Diffusion coefficients mutual

For a binary mixture of two components A and B in the gas phase, the mutual diffusion coefficient such as defined in 4.3.2.3, does not depend on composition. It can be calculated by the Fuller (1966) method ... 

Note the use of a script for the binary pair mutual diffusion coefficient, as distinct from the Roman D already used to represent Knudsen diffusion coefficients. This convention will be adhered to throughout. 

In the special case that A and B are similar in molecular weight, polarity, and so on, the self-diffusion coefficients of pure A and B will be approximately equal to the mutual diffusivity, D g. Second, when A and B are the less mobile and more mobile components, respectively, their self-diffusion coefficients can be used as rough lower and upper bounds of the mutual diffusion coefficient. That is, < D g < Dg g. Third, it is a common means for evaluating diffusion for gases at high pressure. Self-diffusion in liquids has been studied by many [Easteal AIChE]. 30, 641 (1984), Ertl and Dullien, AIChE J. 19, 1215 (1973), and Vadovic and Colver, AIChE J. 18, 1264 (1972)]. 

The description of mass transfer requires a separation of the contributions of convection and mutual diffusion. While convection means macroscopic motion of complete volume elements, mutual diffusion denotes the macroscopically perceptible relative motion of the individual particles due to concentration gradients. Hence, when measuring mutual diffusion coefficients, one has to avoid convection in the system or, at least has to take it into consideration. 

In a system with two components, one finds experimentally the same values for and D, because is not independent from J,. It follows that the system can be described with only one mutual diffusion coefficient D = Dj = D2. 

From the molecular point of view, the self-diffusion coefficient is more important than the mutual diffusion coefficient, because the different self-diffusion coefficients give a more detailed description of the single chemical species than the mutual diffusion coefficient, which characterizes the system with only one coefficient. Owing to its cooperative nature, a theoretical description of mutual diffusion is expected to be more complex than one of self-diffusion [5]. Besides that, self-diffusion measurements are determinable in pure ionic liquids, while mutual diffusion measurements require mixtures of liquids. 

From the applications point of view, mutual diffusion is far more important than self-diffusion, because the transport of matter plays a major role in many physical and chemical processes, such as crystallization, distillation or extraction. Knowledge of mutual diffusion coefficients is hence valuable for modeling and scaling-up of these processes. 

The need to predict mutual diffusion coefficients from self-diffusion coefficients often arises, and many efforts have been made to understand and predict mutual diffusion data, through approaches such as, for example, the following extension of the Darken equation [5j ... 

Since the prediction of mutual diffusion coefficients from self-diffusion coefficients is not accurate enough to be used for modeling of chemical processes, complete data sets of mutual and self-diffusion coefficients are necessary and valuable. 

Typical values of self-diffusion coefficients and mutual diffusion coefficients in aqueous solutions and in molten salt systems such as (K,Ag)N03 are of the order... 

Figure 4.4-3 Self-diffusion and mutual diffusion coefficients in the methanol/[BMIM][PFg] sys-...

Self-diffusion coefficients were measured with the NMR spin-echo method and mutual diffusion coefficients by digital image holography. As can be seen from Figure 4.4-3, the diffusion coefficients show the whole bandwidth of diffusion coeffi-... 

Balcom, B Fischer, A Carpenter, T Hall, L, Diffusion in Aqueous Gels. Mutual Diffusion Coefficients Measured by One-Dimensional Nuclear Magnetic Resonance Imaging, Journal of the American Chemical Society 115, 3300, 1993. 

Various diffusion coefficients have appeared in the polymer literature. The diffusion coefficient D that appears in Eq. (3) is termed the mutual diffusion coefficient in the mixture. By its very nature, it is a measure of the ability of the system to dissipate a concentration gradient rather than a measure of the intrinsic mobility of the diffusing molecules. In fact, it has been demonstrated that there is a bulk flow of the more slowly diffusing component during the diffusion process [4], The mutual diffusion coefficient thus includes the effect of this bulk flow. An intrinsic diffusion coefficient, Df, also has been defined in terms of the rate of transport across a section where no bulk flow occurs. It can be shown that these quantities are related to the mutual diffusion coefficient by... 

For practical purposes, the mutual diffusion coefficient is the quantity commonly reported to characterize diffusional transport in pharmaceutical systems. It is thus the purpose of investigators to determine this quantity experimentally. To this end, both sorption and permeation methods are commonly used. 

The permeation technique is another commonly employed method for determining the mutual diffusion coefficient of a polymer-penetrant system. This technique involves a diffusion apparatus with the polymer membrane placed between two chambers. At time zero, the reservoir chamber is filled with the penetrant at a constant activity while the receptor chamber is maintained at zero activity. Therefore, the upstream surface of the polymer membrane is maintained at a concentration of c f. It is noted that c f is the concentration within the polymer surface layer, and this concentration can be related to the bulk concentration or vapor pressure through a partition coefficient or solubility constant. The amount... 

Diffusion of small molecular penetrants in polymers often assumes Fickian characteristics at temperatures above Tg of the system. As such, classical diffusion theory is sufficient for describing the mass transport, and a mutual diffusion coefficient can be determined unambiguously by sorption and permeation methods. For a penetrant molecule of a size comparable to that of the monomeric unit of a polymer, diffusion requires cooperative movement of several monomeric units. The mobility of the polymer chains thus controls the rate of diffusion, and factors affecting the chain mobility will also influence the diffusion coefficient. The key factors here are temperature and concentration. Increasing temperature enhances the Brownian motion of the polymer segments the effect is to weaken the interaction between chains and thus increase the interchain distance. A similar effect can be expected upon the addition of a small molecular penetrant. 

Figure 1 is a schematic diagram illustrating a typical composition dependence of the mutual diffusion coefficient for a polymer-penetrant system [8], Here the penetrant is apparently a good solvent for the polymer since the entire composition range is realized. Note that four regions can be distinguished. In the... 

Figure 1 A schematic diagram illustrating a typical concentration dependence of mutual diffusion coefficient in a polymer-penetrant system. (From Ref. 8.)...

In addition to temperature and concentration, diffusion in polymers can be influenced by the penetrant size, polymer molecular weight, and polymer morphology factors such as crystallinity and cross-linking density. These factors render the prediction of the penetrant diffusion coefficient a rather complex task. However, in simpler systems such as non-cross-linked amorphous polymers, theories have been developed to predict the mutual diffusion coefficient with various degrees of success [12-19], Among these, the most notable are the free volume theories [12,17], In the following subsection, these free volume based theories are introduced to illustrate the principles involved. 

Dt and the mutual diffusion coefficient, D, are interconvertible by correcting for the penetrant activity in the polymer [12], For highly concentrated systems where the penetrant volume fraction, < >, is low,/can be approximated by... 

In general, mass transfer processes involving polymer-penetrant mixtures are generally analyzed by using a mutual diffusion coefficient. Therefore, a relationship between the mutual diffusion coefficient, D, and self-diffusion coefficients, ZVs is needed. Vrentas et al. [30] proposed an equation relating D to D, for polymer-penetrant systems in which Dx is much larger than Dr. 

Figure 5 The mutual diffusion coefficient, D, of sodium chloride as a function of reciprocal matrix hydration, H, in various methacrylate gels. HPMA-GMA polyfhydroxypro-pyl methacrylate-co-glyceryl methacrylate) HEMA polyfhydroxyethyl methacrylate) MMA-GMA poly(methyl methacrylate-co-glyceryl methacrylate) HEMA-MMA poly-(hydroxyethyl methacrylate-co-methyl methacrylate) HPMA-MMA polyfhydroxypropyl methacrylate-co-methyl methacrylate) HPMA-GDMA polyfhydroxypropyl methacry-late-co-glyceryl dimethacrylate). (From Ref. 64.)...

JL Duda, YC Ni, JS Vrentas. An equation relating self-diffusion and mutual diffusion coefficients in polymer-solvent systems. Macromolecules 12 459-462, 1979. 

Although many different processes can control the observed swelling kinetics, in most cases the rate at which the network expands in response to the penetration of the solvent is rate-controlling. This response can be dominated by either diffu-sional or relaxational processes. The random Brownian motion of solvent molecules and polymer chains down their chemical potential gradients causes diffusion of the solvent into the polymer and simultaneous migration of the polymer chains into the solvent. This is a mutual diffusion process, involving motion of both the polymer chains and solvent. Thus the observed mutual diffusion coefficient for this process is a property of both the polymer and the solvent. The relaxational processes are related to the response of the polymer to the stresses imposed upon it by the invading solvent molecules. This relaxation rate can be related to the viscoelastic properties of the dry polymer and the plasticization efficiency of the solvent [128,129],... 

When applied to a volume-fixed frame of reference (i.e., laboratory coordinates) with ordinary concentration units (e.g., g/cm3), these equations are applicable only to nonswelling systems. The diffusion coefficient obtained for the swelling system is the polymer-solvent mutual diffusion coefficient in a volume-fixed reference frame, Dv. Also, the single diffusion coefficient extracted from this analysis will be some average of concentration-dependent values if the diffusion coefficient is not constant. 

Here fcd is the infinite-time specific rate, and D is the mutual diffusion coefficient of the reactants. Using the time-dependent specific rates, Schwarz reports an increase of molecular yields that is 2% at low concentration, and 5% at high concentration of solutes. 

After the jump, the particle is taken to have reacted with a given probability if its distance from another particle is within the reaction radius. For fully diffusion-controlled reactions, this probability is unity for partially diffusion-controlled reactions, this reaction probability has to be consistent with the specific rate by a defined procedure. The probability that the particle may have reacted while executing the jump is approximated for binary encounters by a Brownian bridge—that is, it is assumed to be given by exp[—(x — a)(y — a)/D St], where a is the reaction radius, x andy are the interparticle separations before and after the jump, and D is the mutual diffusion coefficient of the reactants. After all... 

Great simplification is achieved by introducing the hypothesis of independent reaction times (IRT) that the pairwise reaction times evolve independendy of any other reactions. While the fundamental justification of IRT may not be immediately obvious, one notices its similarity with the molecular pair model of homogeneous diffusion-mediated reactions (Noyes, 1961 Green, 1984). The usefulness of the IRT model depends on the availability of a suitable reaction probability function W(r, a t). For a pair of neutral particles undergoing fully diffusion-con-trolled reactions, Wis given by (a/r) erfc[(r - a)/2(D t)1/2] where If is the mutual diffusion coefficient and erfc is the complement of the error function. 

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