Journal of Electroanalytical Chemistry 522 (2002) 189 198 www.elsevier.

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Reduction of iodine at the organic liquid  aqueous solution  graphite electrode three-phase arrangement
Valentin Mirc eski 1, Fritz Scholz *
Ernst -Moritz -Arndt -Uni6ersita t Greifswald, Institut fu r Chemie und Biochemie, Soldmannstrae 23, D -17489 Greifswald, Germany

Abstract The electrochemistry of the iodine/iodide redox couple was studied at the three-phase arrangement organic liquid  aqueous solution  graphite electrode. A droplet of an organic solvent, e.g. nitrobenzene, containing dissolved iodine was attached to a graphite electrode and immersed in an aqueous electrolyte solution. The reaction mechanism has been studied in the presence of NO and ClO 3 , Cl , Br , F 4 ions in the aqueous supporting electrolyte, and for nitrobenzene, tetrachloromethane, and parafn oil as organic solvents for iodine. The reduction of iodine in the nitrobenzene droplet is either accompanied by a transfer of the iodide ions formed from nitrobenzene to water: (i) I2(nb) + 2e ? 2I (aq), or, in the case that the aqueous electrolyte is an alkali chloride or bromide, by a transfer of chloride or bromide ions from nitrobenzene to water: (ii) I2(nb) + 2X ? 2I (nb) + 2e (nb) + 2X(aq) (X = Cl , Br , possibly in the form of I2X ). The second reaction is possible because with chloride and bromide ions a rather fast reactive partition of the aqueous electrolyte into nitrobenzene occurs, due to the formation of I2X (nb) ions in nitrobenzene. 2002 Published by Elsevier Science B.V.
Keywords: Voltammetry; Iodine; Three-phase junction; Liquid interface; Ion transfer

1. Introduction The interface between two immiscible electrolyte solutions (ITIES) has been studied extensively, especially with the help of electrochemical techniques [1 4]. The interest in these studies is fuelled by the importance of liquid  liquid interfaces for separation membranes, ion selective electrodes, solvent extraction, biomimetic studies of membrane function, etc. [5 13]. Among numerous phenomena occurring at the ITIES, the transfer of ions across the interface is one of the most important processes. Voltammetric techniques appear to be a simple and powerful tool for studying the thermodynamics and kinetics of ion transfer processes. Over the last few decades, the experimental approach for studying the ion transfer was advanced signicantly and many modications of the voltammetric experiments have been
* Corresponding author. Tel.: + 49-3834-86-4450; fax: + 49-383486-4451. E -mail address: fscholz@uni-greifswald.de (F. Scholz). 1 On leave from: Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Sv. Kiril i Metodij University, P.O. Box 162, 1000 Skopje, Macedonia.

proposed. Nevertheless, the general experimental arrangement for investigating the ion transfer across the liquid interface remained the same. Most frequently, supporting electrolytes are added to both solvents and the system is studied utilising a four-electrode potentiostat [13]. Due to some a priori limitations of such an experimental arrangement, which are related mainly to the narrow potential window, the transfer of many organic and inorganic ions is so far not accessible. Osborne et al. [14] suggested that in the complete absence of the electrolyte in the aqueous phase and a micromolar concentration of electrolyte in the organic phase, the potential window of the ITIES method is considerably widened using a single microhole interface. Quinn et al. [12] published a theoretical treatment of this approach. Shi and Anson [15,16] developed a voltammetric method to study the ion transfer by using electrodes that are covered with a lm of an immiscible organic liquid. Recently, a novel experimental approach for exploring the ion transfer between two immiscible solutions was developed [17 19]. According to the method employed, a droplet of a water-immiscible organic solvent containing an electrochemically active compound is at-

0022-0728/02/$ - see front matter 2002 Published by Elsevier Science B.V. PII: S 0 0 2 2 - 0 7 2 8 ( 0 2 ) 0 0 7 2 0 - 9

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tached to the graphite electrode and immersed into an aqueous electrolyte solution. These authors assumed that the electrochemical reaction of the electroactive compound can proceed only along the three-phase junction line graphite  water  organic phase, since the organic phase does not contain a deliberately added supporting electrolyte. With this simple experimental set-up, the transfer of ions across the liquid  liquid interface can be studied utilising a standard three-electrode potentiostat, and, moreover, the potential window of the experiment is extended considerably, as the organic phase does not contain any dissolved electrolyte. The proposed method is interesting because simultaneous electron and ion transfers are realised in the three-phase arrangement via two interfaces, i.e. the electron transfer across the graphite  organic liquid interface and the ion transfer across the water  organic liquid interface. Recently, Marken et al. [20 23] and Schro der et al. [24] studied the voltammetric response of droplets of organic electroactive liquids attached to the surface of an electrode. They also observed that the ion transfer accompanies the redox transformation of the micro droplets. However, in these experiments, the liquid interface is itself electroactive, and its properties change severely in the course of the electrochemical reaction. Furthermore, so far it was not possible to determine the Gibbs energy of ion transfer for these liquids. In this paper, we describe the redox reaction of iodine at the three-phase junction water  organic phase  graphite, where the organic phase is nitrobenzene, tetrachloromethane, or parafn oil. The results obtained widen the understanding of the fundamentals of these experiments, extending our basic knowledge of electrochemical reactions occurring at three-phase arrangements, where an electron transfer between the electron conductor and the organic liquid phase is coupled with an ion transfer between the two liquid phases. The most important news from this study is that a fast partition of the electrolyte that is initially present only in the aqueous phase occurs between the two liquid phases. This allows the electrochemical reaction to proceed as an electron transfer across the electron conductor  organic liquid interface and a simultaneous ion transfer across the organic liquid  aqueous solution interface. Thus the electrochemical reaction is no longer conned to the three-phase junction line, but it can occur simultaneously at the two interfaces. It is still reasonable to assume that the reaction starts at the three-phase junction line, however, due to the presence of partitioned electrolyte in the organic liquid droplet, it may quickly advance through the droplet.

2. Experimental A 0.1 mol l 1 solution of iodine was prepared by dissolving iodine in nitrobenzene, tetrachloromethane, and parafn oil. A drop of these solutions, with a volume of 2 ml was attached to the surface of a parafn impregnated graphite electrode (PIGE) with the help of an Eppendorf-type pipette. The approximate radius of the hemispherical droplet was 0.15 cm. During squarewave voltammetric experiments, neither a signicant distortion nor a change of the colour of the droplet has been observed. The dimension of the droplets inuences only the measured currents, whereas both the position of the response (peak potential) and shape (half-peak width) are not affected. Square-wave voltammograms were recorded using the electrochemical measuring system AUTOLAB (Eco-Chemie, Utrecht, Netherlands). A Ag  AgCl  saturated NaCl solution reference electrode (E = 0.200 V vs. SHE) was used and a platinum wire served as the auxiliary electrode. All salts used for preparation of the supporting electrolytes were used as purchased. All chemicals used were of analytical grade. The parafn oil used (Merck Index 11, 7139) was of IR spectroscopy grade. The preparation of PIGEs is described elsewhere [25]. The water used was Millipore Q. All experiments were carried out at a room temperature of about 20 C.

3. Results and discussion In an aqueous medium iodine can be reversibly reduced to iodide in a simple two-electron redox reaction 0 [26] characterised by the standard potential E = I2(s)/2I 0 0.535 V vs. SHE and E I (aq)/2I = 0.621 V vs. SHE for 2 the solid and dissolved iodine, respectively. The SW voltammetric response of a nitrobenzene droplet containing dissolved iodine, attached to the graphite electrode and immersed in 1 mol l 1 KNO3 aqueous solution, consists of a single well-dened SW peak with a peak potential of 0.467 V vs. Ag  AgCl  NaCl sat. and a half-peak width of DEp/2 = 112 mV (Fig. 1). The forward and backward components of the SW response are well-developed bell-shaped curves characterised by almost equal heights and a peak potential separation of 15 mV. Over the frequency interval from 20 to 300 Hz, the position and the shape of the response remained virtually unaltered, with a peak potential variation within 9 6 mV and half-peak width variation within 9 3 mV. Within the same frequency interval, the peak current is proportional to the square root of the SW frequency, associated with a correlation coefcient of the linear regression line of R 2 = 0.985. The slight scattering of the experimental points of this plot arises from the

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Fig. 1. Forward (1), backward (2), and net SW (3) components of the square-wave voltammetric response of a nitrobenzene droplet with a volume of 2 ml containing 0.1 mol l 1 iodine attached to a PIGE which is immersed in 1 mol l 1 KNO3 solution. The experimental conditions were: SW frequency f = 50 Hz, SW amplitude Esw = 50 mV, and scan increment dE = 0.15 mV.

uncertainty of the dimensions of the nitrobenzene droplet attached to the graphite electrode, which cannot be controlled more precisely. It is also important to emphasise that the ratio of the peak currents of the forward (reduction) and backward (oxidation) components of the SW response remained virtually constant by varying the signal frequency. This indicates that the electrode reaction is not complicated by a follow-up chemical reaction, as can be expected for the reduction of iodine [26]. The square-wave amplitude markedly affects the height and shape of the SW voltammetric response of iodine. Increasing the amplitude from 10 to 80 mV caused the peak current to increase linearly. The halfpeak width DEp/2 increases from 126 to 146 mV, for the amplitude of Esw = 10 and 120 mV, respectively. At the same time, the peak potential scatters slightly around the average value of 0.480 V vs. Ag  AgCl by 9 7 mV. For the sake of brevity, the data of the foregoing analyses are not presented in the form of diagrams.

On the basis of the properties of the voltammetric response observed by varying the SW excitation signal parameters, it can be concluded generally that the electrode reaction of iodine in the three-phase arrangement exhibits properties of a reversible electrochemical process. Moreover, the voltammetric behaviour is typical for planar diffusion mass transport, which appears to be surprising, when the reaction is assumed to proceed only along the three-phase junction line. It is also worth noting that, within the frequency interval explored, ohmic resistance, which would manifest mainly as a deviation from peak shape, does not affect the reaction. Before providing a reasonable explanation for the diffusion regime, an attempt will be made to elucidate the possible electrode mechanism for reduction of iodine at the three-phase boundary. To elucidate the electrode mechanism of iodine reduction, the electroneutrality of the organic phase has to be taken into account. Thus, it is reasonable to expect that the reduction of iodine to iodide is followed either by the transfer of electrochemically formed iodide ions from nitrobenzene into the aqueous phase, or by entering of cations, initially present in the aqueous phase into the nitrobenzene droplet. The postulated scenario occurring in the three-phase system is depicted schematically in Fig. 2, and ascribed to the following electrode reactions:
I2(nb) + 2e ? 2I(aq) I2(nb) + 2Cat+ ? 2I(nb) + 2Cat+ (aq) + 2e (nb)

(I) (II)

Whereas the reaction (I) can occur at the three-phase boundary, the overall process (II) can be split into two reactions occurring simultaneously at the graphite  nitrobenzene interface (IIa) and the nitrobenzene  water interface (IIb):
I2(nb) + 2e ? 2I(nb)

(IIa) (IIb)

2Cat

+ (aq)

? 2Cat

+ (nb)

In order to clarify whether the transfer of cations accompanies the redox reaction from aqueous phase to organic droplet, the reduction of iodine was studied in a variety of nitrate solutions containing different

Fig. 2. Electrode assembly with a droplet of nitrobenzene containing dissolved iodine attached to a PIGE, which is immersed in an aqueous electrolyte solution. Possible electrode reactions are formulated (see text).

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Fig. 3. Net SW voltammetric responses of nitrobenzene droplet containing 0.1 mol l 1 iodine attached to a PIGE, which is immersed in a 1 mol l 1 aqueous solution of NaNO3 (1), LiNO3 (2), KNO3 (3), and Mg(NO3)2 (4). Other experimental conditions were the same as in Fig. 1.

cations (Fig. 3). As can be seen, the particular type of cations present in the aqueous phase exhibits no inuence on the position and shape of the voltammetric response, suggesting that the entering of cations does not preserve the electroneutrality of the organic phase. Therefore, under these experimental conditions, the reduction of iodine at a three-phase boundary most probably proceeds according to the redox mechanism (I). By an analogy of features of the electrode reduction of iodine in an aqueous medium [26] it is reasonable to suppose that the mechanism (I) could be complicated additionally by a follow-up chemical reaction in which I 3 is formed according to the reaction:
I2(nb) + I(nb) ? I3 (nb)

(III)

mechanism of iodine reduction only in the presence of concentrated iodide solutions [26]. At this point, it is also meaningful to consider the possibility of iodine reduction at the graphite  water interface because of the partition of iodine between the organic and aqueous phase. In the classical experiments with a saturated solution of I2 in the aqueous phase, the peak currents of I2 reduction were about 2 3 orders of magnitude smaller than in the droplet experiments. Therefore, the possibility that the response of I2 in the aqueous phase contributes considerably to the results can be excluded. A thermodynamic treatment of reaction (I) yields the following Nernst equation:
0 E = E c%+

However, both products I and I 3 are electroactive and thus both can be reoxidised back to the same reactant I2 at almost an identical potential. If this is not true, the backward component of the SW response should consist of two separated or overlapped peaks. The experimental results do not support this presumption. Therefore, the overall reaction (I) does not proceed as an EC mechanism. It should be also noted that I could be further reduced to 3I. In an aqueous 3 medium, the standard potential of the redox couple I is about 80 mV more negative than that of the 3 /3I I2/2I couple. Therefore, it can be assumed that the overall reduction of iodine can proceed as an ECE% mechanism, where E represents the reduction of iodine to I, C is the chemical step in which I 3 is created, and E% represents its further electrochemical reduction to 3I. It is quite clear that in the present experimental arrangement, there are no indications for such a behaviour; however this possibility cannot be excluded on the basis of our experiments. Generally speaking, the equilibrium (III) plays a signicant role in the overall

RT aI2(nb) ln 2 2F a I(aq)

(1)

where
0 0 0 nb E c % = E I /2I + Daq I
2

(2)

The standard potential of the transfer of ions Xz at the 0 water  nitrobenzene interface Dnb aq Xz is related to the standard Gibbs energy of transfer across the liquid 0 0 nb interface Dnb aq G Xz through the relation: Daq Xz = 0 Dnb G aq Xz (z is 1 for monovalent anions and + 1 for zF 0 1 [27], monovalent cations). As Dnb aq G I = 18 kJ mol the standard potential of iodide transfer at the wa 0 ter  nitrobenzene interface is Dnb aq I = 0.186 mV. Since 0 E I /2I = 0.335 V vs. Ag  AgCl, the position of the SW 2 voltammetric response of iodine in various nitrate solutions (Ep = 0.470 V vs. Ag  AgCl) is close to the ex0 pected formal potential of reaction (I) (E c % = 0.521 V vs. Ag  AgCl) suggesting that the redox reaction (I) describes correctly the reduction pathway of iodine at the three-phase boundary.

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where the formal potential is

0 0 0 nb E c % = E I /2I + Daq cat+ +
2

RT lnacat+(aq). F

(4)

The standard potential difference of a particular monovalent cation is related to the standard Gibbs energy of transfer through the relation:
0 Dnb aq cat+ = 0 Dnb aq G cat+ F

Fig. 4. Net SW voltammetric responses of nitrobenzene droplet containing 0.1 mol l 1 iodine attached to a PIGE, which is immersed in 1 mol l 1 solution of NaCl (1), NH4Cl (2), CsCl (3), and KCl (4). Other experimental conditions were the same as in Fig. 1.

Fig. 5. The dependence of the peak potential of the second SW peak, observed in chloride aqueous solutions, on the concentration of CsCl and NaCl, used as supporting electrolytes. Other experimental conditions were the same as in Fig. 1.

A similar thermodynamic treatment of the postulated reaction mechanism (II) leads to the following form of the Nernst equation:
0 E = E c%+

RT a ln 2 I2(nb) 2 2F a I(nb)a cat +(nb)

(3)

since the Gibbs energies of transfer of all cations present in the supporting electrolytes are positive values 0 0 [27], it follows that Dnb aq cat+ B 0. Therefore, E c %(II) B 0 0 0 E c %(I), where E c %(I) and E c %(II) are the formal potentials of the redox mechanisms (I) and (II), respectively. In other words, the preservation of the electroneutrality of the organic phase by entering of cations requires a higher Gibbs energy than the process in which iodide ions leave the organic phase. Obviously, the redox mechanism (II) cannot occur at all, since it is always preceded by the process (I), which occurs at more positive potentials. This, at least, holds true for the alkali metal cations. The most interesting results have been observed in the presence of chloride ions in the aqueous phase. Fig. 4 represents the SW voltammetric response of iodine recorded in a series of electrolyte solutions containing chloride ions. Very unexpectedly, the presence of chloride gives rise to a new well-dened SW peak at more positive potentials. The position of this peak is not affected by the nature of the particular cations, however it depends strongly on the concentration of chloride ions in the aqueous phase. As can be seen from Fig. 5, the relationship Ep vs. log(cCl) is characterised by a negative slope of 43 and 53 mV using NaCl and CsCl as supporting electrolytes, respectively. It seems that the appearance of the SW peak at more positive potentials is related to an electrode reaction pathway in which the electroneutrality of the organic phase is achieved by the transfer of chloride ions from nitrobenzene into the aqueous solution (see Fig. 6). Considering the fact that no supporting electrolyte was

Fig. 6. Electrode assembly with a droplet of nitrobenzene containing dissolved iodine attached to the graphite electrode, which is immersed in an aqueous electrolyte solution containing chloride ions.

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Fig. 7. Correlation between theoretically calculated and experimentally measured peak potential separations for different concentrations of NaCl and CsCl supporting electrolytes. Other experimental conditions were the same as in Fig. 1.

The peak potential separations have been measured for different concentrations of chloride ions in both NaCl and CsCl solutions and compared to the theoretical values calculated with Eq. (7). A simple correlation of the measured and expected values reveals fairly good agreement between these values (see Fig. 7). All these ndings strongly support the correctness of the postulated electrode reaction (IV). A possible explanation for the presence of chloride ions in the nitrobenzene droplet and their involvement in the electrode reaction (IV) is a rather fast partition of the supporting electrolyte ions between the aqueous and organic phases, once the electrode with the nitrobenzene droplet is introduced into the chloride containing aqueous electrolyte solution:
+ Cat+ (aq) + Cl(aq) ? Cat(nb) + Cl(nb)

(V)

added to the organic phase, the observed electrode mechanism is rather unexpected. The postulated electrode reaction may be described by the following scheme:
+ 2e ? 2I(nb) + 2Cl(aq) I2(nb) + 2Cl(nb)

(IV)

The following form of the Nernst equation describes the electrode reaction:
0 E = E c%+

RT aI2(nb)a 2 Cl(nb) ln 2 2F aI (nb) RT ln aCl-(aq) F

(5)

with a formal potential of E %=E

0 c 0 I2/2I

Governed by the large gradient of electrochemical potentials acting at the liquid  liquid interface, a certain amount of the supporting electrolyte ions enters the organic phase. However, the amount of the chloride ions in the organic phase due to partition of the supporting electrolyte is insufcient to give rise to such a high and well-developed second SW peak. Some additional mechanism has to occur, increasing considerably the chloride concentration in nitrobenzene. Most probably, a signicant role is played by the reaction between iodine and chloride ions to form I2Cl in the organic phase, since the formation of interhalide compounds is a well-known property of iodine [28]: Cl(nb) + I2(nb) ? I2Cl(nb) (VI) Thus, a kind of reacti6e partition occurs at the water  nitrobenzene interface increasing considerably the amount of chloride in the organic phase. Once present in the organic phase, at least close to the three-phase boundary, the partitioned ions can participate in the electrochemical reaction. The amount of ions transferred initially across the liquid  liquid interface is determined by the Gibbs energy of transfer of both anions and cations of the partitioned salt. Thus, ions with a high Gibbs energy of transfer cannot give rise to SW peaks at more positive potentials, since they cannot be partitioned between the aqueous and the organic phase. This can be seen by a comparative analysis carried out in the presence of uoride, bromide and chloride ions (Fig. 8). In a solution containing uoride ions, the peak at more positive potentials was not observed, indicating clearly that the redox process associated with the transfer of uoride ions from the organic into aqueous phase does not occur. Regarding the high energy of transfer of uoride 0 1 ions Dnb [27], it is clear that the aq G F = 70 kJ mol amount of partitioned uoride ions is much too small to allow participation in the electrode mechanism. The inuence of different cations of the partitioned halide salts will be described in the following publication.

+D
nb aq

0 Cl

(6)

According to the latest equation, the formal potential of the redox reaction (IV) should depend linearly on the logarithm of the activity of chloride ions in the aqueous phase, with a negative slope of 57 mV (at 291 K). The experimental results presented in Fig. 5 are in close agreement with the theoretically predicted value. Furthermore, as both the standard Gibbs energy of transfer and the standard potential of transfer of chloride ions at the water  nitrobenzene interface are posi 0 1 tive values (Dnb and aq G Cl = 35 kJ mol 0 nb Daq Cl = 0.362 V), it is clear why this process occurs at more positive potentials than the transfer of iodide ions (reaction mechanism I). If both SW peaks observed in the chloride solutions are correctly assigned to the electrode mechanisms (I) and (IV), then the potential difference between them should correspond to the difference of the formal potentials of the reactions (IV) and (I) dened by Eqs. (6) and (2), respectively:
0 0 nb DEp = Dnb aq Cl Daq I

RT ln aCl-(aq) F

(7)

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In the presence of bromide ions, an electrode reaction with participation of bromide ions occurs only as a shoulder on the positive side of the main SW peak (curve 2 in Fig. 8). The formal potential of the electrode reaction follows as:
0 0 0 nb E c % = E I /2I + Daq Br
2

RT ln aBr-(aq) F

(8)

Since bromide ions are characterised by a lower transfer energy than chloride ions, the following rela 0 0 nb tion holds: Dnb aq Br B Daq Cl. Hence, the process involving bromide ions is situated at more negative potentials than that involving chloride ions (Eqs. (6) and (8)). The extent of partition can also be varied by the choice of the organic solvent. Fig. 9 shows the voltammetric responses when iodine was dissolved in a droplet

Fig. 8. SW voltammetric responses of nitrobenzene droplets containing 0.1 mol l 1 iodine attached to a PIGE, which is immersed in 1 mol l 1 aqueous solution of NaF (1), NaBr (2), and NaCl (3). Other experimental conditions are the same as in Fig. 1.

of parafn, tetrachloromethane, and nitrobenzene. In all three cases the aqueous electrolyte contained 1 mol l 1 NaCl. Using parafn as the organic solvent, only one single SW peak occurs and this peak can be explained by the reaction mechanism in which the electrochemically formed iodide ions leave the organic phase (reaction I). In this case, the partition of chloride ions between the organic and aqueous phases does not take place to a measurable extent and the process at more positive potentials cannot be observed. Although the Gibbs energy of the transfer of chloride from water into parafn is not known, it is reasonable to suppose that this value will be very large, especially when taking into account the non-polarity of parafn. Carrying out an experiment with tetrachloromethane, one observes a voltammogram that is similar to that with nitrobenzene (curves 2 and 3 in Fig. 9). However, the peak ascribed to the transfer of chloride ions from the organic phase into water appears at more positive potentials than the corresponding one in the case of nitrobenzene. This is also an expected result, since the transfer of chloride to tetrachloromethane, as a non-polar solvent, will require a rather high Gibbs energy. If the Gibbs energy of transfer of the supporting electrolyte anions is close to that of iodide, then an electrode reaction analogous to (IV) will not produce a separate SW peak at more positive potentials, since the formal potentials of the mechanisms (I) and (IV) will not differ sufciently. In some cases, when the transfer energy of the present anions in the aqueous phase is low enough to allow a considerable amount of ions to enter into the organic phase, the reaction mechanism analogous to (IV) can become predominant and the single reaction pathway for the reduction of iodine at the three-phase boundary occurs. Such behaviour was observed in the presence of perchlorate ions, which are characterised by 0 a Gibbs energy of transfer of Dnb aq G ClO = 4 1 10 kJ mol . If the concentration of perchloric acid in the aqueous phase is lower than 0.05 mol l 1, then the reduction of iodine mainly occurs according to the mechanism (I). However, at higher concentrations of perchloric acid in the aqueous phase, the amount of partitioned perchlorate ions in the organic droplet increases so much, that the electrode reaction switches from mechanism (I) to mechanism analogous to (IV). The latter is associated with the following formal potential:
0 0 0 nb E c % = E I /2I + Daq ClO
2 4

RT ln aClO(aq) 4 F

(9)

Fig. 9. SW voltammetric response of a parafn (1), a tetrachloromethane (2), and a nitrobenzene (3) droplet containing 0.1 mol l 1 dissolved iodine, attached to a PIGE and immersed in 1 mol l 1 solution of NaCl. Other experimental conditions were the same as in Fig. 1.

Due to the inuence of the last term on the right-hand side of Eq. (9), the voltammetric response is strongly shifted in the negative direction (see Fig. 10). Within the concentration range from 0.05 to 2 mol l 1, the peak potential depends linearly on the logarithm of the

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tion to the assumption that the reaction takes place only at a single reaction line. For these reasons, the theoretical model of Myland and Oldham based on a cylindrical diffusion model as closest approximation to the single reaction line, did not match the experimental results [29]. For these reasons, in Appendix A a theory for modelling reaction (I), based on planar diffusion mass transport is presented. A brief correlation between the experimental and theoretical results is carried out in order to support the presented thesis derived from the experimental results in this paper.

Fig. 10. SW voltammetric response of a nitrobenzene droplet containing 0.1 mol dm 3 iodine attached to a PIGE, which is immersed in a 1 mol l 1 (1), 3 mol l 1 (2), 5 mol l 1 (3), and 6 mol l 1 (4) aqueous solution of HClO4. Other experimental conditions were same as in Fig. 1.

5. List of symbols and abbreviations c* I2(nb) cI2(nb) cI

(aq)

concentration of perchloric acid in aqueous phase with a slope of DEp = 64 mV Dlog(cHClO4) which is in good agreement with Eq. (9).

4. Conclusions The above described results extend the basic knowledge of the nature of electrode reactions proceeding in a three-phase arrangement, when an electron transfer is simultaneously accompanied by an ion transfer across a liquid  liquid interface. Obviously, in many cases, a fast partitioning of the supporting electrolyte ions between the organic and aqueous phases occurs and plays an important role in the electrode reaction. This partitioning considerably increases the number of possible electrode mechanisms. The presence of an appreciable amount of ions in the organic phase, at least in the region where the electrode reaction starts, appears to be the most crucial consequence arising from the partition phenomenon. Consequently, the early hypothesis that the reaction occurs exclusively at the three-phase junction line has to be modied at least by considering a more extended reaction zone that is located around the line where all three phases, organic solvent, aqueous solution, and electrode meet. The reaction zone is large enough to allow the reaction to be controlled by planar diffusion mass-transport without an appreciable IR drop. This fact explains the large currents observed in this study, as well as in the previously reported experiments carried out with ferrocene and decamethylferrocene [17 19]. The current commonly measured with this experimental arrangement was in strong contradic-

D E F f I n R S T t x rs

concentration of iodine in the bulk of nitrobenzene concentration of iodine in nitrobenzene concentration of iodide in the aqueous solution diffusion coefcient potential of the working electrode Faraday constant SW frequency current number of electrons gas constant electrode surface area temperature time coordinate normal to the electrode surface auxiliary constant in units of mol1 cm3

Acknowledgements V. Mirc eski thanks A.V. Humboldt-Stiftung for provision of a Humboldt fellowship and F. Scholz acknowledges kind support by Deutsche Forschungemeinschaft (DFG) and Fonds der Chemischen Industrie (FCI). The authors wish to thank Professor K.B. Oldham for several suggestions and discussion.

Appendix A It is assumed that the mass transport of all species participating in the electrode reaction
I2(nb) + 2e ? 2I(aq)

(AI)

occurs by planar diffusion. As a rst approximation it is supposed that the diffusion coefcients of iodine and iodide are equal, thus the following mathematical model represents reaction (I):

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197

#2cI2(nb) #cI2(nb) =D #t #x 2 #cI(aq) #2cI(aq) =D #t #x 2 t = 0, x ] 0: t \ 0, x 8 : x = 0: D cI2(nb) = c* I2(nb), cI = 0

(aq)

(A1) (A2) (a) (b) (c)

x=0

I (cI2(nb) =D nFS (x

cI2(nb) c* I2(nb), cI 0

(cI2(nb) (x

I 1 (cI (aq) = D nFS 2 (x

 
x=0 x=0

(aq)

(cI 1 (aq) = D (x 2 x=0

 

(d) (e)

Under equilibrium conditions at the three-phase junction line, the following condition holds (activity coefcients neglected): cI2(nb) = rsc 2 I exp( )
(aq)

(A3)

0 0 nb where = (2F )/(RT )(E E I22I Daq I) is the dimensionless potential. The meanings of all symbols are listed in Section 5. The solution expressed in the form of an integral equation reads:

c* I2(nb) = rs

exp( ) (A4) nFS

D
y (t ~ ) The numerical solution of the last equation was
0

&

&

I (~ )

d~

nFS
D
y (t ~ ) 2 I (~ ) d~

Fig. 11. The forward (cf), backward (cb), and net SW (cnet) components of the theoretical square-wave voltammetric response of the reaction (I). The conditions of the simulations were: SW amplitude Esw = 50 mV, scan increment dE = 1.5 mV, and concentration of 3 iodine c * . The dimensionless current is dened I2(nb) = 0.1 mol cm 1 (Df ) 1/2. as: c = I (nFSc * I2(nb))

obtained by the numerical method of Nicholson and Olmstead [30]. The theoretical SW voltammograms are functions of the frequency and amplitude of the excitation signal, as well as of the bulk concentration of iodine, since reaction (I) is of second order with respect to the product of the electrode reaction. The theoretical SW voltammetric response of reaction (I), simulated under identical instrumental parameters as those used in the experimental study, is depicted in Fig. 11. Obviously, the shape of the theoretical response is in accordance with the experimental SW voltammograms (compare Figs. 1 and 11). The separation between the forward and backward components of the theoretical SW response is DEp = 20 mV, whereas the half-width is DEp/2 = 110 mV. The properties of the theoretical response are close to the corresponding values of the experimental voltammogram recorded in 1 mol l 1 KNO3, which are: DEp = 15 mV and DEp/2 = 113 mV (see Fig. 1). The analysis of the system by varying the SW frequency provides the main criterion for characterising a reversible electrode mechanism controlled by a planar diffusion mass transport. The peak current of the theoretical voltammograms is a linear function of the square root of the SW frequency, while both the peak potentials and half-peak widths are independent of frequency. Obviously, the experimental (see Section 3) and the theoretical behaviour are in excellent agreement. The signal amplitude affects mainly the height and the shape of the theoretical voltammograms. The height of the theoretical response increases linearly over the interval from Esw = 10 to Esw = 40 mV, while the peak potentials remain virtually unaltered. Above this range, the peak current is unaffected by the signal amplitude. At the same time, the half peak width increases from 70 to 150 mV, for amplitudes of 10 and 90 mV, respectively. In the experimental study, the results collected from the analysis by varying the signal amplitude deviate slightly from the theoretically predicted data. For instance, the peak current increases linearly over a wide amplitude interval from 10 to 80 mV. For an amplitude of 10 mV, the half-width of the experimental peak is 126 mV, which is larger than the theoretical value of 70 mV, while for an amplitude of 90 mV, the experimental and theoretical values are virtually the same. Most probably, the inuence of the reaction mechanism (III) in the presence of nitrate ions, on the main electrode process (I), leads to a slight deviation between the experimental and theoretical data. In general, the theoretical model is in good qualitative agreement with the experimental results, supporting the conclusion derived from the experimental study of the reduction of iodine at the three-phase boundary.

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V. Mirc eski, F. Scholz / Journal of Electroanalytical Chemistry 522 (2002) 189 198 & . Komorsky-Lovric [17] F. Scholz, S , M. Lovric , Electrochem. Commun. 2 (2000) 112. & . Komorsky-Lovric [18] S , M. Lovric , F. Scholz, J. Electroanal. Chem. 508 (2001) 129. & . Komorsky-Lovric [19] S , M. Lovric , F. Scholz, Collect. Czech. Chem. Commun. 66 (2001) 434. [20] F. Marken, R.D. Webster, S.D. Bull, S.G. Davies, J. Electroanal. Chem. 437 (1997) 209. [21] F. Marken, R.G. Compton, Ch.H. Goeting, J.S. Foord, S.D. Bull, S.G. Davies, Electroanalysis 10 (1998) 821. [22] F. Marken, A.N. Blythe, J.D. Wadhawan, R.G. Compton, S.D. Bull, R.T. Aplin, S.G. Davies, J. Solid State Electrochem. 5 (2001) 17 22. [23] J.D. Wadhawan, R.G. Compton, F. Marken, S.D. Bull, S.G. Davies, J. Solid State Electrochem. 5 (2001) 348. [24] U. Schro der, R.G. Compton, F. Marken, S.D. Bull, S.G. Davies, S. Gilmour, J. Phys. Chem. B 105 (2001) 1344. [25] F. Scholz, B. Meyer, in: A.J. Bard, I. Rubinstein (Eds.), Electroanalytical Chemistry. A Series of Advances, vol. 20, Marcel Dekker, New York, 1998, p. 1. [26] A.J. Bard, R. Parsons, J. Jordan, Standard Potentials in Aqueous Solutions, Marcel Dekker, New York, 1985, p. 84. [27] Y. Marcus, Ion Properties, Marcel Dekker, New York, 1997, p. 216. [28] J.E. Huheey, Anorganische Chemie, Prinzipien von Struktur und Reaktivita t, Walter de Gruyter, Berlin, New York, 1988, p. 853. [29] J.C. Myland, K.B. Oldham, Electrochem. Commun. 2 (2000) 541. [30] R.S. Nicholson, M.L. Olmstead, in: J.S. Mattson, H.B. Mark, H.C. MacDonald (Eds.), Electrochemistry: Calculations, Simulation and Instrumentation, vol. 2, Marcel Dekker, New York, 1972, p. 120.

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