Designation: D94 − 07 (Reapproved 2012)´1

Designation: 136S1/98, 136S2/99

Standard Test Methods for

Saponification Number of Petroleum Products1
This standard is issued under the fixed designation D94; the number immediately following the designation indicates the year of original
adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript
epsilon (´) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the U.S. Department of Defense.

ε1 NOTE—The Research Report number in 23.1 was corrected editorially in May 2015.

1. Scope 1.3 The values stated in SI units are to be regarded as the

1.1 These test methods cover the determination of the standard.
amount of constituents in petroleum products such as 1.4 This standard does not purport to address all of the
lubricants, additives, and transmission fluids that will saponify safety concerns, if any, associated with its use. It is the
under the conditions of the test. responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
NOTE 1—Statements defining this test and its significance when applied
to electrical insulating oils of mineral origin will be found in Guide D117. bility of regulatory limitations prior to use. For specific hazard
Experience has shown that for transformer oils, Test Method D94, statements, see Sections 6, 7, 8, 10, 15, 16, 17, and 19.
modified by use of 0.1 M KOH solution and 0.1 M HCl, is more suitable.
1.1.1 Two test methods are described: Method A—Color 2. Referenced Documents
Indicator Titration (Sections 6 – 13), and Method 2.1 ASTM Standards:2
B—Potentiometric Titration (Sections 14 – 23). D117 Guide for Sampling, Test Methods, and Specifications
1.2 Because compounds of sulfur, phosphorus, the for Electrical Insulating Oils of Petroleum Origin
halogens, and certain other elements that are sometimes added D128 Test Methods for Analysis of Lubricating Grease
to petroleum products also consume alkali and acids, the D1193 Specification for Reagent Water
results obtained indicate the effect of these extraneous materi- D4057 Practice for Manual Sampling of Petroleum and
als in addition to the saponifiable material present. Results on Petroleum Products
products containing such materials, on used internal- D4177 Practice for Automatic Sampling of Petroleum and
combustion-engine crankcase oils, and on used turbine oils Petroleum Products
must be interpreted with caution. D6299 Practice for Applying Statistical Quality Assurance
and Control Charting Techniques to Evaluate Analytical
NOTE 2—The materials referred to above, which are not normally Measurement System Performance
considered saponifiable matter, include inorganic or certain organic acids, D6792 Practice for Quality System in Petroleum Products
most nonalkali soaps, and so forth. The presence of such materials
increases the saponification number above that of fatty saponifiable and Lubricants Testing Laboratories
materials for which the test method is primarily intended. The odor of 2.2 Energy Institute Standards:3
hydrogen sulfide near the end of the back-titration in the saponification IP 136 Method of Test for Saponification Number of Petro-
test is an indication that certain types of reactive sulfur compounds are
present in the sample. In the case of other reactive sulfur, chlorine, and
leum Products
phosphorus compounds and other interfering materials, no simple indica- IP 284 Method of Test for Fatty Acids
tion is given during the test. A gravimetric determination of the actual
amount of fatty acids is probably the most reliable method for such 3. Terminology
compounds. Test Methods D128 or IP Method 284/86 can be used to
determine fatty acids gravimetrically. 3.1 Definitions:

2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
1
These test methods are under the jurisdiction of ASTM Committee D02 on contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Petroleum Products, Liquid Fuels, and Lubricants and are the direct responsibility Standards volume information, refer to the standard’s Document Summary page on
of Subcommittee D02.06 on Analysis of Liquid Fuels and Lubricants. the ASTM website.
3
Current edition approved Nov. 1, 2012. Published November 2012. Originally Available from Institute of Petroleum, 61 New Cavendish St., London, W.I.,
approved in 1921. Last previous edition approved in 2007 as D94–07. DOI: England.Available from Energy Institute, 61 New Cavendish St., London, WIG
10.1520/D0094-07R12E01. 7AR, U.K., http://www.energyinst.org.uk.

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 D94 − 07 (2012)´1
3.1.1 saponification number, n—the number of milligrams all reagents shall conform to the specifications of the Commit-
of potassium hydroxide consumed by 1 g of a sample under the tee on Analytical Reagents of the American Chemical Society,
conditions of the test. where such specifications are available.4 Other grades may be
3.1.1.1 Discussion—The value of the saponification number used, provided it is first ascertained that the reagent is of
in these test methods can be affected by the presence of other sufficiently high purity to permit its use without lessening the
alkali-reactive species, as described in Note 2. accuracy of the determination.
3.1.2 saponify, v—to hydrolyze a fat with alkali to form an NOTE 4—Commercially available reagents may be used in place of
alcohol and the salt of a fatty acid. laboratory preparations, provided they meet the specifications outlined.

4. Summary of Test Method 7.2 Purity of Water—Unless otherwise indicated, references

to water shall be understood to mean reagent water as defined
4.1 A known mass of the sample is dissolved in a suitable by Type I, II, or III in Specification D1193.
solvent, such as butanone (methylethylketone), xylenes, or
Stoddard Solvent, or a combination thereof (Warning— 7.3 Alcohol 5 —95 % ethanol (Warning—Flammable.
Extremely flammable. Vapors can cause flash fire), and is Denatured—Cannot be made nontoxic) (see Note 5) and
heated with a known amount of alcoholic potassium hydroxide (Warning—Flammable) or 95 % ethanol to which has been
(KOH). The excess alkali is titrated with standard acid, and the added 10 volume % of methanol (see Note 5 and Note 6) or
saponification number is calculated. absolute alcohol.
4.2 The titration end point can be detected either colori- NOTE 5—It has been found that 99 % 2-propanol (isopropyl alcohol)
can be substituted for the purified ethanol with entirely satisfactory results.
metrically (Method A) or potentiometrically (Method B). This substitution is not permissible, however, in referee tests.
NOTE 6—This composition is available under the name of “U.S.
5. Significance and Use Department of Treasury Specially Denatured Formula 30 (Regulation No.
5.1 Petroleum products can contain additives that react with 3-1938).”5 Formula 3A plus 5 % methanol is an equivalent.
alkali to form metal soaps. Fats are examples of such additives. 7.4 Aqueous Hydrochloric Acid Standard Solution (0.5
Also, certain used engine oils, especially from turbine or M)—Standardize to detect molarity changes of 0.0005 by
internal combustion engines, can contain chemicals that will titrating with standard alcoholic KOH solution (see 7.8 and
similarly react with alkali. The saponification number ex- Note 7).
presses the amount of base that will react with 1 g of sample
NOTE 7—Where saponification numbers below one are expected, better
when heated in a specific manner. This then gives an estimation precision can be obtained by substituting 0.1 M KOH solution and HCl for
of the amount of acid present in the sample, that is, any free the 0.5 M reagents in Sections 7, 8, 10, 17, and 19.
acid originally present plus any combined (for example, in
7.5 Butanone (Methyl Ethyl Ketone) , technical grade. Store
esters) that have been converted to metal soaps during the
in dark or brown bottles. (Warning— See 4.1.)
heating procedure.
7.6 Naphtha, (Warning— Extremely flammable. Harmful
5.2 Saponification numbers are also used in setting product
if inhaled. Vapors can cause flash fire.) ASTM Precipitation
specifications for lubricants and additives.
Grade (or Petroleum Spirit-60/80 or hexanes) (Warning—
METHOD A—COLOR INDICATOR TITRATION Combustible. Vapor harmful.) Petroleum spirit shall conform
to the current IP 136.
6. Apparatus
7.7 Phenolphthalein Solution, Neutralized—Dissolve 1.0 6
6.1 Erlenmeyer Flask and Condenser— An Erlenmeyer 0.1 g of phenolphthalein in 100 mL of alcohol (see 7.3).
flask, 250 or 300-mL capacity, alkali-resistant (see Note 3) and Neutralize to faint pink color with dilute (0.1 M) alcoholic
(Warning—Causes severe burns; a recognized carcinogen; KOH solution.
strong oxidizer—contact with other material can cause fire;
7.8 Alcoholic Potassium Hydroxide Standard Solution (0.5
hygroscopic ), to which is attached a straight or mushroom-
M)—Prepare approximately 0.5 M solution by dissolving KOH
type reflux condenser. The straight-type condenser is fitted to
in the alcohol specified in 7.3. Allow the solution to settle in a
the flask with a ground-glass joint; the mushroom-type con-
dark place. Filter the solution, and allow to stand for 24 h
denser must fit loosely to permit venting of the flask. Water
before using.
reflux condensers can also be used instead of air condensers.
7.8.1 Alternatively prepare 0.5 or 0.1 M alcoholic KOH by
NOTE 3—Do not use scratched or etched Erlenmeyer flasks because mixing a commercially available KOH ampule (which is
KOH will react with them. The glassware shall be chemically clean. It is
recommended that flasks be cleaned with chromic acid cleaning solution
(Alternatively, Nochromix or similar products can be used.)
4
6.2 Hot Plate—A suitable hot plate heated by either elec- Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
tricity or steam. (Warning—Thermal hazard; in addition to listed by the American Chemical Society, see Annual Standards for Laboratory
other precautions, avoid contact with exposed skin.) Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
7. Reagents MD.
5
Available from the U.S. Bureau of Alcohol, Tobacco, and Firearms, Distilled
7.1 Purity of Reagents—Reagent grade chemicals shall be Spirits and Tobacco Branch, 1200 Pennsylvania Avenue, NW, Washington, DC
used in all tests. Unless otherwise indicated, it is intended that 20226.

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 D94 − 07 (2012)´1
carbonate free) with 95 % alcohol. Using this type solution reached (Note 14). The end point is reached when the indicator
gives consistent blanks and does not give multiple breaks (see color is completely discharged and does not immediately
Note 8). reappear upon further dropwise addition of the indicator
NOTE 8—Because of the relatively large coefficient of cubic expansion
solution. Record as V1 in 11.1.
of organic liquids such as 2-propanol (isopropyl alcohol), the standard NOTE 14—Avoid emulsification of titration mixture, but ensure phase
alcoholic solution has to be standardized at temperatures close to those contact by swirling the flask vigorously as the end point is approached.
employed in the titrations of samples.
9. Sample
7.8.2 The KOH solutions shall be standardized by titrating
with standard potassium hydrogen phthalate solution (see 7.9 9.1 Using Practice D4057 (manual sampling) or Practice
and Note 8). D4177 (automatic sampling) as a guideline for obtaining a
representative sample, make sure that the portion of the sample
7.9 Potassium Hydrogen Phthalate—(C8H5KO4) 0.1 M
to be tested appears homogenous. Choose the size of the
Standard Solution —Weigh 2.0422 6 0.0002 g of potassium
sample so that the back-titration volume is from 40 to 80 % of
hydrogen phthalate that has been dried at 110 6 5°C to a
the blank, but do not exceed a 20-g sample weight (see Note
constant weight into a 100-mL volumetric flask. Dissolve in
15).
reagent water. Some heating may be necessary to dissolve the
solid. Dilute to 100 mL with distilled or deionized water, after NOTE 15—The following sample sizes are suggested:
the solution has cooled. Saponification Number Sample Size, g
181 to 400 1
7.10 Stoddard Solvent, technical grade. (Warning— 111 to 180 2
Extremely flammable. Harmful if inhaled.) 71 to 110 3
31 to 70 5
7.11 Xylene, reagent grade. (Warning—Extremely flam- 16 to 30 10
0 to 15 20
mable. Harmful if inhaled.)
10. Procedure
8. Blank Determinations 10.1 Weigh the specimen to the nearest 0.01 g (record as W
8.1 Perform a blank determination concurrently with each in 11.1), such as by difference, from a small beaker into the
set (see Note 9) (one or more) of samples as follows: measure Erlenmeyer flask. Add 25 6 1 mL of butanone or one of the
accurately from a buret or volumetric pipet (see Note 10) into alternative solvents (Warning—See 4.1), followed by 25 6
the Erlenmeyer flask 25 6 0.03 mL of alcoholic KOH solution 0.03 mL of alcoholic KOH solution (Warning—See 7.3)
and 256 1 mL of butanone (methylethyl-ketone) or one of the measured accurately from a buret or volumetric pipet (see Note
alternative solvents. Connect the condenser to the flask, and 7).
heat for the same amount of time as that used for the sample 10.2 Dissolve the difficult to dissolve samples, such as
after refluxing begins. (Warning—The reflux condenser lubricants and additives, first in 15 to 25 mL of Stoddard
should be clamped securely to prevent it from tipping over onto Solvent (Warning— See 7.10) or xylene (Warning—See
the hot plate with possible breakage of glassware. See also 7.11) before adding butanone (Warning—See 4.1).
Note 11. ) Immediately add 50 mL of ASTM precipitation
naphtha (Warning— See 7.6, also Note 12 and Note 13) by 10.3 Connect the condenser to the flask and heat for 30 min
cautiously pouring the naphtha down the condenser (discon- after refluxing begins (see Note 11). Immediately add 50 mL of
nect condenser if mushroom-type is used), and titrate the blank ASTM precipitation naphtha (Warning—Do not pour naphtha
while hot, without reheating, with 0.5 M hydrochloric acid while the flask is on the hot plate) and (see 7.6) by cautiously
(HCl) using three drops of neutralized phenolphthalein indica- pouring the naphtha down the condenser (see Note 12)
tor solution. (disconnect condenser if mushroom-type before adding the
naphtha).
NOTE 9—Run blank determinations in duplicate on samples requiring
the highest accuracy. The precision data are based on duplicate blank 10.4 Titrate the solution while hot (without reheating) with
determinations. A single blank is sufficient for routine work. 0.5 M HCl using three drops of neutralized phenolphthalein
NOTE 10—If a volumetric pipet is used to measure the alcoholic KOH indicator solution (Warning—See 7.3). When the indicator
solution, wait 30 s after delivery to allow for complete drainage. color is discharged, add, dropwise, more indicator solution. If
NOTE 11—Although standard procedure requires 30 min of reflux, some this addition of indicator restores the color, continue the
fats are readily saponified and complete saponification takes place within
10 min. On the other hand, difficult saponifiable materials require more titration, making further dropwise additions of indicator, if
than 2 h. Neither the shortened period nor the longer period should be used necessary, until the end point is reached (Note 14). The end
except by mutual consent of the interested parties. point is reached when the indicator color is completely
NOTE 12—Pouring 50 mL of naphtha down the condenser at the end of discharged and does not immediately reappear upon further
the saponification not only rinses the condenser but also cools the reaction
mixture.
dropwise addition of the indicator solution. (Record as V2 in
NOTE 13—In the case of insulating oils, the addition of ASTM 11.1.) When testing waxes, it may be necessary to reheat the
precipitation naphtha or petroleum spirit is not necessary. solution during titration to prevent solidification of the sample.
8.2 After the indicator color has been discharged, add, 11. Calculation
dropwise, more indicator solution. If this addition of indicator
11.1 Calculate the saponification number, A, as follows:
restores the color, continue the titration, making further drop-
wise additions of indicator, if necessary, until the end point is A 5 56.1 M ~ V 1 2 V 2 ! /W (1)

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 D94 − 07 (2012)´1
where: 13.1.2 Reproducibility—The difference between two single
M = molarity of the hydrochloric acid, and independent results obtained by different operators work-
V1 = volume of acid used in titrating the blank, mL, ing in different laboratories on identical test materials would, in
V2 = volume of acid used in titrating the sample, mL, the long run, in the normal and correct operation of the test
W = sample, g, and method, exceed the Fig. 1 values only in one case in twenty.
56.1 = molecular weight of KOH.
13.2 Bias—This is an empirical test method, and there are
no accepted reference materials that can be compared; hence,
12. Report
bias cannot be determined.
12.1 For saponification numbers of less than 50, report the
saponification number to the nearest 0.5 mg KOH/g sample. METHOD B—POTENTIOMETRIC TITRATION
12.2 For saponification number of 50 or more, report to the
nearest whole number. 14. Apparatus

12.3 For electrical insulating oils, report the values to the 14.1 Erlenmeyer Flask and Condenser— An Erlenmeyer
nearest 0.1 mg KOH/g sample. flask, 250 or 300-mL capacity, alkali-resistant (see Note 3), to
which is attached a straight or mushroom-type reflux con-
12.4 Report the saponification numbers as obtained by Test denser. The straight-type condenser is fitted to the flask with a
Methods D94, Method A. ground-glass joint; the mushroom-type condenser must fit
loosely to permit venting of the flask. Water reflux condensers
13. Precision and Bias can also be used instead of air condensers.
13.1 Precision—The data shown in Fig. 1 shall be used for 14.2 Hot Plate—A suitable hot plate heated by either
judging the acceptability of results (95 % probability) (see electricity or steam (see 6.2).
Note 16).
14.3 Potentiometric Titrator Automatic, Recording or
NOTE 16—No precision intervals can be given for highly colored new
or used oils, or for oils that produce dark-colored solutions upon
Manual—High-precision titrator capable of distinguishing the
saponification, as color can interfere with the detection of the end point of carbonate from pure caustic in the titration of ACS reagent
the titration. In such cases, potentiometric titration (Method B) can be grade KOH by hydrochloric acid (HCl).4
used.
14.4 Electrodes—High-quality electrodes must be used.
13.1.1 Repeatability—The difference between two test Cleaning and maintenance of the electrodes are vital to their
results, obtained by the same operator with the same apparatus satisfactory operation.
under constant operating conditions on identical test material, 14.4.1 Combination Glass Electrode , or a suitable glass
would in the long run, in the normal and correct operation of electrode and a suitable reference electrode; either silver
the test method, exceed the Fig. 1 values only in one case in chloride (AgCl)/saturated alcoholic lithium chloride (LiCl) or
twenty. saturated potassium chloride (KCl) inverted glass sleeve calo-
mel electrode can be used.
14.5 Magnetic Stirring Bars—Because, on titration, two
immiscible liquid phases appear, and potassium chloride (KCl)
is precipitated, stirring conditions are critical, and very vigor-
ous stirring is essential (see Note 17).
NOTE 17—If a large magnetic stir bar is used, only slow speeds are
possible, and if too small a stir bar is used, the highest rotational speeds
cause insufficient agitation of the bulk of the liquid. The optimum
magnetic stir bar has been found to be a 2.5 by 0.5-cm plain polytetra-
fluoroethylene (PTFE)-coated cylinder. This magnetic stirrer is not needed
if a propeller or paddle stirrer is used.
14.6 Tall Form Beakers—250 or 300-mL size Berzelius type
tall-form glass beaker with or without a spout (see Note 18).
NOTE 18—The potentiometric titration cannot be performed in the
Erlenmeyer flask used in digestion. The small opening of this flask will not
accommodate the electrodes, unless a combination electrode is used.
14.7 Stirrer, Buret Stand, Titration Vessel—A typical cell
assembly is shown in Fig. 2. The propeller or paddle stirrer is
not needed if a magnetic stirrer is used.
14.7.1 Stirrer, either mechanical or electrical, with variable
speeds and with propeller or paddle of chemically inert
material. If an electrical stirrer is used, it must be grounded so
that disconnecting or connecting the power to the motor will
FIG. 1 Precision Data not produce a permanent change in meter reading during the

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 D94 − 07 (2012)´1
15.5 Butanone (Methyl Ethyl Ketone) , technical grade.
Store in dark or brown bottles. (Warning— See 4.1.)
15.6 Naphtha, (Warning— Extremely flammable. Harmful
if inhaled. Vapors can cause flash fire.) ASTM Precipitation
Grade (or Petroleum Spirit-60/80 or hexanes) (Warning—
Combustible. Vapor harmful.) Petroleum spirit shall conform
to the current IP 136.
15.7 Alcoholic Potassium Hydroxide Standard Solution (0.5
M)—Prepare approximately 0.5 M solution by dissolving KOH
in the alcohol specified in 7.3. Allow the solution to settle in a
dark place. Filter the solution, and allow to stand for 24 h
before using.
15.7.1 Alternatively prepare 0.5 or 0.1 M alcoholic KOH by
mixing commercially available KOH ampule (which is carbon-
ate free) with 95 % alcohol. Using this type solution gives
consistent blanks and does not give multiple breaks (see Note
8).
FIG. 2 Cell for Potentiometric Titration 15.7.2 The KOH solutions shall be standardized by titrating
with standard potassium hydrogen phthalate solution (see 15.8
and Note 8).
15.8 Potassium Hydrogen Phthalate—(C8H5KO4) 0.1 M
course of titration. A magnetic stirrer with stirring bar can be Standard Solution —Weigh 2.0422 6 0.0002 g of potassium
used provided it meets the above conditions. hydrogen phthalate that has been dried at 110 6 5°C for 1 h
14.7.2 Buret, 10 or 20-mL, graduated in 0.05-mL divisions into a 100-mL volumetric flask. Dissolve in distilled or
and calibrated with an accuracy of 60.02 mL, or an automatic deionized water. Some heating can be necessary to dissolve the
buret of similar accuracy. solid. Dilute to 100 mL with distilled or deionized water after
14.7.3 Titration Stand, suitable to support the beaker, the solution has cooled.
electrodes, stirrer, and buret. An arrangement that allows for
the removal of the beaker without disturbing the electrodes, 15.9 Stoddard Solvent, technical grade. (Warning—See
buret, and stirrer is desirable (see Note 19). 7.10.)
NOTE 19—Some apparatus can be sensitive to interference by static 15.10 Potassium Chloride, Aqueous (3.0 M)—Prepare by
electricity, shown by erratic movements of recorder pen or meter indicator, dissolving 225.2 g reagent grade KCl in 1.0 L of distilled or
when the titration assembly (beaker and electrodes) is approached by the deionized water.
operator. In that case, surround the beaker closely with a cylinder of
copper gauze that is electrically grounded. 15.11 Xylene, reagent grade. (Warning—See 7.11.) See
15.1.
15. Reagents 15.12 Chlorobenzene, reagent grade. See 15.1.
15.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that 16. Preparation, Testing, and Maintenance of Electrode
all reagents shall conform to the specifications of the Commit- System
tee on Analytical Reagents of the American Chemical Society, 16.1 Preparation of Electrodes:
where such specifications are available.4 Other grades may be 16.1.1 If the calomel electrode is to be changed from
used, provided it is first ascertained that the reagent is of nonaqueous to aqueous bridge, drain out the nonaqueous
sufficiently high purity to permit its use without lessening the solution, wash with water and methanol, then rinse the outer
accuracy of the determination. jacket (salt bridge) several times with 3.0 M aqueous KCl
NOTE 20—Commercially available reagents may be used in place of electrolyte solution. Finally, fill the outer jacket with 3.0 M
laboratory preparations, provided they meet the specifications outlined. aqueous KCl electrolyte solution up to the filling hole.
15.2 Purity of Water—Unless otherwise indicated, refer- 16.1.2 When using the sleeve-type electrode, carefully re-
ences to water shall be understood to mean reagent water as move the ground-glass sleeve and thoroughly wipe both
defined by Type I, II, or III in Specification D1193. ground surfaces. Replace the sleeve loosely and allow a few
drops of electrolyte to drain through to flush the ground-glass
15.3 Alcohol—95 % ethanol (Warning— See 7.3) (see joint and to wet the ground surfaces thoroughly with electro-
Note 5) or 95 % ethanol to which has been added 10 volume % lyte. Set the sleeve firmly in place, refill the outer jacket with
of methanol (see 7.3, Note 5, and Note 6), or absolute alcohol. the 3.0 M aqueous KCl electrolyte solution, and rinse the
15.4 Aqueous Hydrochloric Acid Standard Solution (0.5 electrode with chlorobenzene.
M)—Standardize frequently enough to detect molarity changes 16.1.3 When in use, the electrolyte level in the calomel
of 0.0005, by titrating with standard alcoholic KOH solution electrode should be kept above that of the liquid in the titration
(see 15.7 and Note 7). beaker to prevent entry of contaminants into the salt bridge.

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 D94 − 07 (2012)´1
When not in use, fill the calomel electrode with 3.0 M aqueous the Erlenmeyer flask 25 6 0.03 mL of alcoholic KOH solution
KCl electrolyte solution, leave the bung in the filling orifice, and 256 1 mL of butanone (methyl ethyl ketone) or one of the
and immerse both electrodes in distilled water, keeping the alternative solvents. Connect the condenser to the flask, and
level of the electrolyte above that of the distilled water. heat for 30 min (see 8.1 and Note 11) after refluxing begins.
16.2 Testing of Electrodes—Test when new electrodes are Immediately add 50 mL of ASTM precipitation naphtha
installed, and retest once a month thereafter by standardizing (Warning—See 7.6) (see also Note 12 and Note 13) by
10 mL of 0.5 M alcoholic KOH using 0.5 M aqueous HCl. cautiously pouring the naphtha down the condenser (discon-
nect condenser if mushroom type is used), and potentiometri-
16.3 Maintenance of Electrodes: cally titrate the blank while hot, without reheating, with 0.5 M
16.3.1 Clean the glass electrode at least once every week HCl.
during continual use by immersing in cold chromic acid
cleaning solution (Warning—See 16.3.3) or Nochromix solu- 17.2 Transfer the solution into a 200-mL borosilicate
tion. beaker, taking care to wash the flask with two 10-mL portions
16.3.2 Drain the calomel electrode at least once each week of naphtha (see 7.6).
and refill with fresh 3.0 M aqueous KCl electrolyte as far as the 17.3 Place the titration solution with a magnetic stir bar on
filling hole. Ascertain that crystallized KCl is present. Maintain a magnetic stir plate. Immerse the electrodes as far as possible
the electrolyte level in the calomel electrode above that of the without touching the magnetic stir bar. Adjust the speed of
liquid in the titration beaker of vessel at all times. stirring to maximum possible without causing excessive aera-
16.3.3 Immerse the lower halves of the electrodes in water tion or splattering of solution.
when not in use. Do not allow them to remain immersed in 17.4 Titrate the blank solution with 0.5 M aqueous HCl
titration solvent for any appreciable period of time between added at the rate of 2 mL/min, using potentiometric titrator.
titrations. Although the electrodes are not extremely fragile, Two inflections with corresponding equivalence points are
handle them carefully at all times. (Warning— Cleaning the expected. The first one corresponds to the free KOH (record as
electrodes thoroughly, keeping the ground-glass joint free of VB in 21.1) and the second one to the small amount of
foreign materials, and regularly testing the electrodes are very potassium carbonate (K2CO3) generally present in commercial
important in obtaining repeatable potentials because contami- (KOH) (see Fig. 3).
nation can introduce uncertain erratic and unnoticeable liquid
contact potentials, resulting in nonrepeatable results.) 17.5 A pre-addition of titrant used in the blank to expedite
16.3.4 At the end of the blank titration and between succes- the titration time.
sive titrations a thin film of KCl crystals coats the electrode and 18. Sample
the titrant delivery tip. Use a jet of water from a plastic squeeze
bottle to remove it. Then rinse the electrode by immersion in a 18.1 Make sure that the sample appears homogenous.
beaker full of distilled water for a few seconds. Dry the Choose the size of the sample so that the back-titration volume
electrode by blotting with a paper towel; do not rub the is from 40 to 80 % of the blank, but do not exceed a 20-g
electrode. sample weight (see Note 15).
16.3.5 At the end of a set of sample titrations a mixture of
19. Procedure
KCl crystals and of sample fractions coats the electrode and
titrant delivery tip. Cleaning is performed by immersion in a 19.1 Weigh the specimen to the nearest 0.01 g (record as W
titration beaker containing the following: in 21.1) such as by difference, from a small beaker into the
50 mL of Stoddard Solvent
Erlenmeyer flask. Add 25 6 1 mL of butanone or one of the
38 mL of 2-Propanol alternative solvents (Warning—See 4.1), followed by 25 6
38 mL of Distilled Water
Stir the solution for a time long enough to dissolve the
coating; typically less than 1 min. Remove the traces of
washing solution from the electrode with a jet of water from a
plastic squeeze bottle. Then rinse the electrode further by
immersion in a beaker full of water stirred for a few seconds.
Dry the electrode by blotting with a paper towel; do not rub the
electrode.
16.3.6 The electrode must be held firmly in a steady holder
so that it does not wobble when the liquid is vigorously stirred.
Electrode wobbling creates electrical noise, which interferes
with the determination of the end points, resulting in nonre-
peatable results.

17. Blank Determination

17.1 Make a blank determination concurrently with each set
(see Note 9) (one or more) of samples as follows: Measure
accurately from a buret or volumetric pipet (see Note 10) into FIG. 3 Complete Titration Curve for a Sample

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 D94 − 07 (2012)´1
0.03 mL of alcoholic KOH solution (Warning—see 7.3) routinely analyzed. An ample supply of QC sample material
measured accurately from a buret or volumetric pipet) (see should be available for the intended period of use, and must be
Note 7). homogenous and stable under the anticipated storage condi-
19.2 Dissolve the difficult to dissolve samples such as tions.
lubricants and additive first in 15 to 25 mL of Stoddard Solvent 20.6 See ASTM MNL 7,6 and Practice D6299 for further
(Warning— See 7.10) or xylene (Warning—See 7.9) before guidance on QC and Control Charting techniques.
adding butanone (Warning—See 4.1).
19.3 Connect the condenser to the flask and heat for 30 min 21. Calculation
after refluxing begins (see 8.1 and Note 11). Immediately add 21.1 Calculate the saponification number, A, as follows:
50 mL of ASTM precipitation naphtha (Warning—Do not 56.1 M ~ V B 2 V S !
pour naphtha while the flask is on the hot plate) and (see 7.6) A5
W
(2)
by cautiously pouring the naphtha down the condenser (see
Note 12) (disconnect condenser if mushroom-type before where:
adding the naphtha). 56.1 = molecular weight of KOH,
19.4 Titrate the solution while hot (without reheating) with M = molarity of HCl,
VB = volume of acid used in titrating the blank, mL,
0.5 M aqueous HCl. Follow the titration procedure used for the
VS = volume of acid used in titrating the sample, mL, and
blank (see Section 17) using the potentiometric titrator. Fig. 3
shows a complete titration curve for a sample. The titration of W = sample weight, g.
the sample differs from the blank in that no pre-addition of
titrant is made and the titration conditions are much less 21.2 The first inflection point is due to hydroxide and serves
critical. as the end point in the titration. If the added KOH titrant
19.4.1 The potential readings are fairly constant. The read- contains carbonate contamination, a second inflection point
ing before any addition of titrant is −520 mV. The first may be present (see Fig. 3). If this occurs, use the first
inflection is moderately sharp and takes place around −300 mV. inflection point as the titration end point for the blank (VB) and
The second inflection is extremely sharp and takes place the sample (VS).
around 50 mV.
22. Report
20. Quality Control Checks
22.1 For saponification numbers of less than 50, report the
20.1 Confirm the performance of the test procedure by saponification number to the nearest 0.5 mg KOH/g of sample.
analyzing a quality control (QC) sample that is, if possible,
22.2 For saponification numbers of 50 or more, report to the
representative of the samples typically analyzed.
nearest whole number.
20.2 Prior to monitoring the measurement process, the user
22.3 For electrical insulating oils, report the values to the
of the method needs to determine the average value and the
nearest 0.1 mg KOH/g sample.
control limits of the QC sample (see ASTM MNL 7).6
22.4 Report the saponification test numbers as obtained by
20.3 Record the QC results and analyze by control charts or
Test Methods D94, Method B.
other statistical equivalent technique to ascertain the statistical
control status of the total testing process (see ASTM MNL 7).6
23. Precision and Bias
Any out-of-control data should trigger investigation for root
cause(s). The results of this investigation may, but not 23.1 Based on the round robin conducted using seven lube
necessarily, result in process recalibration. oil additives and automatic transmission fluids and 16
laboratories, the following precision estimates were obtained:7
20.4 The frequency of QC testing is dependent on the
23.1.1 Repeatability—The difference between two test
criticality of the quality being measured, the demonstrated
results, obtained by the same operator with the same apparatus
stability of the testing process, and customer requirements.
under constant operating conditions on identical test material
Generally, a QC sample should be analyzed each testing day.
would in the long run, in the normal and correct operation of
The QC frequency should be increased if a large number of
the test method, exceed 2.76 mg KOH/g saponification number
samples are routinely analyzed. However, when it is demon-
only in one case in twenty.
strated that the testing is under statistical control, the QC
23.1.2 Reproducibility—The difference between two single
testing frequency may be reduced. The QC precision should be
and independent results obtained by different operators work-
periodically checked against the precision listed in the Preci-
ing in different laboratories on identical test material would, in
sion and Bias section of this method to ensure data quality. See
the long run, in the normal and correct operation of the test
Guide D6792 for further discussion of these issues.
method, exceed 10.4 mg KOH/g saponification number only in
20.5 It is recommended that, if possible, the type of QC one case in twenty.
sample that is regularly tested be representative of the samples

6 7
ASTM MNL 7, “Manual on Presentation of Data Control Chart Analysis,” 6th Supporting data have been filed at ASTM International Headquarters and may
ed., ASTM International, W. Conshohocken, PA. be obtained by requesting Research Report RR:D02-1310.

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 D94 − 07 (2012)´1
23.2 Bias—This is an empirical test method and there are no
accepted standard reference materials that can be compared;
hence, bias cannot be determined.
24. Keywords
24.1 additives; lubricating oils; potentiometric titration; sa-
ponification number

APPENDIX

(Nonmandatory Information)

X1. ANALYTICAL HINTS FOR PERFORMING TEST METHODS D94

X1.1 The following is a helpful list of analytical hints for vigorous stirring is essential. Use a polytetrafluorethylene
performing this test method. In no way does it replace the full (PTFE) - 1 coated 2.5 × 0.5 cm stir bar.
text of this test method. X1.1.12 The titration apparatus may need grounding if the
X1.1.1 Do not use scratched or etched Erlenmeyer flasks meter shows erratic movements when approached by an
because KOH is more likely to react with them. Flasks should operator.
be cleaned with chromic acid or some other non-chromium, X1.1.13 Cleaning the electrodes thoroughly, keeping the
strongly oxidizing cleaning solution. ground-glass joint free of foreign materials, and regularly
X1.1.2 Standardize aqueous HCl against alcoholic KOH to testing the electrodes are very important in obtaining repeat-
be able to detect molarity changes of 0.0005. able potentials.
X1.1.3 Standardize alcoholic KOH solution against stan- X1.1.14 At the end of blank titration and between succes-
dard K-H-Phthalate solution. sive titrations, a thin film of KCl crystals may coat the
X1.1.4 During prolonged storage, alcoholic KOH solution electrode and the titrant delivery tip. Use a water jet to remove
becomes discolored, and in such cases, it should be discarded. it, and rinse with distilled water.
X1.1.5 It is preferable to prepare the KOH solution from a X1.1.15 Dry the electrodes by blotting with a paper towel:
commercially available KOH ampule. This type of solution do NOT rub the electrodes.
gives consistent blanks. Since it does not contain carbonate, it X1.1.16 At the end of a set titrations, clean the deposited
does not give multiple inflection points. KCl crystals and sample residue by washing with water, and
X1.1.6 When saponification numbers below one are then rinse the electrodes in a beaker of 50 mL middle distillate
expected, better precision can be obtained by using 0.1 M KOH plus 38 mL isopropanol plus 38 mL water for 1 min. Clean the
and HCl instead of 0.5M solutions. electrodes further with distilled water, and blot-dry with paper
towel.
X1.1.7 Run blanks in duplicate with all samples.
X1.1.17 Hold the electrodes firmly in a steady holder during
X1.1.8 Use the sample masses suggested in Note 15, but do the titration. Wobbling electrodes create nonrepeatable results
not exceed 20 g sample limit. by generating electrical noise.
X1.1.9 Some samples may require digestion for longer than X1.1.18 Two inflection points may be obtained in the
the 30 min period suggested. For unknown samples, the titration curve if the KOH solution is contaminated with a
required optimum period should be checked out. small amount of K2CO3. The first inflection point from KOH,
X1.1.10 For colored dark samples, the potentiometric the second from K2CO3.
method is preferred over the colorimetric method because of its X1.1.19 SAP numbers should not be calculated from TAN
ability to clearly distinguish the end point. numbers. Many times these calculated results are higher than
X1.1.11 Since on titration, two immiscible phases appear the true SAP numbers, due to the presence of free acid by way
and KCl is precipitated, stirring conditions are critical and of hydrolysis of the products.

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 D94 − 07 (2012)´1
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