Pressure interfacial tension

The interfacial tension behaviour of carbon dioxide/decane mixtures appears to be very interesting due to the formation of the second liquid phase at low temperatures. To see the similarities between the interfacial tension behaviour and the phase behaviour at constant temperature, the interfacial tensions are being presented in a similar way as p-x,y sections in Figure 3. In Figure 4 the relations between pressure, interfacial tension and composition are shown schematically for a system in which a three-phase equilibrium is present. 

An example is provided in enhanced oil recovery. In an oil-bearing reservoir the relative oil and water saturations depend on the distribution of pore sizes in the rock, the pressure in a pore, the interfacial tension, and the contact angle according to the Young-Laplace and Young equations. The same relationships determine how water or other fluids can be injected to change pressure, interfacial tension. 

The selected electrol5rte composition is based on the effects of the various components on the physicochemical properties of the molten electrolyte. However, in some cases, the MgCl2 feedstock contains small amounts of another metal chloride such as KCl. Electrical conductivity, density, vapor pressure, interfacial tension, and metal solubility are important properties. A typical composition can be 45 % NaQ, 35 % CaCl2, 10 % KCl, and 10 % MgCl2. The content of MgCl2 must not be too low to avoid codeposition of sodium, although some sodium will always be deposited at a low activity. 

The relationship between the pressure drop across the interface AP, the interfacial tension o, and the radius of the droplet, r, is... 

Figure III-l depicts a hypothetical system consisting of some liquid that fills a box having a sliding cover the material of the cover is such that the interfacial tension between it and the liquid is zero. If the cover is slid back so as to uncover an amount of surface dJl, the work required to do so will he ydSl. This is reversible work at constant pressure and temperature and thus gives the increase in free energy of the system (see Section XVII-12 for a more detailed discussion of the thermodynamics of surfaces).

Application of 150 MPa pressure increases the interfacial tension for w-hex-ane-water from 50.5 to 53.0 mN/m at 25°C. Calculate AV. What is AV for that area corresponding to a molecular size (take a representative molecular area to be 20 A ) Convert this to cm /cm mol. 

Usually one varies the head of mercury or applied gas pressure so as to bring the meniscus to a fixed reference point [118], Grahame and co-workers [119], Hansen and co-workers [120] (see also Ref. 121), and Hills and Payne [122] have given more or less elaborate descriptions of the capillary electrometer apparatus. Nowadays, the capillary electrometer is customarily used in conjunction with capacitance measurements (see below). Vos and Vos [111] describe the use of sessile drop profiles (Section II-7B) for interfacial tension measurements, thus avoiding an assumption as to the solution-Hg-glass contact angle. 

Templeton obtained data of the following type for the rate of displacement of water in a 30-/im capillary by oil (n-cetane) (the capillary having previously been wet by water). The capillary was 10 cm long, and the driving pressure was 45 cm of water. When the meniscus was 2 cm from the oil end of the capillary, the velocity of motion of the meniscus was 3.6 x 10 cm/sec, and when the meniscus was 8 cm from the oil end, its velocity was 1 x 10 cm/sec. Water wet the capillary, and the water-oil interfacial tension was 30 dyn/cm. Calculate the apparent viscosities of the oil and the water. Assuming that both come out to be 0.9 of the actual bulk viscosities, calculate the thickness of the stagnant annular film of liquid in the capillary. 

If an ionic surfactant is present, the potentials should vary as shown in Fig. XIV-5c, or similarly to the case with nonsurfactant electrolytes. In addition, however, surfactant adsorption decreases the interfacial tension and thus contributes to the stability of the emulsion. As discussed in connection with charged monolayers (see Section XV-6), the mutual repulsion of the charged polar groups tends to make such films expanded and hence of relatively low rr value. Added electrolyte reduces such repulsion by increasing the counterion concentration the film becomes more condensed and its film pressure increases. It thus is possible to explain qualitatively the role of added electrolyte in reducing the interfacial tension and thereby stabilizing emulsions. 

The emulsification process in principle consists of the break-up of large droplets into smaller ones due to shear forces (10). The simplest form of shear is experienced in lamellar flow, and the droplet break-up may be visualized according to Figure 4. The phenomenon is governed by two forces, ie, the Laplace pressure, which preserves the droplet, and the stress from the velocity gradient, which causes the deformation. The ratio between the two is called the Weber number. We, where Tj is the viscosity of the continuous phase, G the velocity gradient, r the droplet radius, and y the interfacial tension. 

The molecules of liquids are separated by relatively small distances so the attractive forces between molecules tend to hold firm within a definite volume at fixed temperature. Molecular forces also result in tlie phenomenon of interfacial tension. The repulsive forces between molecules exert a sufficiently powerful influence that volume changes caused by pressure changes can be neglected i.e. liquids are incompressible. 

FIG. 20 (a) Density profiles p(z) vs z for e = —2 and four average bulk densities (f> as indicated, (b) Surface excess vs density in the bulk for four choices of e. (c) Profiles for the diagonal components of the pressure tensor and of the total pressure for (p = l.O and e = —2. Insert in (c) shows the difference between P, and Px to show that isotropic behavior in the bulk of the film is nicely obtained, (d) Interfacial tension between the polymer film and the repulsive wall vs bulk density for all four choices of e. Curve is only a guide for the eye [18]. 

The design factors to prevent blocking involve the use of low-viscosity fluids with minimum interfacial tension, minimum capillary pressure, and minimal fluid loss. 

The diffusion current Id depends upon several factors, such as temperature, the viscosity of the medium, the composition of the base electrolyte, the molecular or ionic state of the electro-active species, the dimensions of the capillary, and the pressure on the dropping mercury. The temperature coefficient is about 1.5-2 per cent °C 1 precise measurements of the diffusion current require temperature control to about 0.2 °C, which is generally achieved by immersing the cell in a water thermostat (preferably at 25 °C). A metal ion complex usually yields a different diffusion current from the simple (hydrated) metal ion. The drop time t depends largely upon the pressure on the dropping mercury and to a smaller extent upon the interfacial tension at the mercury-solution interface the latter is dependent upon the potential of the electrode. Fortunately t appears only as the sixth root in the Ilkovib equation, so that variation in this quantity will have a relatively small effect upon the diffusion current. The product m2/3 t1/6 is important because it permits results with different capillaries under otherwise identical conditions to be compared the ratio of the diffusion currents is simply the ratio of the m2/3 r1/6 values. 

The log of the reciprocal of the bulk concentration of surfactant (C in mol/ L) necessary to produce a surface or interfacial pressure of 20 raN/m, log( 1 / On= 20 i e > a 20 mN/m reduction in the surface or interfacial tension, is considered a measure of the efficiency of a surfactant. The effectiveness of surface tension reduction is the maximum effect the surfactant can produce irrespective of concentration, (rccmc = [y]0 - y), where [y]0 is the surface tension of the pure solvent and y is the surface tension of the surfactant solution at its cmc. 

Eq. (132) states that the interfacial tension has to be balanced by a pressure difference between the two phases. The terms containing derivatives of crin Eqs. (133) and (134) are non-zero only if there are local variations of the interfacial tension, which might be due to differences in concentration or temperature. The flow induced by such an effect is known as Marangoni convection. 

When using any solvent extraction system, one of the most important decisions is the selection of the solvent to be used. The properties which should be considered when choosing the appropriate solvent are selectivity distribution coefficients insolubility recoverability density interfacial tension chemical reactivity viscosity vapour pressure freezing point safety and cost. A balance must be obtained between the efficiency of extraction (the yield), the stability of the additive under the extraction conditions, the (instrumental and analyst) time required and cost of the equipment. Once extracted the functionality is lost and... 

The interphase can be considered as a particular phase s of thickness h. This phase differs from the homogeneous phases only in that the effect of pressure is accompanied by the effect of the interfacial tension y. Consider a rectangle with sides h (perpendicular to the interphase) and / (parallel with the interphase) located perpendicular to the interphase. The force acting on the rectangle is not equal to the product phi (as for an area in the bulk of the solution) but phi — yl. If the volume of the interphase V(s) is increased by dV(s) by increasing the thickness of the interphase by dh, then area A = V(s)lh increases by cL4. The overall work, W, connected with this process consists of volume work accompanying the increase in the thickness of the interphase and volume and surface work connected with an increase of the surface area ... 

The oil-water dynamic interfacial tensions are measured by the pulsed drop (4) technique. The experimental equipment consists of a syringe pump to pump oil, with the demulsifier dissolved in it, through a capillary tip in a thermostated glass cell containing brine or water. The interfacial tension is calculated by measuring the pressure inside a small oil drop formed at the tip of the capillary. In this technique, the syringe pump is stopped at the maximum bubble pressure and the oil-water interface is allowed to expand rapidly till the oil comes out to form a small drop at the capillary tip. Because of the sudden expansion, the interface is initially at a nonequilibrium state. As it approaches equilibrium, the pressure, AP(t), inside the drop decays. The excess pressure is continuously measured by a sensitive pressure transducer. The dynamic tension at time t, is calculated from the Young-Laplace equation... 

---