ASTM D4047-00
(Test Method)Standard Test Method for Phosphorus in Lubricating Oils and Additives by Quinoline Phoshomolybdate Method
Standard Test Method for Phosphorus in Lubricating Oils and Additives by Quinoline Phoshomolybdate Method
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 preferred units are acceptable metric units.
1.4 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. For specific hazard statements, see 6.9.
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Standards Content (Sample)
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An American National Standard
Designation:D4047–00
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 D 4047; 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 3. Summary of Test Method
1.1 This test method covers the determination of 0.005 to 3.1 Additive concentrates are diluted with phosphorus-free
10.0 mass % phosphorus in unused lubricating oil and additive white oil to produce a working blend.
concentrates. There is no reason to doubt its applicability to 3.2 Thesampleisignitedwithexcessofzincoxidewhereby
filtered, used lubricating oils, but no systematic study of this phosphorus is converted to phosphate.The residue is dissolved
application has been made. in hydrochloric acid and any sulfide formed is oxidized with
1.2 The test method is applicable to samples containing any potassium bromate. Phosphorus is then precipitated as quino-
of the phosphorus compounds in normal use. line phosphomolybdate and determined volumetrically by
addition of excess standard alkali and back titration with
NOTE 1—This test method extends the scope of the previous version of
standard acid.
IP149 and replaces IP148 and the previous version of IP149 as a referee
method.
4. Significance and Use
1.3 The preferred units are acceptable metric units.
4.1 Knowledge of the phosphorus content, and thus the
1.4 This standard does not purport to address all of the
phosphorus-containing additives, in a lubricating oil or addi-
safety concerns, if any, associated with its use. It is the
tive can be used to predict performance characteristics.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
5. Apparatus
bility of regulatory limitations prior to use. For specific hazard
5.1 Silica Crucibles, 40-mm internal diameter at the top and
statements, see 6.9.
40 mm in height. The internal surface should be smooth and
free from pitting.
2. Referenced Documents
5.2 Muffle Furnace,capableofmaintainingatemperatureof
2.1 ASTM Standards:
approximately 700°C, and fitted with ports to allow air
D 1193 Specification for Reagent Water
circulation.
D 6299 Practice for Applying Statistical Quality Assurance
5.3 Beakers, 25-mL capacity.
Techniques to Evaluate Analytical Measurement System
Performance
6. Reagents and Materials
2.2 IP Standard:
6.1 Purity of Reagents—Reagent grade chemicals shall be
IP 148 Test Method for Phosphorous in Lubricating Oils
used in all tests. Unless otherwise indicated, it is intended that
and Additives
all reagents shall conform to the specifications of the Commit-
tee onAnalytical Reagents of theAmerican Chemical Society,
1 where such specifications are available. Other grades may be
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.03 on Elemental Analysis.
Current edition approved Nov. 10, 2000. Published November 2000. Originally Reagent Chemicals, American Chemical Society Specifications, American
published as D 4047 – 81. Last previous edition D 4047 – 91 (1995). Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Annual Book of ASTM Standards, Vol 11.01. listed by the American Chemical Society, see Analar Standards for Laboratory
Annual Book of ASTM Standards, Vol 05.03. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Available from the Institute of Petroleum, 61 New Cavendish Street, London, and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
W1M 8AR. MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D4047–00
used, provided it is first ascertained that the reagent is of 8. Procedure
sufficiently high purity to permit its use without lessening the
8.1 For additive concentrates, weigh into a crucible1gof
accuracy of the determination.
the homogenized blend prepared in 7.6.
6.2 Purity of Water—Unless otherwise indicated, references
8.2 For lubricating oils, weigh into a crucible3gof sample
to water shall be understood to mean reagent water as defined
or smaller amount estimated to contain not more than3gof
by Type II or Type III of Specification D 1193.
phosphorus. The amount of sample to be taken is indicated in
6.3 Hydrochloric Acid, approximately 1 N reagent solution.
Table 1.
6.4 Hydrochloric Acid (36 mass %)—Concentrated hydro-
8.3 Cover the sample with8gof zinc oxide and level the
chloric acid (HCl).
surface. Apply heat from a Meker burner to the surface until
6.5 Hydrochloride Acid, (0.1 N)—Hydrochloric acid (HCl)
the zinc oxide becomes red hot; then gently heat the crucible
accurately standardized.
from below with a small bunsen flame so that the oil burns off
6.6 Mixed Indicator—Mix 2 volumes of phenolphthalein
very gently. Finally, when no more vapor is evolved, ignite
solution with 3 volumes of thymol blue solution.
strongly and transfer to a muffle furnace at 700°C to burn off
6.7 Phenolphthalein Solution, (1 g/L in 95 % volume
residual carbon.
ethanol).
8.4 Allow the crucible to cool and carefully transfer its
6.8 Potassium Bromate (KBrO ), solid.
3 contents to a 600-mL beaker (Note 3), completing the transfer
6.9 Quinoline (Warning—Quinoline has a high toxic acute
with a jet of water from a wash bottle. Add about 50 mL of
systemic rating.)—Redistilled synthetic or, if this is unobtain-
water to the contents of the beaker and rinse the crucible with
able, quinoline freshly distilled from the technical product.
a few millilitres of concentrated HCl. Add the acid rinsing to
Collect the colorless distillate in the boiling range from 232 to
the beaker and then sufficient concentrated HCl to bring the
238°C. Store the quinoline in an amber bottle in the dark.
total volume of acid added to 23 mL.
6.10 Quinoline Hydrochloride Solution—Dissolve20mLof
8.5 Heat the contents of the beaker until all the ZnO is
quinoline in 800 mL of hot water acidified with 25 mL of
dissolved,thenboiluntilallhydrogensulfidehasbeenexpelled
concentrated HCl; add a little paper pulp, cool, filter, and make
from the solution (test with lead acetate paper). Allow to cool
up to 1 Lwith water. This solution is stable for about 1 month.
slightly, add 30 to 50 mg of KBrO , and boil until all free
6.11 Sodium Hydroxide Solution (0.1 M)—Sodium hydrox-
bromine has been expelled from the solution (test with fluo-
ide (NaOH) accurately standardized.
rescein paper).
6.12 Sodium Molybdate Solution—Dissolve 10 g of sodium
NOTE 3—Glass apparatus should have good resistance to alkali. Do not
hydroxide (NaOH) and 18 g of ammonia-free molybdenum
use scratched or etched beakers for the precipitation of quinoline
trioxide in 200 mL of water and filter the solution.
phosphomolybdate.
NOTE 2—To avoid high blanks caused by silicate interference with
8.6 Dilute the liquid to a volume of about 150 mL with
alkalinereagents,includingsodiummolybdatesolution,storeinpolythene
water, add 30 mL of concentrated HCl and 30 mL of sodium
containers.
molybdate solution, rinsing the sides of the beaker with a little
water after each addition. Place the beaker on the hot plate and
6.13 Thymol Blue Solution (1 g/L) in 95 % volume ethanol.
6.14 Zinc Oxide (ZnO), finely divided. bring the liquid to the boil. Add a few drops of quinoline
hydrochloride reagent from a coarse-tipped buret or pipet,
swirling during the addition.
7. Blending Procedure
8.7 Bring to the boil again and add 2 mL of the reagent
7.1 Samples having a phosphorus content greater than 0.3
dropwise with swirling. To the gently boiling liquid add the
mass % should be blended in white oil to give a phosphorus
reagent in 2-mL increments until a total of 24 mL has been
content in the range of 0.1 to 0.3 mass %.
added, swirling during the addition. Stand the beaker on the
7.2 Calculate the mass of sample for a 10-g blend as
edge of the hot plate or on a boiling water bath for 15 min for
follows:
the precipitate to settle. Cool to room temperature.
A 5 2/P (1)
8.8 Prepare a paper pulp pad (Note 4) in a funnel fitted with
a porcelain filter disk and tamp down well. Decant the clear
where:
supernatant liquid through the filter with applied suction and
P = approximate percent phosphorus in the sample, and
A = grams of sample required for a 10-g blend.
7.3 Calculate the mass of white oil for a 10-g blend as
TABLE 1 Amo
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