ASTM D5184-00
(Test Method)Standard Test Methods for Determination of Aluminum and Silicon in Fuel Oils by Ashing, Fusion, Inductively Coupled Plasma Atomic Emission Spectrometry, and Atomic Absorption Spectrometry
Standard Test Methods for Determination of Aluminum and Silicon in Fuel Oils by Ashing, Fusion, Inductively Coupled Plasma Atomic Emission Spectrometry, and Atomic Absorption Spectrometry
SCOPE
1.1 These test methods cover the determination of aluminum and silicon in fuel oils at concentrations between 5 and 150 mg/kg for aluminum and 10 and 250 mg/kg for silicon.
1.2 Test Method A--Inductively coupled plasma atomic emission spectrometry is used in this test method to quantitatively determine aluminum and silicon.
1.3 Test Method B--Flame atomic absorption spectrometry is used in this test method to quantitatively determine aluminum and silicon.
1.4 The values given in SI (metric) units are to be regarded as the standard.
1.5 This standard does not purport to address all of the safety problems, 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 precautionary statements are given in 10.1 and 11.5.
General Information
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Standards Content (Sample)
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Designation: D 5184 – 00
Standard Test Methods for
Determination of Aluminum and Silicon in Fuel Oils by
Ashing, Fusion, Inductively Coupled Plasma Atomic
Emission Spectrometry, and Atomic Absorption
Spectrometry
This standard is issued under the fixed designation D 5184; 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 3. Terminology
1.1 These test methods cover the determination of alumi- 3.1 Definition:
num and silicon in fuel oils at concentrations between 5 and 3.1.1 emission spectroscopy—Refer to Terminology E 135.
150 mg/kg for aluminum and 10 and 250 mg/kg for silicon. 3.2 Definitions of Terms Specific to This Standard:
1.2 Test Method A—Inductively coupled plasma atomic 3.2.1 calibration—the process by which the relationship
emission spectrometry is used in this test method to quantita- between signal intensity and elemental concentration is deter-
tively determine aluminum and silicon. mined for a specific element analysis.
1.3 Test Method B—Flame atomic absorption spectrometry 3.2.2 check standard—in calibration, an artifact measured
is used in this test method to quantitatively determine alumi- periodically, the results of which typically are plotted on a
num and silicon. control chart to evaluate the measurement process.
1.4 The values given in SI (metric) units are to be regarded
4. Summary of Test Methods
as the standard.
4.1 A weighed quantity of homogenized sample is heated in
1.5 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the a clean platinum dish, the combustible material is removed by
burning and the carbon finally removed by heating in a muffle
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- furnace at a temperature of 550 6 25°C. The residue is fused
with a lithium tetraborate/lithium fluoride flux. The fused
bility of regulatory limitations prior to use. Specific precau-
tionary statements are given in 10.1 and 11.5. mixture is digested in a solution of tartaric acid and hydrochlo-
ric acid and diluted to volume with water. The resulting
2. Referenced Documents
solution is aspirated into an inductively-coupled plasma and
2.1 ASTM Standards: the emission intensities of aluminum and silicon lines are
D 1193 Specification for Reagent Water measured. Standard calibration solutions are also aspirated and
D 4057 Practice for Manual Sampling of Petroleum and aluminum and silicon intensities are measured for comparison.
Petroleum Products Alternatively, the resulting solution is aspirated into the flame
D 4177 Practice for Automatic Sampling of Petroleum and of an atomic absorption spectrometer and the absorptions of the
Petroleum Products resonance radiation of aluminum and silicon are measured.
D 6299 Practice for Applying Statistical Quality Assurance Standard calibration solutions are also aspirated and aluminum
Techniques to Evaluate Analytical Measurement System and silicon absorption intensities are measured for comparison.
Performance
5. Significance and Use
E 135 Terminology Relating to Analytical Chemistry for
5.1 Catalyst fines in fuel oils can cause abnormal engine
Metals, Ores, and Related Materials
wear. These test methods provide a means of determining
silicon and aluminum, the major constituents of the catalysts.
These test methods are under the jurisdiction of ASTM Committee D02 on
6. Apparatus
Petroleum Products and Lubricants and are the direct responsibility of Subcommit-
tee D02.03.0B on Spectrometric Methods.
6.1 Balance, capable of weighing to 0.1 g, capacity of 150
Current edition approved Nov. 10, 2000. Published December 2000. Originally
g.
published as D 5184 – 91. Last previous edition D 5184 – 91 (1995).
Annual Book of ASTM Standards, Vol 11.01. 6.2 Choice of Instrument:
Annual Book of ASTM Standards, Vol 05.02.
6.2.1 Inductively-Coupled Plasma Atomic Emission
Annual Book of ASTM Standards, Vol 05.04.
Annual Book of ASTM Standards, Vol 03.05.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
D 5184
Spectrometer—Either a sequential or simultaneous spectrom- 7.6 2-Propanol (Isopropyl Alcohol) (Warning—
eter is suitable, if equipped with an ICP torch and RF generator Flammable; can be explosive when evaporated to or near
to form and sustain the plasma. dryness.)
6.2.2 Atomic Absorption Spectrometer—A suitable instru- 7.7 Aqueous Standard Solutions.
ment will consist of modulated hollow cathode lamps or other 7.7.1 Aluminum Standard Solutions—Obtain a ready made,
sources of resonance radiation of aluminum and silicon, a aqueous standard or prepare a standard from aluminum wire.
nitrous oxide/acetylene burner, and a spectrometer with a 7.7.1.1 Aluminum Solution (1000 mg/L)—Aqueous, ready
suitable detection and read-out system. made commercial standard.
6.3 Homogenizer, non-aerating, high-speed shear mixer to 7.7.1.2 Aluminum Solution (1000 mg/L)—Dissolve 1.000 6
homogenize the sample. 0.005 g of aluminum metal (wire form, 99.99 % purity) in 50
mL of concentrated hydrochloric acid. Heat gently. Cool and
NOTE 1—Ultrasonic bath and ultrasonic probe type homogenizers were
transfer the solution to 1000 mL volumetric flask. Dilute to the
not evaluated in the development of these test methods.
mark with water.
6.4 Electric Muffle Furnace, capable of being maintained at
7.7.2 Silicon Standard Solutions—Obtain a ready made,
temperatures of 550 6 25°C and 925 6 25°C. The furnace
aqueous standard or prepare a standard from silicon dioxide.
preferably having suitable apertures at front and rear to allow
7.7.2.1 Silicon Solution (1000 mg/L)—Aqueous, ready
a slow, natural draft of air to pass through.
made commercial standard.
6.5 Electric Hot Plate, with or without magnetic stirring
7.7.2.2 Silicon Solution (1000 mg/L)—Using a zirconium
capability.
crucible with a close fitting lid, fuse 2.140 6 0.0107 g of
6.6 Electric Oven, maintained at a temperature of 50 to
silicon dioxide (99.99 % purity) with8gof sodium hydroxide
60°C.
until a clear melt is obtained. Cool and dissolve the melt in 100
6.7 Graduated Cylinders, 10, 25, 50 and 100 mL.
mL of a solution of 1 part hydrochloric acid by volume and 2
6.8 Pipettes, 1, 2, 5, 10, 20 and 25 mL.
parts water by volume. Transfer this solution to a 1000 mL
6.9 Platinum Dish, 100 mL capacity, cleaned with fused
volumetric flask and dilute to the mark with water. Immedi-
potassium hydrogen sulfate.
ately, transfer the contents of the flask to a plastic bottle.
6.10 Volumetric Flasks, 100 and 1000 mL.
7.8 Tartaric Acid/Hydrochloric Acid Solution—Dissolve 5 g
6.11 All glassware must be carefully cleaned with 1 + 1
of tartaric acid in about 500 mL of water acidified with 40 mL
hydrochloric acid and rinsed thoroughly with water to mini-
of concentrated hydrochloric acid and dilute to 1000 mL with
mize contamination. The use of chromic acid cleaning solution
water.
is not recommended.
7.9 Toluene/2-Propanol Solution (1 + 1)—Mix one vol-
6.12 Zirconium crucible with close fitting zirconium lid, 30
ume of toluene with one volume of 2-propanol.
to 50 mL capacity.
7.10 Quality Control (QC) Samples, preferably are portions
of one or more liquid petroleum materials that are stable and
7. Reagents
representative of the samples of interest. These QC samples
7.1 Purity of Reagents—Reagent grade chemicals shall be
can be used to check the validity of the testing process as
used in all tests. Unless otherwise indicated, it is intended that
described in Section 18.
all reagents conform to the specifications of the Committee on
8. Quality Control (QC) Sample Preparation
Analytical Reagents of the American Chemical Society where
such specifications are available. Other grades may be used, 8.1 Preparation of QC Samples shall follow the same
provided it is first ascertained that the reagent is of sufficiently
protocol as defined for the test specimen (Sections 9, 10 and
high purity to permit its use without lessening the accuracy of 11).
the determination.
9. Sampling
7.2 Purity of Water—Unless otherwise indicated, reference
9.1 The objective of sampling is to obtain a sample for
to water shall be understood to mean reagent water conforming
testing purposes that is representative of the entire quantity.
to Type II of Specification D 1193.
Thus, take samples in accordance with the instructions in
7.3 Flux—Mixture of 90 % lithium tetraborate and 10 %
Practice D 4057 or D 4177 . Typically, a gallon size container
lithium fluoride.
filled to approximately three-fourths of capacity is satisfactory.
NOTE 2—Lithium fluoride is necessary to prevent heavy metal corro-
10. Sample Handling
sion of the platinum dish and to lower the fusion temperature.
10.1 Homogenization—It is extremely important to homog-
7.4 Hydrochloric acid (36 % (m/m))—concentrated hydro-
enize the fuel oil in the sample container in order to obtain a
chloric acid.
representative specimen. (Warning—Failure to use this ho-
7.5 Potassium Hydrogen Sulfate, fused solid.
mogenization procedure can invalidate the results because
non-representative aliquots could be obtained and this could
lead to erroneous results.)
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
10.2 Place the sample container in an oven at a temperature
listed by the American Chemical Society, see Analar Standards for Laboratory
of 50 to 60°C. Keep the container in the oven until the sample
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
comes to temperature. Insert the shaft of a high speed homog-
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. enizer into the sample container so that the head of the shaft is
D 5184
immersed to approximately 5 mm from the bottom of the 12.2 Aluminum—Prepare a 250 mg/L aluminum working
sample vessel. Mix the sample for about 5 min. solution by diluting 25 mL of the 1000 mg/L standard solution
to 100 mL with water. To each of four clean 100 mL volumetric
11. Specimen Preparation
flasks, add 0.4 g of flux and 50 mL of the tartaric acid/
hydrochloric acid solution. To successive flasks add 2, 4, 10
11.1 Weigh a clean platinum dish to the nearest 0.1 g.
and 20 mL of the 250 mg/L aluminum working solution and
Immediately transfer up to 50 g (but not less than 20 g) of the
dilute to 100 mL with water. The calibration solutions contain
well-mixed sample, preferably containing about 1.3 mg alumi-
5, 10, 25 and 50 mg/L of aluminum, respectively.
num, to the platinum dish and re-weigh the dish and contents
12.3 Silicon—Prepare a 250 mg/L silicon working solution
to the nearest 0.1 g to obtain the weight of the specimen.
by diluting 25 mL of 1000 mg/L standard solution to 100 mL
NOTE 3—The specimen mass proposed, based on the aluminum content
with water. To each of four clean 100 mL volumetric flasks,
will suffice for silicon as both elements are usually found in fuel oils at
add 0.4 g of flux and 50 mL of the tartaric acid/hydrochloric
similar concentrations.
acid solution. To successive flasks, add 2, 4, 10 and 20 mL of
11.2 Warm the dish and contents gently with a bunsen flame
the 250 mg/L silicon working solution and dilute to 100 mL
until the sample can be ignited. Maintain the contents of the
with water. These calibration solutions contain 5, 10, 25 and 50
basin at a temperature such that most of the combustible
mg/L of silicon, respectively.
material is removed and only carbon and ash remain.
12.4 Transfer all calibration standards to plastic bottles.
NOTE 4—If the specimen contains considerable amounts of moisture,
NOTE 7—When both aluminum and silicon are being determined, the 5
foaming and frothing can cause loss of material. If this is the case, discard
to 50 mg/L calibration solutions can be combined providing there are no
the specimen and to a fresh portion add 1 to 2 mL of 2-propanol before
incompatibility problems caused by the reagents used in the preparation of
heating. If this is not satisfactory, add 10 mL of a mixture of equal parts
the standard solutions described in 7.7.1 and 7.7.2.
of toluene and 2-propanol and mix thoroughly. Place several strips of
ashless filter paper in the mixture and warm gently. When the paper begins
TEST METHOD A—INDUCTIVELY-COUPLED
to burn, the greater part of the water will have been removed.
PLASMA ATOMIC EMISSION SPECTROMETRY
11.3 Place the dish and contents in a muffle furnace main-
13. Preparation of ICP Instrument
tained at a temperature of 550 6 25°C. Maintain the muffle
13.1 Instrument—Consult the manufacturer’s instructions
furnace at this temperature until all the carbon is removed and
for the operation of the instrument. Design differences between
only ash remains. This may require more than 10 h in the
muffle furnace and may conveniently be done overnight. instruments, ICP excitation sources, and different selected
analytical wavelengths for individual spectrometers make it
11.4 Cool the dish to room temperature, add 0.4 g of flux
and mix with the ash. Place the dish in a muffle furnace impractical to specify the required manipulations in detail.
13.2 Peristaltic Pump—If using a peristaltic pump, inspect
maintained at a temperature of 925 6 25°C for 5 min. Remove
the dish and ensure contact of the flux with the ash. Replace the the pump tubing and replace it, if necessary, before starting
each day. Verify the solution uptake rate and adjust it to the
dish in the muffle furnace and maintain at a temperature of
925 6 25°C for 10 min. desired rate.
13.3 ICP Excitation Source—Ignite the ICP excitation
11.5 Remove the dish, cool the fusion melt to room tem-
source at least 30 min before performing an analysis. During
perature and add 50 mL of the tartaric acid/hydrochloric acid
this warm-up period, nebulize water.
solution. Place the dish and contents on the hot plate main-
tained at a temperature of approximately 80°C. Heat until the
NOTE 8—Some manufacturers recommend even longer warmup peri-
melt is dissolved. (Warning—Vaporization of a significant
ods to minimize the variability of the measurements.
amount of the liquid can lead to precipitation of an insoluble
13.4 Wavelength Profiling—Perform any wavelength profil-
form of silica leading to erroneous results.)
ing that may be called for in the normal operation of the
NOTE 5—Prolonged heating can be necessary to dissolve the melt
instrument.
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