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Gas

Chromatography

Monroe L. Weber-Shirk

School of Civil and


Environmental Engineering

Come to lab prepared to work on


a variety of tasks
Map

the location of a VOC spill


Load samples vials with soil for next
weeks lab
Review your WWTP data logs to see how
the plant is operating
Measure pH and MLVSS of WWTP
Design a better HMI (or GUI)

Gas Chromatograph:
an overview
What

is chromatography
History of chromatography
Applications
Theory of operation
Detectors

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, the other being a
stationary
bedor along the stationary bed.
______ that percolates
through
(Ettre & Zlatkis, 1967,
The Practice of Gas
fluid
Chromatography)

History of Chromatography
1903

- Mikhail Tswett separated plant


pigments using paper chromatography
liquid-solid

chromatography

1930s -

Schuftan & Eucken use vapor as


the mobile phase
gas

solid chromatography

Gas Chromatography
Applications
Compound must exist as a ____gas
at a temperature that can be
produced by the GC and withstood by the column (up to
450C)
Depending on the column
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
______
mass of compound
adsorbed to
stationary phase

Carrier gas

Gas phase concentration

Process Flow Schematic


Sample injection
Carrier gas
(nitrogen or
helium)

Long Column (30 m)

Detector
(flame
ionization
detector or
FID)

Air
Hydrogen

Gas Chromatograph Components


top view
Injection Port

Column
Oven
front view

Flame
Ionization
Detector

Flame Ionization Detector


Teflon insulating ring
Gas outlet
Collector
Sintered disk

Coaxial cable
to Analog to
Digital
Ionsconverter
Flame
Platinum jet

Air
Hydrogen
Capillary tube (column)

Why do we need
hydrogen?

Flame Ionization Detector


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

Responds
all

organic compounds

Little

or no response to (use a Thermal


Conductivity Detector for these gases)
CO,

Linear

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

from the minimum detectable limit


7
10
through concentrations ____ times the
minimum detectable limit

Gas Chromatograph Output


____
area proportional to mass of compound
Strip chart technique?
injected
Peak time dependent on velocity
______ through column
detector
output

Peak

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 ____
low thermal
conductivity (He)
Electron

Capture Detector

Specific

for halogenated organics

Advantage of Selective Detectors

methane
time

ECD
output

Mixture containing
lots of methane
and a small
amount of TCE

FID
output

TCE

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-tocharge 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


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