Anal. Chem.

2010, 82, 69336939

Difference between Ultramicroelectrodes and Microelectrodes: Inuence of Natural Convection

Christian Amatore,* Ce cile Pebay, Laurent Thouin,* Aifang Wang, and J-S. Warkocz Ecole Normale Supe rieure, De partement de Chimie, UMR CNRS-ENS-UPMC 8640 Pasteur, 24 rue Lhomond, F-75231 Paris Cedex 05, France Natural convection in macroscopically immobile solutions may still alter electrochemical experiments performed with electrodes of micrometric dimensions. A model accounting for the inuence of natural convection allowed delineating conditions under which it interferes with mass transport. Several electrochemical behaviors may be observed according to the time scale of the experiment, electrode dimensions, and intensity of natural convection. The range of parameters in which ultramicrelectrodes behave under a true diffusional steady state was identied. Mapping of concentration proles was performed experimentally by scanning electrochemical microscopy in the vicinity of microelectrodes of various radii. The results validated remarkably the predictions of the model, evidencing in particular the alteration of the diffusional steady state by natural convection.
Microelectrodes are versatile tools for the study of electrochemical processes of mechanistic and/or analytical interest. Their advantageous properties stem from their small size. Microelectrodes may be used in highly resistive environments and in very small sample volumes. They enable the detection of very small amounts of material and allow short time responses.1-9 However, the denition of a microelectrode is still nowadays ambiguous. Actually, the notion of a microelectrode differs greatly according to the particular origin of electrochemists, i.e., electroanalytical chemists or molecular electrochemists. The term microelectrode may then encompass electrodes of either millimetric or micrometric dimensions. Electrodes of smaller sizes are referred to as ultramicroelectrodes. Such denitions, based mainly on historical
* To whom correspondence should be addressed. E-mail: christian.amatore@ ens.fr (C.A.); laurent.thouin@ens.fr. (1) Fleischmann, M.; Pons, S.; Rolison, D. R. Ultramicroelectrodes; Datatech Systems, Inc.: Morgantown, NC, 1987. (2) Bond, A. M.; Oldham, K. B.; Zoski, C. G. Anal. Chim. Acta 1989, 216, 177230. (3) Wightman, R. M.; Wipf, D. O. Electroanalytical Chemistry; Marcel Dekker: New York, 1989; Vol. 15, pp 267-353. (4) Montenegro, M. I.; Queiros, M. A.; Daschbach, J. L. Microelectrodes: Theory and Applications; Kluwer Academic Press: Dordrecht, The Netherlands, 1991; Vol. 197. (5) Aoki, K. Electroanalysis 1993, 5, 627639. (6) Heinze, J. Angew. Chem., Int. Ed. 1993, 32, 12681288. (7) Amatore, C. Electrochemistry at ultramicroelectrodes. In Physical Electrochemistry; Rubinstein, I., Ed.; Marcel Dekker: New York, 1995. (8) Stulik, K.; Amatore, C.; Holub, K.; Marecek, V.; Kutner, W. Pure Appl. Chem. 2000, 72, 14831492. (9) Forster, R. J. Encyclopedia of Electrochemistry; John Wiley & Sons: New York, 2003; Vol. 3, pp 160-195. 10.1021/ac101210r 2010 American Chemical Society Published on Web 07/26/2010

criteria, may appear useless since they better dene the origin of the users than the object itself. A better classication of these electrodes would be obtained if it were based on their particular properties. Since electrochemical reactions are interfacial reactions, mass transport is one of the key processes to consider.10 In a liquid, elementary contributions in the mass transport are diffusion, migration, and convection. Under most circumstances, migration is suppressed by adding a large excess of dissociated inert salt or supporting electrolyte. Convection is often neglected at electrodes of micrometric dimensions in macroscopically still solutions. Indeed, convection originates from movement of uid packets of micrometric size.11 It necessarily vanishes close to the electrode interface over distances where concentrations differ signicantly from their bulk values.12,13 In such a case, only diffusion is assumed to govern the nal approach of an electroactive molecule toward the electrode. However, according to the size of these electrodes and time scale of the experiments, convective uxes due to natural convection may still compete with diffusional uxes in motionless solutions. This may occur even in the absence of any density gradients14 or effects induced by a magnetic eld.15 These situations arise as soon as the thickness of the diffusion layer becomes comparable to the thickness of the convection-free domain.7 Under such conditions, the responses do not follow the classical relationships given for currents in dynamic and steady-state regimes. Therefore, under given experimental conditions, it is of importance to decide the largest size of an electrode for eliminating any inuence of natural convection.16,17 Such a criterion may then allow distinguishing properties of ultramicroelectrodes from those of other electrodes of micrometric sizes. To assess the conditions of convection-free regimes at electrodes of micrometric dimensions, we investigated in some previous studies the current responses of micrometric disk
(10) Bard, A. J.; Faulkner, L. R. Electrochemical Methods, 2nd ed.; John Wiley & Sons: New York, 2001. (11) Moreau, M.; Turq, P. Chemical Reactivity in Liquids: Fundamental Aspects; Kluwer Academic/Plenum Press: New York, 1988; pp 561-606. (12) Levich, V. G. Physicochemical Hydrodynamics; Prentice Hall: Englewoods Cliffs, NJ, 1962. (13) Davies, J. E. Turbulence Phenomena; Academic Press: New York, 1972. (14) Li, Q. G.; White, H. S. Anal. Chem. 1995, 67, 561569. (15) Grant, K. M.; Hemmert, J. W.; White, H. S. J. Electroanal. Chem. 2001, 500, 9599. (16) Hapiot, P.; Lagrost, C. Chem. Rev. 2008, 108, 22382264. (17) Molina, A.; Gonzalez, J.; Martinez-Ortiz, F.; Compton, R. G. J. Phys. Chem. C 2010, 114, 40934099.

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electrodes in various conditions, in chronoamperometry18 and cyclic voltammetry.19 The mapping of concentration proles was alsoperformedintheirvicinityusingamethodalreadydescribed.18-23 At the same time, we proposed a theoretical model to evaluate the inuence of natural convection on mass transport in still media.18 The good agreement observed between theory and experiments demonstrated the validity of this model over a wide range of experimental conditions.18,22-26 The purpose of this study is then to take the benet of this model to delineate the experimental conditions that allow convection-free regimes to be observed in dynamic and steady-state regimes. These conditions are better presented in a zone diagram showing the inuence of all the parameters: time scale of the experiment, electrode radius, and thickness of the convection-free domain. Comparison with experimental data will also serve to illustrate the relative contributions of convection and diffusion at electrodes of different sizes performing under the steady-state regime. MODEL OF NATURAL CONVECTION The inuence of convection on the electrode responses can be quantied from deviations of their diffusive currents or from alteration of their diffusion layers. Under pure diffusional conditions, the concentration prole of a species at a disk electrode is given by integration of Ficks second law:10 c(r, z, t) 2c(r, z, t) 2c(r, z, t) 1 c(r, z, t) )D + + 2 2 t r r r z

i ) ( 2nFD

r0

c(r, z, t) r r z

(5)

In still solutions, natural convection operates perpendicularly to the electrode surface. It is based on microscopic motions of the solution except in the very near vicinity of the electrodes, where it vanishes. Experimentally, the resulting velocity eld is extremely difcult to estimate. Moreover, it is almost impossible to master mathematically since it depends on many parameters which are not easy to control (vibrations, temperature gradients, movement of the cell atmosphere, etc.). However, beyond these difculties, we demonstrated successfully that, for electroactive species, the inuence of natural convection can be assimilated to that of an apparent diffusion coefcient depending on the orthogonal distance z from the electrode plane.18 Moreover, since the electrochemical perturbation affects only the viscous sublayer adjacent to the electrode, we showed that Dapp could be evaluated by Dapp ) D 1 + 1.522

( ))
z conv
4

(6)

)
(1)

where conv is the thickness of the convection-free layer. This is the only parameter introduced into the model to account for the effects of natural convection. It is possible to evaluate its inuence on the electrode response by replacing D by Dapp in eq 1 and solving numerically the new mass transport equation in association with the same boundary conditions (eqs 2-4). EXPERIMENTAL SECTION All the solutions were prepared in puried water (Milli-Q, Millipore). A 10 mM concentration of K4Fe(CN)6 (Acros) was dissolved in 1 M KCl (Aldrich), which was used as the supporting electrolyte. Reciprocally 2 mM FcCH2OH (Acros) was prepared in 0.1 M KNO3 (Fluka). The diffusion coefcients were DFe ) (6.0 0.5) 10-6 cm2 s-1 27 for Fe(CN)64-/ Fe(CN)63- and DFc ) (7.6 0.5) 10-6 cm2 s-1 for FcCH2OH/ FcCH2OH+. The working electrodes were Pt disk electrodes of 12.5, 25, 62.5, 125, 250, and 500 m radii. They were obtained from the cross section of Pt wires (Goodfellow) sealed into soft glass. The reference electrode was a Ag/AgCl electrode, and the counter electrode was a platinum coil. A scanning electrochemical microscope (910B CH Instruments) was used to establish the concentration proles. The amperometric probe was a Pt disk electrode of submicrometric dimension (500 nm radius). Its fabrication and the related procedure to map the concentrations have already been reported.23 For Fe(CN)64-/Fe(CN)63- experiments, the working electrode was biased at +0.6 V/ref on the oxidation plateau of Fe(CN)64-. The probe was biased at +0.6 V/ref to collect Fe(CN)64- or -0.1 V/ref to collect Fe(CN)63-. For FcCH2OH/FcCH2OH+ experiments, the working electrode was biased at +0.25 V/ref. In this case, the probe was biased at +0.25 V/ref to collect FcCH2OH and -0.1 V/ref to collect FcCH2OH+. The mass transport equation was solved numerically in the conformal space adapted to the geometry of a microdisk elec(27) Amatore, C.; Szunerits, S.; Thouin, L.; Warkocz, J.-S. Electrochem. Commun. 2000, 2, 353358.

where r describes the radial position normal to the axis of symmetry at r ) 0 and z describes the linear displacement normal to the plane of the electrode at z ) 0. D is the diffusion coefcient. For a chronoamperometric experiment, the pertinent boundary conditions are t < 0; t g 0; r, z g 0; r e r0 ; c(r, z, t) ) c c(r, 0, t) ) 0 c(r, z, t) ) c (2) (3) (4)

r, z f ;

The current is readily obtained from integration of the concentration gradients at the electrode surface with
(18) Amatore, C.; Szunerits, S.; Thouin, L.; Warkocz, J. S. J. Electroanal. Chem. 2001, 500, 6270. (19) Amatore, C.; Pebay, C.; Thouin, L.; Wang, A. F. Electrochem. Commun. 2009, 11, 12691272. (20) Amatore, C.; Pebay, C.; Scialdone, O.; Szunerits, S.; Thouin, L. Chem.sEur. J. 2001, 7, 29332939. (21) Amatore, C.; Szunerits, S.; Thouin, L.; Warkocz, J. S. Electroanalysis 2001, 13, 646652. (22) Amatore, C.; Knobloch, K.; Thouin, L. Electrochem. Commun. 2004, 6, 887 891. (23) Baltes, N.; Thouin, L.; Amatore, C.; Heinze, J. Angew. Chem., Int. Ed. 2004, 43, 14311435. (24) Rudd, N. C.; Cannan, S.; Bitziou, E.; Ciani, L.; Whitworth, A. L.; Unwin, P. R. Anal. Chem. 2005, 77, 62056217. (25) Amatore, C.; Sella, C.; Thouin, L. J. Electroanal. Chem. 2006, 593, 194 202. (26) Amatore, C.; Knobloch, K.; Thouin, L. J. Electroanal. Chem. 2007, 601, 1728.

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trode28 by a nite element using Comsol Multiphysics software. The thickness of the convection-free layer, conv, was determined before each experiment by chronoamperometry as described previously.18 RESULTS AND DISCUSSION An important property of disk ultramicroelectrodes is that their diffusion layers develop with time until reaching a steady-state limit imposed by hemispherical-type diffusion. However, natural convection may interfere with the mass transport as soon as the thickness of the expanding diffusion layer becomes comparable to conv. In such a case, a steady-state regime is still achieved but is then controlled by the respective contributions of diffusion and natural convection. Depending on the electrode radius, r0, and the thickness of the convection-free layer, conv, two situations may be encountered, whether the diffusion at the electrode surface is planar or not. Indeed, at short time scales, the thickness of the diffusion layer is considerably smaller than the electrode radius. The electrodes then behave as electrodes of innite dimensions, and planar diffusion operates. In that particular situation, the Cottrell equation applies with nFADc Dt

iplanar ) (

(7)

for electrodes of surface area A. Using the Nernst formulation, eq 7 is similar to that given in hydrodynamic electrochemical methods:10 nFADc

i)(

(8)
Figure 1. Steady-state concentration prole simulated at a disk electrode without considering the inuence of natural convection: (A) 2D concentration prole with isoconcentration lines ranging from c/c ) 0.1 to c/c ) 0.9. (B) Concentration prole along the vertical axis of symmetry.

where ) (Dt)1/2. Therefore, natural convection interferes signicantly with the mass transport as soon as conv (Dt)1/2. Whenever this condition is not met, the diffusion layer may develop, possibly reaching a hemispherical behavior until being eventually limited by conv. However, since diffusion and natural convection occur together in steady-state regimes, their contributions in mass transport remain difcult to comprehend. To solve this problem, one needs rst to investigate the concentration proles established under the pure diffusional steady-state regime, i.e., without any inuence of natural convection. In such a case, solution of eq 1 shows that most of the concentration gradients operate over a distance comparable to the electrode radius (Figure 1A). Concentration along the z axis (Figure 1B) varies according to 2 c z ) arctan c r0

Using the Nernst formulation again, comparison between eqs 8 and 10 leads to an equivalent diffusion layer thickness, ) r0/ 4. This thickness differs slightly from z, which may be obtained by extrapolating the concentration gradient at z ) 0, r ) 0 along the z axis. Indeed, when z f 0, the concentration prole at r ) 0 tends to (Figure 1B) 2 z c ) c r0

(11)

()

(9)

The diffusion layer presents a hemispherical shape, and the steady-state current is given by: ihemisph ) ( 4nFr0Dc
(28) Amatore, C.; Fosset, B. J. Electroanal. Chem. 1992, 328, 21.

(10)

which gives z ) r0/2. The difference in the and z values results from the nonradial distribution of diffusion elds at disk electrodes. Concentration gradients are higher at the electrode edges than at the center (Figure 1A). Since is evaluated from the integration of concentration gradients over the whole electrode surface (eq 5), it is necessarily smaller than z. In the following, the variation of these two parameters will provide an accurate estimation of the inuence of natural convection, either from the current (i.e., through ) or from the alteration of concentration proles in the z direction (i.e., through z), where natural convection prevails.
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Figure 2. Steady-state concentration proles and steady-state currents simulated at disk electrodes of different radii under the inuence of natural convection. (A) Isoconcentration lines c/c ) 0.9 for disk electrodes of various radii. From left to right, r0/conv ) 0.05, 0.5, 1.0, 1.5, 2.0, 4.2, and 6.0. (B, C) Variations of the diffusion layer thicknesses and z as a function of the electrode radius, with (solid curves) and without (dashed curves) the inuence of natural convection. (D) Error on steady-state currents due to the inuence of natural convection as a function of r0/conv.

Figure 2A displays isoconcentration lines c/c ) 0.9 calculated under the inuence of natural convection for electrodes of various radii. They were obtained from combination of eqs 1-6 under the steady-state regime. To provide a more general representation of the problem, the spatial coordinates r and z were normalized by conv. When the electrode radii are small enough (i.e., r0/ conv < 0.5), one observes that the diffusion layers retain their quasi-hemispherical shapes, like those previously simulated in the absence of natural convection (Figure 1A). For larger electrode radii, the concentration proles become attened, their expansion along the z axis being restricted by the boundary at conv. Therefore, when convection operates, it has two major effects depending on the ratio r0/conv. On one hand, concentration gradients (c/z)z)0 become more uniform over the central area of the electrodes than when natural convection is absent. On the other hand, the development of the diffusion layers still operates laterally along the r axis. This can be easily observed in parts B and C of Figure 2, where the variations of /conv and z/conv, respectively, are reported as a function of r0/conv. In particular, one observes that when r0/conv ) 4, z has reached
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Figure 3. Zone diagrams describing the inuence of natural convection on planar and hemispherical diffusion at disk electrodes. (A) Zone diagram established from two boundary conditions, ) conv (solid curve) and r0/(Dt)1/2 ) 4/ (vertical straight line). Note that this diagram is independent of the model of convection. (B) Zone diagram established on the basis of the present model of natural convection with four boundary conditions: | - diff|/ or |i - idiff|/|idiff| ) 0.1 (curve 1), | conv|/ or |i - iconv|/|iconv| ) 0.1 (curve 2), | - planar|/ or |i - iplanar|/ |iplanar| ) 0.1 (curve 3), and | - hemisph|/ or |i - ihemisph|/|ihemisph| ) 0.1 (curve 4). The black symbols correspond to the experimental conditions considered in Figure 4: from left to right, r0 ) 12.5, 25, 62.5, 125, 250, and 500 m, with conv ) 200-250 m.

its limit conv whereas is only equal to 0.8conv. Accordingly, the convolution of these two effects on the development of diffusion layers leads to a deviation of the currents from eq 10. This alteration may be drastic since the relative error |i ihemisph|/|ihemisph| increases almost linearly with r0/conv (Figure 2D). In particular, |i - ihemisph|/|ihemisph| 0.65 when conv r0. A rst attempt to summarize all these situations is to establish a zone diagram describing the boundary condition imposed by conv on , whether the diffusion is planar or hemispherical. As previously mentioned, two other parameters have to be considered: the electrode radius, r0, and the diffusion length, (Dt)1/2. The transition between planar and quasi-hemispherical diffusion depends on the ratio r0/(Dt)1/2, whereas the inuence of convection is xed by r0/conv. Therefore, a diagram with two coordinates, r0/(Dt)1/2 and r0/conv, allows plotting the limit, which differentiates the domains where convection or diffusion prevails independently. This limit is then ) conv.

Figure 4. Comparison between simulated (curves) and experimental (symbols) steady-state concentration proles along the vertical axis of symmetry at disk electrodes of different radii when the electrode potential is poised on the oxidation plateau of Fe(CN)64-. Concentration proles simulated without (dashed curves) or with (solid curves) natural convection (conv ) 200-250 m). Experimental concentration proles of the substrate Fe(CN)64- (0) and product Fe(CN)63- (O). t ) 60 s. [Fe(CN)64-] ) 10 mM in 1 M KCl.

The diagram is reported in Figure 3A, where the zones above and below this limit correspond to the control of convection and diffusion, respectively. In the lower zone, the equality between eqs 7 and 10 discriminates by a vertical line located at r0/(Dt)1/2 ) 4/ two other domains where planar diffusion (i.e., r0/ (Dt)1/2 > 4/) and quasi-hemispherical diffusion (i.e., r0/ (Dt)1/2 < 4/) dominate. One must note that this diagram is independent of the model of natural convection since was calculated without considering eq 6 and by only assuming ) conv. In this context, the model enables the transitions between the three regimes of the diagram to be determined. For this purpose, the model is used to evaluate and to compare its value to a given reference thickness, ref, predicted by considering only one specic regime: (1) ref ) diff for pure diffusion control without any inuence of convection, (2) ref ) conv, (3) ref ) planar for planar diffusion with planar ) (Dt)1/2, and (4) ref ) hemisph

for hemispherical diffusion with hemisph ) r0/4. The transition from one of these specic regimes to the others may then be estimated by setting a relative threshold on such as | - ref | ) 0.1 Note that eq 12 is equivalent to

(12)

i - iref ) 0.1 iref

(13)

where iref is the reference current obtained from eq 8 with iref ) ( nFADc ref

(14)
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The zone diagram built from eq 12 or 13 is reported in Figure 3B. Thus, three curves (curves 2-4) delineate a new domain corresponding to a mixed regime between the limiting ones previously identied (Figure 3A). In particular, the transitions from hemispherical diffusion to convection (i.e., vertical displacement on the diagram) and from hemispherical diffusion to planar diffusion (i.e., horizontal displacement) are relatively broad since they occur approximately over 2 orders of magnitude on the r0/ conv and r0/(Dt)1/2 scales, respectively. Only the transition from planar diffusion to convection is very sharp. Indeed, as soon as planar conv, the diffusion layer reaches its steadystate limit and mass transport is fully controlled by convection. In contrast, when the condition z conv is met for hemispherical-type diffusion, the layer may still expand laterally along the r axis until reaching its steady-state limit (see Figure 2A-C). This latter condition corresponds to curve 1 in Figure 3B when | - diff|/ ) 0.1 or |i - idiff|/|idiff| ) 0.1. It allows delineating the upper zone of the diagram where convection starts to interfere in the mass transport. A chronoamperometric experiment can be represented on the diagram by a horizontal straight line described from the right to the left when the time duration increases. According to the size of the electrode, r0, and thickness, conv, the nature of the steadystate regime reached at longer time may be different. On the one hand, if log(r0/conv) > 0.95, a sharp transition from planar diffusion to convection occurs. On the other hand, if log(r0/ conv) < -0.7, a broad transition with a mixed regime from planar diffusion to quasi-hemispherical diffusion operates without any inuence of natural convection. When log(r0/ (Dt)1/2) < -0.75, a steady-state regime is always observed though its nature (diffusional or convective) only depends on the ratio r0/conv. Under given experimental conditions (i.e., the same position of the electrode in the cell, temperature, viscosity of the electrolyte, environment, etc.), conv is approximately constant so that the mass transport regime under steady state depends only on the electrode dimension. This was checked experimentally by mapping diffusion layers in the vicinity of electrodes of various radii. Figure 4 shows the concentration proles along the vertical axis of symmetry of the electrodes for both the reactant and product. conv was evaluated independently by chronoamperometry at a large electrode18 and was found to range from 200 to 250 m. It was thus possible to compare the experimental data with concentration proles predicted with or without natural convection. A very good agreement was observed in Figure 4 whatever the size of the electrodes between experimental data and predictions issued from the model when natural convection was taken into account. Alterations on the concentration proles due to convection were apparent as soon as r0 ) 25 m. The experimental conditions pertaining to each concentration prole in Figure 4 are reported as symbols in the zone diagram of Figure 3B. According to the threshold previously dened with | - hemisph|/ ) 0.1 or |i - ihemisph|/|ihemisph| ) 0.1, the results show that a hemispherical diffusion regime was reached for r0 ) 12.5 and 25 m while a mixed regime was achieved for the other radii (r0 ) 62.5-500 m). These experimental data validate the predictions of the present model, yet they involved only the effect of natural convection along
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Figure 5. Comparison between simulated (curves) and experimental (symbols) steady-state concentration proles at a disk electrode of radius r0 ) 25 m when the electrode potential is poised onto the oxidation plateau of FeCH2OH. (A) Experimental concentration proles of the product FcCH2OH+ along the vertical axis of symmetry (circles). (B) Experimental concentration proles of FcCH2OH+ along the r axis at various vertical distances z: z ) 6 (O), 16 (0), 26 (]), 36 (), 46 (+), and 56 m (). The black area indicates the extent of the electrode coordinates along the r axis. The concentration proles are simulated without (dashed curves) and with (solid curves) consideration of the inuence of natural convection (conv ) 200 m). [FeCH2OH] ) 2 mM in 0.1 KNO3.

the axis of symmetry of the electrodes. Conversely, we showed above (see Figure 2) that this effect is also effective along lateral directions due to the compensation of transport between vertical and lateral uxes. In the following, we investigated this latter issue experimentally by performing 2D imaging. Figure 5 reports the mapping of concentration proles established in the steady-state regime along the z axis and r axis when r0 ) 25 m. As in Figure 4, the concentration proles were compared to the predictions established with and without the inuence of convection. Apart from the good agreement obtained between the data and predictions, these results clearly illustrate the fact that convection may still alter the diffusion layers even when quasi-hemispherical diffusion is expected to prevail (Figure 3B). In the present case, the concentration proles are distorted over distances z equivalent to 10 times the electrode radius, r0. Simultaneously, the relative

CONCLUSION The model elaborated in this work predicts within a very good accuracy the relative contributions of diffusion and natural convection to the mass transport at disk electrodes. The electrochemical behaviors of the electrodes not only are related to their dimensions but also depend on the time scale of the experiment and thickness of the convection-free layer (i.e., conv). These results stress once more the futility of trying to propose an absolute denition of ultramicroelectrodes based on the objects themselves. Indeed, the same electrode may behave as a microelectrode or an ultramicroelectrode, depending on these parameters. Our model allowed us to clearly delineate the situations where natural convection alters both the dynamic and steady-state regimes at disk electrodes. The properties of ultramicroelectrodes are mainly achieved when r0/conv < 0.2. This condition has practical consequences if one needs, for example, to exploit the characteristics of ultramicroelectrodes to detect or measure concentrations in restricted volumes, without any alteration of natural convection on the measurements.

Figure 6. Comparison between simulated (curves) and experimental (symbols) thicknesses of the diffusion layer at disk electrodes of various radii: z/conf (dashed lines, O) and /conf (solid curve, 0).

error in the current obtained by the model is |i - ihemisph|/ |ihemisph| ) 0.07. Finally, variation of z issued from the mapping of concentration proles in Figure 4 is reported in Figure 6 as a function of the electrode size and then compared to the predicted one. The diffusion layer thicknesses, , estimated from the experimental steady-state currents (through eq 8) are also plotted. As observed, all these data show that the model applies satisfactorily under the steady-state regime to predict the inuence of natural convection on current responses or concentration proles.

ACKNOWLEDGMENT This work has been supported in part by the CNRS (Grant UMR8640), Ecole Normale Superieure, UPMC, and French Ministry of Research.

Received for review May 7, 2010. Accepted July 9, 2010.

AC101210R

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