Recoil Tritium Reactions in Simple Aliphatic Compounds
-
R. Cipollini
Summary
Some reactions of recoil tritium produced via the 3He (n, p) T- and the 6Li (n, α) T-process, respectively, have been studied in gaseous and liquid aliphatic compounds of the type RX (X = NH2, OH, SH, halogen).
Except for a remarkably high HT-yield in gaseous and liquid labile Η-containing systems the product forming mechanisms seem to follow the general pattern of the chemistry of energetic tritium atoms.
Liquid phase competition experiments in equimolar CH3NH2/C2H5NH2(I2)- and CH3NH2/n-C3H7NH2(I2)-systems show a stronger structure effect on hydrogen replacement than expected on the basis of the "impact model". The ratios of the relative yields per C-Η bond are 1.00 : 0.67 : 0.50 for methyl-, ethyl- and n-propylamine, respectively.
The effect of bond energies on excitation-decomposition following hot hydrogen substitution has been studied using scavenged gaseous, equimolar CH3X/C2He-systems. The CH2TX-yields are shown to decrease in the order
CH2TF > CH2TOH > CH2TCl > CH2TNH2 > CH2TSH
thus indicating that the energy of the weakest bond in the molecule plays a major yield-determining role. Pressure- and phase-effects confirm that a considerable fraction of the hot substitution product can decompose at 1 atmosphere before collisional de-excitation occurs. Primary steric and chemical factors seem to be small compared to the secondary decomposition effects, particulary for compounds with weaker bonds.
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