Chemical Reviews Volume 82. Number 3
June 1982
Reactions of Radioactive Recoil Atoms with (Haio)ethylenes G. A.
BRINKMAN
chemlsby Departfrmnt. NaNonsl Inswule fw Nuclear phvslcs and H W Energy F h y s b (NIKMF. secfbn K, former IKO), P.O. Box 4395, 1009 A J Amsterdam. The Nemerlands Received August 25, 198 1
Contents I. Introductlon 11. 111. IV. V. VI. VII.
245
Fluorine
246
Chlorine
248
Tritium
251
Muonium
253
Bromine. Iodine
254
Carbon, Silicon
254
VIII. Oxygen. Sulfur, Nitrogen IX. References
255 257 Brinkman. born in 1933. is a senior researcher of the Chemistry Department of me ~aticnaiInStnute of Nuclear physics and High Energy Physics Research. NIKHEF. in Amsterdam. He joined the department as a strdent in 1955 and received his Ph.D. degree in 1961 with a thesis on the absolute standardization of radioisotopes wnh liquid scintillators. Later he investigated the reactions of energetic radioactive recoil atoms-Mu, T. ‘IC.18F, 3hCi, and 38CI-with liquid arenes and chloroethylenes. His reSearch is focused on the use of the 500 MeV electron accelerata MEA in Amsterdam. In addtiin to hot atom chemistry studies. he is investigating photonuclear reactions and dosimetric problems.
G. A.
I . Introductlon This article is mainly dealing with the reactions of radioactive recoil F, CI, T, and Mu atoms with ethylene and haloethylenes. The study of the reactions of recoil bromine and iodine is complicated by their lower reactivities and the possible involvement of neutral atoms and positive ions in ground and electronically excited states. The reactions of recoil “C atoms with ethylene are extensively studied, but the results are absolutely different from those obtained with nonradiocarbon atoms. No publication deals with 1 5 0 , and only one deals with %S, although the knowledge about reactions of nonradioactive 0 and S atoms with ethylene is quite well developed. The study about the reactions of N atoms is limited to one publication about I 3 N , the nonradioactive research is limited to the measurements of rate constants. In fact, this article deals with the reactions of three kinds of atoms: translationally excited (hot) and thermal radioactive atoms and thermal nonradioactive atoms (in the case of H atoms, some experiments with photolytically produced hot H atoms are mentioned). Atoms that are released through a nuclear reaction receive a large amount of kinetic (recoil) energy, in general on the order of kiloelectronvolts. Chemical reactions that lead to labeled stable products can only take place after the moderation of the energetic recoil atoms (by collisions with surrounding atoms and mol0009-2665/82/0782-0245$06.00/0
ecules) to energies that are in the electronvolt range. In practice, it means that no differences are expected in the chemical reactions of isotopic atoms (belonging to the same element) that are produced by different nuclear reactions and that have received different amounts of recoil energy, because the energy distribuill be all the same (an exception tions at lower energies w 1 atoms produced from “CI with may be formed by W thermal neutrons’). The production of the radioisotopes and their nuclear physical behavior will be mentioned in the following chapters? Atoms recoiling in inert3 media are slowed down to thermal kinetic energies (3/2kT= 3.7 kJ mol-’ = 0.039 eV mol-’ at 298 K) and can then react with noninert compounds that are added in low concentrations (
