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Journal of Physical Chemistry B, Vol.106, No.45, 11876-11886, 2002
Structural accommodation of osmium tetroxide in tertiary butanol solution
The structure of a 0.053 mol fraction solution of osmium tetroxide (OsO4) in tertiary butanol ((CH3)(3)COH) has been investigated by H/D isotope substitution neutron scattering methods. The three intermolecular correlations of interest, solute-solute, solvent-solvent, and solute-solvent, have been investigated by means of an empirical potential structure refinement of the experimental data. The picture of the system to emerge from the analysis is one in which the OsO4 molecules are generally seen to be well dispersed throughout the liquid as individual, i.e., nonaggregated, solutes. The solute favors a local environment where it is surrounded by the polar hydroxyl groups of the alcohol molecules but manages to accommodate itself without destroying the quantitative extent of the interalcohol hydrogen bonding that takes place, when compared with the pure solvent. Qualitatively, however, some modification of the hydrogen bond network between the alcohol molecules is seen to occur, largely through a small increase in the length of the inter-alcohol hydrogen bond and also through an increase in the breadth of the distribution.