Na on-coated Mercury Thin Film and Glassy Carbon Electrodes for Electroanalysis: Characterization by Electrochemical Impedance

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1 212 Na on-coated Mercury Thin Film and Glassy Carbon Electrodes for Electroanalysis: Characterization by Electrochemical Imedance Christoher M. A. Brett,* + ValeÂria A. Alves, + and Denise A. Fungaro +,++ + Deartamento de QuõÂmica, Universidade de Coimbra, P Coimbra, Portugal; brett@ci.uc.t ++ Instituto de Pesquisas EnergeÂticas e Nucleares (IPEN), DivisaÄo de QuõÂmica Ambiental ± MQA, Travessa ``R'' no. 400, Cidade UniversitaÂria, CEP SaÄo Paulo ± SP, Brasil Received: Aril 7, 2000 Final version: July 7, 2000 Abstract The different behavior of Na on-coated mercury thin- lm electrodes in anodic striing voltammetry in nitrate and acetate buffer electrolytes has been robed by electrochemical imedance studies. Investigations concerned glassy carbon electrodes, glassy carbon coated with Na on, mercury thin lm electrodes and mercury thin lm electrodes deosited between the glassy carbon substrate and the olymer lm, with values of alied otential similar to those emloyed in anodic striing voltammetry. Comarison is made with results obtained using Na on=5 % oly(vinyl sulfonic acid) coatings. In the absence of cationic reducible secies, acetate buffer leads to larger imedance values than nitrate electrolyte and correlates well with better characteristics of striing signals at Na on-based coatings on mercury thin- lm electrodes. Keywords: Electrochemical imedance, Mercury thin- lm electrode, Glassy carbon, Polymer-modi ed electrode, Na on, Cation-exchange olymer, Anodic striing voltammetry 1. Introduction Glassy carbon has been much used in voltammetric studies owing to its low ermeability to gases, low orosity, hardness, good electrical conductivity, inertness in a number of solvents and good ositive otential range [1, 2]. The kinetics of electron transfer are in uenced signi cantly by the rearation method, surface treatment and electrochemical retreatment, e.g. [3]. The negative otential range, which reaches to ca. 1.0 V without signi cant hydrogen evolution in common aqueous media, can be increased by covering glassy carbon with thin mercury lms [4]. This modi cation ermits the investigation of reduction rocesses and the use of striing voltammetric rocedures at solid electrodes, which would not otherwise be ossible without simultaneous hydrogen evolution dominating the observed currents and reventing reagents reaching the electrode surface. A general dif culty with solid electrodes, such as the glassy carbon electrode (GCE), is a diminution in resonse with time due to irreversible blocking of the surface by adsorbable comonents of the contacting solution. However, the surfaces can be modi ed or rotected in various ways to minimize such alterations, which allows the determination of electroactive secies in comlex media. One of the simlest ways is to cover the electrode with a size-exclusion or ion-exchange olymer to revent access to the surface of unwanted comonents. Thus, a number of tyes of olymer have been investigated for this urose, for examle cellulose acetate, e.g. [5, 6], Na on, e.g. [6±10], oly(ester sulfonic acid), e.g. [11, 12], and olyaniline, e.g. [13]. An alternative aroach is to use a gel-tye membrane ± an agarose gel in combination with microelectrodes for in situ measurements in natural waters has been develoed [14, 15]. The er uorosulfonated olymer Na on, a cation exchange olymer owing to the negatively charged sulfonate grous at each end of the uoroolymer chain has also been mixed with other sulfonated olymers to imrove the cation-exchange characteristics and imrove discrimination against interferents [6]. Nevertheless, there is some H and ion size-deendent ermeation of inorganic anions [16]. In the case of mercury thin- lm electrodes (MTFEs), the Na on coating has been alied directly onto a glassy carbon electrode substrate and a mercury thin lm is then electrodeosited between the glassy carbon substrate and the Na on coating from a Hg(II)-containing solution [17]. Such Na onmodi ed MTFEs have been used in square-wave anodic striing voltammetry (SWASV) in conjunction with the batch injection analysis technique [6, 17, 18]. In BIA, samles of volume as small as 50 ml, normally without retreatment or addition of electrolyte, are injected directly over a detector electrode immersed in electrolyte solution in the BIA cell. Adsortion and electrode blocking from interferents is minimized rst by the small samle volume and secondly through rotection by the olymer coating [17]. It has been shown that such mercury lms consist of a large number of closely saced tiny micrometer-sized drolets which behave as though they exist as a uniform mercury lm [18]. The resence of the coating results in a reduction of signal u to 15 % due to diffusion limitations, but leads to good discrimination against interferents. The coating also confers robustness to the mercury thin lm, articularly imortant in ow or induced- ow situations such as in ultrasound-assisted anodic striing voltammetry [18]. Potassium nitrate and acetate buffer electrolytes have been used in these studies. It has been noted that there can be signi cant differences in the voltammetric resonse in the two tyes of electrolyte [6]. In this article, electrochemical imedance has been emloyed to study and comare some of the characteristics of Na on and Na on-coated mercury thin lm electrodes and glassy carbon electrodes, in order to throw light on the rocesses occurring and on the in uence of the electrolyte on the electrode resonse. Acidi ed nitrate and acetate buffer electrolyte media have been emloyed at values of alied otential similar to those emloyed in anodic striing voltammetry at mercury thin- lm electrodes. Studies on Na on=5 % oly(vinyl sulfonic acid) # WILEY-VCH Verlag GmbH, D Weinheim, /01/0303±0212 $ =0

2 Na on-coated Mercury Thin Film Electrodes 213 coated MTFEs are also resented, where differences between electrolytes are more evident in the voltammetric resonse. 2. Exerimental Electrochemical exeriments were carried out using a glassy carbon electrode of diameter 6 mm, a latinum foil auxiliary electrode and a saturated calomel electrode as reference. Polymer coatings and mercury thin lms were reared as described below. Comuter-controlled imedance measurements were done using a Solartron 1250 frequency resonse analyzer couled to a Solartron 1286 electrochemical interface, with Zlot software. A sinusoidal voltage erturbation of rms amlitude 10 mv was alied, scanning from 65 khz to 0.1 Hz with 5 measurements er decade of frequency. Fitting to equivalent circuits was carried out with Zsim software. All reagents were of analytical grade and solutions were reared using Milliore Milli-Q ultraure water (resistivity > 18 MO cm). Electrolytes emloyed were 0.1 M KNO 3 =5mM HNO 3 (H 2.4) and 0.1 M acetate buffer (H 4.6) and exeriments were done at temeratures of 25 1 C without deaeration, in order to be similar to conditions used in ASV exeriments [6, 17]. Exeriments were also carried out in the absence of oxygen. A solution of 5 wt % Na on in low-molecular-weight alcohols (Aldrich) was diluted in ethanol to reare stock solutions for formation of Na on lms Prearation of the Na on-coated GCE and MTFE The rocedure emloyed was as described reviously [17]. Brie y, the glassy carbon electrode was olished with alumina olishing foils down to 0.3 mm article size before each exeriment and washed. A volume of 5 ml of 0.25 wt% Na on solution was alied to the surface followed immediately by 3 ml of N, N 0 -dimethylformamide using a microiette. After evaorating the solvents with a jet of air at room temerature, while the electrode was rotating at 50 rm, the olymer lm was cured with a jet of warm air at 70 C for about 1 min. In order to reare the Na on-coated mercury thin lm electrode (NCMTFE), the electrode coated with Na on was laced in a batch injection analysis cell [19]. Mercury deosition was done in situ by injection of 10 ml of 0.1 M Hg(II) in 0.1 M KNO 3 = 5 mm HNO 3 directly over the center of the electrode, while alying a otential of 1.0 V during 64 s [17]. 3. Results and Discussion The main objective was characterization of Na on-coated mercury thin lm electrodes in nitrate and acetate buffer electrolytes, in order to distinguish the in uence of these commonlyused electrolyte comositions on their behavior. An examle of a BIA square-wave anodic striing voltammetry trace obtained for the analysis of cadmium and lead ions at Na on-coated mercury thin lm electrodes is shown in Figure 1. Imortant arameters in a good voltammetric trace are eak height and width, with the former roortional to concentration. It is also useful for eak height determination to have a background current with as low a sloe as ossible. To robe the differences and for comarative uroses, imedance sectra were recorded for bare glassy carbon electrodes, glassy carbon covered with Na on at 0.0 V, 0.5 V and 1.0 V (vs. SCE) and for mercury thin lm electrodes and mercury thin lm electrodes covered by Na on at 0.5 V and 1.0 V (vs. SCE). These values of otential were chosen to cover the range of otentials used in anodic striing voltammetry. Results obtained in the resence of dissolved oxygen, to be the closest to the conditions emloyed in electroanalytical squarewave voltammetric exeriments, as well as in the absence of oxygen, in order to show the in uence of oxygen, are resented below. Other results obtained using Na on=5 % oly(vinyl sulfonic acid) coatings are also shown, where the differences between electrolytes become more evident. Similar effects have been found with oly(ester sulfonic acid) coatings [12] Glassy Carbon Electrode Comlex lane imedance lots are shown in Figure 2a for the bare glassy carbon electrode in nitrate and acetate buffer electrolytes. The behavior noted at 0.5 V for both electrolytes and at 2.2. Prearation of the Na on=pvsa-coated MTFE A solution of oly(vinyl sulfonic acid) (PVSA) in water of concentration 5 wt % was mixed with 5 wt % Na on in alcohols in the roortion 5% PVSA=95% Na on (v=v) and diluted with ethanol such that the nal olymer concentration was 0.25 wt %. The rocedures for coating the glassy carbon electrode and for rearation of the mercury thin lm were the same as described above Prearation of the MTFE The in situ electrodeosition of the mercury thin lm on the glassy carbon electrode followed the same rocedure as described above for electrodes with Na on-based coatings. However, 100 ml of 0.1 M Hg(II) in 0.1 M KNO 3 =5 mm HNO 3 was injected instead of a 10 ml volume. Fig. 1. Striing voltammetric traces for BIA-SWASV of 10 7 MCd 2 and Pb 2 in 0.1 M KNO 3 =5 mm HNO 3 electrolyte. 50 ml injection at 24.5 mls 1 injection seed; t de ˆ 30 s at 1.3 V (vs. SCE). Squarewave conditions: amlitude 25 mv, frequency 100 Hz, otential increment 2 mv.

3 214 C.M.A. Brett et al. Fig. 2. Comlex lane imedance lots in the resence of oxygen for a) bare glassy carbon electrode and b) Na on-coated glassy carbon electrode: *) 0.1 M KNO 3 =5 mm HNO 3, m) 0.1 M acetic acid=sodium acetate buffer (H 4.6). 1.0 V for nitrate can be modelled by an RC arallel combination with constant hase element, exonent between 0.7 and 0.8; an exonent of 1.0 reresenting a comletely smooth surface and 0.5 a orous electrode [20]. On the other hand, in acetate buffer the form of the sectrum at 1.0 V is different; it does not curve back to the real axis at low frequency, but continues in almost a straight line. This behavior can be modelled by a circuit reresenting diffusion through a rough surface structure, including two distributed elements in series. As a rst aroximation, the observed semicircles could be attributed to the reduction of oxygen at 0.5 V and of rotons also at 1.0 V. However, after solution deaeration (which resulted in an increase of the system imedance) they continue to be observed, which suggests that the time constant must also be related to the surface structure of the glassy carbon. This is in agreement with the observations of Heiduschka et al. [21]. When studying glassy carbon in KCl solution they observed a straight line at low frequencies and an underlying semicircle above 500 Hz. This was interreted in terms of the distributed caacitances of exosed basal and edge lanes of the glassy carbon, as well as the caacitance originating from carboxyl grous on the edge lanes. One main effect that can be noted from the imedance sectra for the two different electrolytes is the larger imedance values obtained in acetate buffer electrolyte. Aroximate values of R and C in the RC arallel combination are shown in Tables 1 and Na on-coated GCE The alication of a Na on coating using the rocedure described in the exerimental section leads to a lm of ca. 1 mm thickness, estimated using otical microscoy with indirect Table 1. Data obtained from analysis of the high frequency art of the imedance sectrum for the various modi ed GC electrodes in 0.1 M KNO 3 =5 mm HNO 3. GC electrode modi ed with Presence of oxygen E(V)(vs. SCE) R(kO) C(mF) ± ± ± Na on Na on ± Na on=hg Na on=hg ± Hg Na on=pvsa=hg

4 Na on-coated Mercury Thin Film Electrodes 215 Table 2. Data obtained from analysis of the high frequency art of the imedance sectrum for the various modi ed GC electrodes in 0.1 M acetate buffer (H 4.6). GC electrode modi ed with Presence of oxygen E(V)(vs. SCE) R(kO) C(mF) ± ± ± Na on Na on ± Na on=hg Na on=hg ± Hg Na on=pvsa=hg (NaOAc) (KOAc) lighting and con rmed using known densities of Na on lms [10]. It can be exected that the main difference is increased dif culty of noncationic secies reaching the substrate electrode surface. The imedance lots obtained are shown in Figure 2b. As can be seen, the imedance values have increased in relation to the bare glassy carbon. As for bare glassy carbon, a semicircle was observed at 0.5 V for both electrolytes, at 1.0 V the sectra do not curve back to the real axis at low frequency, but continue in almost a straight line. This means that the Na on olymer has altered the in uence of the structural roerties of the glassy carbon in some way as would be exected. Solution deaeration leads to an increase in imedance values rather than to a modi cation of the sectrum shae Na on-coated MTFE Mercury thin- lm electrodes were then formed under the Na on lms. This has an interesting effect on the shae of the imedance lots at 0.5 V and 1.0 V, as seen in Figure 3a. Taking into account the roughness factor, the sectrum at 0.5 V can be modelled by an RC arallel element in series with a constant hase angle caacitance, which could not be observed for bare glassy carbon or for Na on-modi ed glassy carbon. The sectrum curves towards the real axis at an alied of 1.0 V. In this case, the imedance values are larger than at the glassy carbon electrode; this is robably due to the fact that roton reduction does not occur at the mercury surface as oosed to the glassy carbon surface, owing to its high hydrogen overotential. Higher imedance values were observed in acetate buffer than in nitrate. Mercury thin lm electrodes without Na on also Fig. 3. Comlex lane imedance lots in the resence of oxygen for a) Na on-coated MTFE b) MTFE on glassy carbon substrate: *) 0.1 M KNO 3 =5 mm HNO 3, m) 0.1 M acetic acid=sodium acetate buffer (H 4.6).

5 216 C.M.A. Brett et al. resented a semicircular shae at 1.0 V (Fig. 3b) the imedance values being lower than those for the Na on-coated MTFEs. The structure of olymer-coated MTFEs should be considered [22]. The mercury lm is, in fact, a collection of drolets, suf ciently closely saced that in ASV exeriments they act in the same way as a uniform lm [17]. The Na on lm adheres to the glassy carbon substrate between the drolets, which is imortant to revent the olymer lm eeling off. Thus the mercury causes distortion of the Na on lm, which may lead to increased orosity, and hels to exlain differences between the sectra for Na on-coated GCEs and Na on-coated MTFEs Na on=pvsa-coated MTFE The reason for introduction of 5 % PVSA into the Na on matrix was to imrove the cation-exchange roerties of Na on by increasing the concentration of sulfonate grous. This aroach has had some success [11], and suggests that structure modi cations had occurred. Differences between electrolytes should thus be more clearly demonstrated. The effect of the introduction of PVSA is to decrease the imedance values at 0.5 V; at 1.0 V there is little change (see Fig. 4). It can be deduced that distortion of the olymer lm after mercury lating reduces the effect of the introduction of PVSA. The observed alteration in cation-exchange roerties [6] can thus be ascribed rimarily to the higher concentration of sulfonate grous. The effect of both the anion and the cation of the electrolyte solution on Na on=pvsa lms from imedance exeriments in H 4.6 sodium and otassium acetate buffers as well as the otassium nitrate electrolyte are also shown in Figure 4. The differences between the various electrolytes are evident at both 0.5 V and 1.0 V. The main in uence on the shae of the sectra is from the anion, with little cation effect Comarison of Different Electrode Materials and Coatings As mentioned above, the sectra were tted using an equivalent circuit which consists of an RC arallel distributed element, necessary due to the deressed semicircle character of the resonses, in the frequency range 1 to Hz. Results from modelling the high frequency data at 0.5 Vand 1.0 V (a tyical metal ion deosition otential in striing voltammetry) are shown in Tables 1 and 2. This circuit, although not leading to erfect tting, was the best that can be used for the large majority of the sectra. In any case, the variability of the olymer lm characteristics, exemli ed by variations in current of u to 10 %, recludes the obtaining of exact data. For this reason each exeriment was tested for reroducibility. Thus, the form of the sectra is always the same for each case and the values of R and C in Tables 1 and 2 have a maximum error of 10 %. In all the tting rocedures, the high frequency intercet was in the range 40±50 O for nitrate electrolyte and 70±80 O for acetate buffer, which re ects the different ionic strengths. The roughness factor, where a value of 1 reresents a comletely smooth surface and 0.5 a orous surface [20], varied between 0.7 and 0.9. Fig. 4. Comlex lane imedance lots in the resence of oxygen for Na on=pvsa covered MTFE. *) 0.1 M KNO 3 =5 mm HNO 3, m) 0.1 M acetic acid=sodium acetate buffer (H 4.6), j) 0.1 M acetic acid= otassium acetate buffer (H 4.6). In general, the caacitance values are higher in acetate buffer than in nitrate. This can be related to the higher ionic strength of the otassium nitrate electrolyte, leading to a more comact electric double layer and consequently resulting in lower values of caacitance. The electrolyte tye and alied otential exert a signi cant effect on the shae of the imedance sectra at bare glassy carbon. Na on-coated glassy carbon, for both electrolytes, resents higher values of caacitance and resistance than that of bare glassy carbon. The higher resistance values can be exlained by the increased dif culty of the charge transfer rocesses at glassy carbon due to the limitations imosed by the olymer coating. The larger caacitance values are robably related to charge searation through the Na on layer. The results obtained at 1.0 V for Na on-coated MTFEs are of articular interest, given that these are the conditions that mimic best the reconcentration ste in anodic striing voltammetry. Unlike Na on-modi ed GC, a semicircle is observed at this otential in the resence of both electrolytes, although higher imedance is clearly seen in the resence of acetate buffer. This resonse is attributed to the resence of the mercury thin lm, which is corroborated by the semicircle

6 Na on-coated Mercury Thin Film Electrodes 217 observed at the same conditions for a mercury thin lm electrode on glassy carbon substrate. However, the Na on coating leads to higher imedance values due to the resistance to secies movement and charge searation it causes. The absence of oxygen in the solution causes a systematic increase of the electrode imedance values rather than altering the shae of the imedance sectra. This increase can be attributed to the fact that, after solution deaeration, oxygen reduction no longer contributes to the charge transfer rocesses occurring at the otentials investigated. With resect to electrolyte identity, it is clear that the imedance values are higher and there is much less evidence of any charge transfer rocess in acetate media. This is true even at bare glassy carbon electrode, so that H effects or a lower ermeation of acetate ion through the Na on lm [13] cannot be invoked as the only exlanation. A likely effect at bare glassy carbon is a stronger interaction of the acetate ion with hydroxyl and carboxylate grous at the electrode surface [2, 23], which will not occur in the same way with nitrate ion. Also, the form of the imedance sectra in acetate buffer solution changes less over the otential range studied, which can be linked to a lesser change in the values of the background current. A robable exlanation of the behavior with Na on=pvsa lm coatings has to do with the swelling of the olymer lm on lacing in electrolyte. It is clear that there will be some incororation of electrolyte ions as well as solvent. Nitrate would result in more oening u of the structure than acetate, in line with the discussion resented in [13]. These deductions corroborate those from Na on thin lm coatings. Once again, there is a lesser change in imedance. Although the in uence of the electrolyte and Na on coating has been shown above, some further exeriments were carried out to examine if there are alterations in the behavior in the resence of metal ions used in anodic striing voltammetry. For these exeriments, ``high'' concentrations of 10 7 MCd 2 and Pb 2 were added to the electrolyte solutions. After deosition at 1.0 V for 10 min, sectra were recorded at 1.0 V and at 0.5 V (after waiting a further 10 min for reoxidation). The sectra obtained are shown in Figure 5a and b shows voltammetric traces obtained from SWASV at these electrodes. Table 3 shows the results obtained from tting of the sectra. In relation to the data in Tables 1 and 2 it can be seen that the caacitance values are similar whereas differences aear in the charge transfer resistance. In articular, the values of R at 1.0 V are lower than at 0.5 V, which can be attributed to assage of cations through the Na on lm and their reduction (at 0.5 V neither cation is reduced). Nevertheless, at 0.5 V (after the sectra recording at 1.0 V) there is a signi cant difference between the results in the two electrolytes, with a higher value of R in nitrate than in acetate buffer electrolyte. Differences between Fig. 5. Exerimental results obtained in electrolyte containing 10 7 MCd 2 and Pb 2 in: *) 0.1 M KNO 3 =5 mm HNO 3, m) 0.1 M acetic acid= sodium acetate buffer (H 4.6). a) Comlex lane imedance sectra in the resence of oxygen obtained after alying the seci ed otential for 10 min. b) Square-wave anodic striing voltammetry after 10 min. deosition at 1.0 V (vs. SCE), other conditions as Figure 1.

7 218 C.M.A. Brett et al. Table 3. Data obtained from analysis of the high frequency art of the imedance sectrum for the Na on-coated MTFE in electrolyte 10 7 MCd 2 and Pb 2 after 10 min conditioning at the sectrum recording otential. Electrolyte E(V)(vs. SCE) R (ko) C (mf) Acetate buffer Nitrate the electrolytes are also manifested in Figure 5b: note the higher background currents in nitrate electrolyte, the higher noise level, and the shift in the lead eak to more ositive otentials. The conditions for these exeriments were not those of BIA, which exlains the different relative heights of the striing eaks, also linked with the solubility of the ions in mercury. A detailed discussion of this henomenon is beyond the scoe of this article. A comlete investigation of the interfacial region would include a study of the variation of imedance with electrolyte concentration and with H. Exeriments undertaken in otassium nitrate electrolyte at H 4.6 [24] have shown that the behavior of the glassy carbon electrode is comletely different than at H 2.4 and from acetate buffer although the differences are less for the Na on-coated mercury electrode. Thus, although art of the difference of behavior can be ascribed to the ionization of surface grous on the glassy carbon surface the identity of the electrolyte also has an imortant role. For these reasons, the work described has concentrated on electrolytes as used in anodic striing voltammetry [6]. In summary, there is a correlation between the imedance values in acetate buffer electrolyte, together with a lesser in uence of alied otential on the sectra, and the often suerior results ± de nition of striing eaks, lower background current with lower sloes ± obtained in acetate buffer electrolyte in striing voltammetry exeriments, articularly noted using the batch injection analysis technique. 4. Conclusions Several conclusions can be taken from this work, regarding the behavior of Na on-coated electrodes and the in uence of the electrolyte solution as examined by electrochemical imedance. First, the cation-exchange lm itself alters the imedance characteristics of the glassy carbon electrode, and they are further changed on creating a mercury thin lm between the glassy carbon substrate and the olymer lm. Secondly, there is evidence for the ronounced in uence of the identity of the electrolyte, which is often neglected. It is shown here that acetate buffer leads to larger imedance values than nitrate electrolyte in the absence of cationic reducible electroactive secies in the otential range of interest. For anodic striing voltammetric exeriments using cationexchange olymer coated mercury thin- lm electrodes, where it is referable to minimize any contribution from the electrolyte medium, it is suggested that acetate buffer be emloyed. 5. Acknowledgements The suort of FundacËaÄo ara a CieÃncia e Tecnologia (FCT), Portugal, roject PEAM=SEL=526=95, is gratefully acknowledged. D.A.F. thanks FAPESP (Brazil) and V.A.A. thanks CNPq (Brazil), roject =99-4, for ost-doctoral fellowshis. 6. References [1] W.E. van der Linden, J.W. Diecker, Anal. Chim. Acta 1980, 119, 1. [2] R.L. McCreery, in Electroanalytical Chemistry (Ed: A.J. Bard), Marcel Dekker, New York Vol.17, [3] H. Maleki, C.D. Cojocaru, C.M.A. Brett, G. Jenkins, J.R. Selman, J. Electrochem. Soc. 1998, 145, 721. [4] M. Stulikova, J. Electroanal. Chem. 1973, 48, 33. [5] J.H. Aldstadt, H.D. Dewald, Anal. Chem. 1993, 65, 922. [6] C.M.A. Brett, D.A. Fungaro, J.M. Morgado, M.H. Gil, J. Electroanal. Chem. 1999, 468, 26. [7] B. Hoyer, T.M. Florence, G.E. Batley, Anal. Chem. 1987, 59, [8] B. Hoyer, N. Jensen, Talanta 1994, 41, 449. [9] M.A.T. Gilmartin, J.P. Hart, Analyst 1995, 120, [10] L.A. Zook, J. Leddy, Anal. Chem. 1996, 68, [11] J. Wang, Z. Taha, Electroanalysis 1990, 1, 458. [12] C.M.A. Brett, D.A. Fungaro, Talanta 2000, 50, [13] E.K. Unnikrishnan, S.D. Kumar, B. Maiti, J. Membr. Sci. 1997, 137, 133. [14] M.E.R. Dam, K.N. Thomsen, P.G. Picku, K.H. Schrùder, Electroanalysis 1995, 7, 70. [15] M.-L. Tercier, J. Buf e, Anal. Chem. 1996, 68, [16] M.-L. Tercier, J. Buf e, F. Graziottin, Electroanalysis 1998, 10, 355. [17] C.M.A. Brett, A.M. Oliveira Brett, F.-M. Matysik, S. Matysik, S. Kumbhat, Talanta 1996, 43, [18] F.-M. Matysik, S. Matysik, A.M. Oliveira Brett, C.M.A. Brett, Anal. Chem. 1997, 69, [19] C.M.A. Brett, A.M. Oliveira Brett, L.C. Mitoseriu, Electroanalysis. 1995, 7, 225. [20] R. de Levie, Electrochim. Acta 1964, 9, [21] P. Heiduschka, A.W. Munz, W. GoÈel, Electrochim. Acta 1994, 39, [22] P. Ugo, L.M. Moretto, Electroanalysis 1995, 7, [23] K.G. Ray III, R.L. McCreery, J. Electroanal. Chem. 1999, 469, 150. [24] V.A. Alves, C.M.A. Brett, unublished results.