Mercury, electrochemistry

The limited anodic potential range of mercury electrodes has precluded their utility for monitoring oxidizable compounds. Accordingly, solid electrodes with extended anodic potential windows have attracted considerable analytical interest. Of the many different solid materials that can be used as working electrodes, the most often used are carbon, platinum, and gold. Silver, nickel, and copper can also be used for specific applications. A monograph by Adams (17) is highly recommended for a detailed description of solid-electrode electrochemistry. 

The properties of anodic layers of HgS formed on mercury in sulfide solutions have been investigated in comparison with anodic sulfide layers of cadmium and bismuth. Also, the electrochemistry of mercury electrodes in aqueous selenite solutions has been studied (see Sect. 3.2.1). The problem with the presence of several cathodic stripping peaks for HgSe in acidic Se(IV) solutions has been addressed using various voltammetric techniques at a hanging-mercury-drop electrode [119]. 

This equation was hrst obtained by Gabriel Lippmann in 1875. The Lippmann equation is of basic importance for electrochemistry. It shows that surface charge can be calculated thermodynamically from data obtained when measuring ESE. The values of ESE can be measured with high accuracy on liquid metals [e.g., on mercury (tf= -39°C)] and on certain alloys of mercury, gallium, and other metals that are liquid at room temperature. 

Studies in the field of electrochemical kinetics were enhanced considerably with the development of the dropping mercury electrode introduced in 1923 by Jaroslav Heyrovsky (1890-1967 Nobel prize, 1959). This electrode not only had an ideally renewable and reproducible surface but also allowed for the first time a quantitative assessment of diffusion processes near the electrode s surface and so an unambiguous distinction between the influence of diffusion and kinetic factors on the reaction rate. At this period a great number of efectrochemical investigations were performed at the dropping mercury efectrode or at stationary mercury electrodes, often at the expense of other types of electrodes (the mercury boom in electrochemistry). 

Zinc dithiocarbamates have been used for many years as antioxidants/antiabrasives in motor oils and as vulcanization accelerators in rubber. The crystal structure of bis[A, A-di- -propyldithio-carbamato]zinc shows identical coordination of the two zinc atoms by five sulfur donors in a trigonal-bipyramidal environment with a zinc-zinc distance of 3.786 A.5 5 The electrochemistry of a range of dialkylthiocarbamate zinc complexes was studied at platinum and mercury electrodes. An exchange reaction was observed with mercury of the electrode.556 Different structural types have been identified by variation of the nitrogen donor in the pyridine and N,N,N, N -tetra-methylenediamine adducts of bis[7V,7V-di- .vo-propyldithiocarbamato]zinc. The pyridine shows a 1 1 complex and the TMEDA gives an unusual bridging coordination mode.557 The anionic complexes of zinc tris( V, V-dialkyldithiocarbamates) can be synthesized and have been spectroscopically characterized.558... 

Nitration of the surface of polypyrrole and the subsequent reduction of the nitrate groups has been reported [244] and Bidan et al. [306, 307] have investigated the electrochemistry of a number of polymers based on pyrroles with /V-substituents which are themselves electrochemically active. Polypyrrole has also been successfully deposited onto polymeric films of ruthenium complexes [387], and has been used as an electrode for the deposition and stripping of mercury [388], As with most conducting polymers, several papers have also appeared on the use of polypyrrole in battery systems (e.g. [327, 389] and Ref. therein). 

Figure 2.1 (a) A schematic representation of the apparatus employed in an electrocapillarity experiment, (b) A schematic representation of the mercury /electrolyte interface in an electro-capillarity experiment. The height of the mercury column, of mass m and density p. is h, the radius of the capillary is r, and the contact angle between the mercury and the capillary wall is 0. (c) A simplified schematic representation of the potential distribution across the metal/ electrolyte interface and across the platinum/electrolyte interface of an NHE reference electrode, (d) A plot of the surface tension of a mercury drop electrode in contact with I M HCI as a function of potential. The surface charge density, pM, on the mercury at any potential can be obtained as the slope of the curve at that potential. After Modern Electrochemistry, J O M. 

It would seem, at first glance, that the place of electrocapillarity ties in the history of electrochemistry rather than its future, since its application appears limited only to the mercury/electrolyte interface. However, the work of Sato and colleagues (1986, 1987, 1991) has very definitely placed the technique, or at least a development of it, very firmly at the frontiers again. 

Up until the mid-1940s, most physical electrochemistry was based around the dropping mercury electrode. However, in 1942, Levich showed that rotating a disc-shaped electrode in a liquid renders it uniformly accessible to diffusion, yet the hydrodynamics of the liquid flow are soluble and the kinetic equations relatively simple. In addition, in contrast to the case of a stationary planar electrode, the current at an RDE rapidly attains a steady-state value. 

D.T. Sawyer and J.L. Roberts, Electrochemistry of oxygen and superoxide ion in dimethyl sulfoxide at platinum, gold, and mercury electrodes. J. Electroanal. Chem. 12, 90-101 (1966). 

The electrochemistry of Mb has been achieved by using mercury electrodes [93], methyl-viologen-modified gold electrodes [94], and ultraclean and hydrophilic indium... 

J.M. Sevilla, T. Pineda, A.J. Roman, R. Madueno, and M. Blazquez, The direct electrochemistry of cytochrome c at a hanging mercury drop electrode modified with 6-mercaptopurine. J. Electroanal. Chem. 451, 89-93 (1998). 

For liquid electrodes thermodynamics offers a precise way to determine the surface charge and the surface excesses of a species. This is one of the reasons why much of the early work in electrochemistry was performed on liquid electrodes, particularly on mercury - another reason is that it is easier to generate clean liquid surfaces than clean solid surfaces. With some caveats and modifications, thermodynamic relations can also be applied to solid surfaces. We will first consider the interface between a liquid electrode and an electrolyte solution, and turn to solid electrodes later. 

Stripping voltammetry or stripping analysis has a special place in electrochemistry because of its extensive application in trace metal analysis. Stripping voltammetry (SV) is a two-step process as shown schematically in Fig. 18b. 12. In the first step, the metal ion is reduced to metal on a mercury electrode (thin mercury film on glassy carbon or a HMDE) as amalgam. 

Researches carried out in electrochemistry on solid electrodes and especially on the mercury-water interface have made a significant contribution to an understanding of interfacial phenomena. Although the electrode-water interfaces are typically... 

Electrochemistry of Zinc, Cadmium, Lead, Gold, Silver, Mercury, and Copper... 

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