Journal of Dispersion Science and Technology, 287:1117–1122, 2007

Copyright # Taylor & Francis Group, LLC

ISSN: 0193-2691 print/1532-2351 online
DOI: 10.1080/01932690701525221

Evaporation Path in a Liquid Crystal/Hydrocarbon Emulsion in the

System Toluene, 5-Phenylvalerate, 4-Pentylphenol and Water
Stig E. Friberg
Chemistry Department, University of Virginia, Charlottesville, Virginia, USA

Johan Sjöblom
Ugelstad Laboratory, Department of Chemical Engineering, Norwegian University of Science and Technology (NTNU),
Trondheim, Norway

The evaporation path in emulsions of a water/5-phenylvalerate/4-pentylphenol lamellar liquid

crystal in toluene was calculated using an algebraic method to extract information from a
partial phase diagram. The equations for the tie lines between the emulsion phases and the
evaporation path were established and used to evaluate the variation in the composition of
the liquid crystal during the evaporation. The evaporation lead to significant changes in the
composition of the liquid crystal and the modification of the vapor pressure during the
process was estimated from published values for similar systems. The deviation of water
pressure from the value for p was too small to influence the evaporation path to a significant
degree, but the departure from the native toluene pressure were sufficient to cause a discern-
able change in the evaporation path. These deviations were small in comparison with the ones
caused by the relative humidity on the evaporation path. The results also gave an example of a
situation in which the assumption of equilibrium between the vapor and the compound in the
emulsion is no longer valid providing an example for which the phase diagram approach to
evaporation is not relevant.

Keywords Phase diagrams, evaporation, emulsions, naphtenic acids, liquid crystals

INTRODUCTION We found an investigation into the evaporation path of an

Stability is the most vital property for emulsions in general
and has with justification been the focal point of the investi-
gations[1,2] into the general area of emulsions. However, for a
significant number of applications, the initial behavior is not
he determining factor in their application. Instead, the structure
changes during evaporation are the final attribute for their com-
mercial employment. On that account, the research into the
fundamentals of emulsion evaporation has been thoroughly
investigated for the classical two-phase emulsions with the
University of York group as the leading institution.[3 – 7]
However, even for emulsions of such unsophisticated kind,
evaporation leads to the formation of new phases and
examples have been published, in which such structures are
lamellar liquid crystals.[8] Hence, research of amphiphilic
association structures in connection with emulsion evaporation
has been recently introduced.[9,10]
Received 10 May 2006; Accepted 3 October 2006.
Address correspondence to Stig E. Friberg, 1695 Goldentree Place,
Charlottesville, VA 22911. E-mail: sfbg@comcast.net
emulsion stabilized by a naphtenic acid soap combination
attractive, because it would add to the knowledge both con-
cerning emulsions of great interest[11,12] and emulsions stabil-
ized by lamellar liquid crystals.[13,14]
The presence of naphtenic acids cause serious problems in
the production of the crude oils as has recently been
reviewed by Sjöblom and collaborators.[12] Of the many
problems caused by the presence of naphtenic acids; such as
corrosion, deposits and stable W/O emulsions, the latter
phenomenon is considered significant from an economical
point of view. Hence, it has been the focus of a large number
of investigations over the years.[12,15 – 18] These studies have
prompted a renewed interest in the phase equilibria in
systems of amphiphilic association structures, because knowl-
edge of these is one of the essential elements to understand the
properties of emulsions.[13,19 – 21] Of the structures of this kind,
the lamellar liquid crystal, La, was early introduced[13,14] as a
stabilizer for emulsions; similar to the action by lamellar gels
Lb.[22,23] Such structures provide an additional stabilizing
mechanism[19,24] to the ones in traditional two-phase
emulsion[1,2] as well as to the effect of solid particles.[25 – 28]

1117
1118 S. E. FRIBERG AND J. SJÖBLOM
The stable crude oil W/O emulsions cause serious problems
in its extraction and handling. In spite of this importance a
number of factors in the total problem remain to be solved
or—at least—clarified. Recently, the potential importance of
the naphtenic acids in the crude has been brought to the atten-
tion of the researchers in the area with a series of
investigations.[11,17,18,29]
In the present contribution the evaporation is explored of
dilute W/O emulsions stabilized by a combination of phenyl-
valerate and pentylphenol. The pH level was chosen to give a
lamellar liquid crystal, when the soap of the acid was
combined with the phenol.[21] The feature of the system of
interest for the present contribution is the composition of a
lamellar liquid crystal in equilibrium with toluene, in which
only insignificant amount of the amphiphiles are dissolved.
The composition of the liquid crystal so engaged is given in
Table 1.
RESULTS
The results will be reported in two sections. In the first
segment the emulsions per se will be given an algebraic
description and in the second part the conditions during
evaporation will be evaluated.
Emulsion Features
The coordinates for different compositions of the emulsion
are given as weight fractions of the total in the order water, sur-
factant, toluene; (W, S, T). The aspects of the emulsion of
interest for the present investigation are the toluene as oil
phase; (0.0.1), the lamellar liquid crystal; (WLC, SLC, TLC),
the emulsion; (WE, SE, TE) and the composition of the vapor
in equilibrium with the emulsion; (WV, 0, TV).
The composition of the lamellar liquid crystalline phase in
equilibrium with toluene (Table 1) was fitted into Equation
(1) for the composition range (W, S) (0.770, 0.210) – (0.342,
0,354).
W ¼ 1:4
3S
The weight fraction of the surfactant combination in the emul-
sions was kept constant at 0.05; illustrating a dilute W/O crude
TABLE 1
The weight fractions of water, toluene and surfactant
combination of the lamellar liquid crystal in equilibrium with
toluene
Toluene Water Surfactant combination
0.02 0.77 0.21
0.05 0.71 0.24
0.093 0.629 0.278
0.23 0.465 0.305
0.304 0.342 0.354
oil emulsion with small surfactant concentrations. The compo-
sition of the emulsions follows a simple relation, since the
fraction of surfactant is constant.
S ¼ 0:05 ½2
The Method
According to Haeger and Sjöblom[21] the solubility of the
remaining compounds in toluene is not at a level to be
significant for the present investigation. The composition of
the liquid crystal in equilibrium with the emulsion is directly
obtained from the equation of the line from the toluene
corner, (0.0.1) of the diagram through the emulsions
composition; (WE, SE, TE).
W ¼ WE S=SE ½3
and Equation (1) to give
SLC ¼ 1:4=ð3 þ 20WE Þ ½4
and
WLC ¼ WE =ð0:107 þ 0:714WE Þ ½5
This information provides the coordinates for the liquid crystal;
(WLC, SLC, TLC) versus the water fraction in the emulsion. This
latter is the deciding factor for the evaporation direction along
a line from the vapor composition, (WV, 0, TV) through the
initial emulsion composition, (WE, 0.05, TE)
W ¼ WV þ 20SðWE
WV Þ ½6
The weight fractions of the components in the vapor are
calculated, assuming equilibrium between the vapor exiting
the emulsion and the compounds in the emulsion. The weight
fraction of water in the vapor is
WV ¼ PW MW =ðPW MW þ PW MW Þ ½7
in which P stands for pressure and M for molecular weight. The
expression for the fraction of released water, on the other hand,
½1 is modified by a term caused by the fact that the rate of water
vapor leaving the emulsion is affected by the relative humidity.
The operative PW is equal to PW –0.01 RH; RH being the
relative humidity in percent.
The general equation for the evaporation line from the
emulsion becomes
W ¼ WV þ ðWE
WV ÞS=SE ½8
Using the modified Equation (7) the complete equation
becomes
W ¼ fPW MW ð1
0.01RHÞ=½PT MT
þ PW MW ð1
0.01RHÞ
þ ½WE
½PW MW ð1
0.01RH=½PT MT
þ PW MW ð1
0.01RHÞgS=SE ½9
The slope of the evapration line from the emulsion
 EVAPORATION PATH IN A LIQUID CRYSTAL/HYDROCARBON EMULSION
FIG. 1. The vapor pressure of phenethyl alcohol in the inverse micellar
solution at maximum water solubilization in the system water, phenethyl alco-
hol and a commercial tetraehylene glycol dodecyl ether.[8]
composition,
ðdW/dSÞ ¼ ðWE
WV Þ=SE
With the available information each shift in the emulsion com-
position is calculated from
Wnþ1 ¼ WnE þ ðdW/dSÞDS
E
The new emulsion composition is used to determine the equi-
librium composition in the liquid crystal and the process is
repeated.
The objective of the investigation is to illustrate the differ-
ence in the evaporation path from the case of constant vapor
pressure, which was treated in an earlier article.[30] With the
distinction between the two cases as the main goal of the inves-
tigation the trends of the vapor pressures is the essential infor-
mation and the paucity of information about the system in
question was not considered material for the value of the
results. Hence, the values from the vapor pressure of water in
a lamellar liquid crystal stabilized by octa-ethyleneglycol
dodecyl ether as reported by Carwell[31] was consulted. They
revealed the vapor pressures of water to deviate by less than
one percent from the value for pure water and in the following
analysis the latter value was used.
As far as the vapor pressure of a hydrocarbon in a lamellar
liquid crystal is concerned careful determinations have shown
it to vary close to that for an ideal solution, if the pressure is
plotted versus the mole fraction hydrocarbon/(hydrocarbon
plus surfactant).[9]
In order to approach the conditions in the system under
investigation, the relation between the mole fraction and the
vapor pressure is applied to the conditions in a cationic
system; the system water- cetyltrimethylammonium chloride
1119
and hexanol.[32] The relation between the water weight
fraction in the lamellar liquid crystal and the weight fraction
volatile compound in the water poor liquid counted on the
amphiphiles is shown in Figure 2.
The features of the two figures show two counteracting
phenomena. The vapor pressure in the range of maximum
water solubilization is higher than the values for an ideal
solution, while the mole fraction in the water poor liquid
shows lower than linear behavior. In a somewhat dubious
attempt to correlate the two factors the “excess” value for the
PEA system was added to the values in the cationic system
resulting a combination curve according to Figure 3.
The approach is, admittedly, extremely approximate, but
not entirely unrealistic as evidenced by the comparison with
a plot of the actual vapor pressure of phenethyl alcohol
versus the water weight fraction in the lamellar liquid crystal
in equilibrium, which is added to the figure for comparison.
The relation between the water weight faction in the liquid
crystal and the vapor pressure of the toluene was accepted as
ðP/P0 ÞT ¼ 0:687 þ 0.275WLC ½12
These relations and values enable the calculation of the evap-
oration path. The results are given in the next section.
½10
RESULTS
Assuming a realistic fraction of water in the original
emulsion of 0.15, the composition of the liquid crystal in equi-
½11 librium is obtained by a combination of Equations (1) and (3)
to give (0.700, 0.233, 0.067).
The water and toluene vapor pressures for that composition
determine the initial evaporation direction of the emulsion.
Available data at 228C are for water P0 ¼ 20 mmHg and
with a relative humidity of 75% the apparent vapor pressure
of water becomes 5 mmHg. The vapor pressure of toluene
P0 ¼ 24.7 mmHg and P/P0 ¼ 0.880 according to Equation
FIG. 2. The hexanol molar fraction, hexanol/(hexanol þ cetyl trimethyl
ammonium bromide), for maximum water solubilization in the inverse micellar
solution versus the water fraction in the equilibrium lamellar liquid crystal.[31]
1120 S. E. FRIBERG AND J. SJÖBLOM
FIG. 3. Modified hexanol fraction (B) (from Figure 2) and the vapor
pressure of phenethyl alcohol (r).[8] The hatched line corresponds to ideal
vapor pressure.
(11). The composition of the exiting vapor is in weight fraction
(0.043, 0.957). The initial evaporation takes place along a line
from (0.043, 0, 0.957) through the emulsion composition 0.15,
0.05, 0.80)
W ¼ 0:043 þ 2.14S
These values were used to calculate subsequent steps in the
evaporation and the results are shown in Figure 4.
The results are remarkable from one point of view. They
show a dependence of the water content of the emulsion to
be almost exactly linearly dependent on the surfactant
content of the emulsion. In fact the deviation from such
behavior is less than one third of one percent for the water
content. The reason for this behavior is found in the vapor
pressure variation with the water fraction in the liquid crystal
(Figure 3). It would be tempting to voice some reservations
about the validity of the results, because of the artificial
manner by which the values of the hydrocarbon vapor
FIG. 4. The variation in emulsion composition during evaporation. (B)
toluene; (r) water.
pressure were obtained. But the comparison with the actual
values for a similar system yields some support to results.
DISCUSSION
The results were found sufficiently interesting to evaluate
the general conditions during evaporation in a model system.
The system is patterned on the results of fragrance emulsions
by Al-Bawab.[33] The model emulsion composition is (WE,
SE, HE) with the two liquid phases in equilibrium; aqueous,
Aq, (1,0,0) and oil, Oi, (0, SOi, HOi).
The oil/surfactant solution is assumed ideal and the vapor
pressure of the oil is proportional to the oil mole fraction in
the solution. The equilibrium composition in the original
emulsion is (0, SOi, HOi), (0, SE/(12WE), HE/(12WE)),
which corresponds to the mole fraction hOi/(sOi þ hOi) in
which the h and s mean moles of the two compounds.
The mole fraction hydrocarbon and with it its vapor pressure
equals HE/(kMSE þ HE) ¼ PH/PH(0), in which PH(0) is
the vapor pressure of pure H and kM ¼ MH/MS in which M
is molecular weight. The evaporation path is calculated as an
iteration process, in which each step corresponds to equal
weight evaporated of water, Dw, because of the constant
water vapor pressure.
½13
After the composition of the vapor phase of the original
emulsion is established, the weight of the aqueous phase
(¼water) is established and the new composition after
reduction of the set water amount, the weights of the com-
ponents of the emulsion are calculated.
The features of the emulsion during evaporation are illus-
trated by the example in Figure 5. The original emulsion has
a total weight of unity and a composition (0.19, 0.05, 0.76)
and the fraction aqueous phase becomes 0.19, while the
fraction oil phase is 0.81. The mole weight of the surfactant
equals 300, while that of the hydrocarbon is equivalent to
FIG. 5. The fractions of surfactant (  10) (p) and hydrocarbon (B) ver-
sus the reduction in water fraction during evaporation of a mode emulsion
system.
 EVAPORATION PATH IN A LIQUID CRYSTAL/HYDROCARBON EMULSION
100; a kM ¼ 1/3. The vapor pressure of the oil becomes 0.76/
((0.05/3) þ 0.76) ¼ 0.9785PH(0). The weight fraction of
hydrocarbon in the vapor is 0.800. Reducing the weight of
the water in the emulsion with 0.02 weight units gives a
reduction in the hydrocarbon weight content by
0.02  (HV 2 HE)/(HV 2 HE) ¼ 0.08. The new weights of
the emulsion is w ¼ 0.17, s ¼ 0.05 and h ¼ 0.68. The fractions
of the compounds in the emulsion are (0.189. 0.0556, 0.756). A
new oil composition is calculated and the iteration is continued.
The results (Figure 5), at a first glance, do not reveal any
exceptional feature. The fraction of surfactant increases inver-
sely to the reduction in the total of the emulsion weight and that
of the hydrocarbon displays a more moderate increase, because
of its own evaporation.
However, these results serve as an excellent illustration to
the need for caution, when representing the evaporation path
solely as fractions of the emulsion components. A represen-
tation of the hydrocarbon weight versus the weight of the
water evaporated divulges a phenomenon with fundamental
consequences (Figure 6).
The curve in Figure 6 was fitted to a simple equation
h ¼
72.15w3 þ 28.02 w2
3.141w ¼ 0:759
ðR2 ¼ 0:999Þ ½14
and the minimum found from the first derivative
ðdh/dwÞ ¼
216:45w2 þ 56.03w
3:141 ½15
w ¼ 0.82 in accordance with the results in Figure 6.
Formally the results show that for evaporated water weights
in excess of a certain value the evaporation process would
proceed by the emulsion attracting hydrocarbon from the
environment.
Obviously, such a result would require rather extraordinary
experimental conditions to prevent the vapor from being dissi-
pated and the applicability of the results for actual evaporation
of emulsions is of limited value.
FIG. 6. The weight of hydrocarbon versus the weight of water during
evaporation.
1121
However, the fundamental conclusion is evident. At this
point the assumption of equilibrium between the vapor and
its compound in the emulsion breaks down. As a consequence
the phase diagram approach to evaporation becomes invalid
and kinetic factors become the decisive phenomenon for
evaporation.
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