Introduction to supercritical fluids

Muslim Dvoyashkin

Introduction
The aim of this report is to introduce to supercritical fluids scope and to review some important applications of supercritical fluids.

Supercritical fluid (SCF). What is this?

1.)
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).

2.)

vapour liquid

vapour

to

liquid

to

SCphase (Tc,Pc)

The result new phase occurs so-called supercritical phase.

A supercritical fluid is a state where matter is compressible and behaves like a gas (i.e. it fills and takes the shape of its container), which is not the case when it is in a liquid state (an incompressible fluid that occupies the bottom of its container). However, a supercritical fluid has the typical density of a liquid and hence its characteristics dissolving power. That is why we cannot define the supercritical fluid as a liquid or as a gas. This is a new state of matter in principle.

Schematic p-T phase diagram

Schematic p-T phase diagram reflects the region, where fluid can exist in supercritical state.
Supercritical area
Pc
Critical point

Table 1. Critical points for typical solvents

Liquid
pressure
ec nc te xis oe c ur v e

Gas
Tc

temperature

Fig. 1

Table 2. Order of density, viscosity and diffusivity of gases, liquids and supercritical fluids.

If the temperature and pressure of a substance are both higher than Tc and Pc for that substance, the substance is defined as supercritical fluid.

Visualization of transition into SC-state for CO2 3

1 2
Here we can see the separate phases of carbon dioxide. The meniscus is easily observed. With an increase in temperature the meniscus begins to diminish.

3
Increasing the temperature further causes the gas and liquid densities to become more similar. The meniscus is less easily observed but still exists.

4 (Tc,Pc)

Once the critical temperature and pressure have been reached, the two distinct phases of liquid and gas are no longer visible. The meniscus can no longer be seen. One homogenous phase called the "supercritical fluid" phase occurs.

Some important properties of SCF

Generate no liquid (condensed phase) under pressure change or on solid surfaces. Also, there is no gas will be formed on increasing temperature. Able to control density (solubility), polarity, viscosity and other properties of the fluids continuously and over a wide range. Can change the property sharply with very little change in pressure, particularly in the vicinity of the critical temperature and pressure. 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.

Fig. 2 Diffusivity of CO2 and solubility of naphtalene in CO2 at 40C.

Industrial applications of SCF

SCF
Supercritical fluid extraction
That are used in: supercritical fluid chromatography (SFC); catalysis; particle formation; cleaning; electronic chip manufacturing (and others).

SC-medium in chemical reactions

SCF in confined systems

Critical point (CP) - bulk

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).

Pcr = (Pcrbulk Pcrpm) > 0 Tcr = (Tcrbulk Tcrpm) > 0

PFG NMR approach

Methods of investigation of supercritical phenomena in porous systems:

Catalytic processes of conversion of reactants in solvent in a presence of porous material as a catalyst (indirect method). Analysis of sorption-desorption isotherms where the sharp jump in adsorption due to capillary condensation just disappears (also indirect method). Molecular Dynamics and Monte Carlo (or MC with DFT) simulations.

Hopefully, the PFG NMR method can provide direct information about:

self-diffusion characteristics of supercritical fluids in porous systems; 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; more than 100oC and 30 atm respectively; Elimination of undesirable influence of convection on measurements due to temperature gradiends along the sample.