Introduction to Voltammetric Analysis: Theory and Practice

Preface

This text is a translation of the German text Polarographie und Voltammetrie: Grundlagen und Analytische Praxis (Springer 2001) by Günter Henze. This English language version, written concurrently with the German version, is a cooperative effort by the two authors incorporating essentially the same material as in the German text but presenting it in an alternative order.

The group of analytical techniques that are included within the term voltammetry are arguably the most versatile of all analytical techniques. They may be used to determine simple metal ions, complex metal species, inorganic anions, and a wide range of organic compounds at concentrations ranging over nine orders of magnitude from 10–2 mol L–1 (g L–1) down to the 10-11 mol L–1 (ng L–1) region with recent developments emphasising analyses in the lower concentration ranges. Samples from a variety of sources—marine, potable, surface and waste waters, plant and animal tissue, body fluids, pharmaceuticals, foodstuffs, soils, agricultural products and a range of industrial products—may be analysed using voltammetric methods. Voltammetric techniques are of particular value to those involved in environmental studies—particularly in studies of metal speciation and of pollutants and their metabolites, clinical analyses, and drug evaluation and metabolism studies. Furthermore, the equipment required for voltammetry is simple and relatively inexpensive—in many cases being an order of magnitude lower in cost than spectrophotometric equipment.

Despite the many advantages of voltammetric techniques, the authors believe that they are under-represented in many analytical laboratories. This is probably due to two factors—the lack, until recently, of fully automated equipment and the limited coverage of electrochemistry, particularly polarography and voltammetry, in many undergraduate courses and general analytical chemistry texts. This text was written in order to try and overcome this latter deficiency. It is aimed at students in final year undergraduate courses and those beginning research programs which require the student to have a knowledge of voltammetric techniques. The text has also been written for graduates working in industrial and commercial analytical laboratories who have little or no experience of voltammetric methods and who wish to extend their professional knowledge and expertise.

The authors consider that good practice in analytical chemistry is based on a sound understanding of the physical and chemical principles underlying the techniques used and so present the theoretical basis of polarography and voltammetry before covering the practical aspects and applications. In chapter 1, the basic electrochemical concepts relevant to an understanding of polarography and voltammetry are introduced. In chapter 2, the underlying theory of the various voltammetric techniques is presented. A detailed account of the original technique, direct current polarography discovered in Prague by Heyrovsky in 1923 and put on a sound theoretical basis by Ilkovic ten years later, is presented first. The various modifications made to this technique in order to improve its sensitivity and selectivity and decrease the time required for a measurement are then discussed. Throughout, a semi-quantitative approach is adopted in presenting the theory in which the mathematical relationships between the relevant physical quantities and the analyte concentration are introduced for understanding the technique but with the derivation of the equations being omitted.

In chapter 3, the sensitive stripping voltammetric techniques are discussed. Then follows a chapter dealing with the practice of voltammetric analyses. Sample pre-treatment and equipment including recent developments in electrode materials and construction are presented. In chapter 5, voltammetric and amperometric flow-through detectors are described. These detectors, which commonly have volumes in the μL range, are the key component for the development of miniaturised and automated microprocessor controlled voltammetric equipment and procedures. Furthermore, the combination of chromatographic separation techniques with flow-through voltammetric or amperometric detectors, results in powerful analytical procedures which are very sensitive and selective and which can be performed rapidly.

In the remainder of the book applications of the various voltammetric methods are presented. An outline of the voltammetric behaviour of the elements, interspersed with details of 15 applications to the determination of inorganic species in a variety of samples is the subject of chapter 6. In chapter 7, the voltammetry of organic functional groups is summarised and includes a selection of 12 applications of voltammetry to the determination of organic compounds. A series of appendices which list the important features of a selection of some 300 applications of voltammetry and polarography to the determination of inorganic and organic species in a wide range of samples concludes the book.

The authors wish to thank Metrohm Ltd and their staff in Switzerland and Australia, especially Dipl.Ing. Uwe Loyall, Product Manager for voltammetric equipment, Herisau, Switzerland.

1

Introduction

1.1 DEFINITION

The term voltammetry is applied to that group of electroanalytical techniques in which the current (ampere) that flows through an electrochemical cell is measured as the potential (volt) applied to the electrodes in the cell is varied. The term, first used by Kolthoff in 1940 [1], is derived from the units of the electrical parameters measured—volt-am (pere)-metry. It is important at this point to distinguish between the terms voltammetry spelt with ‘mm’ and voltametry spelt with only one ‘m’. The term voltametry has been used to describe the technique generally known as ‘controlled current potentiometric titration’.

The essential difference between voltammetric and other potentiodynamic techniques, such as constant current coulometry, is that in voltammetry an electrode with a small surface area (< 10–5 m²) is used to monitor the current produced by the species in solution reacting at this electrode in response to the potential applied to it. Because the electrode used in voltammetry is so small, the amount of material reacting at the electrode can be ignored. This is in contrast to the case in coulometry where large area electrodes are used so that all of a species in the cell may be oxidised or reduced.

When mercury, flowing through a fine capillary so that it emerges as droplets, is used as the small electrode in a voltammetric cell the technique has the special name polarography. This name is derived from the fact that the electrode can be polarised. An electrode is said to be polarised when no direct current flows across its interface with the solution even though there is a potential difference across this interface. In his definitive work published in 1922 [2] on ‘Electrolysis with a dropping mercury electrode’, Jaroslav Heyrovsky referred to this phenomenon and called the recorded current-potential polarisation curves polarograms.

The recommendation of IUPAC [3] is that voltammetry is the general term to be used when current potential relationships are being investigated and that only when a flowing conducting liquid electrode (such as a dropping mercury electrode) is used as the working electrode should the term polarography be used. Polarography, the original technique, is thus a special case of voltammetry.

1.2 THE CELL

The electrochemical cell used in voltammetry is a multi-phase system in which electrical energy is used to bring about a chemical change (electrolysis) in species in the cell. In its simplest form, such a cell consists of two electronic conductors called electrodes immersed in an electrolytic conductor (ionic solution) containing the substance of analytical interest called the analyte. This ionic solution completes the electrical circuit. It is the processes which occur at the solution-electrode interface involving the analyte and the factors that influence these interfacial processes that are exploited in electro-analytical chemistry. The application of a voltage or a current from an external source to the electrodes produces an electrical response from the analyte in the cell solution. The nature and magnitude of this response may be used to both identify and quantify the analyte.

The small electrode used to monitor the response of the analyte is known as the working electrode (WE). Even though only a negligible amount of material is involved in the processes occurring at the working electrode, its small size ensures that a high current density develops at its surface. Consequently, it is the processes which occur at this small electrode that control the current flow through the cell.

The small current-controlling WE may be constructed from a wide variety of conducting materials. The more common materials used include various forms of graphite and metals such as mercury, gold or platinum. These electrodes may be stationary, rotating or, in the case of mercury, flowing with respect to the cell solution. They are usually named after the material from which they are made and in some cases after other physical characteristics. For example, the dropping mercury electrode or DME; the mercury thin film electrode or MTFE; the hanging mercury drop electrode or HMDE; the glassy carbon electrode or GCE; the carbon paste electrode or CPE; the rotating platinum electrode or RPE; a chemically modified electrode or CME; and so on.

The second electrode in the simple cell, called a counter electrode (CE), serves two purposes. It is used to control the potential applied to the working electrode and to complete the circuit for carrying the current generated by the processes occurring at the WE. In the former role it must act as a reference electrode (RE). The ideal reference electrode must be a completely depolarisable electrode, i.e. it must be able to maintain a constant potential at its interface with the cell solution irrespective of any current that may flow across this interface. This can only be achieved if the reaction that controls the potential of this electrode is very fast and if there are no significant changes in the ion concentration profile in the vicinity of the interface—conditions that cannot be realised in practice unless the current that flows through the cell is extremely small and the composition of the cell solution does not change significantly from sample to sample. In the simple two-electrode cell the counter electrode must be much larger in area than the working electrode so that (i) the current density at its surface is so small that the electrode processes occurring at the CE do not affect the current signal generated at the WE in any significant way, and (ii) the flow of current through the cell as a result of the processes at the small WE has a minimal effect on the concentration profile at the CE surface so that its function as a reference electrode is not seriously impaired.

A simple arrangement for measuring the current that flows through a two-electrode cell as the voltage applied to the electrodes is varied is shown in Figure 1.1. Accurate measurements are only possible with this basic set-up when no voltage drop occurs in the cell and, as indicated above, the counter electrode is maintained in a constant-composition solution. The solution in the cell will have a resistance to the flow of current and as a consequence there will be a potential drop across the cell due to the current flow generated by the electrode process. Although this may be minimised by adding a high concentration of a supporting electrolyte (SE) to the cell solution it can never be eliminated. The voltage applied to the cell, Vapp, then is given by:

Figure 1.1    Two-electrode arrangement for measuring current-potential curves.

Since the absolute values of single electrode potentials cannot be measured, it is normal to refer all working electrode potentials to that of the reference electrode so that equation 1.1a becomes:

It is only under zero current conditions when no reaction is occurring at the working electrode that the voltage applied to the two-electrode cell is identical with the sum of the potential drops at the electrode interfaces. Since in a real measurement situation a current flows through the cell and V differs from the sum of the two electrode potentials by icell R—the so-called ‘iR drop’—it is preferable to refer to the plot of icell against Vapp obtained from a two-electrode cell as a current-voltage curve. A very simple experimental arrangement for the two-electrode system is to use the mercury collecting in the bottom of the cell as the counter electrode (i.e. a mercury pool electrode or MPE). However, as the cell solution composition varies so will the potential of the MPE. For more precise control of EWE it is necessary to use as a reference electrode an electrode that can maintain a more constant potential than the mercury pool electrode.

Figure 1.2    (a) Schematic arrangement for electrolysis with the dropping mercury electrode, (b) A simple practical apparatus [4].

In modern measuring systems the current carrying role of the counter electrode is separated from its potential control role by introducing a third electrode, the auxiliary electrode, AE, to the cell to complete the current carrying circuit. The area of this auxiliary electrode must be large compared to that of the working electrode for the reason (i) given above. The addition of the auxiliary electrode means that the counter electrode now is used only to control the potential of the working electrode and so becomes a true reference electrode. Since no current flows through the potential controlling circuit, the size of the reference electrode can be reduced and a conducting salt bridge can be placed between the variable composition cell solution and the reference electrode so that the composition of its solution will remain constant. The increase in resistance resulting from these changes does not affect the potential control of the working electrode. Two electrodes which are commonly used as reference electrodes for the precise control of the working electrode potential in aqueous media are the silver-silver chloride electrode in a solution of fixed chloride concentration and the saturated calomel electrode or SCE (mercury-mercurous chloride electrode in a saturated KCl solution). These electrodes are robust, easily constructed and maintain a constant potential over long periods of time. The three-electrode system will be discussed in more detail in chapter 4.

1.3 ELECTRODE PROCESSES

The term electrode process includes all phenomena which, as a result of applying a voltage to an electrode, lead to a current flow through that electrode. The course of an electrode process is greatly influenced by the nature of the phase boundary of the working electrode and its associated electrical double layer (§ 1.4.3). The importance of this region cannot be over-emphasised since the potential applied to the cell exists only across the double layers of the working and reference electrodes when there is no current flow through the cell; there being no potential drop across the cell solution under zero current conditions. In cells with supporting electrolytes the double layers are only a few nanometers thick yet all the electrochemical reactions occur there.

Most voltammetric and polarographic analyses utilise electrode processes in which electrons or ions are exchanged between the two phases. As a result of this the analyte will be either oxidised or reduced depending on the potential of the WE. Such an electrode process is referred to as a charge transfer reaction and produces a flow of charge, that is a current, through the electrode. This is summarised in equation 1.2:

and illustrated in Figure 1.3. A current flow that results from the oxidation or reduction of a substance is known as a faradak current, iF and its magnitude depends on the concentration profile of that substance in the region of the electrode surface. This profile depends on the concentration of the substance in the cell solution and on the kinetics of all steps in the associated electrode process. If the profile is controlled by the diffusion of the analyte to the electrode, the faradaic current is known as a diffusion current, if controlled by the kinetics of a step in the electrode process, as a kinetic current, and if controlled by a catalytic process, as a catalytic current.

Figure 1.3    Schematic representation of the electrode reaction (for a reduction) as an electron exchange at the electrode–solution boundary.

As a result of the electrode process, the concentration of an analyte at the electrode surface drops until it reaches an equilibrium value determined by the potential of the working electrode and the standard electrode potential, E°ox/red, of the charge transfer reaction (equation 1.2). Once equilibrium is reached it might be expected that the current would fall to zero. But this is not observed. It is found that the charge transfer reaction can be maintained even in a stationary solution. Hence the decrease in concentration of the analyte at the electrode surface due to the electrode reaction must be countered by supplementation of the analyte from the bulk solution in the cell’. In addition, any soluble electrode reaction products must be moving out into the bulk solution. This movement of material to and from the electrode surface may be achieved by a number of mechanisms.

The analyte in the test (cell) solution may be transported to the electrode surface by convection. This is facilitated by movement of the solution relative to the electrode, for example by stirring or by the action of the mercury dropping from the capillary of the DME.

The most important process for transporting molecules through the thin layer of solution (10–100 μm) immediately in contact with the electrode surface is diffusion. This is the case for both the transport of analyte to the electrode surface and the transport of the electrode reaction products away from the electrode surface into the bulk of the solution. Nernst called this important region adjacent to the electrode surface the diffusion layer (Figure 1.3 and § 1.4).

Another mechanism by which ionic analytes may be transported in a cell arises when there is a current flow through the cell. The positive ions move towards the working electrode when it is negatively charged and the negative ions move in the opposite direction. This process is known as migration and leads to the migration current, im. All ions present in the cell solution contribute to the migration current in proportion to their charge, concentration and mobility. Because the concentration of the supporting electrolyte is usually more than one thousand times that of the analyte, the contribution of the analyte itself to the migration current can be neglected. In effect, in addition to reducing the cell resistance, the supporting electrolyte carries the current through the cell solution although it is not involved in the current-determining electrode process at the working electrode.

Other processes which may affect the magnitude of the current at the working electrode include: adsorption onto the working electrode of the analyte, its reaction products or other surface active materials in solution; the de-solvation of solvated species; the formation of an insoluble electrode reaction product; reactions with the electrode material (insoluble salt formation); and chemical reactions involving the analyte prior to the charge transfer reaction or its immediate reduction-oxidation products. In order to fully understand the electrode process, both mechanistic and kinetic information about all the individual steps are required.

An important factor which influences the efficiency of a particular voltammetric analysis (limit of detection, sensitivity and/or resolution of adjacent current signals) is the degree of reversibility of the electrode process. The reversibility of an electrode process will depend on the kinetics and mechanism of the various steps in that process. An electrode process may be irreversible because of a slow charge transfer step, a slow chemical step, a slow adsorption step or a thermody-namically non-equivalent pathway for the reverse electrode process. If the charge transfer step is slow and rate determining the process is electrochemically irreversible, if a chemical step is rate determining then the electrode process is chemically irreversible.

However the experimentally observed degree of reversibility of an electrode process not only depends on the kinetics of the electrode process itself, but also on the particular voltammetric technique being used. The various voltammetric techniques differ in the dynamics of the potential applied to the cell and in their measurement rates (time between individual current measurements). Each technique has a characteristic time as has each electrode process. If we identify the half-life of an electrode process with its characteristic time, then if this is short (a fast reaction) compared to the experimental measurement interval equilibrium will be attained well within this time interval and the process will be seen to be reversible by this technique. On the other hand, if the half-life of the process is long on the experimental time scale, it may have little or no apparent effect on the measured response. For example, the characteristic time of a direct current polarographic experiment (§ 2.1) is related to the drop time of the DME, say about 1 s, whereas that of an alternating current polarographic experiment (§ 2.4) is related to the frequency of the superimposed a.c. voltage, say about 10 ms, so that an electrode reaction which appears reversible in d.c. polarography, may appear irreversible in a.c. polarograpy.

The rate at which the charge transfer step (oxidation or reduction of the analyte) occurs at a particular potential will determine whether or not an electrode process is electrochemically reversible. The time dependence of the electrode reaction may be estimated from the heterogeneous rate constants Kred or kox for the charge transfer step. For a reduction:

and for an oxidation:

Using equation 1.3 or 1.4, the rate of a particular charge transfer reaction can be calculated from a knowledge of its standard rate constant. In polarography, charge transfer reactions are considered to be reversible when k° > 0.1–1 cm s–2, as irreversible when k° < 10–1–10–5 cm s–1 and as quasi-reversible for intermediate values of k°. However as indicated above, the degree of reversibility also depends on the particular voltammetric technique being used. The influence of the reversibility of the charge transfer reaction on the voltammetric response is dealt with in chapter 2.

1.4 VOLTAMMETRIC CURRENTS

1.4.1 Diffusion currents

The current that flows through the working electrode depends upon the kinetics of the overall electrode process and its magnitude will depend on the rate of the slowest individual step in that process. The rate of the charge transfer step is potential dependent (equations 1.3 and 1.4) so that if the working electrode potential is such that this step is fast then diffusion of the analyte from the bulk solution to the electrode surface across the diffusion layer is the slow step which controls the current flow. This is the situation most often encountered in analytical voltammetry, and the currents that flow under these conditions are called diffusion currents. The diffusion current depends on the limiting concentration gradient of the analyte at the electrode surface (dc/dx)x=0, which is related to the difference in analyte concentration at the surface of the electrode, cs, and in the bulk solution, ca, and the thickness of the diffusion layer, δ.

Two cases will be considered, one where the diffusion layer has a constant thickness and the other where the thickness of the diffusion layer increases with time but the concentration of the analyte at the surface is constant and effectively zero.

The first case occurs when the solution is moving at a constant velocity relative to the electrode, for example when using a rotating disc electrode or when the solution is stirred at a constant speed or flows past the electrode at a constant rate. The thin layer of solution close to the electrode surface remains stationary with respect to the electrode surface. According to Nernst it is in this still layer, which extends a distance, δ, into the solution, that the diffusion layer forms. On the solution side of this layer the concentration of the analyte is maintained at the bulk value, ca, by convection, while the concentration at the electrode surface, cs, is determined by the potential of the electrode. The situation is illustrated in Figure 1.4a. Nernst considered the concentration gradient in the diffusion layer to be linear and, since δ is constant, the gradient will increase as the magnitude of the working electrode potential increases (becomes more negative in the case of a reduction and more positive in the case of an oxidation).

Figure 1.4    Concentration profiles in the diffusion layer, (a) Constant layer thickness at different potentials: E1, < E2 < E3 for an oxidation and E1, > E2 > E3 for a reduction, (b) Layer thickness increasing with time, t at a constant potential (E3). ca – bulk solution concentration of analyte; csn – electrode surface concentrations at different potentials En; δn – diffusion layer thicknesses at different times tn.

An expression for the diffusion controlled charge transfer current can be obtained from the general faradaic relationship for current as a function of the number of moles reacted, namely:

and Fick’s first law of diffusion:

Combining equations 1.5 and 1.6 and substituting {–(ca – cs)/δ} for dc/dx in accordance with Nernst’s assumption, the following relationship is obtained for the current at any time:

The concentration gradient increases with voltage as