Determination of the Bond Dissociation Energy D(C2H5Hg—C2H5) by the Toluene Carrier Method

Abstract
The pyrolysis of diethylmercury has been studied in a toluene carrier flow System from 601 to 673 °K using total pressures of 1.04 to 7.75 mm. The progress of the reaction was followed by measuring the amounts of unreacted alkyl. Partial solution of butane in the toluene condensed at the outlet of the reactor made full product analysis difficult. Complete analysis in a number of runs did yield a good material balance between alkyl decomposed and [Formula: see text].[Formula: see text][Formula: see text][Formula: see text][Formula: see text]The Arrhenius equation for reaction 1, log k1(s−1) = 15.4 − (45 700 ± 1 000)/2.3 RT, is in excellent agreement with that estimated by Benson and O'Neal. Based on a number of simplifying approximations, log k3(cm3mol−1s−1) = 10.9 − (9 300 ± 2 000)/2.3 RT. The estimated disproportionation to combination ratio, K5/K4 = 0.09 – 0.12 is in good agreement with earlier work.Approximate correction of E1 to absolute zero yields D(C2H5Hg—C2H5) = 43.7 kcal mol−1 and therefore by difference D(Hg—C2H5) = 6.5 kcal mol−1.