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photooxidation of n-hexanal in air光致氧化n-hexanal的空气.pdf

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photooxidation of n-hexanal in air光致氧化n-hexanal的空气

Molecules 2001, 6, 287–299 molecules ISSN 1420-3049 Photooxidation of n-Hexanal in Air 1 2 3 Jovan Tadić , Ivan Juranić and Geert K. Moortgat 1Center for Chemistry IChTM, POB 815, Studentski trg 12-16, 11001 Belgrade, Yugoslavia, Tel. ++381-11-3236-603, Fax. ++381-11-639-827 2 Faculty of Chemistry, University of Belgrade, POB 158, 11001 Belgrade, Yugoslavia 3 Max-Planck-Institut für Chemie, Atmospheric Chemistry Department, Postfach 3060, 55020 Mainz, Germany * Author to whom correspondence should be addressed; e-mail jtadic@Eunet.yu Received: 21 November 2000; in revised form 11 December 2000 / Accepted: 12 December 2000 / Published: 31 March 2001 Abstract: Dilute mixtures of hexanal in synthetic air (up to 100 ppm) were photolyzed with fluorescent UV lamps (275-380 nm) in air at 298 K. The main photooxidation products, identified and quantitatively analyzed by FTIR spectroscopy, were butene, CO, vinylalcohol and ethanal. The photolysis rates and the absolute quantum yield Φ were found to be slightly dependent on the total pressure. At 100 Torr, Φ100 = 0.43 ± 0.02, whereas at 700 Torr the total quantum yield was Φ700 = 0.38 ± 0.02. These results may be explained by the collisional deactivations of photoexcited molecules. Two decomposition channels were identified: the radical channel C H CHO → C H + HCO, and the molecular channel 5 11 5 11 C H CHO → C H + CH =CHOH, having the re