Pulse radiolysis of alkane/CCl/sub 4/ glasses and liquids
The pulse radiolysis of 3-methylpentane (3MP) glasses and liquids, containing CCl/sub 4/ and various electron and positive ion scavengers, was studied at 75, 77, 85, 95, and 123 K. The results are consistent with a mechanism in which CCl/sub 4/ reacts with excess electrons to form CCl/sub 4//sup -/ (lambda/sub max/ = 370 nm) which dissociates into CCl/sub 3/ and Cl/sup -/, followed by positive charge transfer from a cation to produce CCl/sub 3//sup +/ (lambda/sub max/ = 470 nm). At 95 K, the decay of CCl/sub 4//sup -/ and the growth of CCl/sub 3//sup +/ are complete in less than 1 ms. A value of 1.1 x 10/sup 4/ M/sup -1/ cm/sup -1/ was determined for epsilon/sub max/(CCl/sub 4//sup -/) in 3MP/CCl/sub 4/ glasses by measuring the reduction in the yield of trapped electrons which accompanied CCl/sub 4//sup -/ production. The assignment of the 370-nm band to CCl/sub 4//sup -/, rather than CCl/sub 4//sup +/ as commonly accepted, removes some perplexing problems in understanding the radiolysis of cold alkane/CCl/sub 4/ mixtures. A suggestion in the literature that the free radical CCl/sub 3/ has an absorption band at 365 nm is considered to be improbable.
- Research Organization:
- National Research Council of Canada, Ottawa, Ontario
- OSTI ID:
- 6034050
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 91:13
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ALKANES
RADIOLYSIS
CARBON TETRACHLORIDE
GLASS
ABSORPTION SPECTROSCOPY
EXPERIMENTAL DATA
LIQUIDS
LOW TEMPERATURE
PULSE TECHNIQUES
REACTION INTERMEDIATES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINATED ALIPHATIC HYDROCARBONS
DATA
DECOMPOSITION
FLUIDS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
SPECTROSCOPY
400600* - Radiation Chemistry