Mercury redox reactions

Lalonde JD, Poulain AJ, Amyot M. 2002. The role of mercury redox reactions in snow on snow-to-air mercury transfer. Environ Sci Technol 36 174-178. 

Other Electrode Systems Based on the Mercury Redox Reaction... 

Mediation, and redox reactions in solution, 585 Medical dosage, 371 Mercury... 

FIGURE 11.22 When ammonia is added to a silver chloride precipitate, the precipitate dissolves. However, when ammonia is added to a precipitate of mercury(l) chloride, mercury metal and mercury(ll) ions are formed in a redox reaction and the mass turns gray. Left to right silver chloride in water, silver chloride in aqueous ammonia, mercury(l) chloride in water, and mercury(l) chloride in aqueous ammonia. 

When the area A of the eleetrode/solution interface with a redox system in the solution varies (e.g. when using a streaming mercury electrode), the double layer capacity which is proportional to A, varies too. The corresponding double layer eharging current has to be supplied at open eireuit eonditions by the Faradaic current of the redox reaction. The associated overpotential can be measured with respect to a reference electrode. By measuring the overpotential at different capaeitive eurrent densities (i.e. Faradaic current densities) the current density vs. eleetrode potential relationship can be determined, subsequently kinetic data can be obtained [65Del3]. (Data obtained with this method are labelled OC.)... 

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. 

Electron movement through the electrode. The movement of electrons through an electrode will usually be extremely fast since the material from which the vast majority of electrodes are made will have been chosen by the analyst precisely because of its superior electronic conductivity. Electrodes made of liquid mercury and of solid metals such as platinum, gold, silver or stainless steel, are all used for this reason. Accordingly, it is extremely unlikely that the rate-limiting process during a redox reaction will be movement of the electrons through the electrode. 

The theory for the reaction of an adsorbed redox couple (2.146) has been exemplified by experiments with methylene blue [92], and azobenzene [79], Both redox couples, methylene blue/leucomethylene, and azobenzene/hydrazobenzene adsorb strongly on the mercury electrode surface. The reduction of methlylene blue involves a very fast two-step redox reaction with a standard rate constants of 3000 s and 6000 s for the first and second step, respectively. Thus, for / < 50 Hz, the kinetic parameter for the first electron transfer is log(m) > 1.8, implying that the reaction appears reversible. Therefore, regardless of the adsorptive accumulation, the net response of methylene blue is a small peak, the peak current of which depends linearly on /J. Increasing the frequency above 50 Hz, the electrochemical... 

In some cases, hidden adsorption is responsible for the differences between electrode and purely chemical redox reactions. The aromatic derivatives of divalent sulfur on reduction at the mercury-dropping electrode do not show any adsorption waves within the corresponding polarogam. Thus, the reduction... 

Again, we deal with the simple redox reaction 0 + ne = R. In the present discussion we suppose that 0 is a metal ion and R is the corresponding metal soluble as an amalgam in a mercury electrode or present as the pure metal electrode. It is highly probable that 0 forms several complexes e.g. with the anions of the supporting electrolyte, additives like NH3, EDTA, etc. or OH" ions. For the sake of simplicity, we confine ourselves here to considering the equilibrium between hydrated 0 and only one complex... 

C. E. Ophardt, "Redox Demonstrations and Descriptive Chemistry Part I. Metals/ ]. Chem. Educ., Vol. 64,1987, 716. Redox reactions of iron(III) with thiosulfate, iron(II) with permanganate, and tin(II) with mercury(I) are used to show how an abbreviated table of standard reduction potentials is used to predict the products of these reactions from the relative positions of the oxidizing agents and reducing agents in the table. 

See other INORGANIC ACIDS, OXIDANTS, OXOHALOGEN ACIDS, REDOX REACTIONS 3993. Mercury(II) amide chloride... 

Figure 5.8 Cyclic voltammograms for the Os2+/3+ redox reaction within spontaneously adsorbed [Os(OMebpy)2(p3p)Cl]+ monolayers. From right to left, the electrode materials are platinum, gold, carbon and mercury. The scan rate is 50 Vs-1, with a surface coverage of 1.0 0.1 x 10-1° mol cm-2 the supporting electrolyte is aqueous 1.0 M NaC104. Reprinted with permission from R. J. Forster, P. J. Loughman and T. E. Keyes,/. Am. Chem. Soc., 122,11948 (2000). Copyright (2000) American Chemical Society...

Thus, the synthesis of triphenylscandium is a salt-elimination reaction (or metathesis) whilst the route for the lanthanide phenyls involves a redox reaction. The former has the problem of producing LiCl, which is often significantly soluble in organic solvents and contaminates the desired product, whilst the latter involves disposal of mercury waste, as well as handling toxic organomercury compounds. 

The electrochemical potential for redox reaction controls the situation where atoms of one element are available to be sorbed by a zeolite containing exchangeable cations of another element. Within the zeolite and even in the absence of water, aqueous reduction potentials are usually capable of deciding whether reaction will occur, with an error due to the difference between the zeolitic environment and aqueous solution of no more than 0.1 (or perhaps 0.2) V. Accordingly there is no question that alkali-metal vapors will reduce transition-metal ions within a zeolite, and that vapors of zinc, mercury, or sulfur will not reduce the cations of the alkali or alkaline-earth metals. 

In this reaction, mercury atoms are reduced, while oxygen atoms are oxidized. A single reaction in which an oxidation and a reduction happen is called an oxidation-reduction reaction or redox reaction. 

The zinc-carhon, alkaline-zinc, and mercury cells are classified as primary batteries. Primary batteries produce electric energy by means of redox reactions that are not easily reversed. 

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