The peak current is still proportional to v and CQ and is (11.7.

26) Thin layer methods have been suggested for determination of kinetic parameters of electrode reactions (63 65), but they have not been widely used for this purpose. A difficulty in these methods, especially when nonaqueous solutions or very low sup porting electrolyte concentrations are employed, is the high resistance of the thin layer of solution. Since the reference and auxiliary electrodes are placed outside the thin layer chamber, one can have seriously nonuniform current distributions and high un compensated iR drops (producing for example, nonlinear potential sweeps) (66, 67). Although cell designs that minimize this problem have been devised (63, 64), careful control of the experimental conditions is required in kinetic measurements. Thin layer cells have been applied in a number of electrochemical studies, including investiga tions of adsorption, electrodeposition, complex reaction mechanisms, and value de terminations. They have also become very popular in spectroelectrochemical studies (see Chapter 17). The theory and mathematical treatments used for thin layer cells find application in other electrochemical problems. For example, the deposition of metals (as amalgams) into thin films of mercury and their subsequent stripping (Section 11.8) is fundamentally a thin layer problem. Similarly the electrochemical oxidation or reduction of thin films (e.g., oxides, adsorbed layers, and precipitates) follows an analogous treatment (see Sec tion 14.3). Thin layer concepts are also directly applicable to synthetically modified elec trodes featuring electroactive species bound to the surface (Chapter 14). In many problems involving surface films, mass transfer truly is negligible over wide time do mains and problems with uncompensated resistance are minimal; thus relatively fast ex periments can be performed. Finally, the observed behavior with a scanning electrochemical microscope (Section 16.4), where electrochemistry is examined in the gap between an electrode (tip) and a conducting or insulating substrate can be thought of as that of a leaky thin layer cell.

11.8 STRIPPING AN ALYSIS 11.8.1 Introduction

Stripping analysis is an analytical method that utilizes a bulk electrolysis step (preelec trolysis) to preconcentrate a substance from solution into the small volume of a mercury electrode (a hanging mercury drop or a thin film) or onto the surface of an electrode. After this electrodeposition step, the material is redissolved ("stripped") from the elec trode using some voltammetric technique (most frequently LSV or D PV). If the condi tions during the preelectrolysis step are maintained constant, exhaustive electrolysis of the solution is not necessary and, by proper calibration and with fixed electrolysis times, the measured voltammetric response (e.g., peak current) can be employed to find the so lution concentration. This process is represented schematically in Figure 11.8.1. The major advantage of the method, as compared to direct voltammetric analysis of the origi nal solution, is the preconcentration of the material to be analyzed on or within the elec trode (by factors of 100 to > 1000), so that the voltammetric (stripping) current is less perturbed by charging or residual impurity currents. The technique is especially useful for the analysis of very dilute solutions (down to 10~ 1 0 to 1 0 ~ n M). Stripping analysis

Deposition (preelectrolysis)

Stripping

E -0.5

Figure 11.8.1 Principle of anodic stripping. Values shown are typical ones used; potentials and Ep are typical of Cu 2+ analysis, (a) Preelectrolysis at Ed; stirred solution, (b) Rest period; stirrer off. (c) Anodic scan (v = 10-100 mV/s). [Adapted from E. Barendrecht, Electroanal Chem., 2, 53 (1967), by courtesy of Marcel Dekker, Inc.] lowed by anodic stripping with a linear potential scan and, therefore, is sometimes called

anodic stripping voltammetry (ASV) or, less frequently, inverse voltammetry. The basic theoretical principles and some typical applications will be described here. Several complete reviews describing the history, theory, and experimental methodology of this technique have appeared (68-74).

11.8.2 Principles and Theory

The mercury electrode used in stripping analysis is either a conventional HMDE or a mercury film electrode (MFE). In current practice, the MFE is typically deposited onto a rotating glassy carbon or wax-impregnated graphite disk. One usually adds mercuric ion (10 -10 M) directly to the analyte solution, so that during the preelectrolysis, the mercury codeposits with the species to be determined. The resulting mercury films are often less than 100 A thick. Since the MFE has a much smaller volume than the HMDE, the MFE shows a higher sensitivity. There is evidence that mercury electrodes with platinum contacts dissolve some platinum on prolonged contact, with possible deleterious effects; hence platinum is usually avoided. Solid electrodes (e.g., Pt, Ag, C) are used (less frequently) without mercury for ions that cannot be determined at mercury (e.g., Ag, Au, Hg). The electrodeposition step is carried out in a stirred solution at a potential Ed, which is several tenths of a volt more negative than E for the least easily reduced metal ion to

Section 11.3.1). However, since the electrode area is so small, and td is much smaller than the time needed for exhaustive electrolysis, the current remains essentially constant (at / d) during this step, and the number of moles of metal deposited is then idtdlnF. Because the electrolysis is not exhaustive, the deposition conditions (stirring rate, td, temperature) must be the same for the sample and standards to achieve high accuracy and precision. With an HMDE, one observes a rest period, when the stirrer is turned off, the solu tion is allowed to become quiescent, and the concentration of metal in the amalgam be comes more uniform. The stripping step is then carried out by scanning the potential linearly toward more positive values. When an MFE is used, the stirring during deposition is controlled by rotation of the substrate disk. A rest period usually is not observed, and rotation continues during the stripping step. The behavior governing the i E curve during the anodic scan depends on the type of electrode employed. For an HMDE of radius r 0, the concentration of reduced form, M, at the start of the scan is uniform throughout the drop and is given by
(11.0.1)

nF(4/ 3)7rr 0

When the sweep rate v is sufficiently high that the concentration in the middle of the drop (r = 0) remains at C ^ at the completion of the scan, then the behavior is essen tially that of semi infinite diffusion and the basic treatment of Section 6.2 applies (75). Correction must be made for the sphericity of the drop [see (6.2.23)]. In this case the spherical correction term must be subtracted from the planar term, since the concentra tion gradient builds up inside the drop and the area of the extended diffusion field de creases with time. Thus, the equations that apply for a reversible stripping reaction at the H MD E are (75)
D

nFi \

) (( )

M<J

(11.8.2)

ip AD^ C (2.69 X 10 )n v M

3/ 2 m

(0.725 X 10 5

(11.8.3)

where / p is in A, A in cm 2 , DM in cm 2/ s, C ^ in mol/ cm 3, v in V/s, and TQ in cm; the func tions xi&t) a n d <t>(crt), where a = nFv/ RT, are tabulated in Table 6.2.1. These equations hold for the usual HMDE for v > 20 mV/ s, and clearly, under these conditions, a large fraction of the deposited metal remains in the drop. A comparison of the i E curve pre dicted by (11.8.2) and a typical experimental stripping voltammogram at an HMDE is shown in Figure 11.8.2 (76). At very large scan rates the spherical term becomes negligi ble and linear diffusion scan behavior, with / p proportional to i> 1/ 2, results. Practical strip ping measurements are usually carried out in this regime. At smaller rates, when the diffusion layer thickness exceeds TQ, the finite electrode volume and depletion of M at r = 0 must be considered. At the limit of very small v, when the drop is completely de pleted of M during the scan, the behavior approaches that of a thin layer cell or MFE (see below) with / p proportional to v. Because the volume and thickness of the mercury film on an M F E are small, the stripping behavior with this electrode follows thin layer behavior more closely (see Section 11.7), and depletion effects predominate. The theoretical treatment for the

0.6

Figure 11.8.2 Experimental anodic stripping i E curve for thallium. Experimental conditions: 1.0 X 10~ 5 M Tl + , 0.1 M KC1 solution, E d = 0.7 V vs. SCE, td = 5 min, v 33.3 mV/ s. Circles are theoretical points calculated from (11.8.2). [Reprinted with permission from I. Shain and J. Lewinson, Anal. Chem., 33, 187 (1961). Copyright 1961, American Chemical Society.]

11.8.3. If the stripping reaction is assumed to be reversible, the N ernst equation holds at the surface: CM + n(O, t) = ,

vt)\

(11.8.4)

The solution of the diffusion equations with this condition and the initial and boundary conditions shown in F igure 11.8.3 leads to an integral equation that must be solved nu merically. Typical results for / p for films of different thicknesses, /, as a function of v are shown in Figure 11.8.4a. At small v and /, thin layer behavior predominates and / p u. For high v and large /, semi infinite linear diffusion behavior predominates and m /p ^ v . The limits of these zones are shown in Figure 11.8.4b. MF Es used in current practice fall within the region where thin layer behavior can be expected for virtually all usual sweep rates ( < 500 mV/ s). An approximate equation for the peak current in the thin layer region based on a diffusion layer approximation in solution has also been proposed (79): lpl = 2.1RT (11.8.5)

N otice the similarity between this expression and the corresponding limiting thin layer equation (11.7.17) (where Al = V).

Solution CM + n(y,t)

M(Hg) M +

+ Hg + ne

Figure 11.8.3 Notation, initial conditions, and boundary conditions for theoretical treatment

25

12.5

6.25

1/8

1/4

1/2

2
(b)

16

32

(V/ min)

Figure 11.8.4 (a) Calculated variation of peak current with scan rate for different thickness of MFE. (b) Zones where semi infinite diffusion and thin layer equations apply at MFE. [From W. T. de Vries, J. Electroanal Chem., 9, 448 (1965), with permission.]

11.8.3

Applications and Variations

The technique of controlled potential cathodic deposition followed by anodic stripping with a linear potential sweep has been applied to the determinations of a number of metals (e.g., Bi, Cd, Cu, In, Pb, and Zn) either alone or in mixtures (Figure 11.8.5). An increase in sensitivity can be obtained by using pulse polarographic, square wave, or coulostatic stripping techniques. Other variants, such as stripping by a potential step, current step, or more elaborate programs (e.g., an anodic potential step for a short time followed by a ca thodic sweep) have also been proposed (68 74). Important interferences that sometimes occur with mercury electrodes involve (a) reactions of the metals with the substrate material (e.g., Pt or Au) or with the mercury (e.g., N i H g), or (b) formation of an intermetallic compound between two metals de

0 1

-0.2 1

-0.4 I^

(V vs. SCE) -0.8 -0.6 I I '

-1.0 I

-1.2 I

-1. I

\ / / / / / / f Cu 0.1 ppb

\J
/

A
\ \ 50 nA

\]
V

Zn 0.1 ppb

Pb 0.4 ppb

Cd 0.2 ppb

Figure 11.8.5 Anodic stripping analysis of a solution containing 2 X 1 0 9 M Zn, Cd, Pb, and Cu at an MFE (mercury-plated, wax-impregnated graphite electrode). Stripping carried out by differential pulse voltammetry.

more serious with mercury films than with hanging drops, because MFEs feature fairly concentrated amalgams and a high ratio of substrate area to film volume. They can be overriding concerns in the choice between an MFE and an HMDE. On the other hand, MFEs offer much better sensitivity in linear sweep stripping and better control of mass transfer during the deposition step. If an HMDE is chosen (e.g., to reduce interferences), one can use differential pulse stripping to obtain sensitivities comparable to those attained by LS V at an MFE. Since stripping at an MFE gives total exhaustion of the thin film, the voltammetric peaks are narrow and can allow baseline resolution of multicomponent systems. Thinlayer properties and the sharpness of the peaks permit relatively fast stripping sweeps, which in turn shorten analysis times. In contrast, the falloff in current past the peak in a stripping voltammogram obtained at an HMDE comes from diffusive depletion, rather than exhaustion, and it continues for quite some time. Thus the peaks are broader, and overlap of adjacent peaks is more serious. (Compare, for example, Figures 11.8.6 and 11.8.6d.) This problem is usually minimized for the HMDE by using slow sweep rates, at a cost of lengthened analysis time. Cathodic stripping analysis can also be carried out for species (usually anions) that deposit in an anodic preelectrolysis. For example, the halides (X~) can be determined at mercury by deposition as Hg2X2 Deposition on solid electrodes is also possible. In this case, surface problems (e.g., oxide films) and underpotential deposition effects often ap pear. On the other hand, the sensitivity for stripping from a solid electrode is very high, since the deposit can be removed completely, even at high scan rates. Stripping of films has often been used to determine the thickness of coatings (e.g., Sn on Cu) and oxide lay ers (e.g., CuO on C u). 6
6

I n fact, one of the earliest electroanalytical (coulometric) methods was the determination of the thickness of tin

+0.2

+0.4

+0.6

+0.8
-EN vs. SCE

+0.2

+0.6

+0.8

Figure 11.8.6 Stripping curves for 2 X 10~7 M Cd 2+ , In 3+ , Pb 2 + , and Cu 2+ in 0.1 M KNO3. \v\ = 5 mV/s. {a) HMDE, td = 30 min. (b) Pyrolytic graphite, td = 5 min. (c) Unpolished glassy carbon, td = 5 min. (d) Polished glassy carbon, td = 5 min. For () to (d), &>/2 = 2000 rpm and H g 2 + was added at 2 X 10~ 5 M. [From T. M. Florence, J. Electroanal. Chem., 27, 273 (1970), with permission.]

Another variation involves the stripping or electrolysis of species that have sponta neously adsorbed on the surface of an electrode without the preelectrolysis step. This technique, called adsorptive stripping voltammetry, can be applied, for example, to sul fur containing species, organic compounds, and certain metal chelates that adsorb on Hg and Au (74, 81). Examples include cysteine (and proteins that contain this amino acid), dissolved titanium in the presence of the chelator solochrome violet RS, and the drug diazepam. The amounts found by this method would necessarily be limited to monolayer levels. H owever, similar approaches can be employed with thicker polymer layers that can interact with solution species. Related experiments are described in Chapter 14.

11.9 REFERENCES
1. J. J. Lingane, "Electroanalytical Chemistry," 2nd. ed., Wiley Interscience, N ew York, 1958, Chaps. 13 21. 2. P. Delahay, "N ew Instrumental Methods in Electrochemistry," Wiley Interscience, N ew York, 1954, Chaps. 11 14. 3. N . Tanaka, in "Treatise on Analytical Chem istry," Part I, Vol. 4,1. M. Kolthoff and P. J. Elv ing, Eds., Wiley Interscience, N ew York, 1963, Chap. 48. 4. E. Leiva, Electrochim. Acta, 41, 2185 (1996). 5. (a) L. B. Rogers and A. F. Stehney, J. Elec trochem. Soc, 95, 25 (1949); (b) J. T. Byrne and L. B. Rogers, ibid., 98, 452 (1951). 6. D . M. Kolb, Adv. Electrochem. Electrochem. Engr., 11, 125 (1978).