The second virial coefficients of organic vapours

Abstract

The compressibilities of a num ber of organic vapours have been measured at pressures up to 1 atm. and temperatures ranging from 40 to 130° C. The observed second virial coefficients are compared with values calculated from the critical data by the Berthelot equation. The results show two distinct classes of behaviour. Class I is shown by ethane, ethylene,n-hexane, cyclohexane, benzene, diethyl ether, ethyl chloride, chloroform and carbon tetrachloride, where the measured second virial coefficients are in agreement with the calculated values. Class II by acetaldehyde, acetone, acetonitrile, methyl alcohol, where the measured second virial coefficients are consistently very much higher than the calculated values. It is concluded that the vapours of polar substances for which the energy of attraction between molecules, due to dipole interaction or to hydrogen bonding, is larger thankTundergo dim erization. This view is supported by thermal conductivity data. The range of validity of the Berthelot equation for both non-polar and polar vapours is examined.