Solution binary liquid solutions, behavior

The case of binary solid-liquid equilibrium permits one to focus on liquid-phase nonidealities because the activity coefficient of solid component ij, Yjj, equals unity. Aselage et al. (148) investigated the liquid-solution behavior in the well-characterized Ga-Sb and In-Sb systems. The availability of a thermodynamically consistent data base (measurements of liquidus, component activity, and enthalpy of mixing) provided the opportunity to examine a variety of solution models. Little difference was found among seven models in their ability to fit the combined data base, although asymmetric models are expected to perform better in some systems. 

Behavior of Binary Liquid Solutions Property changes of mixing and excess properties find greatest application in the description of liquid mixtures at low reduced temperatures, i.e., at temperatures well below the critical temperature of each constituent species. The properties of interest to the chemical engineer are V (= AV), (= AH), S, AS, G, and AC. The activity coefficient is also of special importance because of its application in phase equilibrium calculations. 

The behavior of binary liquid solutions is clearly displayed by plots of M , AM, and In y, vs. Xi at constant T and P. The volume change of mixing (or excess volume) is the most easily measured of these quantities and is normally small. However, as illustrated by Fig. 4-1, it is subject to individumistic behavior, being sensitive to the effects of molecular size and shape and to differences in the nature and magnitude of intermolecular forces. 

Liquid Solution Behavior. The component activity coefficients in the liquid phase can be addressed separately from those in the solid solution by direct experimental determination or by analysis of the binary limits, since y p = 1. Because of the large amount of experimental effort required to study a ternary composition field and the high vapor pressures encountered in the arsenide and phosphide melts, a direct experimental determination of ternary activity coefficients has been reported only for the Ga-In-Sb system (26). Typically, the available binary liquidus data have been used to fix the adjustable parameters in a solution model with 0,p determined by Equation 7. The solution model expression for the activity coefficient has been used not only to represent the component activities along the liquidus curve, but also the stoichiometric liquid activities needed in Equation 7. The ternary melt solution behavior is then obtained by extending the binary models to describe a ternary mixture without additional adjustable parameters. In general, interactions between atoms in different groups exhibit negative deviations from ideal behavior... 

The determination of was examined by first considering the liquid solution behavior and then the solid mixture properties. The liquid phase properties are typically determined by using a solution model to interpolate between the binary limits. In general, the use of only the binary phase diagrams in the data base for model parameter estimation does not give good values for the ternary liquid mixture properties. The solid solution behavior is normally determined from an analysis of the pseudo-binary phase diagram. Extrapolation of the solid solution behavior determined in this manner to lower values of temperature should be undertaken with caution. 

For gas-liquid solutions which are only moderately dilute, the equation of Krichevsky and Ilinskaya provides a significant improvement over the equation of Krichevsky and Kasarnovsky. It has been used for the reduction of high-pressure equilibrium data by various investigators, notably by Orentlicher (03), and in slightly modified form by Conolly (C6). For any binary system, its three parameters depend only on temperature. The parameter H (Henry s constant) is by far the most important, and in data reduction, care must be taken to obtain H as accurately as possible, even at the expense of lower accuracy for the remaining parameters. While H must be positive, A and vf may be positive or negative A is called the self-interaction parameter because it takes into account the deviations from infinite-dilution behavior that are caused by the interaction between solute molecules in the solvent matrix. 

A brief discussion of sohd-liquid phase equihbrium is presented prior to discussing specific crystalhzation methods. Figures 20-1 and 20-2 illustrate the phase diagrams for binary sohd-solution and eutectic systems, respectively. In the case of binary solid-solution systems, illustrated in Fig. 20-1, the liquid and solid phases contain equilibrium quantities of both components in a manner similar to vapor-hquid phase behavior. This type of behavior causes separation difficulties since multiple stages are required. In principle, however, high purity... 

From a global assessment of these results, it seems inescapable to conclude that mean-field behavior does not remain valid asymptotically close to the critical point. Rather, ionic systems seem to show Ising-to-mean-field crossover. Such a crossover has been a recurring result observed near liquid-liquid consolute points in Coulombic electrolyte solutions, in ternary aqueous electrolyte solutions containing an organic cosolvent, and in binary aqueous solutions of NaCl near the liquid-vapor critical line. 

The thermodynamic quantity 0y is a reduced standard-state chemical potential difference and is a function only of T, P, and the choice of standard state. The principal temperature dependence of the liquidus and solidus surfaces is contained in 0 j. The term is the ratio of the deviation from ideal-solution behavior in the liquid phase to that in the solid phase. This term is consistent with the notion that only the difference between the values of the Gibbs energy for the solid and liquid phases determines which equilibrium phases are present. Expressions for the limits of the quaternary phase diagram are easily obtained (e.g., for a ternary AJB C system, y = 1 and xD = 0 for a pseudobinary section, y = 1, xD = 0, and xc = 1/2 and for a binary AC system, x = y = xAC = 1 and xB = xD = 0). 

In order to explain the experimental behavior found of X for PVP in the different mixtures, the polarizability was taken into account because of the methyl groups substituents of the aromatic ring. It is possible to And changes in the nature of the interactions between the polar solute, 2 - propanol, and the aromatic component in the binary mixtures and that these changes affect the X values. The importance of dipole - induced dipole interactions and steric factors in the formation of a molecular complex between a polar component and a non - polar aromatic solvent has been emphasized on the basis of NMR studies [111, 112], The molecular interactions in binary liquid mixtures have also been studied on the basis of viscosity measurements. The viscosity data have also been used by Yadava et al. [113,114] to obtain a value for the interchange energy (Wvisc) [115] This parameter can be estimated by the equation ... 

The lifetime (Ti) of a vibrational mode in a polyatomic molecule dissolved in a polyatomic solvent is, at least in part, determined by the interactions of the internal degrees of freedom of the solute with the solvent. Therefore, the physical state of the solvent plays a large role in the mechanism and rate of VER. Relaxation in the gas phase, which tends to be slow and dominated by isolated binary collisions, has been studied extensively (11). More recently, with the advent of ultrafast lasers, vibrational lifetimes have been measured for liquid systems (1,4). In liquids, a solute molecule is constantly interacting with a large number of solvent molecules. Nonetheless, some systems have been adequately described by isolated binary collision models (5,12,13), while others deviate strongly from this type of behavior (14-18). The temperature dependence of VER of polyatomic molecules in liquid solvents can show complex behavior (16-18). It has been pointed out that a change in temperature of a liquid solute-solvent system also results in a change in the solvent s density. Therefore, it is difficult to separate the influences of density and temperature from an observed temperature dependence. 

Binary-Liquid Option. As an alternative to this study of critical behavior in a pure fluid, one can use quite a similar technique to investigate the coexistence curve and critical point in a binary-liquid mixture. Many mixtures of organic liquids (call them A and B) exhibit an upper critical point, which is also called a consolute point. In this case, the system exists as a homogeneous one-phase solution for all compositions if Tis greater than... 

Besides these thermodynamic criteria, the most common approach used in the literature is based on the operation at pressures above the binary (liquid - SC-CO2) mixture critical point, completely neglecting the influence of solute on VLEs of the system. But, the solubility behavior of a binary supercritical COj-containing system is frequently changed by the addition of a low volatile third component as the solute to be precipitated. In particular, the so-called cosolvency effect can occur when a mixture of two components solvent+solute is better soluble in a supercritical solvent than each of the pure components alone. In contrast to this behavior, a ternary system can show poorer solubility compared with the binary systems antisolvent+solvent and antisol-vent+solute a system with these characteristics is called a non-cosolvency (antisolvent) system. hi particular, in the case of the SAS process, they hypothesize that the solute does not induce cosolvency effects, because the scope of this process lies in the use of COj as an antisolvent for the solute, inducing its precipitation. 

Contents Theory of Electrons in Polar Fluids. Metal-Ammonia Solutions The Dilute Region. Metal Solutions in Amines and Ethers. Ultrafast Optical Processes. Metal-Ammonia Solutions Transition Range. The Electronic Structures of Disordered Materials. Concentrated M-NH3 Solutions A Review. Strange Magnetic Behavior and Phase Relations of Metal-Ammonia Compounds. Metallic Vapors. Mobility Studies of Excess Electrons in Nonpolar Hydrocarbons. Optical Absorption Spectrum of the Solvated Electron in Ethers and Binary Liquid Systems. Subject Index. Color Plates. 

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