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Gas Chromatography

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

Specific Retention Volume


Vg - depends on nature of solute and
stationary phase, independent of many of
the column variables

Specific Retention Volume


Tc P - PH2O
F = Fm * ---- * -----------T
P
where F =>av. flow rate within column
Fm =>flow rate at bubble meter
Tc =>column temperature, K
T =>gas temp. at bubble meter, K
p =>pressure at end of column
pH2O =>vapor pressure of water

Specific Retention Volume


VR = tR*F
where

VR =>
retention volume
tR =>retention time

Specific Retention Volume


VM = tM*F
where

VM =>volume of component
not retained
tM =>retention time of
unretained component

Specific Retention Volume


VR & VM depend on av. p within column

Specific Retention Volume


VRo & VMo => corrected retention vol.
VRo = j*tR*F
VMo = j*tM*F
3((pi/p)2 - 1)
where j = --------------------2((pi/p)3 - 1)
where pi =>initial pressure on column

Specific Retention Volume


therefore,
VRo - Vmo 273
Vg = -------------- * ------W
Tc
or
j*F(tR - tM)
273
Vg = ---------------- * ------W
Tc
where

T => 273 K
W => wt of stationary phase

Specific Retention Volume


Relationship between Vg and K, the
partition coefficient
273
j*F*tM*K'
Vg = ---------------- * ------W
Tc

Specific Retention Volume


Relationship between Vg and K, the
partition coefficient
273
VMo*K'
Vg = ------------- * -------W
Tc

Specific Retention Volume


Relationship between Vg and K, the
partition coefficient
273
Vs*K
Vg = ---------- * -------W
Tc
where

Vs =>vol of stationary phase

Specific Retention Volume


W
s = ----Vs
where s =>density of stationary phase

Specific Retention Volume


thus
K
273
Vg = ------ * -------s
Tc
thus Vg is a function of K and s
when Tc = 273 K

Schematic of a gas chromatograph

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

A soap-bubble flow meter

Apparatus
Sample Injection System
introduces "plug" of sample onto front of
column
microsyringe thru septum
sampling valve

Injector

Rotary Sample Valve

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

Used in preparative columns because of its high


capacity for liquid phase.

Used for separation of polar compounds.

Used primarily for hydrocarbon work.

Used for separating highly polar or reactive


compounds such as water, hydrazine, sulfur dioxide
and the halogens.

Used for separtion of polar compounds.

Chemical Analysis of Some


Selected Supports
Firebrick
C22

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

Effect of temperature on gas chromatograms:

(a.) isothermal at 45oC;


(b.) isothermal at 145oC;
(c.) programmed at
30oC to 180oC.

Apparatus
Detectors

Thermal Conductivity Detector (TCD)


Flame Ionization Detector (FID)
Electron Capture Detectors (EC or ECD)
Flame Photometric Detectors
Fourier Transform Infrared Detector (FTIR)
Mass Spectrometer (MS)
Other: UV, FT-NMR

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

Thermal Conductivity Detector Cell

Apparatus
Detectors
Flame Ionization Detector (FID)

sample burned in H2/air flame


sample must be combustible
must use electrometer
flame resistance 1012
ppm sensitivity
destructive

Flame Ionization Detector

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

Atomic Emission Detector

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

Light Pipe for GC/IR Instrument

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

Other: UV, FT-NMR

Capillary Gas Chromatography/Mass Spectrometer.

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

n => # carbons in parafins


TR' = (tR - tm)

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