Determination of Size of Molecular Clusters of Ethanol by Means of NMR Diffusometry and Hydrodynamic Calculations
Abstrakt
The microscopic structure of ethanol in the liquid state is characterized as a dynamic equilibrium of hydrogen-bonded clusters of different sizes and topologies. We have developed a novel method for determination of the average size of the clusters that combines the measurement of diffusion coefficient by means of NMR diffusometry technique and hydrodynamic simulations.
The approach includes the use of HydroNMR [J. Garcia de la Torre, M.
L. Huertas, and B.
Carrasco, J. Magn.
Reson. 147, 2000, 138] for small molecules, which is attained here by the calibration procedure using a dilute solution of tetramethylsilane. It is thus possible to correlate the experimentally determined diffusion coefficient of ethanol with calculated diffusion coefficients of the modeled clusters of different sizes.
We found that average size of the clusters in 0.16 M solution of ethanol in n-hexane corresponds to the monomer above 300 K and to the pentamer/hexamer below 240 K. The clusters in the case of 0.44 M solution are generally slightly larger, from the average size corresponding to the dimer at 320 K and the hexamer at 210 K.