CHAPTER 2

GAS CHROMATOGRAPHY
 Gas Chromatography (GC)

2.1 Principles of gas chromatography

2.2 Carrier gas
2.3 GC injector
2.3.1 Direct/flash Vaporization injector
2.3.2 Split/Splitless injector
2.3.3 On column injector
 Gas Chromatography (GC)

2.4 GC Columns
2.4.1 Types of columns
2.4.2 Types of Stationary Phases
Bonded and Cross-linked Phases
Film thickness
Retention/Kovats Index
2.4.3 Column Temperature
Isothermal
Temperature Programming
 Gas Chromatography (GC)

2.5 GC Detectors
2.5.1 Flame Ionization Detector (FID)
2.5.2 Electron Capture Detector (ECD)
2.5.3 Thermal Conductivity Detector (TCD)
2.5.4 Other types of Detectors (FPD & NPD)
 Gas Chromatography (GC)

2.6 Interfacing GC with Spectroscopic Methods:

GC-MSD and GC-FTIR
2.7 Sample Preparation for Gas Chromatography
2.7.1 Headspace
2.7.2 Pyrolysis
2.7.3 Derivatisation
Gas Chromatography (GC)
Gas Chromatography (GC)
 Principles of GC

Gas chromatography (GC) is an analytical technique

for separating components/solutes based primarily
on their volatilities which means that the
separation is based on differences in boiling points
of the solutes. It may also based on the solutes’
interaction with the stationary phase.
 Principles of GC

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 v aporized into a
gaseous state.
 Principles of GC

Stationary phase is a liquid dispersed on the

solid support. Liquids are used to modify solid
stationary phase. Separation is achieved by
partition of the components of the sample
between the phases.
 Principles of GC

The components of the mixture to be separated must be

volatile (vapor pressures of at least 60 Torr). A very small
amount of sample solution is injected into the injection port of
the chromatograph using a syringe. The mixture is immediately
vaporized and carried by the carrier gas into the column. The
column itself contains a liquid stationary phase which is
adsorbed onto the surface of an inert solid.
 Principles of GC

The column, as well as the injection port and the detector is

kept at a controlled temperature inside an oven so that the
mixture remains in vapor form. From the time the materials are
injected into the instrument until they reach the detector, they
are being retained by the liquid in the column (the stationary
phase). Separation is based on the differences in migration rates
among the sample components. As each component emerges
from the column, it will be detected.
 Principles of GC

Gas chromatographic separation relies on the distribution of

analytes between two phases, the first, the thin liquid film on
the inside of the column and the second, a gas flowing through
the column. Generally, the closer an analyte is to its boiling point,
the more time it spends in the gas phase and the faster it elutes.
Thus, the oven is used to heat the column and optimize the flow
of target compounds through it.
 Principles of GC

Elution time is also affected by the attraction the analyte has for
the liquid phase. If they are of a similar chemistry, the analyte
will associate more closely with the liquid phase ("like dissolves
like") thus increasing retention time beyond what might be
expected merely from its boiling point. Simply stated, the
chrom ato graphi c col umn sepa ra tes a n extract i nto it s
constituent parts so they can be ideally introduced one at a time
into a detector.
 Principles of GC

A gas chromatograph is a chemical analysis instrument

for separating and identifying chemicals in a sample. A
gas chromatograph uses a thin capillary fiber known as
the column, through which different chemicals pass at
different rates depending on various chemical and
physical properties. As the chemicals exit the end of the
column, they are detected and identified electronically.
T h e f u nc t i o n o f t h e co l u m n i s t o s e p a r at e and
concentrate different components in order to maximize
the detection signal.
Gas Chromatography (GC)
Gas Chromatography (GC)
 Principles of GC

In a GC analysis, a known volume of gaseous or liquid analyte is

injected into the entrance of the column, usually using a
microsyringe. Although the carrier gas sweeps the analyte
molecules through the column, this motion is inhibited by the
adsorption of the analyte molecules either onto the column
walls or onto packing materials in the column. The rate at
which the molecules progress along the column depends on
the strength of adsorption, which in turn depends on the type
of molecule and on the column materials.
 Principles of GC

Since each type of molecule has a different rate of progression,

the various components of the analyte mixture are separated as
they progress along the column and reach the end of the column
at different times. A detector is used to monitor the outlet
s t ream f r om t he co l um n; t hu s , th e ti m e a t wh ic h e ach
com po nent rea ches the o utl et a nd the a m o unt of t hat
component can be determined. Generally, substances are
identified by the order in which they emerge from the column
and by the residence time of the analyte in the column.
Principles of GC
 Carrier gas

The mobile phase does not interact with molecules of

the analyte, its only function is to transport the
analyte through the column. The carrier gas must be
chem ica lly iner t. The carr ier ga s fl ow ca n 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.
 Carrier gas

Commonly used gases include nitrogen, helium, argon,

and carbon dioxide. The choice of carrier gas is often
dependant upon the type of detector which is used.
The carrier gas system also contains a molecular sieve
to remove water and other impurities.

Gas Advantages Disadvantages

Nitrogen Cheap, Readily available Long run times

Helium Good compromise, Safe Expensive
Hydrogen Shorter run times, Cheap Explosive
Carrier gas
 GC injector

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.
The results of injection should be:
■ Reproducible
■ Representative of sample
■ No efficiency losses
 GC Columns
Types of Columns

1. Packed
2. Capillary (also known as open tubular).
q The column is the heart of the system.
q t is coated with a stationary phase which greatly influences the
separation of the compounds.
q The structure of the stationary phase affects the amount of
time the compounds take to move through the column.
q Typical stationary phases are large molecular weight
polysiloxane, polyethylene glycol, or polyester polymers of 0.1
to 2.5 micrometer film thickness.
q Columns are available in many stationary phases sizes.
 GC Columns
Types of Columns –Packed Column

ü Packed columns contain a finely divided, inert, solid support

material (eg. diatomaceous earth) coated with a liquid or solid
stationary phase.
ü The nature of the coating material determines what type of
materials will be most strongly adsorbed.
ü Thus numerous columns are available that are designed to
separate specific types of compounds.
ü Most packed columns are 1.5 - 10m in length and have an
internal diameter of 2 - 4mm. The outer tubing is usually made
of stainless steel or glass.
 GC Columns
Types of Columns –Packed Column
Tube made of glass or metal with 2 - 4mm I.D (internal diameter)
and 1.5-10m in length.

Finely divided, inert, solid su pport material (commonly

diatomaceous earth) coated with liquid stationary phase. Ideal
characteristics of solid support: mechanical stability, porous, high
surface area and inert (non-adsorptive) )
 GC Columns
Types of Columns –Capillary Column

Capillary columns have a very small

internal diameter, on the order of a
few tenths of millimeters. The
column walls are coated with the
active materials. Most capilla ry
columns are made of fused-silica with
a polyimide outer coating. These
columns are flexible, so a very long
column can be wound into a small
coil.
 GC Columns
Types of Columns –Capillary Column
Two types of Capillary Columns:
1. Wall-coated open tubular (WCOT)
2. Support-coated open tubular (SCOT).
ü Wall-coated columns consist of a capillary tube whose walls
are coated with liquid stationary phase.
ü In support-coated columns (SCOT), the inner wall of the
capillary is lined with a thin layer of support material such as
diatomaceous earth, onto which the stationary phase has
been adsorbed.
ü SCOT columns are generally less efficient than WCOT
columns. However, both types of capillary column are more
efficient than packed columns.
 GC Columns
Types of Columns –Capillary Column

Tubes (metal, glass or fused silica) with 0.1 to 0.5mm I.D.

and 5 to 100 meters in length. A typical capillary column is
15 to 60 meters in length and 0.25 to 0.32 mm ID.

SCOT: the inner wall of the capillary is lined

with a thin layer of solid support onto which
the stationary phase has been adsorbed.
WCOT: the inner wall are directly coated with
liquid stationary phase (no support material)
 GC Columns
Types of Columns –Capillary Column
In 1979, a new type of WCOT column was devised - the
Fused Silica Open Tubular (FSOT) column;

These have much thinner walls than the glass capillary

columns, and are given strength by the polyimide coating.
These columns are flexible and can be wound into coils.
Th ey h ave th e ad va n tag es o f p h y si c al st r eng t h,
flexibility and low reactivity.
 GC Columns
Types of Columns –Capillary Column

Advantages of open tubular / capillary column:

ü high resolution
ü shorter analysis times due to higher flow rates
ü greater sensitivity compared to packed columns
(Eddy diffusion term is absent or very small)
 GC Columns
Types of Stationary Phases

Ideal characteristics:
Ø low volatility,
Ø thermal stability,
Ø chemical inertness and
Ø low viscosity
 GC Columns
Types of Stationary Phases

q Choice: Depends on the analyte of interest using

the principle “like-dissolves-like” (i.e. polar analyte =
polar stationary phase)
q The most common stationary phases: polysiloxanes
because they are the most stable, robust and
versatile.
q Polyethylene glycols (PEG) are less stable, less
robust and have lower temperature limits than
most polysiloxane.
 GC Columns
Types of Stationary Phases
Polyethylene glycols (PEG) are less stable, less robust and have
lower temperature limits than most polysiloxane
 GC Columns
Types of Stationary Phases
 GC Columns
Types of Stationary Phases

Bonded and Cross-linked Phases

q Purpose
ü Provide a longer-lasting stationary phase that can be
r in s ed wi t h a s o l v ent wh e n t he f i l m b ec o m e s
contaminated.
ü Inhibit ‘ column bleeding’ ie. process whereby a small
amount of immobilized liquid is carried out of the
column during elution.
 GC Columns
Types of Stationary Phases
Bonded and Cross-linked Phases
q Process
ü Bonding : Attaching a monomolecular layer of the stationary
phase to the silica surface of the column by a chemical
reaction.
ü Cross-linking: carried out in situ after the column is coated
with the stationary phase. Eg. Incorporate a peroxide into
the original liquid.
ü When the film is heated, reaction between the methyl groups
in the polymer chain is initiated by a free radical mechanism.
The polymer molecules are then cross-linked through carbon-
to-carbon bonds. Cross-linking can also be initiated by
exposing the coated columns to gamma radiation
 GC Columns
Types of Stationary Phases
Film Thickness
ü Film thickness primarily affect the retentive character
and the capacity of a column.
ü 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.
ü Thin films are useful for separating species of low
volatility in a reasonable time.
 GC Columns
Column Temperature
Ø Isothermal
Ø Temperature Programming
q Because molecular adsorption and the rate of progression along the
column depend on the temperature, the column temperature is carefully
controlled to within a few tenths of a degree for precise work.
q The optimum column temperature is dependant upon the boiling point of
the sample. As a rule of thumb, a temperature slightly above the average
boiling point of the sample results in an elution time of 2 - 30 minutes.
Minimal temperatures give good resolution, but increase elution times.
q If a sample has a wide boiling range, then temperature programming can
be useful. The column temperature is increased (either continuously or in
steps) as separation proceeds.
 GC Columns
Column Temperature
Ø Isothermal Run
Constant column temperature throughout the
analysis

This chromat ogram 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 Program:
temperature was used throughout the run.) 60°C Isothermal
· Head Pressure: 12 psi
· Split Ratio: 1/50
 GC Columns
Column Temperature
Ø Isothermal
 GC Columns
Column Temperature
Temperature Programming
ü Temperature programming is a chromatography development
technique used largely in gas chromatography to accelerate
the elution rate of late peaks that, otherwise, would take a
very long time to elute.
ü It is achieved by continuously raising the column temperature,
usually as a linear function of time, during the elution process.
ü Column temperature is increased either continuously or in
steps as the analysis proceeds
 GC Columns
Column Temperature
Temperature Programming

· Temperature Program: 50°C (1 min) - 10°C/min - 100°C

· Head Pressure: 9 psi
· Split Ratio: 1/50

ü This chromatogram shows the effects of a reduced

head pressure while using the ideal temperature
program.
ü The flow rate was reduced by decreasing the head
pressure.
ü 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.
 GC Columns
Column Temperature
Temperature Programming
 GC Columns
Column Temperature

Oven temperature:
60oC for 1 min
60-180oC at 20o/min
GC Detectors
GC Detectors