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CHAPTER 3
Gas Chromatography
INTENDED LEARNING OUTCOMES
Explain the fundamental principles of Gas
01 Chromatography.

02 Explain the schematic diagram of a gas

chromatography.

Explain functions of each components of a

03 Gas Chromatography.

Explain types of Gas Chromatography.

04
3 Principles of Gas Chromatography

▪ Chromatography is a separation method in

which the components of a sample partition
between two phases.

▪ In Gas Chromatography, one of the phases

is a stationary bed with a large surface
area, and the other is a gas that percolates
through the stationary bed.
4 Principles of Gas Chromatography

▪ Sample (solute) is dissolved in a solvent eg.

Methanol
▪ Sample and solvent are vaporized onto the head
of a column.
▪ Vaporized solvent and solute are carried through
the column by an inert gas (mobile phase)
▪ Note: the mobile phase does not interact with
compounds of interest
▪ All of the solvent passes through the column
(unretained)
▪ Note: the solvent is not the mobile phase
5 Principles of Gas Chromatography

▪ Separation occurs by interaction of solute

with a stationary phase

▪ Detection occurs by a variety of means

(e.g. thermal conductivity, flame ionization,
thermionic or electron capture detectors
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GC- Schematic Diagram
Data System -
Filters/Traps
Chromatography
Software
Package on PC
H

Regulators Syringe/Sampler
RESET

Inlets

Detectors
Gas Carrier
Hydrogen
Air

Column
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Basic Components

▪ Carrier Gas (mobile phase) - He, Ar, N2 and H2

▪ Sample Injection System
▪ Chromatographic Column
• Contains stationary phase
• Many configurations
▪ Oven- Isothermal or temperature programmed
▪ Detector - FID, TC, ECD, MS, etc.
▪ Readout
▪ Chromatography software
▪ (strip chart and integrator package)
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Carrier gas

▪ The carrier gas must be chemically inert.

▪ Commonly used gases are nitrogen, helium,

argon and carbon dioxide.
▪ The carrier gas is often depending on the
type of detector used.
▪ Helium is most commonly used because it is
safer than, but comparable to hydrogen in
efficiency, has a larger range of flow rates and
is compatible with many detectors
10 Sample Injector
▪ Purpose: to introduce sample
as “plug” at the head of the
column
▪ Effects band broadening -
the overall dispersion
or widening of a sample
peak as it passes
through a separation
system.
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Sample Injector

▪ Injector typically 50 °C hotter

than oven
▪ Sample is “flash evaporated”
and expands into gas
expansion chamber
▪ Injection volumes are small
▪ Capillary columns ~ 1 µL
▪ Packed columns 1-20 µL
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Desirable GC injector qualities:

▪ Vaporize all solutes instantaneously without
thermal decomposition.
▪ No sample loss through adsorption
▪ No sample contamination
▪ Injection of sample into mobile phase without
sample dispersion or tailing
▪ Avoid diffusion of sample components in
mobile phase
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Injector types
1. Split/Splitless injector
▪ Advantage: prevent introduction of non-
volatile components in the sample
▪ Disadvantage: discrimination against high
boiling compounds and thermally unstable
compounds
2. Wide bore injector
3. On-column Injector ( OCI )
4. Programmed Temperature Vaporizing
(PTV) Injector
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Split less injection

▪ during injection, split flow line is closed.
▪ Almost all of sample vapor goes into the
column.
▪ Split flow line is re-opened after about 30 sec
to 2 min.
▪ Good for semi-volatile samples.
▪ For trace level compounds.
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Wide bore
injector

On-column
injector
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PTV injector
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Column
▪ The vaporized sample is carried through the column
by a carrier gas.
▪ Two general types of column:
▪ packed column
▪ capillary column ( open tubular)
▪ Tubing is usually made of glass, stainless steel,
copper, aluminum, nickel, glass lined, fused silica.
▪ Column selection depends on the sample to be
analysed.
▪ Resolving power is increased with longer column
▪ Analysis time is increased with longer column
▪ Column temp. – isothermal : RT increase
▪ However, general rule is LIKE SEPARATE LIKE.
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GC Column Types
Packed column
• Used in early gas-liquid chromatography
• Typically made of glass, Teflon and aluminum
• Length typically 2-3 m; ID ~3 mm
• Filled with a material called a “solid support”;
the material which holds the stationary phase
24 Capillary column
• Wall coated Open Tubular ( WCOT ) – polymer film
coated on the inner wall of the column
• Porous Layer Open Tubular ( PLOT ) – porous solid
particles coated on the inner wall of the column
• Packed capillary column – solid particles packed inside
the column
• Length : normally 30- 60m

• Inner diameter : 0.25 mm ( narrow bore ) , 0.32 mm ( semi

wide-bore ) , 0.53 mm ( wide-bore )
• Stationary phase film thickness : normally 0.1 – 3 micron
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Stationary Phases in GC
▪ Often referred to as the “immobilized liquid
phase”
▪ Desirable Properties:
1. Low volatility
2. Thermal Stability
3. Chemical inertness
4. Solvent characteristics that optimize capacity
factor
▪ Choice of stationary phase is often made based
on polarity
▪ For the solute and stationary phase to interact
they must have similar polarities “Like dissolves
like”
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Column Oven

▪ The oven can be operated in two manners:

▪ isothermal programming

▪ temperature programming

▪ Isothermal programming, the temperature of the

column is held constant throughout the entire
separation.
▪ Temperature programming method: the column
temperature is either increased continuously or in
steps as the separation progresses.
▪ Can separate a mixture with a broad boiling point
range.
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Detectors
▪ Detector indicates the presence of each
component that elutes out from the column.
▪ Detector serve as transducers to convert the
detected property changes into an electrical signal
that is recorded as a chromatogram.
▪ Each detector has two main parts that when used
together.
1.sensor which is placed as close the column exit
as possible in order to optimize detection.
2.electronic equipment used to digitize the analog
signal so that a computer may analyze the
acquired chromatogram.
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Detectors
• A variety of detectors exist; choice depends
on analyte and sensitivity required
• Characteristics of the ideal detector
• Sensitivity – wide range (~107)
• Stability and reproducibility
• Linear response to analyte concentration
• Operates in wide temperature range
(ambient to 400 °C)
• Short response time to all solutes
• Similar response to all solutes
• Non-destructive to sample
31 Thermal Conductivity Detector
▪ Detection Principle: analyte gases
have different thermal conductivities
than carrier gases
▪ A platinum, gold or tungsten wire (or
a thermister) is placed in the exit gas
stream from the column
▪ A constant voltage is applied to heat
the wire
▪ Temperature/Resistance of the wire
is proportional to the thermal
conductivity of the surrounding gas
▪ Double detector system: one
detector in carrier gas and one in the
carrier + analyte
▪ Cancels out resistance due to
carrier gas giving signal only for
analyte
 32 Flame Ionization Detector

▪ Organic analytes are

pyrolyzed in an air/H2 flame
▪ Ions are produced in the
plasma around the flame
▪ proportional to number of
carbons present
Air/H2
Flame ▪ Positive voltage is applied to
collector; negative to the
flame body
▪ Ions migrate to collector
producing a current (signal)

Rubinson and Rubinson (2000)

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Thermionic or Nitrogen / Phosphorus
Detector
❖Similar to FID

❖Flame flows around an

heated rubidium silicate
bead
❖Heated bead forms a
plasma (600-800 °C)
❖Sensitive to P and N

❖Ion current for P & N >

104 times that of C
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Electron Capture Detector
How it Works
▪ Column effluent is passed over a ß- emitter
▪ Tritium or 63-Ni
▪ The carrier gas is ionized
▪ A burst of e- is produced with each radioactive
decay
▪ Potential is applied between the collector (anode)
and the detector body (cathode)
▪ Produces a constant background current
▪ The current flow decreases in the presence of
analyte molecules
▪ The analyte captures the emitted electrons

Detector Characteristics
▪ Sensitive to molecules containing electronegative
functional groups (e.g. Cl- )
▪ Non-linear response to analyte concentration

N2 or Ar/CH4 (carrier gas) + ß- ----> N+n (ionized carrier gas) + e- (burst)

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Photoionization Detector

▪ An UV source
ionizes all the
molecules in the
column effluent
▪ Ions produced are
collected resulting
in a current flow
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Other GC Detectors

• Mass Spectrometer
• GC-MS “hyphenated” system
• Used for identification purposes

• Atomic Emission Detector

• GC-AED

• Sulfur Chemiluminescence Detector (SCD)

• Fourier-Transform Infrared (FTIR)

• Used with polar molecules
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Characteristics of GC
Gas Chromatography Detectors
Detectors – Characteristics
Sensitivity
(g solute/mL
Detector Signal Signal of carrier
Type Generator Produced Advantages Disadvantages gas)
Thermal Thermal conductivity Change in the electrical • Universal detector • Low sensitivity
Conductivity of analyte gas (usually resistance of wire in analyte • Simplicity • Often can’t use with ~ 10-8 g
less than that of stream (measure i & R at • Large linear dynamic capillary columns
carrier H2 or He constant applied voltage; or range (10-100 ppm)
change in temperature when • Non-destructive
thermister used) • Sensitive to all
compounds
Flame Ionization of analyte in Ion current • Very sensitive • Insensitive to H2O, CO2,
Ionization H2/air flame • Large linear dynamic SO2, and NOx ~ 10-13 g
range (`107) • Destructive
• General purpose detector
• Responds to reduced
carbon in analytes
Thermionic Ionization of analyte in Ion current • Selective towards organic • Selective towards organic Similar to the
H2/air flame compounds containing P compounds containing P or FID, but for N
or N compared to C (~104 N compared to C (~104 to and P
to 106 X) 106 X)
Electron Reduction in the Ion current; decreases in the • Selective towards organic • Selective towards organic
Capture ionization of a carrier presence of organic compounds containing compounds containing ~ 10-15
gas (e.g. N2) by a molecules which can capture electronegative functional electronegative functional
radioactive (ß- electrons groups (e.g. halogens, groups (e.g. halogens,
emitter) source, peroxides, quinines, and peroxides, quinines, and
usually 63-Ni nitro groups) nitro groups)
• Non-destructive • Insensitive to amines,
• Very sensitive alcohols, hydrocarbons,
• Small linear dynamic range
(~100)
Mass Ionization of analyte Analyte ions; discrimination • Universal detector • Cost
Spectrometer based on mass to charge • Good for complex organic • Complexity ~ 10-12
ratio of analyte ions mixtures • Ease of use
• Speed
• High sensitivity
• Compound identification
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Criteria to optimize separation

01 Capacity factor
• Capacity factor used to describe the migration rate
of an analyte on a column.
• When an analytes retention factor is less than
one, elution is so fast that accurate determination
of the retention time is very difficult.
• High capacity factors (greater than 20) mean that
elution takes a very long time.
• Ideally, the retention factor for an analyte is
between one and five.
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02 Resolution
A characteristic of the separation of two adjacent
peaks.
Factor effecting resolution:
Temperature ramp rate
- Column length
- Carrier gas flow rate
- Film thickness
- Column internal diameter
- Ultra fast technology
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03 Peak shape
• Good peak shape can be defined as a
symmetrical or gaussian peak
• poor peak shape can include both peak fronting
and tailing.
• Good peak shape is important for....
▪ Improved resolution (Rs)

▪ More accurate quantitation

▪ Longer usable column lifetime (based on

system suitability criteria)
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Factor effecting peak shape

▪ the initial column temperature,

▪ the column phase ratio, and

▪ the boiling points of the sample

▪ column selection
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04 Operation Temperature
• Temperature programming

maintaining a low temperature for a short period of

time, and increasing the temperature to help force
out the longer-‘sticking’ compounds.
• Isothermal programming

use constant temperature throughout analysis

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(a)low temperature (45 °C) - good

resolution initially - but too slow
later

(b) higher temperature (145 °C) -

much faster, but poor resolution for
early-eluting species

In general - best results for

temperatures near boiling point of
analyte.

If there is a wide range of boiling

points in the sample - then the best
results are obtained by temperature
programming as shown in (c), for
the same mixture, where the
temperature steps are as shown.
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Types of GC

We distinguish three types of gas chromatography

based on the type of stationary phase involved:

1. Gas-Liquid
• The stationary phase is a liquid adsorbed
on a solid surface
• most common type
2. Gas-Solid
• The stationary phase is a solid material
3. Gas-Bonded Phase
• The stationary phase is an organic material
bonded to a solid surface
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Routine operation procedure

▪ Prepare std and sample

▪ Set temperature of oven, column

and detector
▪ Run a series of standard

▪ Run sample ( at least duplicate )

▪ Establish calibration curve

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Evaluation method - Standard preparation

80ppm

60ppm

Stock Std Soln

(1000ppm) Intermediate Soln 40ppm
(100ppm)
Standard
(normally > 4 stds)
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Calibration curve
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current GC equipment

• GC-MS

• Several GC-MS have left earth. Two were brought to Mars by the Viking
program.[14] Venera 11 and 12 and Pioneer Venus analysed the
atmosphere of Venus with GC-MS.[15] The Huygens probe of the
Cassini-Huygens mission landed one GC-MS on Saturn's largest moon,
Titan.[16] The material in the comet 67P/Churyumov-Gerasimenko will
be analysed by the Rosetta mission with a chiral GC-MS in 2014.[17]
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