2.202 Determination of the Saponification Value (S.V.

)
(Fifth Edition : Method II.D.2)
1.

SCOPE

This Standard describes two methods for the determination of the saponification value of animal
and vegetable oils and fats.
The indicator method should be preferentially chosen to the potentiometric method when it is
applicable.
2.

FIELD OF APPLICATION

This Standard is applicable to animal and vegetable oils and fats.

waxes.
3.

It is not applicable to

DEFINITION

The saponification value (S.V.) is the number of mg of potassium hydroxide required to saponify
1 g of fat.
4.

INDICATOR METHOD

4.1.

Principle

Boiling of the sample under reflux condenser with ethanolic potassium hydroxide solution, and
titration of the excess potassium hydroxide with hydrochloric acid in the presence of an
indicator.
4.2.

Apparatus

4.2.1.

250-ml round-bottomed flasks, or conical flasks, made of alkali-resistant glass.

4.2.2.

1-m reflux tubes, or 30 cm minimum in length reflux condensers, to fit the round-bottomed
flasks or conical flasks (4.2.1).

4.2.3.

25-ml volumetric pipette.

4.2.4.

50-ml burette, graduated in 0.1 ml.

4.2.5.

Boiling chips.

4.2.6.

Heating device (water bath, electric hot-plate,...).

4.3.

Reagents

4.3.1.

Potassium hydroxide, approximately 0.5 N solution in 95 per cent (V/V) ethanol.

Use a solution prepared at least 5 days previously and decanted into a bottle of brown
glass, provided with a rubber stopper. The solution should be colourless or straw
yellow {note 1).

4.3.2.

Hydrochloric acid, 0.5 N aqueous solution, accurately standardized.

4.3.3.

Phenolphthalein, 10 g/1 solution in 95 per cent (V/V) ethanol.

4.4. Procedure
Prepare the sample according to 2.001, "Preparation of the sample".
Into the round-bottomed or conical flask (4.2.1) weigh to the nearest 0.005 g about 2 g of the
prepared sample. With the pipette (4.2.3) add 25 ml of the ethanolic potassium hydroxide
solution (4.3.1) and some boiling chips (4.2.5). Fit a reflux tube or reflux condenser (4.2.2).
Boil gently with occasional shaking,
After 60 minutes, stop heating.

Add to the hot solution 0.5 to 1.0 nl of phenolphthalein (4.3.3)

56

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and titrate with the hydrochloric acid solution (4.3.2) until the colour of the indicator
changes.
Carry out two determinations with the same prepared sample.
Carry out a blank test in the same way.
4.5.

Expression of Results

The saponification value (S.V.) is given by the formula :

.

56.1 (Vn - ?,)

m

where V0 is the number of ml of the standardized hydrochloric acid solution (4.3.2) used for
the blank test,
V\ is the number of ml of the standardized hydrochloric acid solution (4.3.2) used for
the test with the fat,
T is the exact normality of the standardized hydrochloric acid solution (4.3.2) used,
m is the mass, in g, of the test portion.
Take as the result the arithmetic mean of the two determinations, provided that the requirement of repeatability 4.6 is satisfied.
4.6.

Repeatability

The difference between the results of two determinations carried out simultaneously or in
rapid succession by the same analyst should not exceed 0.5 per cent of the mean value.
5.

POTENTIOMETRIC METHOD

5.1.

Foreword

This method should be employed instead of method 4 for the determination of the saponification
value of highly coloured oils and fats.
5.2.

Principle

Reflux boiling of the sample with an isopropanolic potassium hydroxide solution and potentiometric titration of the excess of potassium hydroxide by hydrochloric acid in a non-aqueous
medium.
5.3.

Apparatus

5.3.1.

100-ml flasks with ground joints, made of alkali-resistant glass.

5.3.2.

1-m reflux tubes, or 30 cm minimum in length reflux condensers, to fit the flasks
(5.3.1).

5.3.3.

150-ml tall form beakers.

5.3.4.

1000-ml volumetric flasks.

5.3.5.

25-ml volumetric pipette.

5.3.6.

50-ml burette, graduated in 0.1 ml.

5.3.7.

pH meter equipped with glass and calomel electrodes {note 2).

Contact between the
saturated potassium chloride solution and the test solution is made across a sintered
glass or porcelain disc at least 0.3 cm thick.

5.3.8.

Stirrer, preferably a magnetic stirrer.

5.3.9.

Boiling chips.

5.4.

Reagents

5.4.1.

2-Propanol (isopropanol), analytical reagent quality.

5.4.2.

Ethanediol, analytical reagent quality.

5.4.3.

Acetic acid, analytical reagent quality.

5.4.4.

Sodium carbonate, analytical reagent quality.

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5.4.5.

Potassium hydroxide, approximately 0.5 N solution in 2-propanol (5.4.1) : dissolve

35 g of potassium hydroxide pellets in 1000 ml of 2-propanol (5.4.1).

5.4.6.

Hydrochloric acid, 0.5 N accurately standardized solution in 2-propanol (5.4.1).

Pour 42 ml of hydrochloric acid (p =* 1.18) into a volumetric flask (5.3.4) and make
up to the mark with 2-propanol (5.4.1).
Standardization of the solution : e.g. weigh accurately to within 0.0002 g about 0.35 g
of sodium carbonate (5.4.4), which has been previously calcined to constant weight at
270-300C. Transfer to a beaker (5.3.3). Add gradually and cautiously a slight excess
of acetic acid (5.4.3) to decompose the sodium carbonate completely. When the evolution of carbon dioxide has ceased, add sufficient distillated water to dissolve the
sodium acetate formed and evaporate the solution to dryness on a water bath. Dissolve
the residue in 20 ml of 2-propanol (5.4.1). Add 20 ml of ethanediol (5.4.2). Titrate
by whichever of the two methods described below is preferred :
(a)

Insert the electrodes of the pH meter (5.3.7) and start the stirrer (5.3.8).
Titrate with the ^sopropanolic solution of hydrochloric acid (5.4.6) to the
equivalent point {note 3).

(b) Add 2 drops of a 10 g/1 solution of thymol blue in 2-propanol (5.4.1) and titrate
with the isopropanolic solution of hydrochloric acid (5.4.6) until the colour
changes from yellow to pink.
1000 x m0
.
Normality
= =-r
*
53 x aQ
where aQ is the number of ml of the tsopropanolic solution of hydrochloric acid (5.4.6)
used,
mQ is the mass, in g, of sodium carbonate taken.
5.5. Procedure
Prepare the sample according to 2.001.
Into a ground-necked flask (5.3.1) weigh to within 0.002 g about 2 g of the prepared fat. Add
with the pipette (5.3.5) 25 ml of the istfpropanolic potassium hydroxide solution (5.4.5). Fit
the tube or the condenser (5.3.2) and boil gently, with occasional shaking, until the solution
become homogeneous.
Stop heating after 60 minutes. In order to avoid solidification of the saponified solution,
transfer it quantitatively, while still warm, into a beaker (5.3.3) with the aid of three 10-ml
portions of ethanediol (5.4.2). Finish rinsing with 5 ml of 2-propanol (5.4.1).
Insert the electrodes of the pH meter (5.3.7) and start the stirrer (5.3.8). Titrate with the
-ksopropanolic hydrochloric acid solution (5.4.6) to the equivalence point of the neutralization
curve (note 3).
Carry out two determinations on the same prepared sample.
Carry out a blank test in the same way.
5.6.

Expression of Results

The saponification value (S.V.) is given by the formula :

S.V

56.1 x T x (V0
m

where VQ is the number of ml of the standardized isopropanolic hydrochloric acid solution

(5.4.6) used for the blank test,
V\ is the number of ml of the standardized ispropanolic hydrochloric acid solution
(5.4.6) used for the test with the fat,"
T is the exact normality of the tsopropanolic hydrochloric acid solution (5.4.6) used,
m is the mass, in g, of the test portion.
Take as the result the arithmetic mean of the two determinations, provided that the requirement of repeatability 5.7 is satisfied.

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5.7.

Repeatability

The difference between the results of two determinations carried out simultaneously or in
rapid succession by the same analyst should not exceed 0.5 per cent of the mean value.
6.

TEST REPORT

The test report should show the method used.

7.

NOTES

2.

A stable colourless solution of potassium hydroxide can be prepared in the following manner:
reflux 1000 ml of ethanol with 8 g of potassium hydroxide and 5 g of aluminium pellets for
1 hour, then distil immediately. Dissolve the required amount of potassium hydroxide in
the distillate. Allow the whole to stand for several days and decant the clear supernatant liquid from the deposite potassium carbonate.
The solution can also
add 4 ml of aluminium
several days. Decant
potassium hydroxide.

2.

be prepared without distillation in the following manner :

butylate to 1000 ml ethanol and allow the mixture to stand for
the supernatant liquid and dissolve therein the necessary amount of
The solution is ready for use.

It is advisable to store the glass electrode in water or, better still, in a 6/1 (V/V)
mixture of ethanediol (5.4.2) and 2-propanol (5.4.1) for 12 hours preceding the titration. Dry it very gently with a piece of filter paper before use. Immediately after the
titration, rinse with ethanediol, then with 2-propanol, and finally with distilled water.
If the electrode does not function satisfactorily, it may be possible to regenerate it by
immersion for 24 hours in a 1 N solution of hydrochloric acid in 2-propanol. After this
treatment the electrode should be washed with distilled water, then with 2-propanol and with
a 6/1 (V/V) mixture of ethanediol and 2-propanol.
A thick sintered glass or porcelain disc between the saturated potassium chloride solution
and the test solution prevents diffusion currents and parasitic potentials.

3,

Equivalence point/inflexion point

The equivalence point usually corresponds approximately to the reading 10 on the pH scale,
and can be determined graphically by observing the inflexion point on the neutralization
curve. Alternatively, it can be calculated as the figure for which the first differential
of the variation of pH as a function of the amount of isopropanolic hydrochloric acid
solution added reaches a maximum, or the value for which the second differential becomes
zero.

S.M.A.O.M).-- F