Mechanism of the formation of cationic species in the radiolysis of butyl chlorides. I. [2. 7-2. 8 MeV electron pulses; n- and sec-butyl chlorides]
Radiation chemical studies were carried out on n- and sec-butyl chlorides using low-temperature pulse radiolysis and matrix isolation techniques. The pulse radiolysis of n-butyl chloride at 133/sup 0/K yields the same absorption spectrum as observed for ..gamma..-irradiated n-butyl chloride at 77/sup 0/K. The initial spectrum has a peak at 520 nm, however, the peak shifts to 450 nm within 80 ..mu..s. The absorption decay behavior indicated that the initial spectrum is due to a long-lived species with a peak at 450 nm as well as a short-lived species with a peak at about 550 nm. The effects of additives on both species suggest that the long- and short-lived species are butene cations and n-butyl chloride cations, respectively. The spectra of butene-1, cis-butene-2, and trans-butene-2 cations obtained using a matrix isolation technique also show peaks in the vicinity of 450 nm. In a solution of 0.031 mole percent biphenyl at 133/sup 0/K, a significant amount of biphenyl cations is produced simultaneously with pulse irradiation, although they are also produced slowly by charge transfer between biphenyl molecules and n-butyl chloride and butene cations. Addition of biphenyl to n-butyl chloride at 77/sup 0/K reduces the formation of both butene and n-butyl chloride cations by the same ratio, and is accompanied by the formation of biphenyl cations. Therefore, butene and n-butyl chloride cations must originate from a common precursor, which reacts with biphenyl forming its cation. The nature of the precursor is discussed on the basis of the observed results. It is probably a vibrationally excited n-butyl chloride cation. Radiolysis of sec-butyl chloride gives results similar to n-butyl chloride.
- Research Organization:
- Inst. of Physical and Chemical Research, Saitama, Japan
- OSTI ID:
- 7353295
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 80:18; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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400600* -- Radiation Chemistry
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BEAMS
BIPHENYL
BUTANE
BUTENES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHEMISTRY
CHLORINATED ALIPHATIC HYDROCARBONS
DECOMPOSITION
ELECTRON BEAMS
ENERGY RANGE
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
KINETICS
LEPTON BEAMS
LOW TEMPERATURE
MEV RANGE
MEV RANGE 01-10
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PARTICLE BEAMS
PULSES
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIOLYSIS
REACTION KINETICS
YIELDS