Gas Chromatography:

Essential Hardware
and Operations
Tracy J Benson
Dan F. Smith Department of Chemical
Engineering
Lamar University
December 3, 2009
Definitions
! ChromaLography: a general Lerm applled Lo a wlde varleLy of
separauon Lechnlques based upon Lhe sample paruuonlng
beLween a movlng phase, whlch can be gas or llquld, and a
sLauonary phase, whlch may be elLher a llquld or solld"-
[!ohnson and SLevenson, 1978]
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Definitions
!Analyte: a substance that is the subject of chemical analysis Analyte: a substance that is the subject of chemical analysis
!Chromatography is an equilibrium-driven process:
A
mobile
A
stationary
! Equilibrium constant (K): partition coefficient expressed as the Equilibrium constant (K): partition coefficient expressed as the
molar concentration of the analytein the stationary phase
divided by the molar concentration of the analytein the mobile
phase
!Analyte retention time (t
R
): the elapsed time between analyte
injection and analytepeak reaching a detector at the end of the
column
! Mobile phase retention time (t
M
): the time necessary for the Mobile phase retention time (t
M
): the time necessary for the
mobile phase to pass through the column
Introduction
GC is most widely used analytical technique in
the world
Over 50 years in development
Over 25,000 in use in US
Worldwide market > $1billion
GC is premier technique for separation and
analysis of volatile compounds
Gases, liquids, dissolved solids
Organic and inorganic materials
MW from 2 to > 1,000
Fast analysis
Typically minutes (even sec.)
Can be automated
Small samples (lof injection, ganalyte needed)
High resolution
Record: N ~ 1.3 x 10
6
Reliable, relatively simple and cheap
Non-destructive
Allows on-line coupling, e.g. to MS
Sensitive detectors (easy ppm, often ppb)
Highly accurate quantification (1-5% Relative Std Dev)
Advantages of GC
Limited to volatile samples
T of column limited to ~ 380 C
Need P
vap
of analyte ~ 60 torr at that T
Analytes should have b.p. below 500 C
Not suitable for thermally labile samples
Some samples may require intensive preparation
Samples must be soluble and not react with the
column
Requires spectroscopy (usually MS) to confirm
the peak identity
Disadvantages of GC
Instrument Overview: GC-MS Configuration
Other Analyzers: Flame ionization, Thermal
conductivity, Electron-capture, Atomic Emission,
Flame photometric, and more
Carrier gas Mobile phase (H
2
, He, N
2
)
Flows continuously throughout instrument
Carries the sample vapor through the column to detector
Necessary properties:
INERT
Does not chemically interact with sample
COMPATIBLE with detector
No noise or explosions
HIGHLY PURIFIED
Impurities will degrade column and cause noise in detector
Research grade is expensive but is necessary
Carrier Gas Properties
Flow Rate of Carrier Gas
Flow rates must be precisely controlled
Reproducible retention times, minimize detector drift
Flow rates of carrier gas:
Linear flow rate (cm/s): u = L/tr
Volumetric flow rate (mL/min): u (! r2)
L is length of column, tr is retention time, r is the internal radius
of column
Flow rate depends on type of column
Packed column: 25-100 mL/min
Capillary column: L/min to 1 mL/min
Flow rate will decrease as column T increases
Viscosity of carrier gas increases with T
Properties:
Versatile, rapid, quantitative
Introduce sample to column
as a sharp, symmetric band
Heated injection port
Vaporize sample (50 C >analyte
b.p.)
Low enough to avoid degradation
Packed columns:
Flash vaporizer or on-column
Capillary columns:
Split: 1-2%, Higher resolution
Splitless: ~100%, Trace analysis
Injection Process
Split/Splitless Injector
On Column Injector
" Cool injector to below boiling point
of solvent
" Quickly raise injector temperature
after injection of sample
" Offers less discrimination for
heavy molecules (i.e. acylglycerides)
Types of GC Columns
Packed GC Columns
Easy to make and use
Limited resolution (N < 8,000)
Outside: Solid tubing usually made of stainless steel
Because of strength
Glass when more inert substrate is needed
Inside: Tightly packed with inert support
Solid supports should be inert and have high surface
area
Typically diatomaceous earth or fluorocarbon polymer
Stationary liquid phase is coated on the solid support
3-10% by weight of the solid support
Open (Capillary) Columns
Most common and efficient
High resolution (N > 100,000)
Outside: Solid tubing made from fused silica
Inert, flexible, strong, and easy to use
Inside: Column is an open tube
Very low resistance to flow
Long lengths possible ( L > 100 m)
Stationary phase is a thin, uniform liquid film
coated on the wall of the tubing
Packed Column
Lower resolution
Fewer peaks (16)
Fewer plates
Capillary Column
Small sample needed
Better resolution
More peaks
Faster Analysis
Column Type vs. Separation
Column Efficiency
! 8aLe 1heory of ChromaLography
! More reallsuc descrlpuon of how peak broadenlng occurs
! van ueemLer Lquauon
PL1 = A+8/ + C
where A ls Lhe eddy dluslon Lerm, 8 ls Lhe longlLudlnal
dluslon Lerm, C ls Lhe reslsLance Lo mass Lransfer
coemclenL, and ls Lhe llnear veloclLy
Stationary Phases for GC
Hundreds of SP have been used
Only requirements are:
Low vapor pressure
Thermal stability
Low viscosity (for fast mass transfer)
High selectivity for compounds of interest
How do you decide?
Literature searches
Ask around, talk to manufacturers
Trial and error
Typical Stationary Phases
Derivatization
If changing the column wont help, you
may change the separation by changing the
analyte
Cause a non-volatile sample to become volatile
Improves selectabilityof derivative
Example: silynation
Introduce trimethylsilyl group to make sample
volatile
Common GC Detectors
" Flame Ionization Detector (FID)
" Thermal Conductivity Detector (TCD)
" Electron Capture Detector (ECD)
" Flame Photometric Detector (FPD)
" Mass Spectrometer (MS)
Comparison of Various Common GC Detectors
FID:Detects analytes by measuring an electrical current generated by
electrons from burning carbon particles in the sample
Great for organic
compounds
TCD: Detects changes in thermal conductivity, such as when
organic molecules displace some of the carrier gas, cause a
temperature rise in the element which is sensed as a change in
resistance. The TCD is not as sensitive as other detectors but it is
non-specific and non-destructive
Particularly suited for fixed
gas analysis (i.e. CO, CO
2
, O
2
,
H
2
, etc)
ECD:uses a radioactive Beta emitter (electrons) to ionize some of the carrier gas
and produce a current between a biased pair of electrodes. When organic molecules
that contain electronegative functional groups, such as halogens, phosphorous, and
nitro groups pass by the detector, they capture some of the electrons and reduce the
current measured between the electrodes. The ECD is as sensitive as the FID but has
a limited dynamic range and finds its greatest application in analysis of halogenated
compounds.
Particularly suited for halides,
nitrates, nitriles, peroxides,
anhydrides, and organometallics
MS:The only method of detection that can offer true identification of the
analyte. Productions of ions stems from bombardment by electrons to
produce a fragmentation of ions from the parent compound. The pattern of
fragmentation is governed by gas-phase reactions and are rather unique for
any type of compound.
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References
Braithwaite and Smith
Chromatographic Methods
Grant
Capillary Gas Chromatography
McNair and Miller
Basic Gas Chromatography
Rubinson
Contemporary Instrumental Analysis
Skoog, Holler, and Nieman.
Principles of Instrumental Analysis