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Gas Chromatography
Len Sidisky, Greg Baney, Katherine Stenerson,
and James L. Desorcie
Supelco, Div. of Sigma-Aldrich, Bellefonte, PA 16823 USA
www.sigma-aldrich.com
T411126
Abstract
Nitrogen, helium and hydrogen are the most commonly used carrier gases for
capillary gas chromatographic analyses. We will compare the performance of
these gases focusing on their affects on the speed of analysis, selectivity,
resolution, sensitivity, and safety of use. Theoretical and practical examples
will be presented.
2
Introduction
Carrier Gases for GC
The carrier gas (mobile phase) for gas chromatography should be an inert
gas that does not react with the sample components.
The GC carrier gas should contribute minimally to the partitioning process.
This differs from the mobile phase in liquid chromatography.
In GC the carrier gas is simply stated as just a carrier to transport the
vaporized solute molecules through the column during the partitioning
process.
3
Carrier Gases for GC (contd.)
4
Efficiency Effects of Carrier Gases
Carrier gas linear velocity plays a significant role in the resulting efficiency of
a chromatographic system.
The optimal carrier gas linear velocity is characteristic for each gas.
van Deemter curves and Golay Plots are used to demonstrate optimal
carrier gas linear velocities.
van Deemter plots are used for packed columns since the A term for eddy
diffusion is present.
Golay plots are used for capillary columns (open tubular) and the A term is
dropped.
5
van Deemter Plot
H=A + B/ + c
HETP has also been used for H
A is the Eddy Diffusion term
B is the Molecular Diffusion term
C is the Resistance to Mass Transfer Term
is the carrier gas linear velocity
7
Typical Golay Curves
8
Rate of Band Broadening
2D g
2
2 k d
2
r 1 6k 11k 2
f
H
3 1 k ) 2 D liq 24 D g 1 k
9
Retention Time Effects
10
SUPELCOWAX 10 Isothermal 25 cm/sec.
Helium Carrier
k(C20)=6.10
CE=86% N=119924
C20
0 2 4 6 8 10 12 14 16
Time (min) 11
SUPELCOWAX 10 Isothermal 50 cm/sec.
Helium Carrier
k(C20)=6.10
CE=43% N=60633
C20
12
SUPELCOWAX 10 Isothermal 50 cm/sec.
Hydrogen Carrier
k(C20)=6.03
CE=85% N=114344
C20
k(C20)=6.03
CE=50% N=70223
C20
0 10 20 30
14
Time (min)
The four figures demonstrate the affect of carrier gas linear velocity on the
time of analysis and the efficiency of the chromatography. Helium carrier gas
is near optimum linear velocity at 25 cm/sec. as shown in the first figure. The
analysis time is approximately 14 minutes and the % coating efficiency (CE)
is 86%. When we double the helium carrier gas velocity to 50 cm/sec. we
now decrease the analysis time to about 7 minutes and also see a significant
reduction in the column efficiency to about 43%. This is due to operating the
carrier gas on the far right side of the Golay plot. This demonstrates the
mass transfer term affect on the column performance. A similar effect is
demonstrated for the hydrogen carrier gas analysis. Hydrogen is optimum
near 50 cm/sec. as shown in the third figure. When we lower the hydrogen
carrier gas linear velocity to approximately 10 cm/sec. we see the
corresponding increase in the retention time and a large drop off in the
efficiency of the column as shown in the fourth chromatogram. This
demonstrates the effect of operating on the far left side of the Golay plot
where the molecular diffusion term is the major factor.
15
Linear Velocity/Flow Control
16
Carrier Gas Viscosity
17
Carrier Gas Viscosity (P)
18
Carrier Gas Viscosity & Temperature
350
300 Helium
Viscosity (P)
250 Nitrogen
200
Hydrogen
150
100
50
0
0 50 100 150 200 250 300 350
Temperature (C)
19
Carrier Gas Viscosity & Temperature (contd.)
60
Linear Velocity (cm/sec)
50
40
Hydrogen
30
Helium
20
10
Nitrogen
0
0 100 200 300 400
Temperature (C)
20
Carrier Gas Viscosity & Temperature (contd.)
21
Bacterial Acid Methyl Esters
25 cm/sec. Hydrogen Equity-1
0 10 20
Time (min) 22
Bacterial Acid Methyl Esters
50 cm/sec. Hydrogen Equity-1
0 2 4 6 8 10 12 14 16 18
Time (min)
23
Run Conditions
24
Linear Velocity & Retention Time
25
Safety Concerns with Carrier Gases
26
Summary
Carrier gases in gas chromatography are used to move the solutes through
the column.
Helium, hydrogen and nitrogen are the most widely used gases.
Nitrogen provides the best efficiency but is extremely slow.
Helium provides good efficiency and analysis times but is an expensive
choice for a carrier gas.
Hydrogen provides the fastest analysis times over a broad linear velocity
range.
Temperature programming changes the viscosity of a carrier gas resulting in
a decrease in linear velocity/flow over the programmed range when run in a
constant pressure mode.
Hydrogen is the best choice for capillary GC due to diffusivity and a broad
working range as long as safety concerns and proper controls are in place.
27