Nonequilibrium processes in reactions of hot tritium atoms with cooled solid targets. Influence of the atomizer temperature on formation of labeled substances

A system consisting of a cold target and “hot” atoms generated by dissociation of tritium on a tungsten wire was studied with the aim to determine conditions for preparing tritium-labeled organic compounds with the maximal radiochemical yield. The influence of the atomizer temperature on the result of the reaction of tritium atoms with amino acids and tetraalkylammonium bromides was studied; homological series of the substrates were examined with the aim to evaluate the contributions of functional groups and hydrocarbon tail to the processes occurring in the target. The dependence of the yield of the labeled parent compound on the atomizer temperature varied in the range 1600–2000 K was determined. The rates of decarboxylation and deamination sharply grew with increasing temperature of the tungsten wire. The highest yield of labeled amino acids was attained at an atomizer temperature of 1800–1900 K, and at higher temperature their yield decreased. The difference between the activation energies of the elimination of the carboxy and amino groups and of the isotope exchange of hydrogen for tritium in the C-H bond appeared to be 93 and 59 kJ mol^?1, respectively. For alkyltrimethylammonium bromides with the alkyl radicals C₁₂H₂₅, C₁₄H₂₉, and C₁₆H₃₃, the yield of the labeled parent compound reached 80–90% and was virtually independent of the atomizer temperature. The capability of tritium atoms to penetrate into the targets was evaluated. For the exponential model of the attenuation of the flow of tritium atoms inside the target, the attenuation factor for freeze-dried amino acids and alkyltrimethylammonium bromides as targets was 1.8 nm^?1.