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Gas Chromatography
Chromatography: Separate analytes in a mixture 1
with a resolution 1.5 in the shortest amount of = m.p.
2
5
4
Gas supplies usually have traps to remove any The analyte (GC) necessarily in gas phase.
water, oxygen, hydrocarbons or other Partitions between the mobile phase (carrier
contaminants from compressed gases gas) and the liquid stationary phase
Instruments can have multiple injectors, (predominant) inside capillary column or on
detectors or columns particles inside a packed column
Injectors and detectors temperatures controlled Some packed-column GC uses non-coated
The GC oven has a large fan and a vent door for solid stationary phases; gas-solid adsorption
rapid cooling/heating. chromatography
Data collection /and integration system
Porous
Capacity is small, is of less concern for analytical Column constructed of fused silica tubing
purposes as long as sufficient analyte is available for
Polyamide coating gives it strength
detection; pg/mL (ppt) to g/mL (ppb).
Liquid stationary phases coated or chemically
bonded to the inner wall of capillary
Column diameters 0.10 - 0.53 mm, length 30-60m
Column:
Si Si Si
Temperature range of operation (GC); s.p. dependent,
Si Si
HO
R
O
R
O
R
O
R
O
R
OH
Bonded thermally stable.
They have greater sample capacity vs. open tubular Capillary Columns: Packed Columns
columns but generates broader peaks, longer retention Higher R Low R
times and lower resolutions. Smaller H; high N Larger R, low N
fast Slow
Useful for preparative work.
Greater sensitivity Greater sample
analytical capacity
Lower cost
Smaller sample More rugged
capacity preparative
Higher cost/column
Columns fragile
Select a stationary phase that would retain Lesser retained analytes elute earlier.
(dissolve) the analytes of interest.
Given similar molecular characteristics, more
Stationary phase polarity ~ analyte polarity; volatile analytes (low b.p., high vapor pressure) elutes
(like dissolves like). earlier; i.e. low molecular masses elutes earlier.
Selectivity to individual analytes determines Consider polarity, molecular mass, b.p./vapor pressure
the quality of separation (ability to discern the of analytes in concert with the polarity of the phase(s)
components) measured in terms of relative retention to determine the order of elution.
A/ B .
Intermolecular Forces (attractive):
1. H bonding
2. Ion-ion
3. Ion-dipole
4. Dipole-dipole
5. Acid-base type
6. Conformational interactions
7. Pi-pi attractions
8. London forces (weakest but always present) sp nonpolar; sp strongly polar
Polydimethylsiloxane Polyethylene glycol
RI
CH4 100
C2H6 200
C3H8 300 RI value for n-alkanes
. . i.e. linear homologues.
. .
(hand out) x y z u s
My web page
Utility of McReynolds Constants - Examples: Benzene, cyclohexane; boiling points - very similar.
Temperature Programming: GC
u
Well packed; small dp Better particle morphology, low bonded phase
distribution lowers A density (reduce mass transfer delays)
reduces slope, C
GC Injection
Injection modes
Splitless Injection:
On-Column Injection:
Sample - vaporized in the injector and ALL
used widely in packed-column GC, less in
of the sample is swept onto the column by
capillary GC
the carrier gas
sample - deposited directly on the column
Relatively small samples (10 L)
Good for thermally unstable compounds
Good for quantitative analysis at low
Sample spends a large amount of time in
concentrations the injector
entire sample reaches the detector Best for trace (1 -100 ppm range)
Smaller injections (Capillary GC) concentrations of high boiling point
analytes in low boiling point solvents
extra time in the injector helps volatilize the
analytes.
Split Injection:
injection is split, with only a fraction of the
sample (usually 1% - 20%) actually makes it
to the column
the most common method of injecting
samples onto small diameter, open-tubular
columns.
Even for injections 20 L, only a fraction (which is
adjustable) makes it on to the column
Not for analytes mixtures with a wide range of
boiling points
some may be swept out the split vent before they
are volatilized
TCD
Non Destructive
http://www.srigc.com/ECDman.pdf
MS
The GC eluate is a mixture separated into segments
of pure substances with each analyte segment mixed
with the mobile phase.
vacuum
analytes
vacuum
It is most suited for the analysis of the very light Purge-Trap & Thermal Desorption
volatiles in samples that can be efficiently partitioned
into the head space gas volume from the liquid or
solid matrix sample. Tenax
SPME injection
www.gerstel.com
Gas chromatography is for the separation of volatile increase the volatility by decreasing the polarity of
compounds which are thermally stable. compounds.
GC not always possible (biomedical and environmental reduce thermal degradation of samples by increasing
interest) particularly for those of high molecular weight their thermal stability may reduce tailing. Enable
and/or molecules containing polar functional groups. selective detection of analytes
Derivatization used when analytes are not sufficiently increase specific detector response by incorporating
volatile, tail significantly (too strongly attracted to the functional groups which lead to higher detector
stationary phase) and thermally unstable (decompose). signals, e.g. CF3 groups for ECD(GC); fluorophores to
enable fluorometric detection (LC), chromophores to
enable UV-VIS detection etc (LC).
Column Bleed: At high temperatures s.p. may vaporize
into the carrier gas, resulting in column "bleed".
Gross
contamination