An American National Standard

Designation: D 974 – 02 British Standard 2634

Designation: 139/98

Standard Test Method for

Acid and Base Number by Color-Indicator Titration1,2
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 products3 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 acceptable SI units are to be
or bases whose dissociation constants in water are larger than regarded as the standard.
10−9; extremely weak acids or bases whose dissociation 1.4 This standard does not purport to address all of the
constants are smaller than 10−9 do not interfere. Salts react if safety concerns, if any, associated with its use. It is the
their hydrolysis constants are larger than 10−9.
responsibility of the user of this standard to establish appro-
NOTE 1—In new and used oils, the constituents considered to have priate safety and health practices and determine the applica-
acidic characteristics include organic and inorganic acids, esters, phenolic bility of regulatory limitations prior to use.
compounds, lactones, resins, salts of heavy metals, and addition agents
such as inhibitors and detergents. Similarly, constituents considered to 2. Referenced Documents
have basic properties include organic and inorganic bases, amino com-
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, Specifications,
and Guide for Electrical Insulating Oils of Petroleum
NOTE 2—This test method is not suitable for measuring the basic Origin4
constituents of many basic additive-type lubricating oils. Test Method D 664 Test Method for Acid Number of Petroleum Products
D 4739 can be used for this purpose. by Potentiometric Titration5
1.2 This test method can be used to indicate relative changes D 1193 Specification for Reagent Water6
that occur in an oil during use under oxidizing conditions. D 4175 Terminology Relating to Petroleum, Petroleum
Although the titration is made under definite equilibrium Products, and Lubricants7
conditions, the method does not measure an absolute acidic or D 4739 Test Method for Base Number Determination by
basic property that can be used to predict performance of an oil Potentiometric Titration7
under service conditions. No general relationship between
bearing corrosion and acid or base numbers is known. 3. Terminology
3.1 Definitions:
NOTE 3—Oils, such as many cutting oils, rustproofing oils, and similar
compounded oils, or excessively dark-colored oils, that cannot be ana-
3.1.1 acid number, n—the quantity of base, expressed in
lyzed for acid number by this test method due to obscurity of the milligrams of potassium hydroxide per gram of sample that is
color-indicator end point, can be analyzed by Test Method D 664. The acid required to titrate a sample to a specified end point.
3.1.1.1 Discussion—In this test method, the indicator is
p-naptholbenzein titrated to a green/green-brown end point in
1
This test method is under the jurisdiction of ASTM Committee D02 on a toluene-water-isopropanol solvent.
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.06 on Analysis of Lubricants.
3.1.2 base number, n—the quantity of acid, expressed in
In the IP, this test method is under the jurisdiction of the Standardization milligrams of potassium hydroxide per gram of sample that is
Committee. This test method was adopted as a joint ASTM-IP standard in 1965. required to titrate a sample to a specified end point.
Current edition approved June 10, 2002. Published August 2002. Originally
published as D 974–48T. Last previous edition D 974–01.
2 4
This test method has been adopted for use by government agencies to replace Annual Book of ASTM Standards, Vol 10.03.
5
Method 5105 of Federal Test Method Standard No. 791b. Annual Book of ASTM Standards, Vol 05.01.
3 6
Statements defining this test method, its modification, and its significance when Annual Book of ASTM Standards, Vol 11.01.
7
applied to electrical insulating oils of mineral origin will be found in Guide D 117. Annual Book of ASTM Standards, Vol 05.02.

*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.

1
 D 974 – 02
3.1.2.1 Discussion—In this test method, the indicator is where such specifications are available.8 Other grades may be
p-naptholbenzein titrated to an orange end point in a toluene- used, provided it is first ascertained that the reagent is of
water-isopropanol solvent. sufficiently high purity to permit its use without lessening the
3.1.3 used oil, n—any oil that has been in a piece of accuracy of the determination.
equipment (for example, an engine, gearbox, transformer, or 7.2 Purity of Water—References to water shall be under-
turbine) whether operated or not. (D 4175) stood to mean reagent water as defined by Type III of
3.2 Definitions of Terms Specific to This Standard: Specification D 1193.
3.2.1 strong acid number, n—the quantity of base, ex- 7.3 Isopropyl Alcohol, anhydrous (less than 0.9 % water).
pressed in milligrams of potassium hydroxide per gram of (Warning—Flammable.)
sample, that is required to titrate a hot water extract of the 7.4 Hydrochloric Acid Solution, Standard Alcoholic —(0.1
sample to a golden-brown end point using methyl orange M)—Mix 9 mL of concentrated hydrochloric acid (Warning—
solution. Corrosive, fumes cause irritation) (HCl, sp gr 1.19) with 1000
mL of anhydrous isopropyl alcohol (2-propanol) (Warning—
4. Summary of Test Method See 7.3). Standardize frequently enough to detect molarity
4.1 To determine the acid or base number, the sample is changes of 0.0005 (Note 6), preferably by electrometric
dissolved in a mixture of toluene and isopropyl alcohol titration of approximately 8 mL (accurately measured) of the
containing a small amount of water, and the resulting single- 0.1 M alcoholic KOH solution diluted with 125 mL of carbon
phase solution is titrated at room temperature with standard dioxide-free water. When an electrometric titration is used for
alcoholic base or alcoholic acid solution, respectively, to the the standardization, the end point shall be a well-defined
end point indicated by the color change of the added inflection point closest to the cell voltage for the acidic buffer
p-naphtholbenzein solution (orange in acid and green-brown in solution. When a colorimetric titration is used for the standard-
base). To determine the strong acid number, a separate portion ization, titrate to the first stable appearance of the orange color
of the sample is extracted with hot water and the aqueous with methyl orange indicator.
extract is titrated with potassium hydroxide solution, using
NOTE 5—Commercially available reagents may be used in place of the
methyl orange as an indicator. laboratory preparations when they are certified to be in accordance with
7.1.
5. Significance and Use
NOTE 6—To simplify calculations, both the standard KOH and HCl
5.1 New and used petroleum products can contain basic or solutions can be adjusted so that 1.00 mL is equivalent to 5.00 mg of
acidic constituents that are present as additives or as degrada- KOH. Sodium hydroxide (NaOH) and sulfuric acid (H2SO4) can be
tion products formed during service, such as oxidation prod- substituted for KOH and HCl, respectively.
ucts. The relative amount of these materials can be determined 7.5 Methyl Orange Indicator Solution—Dissolve 0.1 g of
by titrating with acids or bases. This number, whether ex- methyl orange in 100 mL of water.
pressed as acid number or base number, is a measure of this 7.6 p-Naphtholbenzein Indicator 9 Solution—The
amount of acidic or basic substances, respectively, in the p-naphtholbenzein must meet the specifications given in Annex
oil—always under the conditions of the test. This number is A1. Prepare a solution of p-naphtholbenzein in titration solvent
used as a guide in the quality control of lubricating oil equal to 10 6 0.01 g/L.
formulations. It is also sometimes used as a measure of 7.7 Potassium Hydroxide Solution, Standard Alcoholic (0.1
lubricant degradation in service; however, any condemning M)—Add 6 g of solid KOH (Warning—Highly corrosive to all
limits must be empirically established. body tissue) to approximately 1 L of anhydrous isopropyl
5.2 Since a variety of oxidation products contribute to the alcohol (containing less than 0.9 % water) in a 2-L Erlenmeyer
acid number and the organic acids vary widely in corrosive flask. Boil the mixture gently for 10 to 15 min, stirring to
properties, the test cannot be used to predict corrosiveness of prevent the solids from forming a cake on the bottom. Add at
an oil under service conditions. No general correlation is least 2 g of barium hydroxide (Ba(OH)2) (Warning—
known between acid number and the corrosive tendency of oils Poisonous if ingested, strongly alkaline, causes severe irritation
toward metals. Compounded engine oils can and usually do producing dermatitis) and again boil gently for 5 to 10 min.
have both acid and base numbers in this test method. Cool to room temperature, allow to stand for several hours, and
filter the supernatant liquid through a fine sintered-glass or
6. Apparatus
porcelain filtering funnel; avoid unnecessary exposure to
6.1 Buret—A 50-mL buret graduated in 0.1-mL subdivi- carbon dioxide (CO2) during filtration. Store the solution in a
sions, or a 10-mL buret graduated in 0.05-mL subdivisions. chemically resistant dispensing bottle out of contact with cork,
NOTE 4—An automated buret capable of delivering titrant amounts in
0.05-mL or smaller increments can be used but the stated precision data 8
Reagent Chemicals, American Chemical Society Specifications, American
were obtained using manual burets only.
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
listed by the American Chemical Society, see Annual Standards for Laboratory
7. Reagents Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
7.1 Purity of Reagents—Reagent grade chemicals shall be and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD.
used in all tests. Unless otherwise indicated, it is intended that 9
In a 1992 study, only Kodak, Fisher, and Baker (Mallinkrodt)
all reagents shall conform to the specifications of the Commit- p-naphtholbenzein were found to meet the specifications in Annex A1. However,
tee on Analytical Reagents of the American Chemical Society, Kodak brand is no longer available.

2
 D 974 – 02
rubber, or saponifiable stopcock lubricant and protected by a NOTE 10—As used oil can change appreciably in storage, samples
guard tube containing soda lime or soda nonfibrous silicate should be tested as soon as possible after removal from the lubricating
absorbent (Ascarite, Carbosorb, or Indecarb). system and the dates of sampling and testing should be noted.
7.7.1 Standardization of Potassium Hydroxide Solution— 9. Procedure for Acid Number
Standardize frequently enough to detect changes of 0.0005 N.
9.1 Into an appropriate size Erlenmeyer flask or a beaker,
One way to do this is as follows: Weigh, to the nearest 0.1 mg
introduce a weighed quantity of the sample as given in Table 1.
approximately 0.2 g of potassium acid phthalate, which has
Add 100 mL of the titration solvent and 0.5 mL of the indicator
been dried for at least 1 h at 110 6 1°C and dissolve in 406
solution, and without stoppering, swirl until the sample is
1 mL of water, free of CO2. Titrate with the potassium
hydroxide alcoholic solution to either of the following end entirely dissolved by the solvent. If the mixture assumes a
points: (1) When the titration is electrometric, titrate to a yellow-orange color, proceed as directed in 9.2; if it becomes
well-defined inflection point at the voltage that corresponds to green or green-black, proceed as directed in Section 10.
the voltage of the basic buffer solution, or (2) When titration is NOTE 11—In routine analysis, the indicator may be pre-mixed with the
colorimetric, add six drops of phenolphthalein indicator solu- titration solvent before adding to the sample.
tion and titrate to the appearance of a permanent pink color. 9.2 Without delay, titrate at a temperature below 30°C (Note
Perform the blank titration on the water used to dissolve the 14). Add 0.1 M KOH solution in increments and mix to
potassium acid phthalate. Calculate the normality using the disperse the KOH as necessary (see Note 12). Shake vigor-
following equation: ously near the end point, but avoid dissolving carbon dioxide
Wp 1000 (CO2) in the solvent. (In the case of acidic oils, the orange
Normality 5 204.23 3 V2V (1) color changes to a green or green-brown as the end point is
b
approached.) Consider the end point definite if the color
where: change (Note 13) persists for 15 s or if it reverses with two
Wp = weight of the potassium acid phthalate, g, drops of 0.1 M HCl.
204.23 = molecular weight of the potassium acid phthalate,
V = volume of titrant used to titrate the salt to the NOTE 12—When acid numbers about or below one are expected, better
specific end point, mL, and precision can be obtained by substituting 0.01 or 0.05 M solutions in 9.2
Vb = volume of titrant used to titrate the blank, mL. and 9.3. This substitution was not included in the development of a
precision statement.
7.7.2 Prepare a 0.1 6 0.01 m% solution of phenolphthalein
NOTE 13—To observe the end point of dark-colored oil, shake the flask
by dissolving pure solid phenolphthalein in a 1:1 mixture of vigorously to produce momentarily a slight foam when the color change
water, free of CO2, and ethanol. occurs as the last few drops of titrant are added and observe the titration
NOTE 7—Commercially available reagents may be used in place of the under a white fluorescent lamp at bench top level.
laboratory preparations. NOTE 14—The temperature can be measured by any suitable tempera-
NOTE 8—Because of the relatively large coefficient of cubic expansion ture measuring device.
of organic liquids, such as isopropyl alcohol, the standard alcoholic 9.3 Blank—Perform a blank titration on 100 mL of the
solutions should be standardized at temperatures close to those employed titration solvent and 0.5 mL of the indicator solution, adding
in the titrations of samples. 0.1-mL or less increments of the 0.1 M KOH solution.
7.8 Titration Solvent—Prepare by mixing toluene, water, 9.3.1 The titration solvent usually contains weak acid im-
and anhydrous isopropyl alcohol in the ratio 100 : 1 : 99. purities which react with the strongly basic components of the
sample. To correct the base number for the sample, determine
8. Preparation of Used Oil Samples an acid number blank upon the solvent.
8.1 Strict observance of the sampling procedure described
in 8.2 is necessary, since the sediment itself is acidic or basic 10. Procedure for Base Number
or has adsorbed acidic or basic material from the sample. 10.1 If the titration solvent containing the dissolved sample
Failure to obtain a representative sample causes serious errors. assumes a green or greenish-brown color after the indicator is
8.2 Heat the sample (Note 9) of used oil to 60 6 5°C in the added (9.1), carry out the titration as described in 9.2, but use
original container and agitate until all sediment is homoge- 0.1 M HCl and titrate until the green-brown color changes to
neously suspended in the oil (Note 10). If the original container orange.
is of opaque material, or if it is more than three-fourths full,
transfer the entire sample to a clear glass bottle having a
TABLE 1 Size of SampleA
capacity at least one third greater than the volume of the
Acid Number or Size of Sensitivity of
sample, and transfer all traces of sediment from the original Base Number Sample, g Weighing, g
container to the bottle by violent agitation of portions of the New or Light Oils
sample in the original container. After complete suspension of 0.0 to 3.0 20.0 6 2.0 0.05
Over 3.0 to 25.0 2.0 6 0.2 0.01
all sediment, strain the sample or a convenient aliquot through Over 25.0 to 250.0 0.2 6 0.02 0.001
a 100-mesh screen for the removal of large contaminating Used or Dark-Colored Oils
particles (Note 9). 0.0 to 25.0 2.0 6 0.2 0.01
Over 25 to 250.0 0.2 6 0.02 0.001
NOTE 9—When samples are visibly free of sediment, the heating A
Light-colored samples of low acid number permit the use of 20-g samples to
procedure described in 8.2 may be omitted. When samples are visibly free obtain more precise results. The sample size for dark-colored oils is limited to the
of sediment, the straining procedure may also be omitted. quantity specified to minimize possible interference by the dark color.

3
 D 974 – 02
10.2 Blank—Perform a blank titration as directed in 9.3. B = KOH solution required for titration of the blank (9.3),
mL,
11. Procedure for Strong Acid Number M = molarity of the KOH solution, and
11.1 Introduce approximately 25 g of a representative W = sample used, g.
sample, weighed to the nearest 0.1 g, into a 250-mL separatory 13.2 Calculate the strong-acid number as follows:
funnel and add 100 mL of boiling water. Shake vigorously and 13.2.1 If the blank titration is made with acid:
drain the water phase, after separation, into a 500-mL casse- Strong2acid number, mg of KOH/g 5 @~CM 1 Dm! 3 56.1#/W
role. Extract the sample twice more with 50-mL portions of (3)
boiling water, adding both extracts to the casserole. To the
combined extracts add 0.1 mL of methyl orange indicator where:
solution and, if the solution becomes pink or red, titrate with C = KOH solution required to titrate the water extract
0.1 M KOH solution until the solution becomes golden brown (11.1), mL,
in color. If the initial color is not pink or red, report the strong M = molarity of KOH solution,
D = HCl solution required to titrate the blank solution
acid number as zero.
(11.2), mL,
11.2 Blank—Into a 250-mL Erlenmeyer flask, introduce 200
m = molarity of the HCl solution, and
mL of the same boiling water as used for the sample titration. W = sample used, g.
Add 0.1 mL of methyl orange indicator solution. If the 13.2.2 If the blank titration is made with base:
indicator color is yellow-orange, titrate with 0.1 M HCl to the
same depth and shape of color obtained in the titration of the Strong2acid number, mg of KOH/g 5 @C 2 D!M 3 56.1#/W (4)
sample. If the indicator color is pink or red, titrate with 0.1 M where:
KOH solution to the same end point as that used in the sample C = KOH solution required to titrate the water extract
titration. (11.1), mL,
D = KOH solution required to titrate the blank solution
12. Quality Control Checks (11.2), mL,
12.1 Confirm the performance of the equipment or the M = molarity of the KOH solution, and
procedure each day it is in use, by analyzing a quality control W = sample used, g.
(QC) sample. It is advisable to analyze additional QC samples 13.3 Calculate the base number as follows:
as appropriate, such as at the end of a batch of samples or after base number, mg of KOH/g 5 @~Em 1 FM! 3 56.1#/W (5)
a fixed number of samples to ensure the quality of the results.
Analysis of results(s) from these QC samples can be carried out where:
using control chart techniques.10 When the result of a test on a E = HCl solution required for titration of the sample
QC sample exceeds the control limits of the laboratory, (Section 10), mL,
corrective action, such as instrument recalibration may be m = molarity of the HCl solution,
required. An ample supply of QC sample material shall be F = KOH required for titration of the acid number blank,
available for the intended period of use, and shall be homoge- mL,
neous and stable under the anticipated storage conditions. If M = molarity of the KOH solution, and
possible, the QC sample shall be representative of samples W = sample used, g.
typically analyzed and the average value and control limits of 14. Report
the QC sample shall be determined prior to monitoring the
measurements process. The precision for the QC sample must 14.1 Report the result as acid number, strong acid number,
be compared against that given in the Precision and Bias or base number as follows:
section of this test method in order to verify that the instrument Acid number (D 974) = (result)
Strong acid number (D 974) = (result)
is functioning correctly.
Base number (D 974) = (result)
NOTE 15—Because the acid and base numbers can vary while the QC
sample is in storage, when an out-of-control situation arises, the stability 15. Precision and Bias
of the QC sample can be a source of the error. 15.1 Precision—This precision section applies only to new,
13. Calculation light-colored, straight mineral oils and new and used inhibited
steam turbine oils. Insufficient data are available on other oils
13.1 Calculate the acid number as follows: coming within the scope of this test method so that no precision
Acid number, mg of KOH/g 5 @~A 2 B!M 3 56.1#/W (2) is given for such oils.
15.1.1 Repeatability—The difference between two test re-
where: sults, obtained by the same operator with the same apparatus
A = KOH solution required for titration of the sample
under constant operating conditions on identical test material,
(9.2), mL,
would in the long run, in the normal and correct operation of
the test method, exceed the following values only in one case
in twenty:
10
Manual on Presentation of Data Control Chart Analysis, Section 3: Control Acid Base Number Repeatability
Charts for Individuals, ASTM MNL 7, 6th ed., ASTM, 1990. 0.00 to 0.1 0.03

4
 D 974 – 02
Over 0.1 to 0.5 0.05 colored as to obscure the end point color change.
Over 0.5 to 1.0 0.08 NOTE 17—For precision applicable to electrical insulating liquids, refer
Over 1.0 to 2.0 0.12 to Guide D 117.
NOTE 18—The precision statements were based on the use of manual
15.1.2 Reproducibility—The difference between two single
burets only. The user is cautioned that the precision statements may or
and independent results obtained by different operators work- may not be applicable to titrations performed with the use of automated
ing in different laboratories on identical test material would, in burets, since no interlaboratory study has been conducted to date to
the long run, in the normal and correct operation of the test statistically evaluate results determined by both techniques.
method, exceed the following values only in one case in 15.2 Bias—The procedures in this test method have no bias
twenty: because the acid and base values can be defined only in the
Acid Base Number Reproducibility terms of the test method.
0.00 to 0.1 0.04
Over 0.1 to 0.5 0.08
Over 0.5 to 2.0 15 % of the neutralization 16. Keywords
number level 16.1 acid number; base number; color indication titration;
NOTE 16—These precision values do not apply to oils that are so highly petroleum products

ANNEXES

(Mandatory Information)

A1. SPECIFICATIONS FOR p-NAPHTHOLBENZEIN

A1.1 p-Naphtholbenzein shall conform to the following A1.1.5.1 Indicator turns to the first clear green at a relative
requirements: pH of 11 6 0.5 when tested by the method for pHr range of
A1.1.1 Appearance—Red amorphous powder. p-naphtholbenzein indicator as described in Note A2.1.
A1.1.2 Chlorides—Less than 0.5 %. A1.1.5.2 Requires not more than 0.5 mL of 0.01 M KOH
A1.1.3 Solubility—Ten grams shall dissolve completely in 1 solution above that for blank to bring indicator solution to the
L of titration solvent (see A2.7.3). first clear green.
A1.1.4 Minimum Absorbance—Exactly 0.1000 g of sample A1.1.5.3 Requires not more than 1.0 mL of 0.01 M KOH
is dissolved in 250 mL of methanol. (Warning—Flammable. solution above that for blank to bring indicator solution to a
Vapor harmful. Can be fatal or cause blindness if swallowed or
blue color.
inhaled. Cannot be made nonpoisonous.) Five millilitres of this
solution is made up to 100 mL with pH 12 buffer. This final A1.1.5.4 Initial pHr of indicator solution is at least as high
dilution should have a minimum absorbance of 1.20 when read as that of the blank.
at the 650-nm peak using a Beckman DU or alternative type A1.1.5.5 Buffer is made by mixing 50 mL of 0.05 M
spectrophotometer, 1-cm cells, and water as the blank. diabasic sodium phosphate solution with 26.9 mL of 0.1 M
A1.1.5 pH Range: sodium hydroxide solution.

A2. TEST METHOD FOR DETERMINING pHr RANGE OF p-NAPHTHOLBENZEIN INDICATOR

A2.1 Scope A2.3 Summary of Test Method

A2.1.1 This test method is intended for determining the A2.3.1 A prescribed amount of indicator is titrated electro-
acceptability of p-naphtholbenzein indicator for use in Test metrically through the various color changes with alcoholic
Method D 974 with regard to color change over a pHr range. (Warning—Flammable) potassium hydroxide and results plot-
ted against meter readings converted to pHr units.
A2.2. Terminology A2.4 Significance and Use
A2.2.1 Definitions of Terms Specific to This Standard: A2.4.1 This procedure is used to establish the pHr values of
A2.2.1.1 pHr, n—an arbitrary term which expresses the the various color changes of the p-naptholbenzein indicator.
relative hydrogen ion activity in the toluene-isopropanol-water A2.5 Apparatus
medium.
A2.5.1 Meter, Glass Electrode, Calomel Electrode, Stirrer,
A2.2.1.1.1 Discussion—For the purpose of this test method, Beaker and Stand, as specified in the Appendix of Test Method
the pHr acidity scale is defined by two standard buffer solutions D 664.
which have been designated pHr 4 and pHr 11. The exact
relation between pHr and the true pH of a toluene-isopropanol- A2.6 Purity of Reagents
water solution is not known and cannot be readily determined. A2.6.1 Reagent grade chemicals shall be used in all tests.

5
 D 974 – 02
Unless otherwise indicated, it is intended that all reagents shall graph as shown in Fig. A2.1. Use this graph to convert pH
conform to the specifications of the Committee on Analytical meter readings to initial acidity, pHr.
Reagents of the American Chemical Society, where such
specifications are available.8 Other grades may be used, pro- A2.10 Procedure
vided it is first ascertained that the reagent is of sufficiently A2.10.1 Titrate 100 mL of titration solvent (Warning—
high purity to permit its use without lessening the accuracy of Flammable) with 0.01 M KOH solution until the meter
the determination. indicates a pHr between 13 and 14.
A2.6.2 References to water shall be understood to mean A2.10.2 Add 0.5 mL of indicator solution to a fresh portion
distilled water. of titration solvent, and after cleaning the electrodes titrate with
0.01 M KOH solution until the meter indicates a pHr between
A2.7 Reagents 13 and 14.
A2.7.1 Potassium Hydroxide Solution, Standard Alcoholic A2.10.3 During the titration, plot the volume of titrant
(0.2 M)—Prepare, store, and standardize in accordance with against the pHr or meter reading and note on the curve the
Test Method D 644. various color changes at the corresponding pHr values.
A2.7.2 Hydrochloric Acid Solution, Standard Alcoholic (0.2
NOTE A2.1—The following color changes, in order, are intended as a
M)—Prepare and standardize in accordance with Test Method guide:
D 664. Amber to olive green
A2.7.3 Titration Solvent—Add 500 mL of toluene and 5 mL Olive green to clear green
of water to 495 mL of anhydrous isopropyl alcohol (2- Clear green to bluish green
propanol). The titration solvent should be made up in large Bluish green to blue
quantities. A2.10.4 Plot the blank titration on the same paper used for
A2.7.4 Acidic Buffer Solution (pHr = 4.0)—Prepare a stock the indicator.
solution in accordance with Test Method D 664. Add 10 mL of
buffer stock solution to 100 mL of titration solvent. Use the A2.11 Calculation
diluted solution within 1 h. A2.11.1 Subtract the volume of titrant used in the blank
A2.7.5 Alkaline Buffer Solution (pHr = 11.0)—Prepare a titration from that used for the indicator solution titration at the
stock solution in accordance with Test Method D 664. Add 10 same pHr corresponding to the definite color changes between
mL of buffer stock solution to 100 mL of titration solvent. Use 10 to 12 pHr.
the diluted solution within 1 h.
A2.7.6 Potassium Chloride Electrolyte—Prepare a satu- A2.12 Precision and Bias
rated solution of potassium chloride (KCl) in water. A2.12.1 Precision—The precision of this procedure has not
A2.7.7 Naphtholbenzein Indicator Solution—Prepare as de- been determined, and there are no plans to develop one.
scribed in 7.5. A2.12.2 Bias—The procedures in this test method have no
bias because the values can only be defined in terms of the test
A2.8 Preparation of Electrode System method.
A2.8.1 Prepare the electrode system in accordance with 7.1
and 7.2 of Test Method D 664.
A2.9 Standardization of Apparatus
A2.9.1 Prior to each test or series of tests, set the meter to
read on the pH scale, insert the electrodes into a beaker
containing the acidic nonaqueous buffer solution at a tempera-
ture of 25 6 2°C, and stir the solution vigorously. When the pH
meter reading becomes constant adjust the asymmetry potential
dial of the instrument so that the meter reads 4.0.
A2.9.2 Remove the acidic buffer, clean the electrodes, and
immerse them in water for several minutes. Dry the electrodes
and insert them in a beaker containing alkaline nonaqueous
buffer solution at 25 6 2°C. When the pH meter reading has
become steady, record the exact value. If the reading is within
0.2 pH units of 11.0, the initial acidity, pHr, of unknown
solutions may be read directly from the dial of the meter. If the FIG. A2.1 Calibration Curve for Conversion of pH Meter Readings
reading is not within 0.2 units of 11.0, prepare a correction to pHr

6
 D 974 – 02
SUMMARY OF CHANGES

Subcommittee D02.06 has identified the location of selected changes to this standard since the last issue
(D 974-01) that may impact the use of this standard.

(1) In 7.7.2, absolute amounts of reagents required to prepare (2) In 7.8, absolute amounts of reagents required to prepare
solutions have been revised to ratios of reagents for ease of solutions have been revised to ratios of reagents for ease of
preparing varying volumes of solutions. preparing varying volumes of solutions.

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