ASTM D5863-00
(Test Method)Standard Test Methods for Determination of Nickel, Vanadium, Iron, and Sodium in Crude Oils and Residual Fuels by Flame Atomic Absorption Spectrometry
Standard Test Methods for Determination of Nickel, Vanadium, Iron, and Sodium in Crude Oils and Residual Fuels by Flame Atomic Absorption Spectrometry
SCOPE
1.1 These test methods cover the determination of nickel, vanadium, iron, and sodium in crude oils and residual fuels by flame atomic absorption spectrometry (AAS). Two different test methods are presented.
1.2 Test Method A, Sections 7-12 -Flame AAS is used to analyze a sample that is decomposed with acid for the determination of total Ni, V, and Fe.
1.3 Test Method B, Sections 13-17 -Flame AAS is used to analyze a sample diluted with an organic solvent for the determination of Ni, V, and Na. This test method uses oil-soluble metals for calibration to determine dissolved metals and does not purport to quantitatively determine nor detect insoluble particulates.
1.4 The concentration ranges covered by these test methods are determined by the sensitivity of the instruments, the amount of sample taken for analysis, and the dilution volume. A specific statement is given in Note 3.
1.5 For each element, each test method has its own unique precision. The user can select the appropriate test method based on the precision required for the specific analysis.
1.6 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. Specific warning statements are given in Notes 1, 2, 5 and 6.
1.7 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
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Standards Content (Sample)
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An American National Standard
Designation: D 5863 – 00
Standard Test Methods for
Determination of Nickel, Vanadium, Iron, and Sodium in
Crude Oils and Residual Fuels by Flame Atomic Absorption
Spectrometry
This standard is issued under the fixed designation D 5863; 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 D 1193 Specification for Reagent Water
D 4057 Practice for Manual Sampling of Petroleum and
1.1 These test methods cover the determination of nickel,
Petroleum Products
vanadium, iron, and sodium in crude oils and residual fuels by
D 4177 Practice for Automatic Sampling of Petroleum and
flame atomic absorption spectrometry (AAS). Two different
Petroleum Products
test methods are presented.
D 6299 Practice for Applying Statistical Quality Assurance
1.2 Test Method A, Sections 7–12—Flame AAS is used to
Techniques to Evaluate Analytical Measurement System
analyze a sample that is decomposed with acid for the
Performance
determination of total Ni, V, and Fe.
1.3 Test Method B, Sections 13–17—Flame AAS is used to
3. Summary of Test Methods
analyze a sample diluted with an organic solvent for the
3.1 Test Method A—One to twenty grams of sample are
determination of Ni, V, and Na. This test method uses oil-
weighed into a beaker and decomposed with concentrated
soluble metals for calibration to determine dissolved metals
sulfuric acid by heating to dryness. The residual carbon is
and does not purport to quantitatively determine nor detect
burned off by heating at 525°C in a muffle furnace. The
insoluble particulates. Hence, this test method may underesti-
inorganic residue is digested in dilute nitric acid, evaporated to
mate the metal content, especially sodium, present as inorganic
incipient dryness, dissolved in dilute nitric and made up to
sodium salts.
volume with dilute nitric acid. Interference suppressant is
1.4 The concentration ranges covered by these test methods
added to the dilute nitric acid solution. The solution is
are determined by the sensitivity of the instruments, the
nebulized into the flame of an atomic absorption spectrometer.
amount of sample taken for analysis, and the dilution volume.
A nitrous oxide/acetylene flame is used for vanadium and an
A specific statement is given in Note 1.
air/acetylene flame is used for nickel and iron. The instrument
1.5 For each element, each test method has its own unique
is calibrated with matrix-matched standard solutions. The
precision. The user can select the appropriate test method based
measured absorption intensities are related to concentrations by
on the precision required for the specific analysis.
the appropriate use of calibration data.
1.6 The values stated in SI units are to be regarded as the
3.2 Test Method B—Sample is diluted with an organic
standard. The values given in parentheses are for information
solvent to give a test solution containing either 5 % (m/m) or
only.
20 % (m/m) sample. The recommended sample concentration
1.7 This standard does not purport to address all of the
is dependent on the concentrations of the analytes in the
safety concerns, if any, associated with its use. It is the
sample. For the determination of vanadium, interference sup-
responsibility of the user of this standard to establish appro-
pressant is added to the test solution. The test solution is
priate safety and health practices and determine the applica-
nebulized into the flame of an atomic absorption spectrometer.
bility of regulatory limitations prior to use. Specific warning
A nitrous oxide/acetylene flame is used for vanadium and an
statements are given in 7.1, 8.2, 8.5, 10.2, 10.4, and 15.1.
air/acetylene flame is used for nickel and sodium. The mea-
2. Referenced Documents sured absorption intensities are related to concentrations by the
appropriate use of calibration data.
2.1 ASTM Standards:
4. Significance and Use
4.1 When fuels are combusted, metals present in the fuels
These test methods are under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and are the direct responsibility of Subcommit-
tee D02.03.0B on Elemental Analysis.
Current edition approved Nov. 10, 2000. Published November 2000. Originally Annual Book of ASTM Standards, Vol 11.01.
published as D 5863 – 95. Last previous edition D 5863 – 00. Annual Book of ASTM Standards, Vol 05.02.
Annual Book of ASTM Standards, Vol 05.03.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D5863–00
can form low melting compounds that are corrosive to metal
parts. Metals present at trace levels in petroleum can deactivate
catalysts during processing. These test methods provide a
means of quantitatively determining the concentrations of
vanadium, nickel, iron, and sodium. Thus, these test methods
can be used to aid in determining the quality and value of the
crude oil and residual oil.
5. Purity of Reagents
5.1 Reagent grade chemicals shall be used for all tests.
Unless otherwise indicated, it is intended that all reagents
conform to the specifications of the Committee on Analytical
Reagents of the American Chemical Society where such
specifications are available. Other grades may be used, pro-
vided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of
the determination.
5.2 When determining metals at concentrations less than 1
mg/kg, use ultra-pure grade reagents.
5.3 Purity of Water—Unless otherwise indicated, reference
to water shall be understood to mean reagent water conforming FIG. 1 Decomposition Apparatus
to Type II of Specification D 1193.
capacities. When determining concentrations below 1 mg/kg,
6. Sampling and Sample Handling
all glassware must be thoroughly cleaned (or soaked overnight)
with 5 % HNO and rinsed five times with water.
6.1 The objective of sampling is to obtain a sample for
7.4 Electric Muffle Furnace, capable of maintaining 525 6
testing purposes that is representative of the entire quantity.
Only representative samples obtained as specified in Practices 25°C and sufficiently large to accommodate 400-mL beakers.
The capability of an oxygen bleed is advantageous and
D 4057 and D 4177 shall be used. Do not fill the sample
container more than two-thirds full optional.
7.5 Steam Bath.
6.2 Prior to weighing, stir the sample and then shake the
sample in its container. If the sample does not readily flow at 7.6 Temperature Controlled Hot Plate, (optional).
7.7 Drying Oven, (optional), explosion-proof, if used to heat
room temperature, heat the sample to a sufficiently high and
safe temperature to ensure adequate fluidity. crude oils to obtain fluidity.
8. Reagents
TEST METHOD A—FLAME ATOMIC ABSORPTION
AFTER ACID DECOMPOSITION OF THE SAMPLE
8.1 Aqueous Standard Solutions—Individual aqueous stan-
dards with 1000 mg/kg concentrations of vanadium, nickel,
7. Apparatus
and iron, purchased or prepared in acid matrix to ensure
7.1 Atomic Absorption Spectrometer, complete instrument stability.
with hollow cathode lamps and burners with gas supplies to 8.2 Nitric Acid—Concentrated nitric acid, HNO
support air-acetylene and nitrous oxide-acetylene flames (Warning—Poison, oxidizer. Causes severe burns. Harmful or
(Warning—Hazardous. Potentially toxic and explosive. Refer fatal if swallowed or inhaled.).
to the manufacturer’s instrument manual for associated safety 8.3 Nitric Acid 50 % (V/V)—Carefully add, with stirring,
hazards.). one volume of concentrated nitric acid to one volume of water.
7.2 Sample Decomposition Apparatus (optional)—This ap- 8.4 Dilute Nitric Acid, 5 % (V/V)—Carefully add, with
paratus is described in Fig. 1. It consists of a borosilicate glass stirring, one volume of concentrated nitric acid to 19 volumes
400-mL beaker for the test solution, an air bath (Fig. 2) that of water.
rests on a hot plate and a 250 W infrared lamp supported 2.5 8.5 Sulfuric Acid—Concentrated sulfuric acid, H SO
2 4
cm above the air bath. A variable transformer controls the (Warning—Poison, oxidizer. Causes severe burns. Harmful or
voltage applied to the lamp. fatal if swallowed or inhaled.).
7.3 Glassware—Borosilicate glass 400-mL beakers, volu- 8.6 Aluminum Nitrate, Al(NO ) 9HOH.
3 3
metric flasks of various capacities and pipettes of various 8.7 Potassium Nitrate, KNO .
9. Preparation of Standards
9.1 Multi-Element Standard—Using the aqueous standard
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
solutions, prepare a multi-element standard containing 100
listed by the American Chemical Society, see Analar Standards for Laboratory
mg/kg each of vanadium, nickel, and iron. Standards should be
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
prepared to ensure accuracy and stability and should be stored
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. in clean containers to safeguard against physical degradation.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D5863–00
TABLE 1 AAS Conditions for the Determination of Vanadium,
Nickel, and Iron Following Acid Sample Decomposition
Wavelength, Concentration Interference
Element Flame
nm Range, μg/mL Suppressant
Vanadium 318.4 0.5–20 250 μg/mL Al, N O-
Al(NO ) in 5 % C H
3 3 2 2
(V/V)
HNO
Nickel 232.0 0.5–20 None Air-C H
2 2
Iron 248.3 3.0–10 None Air-C H
2 2
and acid. When it is desired to determine higher concentrations, reduce the
sample size accordingly.
10.2 At the same time prepare reagent blanks using the
same amount of sulfuric acid as used for sample decomposi-
tion. Reagent blanks should be carried through the same
procedure as the samples. Warning—Reagent blanks are
critical when determining concentrations below 1 mg/kg. To
simplify the analysis, use the same volume of acid and the
same dilutions as used for the samples. For example, if 20 g of
sample is being decomposed, use 10 mL of sulfuric acid for the
reagent blank.
10.3 The use of the air bath apparatus (Fig. 2) is optional.
Place the beaker in the air bath, which is located in the hood.
The hot plate is off at this time. Heat gently from the top with
Note—All parts 16 gage (1.5 mm, 0.060 in.) aluminum. All dimensions are in the infrared lamp (Fig. 1) while stirring the test solution with a
inches.
glass rod. As decomposition proceeds (indicated by a frothing
and foaming), control the heat of the infrared lamp to maintain
Metric Equivalents
steady evolution of fumes. Give constant attention to each
in. mm in. mm
sample mixture until all risk of spattering and foaming is past.
1 25.4 3 ⁄8 98.4
Then, gradually increase the temperature of both the hot plate
1 ⁄2 38.1 5 127
2 50.8 6 ⁄2 165.1 and lamp until the sample is reduced to a carbonaceous ash.
3 ⁄16 77.8
10.4 If the air bath apparatus is not used, heat the sample
FIG. 2 Air Bath
and acid on a temperature controlled hot plate. As described in
10.3, monitor the decomposition reaction and adjust the
9.2 Working Standards—Prepare at least two working stan- temperature of the hot plate accordingly. Warning—Hot
fuming concentrated sulfuric acid is very corrosive and a
dards to cover the concentration ranges specified in Table 1.
For vanadium, add the specified interference suppressant. Each strong oxidizing acid. The analyst should work in a well-
ventilated hood and wear rubber gloves and a suitable face
working standard must contain 5 % (V/V) nitric acid. Stan-
dards should be prepared to ensure accuracy and stability and shield to protect against spattering acid.
should be stored in clean containers to safeguard against 10.5 Place the sample in the muffle furnace maintained at
physical degradation. 525 6 25°C. Optionally, introduce a gentle stream of oxygen
9.3 Standard Blank, the standard blank contains 5 % (V/V) into the furnace to expedite oxidation. Continue to heat until
nitric acid and any interference suppressant specified in Table the carbon is completely removed.
1. 10.6 Dissolve the inorganic residue by washing down the
9.4 Check Standard—Prepare a calibration check standard wall of the beaker with about 10 mL of the 1 + 1 HNO . Digest
in the same way as the working standards and at analyte on a steam bath for 15 to 30 min. Transfer to a hot plate and
gently evaporate to incipient dryness.
concentrations that are typical of the specimens being ana-
lyzed. 10.7 Wash down the wall of the beaker with about 10 mL of
dilute nitric acid (5 % V/V). Digest on the steam bath until all
10. Preparation of Test Solutions
salts are dissolved. Allow to cool. Transfer quantitatively to a
10.1 Into a beaker, weigh an amount of sample estimated to volumetric flask of suitable volume and make up to volume
contain between 0.0025 and 0.12 mg of each metal to be
with dilute nitric acid. This is the test solution.
determined. A typical mass is 10 g. Add 0.5 mL of H SO for 10.8 Pipette aliquots of the test solution into two separate
2 4
each gram of sample.
volumetric flasks. Retain one flask for the determination of
nickel and iron. To the other flask add aluminum interference
NOTE 1—If it is desired to extend the lower concentration limits of the
suppressant for vanadium determination (refer to Table 1) and
test method, it is recommended that the decomposition be done in 10-g
dilute up to mark with dilute nitric acid (5 % V/V). Similarly,
increments up to a maximum of 100 g. It is not necessary to destroy all the
organic matter each time before adding additional amounts of the sample prepare a reagent blank solution for vanadium analysis.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D5863–00
TABLE 2 AAS Conditions for the Determination of Vanadium,
11. Preparation of Apparatus
Nickel, and Sodium Following Solvent Dilution of the Sample
11.1 Consult the manufacturer’s instructions for the opera-
Wavelength, Concentration Interference
Element Flame
tion of the atomic absorption spectrometer. This test m
...
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