Gas Chromatography

GAS LIQUID CHROMATOGRAPHY

Principles
Partition of molecules between gas (mobile
phase) and liquid (stationary phase).
Gas Chromatography
Filters/Traps Data system
H

RESET

Regulators Syringe/Sampler

Inlets

Detectors
Gas Carrier
Hydrogen
Air

Column
Schematic Diagram of Gas Chromatography
Separation process in GC
Gaseous analytes is transported thru the column
by gaseous mobile phase, called the carrier-gas
Mobile phases: gas
Stationary phases: non volatile liquid on the inside
of column or on a fine solid support
Walt Jennings,
GC Pioneer
Open tubular columns
Made of fused silica
Open tubular columns offer
Higher resolution
Shorter analysis time
Greater sensitivity
Lower sample capacity
ID of open tubular column:
0.1-0.53 mm, length: 15-100m
The thickness of stat. phase:
0.1-5 um
Liquid stat. phases
Polar column is the best for the polar analyte
Columns for GC
Columns for GC/MS
DB-1ms HP-1ms DB-5ms HP-5ms SemiVol HP-5ms DB-
35ms DB-17ms DB-225ms DB-XLB
Polysiloxane Polymers
HP-1 DB-1 DB-5 HP-5 DB-17 DB-23 DB-35 HP-
35 HP-50+ DB-200 DB-210 DB-225 DB-624 DB-
1301 DB-1701 DB-1701P Ultra 1 and Ultra 2
Polyethylene Glycol (PEG)
DB-WAX DB-WAXetr HP-INNOWax DB-FFAP HP-
FFAP DuraGuard
Chiral
CycloSil-B Cyclodex-B HP-Chiral ?/a>
High Temperature
DB-1ht DB-5ht DB-17ht
Life Science
DB-ALC1 and DB-ALC2 HP-Blood Alcohol DB-EVDX HP-Fast
Residual Solvent
Packed columns
Contain a fine solid support
Useful for preparative separations
Solid support: Teflon
Uniform and small particle size: improve
column efficiency
Retention Index (KOVAT Index, RI)

Nonpolar stationary phase

Volatility of the solutes: principal determination
Strongly polar stationary phase
H-bond and dipole-dipole interaction
RI describes the retention behavior of a
compound

log tr (unknown) log tr (n)

RI= 100*(n + (N-n)--------------------------)
log tr (N) log tr (n)
Temperature programming
Raising column temperature solute Vp
decrease retention time and sharpens
peaks
 Sample injection
(Split injection)

Split is preferred if the analyte > 0.1% of

the sample
For high resolution work
Split delivers only 0.2 2% of the sample
to column
Split ratio
Septum purge
 Splitless injection
For trace analysis
Glass liner
Injector temperature is lower than that of
split
Needs cold trapping (solvent trapping)
On-column injection:
Used for samples that decompose above their boiling point
 GC Detectors

Because the physical and chemical properties of carrier

gas differ widely from those of a vapor, a wide range of
detection methods can be employed.

We now monitor some physical, rather than chemical

properties of the effluent gas stream.

This is because most physical changes such as thermal

conductivity, light adsorption to ionization potentials, and
heats of combustions can be converted into an electrical
signal which can then be amplified and recorded in some
other way.
FID
?
ECD

NPD

FPD

TCD
 Thermal Conductivity Detector (TCD)

Non destructive, simple, robust, and cheap detector.

Its sensitivity and linearity are only moderate -good enough

for routine analysis.

The rate of heat loss can be used as a measure of the gas composition.

A heated filament is cooled by the flow of pure carrier gas.

Heat is transferred by conduction when gas molecules strike the heated

filament.

When the carrier gas is contaminated by sample components, the filament

looses less heat and becomes hotter. This change is used to generate the
signal.
 Gas C.G.S. units at 0C Molecular weight
105
Hydrogen 41.6 2
Helium 34.8 4
Methane 7.2 16
Nitrogen 5.8 28
 Flame ionization Detector (FID)

The most useful and commonly used detector in GC analysis.

High sensitivity, selectivity for carbon containing compounds

and wide range of linearity.

Destructive, mass sensing detector.

Cations generated in the flame are
counted and increase electric
current which produce the
detector signal.

The current is approximately

proportional to the amount if
carbon in the form of volatile
organic compounds which enter
the flame in the column effluent.

It normally requires three

separate gas supplies (Hydrogen,
helium, and air) with their
precision flow regulators.
Typical gas chromatogram of the aroma extract isolated from Eucalyptus
polyanthemos Schauer
 Nitrogen Phosphorus Detector (NPD)

Sensitive and a specific detector for a compound containing

nitrogen or phosphorus.

The specific response of this detector makes it especially

useful for the analysis of pharmaceuticals and in particular
in environmental analysis including herbicides.
The heated alkai bead (Rubidium or
cesium bead) emits electrons which are
collected at the anode and provides
background current.

When a solute that contains nitrogen or

phosphorus is eluted, the partially
combusted N and P materials are adsorbed
on the surface of the bead.

This adsorbed material reduced the work

function of the surface and, as a
consequence, the emission of electrons is
increased.

The sensitivity of phosphorus of NPD is 3

times higher than that of nitrogen.
 2

Typical gas chromatogram of a mixture of N-methylhydrazine

derivatives obtained from the products formed by cod liver oil
oxidation with Fe2+/H2O2. Peaks: 1 = 1-methylpyrazole
(malonaldehyde); IS = internal standard (2-methylpyrazine)
 Flame Photometric Detector (FPD)

FPD is an emissivity detector and has unique properties

that response quite specific the compounds containing
phosphorus and sulfur.
 Phosphorus and sulfur containing
hydrocarbons produce chemi-
luminescence at specific wavelengths
when burnt in the hydrogen flame.

These chemi-luminescent species are

monitored at selected wavelength.

An optical filter permits light of the

specific wavelength to enter the
photomultiplier to produce a signal.

R-P HPO* HPO + h (526 nm)

R-S S2* S2 + h (393 nm)
Electron Capture Detector (ECD)

ECD has very high sensitivity and good

selectivity for halogenated compounds.

Its probably one of the most sensitive

GC detector available (minimum
detectable concentration ca. 10-13 g/mL)

Widely used in analysis of pesticides.

A low energy of -ray source is used in

the sensor to produce electrons and ions.

The first source to be used was tritium

absorbed into a silver foil but this was
replaced by the far more thermally stable
63Ni source.
The carrier gas (nitrogen or argon) is ionized by the -radiation from the
source:

N2 N2+ + e-

The small, mobile electrons are attracted to the anode before they can
recombine with the nitrogen cation.

When a component (AM that contains halogenated atoms) that is capable

of capturing electrons enters the detector, it will combine with the
electrons produced by the ionization.

AM + e- AM-

AM- + N2+ AM + N2 + energy

The decrease in the number of electrons and ions will lead to a fall in
current and this is related to the concentration of the component entering
the detector.