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which is not the case when it is in a liquid state (an incompressible fluid that occupies the bottom of its container). This is a new state of matter in principle. A supercritical fluid is a state where matter is compressible and behaves like a gas (i.e. a supercritical fluid has the typical density of a liquid and hence its characteristics dissolving power. 2.Pc) The result – new phase occurs so-called supercritical phase.) vapour liquid vapour to liquid to SCphase (Tc. 1 Supercritical fluid (SCF). That is why we cannot define the supercritical fluid as a liquid or as a gas. What is this? 1. .Introduction The aim of this report is to introduce to „supercritical fluids“ scope and to review some important applications of supercritical fluids. it fills and takes the shape of its container). However.) vapour vapour only vapour to liquid to The result of heating is the gas obeying to usual gas laws (for example Wan-der-Waals equation).
Supercritical area Pc Critical point 2 Table 1.Schematic p-T phase diagram Schematic p-T phase diagram reflects the region. where fluid can exist in supercritical state. 1 Table 2. Critical points for typical solvents Liquid pressure ec nc te xis oe c ur v e Gas Tc temperature Fig. Order of density. the substance is defined as supercritical fluid. . viscosity and diffusivity of gases. If the temperature and pressure of a substance are both higher than Tc and Pc for that substance. liquids and supercritical fluids.
Pc) Once the critical temperature and pressure have been reached.Visualization of transition into SC-state for CO2 3 1 2 Here we can see the separate phases of carbon dioxide. One homogenous phase called the "supercritical fluid" phase occurs. With an increase in temperature the meniscus begins to diminish. The meniscus is less easily observed but still exists. . the two distinct phases of liquid and gas are no longer visible. The meniscus can no longer be seen. 3 Increasing the temperature further causes the gas and liquid densities to become more similar. The meniscus is easily observed. 4 (Tc.
. 4 Fig. 2 Diffusivity of CO2 and solubility of naphtalene in CO2 at 40°C. polarity. Gaseous substance under ordinary temperature and atmospheric pressure can be easily removed after completing of some chemical reaction by returning it to the atmospheric pressure. viscosity and other properties of the fluids continuously and over a wide range. particularly in the vicinity of the critical temperature and pressure.Some important properties of SCF Generate no liquid (condensed phase) under pressure change or on solid surfaces. Can change the property sharply with very little change in pressure. Also. there is no gas will be formed on increasing temperature. Able to control density (solubility).
5 SC-medium in chemical reactions . electronic chip manufacturing (and others). particle formation. cleaning.Industrial applications of SCF SCF Supercritical fluid extraction That are used in: supercritical fluid chromatography (SFC). catalysis.
SCF in confined systems Critical point (CP) .bulk 6 pressure Triple point CP1 (R1) CP2 (R2) Expected shifts in critical parameters due to existense of porous media: temperature Schematic p-T phase diagram of a bulk fluid and pore fluid confined to different sized pores (R1>R2). ΔPcr = (Pcrbulk –Pcrpm) > 0 ΔTcr = (Tcrbulk –Tcrpm) > 0 .
locus of the critical point (critical pressure and critical temperature) of selected liquids in bulk and in porous materials Problems have to be solved: Measurements at sufficiently high temperatures and pressures. . Analysis of sorption-desorption isotherms where the sharp jump in adsorption due to capillary condensation just disappears (also indirect method). the PFG NMR method can provide direct information about: self-diffusion characteristics of supercritical fluids in porous systems. Hopefully. Molecular Dynamics and Monte Carlo (or MC with DFT) simulations.PFG NMR approach Methods of investigation of supercritical phenomena in porous systems: 7 Catalytic processes of conversion of reactants in solvent in a presence of porous material as a catalyst (indirect method). Elimination of undesirable influence of convection on measurements due to temperature gradiends along the sample. more than 100oC and 30 atm respectively.