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 − 18´2 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.

ε1 NOTE—Subsection 13.3.1 and a statement in the Summary of Changes were corrected editorially in December 2018.
ε2 NOTE—Subsections 16.1.1.1 and 16.1.2.1 were corrected editorially in January 2019.
This standard has been approved for use by agencies of the U.S. Department of Defense.

1. Scope* NOTE 2—The acid number obtained by this standard may or may not be
numerically the same as that obtained in accordance with Test Methods
1.1 This test method covers procedures for the determina- D974 and D3339. There has not been any attempt to correlate this method
tion of acidic constituents in petroleum products, lubricants, with other non-titration methods.
biodiesel, and blends of biodiesel. NOTE 3—A few laboratories have made the observation that there is a
1.1.1 Test Method A—For petroleum products and lubricants difference in Test Method D664 results when aqueous versus nonaqueous
buffers are used.
soluble or nearly soluble in mixtures of toluene and propan-2-
ol. It is applicable for the determination of acids whose 1.3 The values stated in SI units are to be regarded as
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dissociation constants in water are larger than 10–9; extremely
weak acids whose dissociation constants are smaller than 10–9
standard. No other units of measurement are included in this
standard.

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do not interfere. Salts react if their hydrolysis constants are
larger than 10–9. The range of acid numbers included in the
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the

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precision statement is 0.1 mg ⁄g KOH to 150 mg ⁄g KOH. responsibility of the user of this standard to establish appro-
1.1.2 Test Method B—Developed specifically for biodiesel priate safety, health, and environmental practices and deter-
and biodiesel blends with low acidity and slightly different mine the applicability of regulatory limitations prior to use.
solubility. This test method requires the use of an automatic 1.5 This international standard was developed in accor-
titrator with automatic endpoint-seeking capability.ASTM D664-18e2 dance with internationally recognized principles on standard-
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NOTE 1—In new and used oils, the constituents that may be considered
to have acidic characteristics include organic and inorganic acids, esters,
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
phenolic compounds, lactones, resins, salts of heavy metals, salts of
ammonia and other weak bases, acid salts of polybasic acids, and addition mendations issued by the World Trade Organization Technical
agents such as inhibitors and detergents. Barriers to Trade (TBT) Committee.
1.2 The test method may be used to indicate relative 2. Referenced Documents
changes that occur in oil during use under oxidizing conditions
regardless of the color or other properties of the resulting oil. 2.1 ASTM Standards:2
Although the titration is made under definite equilibrium D974 Test Method for Acid and Base Number by Color-
conditions, the test method is not intended to measure an Indicator Titration
absolute acidic property that can be used to predict perfor- D1193 Specification for Reagent Water
mance of oil under service conditions. No general relationship D3339 Test Method for Acid Number of Petroleum Products
between bearing corrosion and acid number is known. by Semi-Micro Color Indicator Titration
D4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
1
This test method is under the jurisdiction of ASTM Committee D02 on D4177 Practice for Automatic Sampling of Petroleum and
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Petroleum Products
Subcommittee D02.06 on Analysis of Liquid Fuels and Lubricants.
Current edition approved Nov. 1, 2018. Published November 2018. Originally
approved in 1942. Last previous edition approved in 2017 as D664 – 17a. DOI:
2
10.1520/D0664-18E02. 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

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

1
 D664 − 18´2
E177 Practice for Use of the Terms Precision and Bias in ness of oil or biodiesel and blends under service conditions. No
ASTM Test Methods general correlation is known between acid number and the
corrosive tendency of biodiesel and blends or oils toward
3. Terminology metals.
3.1 Definitions:
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
electronic voltmeter designed to operate on an input of less than 5 × 10−12
sample in the solvent from its initial meter reading in millivolts 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.

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6.1.2 Sensing Electrode, standard pH, suitable for nonaque-
3.1.1.3 Discussion—The causes and effects of the so-called
ous titrations.
strong acids and the causes and effects of the other acids can be

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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

4. Summary of Test Method

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have the Ag/AgCl reference electrode built into the same
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 hydroxideASTM usingD664-18e2
a shall have a sleeve junction on the reference compartment and
shall use an inert ethanol electrolyte, for example, 1M–3M
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glass indicating electrode and a reference electrode or a
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,
5. Significance and Use equipped with a propeller-type stirring paddle. The rate of
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.

2
 D664 − 18´2
6.1.6 Titration Beaker, 250 mL, 125 mL, or suitable 7.7 Potassium Hydroxide. (Warning—Causes severe
capacity, made of borosilicate glass or other suitable material. burns.)
6.1.7 Titration Stand, suitable for supporting the electrodes,
7.8 Propan-2-ol, Anhydrous, (less than 0.1 % H2O).
stirrer, and burette.
(Warning—Flammable.) If adequately dry reagent cannot be
NOTE 6—An arrangement that allows the removal of the beaker without procured, it can be dried by distillation through a multiple plate
disturbing the electrodes and stirrer is desirable. column, discarding the first 5 % of material distilling overhead
6.2 Automatic Titration Apparatus: and using the 95 % remaining. Drying can also be accom-
6.2.1 Automatic titration systems shall be able to carry out plished using molecular sieves such as Linde Type 4A, by
the necessary analyses as prescribed in the method. As a passing the solvent upward through a molecular sieve column
minimum, the automatic titration system shall meet the perfor- using one part of molecular sieve per ten parts of solvent.
mance and specification requirements listed in 6.1 as war- NOTE 7—It has been reported that, if not originally inhibited against it,
ranted. 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
6.2.2 A dynamic mode of titrant addition shall be used. dispensing bottle, is near empty and approaching dryness.
During the titration, the speed and volume of the addition shall
vary depending on the rate of change of the system. The 7.9 Commercial Aqueous pH 4, pH 7, and pH 10 Buffer
recommended maximum volume increment is 0.5 mL and the Solutions—These solutions shall be replaced at regular inter-
recommended minimum volume increment is 0.05 mL. vals consistent with their stability or when contamination is
6.2.3 Graduated Cylinder—50 mL, or dispensing device suspected. Information relating to their stability should be
capable of delivering 50 mL 6 0.5 mL. obtained from the manufacturer.
6.2.4 Pipette—2.0 mL, Class A.
6.2.5 Titration Beaker—250 mL, 125 mL, or suitable 8. Electrode System
capacity, made of borosilicate glass or other suitable material. 8.1 Preparation of Electrodes—When a Ag/AgCl reference
electrode is used for the titration and it contains an electrolyte
7. Reagents which is not 1M–3M LiCl in ethanol, replace the electrolyte.

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7.1 Purity of Reagents—Reagent-grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
Drain the electrolyte from the electrode, wash away all the salt
(if present) with water and then rinse with ethanol. Rinse

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all reagents shall conform to the specifications of the commit- several times with the LiCl electrolyte solution. Finally, replace
tee on Analytical Reagents of the American Chemical Society, the sleeve and fill the electrode with the LiCl electrolyte to the
where such specifications are available.3 Other grades may be filling hole. When refitting the sleeve, ensure that there will be
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used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
a free flow of electrolyte into the system. A combination
electrode shall be prepared in the same manner. The electrolyte
accuracy of the determination. in a combination electrode can be removed with the aid of a
7.1.1 Commercially available solutions may be used in vacuum suction.
ASTM D664-18e2
place of laboratory preparations, provided the solutions have 8.2 Testing of Electrodes—Test the meter-electrode combi-
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been certified as being equivalent. nation when first put into use, or when new electrodes are
7.1.2 Alternate volumes of the solutions may be prepared, installed, and retest at intervals thereafter. Rinse the electrodes
provided the final solution concentration is equivalent. with solvent then with water, and dip them into a pH 4 aqueous
7.2 Purity of Water—Unless otherwise indicated, reference buffer solution. Read the mV value after stirring 1 min.
to water shall be understood to mean reagent water that meets Remove the electrodes and rinse with water. Dip the electrodes
the requirements of either Type I, II, or III of Specification into a pH 7 aqueous buffer. Read the mV value after stirring
D1193. 1 min. Calculate the mV difference. A good electrode system
7.3 Primary Standard—Where specified, these samples, or will have a difference of at least 162 mV (20 °C to 25 °C). If
samples of commercially available primary standards, are to be the difference is less than 162 mV, lift the sleeve of the
used in standardizing the volumetric solutions. electrode and ensure electrolyte flow. Repeat the measure-
ments. If the difference is still less than 162 mV, clean or
7.4 Ethanol. (Warning—Flammable and toxic, especially replace the electrode(s).
when denatured.)
8.2.1 When the sensing electrode and the reference elec-
7.5 Lithium Chloride, LiCl. trode are separate, one pair of electrodes shall be considered as
7.6 Lithium Chloride Electrolyte, Prepare a 1M–3M solu- one unit. If one or the other is changed, it shall be considered
tion of lithium chloride (LiCl) in ethanol. as different pair and shall be retested.
8.3 Maintenance and Storage of Electrodes—Cleaning the
electrodes thoroughly, keeping the ground-glass joint free of
3
Reagent Chemicals, American Chemical Society Specifications, American foreign materials, and regular testing of the electrodes are very
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not important in obtaining repeatable potentials, since contamina-
listed by the American Chemical Society, see Annual Standards for Laboratory
tion may introduce uncertain erratic and unnoticeable liquid
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, contact potentials. While this is of secondary importance when
MD. end points are chosen from inflection points in the titration

3
 D664 − 18´2
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
analysis as the sediment can be acidic or basic or have
NOTE 8—See Appendix X1 for a possible procedure to check the
electrode performance. adsorbed acidic or basic material from the sample. When
necessary, samples are warmed to aid mixing.
8.3.1 Clean the glass electrode at frequent intervals based on
use and type of samples being analyzed (not less than once NOTE 10—As used oil can change appreciably in storage, samples
every week during continual use) by immersing in non- should be tested as soon as possible after removal from the lubricating
system and the dates of sampling and testing, if known, should be noted.
chromium containing, strongly oxidizing cleaning solution.
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,
11.2 Hydrochloric Acid (HCl)—Relative density 1.19.
hold the electrode in a vertical position and gently tap it to
(Warning—Corrosive, causes burns.)
release the bubbles. Maintain the electrolyte level in the
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.

iTeh Standards
to a pH of 4.5 to 5.5. Do not allow electrodes to remain
11.5 Potassium Hydroxide Solution, Standard Alcoholic,
immersed in titration solvent for any appreciable period of time
(0.1 mol//L). (Warning—See 7.7 and 7.8.) Add 6 g of
between titrations. While the electrodes are not extremely
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fragile, handle them carefully at all times. potassium hydroxide (KOH) to approximately 1 L of propan-
2-ol. Boil gently for 10 min to effect solution. Allow the
8.3.3.1 Electrode Life—Typically, electrode usage is limited
solution to stand for two days and then filter the supernatant
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to 3 to 6 months, depending upon usage. Electrodes have a
liquid through a fine sintered-glass funnel. Store the solution in
limited shelf life and shall be tested before use (see 8.2).
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 ASTM D664-18e2
Aqueous
(CO2) by means of a guard tube containing soda lime or soda
non-fibrous silicate absorbents and such that it does not come
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Buffer Solutions—To ensure comparable selection of end points
into contact with cork, rubber, or saponifiable stopcock grease.
when definite inflection points are not obtained in the titration
Standardize frequently enough to detect concentration changes
curve, determine daily, for each electrode pair, the meter
of 0.0005 by potentiometric titration of weighed quantities of
readings obtained with aqueous acidic and basic buffer solu-
potassium acid phthalate dissolved in CO2-free water.
tions.
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 10 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,

4
 D664 − 18´2
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

and stir throughout the determination at a rate sufficient to presence of such acids. Record the volume of KOH added to
produce vigorous agitation without spattering and without reach the mV of the pH 4 aqueous buffer. This value is used to
stirring air into the solution. calculate the strong acid number. Proceed with the automatic
NOTE 11—If it suspected that the recommended sample size will foul titration and record potentiometric curves or derivative curves
the electrodes, a smaller sample size can be taken. Results using smaller as the case may be.
sample size may not be equivalent to results obtained with the recom-
mended sample size. The precision statement does not include results 12.4.3 Titrate with the 0.1 mol ⁄L alcoholic KOH solution.
when using a smaller sample size. The apparatus shall be adjusted or programmed such that,
NOTE 12—A titration solvent that contains chloroform (Warning— when an inflection point, suitable for use in the calculation is
May be fatal if swallowed. Harmful if inhaled. May produce toxic vapors approached, the rate of addition of titrant and volume of titrant
if burned) can be used in place of toluene to completely dissolve certain added are based on the change in slope of the titration curve.
heavy residues of asphaltic materials. Results using chloroform may not
be equivalent to results obtained using toluene. The precision statement The titrant shall be added in increments of a suitable size to
does not include results when using chloroform. achieve a potential difference of 5 mV to 15 mV per increment.
12.2 Select the right burette, fill with the 0.1 mol ⁄L alco- Increment volume shall vary between 0.05 mL and 0.5 mL.
holic KOH solution, and place the burette in position on the The next increment shall be added if the signal does not change
titration assembly, ensuring that the tip is immersed about more than 10 mV in 10 s. The maximum waiting time in

iTeh Standards
25 mm in titration vessel liquid. Record the initial burette and
meter (cell potential) readings.
between increments shall not exceed 60 s.
12.4.4 The titration can be terminated when the signal

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reaches the pH 10 buffer potential past 200 mV. An equiva-
12.3 Manual Titration Method: lence point is recognizable if the first derivative of the titration
12.3.1 Add suitable small portions of 0.1 mol ⁄L alcoholic curve produces a maximum, which is significantly higher than
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KOH solution and wait until a constant potential has been
established, record the burette and meter readings.
12.3.2 At the start of the titration and in any subsequent
the noise produced by electrostatic effects. See also 13.1.1.
12.4.5 The goal of cleaning is to rinse the residue from the
previous sample and to rehydrate the electrode. On completion
regions (inflections) where 0.1 mL of the 0.1 mol ⁄L KOH of the titration, rinse the electrodes and burette tip with titration
solution consistently produces a total change ofASTM D664-18e2
more than solvent. If clean, then rinse with 2-propanol and then with
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30 mV in the cell potential, add 0.05 mL portions. water. Immerse the electrodes in pH 4.5–5.5 water for at least
12.3.3 In the intermediate regions (plateau) where 0.1 mL of 3 min to 5 min to rehydrate the aqueous gel layer of the glass
0.1 mol ⁄L alcoholic KOH changes the cell potential less than electrode. Rinse with 2-propanol prior to beginning the next
30 mV, add larger portions sufficient to produce a total poten- sample to remove the water. If sample residue remains after the
tial change approximately equal to, but not greater than 30 mV. rinse with titration solvent, another solvent such as toluene,
12.3.4 Titrate in this manner until the potential changes less xylene, heptane, or chloroform may be used for rinse. The rinse
than 5 mV ⁄0.1 mL of KOH and the cell potential indicates that may be more effective if a beaker of solvent is used with strong
the solution is more basic than the aqueous basic buffer. stirring. Using automated equipment, cleaning may be done by
12.3.5 Remove the titration solution, rinse the electrodes rinsing with titration solvent, soaking with stirring in a solvent
and burette tip with the titration solvent, then with propan-2-ol such as toluene, xylene, heptane, or chloroform for 45 s,
and finally with reagent grade water. Immerse the electrodes in soaking briefly in 2-propanol to removed the solvent, then
water for at least 5 min before starting another titration to soaking in pH 4.5–5.5 water 3 min to 5 min to rehydrate. Dip
restore the aqueous gel layer of the glass electrode. After 5 min in 2-propanol briefly to remove water before beginning the
in the water, rinse the electrodes with propan-2-ol then the next sample. The same solvent cleaning beaker, 2-propanol
titration solvent before proceeding to the next titration. If the beaker and water beaker may be used for a short series of
electrodes are found to be dirty and contaminated, proceed as samples. They should be changed at reasonable intervals,
in 8.1. Store electrodes according to 8.3.3. before contamination builds up. The user shall ensure that the
12.4 Automatic Titration Method: electrode is adequately cleaned and hydrated. If electrodes are
12.4.1 Adjust the apparatus in accordance with the manu- found dirty and contaminated, proceed as in 8.1. Store elec-
facturer’s instructions to provide a dynamic mode of titrant trodes according to 8.3.3.
addition.
NOTE 13—When acid numbers about or below 0.1 are expected, better
12.4.2 Verify that the instrument will determine the amount precision can be obtained by modifying the method in one or more ways,
of strong acid when the initial mV of the test sample, relative such as by substituting a 0.01 M or 0.05 M alcoholic KOH solution;
to the mV reading of the aqueous acidic buffer, indicates the increasing the sample size above 20 g; or switching from a manual

5
 D664 − 18´2

iTeh Standards
Key:
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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

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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. 1 Illustrative Titration Curves

ASTM D664-18e2
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operated burette (that is, graduated in 0.05 mL divisions) to an automated 13. Calculation
burette that can dispense smaller increments of the KOH solution, if
samples are being analyzed by manual titration. 13.1 Manual Titration—Plot the volumes of the 0.1 mol ⁄L
alcoholic KOH solution added against the corresponding meter
12.5 Blanks: readings (see Fig. 1). Mark as an end point only a well-defined
12.5.1 For each set of samples and for every new batch of inflection point (see Note 14) that is closest to the cell voltage
titration solvent, perform a blank titration of 125 mL or 60 mL corresponding to that obtained with the aqueous acidic or basic
depending on the volume of the solvent that will be used for buffer. If inflections are ill defined or no inflection appears (see
sample analysis. For manual titration, add 0.1 mol ⁄L alcoholic Fig. 1, Curve B), mark the end point at the meter reading
KOH solution in 0.01 mL to 0.05 mL increments, waiting corresponding to that obtained with the appropriate aqueous
between each addition until a constant cell potential is reached. buffer.
Record the meter and readings when the former becomes NOTE 14—One inflection point is generally recognizable by inspection
constant after each increment. For automatic titration, use the whenever several successive 0.05 mL increments each produce a cell
same mode of titration as for the determination of the acidic potential change greater than 15 mV at least 30 % greater than those
produced by previous or subsequent increments of the same size.
property of the sample but use smaller increments of titrant Generally, definite inflection points may be discerned only in regions
addition, 0.01 mL to 0.05 mL. Recheck the blank periodically where increments of the same size are used.
based on the sample load. 13.1.1 Some additive chemistry may produce an inflection
12.5.2 When strong acids are present and a strong acid point beyond the buffer endpoint. For additives, take the last
number is to be determined, perform a blank titration of inflection point for calculation. If using an automatic titrator, a
125 mL or 60 mL depending on the volume of the titration change in the instrument parameters may be required to detect
solvent that will be used for sample analysis. Add 0.1 mol ⁄L this type of endpoint.
alcoholic HCl solution in 0.01 mL to 0.05 mL increments in a 13.1.2 For all acid titrations on used oils, mark as an end
manner comparable to that specified in 12.5.1. point the point on the curve that corresponds to the meter