ASTM D6069-01(2006)
(Test Method)Standard Test Method for Trace Nitrogen in Aromatic Hydrocarbons by Oxidative Combustion and Reduced Pressure Chemiluminescence Detection (Withdrawn 2015)
Standard Test Method for Trace Nitrogen in Aromatic Hydrocarbons by Oxidative Combustion and Reduced Pressure Chemiluminescence Detection (Withdrawn 2015)
SIGNIFICANCE AND USE
This method has been prepared to detect and quantitate nitrogen-containing compounds such as N-formylmorpholine (4-formylmorpholine, Chemical Abstract Service numbers (CAS) No. 250-37-6) or 1-methyl-2-pyrrolidinone (NMP) (CAS) No. 872-50-42 at a concentration of 1.0 mgN/kg or less in aromatic hydrocarbons used or produced in manufacturing processes. These nitrogen-containing compounds are undesirable in the finished aromatic products and may be the result of the aromatic extraction process. This test method may be used in setting specifications for determining the total nitrogen content in aromatic hydrocarbons.
Note 1—Virtually all organic and inorganic nitrogen compounds will be detected by this technique.
This technique will not detect diatomic nitrogen and it will produce an attenuated response when analyzing compounds (that is, s-triazine and azo compounds, etc.) that form nitrogen gas (N2) when decomposed.
This test method requires the use of reduced pressure at the detector. Loss of vacuum or pressure fluctuations impact the sensitivity of the detector and the ability to determine nitrogen concentrations less than 1 mg/kg.
SCOPE
1.1 This test method covers the determination of total nitrogen (organic and inorganic) in aromatic hydrocarbons, their derivatives and related chemicals.
1.2 This test method is applicable for samples containing nitrogen from 0.2 to 2 mgN/kg. For higher nitrogen concentrations refer to Test Method D 4629.
1.2.1 The detector response of this technique within the specified scope of this test method is linear with nitrogen concentration.
1.3 The following applies to all specified limits in this test method: for purposes of determining conformance with this test method, an observed value or a calculated value shall be rounded off "to the nearest unit" in the last right-hand digit used in expressing the specification limit, in accordance with the rounding-off method of Practice E 29.
1.4 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see Section 9.
WITHDRAWN RATIONALE
This test method covers the determination of total nitrogen (organic and inorganic) in aromatic hydrocarbons, their derivitives and related chemicals.
Formerly under the jurisdiction of Committee D16 on Aromatic Hydrocarbons and Related Chemicals, this test method was withdrawn in January 2015 in accordance with section 10.6.3 of the Regulations Governing ASTM Technical Committees, which requires that standards shall be updated by the end of the eighth year since the last approval date.
General Information
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D6069 − 01 (Reapproved2006)
Standard Test Method for
Trace Nitrogen in Aromatic Hydrocarbons by Oxidative
Combustion and Reduced Pressure Chemiluminescence
Detection
This standard is issued under the fixed designation D6069; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope* D3437 Practice for Sampling and Handling Liquid Cyclic
Products
1.1 This test method covers the determination of total
D4629 Test Method for Trace Nitrogen in Liquid Petroleum
nitrogen (organic and inorganic) in aromatic hydrocarbons,
HydrocarbonsbySyringe/InletOxidativeCombustionand
their derivatives and related chemicals.
Chemiluminescence Detection
1.2 This test method is applicable for samples containing
E29 Practice for Using Significant Digits in Test Data to
nitrogen from 0.2 to 2 mgN/kg. For higher nitrogen concen-
Determine Conformance with Specifications
trations refer to Test Method D4629.
E691 Practice for Conducting an Interlaboratory Study to
1.2.1 The detector response of this technique within the
Determine the Precision of a Test Method
specified scope of this test method is linear with nitrogen
2.2 Other Documents:
concentration.
OSHA Regulations, 29 CFR paragraphs 1910.1000 and
1910.1200
1.3 The following applies to all specified limits in this test
method: for purposes of determining conformance with this
3. Terminology
test method, an observed value or a calculated value shall be
rounded off “to the nearest unit” in the last right-hand digit 3.1 Definitions:
used in expressing the specification limit, in accordance with 3.1.1 oxidative pyrolysis, n—a process in which a sample
the rounding-off method of Practice E29. under goes combustion in an oxygen rich environment at
temperatures greater than of 650°C.
1.4 The values stated in SI units are to be regarded as the
3.1.1.1 Discussion—Organic compounds pyrolytically de-
standard. The values given in parentheses are for information
compose to carbon dioxide, water and elemental oxides.
only.
3.1.2 reduced pressure chemiluminescence, n—a chemical
1.5 This standard does not purport to address all of the
reaction at pressure less than 760 mm mercury (Hg) in which
safety concerns, if any, associated with its use. It is the
light is emitted.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
4. Summary of Test Method
bility of regulatory limitations prior to use. For specific hazard
4.1 A specimen is introduced into a gas stream, at a
statements, see Section 9.
controlled rate, and carried into a high temperature furnace
(>900°C) where an excess of oxygen is added. Pyrolysis
2. Referenced Documents
2 converts organic material in the specimen to carbon dioxide
2.1 ASTM Standards:
and water. Organic nitrogen and inorganic nitrogen
D1555 Test Method for Calculation of Volume and Weight
compounds, present in the specimen, are converted to nitric
of Industrial Aromatic Hydrocarbons and Cyclohexane
oxide (NO). Nitric oxide reacts with ozone in the detector
producing nitrogen dioxide molecules in an excited state. As
the excited nitrogen dioxide molecules relax to ground state,
This test method is under the jurisdiction of ASTM Committee D16 on
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of
light is emitted.This light is detected by a photomultiplier tube
Subcommittee D16.04 on Instrumental Analysis.
with the resulting signal proportional to the concentration of
Current edition approved June 1, 2006. Published June 2006. Originally
nitrogen in the sample. Operating the detector at a reduced
approved in 1996. Last previous edition approved in 2001 as D6069 – 01. DOI:
10.1520/D6069-01R06. pressure, lowers the probability of the excited nitrogen dioxide
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments,
the ASTM website. 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6069 − 01 (2006)
molecules colliding with other molecules before they undergo 7.5 Constant Rate Injector System (Optional)—If the
chemiluminescence. Thus, reduced pressure provides im- sample is to be introduced into the pyrolysis furnace via
proved sensitivity and lower noise. syringe, a constant rate injector should be used.
7.6 Boat Inlet System (Optional)—If the instrument is
5. Significance and Use
equipped with a boat inlet system, care must be taken to ensure
5.1 This method has been prepared to detect and quantitate
the boat is sufficiently cooled between analyses to prevent the
nitrogen-containing compounds such as N-formylmorpholine
sample from vaporizing as it is injected into the boat. The
(4-formylmorpholine, Chemical Abstract Service numbers
sample should start vaporizing as it enters the furnace. It is
(CAS) No. 250-37-6) or 1-methyl-2-pyrrolidinone (NMP)
critical that the sample vaporize at a constant and reproducible
(CAS) No. 872-50-42 at a concentration of 1.0 mg N/kg or less
rate. This type of inlet system offers advantage when the
in aromatic hydrocarbons used or produced in manufacturing
sample is viscous or contains heavy components not volatile at
processes. These nitrogen-containing compounds are undesir-
temperatures of approximately 300°C, or for samples that
able in the finished aromatic products and may be the result of
contain polymers or high concentrations of salts that could
the aromatic extraction process. This test method may be used
result in plugging of the syringe needle.
in setting specifications for determining the total nitrogen
7.7 Automatic Boat Drive System (Optional)—If the instru-
content in aromatic hydrocarbons.
ment is equipped with a boat inlet system, a device for driving
NOTE 1—Virtually all organic and inorganic nitrogen compounds will
the boat in to the furnace at a controlled and repeatable rate
be detected by this technique.
may improve data repeatability and reproducibility.
5.2 This technique will not detect diatomic nitrogen and it
7.8 Oxidation Catalyst (Optional)— Catalyst (that is, cupric
will produce an attenuated response when analyzing com-
oxide(CuO)orPlatinum(Pt))maybepackedintothepyrolysis
pounds (that is, s-triazine and azo compounds, etc.) that form
tube to aid in oxidation efficiencies (see manufacturer’s rec-
nitrogen gas (N ) when decomposed.
ommendations).
5.3 This test method requires the use of reduced pressure at
8. Reagents
the detector. Loss of vacuum or pressure fluctuations impact
the sensitivity of the detector and the ability to determine
8.1 Purity of Reagents—Reagent grade chemicals shall be
nitrogen concentrations less than 1 mg/kg.
used in all tests. It is intended that all reagents shall conform to
the specifications of the Committee on Analytical Reagents of
6. Interferences
theAmerican Chemical Society, where such specifications are
6.1 Chlorides,bromides,andiodidescaninterfereifanyone available, unless otherwise indicated. Other grades may be
or all of these elements are present in a sample in concentra- used, provided it is first ascertained that the reagent is of
tions greater than 10 % by total weight of halogen in the sufficiently high purity to permit its use without lessening the
sample. accuracy of the determination.
6.2 Moisture produced during the combustion step can 8.2 Inert Gas—Either argon (Ar) or helium (He) may be
interfere if not removed prior to the detector cell. used. The purity should be no less than 99.99 mol %.
8.3 Oxygen Gas—The purity should be no less than 99.99
7. Apparatus
mol %.
7.1 Pyrolysis Furnace—A furnace capable of maintaining a
8.4 Solvent—The solvent chosen should be capable of
temperaturesufficienttovolatilizeandpyrolyzethesampleand
dissolving the nitrogen containing compound used to prepare
oxidize organically bound nitrogen to NO.The actual tempera-
the standard and if necessary the samples. The solvent of
ture(s) should be recommended by the specific instrument
choice should have a boiling point similar to the samples being
manufacturers.
analyzed and it should contain less nitrogen than the lowest
7.2 Quartz Pyrolysis Tube—Capable of withstanding 900 to
sample to be analyzed. Suggested possibilities include, but are
1200°C.
not limited to: toluene, methanol, tetrahydrofuran, iso-octane.
7.2.1 Quartz Pyrolysis Tube—The suggested maximum
NOTE 2—A quick screening can be conducted by injecting the solvent
temperature for a quartz pyrolysis tube is 1200°C. Samples
and sample once or twice and comparing relative area counts.
containing alkali-metals (elements from the Periodic Group IA
8.4.1 Solvent—Toluene, relative density at 60°F/60°F
(that is, Na, K, etc.)) or alkaline earths (elements from the
0.8718 (see Test Method D1555).
Periodic Group IIA(that is, Ca, Mg, etc.)) will cause quartz to
devitrify (that is, become milky white and brittle). 8.5 Nitrogen Stock Solution, 1000 µg N/mL—Prepare a
stock solution by accurately weighing, to the nearest 0.1 mg,
7.3 Chemiluminescent Detector—Capable of operation at
reduced pressures (less than 760 mm mercury) and able to
measure light emitted from the reaction between NO and
Reagent Chemicals, American Chemical Society Specifications, American
ozone. Includes ozone generator.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
7.4 Microlitre Syringe—Capable of delivering from 5 to 50
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
µL of sample. Check with the instrument manufacturer for
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
recommendations for specific sample needs. MD.
D6069 − 01 (2006)
approximately 707.7 mg of 1-methyl-2-pyrrolidinone (NMP) 11.3 The actual operation of injecting a sample will vary
(CAS No. 872-50-4) into a 100-mL volumetric flask. Fill to depending upon the instrument manufacturer and the type of
volume with solvent as follows: inlet system used (see 7.5-7.8).
exact weight of NMP mg 314.0 31000 µg/mg
~ ! ~ !
µg N/mL 5 (1)
12. Calibration and Standardization
100 mL 399.1
12.1 Prepare the working calibration standards using the
where:
stock solution as des
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