GAS- LIQUID

CHROMATOGRAPHY
INTRODUCTION:

 It is a type of chromatography.
 It is a very sensitive method for the separation and
quantification of chemicals and analysis of fatty acid
components.
 Compounds must be present in gas phase, so that partition
between the gaseous mobile phase and liquid stationary phase
is possible.
 It is used for organic, inorganic compounds must be volatile
compounds.
PRINCIPLE:
When the vapours of sample mixer move between the
stationary phase (liquid) and mobile phase(gas) the different
components of the sample mixture will separate according to
their partition coefficient between the gas and liquid
stationary phase.
INSTRUMENTATION
CARRIER GAS:
 The most common carrier gases (mobile phase) are helium,
nitrogen and argon.
 The type of carrier gas is usually dictated by the type of detector
used.
PRESSURE DIFFERENTIAL:
 The pressure differential over the column plays an
important role in the gas chromatography.
 The gas velocity down the column is obtained by applying
a pressure differential.
 Generally the pressure ratio (p1/p2)of 2-3 is used.
 If the pressure ratio is too low, molecular diffusion remixes
the separated components and efficiency decreased.
 If the ratio is too high, the resistance to mass transfer
increased and again the efficiency of separation decrease.
INJECTION PORT:
 The sample enters the chromatography though the injection
port, which is usually heated so that liquids can be vaporized
immediately upon injection.
 Sample addition is generally done by means of syringe, a volume
of 0.5-1ml being required for gas and 1-100µl for liquids.
 Gas sampling values, backflushing values, pyrolysis systems,
inlet splitters, and solid samples are among other sampling
devices.
 Splitters are used to divide a sample into two equal parts for dual
–column chromatography , or to take only a fraction of the initial
samples.
COLUMN:
 Column is usually made out of copper, stainless steel,
aluminium, nicklel and glass.
 The column must be heated to about two-third of the
boiling point of the highest boiling material in the mixture
to be separated.
 If one part of the column is heated to a different
temperature than another, separations will be made but
they will not be reproducible and good physical constant
measurement cannot be made.
 Better instrument have a separate heater for the column .
Disadvantages of temperature programming:
 The column must be cooled to normal temperature before the
next sample can be added.
 The temperature in the column lags behind the temperature
in the surrounding air chamber, so reproducible results are
difficult to obtain.
Capillary columns:
 It is made up of copper, stainless steel, glass or nylon.
 It is act as a inert phase.
 Thickness of stationary phase is so small, so resistance to mass
transfer and highly efficient, rapid analysis can be obtained
SOLID SUPPORTS:
The function of solid support is to act as an inert platform for
the liquid phase in the column.
 Chromosorb P:
It is a pink diatomaceous earth material.
This material is the least inert of the chromosorb supports
but offers the highest efficiency.
 chromosorbW:
It is a whit diatomaceous earth material.
This material is more inert but less efficient than chromosorb
P.
Chromosorb G:
To a very sustainable degree combines the high
column efficiency and good handling characteristics of
chromosob P with the following advantages:
Greater column efficiency, less surface adsorption,
harder particles and less breakdown in handling.
 Chromosorb G is about 2.4 times as heavy as
chromosorbW.
5% liquid loading on chromosorb G is equal to
12% on chromosorb W.
SOLID ADSORBENTS:
 several important adsorbents are used in gas solid chromatography .
 Charcoal, aluminium , silica gel and molecular sieves are used generally to separate gaseous
mixture.
 Molecular sieves are used to separate O2 and N2 but do not elute CO2 under normal
condition.
STATIONARY PHASES:
1. Non polar: Non polar liquid phases separate solutes in order of increasing boiling points.
2. Polar: These materials differentiate between polar and non polar solutes , retaining only
the polar materials.
3. Intermediate : Members of this group dissolve both polar and non polar solutes with
relative ease.
4. Hydrogen bonding: It contains large no of hydrogen atoms available for hydrogen bonding.
5. Specific: Chemical interaction between solute and solvent to perform separation.
DETECTOR:
A detector is a device that measures the changes of the effluent. Different
kinds of detectors are used in gas chromatograph. The ones described here are
thermal conductivity, hydrogen flame ionization, cross section, argon
ionization, electron capture and flame photometric.
Thermal conductivity detectors:
 If you below air over a hot wire, it will be cooled. This phenomenon is
the basis of thermal conductivity detector.
 Characteristics :
 Sensitive to all organic compounds (10 ^-7g/sec).
 Linear dynamic range: 10,000.
 Sensitive to flow rate and temperature changes.
 Detector temperature range:5,00˚C.
 Carrier gases: He, H2, N2, Ar, CO2.
HYDROGEN FLAME IONIZATION DETECTOR:
 The carrier gas and sample emerge from the column, hydrogen and iron are
added to produce a flame of about 2,1oo˚C which produces + and – ions /ml.
 Free carbon is known to polymerize and the low work function (4.3eV)of
these carbon aggregates, could explain the large ion concentration observed.
 Detector sensitivity is roughly proportional to the carbon content of the
sample.
 Characteristics:
 Sensitive to all organic compounds(10^12g/ sec).
 Linear dynamic range: 10,00,000.
 Insensitive to temperature change.
 Detector temperature limit:400̊C
 Carrier gases:N2, He or Ar.
Precautions in FID:
 A hydrogen flame is colorless, so use a piece of paper and not your finger to check if the
flame is on.
 Durst and dirt contain alkali metals, so be sure your air supply is clean or erratic results
will be obtained.
CROSS SECTION DETECTORS:
 Rather than use a flame to produce ions, high speed electrons (β particles) can be used.
 Strondium 90 and tritium are used as the source of the β particles.
 These electrons can be captured by other gas molecules and become - ions may ionize
other gas molecules.
 The net effect is an increased in the charged particles in the gas stream with the result
that the conductivity of gas increase.
 The absorption cross section is roughly proportional to the mass of the molecule, so as
to get maximum sensitivity.
Characteristics of cross- section detector:
 Sensitive to all gases and vapours and gases;
comparable to a good thermal conductivitydetector
(about 10^-7g/ sec).
 Linear dynamic range:5×5^5 to 100% concentration.
 Insensitive to temperature change.
 Insensitive to carrier gas molecules.
 Detector temperature limt: 220˚C
 carrier gases : H2 to 100˚C or He + 3CH4 (1:3)