Studies on the telomerization of ethylene with carbon tetrachloride : II. Properties of ethylene and tetrachloro-alkanes mixtures

Abstract

The phase equillibria and the P-V-T relations of the mixtures of ethylene and tetrachloro-alkanes Cl(CH_2CH_2)_nCCl_3 under pressures up to 200kg/cm^2 have been investigated to clarify the nature of the telomerization reaction systems of ethylene with carbon tetrachloride. The tetrachloro-alkanes examined were carbon tetrachloride, 1, 1, 1, 3-tetrachloro-propane, 1, 1, 1, 5-tetrachloro-pentane, 1, 1, 1, 7-tetrachloro-heptane and 1, 1, 1, 9-tetrachloro-nonane. Ethylene and carbon tetrachloride dissolve each other in all proportions at certain conditions, for example, at a pressure above 100kg/cm^2 and a temperature below 90℃, to form a homogeneous solution, which has intermediate properties between those of liquid carbon tetrachloride and of compressed ethylene gas. The densities of the solutions with several compositions were measured, and the partial molal volumes of ethylene and carbon tetrachloride, compressibilities and thermal expansion coefficients of the solutions, were calculated. The properties of the mixtures of ethylene and other tetrachloro-alkanes are also similar to the mixture of ethylene and carbon tetrachloride, except that the higher pressures are required to dissolve ethylene. The relations between the properties of the reaction mixtures and the kinetics of the telomerization were discussed.