Dropping mercury electrode DME

Stripping voltammetry involves the pre-concentration of the analyte species at the electrode surface prior to the voltannnetric scan. The pre-concentration step is carried out under fixed potential control for a predetennined time, where the species of interest is accumulated at the surface of the working electrode at a rate dependent on the applied potential. The detemiination step leads to a current peak, the height and area of which is proportional to the concentration of the accumulated species and hence to the concentration in the bulk solution. The stripping step can involve a variety of potential wavefomis, from linear-potential scan to differential pulse or square-wave scan. Different types of stripping voltaimnetries exist, all of which coimnonly use mercury electrodes (dropping mercury electrodes (DMEs) or mercury film electrodes) [7, 17]. 

There are several types of mercury electrodes. Of these, the dropping mercury electrode (DME), the hanging mercury drop electrode (HMDE), and mercury film electrode (MFE) are the most frequently used. 

Copper(II) ions in the presence of chloride ions are reduced at the dropping mercury electrode (dme) in two steps, Cu(II) -> Cu(I) and Cu(I) -> Cu(0) producing a double wave at -1-0.04 and 0.22 V versus sce half-wave potentials. In the presence of peroxydisulphate , when the chloride concentration is large enough, two waves are also observed the first limiting current corresponds to the reduction of the Cu(II) to Cu(I) plus reduction of a fraction of peroxydisulphate and the total diffusion current at a more negative potential is equal to the sum of the diffusion currents of reduction of Cu(II) to Cu(0) and of the peroxydisulphate. There is evidence that peroxydisulphate is not reduced at the potential of the first wave because of the adsorption of the copper(I) chloride complex at... 

In voltammetry as an analytical method based on measurement of the voltage-current curve we can distinguish between techniques with non-stationary and with stationary electrodes. Within the first group the technique at the dropping mercury electrode (dme), the so-called polarography, is by far the most important within the second group it is of particular significance to state whether and when the analyte is stirred. 

Fig. 5.19 Electrodes used in voltammetry. A—dropping mercury electrode (DME). R denotes the reservoir filled with mercury and connected by a plastic tube to the glass capillary at the tip of which the mercury drop is formed. B—ultramicroelectrode (UME). The actual electrode is the microdisk at the tip of a Wollaston wire (a material often used for UME) sealed in the glass tube...

Voltammetry is a part of the repertoire of dynamic electrochemical techniques for the study of redox (reduction-oxidation) reactions through current-voltage relationships. Experimentally, the current response (i, the signal) is obtained by the applied voltage (.E, the excitation) in a suitable electrochemical cell. Polarography is a special form of voltammetry where redox reactions are studied with a dropping mercury electrode (DME). Polarography was the first dynamic electrochemical technique developed by J. Heyrovsky in 1922. He was awarded the Nobel Prize in Chemistry for this discovery. 

The electrode potential obtained with linear-sweep polarography, for example, at a dropping-mercury electrode (DME), is different again and is called the halfwave potential, 1/2, which is also discussed in Chapter 6. 

Figure 6.6 shows a schematic diagram of the apparatus required as a working electrode for polarography. Such a set-up is almost universally called a dropping mercury electrode (DME), with the mercury drop being immersed in a cell that is essentially the same as that shown in Figure 6.1. 

Figure 6.6 Schematic representation of a typical dropping-mercury electrode (DME) for polarography, where the DME acts as a working electrode in a cell such as that shown in Figure 6.1. The platinum electrode at the top right of the diagram is needed to give an electrical connection. The rate of mercury flow is altered by adjusting by changing the height h.

Figure 6J3 Schematic representation of a Luggin capillary used for minimizing IR drop. Calculations of uncompensated solution resistance require a knowledge of the distance d between the reference tip of the capillary and the working electrode (depicted here as a dropping-mercury electrode (DME)).

The current at a dropping-mercury electrode (DME) is a function of potential, as described by the Heyrovsky-Ilkovic equation (equation (6.6)). At less extreme overpotentials, the current rises from zero to a maximum. The potential at which... 

Dropping mercury electrode (DME) Historically, a popular choice of working electrode in polarography. 

Hanging mercury-drop electrode (HMDE) A commonly employed working electrode in polarography. The HMDE is often preferred to the experimentally simpler dropping mercury electrode (DME) because resultant polarograms do not have a sawtoothed appearance and because accumulation (for stripping purposes) is readily achieved at its static surface. 

For many years, the study of the electrode—electrolyte interface and electrode kinetics was confined to the very reproducible mercury-aqueous system because of the availability of the dropping mercury electrode (DME) and development of polarography. Extensive leading work in this field was carried out by Heyrovsky, Frumkin, Grahame, and Randles. 

Moreover, it is difficult to find one s way in the overwhelming amount of literature on this subject because the major part of it is focussed on d.c. polarography and thus to the mass transfer problem at the dropping mercury electrode (DME). Neglecting the sphericity, the expansion of the drop has still to be accounted for in the diffusion equation for a species i. Equation (19b), which we have adopted thus far, should therefore be replaced by [11, 147]... 

In addition to solution resistance, electrodes may have appreciable resistance in themselves. The common example is the mercury in a dropping mercury electrode (DME) capillary. Such resistances are summed with solution resistances since they are in series and the treatment that follows is unchanged. 

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