- Matrix infrared spectroscopic studies of the photo-dissociation at 266 nm of C1NO2 and of C1ONO
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Detailed infrared spectroscopic studies of the photo-dissociation at 266 nm of C1NO2 trapped in argon matrices with subsequent experiments conducted with a xenon lamp at λ > 360 nm are reported. Formation of cis and trans C1ONO in equilibrium with C1NO2 is observed after irradiation at 266 nm. λ > 360 nm the transformation of trans C1ONO into cis C1ONO occurs. On prolonged photolysis at 266 nm, C1ONO dissociates into C1ON and O(1D) atom and into C10 + NO as evidenced in reactive matrices (solid oxygen and nitrogen).
- Coanga,Schriver-Mazzuoli,Schriver,Dahoo
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p. 309 - 320
(2008/10/08)
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- Enhanced formation of ozone by the addition of chloropicrin (trichloronitromethane) to propene/NO/air/photoirradiation systems
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The photolysis of chloropicrin in air at 1 atm was performed in a 6-m3 photochemical reaction chamber with a combination of Xe arc lamps and Pyrex filters as a light source. Phosgene was obtained as one of the main products with a yield of unity. No nitrosyl chloride was observed, which supports the C-N scission mechanism for the photolysis. Photochemical ozone formation was enhanced when chloropicrin was added to the propene/NO/air/photoirradiation system after the ozone concentration maximum had been reached. The ozone- formation factor for chloropicrin under the conditions employed was, however, estimated to be 0.25 mole of ozone formed per mole of the decomposed chloropicrin. This implies that the Cl atom, itself, contributes to the destruction of ozone rather than to the formation of Ozone under the experimental conditions. NO2 released from chloropicrin is the source of enhanced ozone. If the amount of chloropicrin as a soil fumigant increases, it can cause an increase of the ozone concentration in suburban and/for rural areas.
- Hatakeyama, Shiro,Imamura, Takashi,Washida, Nobuaki
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p. 1497 - 1500
(2007/10/03)
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- Reactions of chlorine fluorides and oxyfluorides with the nitrate anion and alkali-metal fluoride catalyzed decomposition of ClF5
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The binary chlorine fluorides ClF5, ClF3, and ClF, when used in an excess, all undergo facile fluorine-oxygen exchange reactions with the nitrate anion, forming FClO2, unstable FClO, and ClONO2, respectively, as the primary products. Whereas FClO3 does not react with LiNO3 at temperatures as high as 75°C, FClO2 readily reacts with either LiNO3 or N2O5 to give ClONO2 and O2 in high yield, probably via the formation of an unstable O2ClONO2 intermediate. With an excess of ClF, chlorine nitrate undergoes a slow reaction to give FNO2 and Cl2O as the primary products, followed by Cl2O reacting with ClF to give Cl2, ClF, and FClO2. The alkali-metal fluorides CsF, RbF, and KF catalyze the decomposition of ClF5 to ClF3 and F2, which can result in the generation of substantial F2 pressures at temperatures as low as 25°C.
- Christe, Karl O.,Wilson, William W.,Wilson, Richard D.
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p. 675 - 677
(2008/10/08)
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