Resistance transfer

Figure Bl.28.8. Equivalent circuit for a tliree-electrode electrochemical cell. WE, CE and RE represent the working, counter and reference electrodes is the solution resistance, the uncompensated resistance, R the charge-transfer resistance, R the resistance of the reference electrode, the double-layer capacitance and the parasitic loss to tire ground.

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. 

In contrast, physical adsorption is a very rapid process, so the rate is always controlled by mass transfer resistance rather than by the intrinsic adsorption kinetics. However, under certain conditions the combination of a diffiision-controUed process with an adsorption equiUbrium constant that varies according to equation 1 can give the appearance of activated adsorption. 

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... 

Eor a linear system f (c) = if, so the wave velocity becomes independent of concentration and, in the absence of dispersive effects such as mass transfer resistance or axial mixing, a concentration perturbation propagates without changing its shape. The propagation velocity is inversely dependent on the adsorption equiUbrium constant. 

The distance requited to approach the constant pattern limit decreases as the mass transfer resistance decreases and the nonlinearity of the equihbrium isotherm increases. However, when the isotherm is highly favorable, as in many adsorption processes, this distance may be very small, a few centimeters to perhaps a meter. 

The main conclusion to be drawn from these studies is that for most practical purposes the linear rate model provides an adequate approximation and the use of the more cumbersome and computationally time consuming diffusing models is generally not necessary. The Glueckauf approximation provides the required estimate of the effective mass transfer coefficient for a diffusion controlled system. More detailed analysis shows that when more than one mass transfer resistance is significant the overall rate coefficient may be estimated simply from the sum of the resistances (7) ... 

For hquid systems v is approximately independent of velocity, so that a plot of JT versus v provides a convenient method of determining both the axial dispersion and mass transfer resistance. For vapor-phase systems at low Reynolds numbers is approximately constant since dispersion is determined mainly by molecular diffusion. It is therefore more convenient to plot H./v versus 1/, which yields as the slope and the mass transfer resistance as the intercept. Examples of such plots are shown in Figure 16. 

This is the important rule of additivity of resistances. In practice, and are often of the same order of magnitude, but the distribution coefficient m can vary considerably. For solutes which preferentially distribute toward solvent B, m is large and the controlling resistance Hes in phased. Conversely, if the distribution favors solvent A the controlling mass-transfer resistance Hes in phase B. 

The enhanced rate expressions for regimes 3 and 4 have been presented (48) and can be appHed (49,50) when one phase consists of a pure reactant, for example in the saponification of an ester. However, it should be noted that in the more general case where component C in equation 19 is transferred from one inert solvent (A) to another (B), an enhancement of the mass-transfer coefficient in the B-rich phase has the effect of moving the controlling mass-transfer resistance to the A-rich phase, in accordance with equation 17. Resistance in both Hquid phases is taken into account in a detailed model (51) which is apphcable to the reversible reactions involved in metal extraction. This model, which can accommodate the case of interfacial reaction, has been successfully compared with rate data from the Hterature (51). 

Mass-transfer theory (eq. 17) iadicates that the overall mass-transfer resistance 1 /consists of contributions from each phase, so that the overall HTU is also the sum of two contributions ... 

This equation predicts that the height of a theoretical diffusion stage increases, ie, mass-transfer resistance increases, both with bed height and bed diameter. The diffusion resistance for Group B particles where the maximum stable bubble size and the bed height are critical parameters may also be calculated (21). 

F r d ic Current. The double layer is a leaky capacitor because Faradaic current flows around it. This leaky nature can be represented by a voltage-dependent resistance placed in parallel and called the charge-transfer resistance. Basically, the electrochemical reaction at the electrode surface consists of four thermodynamically defined states, two each on either side of a transition state. These are (11) (/) oxidized species beyond the diffuse double layer and n electrons in the electrode and (2) oxidized species within the outer Helmholtz plane and n electrons in the electrode, on one side of the transition state and (J) reduced species within the outer Helmholtz plane and (4) reduced species beyond the diffuse double layer, on the other. 

Designed to obtain such fundamental data as chemical rates free of mass transfer resistances or other complications. Some of the heterogeneous reactors of Fig. 23-29, for instance, employ known interfacial areas, thus avoiding one uncertainty. 

Methods for analysis of fixed-bed transitions are shown in Table 16-2. Local equilibrium theoiy is based solely of stoichiometric concerns and system nonlinearities. A transition becomes a simple wave (a gradual transition), a shock (an abrupt transition), or a combination of the two. In other methods, mass-transfer resistances are incorporated. 

Two dimensionless variables play key roles in the analysis of single transition systems (and some multiple transition systems). These are the throughput parameter [see Eq. (16-129)] and the number of transfer units (see Table 16-13). The former is time made dimensionless so that it is equal to unity at the stoichiometric center of a breakthrough cui ve. The latter is, as in packed tower calculations, a measure of mass-transfer resistance. 

Overall Resistance With a linear isotherm (R = 1), the overall mass transfer resistance is the sum of intraparticle and extraparticle resistances. Thus, the overall LDF coefficient for use with a particle-side driving force (column 2 in Table 16-12) is ... 

Axial Dispersion Effects In adsorption bed calculations, axial dispersion effects are typically accounted for by the axial diffusionhke term in the bed conservation equations [Eqs. (16-51) and (16-52)]. For nearly linear isotherms (0.5 < R < 1.5), the combined effects of axial dispersion and mass-transfer resistances on the adsorption behavior of packed beds can be expressed approximately in terms of an apparent rate coefficient for use with a fluid-phase driving force (column 1, Table 16-12) ... 

FIG. 16-12 Correction factors for addition of mass-transfer resistances, relative to effective overall solid phase or fluid phase rates, as a function of the mechanism parameter. Each curve corresponds to both and hj over its entire range. 

With a favorable isotherm and a mass-transfer resistance or axial dispersion, a transition approaches a constant pattern, which is an asymptotic shape beyond which the wave will not spread. The wave is said to be self-sharpening. (If a wave is initially broader than the constant pattern, it will sharpen to approach the constant pattern.) Thus, for an initially uniformly loaded oed, the constant pattern gives the maximum breadth of the MTZ. As bed length is increased, the constant pattern will occupy an increasingly smaller fraction of the bed. (Square-root spreading for a linear isotherm gives this same qualitative result.)... 

The treatment here is restricted to the Langmuir or constant separation factor isotherm, single-component adsorption, dilute systems, isothermal behavior, and mass-transfer resistances acting alone. References to extensions are given below. Different isotherms have been considered, and the theory is well understood for general isotherms. 

Asymptotic Solution Rate equations for the various mass-transfer mechanisms are written in dimensionless form in Table 16-13 in terms of a number of transfer units, N = L/HTU, for particle-scale mass-transfer resistances, a number of reaction units for the reaction kinetics mechanism, and a number of dispersion units, Np, for axial dispersion. For pore and sohd diffusion, q = / // p is a dimensionless radial coordinate, where / p is the radius of the particle, if a particle is bidisperse, then / p can be replaced by the radius of a suoparticle. For prehminary calculations. Fig. 16-13 can be used to estimate N for use with the LDF approximation when more than one resistance is important. 

Correlations of heat and mass-transfer rates are fairly well developed and can be incorporated in models of a reaction process, but the chemical rate data must be determined individually. The most useful rate data are at constant temperature, under conditions where external mass transfer resistance has been avoided, and with small particles... 

Many reactions of solids are industrially feasible only at elevated temperatures which are often obtained by contact with combustion gases, particularly when the reaction is done on a large scale. A product of reaction also is often a gas that must diffuse away from a remaining solid, sometimes through a solid product. Thus, thermal and mass-transfer resistances are major factors in the performance of solid reactions. 

Fuel Characteristics Fuel choice has a major impact on boiler design and sizing. Because of the heat transfer resistance offered by ash deposits in the furnace chamber in a coal-fired boiler, the mean absorbed heat flux is lower than in gas- or oil-fired boilers, so a greater surface area must be provided. Figure 27-42 shows a size comparison between a coal-fired and an oil-fired boiler for the same duty. 

Dispersion Due to Resistance to Mass Transfer Resistance to Mass Transfer in the Mobile Phase... 

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