High-pressure phase equilibrium experimental procedures

We generally distinguish between two methods when the determination of the composition of the equilibrium phases is taking place. In the first method, known amounts of the pure substances are introduced into the cell, so that the overall composition of the mixture contained in the cell is known. The compositions of the co-existing equilibrium phases may be recalculated by an iterative procedure from the predetermined overall composition, and equilibrium temperature and pressure data It is necessary to know the pressure volume temperature (PVT) behaviour, for all the phases present at the experimental conditions, as a function of the composition in the form of a mathematical model (EOS) with a sufficient accuracy. This is very difficult to achieve when dealing with systems at high pressures. Here, the need arises for additional experimentally determined information. One possibility involves the determination of the bubble- or dew point, either optically or by studying the pressure volume relationships of the system. The main problem associated with this method is the preparation of the mixture of known composition in the cell. 

A detailed description of the experimental apparatus and procedure used for the aqueous study are given elsewhere (Roop and Akgerman, Ind. Eng. Chem. R., in review) Static equilibrium extractions were carried out in a high pressure equilibrium cell (300 mL Autoclave). After the vessel is initially charged with 150 mL of water containing 6.8 wt.% phenol and supercritical carbon dioxide (and a small amount of entrainer, if desired), the contents were mixed for one hour followed by a two hour period for phase separation. Samples from both the aqueous phase and the supercritical phase were taken for analysis and the distribution coefficient for phenol calculated. 

The melting curve of sulfur with respect to metastability and experimental procedures has been critically analyzed by Vezzoli and Walsh [194]. The authors also discussed the previously reported phase boundaries of the sohd high-pressure allotropes in the range up to 4 GPa and from room temperature up to about 670 K [132]. However, the structures of these high-pressure polymorphs are unknown and their probability to exist under equilibrium conditions is still awaiting confirmation. 

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