Pressure difference, interfacial method

Since it is relatively easy to transfer molecules from bulk liquid to the surface (e.g. shake or break up a droplet of water), the work done in this process can be measured and hence we can obtain the value of the surface energy of the liquid. This is, however, obviously not the case for solids (see later section). The diverse methods for measuring surface and interfacial energies of liquids generally depend on measuring either the pressure difference across a curved interface or the equilibrium (reversible) force required to extend the area of a surface, as above. The former method uses a fundamental equation for the pressure generated across any curved interface, namely the Laplace equation, which is derived in the following section. 

The apparatus developed for yb measurements of BLM deserves brief comment since it can be used not only to examine the effects of various substances on BLM but is readily adaptable for studying other types of interfacial films and related adsorption phenomena at either air-water or oil-water interfaces (and bifaces). Unlike both the Wil-helmy plate and film balance methods, the present technique measures 7i directly. From the description of the apparatus and procedure that the present method relies on the ability to measure the very small pressure difference across an interface (or biface). For certain BLM s, the pressure heads measured are only fractions of a millimeter of water. Therefore, the method described here has been possible only as a result of developing pressure transducers of high sensitivity. 

The Young-Laplace equation forms the basis for some important methods for measuring surface and interfacial tensions, such as the pendant and sessile drop methods, the spinning drop method, and the maximum bubble pressure method (see Section 3.2.3). Liquid flow in response to the pressure difference expressed by Eqs. (3.6) or (3.7) is known as Laplace flow, or capillary flow. 

The interfacial tension of the binary system a-tocopherol/carbon dioxide was measured using the pendant drop method in the pressure range between 10 and 37 MPa at nine different temperatures 313, 333, 343, 353, 363, 373, 383, 393 and 402 K. The interfacial tension decreases with rising pressure at a constant temperature and increases with increasing temperature at a constant pressure. The interfacial tension was found to be mainly a function of the mutual solubility of the two system components and of the density of pure carbon dioxide. 

Eq. (2.18) is the exact definition of the experimental relationship for the determination of surface tension by measuring the corresponding pressure differences and radii of curvature. This relationship is the basis of many experimental surface and interfacial tension methods measuring for example the volume of detaching drops (Section 5.2), the pressure inside bubbles (Section 5.3) or drops (Section 5.5), and the shape of sessile or pendent drops (Section 5.4). 

A very important part of emulsion study is the availability of methodologies to study emulsions. In the past ten years, both dielectric methods (1) and rheological methods (2) have been exploited to study formation mechanisms and the stability of emulsions formed from many different types of oils. Standard techniques, including NMR, chemical analysis techniques, microscopy, interfacial pressure, and interfacial tension, are also being applied to emulsions. These techniques have largely confirmed findings noted in the dielectric and rheological mechanisms. 

Instability is the most common problem of SLMs, including the loss of solvents and carriers through evaporation and decomposition or the breaking through of the solvent by too high pressure difference across the membranes. SLM stability can be affected by the type of polymeric support and its pore radius, solvents used in the liquid membrane, interfacial tension between the liquid and membrane phase, flow velocity of the aqueous phases, and method of preparation [1]. 

The capillary rise method was the earliest technique by which surface tension was measured and, indeed, was the technique by which the force itself was recognized. If a narrow tube of radius r is partially inserted into a liquid, the liquid rises up inside the tube to some equilibrium position as shown in Fig. 22. This occurs because the attractive interaction of the wetting liquid (aqueous solution) with the solid surface is stronger than that of the gas phase. Gravity opposes the rise, and the equilibrium height H corresponds to the minimum free energy of the system. The treatment is based on the Laplace equation that gives the pressure difference across a curved interface due to the surface or interfacial tension of the liquid [62]. Let us assume that we have a spherical bubble Of gas in a liquid... 

Since the technique developed during this investigation differs from the classical methods for studying films at interfaces, a brief consideration of traditional techniques seems desirable. In general, the interfacial tension of films (e.g., insoluble monolayers) at interfaces is not measured as such. Instead, the so-called interfacial pressure is determined, which is given by ... 

The influence of pressure on the mass transfer in a countercurrent packed column has been scarcely investigated to date. The only systematic experimental work has been made by the Research Group of the INSA Lyon (F) with Professor M. Otterbein el al. These authors [8, 9] studied the influence of the total pressure (up to 15 bar) on the gas-liquid interfacial area, a, and on the volumetric mass-transfer coefficient in the liquid phase, kia, in a countercurrent packed column. The method of gas-liquid absorption with chemical reaction was applied with different chemical systems. The results showed the increase of the interfacial area with increasing pressure, at constant gas-and liquid velocities. The same trend was observed for the variation of the volumetric liquid mass-transfer coefficient. The effect of pressure on kia was probably due to the influence of pressure on the interfacial area, a. In fact, by observing the ratio, kia/a, it can be seen that the liquid-side mass-transfer coefficient, kL, is independent of pressure. 

An almost overwhelmingly large number of different techniques for measuring dynamic and static interfacial tension at liquid interfaces is available. Since many of the commercially available instruments are fairly expensive to purchase (see Internet Resources), the appropriate selection of a suitable technique for the desired application is essential. Dukhin et al. (1995) provides a comprehensive overview of currently available measurement methods (also see Table D3.6.1). An important aspect to consider is the time range over which the adsorption kinetics of surface-active substances can be measured (Fig. D3.6.5). For applications in which small surfactant molecules are primarily used, the maximum bubble pressure (MBP) method is ideally suited, since it is the only... 

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