Thermodynamics of Mixing of n-Alkanes with Polyisobutylene

Abstract

Listen

Translate article

Abstract The volume changes on mixing polyisobutylene (PIB) with n-pentane, n-hexane, n-heptane, n-octane, n-decane, and n-hexadecane have been determined by direct measurements at 45°, and for n-heptane at 0 and 50° as well. They are negative in every case; the magnitude of the excess volume decreases with chain length, and increases with temperature. These results on volume changes, which are beyond the scope of conventional theories of polymer solutions, are rationally taken into account by the recent statistical mechanical theory of solutions which relates properties of the mixture to characteristics of the pure liquids manifested in their equation-of-state parameters. The negative enthalpies of mixing found by Delmas, Patterson, and Somcynsky for all of these systems with the exception of PIB-n-hexadecane are similarly shown to arise from negative equation-of-state contributions to the enthalpy which reflect differences between the liquid characteristics of n-alkane and PIB. The energy contributed by...