GAS

DROCEL JOHN L. MORADA

MAED – SCIENCE EDUCATION
CONTENTS:

WHAT is Gas Chromatography?

HISTORY of GC

GAS-LIQUID CHROMATOGRAPHY

INSTRUMENTATION

DETECTORS
WHAT is Gas Chromatography?

• Gas chromatography is a term used

to describe the group of analytical
separation techniques used to
analyze volatile substances in the
gas phase.
WHAT’s in Gas Chromatography?

• In gas chromatography, the

components of a sample are
dissolved in a solvent and
vaporized in order to separate the
analytes by distributing the
sample between two phases.
 Two PHASES
• is a chemically inert gas
STATIONAR that serves to carry the
Y molecules of the
analyte through the
PHASE heated column.

• is either a solid adsorbant,

termed gas-solid
MOBILE chromatography (GSC), or
a liquid on an inert
PHASE support, termed gas-liquid
chromatography (GLC).
 HISTORY of GC

• Gas chromatography (GC)

was discovered by
Mikhail Semenovich
Tsvett as a separation
technique to separate
compounds.
1900s
GAS-LIQUID CHROMATOGRAPHY

• is the method most

commonly used to separate
organic compounds.
GAS-LIQUID CHROMATOGRAPHY

a solution sample The vaporized

Materials that are
that contains organic samples that are This inert gas goes
less soluble in the
compounds of injected are then through a glass
liquid will increase
interest is injected carried by an inert column packed with
the result faster than
into the sample port gas, which is often silica that is coated
the material with
where it will be used by helium or with a liquid.
greater solubility.
vaporized. nitrogen.
 INSTRUMENTATION

SAMPLE INJECTION
A sample port is necessary for introducing the sample at the head of the
column.

A calibrated microsyringe is used to deliver a sample volume in the range of a few

microliters through a rubber septum and into the vaporization chamber.

A sample splitter is used to direct excess sample to waste.

The vaporization chamber is typically heated 50 °C above the lowest boiling point of the
sample and subsequently mixed with the carrier gas to transport the sample into the
column.
 ●
plays an important role,
and varies in the GC used.
CARRIER ●
Carrier gas must be dry,
free of oxygen and

GAS chemically inert mobile-

phase employed in gas
chromatography.
 CARRIER GAS
• 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.
• Both hydrogen and helium, which are
commonly used on most traditional
detectors such as Flame Ionization(FID),
thermal conductivity (TCD) and Electron
capture (ECD), provide a shorter analysis
time and lower elution temperatures of
the sample due to higher flow rates and
low molecular weight.
• Other detectors such as mass spectroscopy,
uses nitrogen or argon which has a much
better advantage than hydrogen or helium due
to their higher molecular weights, in which
improve vacuum pump efficiency.
 CARRIER GAS
• All carrier gasses are available in
pressurized tanks and pressure regulators,
gages and flow meters are used to
meticulously control the flow rate of the
gas.
• 99.995% - 99.9995% purity range
• contain a low levels (< 0.5 ppm) of oxygen
and total hydrocarbons in the tank.
CARRIER GAS SYSTEM
Molecular sieve

Traps

Gas Clean Filter

GC COLUMN: THE HEART OF A
GC SYSTEM
GC COLUMN: THE HEART OF A
GC SYSTEM
GC COLUMN: THE HEART OF A
GC SYSTEM
TYPES OF COLUMN
 PACKED COLUMN

• Lower column efficiency than that of

capillary columns (smaller in length)
• Larger sample capacity
TUBULAR/CAPILLARY COLUMN

• Most widely used

• High column efficiency
• Small sample capacity (split sample
inside inlet)
TUBULAR/CAPILLARY COLUMN
GC Detection Systems/Detector
 Characteristics of the Ideal
Detector
1. Adequate sensitivity (application
specific, i.e. adequate for certain
tasks)
2. Good stability and
reproducibility
3. A linear response to solutes
that extends over several orders
of magnitude (calibration purposes)
4. A wide temperature range
 Characteristics of the Ideal
Detector
5. A short response time
independent of flow rate
6. High reliability and ease of use
(unfortunately, usually not the case )
7. Similarity in response toward
all solutes/most classes of
solutes
8. The detector should be
nondestructive
Flame Ionization Detector (FID)

• One of most widely

used GC detectors
• good sensitivity to
almost all organic
compounds
• In an FID, effluent from the column is directed
into a small air-hydrogen flame. Most carbon
atoms (except C=O) produce radicals (CHO+) in
the flame:
CH + O→ CHO+ + e-
• Electrons are used to neutralize the CHO+ atoms
and the ions are collected at an electrode to
create a current to be measured. This current is
proportional to the number of molecules present.
• The ionization of carbon compounds in the FID is
not fully understood, although the number of ions
produced is roughly proportional to the number
of reduced carbon atoms in the flame.
 Flame Ionization Detector
Advantages:
1. universal detector for organics
2. does not respond to common
inorganic compounds
3. mobile phase impurities not detected
4. carrier gases not detected
5. limit of detection: FID is 1000x better
than TCD
6. linear and dynamic range better than
TCD
Disadvantage: destructive detector
 Thermal Conductivity Detector
(TCD)
• One of earliest GC detectors
• Not popular today
• Low sensitivity
• Several designs
• Use heated wire or
semiconductor
• Resistance of wire changes
with analyte vs carrier
• The thermal conductivities of helium and
hydrogen (commonly used carrier gases for
TCD) are roughly 6~10 times greater than
those of most organic compounds. Thus,
even small amounts of organic species
cause relatively large decreases in the
thermal conductivity of the column
effluent, which results in a marked rise in
the temperature of the detector.
• Advantages: Simplicity, large linear
dynamic range, nondestructive
• Disadvantages: Low sensitivity (precludes
their use with WCOT columns with small
amounts of sample)
Electron Capture Detector (ECD)

• Sample passes over 63

β emitter 3
(radioactive) like Ni foil or H
adsorbed on Pt or Ti foil
• β particles (i.e. electrons) hit carrier
gas (usually N2) causing a burst of e-
to be released & measured by
electrode = standing current or
constant signal
• When analyte molecule that absorbs
e¯ passes through, current is reduced
= signal
• Response is non-linear unless pulsed
 Electron Capture Detector
Advantages
• Responds well to molecules with
electronegative atoms like halogens (F, Cl, Br,
I), peroxides, quinones, & nitro groups
• Insensitive to amines, alcohols, hydrocarbons
• Chlorinated pesticides are big application
• Highly sensitive
• Easy to use
• Pretty reliable, although foil can get coated
• Selective
 Electron Capture Detector
Disadvantages
• Narrow linear range
• Radioactive
• Regular wipe test
• Bake out contaminants
• Some limits to applicability because highly
selective
 Thermionic Detector/Nitrogen-
Phosphorus Detector

• A NPD is based on the same

basic principles as an FID.
• However, a small amount of
alkali metal vapor in the
flame, which greatly enhances
the formation of ions from
nitrogen and phosphorus
containing compounds.
 Thermionic Detector/Nitrogen-
Phosphorus Detector

• The NPD is about 500-fold more

sensitive that an FID in detecting
phosphorous-containing
compounds, and 50-fold more
sensitive to nitrogen-containing
compounds
• Applications: Organophosphate in
pesticides and in drug analysis for
determination of amine-containing
or basic drugs
 Electrolytic Conductivity
Detector
• Element-selective detector for halogen-, sulfur-
and nitrogen containing compounds
• Compounds containing halogens, sulfur, or
nitrogen are mixed with a reaction gas in a
small reactor tube, usually made of Ni. The
products from the reaction tube are then
dissolved in a liquid, which produces a
conductive solution. The change in conductivity
as a result of the ionic species is then
measured.
 Other GC Detectors
• Photoionization Detector
aromatic hydrocarbons
organosulfur/organophosphorous
• Atomic Emission Detector
element- selective detector
• Flame Photometric Detector
sulfur and phosphorous containing
compounds