LUBRIZOL STANDARD TEST PROCEDURE

TEST PROCEDURE AATM 111A-02

Edition: October 17, 2006
Previous Edition: May 1, 2000

HYDROXYL VALUE

DEFINITION

This method determines the number of hydroxyl groups present which can be acetylated under
the conditions of this test.

Hydroxyl value (or acetyl value) is defined as the number of milligrams of potassium hydroxide
necessary to neutralize the acetic acid which combines on acetylation of 1 gram of sample.

SCOPE

This method is applicable to Noveon products with the following exceptions:

1. Samples which contain hindered (secondary or tertiary) hydroxyl groups will give low
values because there will be incomplete reaction under these conditions. An alternate
method (AATM 111C) should be used in these cases.

2. Significant amounts of water interfere with the analysis by hydrolyzing the reagent before
the acetylation reaction can take place. Samples which contain amounts of water in
excess of 5% may be dried under vacuum prior to analysis.

Excess acetic anhydride is required to drive the reaction to completion. Therefore special
attention must be paid to the ratio of sample size to reagent as set forth in the table shown
in the procedure.

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DESCRIPTION OF METHOD

APPARATUS

1. 250 ml ground neck erlenmeyer flask.

2. Controlled oil bath regulated to maintain the temperature at 95-100°C.
3. Cooling water bath.
4. Class A volumetric pipette calibrated to deliver 5 (±0.03) ml.
5. Balance capable of weighing to the nearest 0.1 mg.
6. Burette (50 ml) Class A with a tolerance of ±0.05 ml.
7. Assorted Mohr pipettes, graduated cylinders, droppers.
8. Magnetic stirrer, stirring bars.

REAGENTS

The acetic anhydride and pyridine used should be pure and dry (analytical reagent grade)
and have as little color as possible.

1. Acetic anhydride -pyridine reagent - 1 volume Acetic Anhydride plus 4 volumes

pyridine - Reagent 1
(note: greater dilution than AOAC to keep titration < 50 ml as specified)
2. Neutralized Ethanol - neutralize Reagent Ethanol to a faint Phenolphthalein pink color
with 0.1N Methanolic Potassium Hydroxide
3. Methanolic potassium hydroxide 0.5N - Commercially available
4. Phenolphthalein Indicator - Commercially available
5. Deionized Water
6. Pyridine, reagent grade

PROCEDURE

All blanks and samples are to be run in duplicate. In-Process samples are to be run in
triplicate.

1. Accurately weigh the specified amount of sample into a 250 ml Erlenmeyer flask
according to the following table and record weight to the nearest 0.1 mg.
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Sample ml
Hydroxyl value Size Reagent 1

0 -20 10g (±0.1) 5 + 5 ml pyridine*

20 - 50** 5g (±0.1) 5
50 - 100 3g (±0.1) 5
00 - 200 2g (±0.05) 5
200 - 250 1g (±0.05) 5
250 - 300 0.5g (±0.05) 5
300 - 350 0.5g (±0.05) 5
350 - 450 0.5g (±0.05) 5
450 - 600 0.5g (±0.05) 5
600 - 700 0.5g (±0.05) 5

* the 5 ml pyridine is added only for samples with Value of 0 - 20

** for DOE-120 use 5 g

Exceptions: Vilvanolin CAB, Vilvanolin LFA LO, Vilvanolin P, Modulan, MP-142: use 2 g

2. Into each flask, using Class A volumetric pipette, accurately pipette the specified
amount of acetic anhydride- pyridine reagent and attach an air condenser. At the same
time set up reagent blanks, containing no sample but the corresponding volume of
reagent.
3. Place the flasks in the 95-100°C oil bath, immersing to the liquid level. Swirl vigorously until
all the solid material is melted and is thoroughly mixed into the solution.
4. Continue heating at 95-100°C for one hour, swirling the flasks frequently to insure uniform
reaction.
5. Remove the flasks from the oil bath and cool for at least ten minutes in a room
temperature shallow water bath.
6. To each flask, add by Mohr pipette through the air condenser 10 ml of water. Swirl
vigorously to mix thoroughly.
7. Return the flasks to the oil bath for 10 minutes to complete the hydrolysis of the excess
acetic anhydride reagent. Swirl at frequent intervals.
8. Cool in the water bath to room temperature for at least ten minutes.
9. To each flask, add a stirring bar and add by cylinder 25 ml neutralized alcohol (around half
through the air condenser), remove the condenser and use the rest to wash down the
sides of the flask. Using a dropper, add 1 ml of phenolphthalein solution.
10. Fill burette and titrate the samples and the blanks using methanolic potassium hydroxide
to a faint pink color. Stir thoroughly during the titration. Read the burette to two decimal
places.
11. In the case of samples which are solid at room temperature place in the ultrasonic bath
until the pink color remains. At that point the flask may be heated under hot water to
release any remaining occluded traces of acid and the titration may be completed.
NOTE: Early application of heat during the titration may drive off some of the acetic acid
and an incorrect titration will result.
12. Determine the acid value of the sample (AATM 109).
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CALCULATIONS

Hydroxyl value = (ml KOH blank - ml KOH sample) X N KOH X 56.1 + Acid Value
g sample

REFERENCE

AOAC Method 965.32 First Action 1965, Final Action 19