This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: D664 − 24 British Standard 4457

Designation 177/19 (2022)

Standard Test Method for

Acid Number of Petroleum Products by Potentiometric
Titration1,2

--`,,`,`,`,`````,`,,,,``````-`-`,,`,,`,`,,`---
This standard is issued under the fixed designation D664; 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 U.S. Department of Defense.

1. Scope* 1.2 For acid number determination of acidic components in

1.1 This test method covers procedures for the determina- crude oil and petroleum products including waxes, bitumen,
tion of acidic constituents in petroleum products, lubricants, base stocks, and asphalts that are soluble in mixtures of xylenes
biodiesel, and blends of biodiesel. and propan-2-ol use test method Test Method D8045. The
1.1.1 Test Method A—Developed for use with petroleum precision for this method has not been determined for any
products and lubricants soluble or nearly soluble in mixtures of products covered by Test Method D8045.
toluene and propan-2-ol. It is applicable for the determination 1.3 The test method may be used to indicate relative
of acids whose dissociation constants in water are larger than changes that occur in oil during use under oxidizing conditions
10–9; extremely weak acids whose dissociation constants are regardless of the color or other properties of the resulting oil.
smaller than 10–9 do not interfere. Salts react if their hydrolysis Although the titration is made under definite equilibrium
constants are larger than 10–9. The range of acid numbers conditions, the test method is not intended to measure an
included in the precision statement is 0.5 mg KOH/g to 90 mg absolute acidic property that can be used to predict perfor-
KOH ⁄g. The precision has only been determined for those mance of oil under service conditions. No general relationship
materials and acid number ranges as shown in the precision between acid number and the corrosive tendency of oils
section. towards metals is known.
1.1.2 Test Method B—Developed specifically for biodiesel NOTE 2—The acid number obtained by this standard may or may not be
and biodiesel blends with low acidity and slightly different numerically the same as that obtained in accordance with Test Methods
solubility. This test method requires the use of an automatic D974 and D3339. There has not been any attempt to correlate this method
titrator with automatic endpoint-seeking capability. with other non-titration methods.
NOTE 1—In new and used oils, the constituents that may be considered NOTE 3—A few laboratories have made the observation that there is a
to have acidic characteristics include organic and inorganic acids, esters, difference in Test Method D664 results when aqueous versus nonaqueous
phenolic compounds, lactones, resins, salts of heavy metals, salts of buffers are used.
ammonia and other weak bases, acid salts of polybasic acids, and addition
agents such as inhibitors and detergents. 1.4 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
1
standard.
This test method is under the jurisdiction of ASTM International Committee
D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct 1.5 This standard does not purport to address all of the
responsibility of ASTM Subcommittee D02.06 on Analysis of Liquid Fuels and safety concerns, if any, associated with its use. It is the
Lubricants. The technically equivalent standard as referenced is under the jurisdic-
tion of the Energy Institute Subcommittee SC-C-4.
responsibility of the user of this standard to establish appro-
Current edition approved May 1, 2024. Published May 2024. Originally priate safety, health, and environmental practices and deter-
approved in 1942. Last previous edition approved in 2018 as D664 – 18ɛ2. DOI: mine the applicability of regulatory limitations prior to use.
10.1520/D0664-24.
This test method was adopted as a joint ASTM-IP standard in 1964. ASTM Test 1.6 This international standard was developed in accor-
Method D4739 has been developed as an alternative to the base number portion of dance with internationally recognized principles on standard-
D664.
2
ization established in the Decision on Principles for the
This test method has been developed through the cooperative effort between
Development of International Standards, Guides and Recom-
ASTM and the Energy Institute, London. ASTM and IP standards were approved by
ASTM and EI technical committees as being technically equivalent but that does not mendations issued by the World Trade Organization Technical
imply both standards are identical. Barriers to Trade (TBT) Committee.

*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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 D664 − 24
2. Referenced Documents 3.2.1.1 Discussion—The causes and effects of the so-called
2.1 ASTM Standards: 3 strong acids and the causes and effects of the other acids can be
D974 Test Method for Acid and Base Number by Color- very significantly different. Therefore, the user of this test
Indicator Titration method shall differentiate and report the two, when they are
D1193 Specification for Reagent Water found.
D3339 Test Method for Acid Number of Petroleum Products
by Semi-Micro Color Indicator Titration 4. Summary of Test Method
D4057 Practice for Manual Sampling of Petroleum and 4.1 The sample is dissolved in a titration solvent and titrated
Petroleum Products potentiometrically with alcoholic potassium hydroxide using a
D4175 Terminology Relating to Petroleum Products, Liquid glass indicating electrode and a reference electrode or a
Fuels, and Lubricants combination electrode. The meter readings are plotted manu-
D4177 Practice for Automatic Sampling of Petroleum and ally or automatically against the respective volumes of titrating
Petroleum Products solution and the end points are taken only at well-defined
D6299 Practice for Applying Statistical Quality Assurance inflections in the resulting curve. When no definite inflections
and Control Charting Techniques to Evaluate Analytical are obtained and for used oils, end points are taken at meter
Measurement System Performance readings corresponding to those found for aqueous acidic and
D6300 Practice for Determination of Precision and Bias basic buffer solutions.
Data for Use in Test Methods for Petroleum Products,
Liquid Fuels, and Lubricants 5. Significance and Use
D6792 Practice for Quality Management Systems in Petro- 5.1 New and used petroleum products, biodiesel, and blends
leum Products, Liquid Fuels, and Lubricants Testing of biodiesel may contain acidic constituents that are present as
Laboratories additives or as degradation products formed during service,
D8045 Test Method for Acid Number of Crude Oils and such as oxidation products. The relative amount of these
Petroleum Products by Catalytic Thermometric Titration materials can be determined by titrating with bases. The acid
--`,,`,`,`,`````,`,,,,``````-`-`,,`,,`,`,,`---

D8126 Test Method for Efficient Basicity Determination by number is a measure of this amount of acidic substance in the
Potentiometric Hydrochloric Acid Titration oil, always under the conditions of the test. The acid number is
E177 Practice for Use of the Terms Precision and Bias in used as a guide in the quality control of lubricating oil
ASTM Test Methods formulations. It is also sometimes used as a measure of
3. Terminology lubricant degradation in service. Any condemning limits must
be empirically established.
3.1 Definitions:
3.1.1 For definitions of terms used in this test method, refer 5.2 Since a variety of oxidation products contribute to the
to Terminology D4175. acid number and the organic acids vary widely in corrosion
3.1.2 acid number, n—the quantity of a specified base, properties, the test method cannot be used to predict corrosive-
expressed in milligrams of potassium hydroxide per gram of ness of oil or biodiesel and blends under service conditions. No
sample, required to titrate a sample in a specified solvent to a general correlation is known between acid number and the
specified endpoint using a specified detection system. corrosive tendency of biodiesel and blends or oils toward
3.1.2.1 Discussion—This test method expresses the quantity metals.
of base as milligrams of potassium hydroxide per gram of
sample, that is required to titrate a sample in a mixture of 6. Apparatus
toluene and propan-2-ol to which a small amount of water has 6.1 Manual Titration Apparatus:
been added from its initial meter reading in millivolts to a 6.1.1 Meter, a voltmeter or a potentiometer that will operate
meter reading in millivolts corresponding to an aqueous basic with an accuracy of 60.005 V and a sensitivity of 60.002 V
buffer solution or a well-defined inflection point as specified in over a range of at least 60.5 V when the meter is used with the
the test method. electrodes specified in 6.1.2 and 6.1.3 and when the resistance
3.2 Definitions of Terms Specific to This Standard: between the electrodes falls within the range from 0.2 MΩ to
3.2.1 strong acid number, n—quantity of base, expressed as 20 MΩ. The meter shall be protected from stray electrostatic
milligrams of potassium hydroxide per gram of sample, re- fields so that no permanent change in the meter readings over
quired to titrate a sample in the solvent from its initial meter the entire operating range is produced by touching, with a
reading in millivolts to a meter reading in millivolts corre- grounded lead, any part of the exposed surface of the glass
sponding to a freshly prepared aqueous acidic buffer solution electrode, the glass electrode lead, the titration stand, or the
as specified in the test method shall be reported as the strong meter.
acid number. NOTE 4—A suitable apparatus could consist of a continuous-reading
electronic voltmeter designed to operate on an input of less than 5 × 10−12
A, when an electrode system having 1000 MΩ resistance is connected
3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or across the meter terminals and provided with a metal shield connected to
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM the ground, as well as a satisfactory terminal to connect the shielded
Standards volume information, refer to the standard’s Document Summary page on connection wire from the glass electrode to the meter without interference
the ASTM website. from any external electrostatic field.

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 D664 − 24
TABLE 1 Recommended Size of Test Portion
(a) 125 mL Solvent (b) 60 mL Solvent
Mass of Test Portion, Accuracy of Weighing, Mass of Test Portion, Accuracy of Weighing,
Acid Number Acid Number
g g g g
0.05 to <1.0 20.0 ± 2.0 0.10 0.05 to <1.0 10.0 ± 1.0 0.10
1.0 to <5.0 5.0 ± 0.5 0.02 1.0 to <5.0 2.5 ± 0.25 0.02
5 to <20 1.0 ± 0.1 0.005 5 to <20 0.5 ± 0.05 0.005
20 to <100 0.25 ± 0.02 0.001 20 to <100 0.25 ± 0.02 0.001
100 to <260 0.1 ± 0.01 0.0005 100 to <260 0.1 ± 0.01 0.0005

6.1.2 Sensing Electrode, standard pH, suitable for nonaque- recommended maximum volume increment is 0.5 mL and the
ous titrations. recommended minimum volume increment is 0.05 mL.
6.1.3 Reference Electrode, silver/silver chloride (Ag/AgCl) 6.2.3 Motor-driven Burette, interchangeable with a volume-
reference electrode, filled with 1M to 3M LiCl in ethanol. dispensing accuracy of 60.01 mL.
6.1.3.1 Combination Electrodes—Sensing electrodes may 6.2.4 Graduated Cylinder—50 mL, or dispensing device
have the Ag/AgCl reference electrode built into the same capable of delivering 50 mL 6 0.5 mL.
electrode body, which offers the convenience of working with 6.2.5 Pipette—2.0 mL, Class A.
and maintaining only one electrode. The combination electrode 6.2.6 Titration Beaker—250 mL, 125 mL, or suitable
shall have a sleeve junction on the reference compartment and capacity, made of borosilicate glass or other suitable material.
shall use an inert ethanol electrolyte, for example, 1M–3M 6.3 Analytical Balance, for sample preparation, capable of
LiCl in ethanol. These combination electrodes shall have the weighing to the appropriate sensitivity given in Table 1.
same response or better response than a dual electrode system.
They shall have removable sleeves for easy rinsing and 7. Reagents
addition of electrolyte.
7.1 Purity of Reagents—Reagent-grade chemicals shall be
NOTE 5—A third electrode, such as a platinum electrode, may be used used in all tests. Unless otherwise indicated, it is intended that
to increase the electrode stability in certain systems. all reagents shall conform to the specifications of the commit-
6.1.4 Variable-Speed Mechanical Stirrer, a suitable type, tee on Analytical Reagents of the American Chemical Society,
equipped with a propeller-type stirring paddle. The rate of where such specifications are available.4 Other grades may be
stirring shall be sufficient to produce vigorous agitation without used, provided it is first ascertained that the reagent is of
spattering and without stirring air into the solution. A propeller sufficiently high purity to permit its use without lessening the
with blades 6 mm in radius and set at a pitch of 30° to 45° is accuracy of the determination.
satisfactory. A magnetic stirrer is also satisfactory. 7.1.1 Commercially available solutions may be used in
6.1.4.1 If an electrical stirring apparatus is used, it shall be place of laboratory preparations, provided the solutions have
electrically correct and grounded so that connecting or discon- been certified as being equivalent.
necting the power to the motor will not produce a permanent 7.1.2 Alternate volumes of the solutions may be prepared,
change in the meter reading during the course of the titration. provided the final solution concentration is equivalent.
6.1.5 Burette, 10 mL capacity, graduated in 0.05 mL divi- 7.2 Purity of Water—Unless otherwise indicated, reference
sions and calibrated with an accuracy of 60.02 mL. The to water shall be understood to mean reagent water that meets
burette shall have a tip that extends 100 mm to 130 mm beyond the requirements of either Type I, II, or III of Specification
the stopcock and shall be able to deliver titrant directly into the D1193.
titration vessel without exposure to the surrounding air or
vapors. The burette for KOH shall have a guard tube containing 7.3 Primary Standard—Where specified, these samples, or
soda lime or other CO2-absorbing substance. samples of commercially available primary standards, are to be
6.1.6 Titration Beaker, 250 mL, 125 mL, or suitable used in standardizing the volumetric solutions. --`,,`,`,`,`````,`,,,,``````-`-`,,`,,`,`,,`---

capacity, made of borosilicate glass or other suitable material. 7.4 Ethanol. (Warning—Flammable and toxic, especially
6.1.7 Titration Stand, suitable for supporting the electrodes, when denatured.)
stirrer, and burette. 7.5 Lithium Chloride, LiCl.
NOTE 6—An arrangement that allows the removal of the beaker without 7.6 Lithium Chloride Electrolyte, Prepare a 1M–3M solu-
disturbing the electrodes and stirrer is desirable.
tion of lithium chloride (LiCl) in ethanol.
6.2 Automatic Titration Apparatus:
7.7 Potassium Hydroxide. (Warning—Causes severe
6.2.1 Automatic titration systems shall be able to carry out
burns.)
the necessary analyses as prescribed in the method. As a
minimum, the automatic titration system shall meet the perfor-
mance and specification requirements listed in 6.1 as warranted 4
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
and record the complete course of the titration. Standard-Grade Reference Materials, American Chemical Society, Washington,
DC. For suggestions on the testing of reagents not listed by the American Chemical
6.2.2 A dynamic mode of titrant addition shall be used.
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
During the titration, the speed and volume of the addition shall U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
vary depending on the rate of change of the system. The copeial Convention, Inc. (USPC), Rockville, MD.

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 D664 − 24
7.8 Propan-2-ol, Anhydrous, (less than 0.1 % H2O). NOTE 8—See Appendix X1 for a possible procedure to check the
(Warning—Flammable.) If adequately dry reagent cannot be electrode performance.
procured, it can be dried by distillation through a multiple plate 8.3.1 Clean the glass electrode at frequent intervals based on
column, discarding the first 5 % of material distilling overhead use and type of samples being analyzed (not less than once
and using the 95 % remaining. Drying can also be accom- every week during continual use) by immersing in non-
plished using molecular sieves such as Linde Type 4A, by chromium containing, strongly oxidizing cleaning solution.
passing the solvent upward through a molecular sieve column The reference electrode shall be cleaned periodically when in
using one part of molecular sieve per ten parts of solvent. use or when a new electrode is installed. Drain the reference
NOTE 7—It has been reported that, if not originally inhibited against it, electrode at least once each week and refill with the fresh LiCl
propan-2-ol can contain peroxides. When this occurs, an explosion is electrolyte as far as the filling hole. Ensure that there are no air
possible when the storage of the vessel or other equipment such as a bubbles in the electrode liquid. If air bubbles are observed,
dispensing bottle, is near empty and approaching dryness. hold the electrode in a vertical position and gently tap it to
7.9 Commercial Aqueous pH 4, pH 7, and pH 10 Buffer release the bubbles. Maintain the electrolyte level in the
Solutions—These solutions shall be replaced at regular inter- reference electrode above that of the liquid in the titration
vals consistent with their stability or when contamination is beaker or vessel at all times.
suspected. Information relating to their stability should be 8.3.2 Prior to each titration, soak the prepared electrodes in
obtained from the manufacturer. water (pH 4.5 to 5.5) for at least 5 min. Rinse the electrodes
with propan-2-ol immediately before use, and then with the
8. Electrode System titration solvent.
8.3.3 When not in use, immerse the lower half of the
8.1 Preparation of Electrodes—When a Ag/AgCl reference reference electrode in LiCl electrolyte. When the glass elec-
electrode is used for the titration and it contains an electrolyte trode is used, store it in water that has been acidified with HCl
which is not 1M–3M LiCl in ethanol, replace the electrolyte. to a pH of 4.5 to 5.5. Do not allow electrodes to remain
Drain the electrolyte from the electrode, wash away all the salt immersed in titration solvent for any appreciable period of time
(if present) with water and then rinse with ethanol. Rinse between titrations. While the electrodes are not extremely
several times with the LiCl electrolyte solution. Finally, replace fragile, handle them carefully at all times.
the sleeve and fill the electrode with the LiCl electrolyte to the 8.3.3.1 Electrode Life—Typically, electrode usage is limited
filling hole. When refitting the sleeve, ensure that there will be to 3 to 6 months, depending upon usage. Electrodes have a
a free flow of electrolyte into the system. A combination limited shelf life and shall be tested before use (see 8.2).
electrode shall be prepared in the same manner. The electrolyte
in a combination electrode can be removed with the aid of a 9. Standardization of Apparatus
vacuum suction.
9.1 Determination of Meter Readings for the Aqueous
8.2 Testing of Electrodes—Test the meter-electrode combi- Buffer Solutions—To ensure comparable selection of end points
nation when first put into use, or when new electrodes are when definite inflection points are not obtained in the titration
installed, and retest at intervals thereafter. Rinse the electrodes curve, determine daily, for each electrode pair, the meter
with solvent then with water, and dip them into a pH 4 aqueous readings obtained with aqueous acidic and basic buffer solu-
buffer solution. Read the mV value after stirring 1 min. tions.
Remove the electrodes and rinse with water. Dip the electrodes
NOTE 9—The response of different glass electrodes to hydrogen ion
into a pH 7 aqueous buffer. Read the mV value after stirring
activity is not the same. Therefore, it is necessary to establish regularly for
1 min. Calculate the mV difference. A good electrode system each electrode system the meter readings corresponding to the buffer
will have a difference of at least 162 mV (20 °C to 25 °C). If solutions arbitrarily selected to represent acidic or basic end points.
the difference is less than 162 mV, lift the sleeve of the 9.2 Immerse the electrodes in the pH 4 and the pH 10
electrode and ensure electrolyte flow. Repeat the measure- aqueous buffers and stir each of them for approximately 5 min,
ments. If the difference is still less than 162 mV, clean or maintaining the temperature of the buffer solution at a tem-
replace the electrode(s).
--`,,`,`,`,`````,`,,,,``````-`-`,,`,,`,`,,`---

perature within 2 °C of that at which the titrations are to be

8.2.1 When the sensing electrode and the reference elec- made. Read the cell voltage for each of them. The readings so
trode are separate, one pair of electrodes shall be considered as obtained are taken as the end points in titration curves having
one unit. If one or the other is changed, it shall be considered no inflection points.
as different pair and shall be retested.
8.3 Maintenance and Storage of Electrodes—Cleaning the 10. Preparation of Sample
electrodes thoroughly, keeping the ground-glass joint free of 10.1 When applicable, refer to Practice D4057 (manual
foreign materials, and regular testing of the electrodes are very sampling) or Practice D4177 (automatic sampling) for proper
important in obtaining repeatable potentials, since contamina- sampling techniques.
tion may introduce uncertain erratic and unnoticeable liquid 10.1.1 When sampling used lubricants, the specimen shall
contact potentials. While this is of secondary importance when be representative of the system sampled and shall be free of
end points are chosen from inflection points in the titration contamination from external sources.
curve, it may be quite serious when end points are chosen at 10.1.2 Agitate used oil samples thoroughly to ensure that
arbitrarily fixed cell potentials. any sediment present is homogeneously suspended before

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 D664 − 24
analysis as the sediment can be acidic or basic or have produce vigorous agitation without spattering and without
adsorbed acidic or basic material from the sample. When stirring air into the solution.
necessary, samples are warmed to aid mixing. NOTE 11—If it suspected that the recommended sample size will foul
the electrodes, a smaller sample size can be taken. Results using smaller
NOTE 10—As used oil can change appreciably in storage, samples sample size may not be equivalent to results obtained with the recom-
should be tested as soon as possible after removal from the lubricating mended sample size. The precision statement does not include results
system and the dates of sampling and testing, if known, should be noted. when using a smaller sample size.
NOTE 12—A titration solvent that contains chloroform (Warning—
Test Method A May be fatal if swallowed. Harmful if inhaled. May produce toxic vapors
if burned) can be used in place of toluene to completely dissolve certain
11. Reagents heavy residues of asphaltic materials. Results using chloroform may not
be equivalent to results obtained using toluene. The precision statement
11.1 See Section 7. does not include results when using chloroform.
11.2 Hydrochloric Acid (HCl)—Relative density 1.19. 12.2 Select the right burette, fill with the 0.1 mol ⁄L alco-
(Warning—Corrosive, causes burns.) holic KOH solution, and place the burette in position on the
11.3 Toluene. (Warning—Flammable.) titration assembly, ensuring that the tip is immersed about
25 mm in titration vessel liquid. Record the initial burette and
11.4 Hydrochloric Acid Solution, Standard Alcoholic, meter (cell potential) readings.
(0.1 mol ⁄L). (Warning—See 11.2 and 7.8.) Mix 9 mL of
hydrochloric (HCl, relative density 1.19) acid with 1 L of 12.3 Manual Titration Method:
anhydrous propan-2-ol. Standardize frequently enough to de- 12.3.1 Add suitable small portions of 0.1 mol ⁄L alcoholic
tect concentration changes of 0.0005 by potentiometric titra- KOH solution and wait until a constant potential has been
tion of approximately 8 mL (accurately measured) of the established, record the burette and meter readings.
0.1 mol ⁄L alcoholic KOH solution diluted with 125 mL of 12.3.2 At the start of the titration and in any subsequent

--`,,`,`,`,`````,`,,,,``````-`-`,,`,,`,`,,`---
CO2-free water. regions (inflections) where 0.1 mL of the 0.1 mol ⁄L KOH
solution consistently produces a total change of more than
11.5 Potassium Hydroxide Solution, Standard Alcoholic,
30 mV in the cell potential, add 0.05 mL portions.
(0.1 mol//L). (Warning—See 7.7 and 7.8.) Add 6 g of
12.3.3 In the intermediate regions (plateau) where 0.1 mL of
potassium hydroxide (KOH) to approximately 1 L of propan-
0.1 mol ⁄L alcoholic KOH changes the cell potential less than
2-ol. Boil gently for 10 min to effect solution. Allow the
30 mV, add larger portions sufficient to produce a total poten-
solution to stand for two days and then filter the supernatant
tial change approximately equal to, but not greater than 30 mV.
liquid through a fine sintered-glass funnel. Store the solution in
12.3.4 Titrate in this manner until the potential changes less
a chemically resistant bottle. Dispense in a manner such that
than 5 mV ⁄0.1 mL of KOH and the cell potential indicates that
the solution is protected from atmospheric carbon dioxide
the solution is more basic than the aqueous basic buffer.
(CO2) by means of a guard tube containing soda lime or soda
non-fibrous silicate absorbents and such that it does not come 12.3.5 Remove the titration solution, rinse the electrodes
into contact with cork, rubber, or saponifiable stopcock grease. and burette tip with the titration solvent, then with propan-2-ol
Standardize frequently enough to detect concentration changes and finally with reagent grade water. Immerse the electrodes in
of 0.0005 by potentiometric titration of weighed quantities of water for at least 5 min before starting another titration to
potassium acid phthalate dissolved in CO2-free water. restore the aqueous gel layer of the glass electrode. After 5 min
in the water, rinse the electrodes with propan-2-ol then the
11.6 Titration Solvent—Add 5 mL 6 0.2 mL of water to titration solvent before proceeding to the next titration. If the
495 mL 6 5 mL of anhydrous propan-2-ol and mix well. Add electrodes are found to be dirty and contaminated, proceed as
500 mL 6 5 mL of toluene. (Warning—Flammable.) The in 8.1. Store electrodes according to 8.3.3.
titration solvent should be made up in large quantities, and its
blank value determined daily by titration prior to use. 12.4 Automatic Titration Method:
12.4.1 Adjust the apparatus in accordance with the manu-
11.7 Chloroform. (Warning—Flammable. Hazardous mate- facturer’s instructions to provide a dynamic mode of titrant
rial.) addition. Ensure all gas bubbles are flushed from titrant lines
and burette openings before proceeding.
12. Procedure for Acid Number and Strong Acid 12.4.2 Verify that the instrument will determine the amount
Number of strong acid when the initial mV of the test sample, relative
12.1 Into a 250 mL beaker or a suitable titration vessel, to the mV reading of the aqueous acidic buffer, indicates the
introduce a weighed quantity of sample as recommended in presence of such acids. Record the volume of KOH added to
Table 1(a) (see Note 11) and add 125 mL of titration solvent reach the mV of the pH 4 aqueous buffer. This value is used to
(see Note 12). Alternatively, into a 125 mL beaker or a suitable calculate the strong acid number. Proceed with the automatic
titration vessel, introduce a weighed quantity of sample as titration and/or record potentiometric curves or derivative
recommended in Table 1(b) and add 60 mL of titration solvent. curves as the case may be. Derivative curves are recorded as a
Prepare the electrodes as directed in 8.1. Place the beaker or function of the delivered volume and are an included feature by
titration vessel on the titration stand and adjust its position so automated titration systems.
that the electrodes are about half immersed. Start the stirrer, 12.4.3 Titrate with the 0.1 mol ⁄L alcoholic KOH solution.
and stir throughout the determination at a rate sufficient to The apparatus shall be adjusted or programmed such that,

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 D664 − 24

FIG. 1 Example Titration Curve with First Deivative Curve

when an inflection point, suitable for use in the calculation is operated burette (that is, graduated in 0.05 mL divisions) to an automated
approached, the rate of addition of titrant and volume of titrant burette that can dispense smaller increments of the KOH solution, if
samples are being analyzed by manual titration.
added are based on the change in slope of the titration curve.
The titrant shall be added in increments of a suitable size to 12.5 Blanks:
achieve a potential difference of 5 mV to 15 mV per increment. 12.5.1 For each set of samples and for every new batch of
Increment volume shall vary between 0.05 mL and 0.5 mL. titration solvent, perform a blank titration of 125 mL or 60 mL
The next increment shall be added if the signal does not change depending on the volume of the solvent that will be used for
more than 10 mV in 10 s. The maximum waiting time in sample analysis. For manual titration, add 0.1 mol ⁄L alcoholic
between increments shall not exceed 60 s. KOH solution in 0.01 mL to 0.05 mL increments, waiting
12.4.4 The titration can be terminated when the signal between each addition until a constant cell potential is reached.
reaches the pH 10 buffer potential past 200 mV. An equiva- Record the meter and readings when the former becomes
lence point is recognizable if the first derivative of the titration constant after each increment. For automatic titration, use the
curve produces a maximum, which is significantly higher than same mode of titration as for the determination of the acidic
the noise produced by electrostatic effects. See also 13.1.1. property of the sample but use smaller increments of titrant
12.4.5 The goal of cleaning is to rinse the residue from the addition, 0.01 mL to 0.05 mL. Recheck the blank periodically
previous sample and to rehydrate the electrode. On completion based on the sample load.
of the titration, rinse the electrodes and burette tip with titration 12.5.2 When strong acids are present and a strong acid
solvent. If clean, then rinse with 2-propanol and then with number is to be determined, perform a blank titration of
water. Immerse the electrodes in pH 4.5–5.5 water for at least 125 mL or 60 mL depending on the volume of the titration
3 min to 5 min to rehydrate the aqueous gel layer of the glass solvent that will be used for sample analysis. Add 0.1 mol ⁄L
electrode. Rinse with 2-propanol prior to beginning the next alcoholic HCl solution in 0.01 mL to 0.05 mL increments in a
sample to remove the water. If sample residue remains after the manner comparable to that specified in 12.5.1.
rinse with titration solvent, another solvent such as toluene,
xylene, heptane, or chloroform may be used for rinse. The rinse 13. Calculation
may be more effective if a beaker of solvent is used with strong 13.1 Manual Titration—Plot the volumes of the 0.1 mol ⁄L
--`,,`,`,`,`````,`,,,,``````-`-`,,`,,`,`,,`---

stirring. Using automated equipment, cleaning may be done by alcoholic KOH solution added against the corresponding meter
rinsing with titration solvent, soaking with stirring in a solvent readings (see Fig. 2). Mark as an end point only a well-defined
such as toluene, xylene, heptane, or chloroform for 45 s, inflection point (see Note 14) that is closest to the cell voltage
soaking briefly in 2-propanol to removed the solvent, then corresponding to that obtained with the aqueous acidic or basic
soaking in pH 4.5–5.5 water 3 min to 5 min to rehydrate. Dip buffer. If inflections are ill defined or no inflection appears (see
in 2-propanol briefly to remove water before beginning the Fig. 2, Curve B), mark the end point at the meter reading
next sample. The same solvent cleaning beaker, 2-propanol corresponding to that obtained with the appropriate aqueous
beaker and water beaker may be used for a short series of buffer.
samples. They should be changed at reasonable intervals,
NOTE 14—One inflection point is generally recognizable by inspection
before contamination builds up. The user shall ensure that the whenever several successive 0.05 mL increments each produce a cell
electrode is adequately cleaned and hydrated. If electrodes are potential change greater than 15 mV at least 30 % greater than those
found dirty and contaminated, proceed as in 8.1. Store elec- produced by previous or subsequent increments of the same size.
trodes according to 8.3.3. Generally, definite inflection points may be discerned only in regions
where increments of the same size are used.
NOTE 13—When acid numbers about or below 0.1 are expected, better
precision can be obtained by modifying the method in one or more ways, 13.1.1 Some additive chemistry may produce an inflection
such as by substituting a 0.01 M or 0.05 M alcoholic KOH solution; point beyond the buffer endpoint. For additives, take the last
increasing the sample size above 20 g; or switching from a manual inflection point for calculation. If using an automatic titrator, a

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--`,,`,`,`,`````,`,,,,``````-`-`,,`,,`,`,,`---
Key:
Curve A—Blank on 125 mL of titration solvent.
Curve B—10.00 g of used crankcase oil plus 125 mL of titration solvent. Since no sharp inflections are apparent, the end points are chosen at the meter readings obtained
with the two aqueous buffer solutions.
Curve C—10.00 g of oil containing a weak acid plus 125 mL of titration solvent. The end point is chosen as the point at which the curve is most nearly vertical.
Curve D—10.00 g of oil containing weak and strong acids plus 125 mL of titration solvent. The end points are chosen as the points at which the curve is most nearly vertical.
FIG. 2 Illustrative Titration Curves

change in the instrument parameters may be required to detect where:

this type of endpoint. The stated precision statement does not A = volume of alcoholic KOH solution used to titrate
account for this adjusted procedure. sample to end point that occurs at the meter reading of
13.1.2 For all acid titrations on used oils, mark as an end the inflection point closest to the meter reading corre-
point the point on the curve that corresponds to the meter sponding to the pH 10 aqueous buffer, or in case of
reading for an aqueous basic buffer (pH 10) and the meter ill-defined or no inflection point, to the meter reading
reading for the aqueous acid buffer (pH 4) when strong acids corresponding to the pH 10 aqueous buffer, mL. For
are indicated. additives, A is the volume of alcoholic KOH at the last
inflection point,
NOTE 15—The cooperative work done on acid number determinations
B = volume corresponding to A for blank titration, mL,
on fresh oils, additive concentrates, and used oils indicated well-defined
inflection points for fresh oils and additive concentrates, and generally M = concentration of alcoholic KOH solution, mol/L,
ill-defined inflections, or no inflection points at all, for used oils. m = concentration of alcoholic HCl solution, mol/L,
W = sample, mass, g,
13.2 Automatic Titration Method—Mark the end points on C = alcoholic KOH solution used to titrate the sample to
the curves obtained in 12.4, in the same way as for the manual end point that occurs at a meter reading corresponding
titration method. to the pH 4 aqueous buffer, mL, and
13.3 Method of Calculation—The method of calculation in D = alcoholic HCl solution used to titrate solvent blank to
13.3.1 is applicable to both manual and automatic methods. end point corresponding to C, mL.
13.3.1 Calculate the acid number and strong acid number as 14. Quality Control Checks
follows:
14.1 Confirm the performance of the test procedure by
Acid number, mg KOH/g 5 ~ A 2 B ! × M × 56.1/W (1) analyzing a quality control (QC) sample that is, if possible,
Strong acid number, mg KOH/g 5 ~ CM1Dm! × 56.1/W (2) representative of the samples typically analyzed.

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 D664 − 24
TABLE 2 Precision for AN Using 60 mL and 125 mL of Solvent with Comparison Data
Volume of Solvent 60 mL 60 mL 125 mL 125 mL
r, Inflection r, Buffer EP (pH 10) r, Inflection r, Buffer EP (pH 10)
Calculation Formula 0.1938 · X0.8199 0.3456 · X0.9758 0.1275 · X1.0431 0.2028 · X1.0513
Precision @ 5 mg KOH/g 0.73 1.71 0.68 1.10
Precision @ 1 mg KOH/g 0.19 0.35 0.13 0.20

R, Inflection R, BEP (pH 10) R, Inflection R, BEP (pH 10)

Calculation Formula 0.4022 · X0.8199 0.5542 · X0.9758 0.2188 · X1.0431 0.3160 · X1.0513
Precision @ 5 mg KOH/g 1.50 2.67 1.17 1.72
Precision @ 1 mg KOH/g 0.40 0.55 0.22 0.32

NOTE 16—Because used oils, particularly used engine oils, are known Acid Number or Strong Acid Number Report Results per mg KOH/g
to change during storage, such samples may not be suitable for this <2.00 nearest 0.05
purpose. 2.0 – 20.0 nearest 0.1
>20 nearest 1
14.2 Prior to monitoring the measurement process, the user
of the method needs to determine the average value and control 15.2 For used oil samples, report also the date of testing
limits of the QC sample (see Practices D6299 and D6792).5 and, when available, the date the sample was taken.
14.3 Record the QC results and analyze by control charts or 16. Precision and Bias67
other statistically equivalent technique to ascertain the statis-
tical control status of the total testing process.5 Any out-of- 16.1 Acid Number:
control data should trigger investigation for root cause(s). The 16.1.1 Precision—The precision of this test method was
results of this investigation may, but not necessarily, result in determined by statistical examination of interlaboratory com-
instrument recalibration. parisons using Practice D6300. The interlaboratory included 14
participants using a mix of reference and combination elec-
14.4 The frequency of QC testing is dependent on the
trodes with manual or automated titrators and tested 16
criticality of the quality being measured, the demonstrated
samples in duplicate that were a mix of used (8) and new (4)
stability of the testing process, and customer requirements.
and additive (4) oils with acid numbers in the range 0.50 mg
Generally, a QC sample should be analyzed each testing day.
KOH/g to 90 mg KOH ⁄g to generate both inflection and buffer
The QC frequency should be increased if a large number of
end point (pH 10) results.7 The samples were tested using both
samples are routinely analyzed. However, when it is demon-
60 mL and 125 mL of solvent. The precision of this test method
strated that the testing is under statistical control, the QC
is as follows.
testing frequency may be reduced. The QC precision should be
periodically checked against the precision listed in the Preci- 16.1.2 Repeatability (r)—The difference between repetitive
sion and Bias section of this test method to ensure data quality. results obtained by the same operator in a given laboratory
applying the same test method with the same apparatus under
14.5 It is recommended that, if possible, the type of QC constant operating conditions on identical test material within
sample that is regularly tested be representative of the samples short intervals of time would exceed the values listed in Table
routinely analyzed. An ample supply of QC sample material 2 about 5 % of the time (one case in 20 in the long run) in the
should be available for the intended period of use, and must be normal and correct operation of the test method, where X is the
--`,,`,`,`,`````,`,,,,``````-`-`,,`,,`,`,,`---

homogeneous and stable under the anticipated storage condi- average of the two results.
tions. Because the acid number can vary while the QC sample 16.1.3 Reproducibility (R)—The difference between two
is in storage, when an out-of-control situation arises, the single and independent results obtained by different operators
stability of the QC sample can be a source of the error. applying the same test method in different laboratories using
different apparatus on identical test material would exceed the
15. Report
values listed in Table 2 about 5 % of the time (one case in 20
15.1 Given there are two different ways to determine the in the long run) in the normal and correct operation of the test
endpoint, report the type of endpoint used: inflection point method, where X is the average of the two results.
(IEP) or buffer endpoint (BEP). Report sample size used if it
16.2 Strong Acid Number:
differs from the recommended sample size. Report the volume
16.2.1 Precision data have not been developed for strong
of solvent used. Also, report if chloroform was used as solvent.
acid number because of its rare occurrence in sample analysis.
Report the results as acid number or strong acid number as
follows:
Acid Number ~ ASTM D664A, IEP/BEP,60⁄125 mL solvent! 5 ~ result!
5
ASTM MNL 7, Manual on Presentation of Data Control Chart Analysis, 9th
(3) edition, ASTM International, W. Conshohocken, PA.
6
Strong Acid Number ~ ASTM D664A,BEP, 60/125 mL solvent! 5 Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1551. Contact ASTM Customer
~ result! (4) Service at service@astm.org.
7
Supporting data have been filed at ASTM International Headquarters and may
15.1.1 Report the acid number and strong acid number be obtained by requesting Research Report RR:D02-1869. Contact ASTM Customer
values as follows: Service at service@astm.org.

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 D664 − 24
16.3 Bias—The procedures in this test method have no bias 19.1.3 Use the three determinations to calculate the average
because the acid values can be defined only in terms of the test concentration (mol/L) of the KOH. The average of the titrant
method. mol/L determinations should agree 60.0005 M.
Test Method B 19.2 Determination of the Solvent Blank—Adjust the appa-
ratus in accordance with the manufacturer’s instructions to
17. Apparatus provide a dynamic mode of titration. Addition of titrant volume
increments should not be greater than 0.2 mL. Measure pre-
17.1 Only automated titration units are used that have
cisely 50 mL of propan-2-ol using a graduated cylinder, pipet
automatic endpoint-seeking capability. See 6.2.
or automated dispensing device capable of dispensing 50 mL
6 0.5 mL into a 125 mL or suitable size beaker. Stir the
18. Reagents
solution and titrate. Record the volume (mL) of KOH to
18.1 See Section 7. 60.01 mL used to titrate to the inflection point.
18.2 Potassium Hydroxide Solution, Standard Alcoholic 19.3 Analysis of the Sample:
(0.01 mol//L)—(Warning—See 7.7 and 7.8.) Add 0.56 g of 19.3.1 Adjust the apparatus in accordance with the manu-
potassium hydroxide (KOH) to approximately 1 L of propan- facturer’s instructions to provide a dynamic mode of titrant
2-ol or weigh 1.122 g 6 0.02 g of 50 % KOH into 1 L of addition.
propan-2-ol. Boil gently for 10 min to effect solution. Allow
19.3.2 Weigh 5 g of biodiesel into a 125 mL or suitable size
the solution to stand protected from carbon dioxide (CO2) for
beaker on an analytical balance and record the weight to the
two days and then filter the supernatant liquid through a fine
nearest 0.0001 g. Measure 50 mL 6 0.50 mL of IPA using a
sintered-glass funnel. Store the solution in a chemically resis-
pipet or automated dispensing device into a suitable beaker.
tant bottle. Dispense in a manner such that the solution is
protected from atmospheric carbon dioxide (CO2) by means of Prepare the electrodes as directed in 8.1. Place the beaker or
a guard tube containing soda lime or soda non-fibrous silicate titration vessel on the titration stand and adjust its position so
absorbents and such that it does not come into contact with that the electrodes are about half immersed. Start the stirrer,
cork, rubber, or saponifiable stopcock grease. Standardize and stir throughout the determination at a rate sufficient to
frequently enough to detect concentration changes of produce vigorous agitation without spattering and without
0.0005 mol ⁄L by potentiometric titration of pipetted quantities stirring air into the solution.
--`,,`,`,`,`````,`,,,,``````-`-`,,`,,`,`,,`---

of potassium acid phthalate solution dissolved in CO2-free NOTE 17—It is important that the same volume of titration solvent
water. 60.5 mL is used for the blank and samples or inconsistent results can
occur.
18.3 Potassium Acid Phthalate (KHC8H4O4), Primary
Standard, Dried—Place 10 g to 20 g of primary standard 19.3.3 Select the right burette, fill with 0.01 mol ⁄L alcoholic
potassium acid phthalate (KHC8H4O4) of 100-mesh fineness, KOH solution, and place the burette in position on the titration
in a weighing bottle at 120 °C for 2 h. Stopper the container assembly, ensuring that the tip is immersed about 25 mm in
and cool it in a dessicator. titration vessel liquid and titrate.
18.4 Potassium Acid Phthalate (KHP) Solution 19.3.4 On completion of the titration, rinse the electrodes
(0.01 mol ⁄L)—For a volumetric standard, weigh approxi- and burette tip with propan-2-ol, followed by water. Immerse
mately 1.0 g and record the weight to the nearest 60.0001 g of the electrodes in water for at least 2 min before starting another
dried potassium acid phthalate primary standard (KHC8H4O4) titration to restore the aqueous gel layer of the glass electrode.
and make up to the mark with DI Type II water in a 500 mL Rinse the electrodes with propan-2-ol prior to running the next
volumetric flask. Alternatively for a weight-based standard, sample. If electrodes are found dirty and contaminated, pro-
weigh the KHP and record the weight to the nearest 0.0001 g ceed as in 8.1. Store electrodes according to 8.3.3.
and record the total amount of water and KHP to the nearest 19.3.5 Multiple titration inflection points are often found
60.01 g and express the concentration as mg KHP/g of during the analysis associated with organic acids which form
solution. Mix thoroughly to dissolve the solution. over time due to the oxidation of biodiesel over prolonged
storage periods. The volume of titrant for the last well-defined
19. Procedure inflection point should be used to calculate the total acidity.
19.1 Standardization of the Titrant 0.01 M Alcoholic KOH:
20. Calculation or Interpretation of Results
19.1.1 Weigh 2 g of KHP solution into a 125 mL or suitable
size beaker and record the weight to the nearest 0.0001 g if 20.1 Calculation of KOH Solution Molarity, mol/L:
using weight-based standard, or pipette 2 mL of KHP solution 20.1.1 Calculation of KOH Molarity, mol/L by Volume of
into a vessel and add approximately 50 mL of CO2 free water. mol/L of KHP Solution:
Titrate the solution to determine the titer of 0.01M KOH. This mol
volume of KHP solution will use approximately 2 mL of the KHP solution concentration,
L
(5)
0.01 M KOH.
19.1.2 Prepare two additional KHP solutions to standardize ~ weight of KHP, g !
5
the titrant as in 19.1. 204.23* ~ total volume of KHP solution, L !

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 D664 − 24
mol
KOH molarity, (6)
L

5
S
~ 2.00 mL KHP solution! concentration of KHP solution, L
mol
D
volume of KOH, mL
20.1.2 Calculation of KOH mol/L by Weight of mg/g of KHP
Solution:
mg
KHP solution concentration, (7)
g

~ weight of KHP, g ! *1000

5
204.23* ~ total weight of KHP solution, g !
mol
KOH molarity, (8)
L

5
S mg
~ weight of KHP solution, g ! concentration of KHP solution, g D
volume of KOH, mL
NOTE 18—The average mol/L of three determinations should be used
for the determination of the acid number. The average should agree within
60.0005 M.
20.2 Calculation of the Acid Number:
Acid number, mg KOH/g 5 ~ A 2 B ! × M × 56.1/W (9)

where:
A = Volume of alcoholic KOH solution used to titrate
sample to last inflection end point, mL,
B = volume corresponding to A for blank titration, mL, FIG. 3 Illustrative Titration Curve of Biodiesel Sample
M = concentration of alcoholic KOH solution, mol/L, and
W = sample, mass, g.
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 D664 − 24
21. Quality Control Checks TABLE 3 Acid Number of BiodieselA
Repeatability = 0.264E-01 · X0.4 mg/kg KOH
21.1 Confirm the performance of the test procedure by Reproducibility = 0.177 ·X0.4 mg/kg KOH
analyzing a quality control (QC) sample that is, representative A
The degree of freedom for R is less than 30 but greater than 15. Samples 4, 5,
of the samples typically analyzed, if possible. 6, 9 were excluded as these samples were below the Limit of Quantitation of the
test method.
NOTE 19—Because biodiesel is known to change during long-term
storage, such samples may not be suitable for this purpose. The analyst
may use the Potassium Acid Phthalate solution 0.01M as an acceptable
QC standard. When used as a QC standard, the KHP solution will provide
a good indicator when restandardization of the titrant (0.01M KOH in laboratories participated in this study, however the results from
IPA) is necessary. No data is available on the shelf life of the KHP one laboratory were excluded from the precision calculations
solution. Commercially prepared standard solutions may also be used.
due to a fairly consistent bias in their reported values. Each of
21.2 Prior to monitoring the measurement process, the user the laboratories was asked to report replicate test results for
of the method needs to determine the average value and control eleven different diesel and biodiesel blends and a blank. Every
limits of the QC sample (see Practices D6299 and D6792).5 “test result” reported represents a single determination or
21.3 Record the QC results and analyze by control charts or measurement. D2PP was used for the analysis of the study
other statistically equivalent technique to ascertain the statis- data; the details are given in ASTM Research Report RR:D02-
tical control status of the total testing process.5 Any out-of- 1727.
control data should trigger investigation for root cause(s). The 23.1.1 Repeatability Limit (r)—Two test results obtained
results of this investigation may, but not necessarily, result in within one laboratory shall be judged not equivalent if they
instrument recalibration. differ by more than the “r” value for that material; “r” is the
21.4 The frequency of QC testing is dependent on the interval representing the critical difference between two test
criticality of the quality being measured, the demonstrated results for the same material, obtained by the same operator
stability of the testing process, and customer requirements. using the same equipment on the same day in the same
Generally, a QC sample should be analyzed each testing day. laboratory. Repeatability limits are listed in Table 3.
The QC frequency should be increased if a large number of 23.1.2 Reproducibility Limit (R)—Two test results shall be
samples are routinely analyzed. However, when it is demon- judged not equivalent if they differ by more than the “R” value
strated that the testing is under statistical control, the QC for that material; “R” is the interval representing the critical
testing frequency may be reduced. The QC precision should be difference between two test results for the same material,
periodically checked against the precision listed in the Preci- obtained by different operators using different equipment in
sion and Bias Section of this test method to ensure data quality. different laboratories. Reproducibility limits are listed in Table
3.
21.5 It is recommended that a QC standard be routinely 23.1.3 The above terms (repeatability limit and reproduc-
analyzed at a concentration level in the same range as the ibility limit) are used as specified in Practice E177.
samples analyzed. An ample supply of QC sample material 23.1.4 Any judgment in accordance with statements 23.1.1
should be available for the intended period of use, and must be and 23.1.2 would have an approximate 95 % probability of
homogeneous and stable under the anticipated storage condi- being correct.
tions.
23.2 The precision statement was determined through sta-
22. Report tistical examination of 138 results, from six laboratories, on a
22.1 Report acid number of biodiesel and blends to the 0.01 total of eleven different petroleum blends and a blank.
as mg KOH/g of sample (Test Method D664, Test Method B). 23.3 Bias—At the time of the study, there was no accepted
23. Precision and Bias 8 reference material suitable for determining the bias for this test
method, therefore no statement on bias is being made.
23.1 The precision of this test method is based on an
interlaboratory study of D664 conducted in 2009. Seven 24. Keywords
8
24.1 acid number; B5; B10; B20; B100; biodiesel; biodiesel
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1727. Contact ASTM Customer blend; lubricants; petroleum products; potentiometric; strong
Service at service@astm.org. acid number; titration
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 D664 − 24
APPENDIX

(Nonmandatory Information)

X1. CHECK FOR ELECTRODE PERFORMANCE

X1.1 The kinetic electrode test measures the kinetic re- X1.3.3 Remove the electrodes from the water, and place
sponse of the electrode. Electrodes can calibrate with accept- them in the pH 4 buffer. Start a stopwatch at about the moment
able slope and intercept values yet still not have a response when the buffer touches the electrode.
good enough for titration. The speed of response and subse-
quent stability is important for a titration electrode. A manual X1.3.4 After 30 s, note the potential. After an additional
check is described in this Appendix that can be carried out with 30 s, note the potential again. The difference between the two
a pH meter or titrator set to read millivolts continuously. potentials is termed the drift.
X1.3.5 Repeat the procedure for pH 7 buffer and pH 10
X1.2 The essence of this check is to challenge the electrode
buffer.
coming from rest in a water solution with buffers and measure
the potential after 30 s and 60 s. A fast electrode reaches a X1.4 Calculate the drift for each of the three buffers. The
stable point in less than 30 s and changes little from 30 s to electrode response may be judged as follows:
60 s. Use buffers pH 4, pH 7, and pH 10 for this check, as
drift < 1 excellent
needed. 1 < drift < 2 good
2 < drift < 3 acceptable
X1.3 Procedure 3 < drift < 4 questionable
4 < drift unacceptable
X1.3.1 Set the titrator or pH meter to read millivolts
continuously. Have provision for stirring the buffer solution at X1.5 The difference between the 60 s potentials for pH 4
the same speed used for the titrations. buffer and pH 7 buffer should be greater than 162 mV, or
X1.3.2 Allow the electrode to stabilize for 1 min in distilled 54 mV ⁄pH number. Electrodes with a slope less than
or equivalent deionized water. 54 mV ⁄pH number are not reliable for titration.

SUMMARY OF CHANGES

Subcommittee D02.06 has identified the location of selected changes to this standard since the last issue
--`,,`,`,`,`````,`,,,,``````-`-`,,`,,`,`,,`---

(D664 – 18ɛ2) that may impact the use of this standard. (Approved May 1, 2024.)

(1) Revised subsections 1.1.1, 1.3, 6.2.1, 12.4.1, 12.4.2, (4) Added Terminology D4175 to Sections 2 and 3.
13.1.1, 14.2, 15.1, 16.1.2, 16.1.3, 19.3.5, and 21.2. (5) Added subsection 3.2 and new definition for strong acid
(2) Added subsections 1.2, 6.2.3, 6.3, 15.1.1, 16.1.1, and number.
renumbered subsequent. (6) Added Fig. 1.
(3) Added Practice D6299, Practice D6792, Test Method (7) Added Section 17 and renumbered subsequent.
D8045, Test Method D8126, and Practice D6300 to Section 2.

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