# 3.2 Basic principles of supercritical fluid chromatography and

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This module is to explain the basic working principles and setups of supercritical fluid chromatography and supercritical fluid extraction methods.

## Introduction

The discovery of supercritical fluids led to novel analytical applications in the fields of chromatography and extraction known as supercritical fluid chromatography (SFC) and supercritical fluid extraction (SFE). Supercritical fluid chromatography is accepted as a column chromatography methods along with gas chromatography (GC) and high-performance liquid chromatography (HPLC). Due to to the properties of supercritical fluids, SFC combines each of the advantages of both GC and HPLC in one method. In addition, supercritical fluid extraction is an advanced analytical technique.

## Definition and formation of supercritical fluids

A supercritical fluid is the phase of a material at critical temperature and critical pressure of the material. Critical temperature is the temperature at which a gas cannot become liquid as long as there is no extra pressure; and, critical pressure is the minimum amount of pressure to liquefy a gas at its critical temperature. Supercritical fluids combine useful properties of gas and liquid phases, as it can behave like both a gas and a liquid in terms of different aspects. A supercritical fluid provides a gas-like characteristic when it fills a container and it takes the shape of the container. The motion of the molecules are quite similar to gas molecules. On the other hand, a supercritical fluid behaves like a liquid because its density property is near liquid and, thus, a supercritical fluid shows a similarity to the dissolving effect of a liquid.

The characteristic properties of a supercritical fluid are density, diffusivity and viscosity. Supercritical values for these features take place between liquids and gases. [link] demonstrates numerical values of properties for gas, supercritical fluid and liquid.

Gas Supercritical fluid Liquid
Density (g/cm 3 ) 0.6 x 10 -3 – 2.0 x 10 -3 0.2 - 0.5 0.6 - 2.0
Diffusivity (cm 2 /s) 0.1 - 0.4 10 -3 - 10 -4 0.2 x 10 -5 - 2.0 x 10 -5
Viscosity (cm/s) 1 x 10 -4 - 3 x 10 -4 1 x 10 -4 - 3 x 10 -4 0.2 x 10 -2 - 3.0 x 10 -2

The formation of a supercritical fluid is the result of a dynamic equilibrium. When a material is heated to its specific critical temperature in a closed system, at constant pressure, a dynamic equilibrium is generated. This equilibrium includes the same number of molecules coming out of liquid phase to gas phase by gaining energy and going in to liquid phase from gas phase by losing energy. At this particular point, the phase curve between liquid and gas phases disappears and supercritical material appears.

In order to understand the definition of SF better, a simple phase diagram can be used. [link] displays an ideal phase diagram. For a pure material, a phase diagram shows the fields where the material is in the form of solid, liquid, and gas in terms of different temperature and pressure values. Curves, where two phases (solid-gas, solid-liquid and liquid-gas) exist together, defines the boundaries of the phase regions. These curves, for example, include sublimation for solid-gas boundary, melting for solid-liquid boundary, and vaporization for liquid-gas boundary. Other than these binary existence curves, there is a point where all three phases are present together in equilibrium; the triple point (TP).

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