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GPC GFC
Principles
Partition of molecules between gas (mobile
phase) and liquid/solid (stationary phase).
The Beginning
concept of GC announced in 1941 by
Martin and Synge (also did liquid partition
chromatography)
10+ years later GC used experimentally
1955, first commercial apparatus for GC
appeared on the market
Today
estimate : 200, 000 gas chromatographs
are currently used through out the world.
30+ instrument manufactures
130 different models
improvements: computers- automatic
control open tubular columns-separate a
multitude of analytes in relatively short
times
Uses of Gas Chromatography
Determination of volatile compounds
(gases & liquids)
Determination of partition coefficients and
absorption isotherms
Isolating pure components from complex
mixtures
Key Information
organic compounds separated due to
differences in their participating behavior
between the mobile gas phase and the
stationary phase in the column
in contrast to other types of
chromatography, the mobile phase does
not interact with molecules of the analyte;
its only function is to transport the analyte
through the column
Gas Chromatography
Filters/Traps Data system
H
RESET
Regulators Syringe/Sampler
Inlets
Detectors gas
system
Gas Carrier
Hydrogen
Air
Column inlet
column
detector
data
system
Carrier gas/ Varian 3350 Gas Computer Controls for
Regulator Chromatograph Method and Output
A sample is
introduced into a heated injector,
carried through a separating column by an
inert gas, and
detected as a series of peaks on a recorder
when components leave the column.
Chromatographic separation involves the
use of a stationary phase and a mobile
phase.
Components of a mixture carried in the
mobile phase are differentially attracted to
the stationary phase and thus move
through the stationary phase at different
rates.
In gas chromatography
T=10’
T=20’
P
l
o
t
Carrier Gas Velocities and Plate Height
Profil Kurva Van Demter
1.2 Gas N2, H2, dan He, pada N2
Kolom WCOT
1.0
H 0.8 He
E
T 0.6
P
H2
0.4
0.2
10 20 30 40 50 60 70 80 90
Column in Oven
Slide 10
Dilute
Solution
Pure
Sample
When the system is ready, as indicated by
the ready light, samples are injected into
the injector port where they are vaporized
and carried into the column by the carrier
gas.
10 ml
Syringe
Injection Techniques
Split injection is used if analytes are > ~0.1% of the sample. High resolution
separations work best with the smallest amount of sample that can be detected. Split
injection also makes sure that impurities do not get onto the column in large
concentrations. Splitless injection is appropriate for trace analyses < (~0.01% of
the sample). On-column injection is for samples that thermally decompose. These
go straight onto the column rather than through an injector oven.
Types of Columns (GC)
Packed Columns
Less than a few meters in length
Usually made using 1/16” (1.59mm) inner
diameter stainless steel tubing
Packed with solid adsorbent or with solid support
with bonded stationary phase
Used mainly for adsorption chromatography
Have a high capacity – can handle a lot of
analyte
Lower separation efficiencies
Inexpensive – can make them in the lab
Types of Columns (GC)
Packed Columns
-ol: -OH
-oate: -COOR
-al :-HC=O b.p.
-one:-C=O
N Massa Molekul
Nama Senyawa Rumus Molekul Titik Didih (˚C) Kepolaran
o Relatif
higher resolution
lower sample capacity
22.1 Gas Chromatography -9
22.1 Gas Chromatography -10
4. Carrier Gas
22.1 Gas Chromatography -11
5. Sample Injection-1
1) gasses, liquids, or solids
vaporized, not decomposition
2) injection time bands broader
3) injected by syringe
(manual or automatic injection)
The column is contained in a heated oven
that is preceded by a heated injector port
and followed by a heated detector unit
which produces the output.
Isothermal
Mengatur suhu
kolom
Temperatur
terprogram
Packed Column
installed in Oven
Compartment.
The detector response is sent to a
computer system where the progress of
the sample is monitored on the computer
monitor in graphical form that displays
detector response as a function of run
time.
The Ideal Detector
http://www.people.virginia.edu/~roa2s/chem_551/8/tsld002.htm
Detector Requirements
1) High Sensitivity:
Sensitivity refers to the change in detector response as a function
of the change in the amount or concentration of the analyte.
S = dR / dC
or S = dR / dQ
DL = 3 Nrms / S
SEL = S1 / S2
CH O CHO e
Exhaust
Chimney
Hydrogen Column
Inlet Effluent
Schematic Diagram of Flame Ionization Detector
Collector
Detector electronics
- 220 volts
Flame
Chassis ground
Jet
Flow
Thermal Conductivity Detector
Relative Thermal
Compound
Conductivity
Carbon Tetrachloride 0.05
Benzene 0.11
Hexane 0.12
Argon 0.12
Methanol 0.13
Nitrogen 0.17
Helium 1.00
Hydrogen 1.28
Thermal Conductivity Detector
The “base line” will decrease and this decrease constitutes the signal.
8
C 16
6
4
C14
2
Retention Time
C
The content % of C14 fatty acids =
C + C+ C
Response
Octane
Decane
1.6 min = RT
Hexane
Response
1.6 min = RT
Response
Unknown compound
1) Chromatographic
a) tR or Retention Index
b) Spiking
2) Spectroscopic
Retention time
methan MEK limitations
ol
toluene tR changes with flow rate,
column temperature,
liquid phase, column
history,
X sample size
*** WARNING
tR identical retention times do
not confirm peak identity
Spiking
methan MEK
ol
toluene
tR
Qualitative Analysis –
Retention Index (I)
I for an analyte is a measure of the rate at which it is
carried through a column compared with the rate of
movement of two normal alkanes one that moves faster
than the analyte and the other that moves more slowly.
I of alkanes, by definition, is 100 times the number of
carbon atom they contain regardless of the column
packing, temperature or other conditions
e.g. butane, I = 400
pentane, I = 500
The Kovats Index
O O
R C OH + CH 3 OH + H 2 SO4 R C O CH3
Reflux
Volatile in Gas
Chromatography
O
CH 2 O C R
O CH 3 ONa O
CH O C R + CH 3 OH 3 R C O CH3
Volatile in Gas
O Chromatography
CH 2 O C R
The Effects of OH groups of Carbohydrates
6
CH2 OH
O
5 6
4 CH2 OH
OH 1
HO O
5
3 2 OH 4
OH OH 1
HO
3 2 OH
OH
Derivation of Glucose with Trimethylchlorosilane
6
CH2 OH
O CH 3
5
4
OH 1 + 5Cl Si CH 3
HO
3 2 OH CH 3
OH
Glucose Trimethylchlorosilane
6
CH2 O-Si(CH3)3
O
5
4 + 5HCl
O-Si(CH ) 1
3 3
(CH3)3-Si-O
3 2 O-Si(CH3)3
O-Si(CH3)3
Effects of Derivation
1. Time consumption
2. Side reaction
3. Loss of sample