Composition and Analysis of

Dehvdrated Castor Oil

J

GEORGE W. P R I E S T AND J. D . VON MIKUSCH

Woburn Degreasing Company of New Jersey, Harrison, N. J.

N T H E dehydration of castor oil, one hydroxyl group and

a neighboring hydrogen are removed from the carbon

chain of the ricinoleic acid to form a new double bond.
Ricinoleic acid already contains one double bond, and dehydration may lead to the formation of two new products,
one of them containing two double bonds in isolated position, the other containing two conjugated double bonds.
The two possible reactions may be written as follows:

rH---&Hl

H H H H H

I
I

CHS(CH~)~C=C-C-C=C-(CH~)~COOH+ HSO

(1)

(9,12-linoleic acid)

H H H H H
CH,(CH2),~-~-~-b=b-(CHl)rCOOH
I
l
l
--+

H H H H H

CH,(CHe),~-~=~-~=~--(CH2)rCOOH
H20

(2)

(9,ll-linoleic acid)

D e t e r m i n a t i o n of Conjugated Portion

It has been generally assumed that the second one of these

two reactions is predominating in the dehydration process
over the first one and that from 75 to 90 per cent of the product
consists of 9,ll-linoleic acid.
This assumption apparently originated with the patents
(26, 27) and numerous publications (24, 25) by Scheiber in
which he claims that 90 per cent of the acids in the commercially produced triglyceride consists of the conjugated compound. At the time this claim was made by Scheiber, no
analytical method was available to determine quantitatively
the percentage of conjugated double bonds present in an oil,
although qualitative tests were used to demonstrate their
presence, such as coagulation with stannic chloride and the
increase of iodine value (Wijs) upon prolonged exposure up to
10 days. Although such tests showed beyond doubt that appreciable amounts of the conjugated isomer were formed,
they did not represent quantitative analytical methods as

would have been required either to prove or disprove

Scheiber's contention that reaction 2 accounted almost exclusively for the process.
When Boeseken and Hoevers ( 5 ) reacted the main fraction
of the distilled ethyl esters of dehydrated ricinoleic acid with
excess maleic anhydride a t 135" C. for one hour, they found
that enough of the anhydride had disappeared to account for
7 5 per cent of conjugated double bonds in the mixture. This
was apparently determined in only one instance. It is understandable that this result was then assumed by others
to indicate that there is generally a preferential formation of
conjugated systems in the dehydration of castor oil and its
fatty acids, although Smit (28), in his extensive studies on
linoleic acids, complains of low yields of the 9,11 isomer.
Only since 1936, when first Kaufmann and Baltes (18) and
then Ellis and Jones (11) worked out the practical application of the diene synthesis to the analysis of oils, have quantitative methods for determining the proportion of conjugated
acid present been available.
A study has since been conducted in this laboratory with
the new methods and their application to dehydrated castor
oils.
I n the first phase we were concerned with the selection of
one of these two methods. The Kaufmann method was found,
as previously reported @ I ) , to show less dependence of the
results on the weight of sample analyzed than the Ellis
method. Furthermore, the diene values given by the Ellis
method were generally several points higher than those found
by the Kaufmann method, and in some cases the former could
be proved definitely to be in error. Diene values of 3.9 and
4.2, for instance, resulted with a sample of thoroughly hydrogenated castor oil with an iodine value of 1.2 which could not
possibly contain the indicated amount of conjugation. The
conclusion that in the Ellis method the maleic anhydride reacts with other groups, such as hydroxyl groups, has since
been confirmed by Bruce and Denley (8) and by Bickford,
Dollear, and Markley ( 3 ) .
The latter authors (4) investigated the effect of hydroxyl
groups on the diene value determination by the Ellis method
and by the Kaufmann reflux and sealed-tube methods in
toluene solution. The original Kaufmann method ( I @ , however, prescribes the use of maleic anhydride in acetone solution and with this method the same sample of hydrogenated
castor oil, which showed a diene value of 3.9 and 4.2 with the
Ellis method, gave only 0.23 (21). This and similar results
indicated that with the original Kaufmann method, the tendency of maleic anhydride to react with the hydroxy group
is very small, if not absent altogether. However, even if the
diene value of 3.2, which Dollear, Bickford, and Markley
found on castor oil in toluene solution, is due to an unavoidable effect of its hydroxyl number of 166, i t is likely that the

1314

OCTOBER, 1940

INDUSTRIAL AND ENGINEERING CHEMISTRY

less than 10 per cent of these hydroxyl groups remaining in

dehydrated castor oil will not affect the results appreciably.
The original form of the Kaufmann method was therefore
selected for the analysis of dehydrated castor oil, but a few
variations in laboratory detail were found advisable. Since
this method, as now used in this laboratory, is believed to be
best suited to dehydrated castor oil, it is given fully a t the end
of this paper, although some of i t is merely a repetition of the
original procedure by Kaufmann and Baltes. This procedure
was used for the analysis of dehydrated castor oils made by
various dehydrating processes and by various manufacturers.
Among the oils analyzed were some made by the Scheiber
process in Europe-i. e., by way of the fatty acids which are
esterified after the dehydration process-and others made directly from the oil. Numerous determinations were carried
out on both plant batches and laboratory samples of dehydrated castor oil made directly from the oil by catalysis (99).
Some of the results obtained with representative samples of
each of the better known dehydrated castor oils now on the
market are tabulated together with other analytical data.
Unfortunately no sample of the dehydrated castor oil made
under the recent patent of Muenzel (do), in which it is also
claimed that all ricinoleic acid is converted into 9,ll-linoleic
acid (octadecadienoic acid) was available. Instead, a laboratory sample made with 4 per cent tungstic acid following the
procedure described in the patent has been included in the
table to take its place.

Contrary to the common belief that dehydrated castor oil consists mostly of the
triglyceride of 9,ll-linoleic acid, i t is found
to contain more of the 9,12-linoleic acid
than of the former.
The diene values of commercial oils, as
well as of samples made by various methods
in the laboratory, range from 15 to 22, indicating a content of 17.3 to 25.4 per cent of
the 9,11 isomer i n the glycerides. From
these diene values i t is calculated that only
one fourth to one third of the dehydration
reaction leads to the formation of conjugated double bonds.
Analytical data are listed for a number of
commercial dehydrated castor oils, including both raw oils and oils processed to
higher viscosjties. The latter have lower
acetyl values than the raw oils; however, i t
is shown that the designation completely
dehydrated for the bodied oils, as opposed
to the raw oils, is not justified. An analysis of the distilled fatty acids, which are
found to contain a somewhat greater proportion of conjugated double bonds than
the oils, is included.
The application of the customary analytical methods to dehydrated castor oil is
discussed, and some changes are recommended.

1315

The surprising results of the diene value determinations

were as follows: (a) The conjugated portion (9,ll-linoleic
acid) in the oil is by no means predominating but actually
greatly exceeded by the isolated portion (9,12-1inoleic acid).
( b ) All oils tested showed diene values in approximately the
same range although in some cases these oils had been made
by entirely different methods; the values for commercially dehydrated castor oil of good quality averaged from 15 to 22
and those for the commercially distilled fatty acids from 20
to 28, although in each case somewhat lower values were occasionally encountered.
Since the theoretical diene value for 9,ll-linoleic acid is
90.7 and that of its triglyceride is 86.6, a diene value of 15 to 22
indicates the presence of 16.5 to 24.3 per cent of the acid, or of
17.3 to 25.4 per cent of its glycerides. Diene values of 20 to 28,
as found in the distilled fatty acid sample, accordingly show
that they contain about 22 to 30.9 per cent of the conjugated
isomer.
Although the values given for the oil have been determined
on the raw oil samples, wherever these were available, the
possibility must be taken into consideration that the conjugated portion originally present may have been slightly higher
and some of these double bonds may have been lost by polymerization during the dehydration process. This, however,
could account for only a few points a t most because the low
viscosity of F to G on the Gardner-Holdt scale, as obtained
in the case of good-grade raw oils, shows that the oil is only
slightly polymerized. Furthermore, if any polymerization
with loss of diene value took place during the dehydration
process, the total iodine value of the product should also be
lower than that calculated from the decrease in acetyl value.
Actually, as will be shown below, the Hanus iodine number
which measures the total unsaturation of dehydrated castor
oil checks fairly closely with the calculated value.
I n the case of raw dehydrated castor oil, the diene value as
determined by the Kaufmann method must therefore be accepted as evidence of practically the total share of reaction 2
in the dehydration process. However, although the diene
values of the bodied oils-.
g., G and H of Table I-are lower
than those of the raw oils, they are higher than would be expected from the decrease in iodine value during bodying.
This permits the conclusion that new conjugated double
bonds are formed in bodying, a phenomenon which has long
been believed to take place in the bodying of nonconjugated
drying oils and recently proved in the case of linseed oil by
means of a spectroscopic method by Bradley and Richardson (6).
As a confirmation of the correctness of our results with the
diene value determination, a recent publication by Forbes
and Neville ( I d ) may be quoted where a diene value of 16.66
(Kaufmann method) was found for a sample of castor oil
which had been dehydrated with 16 per cent of kaolin. A
diene value of 16.66 indicates that 19.2 per cent of the total
acids present were conjugated.
A study by Brod, France, and Evans (7) on the polymerization of the ethyl esters of dehydrated ricinoleic acid, in which
the diene value of the middle portion of the distilled esters
was found to be 28 (Ellis method), further confirms our conclusions. Since the theoretical value of the ethyl ester of
9,ll-linoleic acid (molecular weight, 308) is 82.4, a value of
28 indicates that 34 per cent of this compound was present
in the mixture of pure esters. This would correspond to about
30 per cent of 9,ll-linoleic acid in the distilled fatty acid mixture from dehydrated castor oil, since these also contain the
linoleic, oleic, and saturated fatty acids from the original castor
oil, amounting to about 12 per cent (IO). Their value, therefore, is in agreement with the results obtained by us on the
commercial fatty acids which, as stated, were found to contain between 22 and 30.9 per cent of the conjugated isomer.

INDUSTRIAL AND ENGINEERING CHEMISTRY

1316

SECTION
OF Casma

OIL

The value found by Brod and collaborators, therefore, does

not eonlirm the figure given by Boeseken (6)quoted ahove,
although the same procedure for the dehydration of the acid
and for the preparation of the esters was apparently used in
both cases.

Determination of Total Unsaturation

As i n l h e case of tung oil and other compounds containing

conjugated double bonds, it could be expected that dehydrated
castor oil will he only partially saturated with halogen in the
customary treatment with Wijs solution. Gelber and Boeseken (14) have already found that 9,ll-linoleic acid gives a n
instantaneous Wijs number of 91, which shows that i t behaves
similarly to other conjugated systems in this respect. They
observed that in the case of both eleostearic and 9,ll-linoleic
acid the theoretical iodine value is obtained only upon treatment with large excess and on prolonged standing with the reagent for several days. Excess of reagent alone, however, is
not sufficient to obtain theoretical values for tung nil, as
shown in great detail by Ho, Wan, and Wen (16). Even with
over 400 per cent excess of Wijs solution, only two of the three
double bonds in eleostearic acid are attacked if the time is
short and the temperature low (19). It could similarly be expected that in the case of dehydrated castor oil not all of the
conjugated portion would take up halogen under the ordinary
Wijs procedure, even if a large excess of reagent was used.
The fact that the iodine value of dehydrated castor oil increases steadilv on Drolonzed exmsure durina- 10 days or more
(24) confirms this.
If Wijs reagent reacts primarily with only one of the two
double bonds in 9,ll-linoleic acid, it is obvious that tbis
method alone is not suited for studying the dehydration of
castor oil. Suppose that in comparing two dehydrated castor
oils made with different catalysts, one is found to have a Wijs
iodine value that is 10 points lower than the other. The
lower value may then be due to one of two causes. Either the
catalyst used in this case was less efficient than the other and
the dehydration was not so complete, or the dehydration

VOL. 32, NO. 10

DEnYnaaTloN PLANT
proceeded to a greater extent according to reaction 2 and
formed more conjugated double bonds than in the other case.
Since the two oils may differ from each other as a result of
both nf these causes, the conclusions that can be drawn by
comparing Wijs numbers alone are exactly nil; i. e., they do
not answer the question either as to the total number of new
double bonds formed or as to the quantity of conjugated ones
alone.
Obviously it is necessary to use a method with dehydrated
castor oil which will react as nearly as possible with all of the
double bonds present, isolated as well as conjugated. A few
tests with the Kaufmann iodine (17) and the RosenmundKuhnhenn methods (e$) showed that both of these, like the
Wiis method. eave values which did not indicate the total
unsaturation.
The total unsaturation. on the other hand, can be determined accurately by a' quantitative hydrogenation and
possibly by the method of Rossmann ($3). Furthermore, it
was found in this laboratory (19) that standard Hanus solution (g), when applied in excess of a t least 400 per cent for one
hour a t 20" C., will give reproducible constants which correspond fairly closely to the total unsaturation as calculated
from the drop in hydroxyl value during dehydration.
To demonstrate this, the increase of iodine value expected
from the decrease of acetyl value is calculated for sample A
(Table I). The castor oil used had an acetyl value of 145.5
and an iodine value of 85.0. The hydroxyl value, as calculated
by
. I

hydroxyl value

acetyl value

- 0.00075 acetyl value

was therefore 163.1. The dehydrated oil had an acetyl value

of 13.5-i. e., a hydroxyl value of 13.7. The decresse in hydroxyl value then was 149.4, which expresses milligrams of
potassium hydroxide equivalent to the hydroxyl groups in 1
gram of oil and corresponds to 47.8 mg. of water removed
during dehydration. One gram of the castor nil originally
added 0.850 gram of iodine. After dehydration 1 - 0.0478, or

OCTOBER, 1940

INDUSTRIAL AND ENGINEERING CHEMISTRY

0.9522 gram of oil should add the same 0.850 gram of iodine
plus an additional (0.0478 x 126.9 X 2)/18, or 0.674 grami. e., a total of 1.524 grams; therefore, the total iodine value
Bhould be 1.524/(0.9522 x loo), or 160.1. The Hanus value
found was 155.5, within 4 points of the ealculated total. In
most cases where a similar calculation was carried out, the
Hanus number was found to lie close to, although usually a
few points below, the theoretical unsaturstion. It should be
borne in mind that in oils with only isolated double bonds,
such as linseed, the Hanus numbers are a few points below
the theoretical. It appears, therefore, that the Hauus number determination represents a rapid method for determining,
a t least approximately, the total unsaturation present, irrespective of the arrangement of the bonds in the isolated or
conjugated position.
Although the Wijs uumher alone, on the other hand, is of
no value in comparing dehydrated castor oils, it may be u s e
ful if determined together with the Hanus number. In order
to obtain constant and reproducible results with Wijs solution on dehydrated castor oil, it is necessary to use about 400
per cent excess of reagent, just as in the Hanus number determination. This was shown by Forbes and Neville (IS), who
also noticed that the iodine values thus obtained were considerably lower than those calculated from the amount of
water formed in the dehydration of castor oil (12). Therefore, if the Wijs number is determined on dehydrated castor
oil, using about five times as much reagent as the oil will
consume, constant values are obtained which lie about 10 to
15 points below the Hanus number.
Since oils of the linseed type, which contain only isolated
double bonds, always give a Hanus number which is several
points lower than the Wijs number. i t is evident that the

1317

and other condensation reactions also muse a reduction of the

acetyl value. Any conchision as to the completeness of the
dehydration derived from this value is therefore subject to
the condition that such side reactions have been avoided
during the dehydration of the oil. Among the various methods available for the determination of the acetyl value, the
Andr4Cook procedure mommended by the American Oil
Chemists Society (1) gives the most reproducible results.
Unlike most other methods i t is not materially disturbed by
the presence of any free acids in dehydrated castor oil, 88
shown by the low value obtaiued with the distilled fatty acids
in column I , Table I.

DEHYDRATED
C A ~ TOIL
~ RFILMSHOWINQ
FROSTINO,
TYPICAL
WHENTWNQOIL AND OTHEB Oils WITB Comwnnmn DOWBLE
Boxins ARE DRIEDWITAOUT DRIERS

It had been noticed that in dehydrating eastor oil, even with

the strongest catslysts, the acetyl value does not drop to
zero even on greatly prolonged treatment. A residual value
is instead approached, which in no case has been found to be
below 10 for raw dehydrated castor oil. All analyses which
were made on oils dehydrated by different methods and by
various manufacturers (including those of the samples listed
in Table I) corroborate this observation. The acetyl value of
high-quality raw oil was found to average from 12 to 20.
Since most other raw drying oils have also definite acetyl
values, frequently in the neighborhood of 10, this residual
acetyl value of raw dehydrated castor oil seems immaterial.
This is especially true since the oil is not customarily used in
the raw state but is first bodied to a higher viscosity. In the
bodying processes used commercially by the manufacturers
TABLE
I.
Oil.

Acid value
88pni6astio value
Iodine vdue ( H e n u )
Iodine value (Wiia)
Diene value (Ksufmaon)
Acetyl due
VisoositY (Gerdnei)
Color (HaIliad
Speoific ersvity (25 C.)
Hersbromide d u e
Moisture. %

A
1.8

190.4
155.5

141.2
21.4

13.5
F-0
1-2L
0.9305
0.0
0.0

ANALYSIS OF

DEHYDRATED
CASToR OILS AND
C

B
2.0
190.0
147.1

4.4
192.7
143.8

15.4
14.3

15.5
24.8

1
0.935

Z3L

...

...
...

...

...
...
...

D
13.1
190.9
157.0
145.8
21.9
16.1

E F

2L

...
...

I . .

E
17.0
194.2
152.9

...

17.8

19.1
P
1-ZL

...
...

...

FA-

ACIDS

1.56

3.4
191.9

4.8
191.6

1j.i:6
17.6
10.6

1ii:s

iii:i

192.0

M
2L
0.9365

....
0.0

12.7
6.7
23
ZL-2
0.9505

....

0.0

12.7
9.2
22-23
IL-l

...
...
...

I
195.9
197 3
105.2
153.0
26.5

1.2

<A
12Y-1.3Rh
0.903
0.0
0.45

* A = tyoiaal analysis of s rs- dehydrated Omtor oil made direatly from 088t.i oil type 1. B = aemple of a rsw dehydrated owtor oil, t y w 2. C = sample
of B raw dehydrated 088toi ail type 3; D = asmple made in laboratory according td Muen&a patent (so). E = sample of Euro~eaooil Fad6 by Sohsiber
Proce?e, type 4; F = tyPi0.i analysio of a varniah oil ( d i ~ h t l ybodied) made from raw oil of type 1 : C 2 typical d ample of B hsavy-bc+ed oil made from
r*w 011 of tYDe 1: H = 8smple of hs%vy-badiedoil of different wigin. type 5; I = typioal sample of B distilled fatty aaad made aommerozallv for the manufscture of alkyd resina from raw oil of type 1.
b Lovibond w101.

1318

INDUSTRIAL AND ENGINEERING CHEMISTRY

of dehydrated castor oil, the acetyl value drops to still lower

values as illustrated by samples G and H in Table I. This
lowering of the residual acetyl value is, however, not limited
to these special processes but also occurs when the oil is
bodied by the conventional methods. To show this, a gallon
sample of a raw dehydrated castor oil with an original acetyl
value of 23.5 was bodied under carbon dioxide at atmospheric
pressure a t 575 F. A sample taken when the viscosity read
U on the Gardner scale had an acetyl value of 19.0; and when
the viscosity had reached Z,the acetyl value had dropped to
12.1.

VOL. 32, NO. 10

value of 11.4. If this assumption that the residual acetyl

value is due to dihydroxystearic acid can be verified, the term
completely dehydrated, when referring to the ricinoleic acid
of castor oil, would be justified for all oils that have reached
the minimum acetyl value which is not further reduced by
the dehydrating agents now used in the process.

Share of Reactions 1 a n d 2 i n the Dehydration

If the acetyl values are converted into hydroxyl numbers in
the usual manner, the latter may be subtracted from that of
the castor oil used to give the milligrams of potassium hydroxide equivalent t o the water involved in the dehydration
of 1 gram of the latter. From this, the diene value may be
calculated which the resulting oil should have if, for each
molecule of water removed, one new double bond in conjugated position were formed. I n the example previously used
for the calculation of the theoretical total unsaturation
(sample A , Table I), it was found that 0.9522 gram of oil
should add 0.674 gram more iodine after dehydration than
before, because of the formation of new double bonds. If
these new bonds were all in the conjugated position, the
diene value, expressed as centigrams of iodine absorbed per
gram of oil, should be:
100 X 0.674 = 70,8
0.9522

FIGURE
1. AMPOULEFOR DIENEVALUEDETERMNATION

The processed oils of higher viscosity which have recently

been supplied by the manufacturers of dehydrated castor oil,
such as samples F, G, and H in Table I, are sometimes referred to as 100 per cent dehydrated (9),as opposed to the raw
oils which have been on the market in the United States for a
number of years. This differentiation is apparently based on
the somewhat lower acetyl value and possibly on the better
drying exhibited by oils of higher viscosity. However, since
it has been customary for a long time to body any drying oil
to improve its drying properties, and since it has been shown
that the decrease in acetyl value is not limited to these special
processes, the justification of the term completely dehydrated for the processed oils as opposed to the raw oils is
questionable.
Although these processed oils offer many advantages over
both raw oils and open-kettle-bodied oils, their chemical difference from the former is essentially one of the degree of
polymerization and from the latter, one of lower acidity and
lighter color.
The peculiar behavior of the acetyl number of rapidly approaching a value in the neighborhood of 10 rather than of 0
during dehydration seems to indicate that some of the
hydroxyl groups present are more resistant toward dehydration than the rest of them. This difference in their behavior
may be explained by the assumption that they belong either
to an isomer of ricinoleic acid or to a different hydroxy compound altogether. Although no direct evidence as to the
nature of such a compound is available to date, the authors
are inclined to believe that it may be dihydroxystearic acid;
as much as 3 per cent of the acid had been found in castor oil
( I @ , and it might also, conceivably, be formed during dehydration by the action of HOH i n status nascendi on the
double bond of ricinoleic acid. A dehydrated castor oil containing 3 per cent dihydroxystearic acid would have an acetyl

Since the diene value found for thesample, however, was only
21.4, reaction 2 took place only to the extent of 30.2 per cent,
whereas reaction 1, in which the isolated linoleic acid is
formed, accounted for the remaining 69.8 per cent. Since
many of the other samples analyzed had lower diene values,
the share of reaction 2 in the dehydration averages more
nearly one fourth of the total, although i t seems to approach
one third in a few cases, especially in the distilled fatty acids.
On the basis of the composition of castor oil (10) and the
analytical constants determined on the thoroughly dehydrated
products, the limits in composition of unbodied dehydrated
castor oil may be estimated as shown in the following table,
where the components are expressed in per cent of the total
fatty acids:
Saturated acids
Hydroxy acids
Oleic acid
9 12-Linoleic acid
9:ll-Linoleic acid

0 5- 2 . 5 %
3 - 8
715-10..5
09-64
17-26

Other Analytical D a t a
Other values, such as viscosity, acid number, saponification value, color, specific gravity, refractive index, unsaponifiables, ash, moisture, etc., may all be determined by the usual
methods, no special precautions being required with dehydrated castor oil. A number of these values were determined on the oil samples discussed and are included in
Table I.
The viscosities tabulated are those obtained by comparison
with the standards of the Gardner viscometer; the colors
were read with the Hellige comparator.
The acid values were determined by dissolving 10 grams of
the oil in 100 ml. of a 50-50 mixture of benzene and 95 per
cent ethyl alcohol and titrating with 0.168 N alcoholic potassium hydroxide solution against phenolphthalein.
For the saponification values the method recommended by
the American Oil Chemists Society was used (1).
The specific gravities were determined in a Hubbard
0.1 c.
pycnometer a t 25
The viscosity determinations showed that many of the
better raw oils were below an H viscosity; they never lay
f

OCTOBER,

1940

INDUSTRIAL AND ENGINEERING CHEMISTRY

below F except in a few cases where the acid value was highere. g. in sample D. It should be kept in mind that castor oil
may be bodied to various viscosities without the use of a
proper dehydrating process. A certain amount of dehydration will then Occur simultaneously with the polymerization,
but the resulting oil has poor drying properties
to
the completely dehydrated castor Oil. Such bodied castor Oils
may range in viscosity from about K upward. However, they
have never been observed to have lower viscosities than K,
and a purchaser of low-~scosityoil will therefore be able to
ascertain on the basis of viscosity alone that the product is a
(dehydrated castor oil and not a bodied castor oil,
whereas an unknown modified castor oil of higher viscosity
may represent an oil of the latter type as well.
The acid value in three of the raw oils and in three of the
processed oils listed was below 5, although many raw oil
samples analyzed were below 3. The saponification values
ranged from 190 t o 195; a closer agreement could hardly be
expected in view of the considerable variation in the value for
castor oil, which Jamieson (16) lists as ranging from 177 to 187.
It is further noted that the saponification Value Of the prOCessed oils lie close t o those of the raw oils, which has been
found in this laboratory to be the case for open-kettle-bodied
dehydrated castor oil as well.

Determination of Diene Value on Dehydrated

Castor Oil
The method described here is essentially the same as that first
used by KP,ufmann and Baltes (IS) except for a few changes in
laboratory details which have been found advisable in the analysis
of dehydrated castor oil.
The reagents used were c. P. acetone; a solution of approximately 10 grams of c. P. maleic anhydride in 1 liter of c. P. acetone; standardiz-d 0.1 N potassium hydroxide solution (any
standard caustic solution of suitable concentration available in
the laboratory, such as is used for acid number determination,
may be substituted); 1 per cent solution of phenolphthalein in
alcohol; and freshly boi!ed (carbon-dioxide-free) distilled water.
Tare a 20-m1., round-bottom ampoule of ordinary glass (not
Pyrex) with a neck that must be wide enough to allow an eyedropper to be introduced for a t least 0.5 inch (1.27 cm.), Figure
1A. With the aid of an eyeckopper, weigh in0.5 * 0.1 gram of
dehydrated castor oil without gekting any of it on the neck of the
ampoule. Pipet exactly 10 ml. of the maleic anhydride solution
into the oil and into an empty ampoule as a blank. If any of
this solution or of the oil has adhered t o the neck of the ampoule,
wash it down with a few drops of c. P. asetone, and allow-the neck
to dry before sealing.
To seal, heat the neck of the ampoule cr,vefully in a small blow
flame or a hot Bunsen flame; take care to keep the ampoule in
a nearly vertical position and not to heat its contents. When the
glass has softened, remove it from the flame and draw it out to a
capillary with the aid of a glass rod which has been heated a t the
same time. Sed the capillary quickly by touching it to the flame.
The walls of the capillary should not be too thin to weaken the
container and cause the ampoules to blow up during the subsequent heating period.
Introduce the sealed ampoules into pieces of metal pipe and
place them in a flat iron safety case fitted with a screen cover.
Keep the case with the tubes inside an oven set a t 100 C. for 20
hours. To avoid overheating, place the
case near the temperature regulator
(usually in the top of the oven) rather
than near the heating coils (in the
bottom).
Remove the case with pipes from the
oven and allow it to cool before taking the
ampoules out (this is important), Drive
any li uid from the sealed tips with a
small lame, then cut the tips near the
end to release pressure. Cut the neck of
the ampoule again at a place of larger
diameter to permit easy transfer of the
c o n t e n t s a n d w a s h i n g s (Figure 1B).
Transfer the tips, neckpieces, and contents of the a m o d e into a 250-ml. Erlenmeyer flask. bsing carbon-dioxide-free
wash water, first cold then warm, bring
the volume to about 80 ml. Add some

1319

salt, cover the flasks with watch glasses or inverted beakers, and

e
t
~
~~ !~ z d~ $aaid hpowder,
~ ~ ~~filter
~~ through
~ ~ ~
double filter paper into a 500-ml. Erlenmeyer flask, and wash
flask and filter with cold carbon-dioxide-free water until the washings are neutral to blue litmus paper. If the filtrate is free from
Oil droplets, briilg the volume to 300 ml., add 10 drops Of per
cent phenolphthalein solution, and titrate with standardized
potassium hydroxide solution. If any oil has passed through the
filter paper, add more filter aid powder and repeat the filtration
before titrating. Transfer the blank directly into a 500-ml.
Erlenmeyer flask after removal from the oven, dilute to 300 ml.
with carbon-dioxide-free water, and titrate in the same manner;
filtration is unnecessary for the blank.
The calculation is as follows:
225.5 X C X (a - b )
diene value =
s
where C = concentration of KOH solution, grams/ml.
a = KOH solution used for blank, ml.
b = KOH solution used for sample, ml.
S = Byeight of sample, grams
~

Acknowledgment
Thanks are due J. F. Gerkens, V. A. Kildare, and W. C.
Freed for their cooperation gad help in the determination of
the figures listed in Table 1.
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(1)

Am. Oil Chem. SOL,Official and Tentative iMethods, pp.

(1932).

(2) Assoc. Official Agr. Chem

32, 41

Methods of Analyses, 3rd ed.,

pp. 319-20 (1930).

Bickford, W. G., Dollear, F. G., and Markley, K. S., J . A m .

Chem. Sac., 59, 2744 (1937).
(4) Bickford, W. G., Dollear, F. G . . and Markley, X. S., OiE & Soap,

(3)

15, 256-9 (1938).

(5)

Boeseken, J., and Hoevers, R., Rec. trav. chim.,

(6)

Bradley, T. F., and Richardson, David, IND.ENO.CHEM.,32,

(7)

Brod, J. S., France, W. G., and Evans, T.V. L., I b i d . ,

49, 1165-8

(1930).

963-9 (1940).
31, 114-18

(1939).

(8)

Bruce, R. J., and Denley, P. G., Chemistry

& Industry, 56, 937

(1937).

(11)
(12)

Cincinnati-Dayton-Indianapolis-Columbus Club, paper presented before Federation of Paint and Varnish Production
Clubs, Chicago, Oct., 1939.
Dean, H. K., Utilization of Fats, p. 95, New York, Chemical
Pub. Co. of N. Y . , 1938.
Ellis, B. A., and Jones, R. A., Analyst, 61, 812-16 (1936).
Forbes, W. C., and Neville, H. A., IND.ENG.CHEM.,32,

(13)

Forbes, W. C., and Neville, H. A., Zbid.. Anal. Ed.,

(9)
(10)

(1940).

12, 7 2 - 4

(1940).

Gelber, E. T., and Boeseken, J., Rec. trav. chim.,48, 377 (1929).
Ho, K., W a n , C. S., and Wen, S. H., IND.ENG.CHEM.,Anal.
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(16) Jamieson, G. S., Vegetable Fats and Oils, A. C. S. Monograph
58, p. 46, New York, Chemical Catalog Co., 1932.
(17) Kaufmann, H. P., Studien auf dem Fettgebiet, pp. 23-4 (1935).
(18) Kaufmann, H. P., and Baltes, J., Fette u . Seifen, 43,93-7 (1936).
(19) Mikusch, J. D. yon, OiE & Soap, 15, 186-8 (1938).
(20) Muenzel, F., Swiss Patent 193,931 (1935).
(21) Pelikan, K. A., and Mikusch, J. D. von, Oil & Soap, 14: 209-10
(14)
(15)

(1937).
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(23)
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(25)
(26)
(27)
(28)
(29)

Rosenmund, K. W., and Kuhnhenn, W.,

2. Untersuch. Nahr. u. Genussm., 46,

154-9 (1923).
Rossmann, E., Be?., 65, 1847 (1932).
Scheiber, J , Angew. Chem., 46, 643-7
(1933).
Scheiber, 3 . . Farbe u. Lack. 35, 513-14
(1930).
Scheiber, J., German Patent 513,540
(1928).
Scheiber, ,J., 1;. 8 . Patent 1,942,778
(1934).
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(1930).
Cfer. H., C . S.Patent 1,892,258 (1932).

P R E ~ E N T before
E D t h e Division of Paint and Varnish Chemistry at the 99th Meeting of the Americ a n Chemical S o c k t y , Cinainnati, Ohio.