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By Maria Dolores Luque Castro; Miguel Valcarcel Cases; M T Tena

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GAS Tc TEMPERAT U RE Fig. 1. Solid-liquid-gas-supercritical fluid phase diagram. TP critical point. Pc = critical pressure. Tc = critical temperature = triple point. CP = temperature. This latter property allows for a new definition of supercritical fluids: one that is above its critical pressure and temperature. Increasing the temperature also increases the pressure at which the liquid and vapour phase coexist on the vapour pressure curve. The increase in the vapour pressure is concomitant with a decrease in the difference between the density of the liquid and gaseous phases.

Such regions are bounded by curves indicating the coexistence of two phases (s-g, s-l and l-g, which are involved in sublimation, melting and vaporization equilibria, respectively). The three curves intersect at the so-called Triple point triple point (TP), where the solid, liquid and gaseous phases coexist in equilibrium. At a constant pressure, a phase transition takes place at a transition temperature that is a function of the pressure. Phase transformations involve enthalpy changes. Thus, in the absence of external influences, two phases can coexist indefinitely at a transition temperature for each pressure.

By way of summary, the scheme in Fig. 00 0> 1-500 z 0:: w - I - (f) ,750 I >- z 47 100 300 500 PRESSURE (bar) 'a 700 Fig. 12. Influence of pressure on the dielectric constant and density of SC CO 2 at a constant temperature. (Reproduced with permission of the American Chemical Society) BASIC PROPERTIES OF A SUPERCRITICAL FLUID Fig. 13. Relationships between the basic (intrinsic and solute-related) properties of a supercritical fluid are inherent in the SF itself (intrinsic) or related to the dissolved substances (solutes).

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