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 ______________ of large surface area, stationary bed the other being a ______ that percolates through or fluid 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

1930s
gas

- Schuftan & Eucken use vapor as the mobile phase

solid chromatography

Applications
Compound must exist as a ____ at a temperature that gas can be produced by the GC and withstood by the column (up to 450C) 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
Velocity

of a compound through the column depends upon affinity for the stationary phase Area under curve is

______ of compound mass adsorbed to stationary phase

Carrier gas

Gas phase concentration

Process Flow Schematic

Sample injection Carrier gas (nitrogen or helium) Detector (flame ionization detector or FID)

Air Hydrogen

Long Column (30 m)

Gas Chromatograph Components

top view Injection Port

Flame Ionization Detector

Column Oven

front view

Flame Ionization Detector

Teflon insulating ring
Gas outlet Collector Sintered disk

Coaxial cable to Analog to Digital converter Ions Flame

Platinum jet

Air
Hydrogen Why do we need hydrogen?

Capillary tube (column)

Flame Ionization Detector

Responds
all

to compounds that produce ____ ions when burned in an H2-air flame

organic compounds

Little

or no response to (use a Thermal Conductivity Detector for these gases)

CO,

CO2, CS2, O2, H2O, NH3, inert gasses

Linear

from the minimum detectable limit 107 through concentrations ____ times the minimum detectable limit

Gas Chromatograph Output

Peak

____ proportional to mass of compound area 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 Ideal carrier gas has a very ____ thermal low conductivity (He)
Electron

Capture Detector
for halogenated organics

Specific

Advantage of Selective Detectors

Mixture containing lots of methane and a small amount of TCE FID output 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 massto-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 doesnt take forever Solution

Temperature Control Options

Example Method
Column: Petrocol DH, 100m x 0.25mm ID, 0.5m film Cat. No.: 24160-U Oven: 35C (15 min) to 200C at 2C/min, hold 5 min Carrier: helium, 20cm/sec (set at 35C) Det.: FID, 250C Inj.: 0.1L premium unleaded gasoline, split (100:1), 250C