CA180-917A

GC-No.1

Analysis of Inert Inorganic Gases

Gas chromatography is essential to analysis of inert inorganic refineries and petrochemical plants, and for
gases. It is always used for routine analysis in petroleum determination of gas compositions and purities in gas
works.

CONTENTS

page page
1. Simultaneous Analysis of H2, O2, N2, 10. Analysis of Impurities in Neon………... 5
CH4, and CO with Argon Carrier………. 2
2. Rapid Analysis of O2, N2, CH4 and CO. 2 11. High Sensitivity Detection of CO and
CO2 in H2 or CH4 with Reaction
Furnace………………………………… 5
3. Programmed Temperature GC of 12. Analysis of Trace CO2 in Ar with
Inorganic Gases, Gaseous Reaction Furnace…………………….. 5
Hydrocarbons and Water……………….. 2
4. Analysis of Impurities (H2, O2, N2, Kr) in 13. Analysis of Trace Ammonia in Water... 6
Xenon……………………………………... 3
5. Analysis of H2 in He…………………….. 3 14. Simultaneous Analysis of Inorganic
Gases and Lower Hydrocarbons with
Parallel Column-Parallel Flow System 6
6. Complete Separation of H2, N2, O2, Ar 15. Complete Separation of H2, O2, N2,
and CO with Porapak Q Column………. 3 CO, CO2, CH4, C2H6 and C2H4 by
Applied Flow System………………….. 7
7. Complete Separation of H2, Ar, O2, N2 16. Simultaneous Analysis of Inorganic
and CO with Molecular Sieve 5A Column 4 gases and C1~C4 Hydrocarbons…… 7
8. Analysis of Trace N2 in Ar……………… 4
9. Analysis of NO in N2…………………….. 4
 1. Simultaneous Analysis of H 2, O2 , N2 , CH4, and CO, with
Argon Carrier
As shown in Table 1, H2 is sensed at a far higher sen-
sitivity compared with the other compounds, when argon is
used as the carrier gas. Methane is detected at the next
highest sensitivity and O2, N2 , and CO are sensed at almost
equal sensitivities. . Operational Conditions
Table 1. Relative Molar Responses for Inorganic Gases and Column: Molecular Sieve 5A, 80/100
Lower Hydrocarbons with Argon Carrier mesh, 3mm I.D.x2m
long
Column temp.: 60°C
Injection port
temp.: 60°C
Detector temp.: 60°C
Carrier gas: Ar 50ml/min.
Detector: TCD
Bridge current: 45 mA
Range: 4 mV
Chart speed: 5 mm/min.

Fig. 1 Simultaneous
Analysis of H2, O2, N2,
CH4 and CO with
Note: Measured with a s tandard gas containing 10% of H2 and Argon Carrier
2~ 10% of other gases.

2. Rapid Analysis of H2, O2, N2, CH4, and CO

Town gas was rapidly analyzed for H2, O 2, CH 4 and CO,

with an ordinary gas chromatograph. (The peak for H2 is not
quantitative because helium was used as the carrier gas.)
. Operational Conditions
As shown in Fig. 2, all components are completely Column: Molecular Sieve 13X, 80/100
separated and CO is eluted in as short as 45 seconds. mesh, 3 mm I.D. x 0.75
The data shows that analysis time can be reduced m
considerably by selecting appropriate operational conditions, Column temp.: 80°C
Injection port
even with an ordinary gas chromatograph.
temp.: 80°C
Detector temp.: 100°C
Carrier gas: He 60 ml/min.
Detector: TCD
Bridge current: 80 mA
Range: 16 mV
Chart speed: 40 mm/min.

Fig. 2 Rapid Analysis

3. Programmed Temperature GC of Inorganic Gases, o f H2, O2, N2,
Gaseous Hydrocarbons, and Water CH4, and CO

A Porapak Q column and a Porapak R column were

connected in series, and temperature-programmed.
CO2, N 2 O, C 2H 4, C 2H6 , etc. are completely separated.

Operational Conditions
Column: Porapak Q, 50/80 Detector temp.: 150°C
mesh, 3 mm 1.0. x Carrier gas: He 44 ml/min.
3 m, and Porapak Detector: TCD
R, 50/80 mesh, Bridge current: 120 mA
3mml.D.x3m Range: 32mV
Column temp.: 40°C à150°C at Chart speed: 10 mm/min.
10°C/min.
Injection port temp.: 30°C

Fig. 3 Programmed Temperature GC of

Inorganic Gases, Gaseous Hydrocarbons,
and Water

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4. Analysis of Impurities (H2, O2, N 2, and Kr) in Xenon

. Operational Conditions
Column: Molecular Sieve 5A, 60/80 mesh,
3 mm 1.0. x5m
Column temp.: 50°C
Injection port
temp.: 30°C
Detector temp.: 100°C
Carrier gas: He 55 ml/min.
Detector: TCD
Bridge current: 120 mA
Range: 1 mV
Chart speed: 10 mm/min.

Fig. 4 Analysis of Impurities (H2,

O2, N2, and Kr) in Xenon
5. Analysis of H2 in He

Helium and hydrogen can be separated only by a long

Molecular Sieve 5A column. If one of the gases is far greater
in quantity, however, a comp1ete separation is very difficult.
. Operational Conditions
In the example shown in Fig. 5, though the content of H2 is
Column: Molecular Sieve 5A, 60/80
as small as about 100 ppm, almost a half of the H2 peak is
covered by the He peak despite of such a small sample mesh, 3 mm I.D.x11
mm
volume, 0.1 mi. Column temp.: 30°C
The separation can be improved when almost all of the Injection port
He is removed by means of a valve and then separation is temp.: 30°C
made again by another Molecular Siever column Detector temp.: 60°C
Carrier gas: N2 30 ml/min.
Detector: TCD
Bridge current: 100 mA
Range: 1 mV
Sample size: 0.1 ml
Chart speed: 5 mm/min.

Fig. 5 Analysis of H2 in He
When satisfactory separation cannot be achieved with column temperature kept at, or above, the room temperature, the cryogenic
work technique is often used. Examples are given in Chapters 6, 7, 8, and 9.

6. Complete Separation of H2, N2 , O 2, Ar, and CO .

with Porapak Q Column
The five gases are completely separated by a Porapak
Q column kept in a dry ice-acetone bath (-70°C) Operational Conditions
Column: Porapak Q, 50/80
The elution order is N2, O2, and Ar, which is different mesh, 3mml.D.x6m
Column temp.: -70°C (Dry
from that of a MolecularSiever 5A column. (See Fig. 7). ice-acetone bath)
Injection port
temp.: 30°C
Detector temp.: 60°C
Carrier gas: He
Detector: TCD
Bridge current: 120 mA
Range: 16 mV Fig. 6 Complete Separation of H2,
Sample size: 2 ml
N2, 02, Ar, and CO
Chart speed: 20 mm/min.

3
7. Complete Separation of H2, Ar, O2,
N2, and CO with Molecular Sieve 5A Column

The five gases are completely separated on a . Operational Conditions

Molecular Sieve 5A column, with a cryogenic work Column: Molecular Sieve 5A, 60/80
attachment. mesh, 3 mm I.D. x 3m
Column temp.: -46°C à 82°C at
Note that the elution order of Ar, O2 and N2 is 10°C
reverse of that from a Porapak Q column (Fig. 6)
Injection port
temp.: 40° C
Detector temp.: 100°C
Carrier gas: He 54 ml/min.
Detector: TCD
Bridge current: 180 mA
Range: 4, 256, 8 mV
Chart speed: 5 mm/min.
Fig. 7 Complete Separation of H2, Ar, O2 ,
N2, and CO

8. Analysis of Trace N2 in Ar

Nitrogen contained in argon as an impurity was

determined under the same operational conditions
as the datum in Fig. 6. . Operational Conditions
The 90 ppm N2 is completely separated from Column: Porapak 0,80/100 mesh, 3
argon. mm I.D. x 6m
Column temp.: -70°C (dry ice-
When a preamplifier is used to obtain a higher
methanol bath)
sensitivity, nitrogen of a few ppm concentration can
be detected. Injection port
temp.: Room temp.
Detector temp.: 60°C
Detector: TCD
Bridge current: 180 mA
Range: 1 mV
Sample size: 5 ml
Chart speed: 10 mm/min.

Fig. 8 Analysis of Trace N2 in Ar.

9. Analysis of NO in N2

About 1000 ppm NO in N 2 was determined.

When NO is contained in an inert gas, the . Operational Conditions
detection limit is about tens of ppm. If it is Column: Chromosorb 104, 60/80 mesh,
contained in air or emission from a flue, such a low 3 mm I.D. x 2 m
Column temp.: -70°C (dry ice- acetone
concentration of NO cannot be determined by gas
bath}
chromatography.
Injection port
temp.: 70° C
Detector temp.: 70°C
Carrier gas: He
Detector: TCD
Bridge current: 140 mA
Range: 1 mV
Sample size: 2ml
Chart speed: 10 mm/min.

Fig. 9 Analysis of NO in N2

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10. Analysis of Impurities in Neon

Impurities, O2 + Ar and N 2 in neon

are recorded.

. Operational Conditions
Column: Molecular Sieve 5A 60/80
mesh, 3 mm I.D. x
2m
Column temp.: 55°C
Injection port
temp.: 60°C
Detector temp.: 55°C
Carrier gas: He 40 ml/min.
Detector: TCD
Bridge current: 150 mA
Range: 2 mV
Sample size: 5 ml
Chart speed: 10 mm/mln. Fig. 10 Analysis of Impurities in Neon

One of the popular methods to analyze CO and CO2 of a concentration below the detection limit of TCD is to connect a reaction tube
after the GC column and reduce CO and CO2 into CH4, which is then detected at a high sensitivity by an FID. Examples are given in
Chapters 11 and 12.

. Operational Conditions
11. High Sensitivity Detection of CO and CO2 in Column: Porapak Q, 50/80
H2 or CH4 with Reaction Furnace mesh,3mm l.D.x
6mm
Column temp.: 45°C
Injection port
Trace quantities of CO and CO2 contained in H 2 temp.: Ambient
(or CH4) were reduced into CH 4 and detected by a Detector temp.: 100°C
flame ionization detector. Carrier gas: H2 40 ml/min.
Detector: FID
Hydrogen was used as the carrier gas, and nickel Range: 0.04V and 5.12V
as the reducing catalyst. Input attenuator: 103 MΩ
The detection limits for CO and CO2 are ppm Chart speed: 10 mm/min.
level or lower. Reaction furnace: RAF-1
Catalyst: Nickel held on Fig 11 High sensitivity Detection of
Shimalite, 3 mm I.D CO and CO2 in H2 or CH4
I.D x 20cm
Reaction furnace temp.: 650°C

12. Analysis of Trace CO2 in Ar . Operational Conditions

Column: Activated Charcoal, 60/80
with Reaction Furnace mesh 3 mm I.D. x2
m
Column temp.: 95°C
Injection port temp.: 30°C
Detector temp.: 100°C
Carrier gas: H2 40 ml/min.
Detector: FID
Range: 0.04V
Input attenuator: 103MΩ
Chart speed: 10 mm/min.
Reaction furnace: RAF-1
Catalyst: Nickel held on
Shimalite,3mm
I.D.x20cm
Reaction furnace temp.: 600°C Fig. 12 High Sensitivity Analysis of
Trace CO2 in Ar

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13. Analysis of Trace Ammonia in Water

About 1400 ppm of NH3 contained in water was determined.

The Chromosorb 103 column, which is generally used for
analysis of alkaline low-boiling compounds, is especially
effective for analysis of ammonia. It ensures a good
quantitativeness for ammonia of a few ppm quantity level.

. Operational Conditions
Column: Chromosorb 103, 80/100
mesh, 3 mm I.D. x 3
m, glass
Column temp.: 120°C
Injection port
temp.: 160°C
Detector temp.: 200°C
Carrier gas: He 60 ml/min.
Detector: TCD
Bridge current: 70 mA
Range: 64 mV
Chart speed: 10 mm/min.
Fig. 13 Analysis of Trace Ammonia in Water

In analysis of samples containing inorganic gases and lower hydrocarbons, applied flow systems are often used. Typical examples
are given in Chapters 14, 15 and 16.

14. Simultaneous Analysis of Inorganic Gases and Lower

Hydrocarbons with Parallel Column- Parallel Flow
System

A flow system as shown in Fig. 14, with the flow restriction

adjusted, permits complete separation of O2, N 2, CO, CO2, CH4,
C2H6, C 2H4, C 3H6, and C 3H8 with a single sample introduction.
Fig. 15 shows the chromatogram of analysis repeated
at 16 minute cycle by an automatic sampler.

Fig. 14 Parallel Column- Parallel Flow System

. Operational Conditions
Column: See Fig. 14
Column temp.: 60°C
Injection port
temp.: 60°C
Detector temp.: 60°C
Carrier gas: He 80 ml/min.
Detector: TCD
Bridge current: 70 mA
Range: 16 mV
Chart speed: 5 mm/min.

Fig.15 Simultaneous Analysis of Inorganic Gases and Lower Hydrocarbons

with Parallel Column- Parallel Flow System

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 15. Complete Separation of H2 , O 2, N2 , CO, CO2 ,
CH4, C2 H6 and C2H4 with Applied Flow
System

A mixture sample of H 2, O2, CO, CO 2, CH 4, C 2H6, and

C2H4 can be completely separated by the use of argon
carrier and the flow system shown in Fig. 16.
First, a sample is separated into H 2 + O2 + N 2 + CO +
CH4 group and C 2 H6 + CO2 + C 2 H4 group, by the Silica
Gel-1 column.
Then, when the former group (H2~CH4) has entered
the Molecular Sieve 5A column, the 4-way valve is
Fig. 16 Applied Flow System (1)
changed over to the position of the dotted line. Thus the
H2~CH4 group is separated into five peaks by the
Molecular Sieve 5A column, while the C 2H6~C2H4 group
is separated into the three components by the Silica
Gel-2 column. The two carrier gas streams are
combined into one stream and all the components are
sensed by the TCD. . Operational Conditions
With a suitable flow restriction, the eight components Column: See Fig. 16
Column temp.: 60°C
are completely separated, as shown in Fig. 17. Injection port
temp.: 60°C
Detector temp.: 70°C
Carrier gas: Ar
Detector: TCD
Bridge current: 50 mA
Range: 16 mV
Chart speed: 10 mm/min.

Fig. 17 Complete Separation of H2,

O2, N2, CO, CO2, CH4,
C2H6, C2 H4, with
16. Simultaneous Analysis of Inorganic Gases and C1 ~ C4 Applied Flow System
Hydrocarbons

When it is necessary to separate and determine higher
hydrocarbons, up to C4, the flow system shown in Fig. 18 is
recommended.
Sample is first introduced into the SN (sebaconitrile)
column and separated into the H 2~C2H4 group and the
C3H8~1,3-C4 H6 group. Then, the former group is introduced
into the Silica Gel column and the latter group into the SN
column of the GC-1, by the timely operation of the 4 -way valve.
The H2~C2H4 group that has entered the Silica Gel
column is separated into H 2~CH4 group and the C 2 H6 + CO2 +
C2H4 group, which are then separately analyzed by the
Molecular Sieve 5A column and the Silica Gel column, through
timely operation of the 4-way valve, and are sensed by the
TCD of the GC-2, in the same way as described in the
previous chapter.
The chromatograms obtained by the two gas
chromatographs are shown in Fig. 19. The separation is
complete.

Fig. 18 Applied Flow system (2)