Langmuir 1997, 13, 3345-3348 3345

Phase Diagram of r-Sulfonated Palmitic Acid Methyl Ester

Sodium Salt-Water System
M. Fujiwara,* T. Okano, H. Amano, H. Asano, and K. Ohbu
Material Science Research Center, Lion Corporation,
7-13-12, Hirai, Edogawa-ku, Tokyo 132, Japan

Received July 16, 1996. In Final Form: April 22, 1997X

The phase diagram of the R-sulfonated palmitic acid methyl ester sodium salt (SFMe)-water system
was studied by measuring the phase transition temperatures (Tc) and the X-ray diffraction patterns for
each solid phase of SFMe at various water contents. In the developed phase diagram, one anhydrous solid
phase and three distinct hydrated solid phases (SFMe‚2H2O, SFMe‚5H2O, and SFMe‚10H2O) were recognized
as well as liquid crystalline phases, a micellar phase, and a monomer phase. From the analysis of the
Tc changes due to the water contents of each SFMe solid phase according to the Flory-Huggins-Scott
equation, it was found that these hydrated SFMe solids form eutectic mixtures with each other. When
the dry and wet SFMe solids were left in an atmosphere with ordinary relative humidity and temperature,
the water content of the SFMe solid converged into the water content corresponding to that of the SFMe‚
2H2O.

Introduction Experimental Section

R-Sulphonated fatty acid methyl ester salts, which are
obtained from vegetable sources such as palm oil, have
been put to practical use in heavy-duty detergents due to
their special features of superior detergency1 and favorable
biodegradability.2-4 For applying anionic surfactants to
granular detergents, it is important to understand the
various physicochemical properties of the surfactants, such
as micellar solution properties, lyotropic liquid-crystalline
mesophase behavior, and crystalline solid properties.
Among these physicochemical properties, the crystalline
solid properties are especially important in relation to
the control of the powder properties of the detergents,
such as caking due to moisture absorption and dissolution
rate into water. From the viewpoint of the phase behavior,
various crystal hydrates or plastic crystal phases have
been revealed for several surfactant-water systems such
as the sodium dodecyl sulfate-water system,5 the sodium
palmitate-water system,6 the dioctadecyldimethyl-
ammonium chloride-water system,7 and the hexaethylene
glycol monododecyl ether-water system.8 However, the
phase behavior of the R-sulfonated fatty acid methyl ester
salts has hardly been investigated except for a rough phase
diagram of the R-sulfonated lauric acid methyl ester
sodium salt-water system.9
In this paper, the properties of solid crystalline states
such as hydration, phase transition, hygroscopic, and
dehumidifying behavior were investigated with respect
to the R-sulfonated palmitic acid methyl ester sodium salt
(SFMe), and a phase diagram of the SFMe-water system
was constructed.
X Abstract published in Advance ACS Abstracts, June 15, 1997.
(1) Satsuki, T.; Umehara, K.; Yoneyama, Y. J. Am. Oil Chem. Soc.
1992, 69, 672.
(2) Masuda, M.; Odake, H.; Miura, K.; Oba, K. J. Jpn. Oil Chem. Soc.
1993, 42, 643.
(3) Masuda, M.; Odake, H.; Miura, K.; Ito, K.; Yamada, K.; Oba, K.
J. Jpn. Oil Chem. Soc. 1993, 42, 905.
(4) Masuda, M.; Odake, H.; Miura, K.; Oba, K. J. Jpn. Oil Chem. Soc.
1994, 43, 617.
(5) Kékicheff, P.; Grabielle-Madelmont, C.; Ollivon, M. J. Colloid
Interface Sci. 1989, 131, 112.
(6) Rosevear, F. B. J. Soc. Cosmet. Chem. 1968, 19, 581.
(7) Laughlin, R. G.; Munyon, R. L.; Fu, Y.-C.; Fehl, A. J. J. Phys.
Chem. 1990, 94, 2546.
(8) Clunie, J. S.; Goodman, J. F.; Symons, P. C. Trans. Faraday Soc.
1969, 65, 287.
(9) Schambil, F.; Schwuger, M. J. Tenside, Surfactants, Deterg. 1990,
27, 380.
Materials. The R-sulfonated palmitic acid methyl ester
sodium salt (SFMe) was synthesized according to the previously
described method10 and purified by repeated recrystallization
from ethanol/water mixtures (3/2 by volume). The purity of the
sample was ascertained by its H1-NMR spectrum (JEOL Model
GX-400 NMR spectrometer, Tokyo, Japan) and no existence of
a minimum in the surface tension vs concentration curve of its
aqueous solutions.
Preparation of Samples with Various Moisture Con-
tents. A recrystallized SFMe sample was dried in vacuo at 60
°C for 5 h. The dried sample was then kept at 80% relative
humidity and 50 °C. The relative humidity was adjusted by an
aqueous solution of sulfuric acid in a desiccator. The SFMe
samples having various moisture contents were obtained by
keeping the samples under these conditions for various time
intervals. The moisture contents of the samples were determined
by the Karl-Fischer titration method.
DSC Measurement. Approximately 10 mg of the SFMe
samples with various moisture contents was sealed in aluminum
cells. The DSC measurements were carried out using a model
TAS-200 differential scanning calorimeter (Rigaku Co. Ltd.,
Tokyo, Japan) with temperature rates of 2 °C/min in the range
from -20 to 130 °C.
X-ray Diffraction Measurement. The X-ray diffraction
measurements were carried out using a model RAD-AB X-ray
diffractometer (Rigaku Co., Ltd., Tokyo, Japan) in the diffraction
angle 2θ from 5° to 30° and a model RAD-B X-ray diffractometer
(Rigaku Co., Ltd., Tokyo, Japan) in the diffraction angle range
2θ from 0.5° to 7°. The temperature of the samples was regulated
throughout the measuring procedures by a ceramic plate heater
fitted to the sample holding plate.
Discrimination of Liquid Crystalline Phases. Lamellar
and hexagonal liquid crystalline phases (LR and H1) were
identified by optical microscopy using an optical microscope
(Olympus Co., Ltd., Type 13H) with a fitted hot stage, from the
observed texture11 shown by particular samples with crossed
polarizers. It was difficult to identify the boundaries between
the mesophase and the mesophase two-phase region, so the range
of the LR + H1 phase and the H1 + L1 phase could not be accurately
determined.
Results and Discussion
Determination of the Phase Diagram for the
SFMe-Water System. The phase transition behavior
of the hydrated and nonhydrated solids of SFMe was
(10) Fujiwara, M.; Miyake, M.; Abe, Y. Colloid Polym. Sci. 1993, 271,
780.
(11) Rosevear, F. B. J. Am. Oil Chem. Soc. 1954, 31, 628.

S0743-7463(96)00698-1 CCC: $14.00 © 1997 American Chemical Society

3346 Langmuir, Vol. 13, No. 13, 1997
Figure 1. DSC curves for the SFMe solids with moisture
contents of 0-8.9 wt %.
Figure 2. X-ray diffraction patterns for the SFMe solids with
moisture contents of 0-8.9 wt %. Moisture content: (a) 0; (b)
1.6 wt %; (c) 5.6 wt %; (d) 8.9 wt %.
observed with a temperature-increasing mode utilizing
the DSC method. The DSC curves for the SFMe with
moisture contents of 0-8.9 wt % are shown in Figure 1.
The anhydrous SFMe showed a single endothermic peak,
from which the phase transition temperature (Tc) and the
enthalpy change (∆H) associated with the phase transition
from the solid to the liquid crystal were 112 °C and 22.1
kJ/mol, respectively. With an increase in the moisture
content, the endothermic peak gradually shifted to the
lower temperature range and the peak areas gradually
decreased. Simultaneously, a new peak around 68 °C
appeared, and the area of the new peak gradually
increased while remaining at almost a constant Tc of =68
°C. When the moisture content attained 8.9 wt %, the
endothermic peak became a singlet again with the Tc and
the ∆H being 70 °C and 67.5 kJ/mol, respectively. Because
the moisture content of 8.9 wt % corresponds to the molar
ratio of [H2O]/[SFMe] ) 2.0, it was concluded that the
endothermic peak at 70 °C is due to the phase transition
of the SFMe‚2H2O crystal from the solid to the liquid
crystal.
The X-ray diffraction patterns of the SFMe solids with
moisture contents of 0, 1.6, 5.6, and 8.9 wt % in the
temperature range below their Tc are shown in Figure 2.
In the diffraction patterns of the anhydrous SFMe crystal
(a) and the SFMe‚2H2O crystal (d), single peaks corre-
sponding to spacings of 26.9 Å and 30.1 Å are observed,
respectively. On the other hand, both peaks were
simultaneously observed in the crystals with moisture
contents of 1.6 and 5.6 wt %. This means that two kinds
of crystals independently coexist in the SFMe solids with
moisture contents more than 0 and less than 8.9 wt %.
The phase transition behavior described above would
be explained more quantitatively from the viewpoint of
the phase rule. The hydrated SFMe solids in the above-
mentioned moisture content range can be presumed to
form a eutectic mixture composed of the anhydrous SFMe
solid and the SFMe‚2H2O solid on the basis of the X-ray
results; therefore, we applied the Flory-Huggins-Scott
Fujiwara et al.
Figure 3. Measured Tc values and Tc change curves calculated
by eqs 1 and 2 for the SFMe solids with moisture contents of
0-8.9 wt %.
equation12 to the change in the Tc as typically shown in
Figure 1. In a eutectic mixture composed of two compo-
nents, the phase transition temperature of component 1
(T1) can be expressed by eq 1
1/T1 - 1/T1° ) -(R/∆H1)(V1/V2)(ln Φ1 + χ12Φ22) (1)
where T1° and ∆H1 are the phase transition temperature
and the phase transition enthalpy of the pure component
1, respectively. V1 and V2 are the partial molar volumes
of components 1 and 2 in the mixture, respectively. Φ1
and Φ2 are the volume fractions of components 1 and 2,
respectively. χ12 is the interaction parameter between
components 1 and 2. R is the gas constant. Similarly,
the phase transition temperatures of component 2 (T2)
can be expressed by eq 2
1/T2 - 1/T2° ) -(R/∆H2)(V2/V1)(ln Φ2 + χ12Φ12) (2)
where T2° and ∆H2 are the phase transition temperature
and the phase transition enthalpy of the pure component
2, respectively.
Figure 3 shows the calculated curves using eqs 1 and
2 for the anhydrous SFMe (component 1)-SFMe‚2H2O
(component 2) system, together with the plots of the
experimentally obtained Tc and the eutectic discontinuity
temperatures from Figure 1. The parameters utilized for
the calculations are T1° ) 112 °C, T2° ) 70 °C, ∆H1 ) 22.1
kJ/mol, ∆H2 ) 67.5 kJ/mol, and χ12 ) 1.04. Here, χ12 was
adjusted so that the calculated curves agree well with the
experimental values, and the calculation was carried out
on the assumptions that V1 approximately equals V2 and
that Φ1 and Φ2 are approximately equal to each weight
fraction. From the results that the tendency of the
experimental Tc changes agreed with the curves calculated
using eqs 1 and 2, as shown in Figure 3, and that the two
kinds of crystals were simultaneously observed, as shown
in Figure 2, it will be relevant to conclude that the SFMe
solid with a moisture content range of 0-8.9 wt % below
the eutectic temperature is present as a eutectic mixture
composed of the anhydrous SFMe and the SFMe‚2H2O
crystals. From these results, each region in Figure 3 is
labeled as LR, anhydrous SFMe + LR, SFMe‚2H2O + LR,
and anhydrous SFMe + SFMe‚2H2O, respectively.
Similarly, the DSC curves of the SFMe solids with a
moisture content range of 8.9-32.6 wt % are shown in
Figure 4. The phase transition behavior of SFMe in the
range 8.9-19.5 wt % was similar to that in Figure 1, in
which the shift of the endothemic peak corresponding to
the phase transition of the SFMe‚2H2O crystal to the lower
temperature side and the appearance of a new peak around
51 °C were observed. Furthermore, the endothermic peaks
(12) Wittman, J. C.; Manley, R. St. J. J. Polym. Sci., Polym. Phys.
Ed. 1977, 15, 1089.
Phase Diagram of R-Sulfonated Palmitic Acid
Figure 4. DSC curves for the SFMe solids with moisture
contents of 8.9-32.6 wt %.
Figure 5. Measured Tc values and Tc change curves calculated
using eqs 1 and 2 for the SFMe solids in the moisture content
range 8.9-19.5 wt %.
around 0 °C due to melting of free water were observed
in the SFMe solids with moisture contents more than 8.9
wt %. Because the moisture content of 19.5 wt %
corresponds to that of the SFMe‚5H2O crystal, where the
endothermic peaks converged again into a single peak (53
°C, 39.4 kJ/mol), the endothermic peak at 53 °C seems to
be due to the phase transition of the SFMe‚5H2O crystal
from the solid to the liquid crystal. The Tc changes in the
moisture content range 8.9-19.5 wt % were also calculated
as the eutectic mixture composed of SFMe‚2H2O and
SFMe‚5H2O, as shown in Figure 5. The parameters
utilized for the calculation of the SFMe‚2H2O-SFMe‚
5H2O system are T1° ) 70 °C, T2° ) 53 °C, ∆H1 ) 67.5
kJ/mol, ∆H2 ) 39.4 kJ/mol, and χ12 ) 1.50. In the range
19.5-32.6 wt %, the endothermic peaks corresponding to
the phase transition of the SFMe‚5H2O crystal were almost
constant at around 53 °C, and the appearance of a new
peak around 42 °C was observed. The moisture content
of 32.6 wt % corresponds to that of the SFMe‚10H2O
crystal, so the new peak around 42 °C was considered to
be due to the phase transition of the SFMe‚10H2O crystal
(42 °C, 46.1 kJ/mol). In the moisture content range
exceeding 32.6 wt %, every DSC curve showed a single
peak around 42 °C, which slightly shifted to the lower
temperature region with an increase in the moisture
content.
Relating all the results described above and the results
of the observed liquid crystalline phase and the dilute
solution properties reported in a previous paper,10 the
overall phase diagram of the SFMe-water system is
proposed as shown in Figure 6. With respect to the SFMe
concentration range of ca. 30-80 wt %, we inferred the
hypothetical phase boundaries indicated as the dotted
curves, since 42 and 53 °C are respectively the incongruent
Langmuir, Vol. 13, No. 13, 1997 3347
Figure 6. Phase diagram of the SFMe-water system: S0H2O,
anhydrous SFMe crystal; S2H2O, SFMe‚2H2O crystal; S5H2O,
SFMe‚5H2O crystal; S10H2O, SFMe‚10H2O crystal; LR, lamellar
liquid crystalline phase; H1, hexagonal liquid crystalline phase;
L1, micellar solution phase; M1, monomer solution phase. The
position of the cmc line is schematic.
Figure 7. Plot of enthalpies (J/g of SFMe) for ice melting vs
moisture content of SFMe solid. The dashed line corresponds
to the theoretical curve for pure water melting (∆H ) 318 J/g).
melting points of SFMe‚5H2O and SFMe‚10H2O, and the
hump of the phase boundary of SFMe‚5H2O is approaching
the composition of SFMe‚10H2O. From Figure 6, it was
elucidated that there are four types of hydrated SFMe
crystals (anhydrous SFMe, SFMe‚2H2O, SFMe‚5H2O, and
SFMe‚10H2O), two types of liquid crystalline phases
(lamellar liquid crystal (LR) and hexagonal one (H1)), a
micellar solution phase (L1), and a monomer solution phase
(M1) in the SFMe-water system.
Kékicheff et al.5 reported that the presence of several
hydrated crystals (1/8H2O, 1H2O, and 2H2O) was observed
in the sodium dodecyl sulfate (SDS)-water system. From
the enthalpy change of ice melting in the SDS-water
mixture, the water below the content corresponding to
SDS‚1H2O was unfreezable and was regarded as struc-
tural water strongly interacting with the polar head groups
of the SDS molecules. In Figure 7, the enthalpy change
of ice melting expressed as joules per gram of SFMe vs the
water content is shown for the SFMe-water system. It
was revealed that the unfreezable water content deduced
from Figure 7 is close to that of SFMe‚2H2O.
Hygroscopic and Dehumidifying Behavior of Each
Hydrated Crystal of SFMe. Time dependent changes
in moisture content and the X-ray diffraction patterns for
the SFMe solid with an initial moisture content of 40 wt
% are shown in Figure 8, where the SFMe solid was allowed
to stand in an atmosphere with 10 % relative humidity
at ambient temperature. The moisture content rapidly
decreased for the first 5 h and then remained almost
constant around 32 wt % during 5-20 h. The moisture
content then steeply decreased again at 20-50 h and
attained 10 wt %. After 50 h, the moisture content very
slowly decreased and attained 9 wt %, which corresponds
to the formula of SFMe‚2H2O. Finally, the moisture
content was constant at around 7 wt % even after 60 days.
The X-ray diffraction patterns of the SFMe solid at a
3348 Langmuir, Vol. 13, No. 13, 1997 Fujiwara et al.

Figure 8. Time dependence of moisture content and X-ray diffraction pattern for the hydrated SFMe solid (initial moisture content,
40 wt %; 10% RH; room temperature).

Figure 9. Time dependence of moisture content and X-ray diffraction pattern for the dry SFMe solid (initial moisture content,
0.2 wt %; 80% RH; 50 °C).

moisture content of 10-40 wt % were almost the same
(two peaks: 4.1 and 4.2 Å); then they began to change at
9 wt % and finally changed to the different pattern (single
peak: 4.25 Å) at 7 wt %.
On the other hand, a time dependent change in moisture
content and the X-ray diffraction patterns for the SFMe
solid (initial moisture content was 0.2 wt %) is shown in
Figure 9, where the dried solid was allowed to stand in
an atmosphere with 80% relative humidity at 50 °C. The
moisture content steadily increased within 20 h and
became saturated at around 8 wt % around 25 h. Finally,
the moisture content became constant at around 8.6 wt
%, which corresponds to the SFMe‚2H2O crystal, even
after 120 h. The X-ray diffraction pattern was gradually
changed from the two peaks (4.1 and 4.2 Å) at 0.2-4 wt
% to the single peak (4.25 Å) at 6 wt %. According to the
dehumidifying and the hygroscopic behavior described
above, it may be concluded that SFMe is likely to converge
into the SFMe‚2H2O crystal under ambient conditions.
Acknowledgment. The authors express their sincere
appreciation to Professor M. Seno of Nihon University for
helpful discussion and to Dr. K. Oba for permission to
publish this paper.
LA960698N