ELECTROCHEMICAL POLARIZATION PHENOMENA AT

THE INTERFACE OF TWO IMMISCIBLE ELECTROLYTE

SOLUTIONS-II. PROGRESS SINCE 1978*

J. KORYTA

J. Heyrovsky Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences,

Opletalova 25, 110 00 Prague I, Czechoslovakia

(Receiued 14 September 1983)

Abstract-Since 197Stheelectrolysisat theinterfaceoftwoimmiscibleelectrolytesolutions (1TIES)hasbeen

developing in a number of research groups. First, the subject matter of electrolysis at ITIES has been defmed.
The experimental methodology has advanced, mainly on the basis of modified methods taken from electrode
kinetics. Very general treatments of the equilibrium situation at ITIES have been presented. The theory and
experimental characteristics of electricdouble-layer at ITIES haw been discussed. Experimental data and the
theory of simple ion transfer across ITIES have been presented. New cases of ionophore facilitated ion
transfer and electron transfer have been described. Finally applications, particularly in analytical chemistry,
and perspectives of electrolysis at ITiES have been discussed.

1. INTRODUCTION
Whereas in 197S[l] electrolysis at the interface of two
immiscible electrolyte solutions (ITIES) only was an
extension of liquid membrane electrochemistry it has
become now a well-defined topic of electrochemistry.
While at that time only two groups were working in
this field (Montpellier and Prague) investigation on
this subject has started in Poland, U.K., U.S.A., Japan,
F.R.G., G.D.R., U.S.S.R. and Ethiopia since then.
Several reviews have been published on electrolysis at
ITIES[2-9b].
First, three subjects will be noted that are out of the
scope of this paper. Considerable effort has been
devoted to processes connected with electric current
flow across liquid membranes (see, eg[IO-131). In
connection with membrane electrolysis the term “faci-
litated transport” has also been defined as a chemically
augmented solute permeation across a membrane[14]
which occurs particularly with transport of cations
complexed by various ionophores[1519]. While im-
portant particularly for separation processes, the
membrane electrolysis is too complicated to supply
straightforward information on processes occurring at
the phase boundaries. In relation to electrolysis at
ITIES the membrane electrolysis can be compared to
processes taking place in galvanic cells as a whole in
contrast to investigation of processes at individual
electrodes by electrode kinetics methods.
In phase-transfer catalysis (PTC)[20,21] the ion
fluxes across ITIES (water-rganic phase) accom-
panied with chemical reactions in the organic phase
electrically compensate each other. In this way, in
relation to electrolysis at ITIES, PTC resembles
corrosion processes at isolated metallic phases.
Finally, the group of phenomena at liquid/liquid
* A lecture held in abbreviated form at the 34th ISE
Meeting in Erlangen, 23 September, 1983. For Part I see[l].
interfaces that will not be dealt with here comprise the
systems of aqueous electrolyte/liquid dielectric inter-
faces. As the charge transport into the bulk of the
organic (oil) phase is impossible the processes occur-
ring here are adsorption or electron transfer between
redox systems, at least one of which being adsorbed at
the in&face (see, eg[22-241).
Electrolvsis at ITIES concerned entirelv with the
processes &curring at the interface or in itsimmediate
vicinity (in the diffusion layer) can supply relevant
information to both the membrane electrolysis and
PTC. Its main advantage is that it is suitable for the
transient processes study.
In the subsequent sections the equilibrium situation
at ITIES (including the electric double-layer structure),
the experimental approach to the study of electrolysis
at ITIES, the simple ion transfer, the facilitated ion
transfer, the electron transfer, the applications and the
perspectives will be dealt with.
2. EXPERIMENTAL APPROACH
2.1. Methods and instrumentation
The basic arrangement for potential sweep voltam-
metry based on a four-electrode potentiostat[25] with
positive feedback circuit for elimination of the residual
IR drop[26] was already described in Part I (see
also[27]). Further improvements[28], eg the introduc-
tion of a six-electrode system[29] have also been
suggested. A substantial progress in processing the
data obtained with potential sweep voltammetry has
been achieved by convolution analysis[30,31]. Here
the current data are transformed by means of the
convotution integral[32]
m = n-“’ - J(t)@ -z)-l”dr (1)
J0
where t is the time and I the time-dependent current.

445
446 J. KORYTA

The resulting m-E data are then analyzed in a similar sonium [49] and Crystal Violet[4] cations have been
manner as the current-potential curves in classical used. The system with which extremely negative poten-
polarography (see Fig. 1). tials can be reached contains NaF in the aqueous phase
The electrolyte dropping electrode has been con- and Crystal Violet in nitrobenzene[50].
siderably improved by a four-electrode arrange-
ment[33] (see also[27,34]) and a hanging electrolyte
drop has been introducedC35, 361. In the latter case an
3. EQUILIBRIUM SITUATION AT ITIES
ionic species can be accumulated in the electrolyte drop
and transferred back in the polarization mode of
3.1. Charge-transfer equilibria
differential pulse polarography. In this way a con-
siderable increase in sensitivity of the method is In Part I, besides the simple distribution potential
achieved. Furthermore, the potential-step chronoam- [Equation (3) of Part I], also several types of equilib-
perometric method[37] and the current-scan polaro- rium potentials pertaining to specific electrolyte com-
graphy[34] have been used. positions were discussed. Now, Hung[51] has worked
For the chronopotentiometric method (see Part I) a out a method for calculation of distribution potentials
simple galvanostat has been described[38]. The in the presence of an arbitrary number of ions
Faradaic impedance method has also been applied to participating in the distribution equilibrium. The
ITIES for double-layer[39,40] and kineticC41-43) equilibria of complex formation in one of the phases
studies. and of ion-pair formation in both the phases have been
The interfacial tension of the water/nitrobenzene included in his treatment. On the basis of his theory the
interface has been measured by the Wilhelmy[44] and conditions for the validity of specific cases discussed in
various drop-time[45,46] methods. Part Ican be found,particularly those pertaining to the
systems including base electrolytes and the ions trans-
ferred across ITIES (c$[52], see also [53]).
2.2 Solvents
The basic quantity characterizing the equilibria at
While in most of the studies nitrobenzene has been ITIES is the standard Gibbs energy of transfer of
used as the solvent of the organic phase, 1,2-di- individual ions from water to organic solvents. These
chloroethane[47] and dichlorome?hane[48] have been values based on compilations by Samec et a[.[541 and
applied to several investigations. Van+ek[55] and on the results of Samec et al. [48,5q
and Hundhammer and Solomon[43, 573 are listed in
Table 1.
2.3. Base electrolytes
The “potential window”, ie the potential range Table 1. Standard Gibbs transfer energies and standard
where the ion transfer of individual ions can be transfer electric potential differences
investigated without interference of the transfer of the
ions of the base electrolyte, depends on the hydro- AG:: ‘O A:&
phihty of the ions of the aqueous base electrolyte and Ion (kJrnol- ‘) (V)
on the hydrophobicity of the ions of the base elec-
trolyte of the organic phase. In Part I the tetrabutyl- (a) Water/nitrobenzene
ammonium cation (TBA) and the tetraphenylborate Cations
(TPB) and dicarbollylcobaltate (III) anions were in- Li+ - 38.4 0.398
MS’+ -71.4 0.370
dicated as suitable components of the base electrolyte Na+ - 34.5 0.358
for the organic phase. In order to extend the potential - 68.3 0.354
window towards negative potentials the tetraphenylar- s2:’ - 67.2 0.348
H+ - 32.5 0.337
Baz+ - 63.3 0.328
NH: - 27.4 0.284
nl K+ - 24.3 0.252
Y Rb+ - 19.9 0.206
CS+ - 15.5 0.161
-1 choline - 11.3 0.117
acetylcholine - 4.8 0.049
Me4N* - 3.4 0.035
Et,N + 5.8 - 0.060
4oo- -0 Pr,N* 15.5 - 0.161
Bu+N + 24.2 - 0.251
Ph,As + 35.9 - 0.372
- -1 Crystal Violet cation 39.5 - 0.410
Anions
a3 0.4 0.8 Cl- - 30.5 - 0.316
E/V Br- - 28.5 - 0.295
r-0; - 24.4 - 0.253
Fig. 1. Convolution (m) and logarithmic analysis (Y) of the - 18.8 - 0.195
convoluted current-potential curve of Cs+ transfer from CNS- - 15.5 -0.161
water to nitrobenzene at the polarization rate 5 mVs_’ (1) Cl0; - 8.7 - 0.090
and 10 V 6-l (2). Aqueous phase; 1 mM Cs+, 0.05 M LiCI; 2,6-&nitrophenolate - 8.0 - 0.083
nitrobenzene phase; 0.05 M tetraphenylarsonium TPB. Area 2+dinitrophenolate - 7.3 - 0.076
of ITIES 180 mm2. After[Jl]. laurylsulfate -4.1 - 0.043
 Electrolysis at interface of two immiscible electrolytes~I1 447

Table 1. (Con&.) Experimentally, Gros et ~I.[441 have obtained, using

interfacial-tension measurements at the water/nitro-
AG”“‘O
A:d benzene interface, electrocapillary curves very much
(kJ I%+) (V) like those obtained at mercury electrodes. The dif-
ferential capacity of ITIES has been measured by
4.6 0.048
n-oetoate 8.5 0.089 Osakai ef a/.[391 and Samec et al.[40]. Kakiuchi and
1, 23.4 0.242 Senda[SX] havecompared the values of surface charge
TPB- 35.9 0.372 densities at ITIES obtained by differentiation of their
1; 38.7 0.401 electrocapillary curve with the surface-charge density
dipicrylaminate 39.3 0.407 data obtained by integration of the differential-
picryl-2,6dinitronaphthylaminate 44.0 0.456 capacity curve [39] (see Fig. 2).
dicarbollylcobaltate 50.2 0.520 In their basic theoretical study on electric double-
(b) Water/l,Zdichloroethane layer structure at ITIES published already in 1939
Cations Verwey and Niessen[59] assume that the double-layer
Me,N* - 17.6 0.182 charge is completely situated in two diffuse double-
EtaN+ - 4.2 0.044 layers with no compact layer between them and have
Pr,N+ 8.8 -0.091 calculated the electric potential distribution using the
Bu,N + 21.8 - 0.225
Gouy-Chapman theory (see Fig. 3). This theory has
Ph& + 35.1 - 0.364
been modified by Gavach et a1.[60,61] for thecase that
Anions there still exists a compact layer at ITIES (in the
Cl- - 46.4 - 0.481 absence of specific adsorption). Then, the overall
Br- - 38.5 - 0.399 potential difference between the aqueous (w) and the
I- - 26.4 - 0.273
- 17.2 -0.178
organic (0) phase consists of three components,
c10;
TPB” 35.1 0.364 A:~P = (~z(o)--(p2(w)+(pc (2)
(c) Water/dichloroethane where cpz(w) is the potential difference between the
Cations
Me4N+ - 18.8 0.195
Et,N+ -4.2 0.044
Pr,N + 8.8 - 0.091
Bu,N+ 22.2 - 0.230
Anions
c1- - 46.4 - 0.481
Br- - 39.3 - 0.408
I- - 24.4 - 0.273
ClO, - 21.3 - 0.221
Picrate -6.7 - 0.069

3.2. Electric double-layer at ITIES

As noted already in Part I one of the important
features of ITIES resembling the metal/electrolyte
interface is that, under definite conditions, it becomes
ideally polarized. However, the electric double-layer
formed at ITIES shows several specific properties that
differ from the metal/electrolyte interface.
Fig. 2. Comparison of surface charge densities in aqueous
solution side obtained by differentiationof the eleetroeapil-
lary curve (0) and by integration of the differential capacity
curve (-)_ System 0.1 M LiCl in water, 0.1 TBA TPB in
nitrobenzene. After[SB].

Fig. 3. The electric potential distribution at ITIES

448
outer Helmholtz plane in the aqueous phase and the
bulk of the aqueous phase, q*(o) that between the
outer Helmholtz plane in the organic phase and the
bulk in the organic phase and cp, that between the both
outer Helmholtz planes, respectively. Under these
conditions, we have eg for (p*(w),
RT 1 + X exp [RT/ZF ( - Aycp + cp,)]
rp2(w’=F’n l+Xexp[-RT/2F(-Azlp-tcp,)]
with X = [~(w)r(w)/~(o)c(o)] Ii’, where E(W)and E(O)
are the permittivities and c(w) and c(o) the concen-
trations of uni-univalent electrolytes in the aqueous
and the organic solutions, respectively. For large
positive values of AF(p this equation attains a simpli-
fied form[6lb]
RT
(p2(w) = -$(Az(p-rp,)-~1nX.
Experimentally, however, Gross et al. [61] have found
cpcin the range of + 5 mV. The potential ofzero charge
has been determined as - 1 mV on the potential scale
based on the TATB assumption[62] (see Part I). In an
interesting way, this result should also support the
validity of this assumption. On the other hand
MarelSek and Samec [40] have found the zero-charge
potential as + 42 mV. On the basis of the analysis of
electrocapillary curves Kakiuchi and Senda[63] have
stated that there exists a negative excess of ions in the
inner layer in the system LiCl(w)/TBATPB (nitroben-
zene). The zero-charge potential is approx. + 20 mV,
practically independent of the concentration of the
electrolyte. There is a potential difference in the inner
layer markedly increasing with the charge density at
the interface. In the author’s opinion the ion clouds in
both the phases are separated by monomolecular
layers of oriented water and nitrobenzene molecules.
The contradiction to the results obtained by Gross et
aI.[61] and, particularly, to the kinetic measurements
by D’Epenoux et &.[&I] is still to be clarified.
4. SIMPLE ION TRANSFER ACROSS ITIES
4.1. Experimental results
Already in Part I several examples of simple ion
transfers were given. Since then their number has
considerably increased, in part also due to extension of
the “potential window” owing to new base electrolytes.
The transfer processes are fast so that, in most cases,
they are reversible and diffusion controlled. Thus, in
the first place thermodynamic data on standard Gibbs
transfer energies and on diffusion coefficients have
been obtained from these measurements.
Let us briefly mention the systems recently in-
vestigated, first connected with transfer across water/
nitrobenzene interface. They include cations of tetra-
alkylammoniums[65,66], choline and acetylcholine
[67, 681, cesium[31, 693, tris(2,2’-bipyridine)ruthen-
ium(II) and dialkylviologens[48] and the anions
picrateC65, 703 perchlorate, dodecylsulfate and oc-
toate[71] and iodide, nitrate and thiocyanate[50]. The
complications observed with transfer of several anions
at rather negative potentials, as mentioned in Part I,
arose from the simultaneous transfer of the base
.I. KORYTA
electrolyte cation and were completely removed when
a more hydrophobic base electrolyte cation was
used[50, 711.
The transfer across the water/l,2-dichloroethane
has been studied in the case of tetrabutylam-
monium[47], cesium[72], tris(2,2’-bipyridine)ruthen-
ium(I1) and dialkylviologene cations and with the
two last named cations also in the system water/di-
chloromethane[48].
(3) A pH effect has been observed in the case of
tetracyclines[73]. The particle transferred is the tetra-
cycline cation. However, at pH > pK, the particle
prevailing in the aqueous solution is the zwitterion of
tetracycline. Under these conditions the process at
ITIES consists of the diffusion of the zwitterion to the
interface with subsequent formation of the cation
which is then transferred across the interface. Thus, the
half-wave pbtential depends on pH according to the
(4)
equation
A,“cp1,2 = const. - RT/F In & + & (5)
>
(see Fig. 5).
The rate of ion transfer across ITIES could be
measured in the case of tetraalkylammonium ions[64],
cesium[31] and choline and acetylcholine[56, 741.
4.2. Theory
According the results of D’Epenoux et al.[64] the
kinetics of ion transfer across ITIES has different
features than that of processes occurring at metallic
electrodes while it rather resembles the situation met
with the semiconductor/dilute electrolyte interface.
The electric potential difference between both liquids
being situated mainly, if not at all, in the diffuse
double-layers influences only the concentration of the
ions transferred at the phase boundaries (a sort of
“Frumkin correction”) while the genuine charge trans-
fer step is little potential dependent. The kinetics of this
step depends on the reorganization of the solvent[75]
(a kind of resolvation proposed for uncharged solutes
by Davies and Rideal[76]) and on the rate of the
diffusion shiff between the positions closest to the
boundary in both the phases[9].
Fig. 4. Tetracyclines:
RI &
H OH 2 :A tetracycline
Cl OH H OH ‘I-chlorotetracycline
(chlortetracycline)
H H OH OH G(6-deoxy-5p-oxytetra-
cycline (doxycycline).
The dissociation constants (pK, % 3.3, pK, x 7.7, pK,
z 9.7,pK, Tr 10.7)correspond successively to dissociation of
protons in the position 4, 12, 3 and 2.
 Electrolysis at interface of two immiscibleelectrolytes-11 449

between the phase w and o, C;(W) and ci(O) are its

concentrations in the aqueous and in the organic
360 phase, respectively, and q = Arcp- A;lpi,+,, where
AZ ‘Pi, rp = A: cp; - RT/q F ln ci (w)/ci (0).
Transfer of hydrophobic cations, decyltrimethylam-
monium and dodecyltrimethylammonium, adsorbed
at ITIES, is characterized by low transfer coef-
ficients[42], whereas Equation (6) is valid for cases
with absence of adsorption.
Melroy et ~1l.[77-811 simulated chronopotentio-
metric curves mainly for the case of absence of a base
electrolyte. They claim[81] that chronopotentiometry
at ITIES is not suitable for kinetic measurements,
. which does not seem fully justified.
280 1 .

t 5. FACILITATED ION TRANSFER

i , I

1 2 3 4
P’+
Fig. 5. pH dependence of the haIf-wave potential of tetra-
cycline transfer across the water/nitrobenzene interface. Yu.
N. Kozlov and J. Koryta, unpublished results.
Under the assumption that the transfer coefficient tr
is-constant, that the potential difference in the inner
layer can be neglected and that the simplification (4) is
valid a simple form of the Butler-Volmer equation has
been deduced[9,6lb] (see also[77] and Fig. 6) for the
current density connected with a z,-valent ion transfer
ji = ziFkoexp[ (~-~).z~FA~~~/RTIX*~~
x [ci(w)ci(o)]‘/’ sinh (ziFq/2RT)
where k” is the standard rate constant of the genuine
transfer step (diffusion shift and resolvation), X has
been defined in connection with Equation (3), AEcpp is
the standard potential difference of transfer of the ion i
++++
5
The principles of ionophore facilitated ion transfer
have been outlined in Part I. It should be stressed that
as an ionophore (c$ [X2]) a strongly hydrophobic
(lipophilic) particle is defined that possesses acceptor
properties for ions (a complexformer or a proton
acceptor) while the ionophore-ion associate must be
also hydrophobic. The investigation of ionophore
facilitated ion transfer is effectively carried out in two
procedures. In the first case the ionophore is present at
a low concentration in the organic phase (at equilib-
rium, in the complexed form) and the transferred ion in
the aqueous phase at a considerably higher concen-
tration (see Part I). In the second case the ionophore is
x present at a rather high concentration in the organic
phase and the transferred ion at a much smaller
(6)
concentration in the aqueous phase[S3]. In the first
case, the current is controlled by diffusion of the
ionophore to ITIES and by diffusion of the complex
formed from ITIES to the bulk of the organic phase. In
the second case, the rate-controlling process is dif-
fusion of the free metal ion in the aqueous phase to
ITIES and of the complex from ITIES to the bulk of
the organic phase. No intervention of the rates of
chemical reactions of complex formation and dissoci-
ation has been observed so far. Obviously, besides
chemical volume reactions also fast chemical surface
reactions play a role in the transfer process so that,
finally, there is always an equilibrium practically
established between the free metal ions, the free
ionophore and the complex[X4]. The results obtained
with ionophore facilitated ion transfer across ITIES

b+ t
+++A++*

_
_-_A;- +++
- _-_-_
with an adsorbed phospholipid monolayer[W] show

++ +
+

++++ + - --~~_
+t++* that the particle transferred to the organic phase is the
complex formed in a surface reaction.
In most cases the complexes formed in the 1: 1
+ ++l metal/ionophore ratio have been investigated. The
study of ion-transfer facilitation by macrocyclic
+ - excess charge
(crown) polyethers has been revised and extended
[65,86]. The sodium ion transfer in the presence of
nonactin[65,86] and the potassium ion transfer in the
presence of valinomycin[84] has been described.
The acyclic antibiotic monensin (Fig. 7) forms cyclic
ci3m hydrcxpt&k iolls
complexes with sodium and lithium the terminal
carboxylic and methoxylic groups closing the ring
around the central cation by a hydrogen bond. In
contrast to the behaviour in bilayer lipid mem-
Fig. 6. Ef&zt of charge distributionin the double-layeraf the branesC87, SS] in electrolysis at the water/nitroben-
transfer rate of hydrophilic and hydrophobic ions. zene interface monensin acts either as sodium carrier in
450 I. KORYTA
i stants of ionophore complexes, electrolysis at ITIES is
Fig. 7. Voltammograms of Na+ transfer across the water/
nitrobenzene interface facilitated by monensin. Aqueous
phass 0.1 M HCL, 0.1 M NaN03, nitrobenzene phase;
0.01 M TEA TPB, 1 mM monensin. Polarization rates: (1)
5mVs-‘, (2) lOmVs_‘, (3) 25mVs-‘, (4) 50mVs-‘, (5)
100 mvs-‘[go].
the form of the undissociated acid HX or as proton
carrier in the form of the electroneutral complex
MX [89,90]. The half-wave potential of monensin is
governed by the equation
A~P~,~ = const.+RT/F ln[ki/c,(w)+kz/c,(w)]
(7)
where c~(w) is the sodium or lithium ion concen-
tration, cu(w) is the hydrogen ion concentration, both
in water, The terms k, and k2 are given by the
equations
k, = expIFAEcp&+/RT)K;’
k2 = exp(FAEcp$+/RT)K;’
with KI and K, denoting equilibrium constants of
MHX+ formation in the organic phase
CMHXI,
& = [H+],[MX],-
A proton transfer facilitated by a hydrophobic iono-
phore has also been described[91].
Cation/ionophore ratios 1: 2 have been observed
with the acyclic N, N’-di[ (1 f’ethoxycarb0nyl)
undecyl]-N, N’, 4,5-tetramethyl-3, 6-dioxaoctanedi-
amide[92] and the cyclic ligand 7, lg-dibenzyl-2,3-di-
methyl-7, 19-d&a-l, 4, 10, 13, 16-pentaoxacyclo-
heneicosane-6, 20-dione[93] in the case of divalent
cations (Ca ‘+, Ela’+, Sr2+, Mg2*) while the ratio 1: 1
has been with univalent cations (H,O+, Li+,
Na*)[83]. In the transfer of divalent metals a kinetic
transfer step can be also detected.
6. ELECTRON TRANSFER
In contrast to the transfer of a heavy particle like a
molecular ion, in the case of electron transfer across
ITIES the Marcus-Levich theory based on electron
tunelling can directly be applied. The theory of this
kind of transfer has been worked out by Kharkats
[94] and by Samec[75]. Besides the experiment 0f
Guainazzi er aZ.[95] (see Part I) a new case of electron
transfer has been found by Samec et a/.[96991 based
on electron transfer from ferrocene in nitrobenzene to
ferricyanide ion in water and back.
7. APPLICATIONS AND PERSPECTIVES
Besides obvious applications like determination of
standard Gibbs transfer energies and stability con-
being utilized in several less trivial directions.
In analytical chemistry it can be used for assay of
ionophores (for a review see[ 1001) which are otherwise
determined either by means of time consuming bio-
logical methods or by rather unspecific chemical
methods. An example is the determination of monen-
sin in extracts of cultures of Streptomyces cinnamon-
ensis[89].
On the basis of the data obtained by electroIysis at
ITlES the behaviour of ion-selective electrodes can be
predicted either by simulation[7.8, 101, 1023 or by
calculation of selectivity coeficients[83] or response
times[103].
In the author’s opinion the future development in
electrolysis at ITIES will be connected with processes
taking place at interfaces with adsorbed or spread
amphiphilic substances (for preliminary data obtained
with phospholipids see[85] and with proteins[55]).
Such systems can work as more appropriate models of
biological membranes than the simple ITIES.
Moreover, a possible application may be found in the
field of separation processes. While electrolysis at
ITIES does not seem to have distinct advantages in
comparison with standard extraction methods, be-
cause of rather high rates of charge transfer processes
as well as of difficulties connected with the work with
dispersed systems, an ITIES modtied by adsorption or
spreading may show useful effects of specific inhibition
of some transfer processes.
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