Chapter 27.

Gas Chromatography

z Principle of GLC
z Instruments for GLC
z Gas Chromatography
Columns and Stationary
Phases
z Applications of GC
z Advances in GC
z Gas-Solid
Chromatography

Gas Chromatography
Stainless steel capillary
z Gas Chromatography: partition column (up to 400° C)
between inert gas mobile phase and
solid/liquid stationary phase
z Gas-Liquid Chromatography:
– GC, wide application
– Liquid phase on WCOT or packed
column
z Gas-Solid Chromatography
– Physical absorption/desorption
– Limited application due to severe tailing
(nonlinear adsorption/desorption
process)
– Low molecular-weight gases

1
Principle of GLC

z Retention Volume VR = t R F
VM = t M F

z Corrected retention volume:

– Pressure drop correction factor (compressibility
factor), j 3[( P / p) 2 − 1]
j= i , VR0 = jt R F , VM
0
= jt M F
3
2[( Pi / p ) − 1]
z Specific retention volume, Vg:
– Mass, density of stationary phase
– Column temperature VR0 − VM
0
273 K 273
Vg = × = ×
mS Tc ρ S Tc

Instrumentation for GLC - Gas

Soap
z Carrier Gas: chemically inert gas as mobile phase bubble
flow
– He (most common), N2 and H2 in pressured tank
meter
– Pressure regulator, gauges and flow meter
– Pressure: 10 ~ 50 psi Æ 25 ~ 150 mL/min. with
packed column, or 1 ~ 25 mL/min. with capillary
column

T P − PH 2O
F = Fm × c ×
T P
• T difference
• Partial pressure of
H2O

Aqueous
solution of
soap or
detergent
Block diagram of a GC

2
Instrumentation for GLC - Injection

z Sample injection system

– High efficiency and
reproducibility:
z A suitable size of sample
z As a plug of vapor
– Microsyringes for liquid sample
– Rubber or silicone diaphragm
(septum)
– T: 50°C + Tb
– Packed C: 0.1 to 20 µL
– Capillary C: splitter is used to
deliver a faction of injection
1:50 to 1:500
– Auto sample: 0.5%

Instrumentation for GLC - Column

Effect of T on GC
z Column configuration
Isothermal at 45°C
– Packed column: traditional, 1- 5 m
– Open tubular or capillary column:
more common
– 2 to 100 m of stainless steel, Isothermal at 145°C
glass, fused silica or Teflon into
coils of 10 to 30 cm diameter
– Temperature control: thermostatic
TP from 30 to 180 °C
oven (0.1°C), slight above the
average Tb of the sample
– Temperature programming:
– T↑Æ tR ↓Æ Rs ↓

3
Instrumentation for GLC - Detection

z Ideal detector:
1. Adequate sensitivity: now 0.1 ng to fg solute/s
2. Good stability and reproducibility
3. Linear response to solute over several orders of
magnitudes
4. Temperature range from Troom to at least 400°C
5. Short response time that is independent of flow rate
6. High reliability and ease of use
7. Similarity in response toward all solutes or highly selective
and predictable response toward one or more classes of
solutes
8. Nondestructive of sample

Typical GC Detectors

4
Detectors - FID

z Flame Ionization Detector (FID):

– Most widely used, Air-H2 flame
– > 100 V between burner tip and
collector
– Organic pyrolyze Æ ions and e- Æ pA I
– Mass sensitive to #C atoms, not c
– Flow rate has little effect
– Insensitive to noncombustible gases
(CO2, SO2, NO2 and H2O)
– Insensitive to functional group
(carbonyl, alcohol, halogen and amine)
– High sensitivity: 10-13 g/s, large linear
range (107), low noise, rugged and
easy
– DA: destroy the sample

Flame ionization detector

Detectors - TCD

z Thermal Conductivity Detector Thermal

(TCD): one of the earliest conductivity
detector cell
– Electrically heated source (Pt, Au or
W wire, thermistor)
– T: thermal conductivity k of the
surrounding gas
– Twin detectors: minimize the
variation in T, P and power
– Single filament TCD: 10 Hz
Arrangement of the twin detectors
– k of He or H2 is 6 to 10 larger than
others
– Organic Æ k ↓ Æ T ↑
– A: simplicity, large range (105),
organic + inorganic
– DA: low sensitivity ng/mL, not for
capillary
Before/after sample injection

5
Detectors - ECD

z Electron Capture Detectors (ECD)

– Selectively to X-containing organic sample,
like pesticides
– Ni-63: radioactive β-emitter Æ electron Æ
ionization of carrier gas N2 Æ current
– High electronegative group (halogen,
peroxide, quinones and nitro group) in the
sample capture the electron Æ current ↓
– Highly selective and sensitive,
nondestructive
– Insensitive to amines, alcohols and
hydrocarbons
– Application in environmental sample
– Small linear range (102)
N2 or Ar/CH4 (carrier gas) + ß- ----> N+n
(ionized carrier gas) + e- (burst)

Detectors

z Thermionic detector:
– N- or P-containing compounds: 10X
N, 104 ~106 X C Æ P: 500×FID, N:
50×FID
– Column eluant + H2 + air Æ
electrically hearted Rb2SiO4 bead at
180 V (600 – 800°C) Æ ionization Æ
current ↑
– Organophosphorus pesticides and
pharmaceuticals
z Photoionization detector:
– UV light (10.2 eV H2 or 11.7 eV Ar)
Æ photoionization of molecular Æ
current ↑ between biased electrodes
– Aromatic and S, P easily
photoionized molecules
– LDR: <107

6
Detectors – ELCD, FPD

z Electrolytic conductivity detector (Hall detector)

– Halogen-, S- or N-containing sample Æ reaction
Ædissolved in liquid Æ solution conductivity changes
– X-: + H2 Æ HX Æ n-propyl alcohol (H2S and NH3 weak
ionization): DL ~ 0.5 pg Cl/s, LDR ~ 106
– S-: + air Æ SO2 Æ methyl alcohol with little water Æ SO3-
and SO4- (N2 and NOx little ionization; postreaction scrubber
Æ remove HX) DL ~ 2 pg S/s, LDR ~ 103
– N-: + H2 Æ NH3 Æ water with little organic solvent Æ NH4+
(postreaction scrubber Æ remove HX and H2S): DL ~ 4 pg
N/s, LDR ~ 103
– Dry ELCD: detect the product ion in gas phase
z Flame photometric detector (FPD):
– S and P – compounds
– H2 + air Æ HPO species Æ 510, 526 nm
– H2 + air Æ S2 Æ 394 nm
– X-, N-, Sn, Cr, Se and Ge

Detectors (MS)
z Hyphenated methods:
– IR, UV-Vis, NMR, AES, MS
electrochemistry
z Atomic Emission Detector:
– Column eluant Æ MIP (microwave
induced plasma) Æ atomization Æ
diode array or CCD
– Element-selective detector:
different λ Æ different elements
z Mass spectrometry: (GC/MS)
– Inlet system: normal pressure
after GC and vacuum (10-5 to 10-8
torr) in MS
– Ionization source+ Analyzer + Ion
detector
– total-ion chromatogram or selective-
ion monitoring

7
GLC Columns

z Open tubular or capillary column:

– Wall-coated open tubular (WCOT)
z Capillary coated with a thin layer of stationary phase
z Old: stainless steel, Al, Cu, plastic, glass.
– Support-coated open tubular (SCOT)
z Inner surface of the capillary is lined with a thin film
(~30µm) of a support materials, like diatomaceous earth
z Holds several times more stationary phase Æ sample
capacity ↑
z Lower efficiency than WCOT, higher than packed column
– Fused-silica open tubular column (FSOT):
z Physical strength, low reactivity, flexibility. 0.32 to 0.25 mm
z High R: 0.2 to 0.15 mm

GLC Column

z Packed column:
– Glass or metal tube:
z 2 ~ 3 m and dinside of 2 ~ 4 mm.
df 0.05 ~ 1 µm
– Densely packed supporting
material:
z uniform, fine spherical, >
1m2/g, inert at high T,
uniformly wetted, good
mechanical strength
z Diameter ↓ Æ efficiency ↑ Æ
pressure ↑ (∝ d2)
z GC: pressure < 50 psi Æ 60
~80 mesh or 80 ~ 100 mesh
Photomicrograph of a diatom, 500

8
GLC Column - L

z Liquid Stationary phase:

– Desirable properties: low volatility (Tb 100°C higher), thermal stability,
chemical inertness and solvent characteristics (k and α)
– Separation Æ different k Æ compatibility with the stationary phase (like
dissolves like)
– Polarity Æ dipole moment, like –CN, -CO, -OH
– Polarity of stationary phase matches that of the sample Æ tR is
determined by the Tb of the components
– Bonded or cross-linked stationary phase
– Film thickness, df: 0.1 to 5 µm Æ tR, the capacity

Aliphatic hydrocarbons < olefins < aromatic

hydrocarbons < halides < sulfides < ethers <
nitro compounds < esters, aldehydes, ketones <
alcohols, amines < sulfones <sulfoxides <
amides < carboxylic acids < water

Common liquid stationary phases for GC

Common Maximum
Common applications
Stationary phase trade name T, °C

General-purpose nonpolar phase,

polydimethyl siloxane OV-1, SE-
350 hydrocarbons, polynuclear aromatics,
(-CH3) 30
steroids, PCBs
5% phenyl-polydimethyl OV-3, SE- Fatty acid methyl esters, alkaloids, drugs,
350
siloxane (-C6H5) 52 halogenated compounds
50% phenyl-polydimethyl
OV-17 250 Drugs, steroids, pesticides, glycols
siloxane

50% trifluoropropyl- 200 Chlorinated aromatics nitroaromatics, alkyl

OV-210
polydimethyl siloxane (-C3H6CF3) substituted benzenes

Polyethylene glycol Carbowax Free acids, alcohols, ethers, essential oils,

250
(OCH2CH2)n 20M glycols
50% Cyanopropyl- 240 Polyunsaturated fatty acids, rosin acids,
OV-275
polydimethyl siloxane (-C3H6CN) free acids, alcohols

9
Application of GLC

z Species volatile and thermally stable

Log(tR’)
z Qualitative analysis: purity
determination
– Confirm the presence of absence of a
suspected compounds
– Determine an unknown: hyphenated GC #C atoms
with other methods
– Retention index: Normal alkanes
standards: #CX100
z Quantitative analysis:
– Area (preferred) of a peak vs. C: linearly
– Calibration of standards: straight line
through origin
– Internal standard method

Gas-Solid Chromatography
(crystalline aluminosilicates [zeolites]
z Based on absorption of
gaseous substances on
solids surfaces
z Kc is larger than gas-
liquid
z Separation of hard-to-
retain species, like air,
NxOy, H2S, CS2, CO,
CO2 and noble gas
z Packed, open tubular,
porous-layer open
column

10