Phase diffusion equation coefficient

In the kinetics of formation of carbides by reaction of the metal widr CH4, the diffusion equation is solved for the general case where carbon is dissolved into tire metal forming a solid solution, until the concentration at the surface reaches saturation, when a solid carbide phase begins to develop on the free surface. If tire carbide has a tirickness at a given instant and the diffusion coefficient of carbon is D in the metal and D in the carbide. Pick s 2nd law may be written in the form (Figure 8.1)... 

The reaction of Si02 with SiC [1229] approximately obeyed the zero-order rate equation with E = 548—405 kJ mole 1 between 1543 and 1703 K. The proposed mechanism involved volatilized SiO and CO and the rate-limiting step was identified as product desorption from the SiC surface. The interaction of U02 + SiC above 1650 K [1230] obeyed the contracting area rate equation [eqn. (7), n = 2] with E = 525 and 350 kJ mole 1 for the evolution of CO and SiO, respectively. Kinetic control is identified as gas phase diffusion from the reaction site but E values were largely determined by equilibrium thermodynamics rather than by diffusion coefficients. 

A useful equation for the calculation of liquid phase diffusivities of dilute solutions of non-electrolytes has been given by Wilke and CHANG(I6). This is not dimensionally consistent and therefore the value of the coefficient depends on the units employed. Using SI units ... 

In addition to the fact that MPC dynamics is both simple and efficient to simulate, one of its main advantages is that the transport properties that characterize the behavior of the macroscopic laws may be computed. Furthermore, the macroscopic evolution equations can be derived from the full phase space Markov chain formulation. Such derivations have been carried out to obtain the full set of hydrodynamic equations for a one-component fluid [15, 18] and the reaction-diffusion equation for a reacting mixture [17]. In order to simplify the presentation and yet illustrate the methods that are used to carry out such derivations, we restrict our considerations to the simpler case of the derivation of the diffusion equation for a test particle in the fluid. The methods used to derive this equation and obtain the autocorrelation function expression for the diffusion coefficient are easily generalized to the full set of hydrodynamic equations. 

Finally, the liquid-phase diffusivities and mass-transfer coefficients are related, as a consequence of equation 9.2-7, by... 

The development of a scientific understanding of diffusion in liquid-phase polymeric systems has been largely due to Duda et al. (1982), Ju et al. (1981), and Vrentas and Duda (1977a,b, 1979) whose work in this area has been signal. In their most recent work, Duda et al. (1982) have developed a theory which successfiilly predicts the strong dependence of the diffusion coefficient on temperature and concentration in polymeric solutions. The parameters in this theory are relatively easy to obtain, and in view of its predictive capability this theory would seem to be most appropriate for incorporating concentration-dependent diffusion coefficients in the diffusion equation. 

This equation shows that the saturation greatly affects the effective gas-phase diffusion coefficients. Hence, flooding effects are characterized by the saturation. 

Equation (105) is the basis for the determination of gas-phase diffusion coefficients and ultra low vapor pressures using the methods proposed by Davis and Ray (1977), Ravindran et al. (1979), and Ray et al. (1979). Additional information can be gained by writing the Chapman-Enskog first approximation for the gas-phase diffusivity (Chapman and Cowling, 1970),... 

If the diffusion medium is isotropic in terms of diffusion, meaning that diffusion coefficient does not depend on direction in the medium, it is called diffusion in an isotropic medium. Otherwise, it is referred to as diffusion in an anisotropic medium. Isotropic diffusion medium includes gas, liquid (such as aqueous solution and silicate melts), glass, and crystalline phases with isometric symmetry (such as spinel and garnet). Anisotropic diffusion medium includes crystalline phases with lower than isometric symmetry. That is, most minerals are diffu-sionally anisotropic. An isotropic medium in terms of diffusion may not be an isotropic medium in terms of other properties. For example, cubic crystals are not isotropic in terms of elastic properties. The diffusion equations that have been presented so far (Equations 3-7 to 3-10) are all for isotropic diffusion medium. 

Simple component exchange between solid phases is accomplished by diffusion. If only two components (such as Fe " and Mg) are exchanging, the diffusion is binary. The boundary condition is often such that the exchange coefficient between the surfaces of two phases is constant at constant temperature and pressure. The concentrations of the components on the adjacent surfaces may be constant assuming interface equilibrium. The solution to the diffusion equation... 

Solid diffusion control and infinite solution volume In this case, the diffusion coefficient is not a constant but depends on the concentration of the ions in the solid phase. The basic diffusion equation to be solved is the following (Helfferich, 1962) ... 

Die next parameter we need is the diffusion coefficient Df of hydrogen peroxide in water. Here, we can assume the approximate value of 10 9 m2/s. However, this coefficient will be needed further in this example for the determination of the effective solid-phase diffusion coefficient, in a calculation that is extremely sensitive to the value of the liquid-phase diffusion coefficient. For this reason, coefficient should be evaluated with as much accuracy as possible. The diffusion coefficient of solutes in dilute aqueous solutions can be evaluated using the Hayduk and Laudie equation (see eq. (1.26) in Appendix I) ... 

If zeolitic diffusion is sufficiently rapid so that the sorbate concentration through any particular crystal is essentially constant and in equilibrium with the macropore fluid just outside the crystal, the rate of mass transfer will be controlled by transport through the macropores of the pellet. Transport through the macropores may be assumed to occur by a diffusional process characterized by a constant pore diffusion coefficient Z)p. The relevant form of the diffusion equation, neglecting accumulation in the fluid phase within the macropores which is generally small in comparison with accumulation within the zeolite crystals, is... 

Thermodynamic nonidealities are considered both in the transport equations (A10) and in the equilibrium relationships at the phase interface. Because electrolytes are present in the system, the liquid-phase diffusion coefficients should be corrected to account for the specific transport properties of electrolyte solutions. 

The liquid-phase diffusion coefficients are found with the Nemst-Hartley equation (193), which describes the transport properties in weak electrolyte systems. The gas-phase diffusion coefficients are estimated according to the... 

Basically, DESIGNER can use different physical property packages that are easy to interchange with commercial flowsheet simulators. For the case considered, the vapor-liquid equilibrium description is based on the UNIQUAC model. The liquid-phase binary diffusivities are determined using the method of Tyn and Calus (see Ref. 72) for the diluted mixtures, corrected by the Vignes equation (57), to account for finite concentrations. The vapor-phase diffusion coefficients are assumed constant. The reaction kinetics parameters taken from Ref. 202 are implemented directly in the DESIGNER code. 

Equation (4.11) applies provided that the gas phase resistance to the transfer of HTO is limiting. This requires that the accommodation coefficient of molecules at the surface, the solubility, and the liquid phase diffusion, or mixing, within the drop, are all sufficiently high. 

The kinetic equations for the volume phase of the solid body are equations of the diffusion type (63). Much attention has been given to them in the literature [154,155], therefore here will be reminded only those aspects of the theory of mass transfer for which the lattice-gas model has been used. These are problems involved in the construction of expressions for the diffusion the coefficients and boundary conditions of the diffusion equations. 

Knowing an experimental value of k, it is possible to evaluate the diffusion coefficient of the atoms of a dissolving solid substance across the diffusion boundary layer at the solid-liquid interface into the bulk of the liquid phase using equations (5.6) and (5.7). Its calculation includes two steps. First, an approximate value of D is calculated from equation (5.6). Then, the Schmidt number, Sc, and the correction factor, /, is found (see Table 5.1). The final, precise value is evaluated from equation (5.7). In most cases, the results of these calculations do not differ by more than 10 %. Values of the diffusion coefficient of some transition metals in liquid aluminium are presented in Table 5.9.303... 

The square of this number represents the ratio between the maximum reaction rate of ozone near the water interface (film thickness) and the maximum physical absorption rate (i.e., the absorption without reaction). In Eq. (9), kD and kL are parameters representing the chemical reaction and physical diffusion rate constants, that is, the rate constant of the ozone-compound reaction and water phase mass transfer coefficient, respectively. Their values are indicative of the importance of both the physical and chemical steps in terms of their rates. However, two additional parameters, as shown in Eq. (9), are also needed the concentration of the compound, CM, and the diffusivity of ozone in water, Z)0i. The ozone diffusivity in water can be calculated from empirical equations such as those of Wilke and Chang [55], Matrozov et al. [56], and Johnson and Davies [57] from these equations, at 20°C, D0 is found to be 1.62xl0 9, 1.25xl0-9, and 1.76xl0 9 m2 s 1, respectively. 

The gas-phase diffusion coefficients are calculated using the equation given in Ref. [40]. The liquid-phase diffusion coefficients of components at infinite dilution in... 

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