Gas

Chromatography

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 Schematic Diagram (GC)

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 Introduction
♣ Gas chromatography is an instrumental method for the
separation and identification of volatile or low MP and
BP organic compounds.
♣ A gas is the mobile phase and the stationary phase (*
gas-solid chromatography) can be either a solid or a
non- volatile liquid (**gas-liquid chromatography).
♣ A sample is introduced into a heated injector, carried
through a separating column by an inert gas, and
detected as a series of peaks on a recorder when
components leave the column.

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Most columns contain a liquid stationary phase on a
solid support. Separation of low-molecular weight
gases is accomplished with solid adsorbents.
Carrier Gas :
 O2 is usually avoided since it will oxidize the
stationary phase.
 3 most common gases Nitrogen, Hydrogen,
Helium and Argon.
• *the choice of gas is often dictated by the type of
detector
The injection port consists of a rubber septum through
which a syringe needle is inserted to inject the sample.
The injection port is maintained at a higher temperature
than the boiling point of the least volatile component in
the sample mixture.

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 How a Gas Chromatography Works?

–First, a vaporized sample is injected

onto the chromatographic column.
–Second, the sample moves through the
column through the flow of inert gas.
–Third, the components are recorded as
a sequence of peaks as they leave the
column.

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 GC INSTRUMENTS CONSISTS OF:
(1) Gas system
(2) Injection system
(3) Column
(4) Column oven
(5) Detector
(6) Data system

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1. GAS SYSTEM

 Carrier gas (Inert gas)

 Helium / Hydrogen / Nitrogen
 Choice dictated by detector, cost,
availability
 Pressure regulated for constant inlet
pressure
 Flow controlled for constant flow rate
 Chromatographic grade gases (high
purity)

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 Sample size
 Packed columns, sample size ranges from tenths of a
microliter up to 20 microliters.

 Capillary columns, on the other hand, need much less

sample, typically around 10-3 microliters . For
capillary GC, split / splitless injection is used.

 Samples may be pure compounds.

 However, they are often prepared as dilute solutions

due to the sensitivity of the detection methods.

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 2. INJECTION SYSTEM

Injector port
Syringe /
(sample
Auto sampler
introduction)

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• The injection port consists of a rubber septum
through which a syringe needle is inserted to
inject the sample.
• The injection port is maintained at a higher
temperature than the boiling point of the least
volatile component in the sample mixture.

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 (b) Auto sampler

(a) Manual – Syringe

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 Enter from
Exit to
Injector Detector

Packed Column
installed in Oven
Compartment
(length of column 1-5 m).

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• Liquid samples are injected through a rubber septum into a
heated port. Carrier gas sweeps the vaporized sample into the
chromatography column.
• • Split injection - most common method of injection. Only 0.1
- 10% of the injected sample reaches the column and the
remainder is blown to waste. This method of injection is not
suitable for quantitative analysis.
• • Splitless injection - is more suitable for quantitative
analysis. Solvent is condensed at the beginning of the column
and then the column temperature is raised and the
chromatography starts.
• • On-column injection - solution is directly injected on the
column without going through a hot injection port. The
method of injection is used for sensitive compounds that
decompose above their boiling points. On-column injection is
very suitable for high boiling components because no
evaporation takes place during the injection period

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 3. Separation Column
♣ Chromatography separation involves the use of a
stationary phase and a mobile phase.

♣ Components of a mixture carried in the mobile

phase are differentially attracted to the stationary
phase and thus move through the stationary phase
at different rates.

♣ The mobile phase is an inert carrier gas and the

stationary phase is a solid or liquid coated on a
solid contained in a coil column.
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 GC Column
Columns can be short, large diameter packed
column or long, very small diameter capillary
columns.
Each has its own use and associated
advantages and disadvantages.
• Capillary • Packed

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 GC COLUMN

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 GC Column
PACKED COLUMN OPEN TUBULAR /CAPILARRY COLUMN
Glass, metal (stainless steel, 1) Wall coated open tubular (WCOT)
copper, aluminium) or Teflon -cap. tubes coated with thin layer of stationary phase
-fabricated -stainless steel, copper, aluminium) or
plastic

-length 2-3 m 2) Support coated open tubular (SCOT)

-inner surface of the cap. Is lines with thin film
(~30m) of a support material, such as diatomaceous
earth.
3) Fused-silica open tubular (FSOT)
-replaced WCOT
-drawn from specially purified silica that contains
minimal amounts of metal oxides.

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 GC Oven
• The column is contained in a heated oven
that is preceded by a heated injector port
and followed by a heated detector unit which
produces the output.
• A set of preprogrammed parameters, called a
separation method, regulate the operation of
the system.

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 Inside view of GC

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 Factors Affecting GC Separations
Volatility of compound: Low boiling (volatile) components will
travel faster through the column than will high boiling
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 compounds in a mixture.
Column packing polarity: Usually, all compounds will move slower
on polar columns, but polar compounds will show a larger effect.
Flow rate of the gas through the column: Speeding up the carrier
gas flow increases the speed with which all compounds move
through the column.
Length of the column: The longer the column, the longer it will
take all compounds to elute. Longer columns are employed to
obtain better separation.

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 Temperature Selection
Injection Temperature
• Should be relatively high , consistent with
thermal stability of the sample, to give the
fastest rate of evaporation.
• However, too high an injection temperature,
will tend to degrade the rubber septum and
cause dirtying of the injection port.

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 Column Temperature
 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.
 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.
 At low temperatures, they spend more time in the stationary phase
and elute slowly; resolution increased but sensitivity is decreased.

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 Detector Temperature
• Must high enough to prevent condensation of
sample component .

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 Isothermal or Temperature
Programming
• Isothermal
 if the temperature is held constant during
the entire analysis.
• Temperature programming
 As column temperature raised, vapor
pressure analyte increases, eluted faster.
 Raise column temperature during separation
– temperature programming – separates
species with wide range of polarities or vapor
pressure.

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 Isothermal or Temperature
Programming
As tR increases, the
peak width increase
& the height
decrease, making
detection impossible
after a few peaks
have
eluted.

Since the solubility of a gas in a liquid decrease as temperature

goes up, the retention time can be reduced by increasing the
column temperature  temperature programming
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 Detector Response
• The detector response is sent to a computer
system where the progress of the sample is
monitored on the computer monitor in
graphical form that displays detector
response as a function of run time.

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 Characteristics of the Ideal Detector:
The ideal detector for gas chromatography has the following
characteristics:
1. Adequate sensitivity
2. Good stability and reproducibility.
3. A linear response to solutes that extends over several orders of
magnitude.
4. A temperature range from room temperature to at least 400oC.
5. A short response time that is independent of flow rate.
6. High reliability and ease of use.
7. Similarity in response toward all solutes or a highly selective
response toward one or more classes of solutes.
8. Nondestructive of sample.

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 Types of GC Detector
a)Thermal Conductivity Detectors (TCD)
 respond to changes in the thermal
conductivity of the gas leaving the column.
 Preferred with the used of H2 & He.
 Advantages : universal detector (except for
H2 & He), simple, equal response for most
substances.
 Disadvantages : sensitive to temp & flow
changes, fair sensitivity range.

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• Flame Ionization Detector (FID)
 The most commonly used, specific for
organic compounds.
 Advantages : excellent sensitivity - detection
limit ~ ppb level, good for hydrocarbons.
 Disadvantages : limited dynamic range,
requires very stable gas flow & insensitive
for most inorganic compounds.

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• C) Electron Capture Detector (ECD)
Sensitive to electron withdrawing groups
especially towards organics containing F,
Cl, Br, I and also CN & NO2.
Advantage : excellent for halogen-
containing compounds.
Disadvantage : very sensitive to impurities
and temp changes.

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 Other GC detectors
 Nitrogen-Phosphorous Detector (NPD)
 Flame Photometric Detector (FPD)
 Photoionization Detector (PID)

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 Chromatographic analysis
 The number of peaks correlate with the
number of components in the sample.
 The area under each peak correlates with
the relative amount of that component in
the sample.
 And if standard information is available, the
retention time under defined conditions can
be used to identify each component.

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Analysis of the Gas Chromatogram
• retention time of each peak (in minutes).
• the identity of each component in the
mixture.
• the percent composition of the mixture
 To determine the percent composition, you will
first need to find the area under each curve.

Area = (height) x (width at ½ height)

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 tR in minute

Peak height
Peak width
at ½ height

½ height
Time of
injection

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 Applications

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Petroleum
- Gasoline
- Hydrocarbon gas analysis
- Fuel and fuel oil analysis
- Oxygenated additives in gasoline

Pharmaceutical
- Residual solvents in pharmaceutical -
formulations
- Determination of drugs in race horse urine

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 Environmental
- Determination of pesticides
- Detection of disinfection by-products in
drinking water
- Detection of PCBs (polychlorinated biphenyls)
- Underground storage tank leakage
- Air pollution constituent analysis
- Fast Analysis of Dioxin and Related
Compounds
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 Forensics
- Blood alcohol analysis
- Determination of illegal drugs
- Monitoring drug purity
- Determination of drug impurities to track
sources
- Analysis of commonly abused inhalants

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• Food and Flavor
- Perfume analysis
- Quality control of alcoholic beverages
- Coffee analysis
- Fatty acid analysis
- Detection of 145 components in rose oil -
(identified 127)
- Volatile compounds in food packaging

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