Abstract
The self-association of hydrophobic propan-1-ol has been studied in binary aqueous mixtures and in mixtures containing urea as a third component. We applied an NMR technique to obtain the so-called association parameter A22, which is based on the measurement of intermolecular 1H–1H dipole–dipole relaxation rates and on self-diffusion coefficients of the component of interest. The composition dependence of A22 reflects a weak tendency for the self-association of propan-1-ol in the binary mixture. Addition of urea leads to a strongly increased self-association of propan-1-ol. The same qualitative result has been obtained from recent studies of the Kirkwood–Buff integral G22 by one of the present authors. A22 is governed by short-range contributions but G22 by long-range contributions and the common study of the two quantities has delivered interesting complementary information about liquid mixtures. Propanol–propanol correlations in binary systems were never found to extend longer than one to two propanol diameters, however when urea is added the correlation length can extend up to four diameters. Measurements of BD parameters, showing the influence of urea on the translational motion of propan-1-ol, revealed only a weak effect. Thus no rigid self-associated species could be detected and the self-association found from A22 and G22 can be interpreted as ‘preferential self-solvation’ by relatively weak intermolecular interactions.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have