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 − 17a British Standard 4457

Designation 177/96

Standard Test Method for

Acid Number of Petroleum Products by Potentiometric
Titration1
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* D974 and D3339. There has not been any attempt to correlate this method
with other non-titration methods.
1.1 This test method covers procedures for the determina- NOTE 3—A few laboratories have made the observation that there is a
tion of acidic constituents in petroleum products, lubricants, difference in Test Method D664 results when aqueous versus nonaqueous
biodiesel, and blends of biodiesel. buffers are used.
1.1.1 Test Method A—For petroleum products and lubricants 1.3 The values stated in SI units are to be regarded as
soluble or nearly soluble in mixtures of toluene and propan-2- standard. No other units of measurement are included in this
ol. It is applicable for the determination of acids whose standard.
dissociation constants in water are larger than 10–9; extremely 1.4 This standard does not purport to address all of the
weak acids whose dissociation constants are smaller than 10–9 safety concerns, if any, associated with its use. It is the
do not interfere. Salts react if their hydrolysis constants are responsibility of the user of this standard to establish appro-
larger than 10–9. The range of acid numbers included in the priate safety, health, and environmental practices and deter-
precision statement is 0.1 mg ⁄g KOH to 150 mg ⁄g KOH. mine the applicability of regulatory limitations prior to use.
1.1.2 Test Method B—Developed specifically for biodiesel 1.5 This international standard was developed in accor-
and biodiesel blends with low acidity and slightly different dance with internationally recognized principles on standard-
solubility. This test method requires the use of an automatic ization established in the Decision on Principles for the
titrator with automatic endpoint-seeking capability. Development of International Standards, Guides and Recom-
NOTE 1—In new and used oils, the constituents that may be considered
to have acidic characteristics include organic and inorganic acids, esters, mendations issued by the World Trade Organization Technical
phenolic compounds, lactones, resins, salts of heavy metals, salts of Barriers to Trade (TBT) Committee.
ammonia and other weak bases, acid salts of polybasic acids, and addition
agents such as inhibitors and detergents. 2. Referenced Documents
1.2 The test method may be used to indicate relative 2.1 ASTM Standards:2
changes that occur in oil during use under oxidizing conditions D974 Test Method for Acid and Base Number by Color-
regardless of the color or other properties of the resulting oil. Indicator Titration
Although the titration is made under definite equilibrium D1193 Specification for Reagent Water
conditions, the test method is not intended to measure an D3339 Test Method for Acid Number of Petroleum Products
absolute acidic property that can be used to predict perfor- by Semi-Micro Color Indicator Titration
mance of oil under service conditions. No general relationship D4057 Practice for Manual Sampling of Petroleum and
between bearing corrosion and acid number is known. Petroleum Products
NOTE 2—The acid number obtained by this standard may or may not be D4177 Practice for Automatic Sampling of Petroleum and
numerically the same as that obtained in accordance with Test Methods Petroleum Products
E177 Practice for Use of the Terms Precision and Bias in
ASTM Test Methods
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of 3. Terminology
Subcommittee D02.06 on Analysis of Liquid Fuels and Lubricants. 3.1 Definitions:
Current edition approved Dec. 15, 2017. Published March 2018. Originally
approved in 1942. Last previous edition approved in 2017 as D664 – 17. DOI:
2
10.1520/D0664-17A. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
This test method was adopted as a joint ASTM-IP standard in 1964. ASTM Test contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Method D4739 has been developed as an alternative to the base number portion of Standards volume information, refer to the standard’s Document Summary page on
D664. the ASTM website.

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

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 D664 − 17a
3.1.1 acid number, n—the quantity of a specified base, 6. Apparatus
expressed in milligrams of potassium hydroxide per gram of
6.1 Manual Titration Apparatus:
sample, required to titrate a sample in a specified solvent to a
6.1.1 Meter, a voltmeter or a potentiometer that will operate
specified endpoint using a specified detection system.
with an accuracy of 60.005 V and a sensitivity of 60.002 V
3.1.1.1 Discussion—This test method expresses the quantity
over a range of at least 60.5 V when the meter is used with the
of base as milligrams of potassium hydroxide per gram of
electrodes specified in 6.1.2 and 6.1.3 and when the resistance
sample, that is required to titrate a sample in a mixture of
between the electrodes falls within the range from 0.2 MΩ to
toluene and propan-2-ol to which a small amount of water has
20 MΩ. The meter shall be protected from stray electrostatic
been added from its initial meter reading in millivolts to a
fields so that no permanent change in the meter readings over
meter reading in millivolts corresponding to an aqueous basic
the entire operating range is produced by touching, with a
buffer solution or a well-defined inflection point as specified in
grounded lead, any part of the exposed surface of the glass
the test method.
electrode, the glass electrode lead, the titration stand, or the
3.1.1.2 Discussion—This test method provides additional meter.
information. The quantity of base, expressed as milligrams of
potassium hydroxide per gram of sample, required to titrate a NOTE 4—A suitable apparatus could consist of a continuous-reading
sample in the solvent from its initial meter reading in millivolts 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
to a meter reading in millivolts corresponding to a freshly across the meter terminals and provided with a metal shield connected to
prepared aqueous acidic buffer solution or a well-defined the ground, as well as a satisfactory terminal to connect the shielded
inflection point as specified in the test method shall be reported connection wire from the glass electrode to the meter without interference
as the strong acid number. from any external electrostatic field.
3.1.1.3 Discussion—The causes and effects of the so-called 6.1.2 Sensing Electrode, standard pH, suitable for nonaque-
strong acids and the causes and effects of the other acids can be ous titrations.
very significantly different. Therefore, the user of this test 6.1.3 Reference Electrode, silver/silver chloride (Ag/AgCl)
method shall differentiate and report the two, when they are reference electrode, filled with 1M to 3M LiCl in ethanol.
found. 6.1.3.1 Combination Electrodes—Sensing electrodes may
have the Ag/AgCl reference electrode built into the same
4. Summary of Test Method electrode body, which offers the convenience of working with
4.1 The sample is dissolved in a titration solvent and titrated and maintaining only one electrode. The combination electrode
potentiometrically with alcoholic potassium hydroxide using a shall have a sleeve junction on the reference compartment and
glass indicating electrode and a reference electrode or a shall use an inert ethanol electrolyte, for example, 1M–3M
combination electrode. The meter readings are plotted manu- LiCl in ethanol. These combination electrodes shall have the
ally or automatically against the respective volumes of titrating same response or better response than a dual electrode system.
solution and the end points are taken only at well-defined They shall have removable sleeves for easy rinsing and
inflections in the resulting curve. When no definite inflections addition of electrolyte.
are obtained and for used oils, end points are taken at meter NOTE 5—A third electrode, such as a platinum electrode, may be used
readings corresponding to those found for aqueous acidic and to increase the electrode stability in certain systems.
basic buffer solutions.
6.1.4 Variable-Speed Mechanical Stirrer, a suitable type,
equipped with a propeller-type stirring paddle. The rate of
5. Significance and Use
stirring shall be sufficient to produce vigorous agitation without
5.1 New and used petroleum products, biodiesel, and blends spattering and without stirring air into the solution. A propeller
of biodiesel may contain acidic constituents that are present as with blades 6 mm in radius and set at a pitch of 30° to 45° is
additives or as degradation products formed during service, satisfactory. A magnetic stirrer is also satisfactory.
such as oxidation products. The relative amount of these 6.1.4.1 If an electrical stirring apparatus is used, it shall be
materials can be determined by titrating with bases. The acid electrically correct and grounded so that connecting or discon-
number is a measure of this amount of acidic substance in the necting the power to the motor will not produce a permanent
oil, always under the conditions of the test. The acid number is change in the meter reading during the course of the titration.
used as a guide in the quality control of lubricating oil 6.1.5 Burette, 10 mL capacity, graduated in 0.05 mL divi-
formulations. It is also sometimes used as a measure of sions and calibrated with an accuracy of 60.02 mL. The
lubricant degradation in service. Any condemning limits must burette shall have a tip that extends 100 mm to 130 mm beyond
be empirically established. the stopcock and shall be able to deliver titrant directly into the
5.2 Since a variety of oxidation products contribute to the titration vessel without exposure to the surrounding air or
acid number and the organic acids vary widely in corrosion vapors. The burette for KOH shall have a guard tube containing
properties, the test method cannot be used to predict corrosive- soda lime or other CO2-absorbing substance.
ness of oil or biodiesel and blends under service conditions. No 6.1.6 Titration Beaker, 250 mL, 125 mL, or suitable
general correlation is known between acid number and the capacity, made of borosilicate glass or other suitable material.
corrosive tendency of biodiesel and blends or oils toward 6.1.7 Titration Stand, suitable for supporting the electrodes,
metals. stirrer, and burette.

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 D664 − 17a
NOTE 6—An arrangement that allows the removal of the beaker without column, discarding the first 5 % of material distilling overhead
disturbing the electrodes and stirrer is desirable. and using the 95 % remaining. Drying can also be accom-
6.2 Automatic Titration Apparatus: plished using molecular sieves such as Linde Type 4A, by
6.2.1 Automatic titration systems shall be able to carry out passing the solvent upward through a molecular sieve column
the necessary analyses as prescribed in the method. As a using one part of molecular sieve per ten parts of solvent.
minimum, the automatic titration system shall meet the perfor- NOTE 7—It has been reported that, if not originally inhibited against it,
mance and specification requirements listed in 6.1 as war- propan-2-ol can contain peroxides. When this occurs, an explosion is
possible when the storage of the vessel or other equipment such as a
ranted. dispensing bottle, is near empty and approaching dryness.
6.2.2 A dynamic mode of titrant addition shall be used.
During the titration, the speed and volume of the addition shall 7.9 Commercial Aqueous pH 4, pH 7, and pH 11 Buffer
vary depending on the rate of change of the system. The Solutions—These solutions shall be replaced at regular inter-
recommended maximum volume increment is 0.5 mL and the vals consistent with their stability or when contamination is
recommended minimum volume increment is 0.05 mL. suspected. Information relating to their stability should be
6.2.3 Graduated Cylinder—50 mL, or dispensing device obtained from the manufacturer.
capable of delivering 50 mL 6 0.5 mL. 8. Electrode System
6.2.4 Pipette—2.0 mL, Class A.
6.2.5 Titration Beaker—250 mL, 125 mL, or suitable 8.1 Preparation of Electrodes—When a Ag/AgCl reference
capacity, made of borosilicate glass or other suitable material. electrode is used for the titration and it contains an electrolyte
which is not 1M–3M LiCl in ethanol, replace the electrolyte.
7. Reagents Drain the electrolyte from the electrode, wash away all the salt
7.1 Purity of Reagents—Reagent-grade chemicals shall be (if present) with water and then rinse with ethanol. Rinse
used in all tests. Unless otherwise indicated, it is intended that several times with the LiCl electrolyte solution. Finally, replace
all reagents shall conform to the specifications of the commit- the sleeve and fill the electrode with the LiCl electrolyte to the
tee on Analytical Reagents of the American Chemical Society, filling hole. When refitting the sleeve, ensure that there will be
where such specifications are available.3 Other grades may be a free flow of electrolyte into the system. A combination
used, provided it is first ascertained that the reagent is of electrode shall be prepared in the same manner. The electrolyte
sufficiently high purity to permit its use without lessening the in a combination electrode can be removed with the aid of a
accuracy of the determination. vacuum suction.
7.1.1 Commercially available solutions may be used in 8.2 Testing of Electrodes—Test the meter-electrode combi-
place of laboratory preparations, provided the solutions have nation when first put into use, or when new electrodes are
been certified as being equivalent. installed, and retest at intervals thereafter. Rinse the electrodes
7.1.2 Alternate volumes of the solutions may be prepared, with solvent then with water, and dip them into a pH 4 aqueous
provided the final solution concentration is equivalent. buffer solution. Read the mV value after stirring 1 min.
7.2 Purity of Water—Unless otherwise indicated, reference Remove the electrodes and rinse with water. Dip the electrodes
to water shall be understood to mean reagent water that meets into a pH 7 aqueous buffer. Read the mV value after stirring
the requirements of either Type I, II, or III of Specification 1 min. Calculate the mV difference. A good electrode system
D1193. will have a difference of at least 162 mV (20 °C to 25 °C). If
the difference is less than 162 mV, lift the sleeve of the
7.3 Primary Standard—Where specified, these samples, or electrode and ensure electrolyte flow. Repeat the measure-
samples of commercially available primary standards, are to be ments. If the difference is still less than 162 mV, clean or
used in standardizing the volumetric solutions. replace the electrode(s).
7.4 Ethanol. (Warning—Flammable and toxic, especially 8.2.1 When the sensing electrode and the reference elec-
when denatured.) trode are separate, one pair of electrodes shall be considered as
one unit. If one or the other is changed, it shall be considered
7.5 Lithium Chloride, LiCl.
as different pair and shall be retested.
7.6 Lithium Chloride Electrolyte, Prepare a 1M–3M solu-
8.3 Maintenance and Storage of Electrodes—Cleaning the
tion of lithium chloride (LiCl) in ethanol.
electrodes thoroughly, keeping the ground-glass joint free of
7.7 Potassium Hydroxide. (Warning—Causes severe foreign materials, and regular testing of the electrodes are very
burns.) important in obtaining repeatable potentials, since contamina-
7.8 Propan-2-ol, Anhydrous, (less than 0.1 % H2O). tion may introduce uncertain erratic and unnoticeable liquid
(Warning—Flammable.) If adequately dry reagent cannot be contact potentials. While this is of secondary importance when
procured, it can be dried by distillation through a multiple plate end points are chosen from inflection points in the titration
curve, it may be quite serious when end points are chosen at
3
arbitrarily fixed cell potentials.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not NOTE 8—See Appendix X1 for a possible procedure to check the
listed by the American Chemical Society, see Annual Standards for Laboratory electrode performance.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 8.3.1 Clean the glass electrode at frequent intervals based on
MD. use and type of samples being analyzed (not less than once

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 D664 − 17a
every week during continual use) by immersing in non- should be tested as soon as possible after removal from the lubricating
chromium containing, strongly oxidizing cleaning solution. system and the dates of sampling and testing, if known, should be noted.
The reference electrode shall be cleaned periodically when in Test Method A
use or when a new electrode is installed. Drain the reference
electrode at least once each week and refill with the fresh LiCl 11. Reagents
electrolyte as far as the filling hole. Ensure that there are no air 11.1 See Section 7.
bubbles in the electrode liquid. If air bubbles are observed,
hold the electrode in a vertical position and gently tap it to 11.2 Hydrochloric Acid (HCl)—Relative density 1.19.
release the bubbles. Maintain the electrolyte level in the (Warning—Corrosive, causes burns.)
reference electrode above that of the liquid in the titration 11.3 Toluene. (Warning—Flammable.)
beaker or vessel at all times. 11.4 Hydrochloric Acid Solution, Standard Alcoholic, (0.1
8.3.2 Prior to each titration, soak the prepared electrodes in mol/L). (Warning—See 11.2 and 7.8.) Mix 9 mL of hydro-
water (pH 4.5 to 5.5) for at least 5 min. Rinse the electrodes chloric (HCl, relative density 1.19) acid with 1 L of anhydrous
with propan-2-ol immediately before use, and then with the propan-2-ol. Standardize frequently enough to detect concen-
titration solvent. tration changes of 0.0005 by potentiometric titration of ap-
8.3.3 When not in use, immerse the lower half of the proximately 8 mL (accurately measured) of the 0.1-mol/L
reference electrode in LiCl electrolyte. When the glass elec- alcoholic KOH solution diluted with 125 mL of CO2-free
trode is used, store it in water that has been acidified with HCl water.
to a pH of 4.5 to 5.5. Do not allow electrodes to remain
immersed in titration solvent for any appreciable period of time 11.5 Potassium Hydroxide Solution, Standard Alcoholic,
between titrations. While the electrodes are not extremely (0.1 mol//L). (Warning—See 7.7 and 7.8.) Add 6 g of
fragile, handle them carefully at all times. potassium hydroxide (KOH) to approximately 1 L of propan-
8.3.3.1 Electrode Life—Typically, electrode usage is limited 2-ol. Boil gently for 10 min to effect solution. Allow the
to 3 to 6 months, depending upon usage. Electrodes have a solution to stand for two days and then filter the supernatant
limited shelf life and shall be tested before use (see 8.2). liquid through a fine sintered-glass funnel. Store the solution in
a chemically resistant bottle. Dispense in a manner such that
9. Standardization of Apparatus the solution is protected from atmospheric carbon dioxide
9.1 Determination of Meter Readings for the Aqueous (CO2) by means of a guard tube containing soda lime or soda
Buffer Solutions—To ensure comparable selection of end points non-fibrous silicate absorbents and such that it does not come
when definite inflection points are not obtained in the titration into contact with cork, rubber, or saponifiable stopcock grease.
curve, determine daily, for each electrode pair, the meter Standardize frequently enough to detect concentration changes
readings obtained with aqueous acidic and basic buffer solu- of 0.0005 by potentiometric titration of weighed quantities of
tions. potassium acid phthalate dissolved in CO2-free water.
11.6 Titration Solvent—Add 5 mL 6 0.2 mL of water to
NOTE 9—The response of different glass electrodes to hydrogen ion
activity is not the same. Therefore, it is necessary to establish regularly for 495 mL 6 5 mL of anhydrous propan-2-ol and mix well. Add
each electrode system the meter readings corresponding to the buffer 500 mL 6 5 mL of toluene. (Warning—Flammable.) The
solutions arbitrarily selected to represent acidic or basic end points. titration solvent should be made up in large quantities, and its
9.2 Immerse the electrodes in the pH 4 and the pH 11 blank value determined daily by titration prior to use.
aqueous buffers and stir each of them for approximately 5 min, 11.7 Chloroform. (Warning—Flammable. Hazardous mate-
maintaining the temperature of the buffer solution at a tem- rial.)
perature within 2 °C of that at which the titrations are to be
made. Read the cell voltage for each of them. The readings so 12. Procedure for Acid Number and Strong Acid
obtained are taken as the end points in titration curves having Number
no inflection points. 12.1 Into a 250 mL beaker or a suitable titration vessel,
introduce a weighed quantity of sample as recommended in
10. Preparation of Sample Table 1(a) (see Note 11) and add 125 mL of titration solvent
10.1 When applicable, refer to Practice D4057 (manual (see Note 12). Alternatively, into a 125 mL beaker or a suitable
sampling) or Practice D4177 (automatic sampling) for proper titration vessel, introduce a weighed quantity of sample as
sampling techniques. recommended in Table 1(b) and add 60 mL of titration solvent.
10.1.1 When sampling used lubricants, the specimen shall Prepare the electrodes as directed in 8.1. Place the beaker or
be representative of the system sampled and shall be free of titration vessel on the titration stand and adjust its position so
contamination from external sources. that the electrodes are about half immersed. Start the stirrer,
10.1.2 Agitate used oil samples thoroughly to ensure that and stir throughout the determination at a rate sufficient to
any sediment present is homogeneously suspended before produce vigorous agitation without spattering and without
analysis as the sediment can be acidic or basic or have stirring air into the solution.
adsorbed acidic or basic material from the sample. When NOTE 11—If it suspected that the recommended sample size will foul
necessary, samples are warmed to aid mixing. the electrodes, a smaller sample size can be taken. Results using smaller
sample size may not be equivalent to results obtained with the recom-
NOTE 10—As used oil can change appreciably in storage, samples mended sample size. The precision statement does not include results

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 D664 − 17a
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

when using a smaller sample size. 12.4.3 Titrate with the 0.1 mol ⁄L alcoholic KOH solution.
NOTE 12—A titration solvent that contains chloroform (Warning— The apparatus shall be adjusted or programmed such that,
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
when an inflection point, suitable for use in the calculation is
heavy residues of asphaltic materials. Results using chloroform may not approached, the rate of addition of titrant and volume of titrant
be equivalent to results obtained using toluene. The precision statement added are based on the change in slope of the titration curve.
does not include results when using chloroform. The titrant shall be added in increments of a suitable size to
12.2 Select the right burette, fill with the 0.1 mol ⁄L alco- achieve a potential difference of 5 mV to 15 mV per increment.
holic KOH solution, and place the burette in position on the Increment volume shall vary between 0.05 mL and 0.5 mL.
titration assembly, ensuring that the tip is immersed about The next increment shall be added if the signal does not change
25 mm in titration vessel liquid. Record the initial burette and more than 10 mV in 10 s. The maximum waiting time in
meter (cell potential) readings. between increments shall not exceed 60 s.
12.4.4 The titration can be terminated when the signal
12.3 Manual Titration Method:
reaches the pH 11 buffer potential past 200 mV. An equivalence
12.3.1 Add suitable small portions of 0.1 mol ⁄L alcoholic
point is recognizable if the first derivative of the titration curve
KOH solution and wait until a constant potential has been
produces a maximum, which is significantly higher than the
established, record the burette and meter readings.
noise produced by electrostatic effects. See also 13.1.1.
12.3.2 At the start of the titration and in any subsequent
12.4.5 The goal of cleaning is to rinse the residue from the
regions (inflections) where 0.1 mL of the 0.1 mol ⁄L KOH
previous sample and to rehydrate the electrode. On completion
solution consistently produces a total change of more than
of the titration, rinse the electrodes and burette tip with titration
30 mV in the cell potential, add 0.05 mL portions.
solvent. If clean, then rinse with 2-propanol and then with
12.3.3 In the intermediate regions (plateau) where 0.1 mL of
water. Immerse the electrodes in pH 4.5–5.5 water for at least
0.1 mol ⁄L alcoholic KOH changes the cell potential less than
3 min to 5 min to rehydrate the aqueous gel layer of the glass
30 mV, add larger portions sufficient to produce a total poten-
electrode. Rinse with 2-propanol prior to beginning the next
tial change approximately equal to, but not greater than 30 mV.
sample to remove the water. If sample residue remains after the
12.3.4 Titrate in this manner until the potential changes less
rinse with titration solvent, another solvent such as toluene,
than 5 mV ⁄0.1 mL of KOH and the cell potential indicates that
xylene, heptane, or chloroform may be used for rinse. The rinse
the solution is more basic than the aqueous basic buffer.
may be more effective if a beaker of solvent is used with strong
12.3.5 Remove the titration solution, rinse the electrodes
stirring. Using automated equipment, cleaning may be done by
and burette tip with the titration solvent, then with propan-2-ol
rinsing with titration solvent, soaking with stirring in a solvent
and finally with reagent grade water. Immerse the electrodes in
such as toluene, xylene, heptane, or chloroform for 45 s,
water for at least 5 min before starting another titration to
soaking briefly in 2-propanol to removed the solvent, then
restore the aqueous gel layer of the glass electrode. After 5 min
soaking in pH 4.5–5.5 water 3 min to 5 min to rehydrate. Dip
in the water, rinse the electrodes with propan-2-ol then the
in 2-propanol briefly to remove water before beginning the
titration solvent before proceeding to the next titration. If the
next sample. The same solvent cleaning beaker, 2-propanol
electrodes are found to be dirty and contaminated, proceed as
beaker and water beaker may be used for a short series of
in 8.1. Store electrodes according to 8.3.3.
samples. They should be changed at reasonable intervals,
12.4 Automatic Titration Method: before contamination builds up. The user shall ensure that the
12.4.1 Adjust the apparatus in accordance with the manu- electrode is adequately cleaned and hydrated. If electrodes are
facturer’s instructions to provide a dynamic mode of titrant found dirty and contaminated, proceed as in 8.1. Store elec-
addition. trodes according to 8.3.3.
12.4.2 Verify that the instrument will determine the amount
NOTE 13—When acid numbers about or below 0.1 are expected, better
of strong acid when the initial mV of the test sample, relative precision can be obtained by modifying the method in one or more ways,
to the mV reading of the aqueous acidic buffer, indicates the such as by substituting a 0.01 M or 0.05 M alcoholic KOH solution;
presence of such acids. Record the volume of KOH added to increasing the sample size above 20 g; or switching from a manual
reach the mV of the pH 4 aqueous buffer. This value is used to operated burette (that is, graduated in 0.05 mL divisions) to an automated
calculate the strong acid number. Proceed with the automatic burette that can dispense smaller increments of the KOH solution, if
samples are being analyzed by manual titration.
titration and record potentiometric curves or derivative curves
as the case may be.

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 D664 − 17a
12.5 Blanks:
12.5.1 For each set of samples and for every new batch of
titration solvent, perform a blank titration of 125 mL or 60 mL
depending on the volume of the solvent that will be used for
sample analysis. For manual titration, add 0.1 mol ⁄L alcoholic
KOH solution in 0.01 mL to 0.05 mL increments, waiting
between each addition until a constant cell potential is reached.
Record the meter and readings when the former becomes
constant after each increment. For automatic titration, use the
same mode of titration as for the determination of the acidic
property of the sample but use smaller increments of titrant
addition, 0.01 mL to 0.05 mL. Recheck the blank periodically
based on the sample load.
12.5.2 When strong acids are present and a strong acid
number is to be determined, perform a blank titration of
125 mL or 60 mL depending on the volume of the titration
solvent that will be used for sample analysis. Add 0.1 mol ⁄L
alcoholic HCl solution in 0.01 mL to 0.05 mL increments in a
manner comparable to that specified in 12.5.1.
13. Calculation
13.1 Manual Titration—Plot the volumes of the 0.1 mol ⁄L
alcoholic KOH solution added against the corresponding meter
readings (see Fig. 1). Mark as an end point only a well-defined
inflection point (see Note 14) that is closest to the cell voltage
corresponding to that obtained with the aqueous acidic or basic
buffer. If inflections are ill defined or no inflection appears (see
Fig. 1, Curve B), mark the end point at the meter reading Key:
corresponding to that obtained with the appropriate aqueous 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
buffer. sharp inflections are apparent, the end points are chosen at the meter readings
obtained with the two aqueous buffer solutions.
NOTE 14—One inflection point is generally recognizable by inspection
Curve C—10.00 g of oil containing a weak acid plus 125 mL of titration solvent.
whenever several successive 0.05 mL increments each produce a cell The end point is chosen as the point at which the curve is most nearly vertical.
potential change greater than 15 mV at least 30 % greater than those Curve D—10.00 g of oil containing weak and strong acids plus 125 mL of titration
produced by previous or subsequent increments of the same size. solvent. The end points are chosen as the points at which the curve is most nearly
Generally, definite inflection points may be discerned only in regions vertical.
where increments of the same size are used. FIG. 1 Illustrative Titration Curves
13.1.1 Some additive chemistry may produce an inflection
point beyond the buffer endpoint. For additives, take the last
inflection point for calculation. If using an automatic titrator, a
Acid number, mg KOH/g 5 ~ A 2 B ! 3 M 3 56.1/W (1)
change in the instrument parameters may be required to detect
this type of endpoint. Strong acid number, mg KOH/g 5 ~ CM1Dm! 3 56.1/W (2)
13.1.2 For all acid titrations on used oils, mark as an end where:
point the point on the curve that corresponds to the meter A = volume of alcoholic KOH solution used to titrate
reading for an aqueous basic buffer (pH 11) and the meter sample to end point that occurs at the meter reading of
reading for the aqueous acid buffer (pH 4) when strong acids the inflection point closest to the meter reading corre-
are indicated. sponding to the pH 11 aqueous buffer, or in case of
NOTE 15—The cooperative work done on acid number determinations ill-defined or no inflection point, to the meter reading
on fresh oils, additive concentrates, and used oils indicated well-defined corresponding to the pH 11 aqueous buffer, mL. For
inflection points for fresh oils and additive concentrates, and generally additives, A is the volume of alcoholic KOH at the last
ill-defined inflections, or no inflection points at all, for used oils.
inflection point,
13.2 Automatic Titration Method—Mark the end points on B = volume corresponding to A for blank titration, mL,
the curves obtained in 12.4, in the same way as for the manual M = concentration of alcoholic KOH solution, mol/L,
titration method. m = concentration of alcoholic HCl solution, mol/L,
13.3 Method of Calculation—The method of calculation in W = sample, mass, g,
C = alcoholic KOH solution used to titrate the sample to
13.3.1 is applicable to both manual and automatic methods.
end point that occurs at a meter reading corresponding
13.3.1 Calculate the acid number and strong acid number as
to the pH 4 aqueous buffer, mL, and
follows:

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 D664 − 17a

D = alcoholic HCl solution used to titrate solvent blank to 16. Precision and Bias56
end point corresponding to C, mL. 16.1 Acid Number:
16.1.1 Repeatability Limit (r)—The difference between re-
14. Quality Control Checks petitive results obtained by the same operator in a given
14.1 Confirm the performance of the test procedure by laboratory applying the same test method with the same
analyzing a quality control (QC) sample that is, if possible, apparatus under constant operating conditions on identical test
representative of the samples typically analyzed. material within short intervals of time would in the long run, in
NOTE 16—Because used oils, particularly used engine oils, are known the normal and correct operation of the test method, exceed the
to change during storage, such samples may not be suitable for this following values only in one case in 20.
purpose. 16.1.1.1 Repeatability can also be interpreted as maximum
14.2 Prior to monitoring the measurement process, the user difference between two results, obtained under repeatability
of the method needs to determine the average value and control conditions, that is accepted as plausible due to random causes
limits of the QC sample.4 under normal and correct operation of the test method.
Fresh and used oils 60 mL:
14.3 Record the QC results and analyze by control charts or
other statistically equivalent technique to ascertain the statis- AN Inflection, mg KOH/g 2 Solvent 60 mL (5)
tical control status of the total testing process.4 Any out-of-
Repeatability 5 0.1938 · X 0.8199
control data should trigger investigation for root cause(s). The
results of this investigation may, but not necessarily, result in AN Buffer EP ~pH 11!, mg KOH/g 2 Solvent 60 mL (6)
instrument recalibration.
Repeatability 5 0.2681 · X 0.9748
14.4 The frequency of QC testing is dependent on the where:
criticality of the quality being measured, the demonstrated
stability of the testing process, and customer requirements. X = the average of the two test results.
Generally, a QC sample should be analyzed each testing day. 16.1.2 Reproducibility (R)—The difference between two
The QC frequency should be increased if a large number of single and independent results obtained by different operators
samples are routinely analyzed. However, when it is demon- applying the same test method in different laboratories using
strated that the testing is under statistical control, the QC different apparatus on identical test material would, in the long
testing frequency may be reduced. The QC precision should be run, in the normal and correct operation of the test method,
periodically checked against the precision listed in the Preci- exceed the following values only in one case in 20.
sion and Bias section of this test method to ensure data quality. 16.1.2.1 Reproducibility can also be interpreted as maxi-
14.5 It is recommended that, if possible, the type of QC mum difference between two results, obtained under reproduc-
sample that is regularly tested be representative of the samples ibility conditions, that is accepted as plausible due to random
routinely analyzed. An ample supply of QC sample material causes under normal and correct operation of the test method.
should be available for the intended period of use, and must be Fresh and used oils 60 mL:
homogeneous and stable under the anticipated storage condi- AN Inflection, mg KOH/g 2 Solvent 60 mL (7)
tions. Because the acid number can vary while the QC sample
is in storage, when an out-of-control situation arises, the Reproducibility 5 0.4022 · X 0.8199
stability of the QC sample can be a source of the error. AN Buffer EP ~pH 11!, mg KOH/g 2 Solvent 60 mL (8)

15. Report Reproducibility 5 0.4506 · X 0.9748

15.1 Given there are two different ways to determine the where:
endpoint, report the type of endpoint used: inflection point or X = the average of the two test results.
buffer endpoint. Report sample size used if it differs from the
16.2 Strong Acid Number:
recommended sample size. Also, report if chloroform was used
as solvent. Report the results as acid number or strong acid 16.2.1 Precision data have not been developed for strong
number as follows: acid number because of its rare occurrence in sample analysis.
Acid number ~ Test Method D664, Test Method A! 5 ~ result! (3) 16.3 Bias—The procedures in this test method have no bias
because the acid values can be defined only in terms of the test
Strong acid number ~ Test Method D664, Test Method A! 5 ~ result!
method.
(4)

15.2 For used oil samples, report also the date of testing
and, when available, the date the sample was taken. 5
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1551. Contact ASTM Customer
Service at service@astm.org.
6
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4
ASTM MNL 7, Manual on Presentation of Data Control Chart Analysis, 6th be obtained by requesting Research Report RR:D02-1869. Contact ASTM Customer
edition, ASTM International, W. Conshohocken, PA. Service at service@astm.org.

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 D664 − 17a
TABLE 2 Precision for AN Using 60 mL and 125 mL of Solvent with Comparison Data
AN Levels, Revision: Revision: Current Method: Current Method:
mg KOH/g Solvent – 60 mL Solvent – 60 mL Solvent – 125 mL Solvent – 125 mL
r, Inflection r, BEP (pH 11) Fresh Oils (r) Used Oils BEP (r)
Calculation Formula 0.1938 · X0.8199 0.2681 · X0.9748 0.044(X + 1) 0.117X
Precision @ 5 mg KOH/g 0.73 1.29 0.26 0.59
Precision @ 1 mg KOH/g 0.19 0.27 0.09 0.12

R, Inflection R, BEP (pH 11) R, Inflection Used Oils BEP (R)

Calculation Formula 0.4022 · X0.8199 0.4506 · X0.9748 0.141(X + 1) 0.44X
Precision @ 5 mg KOH/g 1.50 2.16 0.85 2.2
Precision @ 1 mg KOH/g 0.40 0.45 0.28 0.44

Test Method B 18.1.2 Prepare two additional KHP solutions to standardize

the titrant as in 18.1.
17. Reagents 18.1.3 Use the three determinations to calculate the average
17.1 See Section 7. concentration (mol/L) of the KOH. The average of the titrant
17.2 Potassium Hydroxide Solution, Standard Alcoholic mol/L determinations should agree 60.0005 M.
(0.01 mol//L)—(Warning—See 7.7 and 7.8.) Add 0.56 g of 18.2 Determination of the Solvent Blank—Adjust the appa-
potassium hydroxide (KOH) to approximately 1 L of propan- ratus in accordance with the manufacturer’s instructions to
2-ol or weigh 1.122 g 6 0.02 g of 50 % KOH into 1 L of provide a dynamic mode of titration. Addition of titrant volume
propan-2-ol. Boil gently for 10 min to effect solution. Allow increments should not be greater than 0.2 mL. Measure pre-
the solution to stand protected from carbon dioxide (CO2) for cisely 50 mL of propan-2-ol using a graduated cylinder, pipet
two days and then filter the supernatant liquid through a fine or automated dispensing device capable of dispensing 50 mL
sintered-glass funnel. Store the solution in a chemically resis- 6 0.5 mL into a 125 mL or suitable size beaker. Stir the
tant bottle. Dispense in a manner such that the solution is solution and titrate. Record the volume (mL) of KOH to
protected from atmospheric carbon dioxide (CO2) by means of 60.01 mL used to titrate to the inflection point.
a guard tube containing soda lime or soda non-fibrous silicate
absorbents and such that it does not come into contact with 18.3 Analysis of the Sample:
cork, rubber, or saponifiable stopcock grease. Standardize 18.3.1 Adjust the apparatus in accordance with the manu-
frequently enough to detect concentration changes of facturer’s instructions to provide a dynamic mode of titrant
0.0005 mol ⁄L by potentiometric titration of pipetted quantities addition.
of potassium acid phthalate solution dissolved in CO2-free 18.3.2 Weigh 5 g of biodiesel into a 125 mL or suitable size
water. beaker on an analytical balance and record the weight to the
nearest 0.0001 g. Measure 50 mL 6 0.50 mL of IPA using a
17.3 Potassium Acid Phthalate (KHC8H4O4), Primary
pipet or automated dispensing device into a suitable beaker.
Standard, Dried—Place 10 g to 20 g of primary standard
Prepare the electrodes as directed in 8.1. Place the beaker or
potassium acid phthalate (KHC8H4O4) of 100-mesh fineness,
titration vessel on the titration stand and adjust its position so
in a weighing bottle at 120 °C for 2 h. Stopper the container
that the electrodes are about half immersed. Start the stirrer,
and cool it in a dessicator.
and stir throughout the determination at a rate sufficient to
17.4 Potassium Acid Phthalate (KHP) Solution produce vigorous agitation without spattering and without
(0.01 mol ⁄L)—For a volumetric standard, weigh approxi- stirring air into the solution.
mately 1.0 g and record the weight to the nearest 60.0001 g of
dried potassium acid phthalate primary standard (KHC8H4O4) NOTE 17—It is important that the same volume of titration solvent
60.5 mL is used for the blank and samples or inconsistent results can
and make up to the mark with DI Type II water in a 500 mL occur.
volumetric flask. Alternatively for a weight-based standard,
weigh the KHP and record the weight to the nearest 0.0001 g 18.3.3 Select the right burette, fill with 0.01 mol ⁄L alcoholic
and record the total amount of water and KHP to the nearest KOH solution, and place the burette in position on the titration
60.01 g and express the concentration as mg KHP/g of assembly, ensuring that the tip is immersed about 25 mm in
solution. Mix thoroughly to dissolve the solution. titration vessel liquid and titrate.
18.3.4 On completion of the titration, rinse the electrodes
18. Procedure and burette tip with propan-2-ol, followed by water. Immerse
18.1 Standardization of the Titrant 0.01 M Alcoholic KOH: the electrodes in water for at least 2 min before starting another
18.1.1 Weigh 2 g of KHP solution into a 125 mL or suitable titration to restore the aqueous gel layer of the glass electrode.
size beaker and record the weight to the nearest 0.0001 g if Rinse the electrodes with propan-2-ol prior to running the next
using weight-based standard, or pipette 2 mL of KHP solution sample. If electrodes are found dirty and contaminated, pro-
into a vessel and add approximately 50 mL of CO2 free water. ceed as in 8.1. Store electrodes according to 8.3.3.
Titrate the solution to determine the titer of 0.01M KOH. This 18.3.5 Multiple titration inflection points are often found
volume of KHP solution will use approximately 2 mL of the during the analysis associated with organic acids which form
0.01 M KOH. over time due to the oxidation of biodiesel over prolonged

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 D664 − 17a
storage periods. The volume of titrant for the last well-defined
endpoint should be used to calculate the total acidity.
19. Calculation or Interpretation of Results
19.1 Calculation of KOH Solution Molarity, mol/L:
19.1.1 Calculation of KOH Molarity, mol/L by Volume of
mol/L of KHP Solution:
mol
KHP solution concentration, (9)
L

~ weight of KHP, g !
5
204.23* ~ total volume of KHP solution, L !
mol
KOH molarity, (10)
L

5
S
~ 2.00 mL KHP solution! concentration of KHP solution, L
mol
D
volume of KOH, mL

19.1.2 Calculation of KOH mol/L by Weight of mg/g of KHP

Solution:
mg
KHP solution concentration, (11)
g

~ weight of KHP, g ! *1000

5
204.23* ~ total weight of KHP solution, g !
mol
KOH molarity, (12)
L

FIG. 2 Illustrative Titration Curve of Biodiesel Sample

5
S mg
~ weight of KHP solution, g ! concentration of KHP solution, g D
volume of KOH, mL 20.3 Record the QC results and analyze by control charts or
NOTE 18—The average mol/L of three determinations should be used other statistically equivalent technique to ascertain the statis-
for the determination of the acid number. The average should agree within
60.0005 M. tical control status of the total testing process.4 Any out-of-
control data should trigger investigation for root cause(s). The
19.2 Calculation of the Acid Number: results of this investigation may, but not necessarily, result in
Acid number, mg KOH/g 5 ~ A 2 B ! 3 M 3 56.1/W (13) instrument recalibration.
where: 20.4 The frequency of QC testing is dependent on the
A = Volume of alcoholic KOH solution used to titrate criticality of the quality being measured, the demonstrated
sample to last inflection end point, mL, stability of the testing process, and customer requirements.
B = volume corresponding to A for blank titration, mL, Generally, a QC sample should be analyzed each testing day.
M = concentration of alcoholic KOH solution, mol/L, and The QC frequency should be increased if a large number of
W = sample, mass, g. samples are routinely analyzed. However, when it is demon-
strated that the testing is under statistical control, the QC
20. Quality Control Checks testing frequency may be reduced. The QC precision should be
20.1 Confirm the performance of the test procedure by periodically checked against the precision listed in the Preci-
analyzing a quality control (QC) sample that is, representative sion and Bias Section of this test method to ensure data quality.
of the samples typically analyzed, if possible. 20.5 It is recommended that a QC standard be routinely
NOTE 19—Because biodiesel is known to change during long-term analyzed at a concentration level in the same range as the
storage, such samples may not be suitable for this purpose. The analyst samples analyzed. An ample supply of QC sample material
may use the Potassium Acid Phthalate solution 0.01M as an acceptable should be available for the intended period of use, and must be
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 homogeneous and stable under the anticipated storage condi-
IPA) is necessary. No data is available on the shelf life of the KHP tions.
solution. Commercially prepared standard solutions may also be used.
20.2 Prior to monitoring the measurement process, the user 21. Report
of the method needs to determine the average value and control 21.1 Report acid number of biodiesel and blends to the 0.01
limits of the QC sample.4 as mg KOH/g of sample (Test Method D664, Test Method B).

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 D664 − 17a
22. Precision and Bias7 TABLE 3 Acid Number of BiodieselA
Repeatability = 0.264E-01 · X0.4 mg/kg KOH
22.1 The precision of this test method is based on an Reproducibility = 0.177 ·X0.4 mg/kg KOH
interlaboratory study of D664 conducted in 2009. Seven A
The degree of freedom for R is less than 30 but greater than 15. Samples 4, 5,
laboratories participated in this study, however the results from 6, 9 were excluded as these samples were below the Limit of Quantitation of the
one laboratory were excluded from the precision calculations test method.
due to a fairly consistent bias in their reported values. Each of
the laboratories was asked to report replicate test results for
eleven different diesel and biodiesel blends and a blank. Every obtained by different operators using different equipment in
“test result” reported represents a single determination or different laboratories. Reproducibility limits are listed in Table
measurement. D2PP was used for the analysis of the study 3.
data; the details are given in ASTM Research Report RR:D02- 22.1.3 The above terms (repeatability limit and reproduc-
1727. ibility limit) are used as specified in Practice E177.
22.1.1 Repeatability Limit (r)—Two test results obtained 22.1.4 Any judgment in accordance with statements 22.1.1
within one laboratory shall be judged not equivalent if they and 22.1.2 would have an approximate 95 % probability of
differ by more than the “r” value for that material; “r” is the being correct.
interval representing the critical difference between two test
22.2 The precision statement was determined through sta-
results for the same material, obtained by the same operator
tistical examination of 138 results, from six laboratories, on a
using the same equipment on the same day in the same
total of eleven different petroleum blends and a blank.
laboratory. Repeatability limits are listed in Table 3.
22.1.2 Reproducibility Limit (R)—Two test results shall be 22.3 Bias—At the time of the study, there was no accepted
judged not equivalent if they differ by more than the “R” value reference material suitable for determining the bias for this test
for that material; “R” is the interval representing the critical method, therefore no statement on bias is being made.
difference between two test results for the same material,
23. Keywords
7
23.1 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

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-
X1.3.4 After 30 s, note the potential. After an additional
quent stability is important for a titration electrode. A manual
30 s, note the potential again. The difference between the two
check is described in this Appendix that can be carried out with
potentials is termed the drift.
a pH meter or titrator set to read millivolts continuously.
X1.3.5 Repeat the procedure for pH 7 buffer and pH 11
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 11 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 54
X1.3.2 Allow the electrode to stabilize for 1 min in distilled mV/pH number. Electrodes with a slope less than 54 mV/pH
or equivalent deionized water. number are not reliable for titration.

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 D664 − 17a
SUMMARY OF CHANGES

Subcommittee D02.06 has identified the location of selected changes to this standard since the last issue
(D664 – 17) that may impact the use of this standard. (Approved Dec. 15, 2017.)

(1) Section 10 was revised.

Subcommittee D02.06 has identified the location of selected changes to this standard since the last issue
(D664 – 11a (2017)) that may impact the use of this standard. (Approved Oct. 1, 2017.)

(1) Revised subsections 6.1.6, 12.1, 12.5.1, 12.5.2, 16.1.1.1, (2) Revised Table 1.
and 16.1.2.1. (3) Added new Table 2.

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