Mass transfer between phases film coefficients

As the interface offers no resistance, mass transfer between phases can be regarded as the transfer of a component from one bulk phase to another through two films in contact, each characterized by a mass-transfer coefficient. This is the two-film theory and the simplest of the theories of interfacial mass transfer. For the transfer of a component from a gas to a liquid, the theory is described in Fig. 6B. Across the gas film, the concentration, expressed as partial pressure, falls from a bulk concentration Fas to an interfacial concentration Ai- In the liquid, the concentration falls from an interfacial value Cai to bulk value Cai-... 

It can be seen in Figs 7.18 and 7.19 that in range of the impinging velocity w0 from 5.53 TO 16.62 m s-1 the values for volumetric mass transfer coefficient and the gas-film one ranged from 0.577 to 1.037 s l and 0.00641 to 0.0416 m s1, respectively, showing clearly the effect of impinging streams enhancing transfer between phases. 

As is shown in Figure 2, in the two-phase model the fluid bed reactor is assumed to be divided into two phases with mass transfer across the phase boundary. The mass transfer between the two phases and the subsequent reaction in the suspension phase are described in analogy to gas/liquid reactors, i.e. as an absorption of the reactants from the bubble phase with pseudo-homogeneous reaction in the suspension phase. Mass transfer from the bubble surface into the bulk of the suspension phase is described by the film theory with 6 being the thickness of the film. D is the diffusion coefficient of the gas and a denotes the mass transfer coefficient based on unit of transfer area between the two phases. 6 is given by 6 = D/a. 

Fast and satisfactory mass transfer calculations are necessary since we may have to repeat such calculations many times for a rate-based distillation column model or two-phase flow with mass transfer between the phases in the design and simulation process. The generalized matrix method may be used for multicomponent mass transfer calculations. The generalized matrix method utilizes the Maxwell-Stefan model with the linearized film model for diffusion flux, assuming a constant diffusion coefficient matrix and total concentration in the diffusion region. In an isotropic medium, Fick s law may describe the multicomponent molecular mass transfer at a specified temperature and pressure, assuming independent diffusion of the species in a fluid mixture. Such independent diffusion, however, is only an approximation in the following cases (i) diffusion of a dilute component in a solvent, (ii) diffusion of various components with identical diffusion properties, and (iii) diffusion in a binary mixture. 

The thickness of the fictitious film can neither be predicted nor measured experimentally. This limits the use of the film theory to directly calculate the mass transfer coefficients from the diffusivity. Nevertheless, the film theory is often applied in a two-resistance model to describe the interphase mass transfer between the two contacting phases (gas and liquid). This model assumes that the resistance to mass transfer only exists in gas and liquid films. The interfacial concentrations in gas and liquid are in equilibrium. The interphase mass transfer involves the transfer of mass from the bulk of one phase to the interfacial surface, the transfer across the interfacial surface into the second phase, and the transfer of mass from the interface to the bulk of the second phase. This process is described graphically in Fig. 1. 

Figure 10.8. Ratio /C12A115 which are elements of the zero-flux matrix of mass transfer coefficients [/c], as a function of the gas-phase Reynolds number. Mass transfer between a gaseous mixture of acetone (l)-benzene (2)-helium (3) and a liquid film containing acetone and benzene. Calculations by Krishna (1982) based on the von Karman turbulent film model and the Chilton-Colburn analogy.

Mass transfer, an important phenomenon in science and engineering, refers to the motion of molecules driven by some form of potential. In a majority of industrial applications, an activity or concentration gradient serves to drive the mass transfer between two phases across an interface. This is of particular importance in most separation processes and phase transfer catalyzed reactions. The flux equations are analogous to Ohm s law and the ratio of the chemical potential to the flux represents a resistance. Based on the stagnant-film model. Whitman and Lewis [25,26] first proposed the two-film theory, which stated that the overall resistance was the sum of the two individual resistances on the two sides. It was assumed in this theory that there was no resistance to transport at the actual interface, i.e., within the distance corresponding to molecular mean free paths in the two phases on either side of the interface. This argument was equivalent to assuming that two phases were in equilibrium at the actual points of contact at the interface. Two individual mass transfer coefficients (Ld and L(-n) and an overall mass transfer coefficient (k. ) could be defined by the steady-state flux equations ... 

A number of attempts have been made to relate the values of kA obtained for one system with those for other systems. The coefficients involve resistances to mass transfer for both the vapor and the liquid phases, and it has been customary to apply relations based on the Lewis and Whitman two-film theory. It is doubtful that such a theory is applicable in this case since it is difficult to visualize the conditions inherent in this theory for a liquid phase in a packed tower. Further studies of the mechanism of mass transfer between the vapor and the liquid for systems approximating the conditions in a packed tower are needed to furnish a sound basis for correlating the over-all mass-transfer coefficients. 

This equation, due to Higbie, was originally derived to describe mass transfer between rising gas bubbles and a surrounding liquid Tran. AIChE, 31,368 [1935]). It applies quite generally to situations where the contact time between the phases is short and the penetration (or depletion) depth is so small that transfer may be viewed as taking place from a plant to a semiinfinite domain. In Section 4.1.2.3 we will provide a quantitative criterion for this approach, which is also referred to as the Penetration Theory. It also describes both the short- and long-term behavior in diffusion between a plane and a semi-infinite space, and we used this property in Chapter 1, Table 1.4, to help us set upper and lower bounds to mass transfer coefficients and "film" thickness Zp j. 

Here, the A term is due to eddy dispersion and flow contribution to plate height and is independent of ly it is a function of the particle size and the packing efficiency. The next term includes B, which depends on the molecular diffusion coefficient in the longitudinal direction, i.e. the mobile-phase diffusivity. The third term includes C, which results from mass transfer between the mobile and stationary phases and has contributions from (1) diffiision in the film around the particle in the column, (2) diffiision in the Uquid phase that is stagnant in the pores and (3) diffusion in the liquid-phase coating on particles. 

The rate of mass transfer,/, is then assumed to be proportional to the concentration differences existing within each phase, the surface area between the phases,, and a coefficient (the gas or Hquid film mass transfer coefficient, k or respectively) which relates the three. Thus... 

Mass-Transfer Coefficients with Chemical Reaction. Chemical reaction can occur ia any of the five regions shown ia Figure 3, ie, the bulk of each phase, the film ia each phase adjacent to the iaterface, and at the iaterface itself. Irreversible homogeneous reaction between the consolute component C and a reactant D ia phase B can be described as... 

An important mixing operation involves bringing different molecular species together to obtain a chemical reaction. The components may be miscible liquids, immiscible liquids, solid particles and a liquid, a gas and a liquid, a gas and solid particles, or two gases. In some cases, temperature differences exist between an equipment surface and the bulk fluid, or between the suspended particles and the continuous phase fluid. The same mechanisms that enhance mass transfer by reducing the film thickness are used to promote heat transfer by increasing the temperature gradient in the film. These mechanisms are bulk flow, eddy diffusion, and molecular diffusion. The performance of equipment in which heat transfer occurs is expressed in terms of forced convective heat transfer coefficients. 

The relation between CAi[ and CAi2 is determined by the phase equilibrium relationship since the molecular layers on each side of the interface are assumed to be in equilibrium with one another. It may be noted that the ratio of the differences in concentrations is inversely proportional to the ratio of the mass transfer coefficients. If the bulk concentrations, CAt> and CA02 are fixed, the interface concentrations will adjust to values which satisfy equation 10.98. This means that, if the relative value of the coefficients changes, the interface concentrations will change too. In general, if the degree of turbulence of the fluid is increased, the effective film thicknesses will be reduced and the mass transfer coefficients will be correspondingly increased. 

Reaction between an absorbed solute and a reagent lowers the equilibrium partial pressure of the solute and thus increases the rate of mass transfer. The mass transfer coefficient likewise may be enhanced which contributes further to increased absorption rate. Three modes of contacting gas and liquid phases are possible The gas is dispersed as bubbles in the liquid, the liquid is dispersed as droplets, the two phases are contacted on a thin liquid film deposited over a packing or wall. The choice between these modes is an important practical problem. 

The film (individual) coefficients of mass transfer can be defined similarly to the film coefficient of heat transfer. A few different driving potentials are used today to define the film coefficients of mass transfer. Some investigators use the mole fraction or molar ratio, but often the concentration difference AC (kg or kmol m ) is used to define the liquid phase coefficient (m while the partial pressure difference A/i (atm) is used to define the gas film coefficient (kmolh m 2 atm ). However, using and A gp of different dimensions is not very convenient. In this book, except for Chapter 15, we shall use the gas phase coefficient (m h" ) and the liquid phase coefficient ki (m h ), both of which are based on the molar concentration difference AC (kmol m ). With such practice, the mass transfer coefficients for both phases have the same simple dimension (L T" ). Conversion between k and is easy, as can be seen from Example 2.4. 

The relationships between the overall mass transfer coefficient and the film mass transfer coefficients in both phases are not as simple as in the case of heat transfer, for the following reason. Unlike the temperature distribution curves in heat transfer between two phases, the concentration curves of the diffusing component in the two phases are discontinuous at the interface. The relationship between the interfacial concentrations in the two phases depends on the solubility of the diffusing component. Incidentally, it is known that there exists no resistance to mass transfer at the interface, except when a surface-active substance accumulates at the interface to give additional mass transfer resistance. 

The overall coefficients of liquid-liquid mass transfer are important in the calculations for extraction equipment, and can be defined in the same way as the overall coefficients of gas-liquid mass transfer. In liquid-liquid mass transfer, one component dissolved in one liquid phase (phase 1) will diffuse into another liquid phase (phase 2). We can define the film coefficients /C i (nr h" ) and k (m h ) for phases 1 and 2, respectively, and whichever of the overall coefficients A (m h ), defined with respect to phase 1, or Al2 (mh ) based on phase 2, is convenient can be used. Relationships between the two film coefficients and two overall coefficients are analogous to those for gas-liquid mass transfer that is,... 

The experimental determination of the film coefficients kL and kc is very difficult. When the equilibrium distribution between the two phases is linear, over-all coefficients, which are more easily determined by experiment, can be used. Over-all coefficients can be defined from the standpoint of either the liquid phase or gas phase. Each coefficient is based on a calculated over-all driving force Ac, defined as the difference between the bulk concentration of one phase (cL or cc) and the equilibrium concentration (cL or cc ) corresponding to the bulk concentration of the other phase. When the controlling resistance is in the liquid phase, the over-all mass transfer coefficient KLa is generally used ... 

The connection between the film mass transfer coefficients and the over-all mass transfer coefficients is provided by the two-film theory from Lewis and Whitman (1924) the total resistance to mass transfer is the sum of the resistances in each phase. 

In the impinging streams of gas-liquid systems, high relative velocity between phases and collision between droplets favor surface renewing of droplets, resulting in reduced liquid film resistance and thus increased overall mass transfer coefficient. 

When Kh is a function of composition, the concept of overall mass transfer coefficient stops being useful. Instead, the overall resistance to mass transfer is divided between two film resistances, one for each phase. This is done by assuming that equilibrium is achieved at the interface. The equilibrium values are related by a function having the form of Henry s law ... 

A boundary layer is formed between the two phases (fluid and solid). This is a stagnant film that represents a layer of less movement of the fluid and hence builds up a zone with resistance to mass transfer. The mass transfer coefficient and generally the mass transfer rate depend on the fluid dynamics of the system. Higher fluid velocities significantly reduce the thickness of the film. 

The square of this number represents the ratio between the maximum reaction rate of ozone near the water interface (film thickness) and the maximum physical absorption rate (i.e., the absorption without reaction). In Eq. (9), kD and kL are parameters representing the chemical reaction and physical diffusion rate constants, that is, the rate constant of the ozone-compound reaction and water phase mass transfer coefficient, respectively. Their values are indicative of the importance of both the physical and chemical steps in terms of their rates. However, two additional parameters, as shown in Eq. (9), are also needed the concentration of the compound, CM, and the diffusivity of ozone in water, Z)0i. The ozone diffusivity in water can be calculated from empirical equations such as those of Wilke and Chang [55], Matrozov et al. [56], and Johnson and Davies [57] from these equations, at 20°C, D0 is found to be 1.62xl0 9, 1.25xl0-9, and 1.76xl0 9 m2 s 1, respectively. 

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