Gas chromatography (GC), is a common type of

chromatography used in analytical chemistry for separating

and analysing compounds that can be vaporized without
decomposition.
the mobile phase (or "moving phase") is a carrier gas, usually
an inert gas such as helium or an unreactive gas such as
nitrogen. The stationary phase is a microscopic layer of liquid
or polymer on an inert solid support, inside a piece of glass
or metal tubing called a column (a homage to the
fractionating column used in distillation). The instrument
used to perform gas chromatography is called a gas
chromatograph (or "aerograph", "gas separator").
Gas chromatography is in principle similar to column
chromatography (as well as other forms of chromatography, such
as HPLC, TLC), but has several differences.
Firstly, the process of separating the compounds in a mixture is
carried out between a liquid stationary phase and a gas mobile
phase, whereas in column chromatography the stationary phase is
a solid and the mobile phase is a liquid.
(Hence the full name of the procedure is "Gas–liquid
chromatography", referring to the mobile and stationary phases,
respectively.)
Secondly, the column through which the gas phase passes is
located in an oven where the temperature of the gas can be
controlled, whereas column chromatography (typically) has no
such temperature control.

Thirdly, the concentration of a compound in the gas phase is

solely a function of the vapor pressure of the gas.
Columns
Packed and capillary (also known as open tubular). Packed columns contain a
finely divided, inert, solid support material (commonly based on diatomaceous
earth) coated with liquid stationary phase. Most packed columns are 1.5 - 10m in
length and have an internal diameter of 2 - 4mm.
Capillary columns have an internal diameter of a few tenths of a millimeter.
They can be one of two types; wall-coated open tubular (WCOT) or support-
coated open tubular (SCOT). Wall-coated columns consist of a capillary tube
whose walls are coated with liquid stationary phase. In support-coated columns,
the inner wall of the capillary is lined with a thin layer of support material such as
diatomaceous earth, onto which the stationary phase has been adsorbed. SCOT
columns are generally less efficient than WCOT columns. Both types of capillary
column are more efficient than packed columns.
Concentration dependant detectors and mass flow
dependant detectors. The signal from a concentration dependant detector is
related to the concentration of solute in the detector, and does not usually destroy
the sample. Dilution of sample with make-up gas will lower detectors response.
Mass flow dependant detectors usually destroy the sample, and the signal is
related to the rate at which solute molecules enter the detector. The response of a
mass flow dependant detector is unaffected by make-up gas.
The effluent from the column is mixed with H2
and air, ignited. Compounds in the flame produce
ions and electrons which can conduct electricity
through the flame. A large electrical potential is
applied at the burner tip, and a collector
electrode is located above the flame. The current
from the pyrolysis of any organic compounds is
measured. FIDs are mass sensitive than
concentration sensitive; the advantage is that
changes in mobile phase flow rate do not affect
the detector's response, high sensitivity, a large
linear response range, and low noise, is robust
and easy to use,but , destroys the sample.
 Detec Dynam
Detector Type Support gases Selectivity tabilit ic
y range
Flame Hydrogen and 100
Mass Most organic cpds. 107
ionization flow
air pg
(FID)
Thermal
Conce Reference Universal 1 ng 107
conductivit ntrati
y (TCD) on
Electron Halides, nitrates, nitriles, peroxides, anhydrides,
Conce Make-up 50 fg 105
capture ntrati
organometallics
(ECD) on
Nitrogen- Hydrogen and
Mass Nitrogen, phosphorus 10 pg 106
phosphorus flow
air

Flame Hydrogen and Sulphur, phosphorus, tin, boron, arsenic, germanium, 100
Mass 103
photometri flow
air possibly selenium, chromium pg
c (FPD) oxygen
Photo- Aliphatics, aromatics, ketones, esters, aldehydes,
Conce Make-up amines, heterocyclics, organosulphurs, some 2 pg 107
ionization ntrati organometallics
(PID)
Hall on
Hydrogen,
electrolytic Mass Halide, nitrogen, nitrosamine, sulphur
oxygen
conductivit flow
y
Supercritical fluid Chromatography
There is a pressure above which the substance can no longer exist as a gas no
matter how high the temperature is raised. These points are called the
supercritical temperature and supercritical pressure respectively and are the
defining boundaries on a phase diagram for a pure substance.
Beyond which the substance has properties intermediate between a liquid and a
gas and is called a supercritical fluid. In this region the fluid has good solvating
power and high diffusivity, which make it a good choice as a mobile phase in
chromatography.
Separation in SFC is based on the density of
the supercritical fluid which corresponds to
solvating power. As the pressure in the
system is increased, the supercritical fluid
density increases and correspondingly its
solvating power increases. Therefore, as the
density of the supercritical fluid mobile
phase is increased, components retained in
the column can be made to elute. This is
similar to temperature programming in GC
or using a solvent gradient in HPLC.
Supercritical fluids are produced by heating a gas above its
critical temperature or compressing a liquid above its critical
pressure.
The critical temperature of a substance is the temperature above
which a liquid phase cannot exist, regardless of pressure. The
vapour pressure of a substance at its critical temperature is its
critical pressure.
At temperatures and pressures above but close to its critical
temperature and pressure (the critical point), a substance is
called a supercritical fluid.
Supercritical fluids have densities, viscosities and other
properties that are intermediate between those of the
substance in its gaseous and in its liquid state.
Carbon dioxide is the most commonly used supercritical
fluid because of its low critical temperature (31 oC),
inertness, low toxicity and reactivity and high purity at low
cost.
Carbon dioxide does not dissolve polar compounds so when
analysing that type of compounds methanol, cyclic ethers,
water or formic acid can be added to the carbon dioxide.
Supercritical fluid chromatography (SFC) is a hybrid of
gas and liquid chromatography.
SFC is of importance because it permits the separation
and determination of a group of compounds that are not
conveniently handled by either gas or liquid
chromatography.
These compounds are either nonvolatile or thermally
labile so that gas chromatography cannot be used and
they do not contain functional groups that make possible
detection by liquid chromatography.
SFC has been applied to a wide variety of materials
including natural prodcuts, drugs, foods, pesticides and
herbicides, fossil fuels, explosives and propellants.
The mobile phase:
Based on its low cost, low interference with chromatographic detectors,
and good physical properties (nontoxic, nonflammable, low critical
values) carbon dioxide is the standard.
The main disadvantage of carbon dioxide is its inability to elute very
polar or ionic compounds.
This can be overcome by adding a small portion of a second fluid called
a modifier fluid, generally an organic fluid which is completely miscible
with carbon dioxide (alcohols, cyclic ethers) but can be almost any
liquid including water.
The addition of the modifier fluid improves the solvating ability of the
supercritcal fluid and sometimes enhances selectivity of the separation.
It can also help improve separation efficiency by blocking some of the
highly active sites on the stationary phase. Modifier fluids are commonly
used, especially in packed column SFC.
 Columns
Both open-tubular and packed columns are used for SFC. The
open-tubular columns are most useful for separations requiring
high-efficiency separations and for complex samples. Packed columns are
most useful for high-speed separations requiring a moderate column
efficiency and for samples containing fewer components.
Gas Chromatography (GC) detectors and many High Performance Liquid
Chromatography (HPLC) detectors can be used. With packed columns and
organic modifiers the number of detectors available is more limited. The
Flame Ionization Detector (FID) is the most frequently used detector. Other
detectors that often are used are Flame Photometric Detector (FPD),
Electron Capture Detector ECD and Mass Spectrometer (MS).
Due to the low viscosity and high diffusivity of the supercritical CO2,
preparative SFC ensure faster purification than traditional preparative
HPLC.
A supercritical fluid chromatography instrument consists of a mobile phase
container, an injector, a column in an oven, a restrictor and a detector. The
components are similar to those of a gas chromatograph with exception of the
restrictor. The restrictor is needed to maintain the pressure above the critical
point.
Cold liquid CO2 is pumped (1 2). Prior to entering the column, it is heated and
becomes supercritical (2 3). Because of its low viscosity, the pressure at the
column outlet is almost identical to the pressure at the column inlet (3 4). At
the column outlet, the mobile phase is decompressed and heated and
becomes gaseous (4 5). Products are recovered in cyclones of appropriate
design. The gaseous CO2 is then cleaned and cooled down and returned to
the tank.
Supercritical fluid extraction
The principle that solubilities in a supercritical fluid increase dramatically with
increasing density, and that different solutes have different solubilities at the same
conditions.
The problem of removing the extracting liquid is eliminated. An example of the SFE
method is the removal of caffeine from coffee.
SFC Advantages
Supercritical fluid chromatography has several main advantages over other
conventional chromatographic techniques (GC and HPLC). Compared with HPLC,
SFC provides rapid separations without the use of organic solvents or could be
reduced with the use of SFC. Because SFC generally uses carbon dioxide collected
as a byproduct of other chemical reactions or is collected directly from the
atmosphere, it contributes no new chemicals to the environment. In addition, SFC
separations can be done faster than HPLC separations because the diffusion of
solutes in supercritical fluids is about ten times greater than that in liquids (and
about three times less than in gases). This results in a decrease in resistance to mass
transfer in the column and allows for fast high resolution separations. Compared
with GC, capillary SFC can provide high resolution chromatography at much lower
temperatures. This allows fast analysis of thermolabile compounds.