The Pyrolysis of Trimethylthallium and Evaluation of D[(CH₃)₂Tl—CH₃]

Abstract

The pyrolysis of trimethylthallium has been studied in a mercury free toluene carrier flow system (452-536 OK, total pressure 6.7-39.3 mm, contact time 0.9-5.1 s, 5.4-90.2% decomposition). In a vessel cleaned with boiling concentrated H N 0 3 and coated by decomposing 0.1 g TI(CH3)3 no heterogeneous reaction could be detected. The extent of reaction measured by product analysis (CH,, C2H6, C6H5C2H5) assuming three CH, per TI(CH& undergoing reaction 1 is in agreement with that determined by analysis for undecomposed alkyl. Least squares analysis of the first order rate constants gives log kl(s-') = 15.10 -(36 400 f 600)/2.3RT Under the conditions used the activation energy should be a good approximation to D[(CH3)2TI-CH3].Oxidation of TI on the surface of T120 causes a marked increase in the rate. Omission of the coating step following cleaning has no effect on the rate based on undecomposed alkyl but initially causes a sharp drop in the yield o i products, particularly ethane.La pyrolyse du trimCthylthallium a CtC CtudiCe dans un systeme en continu avec du toluene sans mercure comme gaz vecteur (452-536 OK, pression totale 6.7-39.3 mm, duree de contact 0.9-5

Gas chromatography

“…Umilin and coworkers (867) measured the temperature dependence of vapor pressure of bis-arenyl-7r-complexes of vanadium and successfully eluted various ethylbenzoyl-molybdedenum organometallics gas chromatographically (866). Tin (584), selenium and tellurium (262), chromium (467), and thallium (695) organometallic compounds are among those which have now been evaluated gas chromatographically, and research on the elution of nitrogen oxides (76, 334) and organophosphates, and other phosphorus esters was active (399,771).…”