Studies of the augmentation of reaction rates via laser irradiation in the infrared. Final report, 1 Sep 1973--31 Aug 1976. [H/sub 3/BPF/sub 3/ adduct]
The objective of this research project, to discover a reaction, involving a sizable substrate (more than three atoms) the rate of which is selectively augmented by infrared laser radiation, has been achieved. A preliminary analysis led to criteria for the selection of an optimum reaction type, and for setting the most suitable experimental parameters. The self-scavenging decomposition was studied for a borane adduct: 2 H/sub 3/BPF/sub 3/ yields B/sub 2/H/sub 6/ + 2PF/sub 3/. The relative photolytic efficiencies of the various lines emitted by a CO2 laser were measured as was also the dependence of the rate on laser power, gas pressure and reaction cell temperature. Specificity of vibrational excitation was demonstrated in several ways, most directly by the observed isotope fractionation of H/D and /sup 10/B//sup 11/B ratios. The mechanism of the photoactivation process developed is in quantitative agreement with the observed conversion. A dynamic model (based on a normal mode analysis) was proposed for the selective activation. In a parallel study of borane adducts, we evaluated the thermodynamic and kinetic rate parameters for six exchange and abstraction reactions. Rational structures were proposed for the corresponding transition states. (Author)
- Research Organization:
- Cornell Univ., Ithaca, NY (USA). Dept. of Chemistry
- OSTI ID:
- 7223218
- Report Number(s):
- AD-A-033503
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BORANES
PHOTOCHEMISTRY
BORON 10
LASER ISOTOPE SEPARATION
BORON 11
HYDROGEN ISOTOPES
PHOSPHORUS FLUORIDES
CHEMICAL REACTION KINETICS
DECOMPOSITION
DEUTERIUM
LASER RADIATION
BORON COMPOUNDS
BORON ISOTOPES
CHEMICAL REACTIONS
CHEMISTRY
ELECTROMAGNETIC RADIATION
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
ISOTOPE SEPARATION
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
PHOSPHORUS COMPOUNDS
RADIATIONS
REACTION KINETICS
SEPARATION PROCESSES
STABLE ISOTOPES
400500* - Photochemistry
400203 - Isotope Exchange & Isotope Separation- (-1987)