Surfactant Aggregation in Systems Containing

Alkanolamines and Fatty Acids

TORBJORN W,~RNHEIM ~ AND ANGELA JONSSON
Institute for Surface Chemistry, P.O. Box 5607, S-114 86 Stockholm, Sweden

Received August 24, 1989; accepted December 19, 1989

The phase diagrams of six different alkanolammonium carboxylate-water systems have been deter-
mined. Their phase behavior differs from that of ordinary soaps, since there are large differences between
the systems for varying alkyl chain lengths of the carboxylate. In addition, the chemical structure of the
alkanolammonium counterion also affects the phase equilibria. For short alkyl chain carboxylates the
liquid crystalline phases disappear (e.g., for triethanolammonium octanoate) or decrease in extension
(e.g., for monoethanolammonium octanoate), although the surfactant readily aggregates in solution. In
contrast, long alkyl chain carboxylates behave like swelling amphiphiles with a low aqueous solubility
and the immediate formation of a lamellar phase (e.g., for tri- and monoethanolammonium oleate). It
is shown that the distribution between acid and soap causes these effects. The lower surface charge of
the surfactant aggregates compared to that of ordinary soap micelles is also reflected in a lowering of the
critical micellization concentration. © 1990AcademicPress,Inc.

INTRODUCTION containing components forming mixed sur-

Fatty acids, derived from natural fats and
oils, compete with petrochemical compounds
to be raw-materials for surfactant production
(1, 2). Today, environmental aspects have
become more and more important and this
also implies a renaissance for soaps as such.
There is indeed a massive amount of basic re-
search work on soaps, at least with respect to
phase equilibria and association structures (3-
5). Perhaps the most prominent obstacle for
practical use of soaps, their sensitivity toward
divalent cations, can be partly overcome in
technical systems by careful formulation and
addition of complexation agents. The inter-
action between the carboxylate group and dif-
ferent ions (or other components ) in solution
is thus not only a fundamental research issue
but also of considerable technical interest.
One interesting group of compounds is
mixed amine-fatty acid systems. For systems
To whom correspondence should be addressed.
314
0021-9797/90 $3.00
Copyright© 1990by AcademicPress,Inc.
All rightsof reproductionin any formreserved.
factant aggregates (6), i.e., alkylammonium
carboxylates with two alkyl chains of similar
length, experimental and theoretical studies
have explained the phase behavior in detail.
Thus it is possible to predict the phase behavior
and point out the relevant interactions (7).
However, for systems containing more hydro-
philic amines together with the fatty acid, less
basic understanding and information exist.
This is so even for the common "amine soaps"
(2), alkanolammonium carboxylates, despite
that their use as surfactants--and the use of
alkanolamines as additives in soap-fatty acid
systems--is widespread (2, 8 ). One recent ex-
ception is the study of the phase behavior
and the properties of triethanolammonium
oleate (9-11 ).
We have thus found it worthwhile to pursue
a systematic investigation of the phase behav-
ior and the solution phase structure of these
surfactants. In this paper, we give phase dia-
grams for equimolar mixtures of monoetha-
nolamine or triethanolamine and octanoic,
dodecanoic, or oleic acid together with water.
Journal of Colloidand InterfaceScience, Vol. 138,No. 2, September1990
 ALKANOLAMMONIUM CARBOXYLATE SOLUTIONS 315

The formation of liquid crystals is discussed by preparing 10-20 samples by weight in

and compared with the behavior of ordinary sealed ampoules, allowing them to equilibrate
soaps. A similar comparison is made for the at a few fixed temperatures in a thermostated
micellar aggregates formed in the solution bath, and visually determining the number
phase. The results are discussed in terms of and type of phase(s) present. A closer exam-
the differences between alkanolammonium ination was performed by mixing an addi-
ions and ordinary counterions such as Na+: tional number of samples and examining them
the amines are weak bases and they are decid- by optical microscopy, using a Reichert mi-
edly larger than alkali ions. croscope at 60× with polarizers and a fitted
hot-stage. The temperature was raised by 3 °C/
EXPERIMENTAL min. The identification of the liquid crystalline
Chemicals. The investigated surfactants phases made from microscopy (4, 5 ) was con-
were prepared from octanoic acid, Ca (Fluka, firmed by low-angle X-ray diffraction mea-
99%), dodecanoic acid, Cl2 (Aldrich, 99%), surements.
or oleic acid, C18:~ (Fluka, 99.5+%), which The determinations of ternary phase dia-
were mixed in equimolar amounts with grams were performed by titrating surfactant-
monoethanolamine (MEA) (BDH, 99.5% ), or alcohol and water-surfactant samples with
triethanolamine (TEA) (Merck, 99%). (The water and alcohol, respectively, and visually
notations MEA and TEA, respectively, are observing the phase transitions at 25 + 0.5°C.
used in the following to denote the species re- The experimental error in the boundaries of
gardless of charge.) The preparations in some the solution phases is less than 2% (w/w) and
cases were performed directly by mixing (due in the liquid crystalline phases less than
to low melting points of the products, com- 5% (w/w).
plete mixing could be attained) and in other For the binary phase diagrams the experi-
cases in solution with solvent evaporation in mental error in the solid lines is less than 2%
vacuum. No differences in melting point (or (w/w), while the experimental error in the
in other phase behavior) could be detected due dotted lines is less than 5% (w/w). The two-
to differences in methods of preparation. The phase region isotropic + anisotropic phases
compounds in the text are denoted, e.g., TEA- are, when not shown in the diagrams, judged
C~2 for triethanolammonium dodecanoate; all to be narrow.
notations are used regardless of the distribu- X - r a y measurements. Repeat distance, d,
tion of acid-soap in solution and merely to was determined with X-ray low-angle diffrac-
indicate a 1:I molar ratio of amine and fatty tion using CuK~-radiation and a camera
acid of the pure compound. Pentanol (Fluka, equipped with a Tennelec PSD-100 phase-
99%) was used as received. Water was twice sensitive detector. The temperature was 20
distilled. _+ I°C. The setup was repeatedly calibrated
There is always a risk of amidation when with crystalline sodium octanoate (d = 23.0
mixing acid and primary or secondary amines ) and the area per polar group, S, was, in
(e.g., MEA), while, of course, no such possi- the case of the tamellar phase samples, deter-
bility exists with tertiary amines (e.g., TEA). mined from the expression (4)
This reaction occurs readily at elevated tem-
peratures (around 150°C ( 1, 2)), and care was S = 2V/da, [ll
thus taken to avoid preparation or long-time where V is the amphiphile molecular volume
storage of samples at elevated temperature. (i.e., the mean value in the case of ternary
The absence of amides was verified by IR systems) and da the thickness of the amphi-
analysis of chosen samples. phile layers, obtained directly from
Phase diagrams. An overview of the phase
behavior in each binary system was obtained da = dva, [2]
Journal of Colloid and Interface Science, Vol. 138, No. 2, September 1990
316 W,~RNHEIM AND JONSSON

where va is the volume fraction of amphiphile Surface tension measurements. Surface

in the sample. All volume data were derived
from the densities of the pure components.
Some complications arise when the one of the
components is distributed between the am-
phiphilic and the aqueous layers, as in the case
of pentanol. However, the limited solubility
of pentanol leads to maximum uncertainty
estimated at less than 2%.
N M R measurements. Measurements of self-
diffusion coefficients were performed with the
PGSE F T N M R method (12) on a Jeol FX-
100 operating at 99.96 MHz for ~H, at the
ambient temperature 25 _+ 0.5°C. Determi-
nations of the degree ofcounterion association,
/3, were performed by solubilizing trace
amounts of hexamethyldisiloxane (HMDS;
Merck, 99%) into micellar solutions of M E A -
C12 or TEA-C~2. The self-diffusion of H M D S
can be set equal to the self-diffusion of the
micelle, DmiceUe( 13 ), and/3 is obtained from
the measured self-diffusion of MEA or TEA,
( D ) m e . . . . ed, according to
(D}measured = /3Dmicelle+ ( 1 - 3)Dfre~,
where Dfr**is obtained from measurements of
MEA or TEA at low concentrations in
aqueous solution, corrected for the obstruction
effect of the micelles (14). The error in the
self-diffusion coefficients is less than 5% at an
80% confidence interval, leading to maximum
errors in/3 of 10%.
tension measurements were performed with
the de Nofiy ring method at 25 + 1°C (15).
The estimated accuracy is _+0.5 m N / m .
RESULTS
The partial binary phase diagrams for the
investigated amphiphiles together with water
are shown in Figs. 1 and 2. MEA-C8 (Fig. 1a)
forms a solution phase L which extends up to
54 wt% amphiphile at 25 °C, whereafter a hex-
agonal liquid crystalline phase E is formed and
stable in a comparatively limited concentra-
tion and temperature interval. The solution
phase L with MEA-C12 (Fig. lb) is stable up
to 30 wt% amphiphile, until a hexagonal phase
E and, at even higher concentrations, a la-
mellar phase D form. Finally, for MEA-C18:I
(Fig. lc) the aqueous solubility of the amphi-
phile is very limited and a lamellar phase D
precipitates at higher concentrations of sur-
factant.
TEA-C8 (Fig. 2a) forms no liquid crystals
whatsoever, and a miscibility gap occurs be-
[3] tween 3 and 6 wt% at 25°C; the miscibility
gap decreases somewhat with temperature. For
TEA-C1z (Fig. 2b) a miscibility gap occurs at
low concentrations, <0.1 wt%, extends up to
7 wt% surfactant at room temperature, and
increases with increasing temperature. The
miscibility gap and other multiphase regions
are denoted "undetermined" (Undet) in the

O0 100 , 100,

a b .... . . .C . . . . . . . . . L .................

80 80, 80,

?
E 6o L ~ so, L E D 60 i

Under D
40 40 , 40,

20 • • • 2O • • • 2O ° • •
2O 4O 6O 8O 100 0 2O 40 6O 80 tO0 20 4O 6O 8O
% surfactant % surfactant % surfactant

FIG. 1. Partial phase diagrams for the systems (a) monoethanolammonium octanoate-water, (b) mono-
ethanolammonium dodecanoate-water, and, (c) monoethanolammonium oleate-water. The hatched lines
denote less accurately determined phase boundaries, as stated under Experimental. Existence regions for the
solution phase L, hexagonal phase E, lamellar phase D, and solid surfactant (s) are shown. W denotes
aqueous solution dilute in surfactant. The regions of phases E and D in Figs. la and lb include the two-
phase regions E + L and D + L, respectively. The notation "Undet" is explained in the text.
Journal of Colloid and Interface Science, Vol. 138, No. 2, September 1990
 ALKANOLAMMONIUM CARBOXYLATE SOLUTIONS
100
a c
80
~ 6o
40
Under
/"
• ,...4sJ
20 D B
0 20 40 60 80 100
% surfactant
FIG. 2. Partial phase diagrams for the systems(a) triethanolammoniumoctanoate-water(16), (b) trieth-
anolammonium dodecanoate-water( 16), and, (c) triethanolammonium oleate-water.Notations as in Fig.
1. The regions of phases E and D in Fig. 2b include the two-phase regionsE + L and D + L, respectively.
phase diagrams (Figs. lc and 2a-2c), since
the composition of the region varies. The
composition of this region in the system T E A -
C~2-water (Fig. 2b) has been studied in some
detail. At low concentrations of surfactant, one
of the separated phases is crystalline at room
temperature; the phase consists mainly of do-
decanoic acid (m.p., 44°C). At higher con-
centrations of surfactant, the separated phase
is a dilute lamellar dispersion. When the tem-
perature is increased to above 40°C, the un-
determined region becomes an equilibrium
between two liquid phases. TEA-CI8:~ (Fig.
2c) behaves in a manner similar to that of the
corresponding MEA-salt: the aqueous solu-
bility is low and a lamellar phase is stable at
higher concentrations ofsurfactant. Separation
of some samples in the undetermined region
for MEA-C~s:I and TEA-C18:1 shows the pres-
ence of lamellar and solution phases.
We tentatively suggest--and later discuss in
detail--that the occurrence of the miscibility
gaps is due to an incomplete dissociation of
the acid in the systems. The pH of dilute
aqueous solutions of the surfactants is above
7 for MEA-C8 and below 6.5 for TEA-Cs.
This should be compared with the pKa of the
components, which are 7.9 for TEA, 9.5 for
MEA, and 4.8 for the acids (where the chain
length variation of pK~ is negligible for alkyl
chains longer than C6) (17). Using these
numbers to estimate the mole fraction of un-
charged component in solutions of alka-
nolammonium carboxylates, we obtain values
317
100
/ 1oo
8O L
40
niL .J.."?sJ
y~
"d
~ 60
40 Under D
20 ¢" 2o
U m
20 40 6O 80 100 20 40 60 80
% surfactant % surfactant
of 0.005 with MEA and 0.02 with TEA. These
values are uncertain since it is generally ac-
cepted that the effective pKa for surfactant ag-
gregates or monolayers differ from that in bulk
solution. A commonly accepted value for fatty
acid monolayers is 5.7 (18), and for solubi-
lized fatty acids in anionic surfactant aggre-
gates, values ranging from 5.2 to 6.5 have been
suggested (19). Thus, our estimation is, from
this point of view, a minimum value of the
fraction of uncharged component.
The crucial dependence of pH on the phase
behavior is verified by adding base. For ex-
ample, the system 1 M NaOH ( a q ) - T E A - C 8
is a single isotropic solution phase over the
entire composition region. Adding excess base
to the TEA-Cl2 system prevents the precipi-
tation of excess acid, but the formation of a
lamellar dispersion is favored by adding elec-
trolyte, as anticipated. Thus, for 1 M N a O H
( a q ) - T E A - C I 2 the miscibility gap contains
liquid crystals and extends from 0.1 to 20 wt%
at room temperature but the system becomes
a single solution phase region at around 45 °C.
A further comparison can be made with the
extensively studied ternary systems water-
soap-alcohol. For water-TEA-C12-pentanol
or water-MEA-C12-pentanol, the phase dia-
gram is rather similar to that for water-NaCx-
pentanol (the main features of such phase dia-
grams are for ordinary soaps rather insensitive
to the value o f x (4)). An aqueous L1 and an
alcohol-rich L2 solution phase occurs together
with the liquid crystalline phases E and D (Fig.
Journal of Colloid and Interface Science, Vol. 138, No. 2, September 1990
 318 WARNHEIM AND J(~NSSON

C5 OH C 5 OH
b

water MEA-C12 water TEA-C12

FIG. 3. Ternary phase diagrams at 25°C for the systems (a) monoethanolammonium dodecanoate-
water-pentanol and (b) triethanolammonium dodecanoate-water-pentanol.Notations as in Fig. 1.

3). A comparison with a diagram for sodium
soap (4) shows that the diagrams are quali-
tatively similar apart from more extensive so-
lution phases and, of course, the miscibility
gap in the water-rich region for TEA-C~2.
From low-angle X-ray diffraction measure-
ments, the aggregate dimensions in the la-
mellar phases have been obtained. The area
per polar group was determined for samples
in the binary systems water-MEA-C~2 or -
TEA-C12 and for those in the ternary systems
with pentanol (Fig. 4). In the system water-
MEA-C~z, the area increases from 31 fk 2 at
10 wt% water to 39 ~2 at 30 wt%. For pen-
tanol:MEA-C12 at a ratio 30:70 by weight, the
area increases from 26 ~2 at 10 wt% water to
28/~x 2 at 55 wt% (Fig. 4a). The binary system
water-TEA-C12 behaves differently: the area
is constant, 41 ~ 2 between 10 and 25 wt%
water. The ternary system with pentanol:
TEA-C12 at a ratio 30:70 (by weight) behaves
in a manner similar to that of the MEA-C12
system, and the area increases from 26 A 2 at
25 wt% water to 29 ~2 at 55 wt% (Fig. 4b).
The formation of micelles and the counter-
ion association to micelles have been briefly
studied. The critical micellization concentra-
tion, cmc, has, if possible, been determined
by surface tension measurements (Table I and
Fig. 5 ). Compared to ordinary soaps with cor-

(~2) (,~2)
a MEA b TEA
40 40

30 J 30 J 8

20 20

20 40 60 20 40 60
weight % water weight % water

FIG. 4. Areas per polar group at increasing water content for the systems (a) ©, monoethanolammonium
dodecanoate-water; e , monoethanolammonium dodecanoate-water-pentanol at constant weight ratio do-
decanoate:pentanol of 70:30 and (b) (3, triethanolammonium dodecanoate-water; e , triethanolammonium
dodecanoate-water-pentanol at constant weight ratio dodecanoate:pentanol 70:30.
Journal of Colloid and Interface Science, VoL 138,No. 2, September1990
 ALKANOLAMMONIUM CARBOXYLATE SOLUTIONS 319

TABLE I TABLE II

Critical Micellization Concentrations for Different Micelle Self-Diffusion Coefficient Dmicand Counterion
Surfaetants at 25 °C Association ~ for MEA-CI2 and TEA-C~2 in Aqueous So-
lutions at 25 °C
Surfactant cmc (mol/dm 3)
Concentration Dmlc
MEA-C8 0.08 Compound (wt%) 13 (I0 n~m2 s-')

MEA-C,2 0.008
TEA-C8 0.03 MEA-C,2 10 0.65 +_ 0.05 2.6
NaC8 0.35 a 15 0.63 -+ 0.04 1.7
NaC12 0.024 ~ 20 0.62 -+ 0.04 0.9
23 0.65 +- 0.04 0.9
Value taken from Ref. (16). 25 0.63 -+ 0.04 1.0
TEA-C~2 10 0.50 -+ 0.05 2.6
15 0.54 _+ 0.05 1.9
20 0.52 + 0.03 1.3
responding alkyl chain lengths, the cmc's for 25 0.55 -+ 0.04 0.8
MEA-C8 and MEA-CI2 are lower by a factor
of approximately 3-4 (20). There is a weak
minimum in the surface tension around the
cmc for both systems (Fig. 5a), which could self-diffusion measurements (Table II). /3 is
be due either to impurities or to the small 0.60-0.65 in MEA-C12 between 10 and 25
amount of undissociated acid present. For the wt% surfactant and 0.50-0.55 in TEA-el2 in
systems with TEA-Cx, the miscibility gaps the same concentration interval. The values
prohibit measurements; however, we can in- of the micelle self-diffusion coefficient, Din,
terpolate the surface tension above and below determined fi'om the self-diffusion of the hy-
the miscibility gap with TEA-C8 (Fig. 5b), drophobic solubilizate, make it possible to es-
which suggests that aggregation occurs and timate the micelle radii from the Stokes-Ein-
that the deduced cmc is lower than that with stein equation (Table II). However, for ionic
MEA-C8 (Table I). surfactants in concentrated solutions this gives
The degree of counterion association fi in erroneous values due to the neglect of inter-
the micellar solutions of MEA-C12 and TEA- micellar interactions. Using the Dm for an or-
C12 (at concentrations above the miscibility der of magnitude estimation results in low mi-
gap, of course) have been determined from cellar radii, 10-20 A, which at least suggest

(mN/n (raN~m)
a b
60 60

50 50

4o 40

........ Nb
3o 30

20 20

i | | i,
4 3 2 1 4 3 2 1
- log c [M) -log C [M}

FIG. 5. Surface tension of solutions with varying concentration of(a) l , monoethanolammonium octanoate;
O, monoethanolammonium dodecanoate and (b) O, triethanolammonium octanoate. Miscibility gap is
indicated by dotted lines.

Journal of Colloid and Interface Science, Vol. 138, No. 2, September 1990
320
that no extensive micellar growth occurs; this
is supported by the concentration-independent
line width of the surfactant in the N M R
spectra.
DISCUSSION
Under Results we have already noted a
number of differences--and similarities--be-
tween ordinary soaps and the compounds in-
vestigated here. The most drastic effect when
changing counterion from, e.g., sodium to al-
kanolammonium, is that the surfactant alkyl
chain length becomes predominant in deter-
mining the phase behavior. The phase behav-
ior (Figs. 1 and 2) is not that of a typical ionic
surfactant but is more reminiscent of a series
of nonionic surfactants with constant polar
group and varying alkyl chain length.
A number of factors to explain these anom-
alies are considered. Not only should the in-
teraction between the polar group of the am-
phiphile and the counterion differ compared
to that in normal ions, but, in addition, hy-
drophobic interactions are often invoked in
the case of organic counterions. Both factors
should lead to a lowering of the cmc and a
significant increase in counterion association
compared to that in normal surfactant sys-
tems. In addition there is also the more trivial
fact that the acid-base equilibrium could lead
to a neutralization of the aggregate surface.
Turning to the hydrophobic interaction, it
is well-known that the cmc's of a series oftet-
raalkylammonium dodecyl sulfates decrease
with increasing size--and hydrophobicity--
of the alkylammonium ion (21). While we
note a nonnegligible decrease in cmc with the
alkanolammonium soaps compared to that in
the corresponding alkali carboxylates (Table
I), the measured counterion association fl is
more similar; for sodium octanoate, fl is
around 0.6 (22). The variation of/~ with dif-
ferent organic counterions has been exten-
sively studied by Jansson and Stilbs (23, 24).
For decylammonium micelles with carboxyl-
ate counterions, fl can vary from around 0.50,
indicating small interactions, to 1.0, i.e., a
Journal of Colloid and Interface Science, Vol. 138,No. 2, September1990
W,4,RNHEIM AND JONSSON
complete association. In addition, from relax-
ation measurements with an added relaxation
agent it was concluded that the longer alkyl
chain counterions were definitely solubilized
into the micelle (23).
Thus, considering the absolute values of/3
for MEA and TEA we must conclude that
there are no significant signs of extensive
binding due to hydrophobic or polar interac-
tions. A further argument with respect to the
hydrophobic interactions is that both MEA
and TEA are highly immiscible with hydro-
carbon and have no hydrophobic parts, which
facilitates penetration or solubilization into
surfactant aggregates.
Let us instead consider whether the distri-
bution between charged and uncharged com-
ponents is responsible for the effects on the
cmc's. The effects can be estimated in different
models; we use the simplest possible ideal so-
lution theory (25-27), which has been used
to predict the cmc's of mixed surfactant sys-
tems of ionic and nonionic surfactants with
similar alkyl chain lengths. With this simple
approach, it is possible to check whether the
last hypothesis makes sense, by calculating the
cmc of a hypothetical micelle with varying
fractions of charged surfactant or vice versa.
We set the cmc for a completely charged
octanoate micelle to 0.4 M (20) and that for
a completely uncharged--a hypothetical oc-
tanoic acid micelle--to 0.004 M (which equals
the solubility limit of the alcohol or the acid,
approximately, or the cmc for an octyl ethox-
ylate with a low number of ethoxy groups
(20)). Using the ideal solution expression (25-
27)
1/cmCmix = ( 1 -- p)/cmcionic
-[- p / CmCnonionic , [4 ]
where p is the mole fraction of uncharged sur-
factant, we can use the cmc's of the real system
(Table I) to calculate p within the model.
From these values, the fraction of uncharged
component in the micelle becomes 0.04 for
MEA-C8 and 0.06 for TEA-C8. We can com-
pare this with our previous estimation based
 ALKANOLAMMONIUM
on the pKa's, i.e., 0.005 for MEA-C8 and 0.02
for TEA-Cs, in dilute solutions. The discrep-
ancy can be explained by two factors. First,
the ideal solution theory does not normally
suffice to describe the data more accurately;
instead, a regular solution theory with an
added interaction parameter is used (28, 29).
For mixtures of anionic and nonionic surfac-
tants, the interaction normally favors micel-
lization, which leads to a further lowering of
the cmc at constant composition (28, 29).
This is another way of expressing that the cmc
is also affected by specific effects of polar
groups and counterions: hydration forces, hy-
drogen bonding, and so on. Second, using a
slightly higher effective pKa of the acid as sug-
gested previously ( 18, 19) will make the num-
bers more self-consistent.
We can also note that perfluorinated car-
boxylate surfactants with different counterions
show no corresponding drop in critical mi-
cellization concentration with an alkanolam-
monium counterion instead of alkali ions
(29). This is because the fluorocarboxylic acids
are stronger acids and the dissociation is com-
plete even at lower pH.
The phase behavior can be further illumi-
nated by a comparison with water-soap-al-
cohol or water-acid-alcohol systems, where
ample experimental evidence has been col-
lected. Phase separation may readily occur (4,
30) with increasing concentration of surfactant
at a constant fraction of uncharged compo-
nent. At low concentrations of surfactant, hy-
drated and uncharged components precipi-
tates; with increasing concentration of surfac-
tant, there is an equilibrium between a solution
phase and a lamellar phase (4, 30). With in-
creasing temperature, the water-rich lamellar
phase melts and there is a liquid-liquid equi-
librium or a single liquid solution phase, in
perfect agreement with the phase diagram for
TEA-Cj2 (Fig. 2b).
The phase behavior can be rationalized on
similar grounds also at higher concentrations
of surfactant. For a ternary system of water,
acid, and soap, the phase diagram is affected
by increasing the alkyl chain length of the sur-
CARBOXYLATE SOLUTIONS 321
factant: the extension of the solution phases
(L1 and L2) decreases at the expense of the
multiphase region and the one-phase region
with liquid crystals (4). This explains most of
the features of the phase diagrams in Figs. 1
and 2. In addition, the effects when comparing
MEA-Cx or TEA-Cx for a fixed x are consis-
tent with this: the MEA carboxylate has a
lower fraction of uncharged component and
behaves slightly more like ordinary soaps (the
extensions of liquid crystalline phases in the
C8 and C12 systems with respect to concentra-
tion and temperature are larger).
Only one anomaly remains: the solution
phases with both MEA-C8 and TEA-C8 are
anomalously extensive in the high concentra-
tion region, even considering the undissociated
acid. In addition, water-poor D phases nor-
mally have high melting points even at rather
high ratios of incorporated uncharged com-
ponents (4, 30), in contrast to the investigated
systems (Figs. 1 and 2). An increase in the
extension of the solution phases is also noted
in the ternary systems water-MEA-C12 or
TEA-C~2-pentanol, particularly for TEA-C12
(Fig. 3), compared with, e.g., water-NaCx-
pentanol (4). It has previously been shown
that alkanolammonium perfluorocarboxylate
surfactants have very low Krafft points com-
pared to the corresponding alkali compounds
(29). From Figs. 1 and 2 it is clear that this is
the case for hydrogenated carboxylates as well.
A plausible suggestion is to ascribe the decrease
in melting point of the crystalline and liquid
crystalline phases compared to that in ordinary
soaps to the disordering effect of the bulky
counterion.
Let us finally consider the aggregate dimen-
sions of the lamellar phase in the water-poor
region. The areas per polar group reflect a
packing behavior very similar to that of or-
dinary soaps with some differences for the bi-
nary water-TEA-C~2 system. For water-soap
lamellar phases, there is normally an increase
in area per polar group with increasing water
content (4, 5 ), as is found for the water-MEA-
C~2 system (Fig. 4a). Aggregate dimensions in
the lamellar phase can be explained with the
Journal of Colloid and Interface Science, Vol. 138, No. 2, September 1990
322
J r n s s o n - W e n n e r s t r r m model (30). The elec-
trostatic free energy, containing the enthalpic
(surface charge density) and entropic (mixing
of ions in solution) terms, balances the surface
free energy ~/A. In the binary system at low
water content, an area increase implies that
the electrostatic free energy will increase with
increasing water content, which is mainly due
to the decrease in entropy of mixing of the
counterions in the water lamellae at increasing
lamellae separation. There is no increase in
area with TEA-C12; in addition, the area is
high, 41 ~2, throughout the D-phase, which
shows that the slightly lower surface charge
compared to that of MEA-C12 (or alkali car-
boxylates) does not cause the differences. We
ascribe this to the steric interaction within the
counterion layer, i.e., the size of the associated
counterion. The radius of TEA, assuming
spherical shape, is around 4 A, giving a cross-
sectional area of 50 ~2, which, at these areas
per polar group and even at moderate values
of counterion association, leaves very little
space for the TEA molecules. Adding pentanol
to the bilayer decreases the surface charge and
counterion association, which, together with
the additional head group spacing due to the
alcohols, leads to an area decrease as expected.
The very size of TEA should thus help to
increase the curvature of the aggregates. It has
been demonstrated that this factor is most of-
ten of lesser importance and the decrease in
curvature due to lower surface charge wins out.
We have, though, for alkanolammonium er-
ucates, C22:1, previously noted a difference be-
tween MEA and TEA which could be a size
effect and definitely cannot be explained by
their differences in ionization (16). The M E A -
C22:1 and TEA-C22:l phase diagrams with wa-
ter are very similar to the corresponding dia-
grams for oleate. Adding MEA and TEA, re-
spectively, in excess to samples in the lamellar
phase will not, at low concentrations ( ~ 10
wt% excess), lead to a phase transition for
MEA, but the TEA system will, at excess con-
centration, form a hexagonal phase, i.e., with
higher curvature (16).
Journal of Colloid and Interface Science, Vol. 138, No. 2, September 1990
WARNHEIM AND JONSSON
SUMMARY
To conclude, alkanolammonium as coun-
terion in carboxylate systems causes nonneg-
ligible differences in phase behavior and ag-
gregation compared to ordinary soaps. The
behavior in the dilute region, the lowering of
the c m c - - i f such exists--and the occurrence
of miscibility gaps can be ascribed to the acid-
base properties of the system; i.e., an incom-
plete ionization of the acid-amine. The trends
of the phase diagrams with alkyl chain length
are also consistent with the fact that we have
a partitioning between acid and carboxylate
in the system. However, some of the noted
effects should also be ascribed to the size and
the character of the counterion. In particular
the triethanolammonium ion has a destabiliz-
ing effect on ordered phases due to its bulky
shape, an effect useful for practical formula-
tions of solution phases.
ACKNOWLEDGMENTS
This work was financially supported by Stiftelsen Karl-
shamns Forskning (Research Foundation of Karlshamn
ab). Many thanks to Jari Alander. Karlshamn, for dis-
cussions, to Marie Sj6berg for performing the self-diffusion
measurements, and to Lotti Eriksson for patient technical
assistance.
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