Time Evolution of Density Fluctuation in the Supercritical Region. 2. Comparison of Hydrogen- and Non-hydrogen-Bonded Fluids

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2005-08, Vol.109 (33), p.7365-7370
• Main Authors: Kajiya, Daisuke, Nishikawa, Keiko, Saitow, Ken-ichi
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp0522056

The time evolution of the density fluctuation of molecules is investigated by dynamic light scattering in six neat fluids in supercritical states. This study is the first to compare the dynamics of density inhomogeneity between hydrogen- and non-hydrogen-bonded fluids. Supercritical methanol and ethanol are used as hydrogen-bonded fluids, whereas four non-hydrogen-bonded fluids were used:  CHF3, C2H4, CO2, and Xe. We measure the time correlation function of the density fluctuation of each fluid at the same reduced temperatures and densities and investigate the relationship between the dynamic and static density inhomogeneities of those supercritical fluids. In all cases, the profile of the time correlation function of the density fluctuation is characterized by a single-exponential function, whose decay is responsible for the dynamics characterized by hydrodynamic conditions. We obtain correlation times from the time correlation function and discuss dynamic and static inhomogeneity using the Kawasaki theory and the Landau-Placzek theory. While the correlation times in the six fluids show noncoincidence, those values agree well with each other except for the supercritical alcohols when scaled to a dimensionless parameter. Although the principle of corresponding state is observed in the non-hydrogen-bonded fluids, both the supercritical methanol and ethanol deviate from that principle. This deviation is attributed to the presence of hydrogen bonding among alcohol molecules at high temperature and low density. The average cluster size of each fluid is estimated under the same thermodynamic conditions, and it is shown that the clusters of supercritical alcohols are on average 1.5−1.7 times larger than those of the four non-hydrogen-bonded fluids. Moreover, the thermal diffusivity of each neat fluid is obtained over wide ranges of density and temperature.