ASTM D5059-98(2003)e1

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An American National Standard
e1
Designation:D5059–98 (Reapproved 2003)
Designation: 228/79
Standard Test Methods for
Lead in Gasoline by X-Ray Spectroscopy
This standard is issued under the fixed designation D 5059; 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.
e NOTE—Warning notes were editorially moved into the standard text in August 2003.
1. Scope 2. Referenced Documents
1.1 These test methods cover the determination of the total 2.1 ASTM Standards:
lead content of a gasoline within the following concentration D 2599 Test Method for Lead in Gasoline by X-Ray Spec-
ranges: trometry
D 3229 TestMethodforLowLevelsofLeadinGasolineby
0.010 to 5.0 g Pb/US gal
0.012 to 6.0 g Pb/UK gal
Wavelength Dispersive X-Ray Spectrometry
0.0026 to 1.32 g Pb/L
D 3341 Test Method for Lead in Gasoline-Iodine
1.1.1 Test Methods A and B cover the range of 0.10 to 5.0 Monochloride Method
g Pb/US gal. Test Method C covers the range of 0.010 to 0.50
D 4057 Practice for Manual Sampling of Petroleum and
g Pb/US gal. Petroleum Products
1.1.2 These test methods compensate for normal variation
3. Summary of Test Method
ingasolinecompositionandareindependentofleadalkyltype.
1.2 Test Method A (formerly in Test Method D 2599)— 3.1 There are three alternative test methods, as follows.
Sections 5-9.
3.1.1 Test Method A (Bismuth Internal Standard Method
Test Method B (formerly in Test Method D 2599)—Sections High Concentration)—One volume of sample is mixed thor-
10-14. oughly with an equal volume of bismuth internal standard
Test Method C (formerly in Test Method D 3229)—Sections solution. The mixture is placed in the X-ray beam and the
15-19. intensitiesofthelead L-a radiationat1.175 Åandthebismuth
1.3 The values stated in SI are to be regarded as the L-a radiation at 1.144 Å are determined. The lead concentra-
standard. For reporting purposes the values stated in grams per tion of the sample is measured by comparing the ratio of gross
U.S. gallon are the preferred units in the United States. Note counting rate at 1.175 Å with the gross counting rate at 1.144
that in other countries, other units can be preferred. Å to a previous prepared calibration curve of concentration
1.4 This standard does not purport to address all of the versus the same ratios.
safety concerns, if any, associated with its use. It is the 3.1.2 Test Method B (Scattered Tungsten Radiation
responsibility of the user of this standard to establish appro- Method)—The ratio of the net X-ray intensity of the lead L-a
priate safety and health practices and determine the applica- radiation to the net intensity of the incoherently scattered
bility of regulatory limitations prior to use. For specific hazard tungsten L-a radiation is obtained on a portion of the sample.
statements, see Sections 5, 6, 11, and 18. The lead content is determined by multiplying this ratio by a
calibration factor obtained with a standard lead solution of
known concentration.
These test methods are under the jurisdiction of Committee D02 on Petroleum
3.1.3 Test Method C (Bismuth Internal Standard Method,
Products and Lubricants and are the direct responsibility of Subcommittee D02.03
Low Concentration)—Twenty millilitres of sample is mixed
on Elemental Analysis.
thoroughly with two milliliters of bismuth internal standard
Current edition approved May 10, 2003. Published August 2003. (Originally
published as D 2599 – 67T and D 3229 – 73.) Originally approved in 1990. Last
previous edition approved in 1998 as D 5059– 98.
These test methods have been approved by the sponsoring committees and Discontinued. See 1991 Annual Book of ASTM Standards , Vol 05.02.
accepted by the cooperating organizations in accordance with established proce- Discontinued. See 1991 Annual Book of ASTM Standards , Vol 05.03.
dures. Annual Book of ASTM Standards, Vol 05.02.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
e1
D5059–98 (2003)
solution. The mixture is placed in the X-ray beam of a muth 2-ethylhexoate is used, add 2-ethylhexanoic acid as a
spectrometer and the intensities of the lead L-a radiation at stabilizer (see Note 3) to obtain a solution containing the
1.175 Å, the bismuth L-a radiation at 1.144 Å, and a back- following:
ground at 1.194 Å are determined. A blank, made with
3.00 g Bi/US gal at 15.5°C (60°F) or
3.60 g Bi/UK gal at 15.5°C (60°F) or
iso-octane and bismuth internal standard, is run using the same
0.793 g Bi/L at 15°C
procedure. The lead concentration is measured by determining
NOTE 3—Some stability difficulties have been experienced with bis-
the ratio of the net counting rate at 1.175 Å to the gross
muth 2-ethylhexoate internal standard solution. If the standard is blended
counting rate at 1.144 Å for the sample, subtracting the
to contain 5 % 2-ethylhexanoic acid, the standard has been found to last
comparable ratio found for the blank, and comparing to a
almost indefinitely. The 2-ethylhexanoic acid stabilizes iso-octane, tolu-
previously prepared calibration curve of concentration versus
ene, and benzene solutions of the bismuth 2-ethylhexoate which are
the same ratios.
otherwise stable for only a day or two. Normal octanoic acid does not
stabilize solution.
4. Significance and Use
6.4 Iso-octane.(Warning—Extremely flammable.)
4.1 These test methods determine the concentration of lead
6.5 Solvent, capable of dissolving the bismuth internal
(from alkyl addition) in gasoline. These alkyl additives im-
standard. Mixed xylenes and dodecane have been found
prove the antiknock properties.
suitable to use.
4.2 Test Method C is used to ensure compliance of trace
6.6 Hydrocarbon-Soluble Lead—Either tetraethyllead
lead as required by federal regulations for lead-free gasoline
(TEL) or a lead-containing compound (for example, lead
(40 CFR part 80).
naphthenate) with a certifiable lead concentration.
6.7 Lead (Pb) Standard Solution—Dissolve tetraethyllead
TEST METHOD A (BISMUTH INTERNAL
(TEL) (Warning—TEL is toxic by ingestion), lead naphthen-
STANDARD)
ate (see Note 4), or other suitable lead containing compound in
iso-octane (Warning—Extremely flammable), toluene, or a
5. Apparatus
mixture of these two solvents. This standard solution shall
5.1 X-ray Spectrometer, capable of measuring radiations
contain an accurately known lead concentration of approxi-
mentioned in 3.1.1 and of being operated under the following
mately the following magnitude:
instrumental conditions or other giving equivalent results:
5 g Pb/US gal at 15.5°C (60°F) or
Tube Voltage 50 kV
6 g Pb/UK gal at 15.5°C (60°F) or
Tube Current 20 to 45 mA
1.3 g Pb/L at 15.5°C
Analyzing Crystal Lithium Fluoride (LiF)
Optical Path Air, Helium
6.7.1 Keep the standard solution refrigerated when not in
(Warning—Compressed gas under pressure)
use.
Detector Proportional or Scintillation
NOTE 4—A lead naphthenate solution of same lead concentration has
NOTE 1—The X-ray spectrometer and manner of use should comply
also proven satisfactory as a calibration material. ConcentratedTELis not
with the regulations governing the use of ionizing radiation or recommen-
used to make up standard solutions. The concentrated solution is too
dations of the International Commission of Radiological Protection, or
acutely toxic to be handled safely under normal laboratory conditions.
both.
NOTE 5—When this lead standard solution is prepared with TEL, the
6. Reagents and Materials lead concentration can be determined with Test Method D 3341.
6.1 Purity of Reagents—Reagent grade chemicals shall be
6.8 Toluene.(Warning—Flammable. Vapor harmful.)
used in all tests. Unless otherwise indicated, it is intended that
all reagents conform to the specifications of the Committee on
7. Calibration
Analytical Reagents of the American Chemical Society where
7.1 Make dilutions of the lead (Pb) standard solution to give
such specifications are available. Other grades may be used,
0.10, 1.00, 2.00, 3.00, 4.00 and 5.00 g Pb/US gal at 15.5°C
provided it is first ascertained that the reagent is of sufficiently
(60°F) or 0.10, 1.00, 2.50, 3.50, 5.00, and 6.00 g Pb/UK gal at
high purity to permit its use without lessening the accuracy of
15.5°C (60°F) or 0.025, 0.264, 0.529, 0.793, 1.057, 1.322 g
the determinations.
Pb/L at 15°C in toluene, iso-octane, or a mixture of these
6.2 Hydrocarbon-Soluble Bismuth.
solvents.
7.2 Allow the lead standards and bismuth internal standard
NOTE 2—Bismuth2-Ethylhexoatehasbeenfoundsuitabletouse.Other
bismuth containing materials that are hydrocarbon-soluble may also be solutions to come to room temperature.
used when they are certified to conform to 6.1.
7.3 Pipet accurately 10 mL of each standard into separate
glass-stoppered bottles or flasks and add an equal, accurately
6.3 Bismuth Internal Standard Solution—Dilute the
measured volume of the bismuth internal standard solution to
hydrocarbon-soluble bismuth with a suitable solvent. If bis-
each one. Mix thoroughly.
7.4 Place one of these solutions in the sample cell using
techniques consistent with good operating practice for the
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
spectrometer employed. Place the cell in the instrument, allow
listed by the American Chemical Society, see Analar Standards for Laboratory
the spectrometer atmosphere to reach equilibrium (if appropri-
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
ate), and determine the counting rate at the lead L-a line
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 1
MD. (1.175 Å) and at the bismuth L-a line (1.144 Å).
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D5059–98 (2003)
NOTE 6—When possible, collect at least 100 000 counts at each line. NOTE 8—To convert grams per US gallon at 15.5°C (60°F) to: (a)
When sensitivity or concentration, or both, makes it impractical to collect grams per UK gallon at 15.5°C (60°F) multiply by 1.200 and (b) grams
this many counts, the technique that allows the greatest statistical per litre at 15.5°C, multiply by 0.2201.
precision in the time allotted for each analysis should be used. Sample
TEST METHOD B (SCATTERED TUNGSTEN
stability should also be considered in determining counting rate. Variation
in counting rates should be observed and if the counting rate tends to go
RADIATION)
in one direction only, the sample is probably decomposing. If this occurs,
shortercountingtimesshouldbeusedconsistentwithacceptablestatistical
11. Apparatus
precision.
11.1 X-ray Spectrometer, capable of measuring radiations
7.5 Determine the ratio, R, for each standard as follows:
mentioned in 3.1.2 and of being operated under the following
R 5 A/B (1) instrumental conditions or others giving equivalent results:
Tube Voltage 50 kV
where:
Tube Current 20 to 45 mA
A = counting rate at 1.175 Å, and
Tube Target Tungsten
Analyzing Crystal Lithium Fluoride (LiF)
B = counting rate at 1.144 Å.
Optical Path Air, Helium
7.6 Plot a calibration curve relating R to the grams of lead
(Warning—Compressed gas under pressure)
per gallon.
Collimation Fine
Pulse Height Analyzer Threshold discrimination set as low as pos-
NOTE 7—Many modern X-ray spectrometer instruments will plot and
sible consistent with the removal of noise with
storethecalibrationcurve,slope,andrelatedinformationintheinstrument respect to the detector employed.
Detector Proportional or Scintillation
computer system, as an alternative to hand-plotting this information.
Counting Technique Fixed Time
8. Quality Control Checks
11.1.1 Two restrictions are imposed upon the period of the
8.1 Confirm the calibration of the instrument each day it is
fixed time: namely, that it is 30 s or greater, and that it is such
in use by analyzing a quality control (QC) sample containing a that the count on the position of minimum intensity (back-
quantifiable concentration of lead, that is, independent of the
ground at A = 1.211 Å) should exceed 200 000.
calibration curve. It is advisable to analyze additional QC
NOTE 9—The X-ray spectrometer and manner of use should comply
samples as appropriate, such as at the beginning and end of a
with the regulations governing the use of ionizing radiation or recommen-
batch of samples or after a fixed number of samples, to ensure
dations of the International Commission of Radiological Protection, or
the quality of the results. Analysis of result(s) from these QC
both.
samples can be carried out using control chart techniques.
12. Reagents and Materials
When the QC sample result causes the laboratory to be in an
out-of-control situation, such as exceeding the laboratory’s
12.1 Iso-octane.(Warning—Extremely flammable.)
control limits, instrument re-calibration may be required. An 12.2 Lead (Pb) Standard Solution—Dissolve tetraethyllead
ample supply of QC sample material shall be available for the
(TEL) (Warning—TEL is toxic by ingestion), lead naphthen-
intended period of use, and shall be homogeneous and stable ate (see Note 4), or other suitable lead containing compound in
under the anticipated storage conditions. If possible, the QC
iso-octane (Warning—Extremely flammable), toluene, or a
sample shall be representative of samples typically analyzed mixture of these two solvents.WhenTELis used, refer to Note
and the average and control limits of the QC sample shall be 5. This standard solution shall contain an accurately known
determined prior to monitoring the measurement process. The lead concentration of approximately the following magnitude:
QC sample precision shall be checked against the ASTM
5 g Pb/US gal at 15.5°C (60°F)
6 g Pb/UK gal at 15.5°C (60°F)
method precision to ensure data quality.
1.3 g Pb/L at 15.5°C
9. Procedure
12.2.1 Keep the standard solution refrigerated when not in
9.1 Obtain sample in accordance with Practice D 4057.
use.
9.2 Prepare the samples to be analyzed as described in 7.3
and 7.4 for the standard lead solutions and determine the ratio,
13. Calibration
R, as described in 7.5.
13.1 Place the standard lead solution in the sample cell
9.3 Determine the lead content of the samples by relating
using techniques consistent with good operating practice for
the R values obtained to the previously determined calibration
the spectrometer employed. Insert the cell in the X-ray beam
curve.
using the instrumental conditions described
...