1

1

Methods to Investigate Mechanisms of Electroorganic Reactions
Bernd Speiser .. .. Institut f ur Organische Chemie, Auf der Morgenstelle 18, T ubingen, Germany

1.1 1.1.1 1.1.2 1.2 1.2.1 1.2.1.1 1.2.1.2 1.2.1.3 1.2.1.4 1.2.1.5 1.2.2 1.2.2.1 1.2.2.2 1.2.3 1.2.3.1 1.2.3.2 1.2.4 1.2.4.1 1.2.4.2 1.2.4.3 1.2.4.4 1.2.4.5 1.3 1.3.1 1.3.2

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Scope: Methods of Molecular Electrochemistry . . . . . . . . . . . . . . . Historical Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Why and How to Investigate Mechanisms of Electroorganic Reactions Steps of Electrode Reaction Mechanisms . . . . . . . . . . . . . . . . . . . General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Electron Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chemical Kinetic Steps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Organic Electrode Reaction Mechanisms . . . . . . . . . . . . . . . . . . . Electron Transfer Initiates Chemistry . . . . . . . . . . . . . . . . . . . . . Nomenclature of Electrode Reaction Mechanisms . . . . . . . . . . . . . Formal Description of Events at an Electrode . . . . . . . . . . . . . . . . Current-Potential-Time Relationships . . . . . . . . . . . . . . . . . . . . . Concentration Profiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Methods of Mechanistic Electroorganic Chemistry . . . . . . . . . . . . Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Controlled-Potential Techniques . . . . . . . . . . . . . . . . . . . . . . . . Controlled-Current Techniques . . . . . . . . . . . . . . . . . . . . . . . . . Hydrodynamic Voltammetry . . . . . . . . . . . . . . . . . . . . . . . . . . . Exhaustive Electrolysis Techniques . . . . . . . . . . . . . . . . . . . . . . . How to Gain Access to Kinetics, Thermodynamics, and Mechanisms of Electroorganic Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . Qualitative and Quantitative Investigation of Electrode Reaction Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . General Recommendations for Mechanistic Analysis . . . . . . . . . . .

3 3 3 4 4 4 4 5 5 6 6 6 6 7 7 7 7 7 7 11 12 13

14 14 14

3

1.1

Introduction
1.1.1

Scope: Methods of Molecular Electrochemistry

Reaction mechanisms divide the transformations between organic molecules into classes that can be understood by welldefined concepts. Thus, for example, the SN 1 or SN 2 nucleophilic substitutions are examples of organic reaction mechanisms. Each mechanism is characterized by transition states and intermediates that are passed over while the reaction proceeds. It defines the kinetic, stereochemical, and product features of the reaction. Reaction mechanisms are thus extremely important to optimize the respective conversion for conditions, selectivity, or yields of desired products. Reaction mechanisms are also defined for electroorganic reactions, induced by or including an electron transfer at an electrode. Knowledge of such electrode reaction mechanisms includes, preferably but not exclusively, the potential at which the reaction proceeds, the proof of intermediates, the electron stoichiometry, the kinetics of the various reaction steps, and the transport properties of the species involved. Recently, the terms

molecular electrochemistry [1] or dynamic electrochemistry [2] have been used for that part of electrochemistry that studies the mechanistic events at or near an electrode on a molecular level. There are a large number of methods (often also called electroanalytical methods) for such studies of which only the most important ones can be covered in this chapter. Moreover, technical details of the methods cannot be described, and emphasis will be placed on their use in mechanistic electroorganic chemistry.
1.1.2

Historical Development

Although organic electrochemistry had already been established in the nineteenth century, only the 1960s saw the advent of detailed electroorganic mechanistic studies. Most of the techniques employed can be traced back to polarography, which was already in use in 1925, to determine the concentrations of organic molecules [3]. Technical developments in instrumentation (potentiostats) [4], the use of nonaqueous electrolytes [5], and the digital control of experiments [6] led to the spread of electroanalytical techniques. For example, cyclic voltammograms are frequently and routinely used today to define the redox

E. which may considerably influence the overall process. P. E : educt.4 1 Methods to Investigate Mechanisms of Electroorganic Reactions properties of newly synthesized organic compounds similar to the use of NMR spectra for structural characterization. Numerical simulation of the experiments [7] became increasingly available during the 1980s. often rate-determining role.1 Steps of Electrode Reaction Mechanisms General As heterogeneous reactions at the interface electrode–electrolyte. circles indicate adsorbed molecules. P : P’ product. This development contributes to a stillincreasing body of knowledge about the fate of organic molecules upon oxidation and reduction. Migration (in the electrical field between the anode and the cathode) contributes to the movement of charged species. and ultramicroelectrodes [8] opened the way not only to ever-faster timescales but also to finer lateral resolution when characterizing electrode processes. 2. electrochemical reactions are intrinsically more complex than typical (thermal) chemical transformations (Figure 1). Electrode E Electron transfer P Transport P d Chemical reactions P Fig. 1 Steps constituting a typical organic electrode reaction. The electron transfer step occurs at the interface. We mostly neglect the exact structure of the interface in the following description.1 Adsorption E Diffusion layer Transport E Bulk E’ 1. Specific interactions of any species present in the electrolyte with the electrode surface leads to adsorption. the concentration of supporting electrolyte ions is much higher (100–1000 : 1) than that of other ions.2. . Purely chemical reactions may precede or follow these steps. The product of the redox reaction is transported back to the bulk. (substrate) from the bulk of the electrolyte to the electrode plays an important. however.2.2.1. Finally.2 Why and How to Investigate Mechanisms of Electroorganic Reactions 1.2 1.1. At the outward boundary the concentrations approach their bulk values. Diffusion (along a concentration gradient) is observed if the solution near the electrode is depleted from a substrate or a product is accumulated. Transport Three types of mass transport are important at an electrode: 1. Diffusion is characterized by a diffusion coefficient D (typical value: 10−5 cm2 /s) and extends over a diffusion layer (thickness: δ) that develops from the electrode into the electrolyte. In most practical experiments. Transport of the educt 1. combinations with spectroscopic and mass-sensitive devices opened new ways to augment information available from molecular electrochemical experiments.

Electrons pass through the interface. experiments can be performed under conditions of minimal convection. ET much faster than transport (transport control). On the other hand.1. migration becomes important at modified electrodes or in electrolytes of low ion concentration [9]. T = temperature). These are often assumed to occur in a homogeneous solution. The transfer of an electron to (reduction) or from (oxidation) the substrate is an activated process. 3.or secondorder reactions and may be reversible (chemical reversibility) or irreversible. 1. 12]. respectively. that is. for example. Electrochemical equilibrium is attained at the electrode surface at all times and defined by the electrode potential E. The three situations mentioned below can be distinguished: 1. R = gas constant. Chemical Kinetic Steps Most electrode reactions of interest to the organic electrochemist involve chemical reaction steps. Since δ increases with time t in such a case. This mixed-control situation is characterized as quasi-reversible. The current is proportional to the amount of material transported to the electrode in a time unit. which are thus dominated by diffusion. not at the electrode surface itself. Electron Transfer The electron transfer (ET) at the interface between electrode and electrolyte is central to an electrode reaction. ET and transport have comparable rates. follow the Nernst equation (1) (reversible ET) . δ = f (t). characterized by a rate constant ks . A physical interpretation of α is related to the ET transition state (see the comprehensive discussion in ref.2 Why and How to Investigate Mechanisms of Electroorganic Reactions 5 Hence. F = Faraday constant.2. and the transfer coefficient α. nonstationary conditions exist.1. however. defined as the standard (or formal) potential E 0 . Still. and we approach stationary conditions.4 1. The concentrations cox and cred of oxidized and reduced forms of the redox couple. Convection (of the electrolyte liquid phase as a whole) can be natural (due to thermal effects or density gradients) or forced (principal mass transport mode in hydrodynamic techniques). On the other hand. [10]).2. as far as diffusion is concerned. Macroscopically we observe a current i. ET much slower than transport (ET control).1. in particular on the external control of mass transfer. first.3 cox nF = exp (E − E 0 ) cred RT (1) (n = number of electrons transferred. If we neglect migration. A given electrode reaction may correspond to any of these situations depending on the experimental conditions. They are described by the usual chemical kinetic equations. migration of the latter is suppressed. close to the electrode surface a diffusion layer develops. It is furthermore expected that α is potential dependent and important mechanistic conclusions follow [11. 3. The current follows the Butler–Volmer equation (2) i = i0 exp − exp −αnF (E − E 0 ) RT (1 − α)nF (E − E 0 ) RT (2) where i0 defines the exchange current at E = E 0 (irreversible ET). if convection dominates in the electrolyte bulk. 2.

the adsorption of intermediates has been discussed. Nomenclature of Electrode Reaction Mechanisms In order to classify the various mechanisms of organic electrode reactions. ‘‘Eqr ’’. carbanions). Adsorption The involvement of specific attractive interactions of molecules with the electrode surface (adsorption) makes the electrode process even more complex. the electroactive species is formed in a preequilibrium. however. or those with unusual oxidation states (e. solvation.2.2. unpaired electrons (e. 1.g. we produce by ET some reactive species.or high-valent central atoms) are produced at the electrode.2 strong acids or bases are not necessary) and/or the additional selectivity introduced in controlled-potential experiments. radicals. electron transfers at the electrode are denoted by ‘‘E’’. radical ions). fence [18] or cubic schemes [20] have been selected. for example. or structural rearrangement steps. and polymer reconfiguration are important and four-dimensional hyper-cubes are needed to describe the reactions [21]. In the latter case.6 1 Methods to Investigate Mechanisms of Electroorganic Reactions Chemical steps may precede or follow the transport and ET processes. Usually.2 Organic Electrode Reaction Mechanisms 1. which undergoes a (possibly complex) chemical transformation to a more stable product. The instrumental techniques described in this chapter allow the investigation of the course of the reaction accompanying the overall electrolysis. [19]). the symbol ‘‘D’’ is common. The intensity of such interactions ranges from weak (physisorption) to strong (chemical bonds formed between adsorbate and electrode).g. and one may find additional or deviant symbols.g. The ET may further be characterized as ‘‘Er ’’.g. 16]. bond-forming. e. In the former case. a specific nomenclature has been developed [17]. electron excess (e. For more complex mechanisms. the oxidation or reduction step initiates the follow-up chemistry to the reaction products (‘‘doing chemistry with electrodes’’ [14]). The reaction mechanisms of organic electrode reactions are thus composed of at least one ET step at the electrode as well as preceding and follow-up bond-breaking. or irreversible case. . carbocations).5 1. Thus. while an ET between two species in a (homogeneous) solution is denoted ‘‘SET’’ (for solution electron transfer) [18] or ‘‘DISP’’ (see. If the C-step is a dimerization.2.2. 1. For some common organic electrochemical reactions. quasireversible. the Kolbe electrolysis of carboxylates [13].g. ladder.2. metal complexes with low.1. Species with electron deficiency (e. or ‘‘Ei ’’ in the reversible. These chemical steps may be concerted with the electron transfer [15. It is often extended in an informal way to accommodate particular reaction features.1 Electron Transfer Initiates Chemistry The majority of organic electrode reactions is characterized by the generation of a reactive intermediate at the electrode by ET and subsequent reactions typical for that species.2. Electrochemical generation of such intermediates may be advantageous because of the mild reaction conditions employed (room temperature. while chemical steps not involving the electrode are denoted by ‘‘C’’. It is usually not indicated how transport occurs. picturesque names such as square. additional transport of counterions. In redox polymer films.

and the electrolyte extends into the positive x half-space.2. Often. Finally.1 Current-Potential-Time Relationships The equations given in Section 1. on the basis of a hypothesis for the reaction mechanism. Similar i –E –t relationships are derived theoretically from basic equations (simulation. impedance techniques (small amplitude sinusoidal perturbation at the electrode with observation of the system’s response [22]) as well as polarographic methods (at mercury electrodes) will not be described. In general.2.4. Thus. The bulk of the solution is assumed at the right-hand side of the profile.2 Controlled-Potential Techniques Control of the potential E of that electrode where the electrode reaction occurs (working electrode) is accomplished by a 1.1).4 Methods of Mechanistic Electroorganic Chemistry Classification One of several possibilities to classify electroanalytical methods is based on the quantity that is controlled in the experiment. and space coordinate values are normalized with respect to the extension of the diffusion layer δ.2. the hypothesis is either disproved.2. Since the notion of a reaction mechanism requires consumption of substance. and time t. transient methods are different from those that work in an exhaustive way. in turn is related to the concentrations c of various species near the interface.g.1 Concentration Profiles The current through the electrode is proportional to the flux of redox-active material to the surface. concentration values are normalized with respect to the bulk concentration of one species. Simulations usually provide values of c = f (x. Although it is difficult to determine the spatial distribution of species experimentally. Often a single spacecoordinate suffices. equilibrium techniques (such as potentiometry) will also not be discussed here.3. Alternatively. The space dependence of c is termed a concentration 1. current or potential.2 Why and How to Investigate Mechanisms of Electroorganic Reactions 7 1.3. most techniques to investigate electroorganic reaction mechanisms involve the determination of i or E as a function of time (while the other one of these quantities is kept constant) or as a function of each other (while one is varied with t in a defined manner). In this way. we distinguish techniques with stationary or nonstationary diffusion. Thus. since diffusion is an important mode of mass transport in most experiments. More complex systems (e.4.2.2 . profile. that is. ultramicroelectrodes) may require up to three space-coordinates. 1. and the experimental and the theoretical results are compared. Such concentration profiles will be used in the following discussion.1. it provides an illustrative view of the electrode reaction.4. 1. an equivalent description is based on the dependence of c on space x and t. see Section 1. potential E. Only a small selection of the variants in the electrochemical literature can be mentioned here. or proven to be consistent with the events at the electrode. Consequently. the electrode is located at x = 0.1 include the most important quantities for understanding a reaction mechanism at an electrode: current i.2. t) for each species as the primary result.2. which.3 Formal Description of Events at an Electrode 1.

which drives the desired electrode reaction. but not necessarily (see. This is the potential that the working electrode develops in the solution at equilibrium. when no current flows through the electrode. C: counter. After some (pulse) time τ . that is. Often. the concentration of the redox-active 0 compound A. Initially (t < 0). Recorder E Function generator R C W Electrolyte Fig. References [23–25]) the latter is in the transport (diffusion) limited region. E may be switched back to ER or another appropriate value (double-step chronoamperometry). cA .8 1 Methods to Investigate Mechanisms of Electroorganic Reactions Potentio/galvanostat Computer. a recording device and a function generator complement the experimental setup. These concentrations deviate from the bulk concentrations that remain at their initial values throughout the experiment. Chronoamperometry is a technique in which a potential step is applied to the working electrode in a quiet solution at t = 0 (Figure 3). A diffuses to the electrode. This is reflected in the current response given by the Cottrell equation (3) √ 0 nFAcA D i= √ πt (3) . potentiostat in a three-electrode arrangement (Figure 2). e. while B is produced at x = 0 and diffuses to the bulk. The product concentration cB is usually assumed to be zero. the concentrations of A and B at x = 0 adjust to conform to equation (1). R: references electrodes. the electrode attains ER . a potential is selected. W: working. Starting at ER guarantees that at t < 0. and decreases thereafter. An important property of the solution to be investigated is the rest or open-circuit potential ER . The value of ER depends on the components of the solution and the electrode itself. The steepness of the concentration gradient is high shortly after t = 0. The resulting diffusion layer grows into the solution with t (typically 10−2 cm after 10 s in common organic solvents). 2 Schematic representation of experimental set-up for controlled-potential experiments. As a result. After E is stepped. We will assume a simple reversible one±e− −− − electron redox process A −− − B in all cases to introduce the techniques. while E is measured with respect to a currentless reference (R) electrode. For t > 0. Often. equals cA at all x. The current is passed through the working (W) and counter (C) electrodes. and a concentration gradient develops.g.

0 0. product: dotted lines.6 0.0 −0. and concentration profiles [(c) first step. a√ plot of Q vs.5 1.6 0. t [s] 1. t [s] Time. or D. quantitative analysis of chronoamperometric curves includes determination of n. c 0.8 0. Chronocoulometry is similar to chronoamperometry. increasing time shown by arrows] for a double-step chronoamperometric experiment (pulse time τ = 1s). allowing qualitative mechanistic conclusions.0 (a) 1. t for the first.0 0. but the time integral of i.0 0. E [V] 0.0 0.1 0.0 (b) 0.2 Why and How to Investigate Mechanisms of Electroorganic Reactions 0. Furthermore. x Distance. provided two of these quantities are known.8 1.1.2 0.0 −0. Adsorption of redox active species can simply be diagnosed .4 0. c 1.3 0. t − t − τ for the second part of the curve results in two straight lines (‘‘Anson plot’’ [26]).2 1.2 0.2 (d) 0. √ i t is a constant.2 0.0 0.5 2.0 1. and a plot of i vs.8 1. five profiles respectively at various times.2 0.5 1.0 −0.5 2. Any reaction that removes B from the solution will influence the current response.6 0.2 (c) Distance. A. Integration of equation (3) yields √ 0 2nFAcA D √ t (0 < t < τ ) (4) Q= √ π As soon as the potential is stepped back such that a current in the reverse direction flows.0 1. t −1/2 is a straight line. This quantity continuously increases during the first part of the experiment (0 < t < τ ).2 Concentration.0 0. the charge Q. the accumulated charge decreases as shown: √ 0 √ 2nFAcA D √ Q= ( t − t − τ) √ π (τ < t < 2τ ) (5) √ Thus.6 0. in the most simple case (with A = electroactive area of the electrode).4 0.0 1.4 0.2 Time. 3 Chronoamperometry: (a) typical excitation signal. is recorded (Figure 4).2 1.8 0. which has accumulated in the diffusion layer.1 30 20 10 0 −10 −20 −30 −40 9 Current. and √ Q vs. x Fig. i • 106 [A] Potential. diffuses toward the electrode and is transformed back to A.4 0. We observe a current in the opposite direction. (b) current response. educt: solid lines.5 0. B.2 0.0 Concentration. Now.6 0. Switching back E to ER causes the concentrations at x = 0 to return to their original values with the concentration profiles changing accordingly. Thus. (d) second step.4 0.

(d) reverse scan.8 1.0 Charge. Linear sweep and cyclic voltammetry (LSV and CV) are probably the most widely used techniques to investigate electrode reaction mechanisms. They are easy to apply experimentally.4 0. x Distance.2 0.3 0.3 1.0 0.4 0.2 4 3 2 1 0 −1 −2 −3 0.8 2.0 0. this charge ratio increases. t [s] Current.0 1.2 2. readily available in 400 300 200 100 0 −100 −200 −300 −0. E [V] Concentration. five profiles respectively at various times.6 0. if no follow-up reaction destroys B.0 −0.7 (a) 1.4 0.6 0.00 0. (b) current response.4 0.0 0.7 3.10 0. .0 Concentration.3 0.2 0.4 0. x Linear sweep and cyclic voltammetry: (a) typical excitation signal.1 0. product: dotted lines.6 0.2 (d) 0. c 1.2 0.10 1 Methods to Investigate Mechanisms of Electroorganic Reactions 3.2 Time.0 0.2 0.8 1. (b) Anson plot for a double-step chronocoulometric experiment.8 1.2 1.4 0.414.7 0.7 1.2 (a) Time.2 1.04 0.8 0.2 0.2 Potential.12 0.2 0.1 0.0 −0. educt: solid lines.2 −0.2 0. increasing time shown by arrows] for a cyclic voltammetric experiment. t1/2 [s1/2] Fig. if the extrapolated Anson plot lines do not cross close to the origin [27]. Q • 106 [C] 0.0 −0.8 1.3 0.6 0. or D are accessible from chronocoulometric data.2 1.6 0.6 0.02 0. Again.5 0. If B reacts.5 0. and concentration profiles [(c) forward scan.8 0. A. n. t [s] Square root of time. however.06 0. i • 106 [A] Potential. An interesting characteristic of the chronocoulometric curve is that Q(2τ )/Q(τ ) = 0. 4 Chronocoulometry: (a) typical charge response. Because of its integral nature. chronocoulometry is less susceptible to noise 0.1 0. 5 Distance.08 0.3 (b) Charge. E [V] (b) 1.1 0.3 −0.2 0.6 0. c 0.0 0.2 (c) Fig.7 0.4 0.0 1.14 than chronoamperometry. Q • 106 [C] 0.

. Chapter 2).2. In such experiments. Double-step applications [30]. cB (x = 0) increases. The peak current in the forward scan is given by [28] 0 ip = 0. The concentration of A at x = 0 necessarily decreases. depletion of the substrate causes an increase in the diffusion layer thickness. Simultaneously. The potential changes with a scan (or sweep) rate v = dE/dt. Ep . While the steepness of the concentration profiles increases with E (forward scan). Since δ still keeps increasing. 1. Since i is constant. E adjusts according to equation (1). E increases steeply until another electrode process is possible (not shown in Figure 6). follow-up kinetics are accessible from the influence on the position of the peaks. Figure 5. as a function of time. Starting at ER . and provide a wealth of mechanistic information.4463nFAcA Besides determination of n. Thus. for T = 298 K. or D. and in particular. as soon as a current i is imposed. Chronopotentiometry is a transient constant-current technique in which the potential of the electrode is followed. and finally (close to the limiting current region) leads to the formation of a peak with a characteristic asymmetric shape. and E p p p is the potential of the peak on the reverse scan. The current can no longer be maintained by the redox reaction of A. where E b 28 mV. the slope of the concentration profile must also be constant. cA (x = 0) reaches a value of zero and no more decrease is possible. The latter effect slows down the increase of i with E. is related f to E 0 of the redox couple by Ep = E 0 + 0 = (E f + E b )/2. the concentrations at the electrode do not immediately attain their extreme values after the start of the experiment. This quantity is easily variable and is one of the most important parameters for mechanistic analysis. the equivalent flux of redoxactive substrate A to the electrode is established. see also Volume 3. as well as programmed current experiments [31] have been described. After some transition time τ . the shape of the peaks allows conclusions to be drawn about the involvement of adsorption processes. the potential of the working electrode is controlled by a potential ramp (LSV) or one or more potential triangle(s) (CV.3 nF vD RT (6) or. the intensity of the reverse peak. As a consequence. while the steepness of the profile does not change.2 Why and How to Investigate Mechanisms of Electroorganic Reactions 11 commercial instruments. Controlled-Current Techniques Current control of an electroanalytical experiment is accomplished by a galvanoor amperostat [29]. in the case discussed). On the reverse scan (after switching the scan direction at Eλ ). defining the timescale of the experiment. in a quiet solution (Figure 6). they change with E or t according to equation (1). Rather.4. the concentration gradient becomes less steep. Now. Formation of products that are electroactive within the potential window scanned causes the appearance of additional peaks. The peak poc f tential in the forward scan. A. In these techniques. Furthermore. products formed in the forward scan can be detected (B.69 × 105 )n3/2 AcA vD (7) (Randles-Sevˇ ik equation).1. simultaneously δ increases in the quiet solution. √ 0 ip = (2.

8 1.0 (a) 0. 1. The shaft is inserted into the electrolyte and rotated around its vertical axis with an angular velocity ω (RDE [32]. Diffusion occurs across a distance of δ = 1. or D can be determined from chronopotentiometric experiments.12 Current. At 0 ER .8 1. Figure 7).8 1.0 0.4 0. consisting of a disk embedded into the lower cross section of a perpendicularly mounted insulating shaft. It is replenished by fresh solution dragged up vertically from the bulk.2 0. c [mol l−1] 1. Thus.2. i • 106 [A] Potential. Eventually.6 0. diffusion is negligible and no current flows. (b) potential response.6 0. A.0 Time. x [m] Fig. n.2 0.03 −0.02 −0.4 Rotating disk voltammetry uses a potential scan to control the potential of a specially designed working electrode. increasing time shown by arrow).8 0. The relation between i and τ is given by the Sand equation (8) √ 0 nFAcA πD 1/2 iτ = (8) 2 Again.0 1. The electrolyte is set into a circular motion and moves centrifugally along the electrode surface.07 0.4. In a simple model. cA (x = 0) ≈ cA . 6 Chronopotentiometry: (a) typical excitation signal.2 0.6 0.13 0. convection is the principal mode of mass transport.61D 1/3 ω−1/2 ν 1/6 (ν is the kinematic viscosity of the electrolyte).0 0. E [V] 0. t [s] Concentration.4 0.4 0. and is brought about by the controlled movement of the electrode in the solution or by pumping the electrolyte through a pipe or channel.08 −0. t [s] Time.2 0. Hydrodynamic Voltammetry In hydrodynamic techniques.2 0.2 (c) Distance. cA (x = 0) = 0 and a limiting . Scanning E causes cA (x = 0) to change.0 0. and a current results.12 1 Methods to Investigate Mechanisms of Electroorganic Reactions 12 10 8 6 4 2 0 0. the diffusion layer thickness is constant.0 0. (c) concentration profiles of educt for a chronopotentiometric experiment (three profiles at various times.0 (b) 1.6 0. one assumes that convective mass transport keeps the concentration constant at some fixed distance δ from the solid wall.4 0.

by increased convection with high flow rates [37. h = half-height of channel. the diffusion limiting current is wxE (10) (with U = mean solution velocity. The substrate is transported by convection and diffusion to the working electrode surface.2. It is thus important to enhance mass transfer. Exhaustive Electrolysis Techniques In contrast to the techniques discussed up to now in which only a small part of the substrate present in the electrolyte is consumed. the electrodes used have a comparatively large area. 7 Construction [section and bottom view. Channel techniques employ rectangular ducts through which the electrolyte flows. Under suitable geometrical conditions [2] a parabolic velocity profile develops.6 (a) (b) (c) Potential. Here. 36]. for example.6 0.2 0.5 h 2/3 Q= tend i 0 dt (11) .4 0.6 −0. The current decreases with the bulk concentration of the substrate.0 0. In potentiostatic exhaustive electrolysis.165nF cA D 2/3 U 1/3 −1/3 The fact that transport limits the rate of the overall electrode reaction affects the fastest timescale accessible. w = width of the electrode). i • 106 [A] 0. Exhaustive electrolyses can be performed potentio.4.4 −0. Typically. The electrode is embedded into the wall [33]. The charge transferred is 1. Similar to the Levich equation at the RDE. we will now consider approaches that exhaustively convert the substrate to the product. xE = electrode length.0 −0.4 0.2 Why and How to Investigate Mechanisms of Electroorganic Reactions 1. E [V] Fig. (b) RRDE] of rotating disk electrodes.2 0. the potential of the working electrode is constant throughout the experiment. Experimental variables include U and xE (arrays of microbands) [35. and (c) typical RDE response. 38].2 1. Potential-controlled steady state (diffusion limiting conditions) and transient experiments are possible [34].2 13 Current.1. (a) RDE. 0 ilim = 1. current 0 ilim = 0. use of the rotating disk electrode complements the more complex rotating ring disk electrode (RRDE) [32].8 0. Once transport controls the rate. if no further electron transfers occur.0 0. which is held at a separately controlled potential.620nFAcA D 2/3 ω1/2 ν −1/6 (9) is reached [Levich equation (9)]. and the electrolyte is stirred in order to increase mass transport. redox active products can be detected at the ring electrode.or galvanostatically. faster reaction steps cannot be characterized. Since products of the electrode process are quickly transported out of the vicinity of the electrode disk.

for a mechanistic analysis. but not unique stopping criterion is the remaining current. and Mechanisms of Electroorganic Reactions 1. the duration of a potentiostatic electrolysis is much larger than that of a transient experiment as discussed above. in galvanostatic exhaustive electrolysis the current through the working electrode is kept constant. In contrast. since i = f (t): Q = it. 1. at different times various electrode processes may be induced. 1. 41]. Qualitative analysis has the main objective of confirming a given mechanistic hypothesis by rejection of conflicting alternatives. thermodynamic. and/or transport parameters for the various steps. Even more information about the reaction can be gained from electrolysis experiments at various defined potentials.3 How to Gain Access to Kinetics.1 Qualitative and Quantitative Investigation of Electrode Reaction Mechanisms Two extreme forms of mechanistic investigations in organic electrochemistry are frequently applied: 1. Preparative and analytical techniques are available to determine the composition of the product mixture and the structure of its components. Hence. Consequently. in situ or in samples taken from the electrolyte. Quantitative analysis relies on a highly probable mechanistic hypothesis and determines as many as possible kinetic. their relation to experimental data is nonlinear. as many facets as possible of the investigated electrode reaction should be taken into account and the various experimental parameters be varied as widely as possible. the intermediates. a suitable protocol for endpoint detection must be defined [39]. This is often a complex problem. for example. and the data contain artifacts and statistical errors [40. Thermodynamics. Mechanistic reasoning will often allow defining the reaction steps. A frequent. Typically. As in chronopotentiometry. From an exhaustive potentiostatic electrolysis. the electrode potential will vary during the experiment. since the values of the parameters are usually correlated. . The determination of charge in galvanostatic electrolysis is particularly simple.2 General Recommendations for Mechanistic Analysis In general. From Faraday’s first law (Q = nF m/M). this will result in a constant flux of electroactive material to the surface. This may be applied to single elementary steps. and product isolation is possible.3. n is available. or how the steps are linked together. after each peak in the cyclic voltammogram of the substrate. the results of galvanostatic and potentiostatic electrolyses will not necessarily be identical. Q can be related to the amount m of substrate with molecular mass M consumed. One could also test for disappearance of the substrate or some intermediate. 1% of the initial i.3. As a result. Among these are • Time scale: This is particularly important for kinetic studies and the determination of rate constants.14 1 Methods to Investigate Mechanisms of Electroorganic Reactions with tend denoting the time when the experiment is stopped. 2. for example. Both types of mechanistic analysis are supported by the instrumental techniques discussed here. Again. the product(s) formed at the selected electrode potential can be isolated.

Comparison is done by • data transformation. Ep is independent of v. the reaction mechanism is fully described by E 0 (thermodynamics). it is important to diagnose full diffusion control (Er ).4. • feature analysis.3 Some Mechanistic Examples Pure ET Reactions If no chemical steps are coupled to the ET at the electrode. Again.g.3 How to Gain Access to Kinetics.4). but rather to impurities or are caused by non-Faradaic processes (charging of the double layer). Qualitatively. for example. The experimental curves exhibit features (e. experimental artifacts should be avoided. 48]. It is characteristic to find a fully developed reverse peak in the cyclic voltammogram [49]. This is used to great advantage in simulation procedures [45. • full curve analysis. and Mechanisms of Electroorganic Reactions 15 • Concentration: The dependence of results on concentration indicates chemical reactions of an order higher than unity.g. and procedures for correction have also been given [47. n follows from Ep = 58/n mV. and α (kinetics). It is particularly awkward in lowconductivity electrolytes and distorts curves in a nonlinear way. for example. nucleophiles to quench electrogenerated carbenium ions.1 . Of course.3. While E 0 follows from CV directly (Section 1.2)] or R (increasing conductivity or decreasing distance between reference and working electrodes). Usually.3.1. and D is calculated from 1. Anson plot in chronocoulometry) or similar simple curves (semi-integration or differentiation [42]). The results are usually compared to working curves [28] or surfaces [43. while for Eqr an increase of v (faster timescale) causes Ep to increase (Figure 8a) [50]. • iR drop is caused by the resistance R between the reference and the working electrode in a three-electrode cell. Characteristic changes are expected.3. 1. However. in mechanistic electroorganic work these are • Background currents are current components not related to the ET of substrates or products. For diffusioncontrolled ETs. n (stoichiometry). peaks in CV may disappear. In particular. Thermodynamics. Compensation in commercial instruments is often possible. as well as ks . the experimental results are compared with the theoretical model simulations. 46]. D (transport). They are at least approximately corrected by subtraction of a blank curve recorded in the electrolyte without substrate. it is important to consider wide ranges of experimental conditions that have to be adequately modeled using a single set of parameters. For Er . Suitable transformations of the experimental data lead to straight lines (e. Section 1. 44]. peaks in CV) that change characteristically with the experimental conditions. Cyclic voltammetry allows this by inspection of the peak potential f b difference Ep = Ep − Ep . determination of the other parameters is more complex. it is best to avoid an iR drop by decreasing i [decreasing c or A (ultramicroelectrodes. Global analysis of experimental and theoretical data is applied by comparing entire curves.2. • Presence of reagents: Formation of intermediates may be proven by their reaction with intentionally added reagents.

the voltammetric signals merge (dashed line). Transfer of several electrons yields n > 1 from the above procedures.1 0.5 0.2 0.9 80 60 40 20 0 −20 −40 −60 −80 −0.5 0. the results may differ from the CV or potential step techniques.5 in organic electrode reactions. dash-dotted and long-dashed to solid curve.16 1 Methods to Investigate Mechanisms of Electroorganic Reactions 40 30 20 10 0 −10 −20 −30 −0. but clearly this is only a rough approximation. and for dendrimers with a large number of Current.7 0. (a) effect of quasi-reversibility (ks decreases from solid to dashed line). E [V] Fig. 9 Typical cyclic voltammograms of an EC reaction system. in the latter case. Often α 40 30 20 10 0 −10 −20 −30 −0.1 0. i • 106 [A] Current.6 0. Kinetic information for Eqr reactions is not available from techniques that work in the diffusion-controlled regime.5 0.7 0. radical ions are produced. a combination of equations (7) and either (3) or (4) yields n [51].6 0. i • 106 [A] (a) Fig. but CV additionally shows the relative thermodynamics and depending on the individual E 0 values. Note. E [V] (b) Potential. two separated peak couples occur (dash-dotted line).4 0.4 0.0 0. various shapes of i/E curves are obtained (Figure 8b). decreases from dash-dotted through dashed to solid line. rate of follow-up reaction increases from short-dashed through dotted.0 0. equation (7).4).1 0. However. On the other hand.4. E [V] Typical cyclic voltammograms of pure electron transfer reactions.8 0. Because of the longer timescale as compared to transient methods. i • 106 [A] Potential. Often. The transfer coefficient is also accessible from cyclic voltammograms [53]. 53].4 0.3 0. Alternatively.3 0. Further. again. which can be investigated by ESR spectroelectrochemistry (Section 1.0 0. potential inversion occurs). CV allows determination of ks from the dependence of Ep on v [50.3 0. that n must be an integer value. if E 0 decreases below ≈100 mV.2 0. interesting cases are encountered in ‘‘inverted potential’’ [54] situations (solid line in Figure 8b.2 0. E0 .1 0.6 0. 8 Potential.8 0. starting with stable organic molecules.7 is assumed to be 0.1 0. 52. . Exhaustive electrolyses also give n and allow product generation.9 Current.1 0. (b) effect of relative values of formal potentials in an Er Er reaction (difference of formal potentials. If the two E 0 are sufficiently different ( E 0 > 100 mV). second ET thermodynamically easier than the first one).

the chemical reaction of B leads to the oxidized form of the second redox couple B (and not the reduced one as in the earlier case) and a second chemical transformation from A leads back to A [reaction (14)].g.3 How to Gain Access to Kinetics. 10 Typical cyclic voltammograms of ECE reaction systems.3. E [V] .1.5 0. A plot of i vs. for an oxidation step.3 0. while at slower v all product has reacted and the reverse peak disappears. Figure 10 shows some cyclic voltammograms.6 0. rate of C-step increases from dash-dotted through dashed and dotted to solid curve. Several variants are discussed in the literature [18.3. 57]. Follow-up Reactions Irreversible follow-up reactions (most simple case: EC mechanism) decrease the concentration of the primary redox product. 59]. t −1/2 switches from a straight line for n = 1 at small t to the one for n = 2 at large t.2 0. In chronoamperometry. which undergo ET at approximately the same potential [55]. In such cases. and Mechanisms of Electroorganic Reactions 17 redox-active units. A governing factor is k/a (k = rate constant of C-step.0 0. Also.10. Ep and ip depend on k/a [28]. Again SET steps −− − A + B −− −A + B (14) −− − −− − A −− − B − − C −− − D −→ −e− k −e− (12) can be involved. extension to reduction is obvious). the peak current ratio in CV is evaluated as a function of v (and Eλ ) in order to calculate k [49].9 Fig. 56. for a qualitative interpretation.2 (for an oxidation. 58]. 40 30 20 10 0 −10 −20 −30 −0. The most important are cases in which the product of the C-step is again electroactive [ECE mechanism. homogeneous ETs [disproportionation. Current.8 0. Thermodynamics. resulting in rather unusual voltammograms under certain conditions [18. Timescale variation in CV allows to modulate the importance of the Cstep: at fast v the chemical reaction will have no influence on the curves. This is again diagnosed in CV (Figure 9) and also in chronocoulometry. from n = 1 to n = 2). we arrive at a square scheme (Figure 11). Reaction (12)]: 1. The height of the second peak depends on the rate of the C-step. Thus. If. which forms the basis for many important redox systems [18. the formation of a redox-active product leads to an increase in the apparent n during the experiment (e. a = nF v/RT ). or lead to effects approaching those of the irreversible case [28].1 0.7 0. Reaction (13)] have also to be considered: −− − B + C−− −A + D (13) where the equilibrium constant is related to the E 0 of the two heterogeneous ETs. i • 106 [A] Potential. Reversible follow-up reactions may just shift the entire voltammetric signals (fast equilibration) on the E axis.4 0.

if the k are small. Figure 12 shows some CE voltammograms.4 −0.1 0. .9 preequilibrium systems.1 0. On the other hand.1 −0. 61]. All material consumed by that ET will immediately be replenished through the equilibrium reaction. Both partners of the preequilibrium are not always electroactive (CE mechanism).1 0.3.6 0.6 0.3. 1.3. since for high i √ √ K π 1/2 iτ nFAc0 D (15) = 2 1+K 0 (with total concentration c0 = cA + 0 ) [62]. If the k are large (reaction at equilibrium). −→ This mechanistic motif is found in mediated electrode reactions [65] or in sensor applications [66].0 0. Furthermore.4 −− − starting compound: A −− − B − − A. 64]. i • 106 [A] Potential.9 Fig. thus allowing determination of K. kinetics −0. chronopotentiometry was used for analyses[60. hydrodynamic cA techniques were also employed [63.18 1 Methods to Investigate Mechanisms of Electroorganic Reactions ± e− A B Fig. A′ ± e− B′ Preequilibria to ETs The square scheme discussed above already includes a further common motif in electroorganic mechanisms: reaction −− − A−− −A forms a preequilibrium to both ETs in the scheme. Catalytic Reactions In some reactions the product of an ET at the electrode reacts back to the 1.3.4 0.4 voltammograms of −1. only that ET will occur. E [V] of preequilibrium become slower from dotted through dashed to solid curve. The response of such a system in CV depends particularly on the equilibrium constant K = [A]/[A ] and the rate constants kA→A and kA →A .2 0.3 Kinetics and thermodynamics will influence the exact appearance of the concentration profiles.6 1. In particular. which is thermodynamically easier (smaller E 0 ).7 Current. 12 Typical cyclic −1. two peaks will be observed with their relative heights proportional to the equilibrium concentrations of A and A . 11 The square scheme reaction mechanism. The reformation of ±e− k 1.3 0.5 0.

additional .1) is the reproduction of an electroanalytical experiment in the form of a set of mathematical equations and their solutions. 69]. 13 Current. If we decrease the size of the electrode to values roughly in the order of the size of diffusion layers.4 How to Gain Additional Information about Electroorganic Reaction Mechanisms 1. one needs a mechanistic hypothesis that in some programs is translated into the governing equations automatically [45. One solves the equations for given values of these parameters and compares the results to experimental curves in an iterative process. Thus. the main steps of the electrode process (see Section 1.3. mostly for the CV technique [7]. until a ‘‘best fit’’ is obtained. the rate constant k is accessible from [28. The equations express a physical model of the real experiment.1 Simulation A simulation (Volume 3.and (b) cyclic voltammogram of a catalytic system. usually on a digital computer [7].2 −100 (a) Fig.5 0. it is illustrating to see how variations in mechanism and/or parameters change the resulting curves.4 How to Gain Additional Information about Electroorganic Reaction Mechanisms 500 80 70 60 50 40 30 20 10 0 −10 −0.2. Automatic fitting is also available [45]. Various numerical techniques are employed.0 1.1.6 0. 1. simulation is an indispensable tool for both types of analyses described in Section 1.0 0.2 Ultramicroelectrodes In previous sections we have implicitly assumed that diffusion occurs perpendicular to the electrode surface (semi-infinite linear diffusion).1 0.2 0. 68. this assumption becomes invalid. For the elucidation of electrode reaction mechanisms. There are various parameters defining the reaction steps in detail. Now. rate constants or formal potentials. Chapter 3. It is of particular importance to follow the guidelines provided in Section 1.0 0. From the limiting CV current. For a simulation.4 0.1. i • 106 [A] 300 200 100 0 0.1) are included.7 19 Current.4. Alternatively.1 0. in chronoamperometry. i • 106 [A] 400 Time.8 1.2 0. i reaches a nonzero limiting value (Figure 13a). E [V] Typical (a) chronoampero. the electroactive A leads to an increase in current and a decrease of diffusional effects. while in CV the peak disappears in favor of an S-shaped i/E curve (Figure 13b). Thus.3.2 in comparing experiments and simulations.4. 67] √ (16) i = nFAc0 Dk 1. t [s] (b) Potential. and commercial programs are available.4 0.6 0. for example.3 0.

Figure 14) [71]. For organic reactions.4. or in changes of composition of a precipitate or film on the electrode. minimization of the iR drop is of practical value and highly nonpolar solvents (e. these changes are small (ng– µg) and special techniques are necessary for their exact determination. diffusional transport becomes stationary after short settling times. In scanning electrochemical microscopy (SECM [70]). the small size of UMEs is exploited to localize electrode processes in the µm scale.g. mass changes are coupled to the ET. which is important for the study of very fast chemical steps. and the enhanced mass transport leads to a decrease of reaction effects.20 1 Methods to Investigate Mechanisms of Electroorganic Reactions Function generator Potentio/galvanostat Computer. 1. A technique for such measurements is the electrochemical quartz crystal microbalance (EQCM. The resonance frequency f of the quartz crystal is proportional to mass changes m: f ∼ m. At usual timescales. Electrogravimetric experiments lead to a mechanistic understanding of polymer . On the other hand. Thus. benzene or hexane [8]) have been used with low or vanishing concentrations of supporting electrolyte. diffusion components parallel to the surface become important. the working electrode is part of a quartz crystal oscillator that is mounted on the wall of the electrochemical cell and exposed to the electrolyte. Recorder Oscillator Frequency counter R C W Electrolyte Fig. Usually. With base frequencies around 10 MHz.3 Electrogravimetry If the electrode process results in the deposition of some product at the electrode surface. UMEs decrease the effects of nonFaradaic currents and of the iR drop. It is common to call disk electrodes with radii ≤20 µm ‘‘ultramicroelectrodes’’ (UMEs) [8]. Here. 14 Quartz crystal with electrodes Set-up of an electrogravimetric experiment with an electrochemical quartz crystal microbalance. in voltammetry very high scan rates (v up to 106 Vs−1 ) become accessible. the determination of m in the ng range is possible. the current densities are increased.

94. 1268–1288. and extensions. Recl. 1997. J. 1..5 Conclusion This chapter discussed some of the more important electroanalytical techniques with particular emphasis on their . 129–143. 1969. Stojek.: A. B. J. Sav´ ant. giving access to formation and decay kinetics. O’M. Chem. 19. R. they do not provide an insight into the structure of intermediates.4. but other methods should also be applied if necessary. J. 6. Booman. • Temporal resolution records the intensity of a spectroscopic signal with t. 1963. Chim. 105. Bockris. Vol. e 269–271. 1999. this is advantageously accomplished (spectroelectrochemistry) [73]. Ciszkowska. W.-M. These techniques greatly help determine and understand the mechanistic course of electrode reactions in a qualitative and quantitative way. z 591–599. P.5 Conclusion 21 film formation on electrodes. 50. Angew. pp. as discussed in Section 1. cyclic voltammetry is probably the most often used of these techniques. are expected to gain additional importance in the future. Nonaqueous solvents for electrochemical use in Electroanalytical Chemistry (Ed. Chem. Pure Appl. 3. Ed. Comput. W. Besides briefly describing the methods themselves. 1993. 44. 1972. Various spectroscopies have been coupled with electrochemical experiments. R. 8. J. J. B. Chem. Soc. Int. Holbrook. Bard). C.1. the chapter provides examples for their application for some frequently encountered reaction mechanisms. New York. 839–843. Three types of spectroelectrochemical experiments are useful for mechanistic studies: • Spectral resolution records spectra at different potentials. Chem. 3. Chem. 263–350. Vol. Faraday Trans. Trav. 1973. 1993. Marcel Dekker. 1925. References 1. 79]. R. Schroeder.4 Spectroelectrochemistry Although the instrumental techniques described here give detailed mechanistic information. during a CV scan. Rubinstein). 57–134. Engl. 1996. Distinction between alternative mechanisms has been reported [81]. for example. Chem. Speiser. however. 35. L. • Spatial resolution [80] leads to information on the distribution of species within the diffusion layer. 10. 1–108. 4. use in electroorganic chemistry. combine electrochemical and spectroscopic methods. Nagy. Numerical simulation of electroanalytical experiments: recent advances in methodology in Electroanalytical Chemistry (Eds. Heinze. pp. M. In particular. K. among them ESR [74]. 2. Mann. Instrum. Z. as well as mass spectrometry [78. 1327–1349. Angew. J.4. Anal. 9. support the study of film morphology and the diffusional as well as the migrational transport into and within such films [72]. Acknowledgment The authors thank Kai Ludwig for technical assistance in preparing Figures 6 and 7. 2. I. Marcel Dekker. optical [75]. Podrouˇ ek. 1998. Bard. 5. New York. G.: A. Educ. and NMR spectroscopy [76. If we. Chem. 3183–3195. 7. Unwin. Electroanal. J. 1793–1809. Z. 77]. 69. This allows structural characterization of intermediates. Chem. 466. 32. J. 1.

50. 53. Chem. J.. D. T. B. Laviron. Eur. E. 1977. S. A. Faulkner. Electroanal. A. 11. Scand. 56. 1991. Nlate. C. 26. 102. J. G. 1–18. 99. R. Electrochemical Methods. 121. 15. Alden. 70. 458. Chemomet. 92. Heinze. 541–545. Rees. 3983–3990. R. Klocke. J. D. 34. Electroanal. 183–200. O. 41. Chem. 1976. 1996. 18. 1986. R. 313–319. A. 1000. D. 7442–7447. Speiser et al. L. 38. L. Prieto. G. Kissinger. Nicholson. 1966. 62. e 1994. Herman. 457–468. Rieker. Hu. Electroanal. Electroanal. Anson. Phys. 9668–9676. Parker.22 1 Methods to Investigate Mechanisms of Electroorganic Reactions 11. J. A. 1985. 14 813–14 818. Am. J. Compton. 739–751. 23. Chem. Oldham. J. D. V. Chem. B 1997. e Chem. 101. 1993. 54. Speiser.-M. B. 2000 6. A. Bontempelli. 20. Speiser. D. Chem. Compton. Abrantes. 1623–1630. 38. 1996. Rees. Bard. c Commun. Anal. Anal. 2544–2553.. J. 1982.. Angew. P. Faraday Discuss. 999. 2439–2446. a Electrochim. Anal. M. 27. 1966. New York. L. Chem. Ed. B34. Chem. R. 59. A. 53–116. 33. 1983. 1994. Soc. 1390–1397. Acta Chem. E. Anal. 10. 66. V. K. Anal. Prieto. 54–57. R. 1984. Maran. 1991. 24. 88. L. A. 206.. Shain. Draˇ ka. 1977. 324. Chem. Feldberg. 599–603. 37. P. M. V. J. 1493–1494. 2623–2626. 90. Chem. Fischer et al. 25. Anal. 1966. Bruckenstein. I. Wiley. S. 209–229. Kim. Marcoux. A. J. 43. R. 1998. A. J. W. 2nd ed. J. D. 72. Compton. Compton. Speiser. A. J. R. J. Z. 1981. 99. 57–72.. L. Antonello. Gonz´ lez. Parker. D. A. Res. 667–671. V. H. Soc. A. 3254–3259. B. J. W. 74. J. Transient Techniques in Electrochemistry. 370. Phys. 36. O. Dryfe et al. O’Brien. R. G. 108. V. Fischer. 1994. S. 2471–2474. Molina. J. J. Adv. P. F. Soc. Nicholson. 56. 31. S. E. J. 1983. Speiser. Electroanal. Chem. 129–133. P. H. J. 1406. Meunier-Prest. 16. J. R. 1869–1876. Chem. Zoski. 15–35. 69. Chem. Magno. Coles. 48. . Cooper et al. New York. G. Engl. Bard. 76. Faraday Trans. 1995. Chem. J. H. D. M. J. Inorg. P. J. 38. 19. 44. Molina et al. Chem. L. Sav´ ant. Angew. 21. Zhang. 12. Alden. T. Chem. B. 9741–9750. Vieil. L. J. 1979. Evans. Chem. J. Jeftic. 45. K. Chem. Britz. J. 17. H.. 60. pp. Chem. Chem. 36. New York. 29. 1993. R. G. B. C. B. Dobson et al. J. G. 10. Chem. Electroanalysis 1998.. J. Collect. Angew. 47. Phys. Electroanal. Matzeit. R. Phys. P. Electroanal. D. Phys. 1978. Phys. F. 126. 7096–7101. P. 1988. Int. Speiser. 4.. 2768–2774. Chem. Compton. Plenum Press. 309–352. K. Anal. Phys. B. 165–194. Chem. Sartor et al. J. Chem. S. Chem. e Chem. A. Soc. Chem. Chem. 24. Wellington. 3779–3782. 1996. 1970. 85. Scand. Chem. J. 37. Electroanal. A. Dryfe. 874–880. Tessier. P. 42. Malachesky. Sav´ ant. Sav´ ant. J. 44. Kissinger. Dietrich.. 30. Scharbert. D. Electroanal. 1995. 301. 40. 1972. 46. Beran. R. 396–404. Faraday Trans. Acta 1992. 297. 14. 368–416. R. E. Chem. 39. 55. N. 22. J. 98. Opekar. 2001. Phys. 58. M. 61–80. Evans. Chem. 141–155. 35. Chem. 1969. Anal. A. J. G. F. Introduction to analog instrumentation in Laboratory Techniques in Electroanalytical Chemistry (Eds. R. Electroanal. Chem. Electroanal.. E. Chem. Macdonald. Anal. 589A–600A. 1977. Eichhorn. R. 13. Hillman. Chem. Rieker. Ahlberg. J. Anal. S. 89. Chem. 45. B. J. Chem. J.. 243–249. 1996. Chem. Rudolph. 1666–1668. 1972. 57–67. Marcoux. 1999. 76. Fundamentals and Applications. J.-X. Heineman). B. 146. B 1998. 27–46. R. Chem. 52. Acc. Alden. Electroanal. B. Reddy. J. Speiser. J. 2nd ed. Marcel Dekker. 1–9. Acta 1999. E. Feldberg. Electroanalysis 1999. G. Nicholson. 41. 76. F. 3. 1972.: P. Cauquis. 1964 36. 3307–3317. Amatore. Ber. J. Unwin. Bieniasz. B. Yu. 1–17. 57. T. 71. 61. C.. Eichhorn. 49. J. Mahon et al. 1965. S. Chem. Chem. F. Acta Chem. 1990. Electron Transfer Chem.. N. M. 35.. 28. Czech. Gockeln et al. 1992. Chem. J. Rev.-M. M. Cooper. W. Ruiz. 1–105. 706–723. Feldman et al. F. 403. 1980. H. R. 221–232. 53. 1986. 51. A. J. 57. Evans. 1996 pp. S. 148.-S. Faulkner. G. A. J. 1997. Galvez. Chim. 256. 32.

pp. Y. Chem. A. e 1960. R. Chem. L. 1995. C. Chem.. 1992. 66. 1986. 1197–1200. Buttry. Y. 80. 70. Principles. R. Rev. Marcel Dekker. 3368–3376. 45–52. D. 1990. R. H. 117–124. J. Chem. Kayanuma. L. 69. 81. D. Popovich. Ward. Faustino et al. 92. 1995. Phys. R. pp. 79. 2000.: I. Wu. Pure Appl. Electrochem. Unwin. 70.: P. New York. Marcel Dekker. Ed. 70. Polarogr. D. Chem.-P. J. 74. Marcel Dekker. 693. Vianello. Hambitzer. J. Electroanal. Principles and applications of the electrochemical quartz crystal microbalance in Physical Electrochemistry (Ed. A. 3620–3624. 406. Regino. 406. Chem. Deputy. Mirkin. K. 1998. 71. E. 901–960. A. 367–374. 1986. M. 69. B. 73. 33–43. Bieniasz. Electroanal. R. I. 1996. Heineman. W. 62. Chem. A. Methods. Fan. Guti´ rrez de la e Fe. P. H. J. S. Rubinstein). Adv. C. Goldberg. Downing et al. Prenzler. S. Mincey. J. 1996.-C. 2. 293–338. 2771–2777. G. 133. Bieniasz. J. J. P.-R. W. Electroanal. 1395–1414. L. 1995. Rubinstein). pp. Monographs in Electroanalytical Chemistry and Electrochemistry. R. Chem. Chem. Engl. 397. Anal. Chem. Electroanal. M. Chem. 68. McKinney. Sav´ ant. S. 1986. New York. 2.: I.1. 209–242. 681–699. 50. M. 78. 1978. J. Kissinger. L. 516–521. 1997. Martin. Yokoyama. M. Lanny Ng. F. K. 58. 76. L. P. Electrochem. Bard. J. Commun. R. Angew. Chem. Brajter-Toth. E. S. Int. Angew. 1996. R. 98. 75. 65. 72. 1355–1379. Cheh. W. Stassen. 25. Anal. 77. Plieth. 1998. Heitbaum. M. McCreery.5 Conclusion 63. 64. Scanning electrochemical microscopy in Physical Electrochemistry.. Principles and techniques of electrochemical-electron paramagnetic resonance experiments in Laboratory Techniques in Electroanalytical Chemistry (Eds. 5067–5072. F. 390A–402A. Heineman). 447. Anal. Chem. T. 325–329. Steckhan. K. Anal. Wilson. Jan. T. 23 . 1998. Chem. Soc. McCreery. M. W. J. Ward. New York. D. 1990. M. D. D. 1385–1388. Bramley. 2nd ed. G.. 1986. J. Anal. and Applications (Ed. C. 67. I. 94.

.

. . .4 1. . . . . . . . . . . . . . . . .1 1. . . . . . . . .4 1. . . . . Preequilibria to ETs . . . . . . . . . . . . . . . . . . . . . .3 1. . . . . . . . . . . . . . . . . . . . . . .3. . . . . . . . . . .3 1. . . . Acknowledgment . . .2 1. . References . . . . . . . .2 1 Methods to Investigate Mechanisms of Electroorganic Reactions 1. . . . . . . . . . . . . . . . . . . . . . .1 1. . . . . . . . . . . .4 1. . . . . . . . . . . . . . . . . . . . . .5 Some Mechanistic Examples Pure ET Reactions . . . . . . Follow-up Reactions . . . Spectroelectrochemistry . Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 1. . . . . . . .3. .3. . . . . . . . . . . . Electrogravimetry . . . . . . . . .4. .3. . .4. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3. .3. . . . . . . . . . . .4. . . . . . . .3. . . . . . . . . . . . . . 15 15 17 18 18 How to Gain Additional Information about Electroorganic Reaction Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 19 19 20 21 21 21 21 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 1. . Catalytic Reactions . . . . . . . . . . .3. . . . . . . . . . . . . . . . . . . . . Ultramicroelectrodes . . . . . . . . . . . . . . . . .4. . . Conclusion . . . . . . . . . . . . . .3. . . . . . . .