Growth and decay properties of trapped H and D atoms produced by the photolysis of HI, DI, and HBr in 3MP-d/sub 14/ glass. Evidence for tunneling abstraction of D from C-D bonds by H/sup 1/
Earlier results on the production of trapped hydrogen atoms (H/sub tr/) by the 254-nm photolysis of HI in 3-methylpentane-d/sub 14/ (3MP-d/sub 14/) glass at < 50 K, and on their decay, have been extended and elucidated. The profiles of growth of H/sub tr/ and trapped radicals have been explained and the mechanism for the concurrent production of D/sub tr/ has been assigned. The 254-nm photolysis of DI and the 185-nm photolysis of HBr in 3MP-d/sub 14/ at < 50 K produce trapped D and H atoms with yields and decay properties similar to H/sub tr/ produced from HI. The composite first-order decay of H/sub tr/ which is observable from 4 to 50 K on the seconds time scale for which the fractional decay rates are independent of the initial concectrations of H, I, HI, and radicals, has an activation energy of < 50 cal mol/sup -1/. The evidence strongly indicates that the rate-determining step in decay is tunneling abstraction of D from C-D bonds by H/sub tr/. 5 figures.
- Research Organization:
- Univ. of Wisconsin, Madison
- OSTI ID:
- 6480775
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 83:5; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
400500 -- Photochemistry
ACTIVATION ENERGY
ALKANES
ATOMS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DATA FORMS
DECAY
DEUTERIUM
DEUTERIUM COMPOUNDS
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
ENERGY
EXPERIMENTAL DATA
GLASS
HALOGEN COMPOUNDS
HYDRIODIC ACID
HYDROBROMIC ACID
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
INORGANIC ACIDS
IODINE COMPOUNDS
ISOLATED VALUES
ISOTOPE EFFECTS
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC SOLVENTS
PHOTOCHEMICAL REACTIONS
RADIATIONS
RADICALS
REACTION KINETICS
RESONANCE
SOLVENTS
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
TIME DEPENDENCE
TRAPPING
TUNNELING
ULTRAVIOLET RADIATION
VERY LOW TEMPERATURE