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Chapter 27
Gas Chromatography
Introduction:
In gas chromatography (GC), the sample is vaporized and injected onto the head of a
chromatographic column. Elution is brought about by the flow of an inert gaseous mobile
phase. In contrast to most other types of chromatography, the mobile phase does not
interact with molecules of the analyte; its only function is to transport the analyte through
the column.
Gas liquid chromatography is based upon the partition of analyte between a gaseous
mobile phase and a liquid phase immobilized on the surface of an inert solid.
Gas-Liquid Chromatography
Retention Volumes:
To take into account the effects of pressure and temperature in gas chromatography, it
useful to use the retention volumes. The specific retention volume, Vg is defined as
follows:
Vg
JF (t r t m )
273
W
Tc
where, J = the pressure drop factor, F = average flow rate, tr and tm = retention times W =
mass of stationary phase and Tc = column temperature in Kelvin.
Instruments for GC
The schematic of a gas chromatograph is shown below:
Detectors
Characteristics Of The Ideal Detector:
1. Adequate sensitivity.
2. Good stability and reproducibility.
3. A linear response to analyses that extends over
several orders of magnitude.
4. A temperature range from room temperature to
at least 400degC.
5. A short response time that is independent of flow rate.
6. High reliability and ease of use.
7. Similarity in response toward all analyses.
8. Nondestructive of sample.
hydrogen and air and then ignited electrically. Most organic compounds, when pyrolyzed
at the temperature of a hydrogen/air flame, produce ions and electrons that can conduct
electricity through the flame. A potential of a few hundred volts is applied across the
burner tip and a collector electrode is located above the flame. The resulting current is
then directed into a high impedance operational amplifier for measurement. Functional
groups such as carbonyl, alcohol, halogen, and amine, yield fewer ions or none at all in a
flame. In addition, the detector is insensitive toward noncombustible gases such as H 2O,
CO2, SO2, and NOx. These properties make the flame ionization detector a most useful
general detector for the analysis of most organic samples, including those that are
contaminated with water and oxides of nitrogen and sulfur. The flame ionization detector
exhibits a high sensitivity, large linear response range, and low noise. It is generally
rugged and easy to use. A disadvantage of this detector is that it destroys the sample. A
diagram of a typical FID is shown in below.
Thermoionic Detector:
The thermoionic detector (TID) is selective toward organic compounds containing
phosphorous and nitrogen. It is similar in structure to the flame detector.
Electron-Capture Detector:
Electron-capture detector (ECD) operates in
much the same way as a proportional
counter for measurement of X-radiation.
Here the effluent from the column passes
over a beta-emitter, such as nickel-63 or
tritium (adsorbed on platinum or titanium
foil). An electron from the emitter causes
ionization of the carrier gas (often nitrogen) and the production of a burst of electrons. In
the absence of organic species, a constant standing current between a pair of electrodes
results from this ionization process. The current decreases however in the presence of
those organic molecules that tend to capture electrons. The electron-capture detector is
selective in its response, being highly sensitive toward molecules that contain
electronegative functional groups such as halogens, peroxides, quinones, and nitro groups.
Electron-capture detectors are highly sensitive and possesses the advantage of not
altering the sample significantly. On the other hand, their linear response range is usually
limited to about two orders of magnitude.
Acid/Base Interactions
Phase Transitions
Sorption Isotherms
Competitive (Multicomponent)
Adsorption
STATIONARY PHASE
Desirable properties for the immobilized liquid phase in a gas liquid chromatographic
column include:
1.
2.
3.
4.
low volatility
thermal stability
chemical inertness
solvent characteristics such that k and alpha values for
the solutes to be resolved fall within a suitable range.
Generally, the polarity of the stationary phase should match that of the sample
components. Commonly used stationary phases are listed in below.
Stationary Phase
Polydimethyl siloxane
Common
Maximum
Trade Name
Temperature (C)
OV-1, SE-30
350
Common Applications
Poly(phenylmethyldimethyl)
OV-3, SE-52
350
OV-17
250
halogenated compounds
Drugs; steriods; pesticides; glycols
(50% phenyl)
Poly(trifluoropropyldimethyl)
OV-210
200
Carbowax 20M
250
alkyl-substituted benzenes
Free acid; alcohol; ethers; essential oils;
OV-275
240
glycols
Polyunsaturated fatty acids; rosin acids;
siloxane
Polyethylene glycol
Poly(dicyanoallyldimethyl)
siloxane
Film Thickness:
Film thickness primarily affect the retentive character and the capacity of a column. Thick
films are used with highly volatile analytes, because such films retain solutes for a longer
time and thus provide a greater time for separation to take place. Thin films are useful for
separating species of low volatility in a reasonable time.
APPLICATIONS OF GC:
Qualitative Analysis
Gas chromatographs are widely used as criteria for establishing the purity of organic
compounds. Contaminants, if present, are revealed by the appearance of additional peaks.
index system has the advantage of being based upon readily available reference materials
that cover a wide boiling range.
Quantitative Analysis:
The relative concentration of an analyte is proportional to the peak area obtained on the
gas chromatogram. Thus the GC can be calibrated with several standards and a calibration
curve is obtained, then the concentration of the unknown analyte can be determined using
the peak area.
GAS-SOLID CHROMATOGRAPHY
Gas-solid chromatography is based upon absorption of gaseous substances on solid
surfaces. Distribution coefficients are generally much larger than those for gas-liquid
chromatography. Consequently, gas -solid chromatography is useful for the separation of
species that are not retained by gas-liquid columns, such as the components of air,
hydrogen sulfide, carbon disulfide, nitrogen oxides, and rare gases. Gas-solid
chromatography is performed with both packed and open tubular columns. For the latter,
a thin layer of adsorbent is affixed to the inner walls of the capillary. Such columns are
sometimes called porous layer open tubular columns, or PLOT columns. Two types of
adsorbents are molecular sieves and porous polymers.
Molecular Sieves:
Molecular sieves are aluminum silicate ion exchangers, whose pore size depends upon the
kind of cation present. The sieves are classified according to the maximum diameter of
molecules that can enter the pores. Commercial molecular sieves come in pore sizes of 4,
5, 10, and 13 angstroms. Molecular sieves can be used to separate small molecules from
large.
Porous Polymers:
Porous polymer beads of uniform size are manufactured from styrene cross-linked with
divinylbenzene. The pore size of these beads is uniform and is controlled by the amount of
cross-linking. Porous polymers have found considerable use in the separation of gaseous
polar species such as hydrogen sulfide, oxides of nitrogen, water, carbon dioxide,
methanol, and vinyl chloride.
Stationary phase
The stationary phase consists of the support, which is either a porous small-particle material for
packed columns or the inner walls of a glass or fussed-silica capillary column. The stationary
liquid is either fixed merely by adhesion or by chemical bonding in order to produce a
homogeneous coating.
Mobile phase.
In GC an inert gas e.g. He N2 H2 acts as the mobile phase, which effects the transport of the
solutes through the column.
Elution
By transportation in the mobile phase the solutes migrate with a velocity through the separation
column which depends on the partition coefficients of the solutes between the given stationary
phase and mobile phase.
Solutes
Sample components that are being separated.
Detector
The detector generates a continuously recorded electrical signal during the chromatographic
separation, which is proportional to the concentration of the separated solute in the mobile phase.
There are universal and specific types of detectors.
Chromatograph
y
A term for methods of separation based upon the partition of analyte species between a stationary
phase and mobile phase.
Distribution constants, Partition coefficients
An equilibrium constant for the distribution of a solute between two immiscible phases.
Retention times
The time between sample injection and arrival of the analyte peak at the detector.
Gaussian Distribution
A distribution in which small departures from a central result occur more frequently then large
ones and in which positive a negative variation occur with equal frequency.
GC Quiz Question
Compound
Air
Methylcyclohexane
Methylcyclohexene
Toluene
TR min
1,9
10.0
1.09
13.4
Question 1
Calculate,
W min
0.76
0.82
1.06
If Cs and Cm for the column were 19.6 and 62.6 mL, respectively and a non retained air
peak appeared after 1.9 min calculate the
3a) Retention factor for each of the three compounds
3b) Distribution constant for each of the three compounds
3c) Selectivity factor for methylcyclohexane and methylcyclohexene
3d) Selectivity factor for methylcyclohexene and toluene
GC Quiz Answers
References:
www.shahid.ic24.net
http://www.shu.ac.uk/schools/sci/chem/tutorials/chrom/gaschrm.htm
http://www2.arnes.si/~uljffarmac3/theory.htm
http://www.scimed.co.uk/products/product25.htm