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Thermodynamic scaling of the viscosity of van der Waals, H-bonded, and ionic liquids.

Roland CM, Bair S, Casalini R

Chemistry Division, Naval Research Laboratory, Code 6120, Washington, DC 20375-5342.

Viscosities eta and their temperature T and volume V dependences are reported for seven molecular liquids and polymers. In combination with literature viscosity data for five other liquids, we show that the superpositioning of relaxation times for various glass-forming materials when expressed as a function of TV(gamma), where the exponent gamma is a material constant, can be extended to the viscosity. The latter is usually measured to higher temperatures than the corresponding relaxation times, demonstrating the validity of the thermodynamic scaling throughout the supercooled and higher T regimes. The value of gamma for a given liquid principally reflects the magnitude of the intermolecular forces (e.g., steepness of the repulsive potential); thus, we find decreasing gamma in going from van der Waals fluids to ionic liquids. For some strongly H-bonded materials, such as low molecular weight polypropylene glycol and water, the superpositioning fails, due to the nontrivial change of chemical structure (degree of H bonding) with thermodynamic conditions.

Published 3 October 2006 in J Chem Phys, 125(12): 124508.
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