Equation Stokes-Einstein relation

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

The Stokes-Einstein equation relates the diffusion coefficient, D, to continuous phase viscosity t] and the radius of the particle, r thus ... 

The Stokes-Einstein equation, relating the diffusion coefficient to the fluid viscosity, is used to rewrite eq (1.3-1) in terms of viscosity as... 

The Stokes-Einstein equation relates the cooperative diffusion coefficient (Dc) to the bare dynamic correlation length ( d ) defined in terms of the temperature-dependentviscosity ofthe solvent (ri )in Eq. 12 ... 

In order to apply the Smoluchowski equation (Equations (1.3), (2.1), (3.29)), we need values for the least distance of approach (rAn) and the diffusion coefficient (Dab)- The value of tab can be estimated from molecular volumes (Section 2.5.1.2). The diffusion coefficient can be determined by various methods, but experimental values are available only for a minority of the myriad possible situations. A common practice is to use the Stokes-Einstein relation (Section 1.2.3), which rests on the assumption that solute molecules in motion behave like macroscopic particles to which classical hydrodynamic theory can be applied. We shall first outline (a) the relation between the diffusion coefficient D and the mechanics of motion of particles in fluids, leading to the Stokes-Einstein equation relating D to solute size and solvent viscosity and (b) the direct experimental determination of D. We shall then (c) compare the results and note the reservations that are required in relying on the Stokes-Einstein estimates of D in various cases. 

Dilute Brownian probes in a simple Newtonian solvent diffuse as described by the Langevin equation. In these systems g q, t) reduces to a simple exponential txp —Dpq t). The Stokes-Einstein equation relates Dp for spheres of radius R to other parameters, namely... 

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. 

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... 

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... 

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... 

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 ... 

Photon correlation spectroscopy (PCS) has been used extensively for the sizing of submicrometer particles and is now the accepted technique in most sizing determinations. PCS is based on the Brownian motion that colloidal particles undergo, where they are in constant, random motion due to the bombardment of solvent (or gas) molecules surrounding them. The time dependence of the fluctuations in intensity of scattered light from particles undergoing Brownian motion is a function of the size of the particles. Smaller particles move more rapidly than larger ones and the amount of movement is defined by the diffusion coefficient or translational diffusion coefficient, which can be related to size by the Stokes-Einstein equation, as described by... 

Here Tq is — C2 and is a prefactor proportional to which is determined by the transport coefficient (in this case at the given reference temperature. The constant B has the dimensions of energy but is not related to any simple activation process (Ratner, 1987). Eqn (6.6) holds for many transport properties and, by making the assumption of a fully dissociated electrolyte, it can be related to the diffusion coefficient through the Stokes-Einstein equation giving the form to which the conductivity, <7, in polymer electrolytes is often fitted,... 

The Peclet number compares the effect of imposed shear (known as the convective effect) with the effect of diffusion of the particles. The imposed shear has the effect of altering the local distribution of the particles, whereas the diffusion (or Brownian motion) of the particles tries to restore the equilibrium structure. In a quiescent colloidal dispersion the particles move continuously in a random manner due to Brownian motion. The thermal motion establishes an equilibrium statistical distribution that depends on the volume fraction and interparticle potentials. Using the Einstein-Smoluchowski relation for the time scale of the motion, with the Stokes-Einstein equation for the diffusion coefficient, one can write the time taken for a particle to diffuse a distance equal to its radius R, as... 

Diffusion coefficients can be related to molecular weight in three ways first by application of the Stokes-Einstein equation, second by combination with sedimentation data, and third by consideration of homologous polymer solutions. In the first method, an equivalent spherical size of the molecules is calculated from Dt, and an approximate molecular weight is found by combining these data with the appropriate density. In the second method, diffusion measurements are coupled with those of sedimentation velocity to give molecular weights, and in the third method, molecular weights may be determined directly from measurements of diffusion coefficients alone once a calibration has been... 

Stokes-Einstein Relationship. As was pointed out in the last section, diffusion coefficients may be related to the effective radius of a spherical particle through the translational frictional coefficient in the Stokes-Einstein equation. If the molecular density is also known, then a simple calculation will yield the molecular weight. Thus this method is in effect limited to hard body systems. This method has been extended for example by the work of Perrin (63) and Herzog, Illig, and Kudar (64) to include ellipsoids of revolution of semiaxes a, b, b, for prolate shapes and a, a, b for oblate shapes, where the frictional coefficient is expressed as a ratio with the frictional coefficient observed for a sphere of the same volume. 

In dynamic light scattering (DLS), or photon correlation spectroscopy, temporal fluctuations of the intensity of scattered light are measured and this is related to the dynamics of the solution. In dilute micellar solutions, DLS provides the z-average of the translational diffusion coefficient. The hydrodynamic radius, Rh, of the scattering particles can then be obtained from the Stokes-Einstein equation (eqn 1.2).The intensity fraction as a function of apparent hydrodynamic radius is shown for a triblock solution in Fig. 3.4. The peak with the smaller value of apparent hydrodynamic radius, RH.aPP corresponds to molecules and that at large / Hs,Pp to micelles. 

It is interesting to compare conductance behavior with that of the shear viscosity, because conventional hydrodynamic conductance theories relate A to the frictional resistance of the surrounding medium. At first glance, one would expect from the Stokes-Einstein equation a critical anomaly of the... 

The diffusion coefficient is related to the radius r of the diffusing molecule and to the viscosity of the medium rj by the Stokes-Einstein equation... 

The use of the Stokes-Einstein equation (2) relating the diffusion coefficient (D) of a spherical solute molecule to its radius (r), the viscosity of the medium (tj) and the Boltzmann constant (k) permits the rate coefficient ( en) to be expressed in (3) in terms of the viscosity of the medium. In this derivation, the... 

For dilute dispersions of spherical particles, the diffusion coefficient can be related to the hydrodynamic diameter of the particles by the Stokes-Einstein equation... 

This expression is known as the Stokes-Einstein equation. This formula correctly relates diffusivity to molecular dimensions and viscosity for cases in which Stokes law is applicable. 

For Brownian motion, the collision frequency function is based on Fick s first law with the particle s diffusion coefficient given by the Stokes-Einstein equation. The Stokes-Einstein relation states that... 

In electrochemistry several equations are used that bear Einsteins name [viii-ix]. The relationship between electric mobility and diffusion coefficient is called Einstein relation. The relation between conductivity and diffusion coefficient is called - Nernst-Einstein equation. The expression concerns the relation between the diffusion coefficient and the viscosity and is known as the - Stokes-Einstein equation. The expression that shows the proportionality of the mean square distance of the random movements of a species to the diffusion coefficient and the duration of time is called - Einstein-Smoluchowski equation. A relationship between the relative viscosity of suspension and the volume fraction occupied by the suspended particles - which was derived by Einstein - is also called Einstein equation [ix]. 

As a correlation function is recorded, the correlator offers the decay time (x), particles diffusion coefficient (D), and particles mean radius (R). The two latters are related with by Stokes-Einstein equation [6],... 

This expression relates the experimental quantity tr directly to dH provided that all other parameters are known. Alternate expressions can be obtained relating tr to the friction coefficient f or to D through use of the Stokes-Einstein equation D=kT/f giving ... 

The Walden rule is interpreted in the same manner as the Stokes-Einstein relation. In each case it is supposed that the force impeding the motion of ions in the liquid is a viscous force due to the solvent through which the ions move. It is most appropriate for the case of large ions moving in a solvent of small molecules. However, we will see here that just as the Stokes-Einstein equation applies rather well to most pure nonviscous liquids [30], so does the Walden rule apply, rather well, to pure ionic liquids [15]. When the units for fluidity are chosen to be reciprocal poise and those for equivalent conductivity are Smol cm, this plot has the particularly simple form shown in Figure 2.6. 

The Stokes-Einstein equation (4.179) connects the diffusion coefficient and the viscosity of the medium the Nernst-Einstein equation (4.187) relates the diffusion coefficient to the equivalent conductivity. Hence, by eliminating the diffusion coeffi-... 

Thus, the combined SE and the DSE equations predict that the product Dtxc = (A Tc)sedse should equal 2r /9. Measurements of probe translational diffusion and rotational diffusion made in glass-formers have found that the product Dtr can be much larger than this value, revealing a breakdown of the Stokes-Einstein (SE) relation and the Debye-Stokes-Einstein (DSE) relation. There is an enhancement of probe translational diffusion in comparison with rotational diffusion. The time dependence of the probe rotational time correlation functions tit) is well-described by the KWW function,... 

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