Mass surface renewal

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. 

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. 

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-... 

Danckwerts [Jnd. Eng. Chem., 42, 1460(1951)] proposed an extension of the penetration theoiy, called the surface renewal theoiy, which allows for the eddy motion in the liquid to bring masses of fresh liquid continually from the interior to the surface, where they are exposed to the gas for finite lengths of time before being replaced. In his development, Danckwerts assumed that every element of fluid has an equal chance of being replaced regardless of its age. The Danck-werts model gives... 

The predictions of correlations based on the film model often are nearly identical to predictions based on the penetration and surface-renewal models. Thus, in view of its relative simphcity, the film model normally is preferred for purposes of discussion or calculation. It should be noted that none of these theoretical models has proved adequate for maldug a priori predictions of mass-transfer rates in packed towers, and therefore empirical correlations such as those outlined later in Table 5-28. must be employed. 

Bakowsld [B/ Chem. Eng., 8, 384, 472 (1963) 14, 945 (1969)]. It is based on tbe assumption that tbe mass-transfer rate for a component moving to tbe vapor phase is proportional to tbe concentration of tbe component in tbe liquid and to its vapor pressure. Also, tbe interfacial area is assumed proportional to liquid depth, and surface renewal rate is assumed proportional to gas velocity. The resulting general equation for binaiy distillation is... 

With the aid of the surface-renewal concept, Huang and Kuo also derived the equation for the average mass-transfer rate ... 

For mass transfer with irreversible and reversible reactions, the film-penetration model is a more general concept than the film or surface renewal models which are its limiting cases. 

As an example, it may be supposed that in phase 1 there is a constant finite resistance to mass transfer which can in effect be represented as a resistance in a laminar film, and in phase 2 the penetration model is applicable. Immediately after surface renewal has taken place, the mass transfer resistance in phase 2 will be negligible and therefore the whole of the concentration driving force will lie across the film in phase 1. The interface compositions will therefore correspond to the bulk value in phase 2 (the penetration phase). As the time of exposure increases, the resistance to mass transfer in phase 2 will progressively increase and an increasing proportion of the total driving force will lie across this phase. Thus the interface composition, initially determined by the bulk composition in phase 2 (the penetration phase) will progressively approach the bulk composition in phase 1 as the time of exposure increases. 

Average rates of mass transfer can be obtained, as previously, by using either the Higbie or the Danckwerts model for surface renewal. 

Kishinev ski/23 has developed a model for mass transfer across an interface in which molecular diffusion is assumed to play no part. In this, fresh material is continuously brought to the interface as a result of turbulence within the fluid and, after exposure to the second phase, the fluid element attains equilibrium with it and then becomes mixed again with the bulk of the phase. The model thus presupposes surface renewal without penetration by diffusion and therefore the effect of diffusivity should not be important. No reliable experimental results are available to test the theory adequately. 

In the Danekwens model of mass transfer it is assumed that the fractional rate of surface renewal s is constant and independent of surface age. Under such conditions the expression for the surface age distribution function is = If the fractional rate of surface renewal were proportional to surface age (say s — bt. where b is a constant), show that the surface age distribution function would then assume the form ... 

Show that under the conditions specified in Problem 10.7 and assuming the Higbie model of surface renewal, the average mass flux at the interface is given bv ... 

Experiments have been carried out on the mass transfer of acetone between air and a laminar water jet. Assuming that desorption produces random surface renewal with a constant fractional rate of surface renewal, v, but an upper limit on surface age equal to the life of the jet, r, show that the surface age frequency distribution function, 4>(t), for this case is given by ... 

On the assumption that the oxygen transfer can be represented by a surface renewal model, obtain the appropriate equation for mass transfer by starting with Tick s second law of diffusion and calculate ... 

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. 

If for unit area of surface the surface renewal rate is x, by how much will the mass transfer coefficient be changed if no surface has an age exceeding 2A ... 

Danckwerts assumed a random surface renewal process in which the probability of surface renewal is independent of its age. If s is the fraction of the total surface renewed per unit time, obtain the age distribution function for the surface and show that the mean mass transfer rate Na over the whole surface is ... 

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 ... 

When electrically insulated strip or spot electrodes are embedded in a large electrode, and turbulent flow is fully developed, the steady mass-transfer rate gives information about the eddy diffusivity in the viscous sublayer very close to the electrode (see Section VI,C below). The fluctuating rate does not give information about velocity variations, and is markedly affected by the size of the electrode. The longitudinal, circumferential, and time scales of the mass-transfer fluctuations led Hanratty (H2) to postulate a surface renewal model with fixed time intervals based on the median energy frequency. 

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). 

Thin-film and surface renewal evaporators are mostly applied to materials with medium to high viscosity, or to high-boiling contaminated mixtures. A typical thin-film evaporator employs a unique rotor with an array of discrete, plowlike blades attached to the rotor core. The blades transport the viscous concentrate or melt through the evaporator while simultaneously forming films to facilitate heat and mass transfer. 

There are several theories concerned with mass transfer across a phase boundary. One of the most widely used is Whitman s two-film theory in which the resistance to transfer in each phase is regarded as being located in two thin films, one on each side of the interface. The concentration gradients are assumed to be linear in each of these layers and zero elsewhere while at the interface itself, equilibrium conditions exist (Fig. 5). Other important theories are Higbie s penetration theory and the theory of surface renewal due to Danckwerts. All lead to the conclusion that, in... 

Alternatives to the film theory are also in use. These models [Higbie (1935) Danckwerts (1950, 1955)] view that the liquid at the interface is continually washed away and replaced by fresh fluid from the main body of the liquid, and that this is the means of mass transport. These unsteady-state surface renewal theories all predict... 

Since the differential spreading pressure An will oppose the movement of the eddy at the interface, it will also oppose surface renewal and hence mass transfer. Equation (16) explains the form of the plot of l ig. 11. 

One other measurement technique that has been used to measure Kl over a shorter time period, and is thus more responsive to changes in wind velocity, is the controlled flux technique (Haupecker et al., 1995). This technique uses radiated energy that is turned into heat within a few microns under the water surface as a proxy tracer. The rate at which this heat diffuses into the water column is related to the liquid film coefficient for heat, and, through the Prandtl-Schmidt number analogy, for mass as well. One problem is that a theory for heat/mass transfer is required, and Danckwert s surface renewal theory may not apply to the low Prandtl numbers of heat transfer (Atmane et al., 2004). The controlled flux technique is close to being viable for short-period field measurements of the liquid film coefficient. 

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. 

Both the mass transfer kinetic parameters (diffusion in the phases, D, D j, surface renewal frequency, s) and chemical reaction rate constants (kg, kj) strongly influence enhancement of the absorption rate. The particle size, dp, the dispersed liquid holdup, e and the partition coefficient, H can also strongly alter the absorption rate [42-44,46,48]. Similarly, the distance of the first particle from the gas-liquid interface, 6q is an essential factor. Because the diffusion conditions are much better in the dispersed phase (larger solubility and, in most cases, larger diffusivity, as well) the absorption rate should increase with the decrease of the (5g value. 

In 1951,Danckwerts [4] proposed the surface renewal model as an extension ofthe penetration model. Instead of assuming a fixed contact time for all fluid elements, Danckwerts assumed a wide distribution of contact time, from zero to infinity, and supposed that the chance of an element ofthe surface being replaced with fresh liquid was independent of the length of time for which it has been exposed. Then, it was shown, theoretically, that the averaged mass transfer coefficient at the interface is given as... 

It can be seen that a theoretical prediction of values is not possible by any of the three above-described models, because none of the three parameters - the laminar film thickness in the film model, the contact time in the penetration model, and the fractional surface renewal rate in the surface renewal model - is predictable in general. It is for this reason that the empirical correlations must normally be used for the predictions of individual coefficients of mass transfer. Experimentally obtained values of the exponent on diffusivity are usually between 0.5 and 1.0. 

The resistance in each phase is made up of two parts the diffusional resistance in the laminar film and the resistance in the bulk fluid. All current theories on mass transfer, i. e. film, penetration, and surface renewal assume that the resistance in the bulk fluid is negligible and the major resistance occurs in the laminar films on either side of the interface (Figure 3-2). Fick s law of diffusion forms the basis for these theories proposed to describe mass transfer through this laminar film to the phase boundary. 

The theories vary in the assumptions and boundary conditions used to integrate Fick s law, but all predict the film mass transfer coefficient is proportional to some power of the molecular diffusion coefficient D", with n varying from 0.5 to 1. In the film theory, the concentration gradient is assumed to be at steady state and linear, (Figure 3-2) (Nernst, 1904 Lewis and Whitman, 1924). However, the time of exposure of a fluid to mass transfer may be so short that the steady state gradient of the film theory does not have time to develop. The penetration theory was proposed to account for a limited, but constant time that fluid elements are exposed to mass transfer at the surface (Higbie, 1935). The surface renewal theory brings in a modification to allow the time of exposure to vary (Danckwerts, 1951). 

Postulating that n is dependent on the turbulence in the system, Dobbins (1956) proposed that under sufficiently turbulent conditions, n approaches 0.5 (surface renewal or penetration theory), while under laminar or less turbulent conditions n approaches 1.0 (film theory). Thus, the selection of the value for n to predict the mass transfer coefficient should depend on the degree of turbulence in the system ... 

The validity of the penetration theory points out that heat transfer in an agitated viscous thin film (even in the case of evaporation) and the mass transfer are mainly effected by forced convection and continuous surface renewal. 

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