TITLE

Thermal electron attachment to C6F5X and C6H5X (X=I, Br, Cl, and F)

AUTHOR(S)
Shimamori, Hiroshi; Tatsumi, Yoshitsugu; Sunagawa, Takeyoshi
PUB. DATE
November 1993
SOURCE
Journal of Chemical Physics;11/15/1993, Vol. 99 Issue 10, p7787
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Rate constants have been measured for thermal electron attachment to C6F5X (X=I, Br, Cl, F, and H) and C6H5X (X=I, Br, Cl, and F) at room temperature in N2 buffer gas (1–100 Torr) using the pulse-radiolysis microwave cavity method. For all the compounds studied, the rate constants are of the two-body type. Unexpectedly, the values for C6F5X except C6F5H are all the same (∼2×10-7 cm3 molecule-1 s-1), which are higher than most of the previous values, while that for C6F5H, measured in Xe and Ar buffer gases, is very low (7×10-12 cm3 molecule-1 s-1). For C6H5X, the value decreases dramatically with varying X from I to Br to Cl as 1.0×10-8 to 6.5×10-12 to 3×10-14 cm3 molecule-1 s-1, and that for C6H5F must be much lower than 10-13 cm3 molecule-1 s-1. These results for the magnitude of the rate constant are rationalized by the variation in the energy of a transient negative-ion state of each molecule, which results from a combination of the electron affinities of constituents (halogen atom X and C6F5 radical) and the strength of the C6F5–X (or C6H5–X) bond.
ACCESSION #
7645057

 

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