Astm-D2896-11 TBN
Astm-D2896-11 TBN
Astm-D2896-11 TBN
Designation: 276/95
1. Scope*
1.1 This test method covers the determination of basic constituents in petroleum products by titration with perchloric acid in
glacial acetic acid.
1.2 Procedures A and B use different titration solvent volumes and sample weights.
NOTE 1—A round robin on a series of new and used oils and additive concentrates has shown that the two procedures give statistically equivalent
results.
1.3 Appendix X2 provides the use of an alternative solvent system which eliminates the use of chlorobenzene in this test
method. The use of the alternative solvent gives statistically equivalent results; however, the precision is worse. Paragraph X2.5.5
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provides guidance when comparing results using the two different solvents.
1.4 The constituents that may be considered to have basic characteristics include organic and inorganic bases, amino
compounds, salts of weak acids (soaps), basic salts of polyacidic bases, and salts of heavy metals.
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NOTE 2—This test method is applicable to both fresh oils and used oils as described in Sections 16, 17, and 19 and Appendix X1.
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This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.06 on
Analysis of Lubricants.
Current edition approved JulyMay 15, 2007.2011. Published August 2007.July 2011. Originally approved in 1970. Last previous edition approved in 2007 as D2896–07a.
DOI: 10.1520/D2896-11.
This test method has been approved by the sponsoring committees and accepted by the cooperating societies in accordance with established procedures. DOI:
10.1520/D2896-07A.
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For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [email protected]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
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D2896 – 11
potassium hydroxide per gram of sample, required to titrate a sample in a specified solvent to a specified endpoint using a specified
detection system.
6. Apparatus
6.1 Potentiometric Titrimeters , either automatic recording or manual.
6.2 Glass Electrode, pH 0 to 11, general-purpose type.
6.3 Reference Electrode, silver/silver chloride (Ag/AgCl) reference electrode with a nonaqueous bridge as described in Section
10. (See also 19.1.)
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NOTE 3—Some reference electrodes with fritted or fiber diaphragms and some combined glass plus reference electrodes systems are commercially
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available, such as the single-rod glass plus silver/silver chloride electrode assembly. During the development of this test method, the use of electrodes
of these types gave problems in some laboratories, but not in others. Accordingly, these electrodes are permitted in this test method, provided that the
sodium perchlorate bridge is used; however, when stability or other problems arise with their use, the sleeve-type electrode should be used.
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6.4 Stirrer, either mechanical or electrical, with variable speeds and with propeller or paddle of chemically inert material. When
an electrical stirrer is used, it must be grounded so that disconnecting or connecting the power to the motor will not produce a
permanent change in meter reading during the course of a titration. A magnetic stirrer with stirring bar can be used provided it
meets these conditions. ASTM D2896-11
6.5 Buret, 10 or 20-mL, graduated in 0.05-mL divisions and calibrated with an accuracy of 60.02 mL, or an automatic buret
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of similar accuracy.
6.6 Titration Beaker, made of borosilicate glass or other suitable titration beaker, tall form recommended.
6.6.1 For Procedure A, use a beaker of 250 or 300 mL capacity. For Procedure B, use a beaker of about 150 mL capacity such
that 60 mL of titration solvent will cover the electrodes.
NOTE 4—Other beakers of suitable size capacity may be used.
6.7 Titration Stand, suitable to support the beaker, electrodes, stirrer, and buret. An arrangement that allows for the removal of
the beaker without disturbing the electrodes, buret, and stirrer is desirable.
NOTE 5—Some apparatus may be sensitive to interference by static electricity, shown by erratic movements of recorder pen or meter indicator, when
the titration assembly (beaker and electrodes) is approached by the operator. In this case surround the beaker closely with a cylinder of copper gauze that
is electrically grounded.
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Reagent Chemicals, American Chemical Society Specifications , American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by
the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
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D2896 – 11
7.4 Acetic Anhydride (Warning—Toxic and irritant).
7.5 Chlorobenzene (Warning—Toxic and irritant).
7.6 Perchloric Acid, Standard Solution in Acetic Acid (0.1 N)4 (Warning—Powerful oxidant when dry or heated. Great care
should be taken to avoid contact with organic matter under conditions that may result in subsequent drying or heating, and spills
should be washed immediately and thoroughly with water)—Mix 8.5 mL of 70 to 72 % perchloric acid (HClO4, 70 to 72 %) (or
10.2 mL of 60 to 62 % HClO4 solution) with 500 mL of glacial acetic and 30 mL (or 35 mL if the 60 to 62 % HClO4 solution
is used) of acetic anhydride. Dilute to 1 L with glacial acetic acid. Allow the solution to stand for 24 h.
NOTE 6—Excess acetic anhydride should be avoided to prevent acetylation of any primary or secondary amines that may be present.
7.7 Potassium Hydrogen Phthalate—(KHC 8H4O4).
7.8 Sodium Perchlorate Electrolyte—(Warning—Sodium perchlorate is toxic and an irritant. It is also a powerful oxidizing
agent when heated. Great care should be taken to avoid contact with organic matter under conditions that may result in subsequent
drying or heating, and spills should be washed immediately and thoroughly with water.) Prepare a saturated solution of sodium
perchlorate (NaClO4 ) in glacial acetic acid. An excess of undissolved NaClO4 shall always be present at the bottom of the solution.
7.9 Titration Solvent—Add one volume of glacial acetic acid to two volumes of chlorobenzene.
7.10 Sodium Carbonate, anhydrous (Na2CO3).
7.11 Sodium Acetate Solution, 0.1 N in acetic acid (for back titration, see Sections 16 and 17)—Dissolve 5.3 g of anhydrous
Na2CO3 in 300 mL of glacial acetic acid. Dilute to 1 L with acetic acid after solution is complete.
8. Standardization of Reagents
8.1 Perchloric Acid Solution—The standardization of the perchloric acid solution (HClO4) differs for the two procedures as
follows:
8.1.1 Procedure A (120 mL)—Heat a quantity of potassium hydrogen phthalate in an oven at 120°C for 2 h and allow it to cool.
Take 0.1 to 0.2 g of the potassium hydrogen phthalate weighed to the nearest 0.1 mg and dissolve it in 40 mL of warm glacial acetic
acid. Add 80 mL of chlorobenzene, cool, and titrate with 0.1 N HClO4 solution, using the electrode system and procedures given
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in 10.1 to 10.4 and 11.4 to 11.7. Detect the end point by the same procedure used for base number determination (see 14.2). Carry
out a blank titration on 40 mL of glacial acetic acid plus 80 mL of chlorobenzene (see 11.8).
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8.1.2 Procedure B (60 mL)—Heat a quantity of potassium hydrogen phthalate in an oven at 120°C for 2 h and allow it to cool.
Take 0.05 to 0.1 g of the potassium hydrogen phthalate weighed to the nearest 0.1 mg and dissolve it in 20 mL of warm glacial
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acetic acid. Add 40 mL of chlorobenzene, cool, and titrate with 0.1 N HClO4 solution as described in 8.1.1. Carry out a blank
titration on 20 mL of glacial acetic acid and 40 mL of chlorobenzene (see 11.8).
8.1.3 Calculate the normality, N A, of the HClO4 solution as follows:
NA 5 1000W/[204.23·~V– b!# (1)
ASTM D2896-11
where:
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W = potassium hydrogen phthalate, g,
V = HClO4 solution used, mL, and
b = volume corresponding to V for the blank titration, mL.
NOTE 7—Because of the relatively large coefficient of volumetric expansion of organic liquids, the acetous HClO4 solution should be used within 6
5°C of the temperature at which it was standardized. If used at a temperature more than 5°C higher, multiply the volume used by the factor 1 − (t·0.001).
If used at a temperature more than 5°C lower, multiply by the factor 1 + (t·0.001), where tis the difference in degrees Celsius between temperatures of
standardization and use and is always positive.
8.2 Sodium Acetate Solution—The standardization of the sodium acetate solution (Na2CO3) differs for the two procedures as
follows:
8.2.1 Procedure A (120 mL)—Use 120 mL of titration solvent and 8.00 mL of 0.1 NHClO4 solution. Titrate with 0.1 N sodium
acetate solution, using the electrode system and procedure given in 10.1 to 10.4 and 11.4 to 11.7. Detect the end point by the same
procedure as will be used for base number determination (see 14.2). Calculate the normality, NB , of the sodium acetate solution
as follows:
NB 5 [~8.00 – b!NA#/G (2)
where:
b = volume corresponding to V for the blank titration,
NA = normality of the HClO 4 solution, and
G = volume of standard sodium acetate used in the standardization, mL.
8.2.2 Procedure B (60 mL)—Use 60 mL of titration solvent and 4.00 mL of 0.1 N HClO4 solution. Titrate as described in 8.2.1.
Calculate the normality, NB , of the sodium acetate solution as follows:
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Available commercially for purchase already prepared.
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D2896 – 11
NB 5 [~4.00 – b!NA#/G (3)
where:
b = volume corresponding to V for the blank titration,
NA = normality of the HClO4 solution, and
G = volume of standard acetous sodium acetate used in the standardization, mL.
9. Preparation of Sample
9.1 It is essential to ensure that the sample is representative since any sediment can be acidic or basic or have adsorbed acidic
or basic material from the sample. When necessary, samples are warmed to aid mixing. Used oils should be vigorously shaken to
ensure homogeneity before sampling.
NOTE 8—As used oils can change appreciably in storage, samples 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.
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10.2.1 Procedure A—Dip the electrodes into a well-stirred mixture of 100 mL of glacial acetic acid plus 0.2 g of KHC8H4O4
and record the reading given by the meter. Rinse the electrodes with chlorobenzene and immerse in 100 mL of glacial acetic acid
plus 1.5 mL of 0.1 N HClO4 solution. The difference between readings is to be at least 0.3 V.
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10.2.2 Procedure B—Dip the electrodes into a well-stirred mixture of 60 mL of glacial acetic acid plus 0.1 g of KHC8H4O4 and
record the reading vein by the meter. Rinse the electrodes with chlorobenzene and immerse in 50 mL of glacial acetic acid plus
0.75 mL of 0.1 N HClO4 solution. The difference between readings is to be at least 0.3 V.
NOTE 9—See Appendix X4 for a possible procedure to check ASTM D2896-11
the electrode performance.
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Cleaning of Electrodes—Following a titration, first wash the electrodes with titration solvent to remove any adhering oily
material from the previous titration. Then wash the electrodes with water to dissolve any NaClO4 that may have formed around
the sleeve of the reference electrode and to restore the aqueous gel layer of the glass electrode. Rinse again with the titration
solvent. Before starting a series of sample titrations, follow this rinsing procedure, then run one or two blank titrations on the
solvent to condition the electrodes. Repeat the blank titrations if necessary.
10.4 Maintenance of Electrodes—When there is reason to believe that the glass electrode has become contaminated, it can be
cleaned by immersion in cold chromic acid ( Warning—Corrosive and carcinogenic) or an alternative non-chromium-containing
strongly-oxidizing acid cleaning solution for 5 min, followed by thorough water washing. After this cleaning treatment, test the
electrode as described in 10.2. The reference electrode can be cleaned by draining and refilling with fresh NaClO4 solution.
Maintain the electrolyte level in the reference electrode above that of the liquid in the titration beaker at all times. Do not allow
the electrodes to remain immersed in titration solvent for any appreciable period of time between titrations. While the electrodes
are not extremely fragile, handle them carefully at all times and particularly avoid scratching the glass electrode.
10 to 20 0.05
5 to 10 0.02
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D2896 – 11
1 to 5 0.005
0.25 to 1.0 0.001
0.1 to 0.25 0.0005
5 to 10 0.02
1 to 5 0.005
0.25 to 1.0 0.001
0.1 to 0.25 0.0005
NOTE 14—It is especially important for Procedure B that great care be exercised in obtaining accurate weights particularly for the high base number
samples which require small sample weights.
12.2 Add 60 mL of titration solvent to the sample.
12.3 Place the sample on the titration stand and stir the solution until the sample is dissolved.
NOTE 15—If the solution of the sample proves difficult, dissolve it in 40 mL of chlorobenzene in the titration beaker, then add 20 mL of glacial acetic
acid.
12.4 Prepare the electrodes as directed in 10.1, 10.2, and 10.3. Position the electrodes in the solution so that they are immersed
as far as possible. Continue stirring throughout the determination at a rate sufficient to produce vigorous agitation without
spattering and without stirring air into the solution. Adjust the meter so that it reads in the upper part of the millivolt scale; for
example, 700 mV. For simple meters without this adjustment, it may be necessary to incorporate a source of potential in series with
the electrode. A 1.5-V dry cell and potential divider is suitable.
12.5 Fill the buret with 0.1 N HClO 4 solution and place the buret in position in the titration assembly, taking care that the tip
is immersed below the level of the surface of the liquid in the beaker. Record the initial buret and meter (cell potential) readings.
12.6 Titration:
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D2896 – 11
12.6.1 Manual Titration—Add suitable small portions of titrant and after waiting until a constant potential has been established
(Note 12), record the buret and meter readings. At the start of the titration and in any subsequent regions (inflections) where 0.1
mL of titrant consistently produces a total change of more than 0.03 V (corresponding to 0.5 pH scale unit) in the cell potential,
add 0.05-mL portions. In the intermediate regions (plateaus) where 0.1 mL increments change the potential by less than 0.03 V,
add large portions sufficient to produce a total potential change approximately equal to, but not greater than, 0.03 V. Titrate in this
manner until the potential changes less than 0.005 V (corresponding to 0.1 pH scale unit) per 0.1 mL.
12.6.2 Automatic Recording Titration— Adjust the instrument in accordance with the manufacturer’s instructions and set the
titration speed at 1.0 mL/min maximum.
12.7 On completion of the titration, remove the beaker and rinse the electrodes and buret tip with titration solvent, then with
water, then again with titration solvent (see 10.3). Store the electrodes in water when not in use (see 10.1).
12.8 For each set of samples make a blank on 60 mL of titration solvent. For a manual titration add 0.1 N HClO4 solution in
0.05-mL increments, waiting between each addition until a constant cell potential is established. Record meter and buret readings
after each increment. Follow the procedure in 12.6.2 for an automatic titration.
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NOTE 16—Because the base number can vary while the QC sample is in storage, when an out-of-control situation arises, the stability of the QC sample
can be a source of the error.
14. Calculation
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14.1 For a manual titration, plot the volumes of the acid added against the corresponding meter readings.
where:
E = HClO4 solution used to titrate the sample to the inflection point on the titration curve, mL,
F = volume corresponding to E for blank titration at same potential as sample, mL
NA = normality of HClO4 solution, and
S = sample, g.
15. Report
15.1 Report the result as follows:
Base Number ~D28962Procedure A or B! 5 Result (7)
This report format may not be used when using the alternative solvent described in Appendix X2. Instead, use the format
described in X2.4.
15.2 Report the base number values less than 100 to 0.1 mg KOH/g, and values 100 or greater to 1 mg KOH/g.
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ASTM MNL 7, Manual on Presentation of Data Control Chart Analysis, Section 3: Control Charts for Individuals, 6th ed, ASTM International, W. Conshohocken, PA.