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Gas Chromatography

by Warangkana Punrattanasin and Christine Spada

Table of contents

1. Introduction
2. Basic Components of a GC
3. Theory of Gas Chromatography
4. Example Chromatograms
5. EPA 500 Series Methods
6. Key to Terminology
7. Pop Quiz
8. Web Links to Related Topics
9. References

Introduction

Gas chromatography (GC) is an analytical technique for separating compounds based


primarily on their volatilities. Gas chromatography provides both qualitative and
quantitative information for individual compounds present in a sample. Compounds
move through a GC column as gases, either because the compounds are normally gases
or they can be heated and vaporized into a gaseous state. The compounds partition
between a stationary phase, which can be either solid or liquid, and a mobile phase (gas).
The differential partitioning into the stationary phase allows the compounds to be
separated in time and space.

Click here to view a gas chromatogram in motion


Figure 1. Gas Chromatographic System

Figure 2. Schematic of a Gas Chromatographic System

Basic Components of a GC
Gas supply or Carrier Gas

Figure 3. Gas Supply

The carrier gas is usually helium, hydrogen, or nitrogen. This


serves as the mobile phase that moves the sample through the
column. The carrier gas flow can be quantified by either
linear velocity, expressed in cm/sec, or volumetric flow rate,
expressed in mL/min. The linear velocity is independent of
the column diameter while the flow rate is dependent on the
column diameter.

Injector

Figure 4. Auto Sampler Injection System


(Hewlett-Packard Model No. 7673)

The injector is a hollow, heated, glass-lined


cylinder where the sample is introduced into the
GC. The temperature of the injector is controlled
so that all components in the sample will be
vaporized. The glass liner is about 4 inches long
and 4 mm internal diameter.
Column

Figure 5. Capillary GC Column (Supelco ® PAG)

The GC column is the heart of the system. It is coated with a


stationary phase which greatly influences the separation of
the compounds. The structure of the stationary phase affects
the amount of time the compounds take to move through the
column. Typical stationary phases are large molecular weight
polysiloxane, polyethylene glycol, or polyester polymers of 0.1 to 2.5 micrometer film
thickness. Columns are available in many stationary phases sizes. A typical capillary
column is 15 to 60 meters in length and 0.25 to 0.32 mm ID. A typical packed column is
6 to 12 feet long and 2.2 mm ID.

Oven

Figure 6. GC Oven with column in place


The column is placed in an oven where the
temperature can be controlled very accurately over a
wide range of temperatures. Typically, GC oven
temperatures range from room temperature to 300?C,
but cryogenic conditions can be used to operate at
temperatures from about -20?C to 20?C.

Detector

Figure 7. Electron Capture Detector (ECD) and Flame Ionization Detector


(FID) (Shown actual size)

As compounds come off the column, they enter a detector. The compound and detector
interact to generate a signal. The size of the signal corresponds to the amount the
compound present in the sample. There are several different types of detectors that can be
employed, depending on the compounds to be analyzed. These detectors can measure
from 10-15 to 10-6 gram of a single component.

Data Recorder System

Figure 8. Data Recorder

The data recorder plots the signal from the detector over time. This plot is called a
chromatogram. The retention time, which is when the component elutes from the GC
system, is qualitatively indicative of the type of compound. The data recorder also has an
integrator component to calculate the area under the peaks or the height of the peak. The
area or height is indicative of the amount of each component.
Theory of Gas Chromatography

Retention Time (tR)

The retention time is the total time that a compound spends in both the mobile phase and
stationary phase. Retention time is generally reported in minutes.

Dead Time (tm)

The dead time is the time a non-retained compound spends in the mobile phase which is
also the amount of time the non-retained compound spends in the column. Dead time is
generally reported in minutes.

Adjusted Retention Time (tR')

The adjusted retention time is the time a compound spends in the stationary phase. The
adjusted retention time is the difference between the dead time and the retention time for
a compound.

Capacity Factor (or Partition Ratio) (k')

The capacity factor is the ratio of the mass of the compound in the stationary phase
relative to the mass of the compound in the mobile phase. The capacity factor is a unitless
measure of the column's retention of a compound.
Phase Ratio (ß)

The phase ratio relates the column diameter and film thickness of the stationary phase.
The phase ratio is unitless and constant for a particular column and represent the volume
ratioß.

Distribution Constant (KD)

The distribution constant is a ratio of the concentration of a compound in the stationary


phase relative to the concentration of the compound in the mobile phase. The distribution
constant is constant for a certain compound, stationary phase, and column temperature.

Selectivity (or Separation Factor) (alpha)

The selectivity is a ratio of the capacity factors of two peaks. The selectivity is always
equal to or greater than one. If the selectivity equals one the two compounds cannot be
separated. The higher the selectivity, the more separation between two compounds or
peaks.

Linear Velocity (u)


The linear velocity is the speed at which the carrier gas or mobile phase travels through
the column. The linear velocity is generally expressed in centimeters per second.

Efficiency

The efficiency is related to the number of compounds that can separated by the column.
The efficiency is expressed as the number of theoretical plates (N, unitless) or as the
height equivalent to a theoretical plate (HETP, generally in millimeters). The efficiency
increases as the height equivalent to a theoretical plate decreases, thus more compounds
can be separated by the column. The efficiency increases as the number of theoretical
plates increases, thus the column's ability to separate two closely eluting peaks increases.

Example Chromatograms

Sample contains 6 aromatic hydrocarbons dissolved in a solvent (methanol). The


compounds' properties are summarized in Table 2.
The compounds were separated on an nonpolar, 95% methyl, 5% phenylpolysiloxane
column, 30 m long, 0.25 mm ID, and 0.25 micrometer film thickness. About 1 microliter
of the hydrocarbon sample were injected. Approximately 5 nanograms (ng) of each
component was injected per 1 microliter. A flame ionization detector (FID) was used.

Temperature Programming Effects

Figure 9.

 Temperature Program: 50?C (min) - 10?


C/min - 100?C
 Head Pressure: 12 psi
 Split Ratio: 1/50

This chromatogram shows an ideal temperature


program for separation of the 6 aromatic compounds
on this column. The first peak is the solvent,
methanol. The compounds elute in order of
increasing boiling point, that is, compounds with
higher boiling points are more retained by the
stationary phase. Note that para-xylene and meta-
xylene cannot be separated on this column; the peak (#5) containing these compounds is
broad at the baseline and shows a distinct shoulder.

Figure 10.

 Temperature Program: 60?C


Isothermal
 Head Pressure: 12 psi
 Split Ratio: 1/50

This chromatogram shows the effects of an


isothermal* temperature program at 60?C. The
result is an increase in the retention time of all
compounds. The heights of the later eluting
peaks are reduced and the peak widths
increased because they are more affected by the
lower temperature program used. (*isothermal
means a constant oven temperature was used
throughout the run.)
Flow Rate Effects

Figure 11.

 Temperature Program: 50?C (1 min) - 10?


C/min - 100?C
 Head Pressure: 9 psi
 Split Ratio: 1/50

This chromatogram shows the effects of a reduced head


pressure while using the ideal temperature program. The
flow rate was reduced by decreasing the head pressure.
The retention time is slightly increased due to the low
flow rate used. All of the peak heights were reduced and
the peak widths are increased.

Figure 12.

 Temperature Program: 50?C (1 min) - 10?C/min -


100?C
 Head Pressure: 15 psi
 Split Ratio: 1/50

This chromatogram shows the effects of a higher head


pressure while using the ideal temperature program. The
flow rate was increased by increasing the head pressure. The
retention time was reduced and all of the peak heights were
increased.
Split Ratio Effects

Figure 13.

 Temperature Program: 50?C (1 min) - 10?C/min


- 100?C
 Head Pressure: 12 psi
 Split Ratio: 1/25

This chromatogram shows the effects of a low split ratio


while using the ideal temperature program. All of the peak
heights were increased due to the greater amount of the
sample introduced into the column.
Figure 14.

 Temperature Program: 50?C (1 min) - 10?C/min -


100?C
 Head Pressure: 12 psi
 Split Ratio: 1/75

This chromatogram shows the effects of a high split ratio while


using the ideal temperature program. All of the peak heights
were reduced due to the smaller amount of the sample
introduced into the column.
Effect of Stationary Phase on Separation of Para-Xylene and Meta-Xylene

Figure 15.

This chromatogram shows the separation of


benzene, toluene, para-xylene, meta-xylene and
ortho-xylene. The first peak is the solvent, hexane.
A polyalkylene glycol fused silica capillary
column 30 m long, 0.25 mm ID, and 0.25
micrometer film thickness was used for
separation. Para-xylene (peak #4) and meta-xylene
(peak #5) can be separated on this column. This
illustrates the matching of the stationary phase
with the desired compounds to be separated.

EPA 500 Series Methods


• Method 502.1: Volatile haloginated organic compounds in water by purge and
trap gas chromatography
• Method 502.2: Volatile organic compounds in water by purge and trap capillary
column gas chromatography with photoionization and electrolytic conductivity
detectors in series
• Method 503.1: Volatile aromatic and unsaturated organic compounds in water by
purge and trap gas chromatography
• Method 504: 1,2-dibromoethane (EDB) and 1,2-dibromo-3-chloropropane
(DBCP) in water by microextraction and gas chromatography
• Method 505: Analysis of organohaline pesticides and aroclors in drinking water
by microextraction and gas chromatography
• Method 507: Determination of nitrogen-and phosphorus-containing pesticides in
water by gas chromatography with a nitrogen-phosphorus detector
• Method 508: Determination of chlorinated pesticides in water by gas
chromatography with an electron capture detector
• Method 510.1: Determination of the maximum total trihalomethane potential
• Method 515: Determination of chlorinated herbicides in drinking water
• Method 524.1: Volatile organic compounds in water by purge and trap gas
chromatography/ mass spectrometry
• Method 524.2: Volatile organic compounds in water by purge and trap capillary
column gas chromatography/ mass spectrometry
• Method 525: Determination of organic compounds in drinking water by liquid-
solid extraction and capillary column gas chromatography/ mass spectrometry
Key to Terminology
Pop Quiz

Clear Answ ers

1. What is the component that most influences the separation of compounds?

a) injector
b) mobile phase
c) stationary phase

2. Given napthalene (boiling point = 218?C), phenol (boiling point = 181.7?C), and
toluene (boiling point = 110.6?C). Which compound will elute first on a nonpolar
column?

a) naphthalene
b) phenol
c) toluene

3. What will happen to the retention time if the flow rate is increased?

a) increase
b) decrease
c) no change

4. If a variable temperature program is used rather than an isothermal temperature


program, what parameter will not be affected?

a) order in which compounds elute


b) retention time
c) peak height

5. What will happen to the peak height if the split ratio is decreased?

a) increase
b) decrease
c) no change

References

• Hyver, Karen J.: 1989, High Resolution Gas Chromatography, Hewlett-Packard


Company, California.
• McNair, H.M. and Bonelli, E.J.: 1968 Basic Gas Chromatography, Consolidated
Printers, Berkeley, CA.
• Rood, Dean.: 1995,A Practical Guide to the Care, Maintenance, and
Troubleshooting of Capillary Gas Chromatographic Systems, Huthig Verlag
Heidelberg, Germany.
• Willett, John E.: 1987, Gas Chromatography, John Wiley & Sons, London.

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Send comments or suggestions to:


Student Authors: Warangkana Punrattanasin, pum@vt.edu and Christine Spada,
cspada@vt.edu
Faculty Advisor: Andrea Dietrich, andread@vt.edu
Copyright © 1997 Daniel Gallagher
Last Modified: 09-10-1997

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