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Chinese Chemical Letters 21 (2010) 880–883

www.elsevier.com/locate/cclet

Surfactant-free oil/water and bicontinuous microemulsion

composed of benzene, ethanol and water
Fei Song a, Jie Xu b, Wan Guo Hou a,b,*
a
Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100, China
b
College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
Received 13 November 2009

Abstract
Generally, a microemulsion consists of oil, water, surfactant and sometimes cosurfactant. Herein, we report a novel surfactant-
free microemulsion (denoted as SFME) composed of benzene, water and ethanol without the amphiphilic molecular structure of
traditional surfactant. The phase behavior of the ternary system was investigated, finding that there were a single-phase region and a
two-phase region in ternary phase diagram. The electrical conductivity measurement was employed to investigate the microregion
of the single-phase region, and a bicontinuous microregion and a benzene-in-water (O/W) microemulsion microregion were
identified, which was confirmed by freeze-fracture transmission electron microscopy (FF-TEM) observations. The sizes of the
microemulsion droplets are in the range of 20–50 nm.
# 2010 Wan Guo Hou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Keywords: Surfactant-free microemulsion; Phase behavior; Conductivity; FF-TEM

Since their discovery by Hoar and Schulman [1] in 1943, microemulsions have received the attention of a number of
researchers concerned with the theoretical and application aspects of their formation and stabilization [2]. The term
‘‘microemulsion’’ was coined by Schulman and Stoechnius [3] in 1959, now it has been widely accepted that
microemulsion is an optically isotropic, transparent, and thermodynamically stable dispersion formed by two or more
immiscible liquids, which are stabilized by an adsorbed surface-active molecule film at the liquid–liquid interface.
Generally, a microemulsion consists of oil, water, surfactant and sometimes cosurfactant [3], and it is believed that the
surfactant is the important component in stabilizing these systems. However, Smith et al. [4] in 1977 reported an oil-
continuous (or W/O) microemulsion composed of hexane, 2-propanol and water, and this ternary system was
considered as surfactant-free (or detergentless) microemulsion (denoted as SFME) because no traditional surfactant
involved in the system. Subsequently, the SFMEs have attracted much attention [5–13], their many physical properties
were measured, and it was found that the phase and tension behavior of the systems were similar to those observed
with surfactant-based microemulsion systems. Up to now, all SFMEs reported in literatures [4–13] are water-in-oil
(W/O) systems. Herein, we report oil-in-water (O/W) and bicontinuous SFMEs composed of benzene, water and
ethanol.

* Corresponding author at: Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100, China.
E-mail address: wghou@sdu.edu.cn (W.G. Hou).

1001-8417/$ – see front matter # 2010 Wan Guo Hou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
doi:10.1016/j.cclet.2010.01.029
 F. Song et al. / Chinese Chemical Letters 21 (2010) 880–883 881

Fig. 1. Phase diagram of benzene/ethanol/water ternary system at 25 8C. Line a and line b with RB/E = 15 and 25, respectively, are chosen for the
conductivity examinations and sample points A and B are the samples chosen for the FF-TEM study. I and II micoregions are water-in-benzene and
bicontinuous microemulsion regions, respectively.

The ternary phase diagram of the system at 25.0  0.2 8C was constructed on the basis of physical properties of
various compositions of benzene, ethanol and water. Mixtures of benzene and water with various volume ratios of
benzene to water (RB/W) were prepared in dry test tubes, titrated with ethanol under stirring. The ethanol volume at
which the mixtures became clear was noted. The entire experimental procedure was repeated three times and an
average value was used to plot the phase diagram, see Fig. 1. The region marked with ‘‘single-phase’’ includes
transparent compositions, the region marked with ‘‘two-phase’’ includes turbid compositions when freshly prepared or
agitated and these compositions eventually break into two phases.
The electrical conductivity measurement is the most widely used simple technique for examining the
microstructures and their structural changes in surfactant-based microemulsion systems [14–16]. For traditional
aqueous microemulsions, Clausse et al. [17] demonstrated that with increasing water content, the microemulsion
electrical conductivity (K) changes in the following four successive stages: (1) the initial nonlinear increase of K
reveals the existence of a percolation phenomenon that may be attributed to inverse microdroplet aggregation; (2) the
next linear increase is due to the formation of aqueous microdomains which results from the partial fusion of clustered
inverse microdroplets, which suggests that a W/O microemulsion is formed in this low water content region; (3) the
third nonlinear increase of K indicates that the medium undergoes a gradual structural transition and a bicontinuous
microstructure is formed due to the progressive growth and interconnection of the aqueous microdomains; (4) the final
decrease of K with increase of water content corresponds to the appearance of water-continuous microemulsion, that
is, an O/W microemulsion is formed at high water content, and the progressive decrease of K results from the
progressive decrease of the concentration of the O/W microemulsion droplets. On the basis of conductivity
measurement and ultracentrifugation examination, three subregions corresponding to W/O microemulsion, small H-
bonded aggregates of water and alcohol, and normal ternary solution, respectively were identified by Smith et al. [4] in
the single-phase region composed of hexane, 2-propanol and water.
The variations of electrical conductivity K as a function of the water volume fraction (fW) along dilution lines at
different RE/B (volume ratio of ethanol/benzene) values were determined in this study. As two typical examples, Fig. 2
shows the variations of K as a function of fW along dilution lines a and b (Fig. 1). As can be seen, the curves may be
divided into four parts by the dash lines, this variation trend of K is similar to that observed with surfactant-based
microemulsion systems. According to the standpoints of Smith [4] and Clausse [17], we believe that the initial increase
of K with increasing fW corresponds to normal ternary solution; the next increase may be interpreted as the
consequence of the formation of small H-bonded aggregates of water and ethanol dispersed in an benzene medium; the
third increase of K reveals that the medium undergoes a structural transition and becomes bicontinuous, owing to the
progressive growth and interconnection of the H-bonded aggregates of water and ethanol; the final decrease of K
indicates the formation of O/W microemulsions at high fW, and the decrease of K is due to the successive decrease of
882 F. Song et al. / Chinese Chemical Letters 21 (2010) 880–883

Fig. 2. Variations of the electrical conductivity K as a function of the water volume fraction (fW) for the benzene/ethanol/water ternary systems at
different RB/E values (along line a and b in Fig. 1). The curves were divided into four parts by the dash lines.

the concentration of O/W microemulsion droplets with the increasing fW. The conductivity curves in Fig. 2 evidently
illustrate the presence of four different types of microstructure: normal ternary solution, small H-bonded aggregates,
bicontinuous and O/W microemulsions. By repeating the experiment for other samples with different RE/B values, four
types of microregions can be determined. The subregions of bicontinuous and O/W microemulsions identified were
also marked in Fig. 1.

Fig. 3. FF-TEM pictures of the surfactant-free microemulsion, a and b correspond to the samples chosen in Fig. 1.
 F. Song et al. / Chinese Chemical Letters 21 (2010) 880–883 883

Freeze-fracture transmission electron microscopy (FF-TEM) is one of the powerful tools to characterize the shape
and size of the aggregates in microemulsions. In order to examine the presence of the microstructures of bicontinuous
and O/W microemulsions, FF-TEM observations were performed for the two test samples A and B (Fig. 1) with the
volume ratios of benzene/ethanol/water of 1.5:0.1:14.4 and 1.5:0.1:3.73, respectively. The FF-TEM images of samples
A and B are shown in Fig. 3. The spherical droplets can be clearly observed for sample A in O/W microemulsion
microregion, and most of the droplets are in the size range of 20–50 nm. However, no clear droplets are observed for
sample B in the bicontinuous microregion, only some traces of the so-called ‘‘sponge’’ structure may be found, this is
because both water and oil are continuous phases [18].

Acknowledgments

This research was supported by the National Natural Science Foundation of China (No. 20953003), the Natural
Science Foundation of Shandong Province of China (No. Z2008B08 and ZR2009BZ001) and Taishan Scholar
Foundation of Shandong Province of China (No. ts20070713).

References

[1] T.P. Hoar, J.H. Schulman, Nature 152 (1943) 102.

[2] S.P. Moulik, B.K. Paul, Adv. Colloid Interface Sci. 78 (1998) 99.
[3] J.H. Schulman, W. Stoeckenius, L.M. Prince, J. Phys. Chem. 63 (1959) 1677.
[4] G.D. Smith, C.E. Donelan, R.E. Barden, J. Colloid Interface Sci. 60 (1977) 488.
[5] B.A. Kelser, D. Varie, R.E. Barden, et al. J. Phys. Chem. 83 (1979) 1276.
[6] N.F. Borys, S.L. Holt, R.E. Barden, J. Colloid Interface Sci. 71 (1979) 526.
[7] B.M. Knickerbocker, C.V. Pesheck, L.E. Scrlven, et al. J. Phys. Chem. 83 (1979) 1984.
[8] G. Lund, S.L. Holt, J. Am. Oil Chem. Soc. (1980) 264.
[9] J. Lara, G. Perron, J.E. Desnoyers, J. Phys. Chem. 85 (1981) 1600.
[10] B.M. Knickerbocker, C.V. Pesheck, H.T. Davls, et al. J. Phys. Chem. 86 (1982) 393.
[11] J.E. Puig, D.L. Hemker, A. Guta, et al. J. Phys. Chem. 91 (1987) 1137.
[12] Y.L. Khmelnitsky, A. van Hoek, C. Veeger, et al. J. Phys. Chem. 93 (1989) 872.
[13] M. Zoumpanioti, M. Karali, A. Xenakis, et al. Enzyme Microb. Technol. 39 (2006) 531.
[14] M.D. Angelo, D. Fioretto, G. Onori, et al. Phys. Rev. E 54 (1996) 993.
[15] Z.J. Yu, R.D. Neuman, Langmuir 11 (1995) 1081.
[16] S.K. Mehta, X.X. Kavaljit, K. Bala, Phys. Rev. E 59 (1999) 4317.
[17] M. Clausse, A. Zradba, L. Nicolas-Morgantini, Microemulsions Systems, Dekker, New York, 1987, p. 387.
[18] H. Hoffmann, C. Thunig, U. Munkert, et al. Langmuir 8 (1992) 2629.