Diffusivity liquids, Stokes-Einstein

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... 

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]. 

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). 

The gas A must transfer from the gas phase to the liquid phase. Equation (1) describes the specific (per m2) molar flow (JA) of A through the gas-liquid interface. Considering only limitations in the liquid phase, this molar flow notably depends on the liquid molecular diffusion coefficient DAL (m2 s ). Based on the liquid state theories, DA L can be calculated using the Stokes-Einstein expression, and many correlations have been developed in order to estimate the liquid diffusion coefficients. The best-known example is the Wilke and Chang (W-C) relationship, but many others have been established and compared (Table 45.4) [28-33]. 

Diffusion of small solute particles (atoms, molecules) in a dense liquid of larger particles is an important but ill-understood problem of condensed matter physics and chemistry. In this case one does not expect the Stokes-Einstein (SE) relation between the diffusion coefficient D of the tagged particle of radius R and the viscosity r/s of the medium to be valid. Indeed, experiments [83, 112-115] have repeatedly shown that in this limit SE relation (with slip boundary condition) significantly underestimates the diffusion coefficient. The conventional SE relation is D = C keT/Rr]s, where k T is the Boltzmann constant times the absolute temperature and C is a numerical constant determined by the hydrodynamic boundary condition. To explain the enhanced diffusion, sometimes an empirical modification of the SE relation of the form... 

The motion caused by thermal agitation and the random striking of particles in a liquid by the molecules of that liquid is called Brownian motion. This molecular striking results in a vibratory movement that causes suspended particles to diffuse throughout a liquid. If the colloidal particles can be assumed to be approximately spherical, then for a liquid of given viscosity (q), at a constant temperature (T), the rate of diffusion, or diffusion coefficient (D) is inversely related to the particle size according to the Stokes-Einstein relation (ref. 126) ... 

K represents the following constant parameters n is the index of refraction of the liquid, X is the laser wavelength in air, and 0 is the angle at which the scattering intensity is measured. For polydisperse samples, the autocorrelation function plot is the sum of exponentials for each size range. Once the average translational diffusion coefficient of the sample is determined, the equivalent spherical diameter can be determined by using the Stokes-Einstein... 

An important conclusion to be drawn from the Stokes-Einstein equation is that the diffusion coefficient of solutes in a liquid only changes slowly with molecular weight, because the diffusion coefficient is proportional to the reciprocal of the radius, which in turn is approximately proportional to the cube root of the molecular weight. 

Electron spin resonance (ESR) studies of radical probe species also suggest complexity. Evans et al. [250] study the temperature dependence of IL viscosity and the diffusion of probe molecules in a series of dissimilar IL solvents. The results indicate that, at least over the temperature range studied, the activation energy for viscous flow of the liquid correlates well with the activation energies for both translational and rotational diffusion, indicative of Stoke-Einstein and Debye-Stokes-Einstein diffusion, respectively. Where exceptions to these trends are noted, they appear to be associated with structural inhomogeneity in the solvent. However, Strehmel and co-workers [251] take a different approach, and use ESR to study the behavior of spin probes in a homologous series of ILs. In these studies, comparisons of viscosity and probe dynamics across different (but structurally similar) ILs do not lead to a Stokes-Einstein correlation between viscosity and solute diffusion. Since the capacities for specific interactions are... 

The most common basis for estimating diffusion coefficients in liquids is the Stokes-Einstein equation ... 

In general, diffusion coefficients in gases can be often be predicted accurately. Predictions of diffusion coefficients in liquids are also possible using the Stokes-Einstein equation or its empirical parallels. On the contrary in solids and polymers, models allow coefficients to be correlated but predictions are rarely possible. 

For diffusion in amorphous polymers at temperatures above their glass point, Tg, one can assume a behavior with some analogy to a liquid. On the other hand the Stokes-Einstein Eq. (6-4) for liquids was derived under the assumption that the diffusing particle is much larger in size than the matrix particles. If we let the matrix be a... 

The Stokes-Einstein equation can also be used to estimate the diffusivity of binary liquid mixtures... 

For a binary mixture, if experimental diffusivities do not exist over the whole range of concentration, an interpolation of the diffusivities at infinite dilution D k] J is used. In calculating the diffusivities at infinite dilution by the Stokes-Einstein relation, we consider small isolated hard spheres, submerged in a liquid, that are subjected to Brownian motion The friction of the spheres in the liquid is given by the Stokes law Einstein used the Stokes law to calculate the mean-square displacement of a particle. The displacement increases linearly with time, and the proportionality constant is the Stokes-Einstein diffusivity... 

This equation was deduced in Section 4.4.8. It is of interest to inquire here about its degree of appiicabiiity to ionic liquids, i.e., fused salts. To make a test, the experimental values of the self-diffusion coefficient D and the viscosity tj are used in conjunction with the known crystal radii of the ions. The product D r//T has been tabulated in Table 5.22, and the plot of D tj/T versus 1/r is presented in Fig. 5.31, where the line of slope k/6n corresponds to exact agreement with the Stokes-Einstein relation. ... 

Hydrodynamic theory [67], based on Stokes-Einstein equation, postulates that solute is represented by a very large sphere in comparison with the surrounding small liquid phase molecules. Solute mobility, and thus its diffusion coefficient, depends on the frictional drag exerted by liquid phase molecules. For heterogeneous gels (rigid polymeric chains), Cukier [85] suggests... 

These last two equations are derived on the basis of the Eyring theory of holes in liquids. The assumptions here, in contrast to those of the Stokes-Einstein equations, are that the diffusing molecules are of the same order of size as those of the solvent. The discontinuity of the liquid medium thus plays an essential part in the Eyring theory, the fundamental length X being the distance between successive positions of the diffusing solute or solvent molecule as it jumps between the molecules of the liquid. The quantities D and )/, however, refer to the diffusion constant and the viscosity of the system measured in the usual way. They represent the observed effect of very large numbers of such molecular jumps. 

For a large particle in a fluid at liquid densities, there are collective hydro-dynamic contributions to the solvent viscosity r, such that the Stokes-Einstein friction at zero frequency is In Section III.E the model is extended to yield the frequency-dependent friction. At high bath densities the model gives the results in terms of the force power spectrum of two and three center interactions and the frequency-dependent flux across the transition state, and at low bath densities the binary collisional friction discussed in Section III C and D is recovered. However, at sufficiently high frequencies, the binary collisional friction term is recovered. In Section III G the mass dependence of diffusion is studied, and the encounter theory at high density exhibits the weak mass dependence. 

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