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An American National Standard

Designation: D 974 – 07

Designation: 139/98

Standard Test Method for

Acid and Base Number by Color-Indicator Titration1
This standard is issued under the fixed designation D 974; 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* numbers obtained by this color-indicator test method need not be

numerically the same as those obtained by Test Method D 664, the base
1.1 This test method covers the determination of acidic or numbers obtained by this color indicator test method need not be
basic constituents (Note 1) in petroleum products2 and lubri- numerically the same as those obtained by Test Method D 4739, but they
cants soluble or nearly soluble in mixtures of toluene and are generally of the same order of magnitude.
isopropyl alcohol. It is applicable for the determination of acids 1.3 The values stated in SI units are to be regarded as
or bases whose dissociation constants in water are larger than standard. No other units of measurement are included in this
10−9; extremely weak acids or bases whose dissociation standard.
constants are smaller than 10−9 do not interfere. Salts react if
1.4 This standard does not purport to address all of the
their hydrolysis constants are larger than 10−9.
safety concerns, if any, associated with its use. It is the
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NOTE 1—In new and used oils, the constituents considered to have
acidic characteristics include organic and inorganic acids, esters, phenolic
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-

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compounds, lactones, resins, salts of heavy metals, and addition agents bility of regulatory limitations prior to use.
such as inhibitors and detergents. Similarly, constituents considered to
have basic properties include organic and inorganic bases, amino com-
2. Referenced Documents
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pounds, salts of weak acids (soaps), basic salts of polyacidic bases, salts
2.1 ASTM Standards:
of heavy metals, and addition agents such as inhibitors and detergents.
D 117 Guide for Sampling, Test Methods, and Specifica-
NOTE 2—This test method is not suitable for measuring the basic
3

constituents of many basic additive-type lubricating oils. Test Method tions for Electrical Insulating Oils of Petroleum Origin
D 4739 can be used for this purpose. ASTM
D974-07
D 664 Test Method for Acid Number of Petroleum Products
by Potentiometric Titration
1.2https://standards.iteh.ai/catalog/standards/sist/67226529-5a25-4447-9d44-cbb8dd947e59/astm-d974-07
This test method can be used to indicate relative changes
that occur in an oil during use under oxidizing conditions. D 1193 Specification for Reagent Water
Although the titration is made under definite equilibrium D 4175 Terminology Relating to Petroleum, Petroleum
conditions, the method does not measure an absolute acidic or Products, and Lubricants
basic property that can be used to predict performance of an oil D 4739 Test Method for Base Number Determination by
under service conditions. No general relationship between Potentiometric Titration
bearing corrosion and acid or base numbers is known.
3. Terminology
NOTE 3—Oils, such as many cutting oils, rustproofing oils, and similar 3.1 Definitions:
compounded oils, or excessively dark-colored oils, that cannot be ana-
lyzed for acid number by this test method due to obscurity of the
3.1.1 acid number, n—the quantity of base, expressed in
color-indicator end point, can be analyzed by Test Method D 664. The acid milligrams of potassium hydroxide per gram of sample that is
required to titrate a sample to a specified end point.
3.1.1.1 Discussion—In this test method, the indicator is
1
This test method is under the jurisdiction of ASTM Committee D02 on p-naphtholbenzein titrated to a green/green-brown end point in
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.06 on Analysis of Lubricants.
a toluene-water-isopropanol solvent.
In the IP, this test method is under the jurisdiction of the Standardization
Committee. This test method was adopted as a joint ASTM-IP standard in 1965.
3
Current edition approved Nov. 1, 2007. Published November 2007. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 1948. Last previous edition approved in 2006 as D 974–06. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
2
Statements defining this test method, its modification, and its significance when Standards volume information, refer to the standard’s Document Summary page on
applied to electrical insulating oils of mineral origin will be found in Guide D 117. the ASTM website.

*A Summary of Changes section appears at the end of this standard.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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 D 974 – 07
3.1.2 base number, n—the quantity of acid, expressed in 7. Reagents
milligrams of potassium hydroxide per gram of sample that is 7.1 Purity of Reagents—Reagent grade chemicals shall be
required to titrate a sample to a specified end point. used in all tests. Unless otherwise indicated, it is intended that
3.1.2.1 Discussion—In this test method, the indicator is all reagents shall conform to the specifications of the Commit-
p-naphtholbenzein titrated to an orange end point in a toluene- tee on Analytical Reagents of the American Chemical Society,
water-isopropanol solvent. where such specifications are available.4 Other grades may be
3.1.3 used oil, n—any oil that has been in a piece of used, provided it is first ascertained that the reagent is of
equipment (for example, an engine, gearbox, transformer, or sufficiently high purity to permit its use without lessening the
turbine) whether operated or not. D 4175 accuracy of the determination.
3.2 Definitions of Terms Specific to This Standard: 7.2 Purity of Water—References to water shall be under-
3.2.1 strong acid number, n—the quantity of base, ex- stood to mean reagent water that meets the requirements of
pressed in milligrams of potassium hydroxide per gram of either Type I, II, or III of Specification D 1193.
sample, that is required to titrate a hot water extract of the 7.3 Isopropyl Alcohol, anhydrous (less than 0.9 % water).
sample to a golden-brown end point using methyl orange (Warning—Flammable.)
solution. 7.4 Hydrochloric Acid Solution, Standard Alcoholic —(0.1
M)—Mix 9 mL of concentrated hydrochloric acid (Warning—
4. Summary of Test Method Corrosive, fumes cause irritation) (HCl, sp gr 1.19) with 1000
4.1 To determine the acid or base number, the sample is mL of anhydrous isopropyl alcohol (2-propanol) (Warning—
dissolved in a mixture of toluene and isopropyl alcohol See 7.3). Standardize frequently enough to detect molarity
containing a small amount of water, and the resulting single- changes of 0.0005 (Note 6), preferably by electrometric
phase solution is titrated at room temperature with standard titration of approximately 8 mL (accurately measured) of the
alcoholic base or alcoholic acid solution, respectively, to the 0.1 M alcoholic KOH solution diluted with 125 mL of carbon
end point indicated by the color change of the added dioxide-free water. When an electrometric titration is used for
p-naphtholbenzein solution (orange in acid and green-brown in the standardization, the end point shall be a well-defined

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base). To determine the strong acid number, a separate portion
of the sample is extracted with hot water and the aqueous
inflection point closest to the cell voltage for the acidic buffer
solution. When a colorimetric titration is used for the standard-
ization, titrate to the first stable appearance of the orange color
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extract is titrated with potassium hydroxide solution, using
methyl orange as an indicator. with methyl orange indicator.

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NOTE 5—Commercially available reagents may be used in place of the
5. Significance and Use laboratory preparations when they are certified to be in accordance with
7.1.
5.1 New and used petroleum products can contain basic or
NOTE 6—To simplify calculations, both the standard KOH and HCl
acidic constituents that are present as additives or as degrada- solutions can be adjusted so that 1.00 mL is equivalent to 5.00 mg of
tion products formed during service, such as oxidationASTM prod- D974-07
KOH. Sodium hydroxide (NaOH) and sulfuric acid (H2SO4) can be
ucts. https://standards.iteh.ai/catalog/standards/sist/67226529-5a25-4447-9d44-cbb8dd947e59/astm-d974-07
The relative amount of these materials can be determined substituted for KOH and HCl, respectively.
by titrating with acids or bases. This number, whether ex- 7.5 Methyl Orange Indicator Solution—Dissolve 0.1 g of
pressed as acid number or base number, is a measure of this methyl orange in 100 mL of water.
amount of acidic or basic substances, respectively, in the 7.6 p-Naphtholbenzein Indicator 5 , 6 Solution—The
oil—always under the conditions of the test. This number is p-naphtholbenzein shall meet the specifications given in Annex
used as a guide in the quality control of lubricating oil A1. Prepare a solution of p-naphtholbenzein in titration solvent
formulations. It is also sometimes used as a measure of equal to 10 6 0.01 g/L.
lubricant degradation in service; however, any condemning 7.7 Potassium Hydroxide Solution, Standard Alcoholic (0.1
limits must be empirically established. M)—Add 6 g of solid KOH (Warning—Highly corrosive to all
5.2 Since a variety of oxidation products contribute to the body tissue) to approximately 1 L of anhydrous isopropyl
acid number and the organic acids vary widely in corrosive alcohol (containing less than 0.9 % water) in a 2-L Erlenmeyer
properties, the test cannot be used to predict corrosiveness of flask. Boil the mixture gently for 10 to 15 min, stirring to
an oil under service conditions. No general correlation is prevent the solids from forming a cake on the bottom. Add at
known between acid number and the corrosive tendency of oils least 2 g of barium hydroxide (Ba(OH)2) (Warning—
toward metals. Compounded engine oils can and usually do
have both acid and base numbers in this test method.
4
Reagent Chemicals, American Chemical Society Specifications, American
6. Apparatus Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
6.1 Burets (with the following dimensions): Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
50-mL buret graduated in 0.1-mL subdivisions and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
10-mL buret graduated in 0.05-mL or smaller subdivisions MD.
5
5-mL with 0.02-mL subdivisions In a 2006 study, only Kodak, Baker (Mallinkrodt), Fluka, and Aldrich were
found to meet the specifications in Annex A1. However, Kodak brand is no longer
NOTE 4—An automated buret capable of delivering titrant amounts in available.
0.05-mL or smaller increments can be used but the stated precision data 6
Supporting data have been filed at ASTM International Headquarters and may
were obtained using manual burets only. be obtained by requesting Research Report RR:D02–1626.

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 D 974 – 07
Poisonous if ingested, strongly alkaline, causes severe irritation TABLE 1 Size of SampleA
producing dermatitis) and again boil gently for 5 to 10 min. Acid Number or Size of Sensitivity of
Cool to room temperature, allow to stand for several hours, and Base Number Sample, g Weighing, g
New or Light Oils
filter the supernatant liquid through a fine sintered-glass or 0.0 to 3.0 20.0 6 2.0 0.05
porcelain filtering funnel; avoid unnecessary exposure to Over 3.0 to 25.0 2.0 6 0.2 0.01
carbon dioxide (CO2) during filtration. Store the solution in a Over 25.0 to 250.0 0.2 6 0.02 0.001
Used or Dark-Colored Oils
chemically resistant dispensing bottle out of contact with cork, 0.0 to 25.0 2.0 6 0.2 0.01
rubber, or saponifiable stopcock lubricant and protected by a Over 25 to 250.0 0.2 6 0.02 0.001
guard tube containing soda lime or soda nonfibrous silicate A
Light-colored samples of low acid number permit the use of 20-g samples to
absorbent (Ascarite, Carbosorb, or Indecarb). obtain more precise results. The sample size for dark-colored oils is limited to the
quantity specified to minimize possible interference by the dark color.
7.7.1 Standardization of Potassium Hydroxide Solution—
Standardize frequently enough to detect changes of 0.0005 N. sample in the original container. After complete suspension of
One way to do this is as follows: Weigh, to the nearest 0.1 mg all sediment, strain the sample or a convenient aliquot through
approximately 0.2 g of potassium acid phthalate, which has a 100-mesh screen for the removal of large contaminating
been dried for at least 1 h at 110 6 1°C and dissolve in 406 particles (Note 9).
1 mL of water, free of CO2. Titrate with the potassium
hydroxide alcoholic solution to either of the following end NOTE 9—When samples are visibly free of sediment, the heating
points: (1) When the titration is electrometric, titrate to a procedure described in 8.2 may be omitted. When samples are visibly free
of sediment, the straining procedure may also be omitted.
well-defined inflection point at the voltage that corresponds to NOTE 10—As used oil can change appreciably in storage, samples
the voltage of the basic buffer solution, or (2) When titration is should be tested as soon as possible after removal from the lubricating
colorimetric, add six drops of phenolphthalein indicator solu- system and the dates of sampling and testing should be noted.
tion and titrate to the appearance of a permanent pink color.
Perform the blank titration on the water used to dissolve the 9. Procedure for Acid Number
potassium acid phthalate. Calculate the normality using the 9.1 Into an appropriate size Erlenmeyer flask or a beaker,

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following equation: introduce a weighed quantity of the sample as given in Table 1.
Wp 1000 Add 100 mL of the titration solvent and 0.5 mL of the indicator
Normality 5 204.23 3 V2V (1) solution, and without stoppering, swirl until the sample is
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b
entirely dissolved by the solvent. If the mixture assumes a
where: yellow-orange color, proceed as directed in 9.2; if it becomes

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W p = weight of the potassium acid phthalate, g, green or green-black, proceed as directed in Section 10.
204.23 = molecular weight of the potassium acid phthalate,
V = volume of titrant used to titrate the salt to the NOTE 11—In routine analysis, the indicator may be pre-mixed with the
specific end point, mL, and titration solvent before adding to the sample.
Vb = volume of titrant used to titrate the blank, ASTM mL. D974-07
9.2 Without delay, titrate at a temperature below 30°C (Note
7.7.2 Prepare a 0.1 6 0.01 m% solution of phenolphthalein 14). Add 0.1 M KOH solution in increments and mix to
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by dissolving pure solid phenolphthalein in a 1:1 mixture of disperse the KOH as necessary (see Note 12). Shake vigor-
water, free of CO2, and ethanol. ously near the end point, but avoid dissolving carbon dioxide
NOTE 7—Commercially available reagents may be used in place of the
(CO2) in the solvent. (In the case of acidic oils, the orange
laboratory preparations. color changes to a green or green-brown as the end point is
NOTE 8—Because of the relatively large coefficient of cubic expansion approached.) Consider the end point definite if the color
of organic liquids, such as isopropyl alcohol, the standard alcoholic change (Note 13) persists for 15 s or if it reverses with two
solutions should be standardized at temperatures close to those employed drops of 0.1 M HCl.
in the titrations of samples.
NOTE 12—When acid numbers about or below one are expected, better
7.8 Titration Solvent—Prepare by mixing toluene, water, precision can be obtained by substituting 0.01 or 0.05 M solutions in 9.2
and anhydrous isopropyl alcohol in the ratio 100 : 1 : 99. and 9.3. This substitution was not included in the development of a
precision statement.
8. Preparation of Used Oil Samples NOTE 13—To observe the end point of dark-colored oil, shake the flask
vigorously to produce momentarily a slight foam when the color change
8.1 Strict observance of the sampling procedure described
occurs as the last few drops of titrant are added and observe the titration
in 8.2 is necessary, since the sediment itself is acidic or basic under a white fluorescent lamp at bench top level.
or has adsorbed acidic or basic material from the sample. NOTE 14—The temperature can be measured by any suitable tempera-
Failure to obtain a representative sample causes serious errors. ture measuring device.
8.2 Heat the sample (Note 9) of used oil to 60 6 5°C in the NOTE 15—An automated photometric device may also be used to detect
original container and agitate until all sediment is homoge- the titration end point. However, the precision estimates given in Section
neously suspended in the oil (Note 10). If the original container 15 may not apply to this mode of titration.
is of opaque material, or if it is more than three-fourths full, 9.3 Blank—Perform a blank titration on 100 mL of the
transfer the entire sample to a clear glass bottle having a titration solvent and 0.5 mL of the indicator solution, adding
capacity at least one third greater than the volume of the 0.1-mL or less increments of the 0.1 M KOH solution.
sample, and transfer all traces of sediment from the original 9.3.1 The titration solvent usually contains weak acid im-
container to the bottle by violent agitation of portions of the purities which react with the strongly basic components of the