Dielectric Constant of Hydrogen-Bonded Liquids. IV. Equilibrium and Relaxation Studies of Homologous Neo-Alcohols

Abstract

The dielectric constants of H–(CH₂)_n–C(CH₃)₂–CH₂OH with n = 1, 2, 3, 4, 6, and 8 have been measured from about −70° to 100°C with test frequencies 0.05<f5 kc/sec. The equilibrium dielectric constant is analyzed in terms of associative, hydrogen‐bond equilibria as deduced from the temperature variation of the Kirkwood correlation factor and ΔH and ΔS of hydrogen bonding are estimated. Dielectric relaxation has been defined over several decades of time. The principal dispersion locus is Debye‐like irrespective of wide variations of the apparent degree of association and ΔH^‡ and ΔS^‡ for relaxation are similar for all species. The relation of dielectric relaxation to equilibrium liquid structure is discussed and evidence for rotational mobility in solid neopentanol and neohexanol is presented.