Diffusive flux molecular diffusivity coefficient

We will now describe the application of the two principal methods for considering mass transport, namely mass-transfer models and diffusion models, to PET polycondensation. Mass-transfer models group the mass-transfer resistances into one mass-transfer coefficient ktj, with a linear concentration term being added to the material balance of the volatile species. Diffusion models employ Fick s concept for molecular diffusion, i.e. J = — D,v ()c,/rdx, with J being the molar flux and D, j being the mutual diffusion coefficient. In this case, the second derivative of the concentration to x, DiFETd2Ci/dx2, is added to the material balance of the volatile species. 

Reid, Sherwood and Prausnitz [11] provide a wide variety of models for calculation of molecular diffusion. Dr is the Knudsen diffusion coefficient. It has been given in several articles as 9700r(T/MW). Once we have both diffusion coefficients we can obtain an expression for the macro-pore diffusion coefficient 1/D = 1/Dk -i-1/Dm- We next obtain the pore diffusivity by inclusion of the tortuosity Dp = D/t, and finally the local molar flux J in the macro-pores is described by the famiUar relationship J = —e D dcjdz. Thus flux in the macro-pores of the adsorbent product is related to the term CpD/r. This last quantity may be thought of as the effective macro-pore diffusivity. The resistance to mass transfer that develops due to macropore diffusion has a length dependence of R]. 

In the above, D rn is the water diffusion coefficient through the membrane phase only. Note also that the water fluxes through the membrane phase, via electro-osmotic drag and molecular diffusion, represent a source/sink term for the gas mixture mass in the anode and cathode, respectively. 

The thermal motion of molecules of a given substance in a solvent medium causes dispersion and migration. If dispersion takes place by intermolecular forces acting within a gas, fluid, or solid, molecular diffusion takes place. In a turbulent medium, the migration of matter within it is defined as turbulent diffusion or eddy diffusion. Diffusional flux J is the product of linear concentration gradient dCldX multiphed by a proportionality factor generally defined as diffusion coefficient (D) (see section 4.11) ... 

Diffusion in a binary system may also be determined by measurement of the intradiffusion coefficient (sometimes referred to as the self-diffusion coefficient), D. In the case of intradiffusion, no net flux of the bulk diffusant occurs the molecules undergo an exchange process. Measurements are usually carried out by using trace amounts of labelled components in a system free of any gradients in the chemical potential. The molecular movement of the solute is governed by frictional interactions between labelled solute and solvent, and labelled solute and unlabelled solute. 

In these equations is the partial molal free energy (chemical potential) and Vj the partial molal volume. The Mj are the molecular weights, c is the concentration in moles per liter, p is the mass density, and z, is the mole fraction of species i. The D are the multicomponent diffusion coefficients, and the are the multicomponent thermal diffusion coefficients. The first contribution to the mass flux—that due to the concentration gradients—is seen to depend in a complicated way on the chemical potentials of all the components present. It is shown in the next section how this expression reduces to the usual expressions for the mass flux in two-component systems. The pressure diffusion contribution to the mass flux is quite small and has thus far been studied only slightly it is considered in Sec. IV,A,6. The forced diffusion term is important in ionic systems (C3, Chapter 18 K4) if gravity is the only external force, then this term vanishes identically. The thermal diffusion term is impor-... 

One well-known example of the gradient-flux law is Fick s first law, which relates the diffusive flux of a chemical to its concentration gradient and to the molecular diffusion coefficient ... 

It should be pointed out that for a low pressure gas the radial- and axial diffusion coefficients are about the same at low Reynolds numbers (Rediffusion effects may be important at velocities where the dispersion effects are controlled by molecular diffusion. For Re = 1 to 20, however, the axial diffusivity becomes about five times larger than the radial diffusivity [31]. Therefore, the radial diffusion flux could be neglected relative to the longitudinal flux. If these phenomena were also present in a high-pressure gas, it would be true that radial diffusion could be neglected. In dense- gas extraction, packed beds are operated at Re > 10, so it will be supposed that the Peclet number for axial dispersion only is important (Peax Per). 

In Equation (9.6), x is the direction of flux, nt [mol m-3 s 1 ] is the total molar density, X [1] is the mole fraction, Nd [mol m-2 s 1] is the mole flux due to molecular diffusion, D k [m2 s 1] is the effective Knudsen diffusion coefficient, D [m2 s 1] is the effective bimolecular diffusion coefficient (D = Aye/r), e is the porosity of the electrode, r is the tortuosity of the electrode, and J is the total number of gas species. Here, a subscript denotes the index value to a specific specie. The first term on the right of Equation (9.6) accounts for Knudsen diffusion, and the following term accounts for multicomponent bulk molecular diffusion. Further, to account for the porous media, along with induced convection, the Dusty Gas Model is required (Mason and Malinauskas, 1983 Warren, 1969). This model modifies Equation (9.6) as ... 

The final parameter in Equation (4.9) that determines the value of the concentration polarization modulus is the diffusion coefficient A of the solute away from the membrane surface. The size of the solute diffusion coefficient explains why concentration polarization is a greater factor in ultrafiltration than in reverse osmosis. Ultrafiltration membrane fluxes are usually higher than reverse osmosis fluxes, but the difference between the values of the diffusion coefficients of the retained solutes is more important. In reverse osmosis the solutes are dissolved salts, whereas in ultrafiltration the solutes are colloids and macromolecules. The diffusion coefficients of these high-molecular-weight components are about 100 times smaller than those of salts. 

In an SV experiment, the sedimentation and the diffusion forces that determine the net rate of movement of the solvent—solution boundary, stem from two intrinsic properties of the solute molecules, their sedimentation coefficient (s) and their diffusion coefficient (D). Whereas D depends predominantly on the shape of the solute particles, s depends both on its shape and on its mass. The diffusion coefficient, D, is defined as the ratio of the flux of molecules (Jx, moving in the direction x under diffusive forces) to the concentration gradient of the molecules (dc/dx). The dependence of D on the molecular shape stems from its relation to the frictional coefficient f ... 

Implicit in this model is the assumption that molecular diffusivity and Henry s Law constant are directly and inversely proportional, respectively, to the gas flux across the atmosphere-water interface. Molecular diffusion coefficients typically range from 1 x 10-5 to 4 x 10-5 cm2 s-1 and typically increase with temperature and decreasing molecular weight (table 5.3). Other factors such as thickness of the thin layer and wind also have important effects on gas flux. For example, wind creates shear that results in a decrease in the thickness of the thin layer. The sea surface microlayer has been shown to consist of films 50-100 pm in thickness (Libes, 1992). Other work has referred to this layer as the mass boundary layer (MBL) where a similar range of film thicknesses has been... 

For turbulence it is convenient to describe particle flux in terms of an eddy diffusion coefficient, similar to a molecular diffusion coefficient. Unlike a molecular diffusion coefficient, however, the eddy diffusion coefficient is not constant for a given temperature and particle mobility, but decreases as the eddy approaches a surface. As particles are moved closer and closer to a surface by turbulence, the magnitude of their fluctuations to and from that surface diminishes, finally reaching a point where molecular diffusion predominates. As a result, in turbulent deposition, turbulence establishes a uniform aerosol concentration that extends to somewhere within the viscous sublayer. Then molecular diffusion or particle inertia transports the particles the rest of the way to the surface. 

Fast and satisfactory mass transfer calculations are necessary since we may have to repeat such calculations many times for a rate-based distillation column model or two-phase flow with mass transfer between the phases in the design and simulation process. The generalized matrix method may be used for multicomponent mass transfer calculations. The generalized matrix method utilizes the Maxwell-Stefan model with the linearized film model for diffusion flux, assuming a constant diffusion coefficient matrix and total concentration in the diffusion region. In an isotropic medium, Fick s law may describe the multicomponent molecular mass transfer at a specified temperature and pressure, assuming independent diffusion of the species in a fluid mixture. Such independent diffusion, however, is only an approximation in the following cases (i) diffusion of a dilute component in a solvent, (ii) diffusion of various components with identical diffusion properties, and (iii) diffusion in a binary mixture. 

---