Mass transfer, boundary conditions

External Fluid Film Resistance. A particle immersed ia a fluid is always surrounded by a laminar fluid film or boundary layer through which an adsorbiag or desorbiag molecule must diffuse. The thickness of this layer, and therefore the mass transfer resistance, depends on the hydrodynamic conditions. Mass transfer ia packed beds and other common contacting devices has been widely studied. The rate data are normally expressed ia terms of a simple linear rate expression of the form... 

For simplicity, assume that an irreversible reaction of order n occurs on the surface of a catalyst particle. Granted these conditions, mass transfer across an adherent boundary layer may affect the reaction rate. In general at steady state ... 

A proper resolution of Che status of Che stoichiometric relations in the theory of steady states of catalyst pellets would be very desirable. Stewart s argument and the other fragmentary results presently available suggest they may always be satisfied for a single reaction when the boundary conditions correspond Co a uniform environment with no mass transfer resistance at the surface, regardless of the number of substances in Che mixture, the shape of the pellet, or the particular flux model used. However, this is no more than informed and perhaps wishful speculation. 

This rate equation must satisfy the boundary conditions imposed by the equiUbrium isotherm and it must be thermodynamically consistent so that the mass transfer rate falls to 2ero at equiUbrium. It maybe a linear driving force expression of the form... 

Under equiUbrium or near-equiUbrium conditions, the distribution of volatile species between gas and water phases can be described in terms of Henry s law. The rate of transfer of a compound across the water-gas phase boundary can be characterized by a mass-transfer coefficient and the activity gradient at the air—water interface. In addition, these substance-specific coefficients depend on the turbulence, interfacial area, and other conditions of the aquatic systems. They may be related to the exchange constant of oxygen as a reference substance for a system-independent parameter reaeration coefficients are often known for individual rivers and lakes. 

Rata a change o mass per uait Rate of change of mass by coo- Rate of change of mass by Generation per unit volume Boundary Condition(s) (Inierphase Transfer) ... 

In most cases, however, heat transfer and mass transfer occur simultaneously, and the coupled equation (230) thus takes into account the most general case of the coupling effects between the various fluxes involved. To solve Eq (230) with the appropriate initial and boundary conditions one can decouple the equation by making the transformation (G3)... 

The mass transfer process is again governed by equation 10.66, but the third boundary condition is applied at y = L, the film thickness, and not at y = oo. As before, the Laplace... 

As an example, consideration is given to the case where the fluid into which mass transfer is taking place is initially free of solute and is semi-infinite in extent. The surface concentration Cm is taken as constant and the concentration at infinity as zero. The boundary conditions are therefore ... 

The flow conditions in the boundary layer are of considerable interest to chemical engineers because these influence, not only the drag effect of the fluid on the surface, but also the heat or mass transfer rates where a temperature or a concentration gradient exists. 

What are the general principles underlying the two-film, penetration and film-penetration theories for mass transfer across a phase boundary Give the basic differential equations which have to be solved for these theories with the appropriate boundary conditions. 

The inlet and centerline boundary conditions associated with Equation (8.52) are similar to those used for mass transfer ... 

The most important mass transfer limitation is diffusion in the micropores of the catalyst. A simplified model of pore diffusion treats the pores as long, narrow cylinders of length The narrowness allows radial gradients to be neglected so that concentrations depend only on the distance I from the mouth of the pore. Equation (10.3) governs diffusion within the pore. The boundary condition at the mouth of the pore is... 

Traditionally, an average Sherwood number has been determined for different catalytic fixed-bed reactors assuming constant concentration or constant flux on the catalyst surface. In reality, the boundary condition on the surface has neither a constant concentration nor a constant flux. In addition, the Sh-number will vary locally around the catalyst particles and in time since mass transfer depends on both flow and concentration boundary layers. When external mass transfer becomes important at a high reaction rate, the concentration on the particle surface varies and affects both the reaction rate and selectivity, and consequently, the traditional models fail to predict this outcome. 

As reversible ion transfer reactions are diffusion controlled, the mass transport to the interface is given by Fick s second law, which may be directly integrated with the Nernst equation as a boundary condition (see, for instance. Ref. 230 232). A solution for the interfacial concentrations may be obtained, and the maximum forward peak may then be expressed as a function of the interfacial area A, of the potential scan rate v, of the bulk concentration of the ion under study Cj and of its diffusion coefficient D". This leads to the Randles Sevcik equation [233] ... 

Bunimovich et al. (1995) lumped the melt and solid phases of the catalyst but still distinguished between this lumped solid phase and the gas. Accumulation of mass and heat in the gas were neglected as were dispersion and conduction in the catalyst bed. This results in the model given in Table V with the radial heat transfer, conduction, and gas phase heat accumulation terms removed. The boundary conditions are different and become identical to those given in Table IX, expanded to provide for inversion of the melt concentrations when the flow direction switches. A dimensionless form of the model is given in Table XI. Parameters used in the model will be found in Bunimovich s paper. 

Perfect sink conditions externally with finite mass transfer boundary layers. 

The boundary conditions for this early dissolution model included saturated solubility for HA at the solid surface (Cha ) with sink conditions for both HA and A at the outer boundary of a stagnant film (Cha = Ca = 0). Since diffusion is the sole mechanism for mass transfer considered and the process occurs within a hypothesized stagnant film, these types of models are colloquially referred to as film models. Applying the simplifying assumption that the base concentration at the solid surface is negligible relative to the base concentration in the bulk solution (CB CB(o)), it is possible to derive a simplified scaled expression for the relative flux (N/N0) from HPWH s original expressions ... 

The solution of Eqs. (9) is straightforward if the six parameters are known and the boundary conditions are specified. Two boundary conditions are necessary for each equation. Pavlica and Olson (PI) have discussed the applicability of the Wehner-Wilhelm boundary conditions (W3) to two-phase mass-transfer model equations, and have described a numerical method for solving these equations. In many cases this is not necessary, for the second-order differentials can be neglected. Methods for evaluating the dimensionless groups in Eqs. (9) are given in Section II,B,1. 

Equation (23) implies that the current density is uniformly distributed at all times. In reality, when the entire electrode has reached the limiting condition, the distribution of current is not uniform this distribution will be determined by the relative thickness of the developing concentration boundary layer along the electrode. To apply the superposition theorem to mass transfer at electrodes with a nonuniform limiting-current distribution, the local current density throughout the approach to the limiting current should be known. 

---