Solvent macroscopic

Continuum models of solvation treat the solute microscopically, and the surrounding solvent macroscopically, according to the above principles. The simplest treatment is the Onsager (1936) model, where aspirin in solution would be modelled according to Figure 15.4. The solute is embedded in a spherical cavity, whose radius can be estimated by calculating the molecular volume. A dipole in the solute molecule induces polarization in the solvent continuum, which in turn interacts with the solute dipole, leading to stabilization. 

In Buckingham s approach [17,18], it is assumed that the solution is composed of small solvent macroscopic spheres (small with respect to the radiation wavelength) comprising a single solute molecule and surrounded by pure solvent each sphere is independent of the others (i.e. the solution is dilute). The ratio between the integrated absorption in solution and in gas phase can be written as ... 

When discussing solvent effects, it is important to distinguish between the macroscopic and the microscopic properties of the solvent. Macroscopic properties refer to properties of the bulk solvent. An important macroscopic property is the dielectric constant which is a measure of the ability of the bulk material to increase the capacitance of a condenser, relative to a vacuum. In terms of structure, the dielectric constant is a function of both the permanent dipole moment of the molecule and its polarizability. Polarizability refers to the ease of distortion of the molecule s electrons. Dielectric constants increase with dipole moment and with polarizability. An important property of solvent molecules with regard to reactions is the way in which the solvent molecules interact with the changes in charge... 

Long before the advent of SPT, Uhlig" postulated that Gc has to be a function of cavity surface area and solvent macroscopic surface tension... 

The difficulty in applying relationships based on solvent macroscopic surface tension to TCF evaluation for cavities of molecular size, rises from the sensitivity of thermodynamics quantities to the curvature of such small cavities. In fact, the microscopic surface tension is a function of the curvature of cavity surface. ... 

Miscible processes are aimed at recovering oil which would normally be left behind as residual oil, by using a displacing fluid which actually mixes with the oil. Because the miscible drive fluid is usually more mobile than oil, it tends to bypass the oil giving rise to a low macroscopic sweep efficiency. The method is therefore best suited to high dip reservoirs. Typical miscible drive fluids include hydrocarbon solvents, hydrocarbon gases, carbon dioxide and nitrogen. 

At large distances, 0 and w.j r) qfljzry ssxt z is the macroscopic dielectric constant of the solvent. 

As with SCRF-PCM only macroscopic electrostatic contribntions to the Gibbs free energy of solvation are taken into account, short-range effects which are limited predominantly to the first solvation shell have to be considered by adding additional tenns. These correct for the neglect of effects caused by solnte-solvent electron correlation inclnding dispersion forces, hydrophobic interactions, dielectric saturation in the case of... 

Predicting the solvent or density dependence of rate constants by equation (A3.6.29) or equation (A3.6.31) requires the same ingredients as the calculation of TST rate constants plus an estimate of and a suitable model for the friction coefficient y and its density dependence. While in the framework of molecular dynamics simulations it may be worthwhile to numerically calculate friction coefficients from the average of the relevant time correlation fiinctions, for practical purposes in the analysis of kinetic data it is much more convenient and instructive to use experimentally detemiined macroscopic solvent parameters. 

The relation between the microscopic friction acting on a molecule during its motion in a solvent enviromnent and macroscopic bulk solvent viscosity is a key problem affecting the rates of many reactions in condensed phase. The sequence of steps leading from friction to diflfiision coefficient to viscosity is based on the general validity of the Stokes-Einstein relation and the concept of describing friction by hydrodynamic as opposed to microscopic models involving local solvent structure. In the hydrodynamic limit the effect of solvent friction on, for example, rotational relaxation times of a solute molecule is [ ]... 

Sitkoff, D., Sharp, K. A., Honig, B. Accurate calculation of hydration free energies using macroscopic solvent models. J. Phys. Chem. 98 (1994) 1978-1988... 

Sitkoff D, K A Sharp and B Honig 1994. Accurate Calculation of Hydration Free Energies Usin Macroscopic Solvent Models. Journal of Physical Chemistry 98 1978-1988. 

Macroscopically, the solvent and precipitant are no longer discontinuous at the polymer surface, but diffuse through it. The polymer film is a continuum with a surface rich in precipitant and poor in solvent. Microscopically, as the precipitant concentration increases, the polymer solution separates into two interspersed Hquid phases one rich in polymer and the other poor. The polymer concentration must be high enough to allow a continuous polymer-rich phase but not so high as to preclude a continuous polymer-poor phase. 

In continuum boundary conditions the protein or other macromolecule is treated as a macroscopic body surrounded by a featureless continuum representing the solvent. The internal forces of the protein are described by using the standard force field including the Coulombic interactions in Eq. (6), whereas the forces due to the presence of the continuum solvent are described by solvation tenns derived from macroscopic electrostatics and fluid dynamics. 

SASA), a concept introduced by Lee and Richards [9], and the electrostatic free energy contribution on the basis of the Poisson-Boltzmann (PB) equation of macroscopic electrostatics, an idea that goes back to Born [10], Debye and Htickel [11], Kirkwood [12], and Onsager [13]. The combination of these two approximations forms the SASA/PB implicit solvent model. In the next section we analyze the microscopic significance of the nonpolar and electrostatic free energy contributions and describe the SASA/PB implicit solvent model. 

The continuum electrostatic approximation is based on the assumption that the solvent polarization density of the solvent at a position r in space is linearly related to the total local electric field at that position. The Poisson equation for macroscopic continuum media... 

In Section III we described an approximation to the nonpolar free energy contribution based on the concept of the solvent-accessible surface area (SASA) [see Eq. (15)]. In the SASA/PB implicit solvent model, the nonpolar free energy contribution is complemented by a macroscopic continuum electrostatic calculation based on the PB equation, thus yielding an approximation to the total free energy, AVP = A different implicit... 

The continuum model, in which solvent is regarded as a continuum dielectric, has been used to study solvent effects for a long time [2,3]. Because the electrostatic interaction in a polar system dominates over other forces such as van der Waals interactions, solvation energies can be approximated by a reaction field due to polarization of the dielectric continuum as solvent. Other contributions such as dispersion interactions, which must be explicitly considered for nonpolar solvent systems, have usually been treated with empirical quantity such as macroscopic surface tension of solvent. 

Colloidal suspensions are, per definition, mixtures of mesoscopic particles and atomic liquids. What happens if there are several different species of particles mixed in the solvent One can invent several different sorts of mixtures small and large particles, differently charged ones, short and long rods, spheres and rods, and many more. Let us look into the literature. One important question when dealing with systems with several components is whether the species can be mixed or whether there exists a miscibility gap where the components macroscopically phase-separate. 

Most modern discussions of solvent effects rely on the concept of solvent polarity. Qualitative ideas of polarity are based on observations such as like dissolves like and are well accepted. However, quantification of polarity has proven to be extraordinarily difficult. Since the macroscopic property polarity arises from a myriad of possible microscopic interactions, this is perhaps unsurprising. Hence, it is important that care is taken when measuring the polarity of any liquid to ensure that it is clearly understood what is actually being measured. 

At large distances the curve of Fig. 8b is a plot of — (c2/ r)> where t is the macroscopic dielectric constant of the solvent at the temperature considered. For small values of r the curve deviates from this value but at every point the slope of the curve must represent the mean intensity of the mutual attraction or repulsion at the particular temperature considered. If the curve of Fig. 86 for dissociation in solution is to be useful, every point on this curve must belong to the same temperature T. That is to say, when we consider any change in the distance r between the ions, we are interested in an isothermal change in r. 

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