Critical constants of unsaturated aliphatic hydrocarbons

The van der Waals' constanta a andb evaluated from structural considerations of the unsaturated aliphatic hydrocarbons are used to calculate the critical constants for these types of compounds. For these unsaturated hydrocarbons, both van der Waals' constants are calculated through the additive contribution of unsaturated bonds to the van der Waals' constants of the corresponding saturated aliphatic hydrocarbons calculated according to a method previously proposed (6). With both van der Waals' constants available, the critical temperatures, pressures, and volumes for these types of compounds can be obtained. By use of this approach, the critical temperatures, pressures, and volumes of several olefins, diolefins, and acetylenes have been calculated. These calculated values have been compared whenever possible with values reported in the literature to produce an average percentage deviation of 1.3 for the critical temperature, 3.0 for the critical pressure, and 1.5 for the critical volume. In this comparison questionable literature values have been included, and consequently the reported deviations present the worst possible expectation.