TRACE CO AND CO2 IN HYDROGEN AND

LIGHT GASEOUS HYDROCARBONS BY GC

UOP Method 603-88
SCOPE
This method is for determining low concentrations (0.5 to 500 mol-ppm) of carbon monoxide (CO) and
carbon dioxide (CO2) in high purity hydrogen and other gas-phase samples. The lower limit of detection for
either CO or CO2 in hydrogen is 0.5 mol-ppm. The lower limit of detection for CO in samples containing
high concentrations of oxygen, argon or nitrogen is 5 mol-ppm. Methane at concentrations above 5 mol-%
will interfere with the determination of carbon dioxide.

OUTLINE OF METHOD
A reproducible volume of sample is injected into a gas chromatographic column packed with polyester
resin. The components of interest are individually resolved and passed through a catalytic reactor where the
carbon dioxide and carbon monoxide are converted to methane. The converted compounds are passed
through a molecular sieve column to absorb any water formed and to reduce pressure surges in the
chromatographic system. A hydrogen flame ionization detector is used to detect the methane produced.
Concentrations of CO and CO2 are calculated using the external standard method of quantitation.

APPARATUS
Chromatographic column No. 1, 9.1 m of 1/16-inch OD x 0.050-inch ID stainless steel tubing, filled with
80-100 mesh Porapak Q, Alltech Associates, or equivalent
Chromatographic column No. 2, 3 m of 1/16-inch OD x 0.050-inch ID stainless steel tubing, filled with
60-80 mesh 13X molecular sieves, Alltech Associates, or equivalent
Gas chromatograph, capable of isothermal oven temperature control at 30 C, temperature programmable
to 350 C and equipped with a flame ionization detector that will give a minimum response of 10 times
the background noise level for 1 mol-ppm CO
Heating cartridge, 200 watt, 50-mm long by 10-mm OD, ETS Equipment, or equivalent
Integrator, electronic, or equivalent, for obtaining peak areas
Insulation, fiberglass, capable of 600 C, A & M Insulation, or equivalent
IT IS THE USER'S RESPONSIBILITY TO ESTABLISH APPROPRIATE PRECAUTIONARY PRACTICES AND TO
DETERMINE THE APPLICABILITY OF REGULATORY LIMITATIONS PRIOR TO USE. EFFECTIVE HEALTH AND
SAFETY PRACTICES ARE TO BE FOLLOWED WHEN UTILIZING THIS PROCEDURE. FAILURE TO UTILIZE THIS
PROCEDURE IN THE MANNER PRESCRIBED HEREIN CAN BE HAZARDOUS. MATERIAL SAFETY DATA SHEETS
(MSDS) OR EXPERIMENTAL MATERIAL SAFETY DATA SHEETS (EMSDS) FOR ALL OF THE MATERIALS USED IN
THIS PROCEDURE SHOULD BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION
EQUIPMENT (PPE).
COPYRIGHT 1971, 1988 UOP LLC
ALL RIGHTS RESERVED

UOP Methods are available through ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken PA 19428-2959,
United States. The Methods may be obtained through the ASTM website, www.astm.org, or by contacting Customer Service at
service@astm.org, 610.832.9555 FAX, or 610.832.9585 PHONE.

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Hydrogenation tube, 30 cm of 1/16-inch OD x 0.050-inch ID, stainless steel tubing

Recorder, 1-mV full-scale, 1-sec or less full-scale response
Regulator, air, two-stage, high purity, Matheson, Model 3104-590, or equivalent
Regulator, hydrogen, two-stage, high-purity, Matheson, Model 3104-350, or equivalent
Regulator, nitrogen, two-stage, high-purity, Matheson, Model 3104-580, or equivalent
Sample loop, 1-mL, Valco Instrument, Part. No. SLIKC6UW, or equivalent
Temperature controller, Valco Instrument, Model ITC K-10-999, or equivalent
Valve, backflush, Valco Instrument, Model C8UWP, or equivalent
Valve, gas sampling, Valco Instrument, Model C6UWP, or equivalent

REAGENTS AND MATERIALS

All reagents shall conform to the specifications established by the Committee on Analytical Reagents of
the American Chemical Society, when such specifications are available, unless otherwise specified.
References to water mean deionized or distilled water, except where noted.
Air, zero gas, total hydrocarbons less than 2.0 ppm as methane
Blends
No. 1: 5 mol-ppm CO, 5 mol-ppm CO2 and 25 mol-ppm CH4 in hydrogen, Matheson, or equivalent
No. 2: 200 mol-ppm CO, 200 mol-ppm CO2 and 200 mol-ppm CH4 in hydrogen, Matheson, or
equivalent
Glass wool, laboratory
Hydrogen, zero gas, total hydrocarbons less than 0.5 ppm as methane
Hydrogenation catalyst, nickel on kieselguhr, Aldrich, Cat. No. 20, 878-7, or equivalent
Nitrogen, zero gas, total hydrocarbons less than 0.5 ppm as methane

PROCEDURE
Operating Conditions
The recommended operating conditions for this analysis are given in the following Table. Other
conditions may be used provided they produce the required sensitivity and chromatographic separations
equivalent to those shown in the Typical Chromatogram (Fig. 2).

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Table
Carrier gas
Carrier gas flow rates (A & B)
Air flow rate*
Makeup hydrogen flow rate*
Makeup nitrogen flow rate*
Detector temperature
Column temperature
Hydrogenator temperature
Recorder chart speed
Sample size
______________________
*See instrument manufacturers specifications

hydrogen
30 mL/min
240 mL/min
10 mL/min
40 mL/min
150 C
30 C
480-500 C
0.5 cm/min
1 mL

Preparation of Hydrogenator
Install a plug of glass wool approximately 30 mm from one end of the hydrogenation tube. Pour in the
hydrogenation catalyst to produce a catalyst bed approximately 25 mm in length and install a second glass
wool plug to hold it in place.
Coil the hydrogenation tube tightly around the heating cartridge so that the incoming hydrogen gas will
be pre-heated in the empty portion of the tube before it passes through the catalyst. Wrap the assembly with
insulation, and connect the heating cartridge to the temperature controller. Install in the instrument as
described under Preparation of Apparatus.

Column Conditioning
Individually pre-condition the chromatographic columns in the chromatograph column oven using the
following procedures:
Column No. 1 (Porapak Q) Establish a hydrogen flow of 30 mL/min and program the temperature
from 70 to 250 C at 4 C/min and hold it at this temperature for 8 hours. Allow the column to cool to
ambient temperature and remove it from the chromatograph.
Column No. 2 (13X Molecular Sieves) Establish a hydrogen flow of 30 mL/min, program the
temperature from 70 to 350 C at 2 C/min and hold it at this temperature for 2 hours. Allow the column to
cool to ambient temperature and immediately install Columns No. 1 and No. 2 in the instrument as
described under Preparation of Apparatus.

Preparation of Apparatus
Assemble the apparatus as shown in the flow diagram, Fig. 1. The solid lines in the diagram indicate the
direction of gas flow in the forward position, whereas the broken lines indicate the direction of flow in the
backflush position. CAUTION: Hydrogen carrier gas leakage into the confined volume of the column oven
can cause a violent explosion. It is, therefore, mandatory to test for leaks each time a connection is made
and periodically thereafter.
Set the backflush valve in the solid-line position and establish the proper carrier gas flow rate through the
columns. Set carrier gas flow A and measure it at the detector before the H2 makeup is added. Rotate the
backflush valve to the broken-line position and set carrier gas flow B, which is measured at the vent exit of
the backflush valve.
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While maintaining the backflush valve in the broken-line position, heat the hydrogenator to 600 C, and
hold this temperature for 2 hours. Reduce the temperature of the hydrogenator to 500 C and rotate the
backflush valve to the solid-line position.

Chromatographic Technique
Set the proper operating conditions and purge the columns with hydrogen until a stable recorder baseline
is established.
Set the gas sampling valve and the backflush valve in the solid-line position. Purge the sample loop with
the sample to be analyzed. Turn off the sample purge, allow several seconds for the pressure to equilibrate
and inject the sample by rotating the gas sampling valve to the inject (broken-line) position. Start the
integrator and mark the time of injection on the strip chart recorder. See Fig. 2 for a typical chromatogram.
After the converted CO2 peak has eluted, set the backflush valve in the broken-line position and backflush
any heavier components from the column, see Notes 1 and 2.
Allow the backflush valve to remain in the broken-line position until the backflush peak has completely
eluted. Determine the peak areas of the converted CO and CO2 from the resultant chromatogram.

Calibration
Response factors are required to relate the peak areas of the converted CO and CO2 to mol-ppm. A
standard blend containing 5 mol-ppm CO, 5 mol-ppm CO2 and 25 mol-ppm methane in hydrogen is used
for calibration of samples containing low concentrations of CO and/or CO2, while a blend containing 200
mol-ppm CO, 200 mol-ppm CO2 and 200 mol-ppm methane is used for samples containing high
concentrations of CO and/or CO2. The methane is included in the blends to monitor separation efficiency of
the chromatographic columns and the hydrogenation efficiency of the reactor.
Analyze the appropriate blend as described under Chromatographic Technique for CO, CO2 and
methane. Determine the peak areas of the methane and the converted CO and CO2. Calculate the response
factor relating the mol-ppm/unit of peak area for each component as follows:

K=

P
A

where:

A = peak area for converted CO, CO2 or methane

K = response factor for converted CO, CO2 or methane for a one-milliliter sample volume
P = mol-ppm of CO, CO2 or methane
If baseline resolution is obtained between all three components, the separation efficiency of the
chromatographic columns is satisfactory. If the response factors for CO and CO2 are within 5% of the
methane factor, the hydrogenation reactor efficiency is satisfactory.
Determine response factors as directed above daily for each instrument used.

CALCULATIONS
Calculate the mol-ppm of either component of interest in the sample to the nearest 1 mol-ppm using the
following equation:

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Component, mol-ppm = KS
where:

K = response factor for the converted component, previously defined

S = peak area for the converted component

NOTES
1. It is necessary to prevent heavier hydrocarbons from passing over the reactor in order to avoid any
buildup of carbon on the surface of the catalyst.
2. Methane at sample concentrations above 1 mol-% can cause carbon buildup on the catalyst. To remove
this carbon buildup, inject air six times or until the observed CO is less than 0.5 mol-ppm.

PRECISION
Repeatability
Based on two tests performed by each of two analysts, on each of two days (8 tests) in one laboratory, the
within-laboratory estimated standard deviation (esd) was calculated at the concentrations shown in the
following table. Two tests performed in one laboratory by different analysts, on different days, should not
differ by more than the allowable difference shown (95% probability).

Component
Carbon monoxide
Carbon monoxide
Carbon dioxide
Carbon dioxide

Concentration,
mol-ppm

Within-Lab
esd,
mol-ppm

4
214
6
182

0.09
2.4
0.58
2.6

Allowable
Difference,
mol-ppm
0.4
9
2
10

Reproducibility
There is insufficient data to calculate reproducibility of the test at this time.

TIME FOR ANALYSIS

The elapsed time and labor requirements for one analysis are identical, 0.25 hour.

SUGGESTED SUPPLIERS
A&M Insulation, 2614 N. Clybourn Ave., Chicago, IL 60614
Aldrich Chemical Co., P.O. Box 355, Milwaukee, WI 53201
Alltech Associates, 2051 Waukegan Road, Deerfield, IL 60015
ETS Equipment, 408 Plainfield Rd., Darien, IL 60559
Matheson, P.O. Box 96, Joliet, IL 60434
Valco Instrument Co. Inc, P.O. Box 55603, Houston, TX 77255
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Figure 1
Flow Diagram

Figure 2
Typical Chromatogram

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