Solid 4 Liquid Equilibrium

For the equilibrium liquid-solid it is usual to choose the pressure as the sole independent variable. In this way the melting point is fixed as the one temperature at which the solid and the liquid phase are in equilibrium with one another at a given pressure. 

Liquid-Vapor Equilibrium Liquid-Solid Equilibrium ... 

In the previous sections, the role of computational methods in the study of equilibrium liquid-solid interfaces has been discussed. Such studies are motivated by the tremendous difficulty of performing real experiments on such systems. The two computational methods that have been implemented to date are computer simulation and classical DFT. 

The previous consideration shows that the situation with Young s equation (Equation 1.1) is far more difficult than it is usually assumed. This equation is supposed to describe the equilibrium contact angle. We explained in Section 1.1 that the latter equation does not comply with any of the three requirements of the equilibrium liquid-vapor equilibrium, liquid-solid equilibrium, and vapor-solid equilibrium. 

Chemical reactions obey the rules of chemical kinetics (see Chapter 2) and chemical thermodynamics, if they occur slowly and do not exhibit a significant heat of reaction in the homogeneous system (microkinetics). Thermodynamics, as reviewed in Chapter 3, has an essential role in the scale-up of reactors. It shows the form that rate equations must take in the limiting case where a reaction has attained equilibrium. Consistency is required thermodynamically before a rate equation achieves success over tlie entire range of conversion. Generally, chemical reactions do not depend on the theory of similarity rules. However, most industrial reactions occur under heterogeneous systems (e.g., liquid/solid, gas/solid, liquid/gas, and liquid/liquid), thereby generating enormous heat of reaction. Therefore, mass and heat transfer processes (macrokinetics) that are scale-dependent often accompany the chemical reaction. The path of such chemical reactions will be... 

Vapor pressure is an important property of liquids, and to a much lesser extent, of solids. If a liquid is allowed to evaporate in a confined space, tlie pressure of Uie vapor phase increases as Uie amount of vapor increases. If Uiere is sufficient liquid present, Uie pressure in Uie vapor space eventually comes to equal exacUy Uie pressure exerted by the liquid at its own surface. At Uiis point, a dynamic equilibrium exists in wliich vaporization and condensation take place at equal rates and Uie pressure in Uie vapor space remains constant. The pressure exerted at equilibrium is called Uie vapor pressure of the liquid. Solids, like liquids, also exert a vapor pressure. EvaporaUon of solids (sublimaUon) is noUccable only for Uie few solids characterized by appreciable vapor pressures. 

Point A on a phase diagram is the only one at which all three phases, liquid, solid, and vapor, are in equilibrium with each other. It is called the triple point. For water, the triplepoint temperature is 0.01°C. At this temperature, liquid water and ice have the same vapor pressure, 4.56 mm Hg. 

The critical point is unique for (vapor + liquid) equilibrium. That is, no equivalent point has been found for (vapor + solid) or (liquid + solid) equilibria. There is no reason to suspect that any amount of pressure would eventually cause a solid and liquid (or a solid and gas) to have the same //m, Sm, and t/m. with an infinite o and at that point. mC02 was chosen for Figure 8.1 because of the very high vapor pressure at the (vapor + liquid + solid) triple point. In fact, it probably has the highest triple point pressure of any known substance. As a result, one can show on an undistorted graph both the triple point and the critical point. For most substances, the triple point is at so low a pressure that it becomes buried in the temperature axis on a graph with a pressure axis scaled to include the critical point. 

We will begin our discussion by describing (vapor + liquid) equilibrium, which we will extend into the supercritical fluid region as (fluid + fluid) equilibrium. (Liquid + liquid) equilibrium will then be described and combined with (vapor + liquid) equilibrium in the (fluid + fluid) equilibrium region. Finally, we will describe some examples of (solid + liquid) equilibrium. 

All models described up to here belong to the class of equilibrium theories. They have the advantage of providing structural information on the material during the liquid-solid transition. Kinetic theories based on Smoluchowski s coagulation equation [45] have recently been applied more and more to describe the kinetics of gelation. The Smoluchowski equation describes the time evolution of the cluster size distribution N(k) ... 

The determination of adsorption isotherms at liquid-solid interfaces involves a mass balance on the amount of polymer added to the dispersion, which requires the separation of the liquid phase from the particle phase. Centrifugation is often used for this separation, under the assumption that the adsorption-desorption equilibrium does not change during this process. Serum replacement (6) allows the separation of the liquid phase without assumptions as to the configuration of the adsorbed polymer molecules. This method has been used to determine the adsorption isotherms of anionic and nonionic emulsifiers on various types of latex particles (7,8). This paper describes the adsorption of fully and partially hydrolyzed PVA on different-size PS latex particles. PS latex was chosen over polyvinyl acetate (PVAc) latex because of its well-characterized surface PVAc latexes will be studied later. 

The proposed catalyst loading, that is the ratio by volume of catalyst to aniline, is to be 0.03. Under the conditions of agitation to be used, it is estimated that the gas volume fraction in the three-phase system will be 0.15 and that the volumetric gas-liquid mass transfer coefficient (also with respect to unit volume of the whole three-phase system) kLa, 0.20 s-1. The liquid-solid mass transfer coefficient is estimated to be 2.2 x 10-3 m/s and the Henry s law coefficient M = PA/CA for hydrogen in aniline at 403 K (130°C) = 2240 barm3/kmol where PA is the partial pressure in the gas phase and CA is the equilibrium concentration in the liquid. 

The purpose of this chapter is to introduce the effect of surfaces and interfaces on the thermodynamics of materials. While interface is a general term used for solid-solid, solid-liquid, liquid-liquid, solid-gas and liquid-gas boundaries, surface is the term normally used for the two latter types of phase boundary. The thermodynamic theory of interfaces between isotropic phases were first formulated by Gibbs [1], The treatment of such systems is based on the definition of an isotropic surface tension, cr, which is an excess surface stress per unit surface area. The Gibbs surface model for fluid surfaces is presented in Section 6.1 along with the derivation of the equilibrium conditions for curved interfaces, the Laplace equation. 

In a similar way, the Systeme Internationale has defined other common physicochemical variables. The SI unit of temperature T is the kelvin. We define the kelvin as 1/273.16th part of the thermodynamic temperature difference between absolute zero (see Section 1.4) and the triple point of water, i.e. the temperature at which liquid water is at equilibrium with solid water (ice) and gaseous water (steam) provided that the pressure is 610 Pa. 

We call each solid line in this graph a phase boundary. If the values of p and T lie on a phase boundary, then equilibrium between two phases is guaranteed. There are three common phase boundaries liquid-solid, liquid-gas and solid-gas. The line separating the regions labelled solid and liquid , for example, represents values of pressure and temperature at which these two phases coexist - a line sometimes called the melting-point phase boundary . 

We look once more at the phase diagram of C02 in Figure 5.5. The simplest way of obtaining the data needed to construct such a figure would be to take a sample of C02 and determine those temperatures and pressures at which the liquid, solid and gaseous phases coexist at equilibrium. (An appropriate apparatus involves a robust container having an observation window to allow us to observe the meniscus.) We then plot these values of p (as y ) against T (as V). 

The Clapeyron equation, Equation (5.1), yields a quantitative description of a phase boundary on a phase diagram. Equation (5.1) works quite well for the liquid-solid phase boundary, but if the equilibrium is boiling or sublimation - both of which involve a gaseous phase - then the Clapeyron equation is a poor predictor. 

Chemical separations are often either a question of equilibrium established in two immiscible phases across the contact between the two phases. In the case of true distillation, the equilibrium is established in the reflux process where the condensed material returning to the pot is in contact with the vapor rising from the pot. It is a gas-liquid interface. In an extraction, the equilibrium is established by motion of the solute molecules across the interface between the immiscible layers. It is a liquid-liquid, interface. If one adds a finely divided solid to a liquid phase and molecules are then distributed in equilibrium between the solid surface and the liquid, it is a liquid-solid interface (Table 1). 

C) the temperature and pressure where the substance exists in equilibrium as solid, liquid, and gas phases... 

The principle of operation is illustrated in Figure 15.37 which shows the pressme-volume relationship. Curve a shows the phase change of a pure liquid as it is pressurised isother-mally. Crystallisation begins at point Ai and proceeds by compression without any pressure change until it is complete at point A2. Beyond this point, the solid phase is compressed resulting in a very sharp rise in pressure. If the liquid contains impurities, these nucleate at point Bi. As the crystallisation of the pure substance progresses, the impurities are concentrated in the liquid phase and a higher pressure is required to continue the crystallisation process. As a result, the equilibrium pressure of the liquid-solid system rises exponentially with increase of the solid fraction, as shown by curve b which finally approaches... 

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