Competing reaction channels in IR-laser-induced unimolecular reactions
The competing reaction channels in the unimolecular decomposition of two molecules, formaldehyde and tetralin were studied. A TEA CO/sub 2/ laser was used as the excitation source in all experiments. The dissociation of D/sub 2/CO was studied by infrared multiphoton dissociation (MPD) and the small-molecule nature of formaldehyde with regard to MPD was explored. The effect of collisions in MPD were probed by the pressure dependence of the MPD yield and ir fluorescence from multiphoton excited D/sub 2/CO. MPD yield shows a near cubic dependence in pure D/sub 2/CO which is reduced to a 1.7 power dependence when 15 torr of NO is added. The peak amplitude of 5 ..mu..m ir fluorescence from D/sub 2/CO is proportional to the square of the D/sub 2/CO pressure in pure D/sub 2/CO or in the presence of 50 torr of Ar. Results are explained in terms of bottlenecks to excitation at the v = 1 level which are overcome by a combination of vibrational energy transfer and rotational relaxation. The radical/molecule branching ratio in D/sub 2/CO MPD was 0.10 +- 0.02 at a fluence of 125 J/cm/sup 2/ at 946.0 cm/sup -1/. The barrier height to molecular dissociation was calculated to be 3.6 +- 2.0 kcal/mole below the radical threshold or 85.0 +- 3.0 kcal/mole above the ground state of D/sub 2/CO. In H/sub 2/CO, this corresponds to 2.5 +- 2.0 kcal/mole below the radical threshold or 83.8 +- 3.0 kcal/mole above the ground state. Comparison with uv data indicate that RRKM theory is an acceptable description of formaldehyde dissociation in the 5 to 10 torr pressure range. The unimolecular decomposition of tetralin was studied by MPD and SiF/sub 4/ - sensitized pyrolysis. Both techniques induce decomposition without the interference of catalytic surfaces. Ethylene loss is identified as the lowest energy reaction channel. Dehydrogenation is found to result from step-wise H atom loss. Isomerization via disproportionation is also identified as a primary reaction channel.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- DOE Contract Number:
- W-7405-ENG-48
- OSTI ID:
- 6584141
- Report Number(s):
- LBL-12213; TRN: 81-006221
- Resource Relation:
- Other Information: Thesis
- Country of Publication:
- United States
- Language:
- English
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ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
FORMALDEHYDE
PHOTOLYSIS
TETRALIN
CARBON DIOXIDE LASERS
DEUTERIUM COMPOUNDS
DISSOCIATION
FLUORESCENCE
INFRARED RADIATION
LASER RADIATION
RADICALS
SILICON FLUORIDES
ALDEHYDES
AROMATICS
CHEMICAL REACTIONS
DECOMPOSITION
ELECTROMAGNETIC RADIATION
FLUORIDES
FLUORINE COMPOUNDS
GAS LASERS
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
HYDROGEN COMPOUNDS
LASERS
LUMINESCENCE
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADIATIONS
SILICON COMPOUNDS
400500* - Photochemistry