The Solubility of Potassium Acid Soaps in Organic Solvents

HANS SCHOTT AND SHAW-LANG CHANG

School of Pharmacy, Temple University, Philadelphia, Pennsylvania 19140
Received May 13, 1986; accepted June 13, 1986

The potassium acid soaps of lauric (HL), stearic (HSt), and oleic (HO1) acids have molar ratios of
neutral soap:fatty acid of 1.0. The solubility of potassium acid laurate at 25°C was investigated quan-
titatively; the solubility of the stearate was considerably lower. The highest solubility of the laurate was
in methanol; the best solvents had solubility parameter values between 11 and 15 (cal/cm3) In. These
solvents dissolved intact KHL2. Less polar solvents extracted small a m o u n t s of H L while more polar
solvents extracted mostly K L from K H ~ . © 1987AcademicPress,Inc.

INTRODUCTION distilled; water was double-distilled and boiled

The association between fatty acids and
their neutral soaps to form acid soaps was dis-
covered in the 19th century (1), but compre-
hensive physicochemical studies are more re-
cent (2, 3). The association between an organic
acid and its salt is not restricted to fatty acids:
Other carboxylic acids, including aromatic
ones, and even enols form association com-
plexes with their respective salts (4).
All potassium acid soaps examined had a
1:1 molar ratio of neutral soap:fatty acid (2,
3, 5, 6). Acid soaps have low solubility in wa-
ter, which decreases with increasing chain
length (6). Few data exist on their solubility
in organic solvents; sodium acid caprylate dis-
solved in CC14 without decomposition (7).
Such solubility data were required for emul-
sification studies and are presented here.
EXPERIMENTAL
Materials
The fatty acids were used as received. Laurie
acid (HL) (Sigma Chemical Co., L-4250) and
stearic acid (HSt) (Eastman Kodak Co., 402)
had reported purities of 98.6 and 97%, re-
spectively, by GLC. Oleic acid (HO1) (Amend
Drug and Chemical Co.) was National For-
mulary grade. All solvents were fractionally
94
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free of CO2.
Soap Preparation
CO2 was excluded from all steps by working
under a positive N2 pressure. The acid soaps
were prepared by adding the required amount
of freshly prepared, standardized 0.600 M al-
coholic KOH solutions to warm, ca. 0.6 M
alcoholic solutions of weighed amounts of the
fatty acids, heating to 70°C to obtain clear so-
lutions, cooling to room temperature, and then
finally cooling to ca. - 3 ° C . The solids were
filtered, washed with cold alcohol, and recrys-
tallized from alcohol. After being filtered and
washed, they were dried in a vacuum oven at
~<50°C in a slow N2 current.
The acid soaps were analyzed by titration
with 0.100 N K O H and phenolphthalein for
free fatty acid and with 0.100 N HC1 and
bromphenol blue for alkali. The molar ratios,
neutral soap:fatty acid, were 1.00-1.02. Crys-
tals of KHL2 were lath-shaped and those of
KHSt2 were small flakes. KHO12 was a yellow-
ish white, waxy, amorphous solid. Because of
its solubility in alcohol, its yield was low.
Solubility Determination
Qualitative screening tests were made by
heating 1O0 _+ 5 mg of acid soap in stoppered
Journalof ColloidandInterfaceScience,Vol. 117,No. 1, May 1987
 TABLE I

Qualitative Solubilities of Potassium Acid Soaps at 20-24°C in Organic Solvents

Solventsfor
Dissolution
behavior KHI~ KHSt~

Ia Ethyl formate (9.4) b

Cyclohexanol (11.4)
l-Butanol (11.4)
2-Chloroethanol (12.2) c
Propylene glycol (12.6)
Ethanol (12.7)
II d Methylene chloride (9.8)
n-Propanol (11.9)
Dimethyl sulfoxide (12.0) 2-Chloroethanol (12.2) c
Methanol (14.5)
Formamide (19.2)
III e Toluene (8.9)
Benzene (9.2)
Chloroform (9.3) Tetrachloroethane (9.7)
Ethylene dichloride (9.8)
1,4-Dioxane (10.0)
Nitrobenzene (10.0)
Methyl benzoate (10.3)
2-Butanol (10.8) Dimethyl sulfoxide (12.0)
N,N-Dimethylformamide (12.1)
Methanol (14.5)
Glycerin (16.5)
Water (23.4) Formamide (19.2)
IV f Nitrobenzene (10.0)
Isobutanol (10.2)
2-Butanol (10.8)
1-Butanol (11.4)
n-Propanol (11.9)
Propylene glycol (12.6)
Ethanol (12.7)
Vg Cyclohexane (8.2)
Carbon tetrachloride (8.6)
Ethyl acetate (9.1) Toluene (8.9)
Tetrachloroethane (9.7) Benzene (9.2)
Chloroform (9.3)
Ethylene dichloride (9.8)
1,4-Dioxane (10.0)
Water (23.4)
VI h Isooctane (6.9)
n-Heptane (7.4)
Diethyl ether (7.4)
n-Butyl acetate (8.5)
Ethyl acetate (9.1)
Acetone (9.9)

a Completely soluble at room temperature.

b Numbers in parentheses are solubility parameters in (cal/cm3) 1/2 (9-11).
c Chloroethanol reacted with the soaps.
d Almost completely soluble at room temperature; completely dissolved at the boiling point.
e Partially dissolved at room temperature; completely dissolved at the boiling point.
fSlightly soluble at room temperature; completely dissolved at the boiling point.
g Trace dissolution at room temperature; partially dissolved at the boiling point.
h Insoluble at room temperature; trace dissolution at the boiling point.
95 Journal of Colloid and Interface Science, Vol. 117,No. l, May 1987
 96 SCHOTT AND CHANG

30-ml test tubes with 10.0 _+ 0.1 ml solvent at
the boiling point and letting cool to r o o m
temperature. For quantitative solubility de-
terminations, excess solid soap was shaken
with the solvent at 25.0 _+ 0.5°C. Samples were
withdrawn after 5 and 10 days except for glyc-
erin, where samples were withdrawn after 10
and 20 days. T h e y were filtered through 0.22-
# m Millipore m e m b r a n e s in a jacketted and
thermostatted filter holder.
In the case o f volatile solvents, 25.00-ml al-
iquots o f the saturated solutions were dried on
a steam bath and then in a v a c u u m oven at
~<80°C to constant weight. M e t h a n o l was
added to the 1-butanol solutions to lower the
drying temperature. If the a m o u n t o f dissolved
soap was sufficient, some residues were dis-
solved in alcohol and titrated with 0.100 N
HC1 and 0.100 N N a O H . The melting point
was used to characterize small a m o u n t s o f
dried residues. W h e n the solvents had higher
boiling points, their filtered, saturated solu-
tions were diluted with alcohol and titrated.
RESULTS
In Table I, complete dissolution indicates a
solubility limit >t 1% (w/v). Dissolution by re-
fluxing in high-boiling solvents is probably
preceded by dissociation o f the acid soaps,
which for KHL2 occurs at 8 6 o r 91.3°C in the
absence o f solvents (3, 5) and presumably at
a lower temperature in their presence. KHL2
was generally m o r e soluble than KHSt2, in
keeping with the shorter chain length o f the
acid and the higher critical solution temper-
ature or Krafft point o f the neutral soap (8).
The discrepancy between Tables I and II in
the solvent power o f m e t h a n o l for KHL2 is
ascribed to a critical solution temperature o f

TABLE II
Solubility of KHL2 at 25°C
Solubility determined by titration of saturated
solution (% (w/v))b

Solubility Molar ratio Combined Molar ratio

determined by KL:HL of dried KL + HL KL:HL from
Solventa drying (% (w/v))b solution KLcontent HL content solubility titration

Isooctane (6.9) 0.000

Hexadecane (8.0) 0.003 0.002 0.005
Ethyl acetate (9.1) 0.09 Mostly HL c
Benzene (9.2) 0.000
Chloroform (9.3) 0.05 Mostly HL c
Ethyl formate (9.4) 0.49 0.08
Ethyl acetate saturated
with water (9.7)d 0.64 0.13
Methylene chloride (9.7) 0.02 Mostly HL c
2-Butanol (10.8) 0.407 0.428 0.835 0.80
1-Butanol (11.4) 1.01 1.00 0.535 0.454 0.989 0.99
Ethanol (12.7) 1.70 0.98 0.918 0.776 1.694 0.99
Methanol (14.5) 5.59 0.98 3.094 2.547 5.641 1.02
Ethylene glycol (14.6) 1.067 0.831 1.898 1.08
Glycerin (16.5) 0.164 0.034 0.198 4.1
Water (23.4) 0.165 0.002 0.167 56

a Numbers between parentheses are solubility parameters, in ( c a l / c m 3 ) 1/2 (9-11).

b Average of duplicate determinations. A 1.190:1.000 ratio of % (w/v) corresponds to a 1:1 molar ratio of KL:HL.
c Melting range within 6°C of the melting point of HL, namely, 44°C.
a Weighted average of the solubility parameters of ethyl acetate and water.
Journal of Colloid and Interface Science, Vol. 117, No. 1, May 1987
 SOLUBILITY OF POTASSIUM ACID SOAPS
22-24°C. The qualitative test of Table I at
r o o m temperature was apparently done at or
below this temperature.
KHL2 has its m a x i m u m 25°C solubility in
methanol (x2 = 0.0055) and an appreciable
solubility in solvents with solubility parameter
values (9-1 1) between 11 and 15 (cal/cm3) 1/2.
Less polar solvents extracted small amounts
of H L from KHL2 while glycerin and water,
which are more polar, extracted considerable
amounts of KL.
No quantitative solubility studies were
made with KHSt2 because its r o o m tempera-
ture solubility even in the best solvents is so
low that it is useless as an emulsifier. The io-
dine n u m b e r of the oleic acid from recrystal-
lized KHO12 was 88.5 compared to 89.85 for
the pure acid. The molar ratio KO1/HO1 de-
termined by titration was 1.02, identical to the
ratio reported for the KHO12 prepared by the
"dry-melt" procedure (3). The 25°C solubility
of KHO12 was 0.30 + 0.01% in hexadecane,
with a molar ratio KO1/HO1 = 0.065 _+ 0.013
and 0.016% in water, with a ratio of approx-
imately 2.3.
The appreciable dissolution of intact KHL2
by the four alcohols and ethylene glycol shows
that this acid soap is quite stable at r o o m tem-
perature. The fact that hydrogen-bonding liq-
uids are good solvents while less polar liquids
are poor solvents and decompose the acid soap
97
seems to indicate that the association between
K L and H L is not promoted only by hydrogen
bond formation and that other forces, pre-
sumably dispersion forces between the hydro-
carbon chains oflaurate and lauric acid, make
a significant contribution to the association.
ACKNOWLEDGMENT
This paper was adapted from a thesis submitted by
Shaw-Lang Chang to Temple University in partial fulfill-
ment of the Master of Science degree requirements.
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Journal of Colloid and Interface Science, Vol. 117, No. 1, May 1987