Mass transfer liquid interface

The formation of emulsions or microemulsions is conneeted with several dynamic processes the time dependence of surface tensions due to the kinetics of adsorption, the dynamic contact angle, the elasticity of adsorption layers as a mechanic surface property influencing the thiiming of the liquid films between oil droplets, the mass transfer across interfaces and so on. Kahlweit et al. (1990) have recently extended Widom s (1987) concept of wetting or nonwetting of an oil-water interface of the middle phase of weakly-structured mixtures and microemulsions. They pointed out that the phase behaviour of microemulsions does not differ from that of other ternary mixtures, in particular of mixtures of short-chain amphiphiles (cf for example Bourrell Schechter (1988). 

Two-film theory of mass transfer Gas Interface Liquid... 

Mass transfer across interfaces is ubiquitous in industrial processes. For instance, it occurs in separation processes used in the field of biotechnology, in the extraction of metals from aqueous solutions, in the chemical and pharmaceutical industries and also in the treatment of effluents from the same plants. Ho vever, in the design of the contacting equipment the role of the interface and of interfacial phenomena are not taken into account. Take the example of the industrial effluent streams. These are usually not made up of pure components but are soups containing different chemicals and chemicals with surfactant properties. However, in the design of liquid-liquid contactors those streams are considered to be clean and interfacial phenomena (such as Marangoni and gravitational convection), which may exist, are not taken into account. 

In the previous two sections we have presented definitions of mass transfer coefficients and have shown how these coefficients can be found from experiment. Thus we have a method for analyzing the results of mass transfer experiments. This method can be more convenient than diffusion when the experiments involve mass transfer across interfaces. Experiments of this sort include liquid liquid extraction, gas absorption, and distillation. 

Ordinary diffusion involves molecular mixing caused by the random motion of molecules. It is much more pronounced in gases and Hquids than in soHds. The effects of diffusion in fluids are also greatly affected by convection or turbulence. These phenomena are involved in mass-transfer processes, and therefore in separation processes (see Mass transfer Separation systems synthesis). In chemical engineering, the term diffusional unit operations normally refers to the separation processes in which mass is transferred from one phase to another, often across a fluid interface, and in which diffusion is considered to be the rate-controlling mechanism. Thus, the standard unit operations such as distillation (qv), drying (qv), and the sorption processes, as well as the less conventional separation processes, are usually classified under this heading (see Absorption Adsorption Adsorption, gas separation Adsorption, liquid separation). 

Mass-Transfer Principles Dilute Systems When material is transferred from one phase to another across an interface that separates the two, the resistance to mass transfer in each phase causes a concentration gradient in each, as shown in Fig. 5-26 for a gas-hquid interface. The concentrations of the diffusing material in the two phases immediately adjacent to the interface generally are unequal, even if expressed in the same units, but usually are assumed to be related to each other by the laws of thermodynamic equihbrium. Thus, it is assumed that the thermodynamic equilibrium is reached at the gas-liquid interface almost immediately when a gas and a hquid are brought into contact. 

For systems in which the solute concentrations in the gas and hquid phases are dilute, the rate of transfer may be expressed by equations which predic t that the rate of mass transfer is proportional to the difference between the bulk concentration and the concentration at the gas-liquid interface. Thus... 

It is important to understand that when chemical reactions are involved, this definition of Cl is based ou the driving force defined as the difference between the couceutratiou of un reacted solute gas at the interface and in the bulk of the liquid. A coefficient based ou the total of both uureacted and reached gas could have values. smaller than the physical-absorption mass-transfer coefficient /c . 

Figure 14-10 illustrates the gas-film and liquid-film concentration profiles one might find in an extremely fast (gas-phase mass-transfer limited) second-order irreversible reaction system. The solid curve for reagent B represents the case in which there is a large excess of bulk-liquid reagent B. The dashed curve in Fig. 14-10 represents the case in which the bulk concentration B is not sufficiently large to prevent the depletion of B near the liquid interface and for which the equation ( ) = I -t- B /vCj is applicable. 

FK . 15-22 Uqiiid agitation by a disc flat blade turbine in the presence of a gas-liquid interface a) without wall baffles, (h) with wall baffles, and (c) in full vessels without a gas-bqiiid interface (continuous flow) and without baffles. [Couitesy Treyhal, Mass Transfer Operations, 3rd ed., p. 148, McGraw-Hill, NY,... 

Coalescence The coalescence of droplets can occur whenever two or more droplets collide and remain in contact long enough for the continuous-phase film to become so thin that a hole develops and allows the liquid to become one body. A clean system with a high interfacial tension will generally coalesce quite rapidly. Particulates and polymeric films tend to accumulate at droplet surfaces and reduce the rate of coalescence. This can lead to the ouildup of a rag layer at the liquid-hquid interface in an extractor. Rapid drop breakup and rapid coalescence can significantly enhance the rate of mass transfer between phases. 

Equihbrium concentrations which tend to develop at solid-liquid, gas-liquid, or hquid-liquid interfaces are displaced or changed by molecular and turbulent diffusion between biilk fluid and fluid adjacent to the interface. Bulk motion (Taylor diffusion) aids in this mass-transfer mechanism also. 

When the two liquid phases are in relative motion, the mass transfer coefficients in eidrer phase must be related to die dynamical properties of the liquids. The boundary layer thicknesses are related to the Reynolds number, and the diffusive Uansfer to the Schmidt number. Another complication is that such a boundaty cannot in many circumstances be regarded as a simple planar interface, but eddies of material are U ansported to the interface from the bulk of each liquid which change the concenuation profile normal to the interface. In the simple isothermal model there is no need to take account of this fact, but in most indusuial chcumstances the two liquids are not in an isothermal system, but in one in which there is a temperature gradient. The simple stationary mass U ansfer model must therefore be replaced by an eddy mass U ansfer which takes account of this surface replenishment. 

Carbon dioxide gas diluted with nitrogen is passed continuously across the surface of an agitated aqueous lime solution. Clouds of crystals first appear just beneath the gas-liquid interface, although soon disperse into the bulk liquid phase. This indicates that crystallization occurs predominantly at the gas-liquid interface due to the localized high supersaturation produced by the mass transfer limited chemical reaction. The transient mean size of crystals obtained as a function of agitation rate is shown in Figure 8.16. 

More directly related to turbulence and motion at the interface. Includes scale-up for rate of dissolving of solids or mass transfer between liquid phases. Using geometric similarity and equal power per volume results in same n value. 

Water-cooling in towers operates on the evaporative principles, which are a combination of several heat/mass transfer processes. The most important of these is the transfer of liquid into a vapor/air mixture, as, for example, the surface area of a droplet of water. Convective transfer occurs as a result of the difference in temperature between the water and the surrounding air. Both these processes take place at the interface of the water surface and the air. Thus it is considered to behave as a film of saturated air at the same temperature as the bulk of the water droplet. 

Where heat transfer is taking place at the saturation temperature of a fluid, evaporation or condensation (mass transfer) will occur at the interface, depending on the direction of heat flow. In such cases, the convective heat transfer of the fluid is accompanied by conduction at the surface to or from a thin layer in the liquid state. Since the latent heat and density of fluids are much greater than the sensible heat and density of the vapour, the rates of heat transfer are considerably higher. The process can be improved by shaping the heat exchanger face (where this is a solid) to improve the drainage of condensate or the escape of bubbles of vapour. The total heat transfer will be the sum of the two components. 

The simplest theory involved in mass transfer across an interface is film theory, as shown in Figure 3.10. In this model, the gas (CO) is transferred from the gas phase into the liquid phase and it must reach the surface of the growing cells. The rate equation for this case is similar to the slurry reactor as mentioned in Levenspiel.20... 

In a later publication, Kolbel et al. (K16) have proposed a less empirical model based on the assumption that the rate-determining steps for a slurry process are the catalytic reaction and the mass transfer across the gas-liquid interface. When used for the hydrogenation of carbon monoxide to methane, the process rate is expressed as moles carbon monoxide consumed per hour and per cubic meter of slurry ... 

Farkas and Sherwood (FI, S5) have interpreted several sets of experimental data using a theoretical model in which account is taken of mass transfer across the gas-liquid interface, of mass transfer from the liquid to the catalyst particles, and of the catalytic reaction. The rates of these elementary process steps must be identical in the stationary state, and may, for the catalytic hydrogenation of a-methylstyrene, be expressed by ... 

Such a model should take into account at least the following phenomena Mass transfer across gas-liquid interface, mass transfer to exterior particle surface, catalytic reaction, flow and axial mixing of gas phase, and flow and axial mixing of liquid phase. 

The experimental and theoretical work reported in the literature will be reviewed for each of the five major types of ga s-liquid-particle operation under the headings Mass transfer across gas-liquid interface mass transfer across liquid-solid interface holdup and axial dispersion of gas phase holdup and axial dispersion of liquid phase heat transfer reaction kinetics. 

Mass Transfer across Liquid-Solid Interface... 

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