Interfaces liquid-vapor

A case can be made for the usefulness of surface tension as a concept even in the case of a normal liquid-vapor interface. A discussion of this appears in papers by Brown [33] and Gurney [34]. The informal practice of using surface tension and surface free energy interchangeably will be followed in this text. 

Fig. ni-7. (a) Interfacial density profile for an argonlike liquid-vapor interface (density in reduced units) z is the distance normal to the surface, (b) Variations of P-p of Eq. ni-40 (in reduced units) across the interface. [From the thesis of J. P. R. B. Walton (see Ref. 66).]... 

There is, of course, a mass of rather direct evidence on orientation at the liquid-vapor interface, much of which is at least implicit in this chapter and in Chapter IV. The methods of statistical mechanics are applicable to the calculation of surface orientation of assymmetric molecules, usually by introducing an angular dependence to the inter-molecular potential function (see Refs. 67, 68, 77 as examples). Widom has applied a mean-held approximation to a lattice model to predict the tendency of AB molecules to adsorb and orient perpendicular to the interface between phases of AA and BB [78]. In the case of water, a molecular dynamics calculation concluded that the surface dipole density corresponded to a tendency for surface-OH groups to point toward the vapor phase [79]. 

A schematic picture of how concentrations might vary across a liquid-vapor interface is given in Fig. III-ll. The convention indicated by superscript 1, that is, the F = 0 is illustrated. The dividing line is drawn so that the two areas shaded in full strokes are equal, and the surface excess of the solvent is thus zero. The area shaded with dashed strokes, which lies to the right of the dividing... 

The most widely used experimental method for determining surface excess quantities at the liquid-vapor interface makes use of radioactive tracers. The solute to be studied is labeled with a radioisotope that emits weak beta radiation, such as H, C, or One places a detector close to the surface of the solution and measures the intensity of beta radiation. Since the penetration range of such beta emitters is small (a ut 30 mg/cm for C, with most of the adsorption occurring in the first two-tenths of the range), the measured radioactivity corresponds to the surface region plus only a thin layer of solution (about 0.06 mm for C and even less for H). 

Both the Monte Carlo and the molecular dynamics methods (see Section III-2B) have been used to obtain theoretical density-versus-depth profiles for a hypothetical liquid-vapor interface. Rice and co-workers (see Refs. 72 and 121) have found that density along the normal to the surface tends to be a... 

Thus, to encourage wetting, 7sl and 7lv should be made as small as possible. This is done in practice by adding a surfactant to the liquid phase. The surfactant adsorbs to both the liquid-solid and liquid-vapor interfaces, lowering those interfacial tensions. Nonvolatile surfactants do not affect 7sv appreciably (see, however. Section X-7). It might be thought that it would be sufficient merely to lower ytv and that a rather small variety of additives would suffice to meet all needs. Actually it is equally if not more important that the surfactant lower 7sL> and each solid will make its own demands. 

Many complex systems have been spread on liquid interfaces for a variety of reasons. We begin this chapter with a discussion of the behavior of synthetic polymers at the liquid-air interface. Most of these systems are linear macromolecules however, rigid-rod polymers and more complex structures are of interest for potential optoelectronic applications. Biological macromolecules are spread at the liquid-vapor interface to fabricate sensors and other biomedical devices. In addition, the study of proteins at the air-water interface yields important information on enzymatic recognition, and membrane protein behavior. We touch on other biological systems, namely, phospholipids and cholesterol monolayers. These systems are so widely and routinely studied these days that they were also mentioned in some detail in Chapter IV. The closely related matter of bilayers and vesicles is also briefly addressed. 

Raduge C, Pfiumio V and Shen Y R 1997 Surface vibrational spectroscopy of sulfuric acid-water mixtures at the liquid-vapor interface Chem. Phys. Lett. 274 140... 

U Overall coefficient of heat transfer for outside surface basis U for overall coefficient between liquid-vapor interface and coolant J/(s-m -K) Btu/(h-fF- F)... 

Thermal Methods Level-measuring systems may be based on the difference in thermal characteristics oetween the fluids, such as temperature or thermal conductivity. A fixed-point level sensor based on the difference in thermal conductivity between two fluids consists of an electrically heated thermistor inserted into the vessel. The temperature of the thermistor and consequently its electrical resistance increase as the thermal conductivity of the fluid in which it is immersed decreases. Since the thermal conductivity of liquids is markedly higher than that of vapors, such a device can be used as a point level detector for liquid-vapor interface. 

Sonic Methods A fixed-point level detector based on sonic-propagation characteristics is available for detection of a liquid-vapor interface. This device uses a piezoelectric transmitter and receiver, separated by a short gap. When the gap is filled with liquid, ultrasonic energy is transmitted across the gap, and the receiver actuates a relay. With a vapor filling the gap, the transmission of ultrasonic energy is insufficient to actuate the receiver. 

Corrosion is probably the greatest threat to vessel life. Partially filled vessels frequently have severe pitting at the liquid-vapor interface. Vessels usually do not have a corrosion allowance on the outside. Lack of protec tion against the weather or against the drip of corrosive chemicals can reduce vessel life. Insulation may contain damaging substances. Chlorides in insulating materials can cause cracking of stainless steels. 

R. Evans. The role of capillary wave fluctuations in determining the liquid-vapor interface. Analysis of the van der Waals model. Mol Phys 42 1169-1196, 1981. 

Fluid in a container is a combination of hquid and vapor. Before container mpture, the contained liquid is usually in equilibrium with the saturated vapor. If a container mptures, vapor is vented and the pressure in the liquid drops sharply. Upon loss of equilibrium, liquid flashes at the liquid-vapor interface, the liquid-container-wall interface, and, depending on temperature, throughout the liquid. 

A capillary system is said to be in a steady-state equilibrium position when the capillary forces are equal to the hydrostatic pressure force (Levich 1962). The heating of the capillary walls leads to a disturbance of the equilibrium and to a displacement of the meniscus, causing the liquid-vapor interface location to change as compared to an unheated wall. This process causes pressure differences due to capillarity and the hydrostatic pressures exiting the flow, which in turn causes the meniscus to return to the initial position. In order to realize the above-mentioned process in a continuous manner it is necessary to carry out continual heat transfer from the capillary walls to the liquid. In this case the position of the interface surface is invariable and the fluid flow is stationary. From the thermodynamical point of view the process in a heated capillary is similar to a process in a heat engine, which transforms heat into mechanical energy. 

The temperature distribution has a characteristic maximum within the liquid domain, which is located in the vicinity of the evaporation front. Such a maximum results from two opposite factors (1) heat transfer from the hot wall to the liquid, and (2) heat removal due to the liquid evaporation at the evaporation front. The pressure drops monotonically in both domains and there is a pressure jump at the evaporation front due to the surface tension and phase change effect on the liquid-vapor interface. 

At the interface the mass and thermal balance equations are valid. If one assumes that the liquid-vapor interface curvature is constant, accordingly (7)3-71)1111 = c/T men, Where Pq and Pl are the vapor and liquid pressure at the interface, a is the surface tension, and/ men is the meniscus radius. 

For solid contacts in vapor atmosphere, liquid would condense from the vapor into cracks and pores formed between the contacting surfaces. As a result, a small liquid bridge appears around the contact spot and a meniscus with the curvature of (l/rj-i- l/r2) forms at the solid-liquid-vapor interface, as illustrated in Fig. 4 for a microscopic sphere in contact with a solid plane. 

Dang LX, Chang TM (1997) Molecular dynamics study of water clusters, liquid, and liquid-vapor interface of water with many-body potentials. J Chem Phys 106(19) 8149—8159... 

Lekner J (1989) Summation of dipolar fields in simulated liquid vapor interfaces. Physica A 157(2) 826-838... 

Warren GL, Patel S (2008) Comparison of the solvation structure of polarizable and nonpolarizable ions in bulk water and near the aqueous liquid-vapor interface. J Phys Chem C 112(19) 7455-7467... 

Pohorille, A. Benjamin, I., Structure and energetics of model amphiphilic molecules at the water liquid-vapor interface. A molecular dynamic study, J. Phys. Chem. 1993, 97, 2664-2670... 

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