Static dielectric constant, viscosity, and structure of pure isomeric pentanols

Abstract

Static dielectric constants, viscosities, densitites and refractive indices of 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol and 2-methyl-2-butanol were measured at 15, 25, 35 and 45°C. These results together with the previous data on n-pentanol have been analyzed in terms of the Kirkwood correlation factor g k and of the energy of activiation for viscous flow. With the exception of 2-methyl-2-butanol, g k was found to be greater than unity. These results show that the monomeric units of isomeric pentanols interact by means of hydrogen bonding to form dynamic structures essentially of two types: linear chains where co-association raises the total polarizability and cyclic dimers with nearly zero net dipole moment. Energies of activation for viscous flow as well as Kirkwood correlation factors correlate with the molecular parameters (i.e. position of OH group in the molecules, steric hindrance of alkyl chain etc.) of the alcohols. The implication of these parameters on the molecular association of the isomeric pentanols are discussed.