ASTM D4047-00(2011)
(Test Method)Standard Test Method for Phosphorus in Lubricating Oils and Additives by Quinoline Phosphomolybdate Method
Standard Test Method for Phosphorus in Lubricating Oils and Additives by Quinoline Phosphomolybdate Method
SIGNIFICANCE AND USE
Knowledge of the phosphorus content, and thus the phosphorus-containing additives, in a lubricating oil or additive can be used to predict performance characteristics.
SCOPE
1.1 This test method covers the determination of 0.005 to 10.0 mass % phosphorus in unused lubricating oil and additive concentrates. There is no reason to doubt its applicability to filtered, used lubricating oils, but no systematic study of this application has been made.
1.2 The test method is applicable to samples containing any of the phosphorus compounds in normal use.
Note 1—This test method extends the scope of the previous version of IP 149 and replaces IP 148 and the previous version of IP 149 as a referee method.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 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 6.9.
General Information
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D4047 − 00(Reapproved 2011)
Designation: 149/93
Standard Test Method for
Phosphorus in Lubricating Oils and Additives by Quinoline
Phosphomolybdate Method
This standard is issued under the fixed designation D4047; 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 (´) 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 2.2 IP Standard:
IP 148 Test Method for Phosphorous in Lubricating Oils
1.1 This test method covers the determination of 0.005 to
and Additives
10.0 mass % phosphorus in unused lubricating oil and additive
concentrates. There is no reason to doubt its applicability to
3. Summary of Test Method
filtered, used lubricating oils, but no systematic study of this
3.1 Additive concentrates are diluted with phosphorus-free
application has been made.
white oil to produce a working blend.
1.2 The test method is applicable to samples containing any
3.2 Thesampleisignitedwithexcessofzincoxidewhereby
of the phosphorus compounds in normal use.
phosphorus is converted to phosphate.The residue is dissolved
NOTE 1—This test method extends the scope of the previous version of
in hydrochloric acid and any sulfide formed is oxidized with
IP149 and replaces IP148 and the previous version of IP149 as a referee
potassium bromate. Phosphorus is then precipitated as quino-
method.
line phosphomolybdate and determined volumetrically by
1.3 The values stated in SI units are to be regarded as
addition of excess standard alkali and back titration with
standard. No other units of measurement are included in this
standard acid.
standard.
4. Significance and Use
1.4 This standard does not purport to address all of the
4.1 Knowledge of the phosphorus content, and thus the
safety concerns, if any, associated with its use. It is the
phosphorus-containing additives, in a lubricating oil or addi-
responsibility of the user of this standard to establish appro-
tive can be used to predict performance characteristics.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. For specific hazard
5. Apparatus
statements, see 6.9.
5.1 Silica Crucibles, 40-mm internal diameter at the top and
2. Referenced Documents
40 mm in height. The internal surface should be smooth and
free from pitting.
2.1 ASTM Standards:
D1193 Specification for Reagent Water 5.2 Muffle Furnace,capableofmaintainingatemperatureof
D6299 Practice for Applying Statistical Quality Assurance
approximately 700°C, and fitted with ports to allow air
and Control Charting Techniques to Evaluate Analytical circulation.
Measurement System Performance
5.3 Beakers, 25-mL capacity.
6. Reagents and Materials
This test method is under the jurisdiction of ASTM Committee D02 on
6.1 Purity of Reagents—Reagent grade chemicals shall be
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
used in all tests. Unless otherwise indicated, it is intended that
D02.03 on Elemental Analysis.
all reagents shall conform to the specifications of the Commit-
Current edition approved May 1, 2011. Published May 2011. Originally
approved in 1981. Last previous edition approved in 2005 as D4047– 00 (2005).
tee onAnalytical Reagents of theAmerican Chemical Society,
DOI: 10.1520/D4047-00R11.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR,
the ASTM website. U.K., http://www.energyinst.org.uk.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4047 − 00 (2011)
where such specifications are available. Other grades may be where:
used, provided it is first ascertained that the reagent is of
P = approximate percent phosphorus in the sample, and
sufficiently high purity to permit its use without lessening the
A = grams of sample required for a 10-g blend.
accuracy of the determination.
7.3 Calculate the mass of white oil for a 10-g blend as
6.2 Purity of Water—Unless otherwise indicated, references
follows:
to water shall be understood to mean reagent water as defined
B 5 10 2 A (2)
by Type II or Type III of Specification D1193.
where:
6.3 Hydrochloric Acid, approximately 1 N reagent solution.
B = mass of white oil, g.
6.4 Hydrochloric Acid (36 mass %)—Concentrated hydro-
7.4 Weigh a quantity of sample A6 0.01 g into a 25-mL
chloric acid (HCl).
beaker.
6.5 Hydrochloride Acid, (0.1 N)—Hydrochloric acid (HCl)
7.5 Weigh into the same beaker B g of white oil.
accurately standardized.
7.6 Mix the sample and white oil thoroughly by stirring and
6.6 Mixed Indicator—Mix 2 volumes of phenolphthalein
warming to approximately 50°C.
solution with 3 volumes of thymol blue solution.
6.7 Phenolphthalein Solution, (1 g/L in 95 % volume
8. Procedure
ethanol).
8.1 For additive concentrates, weigh into a crucible1gof
6.8 Potassium Bromate (KBrO ), solid. the homogenized blend prepared in 7.6.
6.9 Quinoline (Warning—Quinoline has a high toxic acute 8.2 For lubricating oils, weigh into a crucible3gof sample
systemic rating.)—Redistilled synthetic or, if this is or smaller amount estimated to contain not more than3gof
phosphorus. The amount of sample to be taken is indicated in
unobtainable, quinoline freshly distilled from the technical
product. Collect the colorless distillate in the boiling range Table 1.
from 232 to 238°C. Store the quinoline in an amber bottle in
8.3 Cover the sample with8gof zinc oxide and level the
the dark.
surface. Apply heat from a Meker burner to the surface until
the zinc oxide becomes red hot; then gently heat the crucible
6.10 Quinoline Hydrochloride Solution—Dissolve 20 mLof
from below with a small bunsen flame so that the oil burns off
quinoline in 800 mL of hot water acidified with 25 mL of
very gently. Finally, when no more vapor is evolved, ignite
concentrated HCl; add a little paper pulp, cool, filter, and make
strongly and transfer to a muffle furnace at 700°C to burn off
up to 1 Lwith water. This solution is stable for about 1 month.
residual carbon.
6.11 Sodium Hydroxide Solution (0.1 M)—Sodium hydrox-
8.4 Allow the crucible to cool and carefully transfer its
ide (NaOH) accurately standardized.
contents to a 600-mL beaker (Note 3), completing the transfer
6.12 Sodium Molybdate Solution—Dissolve 10 g of sodium
with a jet of water from a wash bottle. Add about 50 mL of
hydroxide (NaOH) and 18 g of ammonia-free molybdenum
water to the contents of the beaker and rinse the crucible with
trioxide in 200 mL of water and filter the solution.
a few millilitres of concentrated HCl. Add the acid rinsing to
the beaker and then sufficient concentrated HCl to bring the
NOTE 2—To avoid high blanks caused by silicate interference with
alkalinereagents,includingsodiummolybdatesolution,storeinpolythene
total volume of acid added to 23 mL.
containers.
8.5 Heat the contents of the beaker until all the ZnO is
6.13 Thymol Blue Solution (1 g/L) in 95 % volume ethanol.
dissolved,thenboiluntilallhydrogensulfidehasbeenexpelled
from the solution (test with lead acetate paper). Allow to cool
6.14 Zinc Oxide (ZnO), finely divided.
slightly, add 30 to 50 mg of KBrO , and boil until all free
bromine has been expelled from the solution (test with fluo-
7. Blending Procedure
rescein paper).
7.1 Samples having a phosphorus content greater than 0.3
mass % should be blended in white oil to give a phosphorus
content in the range of 0.1 to 0.3 mass %.
7.2 Calculate the mass of sample for a 10-g blend as TABLE 1 Amount of Sample
follows:
Approximate Volume
Phosphorus Content, Approximate Mass of 0.1 M NaOH
A 52/P (1)
mass % of Sample, g solution required
P%m mL
3 0.005 1.3
0.010 2.5
0.005 to 0.10
Reagent Chemicals, American Chemical Society Specifications, American
0.05 13
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
0.10 25
listed by the American Chemical Society, see Analar Standards for Laboratory
0.10 8
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Above 0.10 to 0.30 0.20 17
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 0.30 25
MD.
D4047 − 00 (2011)
NOTE 3—Glass apparatus should have good resistance to alkali. Do not
9. Calculation
use scratched or etched beakers for the precipitation of quinoline
9.1 Blended Samples—Calculate the phosphorus content of
phosphomolybdate.
blended samples as follows:
8.6 Dilute the liquid to a volume of about 150 mL with
Phosphorus, mass % (3)
water, add 30 mL of concentrated HCl and 30 mL of sodium
molybdate solution, rinsing the sides of the beaker with a little
V 2 V 2 5 2 V 30.01191 3 A1B
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