Phase Behavior and Its Effects on Reactions in Liquid and Supercritical Carbon Dioxide

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Carbon dioxide, either as an expanded liquid or as a supercritical fluid, may be a viable replacement for a variety of conventional organic solvents in reaction systems. Numerous studies have shown that many reactions can be conducted in liquid or supercritical CO2 (sc CO2) and, in some cases, rates and selectivities can be achieved that are greater than those possible in normal liquid- or gas-phase reactions (other chapters in this book; Noyori, 1999; Savage et al., 1995). Nonetheless, commercial exploitation of this technology has been limited. One factor that contributes to this reluctance is the extremely complex phase behavior that can be encountered with high-pressure multicomponent systems. Even for simple binary systems, one can observe multiple fluid phases, as shown in Figure 1.1. The figure shows the pressure–temperature (PT) projection of the phase diagram of a binary system, where the vapor pressure curve of the light component (e.g., CO2) is the solid line shown at temperatures below TB. It is terminated by its critical point, which is shown as a solid circle. The sublimation curve, melting curve, and vapor pressure curve of the pure component 2 (say, a reactant that is a solid at ambient conditions) are the solid lines shown at higher temperatures on the right side of the diagram; that is, the triple point of this compound is above TE. The solid might experience a significant melting point depression when exposed to CO2 pressure [the dashed–dotted solid/liquid/vapor (SLV) line, which terminates in an upper critical end point (UCEP)]. For instance, naphthalene melts at 60.1 °C under CO2 pressure (i.e., one might observe a three-phase solid/liquid/vapor system), even though the normal melting point is 80.5 °C (McHugh and Yogan, 1984). To complicate things even further, there will be a region close to the critical point of pure CO2 where one will observe three phases as well, as indicated by the dashed–dotted SLV line that terminates at the lower critical end point (LCEP). The dotted line connecting the critical point of the light component and the LCEP is a vapor/liquid critical point locus.