The penetration theory

The work of Higbie laid the basis of the penetration theory in which it is assumed that the eddies in the fluid bring an element of fluid to the interface where it is exposed to the second phase for a definite interval of time, after which the surface element is mixed with the bulk again. Thus, fluid whose initial composition corresponds with that of the bulk fluid remote from the interface is suddenly exposed to the second phase. It is assumed that equilibrium is immediately attained by the surface layers, that a process 

The diffusion of solute A away from the interface (K-direction) is thus given by equation 10.66  

It is convenient to work in terms of a deviation variable C as opposed to CA, where C is the amount by which the concentration of A exceeds the initial uniform concentration CA( . This change allows some simplification of the algebra. 

These boundary conditions are necessary and sufficient for the solution of equation 10.100 which is first order with respect to f and second order with respect to y. 

The equation is most conveniently solved by the method of Laplace transforms, used for the solution of the unsteady state thermal conduction problem in Chapter 9. 

taking Laplace transforms of both sides of equation 10.100  

---

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... 

The values of d and n are given in Table 3 typical values for can be found in Table 4. The exponent of 0.5 on the Schmidt number (l-L /PiLj) supports the penetration theory. Further examples of empirical correlations provide partial experimental confirmation of equation 78 (3,64—68). The correlation reflecting what is probably the most comprehensive experimental basis, the Monsanto Model, also falls in this category (68,69). It is based on 545 observations from 13 different sources and may be summarized as... 

The penetration theory predicts that should vary by the square root of the molecular difriisivity, as compared with film theoiy, which predicts a first-power dependency on D. Various investigators have reported experimental powers of D ranging from 0.5 to 0.75, and the Chilton-Colburn analogy suggests a 2/3 power. 

Aeeording to the penetration theory, liquid elements or pareels remain in eontaet with the gas for a limited time and subsequently are mixed with the bulk. This eoneept is partieularly suited to bubble flows beeause it refleets their... 

The reaction engineering model links the penetration theory to a population balance that includes particle formation and growth with the aim of predicting the average particle size. The model was then applied to the precipitation of CaC03 via CO2 absorption into Ca(OH)2aq in a draft tube bubble column and draws insight into the phenomena underlying the crystal size evolution. 

Weekman and Myers (W3) measured wall-to-bed heat-transfer coefficients for downward cocurrent flow of air and water in the column used in the experiments referred to in Section V,A,4. The transition from homogeneous to pulsing flow corresponds to an increase of several hundred percent of the radial heat-transfer rate. The heat-transfer coefficients are much higher than those observed for single-phase liquid flow. Correlations were developed on the basis of a radial-transport model, and the penetration theory could be applied for the pulsing-flow pattern. 

The absorption is assumed to occur into elements of liquid moving around the bubble from front to rear in accordance with the penetration theory (H13). These elements maintain their identity for a distance into the fluid greater than the effective penetration of dissolving gas during the time required for this journey. The differential equation and initial and boundary conditions for the rate of absorption are then... 

According to the penetration theory, which assumes equal contact for each element (HI3), one can write that... 

These equations are equivalent, but the first converges rapidly for short times and the second for long times. The equations clearly show that for short times the penetration theory is approached ... 

The penetration theory holds for the region where t is much less than L2jD, the film theory for the region where t is much greater than L2/D. This comparison is shown in Fig. 8, which clearly shows that the film and penetration theories are asymptotes of the film-penetration model. 

In an experimental wetted wall column, pure carbon dioxide, is absorbed in water. The mass transfer rate is calculated using the penetration theory, application of which is limited by the fact that the concentration should not teach more than 1 per cent of the saturation value at a depth below the surface at which the velocity is 95 per cent of the surface velocity. What is the maximum length of column to which the theory can be applied if the flowrate of water is 3 cm3/s per cm of perimeter ... 

In a gas-liquid contactor, a pure gas is absorbed in a solvent and the Penetration Theory provides a reasonable model by which to describe the transfer mechanism. As fresh solvent is exposed to the gas, the transfer rate is initially limited by the rate at which the gas molecules can reach the surface. If at 293 K and a pressure of 1 bar the maximum possible rate of transfer of gas is 50 m3/m2s, express this as an equivalent resistance, when the gas solubility is 0.04 kmol/m3. 

The penetration theory has been used to calculate the rate of mass transfer across an interface for conditions where the concentration CAi of solute A in the interfacial layers (y = 0) remained constant throughout the process. When there is no resistance to mass transfer in the other phase, for instance when this consists of pure solute A, there will be no concentration gradient in that phase and the composition at the interface will therefore at all Limes lie the same as the bulk composition. Since the composition of the interfacial layers of the penetration phase is determined by the phase equilibrium relationship, it, too. will remain constant anil the conditions necessary for the penetration theory to apply will hold. If, however, the other phase offers a significant resistance to transfer this condition will not, in general, be fulfilled. 

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 solution of this equation has been discussed by DANCKWERTSt28), and here a solution will be obtained using the Laplace transform method for a semi-infinite liquid initially free of solute. On the assumption that the liquid is in contact with pure solute gas, the concentration Cm at the liquid interface will be constant and equal to the saturation value. The boundary conditions will be those applicable to the penetration theory, that is ... 

According ro the penetration theory, the instantaneous rate of mass transfer per unit area LV, > at some time i after the commencement of transfer is given by ... 

Given that, from the penetration theory for mass transfer across an interface, the instantaneous rale ol mass transfer is inversely proportional to the square root of the time of exposure, obtain a relationship between exposure lime in the Higbie mode and surface renewal rate in the Danckwerts model which will give the same average mass transfer rate. The age distribution function and average mass transfer rate from the Danckwerts theory must be deri ved from first principles. 

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, ... 

In calculating Ihe mass transfer rate from the penetration theory, two models for the age distribution of the surface elements are commonly used — those due to Higbie and to Danckwerts, Explain the difference between the two models and give examples of situations in which each of them would be appropriate. 

In the Danckwerts model, it is assumed that elements of the surface have an age distribution ranging from zero to infinity. Obtain the age distribution function for this model and apply it to obtain the average, mass Iransfer coefficient at the surface, given that from the penetration theory the mass transfer coefficient for surface of age t is VlD/(7rt, where D is the diffusivity. 

Explain the basis of the penetration theory for mass transfer across a phase boundary. What arc the assumptions in the theory which lead to the result that the mass transfer rate is inversely proportional to the square root of the time for which a surface element has been expressed (Do not present a solution of the differential equal ion.) Obtain the age distribution function for the surface ... 

On the. assumptions involved in the penetration theory of mass transfer across a phase boundary, the concentration Ca of a solute A at a depth v below the interface at a time l after the formation of the interlace is given by ... 

In a liquid-liquid extraction unit, spherical drops of solvent of uniform size are continuously fed to a continuous phase of lower density which is flowing vertically upwards, and hence countercurrently with respect to the droplets. The resistance to mass transfer may be regarded as lying wholly within the drops and the penetration theory may be applied. The upward velocity of the liquid, which may be taken as uniform over the cross-section of the vessel, is one-half of the terminal falling velocity of the droplets in the still liquid. 

According to the penetration theory for mass transfer across an interface, the ratio of the concentration Ca at a depth y and time r to the surface concentration Ca. if the liquid is initially free of solute, is giver by ... 

State the assumptions made in the penetration theory for the absorption of a pure gas inlo a liquid. The surface of an initially solute-free liquid is suddenly exposed to a soluble gas and the liquid is sufficiently deep for no solute to have time to reach the bottom of the liquid. Starting with Hick s second law ol diffusion obtain an expression for (i) the concentration, and (ii) the muss transfer rate at a time t and a depth v below the surface. 

It may be assumed that the penetration model may be used to represent the mass transfer process. The depth of penetration is small compared with the radius of the droplets and the effects of surface curvature may he neglected. From the penetration theory, the concentration C, at a depth y below the surface at time r is given by ... 

Wbat is the penetration theory for mass transfer across a phase boundary Give deiails of she underlying... 

From the penetration theory, the mass transfer rate per unit area N, is given in terms of the concentration difference AC, between the interface and the bulk fluid, the molecular diffusivity D and the age t of the. surface clement by ... 

Two rather similar models have been devised to remedy the problems of simple film theory. Both the penetration theory of Higbie and the surface renewal theory of Danckwerts replace the idea of steady-state diffusion across a film with transient diffusion into a semi-inhnite medium. We give here a brief account of surface renewal theory. 

The devolatilization of a component in an internal mixer can be described by a model based on the penetration theory [27,28]. The main characteristic of this model is the separation of the bulk of material into two parts A layer periodically wiped onto the wall of the mixing chamber, and a pool of material rotating in front of the rotor flights, as shown in Figure 29.15. This flow pattern results in a constant exposure time of the interface between the material and the vapor phase in the void space of the internal mixer. Devolatilization occurs according to two different mechanisms Molecular diffusion between the fluid elements in the surface layer of the wall film and the pool, and mass transport between the rubber phase and the vapor phase due to evaporation of the volatile component. As the diffusion rate of a liquid or a gas in a polymeric matrix is rather low, the main contribution to devolatilization is based on the mass transport between the surface layer of the polymeric material and the vapor phase. 

The experimental results imply that the main reaction (eq. 1) is an equilibrium reaction and first order in nitrogen monoxide and iron chelate. The equilibrium constants at various temperatures were determined by modeling the experimental NO absorption profile using the penetration theory for mass transfer. Parameter estimation using well established numerical methods (Newton-Raphson) allowed detrxmination of the equilibrium constant (Fig. 1) as well as the ratio of the diffusion coefficients of Fe"(EDTA) andNO[3]. 

Penetration theories (Higbie, 1935 Danckwerts, 1951 Dobbins, 1956) according to the penetration theory, diffusion of gases takes place into elements of water transported by turbulence to the surface. 

The volatilization of low-molecular-weight by-products from molten PET can be described by using the classical two-film model or the penetration theory of interfacial transport [95],... 

---