Mass transfer film theory

It may be appropriate here to introduce film theory. As mentioned in reference to the steady diffusion across a thin film, we often hypothesize a film called an unstirred layer to account for the aqueous diffusion resistance to mass transfer. Film theory is valuable not only because of its simplicity but also because of its practical utility. However, the thickness of the film is often difficult to determine. In the following, we try to answer the question, What does the thickness of the film represent ... 

Figure 15.3b is a schematic of the variation of the compositions in the vicinity of the phase interface according to the two-film theory. At a given column height, the liquid and vapor compositions, X and F, are assumed constant, except in the mass transfer films where composition gradients are hypothesized. The compositions at the interface are the equilibrium compositions X and Y. The compositions shown in Figure 15.3b correspond to a component that is being transferred from the vapor to the liquid. 

However, as with the penetration theory analysis, the difference in magnitude of the mass and thermal diffusivities with cx 100 D, means that the heat transfer film is an order of magnitude thicker than the mass transfer film. This is depicted schematically in Fig. 8, The fall in temperature from T over the distance x is (if a = 100 D) about 0% of the overall interface excess temperature above the datum temperature T.. Furthermore, in considering the location of heat release oue to reaction in the mass transfer film, this is bound to be greatest closest to the interface, and this is especially the case when the reaction becomes fast. Therefore, two simplifications can be introduced as a result of this (i) the release of heat of reaction can be treated as am interfacial heat flux and (ii) the reaction can be assumed to take place at the interfacial temperature T. The differential equation for diffusion and reaction can therefore be written... 

Single-screw systems use mass-transfer penetration theory [10], together with certain geometric assumptions, to develop an expression for a film efficiency Ep -... 

The mere presence of a mass-transfer resistance in one phase must have no influence on that in the other the resistances must not interact, in other words. This may be important, since the individual-phase coefficient correlations are frequently developed under conditions where mass-transfer resistance in the second phase is nil, as when the second phase is a pure substance. The analysis of such situations is dependent upon the mechanism assumed for mass transfer (film, surface-renewal, etc., theories), and has been incompletely developed. 

Film Theory. Many theories have been put forth to explain and correlate experimentally measured mass transfer coefficients. The classical model has been the film theory (13,26) that proposes to approximate the real situation at the interface by hypothetical "effective" gas and Hquid films. The fluid is assumed to be essentially stagnant within these effective films making a sharp change to totally turbulent flow where the film is in contact with the bulk of the fluid. As a result, mass is transferred through the effective films only by steady-state molecular diffusion and it is possible to compute the concentration profile through the films by integrating Fick s law ... 

Other Models for Mass Transfer. In contrast to the film theory, other approaches assume that transfer of material does not occur by steady-state diffusion. Rather there are large fluid motions which constantiy bring fresh masses of bulk material into direct contact with the interface. According to the penetration theory (33), diffusion proceeds from the interface into the particular element of fluid in contact with the interface. This is an unsteady state, transient process where the rate decreases with time. After a while, the element is replaced by a fresh one brought to the interface by the relative movements of gas and Uquid, and the process is repeated. In order to evaluate a constant average contact time T for the individual fluid elements is assumed (33). This leads to relations such as... 

Neither the penetration nor the surface renewal theory can be used to predict mass transfer coefficients directiy because T and s are not normally known. Each suggests, however, that mass transfer coefficients should vary as the square root of the molecular diffusivity, as opposed to the first power suggested by the film theory. 

Equation 39 can often be simplified by adopting the concept of a mass transfer unit. As explained in the film theory discussion eadier, the purpose of selecting equation 27 as a rate equation is that is independent of concentration. This is also tme for the Gj /k aP term in equation 39. In many practical instances, this expression is fairly independent of both pressure and Gj as increases through the tower, increases also, nearly compensating for the variations in Gj. Thus this term is often effectively constant and can be removed from the integral ... 

Mass-Transfer Coefficient Denoted by /c, K, and so on, the mass-transfer coefficient is the ratio of the flux to a concentration (or composition) difference. These coefficients generally represent rates of transfer that are much greater than those that occur by diffusion alone, as a result of convection or turbulence at the interface where mass transfer occurs. There exist several principles that relate that coefficient to the diffusivity and other fluid properties and to the intensity of motion and geometry. Examples that are outlined later are the film theoiy, the surface renewal theoiy, and the penetration the-oiy, all of which pertain to ideahzed cases. For many situations of practical interest like investigating the flow inside tubes and over flat surfaces as well as measuring external flowthrough banks of tubes, in fixed beds of particles, and the like, correlations have been developed that follow the same forms as the above theories. Examples of these are provided in the subsequent section on mass-transfer coefficient correlations. 

The factors and Xbm cannot be justified on the basis of mass-transfer theory since they are based on overall resistances. These factors therefore are included in the equations by analogy with the corresponding film equations. 

Simplified Mass-Transfer Theories In certain simple situations, tne mass-transfer coefficients can be calculated from first principles. The film, penetration, and surface-renewal theories are attempts to extend tnese theoretical calculations to more complex sit-... 

Effects of Total Pressure on Uq and The influence of total system pressure on the rate of mass transfer from a gas to a licniid or to a solid has been shown to be the same as would be predicted from stagnant-film theory as defined in Eq. (5-285), where... 

Mass-transfer theory indicates that for trays of a given design the factors most hkely to inflnence E in absorption and stripping towers are the physical properties of the flnids and the dimensionless ratio Systems in which the mass transfer is gas-film-controlled may be expected to have plate efficiencies as high as 50 to 100 percent, whereas plate efficiencies as low as 1 percent have been reported for the absorption of gases of low sohibility (large m) into solvents of relatively high viscosity. 

F = Function of the molecular volume of the solute. Correlations for this parameter are given in Figure 7 as a function of the parameter (j), which is an empirical constant that depends on the solvent characteristics. As points of reference for water, (j) = 1.0 for methanol, (j) = 0.82 and for benzene, (j) = 0.70. The two-film theory is convenient for describing gas-liquid mass transfer where the pollutant solute is considered to be continuously diffusing through the gas and liquid films. 

The simplest theory involved in mass transfer across an interface is film theory, as shown in Figure 3.10. In this model, the gas (CO) is transferred from the gas phase into the liquid phase and it must reach the surface of the growing cells. The rate equation for this case is similar to the slurry reactor as mentioned in Levenspiel.20... 

Increase in mass-transfer rate per unit area. As stated above, agitated gas-liquid contactors are used, in general, when it is necessary to deal with sparingly soluble gases. According to the terminology of the film theory, absorption is then controlled by the liquid resistance, and agitation of the liquid phase could increase the mass-transfer rate per unit area. As will be... 

In evaluating their results they assumed the film theory, and, because the oxygen is sparingly soluble and the chemical reaction rate high, they also assumed that the liquid film is the controlling resistance. The results were calculated as a volumetric mass-transfer coefficient based, however, on the gas film. They found that the volumetric mass-transfer coefficient increased with power input and superficial gas velocity. Their results can be expressed as follows ... 

The mass transfer is treated as a steady state process and therefore the theory can be applied only if the time taken for the concentration gradients to become established is very small compared with the time of transfer, or if the capacities of the films are negligible. 

HARRIOTT 25 suggested that, as a result of the effects of interfaeial tension, the layers of fluid in the immediate vicinity of the interface would frequently be unaffected by the mixing process postulated in the penetration theory. There would then be a thin laminar layer unaffected by the mixing process and offering a constant resistance to mass transfer. The overall resistance may be calculated in a manner similar to that used in the previous section where the total resistance to transfer was made up of two components—a Him resistance in one phase and a penetration model resistance in the other. It is necessary in equation 10.132 to put the Henry s law constant equal to unity and the diffusivity Df in the film equal to that in the remainder of the fluid D. The driving force is then CAi — CAo in place of C Ao — JPCAo, and the mass transfer rate at time t is given for a film thickness L by ... 

Thus either the penetration theory or the film theory (equation 10.144 or 10.145) respectively can be used to describe the mass transfer process. The error will not exceed some 9 per cent provided that the appropriate equation is used, equation 10.144 for L2 jDt > n and equation 10.145 for L2/Dt < n. Equation 10.145 will frequently apply quite closely in a wetted-wall column or in a packed tower with large packings. Equation 10.144 will apply when one of the phases is dispersed in the form of droplets, as in a spray tower, or in a packed tower with small packing elements. 

The penetration and film-penetration theories have been developed for conditions of equimolecular counterdiffusion only the equations are too complex to solve explicitly for transfer through a stationary carrier gas. For gas absorption, therefore, they apply only when the concentration of the material under going mass transfer is low. On the other hand, in the two-fihn theory the additional contribution to the mass transfer which is caused by bulk flow is easily calculated and hp (Section 10.23) is equal to (D/L)(Cr/Cum) instead of D/L. 

In a process where mass transfer takes place across a phase boundary, the same theoretical approach can be applied to each of the phases, though it does not follow that the same theory is best applied to both phases. For example, the film model might be applicable to one phase and the penetration model to the other. This problem is discussed in the previous section. 

When the film theory is applicable to each phase (the two-film theory), the process is steady state throughout and the interface composition does not then vary with time. For this case the two film coefficients can readily be combined. Because material does not accumulate at the interface, the mass transfer rate on each side of the phase boundary will be the same and for two phases it follows that ... 

A pure gas is absorbed into a liquid with which it reacts. The concentration in the liquid is sufficiently low for the mass transfer to be covered by Fick s Law and the reaction is first-order with respect to the solute gas. It may be assumed that the film theory may be applied to the liquid and that the concentration of solute gas falls from the saturation value to zero across the film. The reaction is initially carried out at 293 K. By what factor will the mass transfer rate across the interface change, if the temperature is raised to 313 K ... 

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. 

Ammonia is absorbed in a falling film of water in an absorption apparatus and the film is disrupted and mixed at regular intervals as it flows down the column. The mass transfer rate is calculated from the penetration theory on the assumption that all the relevant conditions apply. It is found from measurements that the muss transfer rate immediately before mixing is only 16 pet cent of that calculated from the theory anil the difference has been attributed to the existence of a surface film which remains intact and unaffected by the mixing process. If the liquid mixing process lakes place every second, what thickness of surface film would account for the discrepancy, ... 

Surface Renewal Theory. The film model for interphase mass transfer envisions a stagnant film of liquid adjacent to the interface. A similar film may also exist on the gas side. These h5q>othetical films act like membranes and cause diffu-sional resistances to mass transfer. The concentration on the gas side of the liquid film is a that on the bulk liquid side is af, and concentrations within the film are governed by one-dimensional, steady-state diffusion ... 

Equation (11.36) gives the central result of film theory and, as is discussed in any good text on mass transfer, happens to be wrong. Experimental measurements show that k, is proportional to rather than to 3>a, at least when the liquid phase is turbulent. 

In the above theory, the interfacial concentrations Coi and Cli are not measurable directly and are therefore of relatively little immediate use. In order to overcome this apparent difficulty, overall mass transfer rate equations are defined by analogy to the film equations. These are based on overall... 

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