INDUSTRIAL OILS AND DERIVATIVES

AOCS Official Method Tl 1a-64

Reapproved 2009

Saponification Value
DEFINITION
The saponification value is a measure of the alkali reactive groups in industrial oils and derivatives and is
expressed as the mg of potassium hydroxide which react with 1 g of the test sample.
SCOPE
Applicable to industrial oils and derivatives.
APPARATUS
1. Erlenmeyer flasksCorning Alkali Resistant, Kimble Resistant or equivalent, 250300 mL.
2. Air condensersminimum 650 mm long.
3. Water bath or a hot platewith variable heat control.
4. Pipet50 mL, volumetric.
SOLUTIONS
1. Hydrochloric acid, 0.5 Maccurately standardized (see AOCS Specification H 14-52).
2. Alcoholic potassium hydroxide (KOH)place a few grams (510) of KOH in a 2 L flask and add from 11.5 liters of 95%
ethyl alcohol (SDA Formulas 30 and 3A are permitted) and boil in a water bath under a reflux condenser for 3060 min.
Distill and collect the alcohol. Dissolve 27 g of potassium hydroxide, low in carbonate, in 1 L of the distilled alcohol.

CautionThere is considerable evolution of heat during the dissolution. Place in a water bath, keeping the temperature
below 15.5C (60F) while the alkali is being dissolved. The solution should remain clear.
3. Phenolphthalein indicator solution1% in 95% alcohol (see Notes, 1).
PROCEDURE
1. Melt the test sample if it is not already liquid and filter through filter paper to remove solid impurities and traces of moisture.
The test sample must be completely dry (see Notes, 2 and 3).
2. Weigh a test sample of such size that the back titration is 4555% of the blank. Add 50 mL of the alcoholic KOH with the
pipet and allow the pipet to drain for a definite period of time.

(a) For natural and synthetic drying oils and their fatty acids weigh approximately 45 grams.

(b) For commercial fatty acids, weigh approximately 34 grams.

(c) A 20 g test sample should be used for materials with a saponification value in the 010 range and a melting point
above 30C.
3. Prepare and conduct blank determinations simultaneously with the test sample, similar in all respects to the test sample.
4. Connect the air condenser and boil gently, but steadily until the test sample is completely saponified (see Notes, 46). Be
careful that the vapor ring in the condenser does not rise to the top of the condenser or there may be some loss of solvent.
5. After the flask and condenser have cooled somewhat, but not sufficiently to jell, wash down the inside of the condenser with
a little distilled water. Disconnect the condenser, add about 1 mL of indicator, and titrate with 0.5 M HCl until the pink
color has just disappeared.
6. Return flask to hot plate, heat to boiling, and again titrate to disappearance of whatever pink color may have developed in
bringing the contents of the flask to a boil. Add this titration volume to that obtained in obtained in Procedure 5.
CALCULATIONS
Saponification Value =

56.10 M volume of titrant, mL of blank volume of titrant, mL of test portion

mass of test portion, g

Where

M = molarity of standardized HCl solution

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INDUSTRIAL OILS AND DERIVATIVES

Tl 1a-64 Saponification Value

PRECISION


Polymerized

Fatty Acids
At a confidence level of 95%
in the range of values of:
1. Two single determinations
performed in one laboratory
shall not differ from the mean
value by more than:
2. Single determinations
performed in different
laboratories shall not differ
from the mean value by
more than:

Fatty Acids
Tallow Coconut
Soybean Linseed

187197

195275

5.5%

1.6%

5.7%

1.7%

NOTES
1. A masked phenolphthalein indicator may be used with off-color material. Prepare by dissolving 1.6 g of phenolphthalein
and 2.7 g of methylene blue in 500 mL of alcohol (SDA Formula 30 or 3A). Adjust the pH with alcoholic alkali solution
so that the greenish-blue color is faintly tinged with purple. Color change is from green to purple when going from acid to
alkali.
2. Drying oils of high viscosity should not be filtered.
3. For preparation of fatty acids from oils see AOCS Official Method Cd 6-38.
4. Some test samples, particularly those difficult to saponify, may require more than 1 hr. This can only be determined by trial.
Clarity and homogeneity of the test solution are partial indicators of complete saponification, but they are not necessarily
absolute criteria.
5. For normal materials, reflux for about 1 hr.
6. For certain synthetic and chemically modified drying oils, run in duplicate using 1 and 2 hr heating periods. If 2 hr heating
gives appreciably higher results than the 1 hr run, additional determinations for 4 and 6 hr should be run to establish the
time required for complete reaction.

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