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Manoj Sigdel
GAS CHROMATOGRAPHY
DEFINITION: Gas Chromatography is a technique in which the
vaporized sample components are separated based on
their partition /adsorption between the mobile phase & a
stationary phase liquid / solid, held in a column.
CLASSIFICATION: Based on the nature of stationary phase, the
methodology is divided into
Gas solid Chromatography
Gas liquid Chromatography.
ACYLATION
When the sample under study contains a phenol, primary or
secondary alcohol or amine, derivatization by acylating is frequently
used.
This was performed by use of acetic anhydride and a catalyst like
acetic acid, p-toluene, sulfonic acid, pyridine, N-methylimidazole
Perfluoroacylation:
Although acetylation is usually adequate to give good gas
chromatographic characteristics, trifluoroacetates,
pentafluoropropionates or heptafluorobutyrates are currently used
to increase the sensitivity of the analysis.This group significantly
increases the mol wt of the sample relative to the analogous
hydrocarbon which is best method to increase the retension time
Alkylation:
SILYLATION: The active hydrogen of OH, - COOH, - NH2, SH, can be replaced by silyl groups to give more
volatile derivatives.
Several silylating agents are used & all of them
have a general formula (CH3)3 SiX
R OH + (CH3)3 SiCl
(Trimethyl chlorosileane)
R O Si (CH3)3 + HCL
(Tri methyl silyl ether)
Uses of Derivatization:
b) RATE THEORY
Plate theory failed to explain the ways to improve the
performance of the column, which the rate theory did.
This theory explained the fact that the phase flows
continuously & that the solute particles are constantly
being transported & partitioned in the column.
It can be explained by Vandeemeter Equation
H = A+B + C i) A Eddys diffusion
ii) B Longitudinal diffusion
iii) C Mass transfer resistance
Instrumentation
Whether GLC or GSC consists of basic
components are,
1) A carrier gas, which is maintained at a high
pressure and is delivered to the instrument
at a rapid and reproducible rate.
2) Flow meters.
3) Sample injection system.
4) Separation column.
5) One or more detectors.
6) Thermostated chambers for the temperature
regulation of the column & detector.
Carrier gas
The choice of the carrier gas is some time
dependent upon the type of the detector used in gas
chromatography. Most widely used carrier gases are
nitrogen, helium, hydrogen, and argon.
Hydrogen
Better thermal conductivity,
Low density.
It is not useful often as the other gases because it is
associated with fire hazards and it react with
unsaturated compounds.
Helium
Excellent thermal conductivity, but it expensive.
Is the one of the gas most widely employed.
Nitrogen
Inertness
Suitable to the detector used
High purity
Easily available
Cheap
Less risk of the explosion
Should give best column performance
consistent with the required speed of the
analysis.
Flow meters
As we know that the carrier gas are
stored at high pressure. In order to
maintain the uniform flow rate of carrier
gas we use flow meters &flow regulator.
Flow meters are used to measure the
flow rate of carrier gas. They are
Rotameter & Soap bubble meter.
*Liquids can be
injected through loop /septum devices. Usually a rubber septum
made up of silicone rubber which can withstand high temp is used.
*Solid samples are dissolved in solvent and then injected into the
septum.
The ideal introduction of sample into the gas ' chromatography system
would be to inject it as a compact "plug" onto the first theoretical
plate of the column.
Column
Two categories of column are used for gas
chromatography.
a) Packed column
b) Open tubular column or capillary column
intermediate polarity
upto 2800C
Polar
Polar
30 to2200C
50 to 2800C
Packed Columns
separatesgreater range
fractions of
oil for
petroleum
products
500 L
chromatograp
hy column
Detectors
Characteristics of a good detector
o
o
o
o
o
o
o
Differential Detectors
Those detectors that respond to the conc. (in
mole fraction) of solute in the carrier gas. Eg:
Thermal conductivity & electron capture
detectors, Photo Ionization Detectors
Advantages:
Do not destroy the sample in the process of
detecting it.
Thus collection of successive fractions of the
solute for the further characterization is
possible.
Disadvantages:
Precise or efficient quantitative analysis is
Integrating Detectors
Those detectors that respond to the mass flow rate
of the
solute in moles per unit time. Eg:
flame ionization detectors, flame photometric
detectors.
Advantages:
Precise or efficient quantitative analysis is
possible.
Disadvantages:
destroy the sample in the process of detecting
it.
Comparison Of Detectors
DETECTOR
DETECT DYNAM
IBILITY IC
RANGE
FID (Flame
Ionization
Detector )
Mass
flow
100pg
107
TCD (Thermal
Conductivity
Detector )
1ng
107
ECD
(Electron
Capture
Detector )
Con.
PID (Photo
Ionization
Detectors )
Conc, Make-up
Aliphatic,aromatic, 2pg
ketones,esters,ald
ehydes,amines
FPD (Flame
Photometric
Detectors )
Mass
flow
SO4,PO4,tin,boron,
arsenic,germaniu
m,selenium,chrom
ium
Hydrogen
& air
Make-up
Hydrogen
& air or
oxygen
Most organic
compounds
Halides,nitrates,nit 50pg
riles,peroxides,anh
ydriedes,organom
etallics
100pg
105
10
103
Thank You