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CO 2 laser‐induced decomposition of ethanol
Author(s) -
Holbrook K. A.,
Oldershaw G. A.,
Shaw C. J.
Publication year - 1993
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550250410
Subject(s) - chemistry , fluence , decomposition , photodissociation , irradiation , carbon monoxide , absorption (acoustics) , thermal decomposition , hydrogen , methane , analytical chemistry (journal) , photochemistry , ethanol , yield (engineering) , absorption cross section , organic chemistry , cross section (physics) , thermodynamics , optics , ion , physics , quantum mechanics , nuclear physics , catalysis
The multiple photon absorption and decomposition of ethanol irradiated by pulsed 9P18 infrared radiation (1048.7 cm −1 ) from a TEA CO 2 laser has been studied in the fluence range 15 to 5 J cm −2 . The absorption cross‐section is pressure‐dependent due to rapid collisional rotational hole‐filling. At low pressures the only important decomposition channel following absorption is molecular dehydration of ethanol to yield ethene, but at higher pressures hydrogen, methane, carbon monoxide, ethane, and ethyne are also produced. In the irradiation of pure ethanol under ‘collision‐free’ conditions, thermal decomposition following collisional redistribution of energy makes only a small contribution to the overall decomposition yield at fluences above 3.5 J cm −2 but may become more significant at lower fluences. Modelling using RRKM calculations has been employed to link measured absorbed energies to extents of decomposition of ethanol. Both these calculations and the absorption measurements indicate that at low pressures only a fraction of the irradiated ethanol molecules absorb the 9P18 radiation. © 1993 John Wiley & Sons, Inc.