Cadmium metal dissolution

Fig. 9-4. Anodic and cathodic polarization curves measured for transfer of divalent cadmium ions (dissolution-deposition) at a metallic cadmium electrode in a sulfate solution (0.005MCd + 0.4MS04 ) i (i )= anodic (cathodic) reaction current a = Tafel constant (transfer coefficient). [From Lorenz, 1954.]...

The properties of Cd species formed by the dissolution of cadmium metal in molten cadmium halides and at electrode interface were investigated [216]. 

As an example, consider the dissolution of a cadmium metal electrode... 

For some non-ferrous metals (copper, lead, nickel) the attack by sulphuric acid is probably direct with the formation of sulphates. Lead sulphate is barely soluble and gives good protection. Nickel and copper sulphates are deliquescent but are gradually converted (if not leached away) into insoluble basic sulphates, e.g. Cu Cu(OH)2)3SO4, and the metals are thus protected after a period of active corrosion. For zinc and cadmium the sulphur acids probably act by dissolution of the protective basic carbonate film. This reforms, consuming metal in the process, redissolves, and so on. Zinc and cadmium sulphates are formed in polluted winter conditions whereas in the purer atmospheres of the summer the corrosion products include considerable amounts of oxide and basic carbonate. ... 

Usually, samples are presented for analysis as liquids. Thus, solid samples must be dissolved. Analytical or ultra-high-purity grade reagents must be used for dissolution to prevent contamination at trace levels. Certain volatile metals (e.g. cadmium, lead and zinc) may be lost when dry ashing, and volatile chlorides (e.g. arsenic and chromium) lost upon wet digestion. It is particularly easy to lose mercury during sample preparation. Appropriate steps must be taken in the choice of method of dissolution, acids and conditions (e.g. whether to use reflux conditions) to prevent such losses. 

As a result of that reductive process, a deposit of copper metal (denoted in Eq. 2.2 by s for solid ) is formed on the carbon electrode surface. The prominent anodic peak recorded in the reverse scan corresponds to the oxidative dissolution of the deposit of copper metal previously formed. The reason for the very intense anodic peak current is that the copper deposit is dissolved in a very small time range (i.e., potential range) because, in the dissolution of the thin copper layer, practically no diffusion limitations are involved, whereas in the deposition process (i.e., the cathodic peak), the copper ions have to diffuse through the expanding diffusion layer from the solution to the electrode surface. These processes, labeled as stripping processes, are typical of electrochemically deposited metals such as cadmium, copper, lead, mercury, zinc, etc., and are used for trace analysis in solution [84]. Remarkably, the peak profile is rather symmetrical because no solution-like diffusive behavior is observed. 

Raman spectral studies of solutions of metal nitrates in liquid ammonia show a coordination number of four for zinc and mercury, but six for cadmium. Dissolution of Znd2 and InCl3 in a 1 2 ratio in liquid HCN yields [Zn(NCH)6] [InCLJ2 with HCN coordination via nitrogen.137 A Raman study of the compounds [Cd(NH3)6]X2 (X = C1, Br or I) has been reported.138 Structural determinations of A2Zn(NH2)4 (A = Rb or K) reveal monomeric tetrahedral anions.139... 

A dissolution mechanism for zinc, cadmium and mercury in their molten halides has been proposed on the basis of experimental and literature data.949 Dissolution occurs at the metal-salt phase boundary. Adsorbed M24- cations are reduced to M+ ions which then migrate into the salt phase where Mi4" dimers form. The stability of the M2+ ions was found to increase in the order Zn < Cd Hg (the latter is so stable that Hg+ is undetectable in solution). 

Cementation, the process by which a metal is reduced from solution by the dissolution of a less-noble metal, has been used for centuries as a means for extraction of metals from solution, and is probably the oldest of the hydrometallurgical processes. It is also known by other terms such as metal displacement or contract reduction, and is widely used in the recovery of metals such as silver, gold, selenium, cadmium, copper and thallium from solution and the purification of solutions such as those used in the electrowinning of zinc. The electrochemical basis for these reactions has been well established414 and, as in leaching reactions, comprises the anodic dissolution of the less-noble metal coupled to the cathodic reduction of the more-noble metal on the surface of the corroding metals. Therefore, in the well-known and commercially exploited44 cementation of copper from sulfate solution by metallic iron, the reactions are... 

There have been only a few reports of mesostructured metal sulfides. Mesoporous cadmium sulfide was prepared from polyethylene oxide surfactants and cadmium salts exposed to hydrogen sulfide [35], A study of the effects of the counter-anion on the formation of CdS mesostructures led to the conclusion that the use of cadmium nitrate and perchlorate salts improved the degree of order of the mesostructure over the chloride, sulfate and acetate salts. This effect was attributed to the stronger acidity of conjugate acid by-products of the reaction in the case of nitrates that leads to the dissolution of high-energy defects and enhances structural order. 

LISEC Staff, Final report transformation/dissolution of metals and sparingly soluble metal compounds in aqueous media - cadmium , LISEC no. WE-14-002 (January, 1998)... 

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