Surface renewal

If, on the other hand, it is assumed that contact times for the individual fluid elements vary at random, an exponential surface age distribution characterized by a fractional rate of renewal s may be used (34). This approach is caUed surface renewal theory and results in... 

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... 

Note that both the penetration and the surface-renewal theories predict a square-root dependency on D. Also, it should be recognized that values of the surface-renewal rate s generally are not available, which presents the same problems as do 6 and t in the film and penetration models. 

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... 

Pasveer (PI) studied oxygen absorption from air bubbles by water and found that the experimental results could be adequately correlated in terms of a penetration or surface-renewal theory. 

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. 

Marchello and Toor (M2) proposed a mixing model for transfer near a boundary which assumes that localized mixing occurs rather than gross displacement of the fluid elements. This model can be said to be a modified penetration-type model. Kishinevsky (K6-K8) assumed a surface-renewal mechanism with eddy diffusion rather than molecular diffusion controlling the transfer at the interface. 

Q Flux of absorbed surfactants p Rate of surface renewal by eddies P Power input to impeller P Flux of desorbed surfactants P0 Power input to impeller, no-gas condition... 

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 ... 

If the probability of surface renewal is linearly related to age, as opposed to being constant, obtain the corresponding form of the age distribution function. 

Using the Danckwerts surface renewal model, estimate ... 

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 ... 

In a particular application, it is found that the older surface is renewed more rapidly than the recently formed surface, and that after a lime l/s, the surface renewal rate doubles, that is increases from s to 2s, Obtain the new age distribution function. 

When the electrode/solution system contains substances that are oxidized or reduced faster than the surface can be renewed, the potentials observed during the surface renewal are shifted. 

---