Interfacial area physical methods

Model Reactions. Independent measurements of interfacial areas are difficult to obtain in Hquid—gas, Hquid—Hquid, and Hquid—soHd—gas systems. Correlations developed from studies of nonreacting systems maybe satisfactory. Comparisons of reaction rates in reactors of known small interfacial areas, such as falling-film reactors, with the reaction rates in reactors of large but undefined areas can provide an effective measure of such surface areas. Another method is substitution of a model reaction whose kinetics are well estabUshed and where the physical and chemical properties of reactants are similar and limiting mechanisms are comparable. The main advantage of employing a model reaction is the use of easily processed reactants, less severe operating conditions, and simpler equipment. 

According to this method, it is not necessaiy to investigate the kinetics of the chemical reactions in detail, nor is it necessary to determine the solubihties or the diffusivities of the various reactants in their unreacted forms. To use the method for scaling up, it is necessaiy independently to obtain data on the values of the interfacial area per unit volume a and the physical mass-transfer coefficient /c for the commercial packed tower. Once these data have been measured and tabulated, they can be used directly for scahng up the experimental laboratory data for any new chemic ly reac ting system. 

Mass-transfer rates have been determined by measuring the absorption rate of a pure gas or of a component of a gas mixture as a function of the several operating variables involved. The basic requirement of the evaluation method is that the rate step for the physical absorption should be controlling, not the chemical reaction rate. The experimental method that has gained the widest acceptance involves the oxidation of sodium sulfite, although in some of the more recent work, the rate of carbon dioxide absorption in various media has been used to determine mass-transfer rates and interfacial areas. 

For development of nonequilibrium methods to continue, the calculations for mass transfer coefficients and interfacial areas required by these models will have to be added to physical property packages. Krishnamurthy and Taylor (89) present methods and recommendations for calculating the mass and energy transfer coefficients and rates. Help may be available from published manuals or supplier literature. 

In this polymerization, the biofunctional component (enzyme) can be concentrated in an interfacial area between the frozen ice crystal and the supercooled monomer phase, and immobilized by molecular entanglement between the enzyme and polymer molecules. This is a different procedure for fixation from the usual entrapping method with a crosslinked structure in a gel. Therefore, we may call this procedure the adhesion-method to distinguish it from the usual entrapping. This term was extended to cover the use of the usual synthetic polymers including hydrophobic polymers as the supports. One of the characteristic properties of products obtained in this way was that there is a maximum activity at a certain monomer concentration. The maximum activity is observed when the increased inner surface area is balanced by the increased leakage of enzyme and these occur with a decrease of monomer concentration. Immobilization by physical entrapping was also studied by Rosiak [26], Carenza [27] and Ha [28]. 

In many practical applications, gas-liquid mass transfer plays a significant role in the overall chemical reaction rate. It is, therefore, necessary to know the values of effective interfacial area (aL) and the volumetric or intrinsic gas-liquid mass transfer coefficients such as kLah, kL, ktaL, kg, etc. As shown in Section IX, the effective interfacial area is measured by either physical e.g., photography, light reflection, or light scattering) or chemical methods. The liquid-side or gas-side mass-transfer coefficients are also measured by either physical (e.g., absorption or desorption of gas under unsteady-state conditions) or chemical methods. A summary of some of the experimental details and the correlations for aL and kLaL reported in the literature are given by Joshi et al. (1982). In most practical situations, kgaL does not play an important role. 

The overall interfacial area for the whole reactor can be determined by chemical techniques. These techniques, however, must be used with restrictions. For example, chemical methods are difficult to use for fast-coalescing systems, since the presence of a chemical compound may reduce coalescence rates. Furthermore, in fast-coalescing systems, the specific area may depend strongly on the position in the reactor, which complicates the interpretation of an average value obtained with chemical methods. Indeed, both physical and chemical techniques should be used together to describe the phenomena that occur within gas-liquid reactors. While chemical methods allow the determination of the much-needed average interfacial area, information on the variations of the interfacial parameters, such as aL and dsv, within the reactor, which is important for scale-up, cannot be obtained by this method. 

The gas-liquid interfacial area measured form the physical techniques is generally about 35% higher than the one measured by the chemical technique. The chemical technique is generally more accurate than the physical technique. The reaction systems described in Table XXXI are reliable for the gas-liquid system. For gas-liquid-solid systems, the method is not reliable even when solids are inert, because of possible adsorptions of gas and/or liquid on the solid surface. 

The gas-liquid interfacial area has been measured by both physical and chemical methods. The accuracy of these measurements is generally very poor (15). The interfacial area has been related to the energy input per unit volume and the gas holdup by the expression (6-19)... 

Various physical and chemical methods can be applied to determine interfacial areas. Unfortunately, the different methods yield largely differing results. The methods used most often are photography and sulfite oxidation. Schumpe and Deckwer recently showed... 

The specific surface area of contact for mass transfer in a gas-liquid dispersion (or in any type of gas-liquid reactor) is defined as the interfacial area of all the bubbles or drops (or phase elements such as films or rivulets) within a volume element divided by the volume of the element. It is necessary to distinguish between the overall specific contact area S for the whole reactor with volume Vr and the local specific contact area 51 for a small volume element AVi- In practice AVi is directly determined by physical methods. The main difficulty in determining overall specific area from local specific areas is that Si varies strongly with the location of AVi in the reactor—a consequence of variations in local gas holdup and in the local Sauter mean diameter [Eq. (64)]. So there is a need for a direct determination of overall interfacial area, over the entire reactor, which is possible with use of the chemical technique. 

At the outset, we recognize that a technique that measures overall values cannot be used without the restrictions that arise from the results observed with physical methods. For example, the chemical method can hardly be used with fast-coalescing systems, since the presence of a chemical compound may well reduce the coalescence rates. In fast-coalescing systems, as observed with physical methods, the wide variation of specific contact area at different locations in the reactor negates the meaning of an average value. In fact, physical and chemical techniques should be used simultaneously to identify more fully the phenomena that occur in gas-liquid reactors. While chemical methods provide overall values of interfacial area that are immediately usable for design, we must also know the variations in the local interfacial parameters (a, dgM) within the reactor in order to deal competently with scale-up. These complementary data, measured by physical methods, should be obtained from local simultaneous measurements of two of the three interfacial parameters as discussed above. 

The NEQ model requires thermodynamic properties, not only for calculation of phase equilibrium but also for calculation of driving forces for mass transfer. In addition, physical properties such as surface tension, diffusion coefficients, and viscosities, for calculation of mass (and heat) transfer coefficients and interfacial areas are required. The steady-state model equations most often are solved using Newton s method or by homotopy-continuation. A review of early applications of NEQ models is available [5]. 

Light transmittance methods for interfacial area have been widely employed in gas-liquid systems. Sridhar and Potter (1978) describe one of the more successful versions. The techniques are described in more detail in the liquid-liquid section. Chemical methods can be used to measure interfacial area, as described above (Section 4-7.5 Robinson and Wilke, 1974). Sampling methods are not suitable since it is impossible to withdraw a sample isokinetically. Generally, the results from chemical and physical methods do not agree. Chemical methods tend to have a bias toward the smaller bubbles of the distribution, whereas these may be missed by physical methods. 

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