Cavities in liquids

We have already mentioned that silver chloride is readily soluble in liquid ammonia. Because it is slighdy less polar than water and has lower cohesion energy, intermolecular forces make it possible for organic molecules to create cavities in liquid ammonia. As a result, most organic compounds are more soluble in liquid ammonia than they are in water. Physical data for liquid ammonia are summarized in Table 10.2. 

Simple cavity models have been used to study solvated electrons in liquid ammonia. In that case the dominant interactions arise from long range polarization effects, so that the energy of the localized state is not very sensitive to the fluid deformation in the vicinity of the localized charge. In the case of an excess electron in liquid helium, however, the electron-fluid interaction arises mainly from short range electron-atom interactions, and we shall show that the localized excess electron in a cavity in liquid helium lies lower in energy than the quasi-free electron. 

Formation of Gas Cavities in Liquid-saturated Porous Medium... 

In Ftirth s theory of cavities in liquids, there is a distribution function for the probability of the hole size. It is... 

Several attempts to calculate the properties of alkali metal halides on the basis of the equation of state can be found in the literature. Reiss et al. (1959, 1960) estimated the reversible work needed for creation of a spherical cavity in liquids of rigid spheres and derived the equation of state for these liquids... 

The scaled particle theory SPT) was developed mainly for the study of hard-sphere liquids. It is not an adequate theory for the study of aqueous solutions. Nevertheless, it has been extensively applied for aqueous solutions of simple solutes. The scaled particle theory (SPT) provides a prescription for calculating the work of creating a cavity in liquids. We will not describe the SPT in detail only the essential result relevant to our problem will be quoted. Let aw and as be the effective diameters of the solvent and the solute molecules, respectively. A suitable cavity for accommodating such a solute must have a radius of c ws = ((Tw + cTs) (Fig. 3.20b). The work required to create a cavity of radius a s at a fixed position in the liquid is the same as the pseudo-chemical potential of a hard sphere of radius as. The SPT provides the following approximation for the pseudochemical potential ... 

Cavitation is the process of nucleation in a liquid and subsequent formation of gas/vapor phase when the pressure falls below a critical value. Researchers studying cavitation address topics ranging from the initial appearance of cavities in liquids (cavitation inception) to the development of large-scale cavities (supercavitation). 

Modelling cavities in liquids. Assume that you have... 

Here reactions (10) and (11) highlight the comparison that can be drawn between an electron trapped in a cavity defined by a tetrahedron of sodium cations in the sodalite cage, and an electron trapped within solvent cavities in liquid ammonia. Furthermore, the ability to prepare trapped electrons in zeolites, in stoichiometric or near stoichiometric amounts, has led to the description inorganic electrides [88, 90]. Together these ideas have been found to constitute a remarkably robust conceptual framework for rationalizing the properties of a wide range of metal-zeolite compounds [88], whose main strength lies in its ability to do so without recourse to detailed structural information, which is available in only a few cases. 

It is especially useflil for liquid samples in flat cells, which may extend through tlie entire height of the cavity. In the cylindrical cavity a TEq mode is frequently used because of its fairly high g-factor and the very strong along the sample axis. 

Swalin then uses a Maclaurin expansion of the Anhenius term to obtain the energy of formation of a cavity in the liquid which permits a small jump, to obtain the equation... 

Recently, many experiments have been performed on the structure and dynamics of liquids in porous glasses [175-190]. These studies are difficult to interpret because of the inhomogeneity of the sample. Simulations of water in a cylindrical cavity inside a block of hydrophilic Vycor glass have recently been performed [24,191,192] to facilitate the analysis of experimental results. Water molecules interact with Vycor atoms, using an empirical potential model which consists of (12-6) Lennard-Jones and Coulomb interactions. All atoms in the Vycor block are immobile. For details see Ref. 191. We have simulated samples at room temperature, which are filled with water to between 19 and 96 percent of the maximum possible amount. Because of the hydrophilicity of the glass, water molecules cover the surface already in nearly empty pores no molecules are found in the pore center in this case, although the density distribution is rather wide. When the amount of water increases, the center of the pore fills. Only in the case of 96 percent filling, a continuous aqueous phase without a cavity in the center of the pore is observed. 

The interpretation of these remarkable properties has excited considerable interest whilst there is still some uncertainty as to detail, it is now generally agreed that in dilute solution the alkali metals ionize to give a cation M+ and a quasi-free electron which is distributed over a cavity in the solvent of radius 300-340 pm formed by displacement of 2-3 NH3 molecules. This species has a broad absorption band extending into the infrared with a maximum at 1500nm and it is the short wavelength tail of this band which gives rise to the deep-blue colour of the solutions. The cavity model also interprets the fact that dissolution occurs with considerable expansion of volume so that the solutions have densities that are appreciably lower than that of liquid ammonia itself. The variation of properties with concentration can best be explained in terms of three equilibria between five solute species M, M2, M+, M and e ... 

The liquid phase of saturated saltwater muds is saturated with sodium chloride. Saturated saltwater muds are most frequently used as workover fluids or for drilling salt formations. These muds prevent solution cavities in the salt formations, making it unnecessary to set casing above the salt beds. If the salt formation is too close to the surface, a saturated saltwater mud may be mixed in the surface system as the spud mud. If the salt bed is deep, freshwater mud is converted to a saturated salt water mud. 

The effect of carbon on the corrosion of stainless steels in liquid sodium depends upon the test conditions and the composition of the steels . Stabilised stainless steels tend to pick up carbon from sodium, leading to a degree of carburisation which corresponds to the carbon activity in the liquid metal. Conversely, unstabilised stainless steels suffer slight decarburisation when exposed to very pure sodium. The decarburisation may promote corrosion in the surface region of the material and, under creep rupture conditions, can lead to cavity formation at the grain boundaries and decreased strength. 

There are many ways in which foams can be processed and used as slabs, blocks, boards, sheets, molded shapes, sprayed coatings, extruded profiles, foamed in place in existing cavities, in which the liquid material is poured and allowed to foam, and as structural foams (Chapter 6, STRUCTURAL FOAM). Conventional equipment such as extruders, injection, or compression machines is used. However specially designed machines are available to just produce foamed products. 

Let us imagine that the liquid cage is a spherical cavity in a continuous medium. When the molecule is in its centre, the orienting field is equal to zero. At this point the anisotropic part of the rotator-neighbourhood interaction appears only in the case of asymmetrical breathing of the... 

The alkali metals also release their valence electrons when they dissolve in liquid ammonia, but the outcome is different. Instead of reducing the ammonia, the electrons occupy cavities formed by groups of NH3 molecules and give ink-blue metal-ammonia solutions (Fig. 14.14). These solutions of solvated electrons (and cations of the metal) are often used to reduce organic compounds. As the metal concentration is increased, the blue gives way to a metallic bronze, and the solutions begin to conduct electricity like liquid metals. 

The mobility of ions in melts (ionic liquids) has not been clearly elucidated. A very strong, constant electric field results in the ionic motion being affected primarily by short-range forces between ions. It would seem that the ionic motion is affected most strongly either by fluctuations in the liquid density (on a molecular level) as a result of the thermal motion of ions or directly by the formation of cavities in the liquid. Both of these possibilities would allow ion transport in a melt. 

Thus it can be seen that the degree of superheat is much greater in liquid metals than in water for the same pressure and cavity size, because of their much higher values of (7sat)2. Also, for the same cavity size, pressure, and heat flux, the time required to build the thermal layer as well as its thickness will be much greater in liquid metals than in other liquids (see Sec. 2.2.2). 

---