Electrolytes, cadmium

Eor the negative electrolyte, cadmium nitrate solution (density 1.8 g/mL) is used in the procedure described above. Because a small (3 —4 g/L) amount of free nitric acid is desirable in the impregnation solution, the addition of a corrosion inhibitor prevents excessive contamination of the solution with nickel from the sintered mass (see Corrosion and corrosion inhibitorsCorrosion and corrosion control). In most appHcations for sintered nickel electrodes the optimum positive electrode performance is achieved when one-third to one-half of the pore volume is filled with active material. The negative electrode optimum has one-half of its pore volume filled with active material. 

A method was proposed for electrolytic cadmium refining in molten CdCl2 using electrolyzer with bipolar cadmium electrode [235]. The results demonstrated that high-purity Cd could be obtained in a single electrolysis cycle. 

Electrolytic cadmium coatings [25] have been widely used to protect fasteners, particularly for exposure in chloride environments. The lubricity of cadmium coatings aids in uniformly tightening threaded fasteners. However, use of cadmium is declining because of toxicity and environmental concerns. 

Cadmium is usually found in zinc ores and is extracted from them along with zinc (p. 416) it may be separated from the zinc by distillation (cadmium is more volatile than zinc. Table 14.2) or by electrolytic deposition. 

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. 

Fused-salt electrolysis of K2NbFy is not an economically feasible process because of the low current efficiency (31). However, electrowinning has been used to obtain niobium from molten alkaU haUde electrolytes (32). The oxide is dissolved in molten alkaU haUde and is deposited in a molten metal cathode, either cadmium or zinc. The reaction is carried out in a ceramic or glass container using a carbon anode the niobium alloys with the cathode metal, from which it is freed by vacuum distillation, and the niobium powder is left behind. 

Solvent for Electrolytic Reactions. Dimethyl sulfoxide has been widely used as a solvent for polarographic studies and a more negative cathode potential can be used in it than in water. In DMSO, cations can be successfully reduced to metals that react with water. Thus, the following metals have been electrodeposited from their salts in DMSO cerium, actinides, iron, nickel, cobalt, and manganese as amorphous deposits zinc, cadmium, tin, and bismuth as crystalline deposits and chromium, silver, lead, copper, and titanium (96—103). Generally, no metal less noble than zinc can be deposited from DMSO. 

Silver [7440-22-4] Ag, as an active material in electrodes was first used by Volta, but the first intensive study using silver as a storage battery electrode was reported in 1889 (5) using silver oxide—iron and silver oxide—copper combinations. Work on silver oxide—cadmium followed. In the 1940s, the use of a semipermeable membrane combined with limited electrolyte was introduced by Andrir in the silver oxide—2inc storage battery. 

The positive plates are siatered silver on a silver grid and the negative plates are fabricated from a mixture of cadmium oxide powder, silver powder, and a binder pressed onto a silver grid. The main separator is four or five layers of cellophane with one or two layers of woven nylon on the positive plate. The electrolyte is aqeous KOH, 50 wt %. In the aerospace appHcations, the plastic cases were encapsulated in epoxy resins. Most usehil cell sizes have ranged from 3 to 15 A-h, but small (0.1 A-h) and large (300 A-h) sizes have been evaluated. Energy densities of sealed batteries are 26-31 W-h/kg. 

Spontaneous low resistance internal short circuits can develop in silver—zinc and nickel—cadmium batteries. In high capacity cells heat generated by such short circuits can result in electrolyte boiling, cell case melting, and cell fires. Therefore cells that exhibit high resistance internal short circuits should not continue to be used. Excessive overcharge that can lead to dry out and short circuits should be avoided. 

Air pollution problems and labor costs have led to the closing of older pyrometaHurgical plants, and to increased electrolytic production. On a worldwide basis, 77% of total 2inc production in 1985 was by the electrolytic process (4). In electrolytic 2inc plants, the calcined material is dissolved in aqueous sulfuric acid, usually spent electrolyte from the electrolytic cells. Residual soHds are generally separated from the leach solution by decantation and the clarified solution is then treated with 2inc dust to remove cadmium and other impurities. 

Fig. 2. Electrolytic production of cadmium from 2inc electrolyte purification residue (5,6).

In Jiltemative 3 (Fig. 3), the electrolysis may be operated on a semicontinuous basis with the cadmium eventually being stripped completely from the electrolyte, which is then discarded after suitable treatment. Instead of the usual silver—lead anodes, high siUcon-iron anodes, such as Duriron, are commonly used. 

Cadmium is usually plated from a cyanide bath that consists of an aqueous solution of cadmium oxide (35 g/L) and sodium cyanide (75 g/L). An additive and a brightener are used to produce smooth, fine-grain deposits. Current density ranges from 1.4 to 3.7 A/dm, depending on the concentration of cadmium cations in the electrolyte. 

Cadmium sulfate solutions are used ia the standard Weston cell and as electrolytes ia electroplatiag as alternatives to cyanide baths. Other uses iaclude phosphors and as a nematocide. 

This conversion is normally accompHshed by immersion, but spraying, swabbing, bmshing, and electrolytic methods are also employed (178) (see Metal SURFACE treatments). The metals that benefit from chromium surface conversion are aluminum, cadmium, copper, magnesium, silver, and 2inc. Zinc is the largest consumer of chromium conversion baths, and more formulations are developed for 2inc than for any other metal. 

The isolation of zinc, over 90% of which is from sulfide ores, depends on conventional physical concentration of the ore by sedimentation or flotation techniques. This is followed by roasting to produce the oxides the SO2 which is generated is used to produce sulfuric acid. The ZnO is then either treated electrolytically or smelted with coke. In the former case the zinc is leached from the crude ZnO with dil H2SO4, at which point cadmium is precipitated by the addition of zinc dust. The ZnS04 solution is then electrolysed and the metal deposited — in a state of 99.95% purity — on to aluminium cathodes. 

Unlike the cells above, which are all primary cells, this is a secondary (i.e. rechargeable) cell, and the two poles are composed in the uncharged condition of nickel and cadmium hydroxides respectively. These are each supported on microporous nickel, made by a sintering process, and separated by an absorbent impregnated with electrolyte. The charging reactions are ... 

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