LUBRIZOL TEST PROCEDURE

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TP-AATM-111C-02
Edition: October 17, 2006
Previous Edition: May 29, 2000


Hydroxyl Value (Hindered Hydroxyls)

DEFINITION

This method determines the number of hydroxyl
groups present which can be acetylated under the
conditions of this test. It is useful for determining
hindered (secondary or tertiary) hydroxyl groups
which are not acetylated in the pyridine - acetic
anhydride system described in Lubrizol Test
Procedure TP-AATM-111A-02.

Hydroxyl value is defined as the number of milligrams
of potassium hydroxide necessary to neutralize the
acetic acid which combines on the acetylation of one
gram of sample.


DESCRIPTION OF METHOD

A specified weight of sample is acetylated by heating
at 70-72C for one hour with a measured amount of
acetic anhydride in an ethyl acetate solution which
contains p-toluenesulfonic acid as catalyst. The
hydroxyl groups react with the acetic anhydride to
form the acetate and free acetic acid. At the end of the
reaction period, all the unconsumed acetic anhydride
is hydrolyzed to free acetic acid by the addition of
water (and pyridine), and heated for ten minutes to
insure complete hydrolysis. The sample and a
corresponding reagent blank which has been run at
the same time are titrated with 0.5N methanolic
potassium hydroxide. A mixed indicator consisting of
cresol red and thymol blue is used for the titration.

The difference between the blank and the sample
titrations represents the amount of acetic acid
consumed by the sample. The hydroxyl value is
calculated (by definition) as the equivalent
milligrams of potassium hydroxide per gram of
sample. The amount of potassium hydroxide
consumed by the free acids present in the sample
must be included in the calculations.

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.


APPARATUS

1. 250 ml ground neck erlenmeyer flasks, TS
24/40, with air condenser.
2. Controlled oil bath regulated to maintain the
temperature at 70-72C.
3. Cooling bath. ( Shallow water-filled pan).
4. Class A volumetric pipette calibrated to deliver
5 (0.03) ml or appropriate dispenser.
5. Analytical 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.


Lubrizol Test Procedure TP-AATM-111C-02
Hydroxyl Value (Hindered Hydroxyls)
Page 2 of 3



REAGENTS AND SOLUTIONS

1. Acetic Anhydride Reagent - 60ml acetic anhy-
dride, 7.2g p-toluenesulfonic acid and 180ml ethyl
acetate.
2. Pyridine-water solution - approximately 3ml
pyridine for each 1ml water.
3. Cresol Red-Thymol Blue Indicator Solution - 1 part
Cresol Red (0.1% in H2O)+3 parts Thymol Blue
(0.1% in ethanol).
4. Methanolic potassium hydroxide 0.5N -
commercially available.


PROCEDURE

It is recommended that all blanks and sample be run
in duplicate.

1. Accurately weigh the specified amount of sample
into a 100 ml acetylation flask according to the
following table and record weight to the nearest
0.1 mg.

Hydroxyl value Sample Size
0-20 5.0g (0.1)
20-100 2.0g (0.1)
100-150 1.5g (0.1)
150-200 1.0g (0.05)
200-250 0.75g (0.05)

2. Into each flask, accurately add 5 ml of acetic
anhydride 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 70-72C 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 70-72C 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 through the air condenser, using a
Mohr pipette, add 2 ml of deionized water.
7. Using a Mohr pipette, add 10 ml of pyridine-water
solution (reagent) to each flask through the air
condenser.
8. Swirl vigorously to mix thoroughly. Return the
flasks to the oil bath for 10 minutes to complete
the hydrolysis of the excess acetic anhydride
reagent. Swirl at frequent intervals.
9. Remove the flasks from the oil bath and place
them in the cooling bath for at least ten
minutes.
10. Remove the condenser. Using a dropper, add
1 ml of the indicator solution. Add a magnetic
stirring bar.
11. Fill burette and titrate the blanks and the
samples using 0.5 N methanolic potassium
hydroxide.

NOTE: The end point color of the blank is a
bold blue color with no trace of red when
viewed against the light.

The end point color of the sample will vary to
some extent depending upon the color of
the test sample. The final color is usually a
deep gray blue with the disappearance of
the last traces of red color marking the end
point. The sample should be heated under
hot water to release any remaining occluded
traces of acid just before the end of the
titration.

An alternate method may be used by adding
(by pipette) 10 ml pyridine to each flask just
before titration. This is found to be preferable
by some analysts who feel that it improves the
sharpness of the end point. Either method of
titration may be used only if all samples and
blanks receive identical treatment.

12. Read the burette to two decimal places and
record the mls used by all samples and blanks.
13. Determine the acid value of the sample (AATM
109).


Lubrizol Test Procedure TP-AATM-111C-02
Hydroxyl Value (Hindered Hydroxyls)
Page 3 of 3



CALCULATIONS

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

PRECISION

Product Average Std Dev Coeff of Var df Cm

Cremerol 35.01 1.186 3.378 16 *

* Specification is D&R