23/04/24, 16.

46 Gas Chromatography Theory

updated Friday, April 01, 2016

Gas Chromatography (GC or GLC) is a commonly used analytic technique in many research and industrial
laboratories for quality control as well as identification and quantitation of compounds in a mixture. GC is
also a frequently used technique in many environmental and forensic laboratories because it allows for the
detection of very small quantities. A broad variety of samples can be analyzed as long as the compounds are
sufficiently thermally stable and reasonably volatile.

How does gas chromatography work?

Like for all other chromatographic techniques, a mobile and a stationary phase are required for this
technique. The mobile phase (=carrier gas) is comprised of an inert gas i.e., helium, argon, or nitrogen. The
stationary phase consists of a packed column in which the packing or solid support itself acts as stationary
phase, or is coated with the liquid stationary phase (=high boiling polymer). Most analytical gas
chromatographs use capillary columns, where the stationary phase coats the walls of a small-diameter tube
directly (i.e., 0.25 μm film in a 0.32 mm tube).

The separation of compounds is based on the different strengths of interaction of the compounds with the
stationary phase (“like-dissolves-like”-rule). The stronger the interaction is, the longer the compound
interacts with the stationary phase, and the more time it takes to migrate through the column (=longer
retention time). In the example above, compound X interacts stronger with the stationary phase, and therefore
lacks behind compound O in its movement through the column. As a result, compound O has a much shorter
retention time than compound X.

Which factors influence the separation of the components?

1. Vapor pressure

The boiling point of a compound is often related to its polarity (see also polarity chapter). The lower the
boiling point is, the higher the vapor pressure of the compound and the shorter retention time usually is
because the compound will spent more time in the gas phase. That is one of the main reasons why low
boiling solvents (i.e., diethyl ether, dichloromethane) are used as solvents to dissolve the sample. The
temperature of the column does not have to be above the boiling point because every compound has a non-
zero vapor pressure at any given temperature, even solids. That is the reason why we can smell compounds
like camphor (0.065 mmHg/25 oC), isoborneol (0.0035 mmHg/25 oC), naphthalene (0.084 mmHg/25 oC),
etc. However, their vapor pressures are low compared to liquids (i.e., water (24 mmHg/25 oC), ethyl acetate
(95 mmHg/25 oC), diethyl ether (520 mmHg/25 oC)).

2. The polarity of components versus the polarity of stationary phase on column

If the polarity of the stationary phase and compound are similar, the retention time increases because the
compound interacts stronger with the stationary phase. As a result, polar compounds have long retention
times on polar stationary phases and shorter retention times on non-polar columns using the same
temperature. Chiral stationary phases that are based on amino acid derivatives, cyclodextrins and chiral
silanes are capable of separating enantiomers because one enantiomer interacts slightly stronger than the
other one with the stationary phase, often due to steric effects or other very specific interactions. For instance,
a modified -cyclodextrin column is used in the determination of the enantiomeric excess in the chiral
epoxidation experiment (Chem 30CL).

3. Column temperature

A excessively high column temperature results in very short retention time but also in a very poor separation
because all components mainly stay in the gas phase. However, in order for the separation to occur the
components need to be able to interact with the stationary phase. If the compound does not interact with the
stationary phase, the retention time will decrease. At the same time, the quality of the separation deteriorates,
because the differences in retention times are not as pronounced anymore. The best separations are usually
observed for temperature gradients, because the differences in polarity and in boiling points are used here.
https://www.chem.ucla.edu/~bacher/General/30BL/gc/theory.html 1/3
23/04/24, 16.46 Gas Chromatography Theory

4. Carrier gas flow rate

A high flow rate reduces retention times, but a poor separation would be observed as well. Like above, the
components have very little time to interact with the stationary phase and are just being pushed through the
column.

5. Column length

A longer column generally improves the separation. The trade-off is that the retention time increases
proportionally to the column length and a significant peak broadening will be observed as well because of
increased longitudinal diffusion inside the column. One has to keep in mind that the gas molecules are not
only traveling in one direction but also sideways and backwards. This broadening is inversely proportional to
the flow rate. Broadening is also observed because of the finite rate of mass transfer between the phases and
because the molecules are taking different paths through the column.

6. Amount of material injected

Ideally, the peaks in the chromatogram display a symmetric shape (Gaussian curve). If too much of the
sample is injected, the peaks show a significant tailing, which causes a poorer separation. Most detectors are
relatively sensitive and do not need a lot of material in order to produce a detectable signal. Strictly speaking,
under standard conditions only 1-2 % of the compound injected into the injection port passes through the
column because most GC instruments are operated in split-mode to prevent overloading of the column and
the detector. The splitless mode will only be used if the sample is extremely low in concentration in terms of
the analyte.

7. Conclusion

High temperatures and high flow rates decrease the retention time, but also deteriorate the quality of
the separation.

Which detectors are used?

1. Mass Spectrometer (GC/MS)

Many GC instruments are coupled with a mass spectrometer, which is a very good combination. The GC
separates the compounds from each other, while the mass spectrometer helps to identify them based on their
fragmentation pattern (see Mass Spectrometry chapter).

2. Flame Ionization Detector (FID)

This detector is very sensitive towards organic molecules (10-12 g/s = 1 pg/s, linear range: 106-107), but
relative insensitive for a few small molecules i.e., N2, NOx, H2S, CO, CO2, H2O. If proper amounts of
hydrogen/air are mixed, the combustion does not afford any or very few ions resulting in a low background
signal. If other carbon containing components, are introduced to this stream, cations will be produced in the
effluent stream. The more carbon atoms are in the molecule, the more fragments are formed and the more
sensitive the detector is for this compound. Unfortunately, there is no direct relationship between the number
of carbon atoms and the size of the signal. As a result, the individual response factors for each compound
have to be experimentally determined for each instrument. Due to the fact that the sample is burnt
(pyrolysis), this technique is not suitable for preparative GC. In addition, several gases are usually required to
operate a FID: hydrogen, oxygen (or compressed air), and a carrier gas.

3. Thermal Conductivity Detector (TCD)

This detector is less sensitive than the FID (10-5-10-6 g/s, linear range: 103-104), but is well suited for
preparative applications, because the sample is not destroyed. The detection is based on the comparison of
https://www.chem.ucla.edu/~bacher/General/30BL/gc/theory.html 2/3
23/04/24, 16.46 Gas Chromatography Theory

two gas streams, one containing only the carrier gas, the other one containing the carrier gas and the
compound. Naturally, a carrier gas with a high thermal conductivity i.e., helium or hydrogen is used in order
to maximize the temperature difference (and therefore the difference in resistance) between two filaments (=
thin tungsten wires). The large surface-to-mass ratio permits a fast equilibration to a steady state. The
temperature difference between the reference and the sample cell filaments is monitored by a Wheatstone
bridge circuit (the student learnt about this circuitry in physics!).

4. Electron Capture Detector (ECD)

This detector consists of a cavity that contains two electrodes and a radiation source that emits -radiation (i.e.,
63Ni, 3H). The collision between electrons and the carrier gas (methane plus an inert gas) produces a plasma-
containing electrons and positive ions. If a compound is present that contains electronegative atoms, those
electrons will be “captured” to form negative ions and the rate of electron collection will decrease. The
detector is extremely selective for compounds with atoms of high electron affinity (10-14 g/s), but has a
relatively small linear range (~102-103). This detector is frequently used in the analysis of chlorinated
compounds i.e., pesticides (herbicides, insecticides), polychlorinated biphenyls, etc. for which it exhibits a
very high sensitivity.

https://www.chem.ucla.edu/~bacher/General/30BL/gc/theory.html 3/3