(191ac) Aggregation of Hexanol Isomers and of 2-Alkoxyethan-1-Ol Compounds in n-Hexane

Stubbs, J. M., Chemistry, University of Minneapolis
Siepmann, J. I., University of Minnesota

Configurational-bias Monte Carlo simulations were carried out for dilute solutions of 1-hexanol, 2-hexanol, 3-hexanol, 2-methylpentan-2-ol, 3-methylpentan-3-ol, 2-butoxyethanol, 2-ethoxyethanol and 2-methoxyethanol in n-hexane to determine the influence of molecular architecture on the thermodynamic and structural properties of hydrogen-bonded aggregates. Analysis of radial distribution functions and aggregate size distributions show that the fraction of molecules belonging to hydrogen-bonded aggregates decreases with increasing steric hindrance. However, for all alcohols the preferred aggregation sizes are tetramers and pentamers. Competition from intramolecular hydrogen bonding leads to a dramatic increase of the monomer fraction for 2-butoxyethan-1-ol, 2-ethoxyethan-1-ol and 2-methoxyethan-1-ol as well as different aggregate distributions and structures.