Einstein equation, Stokes

Jeong et al. [101] studied the counteractive facilitated transport of Co-Ni mixture by HFSLM. The mass conservation equations were written along with boundary conditions and solved to get the permeation profiles of metal ions. The diffusivity of Co(Il) and Ni(ll) was used from the literature while that of hydrogen ion was calculated by Nemst-Haskell equation. Stokes-Einstein equation was used for calculating the diffusivity of cobalt-carrier complex and nickel-carrier complex. The authors have shown the concentration profiles of cobalt inside the fiber at various flow rates and described that at low flow rate of feed phase, the concentration of cobalt decreases from the center to the feed-membrane interface. 

Figure 5 relates N j to collection efficiency particle diffusivity from Stokes-Einstein equation assumes Brownian motion same order of magnitude or greater than mean free path of gas molecules (0.1 pm at... 

StoKes-Einstein and Free-Volume Theories The starting point for many correlations is the Stokes-Einstein equation. This equation is derived from continuum fluid mechanics and classical thermodynamics for the motion of large spherical particles in a liqmd. 

For this case, the need for a molecular theory is cleverly avoided. The Stokes-Einstein equation is (Bird et al.)... 

Wilke-Chang This correlation for D°b is one of the most widely used, and it is an empirical modification of the Stokes-Einstein equation. It is not very accurate, however, for water as the solute. Otherwise, it apphes to diffusion of very dilute A in B. The average absolute error for 251 different systems is about 10 percent. ( )b is an association factor of solvent B that accounts for hydrogen bonding. 

The Stokes-Einstein equation has already been presented. It was noted that its vahdity was restricted to large solutes, such as spherical macromolecules and particles in a continuum solvent. The equation has also been found to predict accurately the diffusion coefficient of spherical latex particles and globular proteins. Corrections to Stokes-Einstein for molecules approximating spheroids is given by Tanford. Since solute-solute interactions are ignored in this theory, it applies in the dilute range only. 

In connection with the earlier consideration of diffusion in liquids using tire Stokes-Einstein equation, it can be concluded that the temperature dependence of the diffusion coefficient on the temperature should be T(exp(—Qvis/RT)) according to this equation, if the activation energy for viscous flow is included. 

Using the Stokes-Einstein equation for the viscosity, which is unexpectedly useful for a range of liquids as an approximate relation between diffusion and viscosity, explains a resulting empirical expression for the rate of formation of nuclei of the critical size for metals... 

By equating Fiek s seeond law and the Stokes-Einstein equation for diffusivity, Smoluehowski (1916,1917) showed that the eollision frequeney faetor takes the form... 

Very commonly Eq. (4-5) is combined with Eq. (4-6), the Stokes-Einstein equation relating the diffusion coefficient to the viscosity -q. 

Equations (4-5) and (4-7) are alternative expressions for the estimation of the diffusion-limited rate constant, but these equations are not equivalent, because Eq. (4-7) includes the assumption that the Stokes-Einstein equation is applicable. Olea and Thomas" measured the kinetics of quenching of pyrene fluorescence in several solvents and also measured diffusion coefficients. The diffusion coefficients did not vary as t) [as predicted by Eq. (4-6)], but roughly as Tf. Thus Eq. (4-7) is not valid, in this system, whereas Eq. (4-5), used with the experimentally measured diffusion coefficients, gave reasonable agreement with measured rate constants. 

Following the general trend of looldng for a molecular description of the properties of matter, self-diffusion in liquids has become a key quantity for interpretation and modeling of transport in liquids [5]. Self-diffusion coefficients can be combined with other data, such as viscosities, electrical conductivities, densities, etc., in order to evaluate and improve solvodynamic models such as the Stokes-Einstein type [6-9]. From temperature-dependent measurements, activation energies can be calculated by the Arrhenius or the Vogel-Tamman-Fulcher equation (VTF), in order to evaluate models that treat the diffusion process similarly to diffusion in the solid state with jump or hole models [1, 2, 7]. 

T0 is a reference temperature which can be identified with T, and although the constant B is not related to any simple activation process, it has dimensions of energy. This form of the equation is derived by assuming an electrolyte to be fully dissociated in the solvent, so it can be related to the diffusion coefficient through the Stokes-Einstein equation. It suggests that thermal motion above T0 contributes to relaxation and transport processes and that... 

The same equation applies to other solvents. It is often easier to incorporate an expression for the diffusion coefficient than a numerical value, which may not be available. According to the Stokes-Einstein equation,6 diffusion coefficients can be estimated from the solvent viscosity by... 

To = temperature of the solvent at which tan A goes through a maximum. These values are presented in Table II. VSE (the Stokes-Eeinstein volume) is calculated for a spherical molecule if the molecule is aspherical this calculation (VSE) is called Vapparent The Vapparent can be smaller or larger than the Stokes-Einstein volume and varies from the equivalent sphere volume obtained by solution of equations 3,4 and 5. 

Using the Stokes-Einstein equation of diffusion coefficient ... 

According to Stokes-Einstein equation, the diffusion coefficient is inversely proportional to the solution viscosity which increases with temperature. Hence, a lower diffusion coefficient corresponds to a lower size molecule. 

The Stokes-Einstein equation can be successfully used to explain diffusion under the following conditions [401], where (a) the diffusing molecule is large with respect to the molecules defining the medium, (b) the medium has a very low viscosity, and (c) no solute-solvent interactions occur. 

Thus, the Stokes-Einstein equation is expected to be valid for colloidal particles and suspensions of large spherical particles. Experimental evidence supports these assumptions [101], and this equation has occasionally been used for much smaller species. 

The Stokes-Einstein equation predicts that DfxITa is independent of the solvent however, for real solutions, it has long been known that the product of limiting interdiffusion coefficient for solutes and the solvent viscosity decreases with increasing solute molar volume [401]. Based upon a large number of experimental results, Wilke and Chang [437] proposed a semiempirical equation,... 

Perrin model and the Johansson and Elvingston model fall above the experimental data. Also shown in this figure is the prediction from the Stokes-Einstein-Smoluchowski expression, whereby the Stokes-Einstein expression is modified with the inclusion of the Ein-stein-Smoluchowski expression for the effect of solute on viscosity. Penke et al. [290] found that the Mackie-Meares equation fit the water diffusion data however, upon consideration of water interactions with the polymer gel, through measurements of longitudinal relaxation, adsorption interactions incorporated within the volume averaging theory also well described the experimental results. The volume averaging theory had the advantage that it could describe the effect of Bis on the relaxation within the same framework as the description of the diffusion coefficient. 

Viscosity is a useful quantity, in that both rotational and translation mobility of molecules in solution are viscosity dependent and can be related to viscosity through the Stokes-Einstein equation ... 

The method preferred in our laboratory for determining the UWL permeability is based on the pH dependence of effective permeabilities of ionizable molecules [Eq. (7.52)]. Nonionizable molecules cannot be directly analyzed this way. However, an approximate method may be devised, based on the assumption that the UWL depends on the aqueous diffusivity of the molecule, and furthermore, that the diffusivity depends on the molecular weight of the molecule. The thickness of the unstirred water layer can be determined from ionizable molecules, and applied to nonionizable substances, using the (symmetric) relationship Pu = Daq/ 2/iaq. Fortunately, empirical methods for estimating values of Daq exist. From the Stokes-Einstein equation, applied to spherical molecules, diffusivity is expected to depend on the inverse square root of the molecular weight. A plot of log Daq versus log MW should be linear, with a slope of —0.5. Figure 7.37 shows such a log-log plot for 55 molecules, with measured diffusivities taken from several... 

For benzene solution, kMta calculated from this equation is 1 x 1010 liters/mole-sec. Actually Hammond used a formulation<3,4) that gave fcdiffn = 2 x 109 liters/mole-sec. This is probably a more realistic value than that calculated from the Stokes-Einstein equation and will be used for this discussion. 

The Stokes-Einstein equation gives a good approximation of the molecular radius (r) for spherical or nearly spherical molecules ... 

Measurements of CuS04 molecular diffusivity by Cole and Gordon (C12a), referred to above, were carried out in diaphragm cells, mostly at 18°C. Their results were correlated by Fenech and Tobias (F3) using the Stokes-Einstein equation... 

Baxendale and Wardman (1973) note that the reaction of es with neutrals, such as acetone and CC14, in n-propanol is diffusion-controlled over the entire liquid phase. The values calculated from the Stokes-Einstein relation, k = 8jtRT/3jj, where 7] is the viscosity, agree well with measurement. Similarly, Fowles (1971) finds that the reaction of es with acid in alcohols is diffusion-controlled, given adequately by the Debye equation, which is not true in water. The activation energy of this reaction should be equal to that of the equivalent conductivity of es + ROH2+, which agrees well with the observation of Fowles (1971). 

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