Tin-to-copper exchange

Tinned copper and copper alloys Copper itself has a fair corrosion resistance but traces of copper salts are often troublesome and a tin coating offers a convenient means of preventing their formation. Thus copper wire to receive rubber insulation is tinned to preserve the copper from sulphide tarnish and the rubber from copper-catalysed oxidation, and also to keep the wire easily solderable. Vessels to contain water or foodstuffs, including cooking vessels, water-heaters and heat exchangers, may all be tinned to avoid copper contamination accompanied by possible catalysis of the oxidation of such products as milk, and discolouration in the form of, for example, green stains in water and food. 

These alloy coatings have advantages over tin in atmospheric exposure where there is heavy pollution by oxides of sulphur. They are cathodic to steel and anodic to copper. In industrial atmospheres, however, formation of a layer of lead sulphate seals pores and produces a generally stable surface and terne-plate has been used extensively as roofing sheet, especially in the USA. It is easily and effectively painted when additional protection is required. Copper heat exchangers in gas-fired water-heaters may be coated by hot dipping in 20% tin alloy . 

The coupling of terminal alkynes with aryl or vinyl halides under palladium catalysis is known as the Sonogashira reaction. This catalytic process requires the use of a palladium(0) complex, is performed in the presence of base, and generally uses copper iodide as a co-catalyst. One partner, the aryl or vinyl halide, is the same as in the Stille and Suzuki couplings but the other has hydrogen instead of tin or boron as the metal to be exchanged for palladium. 

Nakai and coworkers have reported that a mixture of diastereomeric tin precursors 28 can be used to provide highly enantio enriched products, as shown for the conversion of 28 to 29 (Scheme 8). Furthermore, reduction of 29 is diastere-oselective to afford (following chiral auxiliary removal) enantio enriched (3-amino alcohols, 30 [22]. In another report, Nakai has described the conversion of the diastereomeric organolithium intermediates from tin-lithium exchange of 28 to copper species which can be used for 1,4 additions to a, 3-unsaturated aldehydes... 

These considerations show the essentially thermodynamic nature of and it follows that only those metals that form reversible -i-ze = A/systems, and that are immersed in solutions containing their cations, take up potentials that conform to the thermodynamic Nernst equation. It is evident, therefore, that the e.m.f. series of metals has little relevance in relation to the actual potential of a metal in a practical environment, and although metals such as silver, mercury, copper, tin, cadmium, zinc, etc. when immersed in solutions of their cations do form reversible systems, they are unlikely to be in contact with environments containing unit activities of their cations. Furthermore, although silver when immersed in a solution of Ag ions will take up the reversible potential of the Ag /Ag equilibrium, similar considerations do not apply to the NaVNa equilibrium since in this case the sodium will react with the water with the evolution of hydrogen gas, i.e. two exchange processes will occur, resulting in an extreme case of a corrosion reaction. 

After adjusting to 2 mol 1 1 in hydrochloric acid, 500 ml of the sample is adsorbed on a column of Dowex 1-XS resin (Cl form) and elution is then effected with 2 M nitric acid. The solution is evaporated to dryness after adding 1M hydrochloric acid, and the tin is again adsorbed on the same column. Tin is eluted with 2 M nitric acid, and determined in the eluate by the spectrophotometric catechol violet method. There is no interference from 0.1 mg of aluminium, manganese, nickel, copper, zinc, arsenic, cadmium, bismuth, or uranium any titanium, zirconium, or antimony are removed by ion exchange. Filtration of the sample through a Millipore filter does not affect the results, which are in agreement with those obtained by neutron activation analysis. 

Special consideration should be paid to metal complexes such as azomethine pigments (Sec. 2.10). At high temperatures, the yellow copper complex with the chemical constitution 10, incorporated in PVC, will exchange its chelated copper atoms with the metal atoms present in the application medium. Stabilizers containing barium/cadmium or lead produce yellow shades, while dibutyl tin thiogly-colate or other tin compounds produce a brilliant medium red. Color change is slow at low temperatures, but at 160°C the effect is rapid [108],... 

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