SOP ASTM D1946-90 (Rev. 1.7)

SOP ID Number: SOP- ASTM D1946-90
Entech Engineering Inc. Revision: 1.7

P.O. Box 890746 • Houston, Texas 77289-0746 •281-332-3118 Date: June 24, 2016
Page: 1 of 16
Standard Operating Procedure
ASTM D1946-90: Standard Practice for Analysis of Reformed Gas by Gas

Title:
Chromatography
Effective Date: June 24, 2016 File Location: \\Entengdellserve\qaqc\EE S.O.P.s\Current
QA Manager: Billy T.Y. Lee Technical Director: Edward J. Pasternak
Signature: Signature:
1.0 Scope and Application.
1.1 Analytes. Reformed gases and other gaseous mixtures containing the following
components: hydrogen, oxygen, nitrogen, carbon monoxide, methane, ethane, and
ethylene.
NOTE: a TCD detector is utilized for the inorganics and a FID for the organics. See
Entech’s most current version of the SOPs for GC/TCD analysis and GC/FID
analysis.
1.2 Applicability. This practice covers the determination of the chemical composition of
reformed gases and similar gaseous mixtures. The information about the chemical
composition may be used to calculate physical properties of the gas, such as heating
(calorific) value and relative density. Combustion characteristics, products of
combustion, toxicity, and interchangeability with other fuel gases may also be
inferred from the chemical composition.
Options and exceptions to this method, if approved by the appropriate regulatory

authorities, must be addressed on a case by case basis. If options and exceptions are
required for a project, hard copies and an electronic copy of the SOP and the options
and exceptions will be distributed, discussed, and implemented by the field
supervisor prior to project commencement.
1.3 Principles of Operation. Components in a sample of reformed gas are physically

separated by GC and compared to corresponding components of a reference standard
separated under identical operating conditions, using a reference standard of known
composition. The composition of the reformed gas is calculated by comparison of
either the peak height or area response of each component with the corresponding
value of that component in the references standard. Adherence to the requirements of
this method will enhance the quality of the data obtained from air pollutant sampling
methods.
NOT A CONTROLLED DOCUMENT ONCE PRINTED
This document is the confidential property of Entech Engineering Inc. It must be returned on
demand and must not be disclosed or reproduced without prior written consent from a duly
authorized representative of Entech Engineering Inc
Page: 2 of 16
1.4 Range and Sensitivity.
Concentration Concentration
Range (Mol.%) Range (Mol.%)
FID: Methane 0.01 - 100 TCD: Hydrogen 0.5 - 100
Ethane 0.01 - 100 Nitrogen 0.1 - 100
Propane 0.01 - 100 Oxygen 0.1 - 50
Isobutane 0.01 - 10 Carbon monoxide 0.1 - 100
n-Butane 0.01 - 10 Carbon dioxide 0.1 - 100
neo-Pentane 0.01 - 2
iso-Pentane 0.01 - 2
n-Pentane 0.01 - 2
n-Hexame 0.01 - 2
n-Heptane 0.01 - 2
1.5 Interferences.
The analytical system could be cross-contaminated due to carryover from high

concentration of compounds in standards or samples. To demonstrate the system is
free from contaminants, purge the sample loop and analyze blanks (hydrocarbon-free
air or nitrogen) prior sample analysis. To prevent standard or sample carryover, set
up a sufficient GC run time and temperature program, allowing all compounds elute
from column before proceeding to the next run.
The sample matrix can interfere with peak resolution. A proper analytical
condition may be established by choosing an appropriate GC column, adjusting
column carry gas flow, and setting the GC temperature program accordingly.
Moisture in the sample or air may also affect detectors response. The instrument
should be heated to operation condition prior standard and sample analysis.
Since the TCD exhibits universal response and detects all gas compounds except the
carrier gas, interference may occur. Choosing the appropriate GC condition or
changing the column flow rate to shift the retention time may help to eliminate
resolution interferences.
To assure consistent detector response, use helium to prepare calibration gases.

Frequent exposure to samples containing oxygen may gradually destroy detector’s
filaments.

Page: 3 of 16
2.0 Summary of Method.
See Section 1.3.
3.0 Definitions.
This section does not apply to this SOP.
4.0 Safety.
4.1 This method may involve hazardous materials, operations, and equipment. It is
the responsibility of the user of this method to establish appropriate safety and
health practices and procedures prior performing this method. Always consult the
instrument operator’s manual, chemical’s MSDS, and sampling source
information for specific precautions regarding the analytical procedure.
4.2 Follow the procedures in the most current version of Entech Engineering’s Accident
Prevention Plan and Employee Safety Manual.
5.0 Equipment and Supplies.
Instrument: Shimadzu GC14-A configured with

Detector A: Flame ionization detectors (FID)
Detector B: Thermal Conductivity Detector (TCD)
Data acquisition system: Microsoft Windows 98SE or Windows XP based computer

workstation installed with Shimadzu Class VP Version 4.3 or 7.2 SP2 software.
FID Injection port: Valco UW type 10-port sampling and switching valve with a
250ul capacity sample loop installed.
TCD Injection port: Shimadzu on-column type.
Column A: Supleco Hayesep Q polymer (80/100 mesh) stainless steel packed column, 6’long
x 1/8” OD.
Column B: Supleco Hayesep DB polymer (100/120 mesh) stainless steel packed column,
30’long x 1/8” OD.
Syringe: SGE 1-liter jumbo syringe (model 1000MAR-LL-GT), SGE 100ml syringe
(model 100MAX-LL-GT), Hamilton 10ml syringe (model GASTIGHT #1010), Hamilton
Page: 4 of 16
100ul syringe (model GASTIGHT#1710), or equivalent.

Tedlar Bag: SKC 1 liter bag (Cat# 232-01) and 10 liter bag (Cat# 232-08) or equivalent.
Cylinder gauge and regulator: CGA 350 and CGAS 580 regulator with gauges.
Gases: Hydrocarbon-free compress air system or Ultra zero grade compressed air; Ultra
High Purity (UHP) compressed nitrogen; UHP compressed hydrogen.
NOTE: In order to trace the supply gases were used during the analysis procedure, when
install or remove supply gas cylinders, record the cylinder’s serial number onto the
laboratory’s cylinder gases logbook with date and operator’s initial.
6.0 Reagents and Materials.
6.1 Moisture-free mixtures of known compositions are required for comparison with the
test sample. They must contain known percentages of the components that are to be
determined in the unknown sample. All components in the reference standard must be
homogenous in the vapor state at the time of use.
6.2 Primary reference standard gas mixture – Air Liquide certified master class
calibration standard and Alphagaz class gases or equivalent. Alternative calibration
standard – Scott Gases, PortaGas, and SigmaAldrich certified standards.
7.0 Sample Collection, Preservation, Transport, and Storage.
Follow the procedures presented in project proposal and EPA Reference Method,
whichever is applicable.
8.0 Sample Recovery.
Upon the arriving the laboratory, check the integrity of the sample bag for leaking or
deflecting. Logging samples into the chain-of-custody (COC) according to the procedures
presented in sample acceptance SOP with appropriate remarks.
9.0 Analytical Procedure
9.1 Instrument Setup

Establish a GC operating condition as described in Table 2. Make sure FID is on
and is in working condition. Consult the instrument operator’s manual for
detailed instructions on how to set up the instrument.

Page: 5 of 16
9.2 Data Acquisition System Setup

Use Windows Explorer to create a working directory in the computer data system
according to the analysis and project. To use the Data Acquisition System
(Shimadzu Class VP) to acquire the GC’s data, open the designated GC interface
window according to each instrument’s ID assignment. Use the “Preview”
function of the software to synchronize (ensure the “handshake” between) the GC
and computer, and also check the detector signal, detector range, and baseline for
stability.
9.3 Making A Single Run

Using the “Single Run” function to select a GC method and assign a unique file
name (no more than 8 characters) for each GC run. When the “Start” button of the
“Single Run” is clicked, the Data Acquisition System goes into standby mode.
When GC condition is ready, pressing the GC’s “START” button to start the GC
run program and the Data Acquisition System to acquire data in real time.
Repeat the steps in 9.3 for each GC run.
10.0 Calibration and Standardization.
10.1 FID Initial Pre-Calibration

A minimum of three levels of gas standards is required to establish a standard curve.
Refer to section 9.3 to setup a proper data acquisition. Remember to include the gas
standard’s cylinder lot number or lab designated unique number in raw data file.
Connect a low level standard bag to the sampling valve. When the GC is ready, open
the bag valve by turning it counter clockwise and press the bag to feed standard into
the sample loop for 20 seconds. Immediately, press the GC’s “START” button to
start the GC run, and close the bag valve by turning it clockwise.
Note: when pressing the bag, air bubbles should appear at the sample loop exit; if no
bubbles appear, no sample is going into the loop. It is possible that the sample bag
valve may be closed or there is not enough pressure on the bag. Always keep a
consistent pressure on the bag.
Repeat steps in 10.1 to run the standard in triplet. Repeat steps in 10.1 for mid and
high level standards.
Collect all the results from standards analysis, calculate the individual response for
each standard run, and the average response for each level. Use the known
Page: 6 of 16
concentration of standards as dependent, and the average response of each level as

independent to plot a calibration curve to obtain the response factor for each
compound. The calibration is acceptable when three individual responses agree to
within 5 percent of their average, and R squared of the curve is greater than 0.995.
See Table 3 for an example of calculation.
10.2 FID Calibration Post-Check

After all samples have been analyzed, repeat the analysis of the mid-level standard,
and compare the response factor of post-check for each target compounds with the
average response factor of initial calibration. If the difference of two response factors
average is less than 5 percent, the response factor of initial calibration can be used to
calculate the concentration values for each sample. If the difference is greater than 5
percent, re-analyzing all level of standards as described in 10.1 for the compound that
failed. Combine both pre- and post-calibration results to obtain a curve and the
response factor for that compound. Use the new response factor to calculate the
concentration of the compound in the sample.
10.3 Sample Analysis

Refer to section 9.3 to setup the data acquisition.
Connect the sample bag to the sampling valve, and introduce sample gas into the
sample loop in the same manner as in the standards calibration, under the same GC
condition. Run each sample in triplet. The results are acceptable when the peak area
of each injection agrees with the others to within 5 percent of their average.
Additional runs may be needed until this requirement is met.
NOTE: Run a blank before sample analysis to demonstrate the cleanness of the
instrument.
10.4 TCD Calibration and Sample Analysis

Use similar procedures as section 10.1 and 10.3 except using 100ul syringe to
introducing gas sample into injection port. A minimum of replicate run is required.
See Table 4 for an example of calculation.
Note: Perform an air sample check before sample analysis to verify TCD response.
11.0 Sample Preservation and Handling
Integrated bag sample should be analyzed within the same period as the laboratory’s
quality control sample for each project. The bag sample will be retained in the laboratory
for 90 days after the report has been submitted to the client.
Follow the procedures presented in Entech Engineering Inc. Quality Assurance & Quality
Control (QA/QC) Manual, Sections 5.2.3 through 5.2.6.
Page: 7 of 16
12.0 Chain of Custody.
Follow the procedures listed in the most current version of Entech Engineering’s QA and QC
Manual.
13.0 Sample Storage.
Follow the procedures presented in Entech Engineering Inc. QA/QC Manual, Section
6.2.3.
14.0 Calculations.
14.1 The number of significant digits retained for the quantitative value of each
component shall be such that accuracy is neither sacrificed nor exaggerated. The
expressed numerical value of any component in the sample should not be presumed
to be more accurate than the corresponding certified value of that component in the
calibration standard.
14.2
(Known concentration of the compound in standard)
Response Factor =
(Compound peak area)
Where,
Response Factor = x coefficient of the calibration curve.
For sample in dry basis,
(Concentration of the Compound) = (Response Factor) x (Compound Peak Area)
For sample in wet basis,
Follow the procedures presented in EPA 40 CFR 60, Appendix A, Reference Method 18,
Section 8.2.1.6 to determine the moisture content in the sample
(Concentration of the Compound) =
(Response Factor) x (Compound Peak Area) x (moisture correction factor)
Where, Moisture correction factor = 1 – (% moisture / 100)

Page: 8 of 16
15.0 Quality Control
15.1 FID/TCD Initial Calibration

The detector shell meet the linearity check criteria for target compounds as described
in 10.0.
15.2 FID Calibration Post-Check

If the post-standard calibration failed the requirement, re-analyzing all level of
standards for the compound that failed. Combine both pre- and post-calibration
results to prepare a curve and calculate the response factor for that compound. Use
the new response factor to calculate the concentration of the compound in the sample
15.3 Continue Calibration Verification (CCV)
15.3.1 FID - If applicable, perform a mid level standard analysis as CCV at the
beginning of a set sample analysis to verify the instrument response drift is
within 5 percent of initial calibration. If a CCV failed the criteria due to the
matrix interference from pervious sample analysis, a new calibration, as
described in 10.1, may be required.
15.3.2 TCD - If applicable, perform an air analysis as a CCV at the beginning of a

set sample analysis to verify the instrument response drift. If the response
drifted more than 10 percent from initial calibration, re-analyzing all level of
standards as a new initial calibration. Use the new response factor to
calculate the concentration of the compound in the sample afterward.
15.4 Laboratory Control Sample (LCS)

LCS is prepared from a second source standard or different lot of primary source
standard. LCS is analyzed under the same condition and procedures as calibration
standards and samples. The acceptable LCS recovery limit is form 70 to 130 percent.
NOTE: LCS also is used for the purpose of the initial calibration verification (ICV)
to verify the initial calibration response is within the 10% of the second source
standard response. If ICV did not meet the criteria, a new initial calibration or LCS
may be required.
16.0 Method Performance.
16.1 The sample introduced into the GC column should have a volume between 0.2 and
0.5 ml. Sufficient accuracy can be obtained for the determination of all but the very
minor components with this sample size. When increased sensitivity is required for
the determination of components present in low concentrations, a sample size of up to
Page: 9 of 16
5 ml is permissible. However, components whose concentration is in excess of 5%

should not be analyzed by using sample volumes great than 0.5 ml.
16.2 Precision: The following data should be used to judge the acceptability of the results:
16.2.1 Repeatability: Duplicate results by the same operator should not be

considered suspect unless they differ by more than the following amounts:
Component mol% Repeatability
0 to 1 0.05
1 to 5 0.1
5 to 25 0.3
Over 25 0.5
16.2.2 Reproducibility: Results submitted by different analysis should not differ by

more than the amounts listed above when the same reference standard is used
for calibration and the same composition is used for calculations. If
calibration is made with pure components or with different reference
standards, results submitted by each of 2 analysis should not be considered
suspect unless the results differ by more than the following amounts:
Component mol% Reproducibility
0 to 1 0.1
1 to 5 0.2
5 to 25 0.3
Over 25 1.0
17.0 Pollution Prevention and Waste Management.
During and upon completion of a project, Entech will be responsible for adhering to
applicable federal and state pollution prevention and waste management procedures.
18.0 Procurement and Inventory.
Follow the procedures presented in Entech Engineering Manual sections 6.1-6.5.
19.0 Preventative Maintenance.
Note: Inspect and calibrate instrument before and after each field use.
Page: 10 of 16
Check laboratory routine supplies and standards periodically to ensure an effective and
efficient operation.
19.1 Sample transfer line

Run a blank sample (nitrogen for FID, helium for TCD) before sample analysis.
Inspect the presence of any peaks in chromatogram. If carry over or contamination is
suspected, change the transfer line.
19.2 Sample loop

Similar to sample transfer line. If “ghost” peaks or contaminates is suspected in
chromatogram, change sample loop. Run a mid-level standard to conform the
calibration is still valid. If not, recalibrate the instrument.
19.3 10-port valve

Check once a year for possible leaking. Replace it as needed.
19.4 Column
Evaluate performance proudly. Replace when it falls below performance
requirement, such as contamination, column bleeding, and fail to resolve adjacent
peaks.
19.4 TCD baseline

If TCD baseline is unstable or new helium carry gas is installed, rise GC oven
temperature to 175C for 30 minutes. Check the baseline again at GC ready condition.
20.0 Record keeping and Record Storage.
Follow the procedures listed in the most current version of Entech Engineering’s QA and QC
Manual.
21.0 Data Reduction, Validation, and Reporting.
Follow the procedures presented in Entech Engineering Inc. QA/QC Manual, Section 7.0.
22.0 Correcting Erroneous Reports.
23.0 Complaints.
Page: 11 of 16
24.0 References.
1. July 2001. ASTM Standard Test Method D1946-90 “Standard Practice for Analysis of
Reformed Gas by Gas Chromatography (GC)” ASTM 1990.
2. Entech Engineering Inc., Quality Assurance & Quality Control Manual, most recent
version.
3. Thomas A. Ratliff, Jr., The Laboratory Quality Assurance System. (New York: Wiley,
1991).
25.0 Table of Changes
From Ver. to Ver. Section Changes Made By/Date

Added table of changes
1.3 - 1.4 25.0 jwj/08/2011
section
1.4 - 1.5 6.0 and 10.0 Added details. sly 04/20/2014
1.5 – 1.6 3.0 Updated section content Gta 04/26/16
1.6 – 1.7 10.0 and 15.0 Updated section content sly 06/24/16

Page: 12 of 16
Table – 1
Routine Calibration Standards

Vender: Air Liquide
Low Level Mid Level High Level

Concentration Concentration Concentration
(%) (%) (%)
FID: Methane 22.194 44.387 88.774

Ethane 0.853 1.705 3.410
Propane 0.243 0.485 0.970
iso-Butane 0.099 0.198 0.396
n-Butane 0.099 0.198 0.395
neo-Pentane 0.024 0.048 0.096
iso-Pentane 0.033 0.067 0.133
n-Pentane 0.038 0.075 0.150
n-Heptane 0.049 0.098 0.196
n-Hexane 0.012 0.025 0.050
TCD: Hydrogen 20 50 100

Nitrogen 10 50 100
Oxygen 5 10 50
Carbon monoxide 10 49.8 99.5
Carbon dioxide 9.9 49.5 99.0
NOTE:
(1) FID low and mid level standard: dilute 25 ml and 50 ml of high level standard with nitrogen
to the final volume of 1 liter, respectively.
(2) TCD low and mid level standard: (a) dilute 100 ml and 500 ml of high level standard with
helium to the final volume of 1 liter for nitrogen, carbon monoxide, and carbon dioxide,
respectively; (b) dilute 100 ml and 200 ml of high level standard with helium to the final
volume of 1 liter for oxygen, respectively; (c) dilute 200 ml and 500 ml of high level standard
with helium to the final volume of 1 liter for hydrogen, respectively;
(3) High level standard concentration may vary due to manufacturing process.
Page: 13 of 16
Table – 2
GC configuration
GC Type: Shimadzu GC-14A

Detector A: Flame Ionization Detector (FID)
Detector B: Thermal Conductivity Detector (TCD)
Column A: Supleco Hayesep Q polymer (80/100 mesh) stainless
steel packed column, 6’long x 1/8” OD.
Column B: Supleco Hayesep DB polymer (100/120 mesh)
stainless steel packed column, 30’long x 1/8” OD.
GC Operating Parameters
Detector A Signel Range: 3

Injector Temperature (°C): 220
Detector Temperature (°C): 220
Initial Oven Temperature (°C): 50
Initial Time (min): 5.0
Temp. Program Rate (°C/min): 10
Final Oven Temperature (°C): 175
Final Time (min): 13.0
Total Run Time (min): 30.0
Back-Flush Time (min) 22
Carrier Gas A Type Nitrogen

Carrier Gas B Type Helium
Carrier Gas A Mass Flow (Kpa): 80
Carrier Gas B Mass Flow (Kpa) 300
Air Flow (Kpa) 250
Hydrogen Flow (Kpa): 50
TCD Bridge Current (mA) 100

This document is the confidential property of Entech Engineering Inc. It must be returned
on demand and must not be disclosed or reproduced without prior written consent from a
duly authorized representative of Entech Engineering Inc
SOP ID Number: SOP- ASTM D1946-
Entech Engineering Inc. 90
P.O. Box 890746 • Houston, Texas 77289-0746 •281-332-3118 Revision: 1.7
Date: April 26, 2016
Page: 14 of 16
Table - 3
FID Initial Calibration
(Example)
This document is the confidential property of Entech Engineering Inc. It must be returned on demand and must not be disclosed
or reproduced without the prior written consent from a duly authorized representative of Entech Engineering Inc.
Page: 15 of 16
Table - 4
TCD Initial Calibration
(Example)
Page: 16 of 16
Table - 5
Reference Chromatogram
FID
TCD

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SOP ID Number: SOP- ASTM D1946-90

Entech Engineering Inc. Revision: 1.7

ASTM D1946-90: Standard Practice for Analysis of Reformed Gas by Gas

QA Manager: Billy T.Y. Lee Technical Director: Edward J. Pasternak

1.0 Scope and Application.

Options and exceptions to this method, if approved by the appropriate regulatory

1.3 Principles of Operation. Components in a sample of reformed gas are physically

1.4 Range and Sensitivity.

The analytical system could be cross-contaminated due to carryover from high

To assure consistent detector response, use helium to prepare calibration gases.

NOT A CONTROLLED DOCUMENT ONCE PRINTED

2.0 Summary of Method.

See Section 1.3.

This section does not apply to this SOP.

5.0 Equipment and Supplies.

Instrument: Shimadzu GC14-A configured with

Data acquisition system: Microsoft Windows 98SE or Windows XP based computer

TCD Injection port: Shimadzu on-column type.

100ul syringe (model GASTIGHT#1710), or equivalent.

6.0 Reagents and Materials.

7.0 Sample Collection, Preservation, Transport, and Storage.

8.0 Sample Recovery.

9.0 Analytical Procedure

9.1 Instrument Setup

NOT A CONTROLLED DOCUMENT ONCE PRINTED

9.2 Data Acquisition System Setup

9.3 Making A Single Run

Repeat the steps in 9.3 for each GC run.

10.0 Calibration and Standardization.

10.1 FID Initial Pre-Calibration

concentration of standards as dependent, and the average response of each level as

10.2 FID Calibration Post-Check

10.3 Sample Analysis

10.4 TCD Calibration and Sample Analysis

11.0 Sample Preservation and Handling

12.0 Chain of Custody.

13.0 Sample Storage.

Response Factor = x coefficient of the calibration curve.

For sample in dry basis,

(Concentration of the Compound) = (Response Factor) x (Compound Peak Area)

For sample in wet basis,

(Concentration of the Compound) =

(Response Factor) x (Compound Peak Area) x (moisture correction factor)

Where, Moisture correction factor = 1 – (% moisture / 100)

15.0 Quality Control

15.1 FID/TCD Initial Calibration

15.2 FID Calibration Post-Check

15.3 Continue Calibration Verification (CCV)

15.3.2 TCD - If applicable, perform an air analysis as a CCV at the beginning of a

15.4 Laboratory Control Sample (LCS)

16.0 Method Performance.

5 ml is permissible. However, components whose concentration is in excess of 5%

16.2.1 Repeatability: Duplicate results by the same operator should not be

Component mol% Repeatability

16.2.2 Reproducibility: Results submitted by different analysis should not differ by

Component mol% Reproducibility