9

Dynamic Behaviors of Molecules at

Liquid^Liquid Interfaces Using the Time-
Resolved Quasi^Elastic Laser Scattering
Method
ISAO TSUYUMOTO Department of Environmental Systems Engineering,
Kanazawa Institute of Technology, Ishikawa, Japan
TSUGUO SAWADA Department of Advanced Materials Science,
University of Tokyo, Tokyo, Japan

I. INTRODUCTION

Experimental probes of liquid–liquid interfaces have been done mainly by spectroscopic

and electrochemical techniques, which are suited to monitoring the interface between two
bulk phases because their measurements result in no mechanical perturbation [1,2]. The
quasi-elastic laser scattering (QELS) method has advantages as a tool for in situ, non-
contact time-resolved measurements of dynamic behavior of molecules at liquid–liquid
interfaces and liquid–air interfaces [3–9]. The method monitors the frequencies of capillary
waves, which are spontaneously generated by a thermal fluctuation at liquid–liquid inter-
faces. Since the capillary wave frequency is a function of interfacial tension, and the
change in the interfacial tension reflects the change in the number density of surfactant
molecules at the interface, the QELS method allows observation of dynamic changes of
liquid–liquid interfaces such as the change in number density of surfactant molecules and
the formation of a lipid monolayer. Owing to its improved time resolution, each power
spectrum can be obtained in 1 ms to 1 s, so the method can be used to monitor dynamic
changes at liquid–liquid interfaces in a real environment. Furthermore, this method has
good interface selectivity for overcoming the problem of interference by bulk phases,
because the capillary wave is a characteristic phenomenon at the interfaces and its fre-
quency can be detected by an optical heterodyne technique.
In the past five years, it has been demonstrated that the QELS method is a versatile
technique which can provide much information on interfacial molecular dynamics [3–9].
In this review, we intend to show interfacial behavior of molecules elucidated by the QELS
method. In Section II, we present the principle and the experimental apparatus of the
QELS along with the historical background. The dynamic collective behavior of molecules
at liquid–liquid interfaces was first obtained by improving the time resolution of the QELS
method. In Section III, we show the molecular collective behavior of surfactant molecules
derived from the analysis of the time courses of capillary wave frequencies. Since the
229

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 230 Tsuyumoto and Sawada

method is useful for monitoring the interfacial behavior of surfactants, it is applicable to

practical systems which utilize the specificity of liquid–liquid interfaces, such as phase
transfer catalysis and chemical oscillation systems. In Section IV we present an application
of the QELS method to a phase-transfer catalyst system and describe new results on the
reaction place of the catalyst. This is the first application of the QELS method to a
practical liquid–liquid interface system.

II. QUASI–ELASTIC LASER SCATTERING METHOD

A. Capillary Waves
Capillary waves occur spontaneously at liquid surfaces or liquid–liquid interfaces due to
thermal fluctuations of the bulk phases. These waves have been known as surface tension
waves, ripples, or ripplons for the last century, and Lamb described their properties in his
book Hydrodynamics in 1932 [10]. Before that, William Thomson (Lord Kelvin) men-
tioned these waves in some of his many writings.
Here we briefly present the relevant theory of capillary waves. The thermally excited
displacement ðr; tÞ of the free surface of a liquid from the equilibrium position normal to
the surface can be Fourier-decomposed into a complete set of surface modes as
X
ðr; tÞ ¼ 0 exp½ik  r þ t ð1Þ
k

The complex wave frequency  ð¼ i!0  Þ is related to k via a dispersion relation. For an
inviscid liquid, Lamb’s equation is well-known as a classical approximation for the dis-
persion relation [10]
 12
1  3
f ¼ k2 ð2Þ
2 U þ L
where f is the capillary wave frequency; , the interfacial tension; U , the density of the
upper phase; L , the density of the lower phase; and k, the wavenumber of the capillary
wave. This equation is valid for both liquid surfaces and liquid–liquid interfaces. For
capillary wave at a liquid surface, U is regarded as zero in Eq. (2). In this equation,
only the normal component of the interfacial tension is considered to act as a restoring
force on the thermally excited displacement ðr; tÞ. Although this equation neglects the
effect of surface viscosity, it gives a good fit in the relation between frequency and wave-
number of capillary waves at a liquid surface such as ethanol, anisole, or water [10,11].
For the surface of a low-viscosity liquid, Levich [12] has derived the following dis-
persion relation:

DðSÞ ¼ ðS þ 1Þ2 þ y  ð2S þ 1Þ1=2 ¼ 0 ð3Þ

where S ¼ =2k2 , y ¼ =42 k. Here  is the kinematic viscosity ð=, where  is the
viscosity of the liquid). In this equation, both the normal components of the surface
tension and the stress by the viscosity are considered to act as a restoring force on the
displacement ðr; tÞ. Based on this equation, a heterodyne power spectrum in the frequency
domain becomes a Lorentzian profile centered at
!0 ¼ 2f ¼ jImðÞj ð4Þ

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 Dynamic Behaviors of Molecules 231

having the full width at half-maximum (FWHM)


f ¼ jReðÞj ð5Þ
Equation (3) is simplified to
 1
1  2 32
f ¼ k ð6Þ
2 
and

f ¼ 2k2 = ð7Þ
Equation (6) is the same as Lamb’s classical approximation, Eq. (2).

B. Historical Overview
Capillary waves at liquid surfaces were observed some years before the invention of
lasers. Goodrich [13] reported on using a cathetometer to observe the damping of water
waves by monomolecular films. Strictly speaking, this wave was a forced one and not a
spontaneously generated capillary wave. The observation of spontaneously generated
capillary waves was first reported by Katyl and Ingard [14,15]. They measured spectra
from a methanol surface and an isopropanol surface using a He–Ne laser. Lucassen
[16,17] theoretically derived the transverse mode of capillary waves and experimentally
verified its existence. Bouchiat and Meunier [18] measured the liquid–gas interface of
carbon dioxide near the critical point and reported agreement with theoretical predic-
tions on the surface tension and viscosity. Mann et al. [19] investigated the dispersion
relation at air–water interfaces using the QELS method and reported conformity with
Lamb’s equation. They also mentioned the possibility of application to interfacial ten-
sion measurements. Härd et al. [20] measured surface tensions using the QELS method
and reported that the experimental values agreed with the theoretical ones within devia-
tions of 2–10%. Sano et al. [11] measured the surface tensions of water and anisole and
reported they were within deviations 5% of the theoretical values. They also reported
that the first-order approximation, i.e., Lamb’s equation, was sufficient to calculate the
surface tensions from capillary wave frequencies. Earnshaw and coworkers [21–23] have
investigated liquid surfaces of surfactant solutions and reported on such fundamental
properties as surface viscosity.
As reviewed above, there have been many QELS studies on liquid surfaces.
However, until a few years ago, reports were scarce on molecular dynamics at liquid–
liquid interfaces which used time courses of capillary wave frequency. Molecular collective
behavior at liquid–liquid interfaces from a QELS study was first reported by Zhang et al.
in 1997 [5].

C. Principle
The incident beam normal to the interface is quasi-elastically scattered by the capillary
wave with a Doppler shift at an angle determined by the following equation (Fig. 1):
K tan ¼ k ð8Þ
where K and k are the wavenumbers of the incident beam and the capillary wave, respec-
tively. Thus, the wavenumber k of the capillary wave is obtained by giving . A transmis-

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 232 Tsuyumoto and Sawada

FIG. 1 Principle of the quasielastic laser scattering method.

sion diffraction grating is arranged in front of the cell to adjust the angle [20]. The angle
is determined by the following equation using the spacing d and the order n of the
diffraction grating,

d sin ¼ n ð9Þ

where  is the wavelength of the laser beam.

From Eqs. (8) and (9), we obtain the wavenumber k and the wavelength  of the
observed capillary wave:

k ¼ 2n=d ð10Þ
 ¼ d=n ð11Þ

The capillary wave frequency is detected by an optical heterodyne technique. The laser
beam, quasi-elastically scattered by the capillary wave at the liquid–liquid interface, is
accompanied by a Doppler shift. The scattered beam is optically mixed with the diffracted
beam from the diffraction grating to generate an optical beat in the mixed light. The beat
frequency obtained here is the same as the Doppler shift, i.e., the capillary wave frequency.
By selecting the order of the mixed diffracted beam, we can change the wavelength of the
observed capillary wave according to Eq. (11).

D. Experimental Apparatus
A schematic diagram of the experimental setup is shown in Fig. 2. The beam from a
diode-pumped YAG laser is incident on the transmitting diffraction grating and passes
through the bottom of the sample cell. The cell is made of quartz glass and has an
optically flat bottom, which is indispensable to maintaining good reproducibility of the
experimental results. After passing through the sample, the diffracted beams are mixed
with scattered light from the capillary wave, and one of them is selected by an aperture
positioned in front of a photodiode. The optical beat of the mixed light is measured by
the photodiode. The signals are Fourier transformed and saved by a digital spectrum
analyzer.

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 Dynamic Behaviors of Molecules 233

FIG. 2 Schematic diagram of the experimental setup. T, glass tube; W, water phase; NB, nitro-
benzene; PD, photodiode; AMP, preamplifier; FFT, FFT analyzer.

III. DYNAMIC MOLECULAR BEHAVIOR OF SURFACTANT

MOLECULES AT LIQUID–LIQUID INTERFACE

The molecular collective behavior of surfactant molecules has been analyzed using the
time courses of capillary wave frequency after injection of surfactant aqueous solution
onto the liquid–liquid interface [5,8]. Typical power spectra for capillary waves excited at
the water–nitrobenzene interface are shown in Fig. 3: (a) without CTAB (cetyltrimethy-
lammonium bromide) molecules, and (b) 10 s after the injection of CTAB solution to the
water phase [5]. The peak appearing around 10–13 kHz represents the beat frequency,
i.e., the capillary wave frequency. The peak of the capillary wave frequency shifts from
12.5 to 10.0 kHz on the injection of CTAB solution. This is due to the decrease in
interfacial tension caused by the increased number density of surfactant molecules at
the interface. Time courses of capillary wave frequency after the injection of different
CTAB concentrations into the aqueous phase are reproduced in Fig. 4. An anomalous
temporary decrease in capillary wave frequency is observed when the CTAB solution
beyond the CMC (critical micelle concentration) was injected. The capillary wave fre-
quency decreases rapidly on injection, and after attaining its minimum value, it increases

FIG. 3 Power spectra for capillary waves excited at the water–nitrobenzene interface (a) without
CTAB molecules and (b) 10 s after injection of a CTAB solution (0.5 mL, 10 mM) into the water
phase.

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 234 Tsuyumoto and Sawada

FIG. 4 Capillary wave frequency vs. time after injection of the CTAB aqueous solutions (0.5 mL,
2–30 mM). The concentrations of the injected solution (C) are shown, along with the average con-
centrations (Ceq ) in the aqueous phase.

gradually. The initial sudden change means an abrupt increase in the molecular number
density at the interface.
The relationship between the interfacial coverage and the concentration of CTAB
was estimated using the minimum value of the capillary wave frequency, as shown in Fig.
5. The experimental data are in good agreement with the calculated Langmuir adsorption
isotherm. The experimental adsorption energy of CTAB onto the interface is calculated as
29:4 kJ/mol from the isotherm. The theoretical adsorption energy of the CTAB micelles
is estimated as 25:0 kJ/mol from the difference between the theoretical adsorption energy
of CTAB molecules (51:4 kJ/mol) and the micelle formation energy (26:4 kJ/mol). The
experimental adsorption energy ð29:4 kJ/mol) calculated from the Langmuir isotherm is
in agreement with the theoretical adsorption energy of CTAB micelles (25:0 kJ/mol), and
not with that of CTAB molecules (51:4 kJ/mol). This indicates that the CTAB micelles
are in equilibrium with the adsorbed CTAB molecules, and consequently, the CTAB
micelles collapse to molecules immediately before the adsorption onto the interface.

FIG. 5 Interface coverage with CTAB molecules vs. CTAB average concentration in the water
phase. Experimental data are shown as squares, and the calculated Langmuir adsorption isotherm is
the solid line.

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 Dynamic Behaviors of Molecules 235

FIG. 6 Time courses of the capillary wave frequencies after injection of (a) SDS and (b) Triton X-
100 aqueous solutions into the interface.

Similar experiments and discussions have also been made for different surfactant
molecules, such as SDS (sodium dodecyl sulfate) and Triton X-100 [8]. SDS, Triton X-100,
and CTAB are anionic, nonionic, and cationic surfactants, respectively. The relationship
between the relative number density of SDS molecules and the bulk aqueous concentration
is shown in Fig. 6(a). When the concentration is below the CMC (9.8 mM at 25 C), the
number density increases with an increase in concentration. The experimental data are in
agreement with the Langmuir adsorption isotherm, suggesting that the SDS molecules are
adsorbed onto the interface as a monolayer. The adsorption energy of the SDS molecules
at the interface is estimated as ca. 21:9 kJ/mol from the experimental data. The theore-
tical free energy change when the molecules move from the water phase to the interface is
estimated as higher than 37:6 kJ/mol. This discrepancy suggests that about 60% of the
methylene groups in the SDS molecules are transported to the nitrobenzene phase and
may be a reflection of molecular orientation, because SDS does not form a well-ordered
monolayer at the water–nitrobenzene interface. When the concentration is above the
CMC, the number density of SDS molecules at the interface decreases with an increase
in the concentration. This may be due to a local change in the aggregation state at the
interface from the monolayer to molecular aggregates. The molecular aggregates observed
here are assumed to be micelles or reversed micelles, but further investigation is necessary
to verify this. Using resonant TIR-SFG, Richmond’s group observed a reduction in
ordering of the chain of the SDS at the D2 O/CCl4 interface at higher concentrations
[24,25]. They also reported that the alkyl chains of the cationic surfactants DTAC and
DAC possess the fewest gauche defects, whereas the anionic surfactants SDS and DDS
display more disorder in the hydrocarbon chains at similar surface concentrations [25].
Similar results have been reported by others for SDS adsorption onto hydrophobic sub-
strates from water [26,27].

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 236 Tsuyumoto and Sawada

The relationship between the relative number density of Triton X-100 molecules and
the bulk aqueous concentration is shown in Fig. 6(b). When the concentration is below the
CMC (0.2 mM at 25 C), the experimental data in Fig. 6(b) are in good agreement with the
calculated Langmuir adsorption isotherm. This indicates that the adsorbed Triton X-100
molecules are confined to a monolayer. When the concentration is above the CMC, a
slight decrease in the number density appears. It is reasonable to consider that the slight
decrease is due to a change in aggregation state at the interface, such as by formation of
micelles, whereas the latter slow increase is due to the increase of molecular aggregates at
the interface. This result suggests that the phase transition from a monolayer to molecular
aggregates occurs at a certain concentration, unlike the case with SDS. The molecular
behavior at the interface may be affected by the ionic nature, ion pair formation, solvent
polarity, or the chain conformation of surfactants.

IV. MOLECULAR BEHAVIOR OF PHASE-TRANSFER CATALYST AT

LIQUID–LIQUID INTERFACE IN ITS CYCLIC REACTION

The interfacial behavior of a phase-transfer catalyst, tetrabutylammonium bromide

(TBAB), has been investigated using the QELS method [9]. The scheme of the phase-
transfer catalytic reaction in a water–nitrobenzene system is shown in Fig. 7 [28]. At the
beginning of the reaction, TBAB reacts with C6 H5 ONa to form TBAþ C6 H5 O . This ion
pair is transported into the organic phase where it reacts with DPPC to produce triphenyl
phosphate [ðC6 H5 OÞ3 PO]. During this reaction, TBAþ Cl is also formed and transported
into the water phase to react again with C6 H5 ONa. TBAB activates the production of
triphenyl phosphate by circulating between the two phases.
Capillary wave frequency dependence on concentrations of TBAB and C6 H5 ONa
is shown in Fig. 8. The adsorption behavior of the ion pair, TBAþ C6 H5 O , in one
transfer process in which the formed ion pair is transferred from the water phase to the
nitrobenzene phase is described by the data. When C6 H5 ONa alone is in the water
phase, the frequency is independent of the C6 H5 ONa concentration. On the other hand,
when both TBAB and C6 H5 ONa are present, the frequency decreases gradually and
only slightly with increasing C6 H5 ONa concentration and then becomes constant at a
certain C6 H5 ONa concentration. Thus, the decrease of frequency corresponds to the
formation of ion pairs such as TBAþ C6 H5 O , and these ion pairs are adsorbed at the
interface. The constant frequency above a certain concentration indicates that the

FIG. 7 Reaction scheme between C6 H5 ONa and DPPC in the water–nitrobenzene system. The part
surrounded by the dashed line is the investigated process.

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 Dynamic Behaviors of Molecules 237

FIG. 8 Capillary wave frequency dependence on the concentrations of TBAB and C6 H5 ONa.

number of interfacial adsorptions of ion pairs that occurs has become constant. This
suggests that the reaction between C6 H5 ONa and TBAB is in equilibrium, and the
number of ion pairs that occurs has become constant. This stable formation brings
about the saturated interface.
The equilibrium concentration of C6 H5 ONa above which the adsorption was satu-
rated depends on the TBAB concentration. The relationship between the TBAB concen-
tration and the C6 H5 ONa concentration is shown in Fig. 9. These equilibrium
concentrations were used to analyze the reaction between the two reactants, assuming
that at these concentrations the reaction proceeds without residue and deficiency. The
ratio of the TBAB concentration to the C6 H5 ONa concentration deviates from the line
for 1:1 below 50 mM. When the TBAB concentration is above 50 mM, the ratio of the
TBAB concentration to the C6 H5 ONa concentration at the water–nitrobenzene interface
is unity. On the other hand, when the TBAB concentration is below 50 mM, the ratio of
the C6 H5 ONa concentration to the TBAB concentration is more than unity.
In general, the formation of an ion pair TBAþ C6 H5 O occurs by the reaction
between one TBAB molecule and one C6 H5 ONa molecule in the water phase. Thus, the
ratio of the C6 H5 ONa concentration to the TBAB concentration should be unity if the
reaction has occurred in the water phase. The behavior above 50 mM can be simply
explained by the reaction in the water phase between one TBAB molecule and one
C6 H5 ONa molecule. However, the behavior below 50 mM cannot be explained by this

FIG. 9 Relationship between the TBAB and C6 H5 ONa concentrations in equilibrium.

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 238 Tsuyumoto and Sawada

simple water phase reaction. It is generally said that the concentration or activity at the
interface differs from that in the water phase. From these results, the following model is
suggested. Below 50 mM, the ratio of the two concentrations at the interface is unity, and
the reaction between the TBAB molecules and the C6 H5 ONa molecules occurs at the
interface. Below 50 mM the formation reaction for ion pairs occurs at the interface,
while above 50 mM the reaction occurs in the water phase.

V. FINAL REMARKS

In this chapter, the quasi-elastic laser scattering (QELS) method was introduced and
recent reports on molecular dynamics at liquid–liquid interfaces using this method are
reviewed. The QELS method has been applied to monitor the dynamics of surfactant
molecules at the liquid–liquid interfaces. Time-resolved measurements of interfacial mole-
cular number density can provide new information on molecular collective behavior of
surfactants at the liquid–liquid interface. The transfer of CTAB micelles across the inter-
face was found to occur according to the following scheme: the collapse of micelles at the
interface region; the oriented adsorption onto the interface with formation of a mono-
layer; and the desorption from the interface. Findings suggested that below the critical
micelle concentration (CMC), sodium dodecyl sulfate (SDS) molecules were adsorbed
onto the interface, forming a monolayer; above the CMC the monolayer was disrupted
and some molecular aggregates such as micelles or reversed micelles were formed. In the
case of Triton X-100 molecules below the CMC the molecules were adsorbed onto the
interface, forming a monolayer; above the CMC, the monolayer was disrupted and some
molecular aggregates such as micelles were formed, and with further increases in concen-
tration, the number of micelles increased. The QELS method was also applied to monitor
the interfacial molecular behavior of phase-transfer catalyst. Findings suggested that the
reaction place between tetrabutylammonium bromide (TBAB) and C6 H5 ONa changed
with TBAB concentration; the reaction place was in the water phase above 50 mM,
whereas it was at the interface below 50 mM.
The results above reflect interfacial specificity for mass transfer and chemical reac-
tion. In future studies the advantages of the QELS method can be used to provide details
on interfacial specificity for chemical processes by nonperturbative measurements.

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