for the prediction of chemical effects in the environment has improved. An Eulerian photochemical air quality model for the prediction of the atmospheric transport and chemical reactions of gas-phase toxic organic air pollutants has been published. The organic compounds were drawn from a list of 189 species selected for control as hazardous air pollutants in the Clean Air Act Amendments of 1990. The species considered include benzene, various alkylbenzenes, phenol, cresols, 1,3-butadiene, acrolein, formaldehyde, acetaldehyde, and perchloroethyl-ene, among others. The finding that photochemical production can be a major contributor to the total concentrations of some toxic organic species implies that control programs for those species must consider more than just direct emissions (Harley and Cass, 1994). This further corroborates the present weakness in many atmospheric models. 

Cyclohexylamine is reported to react with formaldehyde giving a 60% yield of 1,3-diazetidine. One additional example reports a photochemical closure of iV-cyclohexylben-zaldehydeimine (68JA1666). An excellent review covers much of the earlier work on dimerizations of isocyanates (69ACR186). Aromatic isocyanates readily dimerize to uretidinediones (l,3-diazetidine-2,4-diones) when catalyzed by trialkyl phosphites or pyridine presumably by a dipolar intermediate AH = 2.1 to 4.2 kJ mol-1, AS = -251 to -293 JK-1 mol- (Scheme 86) (66JA3582, 76JGU799). 

Three specific eye irritants have been identified in photochemical smog formaldehyde, acrolein and peroxyactyl nitrate (PAN). The possible reaction sequences are ... 

Hoare and Wellington (22) produced CH3O radicals from the photochemical (50° and 100°C.) and thermal (135°C.) decompositions of di-terf-butyl peroxide in the presence of 02. The initially formed tert-butoxy radicals decomposed to acetone plus methyl radicals, and the methyl radicals oxidized to methoxy radicals. Formaldehyde and CH3OH were products of the reaction the formation of the former was inhibited, and the latter was enhanced as the reaction proceeded. If the sole fate of CH3O were either... 

However, if the photochemical reaction is run in the presence of oxygen, then of course, the methyl radicals are oxidized, and one obtains instead methanol, formaldehyde, and their decomposition products. Now, if the vessel is pumped out after a photo-oxidation and once again a normal photolysis of acetone is run, the products in the first 10 or 15 minutes are still oxidation products rather than hydrocarbon products. It takes from 15 to 30 minutes to remove whatever it is that is attached to the wall before the normal photochemical decomposition of pure acetone products are produced. These results should remind us that oxidation system do produce species, some of which are not known or understood. 

Tracers of photochemical reactions include low-molecular-weight compounds, such as formaldehyde, pyruvate, and acetylaldehyde. The rates of these photochemical reactions are important to measure so that natural degradation of DOM can be quantified. Also, their variability due to increased ultraviolet radiation (from decreases in tropospheric ozone levels) should be studied. The ChemRawn IV conference had a major focus on photochemical reactions (Goldberg, 1988). 

A flow apparatus for detroying 98% of the w-dissolved RDX at flow rates of 2500fi/min is described in Ref 114. The photolysis products include nitrogen gas, nitrous oxide gas. nitrate and nitrite ions, formaldehyde and ammonia. One intermediate product has been identified as l-nitroso-3,5-dimtro-l,3,5-triazacyclohexane. The primary photochemical steps involved in the photolysis are postulated... 

The photochemical reactivity goes up with increasing number of methyl groups at the double bond and decreasing ionization potential28. Key intermediates in both the photochemical and the thermal oxidation of silenes 12, 7 and 13 are the siladioxetanes 14. These species are labile even in low-temperature matrices and could not be identified spectroscopically. Evidence for their formation comes from the observed oxidation products such as complexes 15 between silanones and formaldehyde and formylsilanols 16. 

A recent study of the photolysis of simple diazoalkanes 314 or diazirines 315, compounds known to lead to the formation of silenes under inert conditions, led, in oxygen-doped argon matrices, via the silene 316 to the siladioxirane 317. While previously postulated as an intermediate in silene oxidations, this is important experimental evidence for this intermediate. Continued photolysis of the system led to a compound identified as the silanone-formaldehyde complex 318, which on further irradiation led to the silanol-aldehyde 319. The latter compound itself underwent further photochemical oxidation leading to the silanediol 320160. The reactions are summarized in Scheme 58. Detailed infrared studies, including the use of isotopes, and calculations, were used to establish the structures of the compounds. 

The primary process for BCME degradation in air is believed to be reaction with photochemically-generated hydroxyl radicals,. Reaction products are believed to include chloromethyl formate, C1HC0, formaldehyde and HC1 (Cupitt 1980 EPA 1987a). The atmospheric halflife due to reaction with hydroxyl radicals is estimated to be... 

From the photochemical viewpoint considerable interest attaches to the photodecomposition of formaldehyde into CHO + H. Evidence of isotope exchange (Klein and Schoen, 1956, 1958) suggests that dissociation occurs at 3650 A even though the rotational lines are not noticeably diffuse above 3000 A. These observations are not mutually inconsistent, however, for the probability of the radiationless transition leading to... 

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