Designation: D4739 11

Standard Test Method for

Base Number Determination by Potentiometric Hydrochloric
Acid Titration1
This standard is issued under the fixed designation D4739; 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.

INTRODUCTION

Currently, there are two ASTM test methods under the jurisdiction of Committee D02 used for
determining base number by potentiometric titration: Test Method D2896 and Test Method D4739.
They are both used throughout the petroleum industry. Test Method D2896 is for new oils and is used
in setting specifications since it is more accurate than Test Method D4739. Test Method D4739 shall
be used exclusively for the purpose of tracking base number loss as an oil proceeds in service. In many
cases, the test methods will provide different results. Some comparisons are given in the Scope and
the Significance and Use sections of this test method to distinguish between the two standards and to
provide guidance to users.

1. Scope* be used to indicate relative changes that occur in oil during use
1.1 This test method covers a procedure for the determina- under oxidizing or other service conditions regardless of the
tion of basic constituents in petroleum products and new and color or other properties of the resulting oil. The values
used lubricants. This test method resolves these constituents obtained, however, are intended to be compared with the other
into groups having weak-base and strong-base ionization values obtained by this test method only; base numbers
properties, provided the dissociation constants of the more obtained by this test method are not intended to be equal to
strongly basic compounds are at least 1000 times than that of values by other test methods. Although the analysis is made
the next weaker groups. This test method covers base numbers under closely specified conditions, this test method is not
up to 250. intended to, and does not, result in reported basic properties
that can be used under all service conditions to predict
1.2 In new and used lubricants, the constituents that can be performance of an oil; for example, no overall relationship is
considered to have basic properties are primarily organic and known between bearing corrosion or the control of corrosive
inorganic bases, including amino compounds. This test method wear in the engine and base number.
uses hydrochloric acid as the titrant, whereas Test Method
D2896 uses perchloric acid as the titrant. This test method may 1.4 This test method was developed as an alternative for the
or may not titrate these weak bases and, if so, it will titrate former base number portion of Test Method D664 (last
them to a lesser degree of completion; some additives such as published in Test Method D66481).
inhibitors or detergents may show basic characteristics. 1.4.1 Colorimetric test methods for base number are Test
Method D974, IP 139, and 5102.1 on acid and base number by
1.3 When testing used engine lubricants, it should be
extraction (color-indicator titration) of Federal Test Method
recognized that certain weak bases are the result of the service
Standard No. 791b. Test results by these methods may or may
rather than having been built into the oil. This test method can
not be numerically equivalent to this test method.
1
1.5 The values stated in SI units are to be regarded as
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee standard. No other units of measurement are included in this
D02.06 on Analysis of Lubricants. standard.
Current edition approved May 15, 2011. Published July 2011. Originally
approved in 1987. Last previous edition approved in 2008 as D473908 1. DOI: 1.6 This standard does not purport to address all of the
10.1520/D4739-11. safety concerns, if any, associated with its use. It is the

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

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 D4739 11
responsibility of the user of this standard to establish appro- titration curve according to the criteria given in Section 12 and
priate safety and health practices and determine the applica- used to calculate a base number.
bility of regulatory limitations prior to use.
5. Significance and Use
2. Referenced Documents 5.1 New and used petroleum products can contain basic
2.1 ASTM Standards:2 constituents that are present as additives. The relative amount
D664 Test Method for Acid Number of Petroleum Products of these materials can be determined by titration with acids.
by Potentiometric Titration The base number is a measure of the amount of basic
D974 Test Method for Acid and Base Number by Color- substances in the oil always under the conditions of the test. It
Indicator Titration is sometimes used as a measure of lubricant degradation in
D1193 Specification for Reagent Water service. However, any condemning limit shall be empirically
D2896 Test Method for Base Number of Petroleum Products established.
by Potentiometric Perchloric Acid Titration 5.2 As stated in 1.2, this test method uses a weaker acid to
D4057 Practice for Manual Sampling of Petroleum and titrate the base than Test Method D2896, and the titration
Petroleum Products solvents are also different. Test Method D2896 uses a stronger
D4177 Practice for Automatic Sampling of Petroleum and acid and a more polar solvent system than Test Method D4739.
Petroleum Products As a result, Test Method D2896 will titrate salts of weak acids
2.2 IP Standard:3 (soaps), basic salts of polyacidic bases, and weak alkaline salts
IP 139 Petroleum products and lubricants Determination of some metals. They do not protect the oil from acidic
of acid and base number Colour-indicator titration components due to the degradation of the oil. This test method
method may produce a falsely exaggerated base number. Test Method
2.3 U.S. Federal Test Method:4 D4739 will probably not titrate these weak bases but, if so, will
Federal Test Method Standard No. 791b Lubricants Liquid titrate them to a lesser degree of completion. It measures only
Fuels and Related Products; Methods of Testing the basic components of the additive package that neutralizes
acids. On the other hand, if the additive package contains weak
3. Terminology basic components that do not play a role in neutralizing the
3.1 Definitions: acidic components of the degrading oil, then the Test Method
3.1.1 base number, nthe quantity of a specified acid, D4739 result may be falsely understated.
expressed in terms of the equivalent number of milligrams of 5.3 Particular care is required in the interpretation of the
potassium hydroxide per gram of sample, required to titrate a base number of new and used lubricants.
sample in a specified solvent to a specified endpoint using a 5.3.1 When the base number of the new oil is required as an
specified detection system. expression of its manufactured quality, Test Method D2896 is
3.1.1.1 DiscussionIn this test method, the sample is preferred, since it is known to titrate weak bases that this test
titrated to a meter reading corresponding to aqueous acidic method may or may not titrate reliably.
buffer solution or appropriate inflection point. 5.3.2 When the base number of in-service or at-term oil is
3.2 Definitions of Terms Specific to This Standard: required, this test method is preferred because in many cases,
3.2.1 strong base number, nthe quantity of acid, expressed especially for internal combustion engine oils, weakly basic
in terms of the equivalent number of milligrams of potassium degradation products are possible. Test Method D2896 will
hydroxide per gram of sample, that is required to titrate a titrate these, thus giving a false value of essential basicity. This
sample dissolved in the specified solvent from the initial meter test method may or may not titrate these weak acids.
reading to a meter reading corresponding to a basic buffer 5.3.3 When the loss of base number value, as the oils
solution. proceed in service, is the consideration, this test method is to be
preferred and all values including the unused oil shall be
4. Summary of Test Method determined by this test method. Base numbers obtained by this
4.1 The sample is dissolved in a mixture of toluene, test method shall not be related to base numbers obtained by
propan-2-ol (isopropyl alcohol), chloroform, and a small another test method such as Test Method D2896.
amount of water and titrated potentiometrically with alcoholic 5.3.4 In ASTM Interlaboratory Crosscheck Programs for
hydrochloric acid solution. The test results of this procedure both new and used lubricants, historically Test Method D2896
are obtained by titration mode of fixed increment and fixed gives a higher value for base number.
time additions of the titrant. An endpoint is selected from a
6. Apparatus
2
6.1 Potentiometric Titration, automatic or manual, with
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM capability of adding fixed increments of titrant at fixed time
Standards volume information, refer to the standards Document Summary page on intervals (see Annex A1).
the ASTM website.
3
6.1.1 The titrimeter must automatically (or manually) con-
Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR,
trol the rate of addition of titrant as follows: Delivery of titrant
U.K.
4
Available from Standardization Documents Order Desk, DODSSP, Bldg. 4, will be incremental; after delivery of precisely a 0.100-mL
Section D, 700 Robbins Ave., Philadelphia, PA 19111-5098. increment (see 6.1.2), the delivery is stopped and a fixed time

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 D4739 11
period of 90 s is allowed to pass before another 0.100-mL 7.4 Buffer, Aqueous BasicCommercial pH 10 buffer solu-
increment of titrant is delivered. This procedure is repeated tion with a tolerance of 60.02 pH units at 25C. This solution
until the titration is completed. shall be replaced at regular intervals consistent with its stability
6.1.2 The precision of addition of the 0.100-mL increments or when contamination is suspected. Information related to the
of titrant must be 60.001 mL for automatic titrators. For stability should be obtained from the manufacturer.
manual buret, it should be 60.005 mL. A higher incremental 7.5 ChloroformReagent grade. (WarningToxic and
precision is required for an automatic buret, because the total suspected carcinogen.)
volume to the end point is summed from the individual
increments; it is read from a scale with a manual buret. 7.6 Hydrochloric Acid Solution, Standard Alcoholic
(0.1 M)Mix 9 mL of reagent grade hydrochloric acid (HCl,
6.2 Sensing Electrode, standard pH with glass membrane,
sp gr 1.19) (WarningToxic and corrosive), with 1 L of
suitable for non-aqueous titrations.
anhydrous isopropyl alcohol. Standardize frequently enough to
6.3 Reference Electrode, Silver/Silver Chloride (Ag/AgCl) detect normality changes of 0.0005 by potentiometric titration
reference electrode with sleeve junction, filled with 1 to 3 M of approximately 8 mL (accurately measured) of the 0.1 M
LiCl in ethanol. alcoholic KOH solution diluted with 125 mL CO2-free water.
6.3.1 Combination ElectrodeSensing electrodes may have
7.7 Ethanolreagent grade. (WarningFlammable and
the Ag/AgCl reference electrode built into the same electrode
toxic, especially when denatured.)
body, which offers the convenience of working with and
maintaining only one electrode. The combination electrode 7.8 Lithium Chloride Electrolyte Prepare a solution of 1 to
shall have a sleeve junction type of reference and shall use an 3 M LiCl in ethanol.
inert ethanol electrolyte, for example, 1 to 3 M LiCl in ethanol.
7.9 Potassium Hydroxide(WarningCauses severe
In the reference compartment, the sensing electrode part shall
burns.)
use a glass membrane designed for non-aqueous titrations.
These combination electrodes shall have the same response or 7.10 Potassium Hydroxide Solution, Standard Alcoholic
better response than a dual electrode system. They shall have (0.1 M)Add 6 g of reagent grade potassium hydroxide
removable sleeves for easy rinsing and addition of electrolyte. (KOH) (WarningToxic and corrosive), to approximately 1 L
(WarningWhen a movable sleeve is part of the electrode of anhydrous isopropyl alcohol. Boil gently for 10 min to effect
system, ensure that the sleeve is unimpaired before every solution. Allow the solution to stand for 2 days, and then filter
titration.) the supernatant liquid through a fine sintered-glass funnel.
6.4 Stirrer, Buret, Stand, Titration Vessel, as specified in Store the solution in a chemically resistant bottle. Dispense in
Annex A1, are required. a manner such that the solution is protected from atmospheric
carbon dioxide (CO2) by means of a guard tube containing
soda lime or soda non-fibrous silicate absorbent, and such that
7. Reagents
it does not come into contact with cork, rubber, or saponifiable
7.1 Purity of ReagentsReagent-grade chemicals shall be stopcock grease. Standardize frequently enough to detect
used in all tests. Unless otherwise indicated, it is intended that normality changes of 0.0005 by potentiometric titration of
all reagents shall conform to the specifications of the Commit- weighed quantities of potassium acid phthalate dissolved in
tee on Analytical Reagents of the American Chemical Society, CO2-free water.
where such specifications are available.5 Other grades may be
used, provided it is first ascertained that the reagent is of 7.11 Propan-2-ol (Isopropyl Alcohol)Anhydrous, (less
sufficiently high purity to permit its use without lessening the than 0.1 % H2O). (WarningFlammable.) If dry reagent
accuracy of the determination. cannot be procured, dry it by distillation through a multiple
plate column, discarding the first 5 % of material distilling over
7.2 Purity of WaterUnless otherwise indicated, references and using the 95 % remaining. Also, drying can be accom-
to water shall be understood to mean reagent water that meets plished using molecular sieves by passing the solvent upward
the requirement of either Type I, II, or III of Specification through a molecular sieve column using one part of molecular
D1193. sieve per ten parts of solvent. (WarningIt has been reported
7.3 Buffer, Aqueous AcidCommercial pH 3 buffer solution that, if not inhibited against it, propan-2-ol can contain
with a tolerance of 60.02 pH units at 25C. This solution shall peroxides. When this occurs, an explosive mixture is possible
be replaced at regular intervals consistent with its stability or when the storage vessel or other equipment such as a dispens-
when contamination is suspected. Information related to the ing bottle, are near empty and approaching dryness.
stability should be obtained from the manufacturer. 7.12 Commercially available solutions may be used in place
of laboratory preparations provided the solutions have been
certified as equivalent.
5
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
7.13 Alternate volumes of solutions may be prepared pro-
listed by the American Chemical Society, see Annual Standards for Laboratory vided the final solution concentration is equivalent.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 7.14 TolueneReagent grade. (WarningExtremely flam-
MD. mable.)

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7.15 Titration SolventIn a brown reagent bottle, add 9. Standardization of Apparatus
30 mL of water to 1 L of isopropyl alcohol, and mix thor- 9.1 Determination of Meter Readings for the Aqueous
oughly. Add 1 L each of toluene and chloroform, and mix Buffer SolutionEnsure comparable selection of end points
thoroughly. when definite inflection points are not obtained in the titration
curve. Determine daily, for each electrode pair, the meter
8. Preparation of Electrode System readings obtained with the aqueous acidic buffer solution to be
8.1 Maintenance and Storage of ElectrodesCleaning the used for the determination of base numbers and with the
electrode thoroughly, keeping the ground-glass joint free of aqueous basic buffer solution to be used for the determination
foreign materials, and regular testing of the electrodes are very of strong base numbers.
important in obtaining repeatable potentials, since the contami- 9.2 Prepare the electrodes as described in 8.2, immerse them
nation may introduce uncertain erratic and unnoticeable liquid in the appropriate aqueous buffer solution, and stir for at least
contact potentials. While this is of secondary importance when 2 min, maintaining the temperature of the buffer solution at a
end points are chosen from inflection points in the titration temperature within 2C of that at which the titrations are to be
curve, it may be very serious when end points are chosen at made. Read the cell voltage. The reading so obtained in the
experimentally determined cell potentials as outlined in the acidic buffer solution is taken as the end point for the base
procedure. number if an inflection is not observed as specified in 12.1, and
8.1.1 Clean the pH indicating electrode or the pH indicating the reading obtained in the basic buffer solution is taken as the
part of the combination electrode at frequent intervals based on end point for the strong base number.
use and type of samples being analyzed by immersing in
10. Preparation of Sample of Used Oil
non-chromium containing, strongly oxidizing cleaning solu-
tion. The electrode shall be cleaned periodically when in use or 10.1 Strict observation of the sampling procedure is neces-
when a new electrode is installed. Drain the LiCl electrolyte sary, since the sediment itself is acidic or basic or has absorbed
from the electrode at least once each week, and refill with fresh acidic or basic material from the sample. Failure to obtain a
LiCl electrolyte as far as the filling hole. Ensure that there are representative sample causes serious errors.
no air bubbles in the electrode liquid. If air bubbles are 10.1.1 When applicable, refer to Practice D4057 (Manual
observed, hold the electrode in a vertical position and gently Sampling) or Practice D4177 (Automatic Sampling) for proper
tap it to release the bubbles. Maintain the electrolyte level in sampling techniques.
the electrode above that of the liquid in the titration beaker at 10.1.2 When sampling used lubricants, the specimen shall
all times. be representative of the system samples and shall be free of
contamination from external sources. As used oil can change
8.1.2 When not in use, immerse the lower halves of the
appreciably in storage, test samples as soon as possible after
electrodes in either water (sensing) or the LiCl in isopropyl
removal from the lubricating system, and note the dates of
alcohol electrolyte (reference). Do not allow them to remain
sampling and testing.
immersed in titration solvent for any appreciable period of time
between titrations. While the electrodes are not extremely 10.2 Heat the sample (Note 1) of used oil to 60 6 5C in the
fragile, handle them carefully at all times. original container, and agitate the sample until all of the
8.1.3 Electrode LifeTypically, electrode usage is limited sediment is homogeneously suspended in the oil. If the original
to 3 to 6 months, depending upon usage. Electrodes have a container is a can, or if it is glass and more than three-fourths
limited shelf life and shall be tested before use (8.3). full, transfer the entire sample to a clear glass bottle having a
capacity at least one-third greater than the volume of the
8.2 Preparation of Electrodes: sample. Transfer all traces of sediment from the original
8.2.1 When Ag/AgCl reference electrode is used for the container to the bottle by vigorous agitation of portions of the
titration and it contains an electrolyte that is not 1 to 3 M LiCl sample in the original container.
in ethanol, replace the electrolyte. Drain the electrolyte from 10.3 After complete suspension of all sediment, strain the
the electrode, wash away all the salt (if present) with water and sample or a convenient aliquot through a 100-mesh screen for
then rinse with ethanol. Rinse several times with the LiCl the removal of large particles.
electrolyte solution. Finally, replace the sleeve and fill the
electrode with the LiCl electrolyte to the filling hole. When NOTE 1When samples are visibly free of sediment, the heating
procedures described may be omitted.
refitting the sleeve, ensure that there will be a free flow of
electrolyte into the system. A combination electrode shall be 11. Procedure for Base Number and Strong Base
prepared in the same manner. The electrolyte in a combination Number
electrode can be removed with the aid of a vacuum suction. 11.1 Calculate the quantity of sample required for its
8.2.2 Prior to each titration, soak the prepared electrodes in expected base number as follows:
water, pH 4.5 5.5 acidified with HCL, for at least 5 min.
A 5 7/E (1)
Rinse the electrode with propan-2-ol immediately before use,
and then with the titration solvent. where:
8.3 Testing of ElectrodesSee Appendix X2 for the proce- A = approximate mass of sample, g and
dure to check electrode performance. E = expected base number.

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11.1.1 Take a maximum of 5 g and a minimum of 0.1 g for
analysis. The precision of weighing is as follows:
Size of Sample, g Precision of Weighing, g
15 0.005
0.11 0.002

11.2 Into a suitable titration vessel, introduce a weighed

quantity of sample as prescribed in 11.1.1, and add 75 mL of
titration solvent. If 75 mL of solvent is not sufficient to
properly cover the electrodes, add just enough additional
solvent to do so. Ensure the electrodes are properly immersed.
Prepare the electrodes as directed in 8.2. Place the beaker or
titration vessel on the titration stand, and adjust its position so
that the electrodes are about half immersed. Start the stirrer,
and stir throughout the determination at a rate sufficient to
produce vigorous agitation without spattering and without
stirring air into the solution. (A) Titration curve has no inflections. Take end point at the buffer potential.
(B) Titration curve has well-defined inflection within prescribed window. Take
11.3 Select and fill a suitable buret with the 0.1 M alcoholic well-defined inflection as the end point.
(C) Titration curve has inflection prior to buffer potential but not in prescribed
HCl solution, and place the buret in position on the titration window. Take end point at buffer potential.
assembly, taking care that the tip is immersed about 25 mm in FIG. 1 Example Titration Curves to Illustrate Selection of End
the liquid in titration vessel. Record the initial buret and meter Points
(cell potential) readings.
11.4 TitrationThe reaction of the hydrochloric acid with blank, add KOH titrant under the same conditions until the
the basic components is very slow with most titrations for base potential corresponding to the basic buffer solution is reached.
number. As a result, these titrations are not at equilibrium. 12. Calculation
Because of this, the titration conditions are tightly specified
and must be strictly adhered to in order to achieve the precision 12.1 If an inflection (see Note 4) occurs in the potential
as stated. region between the pH 3 buffer potential (see 11.4) and a point
100 mV past this potential, mark this inflection as the end
NOTE 2When best precision of titration is desired, if the titrant tip has point. If more than one inflection points are observed, use the
been sitting for more than 30 min without being used, it is best to purge
the tips by dispensing a few millilitres of titrant before beginning a
last well-defined inflection point. If no well-defined inflection
titration. occurs in the above mentioned potential region, mark as the
NOTE 3See Appendix X1 for techniques for reducing the titration end point the point on the curve that corresponds to the acidic
time of a sample. Pre-dosing techniques have been found to provide aqueous pH 3 buffer potential. See Fig. 1 for examples of end
satisfactory results, although the precision using these techniques has not points.
been determined.
NOTE 4An inflection point is generally recognizable by inspection
11.4.1 Whether the titration is carried out manually or whenever at least five successive cell potential changes, D, caused by the
automatically, the following procedure of fixed increment, fixed addition of the corresponding five increments of titrant, exhibit a maxi-
time addition of titrant shall be followed. Add 0.1 M HCl in mum illustrated as follows:
increments of 0.100 mL throughout the titration with a 90-s Titrant, mL D, mV
pause between each incremental addition. Take millivolt read- 1.8 8.3
1.9 10.7
ings at the end of each 90-s interval. 2.0 11.3
11.4.1.1 The meter readings of potential difference are 2.1 10.0
2.2 7.9
plotted manually or automatically against the respective vol-
umes of titrant, and the end point is taken as described in 12.1. The D at the maximum should be at least 5 mV, and the difference in D
between the maximum and both the first and last D should be at least 2
11.4.2 On completion of the titration, remove the titration mV.
vessel and rinse the electrodes and buret tip with the titration
12.2 Calculate the base number and strong base number as
solvent, then with water, then again with titration solvent.
follows:
(Soak electrodes in distilled water for at least 5 min before
using for another titration.) Store the sensing electrode in Base number, mg KOH/g 5 @ ~ A 2 B ! 3 M 3 56.1# /W (2)
deionized or distilled water and the reference electrode in a Strong base number, mg KOH/g 5 @ ~ CM1Dm! 3 56.1# /W (3)
saturated solution of LiCl in isopropyl alcohol when not in use
where:
(see 8.1).
11.4.3 BlanksFor each set of samples, make a blank A = alcoholic HCl solution, mL, used to titrate the sample to
titration of the same volume of titration solvent used for the the end point (aqueous acidic pH 3 buffer or
sample. For the base number blank, add 0.1 M alcoholic HCl inflectionsee 7.3 and 12.1),
solution in 0.01-mL increments, waiting 12 s between each B = alcoholic HCl, mL, used to titrate the solvent blank to
addition, until a potential which is 100 mV past the buffer the same potential at which the sample end point
potential (see 11.4) is reached. For the strong base number occurs,

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 D4739 11

M = molarity of the alcoholic HCl solution, 15. Precision and Bias

W = sample, g, 15.1 PrecisionThe precision of this test method as deter-
C = alcoholic HCl solution, mL, used to titrate the sample to mined by statistical examination of results on 11 fresh samples,
an end point that occurs at a meter reading correspond- and 6 used oils samples run in duplicates by 14 different
ing to the aqueous basic pH 10 buffer (see 7.4 and laboratories is as follows:6,7
12.1), 15.1.1 Base Number:
D = alcoholic KOH solution, mL, used to titrate the solvent 15.1.1.1 RepeatabilityThe difference between two test
blank to the potential corresponding to C, and results, obtained by the same operator with the same apparatus
m = molarity of the alcoholic KOH solution.
under constant operating conditions on identical test material,
would, in the long run, in the normal and correct operation of
13. Report the test method, exceed the following value only in one case in
13.1 Report the results as base number and strong base twenty:
number, Test Method D4739. Fresh oils and additives:r 5 0.11 ~ X10.0268! 0.79
13.2 Report the base number values less than 10 mg KOH/g Used oils:r 5 0.22 X 0.47
to 0.1 mg KOH/g; and values between 10 and greater than 10
to 1 mg KOH/g. 15.1.1.2 ReproducibilityThe difference between two
single and independent results obtained by different operators
14. Quality Control Checks working in different laboratories on identical test material,
would, in the long run, in the normal and correct operation of
14.1 Confirm the performance of the test procedure by the test method, exceed the following value only in one case in
analyzing a quality control (QC) sample that is, if possible, twenty:
representative of the samples typically analyzed.
Fresh oils and additives:R 5 0.42 ~ X10.0268! 0.79
14.2 Prior to monitoring the measurement process, the user
Used Oils: R 5 1.53 X 0.47
of this test method needs to determine the average value and
control limits of the QC sample. 15.1.1.3 X is the mean of two or more results, in mg
14.3 Record the QC results and analyze by control charts or KOH/g.
other statistically equivalent technique to ascertain the statis- 15.1.2 Strong Base NumberPrecision data have not been
tical control status of the total testing process. Any out of developed for strong base number because of its rare occur-
control data should trigger investigation for root cause(s). The rence.
results of this investigation may, but not necessarily, result in 15.2 BiasA statement of bias is not applicable since a
instrument recalibration. standard reference material for this property is not available.
14.4 The frequency of QC testing is dependent on the 16. Keywords
criticality of the quality being measured, the demonstrated
stability of the testing process, and customer requirement. 16.1 base number; lubricants; petroleum products; potentio-
Generally, a QC sample should be analyzed each testing day. metric titration
The QC frequency should be increased if a large number of 6
Supporting data have been filed at ASTM International Headquarters and may
samples are routinely analyzed. However, when it is demon-
be obtained by requesting Research Report RR:D02-1217.
strated that the testing is under statistical control, the QC 7
Supporting data have been filed at ASTM International Headquarters and may
testing frequency may be reduced. be obtained by requesting Research Report RR:D02-1638.

ANNEX

(Mandatory Information)

A1. APPARATUS

A1.1 Apparatus for Manual Titration touching with a grounded lead (Note A1.1), any part of the
A1.1.1 MeterA voltmeter or potentiometer that will oper- exposed surface of the glass electrode, the glass electrode lead,
ate with an accuracy of 60.005 V and a sensitivity of the titration stand, or the meter. A desirable apparatus may
60.002 V, over a range of at least 60.5 V, when the meter is consist of a continuous-reading electronic voltmeter with
used with the electrodes specified in A1.1.2 and A1.1.3, and specified range, accuracy, and sensitivity, that is designed to
when the resistance between the electrodes falls within the operate on an input of less than 5 1012 A when an electrode
range from 0.2 to 20 MV. The meter shall be protected from system having 1000 MV resistance is connected across the
stray electrostatic fields so that no permanent change in the meter terminals, and that is provided with a satisfactory
meter readings over the entire operating range is produced by terminal to connect the shielded connection wire from the glass

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 D4739 11
electrode to the meter without interferences from the presence A1.1.6 Titration StandA suitable stand to support the
of external electrostatic field. electrodes, stirrer, and buret. An arrangement that allows the
NOTE A1.1Grounded or connected to the ground means connected removal of the beaker without disturbing the electrodes, buret,
through a resistance of not more than 100 V to a standard ground potential and stirrer is desirable.
such as that of a water-service pipe.
A1.1.2 ElectrodesSee 6.2 and 6.3. A1.2 Apparatus for Automatic Titration
A1.1.3 StirrerA variable-speed mechanical stirrer of any A1.2.1 Automatic titration system shall be generally in
suitable type, equipped with a glass, propeller-type-stirring accordance with A1.1 and provide the following technical
paddle.A propeller with blades 6 mm in radius and set at a pitch performance characteristics of features:
of 30 to 45 is satisfactory. A magnetic stirrer is also satisfac-
tory. If electrical stirring apparatus is used, it must be grounded A1.2.1.1 The addition of titrant must be automatically
so that connecting or disconnecting the power to the motor will controlled to dispense discontinuously 0.100 6 0.001-mL
not produce a permanent change in meter reading during the increments of titrant, with a waiting period of 90 s between
courses of titration. increments.
A1.1.4 BuretA 5-mL buret graduated in 0.01-mL divi- A1.2.1.2 Interchangeable precision motor-driven burets
sions and calibrated with an accuracy of 60.005 mL. The buret with volume dispensing accuracy of 60.001 mL.
shall have a chemically-resistant stopcock and shall have a tip A1.2.1.3 A record of the complete course of a titration by
that extends 100 to 130 mm beyond the stopcock. continuously printing out the potential or change in potential,
A1.1.5 Titration BeakerA 250-mL beaker made of boro- with the addition of each increment of titrant versus volume of
silicate glass, or other suitable titration beaker. titrant added.

APPENDIXES

(Nonmandatory Information)

X1. REDUCING TITRATION TIME

X1.1 A long, equilibration period of 90 s/increment was tions has not been determined.
selected for the base number titration because the titration
reaction and electrode equilibration are generally slow. This, of X1.2 There are many cases where the optimum in precision
course, can lead to long titration time/sample, with a maximum in the base number is not required, and in these cases the
time of 1 h based on a maximum volume of titrant of 4 mL and titration time can be shortened by taking a smaller sample. For
a rate of titrant addition of 0.1 mL/90 s. It is possible to example, for a base number of 2 and using a sample size
substantially reduce the titration time by predosing with rapid calculated from Eq 1, a total titration time of 24 min would be
addition of titrant until a potential within 25 mV of the buffer required. By taking only one half of the prescribed sample size
potential is reached, then allowing 90 s for equilibration and the titration time would be reduced to 12 min. The affect of
completing the titration under normal conditions. This proce- halving the sample size on the precision of this test method has
dure is not expected to have an adverse affect on the precision not been determined, but it would be expected to be small.
of this test method; however, the precision under these condi-

X2. CHECK FOR ELECTRODE PERFORMANCE

X2.1 The kinetic electrode test measures the kinetic re- reaches a stable point in less than 30 s and changes little from
sponse of the electrode. Electrodes can calibrate with accept- 30 to 60 s. Use buffers pH 4, pH 7, and pH 11 for this check,
able slope and intercept values yet still not have a response as needed.
good enough for titration. The speed of response and subse-
quent stability is important for a titration electrode. A manual X2.3 Procedure
method is described in X2.3 that can be carried out with a pH X2.3.1 Set the titrator or pH meter to read millivolts
meter or titrator set to read millivolts continuously. continuously. Have provision for stirring the buffer solution at
X2.2 The essence of the test method is to challenge the the same speed used for the titrations.
electrode coming from rest in a water solution with buffers and X2.3.2 Allow the electrode to stabilize for 1 min in distilled
measure the potential after 30 s and 60 s. A fast electrode or equivalent deionized water.

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 D4739 11
X2.3.3 Remove the electrodes from the water, and place drift < 1 excellent
them in the pH 4 buffer. Start a stopwatch at about the moment 1 < drift < 2 good
2 < drift < 3 acceptable
when the buffer touches the electrode. After 30 s, note the 3 < drift < 4 questionable
potential. 4 < drift unacceptable
X2.3.4 After another 30 s, note the potential again. The
X2.5 The difference between the 60 s potentials for pH 4
difference between the two potentials is termed the drift.
buffer and pH 7 buffer should be greater than 162 mV, or
X2.3.5 Repeat the procedure for pH 7 buffer and pH 11 54 mV/pH number. Electrodes with a slope less than 54
buffer. mV/pH number are not reliable for titration.
X2.4 Calculate the drift for each of the three buffers. The
electrode response may be judged as follows:

SUMMARY OF CHANGES

Subcommittee
1
D02.06 has identified the location of selected changes to this standard since the last issue
(D473908 ) that may impact the use of this standard.

(1) Updated 3.1.1. (2) Added reporting of significant figures in 13.2.

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