Colloids and Surfaces A: Physicochem. Eng.

Aspects 324 (2008) 9397

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

A phase diagram approach to determine the composition of vapor from

a microemulsion base
Stig E. Friberg a , P.A. Aikens b,
a
b

Chemistry Department, University of Virginia, Charlottesville, VA, United States

BASF Corp., Stony Brook, NY, United States

a r t i c l e

i n f o

Article history:
Received 25 June 2007
Received in revised form 20 March 2008
Accepted 3 April 2008
Available online 12 April 2008
Keywords:
Microemulsion
Phase diagram
Vapor composition
Evaporation
Emulsions
Vapor pressures
Detergents

a b s t r a c t
The tangents to the evaporation path curves in the W/O microemulsion base of water, (W), pentanol, (P),
and sodium dodecyl sulfate, (S), were extended to the W/P axis to establish the relative composition, (WV ,
PV ), of the vapor leaving the liquid.
The composition of the vapor, with which the microemulsion is in contact includes also the contribution
from the relative humidity of the surrounding atmosphere. The difference between the composition of
these gases is claried using the algebraic expressions from the phase diagram, but the quantitative
composition of the equilibrium vapor is not available without further numerical information. The limits
of the vapor for evaporation direction under different relative humidities were claried.
2008 Elsevier B.V. All rights reserved.

1. Introduction
Evaporation from microemulsions is an essential process in a
number of elds such as the preparation of nano-particles, where
the potential was realized early on for medical products [1]. In
addition, their potential as catalysts was evident and the preparation of mixed oxides [2] and metal alloys [3] was achieved early
on. The recent application of a hydrophobized polymer useful in
retaining the monodispersity of barium sulfate particles at a size
of 50 A [4] is interesting and note-worthy. For many applications
porosity is an essential property and the potential for the preparation of such particles in microemulsions was recognized at an
early stage [5]. Among the recent applications the utilization in
the area of ink jet printing [6] is certainly of more than average
interest.
As expected, with this wide importance, the process of evaporation from microemulsions has received attention from a
fundamental point of view. One of the rst contributions [7]
used neutron-specular-reectivity measurements on liquid surfaces of disordered bi-continuous microemulsions to demonstrate
that evaporation causes the formation of an ordered lm on the
surface of the microemulsion. Another contribution [8] related the

Corresponding author. Tel.: +1 631 380 2351; fax: +1 631 689 2904.
E-mail address: patricia.aikens@basf.com (P.A. Aikens).
0927-7757/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2008.04.001

evaporation rate to the binding of water to the polar group of the

surfactant. Professor Fletchers group [9] compared the evaporation rates of water from pure water and from a water-in-dodecane
microemulsion under carefully monitored air ow rates. The results
revealed the evaporation rate from the microemulsion to be lower
by more than an order of magnitude even in those parts of the
microemulsion compositions, where the water vapor pressure was
close to that of pure water. The results were interpreted as the
evaporation rate being inuenced by the diffusion rate of the
microemulsion drops through the hydrophobic environment. Later,
Hamdan et al. reported a water evaporation dependence on the relative humidity, when investigating perfume microemulsions under
atmospheric conditions [10].
A different approach to the analysis of emulsion evaporation
in general was taken by Friberg et al. [11] who found that new
phases appeared during the evaporation of a simple two-phase
emulsion. This initial investigation was followed by a series of
investigations into microemulsions and emulsions where vapor
pressures calculated from the phase diagram and those measured
above the evaporating emulsion were compared [12]. In these cases
the vapor pressure of the oil was low, the relative evaporating rate
had insignicant effect on the evaporation path and the agreement
was satisfactory between the path predicted by the phase diagram
and the experimental one. In a subsequent development phase diagrams were used to estimate the evaporation direction in several
emulsion systems in which both water and the oil were evaporat-

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S.E. Friberg, P.A. Aikens / Colloids and Surfaces A: Physicochem. Eng. Aspects 324 (2008) 9397

ing, but in which the major part of the volatile material came from
the continuous phase [13,14].
The approach obviously has some predictive limitations, considering the results by the Hull group [1518], who reported a 10-fold
reduction of the water evaporation rate of a microemulsion over
that of pure water. The phase diagram approach, however, is concerned with ratios of water and volatile organic compounds, thus
reducing the discrepancy to more manageable magnitudes; at least
for extremely slow evaporation.
The present contribution introduces a new application of the
phase diagram approach to evaporation. It is used here to determine the composition of the departing vapor from an evaporating
microemulsion without the need for analysis of the vapor per
se. Instead the composition of the departing vapor is calculated
from the experimentally determined evaporation path in the
microemulsion liquid. Before outlining the method it is imperative to emphasize that the approach per se is not thermodynamic;
the results only, but exactly, show the composition of the released
vapor. Hence, the approach involves no approximations or assumptions; its accuracy is limited only by the restrictions posed by the
methods of analysis.
It would be tempting to relate the composition of the evaporating vapor to the activity of the components in the microemulsion
liquid; assuming equilibrium between gas and liquid as well as ideal
gas behavior of the vapor. However, such a computation is not possible, because any equilibrium, if existing, is not with the vapor
leaving the liquid, (which is given by the experimental results,) but
with the composition of the atmosphere, with which the liquid is
in contact.
As a summery, the goal of the article is to introduce the method
per se; the use of the evaporation path in the liquid to offer exact
information about the composition of the released vapor.
2. Theory and calculation
2.1. The fundamentals of the system
The evaporation path of the microemulsion, Fig. 1, is represented
by a function, C(S), obtained by tting the experimental results to
a polynomial. (C is the weight fraction of co-surfactant, while S
represents the same measure of surfactant.)

The equation for the tangent to the curve at the point (W1 , C1 ,
S1 ) is:
C = C1 + (S S1 )

dC1
dS1

(1)

Putting S = 0 gives the weight fraction of C in the evaporating vapor.

C V = C1

S1 dC1
dS1

(2)

There is no evaporation of the surfactant, hence

WV = 1 CV = 1 C1 +

S1 dC1
dS1

(3)

It is essential to emphasize these conditions are valid for the

vapor released from the liquid during the evaporation. The values
are kinetically dependent and would only represent the equilibrium
vapor pressures of the volatile components of the microemulsion,
if equilibrium were established and the evaporation took place into
an atmosphere of zero relative humidity.
2.2. Numerical example
The path for a slow rate of evaporation from an early publication [20] is given in Fig. 2 as water (W) and pentanol (P) weight
fractions versus surfactant weight fraction (S) for the composition
of the liquid. The co-surfactant in this case is pentanol, represented
by a capital P to distinguish it from the general case, in which the
co-surfactant is denoted C.
The results reveal two features of interest. At rst the relative
content of water in the released vapor is reduced during the evaporation; a consequence of the reduced inverse micellization with
increased surfactant content [19]. Secondly, this trend is signicantly enhanced at the higher temperature; an expected tendency,
considering the association structures not to be prevalent at this
temperature level.
The data points on the curve for water fraction versus surfactant
fraction in the liquid, Fig. 2, at room temperature were approximated by a second order equation
W = 6.29S 2 4.944S + 0.912;

(R2 = 0.999)

(4)

providing a value for the derivative

 dW 
dS

= 12.58S 4.944

(5)

The calculated water fraction in the vapor liberated from the

microemulsion, (WV ), is now obtained for each fraction W of water

Fig. 1. The solubility region in the top part of the diagram is the W/O microemulsion
base, to which oil may be added to form a W/O microemulsion. In this article, the
liquid is labeled microemulsion and the co-surfactant serves a dual purpose as active
at the interface, but also as the organic solvent; the oil. The composition during
evaporation is given by the dotted line.

Fig. 2. The weight fractions of water (Filled symbols) and pentanol (Open symbols)
versus weight fraction of surfactant in the microemulsion liquid at room temperature (Squares) and at 90 C (Triangles).

S.E. Friberg, P.A. Aikens / Colloids and Surfaces A: Physicochem. Eng. Aspects 324 (2008) 9397

95

Fig. 3. The ratios between water and pentanol weight fractions in the vapor at
room temperature () and at 90 C () versus the surfactant weight fraction in the
microemulsion liquid.
Fig. 4. The evaporation directions of specic interest.

in the microemulsion.
WV = W

 dW 
dS

S = 0.912 6.29S 2

(6)

CV =

and
app

PV = 1 WV

= 6.29S 2 + 0.088

(7)

where the subscript v denotes vapor and the capitals are weight
fractions.
The corresponding equations for 90 C are:
W = 2.568S 2 2.787S + 0.7438;

 dW 
dS

The basic relationships are:

(R2 = 0.999)

= 5.136S 2.7887

WV = W

 dW 
dS
app

PV = 1 WV

S = 0.7438 2.568S 2

= 6.29S 2 + 0.088

(8)
(9)
(10)
(11)

Eqs. (6)(11) provide the weight fractions of water and pentanol

in the released vapor, but do not give information about the chemical potential of the two compounds in the released vapor. With this
in mind it was judged proper not to display the values in a diagram
to avoid misinterpretations. Instead the ratio between the fractions
is shown in Fig. 3.
The results in Fig. 3 are easily converted to a ratio between
vapor pressures of the two compounds and subsequently to the
ratio between the activities in the released vapor. However, such
an evaluation would serve no purpose, because the values would
be kinetically dependent and could not be meaningfully related to
the composition of the liquid. In fact, even if the value for the relative humidity were available, it would not be possible to relate the
total vapor pressure of water in the atmosphere
PW (tot) = PW + 0.01RH PW (0)

(12)

WV =

PC MC
[PC MC + MW PW 0.01RHMW PW (0)]
MW PW 0.01RHMW PW (0)
[PC MC + MW PW 0.01RHMW PW (0)]

(13)
(14)

in which the dimensions are now presumed to be consistent. PW is

now the vapor pressure of water from the microemulsion at equilibrium and PW (0) is the vapor pressure of pure water. The results
of such an evaluation are relevant to two features of the evaporation process; they furnish information about the direction and the
relative volume of compounds in the released vapor.
The directions of specic interest are displayed in Fig. 4 with
their conditions outlined in the following text.
1. For the RH value equal to zero and evaporation at equilibrium
the composition of the vapor offers limited information about
the thermodynamic factors of the liquid microemulsion, as is
evident from Eq. (11), which under these conditions becomes
CV =

PC MC
[PC MC + MW PW ]

(15)

As remarked, Eq. (15) inherently contains information about

the ratio of activities of the volatile compounds in the micromulsion liquid for this condition of evaporation under equilibrium.
The ratio is

a 
C

aW

M 
W

MC

CV
MW CV
=
MC WV
(1 CV )

(16)

2. The weight fraction of C during the evaporation remains constant

during evaporation; CV = C1 , which gives
RH =

{PC MC [1 (1/C1 )] + MW PW }
0.01MW (PW (0))

(17)

because the dimension of PW is not known.

Instead the effect of differences in the relative humidity will be
explored in a separate section.

3. The water and the co-surfactant are depleted concurrently;

CV = C1 /(1 S1 ) and

3. Effect of relative humidity on the evaporation

4. The water weight fraction remains constant during evaporation;

CV = 1 W1

In the following analysis the co-surfactant is denoted C to distinguish this general case from the earlier numerical example of
pentanol.

RH =

RH =

{MW PW (PC MC W1 /C1 )]}

0.01 MW PW (0)

{[PC MC W1 /(W1 1)] + MW PW }

0.01MW PW (0)

(18)

(19)

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S.E. Friberg, P.A. Aikens / Colloids and Surfaces A: Physicochem. Eng. Aspects 324 (2008) 9397

Table 1
Relative humidity (RH) and evaporation directions for specic scenarios
Feature #

CV

RH

Water

Co-surfactant

Emulsion weight

1
2
3
4
5
6
7

0.14
0.6
0.8
0.85
1

0
66.7
71.9
72.8
75
87.5
100

Evaporation
Evaporation
Evaporation
Evaporation
Remain constant
Uptake
Uptake

Evaporation
Evaporation
Evaporation
Evaporation
Evaporation
Evaporation
Evaporation

Reduced
Reduced
Reduced
Reduced
Reduced
Constant
Increased

5. The ratio between water and surfactant remains constant during

the evaporation.
RH =

MW PW
0.01 MW PW (0)

(20)

6. The weight fraction of surfactant remains constant during the

process; e.g. the loss of co-surfactant from the liquid is exactly
compensated by the uptake of water.
RH =

(PC MC + PW MW )
0.01RHMW PW (0)

(21)

7. The relative humidity equals 100%.

CV =

PC MC
[PC MC + MW {PW (em) PW (0)}]

(22)

The relationship between features 17 in Fig. 4 and the relative humidity (Table 1) are illustrated by the following numerical
example chosen with realistic values of the vapor pressures and
compositions:
C1 = 0.6,
MC = 150,

PW = 15,

Fig. 6. Evaporation/precipitation path for water, surfactant, and co-surfactant.

PC = 0.3,

PW (0) = 20

MW = 18,
(22)

A more representative overview is found in a diagram displaying

the ratio between CV and WV . The ratio advances toward the positive
innity with increasing RH and reduced water evaporation shifting
from positive innity to negative innity, when the uptake of water
begins, Fig. 5.
The shape of the curves in Fig. 5 is generic, but the value of the
relative humidity for the reversal of the sign is specic for each
system.
These results illustrate the decisive effect the relative humidity
may have on the direction of the evaporation path from a composition of the microemulsion, but the phase diagram approach
to evaporation has another equally essential consequence. It gives

information about the sudden changes in the evaporation process

due to alteration in the number of phases in the system.
The most relevant of these for the present subject is the limited
solubility of the ionic surfactant in the co-surfactant [19]. The conditions are described in Fig. 6, in which the deviation from a straight
line of the limit and the content of water in the surfactant hydrate
are neglected.
The evaporation path through the area for the microemulsion
base according to the earlier analysis, but its direction changes in
a most signicant manner, when the limit for solubility of the surfactant is reached. From that point on the evaporation path the
loss from evaporation is complemented by precipitation of surfactant and one of the volatile compounds to give a composition path
according to the limit for surfactant solubility. The limit for precipitation is well established [19] as characterized by a constant ratio
between water and surfactant
The general algebraic expressions for the combined evaporation/precipitation path tend to be unwieldy and a complete
treatment of the phenomenon will be referred to a later communication. The following sketch is limited to a few points in the
treatment.
At the stage, when the evaporation path of a liquid of mass m
reaches the limit of surfactant solubility, (WL , CL , SL ) the weights
of the components are mWL , mCL and mSL and the composition of
the released vapor is (WV , CV , 0) in weight fractions. A new composition is reached by rst assuming an evaporation of the weight
dw of water. The corresponding evaporation of the co-surfactant
is dc = dw(CV /WV ). Since the surfactant does not evaporate the
new composition (as weights) is mWL dw, mCL dw(CV /WV ).
This composition is unstable and is modied to t the conditions
for the line of maximum surfactant solubility, which is identied
by
C =1+

W (CL 1)
WL

(23)

and
S=

Fig. 5. The ratio between the co-surfactant and water content in the released vapor.
From a relative humidity of 75% the water is absorbed and its fraction in the vapor
becomes negative, hence the change of the ratio sign.

WSL
WL

(24)

expressed as weight fractions.

The values of weight fractions are recalculated to weights and
the difference in surfactant weight as well as in one of the volatiles
constitute the precipitation part of the process.

S.E. Friberg, P.A. Aikens / Colloids and Surfaces A: Physicochem. Eng. Aspects 324 (2008) 9397

4. Discussion
Several issues are essential with regard to this article. The
key contribution is the introduction of a method to obtain exact
information about the composition of the departing vapor from
a microemulsion during evaporation without resorting to costly
and time consuming analysis of the vapor per se. The advantage of
the method is obvious; in comparison with gas chromatography or
other analytical processes requiring costly equipment, the determinations of the liquid include simple non-analytic operations such
as registering the weight loss combined with fast and inexpensive
routine measurements such as determination of refractive index,
density, etc.
The method in its present state has a decisive limitation; it is
restricted to systems with only one volatile compound in addition to the water. However, the extension to systems with several
volatile compounds encounters no systematic problems; for each
added compound another method to determine a property of the
system is added and the algebra extended to functions covering
three or more dimensions.
The system offers an additional advantage that is specic for
the approach; it provides intelligence about the inuence of phase
changes on the evaporation process and these may be signicant
considering the features in Fig. 6.
5. Conclusion
A method has been introduced to obtain exact information
about the relative composition of the released vapor from a simple
microemulsion system without retorting to analysis of the vapor
per se. The method also offers information about the consequence
of relative humidity on the process as well as the pronounced effect
of phase transitions on the evaporation path.
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