Photolysis formaldehyde

Quantum yields for formaldehyde photolysis have not received the same attention as those for ozone photolysis and are clearly important even in an unpolluted environment. The absorption spectmm is highly structured and more detailed measurements, under atmospheric conditions, are needed. In this work the uncertainty in HCHO measurements was es-... 

Thus, formaldehyde photolysis is a major source of H02 during the day ... 

CO -HCHO-air 2 NOx offgasing. Insensitive to radical source parameters but O3 formation is very sensitive to NO offgasing rates. Also can be used to obtain formaldehyde photolysis rates... 

Formaldehyde photolysis is a significant source of free radicals in the troposphere. Absorption cross sections for HCHO are given by DeMore et al. (1994). DeMore et al. (1994) give quantum yields, i and [Pg.145]

The former enters into the oxidation sequence (38)-(41) the latter undergoes oxidation to formaldehyde. Photolysis generates two new radicals and therefore augments the oxidation chain, whereas oxidation induced by OH will do so only partly by the subsequent photolysis of formaldehyde. 

Horowitz, A., Calvert, J.G. Wavelength dependence of the quantum efficiencies of the primary processes in formaldehyde photolysis at 25°C. Int. J. Chem. Kinet. 10, 805-819 (1978) Horowitz, A., Calvert, J.G. Wavelength dependence of the primary processes in acetaldehyde photolysis. J. Phys. Chem. 86, 3105-3114 (1982)... 

Smith, G.D., Molina, L.T., Molina, M.J. Measurement of radical quantum yields from formaldehyde photolysis between 269 and 339 run. J. Phys. Chem. A 106, 1233-1240 (2002)... 

Positive-Tone Photoresists based on Dissolution Inhibition by Diazonaphthoquinones. The intrinsic limitations of bis-azide—cycHzed mbber resist systems led the semiconductor industry to shift to a class of imaging materials based on diazonaphthoquinone (DNQ) photosensitizers. Both the chemistry and the imaging mechanism of these resists (Fig. 10) differ in fundamental ways from those described thus far (23). The DNQ acts as a dissolution inhibitor for the matrix resin, a low molecular weight condensation product of formaldehyde and cresol isomers known as novolac (24). The phenoHc stmcture renders the novolac polymer weakly acidic, and readily soluble in aqueous alkaline solutions. In admixture with an appropriate DNQ the polymer s dissolution rate is sharply decreased. Photolysis causes the DNQ to undergo a multistep reaction sequence, ultimately forming a base-soluble carboxyHc acid which does not inhibit film dissolution. Immersion of a pattemwise-exposed film of the resist in an aqueous solution of hydroxide ion leads to rapid dissolution of the exposed areas and only very slow dissolution of unexposed regions. In contrast with crosslinking resists, the film solubiHty is controUed by chemical and polarity differences rather than molecular size. 

Here the rate constants k refer to the rates of the numbered reactions above the value ho2/ro2 an average for different R02 entities. The A term accounts for HOjj production via ozone photolysis R1-R3, the Bj term accounts approximately for the source from aldehyde photolysis (R12 plus higher aldehydes), and the B2 term is a composite source from formaldehyde (RIO) and dicarbonyls (Cj) less the HOjj sink from PAN formation (R22) B2=Ci-C2). Values for Bj,... 

An attempt to measure the IR spectrum of the hydroxy carbene [28] after UV photolysis (A>220 nm) of formaldehyde isolated in an argon matrix was unsuccessful (Sodeau and Lee, 1978). Instead of [28] only hydroxyacetal-dehyde resulting from carbene insertion into the C—H bond of the starting formaldehyde was found in the reaction products. Due to its small size, the... 

Recently, results of careful experiments were reported by Ito et a/.101 They claimed that formic acid, formaldehyde, and methanol, which had been previously reported as photoelectrochemical reduction products of carbon dioxide, were observed also by photolysis of cell materials, such as electrolytes, including 15-crown-5 ether, and epoxy resin, which has often been used as the molding material of semiconductor electrodes in aqueous solutions. Previously reported reduction products were obtained also under nitrogen with (Table 4) and without (Table 5) a p-GaP photocathode under illumination. These precise experiments under improved conditions, where no photolytic products were observed, gave the result that the main reduction product of carbon dioxide at a p-GaP photocathode in aqueous electrolytes was formic acid. Thus, many kinds of products reported in previous papers83,97,100 were suggested to be due to photolysis of cell materials. 

The photolysis of methyl nitrite at low temperature in an argon matrix was studied157. The products include formaldehyde, and nitroxyl HNO which also reacts to form N2O and water. The 355-nm photodissociation of gaseous methyl nitrite has been studied by monitoring the nascent NO product using a two-photon laser-induced fluorescence... 

Laser-induced electronic fluorescence. Two devices reported recently look very promising for continuous atmospheric monitoring. Sensitivities of 0.6 ppb for nitrogen dioxide and ppb for formaldehyde are claimed. Careful attention to possible interference from other species is necessary. Detection of the hydroxyl radical in air ( 10 molecules/cm ) has been claimed for this technique, but it has been pointed out that this concentration seems much too high, especially because the air had been removed fix>m the sunlight 6 s before analysis spurious effects, such as photolysis of the ozone in the air by the laser beam and two-photon absorption by water vapor, might have been responsible for the hydroxyl radical that was observed. 

Photolytic. Photolysis products include carbon monoxide, ethylene, free radicals, and a polymer (Calvert and Pitts, 1966). Anticipated products from the reaction of acrolein with ozone or OH radicals in the atmosphere are glyoxal, formaldehyde, formic acid, and carbon dioxide (Cupitt,... 

Photolytic. Atkinson (1985) reported a rate constant of 2.59 x 10 " cmVmolecule-sec at 298 K. Based on an atmospheric OH concentration of 1.0 x 10 molecule/cm , the reported half-life of allyl alcohol is 0.35 d. The reaction of allyl alcohol results in the OH addition to the C=C bond (Grosjean, 1997). In a similar study, Orlando et al. (2001) studied the reaction of allyl alcohol with OH radicals at 298 K. Photolysis was conducted using a xenon-arc lamp within the range of 240-400 nm in synthetic air at 700 mmHg. A rate constant of 4.5 x 10 " cm /molecule-sec was reported. Products identified were formaldehyde, glycolaldehyde, and acrolein. 

Irradiation of gaseous formaldehyde containing an excess of nitrogen dioxide over chlorine yielded ozone, carbon monoxide, nitrogen pentoxide, nitryl chloride, nitric and hydrochloric acids. Peroxynitric acid was the major photolysis product when chlorine concentration exceeded the nitrogen dioxide concentration (Hanst and Gay, 1977). Formaldehyde also reacts with NO3 in the atmosphere at a rate of 3.2 x 10 cmVmolecule-sec (Atkinson and Lloyd, 1984). 

Photolytic. A -nitrosodimethylamine absorbs UV at 228 nm. An enhanced oxidation process equipped with UV lamps (195 to 240 nm), mineralized >99.9 % of Amitrosodimethylamine in water to concentrations <0.25 pg/L (Smith, 1992). A Teflon bag containing air and A-nitrosodimethylamine was subjected to sunlight on two different days. On a cloudy day, half of the A-nitrosodimethylamine was photolyzed in 60 min. On a sunny day, half of the A-nitrosodimethylamine was photolyzed in 30 min. Photolysis products include nitric oxide, carbon monoxide, formaldehyde, and an unidentified compound (Hanst et al, 1977). 

Tuazon et al. (1984a) investigated the atmospheric reactions of TV-nitrosodimethylamine and dimethylnitramine in an environmental chamber utilizing in situ long-path Fourier transform infared spectroscopy. They irradiated an ozone-rich atmosphere containing A-nitrosodimethyl-amine. Photolysis products identified include dimethylnitramine, nitromethane, formaldehyde, carbon monoxide, nitrogen dioxide, nitrogen pentoxide, and nitric acid. The rate constants for the reaction of fV-nitrosodimethylamine with OH radicals and ozone relative to methyl ether were 3.0 X 10 and <1 x 10 ° cmVmolecule-sec, respectively. The estimated atmospheric half-life of A-nitrosodimethylamine in the troposphere is approximately 5 min. 

Figure 18. Diazonaphthoquinone-novolac resist. The novolac (Novolak) matrix resin is prepared by acid catalyzed copolymerization of cresol and formaldehyde. The base insoluble sensitizer, a diazohaphthoquinone, undergoes photolysis to produce a carbene which then undergoes Wolff rearrangement to form a ketene. The ketene adds water which is present in, the film, to form a base soluble, indenecarboxylic acid photoproduct.

Figures 4.26, 4.27, and 4.28 show typical UV absorption spectra for some simple aldehydes and ketones (Rogers, 1990 Martinez et al., 1992 see also Cronin and Zhu, 1998, for n-pentanal). Formaldehyde stands out from the higher aldehydes and ketones in that it has a highly structured spectrum and furthermore, the absorption extends out to longer wavelengths. The latter difference is particularly important because the solar intensity increases rapidly with wavelength here (Chapter 3.C.1) and hence the photolysis rate constant for HCHO and the rate of production of free radicals...

However, as discussed in Chapter 4, the absorption spectrum of higher aldehydes cuts off at shorter wavelengths than formaldehyde. This, combined with higher quantum yields for radical production in the 290- to 340-nm range and the fact that HCHO produces 2H02 essentially immediately upon dissociation, makes the photolysis of aldehydes larger than formaldehyde less important at equal concentrations of the aldehydes. 

One example of the use of chambers to study the effects of addition of copollutants is seen in Fig. 16.9 (Pitts et al., 1976). As discussed earlier, one source of H02 free radicals in ambient air is the photolysis of formaldehyde ... 

Formaldehyde reacts rapidly in air through photolysis (see Chapter 4.M) and through attack by OH, N03, and, in coastal areas, likely chlorine atoms as well ... 

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