Supercritical fluids

What is supercritical fluids?

- A supercritical fluids (SCF) is any substance at a temperature and pressure above its
critical point, where particular liquid and gas phases don't exist. It can effuse through
solids like a gas, and dissolves materials like a liquid. In addition, near the critical point,
there will be a small changes in pressure or temperature resulting in a large changes in
density, allowing many properties of a supercritical fluids to be "fine-tuned".
Supercritical fluids are suitable as a substitute for natural solvents (organic solvents) in a
range of mechanical and laboratory processes. Carbon dioxide and water are the most
usually utilized supercritical fluids, being utilized for decaffeination and power
generation.
- A supercritical fluids (SCF) do not have a definite phase. Supercritical fluids have the
low viscosity of a gas and the high density of a liquid, making it impossible to liquefy the
matter using any amount of pressure. However, it is possible to go from a gas to a liquid
without crossing the boundary between the vapor and liquid phase using a supercritical
fluid just by lowering the temperature of the liquid. Volatile liquids and solids, or liquids
and solids with a high vapor pressure or low boiling point, are soluble in gas. It becomes
especially easy to dissolve liquids and solids such as these in a supercritical fluid because
of the high density. As can be noted from the Mole Fraction Solubility. The Mole
Fraction Solubility is simply the ratio of the sublimation (or vapor pressure) to the total
gas pressure.
- Supercritical fluids have no surface tension because they are not subject to the vapor-
liquid boundary so no molecules have the attraction to the interior of the liquid. The
densities and viscosity of a supercritical fluid are subject to change when pressure or
temperature are tampered with, and the supercritical fluid of a substance can have very
different properties than the regular fluids. For instance, water that is supercritical differs
from regular water in the fact that it is non-polar and acidic.
- Supercritical fluids can occur in nature. For example, in places like underwater
volcanoes, specifically those located deep beneath the ocean's surface, supercritical water
is formed because of the immense pressure due to the depth and the intense heat from the
vents of the volcano. This water can lead to the formation of crystals used in some
jewellery.
 Example: phase diagram:

Notice the yellow and blue mixed to make green region that follows the Coordinates of the
critical point where the supercritical fluids occur on the graph. Every element and molecules
have unique critical points. The arrow demonstrates how it is possible to go from a vapor to a
liquid by utilizing supercritical fluids, pressure and temperature. Notice how pressure and
temperature on a gas are increased into the supercritical range, and the temperature is brought
down (lowered), the substance moves into the liquid phase

Applications

Supercritical fluids based technologies are involved in a wide variety of industrial applications
which have shown significant progress in recent years. Many industrial sectors are concerned
including food, cosmetics, pharmaceutics, materials, chemistry, energy and waste treatment. The
related supercritical fluid processes include extraction, impregnation, formulation, sterilization,
cleaning, energy and waste treatment among others.

Here are some examples of the industrial applications based on the utilization of supercritical
fluids:
FOOD INDUSTRY
- Decaffeination of coffee: decaffeination of coffee produced presents a full aromatic
profile (as a result of the low temperatures used and the absence of organic solvent). The
extracted caffeine is, on the other side, sold to the pharmaceutical and food industries.
Therefore there is very little waste formed at the end of this process, making it
economically and environmentally sustainable.

COSMETIC INDUSTRY
- Antioxidant such as polyphenols, carotenoids and tocopherols (vitamin E), which are
found in a wide variety of fruits and vegetables (beta carotene in carrots, lycopene in
tomato…) can be selectively extracted using supercritical CO2. In addition, the textures of
the extracts obtained (thyme, rosemary, lavender, chamomile..) are free from traces of
organic solvents.
CHEMICAL INDUSTRY

- Catalysis and biocatalysts of various organic compounds can be efficiently carried out in
supercritical CO2. Industrialization of the process include the continuous catalytic
hydrogenation of aromatic compounds.

WOOD INDUSTRY

- Super wood (Denmark) has industrialised the impregnation of wood with fungicides
dissolved Supercritical CO2 ensuring a lack of mould, avoiding long baths and saving
substantial amounts of fungicides.

ENERGY PRODUCTION
- The very promising recent developments observed in the areas of liquefaction and
gasification of biomass (from agricultural wastes) in subcritical and supercritical water
opens up the way to novel energy sources.
 PROPERTIES OF
SUPERCRITICAL FLUIDS

 Physical and thermal properties of SCFs are in between pure liquid and gas, hence can
also be known as “Compressible Liquid” or “Dense Gases”.
 Changes in properties for SCF are the following:
- Liquid like densities (100-1000 times greater than gases)
- Diffusivities higher than liquids (10−3 and 10−4 𝑐𝑚2 /𝑠)
- Good solvating power
- Reduction in surface tension
- Low viscosity (10- 100 times less than liquid)
- Gas like compressibility properties

Therefore they posses high penetrating power.