Harris: Quantitative Chemical Analysis, Eight Edition

CHAPTER 23:
GAS CHROMATOGRAPHY
Chapter 23. Gas Chromatography
What did they eat in the year 1,000 ?
GC of Cholesterol and other lipids extracted from British bones (AD 500~1,800)
Chapter 23. Gas Chromatography
23-1 The Separation Process in Gas Chromatography
Mobilephase : Carrier gas(He H
2
N
2
) Mobile phase : Carrier gas (He, H
2
, N
2
...)
Stationary phase: i) nonvolatile liquid on a solid support
(gas-liquid partition chromatography) (g q p g p y)
ii) solid particles (gas-solid adsorption chromatography)
Analyte : gas or volatile liquid
23-1 The Separation Process in Gas Chromatography
- Thecolumnmust behot enoughtoprovidesufficient vapor pressurefor analytes The column must be hot enough to provide sufficient vapor pressure for analytes
to be eluted in a reasonable time.
Thedetector ismaintainedat ahigher temperaturethanthecolumn - The detector is maintained at a higher temperature than the column
so that all analytes will be gaseous.
23-1 Open Tubular Columns
Fi 23 2 T i l di i f t b l Fig 23-2a Typical dimensions of open tubular
gas chromatography column.
Fig 23-2b Fused silica column with g
a cage diameter of 0.2 m and column
Length of 15-100 m.
23-1 Open Tubular Columns
Fig 23-2c Cross sectional view of open tubular column.
23-1 Open Tubular Columns
-Narrow columns provide higher resolution than wider columns,
but require higher operating pressure and have less sample capacity
Resolution is proportional to then square root of plate number or to the column length
- Increasing thickness (0.25 to 1.0 um) increases retention time and thus
increases resolution of early eluting peaks.
The choice of liquid stationary column like dissoves like
Common Stationary Phases
Choice of liquid stationary phase
like dissolves like rule
- Nonpolar columns arebest for thenonpolar solutes - Nonpolar columns are best for the nonpolar solutes.
- Intermediate columns are best for the intermediate solutes.
- Polar columns are best for the polar solutes. p
23-1 The Separation Process in Gas Chromatography : Packed Columns
Packed columns :
- Stationary phase : i) Fine particles of solid support coated with nonvolatile liquid y p ) p pp q
ii) or Fine particle itself
- Comparison of packed column with open tubular column
1) i f 1) Weak points of packed column :
i)broader peaks, ii) longer retention times, iii) lower resolution
2) If uniform particle size smaller multiple path term
If small particle size smaller equilibration time termbut, needs higher pressure p q , g p
3) Strong point : larger capacity due to a great deal of stationary phase
useful for preparative separations which require a great deal of
stationary phase or to separate gases that are poorly retained.
Fig. 23-8 Chromatogram of alcohol mixture using Packed Column
poor resolution
23-1 The Retention Index
* The relative retention times (t
r
) of polar and nonpolar solutes change
asthepolarityof thestationaryphasechanges: as the polarity of the stationary phase changes :
1) Non-polar stationary phase :
th d f l tilit f th l t (Fi 23 9 ) the order of volatility of the solutes (Fig.23-9a)
2) polar stationary phase strongly retain the polar solutes
Alcohols (3, 6, 9) > Ketones (1, 4, 7) > Alkanes (2, 5, 8, 10)
(Fig. 23-9b)
Fig 23-9. Separation of 10 compounds on a) Nonpolar and b) Strongly polar
1 um thick stationary phase in open tubular column at 70
0
C.
23-1 Temperature and Pressure Programming
Temperature programming : the temperature of a column is raised during separation
toincreasesolutevapor pressure to increase solute vapor pressure.
1) It decreases retention time of late- eluting components.
2) h k 2) It sharpens peaks.
*Avoid raising the temp. so high that analytes and stationary phase decompose.
Pressure programming: The inlet pressure increases to increase the flow of mobile
phase phase.
1) It decreases retention time of late- eluting components.
2) The pressure can be rapidly to the initial value for the next run, whereas
in temperature programming, time is wasted waiting for a hot column to
cool before the next injection.
3) Programmed pressure is useful for analytes that cannot tolerate high temperature.
Figure. Comparison of a) Isothermal (constant) and b) programmed temperature
chromatography of linear alkanes.
Figure. Comparison of a) Isothermal (constant) and b) programmed temperature
chromatography of linear alkanes.
- At a constant temperature of 150
0
C, the more volatile compounds emerge
close together, and less volatile compounds may not even be eluted from the column.
Figure. Comparison of a) Isothermal (constant) and b) programmed temperature
chromatography of linear alkanes.
- If the temperature increases from 50
0
C to 250
0
C at a rate of 8
0
C /min,
all compounds are eluted and the separation of peaks is fairly unifrom.
23-1 Carrier Gas
x
x
Cu
u
B
A H + + ~
[22-33]
x m s x
u C C Cu H ) (
transfer mass
+ = =
[22-35]
2 2 2
) 35 22 (
) 1 ( 3
2
s
2
2
s
a
D
d
k
k
C
+
= ) 35 22 (
) 1 ( 24
11 6 1
m
2
2
2
m
b
D
r
k
k k
C
+
+ +
=
If the stationary phase is thin enough ( <0.5 um), mass transfer is dominated
by slow diffusion through the mobile phase rather than through the stationary phase.
Inother ords C <<C ineqs 22 35a & b In other words, C
s
<<C
m
in eqs. 22-35a & b.
-For a column of a given radius, r, and a solute of a given retention factor k,
h l i bl ff i h f f i h bil h i
(Diffusioncoefficientsof solute: H
2
>He >N
2
) decreaseinC (eq 22-35b)
the only variable affecting the rate of mass transfer in the mobile phase is
the diffusion coefficient of solute through the mobile phase.
(Diffusion coefficients of solute: H
2
>He >N
2
) decrease in C
m
(eq. 22-35b)
23-1 Carrier Gas
- H
2
, He andN
2
givethesameoptimal plateheight (0.3mm) at different flowrates.
(Diffusion coefficients of solute: H
2
>He >N
2
) decrease in C
m
(eq. 22-35b)
H
2
, He and N
2
give the same optimal plate height (0.3 mm) at different flow rates.
- H
2
, He give better resolution (smaller H) than N
2
at high flow rate
because solute diffuse more rapidly through H
2
, He than through N
2 .
- Faster separation can be achieved with H
2
as a carrier gas, and H
2
can be run much
faster than its optimal velocity with little penalty in resolution.
Fig.24-11 Van Deemter curves for GC
of n-C
17
H
36
at 175
0
C
Fig 23-12. Separation of two polyaromatic
hydrocarbons on a open tubular column
withdifferent carrier gases. with different carrier gases.
- As the carrier gas changed from N
2
to He
to H
2
, resolution increased and analysis
time decreased.
- H
2
: speed of analysis (advantage),
2
p y ( g ),
good column efficiency
: dangerous (explosive with air) and
reactive (hydrogenation of C=C bonds) at elevated temp.
He : good alternative for H
2
23-3 Detectors
23-3 Detectors
Thermal Conductivity Detector (TCD)
Filament; hot tungsten (w)-rhenium (Re) filament
Stream; Analyte of different thermal conductivity + carrier gas (He)
23-3 Detectors
The thermal conductivity of the mixed stream decrease
because He has the second highest thermal conductivity (next slide).
h fil h The filament gets hotter.
Its electrical resistance increases.
Thevoltagedropthroughthefilament changes The voltage drop through the filament changes.
The detector (TCD) measures the change in voltage
Thermal Conductivity Detector (TCD)
Remark :
i) The thermal conductivity (TC) of
H
2
and He = 6 ~10 times
greater than those of most
organic compounds.
Consequently thedetector Consequently, the detector
undergoes a relatively large
decrease in TC even at the
presence of small amount
of organic materials.
ii) H
2
and He give the lowest
detection limit.
Thermal Conductivity Detector (TCD)
Remark :
iii) Sensitivity increases with ) y
increasing filament current
decreasing flow rate
decreasing detector surrounding block temp.
iv) In the past, TCD was the most common in GC
becausetheyaresimpleanduniversal because they are simple and universal.
v) Its not sensitive enough to detect minute quantities of analytes.
Flame Ionization Detector (FID)
- Most organic compounds, when pyrolyzed
at the temp. of H
2
/air flame, produce CH
radicals, which are thought to produce
CHO
+
ions in the flame.
CH di l +O CHO
+
+ CH radicals +O CHO
+
+e
-
- Thechargedspecies(CHO
+
) areattracted The charged species (CHO ) are attracted
to and captured by a collector.
- The ion current that results is then
amplified and recorded.
Flame Ionization Detector (FID)
- In the absence of organic solutes,
the current is almost zero.
(The ionization in a flame is a poorly
understood process) understood process)
- Only about 1 in 10
5
carbon atoms produces y p
an ion, but ion production is strictly
proportional to the number of susceptible
carbon atoms entering the flame.
Flame Ionization Detector (FID)
Remark :
i) FIDisinsensitivetononcombustiblegases(N O H O CO SO H S No etc) i) FID is insensitive to noncombustible gases (N
2,
O
2
, H
2
O, CO
2
, SO
2
, H
2
S, No
x,
etc)
These properties make FID a useful general detector for most organic
samples, including those contaminated with water and the oxides of
nitrogen and sulfur.
ii) d hi h i i i (
13
/ ) ii) Advantages high sensitivity (~ 10
-13
g/mL),
The detection limit is ~100 times smaller than TCD.
Thedetectionlimit isfurther reducedby50%whenN
2
is The detection limit is further reduced by 50 % when N
2
is
used instead of He (N
2
gives best detection limit ).
large linear response (~ 10
7
),
low noise,
ruggedness
i convenience
iii) Disadvantages destroy the sample
Electron Capture Detector (ECD)
El t C t
* Most detectors other than FID and TCD respond to much more
limited classes of analytes.
Electron Capture
Detector (ECD)
Carrier gas : N or 5%CH in Ar - Carrier gas : N
2
or 5% CH
4
in Ar.
(Moisture decrease sensitivity)
A ( ffl f h l ) - A gas (or effluent from the column)
is passed over a beta emitter (Ni
63
or H
3
).
An electron from the emitter causes
ionization of the carrier gas and
production of a burst of electrons.
Electron Capture Detector (ECD)
- Electrons thus formed are attracted to
ananode, producingasmall steady an anode, producing a small steady
current,
- However, in the presence of analyte
molecules with a high e
-
affinity which
capturesomeof theelectrons, thecurrent capture some of the electrons, the current
decreases.
- TheECDrespondsbyvaryingthe frequency - The ECD responds by varying the frequency
of voltage pulses between the anode and
th d t i t i t t t cathode to maintain a constant current.
Electron Capture Detector (ECD)
- Remark :
i) Highly sensitive to electronegative functional groups
(halogens, conjugated C=O, -CN, -NO
2
, -O-O-)
See detection limit in Table 23-4.
ii) Insensitive to compounds (amine, alcohols, hydrocarbons)
iii) Application : detection of chlorinated pesticides
iv) Advantage : Not consuming the sample to any significant extent
Fig. . Partial gas chromatogram using an ECD to measure halogenated
compounds (green house gases) in the air at an altitude of 800 m.
Flame Photometric Detector (FPD)
Eluate fromthe column passes through a H Air flame - Eluate from the column passes through a H
2
-Air flame
E it d t (S P Pb S t ) it h t i ti li ht - Excited atoms (S, P, Pb, Sn. etc.) emit characteristic light
- P (536 nm), S (394 nm) emission is isolated by a narrow-band
interference filter and detected with a photo multiplier tube
- Application: For example, detection of pesticides containing P & S
Sulfur Chemiluminescence Detector
- It takes the exhaust from FID detector where
S compound SO +Products
H
2
-O
2
flame
FID
- Mixing it with ozone to form an excited state of SO
2.
SO + O
3
SO
2
*
+ O
2 3 2 2
_
- Excited state of SO
2
emits blue light and UV.
SO
2
*
SO
2
+hv (emission of blue light and U.V.)
Emission intensity mass of S in sample
- A Nitrogen Chemiluminescence Detector works in an analogous manner.
- 10
7
times greater sensitivity to S or N than to hydrocarbons.
Fig. 23-20 Gas chromatograms showing sulfur compounds in natural gas.
a) FID, b) sulfur chemiluminescence detector.
23-3 Detectors