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Gas Chromatography
separation by partition between gaseous
mobile phase and liquid stationary phase
supported by inert packing
developed in 1941 by Martin and Synge
applications did not come till 1950s
VR =>
retention volume
tR =>retention time
VM =>volume of component
not retained
tM =>retention time of
unretained component
T => 273 K
W => wt of stationary phase
Apparatus
Carrier Gas Supply
chemically inert gases:
He, Ar, N2 & H2
high purity, 99.9995% pure or better
Apparatus
Carrier Gas Supply
pressure regulators:
- reduce pressure of gas
- control the flow rate
gauges
flow meters: rotameters
soap bubble
Apparatus
Sample Injection System
introduces "plug" of sample onto front of
column
microsyringe thru septum
sampling valve
Injector
Apparatus
Column
column preparation
column:
glass, stainless steel, copper, or aluminum
capillary
packed
Apparatus
Column
packed
solid support
small, uniform spherical particles
inert at elevated temperatures
examples:
firebrick
alumina
diatomaceous earth
ChromosorbR A, G, P, W and T
ChromosorbR Packing
Materials and Their Uses
A
Celite 545
Chromosorb
P
Chromosorb
W
SiO2
89.7
89.9
89.2
91.2
Al2O3
5.1
3.6
5.1
4.1
Fe2O3
1.55
1.65
1.50
1.15
TiO2
0.30
0.30
0.30
0.25
CaO
1.30
1.75
0.90
0.40
MgO
0.90
0.70
1.00
0.65
Apparatus
Liquid Phase
low volatility
thermal stability
chemical inertness
solvent characteristics
tR falls within proper limits
Apparatus
Liquid Phase
classifications:
Non-polar
polar
intermediate
hydrogen bonding
specific
Apparatus
Column Thermostating
temperature:
slightly below or equal to av. b.p. of
components
allows for tR between 2 and 30 min
programmable
Apparatus
Detectors
Apparatus
Detectors
Thermal Conductivity Detector (TCD)
universal
relies on change of cooling ability of carrier gas
over filaments as solutes elute
few ppt sensitivity
nondestructive
Apparatus
Detectors
Flame Ionization Detector (FID)
Apparatus
Detectors
Electron Capture Detectors (EC or ECD)
must have emitter source, H3 usually
Radioactive rays cause carrier gas to emit
electrons which are collected by solute particles
particularly sensitive to halogens, few ppbs
destructive
Electron-Capture Detector
Apparatus
Detectors
Atomic Emission Detectors
similar to FID
sample burns in plasma emitting light
characteristic to selected elements
uses low band pass filter to be specific to
selected elemental emissions
especially sensitive to P and S, several ppbs
destructive
Apparatus
Detectors
Fourier Transform Infrared Detector
(FTIR)
first technique which tried to really identify
solutes
difficulty with sample cell transmission of IR
radiation to detector
nondestructive
Apparatus
Detectors
Mass Spectrometer (MS)
another technique aimed at identifying solutes
main difficulty, changing from highly
pressurized gas mixture to vacuum containing
isolated components
destructive
Jet Separator
Apparatus
Detectors
Other:
UV
FT-NMR
Applications
1.separation
2.complete analysis: quantitative as well as
qualitative
better if use more informative detector: MS,
FTIR, UV, NMR
Quantitative Analysis
integration of area under peak
triangulation
"weighing paper dolls"
mechanical
electronic
Qualitative Analysis
TR vs. VR
VR
better
depends only on K, analyte, column T, Ps
Qualitative Analysis
Relative Retention Times
(tR)Y - tm
= ---------------(tR)X - tm
Qualitative Analysis
Retention Index
good for homologous series, straight line
log(tR')x - log(tR')n
IX = 100 * ----------------------------- + 100 * n
log(tR')n+1 - log(tR)n
where
Qualitative Analysis
use 2 paraffin's whose tR bracket the value
for the unknown
Summary
single chromatograph inconclusive
3 chromatographs with columns of
varying polarity, comparing retention
index - good way of identifying analyte