화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.109, No.1, 83-91, 2005
Time evolution of density fluctuation in supercritical region. I. Non-hydrogen-bonded fluids studied by dynamic light scattering
The time evolution of the density fluctuation of molecules inhomogeneously dispersing in a mesoscopic volume is investigated by dynamic light scattering in several fluids in supercritical states. This study is the first time-domain investigation to compare the dynamics of density fluctuation among several fluids. The samples used are non-hydrogen-bonded fluids in the supercritical states: CHF3, C2H4 CO2, and xenon. These four molecules have different properties but are of similar size. Under these conditions. the relationship between dynamic and static density inhomogeneities is studied by measuring the time correlation function of the density fluctuation. In all cases, this function is characterized by a single exponential function. decaying within a few, microseconds. While the correlation times in the four fluids show noncoincidence, those values agree well with each other when scaled to a dimensionless parameter. From the results of this scaling based on the Kawasaki theory and Landau-Placzek theory, the relation between dynamics and static structures is analyzed, and the following four insights are obtained; (i) viscosity is the main contributor to the time evolution of density fluctuation; (ii) the principle of corresponding state is observed by the use of time-domain data; (iii) the Kawasaki theory and the Landau-Placzek theory are confirmed to be applicable to polar. nonpolar, and nondipolar fluids that have no hydrogen bonding, at temperatures relatively far from critical temperature; and (iv) the density fluctuation correlation length and the value of density fluctuation are estimated from the time-domain data and agree with the values from other experiments and calculations.