Progr Colloid Polym Sci (1998) 1ll:113 116
© Steinkopff Verlag 1998
T. Wolff
D. Nees
Influence of solubilized stilbazolium
salts in trans and cis configuration
on the percolation equilibrium in AOT-
isooctane-water microemulsions:
Light induced switching of conductivity
Prof. Dr. T. Wolff(l~)
Technische Universit~it Dresden
Institut ffir Physikalische Chemie
und Elektrochemie
D-01062 Dresden
Germany
Dr. D. Nees*
Universit~it Siegen
Physikalische Chemie
Siegen
Germany
*Present address
Surfactant Science Group
School of Chemistry
University of Hull
Hull HU6 7LS
United Kingdom
Abstract Solubilized trans and cis
isomers of N-methyl and N-hexadecyl
hydroxystilbazolium bromide had
specific influences on the percolation
temperature (as revealed by the onset
of conductivity) in microemulsions
composed of AOT, isooctane, and
water: in the methyl derivative both
cis- and trans-HSB induce shifts of the
temperature at which conductivity
sets on, the cis form being more
efficient. In the hexadecyl compound
a conductivity onset at increased
temperature induced by the trans
form was partially reverted when the
cis isomer was present. Since trans
and cis stilbazolium salts can be
interconverted photochemically,
conductivity may be switched
isothermally by exposing samples to
light. Some competition between
trans --, cis photoisomerization and
photodimerization was found
depending on concentration ratios in
the systems.
Key words Conductivity
microemulsion - percolation -
photoisomerization
Introduction
Microemulsions composed of surfactant, water and oil are
thermodynamically stable systems which are macroscopi-
cally monophasic [1]. They exist in two types: in water
rich systems, the so-called oil-in-water o/w microemul-
sions form consisting of oil droplets in a continuous water
phase; oil rich systems exhibit water droplets in a continu-
ous oil phase (water-in-oil - w/o microemulsion), cf. Fig. 5
in [2] or more generally Figs. 9 15 in [1]. In both cases,
surfactants are accumulated in the interfacial regions me-
diating the dispersed state. When starting with a w/o
microemulsion containing an ionic surfactant the water-
to-oil ratio is gradually increased (at an appropriate tem-
perature) the system may convert to an o/w microemulsion
passing through a bicontinuous region with an average
interracial surface curvature equal to zero. At a certain
ratio called percolation point the system changes from
almost non-conductive (in the w/o case) to conductive
since water becomes a continuous phase. As percolation
points depend on temperature, systems at water-to-oil
ratios close to the percolation point can be switched from
conductive to non-conductive (and vice versa) upon vary-
ing the temperature.
isothermally percolation can be induced by applying
electric fields [3] or by the addition of certain solubilizates
that affect percolation temperatures specifically [4].
Recently we reported photochemical switching of conduct-
ivity in microemulsions brought about by solubilized acri-
dizinium bromide and its photodimerization [-5]: since
monomer and dimer induce different percolation temper-
atures the conductivity could be varied isothermally upon
exposure of samples to light. As one of the possible origins
of the effect it was discussed that the divalent cations as
formed upon photodimerization of acridizinium monoca-
tions may vary the ionic strength in the system. We will
show below that this is not a necessary prerequisite for
photochemical switching of conductivity in microemul-
sions, since monomolecular reactions such as the trans-cis