ASTM D6366-99

Standard Test Method for Total Trace Nitrogen and Its Derivatives in Liquid Aromatic Hydrocarbons by Oxidative Combustion and Electrochemical Detection (Withdrawn 2006)

SCOPE
1.1 This test method covers the determination of the total trace nitrogen (organic and inorganic) naturally found in liquid aromatic hydrocarbons, its derivatives and related chemicals.
1.2 This test method is applicable for samples containing nitrogen from 0.05 to 100 mgN/kg. For higher concentrations refer to Test Method D 4629.
1.3 The detector response for the technique within the scope of this test method is linear with nitrogen concentration.
1.4 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.
1.5 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 and Note 2, Note 3, Note 4, and Note 8.
WITHDRAWN RATIONALE
This test method covers the determination of the total trace nitrogen (organic and inorganic) naturally found in liquid aromatic hydrocarbons, its derivatives and related chemicals.
Formerly under the jurisdiction of Committee D16 on Aromatic Hydrocarbons and Related Chemicals, this test method was withdrawn in January 2006. This standard is being withdrawn without replacement because the equipment used for this method is no longer supported by the manufacturer.

General Information

• Status: Withdrawn
• Publication Date: 09-Jan-1999
• Withdrawal Date: 15-Jan-2006
• ICS: 71.040.99 - Other standards related to analytical chemistry
• ICS: 71.080.15 - Aromatic hydrocarbons
• Technical Committee: D16 - Aromatic, Industrial, Specialty and Related Chemicals
• Drafting Committee: D16.04 - Instrumental Analysis

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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:D6366–99
Standard Test Method for
Total Trace Nitrogen and Its Derivatives in Liquid Aromatic
Hydrocarbons by Oxidative Combustion and
Electrochemical Detection
This standard is issued under the fixed designation D 6366; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope Determine Conformance with Specifications
2.2 Other Document:
1.1 This test method covers the determination of the total
OSHA Regulations, 29 CFR, paragraphs 1910.1000 and
trace nitrogen (organic and inorganic) naturally found in liquid
1910.1200
aromatic hydrocarbons, its derivatives and related chemicals.
1.2 This test method is applicable for samples containing
3. Terminology
nitrogen from 0.05 to 100 mgN/kg. For higher concentrations
3.1 Definitions:
refer to Test Method D 4629.
3.1.1 oxidative combustion, n—a process in which a sample
1.3 Thedetectorresponseforthetechniquewithinthescope
undergoes combustion in an oxygen-rich environment at tem-
of this test method is linear with nitrogen concentration.
peratures greater than 650°C and compounds decompose to
1.4 The following applies to all specified limits in this test
form carbon dioxide, water and elemental oxides.
method: for purposes of determining conformance with this
test method, an observed value or a calculated value shall be
4. Summary of Test Method
rounded off “to the nearest unit” in the last right-hand digit
4.1 A sample of liquid aromatic hydrocarbon is injected, at
used in expressing the specification limit, in accordance with
a controlled rate, into a stream of inert gas (helium or argon) or
the rounding-off method of PracticeE29.
inert gas mixed with oxygen. The sample is vaporized and
1.5 This standard does not purport to address all of the
carried to a high temperature zone (> 900°C), where oxygen is
safety concerns, if any, associated with its use. It is the
introduced. Organic and inorganic nitrogen compounds,
responsibility of the user of this standard to establish appro-
present in the specimen, are converted to nitric oxide (NO).
priate safety and health practices and determine the applica-
Nitric oxide is reacted with the sensing electrode in a
bility of regulatory limitations prior to use. For specific hazard
3-electrode electrochemical cell. This reaction produces a
statements, see Section 9 and Note 2, Note 3, Note 4, and Note
measurable current that is directly proportional to the amount
8.
of nitrogen in the original sample material.
2. Referenced Documents 4.1.1 The reaction that occurs is as follows:
Combustion: R2N 1 O . 900°C→ CO 1 H O 1 NO 1 oxides
2.1 ASTM Standards:
2 2 2
(1)
D 3437 Practice for Sampling and Handling Liquid Cyclic
1 –
Products
Detection: NO 12H O electrolyte HNO 1~3H !1~3e !
2 3
D 3852 Practice for Sampling and Handling Phenol and
5. Significance and Use
Cresylic Acid
D 4629 Test Method for Trace Nitrogen in Liquid Petro-
5.1 Some process catalysts used in petroleum and chemical
leum Hydrocarbons by Syringe/Inlet Oxidative Combus-
refining may be poisoned when even trace amounts of nitrog-
tion and Chemiluminescence Detection
enous materials are contained in the feedstocks. This test
E29 Practice for Using Significant Digits in Test Data to
methodcanbeusedtodeterminetotalnitrogeninprocessfeeds
and may also be used to control nitrogen compounds in
finished products that fall within the scope of this test method.
NOTE 1—Virtually all organic and inorganic nitrogen compounds will
This test method is under the jurisdiction of ASTM Committee D16 on
Aromatic Hydrocarbons and Related Materials , and is the direct responsibility of
Subcommittee D16.04 on Instrumental Analysis.
Current edition approved Jan. 10, 1999. Published March 1999. Annual Book of ASTM Standards, Vol 14.02.
2 5
Annual Book of ASTM Standards, Vol 06.04. Available from Superintendent of Documents, U.S. Government Printing
Annual Book of ASTM Standards, Vol 05.02. Office, Washington, DC 20402.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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.
D6366–99
detected by this technique.
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
5.2 This technique will not detect diatomic nitrogen and it
accuracy of the determination.
will produce an attenuated response when analyzing com-
8.2 Magnesium Perchlorate Mg(ClO ) —for drying prod-
pounds (that is, 5-triazine and azo compounds, etc.) that form 4 2
ucts of the combustion (if a permeation drier is not used).
nitrogen gas (N ) when decomposed.
NOTE 2—Warning: Strong oxidizer, irritant.
6. Interferences
8.3 Inert Gas—Either argon (Ar) or helium (He) may be
6.1 Moisture produced during the combustion step can
used; the purity should be no less than 99.99 mol %.
interfere if not removed prior to the detector.
8.4 Oxygen—The purity should be no less than 99.99 mol
%.
7. Apparatus
NOTE 3—Warning: Vigorously accelerates combustion.
7.1 Pyrolsis Furnace, capable of maintaining a temperature
sufficient to volatilize and combust all of the sample and
8.5 Solvent—The solvent of choice should be capable of
oxidize the organically bound nitrogen to NO. The furnace
dissolving the nitrogen-containing compound used to prepare
temperatures for petroleum substances shall be as recom-
the standard and, if necessary, the samples. The solvent of
mended by the manufacturer.
choice should have a boiling point similar to the samples being
7.2 Quartz Combustion Tube, capable of withstanding 900
analyzed, and it should contain less nitrogen than the lowest
to 1200°C.The inlet end of the tube holds a septum for syringe
sample to be analyzed. Suggested possibilities include, but are
entry of the sample and has inlet fittings or side arms for the
not limited to: toluene, iso-octane, methanol, cetane, or other
introduction of oxygen (O ) and inert gas. The construction is
solvent similar to compound present in the sample to be
suchthattheinertgas(orinertgasandoxygenmixture)sweeps
analyzed.
the inlet zone, transporting all of the volatilized sample into a
NOTE 4—Warning: Flammable solvents.
high-temperature oxidation zone. The oxidation section shall
NOTE 5—A quick screening can be conducted by injecting the solvent
be large enough to ensure complete oxidation of the sample.
and sample once or twice and comparing relative integral response.
7.2.1 Quartz Combustion Tube Devitrification—the sug-
gested maximum temperature for a quartz combustion tube is 8.6 Nitrogen Stock Sample, 1000 µg N/mL—Prepare a stock
solution by accurately weighing to the nearest 0.1 mg, 1.195 g
1200°C. Samples containing alkai-metals (elements from the
Periodic Group IA (that is, Na, K, etc.)) or alkaline earth of carbozole or 0.565 g of pyridine into a tared 100 mL
volumetric flask. A small amount of acetone may be used to
(elements from the Periodic Group IIA (that is, Ca, Mg, etc.))
will cause quartz to devitrify (that is, become milky white and dissolve the carbozole. Dilute to volume with selected solvent.
This stock may be further diluted to desired sulfur concentra-
brittle).
tions, using the following equation:
7.3 Drying Tube, a magnesium perchlorate Mg(ClO )
4 2
scrubber or a membrane drying tube (permeation drier), or
µg N/mL 5 W 3 14.03 1000 µg/mg /100 mL 3 MW (2)
both, for removing water vapor produced during the reaction.
where:
Such water vapor must be removed prior to measurement by
W = exact weight of pyridine or carbazole, mg, and
the electrochemical detector.
MW = the mass weight of the reference material weighed.
7.4 Electrochemical Detector, capable of measuring NO in
the combustion gas stream.
NOTE 6—Carbazole may be used for calibration throughout the boiling
7.5 Data Reduction System, having the capability of mea- range of this test method.
suring, amplifying, and integrating the current from the elec-
NOTE 7—Pyridine should be used with low boiling solvents (< 230°C).
trochemical detector. The amplified or integrated output signal
8.7 Acetone (C H O)—mw 58.08.
3 6
shallbeappliedtoadigitaldisplayorsomeotherdatareporting
NOTE 8—Warning: Flammable.
device.
7.6 Microliter Syringe, of 5, 10, 25, 50, or 100-µL capacity
8.8 Carbazole (C H N)—mw 167.20.
12 9
capable of accurately delivering microliter quantities. The
NOTE 9—Warning: Irritant.
needle should be long enough to reach the hottest portion of
inlet section of the furnace when injecting the sample.
8.9 Pyridine (C H N)—mw 79.10.
5 5
7.7 Recorder, optional.
NOTE 10—Warning: Flammable, ir
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