ESR and optical evidence on formation on the Cl sup minus. CCl sub 3 sup + ion pair in 3-methylpentane matrices. gamma. -irradiated at 77 K

Journal Article · Thu Jun 01 04:00:00 EDT 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100348a026· OSTI ID:7022075

Truszkowski, Stanislaw; Ichikawa, Takahisa ^[1]

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1. Hiroshima Univ. (Japan)

The well-known absorption band at 470 nm in CCl{sub 4}-alkane systems is investigated. The results obtained are as follows: (1) The absorption band due to the radical cation of 5-methyldecane (5MD{sup +}) in 5MD-CCl{sub 4}-3MP systems converts into the 470-nm band. (2) In the conversion, the positive charge of the 5MD{sup +} reacts with the unpaired electron of the CCl{sub 3}{sup {sm bullet}} radical. (3) CBrCl{sub 3} and CCl{sub 3}F in 3MP glasses produce the absorption bands at 480 and 438 nm, respectively, and the nature of these bands is the same with that of the 470-nm band in the all points examined. Results 1 and 2 lead to the formation of CCl{sub 3}{sup +} cations from CBrCl{sub 3} and CCl{sub 2}F{sup +} cations from CCl{sub 3}F. It is evident that the band shift observed in the case of CBrCl{sub 3} is not attributable to the free ions CCl{sub 3}{sup +} nor to the solvent-separated ion pairs Br{sup {minus}} solvent CCl{sub 3}{sup +} but to the formation of charge-transfer contact ion pairs Br{sup {minus}}...CCl{sub 3}{sup +}. Therefore, it is concluded that CCl{sub 4} and CCl{sub 3}F in 3MP produce Cl{sup {minus}}...CCl{sub 3}{sup +} and Cl{sup {minus}}...Cl{sub 2}F{sup +}, respectively. We also obtain the results that CBrF{sub 3}, CClF{sub 3}, and CCl{sub 2}F{sub 2} in 3MP glasses yield the corresponding radical anions with absorption bands at 314, 300, and 314 nm, respectively, and that these radical anions are neutralized with the migrating positive charges of the 5MD{sup +} formed.

• OSTI ID: 7022075
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:11; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTRA
ALKANES
CARBON TETRACHLORIDE
CHLORINATED ALIPHATIC HYDROCARBONS
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
INFORMATION
ION PAIRS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PENTANE
PHYSICAL RADIATION EFFECTS
RADIATION EFFECTS
SPECTRA