Abstract
The excess molar volume VE, viscosity deviation Δη, and excess Gibbs energy of activation ΔG*E of viscous flow have been investigated from the density ρ and viscosity η measurements of four binary mixtures of methanol and ethanol with triethylamine and tri-n-butylamine over the entire range of mole fractions at 303.15, 313.15, and 323.15 K. The viscosity data have been correlated with the equations of Grunberg and Nissan, Hind, McLaughlin, and Ubbelohde, Tamura and Kurata, and McAllister. The systems studied exhibit very strong cross association through strong O–H…N bonding between –OH and –N < groups. As a consequence of this strong intermolecular association, all four systems have very large negative VE. The VE of the studied mixtures is consistently described by the ERAS model. The values of cross association constants KAB illustrate the fact that cross-associates are more pronounced in a mixture of a short-chain tertiary amine.
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