Thermal conductivity measurements and molecular association in a series of alcohol vapors: Methanol,ethanol, isopropanol,and t-butanol

Thermal conductivity measurements on the vapors of methanol, ethanol, isopropanol, and t-butanol are reported as a function of temperature (330–420 K) and pressure (11–240 kPa). The thermal conductivity versus pressure isotherms for all four alcohols exhibit upward curvatures at the lower temperatures and nearly linear increases at higher temperatures. This behavior is indicative of a dimeric species and one or more polymeric clusters in the vapor in addition to the monomer. Quantum mechanical calculations have indicated that tetramers are the most likely polymeric species. Detailed analyses of the data provide thermodynamic data (H,S) for the dimerization and tetramerization reactions and show interesting correlations with the size of the monomer unit.