Equilibrium solid-supercritical fluid

The pressure-temperature phase diagrams also serve to highlight the fact that the polymorphic transition temperature varies with pressure, which is an important consideration in the supercritical fluid processing of materials in which crystallization occurs invariably at elevated pressures. Qualitative prediction of various phase changes (liquid/vapor, solid/vapor, solid/liquid, solid/liquid/vapor) at equilibrium under supercritical fluid conditions can be made by reference to the well-known Le Chatelier s principle. Accordingly, an increase in pressure will result in a decrease in the volume of the system. For most materials (with water being the most notable exception), the specific volume of the liquid and gas phase is less than that of the solid phase, so that... 

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. 

Supercritical fluids represent a different type of alternative solvent to the others discussed in this book since they are not in the liquid state. A SCF is defined as a substance above its critical temperature (Tc) and pressure (Pc)1, but below the pressure required for condensation to a solid, see Figure 6.1 [1], The last requirement is often omitted since the pressure needed for condensation to occur is usually unpractically high. The critical point represents the highest temperature and pressure at which the substance can exist as a vapour and liquid in equilibrium. Hence, in a closed system, as the boiling point curve is ascended, increasing both temperature and pressure, the liquid becomes less dense due to thermal expansion and the gas becomes denser as the pressure rises. The densities of both phases thus converge until they become identical at the critical point. At this point, the two phases become indistinguishable and a SCF is obtained. 

Weidner E, Wiesmet V, Knez Z et al (1997) Phase equilibrium (solid-liquid-gas) in polyethylene glycol-carbon dioxide systems. J Supercrit Fluids 10(3) 139-147... 

The potential of supercritical extraction, a separation process in which a gas above its critical temperature is used as a solvent, has been widely recognized in the recent years. The first proposed applications have involved mainly compounds of low volatility, and processes that utilize supercritical fluids for the separation of solids from natural matrices (such as caffeine from coffee beans) are already in industrial operation. The use of supercritical fluids for separation of liquid mixtures, although of wider applicability, has been less well studied as the minimum number of components for any such separation is three (the solvent, and a binary mixture of components to be separated). The experimental study of phase equilibrium in ternary mixtures at high pressures is complicated and theoretical methods to correlate the observed phase behavior are lacking. 

Solubilities of meso-tetraphenylporphyrin (normal melting temperature 444°C) in pentane and in toluene have been measured at elevated temperatures and pressures. Three-phase, solid-liquid-gas equilibrium temperatures and pressures were also measured for these two binary mixtures at conditions near the critical point of the supercritical-fluid solvent. The solubility of the porphyrin in supercritical toluene is three orders of magnitude greater than that in supercritical pentane or in conventional liquid solvents at ambient temperatures and pressures. An analysis of the phase diagram for toluene-porphyrin mixtures shows that supercritical toluene is the preferred solvent for this porphyrin because (1) high solubilities are obtained at moderate pressures, and (2) the porphyrin can be easily recovered from solution by small reductions in pressure. 

Fundamental studies on the adsorption of supercritical fluids at the gas-solid interface are rarely cited in the supercritical fluid extraction literature. This is most unfortunate since equilibrium shifts induced by gas phase non-ideality in multiphase systems can rarely be totally attributed to solute solubility in the supercritical fluid phase. The partitioning of an adsorbed specie between the interface and gaseous phase can be governed by a complex array of molecular interactions which depend on the relative intensity of the adsorbate-adsorbent interactions, adsorbate-adsorbate association, the sorption of the supercritical fluid at the solid interface, and the solubility of the sorbate in the critical fluid. As we shall demonstrate, competitive adsorption between the sorbate and the supercritical fluid at the gas-solid interface is a significant mechanism which should be considered in the proper design of adsorption/desorption methods which incorporate dense gases as one of the active phases. 

For the design of a process for formation of solid particles using supercritical fluids, data on solid - liquid and vapour - liquid phase equilibrium are essential. PGSS process is only possible for systems where enough gas is solubilized in the liquid. 

Several authors [3-9] studied the solubility of polymers in supercritical fluids due to research on fractionation of polymers. For solubility of SCF in polymers only limited number of experimental data are available till now [e.g. 4,5,10-12], Few data (for PEG S with molar mass up to 1000 g/mol) are available on the vapour-liquid phase equilibrium PEG -CO2 [13]. No data can be found on phase equilibrium solid-liquid for the binary PEG S -CO2. Experimental equipment and procedure for determination of phase equilibrium (vapour -liquid and solid -liquid) in the binary system PEG s -C02 are presented in [14]. It was found that the solubility of C02 in PEG is practically independent from the molecular mass of PEG and is influenced only by pressure and temperature of the system. 

Supercritical fluids are found in numerous applications thanks to their properties which vary with temperature and pressure. Supercritical fluids are put in contact with various compounds which also have physico-chemical properties dependant on temperature and pressure. Consequently, mixtures of these compounds with the supercritical solvent must be expected to behave in a complex way. For a binary mixture, for example, several types of phase equilibrium exist solid-fluid for low temperatures, solid-fluid-liquid when temperature rises, and liquid-fluid. 

Competent design of chemical processes requires accurate knowledge of such process variables as the temperature, pressure, composition and phase of the process contents. Current predictive models for phase equilibria Involving supercritical fluids are limited due to the scarcity of data against which to test them. Phase equilibria data for solids In equilibrium with supercritical solvents are particularly sparse. The purpose of this work Is to expand the data base to facilitate the development of such models with emphasis on the melting point depressions encountered when solid mixtures are contacted with supercritical fluids. 

Phase Equilibrium in Solid-Liquid-Supercritical Fluid Systems... 

Sandro RPdR, Olivera JVd, Avila SGD. A three-phase ternary model for CO2-solid-liquid equilibrium at moderate pressures. J Supercrit Fluids 1996 9 ... 

Fig. 4.28 Generalized phase diagram. Only a supercritical fluid exists above the critical temperature (T ) and critical pressure (p ), which has properties intermediate between liquid and gas. (Note water is unusual in having a negative slope for the solid-liquid phase equilibrium line.)...

PHASE EQUILIBRIA. A useful solvent for supercritical extraction, especially in food processing, is carbon dioxide, which has a critical point of 31.06 C and 73.8 bars (1070 Iby/in. ). The phase diagram for pure COj (Fig. 20.16) shows the equilibrium regions of solid, liquid, and gas and the conditions under which a supercritical fluid exists. In the supercritical region there is no distinction between liquid and gas and no phase transition from one to the other the supercritical fluid acts like a very dense gas or a light, mobile liquid. 

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