Mercury complexes applications

Mass spectrometry (MS) in its various forms, and with various procedures for vaporization and ionization, contributes to the identification and characterization of complex species by their isotopomer pattern of the intact ions (usually cation) and by their fragmentation pattern. Upon ionization by the rough electron impact (El) the molecular peak often does not appear, in contrast to the more gentle field desorption (FD) or fast-atom bombardment (FAB) techniques. An even more gentle way is provided by the electrospray (ES) method, which allows all ionic species (optionally cationic or anionic) present in solution to be detected. Descriptions of ESMS and its application to selected problems are published 45-47 also a representative application of this method in a study of phosphine-mercury complexes in solution is reported.48... 

Organometallic complexes of Sn, Bi, Hg, Zn, Fe, and Co are all potent urethane catalysts, with Sn carboxylates being the most common. Hg catalysts have long induction periods that allow long open times. Hg catalysts also promote the isocyanate hydroxyl reaction much more strongly than the isocyanate water reaction. This allows their use in casting applications where pot life and bubble-free parts are critical. Bismuth catalysts are replacing mercury salts in numerous applications as the mercury complexes have come under environmental pressure. 

Tossell JA (1999) Theoretical studies of the formation of mercury complexes in solution and the dissolution and reaction of ciruiabar. Am Mineral 84 877-883 Tossell JA, Vaughan DJ (1992) Theoretical Geochemistry. Application of Quantum Mechanics in the Earth and Mineral Sciences. Oxford University Press... 

In an earlier paper Westoo pointed out that if methylmercury attached itself to a sulphur atom by reaction with a thiol or hydrogen sulphide then the non-volatile HgS compound produced would not be included in the determination. More recently he has developed a modification to this method described below, to render it applicable to a wider range of foodstuffs (egg-yolk and white, meat and liver) by binding interfering thiols in the benzene extract of the sample to mercuric ions added in excess or, by extracting the benzene extract with aqueous cysteine to form the cysteine-methyl mercury complex. 

Precipitation is often applied to the removal of most metals from wastewater including zinc, cadmium, chromium, copper, fluoride, lead, manganese, and mercury. Also, certain anionic species can be removed by precipitation, such as phosphate, sulfate, and fluoride. Note that in some cases, organic compounds may form organometallic complexes with metals, which could inhibit precipitation. Cyanide and other ions in the wastewater may also complex with metals, making treatment by precipitation less efficient. A cutaway view of a rapid sand filter that is most often used in a municipal treatment plant is illustrated in Figure 4. The design features of this filter have been relied upon for more than 60 years in municipal applications. 

In a first part, experimental methods for studying formation, properties, structures and bonding in complex compounds of cadmium and mercury are briefly surveyed, usually with hints to reviews of the respective field and to examples of recent applications. 

Hawthorne and co-workers have also produced a series of macrocyclic Lewis acid hosts called mercuracarborands (156, 157, and 158) (Fig. 84) with structures incorporating electron-withdrawing icosahedral carboranes and electrophilic mercury centers. They were synthesized by a kinetic halide ion template effect that afforded tetrameric cycles or cyclic trimers in the presence or absence of halide ion templates, respectively.163 These complexes, which can bind a variety of electron-rich guests, are ideal for catalytic and ion-sensing applications, as well as for the assembly of supramolecular architectures. 

Heavy metals are widely used as catalysts in the manufacture of anthraquinonoid dyes. Mercury is used when sulphonating anthraquinones and copper when reacting arylamines with bromoanthraquinones. Much effort has been devoted to minimising the trace metal content of such colorants and in effluents from dyemaking plants. Metal salts are used as reactants in dye synthesis, particularly in the ranges of premetallised acid, direct or reactive dyes, which usually contain copper, chromium, nickel or cobalt. These structures are described in detail in Chapter 5, where the implications in terms of environmental problems are also discussed. Certain basic dyes and stabilised azoic diazo components (Fast Salts) are marketed in the form of tetrachlorozincate complex salts. The environmental impact of the heavy metal salts used in dye application processes is dealt with in Volume 2. 

In classical polarographic techniques, a dropping mercury electrode is used. This is a complex device in which continuously produced small droplets of mercury are used as the active electrode in order to prevent poisoning of the electrode and to provide constant conditions throughout the analysis. For many applications, specifically designed electrodes are available which are simpler to use. 

Forrester Environmental Services, Inc., has developed a group of technologies for the stabilization of wastes containing heavy metals, such as lead, cadmium, arsenic, mercury, copper, zinc, and antimony. These technologies have been used in both industrial pollution prevention and remediation applications. One version of the technology involves the use of water-soluble phosphates and various complexing agents to produce a less soluble lead waste. This process results in a leach-resistant lead product. 

Concerning more general application of mercury electrode in the studies on com-plexation equilibria, one should mention the paper by Jaworski et al. [59], who have investigated oxidation of mercury microelectrode in solutions with thiocyanates without any background electrolyte added. In the experiments, normal pulse voltammetry and staircase voltammetry were used. The authors have developed a general procedure for the determination of the stability constants, based on the data taken from the voltammograms. They have applied it to the analysis of Hg(II)-SCN complexes. 

Analytical Applications In addition to the above-mentioned analytical aspects of the processes at Hg electrodes, in this section, we briefly review the papers focused on the subject of the affinity of various compounds to the mercury electrode surface, which allowed one to elaborate stripping techniques for the analysis of inorganic ions. Complexes of some metal ions with surface-active ligands were adsorptively accumulated at the mercury surface. After accumulation, the ions were determined, usually applying cathodic stripping voltammetry (CSV). Representative examples of such an analytical approach are summarized as follows. 

Using supporting electrolytes such as tetraalkylammonium salts, one may apply potentials as negative as -2.6 V vs. SCE in aqueous solutions, while in some nonaqueous systems even -3.0 V vs. SCE (aqueous) is accessible. Unfortunately, mercury electrodes have serious limitations in applications at positive potentials (with the exception of passivated mercury electrodes, which are described in Section VI), and this has led to extensive research in the development of solid metal and carbon electrodes. Oxidation of mercury occurs at approximately +0.4 V vs. SCE in solutions of perchlorates or nitrates, since these anions do not form insoluble salts or stable complexes with mercury cations. In all solutions containing anions that form such compounds, oxidation of the mercury proceeds at potentials less than +0.4 V vs. SCE. For example, in 0.1 M KC1 this occurs at +0.1 V, in 1.0 M KI at -0.3 V, and so on. 

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