Mercury Dropping Electrode

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]. 

Mercury electrodes (a) hanging mercury drop electrode (b) dropping mercury electrode (c) static mercury drop electrode. 

A form of voltammetry using a dropping mercury electrode or a static mercury drop electrode. 

In hydrodynamic voltammetry the solution is stirred either by using a magnetic stir bar or by rotating the electrode. Because the solution is stirred, a dropping mercury electrode cannot be used and is replaced with a solid electrode. Both linear potential scans or potential pulses can be applied. 

Dixon s Q-test statistical test for deciding if an outlier can be removed from a set of data. (p. 93) dropping mercury electrode an electrode in which successive drops of Hg form at the end of a capillary tube as a result of gravity, with each drop providing a fresh electrode surface, (p. 509)... 

Electrochemical reduction of iridium solutions in the presence azodye (acid chrome dark blue [ACDB]) on slowly dropping mercury electrode is accompanied by occurrence of additional peaks on background acetic-ammonium buffer solutions except for waves of reduction azodye. Potentials of these peaks are displaced to cathode region of the potential compared to the respective peaks of reduction of the azodye. The nature of reduction current in iridium solutions in the presence ACDB is diffusive with considerable adsorptive limitations. The method of voltamiuetric determination of iridium with ACDB has been developed (C 1-2 x 10 mol/L). 

Boujlel and Simonet used an electrochemical method to prepare a group of similar compounds, including compound ]5, shown in Eq. (3.41). In a typical case, benzil was reduced in DMF solution at the dropping mercury electrode in the presence of tetrabutylammonium iodide, used in this case as a supporting electrolyte rather than phase transfer catalyst. In the presence of diethylene glycol ditosylate, compound 15 (mp 77— 78°) was isolated in 10% yield. Using the same approach, acenaphthenedione was reduc-tively cyclized with triethylene glycol ditosylate to afford the product (mp 84—85°, 42% yield) shown in Eq. (3.42). 

Controlled-potential separation of many metals can be effected with the aid of the mercury cathode. This is because the optimum control potential and the most favourable solution conditions for a given separation can be deduced from polarograms recorded with the dropping mercury electrode see Chapter 16. 

The basic apparatus for polarographic analysis is depicted in Fig. 16.1. The dropping mercury electrode is here shown as the cathode (its most common function) it is sometimes referred to as the working or micro-electrode. The... 

The polarographic determination of metal ions such as Al3 + which are readily hydrolysed can present problems in aqueous solution, but these can often be overcome by the use of non-aqueous solvents. Typical non-aqueous solvents, with appropriate supporting electrolytes shown in parentheses, include acetic acid (CH3C02Na), acetonitrile (LiC104), dimethylformamide (tetrabutyl-ammonium perchlorate), methanol (KCN or KOH), and pyridine (tetraethyl-ammonium perchlorate), In these media a platinum micro-electrode is employed in place of the dropping mercury electrode. 

TECHNIQUE OF AMPEROMETRIG TITRATIONS WITH THE DROPPING MERCURY ELECTRODE... 

Both lead ion and dichromate ion yield a diffusion current at an applied potential to a dropping mercury electrode of —1.0 volt against the saturated calomel electrode (S.C.E.). Amperometric titration gives a V-shaped curve [Fig. 16.14 (C)]. The exercise described refers to the determination of lead in lead nitrate the application to the determination of lead in dilute aqueous solutions (10-3 — 10-4lVf) is self-evident. 

The titrations so far discussed in this chapter have been concerned with the use of a reference electrode (usually S.C.E.), in conjunction with a polarised electrode (dropping mercury electrode or rotating platinum micro-electrode). Titrations may also be performed in a uniformly stirred solution by using two small but similar platinum electrodes to which a small e.m.f. (1-100 millivolts) is applied the end point is usually shown by either the disappearance or the appearance of a current flowing between the two electrodes. For the method to be applicable the only requirement is that a reversible oxidation-reduction system be present either before or after the end point. 

Drop time in polarography, 597, 608 Dropping mercury electrode 608, 628 Dry ashing 114 Dry box lOl Drying reagents 99 comparative efficiencies of, (T) 99 Drying of precipitates 119 Duboscq colorimeter 656 Duplication method 701... 

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