Surface area tension

Surface tension arises at a fluid to fluid interface as a result of the unequal attraction between molecules of the same fluid and the adjacent fluid. For example, the molecules of water in a water droplet surrounded by air have a larger attraction to each other than to the adjacent air molecules. The imbalance of forces creates an inward pull which causes the droplet to become spherical, as the droplet minimises its surface area. A surface tension exists at the interface of the water and air, and a pressure differential exists between the water phase and the air. The pressure on the water side is greater due to the net inward forces... 

A general prerequisite for the existence of a stable interface between two phases is that the free energy of formation of the interface be positive were it negative or zero, fluctuations would lead to complete dispersion of one phase in another. As implied, thermodynamics constitutes an important discipline within the general subject. It is one in which surface area joins the usual extensive quantities of mass and volume and in which surface tension and surface composition join the usual intensive quantities of pressure, temperature, and bulk composition. The thermodynamic functions of free energy, enthalpy and entropy can be defined for an interface as well as for a bulk portion of matter. Chapters II and ni are based on a rich history of thermodynamic studies of the liquid interface. The phase behavior of liquid films enters in Chapter IV, and the electrical potential and charge are added as thermodynamic variables in Chapter V. 

The automated pendant drop technique has been used as a film balance to study the surface tension of insoluble monolayers [75] (see Chapter IV). A motor-driven syringe allows changes in drop volume to study surface tension as a function of surface areas as in conventional film balance measurements. This approach is useful for materials available in limited quantities and it can be extended to study monolayers at liquid-liquid interfaces [76],... 

Bartell and Flu [19] were able to determine the adhesion tension, that is, ysv -7SL. for the water-silica interface to be 82.8 ergs/cm at 20°C and its temperature change to be -0.173 erg cm K . The heat of immersion of the silica sample in water was 15.9 cal/g. Calculate the surface area of the sample in square centimeters per gram. 

This equation describes the additional amount of gas adsorbed into the pores due to capillary action. In this case, V is the molar volume of the gas, y its surface tension, R the gas constant, T absolute temperature and r the Kelvin radius. The distribution in the sizes of micropores may be detenninated using the Horvath-Kawazoe method [19]. If the sample has both micropores and mesopores, then the J-plot calculation may be used [20]. The J-plot is obtained by plotting the volume adsorbed against the statistical thickness of adsorbate. This thickness is derived from the surface area of a non-porous sample, and the volume of the liquified gas. 

The separation of two surfaces in contact is resisted by adhesive forces. As the nonnal force is decreased, the contact regions pass from conditions of compressive to tensile stress. As revealed by JKR theory, surface tension alone is sufficient to ensure that there is a finite contact area between the two at zero nonnal force. One contribution to adhesion is the work that must be done to increase surface area during separation. If the surfaces have undergone plastic defonnation, the contact area will be even greater at zero nonnal force than predicted by JKR theory. In reality, continued plastic defonnation can occur during separation and also contributes to adhesive work. 

SInanojIu O 1981 Microscopic surface tension down to molecular dimensions and microthermodynamic surface areas of molecules or clusters J. Chem. Phys. 75 463—8... 

This method does not attempt to distinguish between the various energy contributions. The surface tension parameter acts to include all interactions as much as possible. There are a number of algorithms for implementing this method, most of which differ in the means for determining the surface area associated with a particular group. This method is particularly popular for very large molecules, which can only be modeled by molecular mechanics. 

The surface tension of a liquid, -y, is the force per unit length on the surface that opposes the expansion of the surface area. In the literature the surface tensions are expressed in dyn cm 1 dyn cm = 1 mN in the SI system. For the large majority of compounds the dependence of the surface tension on the temperature can be given as... 

Important physical properties of catalysts include the particle size and shape, surface area, pore volume, pore size distribution, and strength to resist cmshing and abrasion. Measurements of catalyst physical properties (43) are routine and often automated. Pores with diameters <2.0 nm are called micropores those with diameters between 2.0 and 5.0 nm are called mesopores and those with diameters >5.0 nm are called macropores. Pore volumes and pore size distributions are measured by mercury penetration and by N2 adsorption. Mercury is forced into the pores under pressure entry into a pore is opposed by surface tension. For example, a pressure of about 71 MPa (700 atm) is required to fill a pore with a diameter of 10 nm. The amount of uptake as a function of pressure determines the pore size distribution of the larger pores (44). In complementary experiments, the sizes of the smallest pores (those 1 to 20 nm in diameter) are deterrnined by measurements characterizing desorption of N2 from the catalyst. The basis for the measurement is the capillary condensation that occurs in small pores at pressures less than the vapor pressure of the adsorbed nitrogen. The smaller the diameter of the pore, the greater the lowering of the vapor pressure of the Hquid in it. 

The stabihty of a single foam film can be explained by the Gibbs elasticity E which results from the reduction ia equiUbrium surface concentration of adsorbed surfactant molecules when the film is extended (15). This produces an iacrease ia equiUbrium surface tension that acts as a restoring force. The Gibbs elasticity is given by equation 1 where O is surface tension and is surface area of the film. 

Capillarity. The outer surface of porous material has pore entrances of various sizes. As surface Hquid is evaporated during constant rate drying, a meniscus forms across each pore entrance and interfacial forces are set up between the Hquid and material. These forces may draw Hquid from the interior to the surface. The tendency of Hquid to rise in porous material is caused pardy by Hquid surface tension. Surface tension is defined as the work needed to increase a Hquid s surface area by one square meter and has the units J/m. The pressure increase caused by surface tension is related to pore size ... 

The molecules in a gas-hquid interface are in tension and tend to contract to a minimum surface area. This tension may be quantified by the surface tension, which is defined as the force in the plane of the surface per unit length. Jasper" has made a critical evaluation of experimental surface tension data for approximately 2200 pure chem-ic s. He correlates surface tension C (mN/m = dyn/cm) with temperature T (°C) over a specified temperature range as... 

Based on 23 data points for 3 systems. Average absolute deviation 26%. Use with surface area of drop after detachment occurs, = velocity through nozzle <3 = iuterfacial tension. 

E] Gas absorption aud desorption from water aud organics plus vaporization of pure liquids for Raschig riugs, saddles, spheres, aud rods, dp = nominal pacldug size, Cp = dry pacldug surface area/volume, = wetted pacldug surface area/volume. Equations are dimensionally consistent, so any set of consistent units can be used. <3 = surface tension, dynes/cm. 

Attempts have been made to distinguish between these theories on the basis of the AH° and values anticipated for the two theories, but it may be illusory to think of them as independent alternatives. The eavity model has been criticized on the basis that it eannot account for certain observations such as the denaturing effect of urea, but it must be noted that the cavity theory includes not only the cavity term AAy, but also a term (or terms) for the interaction of the solutes and the solvent. A more eogent objeetion might be to the extension of the macroseopic concepts of surface area and tension to the molecular scale. A demonstration of the validity of the cavity concept has been made with silanized glass beads, which aggregate in polar solvents and disperse in nonpolar solvents. 

In the models discussed thus far in this section, emphasis has been placed on electrostatic effects and solvent polarity. An alternative view that to some extent takes other forces into account begins with the idea that, in order to dissolve a solute molecule in a solvent, energy is required to create a cavity in the solvent the solute is then inserted into this cavity. In Section 8.2 we saw that the energy to create a cavity can be expressed as a product of the surface area of the cavity and the surface tension of the solvent. An equivalent expression is obtained as the product of the volume of the cavity and the pressure exerted by the solvent, and we now explore this concept. 

Other variables come into play for specific kinds of problems. For example, surface area / s and surface tension 7 are used when surface effects are considered, and electrical potential E and quantity of electrical charge Q are included when electrical work is involved. 

The most difficult part of the theory lies in obtaining actual values for AF and v. For a large cluster of N molecules the extra surface tension due to the incremental surface area, edA, contributes an increase to the total free energy, whilst the bulk free energy per volume summed over the incremental volume, AF dV, gives a decrease to the total free energy. Hence, AF can be estimated as the maximum value of ad A — AF dV as a function of N. It is found that AF is proportional... 

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