Mercury-cadmium amalgams

The photochemical or thermal reaction between petfluoroalkyl iodides and mercury-cadmium amalgams has been used for the synthesis of perfluoro-alkylmercury compounds [150] Functionalized analogues have been prepared similarly via this route [151, 152] (equation 117), and the preparation of bis(tri-fluoromethyl)mercury has been described [153]... 

Ideally a standard cell is constmcted simply and is characterized by a high constancy of emf, a low temperature coefficient of emf, and an emf close to one volt. The Weston cell, which uses a standard cadmium sulfate electrolyte and electrodes of cadmium amalgam and a paste of mercury and mercurous sulfate, essentially meets these conditions. The voltage of the cell is 1.0183 V at 20°C. The a-c Josephson effect, which relates the frequency of a superconducting oscillator to the potential difference between two superconducting components, is used by NIST to maintain the unit of emf. The definition of the volt, however, remains as the Q/A derivation described. 

Batteries. Many batteries intended for household use contain mercury or mercury compounds. In the form of red mercuric oxide [21908-53-2] mercury is the cathode material in the mercury—cadmium, mercury—indium—bismuth, and mercury—zinc batteries. In all other mercury batteries, the mercury is amalgamated with the zinc [7440-66-6] anode to deter corrosion and inhibit hydrogen build-up that can cause cell mpture and fire. Discarded batteries represent a primary source of mercury for release into the environment. This industry has been under intense pressure to reduce the amounts of mercury in batteries. Although battery sales have increased greatly, the battery industry has aimounced that reduction in mercury content of batteries has been made and further reductions are expected (3). In fact, by 1992, the battery industry had lowered the mercury content of batteries to 0.025 wt % (3). Use of mercury in film pack batteries for instant cameras was reportedly discontinued in 1988 (3). 

The main advantage of Weston s cell was its insensitivity to temperature, and the emf of almost 1 V to be precise, 1.0183 V at 20 °C. It is usually constructed in an Id-shaped glass vessel. One arm contains a cadmium amalgam electrode beneath a paste of hydrated cadmium sulphate (3CdS04 5H20) cadmium sulphate and mercury sulphate. The other arm contains elemental mercury. Its schematic is Cd(Hg) CdS04(aq), Hg2S04 Hg. 

Figure 16.4 Cyclic voltammogram of 4.5 mM 2,3-dinitro-2,3-dimethylbutane in N,N-dimethylformamide/0.20 M Bu4NPF6 at a 25-pm-diameter mercury electrode. Curves experimental voltammograms after subtraction of background current. Points digital simulations. Potentials referred to cadmium reference electrode [cadmium amalgam/CdCl2 (sat d) in DMF]. [Reprinted with permission from W.J. Bowyer and D.H. Evans, J. Org. Chem. 53 5234 (1988). Copyright 1988 American Chemical Society.]...

An H shaped glass container has electrodes at the bottom of the lower arms connected to the external wires by sealed-in platinum wires. The negative electrode is of cadmium amalgam containing 12.5 % cadmium, while the positive electrode is formed by mercury with a layer of paste, which consists of mercurous sulphate, dispersed mercury and small crystals of cadmium sulphate. 

Weston normal element (cell) — Electrochemical -> standard cell showing a particularly stable and reproducible cell voltage. In the international Weston normal element a cadmium amalgam (cadmium content in the solid phase approx. 15 wt %, in the liquid phase approx. 5wt%, total average 12 to 12.5 wt%, the electrode potential depends only on the temperature, not on the mass ratio of liquid and solid phases) and a mercury electrode (half-cell) are combined according to... 

Perfluoroalkylmercury compounds have been prepared by reaction of perfluoroalkyl halides with cadmium amalgam or by reaction of fluoroalkenes with mercury(II) fluoride. Due to the high thermal stability of perfluoroalkylmercury compounds, they can be sublimed from concentrated sulfuric acid without decomposition and are of limited synthetic utility. These reagents have found use as difluorocarbene sources and do react with elemental sulfur at elevated temperatures to afford thioacid fluorides, di- and polysulfides, and thioketones. ... 

It is important to note that the mercury electrode of a commercial Weston cell is always marked positive while the cadmium amalgam electrode is marked negative,... 

Nitrates can also be determined after their reduction with zinc or cadmium amalgam to nitrites, employing photometry with sulphanilic acid and a-naphthylamine. In the case of polarographic determination nitrates are reduced on the mercury droping electrode in a weak acid medium under catalytic effects of uranyl ions. 

Weston cell (cadmium cell) A type of primary voltaic cell, which is used as a standard it produces a constant e.m.f. of 1.0186 volts at 20°C. The cell is usually made in an H-shaped glass vessel with a mercury anode covert with a paste of cadmium sulphate and mercury(l) sulphate in one leg and a cadmium amalgam cathode covered with cadmium sulphate in the other leg. The electrolyte, which connects the two electrodes by means of the bar of the H, is a saturated solution of cadmium sulphate. In some cells sulphuric acid is added to prevent the hydrolysis of mercury sulphate. It is named after Edward Weston (1850-1936). 

Standard methods which convert alkylmercury iodides into bis(alkyl)-mercurials fail to convert perfluoroalkylmercury iodides into bis(perfluoro-alkyl)mercurials. The preparation of primary bis(perfluoroalkyl)mercurials can be accomplished by treating perfluoroalkylmercury iodides with silver, copper, or cadmium amalgams. Alternatively, the parent perfluoroalkyl iodide will react directly with the amalgam. By either method yields are from 40 to 90%. 

The Weston cell is the most common standard cell, in which mercury forms the positive pole and a 12.5% cadmium amalgam the negative pole. The electrolyte is a saturated solution of cadmium sulphate. The cell can be formulated ... 

The corrosion reactions may be slowed down by using zinc alloys (with lead and cadmium, also improving the mechanical properties of zinc to simplify the production process) instead of the pure metal, or by amalgamating the inner surface of the can by adding a small amount of a mercury compound to the electrolyte. 

Mercury forms alloys, called amalgams, with other metals such as gold, silver, zinc, and cadmium. It is not soluble in water, but will dissolve in nitric acid. It has a high electric conductivity, making it useful in the electronics industry. However, unlike most other metals, it is a poor conductor of heat. Because of its high surface tension, it does not wet the surfaces that it touches. This characteristic also accounts for its breakup into tiny droplets when poured over a surface. If spilled, it should not be collected with bare hands, but with a thin piece of cardboard to scoop it up. 

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