Gas

Chromatography
 Gas Chromatograph:
an overview

 What is “chromatography”
 History of chromatography
 Applications
 Theory of operation
 Detectors
 Syringe technique
 What is “Chromatography”
 “color writing”
 the separation of mixtures into their constituents by
preferential adsorption by a solid” (Random House
College Dictionary, 1988)
 “Chromatography is a physical method of separation
in which the components to be separated are
distributed between two phases, one of the phases
constituting a ______________
stationary bed of large surface area,
the other being a ______
fluid that percolates through or
along the stationary bed.” (Ettre & Zlatkis, 1967,
“The Practice of Gas Chromatography)
 History of Chromatography

 1903
- Mikhail Tswett separated plant
pigments using paper chromatography
 liquid-solid chromatography
 1930’s
- Schuftan & Eucken use vapor as
the mobile phase
 gas solid chromatography
 Applications
 gas at a temperature that
Compound must exist as a ____
can be produced by the GC and withstood by the
column (up to 450°C)
 Alcohols in blood
 Aromatics (benzene, toluene, ethylbenzene, xylene)
 Flavors and Fragrances
 Permanent gases (H2, N2, O2, Ar, CO2, CO, CH4)
 Hydrocarbons
 Pesticides, Herbicides, PCBs, and Dioxins
 Solvents
 Advantages of Gas
Chromatography
 Requires only very small samples with little
preparation
 Good at separating complex mixtures into
components
 Results are rapidly obtained (1 to 100 minutes)
 Very high precision
 Only instrument with the sensitivity to detect
volatile organic mixtures of low concentrations
 Equipment is not very complex (sophisticated
oven)
 Chromatogram of Gasoline
1. Isobutane
2. n-Butane
3. Isopentane
4. n-Pentane
5. 2,3-Dimethylbutane
6. 2-Methylpentane
7. 3-Methylpentane
8. n-Hexane
9. 2,4-Dimethylpentane
10. Benzene
11. 2-Methylhexane
12. 3-Methylhexane
13. 2,2,4-Trimethylpentane
14. n-Heptane
15. 2,5-Dimethylhexane
16. 2,4-Dimethylhexane
17. 2,3,4-Trimethylpentane
18. Toluene
19. 2,3-Dimethylhexane
20. Ethylbenzene
21. m-Xylene
22. p-Xylene
23. o-Xylene
 Theory of Operation

 Velocityof a compound through the column

depends upon affinity for the stationary
phase Area under curve is
______
mass of compound
adsorbed to stationary
phase

Carrier gas
Gas phase concentration
 Process Flow Schematic
Detector (flame
Sample injection ionization
detector or FID)
Carrier gas
Air
(nitrogen or
helium) Hydrogen

Long Column (30 m)

 Gas Chromatograph Components
top view
Flame
Injection Port Ionization
Detector

Column

Oven

front view
 Flame Ionization Detector
Teflon insulating ring Coaxial cable to
Analog to Digital
Gas outlet converter
Collector
Ions
Flame
Sintered disk
Platinum jet
Air

Hydrogen Why do we need

hydrogen?

Capillary tube (column)

 Flame Ionization Detector
 Responds to compounds that produce ____
ions
when burned in an H2-air flame
 all organic compounds
 Little
or no response to (use a Thermal
Conductivity Detector for these gases)
 CO, CO2, CS2, O2, H2O, NH3, inert gasses
 Linearfrom the minimum detectable limit
107 times the
through concentrations ____
minimum detectable limit
 Gas Chromatograph Output
 Peak ____
area proportional to mass of compound
injected
 Peak time dependent on velocity
______ through column
detector
output

time (s)
 Other Detectors

 Thermal Conductivity Detector

 Difference in thermal conductivity between the
carrier gas and sample gas causes a voltage
output
low thermal
 Ideal carrier gas has a very ____
conductivity (He)
 Electron Capture Detector
 Specific for halogenated organics
 Advantage of Selective Detectors

TCE

FID output
Mixture containing
lots of methane and a
small amount of TCE methane

time
ECD output

time
 Mass Spectrophotometer

 Uses the difference in mass-to-charge ratio (m/e)

of ionized atoms or molecules to separate them
from each other.
 Molecules have distinctive fragmentation patterns
that provide structural information to identify
structural components.
 The general operation of a mass spectrometer is:
 create pure gas-phase ions ( Gas
__________________
chromatograph )
 separate the ions in space or time based on their mass-
to-charge ratio
 measure the quantity of ions of each mass-to-charge
ratio
 Mass Spec Output

 Each peak of a chromatogram becomes a

“fingerprint” of the compound
 The fingerprints are compared with a library
to identify the
compounds

mass-to-charge ratio
 Purge and Trap

 Way to measure dilute samples by concentration

of constituents
 Trap constituents under low temperature
 Heat trap to release constituents and send to GC
column

N2

Trap
 Techniques to Speed Analysis
 Problem: some components of a mixture
may have very high velocities and others
extremely low velocities.
 slow down fast components so they can be
separated
 speed up slow components so analysis
doesn’t take forever
 Solution…
 Temperature Control Options
Example Method
Column: Petrocol DH, 100m
x 0.25mm ID, 0.5µm film
Cat. No.: 24160-U
Oven: 35°C (15 min) to
200°C at 2°C/min, hold 5
min
Carrier: helium, 20cm/sec
(set at 35°C)
Det.: FID, 250°C
Inj.: 0.1µL premium
unleaded gasoline, split
(100:1), 250°C