Copper metallization

Given that the concentration of both the copper atoms and the electrons m the copper metal will be effectively constant, so that two of the activity tenns can be neglected, we finally have, on rearranging A2.4.107,... 

In contrast to the + 2 state, copper(I) compounds are less frequently coloured and are diamagnetic, as expected since the 3d level is full. However, the copper(I) ion, unlike copper(II), is unstable in aqueous solution where it disproportionates into copper(II) and copper(O) (i.e. copper metal). 

When copper metal and powdered sulfur are placed in a... 

Selecting a Constant Potential In controlled-potential coulometry, the potential is selected so that the desired oxidation or reduction reaction goes to completion without interference from redox reactions involving other components of the sample matrix. To see how an appropriate potential for the working electrode is selected, let s develop a constant-potential coulometric method for Cu + based on its reduction to copper metal at a Pt cathode working electrode. 

Even ia 1960 a catalytic route was considered the answer to the pollution problem and the by-product sulfate, but nearly ten years elapsed before a process was developed that could be used commercially. Some of the eadier attempts iacluded hydrolysis of acrylonitrile on a sulfonic acid ion-exchange resia (69). Manganese dioxide showed some catalytic activity (70), and copper ions present ia two different valence states were described as catalyticaHy active (71), but copper metal by itself was not active. A variety of catalysts, such as Umshibara or I Jllmann copper and nickel, were used for the hydrolysis of aromatic nitriles, but aUphatic nitriles did not react usiag these catalysts (72). Beginning ia 1971 a series of patents were issued to The Dow Chemical Company (73) describiag the use of copper metal catalysis. Full-scale production was achieved the same year. A solution of acrylonitrile ia water was passed over a fixed bed of copper catalyst at 85°C, which produced a solution of acrylamide ia water with very high conversions and selectivities to acrylamide. 

Lead azide tends to hydrolyze at high humidities or in the presence of materials evolving moisture. The hydrazoic acid formed reacts with copper and its alloys to produce the sensitive cupric azide [14215-30-6] Cu(N2)2- Appropriate protection must be provided by hermetic sealing and the use of noncopper or coated-copper metal. 

Mercury spills should be cleaned up immediately by use of a special vacuum cleaner. The area should then be washed with a dilute calcium sulfide solution. Small quantities of mercury can be picked up by mixing with copper metal granules or powder, or with zinc granules or powder. To avoid or minimize spills, some plants use steel trays as pallets so that a spih, whether of mercury or a mercury compound, is contained on the steel tray. 

Electrolytic Precipitation. In 1800, 31 years before Faraday s fundamental laws of electrolysis, Cmikshank observed that copper metal could be precipitated from its solutions by the current generated from Volta s pile (18). This technique forms the basis for the production of most of the copper and 2inc metal worldwide. 

Copper. Domestic mine production of copper metal in 1994 was over 1,800,000 t. Whereas U.S. copper production increased in the 1980s and 1990s, world supply declined in 1994. There are eight primary and five secondary smelters, nine electrolytic and six fire refiners, and fifteen solvent extraction—electro winning (SX—EW) plants. Almost 540,000 t/yr of old scrap copper and alloy are recycled in the United States accounting for - 24% of total U.S. consumption (11). New scrap accounted for 825,000 t of contained copper. Almost 80% of the new scrap was consumed by brass mills. The ratio of new-to-old scrap is about 60 40% representing 38% of U.S. supply. 

The New York Commodity Exchange (Comex) prices for cathode copper in January 1993, 1994, and 1994 were 2.218/kg, 1.844/kg, and 3.084/kg, respectively. The primary uses for copper metal and alloy are constmction, 42% electrical/electronic, 24% industrial machinery, 13% transportation equipment, 11% and consumer/general products, 10%. Copper compounds for use in agriculture and industry account for about 1% of total copper consumption. 

Silane reacts with methanol at room temperature to produce methoxymonosilanes such as Si(OCH2)4 [78-10-4] HSi(OCH2)3, and H2Si(OCH3)2 [5314-52-3] but not H SiOCH [2171 -96-2] (23). The reaction is catalyzed by copper metal. In the presence of alkoxide ions, SiH reacts with various alcohols, except CH OH, to produce tetraalkoxysHanes and hydrogen (24). 

The metal fillers act as a reinforcing material that results in added strength and stiffness (126). They color the plastic gray for nickel, 2inc, stainless steel, and aluminum, and brown for copper. Metal additives are more expensive than carbon black or surface-active agents, but they get extensive use in EMI shielding appHcations. 

In the presence of metallic copper, metallic silver, or a copper-silver alloy used in the form of gauze or as metal deposited on a low surface area inert support, methanol can be dehydrogenated to formaldehyde at 400—500°C. 

The tri- or tetraamine complex of copper(I), prepared by reduction of the copper(II) tetraamine complex with copper metal, is quite stable ia the absence of air. If the solution is acidified with a noncomplexiag acid, the formation of copper metal, and copper(II) ion, is immediate. If hydrochloric acid is used for the neutralization of the ammonia, the iasoluble cuprous chloride [7758-89-6], CuCl, is precipitated initially, followed by formation of the soluble ions [CuClj, [CuCl, and [CuCl as acid is iacreased ia the system. 

Cupric chloride or copper(II) chloride [7447-39 ], CUCI2, is usually prepared by dehydration of the dihydrate at 120°C. The anhydrous product is a dehquescent, monoclinic yellow crystal that forms the blue-green orthohombic, bipyramidal dihydrate in moist air. Both products are available commercially. The dihydrate can be prepared by reaction of copper carbonate, hydroxide, or oxide and hydrochloric acid followed by crystallization. The commercial preparation uses a tower packed with copper. An aqueous solution of copper(II) chloride is circulated through the tower and chlorine gas is sparged into the bottom of the tower to effect oxidation of the copper metal. Hydrochloric acid or hydrogen chloride is used to prevent hydrolysis of the copper(II) (11,12). Copper(II) chloride is very soluble in water and soluble in methanol, ethanol, and acetone. 

Copper(II) oxychloride [1332-65-6], Cu2Cl(OH)2, is found in nature as the green hexagonal paratacamite [12186-OOA] or rhombic atacamite [1306-85-0]. It is usually precipitated by air oxidation of a concentrated sodium chloride solution of copper(I) chloride (13—15). Often the solution is circulated through a packed tower of copper metal, heated to 60—90°C, and aerated. 

Cu(N03 )26H2 0, is produced by crystallization from solutions below the transition poiat of 26.4°C. A basic copper nitrate [12158-75-7] Cu2(N02)(0H)2, rather than the anhydrous product is produced on dehydration of the hydrated salts. The most common commercial forms for copper nitrate ate the ttihydtate and solutions containing about 14% copper. Copper nitrate can be prepared by dissolution of the carbonate, hydroxide, or oxides ia nitric acid. Nitric acid vigorously attacks copper metal to give the nitrate and evolution of nitrogen oxides. 

Coppet(I) oxide is stable in dry air, but reacts with oxygen to form coppet(II) oxide in moist air. CU2O is insoluble in water, but dissolves in ammonia or hydrochloric acid. The product disproportionates to copper metal and coppet(II) in dilute sulfuric or nitric acid. 

Copper(II) oxide is less often prepared by pyrometaHurgical means. Copper metal heated in air to 800°C produces the copper(II) oxide. Decomposition of nitrates, carbonates, and hydroxides at various temperatures also occurs. 

Anhydrous copper(II) sulfate [7758-98-7] is a gray to white rhombic crystal and occurs in nature as the mineral hydrocyanite. CuSO is hygroscopic. It is produced by careful dehydration of the pentahydrate at 250°C. An impure product can also be produced from copper metal and hot sulfuric acid ... 

The complexers maybe tartrate, ethylenediaminetetraacetic acid (EDTA), tetrakis(2-hydroxypropyl)ethylenediamine, nittilotriacetic acid (NTA), or some other strong chelate. Numerous proprietary stabilizers, eg, sulfur compounds, nitrogen heterocycles, and cyanides (qv) are used (2,44). These formulated baths differ ia deposition rate, ease of waste treatment, stabiHty, bath life, copper color and ductiHty, operating temperature, and component concentration. Most have been developed for specific processes all deposit nearly pure copper metal. 

Steam reforming is the reaction of steam with hydrocarbons to make town gas or hydrogen. The first stage is at 700 to 830°C (1,292 to 1,532°F) and 15-40 atm (221 to 588 psih A representative catalyst composition contains 13 percent Ni supported on Ot-alumina with 0.3 percent potassium oxide to minimize carbon formation. The catalyst is poisoned by sulfur. A subsequent shift reaction converts CO to CO9 and more H2, at 190 to 260°C (374 to 500°F) with copper metal on a support of zinc oxide which protects the catalyst from poisoning by traces of sulfur. 

The production of copper from sulphide minerals is accomplished with a preliminary partial roast of die sulphides before reaction widr air in the liquid state, known as mattes, to form copper metal (conversion). The principal sources of copper are minerals such as chalcopyrite, CuFeSa and bornite CuaFeSa, and hence the conversion process must accomplish the preferential oxidation of non, in the form of FeO, before the copper metal appears. As mentioned before, tire FeO-SiOa liquid system is practically Raoultian, and so it is relatively easy to calculate the amount of iron oxidation which can be canned out to form this liquid slag as a function of the FeO/SiOa ratio before copper oxidation occurs. The liquid slag has a maximum mole fraction of FeO at the matte blowing temperatures of about 0.3, at solid silica saturation. 

Cupric nitrate (3H2O) [10031-43-3 (3H2O) 3251-23-8 (anhydr)] M 241.6, m 114 , b 170 (dec), d 2.0. Crystd from weak aqueous HNO3 (0.5mL/g) by cooling from room temperature. The anhydrous salt can be prepared by dissolving copper metal in a 1 1 mixture of liquid NO2 and ethyl acetate and purified by sublimation [Evans et al. J Chem Soc, Faraday Trans 1 75 1023 1979], The hexahydrate dehydr to trihydrate at 26°, and the anhydrous salt sublimes between 150 and 225°, but melts at 255-256° and is deliquescent. 

Recovery of copper metal and alloys from copper-bearing scrap metal and smelting residues requires preparation of the scrap (e.g., removal of insulation) prior to feeding into the primary process. Electric arc furnaces using scrap as feed are also common. 

Trifluoromethylation is the most important perfluoroalkylation reaction. The initial work was earned out with trifluoromethyl iodide and copper metal in the... 

A similar distribution of copper reagents can be obtained via the du ect reaction of copper metal with dibromodifluoromethane or bromochlorodifluoromethane in DMF at 85-95 °C [2J2] The oligomerization can be supressed via the addition of alkali metal fluorides to the reaction mixture [272] When HMPAis added to the trifluoromethylcopper solution, decomposition is slowed, and this solution can be used to trifluoromethylate aromatic iodides [270] (equation 143). 

Tnfluorometltylation of aryl, alkenyl, and alkyl halides can be accomplished by heating methyl fluorosulfonyldifluoroacetate and the appropriate halide precursor with copper(I) iodide at 60-80 °C in DMF [27 7] (equation 145). Similar trifluoromethylations of aryl, benzyl, and vinyl halides can be carried out with fluorosulfonyldifluoromethyl iodide and copper metal in DMF at 60-80 °C [2 75] (equation 146). 

Perfluoroalkylation can be accomplished via direct reaction of peifluoroalkyl halides and copper with aromatic substrates [232, 233, 234, 235, 236] Thus, perfluoroalkyl iodides or bromides react with functionalized benzenes m DMSO m the presence of copper bronze to give the corresponding perfluoroalkylated products directly in moderate to good yields [233] (equation 157) Mixtures of ortho, meta, and para isomers are obtained [232, 233], The use of acetic anhydride as solvent gives similar results [234, 235], Similarly, the direct reaction of perfluoroalkyl iodides and pyrroles with copper metal regiospecifically gives the 2-perfluoroalkylpyrroles [236] (equation 158). 

Perfluoroalkylation of perfluoroalkylethylenes and addition of perfluoroalkyl iodides to olefins or acetylenes are catalyzed by copper metal [238, 239] Similar copper-catalyzed addition of iododifluoroacetates to olefins has been observed [241]... 

Reductive coupling reaction of fluonnated vinyl iodides or bromides has been used as a route to fluorinated dienes [246, 247, 248, 249, 250. Generally, the vinyl iodide is heated with copper metal in DMSO or DMF no 1 ntermediate perfluorovmy I-copper reagent is detected. Typical examples are shown m equations 163-165 [246, 247, 249. The X-ray crystal structure of perfluorotetracyclobutacyclooctatetraene, prepared via coupling of tetrafluoro-l,2-diiodocyclobutene with copper, is planar... 

The analogous trifluoromethylseleno and pentafluorophenylseleno copper compounds are prepared via reaction of the corresponding diselenide with copper metal [265, 269] Coupling with aryl iodides gives the arylselenium denvative [265] (equation 185)... 

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