DIENE VALUE BY MALEIC ANHYDRIDE

ADDITION REACTION
UOP Method 326-82
SCOPE
This visual indicator titration method is for determining maleic anhydride reactivity with a wide variety
of oils ranging from debutanized light hydrocarbon distillates to heavy drying oils.
The method gives a measure of the conjugated diolefin content of the sample. The determination is
somewhat empirical1 since some diolefins may not react completely, while certain compounds other than
conjugated diolefins may be reactive, also. For example, anthracene, many of its homologs, and the
corresponding alkylated compounds react quantitatively as dienes with maleic anhydride. Similarly, certain
vinyl aromatics react. The molecular weight of the conjugated diolefins must either be known or estimated.
Therefore, the results obtained by this method must be carefully interpreted in the light of these specified
limitations.

OUTLINE OF METHOD
Maleic anhydride is refluxed with sample in boiling toluene for 3 hours. The unreacted maleic anhydride
is hydrolyzed to maleic acid, extracted from the reaction mixture, and titrated with 1 M sodium hydroxide.
A blank is run using the same amount of maleic anhydride as charged to the reaction flask. The amount
reported as having reacted with the sample is the net value obtained by titration difference, and from this the
diene value and/or the percent dienes can be calculated.

DEFINITION
Diene Value is defined as the number of grams of iodine equivalent to the amount of maleic anhydride
that reacts with 100 g of sample (on the basis of 2 atoms of iodine per mole of maleic anhydride) under the
specified reaction conditions of 3 hours in boiling toluene solution.

APPARATUS
Bottle, polyethylene, 1000-mL, Sargent-Welch Scientific Co., Cat. No. S-8482-A, or equivalent
Buret, 50-mL, with Teflon plug stopcock, 0.1-mL subdivisions
IT IS THE USERS RESPONSIBILITY TO ESTABLISH APPROPRIATE PRECAUTIONARY PRACTICES AND TO
DETERMINE THE APPLICABILITY OF REGULATORY LIMITATIONS PRIOR TO USE. EFFECTIVE HEALTH AND
SAFETY PRACTICES ARE TO BE FOLLOWED WHEN UTILIZING THIS PROCEDURE. FAILURE TO UTILIZE THIS
PROCEDURE IN THE MANNER PRESCRIBED HEREIN CAN BE HAZARDOUS. MATERIAL SAFETY DATA SHEETS
(MSDS) OR EXPERIMENTAL MATERIAL SAFETY DATA SHEETS (EMSDS) FOR ALL OF THE MATERIALS USED IN
THIS PROCEDURE SHOULD BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION
EQUIPMENT (PPE).

COPYRIGHT 1965, 1982 UOP LLC

ALL RIGHTS RESERVED

UOP Methods are available through ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken PA 19428-2959,
United States. The Methods may be obtained through the ASTM website, www.astm.org, or by contacting Customer Service at
service@astm.org, 610.832.9555 FAX, or 610.832.9585 PHONE.

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Condenser, Liebig, with Ts 24/40 ground-glass joint, Sargent-Welch Scientific Co., Cat. No. S-22655-C,
or equivalent
Flask, Erlenmeyer, 250-mL, with Ts 24/40 ground-glass joint, Sargent-Welch Scientific Co., Cat. No. S34114-F, or equivalent, (2 required)
Flask, volumetric, 1000-mL
Funnel, separatory, 150-mL
Hot plate
Pipets, volumetric transfer, 3-, 5-, 10- and 20-mL

REAGENTS AND MATERIALS

All reagents shall conform to the specifications established by the Committee on Analytical Reagents of
the American Chemical Society, when such specifications are available, unless otherwise specified.
References to water mean deionized or distilled water.
Boiling chips, carborundum, Arthur H. Thomas Co., Cat. No. 1590-D30, or equivalent
Filter paper, qualitative, medium, Whatman No. 1, Sargent-Welch Scientific Co., Cat. No. S-33215, or
equivalent
Maleic anhydride in toluene. Dissolve 60 g of maleic anhydride (mp 52-54 C) in warm toluene. Cool,
transfer to a one-liter volumetric flask, and dilute to the mark with toluene. Allow the solution to stand
at least one day, and filter through a qualitative-grade filter paper before using.
Methyl-tert-butyl ether, (MTBE), or tert-butyl methyl ether, 3 degree boiling range, Fisher Scientific Co.,
Cat. No. E-128, or equivalent
Phenophthalein indicator solution. Dissolve 1 g of phenolphthalein in 100 mL of denatured ethyl alcohol.
Sodium hydroxide, 1.0-M, Fisher Scientific Co., Cat. No. SO-S-266, or equivalent, or weigh 80-90 g of a
purchased 50% sodium hydroxide solution into a beaker, add 200 mL of water and transfer the mixture
to a one-liter volumetric flask. Dilute to the mark with water. Standardize this solution against one
gram of pure maleic acid dissolved in 100 mL of water, using phenolphthalein as the indicator. Store in
a polyethylene bottle.

PROCEDURE
Pipet or weigh a sample of appropriate size, usually 5-20 g, into the dry 250-mL Erlenmeyer flask. With a
volumetric pipet add 20 mL of the filtered maleic anhydride-toluene solution, and a few carborundum chips
to prevent bumping. Lubricate the joint on the condenser with a thin layer of graphite by marking with a
soft pencil. Fit the Erlenmeyer flask to the condenser and suspend the assembly over a hot plate. Adjust the
boiling rate by raising or lowering the assembly. Reflux for 3 hours.
Allow to cool to ambient temperature, pour 5 mL of water into the flask through the top of the condenser,
then gently boil the contents for an additional 15 minutes. Allow to cool to ambient temperature and then
add 5 mL of MTBE through the top of the condenser, followed by 20 mL of water.
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Remove the condenser and carefully transfer the contents of the flask into a 150-mL separatory funnel.
Wash the flask with 20 mL of MTBE in 3 portions, then with 25 mL of water, also added in 3 increments.
Add the washings in each case to the separatory funnel.
Shake the contents of the separatory funnel 4-5 minutes, then let stand until separation of the 2 phases has
taken place. Draw off the aqueous layer into a 250-mL Erlenmeyer flask. Extract the residual liquid in the
separatory funnel 3 times with successive 25-, 10- and 10-mL portions of water, in each case adding the
water extracts to the 250-mL flask containing the aqueous layer drawn off previously. Titrate the combined
aqueous extracts with the standard sodium hydroxide solution, using phenolphthalein as the indicator.
In some cases an insoluble substance forms which makes the recovery of the maleic acid difficult. In the
event this has occurred, break up the insoluble compound with a stirring rod and extract with hot water.
Extract by adding 15 mL of water to the reflux flask, heat to boiling and continue boiling for several
minutes. Cool and transfer the water extract to the separatory funnel. Repeat at least twice more, adding
each extract to the separatory funnel. Continue as in the preceding paragraph.
Run a blank on the reagents in an identical manner to the samples.

CALCULATIONS
Diene value =

(B A )(M )(12.69 )
W

Conjugated dienes, mass-% =

C M (B A )
20W

where:

A
B
C
M
W

= volume of sodium hydroxide solution required to titrate sample, mL

= volume of sodium hydroxide solution required to titrate blank, mL
= molecular weight of conjugated dienes
= molarity of the sodium hydroxide solution
= mass of sample, g

PRECISION
The estimated standard deviation (esd) based on 10 duplicate analyses at each level is shown in the
following table. Duplicate results by the same operator should not differ by more than the allowable
difference shown (95% probability).

Diene
Value

esd

Allowable
Difference

<5
5-50
>50

0.07
0.25
0.40

0.2
0.8
1.3

TIME FOR ANALYSIS

The elapsed time for one determination is 5 hours. The labor requirement is one hour.
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REFERENCES
1. Norton, J. A., Chem. Rev. 31, 319 (1942)
2. Ellis, B. A. and Jones, R. A., Analyst 61, 812 (1936)
3. McKinney, R. S., Hallbrook, N. J., and Rose, W. G., Oil and Soap 19, 141-143 (1942)
4. Official and Tentative Methods Manual of the American Oil Chemists Society, Ka 12-55

SUGGESTED SUPPLIERS
Arthur H. Thomas Co., P.O. Box 779, Philadelphia, PA 19105
Fisher Scientific Co., 1600 W. Glenlake Avenue, Itasca, IL 60143
Sargent-Welch Scientific Co., 7300 N. Linder, Skokie, IL 60077

326-82