UNIT THREE

3. Gas Chromatography (GC)

 Gas chromatography is a process by which a mixture is separated

into its constituents by a moving gas phase passing over a
stationary sorbent.

 The technique is thus similar to liquid-liquid chromatography

except that the mobile liquid phase is replaced by a moving gas
phase.

 Gas chromatography is divided into two major categories: gas-

liquid chromatography (GLC),

where separation occurs by partitioning a sample between a

mobile gas phase and a thin layer of non-volatile liquid
coated on an inert support, and
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• Gas-solid chromatography (GSC), which employs a solid of large
surface area as the stationary phase.

• In gas chromatography the mobile phase is gas, the stationary

phase is usually a nonvolatile liquid, but sometimes a solid.

• The analyte is gas or volatile liquid.

3.1. Instruments for GC

 The components of GC consists of

• Gas supply ( gas carrier)
• Sample injector
• Column
• Detector & computer or recorder
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 Instrumentation of GC

Flow meter

Injector Septum Detector GC

Pressure Flow Chart
regulator controller 
Recorder

Oven

Gas
supply Column

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 Gas supply ( carrier gas)

 The mobile phase (carrier gas) should be chemically inert, dry

and free from O2 (helium, argon, nitrogen and hydrogen).

 Helium is the most common mobile phase gas.

 The carrier gas should be of high purity; impurities in the carrier

gas such as water vapour, air and trace gaseous hydrocarbons can
cause reactions with sample and cause column deterioration and
affect detector performance.

 The gas supply is associated with pressure regulator and flow

controller.
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Sample Injection System

Preparation of the Sample :

• Samples GC must be volatile.

• Samples which are non volatile are converted into a volatile

derivative.

• The most commonly method is the silylation (reaction of

trimethylsilyl, - Si(CH3)3 with an active hydrogen atoms in the
analyte (carboxylic acids, amines, imines, alcohols, phenols, and
thiols).

• Inorganic metals (aluminum, beryllium, and chromium) can be

analyzed by GC via formation of stable,volatile metal chelates with
trifluoroacetylacetone (TFA) and hexafluoroacetylacetone (HFA).
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• I njection of the Sample

The injector block; is heated to a temperature that is at least 50 C

above the sample component with the highest boiling point; this to
ensure rapid vaporization of the entire sample.
The injection system is a self-sealing silicone septum.
The sample is injected by a microliter syringe. The needle of the
syringe is inserted through and the sample injected smoothly into a
heated metal block at the head of the column.

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GC Column
Oven
 The GC column on which the
actual separation of sample
Column
components is effected.

• Most GC columns are made from high-purity fused silica capillary,

the inner wall of the capillary coated with the stationary phase.

• GC columns vary in length from less than 2 m to 50 m or more.

• In order to fit into the column oven, they are usually formed as
coils.

• The control of column’s temperature is critical to attain a good

separation in GC, thus the column is located inside a thermostated
oven to control the temperature. 7
Choice of GC Columns

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• Column Configuration

Capillary Columns

• 100 mm to 500 mm I.D. and 10 m to 100 m

Packed Columns long
• 2 to 4 mm I.D. and 1 to 4 meters long.
• Stationary phase is coated on the internal
wall of the column as a film 0.2 mm to 1
• Packed with a suitable adsorbent. mm thick

• Mostly used for gas analysis. • Sharper peaks – no eddy diffusion.

• Peak broadening due to zone (eddy) • Up to 500,000 theoretical plates – excellent

diffusion resulting from multitude of separations.
pathways a molecule can pass through
column. 9
• Most popular type of column in use.
GC Detector Flow meter
Flow
• The function: controller
Pressure
Injector Septum Detector GC
chart
regulator  Recorder

• Monitoring the carrier gas as

Oven
it emerges from the column.
• Types of GC detectors: Gas
supply
Column

 Thermal conductivity detector (TCD)

 Electron capture detector (ECD)
 Flame ionization detector (FID)
 Nitrogen phosphorous detectors (NPD)

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Thermal Conductivity Detector (TCD)

- hot-wire detector
- first universal detector developed for GC

Process
- measures a bulk property of the mobile phase leaving the column.

- measures ability to conduct heat away from a hot-wire (i.e.,

thermal conductivity).

• Considerations

- mobile phase must have very different thermal conductivity then

solutes being separated.
- most compounds separated in GC have thermal conductivity of
about 1.4X10-5.
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Advantages:

- truly universal detector,

• applicable to the detection of any compound in GC
- non-destructive
• useful for detecting compounds from preparative-scale
columns
• useful in combination with other types of GC detectors

• Disadvantages:

- detect mobile phase impurities

- sensitive to changes in flow-rates
- limit of detection ~ 10-7 M , much higher than other GC
detectors 12
Flame Ionization Detector (FID)
- most common type of GC detector
-“universal” detector capable of measuring the presence of almost any
organic
Principle of operation:
- measures the production of ions when a solute is burned in a flame.
ions are collected at an electrode to create a current
Advantages:
- universal detector for organics
- doesn’t respond to common inorganic compounds
- mobile phase impurities not detected, carrier gases not detected
- limit of detection: FID is 1000x better than TCD,
- linear and dynamic range better than TCD
Disadvantage:
• - destructive detector 13
Nitrogen-Phosphorus Detector (NPD)

- used for detecting nitrogen- or phosphorus containing compounds

also known as alkali flame ionization detector or thermionic
detector (TID)

Principle of Operation

- same basic principal as FID

- measures production of ions when a solute is burned in a flame
- ions are collected at an electrode to create a current
- contains a small amount of alkali metal vapor in the flame
- enhances the formation of ions from nitrogen- and phosphorus-
containing compounds
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Advantages:
- useful for environmental testing detection of organophosphate
pesticides
- useful for drug analysis determination of amine-containing or basic
drugs
- Like FID, does not detect common mobile phase impurities or
carrier gases
- limit of detection: NPD is 500x better than FID in detecting
nitrogen- and phosphorus- containing compounds
- NPD more sensitive to other heterocompounds, such as sulfur-,
halogen-, and arsenic- containing molecules
Disadvantages:
- destructive detector
- NPD is less sensitive to organic compounds compared to FID

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Electron Capture Detector (ECD)

- radioactive decay-based detector

-selective for compounds containing electronegative atoms, such as
halogens

Principle of Operation
- based on the capture of electrons by electronegative atoms in a
molecule
- electrons are produced by ionization of the carrier gas with a
radioactive source such as 63Ni ( emitter)
- in absence of solute, steady stream of these electrons is produced
- electrons go to collector electrode where they produce a current
- compounds with electronegative atoms capture electrons, reducing
current
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Advantages:

- useful for environmental testing

• detection of chlorinated pesticides or herbicides
• detection of polynuclear aromatic carcinogens
• detection of organometallic compounds
- selective for halogen- (I, Br, Cl, F), nitro-, and sulfur-containing
compounds
- detects polynuclear aromatic compounds, anhydrides and conjugated
carbonyl compounds

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Applications of GC

Qualitative analysis

• GC’s are widely used to establish the purity of organic compounds.

• Contaminants, if present, are revealed by the appearance of

additional peaks: the areas under these peaks provide rough
estimates of the extent of contamination.

• In theory, GC retention times should be useful for identifying

components in mixture.

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Quantitative Analysis
• Separation of Mixture Components
• Identification of Compounds:

Aspects of GC Applications:
• Food Analysis

• Analysis of foods is concerned with confirming the presence and

determination the quantities of the analytes (lipids, proteins,
carbohydrates, preservatives, flavours, colorants, and also
vitamins, steroids, and pesticide residues).
Drug Analysis

 GC is widely applied to identification of the active components,

possible impurities as well as the metabolites. 19
• Environmental Analysis

• The environmental contaminants; e.g. dichlorodiphenyltrichloro-

ethane (DDT) and the polychlorinated biphenyls (PCBs) are
present in the environment at very low concentrations and are
found among many of other compounds.

• GC, with its high sensitivity and high separating power, is mostly
used in the analysis of environmental samples.

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