Einsteins Equation

We saw that the frictional coefficient that is needed in all the above calculations is a drIBcult parameter to obtain for non-spherical molecules. Shape and solvation affect the values of the frictional coefficient. Recognizing that the driving force for diHiision is thermodynamic in origin and assuming dilute ideal dispersions, Einstein combined Pick s law and the equation for the drag force and derived the very simple equation  

In combination with a general force balance, Einstein s diffiision law results in Equation 8.5b, which permits the estimation of the mass of each particle. Thus, upon combining diffiision experiments (for obtaining D) and sedimentation (gravitational) experiments (for obtaining ), we can estimate the mass of colloidal particles without any assumption about their shape. Finally, due to Einstein s diffiision law Df= kgT), the ratio f/fo is equal to DqID, where Do is the diffusion coefficient of a system containing the equivalent unsolvated spheres. 

As expected, the larger the diffusion coefficient, the lower the drag force. Of course, Einstein s diffusion law can be combined with Stokes equation for/ and the resulting equation is called Stokes-Einstein law (Problem 8.1). Together with the equation for the Brownian displacement, it was used by Perrin for early, rather accurate calculations of the Avogadro number. 

The ratio//o can be estimated, based on the Stokes and Einstein equations  

Moreover, since m = M/N, Equation 8.5b can be used to estimate the molecular weight (M) of a colloid particle  

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The dififiision time gives the same general picture. The bulk self-diffusion coefficient of copper is 10"" cm /sec at 725°C [12] the Einstein equation... 

Reference 115 gives the diffusion coefficient of DTAB (dodecyltrimethylammo-nium bromide) as 1.07 x 10" cm /sec. Estimate the micelle radius (use the Einstein equation relating diffusion coefficient and friction factor and the Stokes equation for the friction factor of a sphere) and compare with the value given in the reference. Estimate also the number of monomer units in the micelle. Assume 25°C. 

The final technique addressed in this chapter is the measurement of the surface work function, the energy required to remove an electron from a solid. This is one of the oldest surface characterization methods, and certainly the oldest carried out in vacuo since it was first measured by Millikan using the photoelectric effect [4]. The observation of this effect led to the proposal of the Einstein equation ... 

The relation between energy and mass is given by the Einstein equation ... 

A somewhat similar problem arises in describing the viscosity of a suspension of spherical particles. This problem was analyzed by Einstein in 1906, with some corrections appearing in 1911. As we did with Stokes law, we shall only present qualitative arguments which give plausibility to the final form. The fact that it took Einstein 5 years to work out the bugs in this theory is an indication of the complexity of the formal analysis. Derivations of both the Stokes and Einstein equations which do not require vector calculus have been presented by Lauffer [Ref. 3]. The latter derivations are at about the same level of difficulty as most of the mathematics in this book. We shall only hint at the direction of Lauffer s derivation, however, since our interest in rigid spheres is marginal, at best. 

Both the Stokes and Einstein equations have certain features in common... 

As in osmotic pressure experiments, polymer concentations are usually expressed in mass volume units rather than in the volume fraction units indicated by the Einstein equation. For dilute solutions, however, Eq. (8.100) shows that

partial molar volume of the polymer in solution, and M is the molecular weight of the polymer. Substituting this relationship for (pin Eq. (9.9)gives... 

In the polymer literature each of the five quantities listed above is encountered frequently. Complicating things still further is the fact that a variety of concentration units are used in actual practice. In addition, lUPAC terminology is different from the common names listed above. By way of summary, Table 9.1 lists the common and lUPAC names for these quantities and their definitions. Note that when

[Pg.593]

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... 

The relative viscosity of a dilute dispersion of rigid spherical particles is given by = 1 + ft0, where a is equal to [Tj], the limiting viscosity number (intrinsic viscosity) in terms of volume concentration, and ( ) is the volume fraction. Einstein has shown that, provided that the particle concentration is low enough and certain other conditions are met, [77] = 2.5, and the viscosity equation is then = 1 + 2.50. This expression is usually called the Einstein equation. 

For higher (0 > 0.05) concentrations where particle—particle interactions are noticeable, the viscosity is higher than predicted by the Einstein equation. The viscosity—concentration equation becomes equation 10, where b and c are additional constants (87). 

The deviation from the Einstein equation at higher concentrations is represented in Figure 13, which is typical of many systems (88,89). The relative viscosity tends to infinity as the concentration approaches the limiting volume fraction of close packing ( ) (0 = - 0.7). Equation 10 has been modified (90,91) to take this into account, and the expression for becomes (eq. 11) ... 

Emulsions. Because emulsions are different from dispersions, different viscosity—concentration relationships must be used (71,87). In an emulsion the droplets are not rigid, and viscosity can vary over a wide range. Several equations have been proposed to account for this. An extension of the Einstein equation includes a factor that allows for the effect of variations in fluid circulation within the droplets and subsequent distortion of flow patterns (98,99). 

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. 

The Einstein equation for the flux of atoms across the interface is... 

Substituting for the mobility using the Nernst-Einstein equation and die deh-nition of die naiisport number... 

Furdiertiiore, using the Nernst-Einstein equation to substimte in the general equation above yields... 

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. 

An estimation of the multiphase viscosity is a preliminary necessity for convenient particle processing. For particle-doped liquids the classical Einstein equation [20] relates the relative viscosity to the concentration of the solid phase ... 

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... 

For cpr < 1 Mooney formula transforms in a natural way into Einstein equation, and for cpr -> 1 this formula predicts thatp -> oo, which corresponds to the physical meaning of the phenomenon. 

But at low temperatures, equation (10.148) does not quantitatively predict the shape of the CV. m against T curve. For example, Figure 10.12 compares the experimental value of CV m for diamond with that predicted from equation (10.148). It is apparent that the Einstein equation predicts that CV.m for diamond will decrease too rapidly at low temperatures. Similar results would be obtained for Ag and other atomic solids. 

This is the same high temperature limit predicted by the Einstein equation and is the limit approached by experimental results for monatomic solids.rr... 

Intermediate values for C m can be obtained from a numerical integration of equation (10.158). When all are put together the complete heat capacity curve with the correct limiting values is obtained. As an example, Figure 10.13 compares the experimental Cy, m for diamond with the Debye prediction. Also shown is the prediction from the Einstein equation (shown in Figure 10.12), demonstrating the improved fit of the Debye equation, especially at low temperatures. 

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