NOTICE:Thisstandardhaseitherbeensupersededandreplacedbyanewversionor

discontinued.ContactASTMInternational(www.astm.org)forthelatestinformation.
Designation: D 664 95 An American National Standard
British Standard 4457

Designation 177/96
AMERICAN SOCIETY FOR TESTING AND MATERIALS
100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Method for

Acid Number of Petroleum Products by Potentiometric
Titration1
This standard is issued under the fixed designation D 664; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

This test method was adopted as a joint ASTM-IP standard in 1964.

This test method has been adopted for use by government agencies to replace Method 5106 of Federal Test Method Standard No. 791b.
ASTM Test Method D 4739 has been developed as an alternative to the base number portion of D 664.

1. Scope responsibility of the user of this standard to establish appro-

1.1 This test method covers procedures for the determina- priate safety and health practices and determine the applica-
tion of acidic constituents in petroleum products and lubricants bility of regulatory limitations prior to use.
soluble or nearly soluble in mixtures of toluene and propan-
2-ol (Note 1). It is applicable for the determination of acids 2. Referenced Documents
whose dissociation constants in water are larger than 109; 2.1 ASTM Standards:
extremely weak acids whose dissociation constants are smaller D 974 Test Method for Acid and Base Number by Color-
than 109 do not interfere. Salts react if their hydrolysis Indicator Titration2
constants are larger than 109. D 1193 Specification for Reagent Water3
D 3339 Test Method for Acid Number of Petroleum Prod-
NOTE 1In new and used oils, the constituents that may be considered
ucts by Semi-Micro Color Indicator Titration4
to have acidic characteristics include organic and inorganic acids, esters,
phenolic compounds, lactones, resins, salts of heavy metals, salts of
ammonia and other weak bases, acid salts of polybasic acids, and addition 3. Terminology
agents such as inhibitors and detergents. 3.1 Definitions:
1.2 The test method may be used to indicate relative 3.1.1 acid number, nthe quantity of base, expressed as
changes that occur in an oil during use under oxidizing milligrams of potassium hydroxide per gram of sample, re-
conditions regardless of the color or other properties of the quired to titrate a sample to a specified end point.
resulting oil. Although the titration is made under definite 3.1.1.1 DiscussionThis test method expresses the quantity
equilibrium conditions, the test method is not intended to of base as milligrams of potassium hydroxide per gram of
measure an absolute acidic property that can be used to predict sample, that is required to titrate a sample in the solvent from
performance of an oil under service conditions. No general its initial meter reading in millivolts to a meter reading in
relationship between bearing corrosion and acid number is millivolts corresponding to a freshly prepared non-aqueous
known. basic buffer solution or a well-defined inflection point as
specified in the test method.
NOTE 2The acid number obtained by this standard may or may not be 3.1.1.2 DiscussionThis test method provides additional
numerically the same as that obtained in accordance with Test Methods
D 974 and D 3339.
information. The quantity of base, expressed as milligrams of
potassium hydroxide per gram of sample, required to titrate a
1.3 The values stated in acceptable SI units are to be sample in the solvent from its initial meter reading in millivolts
regarded as the standard. to a meter reading in millivolts corresponding to a freshly
1.4 This standard does not purport to address all of the prepared nonaqueous acidic buffer solution or a well-defined
safety concerns, if any, associated with its use. It is the inflection point as specified in the test method shall be reported
as the strong acid number.
1
This test method is under the jurisdiction of ASTM Committee D-2 on
Petroleum Products and Lubricantsand is the direct responsibility of Subcommittee
2
D02.06on Analysis of Lubricants. Annual Book of ASTM Standards, Vol 05.01.
3
Current edition approved Oct. 10, 1995. Published December 1995. Originally Annual Book of ASTM Standards, Vol 11.01.
4
published as D 664 42 T. Last previous edition D 664 89. Annual Book of ASTM Standards, Vol 05.02.

1
 D 664
3.1.1.3 DiscussionThe causes and effects of the so-called electrodes specified in 6.1.2 and 6.1.3 and when the resistance
strong acids and the causes and effects of the other acids can be between the electrodes falls within the range from 0.2 to 20
very significantly different. Therefore, the user of this test MV. The meter shall be protected from stray electrostatic fields
method shall differentiate and report the two, when they are so that no permanent change in the meter readings over the
found. entire operating range is produced by touching, with a
grounded lead, any part of the exposed surface of the glass
4. Summary of Test Method electrode, the glass electrode lead, the titration stand, or the
4.1 The sample is dissolved in a mixture of toluene and meter.
propan-2-ol containing a small amount of water and titrated NOTE 3A suitable apparatus could consist of a continuous-reading
potentiometrically with alcoholic potassium hydroxide using a electronic voltmeter designed to operate on an input of less than 5 3 1012
glass indicating electrode and a calomel reference electrode. A, when an electrode system having 1000-MV resistance is connected
The meter readings are plotted manually or automatically across the meter terminals and provided with a metal shield connected to
against the respective volumes of titrating solution and the end the ground, as well as a satisfactory terminal to connect the shielded
points are taken only at well defined inflections in the resulting connection wire from the glass electrode to the meter without interference
curve. When no definite inflections are obtained, end points are from any external electrostatic field.
taken at meter readings corresponding to those found for 6.2.2 Glass Electrode, pencil type, 125 to 180 mm in length
freshly prepared nonaqueous acidic and basic buffer solutions. and 8 to 14 mm in diameter (C in Fig. 1).
6.2.2.1 The body of the electrode shall be made of a
5. Significance and Use chemically resistant glass tube with a wall thickness of 1 to 3
5.1 New and used petroleum products may contain acidic mm.
constituents that are present as additives or as degradation 6.2.2.2 The end dipping into the solution shall be closed
products formed during service, such as oxidation products. with a hemisphere of glass sealed on to the electrode tube and
The relative amount of these materials can be determined by the radius of this hemisphere shall be about 7 mm. The
titrating with bases. The acid number is a measure of this thickness of the glass in the hemisphere shall be great enough
amount of acidic substance, in the oil-always under the so that the resistance of the hemisphere is 100 to 1000 MV at
conditions of the test. The acid number is used as a guide in the 25C.
quality control of lubricating oil formulations. It is also 6.2.2.3 The electrode shall contain a reproducible, perma-
sometimes used as a measure of lubricant degradation in nently sealed liquid cell for making electrical connection with
service. Any condemning limits must be empirically estab- the inner surface of the hemisphere.
lished. 6.2.2.4 The entire electrical connection from the sealed
5.2 Since a variety of oxidation products contribute to the contact cell to the meter terminal shall be surrounded by an
acid number and the organic acids vary widely in corrosion electrical shield that will prevent electrostatic interference
properties, the test method cannot be used to predict corrosive- when the shield is grounded.
ness of an oil under service conditions. No general correlation 6.2.2.5 The shield shall be insulated from the electrical
is known between acid number and the corrosive tendency of connection by insulating material of the highest quality, such as
oils toward metals. rubber and glass, so that the resistance between the shield and
the entire length of the electrical connection is greater than
6. Apparatus 50 000 MV.
6.1 The cell assembly used for the potentiometric titration is 6.2.3 Calomel Reference Electrode, pencil type, 125 to 180
shown in Fig. 1. mm in length and 8 to 14 mm in diameter (B in Fig. 1).
6.2 Manual Titration Apparatus: 6.2.3.1 This electrode shall be made of glass and shall be
6.2.1 Meter, a voltmeter or a potentiometer that will operate provided with an external, removable glass sleeve on the sealed
with an accuracy of 60.005 V and a sensitivity of 60.002 V end that is dipped into the titration solution.
over a range of at least 60.5 V when the meter is used with the 6.2.3.2 The glass sleeve shall be 8 to 25 mm in length, shall
be slightly tapered, and shall be ground to fit the electrode so
that the sealed end of the electrode protrudes 2 to 20 mm
beyond the sleeve. The ground surface shall be continuous and
free of smooth spots.
6.2.3.3 At a point between the extremities of the ground
surface, the electrode tube shall be pierced by a hole or holes
1 mm in diameter. The electrode shall contain the necessary
mercury, calomel, and electrical connection to the mercury, all
arranged in a permanent manner.
6.2.3.4 The electrode shall be filled almost to capacity with
saturated KCl electrolyte and shall be equipped with a stop-
pered port through which the electrolyte may be replenished.
6.2.3.5 When suspended in the air and with the sleeve in
place, the electrode shall not leak electrolyte at a rate greater
FIG. 1 Cell for Potentiometric Titration than one drop in 10 min.
2
 D 664
NOTE 4Certain alternative electrode-electrolyte combinations have 7.2 Purity of WaterUnless otherwise indicated, references
been shown to give satisfactory results although the precision using these to water shall be understood to mean reagent water as defined
alternatives has not been determined. Combination electrodes can be used by Type III of Specification D 1193.
for this test method provided they have sufficiently fast response time.5
7.3 Hydrochloric Acid (HCl)Relative density 1.19
6.2.4 Variable-Speed Mechanical Stirrer, a suitable type, (WarningSee Note 6).
equipped with a glass, propeller-type stirring paddle (D in Fig.
NOTE 6Warning: Corrosive, causes burns.
1). A propeller with blades 6 mm in radius and set at a pitch of
30 to 45 is satisfactory. A magnetic stirrer is also satisfactory. 7.4 Propan-2-ol, Anhydrous, (less than 0.1 % H 2 O)
6.2.4.1 If electrical stirring apparatus is used, it shall be (WarningSee Note 7). If adequately dry reagent cannot be
electrically correct and grounded so that connecting or discon- procured, it can be dried by distillation through a multiple plate
necting the power to the motor will not produce a permanent column, discarding the first 5 % of material distilling overhead
change in the meter reading during the course of the titration. and using the 95 % remaining. Drying can also be accom-
6.2.5 Burette, 10-mL capacity, graduated in 0.05-mL divi- plished using molecular sieves such as Linde Type 4A, by
sions and calibrated with an accuracy of6 0.02 mL (E in Fig. passing the solvent upward through a molecular sieve column
1). The burette shall have a glass stopcock and shall have a tip using one part of molecular sieve per ten parts of solvent.
that extends 100 to 130 mm beyond the stopcock. The burette NOTE 7Warning: Flammable.
for KOH shall have a guard tube containing soda lime or other
CO2-absorbing substance. 7.5 2,4,6 Trimethyl Pyridine (g Collidine)((CH3)3C5H2N)
6.2.6 Titration Beaker, 250-mL capacity, made of borosili- (mol weight 121.18), (WarningSee Note 8) conforming
cate glass (A in Fig. 1). to the following requirements:
6.2.7 Titration Stand, suitable for supporting the electrodes, Boiling range 168 to 170C
Refractive index, nD20 1 498 2 6 0 000 5
stirrer, and burette in the positions shown in Fig. 1. Color colorless
NOTE 5An arrangement that allows the removal of the beaker without NOTE 8Warning: 2,4,6-Trimethyl Pyridine (g collidine) is hazardous
disturbing the electrodes, burette, and stirrer is desirable. if swallowed, breathed, or spilled on skin or eyes. PrecautionWear
6.3 Automatic Titration Apparatus: chemical safety goggles, neoprene or rubber gloves and apron. Use only
in a well-ventilated hood, or wear an approved respirator for organic vapor
6.3.1 Automatic titration systems shall be generally in or a supplied-air respirator. Do not take internally.
accordance with 6.2 and provide the following technical
performance characteristics or features. 7.5.1 Store the reagent over activated alumina and keep in a
6.3.1.1 Automatic adaptation of the titration speed in the brown glass bottle.
continuous titrant delivery mode to the slope of the titration 7.6 m-Nitrophenol (NO2C6H4OH)(mol weight 139.11),
curve with the capability of complying with the potential conforming to the following requirements (WarningSee
equilibrium specified and providing titration rates of less than Note 9):
0.2 mL/min during titration and preferably 0.05 mL/min at Melting point 96 to 97C
Color pale yellow
inflections and at nonaqueous acid and base end points.
6.3.1.2 Interchangeable precision motor-driven burettes NOTE 9Warning: m-Nitrophenol can be hazardous if swallowed,
with a volume dispensing accuracy of 60.01 mL. breathed, or spilled on skin or eyes. Wear chemical-safety goggles,
neoprene or rubber gloves, and apron. Use only in a well-ventilated hood,
6.3.1.3 A record of the complete course of the titration by
or wear an approved respirator for organic vapor or a supplied-air
continuously printing out the relative potential versus volume respirator. Do not take internally.
of titrant added.
7.6.1 Store the reagent in a brown glass bottle.
7. Reagents 7.7 Potassium Chloride ElectrolytePrepare a saturated
7.1 Purity of ReagentsReagent grade chemicals shall be solution potassium chloride (KCl) in water.
used in all tests. Unless otherwise indicated, it is intended that 7.8 Potassium Hydroxide(WarningSee Note 10).
all reagents shall conform to the specifications of the commit- NOTE 10Warning: Causes severe burns.
tee on Analytical Reagents of the American Chemical Society,
7.9 Toluene(Warningsee Note 7).
where such specifications are available.6 Other grades may be
7.10 Hydrochloric Acid Solution, Standard Alcoholic (0.1
used, provided it is first ascertained that the reagent is of
mol/L) (WarningSee Note 6 and Note 7). Mix 9 mL of
sufficiently high purity to permit its use without lessening the
hydrochloric (HCl, relative density 1.19) acid with 1 L of
accuracy of the determination.
anhydrous propan-2-ol. Standardize frequently enough to de-
tect concentration changes of 0.0005 by potentiometric titra-
5
Examples; of suitable electrodes are: (a) Glass electrodes: Beckman 41263, tion of approximately 8 mL (accurately measured) of the
Corning 476022, and Metrohom E107, (b) Reference electrodes: Beckman 40463, 0.1-mol/L alcoholic KOH solution diluted with 125 mL of
Corning 476012, and Metrohom EA430, and (c) Combination electrodes: Metrohom
EA121 and EA157. CO2-free water.
6
Reagent Chemicals, American Chemical Society Specifications, American 7.11 Hydrochloric Acid Solution, Standard Alcoholic (0.2
Chemical Society, Washington, DC. For suggestions on the testing of reagents not mol/L), (WarningSee Note 6 and Note 7). Prepare and
listed by the American Chemical Society, see Analar Standards for Laboratory
standardize as directed in 7.10 but use 18 mL of HCl (relative
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, density 1.19).
MD. 7.12 Buffer Stock Solution A(WarningSee Note 7 and
3
 D 664
Note 8). Accurately weigh 24.2 6 0.1 g of 2,4,6-trimethyl When not in use, immerse the lower halves of the electrodes in
pyridine (g-collidine), and transfer to a 1-L volumetric flask water. Do not allow them to remain immersed in titration
containing 100 mL of propan-2-ol. Using a 1-L graduated solvent for any appreciable period of time between titrations.
cylinder, add to the flask, while continuously stirring its While the electrodes are not extremely fragile, handle them
contents, 150/C 6 5 mL of 0.2-mol/L alcoholic HCl solution carefully at all times.
(C being the exact molarity concentration of the HCl solution
NOTE 12Cleaning the electrodes7 thoroughly, keeping the ground-
found by standardization). Dilute to the 1000-mL mark with glass joint free of foreign materials, and regular testing of the electrodes
propan-2-ol, and mix thoroughly. Use within two weeks. are very important in obtaining repeatable potentials, since contamination
7.13 Buffer, Nonaqueous AcidicAdd 10 mL of buffer may introduce uncertain erratic and unnoticeable liquid contact poten-
stock Solution A to 100 mL of titration solvent. Use within 1 h. tials.6 While this is of secondary importance when end points are chosen
7.14 Buffer Stock Solution B(WarningSee Note 7 and from inflection points in the titration curve, it may be quite serious when
end points are chosen at arbitrarily fixed cell potentials.
Note 9). Accurately weigh 27.8 6 0.1 g of m-nitrophenol and NOTE 13Warning: :Causes severe burns. A recognized carcinogen.
transfer to a 1-L volumetric flask containing 100 mL of Strong oxidizer. Contact with materials may cause fire. Hygroscopic.
propan-2-ol. Using a 250-mL graduated cylinder, add to the
flask while continuously stirring its contents, 50/C26 1 mL of 8.2 Preparation of ElectrodesBefore and after using,
0.2-mol/L alcoholic KOH solution (C2 being the exact molarity wipe the glass electrode thoroughly with a clean cloth, or a soft
concentration of the KOH solution found by standardization). absorbent tissue, and rinse with water. Wipe the calomel
Dilute to the 1000-mL mark with propan-2-ol and mix thor- reference electrode with a cloth or tissue, carefully remove the
oughly. Use within two weeks. ground-glass-sleeve and thoroughly wipe both ground sur-
faces. Replace the sleeve loosely and allow a few drops of
7.15 Buffer Nonaqueous BasicAdd 10 mL of buffer stock
electrolyte to drain through to flush the ground-glass joint
Solution B to 100 mL of titration solvent. Use within 1 h.
(Note 10). Wet the ground surfaces thoroughly with electrolyte,
7.16 Potassium Hydroxide Solution, Standard Alcoholic
set the sleeve firmly in place, and rinse the electrode with
(0.1 mol/L)(WarningSee Note 7 and Note 10). Add 6 g of
water. Prior to each titration, soak the prepared electrodes in
potassium hydroxide (KOH) to approximately 1 L of anhy-
water for at least 5 min immediately before use, and touch the
drous propan-2-ol. Boil gently for 10 min to effect solution.
tips of the electrodes with a dry cloth or tissue to remove the
Allow the solution to stand for two days and then filter the
excess of water.
supernatant liquid through a fine sintered-glass funnel. Store
8.3 Testing of ElectrodesTest the meter-electrode combi-
the solution in a chemically resistant bottle. Dispense in a
nation when first put into use, or when new electrodes are
manner such that the solution is protected from atmospheric
installed, and retest at intervals thereafter by dipping the
carbon dioxide (CO2) by means of a guard tube containing
electrodes into a well-stirred mixture of 100 mL of the titration
soda lime or soda non-fibrous silicate absorbants and such that
solvent and 1.0 to 1.5 mL of 0.1-mol/L alcoholic KOH
it does not come into contact with cork, rubber, or saponifiable
solution. For the meter-electrode combination to be suitable for
stopcock grease. Standardize frequently enough to detect
use, the potential between the electrodes should change by
concentration changes of 0.0005 by potentiometric titration of
more than 480 mV from the potential between the same
weighed quantities of potassium acid phthalate dissolved in
electrodes when dipped in the nonaqueous acidic buffer solu-
CO2-free water.
tion (Note 14).
7.17 Potassium Hydroxide Solution, Standard Alco-
holic (0.2 mol/L), (WarningSee Note 7 and Note 10). NOTE 14Considerably more sensitive electrodes are now available
Prepare, store, and standardize as directed in 7.16, but use 12 that will show a potential change of at least 590 mV under these
conditions, and their use is recommended. When combination electrodes
to 13 g of KOH to approximately 1 L of propan-2-ol.
are used, test as in 8.3.
7.18 Titration SolventAdd 500 mL of toluene
(WarningSee Note 7) and 5 mL of water to 495 mL of 9. Standardization of Apparatus
anhydrous propan-2-ol. The titration solvent should be made 9.1 Determination of Meter Readings for the Nonaqueous
up in large quantities, and its blank value determined daily by Buffer Solutions Corresponding to Acid End PointsTo ensure
titration prior to use. comparable selection of end points when definite inflection
NOTE 11Commercially available reagents can be used in place of points are not obtained in the titration curve, determine daily,
laboratory preparations. for each electrode pair, the meter readings obtained with
freshly prepared nonaqueous acidic and basic buffer solutions.
8. Preparation of Electrode System
NOTE 15The response of different glass electrodes to hydrogen ion
8.1 Maintenance of ElectrodesClean the glass electrode activity is not the same. Therefore, it is necessary to establish regularly for
(Note 12) at frequent intervals (not less than once every week each electrode system the meter readings corresponding to the buffer
during continual use) by immersing in cold chromic acid solutions arbitrarily selected to represent acidic or basic end points.
cleaning solution (WarningSee Note 13) or in other equip- 9.2 Prepare the electrodes as described in 8.2, immerse them
ment cleaning solutions. Drain the calomel electrode at least
once each week and refill with fresh KCl electrolyte as far as 7
For a detailed discussion of the need for care in preparation of the electrodes,
the filling hole. Ascertain that crystallized KCl is present.
see Lykken, L., Porter, P., Ruliffson, H. D., and Tuemmler, F. D., Potentiometric
Maintain the electrolyte level in the calomel electrode above Determination of Acidity in Highly Colored Oils, Industrial and Engineering
that of the liquid in the titration beaker or vessel at all times. Chemistry, Analytical Edition, IENAA, Vol 16, 1944, pp. 219234.

4
 D 664
in the nonaqueous buffer solution, and stir for 5 min, main- 11.3 Manual Titration Method:
taining the temperature of the buffer solution at a temperature 11.3.1 Add suitable small portions of 0.1-mol/L alcoholic
within 2C of that at which the titrations are to be made. Read KOH solution and wait until a constant potential has been
the cell voltage. The readings so obtained are taken as the end established, record the burette and meter readings.
points in titration curves having no inflection points. 11.3.2 At the start of the titration and in any subsequent
regions (inflections) where 0.1 mL of the 0.1-mol/L KOH
10. Preparation of Sample of Used Oil solution consistently produces a total change of more than 30
10.1 Strict observance of the sampling procedure is neces- mV in the cell potential, add 0.05-mL portions.
sary since the sediment itself is acidic or basic or has absorbed 11.3.3 In the intermediate regions (plateaux) where 0.1 mL
acidic or basic material from the sample. Failure to obtain a of 0.1-mol/L alcoholic KOH changes the cell potential less
representative sample causes serious errors. than 30 mV, add larger portions sufficient to produce a total
NOTE 16As used oil can change appreciably in storage, test samples potential change approximately equal to, but not greater than
as soon as possible after removal from the lubricating system; and note the 30 mV.
dates of sampling and testing. 11.3.4 Titrate in this manner until the potential changes less
10.2 Heat the sample (Note 17) of used oil to 60 6 5C in than 5 mV/0.1 mL of KOH and the cell potential indicates that
the original container and agitate until all of the sediment is the solution is more basic than the freshly prepared nonaqueous
homogeneously suspended in the oil. If the original container is basic buffer.
a can or if it is glass and more than three-fourths full, transfer 11.3.5 Remove the titration solution, rinse the electrodes
the entire sample to a clear-glass bottle having a capacity at and burette tip with the titration solvent, then with propan-2-ol
least one third greater than the volume of the sample. Transfer and finally with reagent grade water. Immerse the electrodes in
all traces of sediment from the original container to the bottle water for at least 5 min before using for another titration to
by violent agitation of portions of the sample in the original restore the aqueous gel layer of the glass electrode. Store the
container. electrodes in reagent water when not in use. If the electrodes
are found to be dirty and contaminated, proceed as in 8.1.
NOTE 17When samples are visibly free of sediment, the heating
procedures described can be omitted.
11.4 Automatic Titration Method:
11.4.1 Adjust the apparatus in accordance with the manu-
10.3 After complete suspension of all sediment, strain the facturers instructions to comply with the potential equilibrium
sample or a convenient aliquot through a 100-mesh screen for mode requirements established for the manual titration as
the removal of large contaminating particles. explained in 11.3.1 or to provide a variable continuous delivery
11. Procedure for Acid Number and Strong Acid Number rate mode of titration of less than 0.2 mL/min during the
titration and preferably 0.05 mL/min through the region of
11.1 Into a 250-mL beaker or a suitable titration vessel, inflections and at the end point corresponding to that found for
introduce a weighed quantity of sample as prescribed in Table the freshly prepared standard nonaqueous basic buffer solution.
1 and add 125 mL of titration solvent (Note 18). Prepare the
11.4.2 Proceed with the automatic titration and record
electrodes as directed in 8.2. Place the beaker or titration vessel
potentiometric curves or derivative curves as the case may be.
on the titration stand and adjust its position so that the
11.4.3 Titrate in this manner with the 0.1-mol/L alcoholic
electrodes are about half immersed. Start the stirrer, and stir
KOH solution until the potential becomes constant, for ex-
throughout the determination at a rate sufficient to produce
ample, changing less than 5 mV/0.1 mL (automatic end point)
vigorous agitation without spattering and without stirring air
or until the potential reading indicates that the solution is more
into the solution. If feasible, adjust the meter so that it reads in
basic than the freshly prepared nonaqueous basic buffer solu-
the upper part of the millivolt scale, for example 700 mV.
tion (preselected end point).
NOTE 18A titration solvent that contains chloroform (Warning 11.4.4 On completion of the titration, rinse the electrodes
May be fatal if swallowed. Harmful if inhaled. May produce toxic vapors and burette tip with the titration solvent, then with propan-2-ol,
if burned) can be used in place of toluene to completely dissolve certain
and finally with reagent grade water. Keep the electrodes
heavy residues of asphaltic materials.
immersed in water for at least 5 min before reusing for another
11.2 Select the right burette, fill with the 0.1-mol/mL titration to restore the aqueous gel layer of the glass electrode.
alcoholic KOH solution, and place the burette in position on If electrodes are found dirty and contaminated proceed as in
the titration assembly, ensuring that the tip is immersed about 8.1. Store the electrodes in reagent grade water when not in
25 mm in the liquid in titration vessel. Record the initial burette use.
and meter (cell potential) readings. 11.5 Blanks:
11.5.1 For each set of samples, make a blank titration of 125
TABLE 1 Size of Test Portion mL of the titration solvent. For manual titration, add 0.1-mol/L
Acid Number
Mass of Test Portion, Accuracy of Weighing, alcoholic KOH solution in 0.05-mL increments, waiting be-
g g
tween each addition until a constant cell potential is reached.
0.051.0 20.0 6 2.0 0.10 Record the meter and burette readings when the former
1.05.0 5.0 6 0.5 0.02
520 1.0 6 0.1 0.005 becomes constant after each increment. For automatic titration
20100 0.25 6 0.02 0.001 proceed as in 11.4.
100260 0.1 6 0.01 0.0005
11.5.2 For each set of samples, make a blank titration of 125
5
 D 664
mL of titration solvent, adding 0.1 mol/L alcoholic HCl point, the point on the curve that corresponds to the freshly
solution in 0.05-mL increments in a manner comparable to that prepared nonaqueous basic buffer end point (Note 20).
specified in 11.5.1.
NOTE 20The cooperative work done on acid number determinations
12. Calculation on fresh oils, additive concentrates, and used oils indicated well-defined
inflection points for fresh oils and additive concentrates, and generally
12.1 Manual TitrationPlot the volumes of the 0.1-mol/L ill-defined inflections, or no inflection points at all, for used oils.
alcoholic KOH solution added against the corresponding meter 12.2 Automatic Titration MethodMark the end points on
readings (see Fig. 2). Mark as an end point, only well-defined the curves obtained in 11.4, in the same way as for the manual
inflection point (Note 19) that is closest to the cell voltage titration method.
corresponding to that obtained with the freshly prepared 12.3 Method of CalculationThe method in 12.3.1 is
nonaqueous acidic and basic buffers. If inflections are ill- applicable to both manual and automatic methods.
defined or no inflection appears (see Fig. 2, Curve B), mark the 12.3.1 Calculate the acid number and strong acid number as
end point at the meter reading corresponding to that obtained follows:
with the appropriate freshly prepared nonaqueous buffer.
Acid number, mg KOH/g 5 ~A 2 B! 3 M 3 56.1/W (1)
NOTE 19One inflection point is generally recognizable by inspection
whenever several successive 0.05-mL increments each produce a cell Strong acid number, mg KOH/g 5 ~CM 1 Dm! 3 56.1/W (2)
potential change greater than 15 mV at least 30 % greater than those
produced by previous or subsequent increments of the same size.
where:
Generally, definite inflection points may be discerned only in regions A 5 alcoholic KOH solution used to titrate sample to end
where increments of the same size are used. point that occurs at the meter reading of the inflection
point closest to the meter reading corresponding to
12.1.1 For all acid titrations on used oils, mark as an end
basic nonaqueous buffer, or in case of ill-defined or
no inflection point, to the meter reading
corresponding to the basic nonaqueous buffer, mL,
B 5 volume corresponding to A for blank titration, mL,
M 5 concentration of alcoholic KOH solution, mol/L,
m 5 concentration of alcoholic HCl solution, mol/L,
W 5 sample, mass, g,
C 5 alcoholic KOH solution used to titrate the sample to
end point that occurs at a meter reading
corresponding to acid nonaqueous buffer, mL, and
D 5 alcoholic HCl solution used to titrate solvent blank to
end point corresponding to C, mL.

13. Report
13.1 Report the results as acid number or strong acid
number as follows:
Acid number ~Test Method D 664! 5 ~result! (3)
Strong acid number ~Test Method D 664! 5 ~result! (4)
13.2 No modifications to this test method are permitted.

14. Precision and Bias

14.1 Acid Number:
14.1.1 RepeatabilityThe difference between successive
test results obtained by the same operator with the same
apparatus under constant operating conditions on identical test
material would in the long run, in the normal and correct
operation of the test method, exceed the following values only
in one case in twenty. See Table 2.
NOTE 1Key: Curve ABlank on 125 mL of titration solvent. 14.1.2 ReproducibilityThe difference between two single
Curve B10.00 g of used crankcase oil plus 125 mL of titration solvent. and independent results obtained by different operators
Since no sharp inflections are apparent, the end points are chosen at the
meter readings obtained with the two nonaqueous buffer solutions.
Curve C10.00 g of oil containing a weak acid plus 125 mL of titration TABLE 2 Repeatability of Acid Number Determination
solvent. The end point is chosen as the point at which the curve is most Fresh Oils and Additive
nearly vertical. Concentrates at Used Oils at Buffer
Curve D10.00 g of oil containing weak and strong acids plus 125 mL Titration Mode Inflection End Points
of titration solvent. The end points are chosen as the points at which the Points
curve is most nearly vertical. Manual Automatic Manual Automatic
Percentage of mean 7 6 5 12
FIG. 2 Illustrative Titration Curves

6
 D 664
working in different laboratories on identical test material TABLE 3 Reproducibility of Acid Number Determination
would, in the long run, in the normal and correct operation of Fresh Oils and Additive
the test method, exceed the following values only in one case Concentrates at Used Oils at Buffer
Titration Mode Inflection End Points
in twenty. See Table 3. Points
14.2 Strong Acid Number: Manual Automatic Manual Automatic
14.2.1 Precision data have not been developed for strong Percentage of mean 20 28 39 44

acid number because of its rare occurrence in sample analysis.

14.3 BiasThe procedures in this test method have no bias 15. Keywords
because the acid values can be defined only in terms of the test 15.1 acid number; lubricants; petroleum products;
method. potentiometric; strong acid number; titration

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