An American National Standard

Designation: D 4629 – 02

Designation: 379/88

Standard Test Method for

Trace Nitrogen in Liquid Petroleum Hydrocarbons by
Syringe/Inlet Oxidative Combustion and Chemiluminescence
Detection1
This standard is issued under the fixed designation D 4629; 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.

This standard has been approved for use by agencies of the Department of Defense.

1. Scope Gravity), or API Gravity of Crude Petroleum and Liquid

1.1 This test method covers the determination of the trace Petroleum Products by Hydrometer Method2
total nitrogen naturally found in liquid hydrocarbons boiling in D 4052 Test Method for Density and Relative Density of
the range from approximately 50 to 400°C, with viscosities Liquids by Digital Density Meter3
between approximately 0.2 and 10 cSt (mm2/s) at room D 4057 Practice for Manual Sampling of Petroleum and
temperature. This test method is applicable to naphthas, distil- Petroleum Products2
lates, and oils containing 0.3 to 100 mg/kg total nitrogen. For D 4177 Practice for Automatic Sampling of Petroleum and
liquid hydrocarbons containing more than 100 mg/kg total Petroleum Products2
nitrogen, Test Method D 5762 can be more appropriate. This D 5762 Test Method for Nitrogen in Petroleum and Petro-
test method has been successfully applied, during interlabora- leum Products by Boat-Inlet Chemiluminescence4
tory studies, to sample types outside the range of the scope by D 6299 Practice for Applying Statistical Quality Assurance
dilution of the sample in an appropriate solvent to bring the Techniques to Evaluate Analytical Measurement System
total nitrogen concentration and viscosity to within the range Performance5
covered by the test method. However, it is the responsibility of 3. Summary of Test Method
the analyst to verify the solubility of the sample in the solvent
and that direct introduction of the diluted sample by syringe 3.1 The sample of liquid petroleum hydrocarbon is intro-
into the furnace does not cause low results due to pyrolysis of duced either by syringe or boat inlet system, into a stream of
the sample or solvent in the syringe needle. inert gas (helium or argon). The sample is vaporized and
1.2 The values stated in SI units are to be regarded as carried to a high temperature zone where oxygen is introduced
standard. and organically bound nitrogen is converted to nitric oxide
1.3 This standard does not purport to address all of the (NO). The NO contacts ozone, and is converted to excited
safety concerns, if any, associated with its use. It is the nitrogen oxide (NO2). The light emitted as the excited NO2
responsibility of the user of this standard to establish appro- decays is detected by a photomultiplier tube and the resulting
priate safety and health practices and determine the applica- signal is a measure of the nitrogen contained in the sample.
bility of regulatory limitations prior to use. See 6.2, 6.4, 6.5, 4. Significance and Use
6.9, and Section 7.
4.1 Some process catalysts used in petroleum and chemical
2. Referenced Documents refining may be poisoned when even trace amounts of nitrog-
2.1 ASTM Standards: enous materials are contained in the feedstocks. This test
D 1298 Practice for Density, Relative Density (Specific method can be used to determine bound nitrogen in process
feeds and may also be used to control nitrogen compounds in
finished products.
1
This test method is under the jurisdiction of ASTM Committee D02 on
2
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee Annual Book of ASTM Standards, Vol 05.01.
3
D02.03 on Elemental Analysis. Annual Book of ASTM Standards, Vol 05.02.
4
Current edition approved April 10, 2002. Published July 2002. Originally Annual Book of ASTM Standards, Vol 05.03.
5
published as D 4629–86. Last previous edition D 4629–96. Annual Book of ASTM Standards, Vol 05.04.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 D 4629 – 02
5. Apparatus all reagents shall conform to the specifications of the Commit-
5.1 Furnace, electric, held at a temperature sufficient to tee on Analytical Reagents of the American Chemical Society,6
volatilize and pyrolyze all of the sample and oxidize the where such specifications are available. Other grades may be
organically bound nitrogen to NO. Furnace temperature(s) used, provided it is first ascertained that the reagent is of
shall be as recommended by the manufacturer (typically sufficiently high purity to permit its use without lessening the
around 1000°C). accuracy of the determination.
5.2 Combustion Tube, fabricated to meet the instrument 6.2 Magnesium Perchlorate Mg(ClO4)2, for drying products
manufacturer’s specifications. of combustion (if permeation drier is not used.) (Warning—
5.3 Drier Tube—The reaction products include water vapor Strong oxidizer, irritant.)
that must be eliminated prior to measurement by the detector. 6.3 Inert Gas, argon or helium, ultra-high purity grade
This can be accomplished with a magnesium perchlorate (UHP).
Mg(ClO4)2 scrubber or a membrane drying tube (permeation 6.4 Oxygen, (99.8 % or better, 99.996 % is recommended).
drier), or by whatever other means the instrument manufacturer (Warning—Vigorously accelerates combustion.)
specifies as appropriate for the instrument being used. 6.5 Solvents, for diluting and matrix matching such as,
5.4 Chemiluminescent Detector, capable of measuring light toluene, isooctane, xylene, acetone, cetane. (Other solvents
emitted from the reaction between NO and ozone. similar to those occurring in samples to be analyzed are also
5.5 Totalizer, having variable attenuation, and capable of acceptable). Solvents should contain less than 0.1 µg N/mL.
measuring, amplifying, and integrating the current from the (Warning—Flammable solvents.)
chemiluminescent detector. A built in microprocessor or at- 6.6 Nitrogen Stock Solution, 1000 µg N/mL, Prepare a stock
tached computer system may perform these functions. solution by accurately weighing approximately 1.195 g of
5.6 Micro-litre Syringe, of 5, 10, 25, 50, or 250 µL capacity carbazole or 0.565 g of pyridine to the nearest milligram, into
capable of accurately delivering micro-litre quantities is re- a tared 100-mL volumetric flask. Fifteen millilitres of acetone
quired. The needle should be long enough to reach the hottest may then be added when using carbazole to help dissolve it.
portion of the inlet section of the furnace when injecting the Dilute to volume with the selected solvent. Calculate the exact
sample. The syringe may be part of an automatic sampling and concentration of the stock solution based on the actual mass of
injection device used with the instrument. pyridine or carbazole used and corrected for any known purity
5.7 Strip Chart Recorder (Optional). factors for the specific lot of pyridine or carbazole. This stock
5.8 Sample Inlet System—One of the following must be may be further diluted to desired nitrogen concentrations.
used: NOTE 1—Pyridine should be used with low boiling solvents (<220°C).
5.8.1 Manually Operated Syringe. NOTE 2—Carbazole should be used with high boiling solvents
5.8.2 Syringe, with a constant rate injector system, capable (>220°C).
NOTE 3—Working standards should be remixed on a regular basis
of delivering a sample at a precisely controlled rate.
depending upon frequency of use and age. Typically, standards have a
5.8.3 Boat Inlet System, to facilitate analysis of samples that useful life of about 3 months, and should be refrigerated when not being
would react with the syringe or syringe needle. The pyrolysis used.
tube for boat inlet use may require specific construction to
6.7 Cupric Oxide Wire, as recommended by instrument
permit insertion of a boat fully into the inlet section of the
manufacturer.
furnace. The boat inlet system external to the furnace may be
6.8 Quartz Wool.
cooled to a temperature below room temperature to aid in
6.9 Pyridine. (Warning—Flammable, irritant.)
dissipating the heat from the boat when it is removed from the
6.10 Carbazole.
furnace. Cooling the boat inlet system may also reduce the
chances of the sample combusting in the boat before introduc- 7. Hazards
tion into the furnace and may be necessary when running
7.1 High temperature is employed in this test method.
volatile samples such as naphtha using a boat inlet system.
Exercise care when using flammable materials near the pyroly-
5.9 Quartz Insert Tube (Optional), may be packed with
sis furnace.
cupric oxide (CuO) or other oxidation catalyst as recom-
mended by the instrument manufacturer, to aid in completing 8. Sampling
oxidation. This is inserted into the exit end of the pyrolysis
8.1 To preserve volatile components, which may be in some
tube.
samples, do not uncover samples any longer than necessary.
5.10 Vacuum System (Optional), The chemiluminescence
Analyze samples as soon as possible after taking from the bulk
detector may be equipped with a vacuum system to maintain
supplies to prevent loss of nitrogen or contamination due to
the reaction cell at reduced pressure (typically 20 to 25 mm
exposure or contact with sample container.
Hg). This can improve the signal to noise ratio of the detector.
5.11 Analytical Balance (Optional), with a precision of
60.01 mg. 6
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
6. Reagents listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
6.1 Purity of Reagents—Reagent grade chemicals shall be and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
used in all tests. Unless otherwise indicated, it is intended that MD.

2
 D 4629 – 02
9. Assembly Apparatus boat is moved into the hot portion of the combustion tube.
9.1 Assemble apparatus in accordance with manufacturer’s Refer to the manufacturer’s instructions for selecting the rate of
instructions. boat movement into the furnace and boat residence time in the
9.2 Adjust the gas flows and the pyrolysis temperature as hot portion of the combustion tube.
recommended by the instrument manufacturer. 10.5 Calibration curves shall be generated in one of the
following manners depending on the capability of the instru-
10. Calibration and Standardization mentation used.
10.1 Prepare a series of calibration standards from the stock 10.5.1 For systems that use a microprocessor or computer
solution (see 6.6) covering the range of operation and consist- system for data collection and calibration curve generation, the
ing of nitrogen type and matrix similar to samples to be calibration curve shall be based on the linear regression of a
analyzed. There shall be a minimum of two calibration minimum of three repeat measurements of each calibration
standards in addition to the solvent blank, used to generate the standard.
calibration curve. 10.5.2 For those detectors not equipped with a micropro-
10.2 Determine the volume or mass of the material to be cessor or computer system for generating a calibration curve,
analyzed by using one of the volumetric or gravimetric construct a standard curve as follows. Repeat the determination
methods described below. of each calibration standard and the blank three times to
10.2.1 Volumetric measurement of the injected material is determine the average net response for each. Construct a curve
obtained by filling the syringe to the 80 % level, retracting the plot of detector response (integration counts) versus nanograms
plunger so that the lower liquid meniscus falls on the 10 % of nitrogen injected and apply the best straight line fit through
scale mark, and recording the volume of liquid in the syringe. the plotted data.
After the material has been injected, again retract the plunger 10.6 The response curve should be linear with a minimum
so that the lower liquid meniscus falls on the 10 % scale mark R2 of 0.999. The intercept should not be forced through zero.
and record the volume of liquid in the syringe. The difference The calibration curve shall be checked each day that the
between the two volume readings is the volume of material instrument is used (see Section 13).
injected.
11. Procedure
10.2.2 Alternatively, an automatic sampling and injection
device may be used to volumetrically inject a reproducible 11.1 Obtain a test specimen using the procedure in Section
volume of the material into the furnace. 8. The nitrogen concentration in the test specimen must be less
10.2.3 Gravimetric measurement of the injected material is than the concentration of the highest standard used in the
obtained by weighing the syringe before and after injection to calibration. Injection volumes ranging from 3 to 100 µL are
determine the amount of material injected. This procedure acceptable depending on the instrument being used. The size of
provides greater precision than the volumetric procedure, the injected sample shall be similar to the size of the injected
provided a balance with a precision of at least 60.01 mg is standards used for calibration.
used. 11.2 Flush a clean microlitre syringe several times with the
10.3 To introduce the sample into the furnace, insert the sample to be determined, and introduce it into the furnace
syringe needle through the inlet septum up to the syringe barrel using the procedure outlines in 10.2-10.4 (depending on
and inject the sample or standard at a uniform rate as specified whether a boat inlet system is being used). For samples with
by the instrument manufacturer (typically 0.2 to 1.0 µL/s). Rate total nitrogen concentration in the range 1 to 100 mg/kg,
of injection is dependent on such factors as viscosity, hydro- sample sizes injected are typically up to 10 µL. For samples
carbon type, and nitrogen concentration. Each user must adopt with total nitrogen concentration less than 1 mg/kg, injected
a method whereby a consistent and uniform injection rate is sample size can be up to 100 µL. Follow the instrument
ensured. An automatic sampling and injection device may be manufacturer’s recommendation on sample size based on type
used to introduce the material at a reproducible rate. If an of sample and level of nitrogen present.
automatic sampling and injection device is not being used, 11.3 To obtain one result, measure each test specimen a
determine the quantity of material injected using either 10.2.1 minimum of three times and calculate the average detector
(volumetric injection procedure) or 10.2.3 (gravimetric injec- response.
tion procedure).
12. Calculation
NOTE 4—For the most consistent injection rate and best analytical
12.1 For samples introduced volumetrically (10.2.1 or
results, a constant rate injection unit or automatic sampling and injection
device may be helpful. Coke formation at the outlet of the combustion 10.2.2), density values used for calculations are to be measured
tube may indicate too rapid of an injection rate. Consult manufacturer for using Practice D 1298, Test Method D 4052 or their equivalent,
recommendations. at ambient temperature.
NOTE 5—With direct injection below 5 mg/kg of nitrogen, the needle 12.2 Calculate the nitrogen content of the sample in mg/kg
septum blank may become increasingly important. Error due to this can be for the average of the three determinations that make up a
avoided by inserting the syringe needle into the hot inlet and allowing the single result as follows:
needle-septum blank to dissipate before injecting the sample.
nitrogen, mg/kg 5 ~I 2 I0! 3 K/~S 3 V 3 D! (1)
10.4 If a boat inlet system is used, then the material to be
analyzed is injected into a quartz boat using one of the or
procedures described in 10.2.1, 10.2.2, or 10.2.3 and the quartz nitrogen, mg/kg 5 ~I 2 I0! 3 K/~S 3 M! (2)

3
 D 4629 – 02

where: TABLE 1 Repeatability and Reproducibility

D = density of sample, g/mL, Concentration (mg/kg N) r R
S = slope of the calibration curve, counts/ng N, 100 2.0 8.7
V = volume of sample, µL, 75 1.7 7.5
K = dilution factor, 50 1.4 6.1
25 1.0 4.2
M = mass of sample, mg, 10 0.6 2.6
I = average detector response, integration counts, and 1 0.18 0.81
I0 = intercept of the calibration curve, integration counts. 0.3 0.10 0.44
12.3 For analyzers equipped with a calibration adjust, cal-
culate the nitrogen content of the sample in mg/kg as follows 14. Precision and Bias 7
(the average of three determinations make up a single result):
14.1 The precision of this test method as determined by
nitrogen, mg/kg 5 ~I 2 B! 3 K/~V 3 D! (3) statistical examination of interlaboratory results is as follows
or (see Table 1):
nitrogen, mg/kg 5 ~I 2 B! 3 K/M (4) 14.1.1 Repeatability—The difference between two test re-
sults obtained by the same operator with the same apparatus
where: under constant operating conditions on identical test material
D = density of sample, g/mL, would, in the long run, in the normal and correct operation of
S = slope of the calibration curve, counts/ng N, the test method, exceed the following values in only one case
V = volume of sample, µL, in twenty, where X = the average of the two test results.
K = dilution factor,
M = mass of sample, mg, r 5 0.1825~X! 0.5149 (5)
I = visual display reading of the sample, ng N 14.1.2 Reproducibility—The difference between two single
B = average of visual display readings of the blank, ng N. and independent test results obtained by different operators
working in different laboratories on identical test material
13. Quality Assurance/Quality Control (QA/QC)
would, in the long run, in the normal and correct operation of
13.1 Confirm the performance of the instrument and the test the test method, exceed the following values in only one case
procedure by analyzing a quality control (QC) sample. in twenty, where X = the average of the two test results.
13.1.1 When QA/QC protocols are already established in
the testing facility, these may be used when they confirm the R 5 0.8094~X! 0.5149 (6)
reliability of test results. 14.2 The bias of this test method cannot be determined since
13.1.2 When there is no QA/QC protocol established in the an appropriate standard reference material containing a known
testing facility, Appendix X1 may be used as the QA/QC trace level of nitrogen in a liquid petroleum hydrocarbon is not
system. available to form the basis of a bias study.
13.2 Users of this test method are advised that in contractual
agreements, one or more of the contracting parties can and may 7
Supporting data have been filed at ASTM International Headquarters and may
make Appendix X1 a mandatory practice. be obtained by requesting Research Reports RR: D02-1199 and RR: D02–1527.

APPENDIX

(Nonmandatory Information)

X1. QUALITY CONTROL MONITORING

X1.1 Confirm the performance of the instrument or the test Practice D 6299 and ASTM MNL 7. Investigate any out-of-
procedure by analyzing QC sample(s). control data for root cause(s). The results of this investigation
may, but not necessarily, result in instrument recalibration.
X1.2 Prior to monitoring the measurement process, deter-
mine the average value and control limits of the QC sample. X1.4 The frequency of QC testing is dependent on the
Refer to Practice D 6299 and ASTM MNL 7.8 criticality of the quality being measured, the demonstrated
stability of the testing process, and customer requirements.
X1.3 Record the QC results and analyze by control charts Generally, a QC sample is analyzed each testing day with
or other statistically equivalent techniques to ascertain the routine samples. The QC frequency should be increased if a
statistical control status of the total test process.9 Refer to large number of samples are routinely analyzed. However,
when it is demonstrated that the testing is under statistical
8
control, the QC testing frequency may be reduced. The QC
ASTM MNL 7, “Manual on Presentation of Data and Control Chart Analysis,”
ASTM International, West Conshohocken, PA.
sample precision should be periodically checked against the
9
In the absence of explicit requirements given in the test method, this clause ASTM method precision to ensure data quality. Refer to
provides guidance in QC testing frequency. Practice D 6299 and ASTM MNL 7.

4
 D 4629 – 02
X1.5 It is recommended that, if possible, the type of QC X1.6 See Practice D 6299 and ASTM MNL 7 for further
sample that is regularly tested be representative of the material guidance on QC and control charting techniques.
routinely analyzed. An ample supply of QC sample material
should be available for the intended period of use, and must be
homogenous and stable under the anticipated storage condi-
tions.

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