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Organocopper chemistry

Copper

Copper is a chemical element with symbol Cu (from Latin: cuprum) and atomic number 29. It is a ductile metal with very high thermaland electrical conductivity. Pure copper is soft and malleable; a freshly exposed surface has a reddish-orange color. It is used as a conductor of heat and electricity, a building material, and a constituent of various metal alloys.

The metal and its alloys have been used for thousands of years. In the Roman era, copper was principally mined on Cyprus, hence the origin of the name of the metal as ńyprium (metal of Cyprus), later shortened to ńuprum. Its compounds are commonly encountered as copper(II) salts, which often impart blue or green colors to minerals such as azurite and turquoise and have been widely used historically as pigments. Architectural structures built with copper corrode to give green verdigris (or patina). Decorative art prominently features copper, both by itself and as part of pigments.

Copper is essential to all living organisms as a trace dietary mineral because it is a key constituent of the respiratory enzyme complexcytochrome c oxidase. In molluscs and crustacea copper is a constituent of the blood pigment hemocyanin, which is replaced by the iron-complexed hemoglobin in fish and other vertebrates. The main areas where copper is found in humans are liver, muscle and bone. Copper compounds are used as bacteriostatic substances, fungicides, and wood preservatives.

Physical

Copper, silver and gold are in group 11 of the periodic table, and they share certain attributes: they have one s-orbital electron on top of a filled d-electron shell and are characterized by high ductility and electrical conductivity. The filled d-shells in these elements do not contribute much to the interatomic interactions, which are dominated by the s-electrons through metallic bonds. Unlike in metals with incomplete d-shells, metallic bonds in copper are lacking a covalent character and are relatively weak. This explains the low hardness and high ductility of single crystals of copper.[3] At the macroscopic scale, introduction of extended defects to the crystal lattice, such as grain boundaries, hinders flow of the material under applied stress, thereby increasing its hardness. For this reason, copper is usually supplied in a fine-grained polycrystalline form, which has greater strength than monocrystalline forms.

The softness of copper partly explains its high electrical conductivity (59.6×106 S/m) and thus also high thermal conductivity, which are the second highest among pure metals at room temperature. This is because the resistivity to electron transport in metals at room temperature mostly originates from scattering of electrons on thermal vibrations of the lattice, which are relatively weak for a soft metal. The maximum permissible current density of copper in open air is approximately 3.1×106 A/m2 of cross-sectional area, above which it begins to heat excessively.] As with other metals, if copper is placed against another metal, galvanic corrosion will occur.[



Together with caesium and gold (both yellow), and osmium (bluish), copper is one of only four elemental metals with a natural color other than gray or silver. Pure copper is orange-red and acquires a reddishtarnish when exposed to air. The characteristic color of copper results from the electronic transitions between the filled 3d and half-empty 4s atomic shells – the energy difference between these shells is such that it corresponds to orange light. The same mechanism accounts for the yellow color of gold and caesium.

Chemical

Copper does not react with water but it does slowly react with atmospheric oxygen to form a layer of brown-black copper oxide which, unlike the rust which forms when iron is exposed to moist air, protects the underlying copper from more extensive corrosion. A green layer of verdigris (copper carbonate) can often be seen on old copper constructions such as the Statue of Liberty. Copper tarnishes when exposed to sulfides, which react with it to form various copper sulfides.

Compounds

Copper forms a rich variety of compounds, usually with oxidation states +1 and +2, which are often called cuprous and cupric, respectively.[31]

Binary compounds

As with other elements, the simplest compounds of copper are binary compounds, i.e. those containing only two elements. The principal ones are the oxides, sulfides, and halides. Both cuprous and cupric oxides are known. Among the numerous copper sulfides, important examples include copper(I) sulfide and copper(II) sulfide.

The cuprous halides with chlorine, bromine, and iodine are known, as are the cupric halides with fluorine, chlorine, and bromine. Attempts to prepare copper(II) iodide give cuprous iodide and iodine.[31]

2 Cu2+ + 4 I → 2 CuI + I2

Copper, like all metals, forms coordination complexes with ligands. In aqueous solution, copper(II) exists as [Cu(H2O)6]2+. This complex exhibits the fastest water exchange rate (speed of water ligands attaching and detaching) for any transition metal aquo complex. Adding aqueous sodium hydroxide causes the precipitation of light blue solid copper(II) hydroxide. A simplified equation is:

Cu2+ + 2 OH → Cu(OH)2

Aqueous ammonia results in the same precipitate. Upon adding excess ammonia, the precipitate dissolves, forming tetraamminecopper(II):

Cu(H2O)4(OH)2 + 4 NH3 → [Cu(H2O)2(NH3)4]2+ + 2 H2O + 2 OH

Many other oxyanions form complexes; these include copper(II) acetate, copper(II) nitrate, and copper(II) carbonate. Copper(II) sulfate forms a blue crystalline pentahydrate, which is the most familiar copper compound in the laboratory. It is used in a fungicide called the Bordeaux mixture.[32]

 

Polyols, compounds containing more than one alcohol functional group, generally interact with cupric salts. For example, copper salts are used to test for reducing sugars. Specifically, using Benedict's reagent and Fehling's solution the presence of the sugar is signaled by a color change from blue Cu(II) to reddish copper(I) oxide.[33] Schweizer's reagent and related complexes with ethylenediamine and other amines dissolve cellulose.[34] Amino acids form very stable chelate complexes with copper(II). Many wet-chemical tests for copper ions exist, one involving potassium ferrocyanide, which gives a brown precipitate with copper(II) salts.

Organocopper chemistry

Main article: Organocopper compound

Compounds that contain a carbon-copper bond are known as organocopper compounds. They are very reactive towards oxygen to form copper(I) oxide and have many uses in chemistry. They are synthesized by treating copper(I) compounds with Grignard reagents, terminalalkynes or organolithium reagents;[35] in particular, the last reaction described produces a Gilman reagent. These can undergo substitution withalkyl halides to form coupling products; as such, they are important in the field of organic synthesis. Copper(I) acetylide is highly shock-sensitive but is an intermediate in reactions such as the Cadiot-Chodkiewicz coupling[36] and the Sonogashira coupling.[37] Conjugate additionto enones[38] and carbocupration of alkynes[39] can also be achieved with organocopper compounds. Copper(I) forms a variety of weak complexes with alkenes and carbon monoxide, especially in the presence of amine ligands.[40]

Copper(III) and copper(IV)

Copper(III) is most characteristically found in oxides. A simple example is potassium cuprate, KCuO2, a blue-black solid. The best studied copper(III) compounds are the cuprate superconductors. Yttrium barium copper oxide (YBa2Cu3O7) consists of both Cu(II) and Cu(III) centres. Like oxide, fluoride is a highly basic anion and is known to stabilize metal ions in high oxidation states. Indeed, both copper(III) and even copper(IV) fluorides are known, K3CuF6 and Cs2CuF6, respectively.[31]

Some copper proteins form oxo complexes, which also feature copper(III).[41] With di- and tripeptides, purple-colored copper(III) complexes are stabilized by the deprotonated amideligands.[42]

Complexes of copper(III) are also observed as intermediates in reactions of organocopper compounds.

Wire and cable

Main article: Copper wire and cable

Despite competition from other materials, copper remains the preferred electrical conductor in nearly all categories of electrical wiring with the major exception being overhead electric power transmission where aluminium is often preferred.[67][68] Copper wire is used in power generation, power transmission, power distribution, telecommunications, electronics circuitry, and countless types of electrical equipment.[69]Electrical wiring is the most important market for the copper industry.[70] This includes building wire, communications cable, power distribution cable, appliance wire, automotive wire and cable, and magnet wire. Roughly half of all copper mined is used to manufacture electrical wire and cable conductors.[71] Many electrical devices rely on copper wiring because of its multitude of inherent beneficial properties, such as its high electrical conductivity, tensile strength, ductility, creep (deformation) resistance, corrosion resistance, low thermal expansion, high thermal conductivity, solderability, and ease of installation.

History

Copper Age

Copper occurs naturally as native copper and was known to some of the oldest civilizations on record. It has a history of use that is at least 10,000 years old, and estimates of its discovery place it at 9000 BC in the Middle East;[43] a copper pendant was found in northern Iraq that dates to 8700 BC.[44] There is evidence that gold and meteoric iron (but not iron smelting) were the only metals used by humans before copper.[45] The history of copper metallurgy is thought to have followed the following sequence: 1) cold working of native copper, 2)annealing, 3) smelting, and 4) the lost wax method. In southeastern Anatolia, all four of these metallurgical techniques appears more or less simultaneously at the beginning of the Neolithic c. 7500 BC.[46] However, just as agriculture was independently invented in several parts of the world (including Pakistan, China, and the Americas) copper smelting was invented locally in several different places. It was probably discovered independently in China before 2800 BC, in Central America perhaps around 600 AD, and in West Africa about the 9th or 10th century AD.[47] Investment casting was invented in 4500–4000 BC in Southeast Asia[43] and carbon dating has established mining atAlderley Edge in Cheshire, UK at 2280 to 1890 BC.[48] Ötzi the Iceman, a male dated from 3300–3200 BC, was found with an axe with a copper head 99.7% pure; high levels of arsenic in his hair suggest his involvement in copper smelting.[49] Experience with copper has assisted the development of other metals; in particular, copper smelting led to the discovery of iron smelting.[49] Production in the Old Copper Complex in Michigan and Wisconsin is dated between 6000 and 3000 BC.[50][51] Natural bronze, a type of copper made from ores rich in silicon, arsenic, and (rarely) tin, came into general use in the Balkans around 5500 BC.[citation needed]

Bronze Age

Main article: Bronze Age

Alloying copper with tin to make bronze was first practiced about 4000 years after the discovery of copper smelting, and about 2000 years after "natural bronze" had come into general use. Bronze artifacts from the Vinča culture date to 4500 BC.[52] Sumerian and Egyptianartifacts of copper and bronze alloys date to 3000 BC.[53] The Bronze Age began in Southeastern Europe around 3700–3300 BC, in Northwestern Europe about 2500 BC. It ended with the beginning of the Iron Age, 2000–1000 BC in the Near East, 600 BC in Northern Europe. The transition between the Neolithic period and the Bronze Age was formerly termed the Chalcolithic period (copper-stone), with copper tools being used with stone tools. This term has gradually fallen out of favor because in some parts of the world the Chalcolithic and Neolithic are coterminous at both ends. Brass, an alloy of copper and zinc, is of much more recent origin. It was known to the Greeks, but became a significant supplement to bronze during the Roman Empire.[53]

 


Date: 2015-12-18; view: 301


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