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Carrier Gas Selection for Capillary

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.

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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.

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Carrier Gases for GC (contd.)

Carrier gases are compressible gases that expand with increasing


temperature. This results in a change in the gas viscosity.
The selection and linear velocity of the carrier gas will affect resolution and
retention times.
Carrier gases should be inert to the stationary phase and free of detectable
contaminants.

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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.

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van Deemter Plot

Average Linear Velocity


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Simplified van Deemter Equation

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

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Typical Golay Curves

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Rate of Band Broadening

Capillary Columns - Golay:

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

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Retention Time Effects

Analyses can be either isothermal or temperature programmed runs in GC.


The carrier gas linear veloctiy can influence the overall time of analysis and
the efficiency of the separations. The following equation demonstrates the
affect of linear velocity on retention time.
tr = L (k+1)

where
tr = retention time
L = column length
k = retention factor
= carrier gas linear velocity

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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

1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0


Time (min)

12
SUPELCOWAX 10 Isothermal 50 cm/sec.
Hydrogen Carrier

k(C20)=6.03
CE=85% N=114344

C20

1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0


Time (min)
13
SUPELCOWAX 10 Isothermal 10 cm/sec.
Hydrogen Carrier

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.

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Linear Velocity/Flow Control

Linear velocity or flow can either be run in a constant pressure or constant


flow mode.
This is important in temperature programmed analyses. In the constant
pressure mode, the column head pressure is set at a temperature and the
pressure remains constant throughout the analysis. This can result in linear
velocity changes especially over a wide temperature programming range.
In the constant flow mode, the column head pressure will change throughout
a temperature programmed analysis in order to keep the carrier gas flow at a
constant flow rate.

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Carrier Gas Viscosity

Carrier gas viscosity is a temperature dependent parameter.


As temperature increases, the viscosity of the gas increases.
When using a constant pressure mode for carrier gas and temperature
programming, the viscosity of the gas will increase and the average linear
velocity will decrease.

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Carrier Gas Viscosity (P)

Temperature C Nitrogen Helium Hydrogen


0 167.36 186.62 83.99
20 175.03 194.60 87.64
40 182.71 202.59 91.30
60 190.38 210.57 94.95
120 213.41 234.53 105.02
160 228.76 250.50 113.23
200 244.11 266.48 120.53
240 259.46 282.45 127.84
260 267.14 290.43 131.5
280 274.81 298.42 135.15
300 282.49 306.41 138.81
Adapted from Ettre & Hinshaw, Basic Relationships of Gas Chromatography, 1993, Advanstar.

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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)

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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)

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Carrier Gas Viscosity & Temperature (contd.)

Hydrogen Experimentally determined tR &


Equity-1
40 C tR = 1.025 minutes and = 48.78 cm/sec.
300 C tR = 1.553 minutes and = 32.20 cm/sec.

Linear velocity () change was 34.0% over a 260 C temperature window

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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)
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Run Conditions

column: Equity-1, 30 m x 0.25 mm I.D. x 0.25 m


oven: 150 C (4 min.), 8 C/min. to 250 C (10 min.)
inj.: 250 C
det.: FID, 250 C
carrier gas: hydrogen as listed
injection: 1 L, 100:1 split
liner: 4 mm I.D. cup style
sample: 10 mg/mL bacterial acid methyl ester standard in methyl caproate, Cat. No. 47080-U

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Linear Velocity & Retention Time

tR is inversely proportional to double , cut tR in half for an isothermal


analysis.
Retention time in temperature programmed analyses is primarily
dependent on programming rate.
Viscosity impacts the linear velocity of the carrier gas over a wide
temperature programming range and can change peak elution patterns.
Constant flow mode can be used to minimize the changes in carrier gas
viscosity for temperature programmed analyses.

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Safety Concerns with Carrier Gases

Safety concerns with nitrogen and helium are minimal.


Both are compressed gases and can cause asphyxiation if rapidly released
in a small confined area.
Hydrogen is combustible over a concentration range of 4% to 74.2% by
volume.
Combustion can occur due to rapid expansion of the gas from a high
pressure cylinder.
Hydrogen is a highly diffusive gas in air.
Hydrogen generators and EPC typically have automatic built-in shut down
devices when a leak is detected.

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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.

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