Mass transfer rate theory

In this type of apparatus, the two phases do not come to equilibrium, at any point in the contactor and the simulation approach is based, therefore, not on a number of equilibrium stages, but rather on a consideration of the relative rates of transport of material through the contactor by flow and the rate of interfacial mass transfer between the phases. For this, a consideration of mass transfer rate theory becomes necessary. 

In many types of contactors, such as stirred tanks, rotary agitated columns, and pulsed columns, mechanical energy is appHed externally in order to reduce the drop si2e far below the values estimated from equations 36 and 37 and thereby increase the rate of mass transfer. The theory of local isotropic turbulence can be appHed to the breakup of a large drop into smaller ones (66), resulting in an expression of the form... 

The rate of mass transfer in the liquid phase in wetted-waU columns is highly dependent on surface conditions. When laminar-flow conditions prevail without the presence of wave formation, the laminar-penetration theory prevails. When, however, ripples form at the surface, and they may occur at a Reynolds number exceeding 4, a significant rate of surface regeneration develops, resulting in an increase in mass-transfer rate. 

In general, the observed mass-transfer rates are greater than those predicted by theory and may be related to the development of surface ripphng, a phenomenon which increases in intensity with increasing liquid path. 

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... 

The theory is equally applicable when bulk flow occurs. In gas absorption, for example where may be expressed the mass transfer rate in terms of the concentration gradient in the gas phase ... 

When mass transfer rates are very high, limitations may be placed on the rate at which a component may be transferred, by virtue of the limited frequency with which the molecules collide with the surface. For a gas, the collision rate can be calculated from the kinetic theory and allowance must then be made for the fact that only a fraction of these molecules may be absorbed, with the rest being reflected. Thus, when even a pure gas is brought suddenly into contact with a fresh solvent, the initial mass transfer rate may be controlled by the rate at which gas molecules can reach the surface, although the resistance to transfer rapidly builds up in the liquid phase to a level where this effect can be neglected. The point is well illustrated in Example 10.4. 

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 ... 

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 ... 

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 ... 

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. 

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 ... 

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 ... 

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... 

In Ref. 30, the transfer of tetraethylammonium (TEA ) across nonpolarizable DCE-water interface was used as a model experimental system. No attempt to measure kinetics of the rapid TEA+ transfer was made because of the lack of suitable quantitative theory for IT feedback mode. Such theory must take into account both finite quasirever-sible IT kinetics at the ITIES and a small RG value for the pipette tip. The mass transfer rate for IT experiments by SECM is similar to that for heterogeneous ET measurements, and the standard rate constants of the order of 1 cm/s should be accessible. This technique should be most useful for probing IT rates in biological systems and polymer films. 

The experiments were conducted at four different temperatures for each gas. At each temperature experiments were performed at different pressures. A total of 14 and 11 experiments were performed for methane and ethane respectively. Based on crystallization theory, and the two film theory for gas-liquid mass transfer Englezos et al. (1987) formulated five differential equations to describe the kinetics of hydrate formation in the vessel and the associate mass transfer rates. The governing ODEs are given next. 

For a number of flow situations, the mass-transfer rate can be derived directly from the equation of convective diffusion (see Table VII, Part A). The velocity profile near the electrode is known, and the equation is reduced to a simpler form by appropriate similarity transformations (N6). These well-defined flows, therefore, are being exploited increasingly by electrochemists as tools for the kinetic characterization of electrode reactions. Current distributions at, or below, the limiting current, transient mass transfer, and other aspects of these flows are amenable to analysis. Especially noteworthy are the systematic investigations conducted by Newman (review until 1973 in N7 also N9b, N9c, H6b and references in Table VII), by Daguenet and other French workers (references in Table VII), and by Matsuda (M4a-d). Here we only want to comment on the nature of the velocity profile near the electrode, and on the agreement between theory and mass-transfer experiment. 

Numerous turbulent mass-transfer relationships are given in Eqs. (39)-(50), Table VII. Although the most important ones in practical applications are those for channels and tubes, several other configurations also have been investigated because of their hydrodynamic interest. Generally, it is not possible to predict mass-transfer rates quantitatively by recourse to turbulent flow theory. An exception to this is for the region of developing mass transfer, where a Leveque-type correlation between the mass-transfer coefficient and friction coefficient/can be established ... 

By substituting the well-known Blasius relation for the friction factor, Eq. (45) in Table VII results. Van Shaw et al. (V2) tested this relation by limiting-current measurements on short pipe sections, and found that the Re and (L/d) dependences were in accord with theory. The mass-transfer rates obtained averaged 7% lower than predicted, but in a later publication this was traced to incorrect flow rate calibration. Iribame et al. (110) showed that the Leveque relation is also valid for turbulent mass transfer in falling films, as long as the developing mass-transfer condition is fulfilled (generally expressed as L+ < 103) while Re > 103. The fundamental importance of the Leveque equation for the interpretation of microelectrode measurements is discussed at an earlier point. 

When the concentration profile is fully developed, the mass-transfer rate becomes independent of the transfer length. Spalding (S20a) has given a theory of turbulent convective transfer based on the hypothesis that profiles of velocity, total (molecular plus eddy) viscosity, and total diffusivity possess a universal character. In that case the transfer rate k + can be written in terms of a single universal function of the transfer length L and fluid properties (expressed as a molecular and a turbulent Schmidt number) ... 

Janssen and Hoogland (J3, J4a) made an extensive study of mass transfer during gas evolution at vertical and horizontal electrodes. Hydrogen, oxygen, and chlorine evolution were visually recorded and mass-transfer rates measured. The mass-transfer rate and its dependence on the current density, that is, the gas evolution rate, were found to depend strongly on the nature of the gas evolved and the pH of the electrolytic solution, and only slightly on the position of the electrode. It was concluded that the rate of flow of solution in a thin layer near the electrode, much smaller than the bubble diameter, determines the mass-transfer rate. This flow is affected in turn by the incidence and frequency of bubble formation and detachment. However, in this study the mass-transfer rates could not be correlated with the square root of the free-bubble diameter as in the surface renewal theory proposed by Ibl (18). 

Mass transfer rate processes, 25 279 Mass-transfer resistance, 11 808 external, 25 290—293 Mass-transfer theory, 10 761 Mass transport, electrochemical cell, 9 658-659... 

All three of these proposals give the mass transfer rate N A directly proportional to the concentration difference (CAi — CAL) so that they do not directly enable a decision to be made between the theories. However, in the Higbie-Danckwerts theory N A a s/Dj whereas NA film theory. Danckwerts applied this theory to the problem of absorption coupled with chemical reaction but, although in this case the three proposals give somewhat different results, it has not been possible to distinguish between them. 

On the basis of the simplified view of the flow patterns just described, a model for predicting mass transfer rates can be developed using penetration theory and the fact that mass is transferred simultaneously from both the nip and the wiped film. We can therefore write that the total molar mass transfer rate from an element of fluid over a length dk in the extruder is... 

A specific expression for the mass transfer rate in Eq. (11) was first developed by Latinen (1962) in a classic paper that showed how penetration theory can be applied to the analysis of devolatilization processes in single-screw extruders. The derivation presented here parallels that by Latinen but differs in some respects for reasons of clarity. 

Finally, a number of experimental studies have been conducted in a pressure range where the polymeric solution could boil. The vapor bubbles thus created would provide a much larger surface area for mass transfer than the surface area of the wiped film alone. And therefore, for fixed values of the diffusivity and the driving force, predicted values for mass transfer rates would be substantially lower than the measured values. Conversely, for a fixed mass transfer rate and driving force, use of the wiped film surface area alone would require unusually high values of the diffusivity in order to obtain agreement between theory and experiment. 

In a study in which styrene was stripped from polystyrene, Latinen (1962) concluded that his theory correctly described the dependence of mass transfer rates on screw speed and flow rate. This conclusion was based on the agreement obtained between the measured and predicted exit concentration of styrene over a broad range of screw speeds and flow rates (Fig. 8). But, agreement between the theoretical expression and the experimental data was obtained using a diffusion coefficient of the order of 3 X 10 m sec , at 2(X)°C a value which is unrealistically high for this system. If the system ethylbenzene-polystyrene—which has a diffusion... 

The mass transfer rates for the case when d > d can easily be obtained from Eqs. 9 or 12 (see [48]). Using the surface renewal theory this case is not relevant because the boundary layer thickness is here considered to be infinite. 

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