CHAPTER 5

GAS CHROMATOGRAPHY (GC)

LESSON OUTCOMES
 Explain the principles of gas chromatography
 Draw and label the schematic diagram of the
components in GC
 Able to explain the functions of each component in
GC
 Discuss the difference between each component in
terms of parts and functions
 Interpret analytical information from spectral and
chromatographic data for GC
 Recognize problems arising from resultant
chromatograms and suggest probable solutions
2
SYLLABUS
 5. Gas-Liquid Chromatography
 5.1 Scope of gas-liquid chromatography
 5.2 Apparatus
 5.2.1 Carrier gas supply
 5.2.2 Sample injection system
 5.2.3 Columns
 Packed columns

 Open-tubular columns

 Isothermal Analysis

 Temperature Programming

 5.2.4 Detectors
 Thermal conductivity detector

 Flame ionization detector

 Electron Capture Detector

 5.3 Stationary Phases for gas-liquid chromatography

 5.4 Applications of gas-liquid chromatography

3
5.1 SCOPE OF GC

4
INTRODUCTION
 GC is an technique for separating components
based on their volatilities (based on differences of
boiling point)
 In GC, the components of a vaporized sample are
separated as a result of being partitioned between
a mobile gaseous phase and a liquid or a solid
stationary phase held in the column
 Gas is called “carrier gas”
 Typical carrier gas: helium or nitrogen
 Pressure from a compressed gas cylinder
containing the carrier gas is sufficient to create the
flow through the column 5
There are two types of GC
❑ Gas-liquid chromatography (GLC)

mobile phase – gas

stationary phase - liquid

❑ Gas-solid chromatography (GSC)

mobile phase – gas
stationary phase - solid

6
PRINCIPLES
 A sample is being injected at the inlet/injector and
vaporized into the chromatographic column
 The sample is transported through the column by the
flow of inert gaseous mobile phase
 As the sample passes through the column, they are
separated and detected electronically by detector

7
5.2 INSTRUMENTATION

8
INSTRUMENTATION

A. Carrier gas
B. Injector
C. Column
Thermostated
D. Detector
oven
E. Display system -printer/monitor
9
10
5.2.1 CARRIER GAS (MOBILE PHASE)
 Function of carrier gas: to transport the analyte
through the column
 Does not interact with analyte
 Carrier gas flow quantified by linear velocity
(cm/sec) or volumetric flow rate (mL/min)
 Carrier gas contains a molecular sieve to remove
water and impurities
Gas Advantages Disadvantages
Nitrogen Cheap, readily available Long run times
Helium Good compromise, safe Expensive
Hydrogen Shorter run times, cheap Explosive
11
5.2.2 SAMPLE INJECTION SYSTEM
 The injector is a hollow, heated, glass-lined
cylinder where the sample is introduced into GC
 The results of injection should be:
- reproducible
- representative of sample
- no efficiency losses
 For optimum column efficiency, the sample
shouldn't be too large & must be injected as
quick as possible (slow injection of large
sample can causes band broadening & low
resolution)
12
 The temperature of the sample port is usually about 50
°C higher than the boiling point of the least volatile
component (warmer than oven temp.)
- to promote rapid vaporization of the injected sample.
- to prevent sample condensation in the detector.
 Sample introduction usually……
1. In the form of neat liquid or solution.

2. Introduced in a small volumes.

a. 1 μL - 20 μL for packed column.

b. 1 x 10-3 μL for capillary column

13
INJECTION MODE
1. Split Mode:
 Introduces only small amount of sample into the
column
 Used for concentrated sample

 Produces narrow and sharp peaks

2. Splitless Mode:
 Most of the sample introduced into the column

 Used for low concentration samples

 Wider peaks are obtained than for split injections

14
15
5.2.3 COLUMN
 There are 2 types of column:
i- Packed column
ii- Capillary column (open tubular)

Packed column: Capillary Column:

1-5m in length, 2-4mm i.d 10-100m in length, very small i.d
16
PACKED COLUMN

 Less commonly used

 Made of glass or steel
 Length: 1 to 5 m Cross-sectional view of
packed column
 Internal diameter: 2 to 4 mm
 These column is densely packed with uniform,
finely divided solid support, coated with thin
layer (0.05 to1μm) of liquid stationary phase.
 Accommodate larger samples

17
 Carrier gas flow between 10 – 40 mL/min
 Not well adapted for trace analysis
 Contain an inert & stable porous support on
which the stationary phase can be
impregnated(coated) or bound.
 Advantages:
1. Large sample size

2. Ease & convenience of use

18
CAPILLARY COLUMN (OPEN TUBULAR)
 Widely used in GC analysis
 Length: 10 – 100 m

 Coiled around a light weight of metallic support

❑ Types of capillary column
1. FSOT (Fused Silica Wall Coated) - i.d. 0.1 - 0.3
mm
2. WCOT (Wall Coated) - i.d. 0.25 – 0.75 mm
3. SCOT (Support Coated) - i.d. 0.5 mm
❑ Advantages:
1. High resolution
2. Short analysis time
3. High sensitivity
19
COLUMN TEMPERATURE
 The optimum column temperature is dependent
upon the boiling point of the sample
 Minimal temperatures give good resolution but
increase elution times
 A temperature that is roughly ≥ the average boiling
point of the sample results in a reasonable elution
period

20
ISOTHERMAL RUN
 Constant column temperature throughout the
analysis
 Eg: This chromatogram shows the effect of
isothermal temperature program at 60°C
 Results:
- increase in tR of all compounds
- the height of the later eluting peaks are reduced &
the widths increased because they are more
affected by the lower temp. program used

21
Temperature program: 60°C isothermal
Head pressure: 12 psi
Split ratio: 1/50

22
TEMPERATURE PROGRAMMING
 Temperature programming is used to accelerate
the elution rate of the late peaks (otherwise take a
very long time to elute)
 Column temperature is increased either by
continuously or in steps as the analysis proceeds
 If the sample contains a combination of low b.p
components & high b.p components, setting a high
column temp. will cause the lower b.p component
to be eluted fast & vice versa

23
 Therefore, with temp. programming, we can set the
temp. low at the beginning to separate low b.p
component & high temp. to elute high b.p components
at reasonable rate
 Eg: This chromatogram shows an ideal temp. program
for separation of 6 aromatic compounds
 Results:
- the compounds elute in order of increasing b.p
(compounds with higher b.p are more retained)

24
Temperature program: 50°C/min-100°C/min
Head pressure: 12 psi
Split ratio: 1/50

25
26
5.2.4 DETECTORS
 Some detectors are universal.
 They are sensitive to almost every compound that
elutes from the column
 They are sensitive to a particular type of compound.
Give response that is dependent on the concentration
of analyte in the carrier gas
❑ Characteristics of ideal detector
1. High reliability & ease to use
2. Similarity response toward all solutes or
alternatively a high predictable & selective
response toward one or more classes of solute
3. Detector should be nondestructive
27
4. Adequate sensitivity
5. Good stability and reproducibility
6. A linear response to solutes that extends over several
orders of magnitude
7. A temperature range from room temperature to at
least 400⁰C
8. A short response time that is independent of flow rate

28
 Several types of detectors;

1. Flame Ionization Detector (FID)

2. Thermal Conductivity Detector (TCD)
3. Electron Captured Detector (ECD)

29
Detector Principle of Principle class of
operation compound detected

FID Ionization of solute Organics molecule that

molecules in a can be ionized
flame
TCD Thermal Any samples
conductivity
ECD Current Compounds containing
electronegative
elements

30
FLAME IONIZATION DETECTOR (FID)
Principle of operations:
 Effluent from the column is mixed
with H2 and air, then ignited
 Organic compounds burning in the
flame creates ions & electrons which
can conduct electricity through flame
 The burner, held at ground potential
acts as one of the electrodes.
 The second electrode called as a
collector, is kept at a positive voltage
& collects the current that is
generated.
 Signal amplified by electrometer that
generate measurable voltage. 31
Advantages Disadvantages
 Rugged  Weakly sensitive to
 Sensitive (10-13 g/s) carbonyl, alcohol &
 Wide dynamic range
amine groups
(107)  Not sensitive to non-

 Signal depends on
combustibles analyte
number of C atoms in such as H2O, CO2,
organic analyte - SO2, NOx
mass sensitive not  Destructive method.
concentration
sensitive

32
THERMAL CONDUCTIVITY DETECTOR (TCD)
Principle of operation:
 Consists of an electrically heated wire
 Operating principles relies on the
thermal conductivity of the gaseous
mixture.
 When the solutes elutes from the
column there is a change in the
composition of the mobile phase &
thermal conductivity
 Resulting in a deviation from thermal
equilibrium, causing a variation in the
resistance
 This variation is proportional to the
concentration of the analyte
33
Advantages Disadvantages
 Simple  Relatively low
 Large linear dynamic sensitivity
range
 Responds to both
organic and inorganic
species
 Nondestructive;
permits collection of
solutes after
detection

34
ELECTRON CAPTURE DETECTOR (ECD)

Principle of operation:
 Sample elute from a column is passed over a radioactive β emitter,
usually nickel-63
 An electron from the emitter causes ionization of carrier gas (often
N2) and the production of a burst of electrons
 In the absence of organic species, a constant standing of current
 In the presence of organic molecules containing electronegative
functional groups that tend to capture electrons, the current
35
decreases markedly
Advantages Disadvantages
 Selectively responds to  Insensitive to functional
halogen-containing groups such as amines,
organic compounds alcohols and
such as pesticides and hydrocarbons
polychlorinated
biphenyls
 Highly sensitive
towards halogens,
peroxides, quinones
and nitro groups
36
5.3 STATIONARY PHASE
 Desirable properties for the immobilized liquid
stationary phase:
- Low volatility (ideally the boiling point of the liquid at
least 1000C higher than the maximum operating
temperature for the column)
- Thermal stability
- Chemical inertness.
- Solvent characteristics such as k and α values for
the solutes to be resolved fall within a suitable range.

37
 Separation principles
- Use the principle of “like dissolve like” where like refers to
the polarity of the analyte and the immobilized liquid
stationary phase
 Polarity of organic functional group in increasing order
- Aliphatic hydrocarbons < olefins < aromatic hydrocarbons
< halides < ethers < esters/aldehydes/ketones
<alcohols/amines < amides < carboxylic acids < water
 Polarity of the stationary phase should match that of
sample components
- When the match is good, the order of elution is
determined by the boiling point of the eluents

38
POLARITY OF STATIONARY PHASE
Water
Polar Carboxylic acids
Amides
Alcohol/amines
Esters/aldehydes/ketones
Ethers
Halides
Aromatic hydrocarbons
Olefins
Non-polar
Aliphatic hydrocarbons
39
Non-polar Polar

ALIPHATIC HYDROCARBONS < ESTERS / ALDEHYDES / KETONES < ALCOHOLS / AMINES < WATER

Pentane, Hexane Acetone, 3-pentanone Propanol, Butanol

Heptane, Octane Methyl ethyl ketone Pentanol
40
  Many liquid statationary phase are based on
polysiloxanes or polyethylene glycol (PEG)

H H H H

HO C C O C C OH Polyethylene glycol (PEG)

Use for separating polar species
H H H H
n

R R R
Polydimethyl siloxane, the R
R Si O Si O Si R
groups are all CH3. (Non-
R R R polar)
n

41
FACTORS AFFECTING GC SEPARATIONS
 Volatility of compound: Low b.p (volatile) components
will travel faster through the column than the high b.p
components
 Polarity of compounds: Polar compounds will move
more slowly, especially if the column is polar
 Column temperature: Raising the column temperature
speeds up all the compound in a mixture
 Flow rate of the gas through the column: Speeding up
the carrier gas flow increases the speed with which all
compounds move the column
 Length of the column: The longer the column, the longer
the elution time (sometimes employed for better
separation) 42