PETE 218 Gas Composition by Gas Chromatography Spring 2016-2017

Gas Chromatography
Gas chromatography (GC) is a chemical analysis instrument used to separate and identify volatile
compounds in a mixture. Gas chromatography uses a flow-through narrow tube known as the column.
The column is a very long, thin tube of metal or glass, and it is housed in coiled form in an oven. Through
the column, mixture of volatile substances are carried by mobile phase (inert or nonreactive carrier
gas; i.e. He, N2) at different rates depending on their various chemical/physical properties and their
interaction with stationary phase (specific column filling).

The partitioning of components occurs mostly according their boiling points; therefore, low boiling or
volatile components elute first, followed by the relatively heavy components. The temperature of the
oven is programmed according to the boiling point ranges of various components. As the individual
compounds emerge from the GC, they reach a detector, and their presence is recorded on the chart.
The recorded graph is known as gas chromatogram. In the gas chromatogram, the height of each peak
is proportional to the percentage of that particular compound represented in the sample. The
individual peaks are identified by comparing their retention times inside the column with those of
components previously analyzed at the same GC conditions.

Figure 1: Gas Chromatogram

The two most commonly used detectors in a typical GC setup are thermal conductivity detector (TCD)
and flame ionization detector (FID).

Thermal Conductivity Detector (TCD)

The TCD compares the thermal conductivity of two gas flows the pure carrier (reference) gas and the
sample. Changes in the temperature of the electrically-heated wires in the detector are affected by
the thermal conductivity of the gas which flows around this. The changes in this thermal conductivity
are sensed as a change in electrical resistance by a Wheatstone bridge circuit which produces a
measurable voltage change. The column effluent flows over one of the resistors while the reference
flow is over a second resistor in the four-resistor circuit.

TCD is primarily used for detecting nonhydrocarbon components N2, CO2, and H2S. However, since all
compounds, organic and inorganic, have a thermal conductivity different from helium, all compounds
can be detected by this detector. The TCD is often called a universal detector because it responds to
all compounds.

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PETE 218 Gas Composition by Gas Chromatography Spring 2016-2017

Figure 2: Schematic Design of a Thermal Conductivity Detector

Flame Ionization Detector (FID)

Used for detecting only the hydrocarbon constituents. It is a scientific instrument that measures the
concentration of organic species in a gas stream. It is frequently used as a detector in gas
chromatography. The effluent from the column is mixed with hydrogen and air, then combusted. The
operation of the FID is based on the detection of ions formed during this combustion of organic
compounds in a hydrogen flame. The generation of these ions is proportional to the concentration of
organic species in the sample gas stream. Hydrocarbons generally have molar response factors that
are equal to number of carbon atoms in their molecule, while oxygenates and other species that
contain heteroatoms tend to have a lower response factor. Carbon monoxide and carbon dioxide are
not detectable by FID.

Figure 3: Schematic Design of a Flame Ionization Detector

Experimental Set-up

Essential elements of a GC setup are:

Injection valve
A column
A carrier gas
Temperature-programmed oven
Detectors

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PETE 218 Gas Composition by Gas Chromatography Spring 2016-2017

Figure 4: Gas Chromatography Diagram

Gas cylinder: The mobile gas used in gas chromatography is inert, inexpensive, non-explosive
and very pure in its composition. Generally, Helium or Argon.
The flow regulator: Flow regulator let the gas from cylinder pass with a fixed rate. Any
alteration in the rate of gas flow leads to improper measurement and analysis.
GC Columns: The GC columns are metallic column preferably. They are very long and hence
coiled to reduce the space required. Theoretically the rise in the length of column enhance the
separation capacity and there by better resolution column is so long unlike other
chromatography columns. Increase in column length increases the area of exposure of
components to the mobile phase better and they are not just carried away under the speed of
gas flow.
Thermal chamber: This encloses the column and maintains the column at fixed temperature.
Maintenance of column at high temperature helps the sample to remain in volatile and there
by easy flow and separation of the components under the influence of mobile gas.
Detector: Mostly TCD and FID detectors are used.

Experiment Procedure
1. Set Hydrogen, Helium, and Dry Gas valves below 7 bar.
2. Set chromatography method on the software according to the column used in the
chromatogram. Carboxen-1010 PLOT 30m x 0.53 mm I.D.
a. Oven: 35 0C (7.5 min.) to 250 0C at 24 0C/min
b. Injector: 200 0C
c. Detector: TCD/methanizer-FID, 230 0C
d. Flow rate: Helium, 3.0 mL/min
e. Injection: 10.0 L valve injection
f. Sample: 500 ppm each, transformer gas for ASTM Method D3612-96
3. Inject gas sample below 3 bar pressure.
4. Start gas chromatography method.
5. Wait until analysis is completed.
6. Manually correct the integration lines below the peaks on the chromatogram on the software.
7. Get the analysis report from the software.