18 research outputs found
Site-site memory equation approach in study of density/pressure dependence of translational diffusion coefficient and rotational relaxation time of polar molecular solutions: acetonitrile in water, methanol in water, and methanol in acetonitrile
We present results of theoretical study and numerical calculation of the
dynamics of molecular liquids based on combination of the memory equation
formalism and the reference interaction site model - RISM. Memory equations for
the site-site intermediate scattering functions are studied in the
mode-coupling approximation for the first order memory kernels, while
equilibrium properties such as site-site static structure factors are deduced
from RISM. The results include the temperature-density(pressure) dependence of
translational diffusion coefficients D and orientational relaxation times t for
acetonitrile in water, methanol in water and methanol in acetonitrile, all in
the limit of infinite dilution. Calculations are performed over the range of
temperatures and densities employing the SPC/E model for water and optimized
site-site potentials for acetonitrile and methanol. The theory is able to
reproduce qualitatively all main features of temperature and density
dependences of D and t observed in real and computer experiments. In
particular, anomalous behavior, i.e. the increase in mobility with density, is
observed for D and t of methanol in water, while acetonitrile in water and
methanol in acetonitrile do not show deviations from the ordinary behavior. The
variety exhibited by the different solute-solvent systems in the density
dependence of the mobility is interpreted in terms of the two competing origins
of friction, which interplay with each other as density increases: the
collisional and dielectric frictions which, respectively, increase and decrease
with increasing density.Comment: 13 pages, 8 eps-figures, 3 tables, RevTeX4-forma
Preisanpassungsklauseln in Kaufverträgen über Neuwagen
Beggerow M. Preisanpassungsklauseln in Kaufverträgen über Neuwagen. Europäische Hochschulschriften : Reihe 2, Rechtswissenschaft ; 651. Frankfurt am Main: Lang; 1987
Local fluctuations in solution mixtures
An extension of the traditional Kirkwood-Buff (KB) theory of solutions is outlined which provides additional fluctuating quantities that can be used to characterize and probe the behavior of solution mixtures. Particle-energy and energy-energy fluctuations for local regions of any multicomponent solution are expressed in terms of experimentally obtainable quantities, thereby supplementing the usual particle-particle fluctuations provided by the established KB inversion approach. The expressions are then used to analyze experimental data for pure water over a range of temperatures and pressures, a variety of pure liquids, and three binary solution mixtures – methanol and water, benzene and methanol, and aqueous sodium chloride. In addition to providing information on local properties of solutions it is argued that the particle-energy and energy-energy fluctuations can also be used to test and refine solute and solvent force fields for use in computer simulation studies