Oxidation of copper

Copper and silver combined with refractory metals, such as tungsten, tungsten carbide, and molybdenum, are the principal materials for electrical contacts. A mixture of the powders is pressed and sintered, or a previously pressed and sintered refractory matrix is infiltrated with molten copper or silver in a separate heating operation. The composition is controlled by the porosity of the refractory matrix. Copper—tungsten contacts are used primarily in power-circuit breakers and transformer-tap charges. They are confined to an oil bath because of the rapid oxidation of copper in air. Copper—tungsten carbide compositions are used where greater mechanical wear resistance is necessary. 

Metals in the platinum family are recognized for their ability to promote combustion at lowtemperatures. Other catalysts include various oxides of copper, chromium, vanadium, nickel, and cobalt. These catalysts are subject to poisoning, particularly from halogens, halogen and sulfur compounds, zinc, arsenic, lead, mercury, and particulates. It is therefore important that catalyst surfaces be clean and active to ensure optimum performance. 

For definiteness, the oxidation of copper to copper(l) oxide may be considered. Our picture of the process is that cation vacancies and positive holes formed at the Cu O/Oj interface by equation, 1.166 are transported to the Cu/CujO interface where they are destroyed by copper dissolving in the non-stoichiometric oxide. We require an expression for the rate of oxidation. 

The effects on oxidation resistance of copper as a result of adding varying amounts of one or more of aluminium, beryllium, chromium, manganese, silicon, zirconium are described in a number of papers Other authors have investigated the oxidation of copper-zincand copper-nickel alloys , the oxidation of copper and copper-gold alloys in carbon dioxide at 1 000°C and the internal oxidation of various alloys ". ... 

The copper obtained from this process is about 99% pure, yet this is not pure enough for most uses, especially those involving electrical conductivity. To refine the copper further, it is made the anode of an electrolytic cell containing copper sulfate solution. With careful control of the voltage to regulate the half-reactions that can occur, the copper is transferred from the anode (where it is about 99 % Cu) to the cathode where it can be deposited as 99.999% Cu. At the anode there is oxidation of copper,... 

The relatively high cost and lack of domestic supply of noble metals has spurred considerable efforts toward the development of nonnoble metal catalysts for automobile exhaust control. A very large number of base metal oxides and mixtures of oxides have been considered, especially the transition metals, such as copper, chromium, nickel, manganese, cobalt vanadium, and iron. Particularly prominent are the copper chromites, which are mixtures of the oxides of copper and chromium, with various promoters added. These materials are active in the oxidation of CO and hydrocarbons, as well as in the reduction of NO in the presence of CO (55-59). Rare earth oxides, such as lanthanum cobaltate and lanthanum lead manganite with Perovskite structure, have been investigated for CO oxidation, but have not been tested and shown to be sufficiently active under realistic and demanding conditions (60-63). Hopcalities are out-... 

The decomposition of NO is a very slow catalytic reaction. Amirazmi, Benson, and Boudart recently studied the kinetics over platinum and over oxides of copper, cobalt, nickel, iron and zirconium from 450 to 900°C. They found that the kinetics is first order in NO with concentrations from 1.5 to 15%, and that oxygen has a strong inhibiting effect. Even at these temperatures, the kinetics is about a factor of 1000 too low for automotive usage (97). 

The kinetics of NO reduction by hydrogen and CO was studied by Ayen and Peters. Hydrogen reduction of NO over oxides of copper, zinc, and chromium was studied at 375-425°C. The products formed include... 

For example, consider the net ionic equation for the oxidation of copper metal to copper(II) ions by silver ions (Fig. K.6) ... 

An electrochemical cell in which electrolysis takes place is called an electrolytic cell. The arrangement of components in electrolytic cells is different from that in galvanic cells. Typically, the two electrodes share the same compartment, there is only one electrolyte, and concentrations and pressures are far front standard. As in all electrochemical cells, the current is carried through the electrolyte by the ions present. For example, when copper metal is refined electrolytically, the anode is impure copper, the cathode is pure copper, and the electrolyte is an aqueous solution of CuS04. As the Cu2f ions in solution are reduced and deposited as Cu atoms at the cathode, more Cu2+ ions migrate toward the cathode to take their place, and in turn their concentration is restored by Cu2+ produced by oxidation of copper metal at the anode. 

The presence of metal oxides have a different influence on PBDD/F concentration and pattern (ref. 11), see Figure 8. Oxides of zinc and copper reduce the PBDD/F yields due to debromination reactions. The two oxides of copper show... 

Clearly oxidation and reduction always occur together. The oxidation of copper by oxygen is accompanied by reduction of the oxygen to copper oxide. Similarly, whilst metal oxides such as CuO, HgO, SnO and PbO are reduced to the metal by hydrogen the latter becomes oxidized to water during the process ... 

Among the high-temperature superconductors one finds various cuprates (i.e., ternary oxides of copper and barium) having a layered structure of the perovskite type, as well as more complicated oxides on the basis of copper oxide which also include oxides of yttrium, calcium, strontium, bismuth, thallium, and/or other metals. Today, all these oxide systems are studied closely by a variety of specialists, including physicists, chemists, physical chemists, and theoreticians attempting to elucidate the essence of this phenomenon. Studies of electrochemical aspects contribute markedly to progress in HTSCs. 

Deoxygenation can oxidize the metal surfaces. It was found that the partially oxidized Cu surface was the most active in the isomerization of methy-loxirane to propanal.288 The same is true for Ni. Therefore, it is very likely that the metal ions produced by the oxidation of copper or nickel surfaces during deoxygenation play an important role in isomerization to aldehyde. 

Decomposition of either nickel hydroxide or nickel carbonate yields NiO, the only oxide of nickel of any importance. However, two oxides of copper are known, Cu20 and CuO. Of these, Cu20 is the more stable, and it is the product when CuO is heated to very high temperature. 

Fourier transform infrared reflection-absorption spectroscopy (FT-IFRAS) is applied to the study of corrosion protection of copper by an organic coating. Poly-N-vinyliroidazole (PVI(D) and poly-4(5)-vinylimidazole (PVI(4)) are demonstrated to be effective new polymeric anti-corrosion agents for copper at elevated temperatures. Oxidation of copper is suppressed even at 400° C. PVI(1) and PVI(4) are more effective anti-oxidants than the most commonly used corrosion inhibitors, benzotriazole and undecyllmldazole, at elevated temperatures. These new polymeric agents are water soluble and easy to treat the metal surface. 

Although all of the above elements catalyze hydrogenation, only platinum, palladium, rhodium, ruthenium and nickel are currently used. In addition some other elements and compounds were found useful for catalytic hydrogenation copper (to a very limited extent), oxides of copper and zinc combined with chromium oxide, rhenium heptoxide, heptasulfide and heptaselen-ide, and sulfides of cobalt, molybdenum and tungsten. 

Catalysts suitable specifically for reduction of carbon-oxygen bonds are based on oxides of copper, zinc and chromium Adkins catalysts). The so-called copper chromite (which is not necessarily a stoichiometric compound) is prepared by thermal decomposition of ammonium chromate and copper nitrate [50]. Its activity and stability is improved if barium nitrate is added before the thermal decomposition [57]. Similarly prepared zinc chromite is suitable for reductions of unsaturated acids and esters to unsaturated alcohols [52]. These catalysts are used specifically for reduction of carbonyl- and carboxyl-containing compounds to alcohols. Aldehydes and ketones are reduced at 150-200° and 100-150 atm, whereas esters and acids require temperatures up to 300° and pressures up to 350 atm. Because such conditions require special equipment and because all reductions achievable with copper chromite catalysts can be accomplished by hydrides and complex hydrides the use of Adkins catalyst in the laboratory is very limited. 

Poling, G.W. (1969) Infrared reflection studies of the oxidation of copper and iron. J. Electro-chem. Soc. 116 958... 

Reacts with oxides of copper, zinc, silver and many metals other than those of Group lA and Mg at high temperatures, decomposing to N2 and water. 

There are three well-established oxides of copper containing Cu and/or Cu" viz. CU2O, CU4O3 and CuO. Their structures are all based on a cubic-close packing (c.c.p.) of copper (somewhat distorted in C114O3 and CuO) with oxygen inserted into tetrahedral sites in such a way as to be a solution to the problem of having Cu in linear two-fold coordination and Cu in planar four-fold coordination. These have been discussed from this point of view elsewhere , and it has been speculated that the observed structures are, in fact, the only solutions to the problem. 

Other Ternary Copper Oxides Two other ternary oxides of copper(II) are worthy of mention. These are BaCu02 and the Ln2Cu04 series in which Ln = Nd, Sm, Eu, and Gd. The former compound, BaCu02, was first reported in 1975 by Arjomand and Machin (120), and they briefly reported on its powder pattern and magnetic properties. Further studies on BaCu02 were carried out the... 

---