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CHIMICA ACTA

ELSEVIER
Analytica Chimica

ANALYTICA

Acta 30.5(199.5)96-105

Ultramicroelectrodes in kinetic investigations supported bY simulation. A review with some additional examples
Franc0 Magno
Dipartimento di Chimica Inorganica, Metallorganica

*,

Irma Lavagnini

ed Analitica, Universitir di Padova, Via Marzolo 1, 35131 Padova, Italy

Received7 June 1994; revised manuscript received 30 August 1994

Abstract The potentialities of coupling ultramicroelectrodes and digital simulation techniques in the evaluation of the charge transfer constant, k, of the half-wave potentials, E,,,, in multistep electrochemical reactions, of kinetic rate constants in complexation reactions, and of the responses of a ultramicroelectrode-based channel detector, are presented. The advantages of carrying out experiments under intermediate mass-transfer conditions are assessed. In the lack of theoretical studies, the digital simulation can offer quite accurate solutions to these complicated questions, which can be faced introducing proper modifications into a unique algorithm as long as the geometry of the electrode and the boundary conditions of the diffusion equation describing the electrochemical processes remain unchanged. The characteristic equations of the finite difference methods used in the simulations of the mass-transfer at ultramicroelectrodes are also described.
Keywords: Ultramicroelectrodes; Digital simulation; Mass transport; Kinetic hindering; Review

1. Introduction The advent of ultramicroelectrodes as tools in voltammetric investigations marked a noticeable step in the development of electroanalytical research. Electrodes, characterized by one dimension of the order of micrometers, namely less than 25 pm [1,2], offer unique properties [3,4] which can be summarized as follows: high mass flux, steady-state current, low ohmic drop, low cell time constant, influence of the electrode size on the kinetics of the electrochemical reaction, expansion of the working range of potentials and possibility of performing voltammetry in highly resistive media. Following these advantageous properties, ultramicroelectrodes have found application in many fields such as voltammetry under dif* Corresponding
author.

ferent mass transfer conditions (from planar to steady-state or pseudo steady-state), liquid chromatography [5-81, in vivo monitoring [9], capillary electrophoresis [lo] and electrochemiluminescence [ill. In particular, since the size of an electrode dictates the spatial as well as the time domain that is probed [12], a specific application of ultramicroelectrodes is found in the area of kinetic studies on the heterogeneous charge-transfer step [13,14] and on the coupled homogeneous reactions [l&16]. The digital simulation technique [17], on the other hand, is an effective and sometimes necessary approach in elucidating reaction mechanisms so that the coupling of the digital simulation to voltammetric data obtained at ultramicroelectrodes becomes obvious. This paper is intended to show the effectiveness of this coupling by considering equilibrium and non-equilibrium heterogeneous and homogeneous reactions. In particu-

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lar, the determination of the heterogeneous constant from fast voltammetric measurements and from data obtained for intermediate mass transfer conditions is discussed, together with how to extract the thermodynamic parameters from a two electron system under steady-state conditions, how to rationalize a host-guest complexation reaction considered as a second order CE mechanisms, and the response of a channel flow-through amperometric detector. Finally, the basic concepts of the digital simulation methods used are briefly illustrated. Among the different geometries proposed in the literature the disk and the band will be considered here since these electrodes are the most common because of their ease of preparation.

2. Basic concepts and applications On the basis of the stepwise nature of the electrochemical processes [18], the determination of the heterogeneous rate constant, k, requires that the rate of mass transfer of the electroactive material be larger than that of the heterogeneous charge transfer step. This condition is fulfilled for m > k, where m is the mass-transfer coefficient appropriate for a particular electrochemical technique. The use of an ultramicroelectrode is convenient to achieve a very large mass transfer both in transient and in steady-state measurements, that is when the controlling parameter in the voltammetric experiment is the time or the radius, respectively. In the first case large values of m a (D/t) I [19 201 (D is the diffusion coefficient) are obtained at short times where perturbations due to the RC characteristics of the experimental device represent a severe drawback. However owing to the fact that the ohmic drop for a disk ultramicroelectrode is given by [4] AE, = R,i = p(i, + i,)/(4a) a (a* + a*>/~ a a where p is the resistivity of the solution and a the radius of the electrode, the use of an ultramicroelectrode allows very fast voltammetric experiments limiting the occurrence of prohibitive perturbations. Under diffusive steady-state conditions, m a D/a [19], high mass-transfer rates can be obtained as long as the electrode radius, a, is sufficiently small. Also for electrochemical processes with coupled chemical reactions the two approaches, use of the time or of the dimension of the electrode as controlling parameters,

are possible. In the former case where the experimental time defines a time window, t, in which the chemical reaction occurs to a definite extent depending on its characteristic lifetime, t,, (for a first order reaction the usual dimensionless kinetic parameter is h = kt = t/t, [18]) the advantageous properties of ultramicroelectrodes in reducing the noise remain and the treatment of data is that typical of the planar diffusion electrodes. In the latter case the extent of the kinetic effect is dependent on the ratio of the concentration change due to chemical reaction and the restoring effect of the mass transfer, that is by the value of the dimensionless parameter k/CD/u*> a t/t, [15]. The variety of the systems studied, of the experimental conditions adopted and of the objects pursued points out that a digital simulation approach is in many cases an obvious choice. 2.1. Evaluation of k In the determination of the parameters of the charge transfer reaction, different experimental conditions can be chosen and the digital simulation approach represents a valid support. Data obtained at fast scan rates are distorted by ohmic drops so that different strategies, on-line [20] or post factum [21251, must be followed for extracting the correct Faradaic component from the total current, which for an anodic scan is given by dE( t)

i tuf=iF+iC.=iF+Cd---

dt

(1)

where i, and i, indicate the Faradaic and the charging components, respectively, and E(t) is the effective potential applied to the working electrode with

E(t) =E(t)

-R,i,,,=E,+vt-RR,it,,

(2)

Other symbols in Eqs. 1 and 2 have their usual meaning. Substituting Eq. 2 into Eq. 1 yields

i tot= i, + CC, - R,C,x

Go,

It appears that the Faradaic current is not obtained by the simple subtraction of the capacitive current UC, of the blank, recorded in the absence of electroactive species, from the total current because the voltammograms at fast scan rates are distorted to a varying degree depending on the change of the total current and the time constant of the cell. The calculation of the term R,C,di,,,/dt from the experimental

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0.6

voltammogram allows the Faradaic current to be properly evaluated. However, for the evaluation of k the corrected voltammogram representing i, against the effective potential E(t) cannot be treated following the well known theory reported in the literature, since the potential waveform is no longer triangular in shape [2,26]. Fig. 1A shows the modification of the real applied potential waveform and Fig. 1B proves that the Faradaic current, properly extracted, never coincides perfectly with the voltammetric curve obtained in the absence of an uncompensated resistance. Correct procedures can be the convolution approach [21], the global analysis [27] and the digital simulation [2,28]. In the context of the digital simulation approach, the term Z?,Z,,, in Eq. 2 can be accounted for by calculating numerically the real potential applied to the working electrode, E(t), for any potential step in which the potential range is divided. Fig. 2 shows quasi-reversible voltammetric curves (A) free of significant ohmic drop, (B) affected only by uncompensated solution resistance R,, (C) by double-layer capacitance C,, and (D) by a finite R,C, time constant. The ohmic drop effects in the above figures were calculated introducing in a well established algorithm [29] an iterative procedure 1301 which searches for the effective potential E(t) as a root of the Eq. 4 E(t) -E(t) +R;i,(E(t))

0.4

02

2
1.4

s a

-0

-0.4

-06

RCd RCd + I+-dtE(r-Ar)=O

-0.4

I-I

(4)

This equation was derived inserting Eq. 1 in Eq. 2 and approximating the first derivative d E(t)/d t with (E(t - At) - E(t))/At. The Faradaic current i,(E(t)) is calculated by the Butler-Volmer equation. Consequently the k value can be calculated by fitting simulated curves on experimental responses even if they are affected by RC distortion. On decreasing the scan rate the effects due to R, and C, become negligible so that it is worthwhile to explore the possibility of extracting k values from data obtained under mixed spherical/semi-infinite linear diffusion conditions. At the same time the shape of the voltammograms changes from that characterized by potential separated anodic and cathodic peaks to a sigmoidal one (Fig. 3).

I:.:
-0 75 -0.5

-0.25

0.25

0.5

0.75

E /volt

Fig. 1. (A) Potential-time curves relative to the cyclic voltammograms in Fig. 1B. (solid line) applied potential; (broken line) effective potential in the presence of an uncompensated solution resistance of 55,000 0, and of a double-layer capacitance of 5~ lo-* F. (B) Faradaic currents against the effective potential in the absence (solid line) and presence (broken lined) of ohmic drop effects. Calculations based on: transfer coefficient, 0.5; charge transfer constant, 3.3 cm/s; scan rate, 128,700 V/s; electrode radius, 2.5 pm; electroactive species concentration, 10 mM, diffusion coefficient, 8.4 X 10m6 cm*/s.

Since no analytical description of the voltammetric signal for intermediate situations has been reported until now, the resort to the digital simulation

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E /Volt

E /Volt

Fig. 2. Simulated cyclic voltammograms versus the applied potential (A) in the absence of ohmic drop, in the presence (B) of only an uncompensated solution resistance of 55,000 0, (C) of only a double layer capacitance of 5 X IO-t2 F, and (D) of a combination of these properties. Other simulation parameters as in Fig. 1. problem is mandatory [14,28,31]. Fig. 4 shows calculated dimensionless peak separation values A&, (the dimensionless potential 5 is defined by &= nF(E - E)/RT) against the dimensionless kinetic parameter A = ka/D for a fixed value of the dimensionless diffusion parameter p = a( nFu/RTD) I*. On a particular p curve determined by the experimental values of the parameters a and u, a measured value of A$, gives one A value which in its turn furnishes k via A = ka/D. The k valfor this particular

ues calculated by derived applying obtained at scan hundreds V s- r, more sophisticated 2.2. Determination multistep process

this procedure are larger than those the Nicholson method 1321 to data rates of the order of magnitude of but agree with those obtained by techniques [ 191. of the half-wave potentials of a

The digital simulation approach holds its validity also when the steady-state conditions are operative.

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nF(E

E)/RT

Fig. 3. Simulated cyclic voltammograms for a disk electrode under different diffusion conditions. Dimensionless diffusion parameter, (a) 12; (b) 2; (c) 0.01. Other simulation parameters as in Fig. 1.

charge transfer which involves n 2 1 electrons. Polcyn and Shain [33] and later Ryan [34] have demonstrated that, in cyclic voltammetric experiments, a reversible two-step charge transfer process can be reduced to a reversible two-electron one-step process when the difference between the standard potentials assumes appropriate values. Otherwise the shape changes from reversible to apparently quasi-reversible and in the presence of a kinetic hindering the disproportionation-comproportionation reaction may play a relevant role. Fig. 5 compares linear sweep (A> and steady-state (B) voltammetric curves relative to three different electrochemical systems. It features a quite lower resolution of the steady-state voltammetry but its superiority in defining the overall number of electrons transferred since the height of the curve does not change for different values of the thermodynamic and kinetic parameters approaching in any case the limiting value ifisk = 8FDcba. It can be remarked that the curves shown in Fig. 5A and B are calculated with the same algorithm, inserting only different values of the dimensionless p parameter. 2.3. Study of coupled chemical reactions. The application of ultramicroelectrodes to studies of homogeneous reactions coupled to the charge transfer step has been thoroughly discussed. In particular, the voltammetric responses relative to CE, EC, ECE, EC mechanisms under steady-state conditions for the spherical and the hemispherical geometries have been mathematically described [15,35,36]. Apart from the problem of the equivalence among sphere, hemisphere and disk, which is usually accounted for by using a simple transformation coefficient [37], the digital simulation is particularly effective when treating higher order kinetics or intermediate mass transfer conditions. However the complexity of an accurate description of the edge effect in the digital simulation model results in only few papers dealing with complicated electrochemical processes [16,24,31,38,39]. In the context of a research on the application of disk ultramicroelectrodes in studies of the complexation between electroinactive-host ( @cyclodextrin) electroactive-guest (ferrocene carboxylic acid) species, we simulated the voltammetric responses relative to a second order CE mechanism under dif-

Typically this is true when one considers a multistep charge transfer process since the analytical relationships developed until now [12] treat only a one step

,L
0

10

20

30 li

40

50

60

Fig. 4. Calculated dimensionless peak separation values A$ versus the dimensionless kinetic parameters A for a dimensionless diffusion parameter p of 12.

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101

I,,,,L!,,,,,,,,,,,,,,,,I,,,I
10 -5 0 5

,o E)/

15

23

25

Jo

nF(E

RT

Fig. 5. (A) Linear sweep and (B) steady-state voltammetric curves for a reversible one-electron two-step charge transfer. (a) Ef = 200 mV and Ei = 0 mV, (b) EF = 0 mV and Ef = 0 mV, (c) Ef = 0 mV and Et = 200 mV.

pawhere K,, and E,+ ,A are the thermodynamic rameters of the coupled reactions. The complex AL is considered to be electroinactive with a diffusion coefficient equal to that of L and smaller than that of A. Table 1 shows characteristic data relative to simulated voltammograms at a disk electrode under totally convergent mass transfer conditions for different host-guest concentration ratios. In particular the calculations were done assuming a reversible charge transfer process, a fast chemical equilibrium, a ratio of the diffusion coefficients DAL/DA equal to 0.41. These results proved the progressive decrease of the limiting currents with increasing ligand concentration, the shift of the half-wave potentials, and apparently sluggish electron-transfer kinetics at intermediate ligand concentrations. The first finding is due to the change of the principal diffusive species, from A to AL, the second to the stabilization of the electroactive species in the complex, the third to the circumstance that L and A are present in comparable concentrations. It must be remarked that the last current ratio in the first column of Table 1 is coincident with the diffusion coefficient ratio of the complex to the guest species. This comes from the dependence of the limiting current on the diffusion coefficient raised to the power of 1, instead of l/2, as usually found under transient conditions. The superiority of ultramicroelectrodes appears evident since the adoption of steady-state conditions allows an enlargement of the measurement range and an independence of the degree of reversibility of the heterogeneous charge transfer step. The calculations performed allowed us to verify that, under mobile equilibrium conditions, the digital simulation approach becomes unnecessary. A simple relationship gives the dependence of
Table 1 Summary of voltammctric concentration ratios a Host concentration results obtained at various host to guest Half-wave potential shift Tomes criterion

ferent mass-transfer and kinetic conditions [40]. The host (L&guest (A) inclusion system considered reduces to the following reaction sequence A+L-----AL K,, =

Limiting current ratio

(mM)
0 1 3.16 100 0.996 0.853 0.607 h 0.413 h

(mV1
0 5.8 h 22.7 112.8 h

(rnv)
.5x. 1 63.5 b 68.0 h 59.3 h

$
I

A<mA++e-

EA+,A

a Guest concentration, 3.37 mM. h Calculations based on equilibrium constant, 2200 M- ; dimensionless kinetic parameter, 10; host to guest diffusion coefficient ratio, 0.41; temperature, 20C.

102 Table 2 Voltammetric Acid

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data relative to acid dissociation

equilibria

Limiting currents normalized to the value of the reduction of free hydrogen ions a b 0.231 e 0.093 f
C

control of the complex dissociation can be experimentally tested by noting that the limiting current depends not only on the ratio of the host to the guest species but also on the radius of the microelectrode used [15]. 2.4. Response of a channel flow-through amperometric detector Passing from quiescent solutions to hydrodynamically forced mass-transfer conditions, the resort to a numerical approach is even more advisable. Recent studies have dealt with ultramicroelectrode-based channel detectors to support theoretically the use of these tools in flow injection and chromatographic analysis. The main objects of these investigations are the prediction of the effect of the size of the electrode, disk and band, and of the solution flow rate on the mass-transport limited current [5-71, the achievement of a steady-state response during scanning experiments and the extension of the use to normal phase chromatography [8]. Following the scheme reported in Fig. 6, the general two-dimensional diffusion-convection equation reduces to
-=

CH,COOH H,PO;

0.240 d 0.094 d

0.235 0.120 f

a Experimental values recorded with a disk electrode of radius 12.5 pm, and an acidic analytical concentration of 1 X 10m3 M. b Values simulated with a kinetic model. Values calculated via Eq. 5. d From Ref. 41. Input parameters: k, = 7.56 X lo5 s-; k_ 1= 4.2 X 10 M- s-; D, = 0.125. f Input parameters: k, = 2.5 X lo4 s-; k_ 1 = 6.2X 10 M- s-; D, = 0.102.

the ratios of the limiting currents in the presence, i,, of the ligand species on the bulk and absence, z,,~, ligand concentration over the entire range of the concentrations explored: I++
11 -= $0 I,,,,.

lLlb (Lib (5)

A related second example, currently in progress, is the study of the reduction of the hydrogen ions coming from weak acids. Considering a weak acid as a complex between the hydrogen ion and the conjugated anion, the limiting currents recorded at ultramicroelectrodes must depend on the ratio between the diffusion coefficients of hydrogen ions and the weak acid, the value of the equilibrium constant, the value of the rate constants and the ratio of the analytical HA and A- concentrations. The data reported in Table 2 show that at a concentration level of 1 X 10m3 M, acetic acid gives an equilibrium current whilst H,PO, produces a kinetically controlled current. In fact for the acetic acid the experimental limiting current ratio practically coincides with the value calculated simulating the kinetic model inserting the reported kinetic constants [35] and with that calculated by Eq. 5. On the contrary, H,POi gives an experimental current ratio quite inferior to the equilibrium response and coincident with that derived simulating the kinetic model [42]. Therefore the coupling of the digital simulation with steady-state current measurements can furnish, in principle, the parameters of different acids in different media. The onset of a kinetic

ac at
D

ra2c -+I ax2

a2cl az2 1

ac - K-g

assuming V, depending only on z via a parabolic reA

Fig. 6. (A) Real three-dimensional model of the flow through channel and (B) two-dimensional model used with the parabolic velocity profile of the solution.

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combine explicit and implicit finite difference approximation and finally result in implicit (ADI and CN), quasi explicit (FQEDF) or explicit (Hopscotch) methods. In particular, for a two-dimensional diffusion model, in the CN scheme the concentration of each species at the time n + 1 in the i,j node of the space grid is given by

DAt

s2c,y + sy2cyj x . l + sx2cyj+ sy2c,fl;


where
001 -1
I I

I
1 .o

-0.5

0.0 6

0.5

Fig. 7. Dimensionless concentration profiles over the whole space 6 = tanh(2.x) at a flow rate of (1) 0.005 ml/min, (2) 0.5 ml/min, (3) 2.0 ml/min. The band electrode lies between 6 = -0.5 and 6 = 0.5. Calculations based on channel thickness, 50 pm; channel width, 0.4 cm; band electrode length, 5 pm; electroactive species diffusion coefficient, 5 X lo- cm2/s.

lationship, and V, equal to zero. By the digital simulation technique it is possible to calculate the concentration profiles of the analyte over the electrode (Fig. 7) and to assess edge effects also under laminar flow conditions. At low flow rate the concentration profile develops in the bulk of the solution from the edges of the band, while at high flow rate the convective mass-transfer cancels the depletion of the electroactive species due to the electrochemical reaction. The presence of the edge effects causes an enhancement of the current values in respect to those predicted by the classical Weber and Purdy equation [43] which requires a dependence of the current on the volume flow rate value raised to l/3. 2.5. Simulation algorithms The essence of any digital simulation approach consists of a finite difference approximation of the partial differential equation describing the spatial mass-transfer towards an electrode. The methods proposed for simulating voltammetric responses on ultramicroelectrodes are the implicit alternating direction (ADI) [31], the Crank-Nicholson (CN) [25], the fast quasi-explicit finite difference (FQEFD) [44] and the Hopscotch methods [45]. All these methods, unconditionally stable and potentially very accurate,

2 S,Cltj = C,!+r,j - 2c:, + c:\ ,.j; s;c;, = 2C:f, + Czj_ i; and Ax = Ay. c:,+ I The determination of the concentration values at time 12+ 1 needs the solution of coupled linear equations. The mathematical problems arising in this approach are simplified when a modified CN formalism is used (i.e., the ADI method). In this algorithm each time step is subdivided into two equal steps in which a different dimension is treated implicitly. The diffusion equation modifies into

and 1 DAt n+l =C+i + _s2c$ C .I !,I 2 Ax2 1 x The FQEFD classical explicit it is more stable. from that of the
cn+l

+ s,c:,+]

method is an improvement of the finite difference (EFD) method since The finite difference equation comes EFD method

1.J

- fyj

~[c~+l,j-2c:lj+c:~l,J]

where Clyj is substituted by the average of the previous and of the new concentration values, that is C:j = cc:; + C&Y )/2. In the Hopscotch method the finite difference equation assumes the form

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where 19:~= 1 or 0 depending on n + i + j is odd or even, respectively. Taking advantage from the definition of the function Oyj it is possible to obtain the operative equa+ = 2C[f1 - Clj [46] and to calculate the tion Ci,j new concentrations explicitly. In the study of the ohmic drop effects we used the well-known EFD method [29] since the very large value of the scan rate used in conjunction with an ultramicroelectrode makes the diffusion condition planar in character. The employment of the two-dimensional model in this particular case would have been unnecessary time-consuming. The Hopscotch algorithm was used in the other cases. In particular, our starting point was the study of Michael et al. [39] where the diffusion equation was rewritten in a suitable conformal space. Refinements were introduced concerning the a priori definitions of the thickness of the diffusion layer and of the reaction layer. The former was expressed in terms of the dimensionless mass-transfer parameter p =_ constant P so modelling the diffusion layer on the experimental conditions chosen [47]; the latter was calculated as a fraction of the diffusion thickness [16],

[49] able to treat different problems.

mass transfer and kinetic

Acknowledgements
The financial support of the National Council of Research (CNR) and the Ministry of University and Scientific Research (MURST) is acknowledged.

References
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diff

1 + constant( Al/)

kinetic parameter

where A is the usual dimensionless

M.

3. Conclusions The examples reported are a fair illustration of the effectiveness of the coupling of a digital simulation approach with voltammetric data recorded at ultramicroelectrodes. The main feature of the algorithm used by us is its quite wide applicability to describe different mass transfer conditions only by changing an input parameter. In our opinion this approach can represent a valid indication to the development of a generalized simulator [48] and of an expert system

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