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Copper, ₂₉Cu

Copper
Appearance	red-orange metallic luster
Standard atomic weight Ar°(Cu)	63.546±0.003 63.546±0.003 (abridged)[1]
Copper in the periodic table
Hydrogen Helium Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson – ↑ Cu ↓ Ag nickel ← copper → zinc
Atomic number (Z)	29
Group	group 11
Period	period 4
Block	d-block
Electron configuration	[Ar] 3d10 4s1
Electrons per shell	2, 8, 18, 1
Physical properties
Phase at STP	solid
Melting point	1357.77 K ​(1084.62 °C, ​1984.32 °F)
Boiling point	2835 K ​(2562 °C, ​4643 °F)
Density (near r.t.)	8.96 g/cm3
when liquid (at m.p.)	8.02 g/cm3
Heat of fusion	13.26 kJ/mol
Heat of vaporization	300.4 kJ/mol
Molar heat capacity	24.440 J/(mol·K)
Vapor pressure P (Pa) 1 10 100 1 k 10 k 100 k at T (K) 1509 1661 1850 2089 2404 2834
Atomic properties
Oxidation states	−2, 0,[2] +1, +2, +3, +4 (a mildly basic oxide)
Electronegativity	Pauling scale: 1.90
Ionization energies	1st: 745.5 kJ/mol 2nd: 1957.9 kJ/mol 3rd: 3555 kJ/mol (more)
Atomic radius	empirical: 128 pm
Covalent radius	132±4 pm
Van der Waals radius	140 pm
Spectral lines of copper
Other properties
Natural occurrence	primordial
Crystal structure	​face-centered cubic (fcc)
Speed of sound thin rod	(annealed) 3810 m/s (at r.t.)
Thermal expansion	16.5 µm/(m⋅K) (at 25 °C)
Thermal conductivity	401 W/(m⋅K)
Electrical resistivity	16.78 nΩ⋅m (at 20 °C)
Magnetic ordering	diamagnetic[3]
Molar magnetic susceptibility	−5.46×10−6 cm3/mol[4]
Young’s modulus	110–128 GPa
Shear modulus	48 GPa
Bulk modulus	140 GPa
Poisson ratio	0.34
Mohs hardness	3.0
Vickers hardness	343–369 MPa
Brinell hardness	235–878 MPa
CAS Number	7440-50-8
History
Naming	after Cyprus, principal mining place in Roman era (Cyprium)
Discovery	Middle East (9000 BC)
Symbol	«Cu»: from Latin cuprum
Main isotopes of copper v e
Iso­tope Decay abun­dance half-life (t1/2) mode pro­duct 63Cu 69.17% stable 64Cu syn 12.70 h ε 64Ni β− 64Zn 65Cu 30.83% stable 67Cu syn 61.83 h β− 67Zn
Category: Copper view talk edit | references

Copper is a chemical element with the symbol Cu (from Latin: cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkish-orange color. Copper is used as a conductor of heat and electricity, as a building material, and as a constituent of various metal alloys, such as sterling silver used in jewelry, cupronickel used to make marine hardware and coins, and constantan used in strain gauges and thermocouples for temperature measurement.

Copper is one of the few metals that can occur in nature in a directly usable metallic form (native metals). This led to very early human use in several regions, from circa 8000 BC. Thousands of years later, it was the first metal to be smelted from sulfide ores, circa 5000 BC; the first metal to be cast into a shape in a mold, c. 4000 BC; and the first metal to be purposely alloyed with another metal, tin, to create bronze, c. 3500 BC.^[5]

In the Roman era, copper was mined principally on Cyprus, the origin of the name of the metal, from aes cyprium (metal of Cyprus), later corrupted to cuprum (Latin). Coper (Old English) and copper were derived from this, the later spelling first used around 1530.^[6]

Commonly encountered compounds are copper(II) salts, which often impart blue or green colors to such minerals as azurite, malachite, and turquoise, and have been used widely and historically as pigments.

Copper used in buildings, usually for roofing, oxidizes to form a green verdigris (or patina). Copper is sometimes used in decorative art, both in its elemental metal form and in compounds as pigments. Copper compounds are used as bacteriostatic agents, fungicides, and wood preservatives.

Copper is essential to all living organisms as a trace dietary mineral because it is a key constituent of the respiratory enzyme complex cytochrome c oxidase. In molluscs and crustaceans, copper is a constituent of the blood pigment hemocyanin, replaced by the iron-complexed hemoglobin in fish and other vertebrates. In humans, copper is found mainly in the liver, muscle, and bone.^[7] The adult body contains between 1.4 and 2.1 mg of copper per kilogram of body weight.^[8]

Characteristics

Physical

Copper, silver, and gold are in group 11 of the periodic table; these three metals have one s-orbital electron on top of a filled d-electron shell and are characterized by high ductility, and electrical and thermal conductivity. The filled d-shells in these elements contribute little to interatomic interactions, which are dominated by the s-electrons through metallic bonds. Unlike metals with incomplete d-shells, metallic bonds in copper are lacking a covalent character and are relatively weak. This observation explains the low hardness and high ductility of single crystals of copper.^[9] 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.^[10]

The softness of copper partly explains its high electrical conductivity (59.6×10⁶ S/m) and high thermal conductivity, second highest (second only to silver) among pure metals at room temperature.^[11] This is because the resistivity to electron transport in metals at room temperature originates primarily from scattering of electrons on thermal vibrations of the lattice, which are relatively weak in a soft metal.^[9] 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.^[12]

Copper is one of a few metallic elements with a natural color other than gray or silver.^[13] Pure copper is orange-red and acquires a reddish tarnish when exposed to air. The is due to the low plasma frequency of the metal, which lies in the red part of the visible spectrum, causing it to absorb the higher-frequency green and blue colors.^[14]

As with other metals, if copper is put in contact with another metal, galvanic corrosion will occur.^[15]

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 that forms on iron in moist air, protects the underlying metal from further corrosion (passivation). A green layer of verdigris (copper carbonate) can often be seen on old copper structures, such as the roofing of many older buildings^[16] and the Statue of Liberty.^[17] Copper tarnishes when exposed to some sulfur compounds, with which it reacts to form various copper sulfides.^[18]

Isotopes

There are 29 isotopes of copper. ⁶³
Cu
and ⁶⁵
Cu
are stable, with ⁶³
Cu
comprising approximately 69% of naturally occurring copper; both have a spin of 3⁄2.^[19] The other isotopes are radioactive, with the most stable being ⁶⁷
Cu
with a half-life of 61.83 hours.^[19] Seven metastable isotopes have been characterized; ^68m
Cu
is the longest-lived with a half-life of 3.8 minutes. Isotopes with a mass number above 64 decay by β⁻, whereas those with a mass number below 64 decay by β⁺. ⁶⁴
Cu
, which has a half-life of 12.7 hours, decays both ways.^[20]

⁶²
Cu
and ⁶⁴
Cu
have significant applications. ⁶²
Cu
is used in ⁶²
Cu
Cu-PTSM as a radioactive tracer for positron emission tomography.^[21]

Occurrence

Copper is produced in massive stars^[22] and is present in the Earth’s crust in a proportion of about 50 parts per million (ppm).^[23] In nature, copper occurs in a variety of minerals, including native copper, copper sulfides such as chalcopyrite, bornite, digenite, covellite, and chalcocite, copper sulfosalts such as tetrahedite-tennantite, and enargite, copper carbonates such as azurite and malachite, and as copper(I) or copper(II) oxides such as cuprite and tenorite, respectively.^[11] The largest mass of elemental copper discovered weighed 420 tonnes and was found in 1857 on the Keweenaw Peninsula in Michigan, US.^[23] Native copper is a polycrystal, with the largest single crystal ever described measuring 4.4 × 3.2 × 3.2 cm.^[24] Copper is the 25th most abundant element in Earth’s crust, representing 50 ppm compared with 75 ppm for zinc, and 14 ppm for lead.^[25]

Typical background concentrations of copper do not exceed 1 ng/m³ in the atmosphere; 150 mg/kg in soil; 30 mg/kg in vegetation; 2 μg/L in freshwater and 0.5 μg/L in seawater.^[26]

Production

Most copper is mined or extracted as copper sulfides from large open pit mines in porphyry copper deposits that contain 0.4 to 1.0% copper. Sites include Chuquicamata, in Chile, Bingham Canyon Mine, in Utah, United States, and El Chino Mine, in New Mexico, United States. According to the British Geological Survey, in 2005, Chile was the top producer of copper with at least one-third of the world share followed by the United States, Indonesia and Peru.^[11] Copper can also be recovered through the in-situ leach process. Several sites in the state of Arizona are considered prime candidates for this method.^[27] The amount of copper in use is increasing and the quantity available is barely sufficient to allow all countries to reach developed world levels of usage.^[28] An alternative source of copper for collection currently being researched are polymetallic nodules, which are located at the depths of the Pacific Ocean approximately 3000–6500 meters below sea level. These nodules contain other valuable metals such as cobalt and nickel.^[29]

Reserves and prices

Copper has been in use at least 10,000 years, but more than 95% of all copper ever mined and smelted has been extracted since 1900.^[30] As with many natural resources, the total amount of copper on Earth is vast, with around 10¹⁴ tons in the top kilometer of Earth’s crust, which is about 5 million years’ worth at the current rate of extraction. However, only a tiny fraction of these reserves is economically viable with present-day prices and technologies. Estimates of copper reserves available for mining vary from 25 to 60 years, depending on core assumptions such as the growth rate.^[31] Recycling is a major source of copper in the modern world.^[30] Because of these and other factors, the future of copper production and supply is the subject of much debate, including the concept of peak copper, analogous to peak oil.^{[citation needed]}

The price of copper has historically been unstable,^[32] and its price increased from the 60-year low of US$0.60/lb (US$1.32/kg) in June 1999 to $3.75 per pound ($8.27/kg) in May 2006. It dropped to $2.40/lb ($5.29/kg) in February 2007, then rebounded to $3.50/lb ($7.71/kg) in April 2007.^{[33][better source needed]} In February 2009, weakening global demand and a steep fall in commodity prices since the previous year’s highs left copper prices at $1.51/lb ($3.32/kg).^[34] Between September 2010 and February 2011, the price of copper rose from £5,000 a metric ton to £6,250 a metric ton.^[35]

Methods

The concentration of copper in ores averages only 0.6%, and most commercial ores are sulfides, especially chalcopyrite (CuFeS₂), bornite (Cu₅FeS₄) and, to a lesser extent, covellite (CuS) and chalcocite (Cu₂S).^[36] Conversely, the average concentration of copper in polymetallic nodules is estimated at 1.3%. The methods of extracting copper as well as other metals found in these nodules include sulphuric leaching, smelting and an application of the Cuprion process.^[37][38] For minerals found in land ores, they are concentrated from crushed ores to the level of 10–15% copper by froth flotation or bioleaching.^[39] Heating this material with silica in flash smelting removes much of the iron as slag. The process exploits the greater ease of converting iron sulfides into oxides, which in turn react with the silica to form the silicate slag that floats on top of the heated mass. The resulting copper matte, consisting of Cu₂S, is roasted to convert the sulfides into oxides:^[36]

2 Cu₂S + 3 O₂ → 2 Cu₂O + 2 SO₂

The cuprous oxide reacts with cuprous sulfide to converted to blister copper upon heating:

2 Cu₂O + Cu₂S → 6 Cu + 2 SO₂

The Sudbury matte process converted only half the sulfide to oxide and then used this oxide to remove the rest of the sulfur as oxide. It was then electrolytically refined and the anode mud exploited for the platinum and gold it contained. This step exploits the relatively easy reduction of copper oxides to copper metal. Natural gas is blown across the blister to remove most of the remaining oxygen and electrorefining is performed on the resulting material to produce pure copper:^[40]

Cu²⁺ + 2 e⁻ → Cu

Recycling

Like aluminium,^[41] copper is recyclable without any loss of quality, both from raw state and from manufactured products.^[42] In volume, copper is the third most recycled metal after iron and aluminium.^[43] An estimated 80% of all copper ever mined is still in use today.^[44] According to the International Resource Panel’s Metal Stocks in Society report, the global per capita stock of copper in use in society is 35–55 kg. Much of this is in more-developed countries (140–300 kg per capita) rather than less-developed countries (30–40 kg per capita).

The process of recycling copper is roughly the same as is used to extract copper but requires fewer steps. High-purity scrap copper is melted in a furnace and then reduced and cast into billets and ingots; lower-purity scrap is refined by electroplating in a bath of sulfuric acid.^[45]

Alloys

Numerous copper alloys have been formulated, many with important uses. Brass is an alloy of copper and zinc. Bronze usually refers to copper-tin alloys, but can refer to any alloy of copper such as aluminium bronze. Copper is one of the most important constituents of silver and karat gold solders used in the jewelry industry, modifying the color, hardness and melting point of the resulting alloys.^[48] Some lead-free solders consist of tin alloyed with a small proportion of copper and other metals.^[49]

The alloy of copper and nickel, called cupronickel, is used in low-denomination coins, often for the outer cladding. The US five-cent coin (currently called a nickel) consists of 75% copper and 25% nickel in homogeneous composition. Prior to the introduction of cupronickel, which was widely adopted by countries in the latter half of the 20th century,^[50] alloys of copper and silver were also used, with the United States using an alloy of 90% silver and 10% copper until 1965, when circulating silver was removed from all coins with the exception of the Half dollar — these were debased to an alloy of 40% silver and 60% copper between 1965 and 1970.^[51] The alloy of 90% copper and 10% nickel, remarkable for its resistance to corrosion, is used for various objects exposed to seawater, though it is vulnerable to the sulfides sometimes found in polluted harbors and estuaries.^[52] Alloys of copper with aluminium (about 7%) have a golden color and are used in decorations.^[23] Shakudō is a Japanese decorative alloy of copper containing a low percentage of gold, typically 4–10%, that can be patinated to a dark blue or black color.^[53]

Compounds

Copper forms a rich variety of compounds, usually with oxidation states +1 and +2, which are often called cuprous and cupric, respectively.^[54] Copper compounds, whether organic complexes or organometallics, promote or catalyse numerous chemical and biological processes.^[55]

Binary compounds

As with other elements, the simplest compounds of copper are binary compounds, i.e. those containing only two elements, the principal examples being 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.^{[citation needed]}

Cuprous halides with fluorine, chlorine, bromine, and iodine are known, as are cupric halides with fluorine, chlorine, and bromine. Attempts to prepare copper(II) iodide yield only copper(I) iodide and iodine.^[54]

2 Cu²⁺ + 4 I⁻ → 2 CuI + I₂

Coordination chemistry

Copper forms coordination complexes with ligands. In aqueous solution, copper(II) exists as [Cu(H
₂O)
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(H
₂O)
₄(OH)
₂ + 4 NH₃ → [Cu(H
₂O)
₂(NH
₃)
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, the most familiar copper compound in the laboratory. It is used in a fungicide called the Bordeaux mixture.^[56]

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.^[57] Schweizer’s reagent and related complexes with ethylenediamine and other amines dissolve cellulose.^[58] Amino acids such as cystine form very stable chelate complexes with copper(II)^[59][60][61] including in the form of metal-organic biohybrids (MOBs). Many wet-chemical tests for copper ions exist, one involving potassium ferrocyanide, which gives a brown precipitate with copper(II) salts.^{[citation needed]}

Organocopper chemistry

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, terminal alkynes or organolithium reagents;^[62] in particular, the last reaction described produces a Gilman reagent. These can undergo substitution with alkyl 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^[63] and the Sonogashira coupling.^[64] Conjugate addition to enones^[65] and carbocupration of alkynes^[66] 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.^[67]

Copper(III) and copper(IV)

Copper(III) is most often found in oxides. A simple example is potassium cuprate, KCuO₂, a blue-black solid.^[68] The most extensively 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^[69] and is known to stabilize metal ions in high oxidation states. Both copper(III) and even copper(IV) fluorides are known, K₃CuF₆ and Cs₂CuF₆, respectively.^[54]

Some copper proteins form oxo complexes, which also feature copper(III).^[70] With tetrapeptides, purple-colored copper(III) complexes are stabilized by the deprotonated amide ligands.^[71]

Complexes of copper(III) are also found as intermediates in reactions of organocopper compounds.^[72] For example, in the Kharasch–Sosnovsky reaction.^{[citation needed]}

History

A timeline of copper illustrates how this metal has advanced human civilization for the past 11,000 years.^[73]

Prehistoric

Copper Age

Copper occurs naturally as native metallic copper and was known to some of the oldest civilizations on record. The history of copper use dates to 9000 BC in the Middle East;^[74] a copper pendant was found in northern Iraq that dates to 8700 BC.^[75] Evidence suggests that gold and meteoric iron (but not smelted iron) were the only metals used by humans before copper.^[76] The history of copper metallurgy is thought to follow this sequence: First, cold working of native copper, then annealing, smelting, and, finally, lost-wax casting. In southeastern Anatolia, all four of these techniques appear more or less simultaneously at the beginning of the Neolithic c. 7500 BC.^[77]

Copper smelting was independently invented in different places. It was probably discovered in China before 2800 BC, in Central America around 600 AD, and in West Africa about the 9th or 10th century AD.^[78] Investment casting was invented in 4500–4000 BC in Southeast Asia^[74] and carbon dating has established mining at Alderley Edge in Cheshire, UK, at 2280 to 1890 BC.^[79] Ötzi the Iceman, a male dated from 3300 to 3200 BC, was found with an axe with a copper head 99.7% pure; high levels of arsenic in his hair suggest an involvement in copper smelting.^[80] Experience with copper has assisted the development of other metals; in particular, copper smelting led to the discovery of iron smelting.^[80] Production in the Old Copper Complex in Michigan and Wisconsin is dated between 6000 and 3000 BC.^[81][82] 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.^[83]

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.^[84] Bronze artifacts from the Vinča culture date to 4500 BC.^[85] Sumerian and Egyptian artifacts of copper and bronze alloys date to 3000 BC.^[86] 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, and 600 BC in Northern Europe. The transition between the Neolithic period and the Bronze Age was formerly termed the Chalcolithic period (copper-stone), when copper tools were used with stone tools. The 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.^[86]

Ancient and post-classical

In Greece, copper was known by the name chalkos (χαλκός). It was an important resource for the Romans, Greeks and other ancient peoples. In Roman times, it was known as aes Cyprium, aes being the generic Latin term for copper alloys and Cyprium from Cyprus, where much copper was mined. The phrase was simplified to cuprum, hence the English copper. Aphrodite (Venus in Rome) represented copper in mythology and alchemy because of its lustrous beauty and its ancient use in producing mirrors; Cyprus, the source of copper, was sacred to the goddess. The seven heavenly bodies known to the ancients were associated with the seven metals known in antiquity, and Venus was assigned to copper, both because of the connection to the goddess and because Venus was the brightest heavenly body after the Sun and Moon and so corresponded to the most lustrous and desirable metal after gold and silver.^[87]

Copper was first mined in ancient Britain as early as 2100 BC. Mining at the largest of these mines, the Great Orme, continued into the late Bronze Age. Mining seems to have been largely restricted to supergene ores, which were easier to smelt. The rich copper deposits of Cornwall seem to have been largely untouched, in spite of extensive tin mining in the region, for reasons likely social and political rather than technological.^[88]

In North America, copper mining began with marginal workings by Native Americans. Native copper is known to have been extracted from sites on Isle Royale with primitive stone tools between 800 and 1600.^[89] Copper metallurgy was flourishing in South America, particularly in Peru around 1000 AD. Copper burial ornamentals from the 15th century have been uncovered, but the metal’s commercial production did not start until the early 20th century.^{[citation needed]}

The cultural role of copper has been important, particularly in currency. Romans in the 6th through 3rd centuries BC used copper lumps as money. At first, the copper itself was valued, but gradually the shape and look of the copper became more important. Julius Caesar had his own coins made from brass, while Octavianus Augustus Caesar’s coins were made from Cu-Pb-Sn alloys. With an estimated annual output of around 15,000 t, Roman copper mining and smelting activities reached a scale unsurpassed until the time of the Industrial Revolution; the provinces most intensely mined were those of Hispania, Cyprus and in Central Europe.^[90][91]

The gates of the Temple of Jerusalem used Corinthian bronze treated with depletion gilding.^{[clarification needed][citation needed]} The process was most prevalent in Alexandria, where alchemy is thought to have begun.^[92] In ancient India, copper was used in the holistic medical science Ayurveda for surgical instruments and other medical equipment. Ancient Egyptians (~2400 BC) used copper for sterilizing wounds and drinking water, and later to treat headaches, burns, and itching.^{[citation needed]}

Modern

The Great Copper Mountain was a mine in Falun, Sweden, that operated from the 10th century to 1992. It satisfied two-thirds of Europe’s copper consumption in the 17th century and helped fund many of Sweden’s wars during that time.^[93] It was referred to as the nation’s treasury; Sweden had a copper backed currency.^[94]

Copper is used in roofing,^[16] currency, and for photographic technology known as the daguerreotype. Copper was used in Renaissance sculpture, and was used to construct the Statue of Liberty; copper continues to be used in construction of various types. Copper plating and copper sheathing were widely used to protect the under-water hulls of ships, a technique pioneered by the British Admiralty in the 18th century.^[95] The Norddeutsche Affinerie in Hamburg was the first modern electroplating plant, starting its production in 1876.^[96] The German scientist Gottfried Osann invented powder metallurgy in 1830 while determining the metal’s atomic mass; around then it was discovered that the amount and type of alloying element (e.g., tin) to copper would affect bell tones.^{[citation needed]}

During the rise in demand for copper for the Age of Electricity, from the 1880s until the Great Depression of the 1930s, the United States produced one third to half the world’s newly mined copper.^[97] Major districts included the Keweenaw district of northern Michigan, primarily native copper deposits, which was eclipsed by the vast sulphide deposits of Butte, Montana in the late 1880s, which itself was eclipsed by porphyry deposits of the Souhwest United States, especially at Bingham Canyon, Utah and Morenci, Arizona. Introduction of open pit steam shovel mining and innovations in smelting, refining, flotation concentration and other processing steps led to mass production. Early in the twentieth century, Arizona ranked first, followed by Montana, then Utah and Michigan.^[98]

Flash smelting was developed by Outokumpu in Finland and first applied at Harjavalta in 1949; the energy-efficient process accounts for 50% of the world’s primary copper production.^[99]

The Intergovernmental Council of Copper Exporting Countries, formed in 1967 by Chile, Peru, Zaire and Zambia, operated in the copper market as OPEC does in oil, though it never achieved the same influence, particularly because the second-largest producer, the United States, was never a member; it was dissolved in 1988.^[100]

Applications

The major applications of copper are electrical wire (60%), roofing and plumbing (20%), and industrial machinery (15%). Copper is used mostly as a pure metal, but when greater hardness is required, it is put into such alloys as brass and bronze (5% of total use).^[23] For more than two centuries, copper paint has been used on boat hulls to control the growth of plants and shellfish.^[101] A small part of the copper supply is used for nutritional supplements and fungicides in agriculture.^[56][102] Machining of copper is possible, although alloys are preferred for good machinability in creating intricate parts.

Wire and cable

Despite competition from other materials, copper remains the preferred electrical conductor in nearly all categories of electrical wiring except overhead electric power transmission where aluminium is often preferred.^[103][104] Copper wire is used in power generation, power transmission, power distribution, telecommunications, electronics circuitry, and countless types of electrical equipment.^[105] Electrical wiring is the most important market for the copper industry.^[106] This includes structural power wiring, power distribution cable, appliance wire, communications cable, automotive wire and cable, and magnet wire. Roughly half of all copper mined is used for electrical wire and cable conductors.^[107] 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, ease of soldering, malleability, and ease of installation.

For a short period from the late 1960s to the late 1970s, copper wiring was replaced by aluminium wiring in many housing construction projects in America. The new wiring was implicated in a number of house fires and the industry returned to copper.^[108]

Electronics and related devices

Integrated circuits and printed circuit boards increasingly feature copper in place of aluminium because of its superior electrical conductivity; heat sinks and heat exchangers use copper because of its superior heat dissipation properties. Electromagnets, vacuum tubes, cathode ray tubes, and magnetrons in microwave ovens use copper, as do waveguides for microwave radiation.^[109]

Electric motors

Copper’s superior conductivity enhances the efficiency of electrical motors.^[110] This is important because motors and motor-driven systems account for 43%–46% of all global electricity consumption and 69% of all electricity used by industry.^[111] Increasing the mass and cross section of copper in a coil increases the efficiency of the motor. Copper motor rotors, a new technology designed for motor applications where energy savings are prime design objectives,^[112][113] are enabling general-purpose induction motors to meet and exceed National Electrical Manufacturers Association (NEMA) premium efficiency standards.^[114]

Renewable energy production

Architecture

Copper has been used since ancient times as a durable, corrosion resistant, and weatherproof architectural material.^{[129][130][131][132]} Roofs, flashings, rain gutters, downspouts, domes, spires, vaults, and doors have been made from copper for hundreds or thousands of years. Copper’s architectural use has been expanded in modern times to include interior and exterior wall cladding, building expansion joints, radio frequency shielding, and antimicrobial and decorative indoor products such as attractive handrails, bathroom fixtures, and counter tops. Some of copper’s other important benefits as an architectural material include low thermal movement, light weight, lightning protection, and recyclability

The metal’s distinctive natural green patina has long been coveted by architects and designers. The final patina is a particularly durable layer that is highly resistant to atmospheric corrosion, thereby protecting the underlying metal against further weathering.^{[133][134][135]} It can be a mixture of carbonate and sulfate compounds in various amounts, depending upon environmental conditions such as sulfur-containing acid rain.^{[136][137][138][139]} Architectural copper and its alloys can also be ‘finished’ to take on a particular look, feel, or color. Finishes include mechanical surface treatments, chemical coloring, and coatings.^[140]

Copper has excellent brazing and soldering properties and can be welded; the best results are obtained with gas metal arc welding.^[141]

Antibiofouling

Copper is biostatic, meaning bacteria and many other forms of life will not grow on it. For this reason it has long been used to line parts of ships to protect against barnacles and mussels. It was originally used pure, but has since been superseded by Muntz metal and copper-based paint. Similarly, as discussed in copper alloys in aquaculture, copper alloys have become important netting materials in the aquaculture industry because they are antimicrobial and prevent biofouling, even in extreme conditions^[142] and have strong structural and corrosion-resistant^[143] properties in marine environments.

Antimicrobial

Copper-alloy touch surfaces have natural properties that destroy a wide range of microorganisms (e.g., E. coli O157:H7, methicillin-resistant Staphylococcus aureus (MRSA), Staphylococcus, Clostridium difficile, influenza A virus, adenovirus, SARS-Cov-2, and fungi).^[144][145] Indians have been using copper vessels since ancient times for storing water, even before modern science realized its antimicrobial properties.^[146] Some copper alloys were proven to kill more than 99.9% of disease-causing bacteria within just two hours when cleaned regularly.^[147] The United States Environmental Protection Agency (EPA) has approved the registrations of these copper alloys as «antimicrobial materials with public health benefits»;^[147] that approval allows manufacturers to make legal claims to the public health benefits of products made of registered alloys. In addition, the EPA has approved a long list of antimicrobial copper products made from these alloys, such as bedrails, handrails, over-bed tables, sinks, faucets, door knobs, toilet hardware, computer keyboards, health club equipment, and shopping cart handles (for a comprehensive list, see: Antimicrobial copper-alloy touch surfaces#Approved products). Copper doorknobs are used by hospitals to reduce the transfer of disease, and Legionnaires’ disease is suppressed by copper tubing in plumbing systems.^[148] Antimicrobial copper alloy products are now being installed in healthcare facilities in the U.K., Ireland, Japan, Korea, France, Denmark, and Brazil, as well as being called for in the US,^[149] and in the subway transit system in Santiago, Chile, where copper-zinc alloy handrails were installed in some 30 stations between 2011 and 2014.^{[150][151][152]}
Textile fibers can be blended with copper to create antimicrobial protective fabrics.^{[153][unreliable source?]}

Speculative investing

Copper may be used as a speculative investment due to the predicted increase in use from worldwide infrastructure growth, and the important role it has in producing wind turbines, solar panels, and other renewable energy sources.^[154][155] Another reason predicted demand increases is the fact that electric cars contain an average of 3.6 times as much copper as conventional cars, although the effect of electric cars on copper demand is debated.^[156][157] Some people invest in copper through copper mining stocks, ETFs, and futures. Others store physical copper in the form of copper bars or rounds although these tend to carry a higher premium in comparison to precious metals.^[158] Those who want to avoid the premiums of copper bullion alternatively store old copper wire, copper tubing or American pennies made before 1982.^[159]

Folk medicine

Copper is commonly used in jewelry, and according to some folklore, copper bracelets relieve arthritis symptoms.^[160] In one trial for osteoarthritis and one trial for rheumatoid arthritis, no differences is found between copper bracelet and control (non-copper) bracelet.^[161][162] No evidence shows that copper can be absorbed through the skin. If it were, it might lead to copper poisoning.^[163]

Compression clothing

Recently, some compression clothing with inter-woven copper has been marketed with health claims similar to the folk medicine claims. Because compression clothing is a valid treatment for some ailments, the clothing may have that benefit, but the added copper may have no benefit beyond a placebo effect.^[164]

Degradation

Chromobacterium violaceum and Pseudomonas fluorescens can both mobilize solid copper as a cyanide compound.^[165] The ericoid mycorrhizal fungi associated with Calluna, Erica and Vaccinium can grow in metalliferous soils containing copper.^[165] The ectomycorrhizal fungus Suillus luteus protects young pine trees from copper toxicity. A sample of the fungus Aspergillus niger was found growing from gold mining solution and was found to contain cyano complexes of such metals as gold, silver, copper, iron, and zinc. The fungus also plays a role in the solubilization of heavy metal sulfides.^[166]

Biological role

Biochemistry

Copper proteins have diverse roles in biological electron transport and oxygen transportation, processes that exploit the easy interconversion of Cu(I) and Cu(II).^[167] Copper is essential in the aerobic respiration of all eukaryotes. In mitochondria, it is found in cytochrome c oxidase, which is the last protein in oxidative phosphorylation. Cytochrome c oxidase is the protein that binds the O₂ between a copper and an iron; the protein transfers 8 electrons to the O₂ molecule to reduce it to two molecules of water. Copper is also found in many superoxide dismutases, proteins that catalyze the decomposition of superoxides by converting it (by disproportionation) to oxygen and hydrogen peroxide:

• Cu²⁺-SOD + O₂⁻ → Cu⁺-SOD + O₂ (reduction of copper; oxidation of superoxide)
• Cu⁺-SOD + O₂⁻ + 2H⁺ → Cu²⁺-SOD + H₂O₂ (oxidation of copper; reduction of superoxide)

The protein hemocyanin is the oxygen carrier in most mollusks and some arthropods such as the horseshoe crab (Limulus polyphemus).^[168] Because hemocyanin is blue, these organisms have blue blood rather than the red blood of iron-based hemoglobin. Structurally related to hemocyanin are the laccases and tyrosinases. Instead of reversibly binding oxygen, these proteins hydroxylate substrates, illustrated by their role in the formation of lacquers.^[169] The biological role for copper commenced with the appearance of oxygen in earth’s atmosphere.^[170] Several copper proteins, such as the «blue copper proteins», do not interact directly with substrates; hence they are not enzymes. These proteins relay electrons by the process called electron transfer.^[169]

A unique tetranuclear copper center has been found in nitrous-oxide reductase.^[171]

Chemical compounds which were developed for treatment of Wilson’s disease have been investigated for use in cancer therapy.^[172]

Nutrition

Copper is an essential trace element in plants and animals, but not all microorganisms. The human body contains copper at a level of about 1.4 to 2.1 mg per kg of body mass.^[173]

Absorption

Copper is absorbed in the gut, then transported to the liver bound to albumin.^[174] After processing in the liver, copper is distributed to other tissues in a second phase, which involves the protein ceruloplasmin, carrying the majority of copper in blood. Ceruloplasmin also carries the copper that is excreted in milk, and is particularly well-absorbed as a copper source.^[175] Copper in the body normally undergoes enterohepatic circulation (about 5 mg a day, vs. about 1 mg per day absorbed in the diet and excreted from the body), and the body is able to excrete some excess copper, if needed, via bile, which carries some copper out of the liver that is not then reabsorbed by the intestine.^[176][177]

Dietary recommendations

The U.S. Institute of Medicine (IOM) updated the estimated average requirements (EARs) and recommended dietary allowances (RDAs) for copper in 2001. If there is not sufficient information to establish EARs and RDAs, an estimate designated Adequate Intake (AI) is used instead. The AIs for copper are: 200 μg of copper for 0–6-month-old males and females, and 220 μg of copper for 7–12-month-old males and females. For both sexes, the RDAs for copper are: 340 μg of copper for 1–3 years old, 440 μg of copper for 4–8 years old, 700 μg of copper for 9–13 years old, 890 μg of copper for 14–18 years old and 900 μg of copper for ages 19 years and older. For pregnancy, 1,000 μg. For lactation, 1,300 μg.^[178] As for safety, the IOM also sets tolerable upper intake levels (ULs) for vitamins and minerals when evidence is sufficient. In the case of copper the UL is set at 10 mg/day. Collectively the EARs, RDAs, AIs and ULs are referred to as Dietary Reference Intakes.^[179]

The European Food Safety Authority (EFSA) refers to the collective set of information as Dietary Reference Values, with Population Reference Intake (PRI) instead of RDA, and Average Requirement instead of EAR. AI and UL defined the same as in United States. For women and men ages 18 and older the AIs are set at 1.3 and 1.6 mg/day, respectively. AIs for pregnancy and lactation is 1.5 mg/day. For children ages 1–17 years the AIs increase with age from 0.7 to 1.3 mg/day. These AIs are higher than the U.S. RDAs.^[180] The European Food Safety Authority reviewed the same safety question and set its UL at 5 mg/day, which is half the U.S. value.^[181]

For U.S. food and dietary supplement labeling purposes the amount in a serving is expressed as a percent of Daily Value (%DV). For copper labeling purposes 100% of the Daily Value was 2.0 mg, but as of May 27, 2016 it was revised to 0.9 mg to bring it into agreement with the RDA.^[182][183] A table of the old and new adult daily values is provided at Reference Daily Intake.

Deficiency

Because of its role in facilitating iron uptake, copper deficiency can produce anemia-like symptoms, neutropenia, bone abnormalities, hypopigmentation, impaired growth, increased incidence of infections, osteoporosis, hyperthyroidism, and abnormalities in glucose and cholesterol metabolism. Conversely, Wilson’s disease causes an accumulation of copper in body tissues.

Severe deficiency can be found by testing for low plasma or serum copper levels, low ceruloplasmin, and low red blood cell superoxide dismutase levels; these are not sensitive to marginal copper status. The «cytochrome c oxidase activity of leucocytes and platelets» has been stated as another factor in deficiency, but the results have not been confirmed by replication.^[184]

Toxicity

Gram quantities of various copper salts have been taken in suicide attempts and produced acute copper toxicity in humans, possibly due to redox cycling and the generation of reactive oxygen species that damage DNA.^[185][186] Corresponding amounts of copper salts (30 mg/kg) are toxic in animals.^[187] A minimum dietary value for healthy growth in rabbits has been reported to be at least 3 ppm in the diet.^[188] However, higher concentrations of copper (100 ppm, 200 ppm, or 500 ppm) in the diet of rabbits may favorably influence feed conversion efficiency, growth rates, and carcass dressing percentages.^[189]

Chronic copper toxicity does not normally occur in humans because of transport systems that regulate absorption and excretion. Autosomal recessive mutations in copper transport proteins can disable these systems, leading to Wilson’s disease with copper accumulation and cirrhosis of the liver in persons who have inherited two defective genes.^[173]

Elevated copper levels have also been linked to worsening symptoms of Alzheimer’s disease.^[190][191]

Human exposure

In the US, the Occupational Safety and Health Administration (OSHA) has designated a permissible exposure limit (PEL) for copper dust and fumes in the workplace as a time-weighted average (TWA) of 1 mg/m³.^[192] The National Institute for Occupational Safety and Health (NIOSH) has set a recommended exposure limit (REL) of 1 mg/m³, time-weighted average. The IDLH (immediately dangerous to life and health) value is 100 mg/m³.^[193]

Copper is a constituent of tobacco smoke.^[194][195] The tobacco plant readily absorbs and accumulates heavy metals, such as copper from the surrounding soil into its leaves. These are readily absorbed into the user’s body following smoke inhalation.^[196] The health implications are not clear.^[197]

See also

• Copper in renewable energy
• Copper nanoparticle
• Erosion corrosion of copper water tubes
  • Cold water pitting of copper tube
• List of countries by copper production
• Metal theft
  • Operation Tremor

• Anaconda Copper
• Antofagasta PLC
• Codelco
• El Boleo mine
• Grasberg mine

References

Notes

Pourbaix diagrams for copper

in pure water, or acidic or alkali conditions. Copper in neutral water is more noble than hydrogen.	in water containing sulfide	in 10 M ammonia solution	in a chloride solution

Further reading

• Massaro, Edward J., ed. (2002). Handbook of Copper Pharmacology and Toxicology. Humana Press. ISBN 978-0-89603-943-8.
• «Copper: Technology & Competitiveness (Summary) Chapter 6: Copper Production Technology» (PDF). Office of Technology Assessment. 2005.
• Current Medicinal Chemistry, Volume 12, Number 10, May 2005, pp. 1161–1208(48) Metals, Toxicity and Oxidative Stress
• William D. Callister (2003). Materials Science and Engineering: an Introduction (6th ed.). Wiley, New York. Table 6.1, p. 137. ISBN 978-0-471-73696-7.
• Material: Copper (Cu), bulk, MEMS and Nanotechnology Clearinghouse.
• Kim BE; Nevitt T; Thiele DJ (2008). «Mechanisms for copper acquisition, distribution and regulation». Nat. Chem. Biol. 4 (3): 176–85. doi:10.1038/nchembio.72. PMID 18277979.

External links

• Copper at The Periodic Table of Videos (University of Nottingham)
• Copper and compounds fact sheet from the National Pollutant Inventory of Australia
• Copper.org – official website of the Copper Development Association with an extensive site of properties and uses of copper
• Price history of copper, according to the IMF

Copper, ₂₉Cu

Copper
Appearance	red-orange metallic luster
Standard atomic weight Ar°(Cu)	63.546±0.003 63.546±0.003 (abridged)[1]
Copper in the periodic table
Hydrogen Helium Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson – ↑ Cu ↓ Ag nickel ← copper → zinc
Atomic number (Z)	29
Group	group 11
Period	period 4
Block	d-block
Electron configuration	[Ar] 3d10 4s1
Electrons per shell	2, 8, 18, 1
Physical properties
Phase at STP	solid
Melting point	1357.77 K ​(1084.62 °C, ​1984.32 °F)
Boiling point	2835 K ​(2562 °C, ​4643 °F)
Density (near r.t.)	8.96 g/cm3
when liquid (at m.p.)	8.02 g/cm3
Heat of fusion	13.26 kJ/mol
Heat of vaporization	300.4 kJ/mol
Molar heat capacity	24.440 J/(mol·K)
Vapor pressure P (Pa) 1 10 100 1 k 10 k 100 k at T (K) 1509 1661 1850 2089 2404 2834
Atomic properties
Oxidation states	−2, 0,[2] +1, +2, +3, +4 (a mildly basic oxide)
Electronegativity	Pauling scale: 1.90
Ionization energies	1st: 745.5 kJ/mol 2nd: 1957.9 kJ/mol 3rd: 3555 kJ/mol (more)
Atomic radius	empirical: 128 pm
Covalent radius	132±4 pm
Van der Waals radius	140 pm
Spectral lines of copper
Other properties
Natural occurrence	primordial
Crystal structure	​face-centered cubic (fcc)
Speed of sound thin rod	(annealed) 3810 m/s (at r.t.)
Thermal expansion	16.5 µm/(m⋅K) (at 25 °C)
Thermal conductivity	401 W/(m⋅K)
Electrical resistivity	16.78 nΩ⋅m (at 20 °C)
Magnetic ordering	diamagnetic[3]
Molar magnetic susceptibility	−5.46×10−6 cm3/mol[4]
Young’s modulus	110–128 GPa
Shear modulus	48 GPa
Bulk modulus	140 GPa
Poisson ratio	0.34
Mohs hardness	3.0
Vickers hardness	343–369 MPa
Brinell hardness	235–878 MPa
CAS Number	7440-50-8
History
Naming	after Cyprus, principal mining place in Roman era (Cyprium)
Discovery	Middle East (9000 BC)
Symbol	«Cu»: from Latin cuprum
Main isotopes of copper v e
Iso­tope Decay abun­dance half-life (t1/2) mode pro­duct 63Cu 69.17% stable 64Cu syn 12.70 h ε 64Ni β− 64Zn 65Cu 30.83% stable 67Cu syn 61.83 h β− 67Zn
Category: Copper view talk edit | references

Copper is a chemical element with the symbol Cu (from Latin: cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkish-orange color. Copper is used as a conductor of heat and electricity, as a building material, and as a constituent of various metal alloys, such as sterling silver used in jewelry, cupronickel used to make marine hardware and coins, and constantan used in strain gauges and thermocouples for temperature measurement.

Copper is one of the few metals that can occur in nature in a directly usable metallic form (native metals). This led to very early human use in several regions, from circa 8000 BC. Thousands of years later, it was the first metal to be smelted from sulfide ores, circa 5000 BC; the first metal to be cast into a shape in a mold, c. 4000 BC; and the first metal to be purposely alloyed with another metal, tin, to create bronze, c. 3500 BC.^[5]

In the Roman era, copper was mined principally on Cyprus, the origin of the name of the metal, from aes cyprium (metal of Cyprus), later corrupted to cuprum (Latin). Coper (Old English) and copper were derived from this, the later spelling first used around 1530.^[6]

Commonly encountered compounds are copper(II) salts, which often impart blue or green colors to such minerals as azurite, malachite, and turquoise, and have been used widely and historically as pigments.

Copper used in buildings, usually for roofing, oxidizes to form a green verdigris (or patina). Copper is sometimes used in decorative art, both in its elemental metal form and in compounds as pigments. Copper compounds are used as bacteriostatic agents, fungicides, and wood preservatives.

Copper is essential to all living organisms as a trace dietary mineral because it is a key constituent of the respiratory enzyme complex cytochrome c oxidase. In molluscs and crustaceans, copper is a constituent of the blood pigment hemocyanin, replaced by the iron-complexed hemoglobin in fish and other vertebrates. In humans, copper is found mainly in the liver, muscle, and bone.^[7] The adult body contains between 1.4 and 2.1 mg of copper per kilogram of body weight.^[8]

Characteristics

Physical

Copper, silver, and gold are in group 11 of the periodic table; these three metals have one s-orbital electron on top of a filled d-electron shell and are characterized by high ductility, and electrical and thermal conductivity. The filled d-shells in these elements contribute little to interatomic interactions, which are dominated by the s-electrons through metallic bonds. Unlike metals with incomplete d-shells, metallic bonds in copper are lacking a covalent character and are relatively weak. This observation explains the low hardness and high ductility of single crystals of copper.^[9] 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.^[10]

The softness of copper partly explains its high electrical conductivity (59.6×10⁶ S/m) and high thermal conductivity, second highest (second only to silver) among pure metals at room temperature.^[11] This is because the resistivity to electron transport in metals at room temperature originates primarily from scattering of electrons on thermal vibrations of the lattice, which are relatively weak in a soft metal.^[9] 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.^[12]

Copper is one of a few metallic elements with a natural color other than gray or silver.^[13] Pure copper is orange-red and acquires a reddish tarnish when exposed to air. The is due to the low plasma frequency of the metal, which lies in the red part of the visible spectrum, causing it to absorb the higher-frequency green and blue colors.^[14]

As with other metals, if copper is put in contact with another metal, galvanic corrosion will occur.^[15]

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 that forms on iron in moist air, protects the underlying metal from further corrosion (passivation). A green layer of verdigris (copper carbonate) can often be seen on old copper structures, such as the roofing of many older buildings^[16] and the Statue of Liberty.^[17] Copper tarnishes when exposed to some sulfur compounds, with which it reacts to form various copper sulfides.^[18]

Isotopes

There are 29 isotopes of copper. ⁶³
Cu
and ⁶⁵
Cu
are stable, with ⁶³
Cu
comprising approximately 69% of naturally occurring copper; both have a spin of 3⁄2.^[19] The other isotopes are radioactive, with the most stable being ⁶⁷
Cu
with a half-life of 61.83 hours.^[19] Seven metastable isotopes have been characterized; ^68m
Cu
is the longest-lived with a half-life of 3.8 minutes. Isotopes with a mass number above 64 decay by β⁻, whereas those with a mass number below 64 decay by β⁺. ⁶⁴
Cu
, which has a half-life of 12.7 hours, decays both ways.^[20]

⁶²
Cu
and ⁶⁴
Cu
have significant applications. ⁶²
Cu
is used in ⁶²
Cu
Cu-PTSM as a radioactive tracer for positron emission tomography.^[21]

Occurrence

Copper is produced in massive stars^[22] and is present in the Earth’s crust in a proportion of about 50 parts per million (ppm).^[23] In nature, copper occurs in a variety of minerals, including native copper, copper sulfides such as chalcopyrite, bornite, digenite, covellite, and chalcocite, copper sulfosalts such as tetrahedite-tennantite, and enargite, copper carbonates such as azurite and malachite, and as copper(I) or copper(II) oxides such as cuprite and tenorite, respectively.^[11] The largest mass of elemental copper discovered weighed 420 tonnes and was found in 1857 on the Keweenaw Peninsula in Michigan, US.^[23] Native copper is a polycrystal, with the largest single crystal ever described measuring 4.4 × 3.2 × 3.2 cm.^[24] Copper is the 25th most abundant element in Earth’s crust, representing 50 ppm compared with 75 ppm for zinc, and 14 ppm for lead.^[25]

Typical background concentrations of copper do not exceed 1 ng/m³ in the atmosphere; 150 mg/kg in soil; 30 mg/kg in vegetation; 2 μg/L in freshwater and 0.5 μg/L in seawater.^[26]

Production

Most copper is mined or extracted as copper sulfides from large open pit mines in porphyry copper deposits that contain 0.4 to 1.0% copper. Sites include Chuquicamata, in Chile, Bingham Canyon Mine, in Utah, United States, and El Chino Mine, in New Mexico, United States. According to the British Geological Survey, in 2005, Chile was the top producer of copper with at least one-third of the world share followed by the United States, Indonesia and Peru.^[11] Copper can also be recovered through the in-situ leach process. Several sites in the state of Arizona are considered prime candidates for this method.^[27] The amount of copper in use is increasing and the quantity available is barely sufficient to allow all countries to reach developed world levels of usage.^[28] An alternative source of copper for collection currently being researched are polymetallic nodules, which are located at the depths of the Pacific Ocean approximately 3000–6500 meters below sea level. These nodules contain other valuable metals such as cobalt and nickel.^[29]

Reserves and prices

Copper has been in use at least 10,000 years, but more than 95% of all copper ever mined and smelted has been extracted since 1900.^[30] As with many natural resources, the total amount of copper on Earth is vast, with around 10¹⁴ tons in the top kilometer of Earth’s crust, which is about 5 million years’ worth at the current rate of extraction. However, only a tiny fraction of these reserves is economically viable with present-day prices and technologies. Estimates of copper reserves available for mining vary from 25 to 60 years, depending on core assumptions such as the growth rate.^[31] Recycling is a major source of copper in the modern world.^[30] Because of these and other factors, the future of copper production and supply is the subject of much debate, including the concept of peak copper, analogous to peak oil.^{[citation needed]}

The price of copper has historically been unstable,^[32] and its price increased from the 60-year low of US$0.60/lb (US$1.32/kg) in June 1999 to $3.75 per pound ($8.27/kg) in May 2006. It dropped to $2.40/lb ($5.29/kg) in February 2007, then rebounded to $3.50/lb ($7.71/kg) in April 2007.^{[33][better source needed]} In February 2009, weakening global demand and a steep fall in commodity prices since the previous year’s highs left copper prices at $1.51/lb ($3.32/kg).^[34] Between September 2010 and February 2011, the price of copper rose from £5,000 a metric ton to £6,250 a metric ton.^[35]

Methods

The concentration of copper in ores averages only 0.6%, and most commercial ores are sulfides, especially chalcopyrite (CuFeS₂), bornite (Cu₅FeS₄) and, to a lesser extent, covellite (CuS) and chalcocite (Cu₂S).^[36] Conversely, the average concentration of copper in polymetallic nodules is estimated at 1.3%. The methods of extracting copper as well as other metals found in these nodules include sulphuric leaching, smelting and an application of the Cuprion process.^[37][38] For minerals found in land ores, they are concentrated from crushed ores to the level of 10–15% copper by froth flotation or bioleaching.^[39] Heating this material with silica in flash smelting removes much of the iron as slag. The process exploits the greater ease of converting iron sulfides into oxides, which in turn react with the silica to form the silicate slag that floats on top of the heated mass. The resulting copper matte, consisting of Cu₂S, is roasted to convert the sulfides into oxides:^[36]

2 Cu₂S + 3 O₂ → 2 Cu₂O + 2 SO₂

The cuprous oxide reacts with cuprous sulfide to converted to blister copper upon heating:

2 Cu₂O + Cu₂S → 6 Cu + 2 SO₂

The Sudbury matte process converted only half the sulfide to oxide and then used this oxide to remove the rest of the sulfur as oxide. It was then electrolytically refined and the anode mud exploited for the platinum and gold it contained. This step exploits the relatively easy reduction of copper oxides to copper metal. Natural gas is blown across the blister to remove most of the remaining oxygen and electrorefining is performed on the resulting material to produce pure copper:^[40]

Cu²⁺ + 2 e⁻ → Cu

Recycling

Like aluminium,^[41] copper is recyclable without any loss of quality, both from raw state and from manufactured products.^[42] In volume, copper is the third most recycled metal after iron and aluminium.^[43] An estimated 80% of all copper ever mined is still in use today.^[44] According to the International Resource Panel’s Metal Stocks in Society report, the global per capita stock of copper in use in society is 35–55 kg. Much of this is in more-developed countries (140–300 kg per capita) rather than less-developed countries (30–40 kg per capita).

The process of recycling copper is roughly the same as is used to extract copper but requires fewer steps. High-purity scrap copper is melted in a furnace and then reduced and cast into billets and ingots; lower-purity scrap is refined by electroplating in a bath of sulfuric acid.^[45]

Alloys

Numerous copper alloys have been formulated, many with important uses. Brass is an alloy of copper and zinc. Bronze usually refers to copper-tin alloys, but can refer to any alloy of copper such as aluminium bronze. Copper is one of the most important constituents of silver and karat gold solders used in the jewelry industry, modifying the color, hardness and melting point of the resulting alloys.^[48] Some lead-free solders consist of tin alloyed with a small proportion of copper and other metals.^[49]

The alloy of copper and nickel, called cupronickel, is used in low-denomination coins, often for the outer cladding. The US five-cent coin (currently called a nickel) consists of 75% copper and 25% nickel in homogeneous composition. Prior to the introduction of cupronickel, which was widely adopted by countries in the latter half of the 20th century,^[50] alloys of copper and silver were also used, with the United States using an alloy of 90% silver and 10% copper until 1965, when circulating silver was removed from all coins with the exception of the Half dollar — these were debased to an alloy of 40% silver and 60% copper between 1965 and 1970.^[51] The alloy of 90% copper and 10% nickel, remarkable for its resistance to corrosion, is used for various objects exposed to seawater, though it is vulnerable to the sulfides sometimes found in polluted harbors and estuaries.^[52] Alloys of copper with aluminium (about 7%) have a golden color and are used in decorations.^[23] Shakudō is a Japanese decorative alloy of copper containing a low percentage of gold, typically 4–10%, that can be patinated to a dark blue or black color.^[53]

Compounds

Copper forms a rich variety of compounds, usually with oxidation states +1 and +2, which are often called cuprous and cupric, respectively.^[54] Copper compounds, whether organic complexes or organometallics, promote or catalyse numerous chemical and biological processes.^[55]

Binary compounds

As with other elements, the simplest compounds of copper are binary compounds, i.e. those containing only two elements, the principal examples being 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.^{[citation needed]}

Cuprous halides with fluorine, chlorine, bromine, and iodine are known, as are cupric halides with fluorine, chlorine, and bromine. Attempts to prepare copper(II) iodide yield only copper(I) iodide and iodine.^[54]

2 Cu²⁺ + 4 I⁻ → 2 CuI + I₂

Coordination chemistry

Copper forms coordination complexes with ligands. In aqueous solution, copper(II) exists as [Cu(H
₂O)
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(H
₂O)
₄(OH)
₂ + 4 NH₃ → [Cu(H
₂O)
₂(NH
₃)
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, the most familiar copper compound in the laboratory. It is used in a fungicide called the Bordeaux mixture.^[56]

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.^[57] Schweizer’s reagent and related complexes with ethylenediamine and other amines dissolve cellulose.^[58] Amino acids such as cystine form very stable chelate complexes with copper(II)^[59][60][61] including in the form of metal-organic biohybrids (MOBs). Many wet-chemical tests for copper ions exist, one involving potassium ferrocyanide, which gives a brown precipitate with copper(II) salts.^{[citation needed]}

Organocopper chemistry

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, terminal alkynes or organolithium reagents;^[62] in particular, the last reaction described produces a Gilman reagent. These can undergo substitution with alkyl 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^[63] and the Sonogashira coupling.^[64] Conjugate addition to enones^[65] and carbocupration of alkynes^[66] 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.^[67]

Copper(III) and copper(IV)

Copper(III) is most often found in oxides. A simple example is potassium cuprate, KCuO₂, a blue-black solid.^[68] The most extensively 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^[69] and is known to stabilize metal ions in high oxidation states. Both copper(III) and even copper(IV) fluorides are known, K₃CuF₆ and Cs₂CuF₆, respectively.^[54]

Some copper proteins form oxo complexes, which also feature copper(III).^[70] With tetrapeptides, purple-colored copper(III) complexes are stabilized by the deprotonated amide ligands.^[71]

Complexes of copper(III) are also found as intermediates in reactions of organocopper compounds.^[72] For example, in the Kharasch–Sosnovsky reaction.^{[citation needed]}

History

A timeline of copper illustrates how this metal has advanced human civilization for the past 11,000 years.^[73]

Prehistoric

Copper Age

Copper occurs naturally as native metallic copper and was known to some of the oldest civilizations on record. The history of copper use dates to 9000 BC in the Middle East;^[74] a copper pendant was found in northern Iraq that dates to 8700 BC.^[75] Evidence suggests that gold and meteoric iron (but not smelted iron) were the only metals used by humans before copper.^[76] The history of copper metallurgy is thought to follow this sequence: First, cold working of native copper, then annealing, smelting, and, finally, lost-wax casting. In southeastern Anatolia, all four of these techniques appear more or less simultaneously at the beginning of the Neolithic c. 7500 BC.^[77]

Copper smelting was independently invented in different places. It was probably discovered in China before 2800 BC, in Central America around 600 AD, and in West Africa about the 9th or 10th century AD.^[78] Investment casting was invented in 4500–4000 BC in Southeast Asia^[74] and carbon dating has established mining at Alderley Edge in Cheshire, UK, at 2280 to 1890 BC.^[79] Ötzi the Iceman, a male dated from 3300 to 3200 BC, was found with an axe with a copper head 99.7% pure; high levels of arsenic in his hair suggest an involvement in copper smelting.^[80] Experience with copper has assisted the development of other metals; in particular, copper smelting led to the discovery of iron smelting.^[80] Production in the Old Copper Complex in Michigan and Wisconsin is dated between 6000 and 3000 BC.^[81][82] 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.^[83]

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.^[84] Bronze artifacts from the Vinča culture date to 4500 BC.^[85] Sumerian and Egyptian artifacts of copper and bronze alloys date to 3000 BC.^[86] 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, and 600 BC in Northern Europe. The transition between the Neolithic period and the Bronze Age was formerly termed the Chalcolithic period (copper-stone), when copper tools were used with stone tools. The 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.^[86]

Ancient and post-classical

In Greece, copper was known by the name chalkos (χαλκός). It was an important resource for the Romans, Greeks and other ancient peoples. In Roman times, it was known as aes Cyprium, aes being the generic Latin term for copper alloys and Cyprium from Cyprus, where much copper was mined. The phrase was simplified to cuprum, hence the English copper. Aphrodite (Venus in Rome) represented copper in mythology and alchemy because of its lustrous beauty and its ancient use in producing mirrors; Cyprus, the source of copper, was sacred to the goddess. The seven heavenly bodies known to the ancients were associated with the seven metals known in antiquity, and Venus was assigned to copper, both because of the connection to the goddess and because Venus was the brightest heavenly body after the Sun and Moon and so corresponded to the most lustrous and desirable metal after gold and silver.^[87]

Copper was first mined in ancient Britain as early as 2100 BC. Mining at the largest of these mines, the Great Orme, continued into the late Bronze Age. Mining seems to have been largely restricted to supergene ores, which were easier to smelt. The rich copper deposits of Cornwall seem to have been largely untouched, in spite of extensive tin mining in the region, for reasons likely social and political rather than technological.^[88]

In North America, copper mining began with marginal workings by Native Americans. Native copper is known to have been extracted from sites on Isle Royale with primitive stone tools between 800 and 1600.^[89] Copper metallurgy was flourishing in South America, particularly in Peru around 1000 AD. Copper burial ornamentals from the 15th century have been uncovered, but the metal’s commercial production did not start until the early 20th century.^{[citation needed]}

The cultural role of copper has been important, particularly in currency. Romans in the 6th through 3rd centuries BC used copper lumps as money. At first, the copper itself was valued, but gradually the shape and look of the copper became more important. Julius Caesar had his own coins made from brass, while Octavianus Augustus Caesar’s coins were made from Cu-Pb-Sn alloys. With an estimated annual output of around 15,000 t, Roman copper mining and smelting activities reached a scale unsurpassed until the time of the Industrial Revolution; the provinces most intensely mined were those of Hispania, Cyprus and in Central Europe.^[90][91]

The gates of the Temple of Jerusalem used Corinthian bronze treated with depletion gilding.^{[clarification needed][citation needed]} The process was most prevalent in Alexandria, where alchemy is thought to have begun.^[92] In ancient India, copper was used in the holistic medical science Ayurveda for surgical instruments and other medical equipment. Ancient Egyptians (~2400 BC) used copper for sterilizing wounds and drinking water, and later to treat headaches, burns, and itching.^{[citation needed]}

Modern

The Great Copper Mountain was a mine in Falun, Sweden, that operated from the 10th century to 1992. It satisfied two-thirds of Europe’s copper consumption in the 17th century and helped fund many of Sweden’s wars during that time.^[93] It was referred to as the nation’s treasury; Sweden had a copper backed currency.^[94]

Copper is used in roofing,^[16] currency, and for photographic technology known as the daguerreotype. Copper was used in Renaissance sculpture, and was used to construct the Statue of Liberty; copper continues to be used in construction of various types. Copper plating and copper sheathing were widely used to protect the under-water hulls of ships, a technique pioneered by the British Admiralty in the 18th century.^[95] The Norddeutsche Affinerie in Hamburg was the first modern electroplating plant, starting its production in 1876.^[96] The German scientist Gottfried Osann invented powder metallurgy in 1830 while determining the metal’s atomic mass; around then it was discovered that the amount and type of alloying element (e.g., tin) to copper would affect bell tones.^{[citation needed]}

During the rise in demand for copper for the Age of Electricity, from the 1880s until the Great Depression of the 1930s, the United States produced one third to half the world’s newly mined copper.^[97] Major districts included the Keweenaw district of northern Michigan, primarily native copper deposits, which was eclipsed by the vast sulphide deposits of Butte, Montana in the late 1880s, which itself was eclipsed by porphyry deposits of the Souhwest United States, especially at Bingham Canyon, Utah and Morenci, Arizona. Introduction of open pit steam shovel mining and innovations in smelting, refining, flotation concentration and other processing steps led to mass production. Early in the twentieth century, Arizona ranked first, followed by Montana, then Utah and Michigan.^[98]

Flash smelting was developed by Outokumpu in Finland and first applied at Harjavalta in 1949; the energy-efficient process accounts for 50% of the world’s primary copper production.^[99]

The Intergovernmental Council of Copper Exporting Countries, formed in 1967 by Chile, Peru, Zaire and Zambia, operated in the copper market as OPEC does in oil, though it never achieved the same influence, particularly because the second-largest producer, the United States, was never a member; it was dissolved in 1988.^[100]

Applications

The major applications of copper are electrical wire (60%), roofing and plumbing (20%), and industrial machinery (15%). Copper is used mostly as a pure metal, but when greater hardness is required, it is put into such alloys as brass and bronze (5% of total use).^[23] For more than two centuries, copper paint has been used on boat hulls to control the growth of plants and shellfish.^[101] A small part of the copper supply is used for nutritional supplements and fungicides in agriculture.^[56][102] Machining of copper is possible, although alloys are preferred for good machinability in creating intricate parts.

Wire and cable

Despite competition from other materials, copper remains the preferred electrical conductor in nearly all categories of electrical wiring except overhead electric power transmission where aluminium is often preferred.^[103][104] Copper wire is used in power generation, power transmission, power distribution, telecommunications, electronics circuitry, and countless types of electrical equipment.^[105] Electrical wiring is the most important market for the copper industry.^[106] This includes structural power wiring, power distribution cable, appliance wire, communications cable, automotive wire and cable, and magnet wire. Roughly half of all copper mined is used for electrical wire and cable conductors.^[107] 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, ease of soldering, malleability, and ease of installation.

For a short period from the late 1960s to the late 1970s, copper wiring was replaced by aluminium wiring in many housing construction projects in America. The new wiring was implicated in a number of house fires and the industry returned to copper.^[108]

Electronics and related devices

Integrated circuits and printed circuit boards increasingly feature copper in place of aluminium because of its superior electrical conductivity; heat sinks and heat exchangers use copper because of its superior heat dissipation properties. Electromagnets, vacuum tubes, cathode ray tubes, and magnetrons in microwave ovens use copper, as do waveguides for microwave radiation.^[109]

Electric motors

Copper’s superior conductivity enhances the efficiency of electrical motors.^[110] This is important because motors and motor-driven systems account for 43%–46% of all global electricity consumption and 69% of all electricity used by industry.^[111] Increasing the mass and cross section of copper in a coil increases the efficiency of the motor. Copper motor rotors, a new technology designed for motor applications where energy savings are prime design objectives,^[112][113] are enabling general-purpose induction motors to meet and exceed National Electrical Manufacturers Association (NEMA) premium efficiency standards.^[114]

Renewable energy production

Architecture

Copper has been used since ancient times as a durable, corrosion resistant, and weatherproof architectural material.^{[129][130][131][132]} Roofs, flashings, rain gutters, downspouts, domes, spires, vaults, and doors have been made from copper for hundreds or thousands of years. Copper’s architectural use has been expanded in modern times to include interior and exterior wall cladding, building expansion joints, radio frequency shielding, and antimicrobial and decorative indoor products such as attractive handrails, bathroom fixtures, and counter tops. Some of copper’s other important benefits as an architectural material include low thermal movement, light weight, lightning protection, and recyclability

The metal’s distinctive natural green patina has long been coveted by architects and designers. The final patina is a particularly durable layer that is highly resistant to atmospheric corrosion, thereby protecting the underlying metal against further weathering.^{[133][134][135]} It can be a mixture of carbonate and sulfate compounds in various amounts, depending upon environmental conditions such as sulfur-containing acid rain.^{[136][137][138][139]} Architectural copper and its alloys can also be ‘finished’ to take on a particular look, feel, or color. Finishes include mechanical surface treatments, chemical coloring, and coatings.^[140]

Copper has excellent brazing and soldering properties and can be welded; the best results are obtained with gas metal arc welding.^[141]

Antibiofouling

Copper is biostatic, meaning bacteria and many other forms of life will not grow on it. For this reason it has long been used to line parts of ships to protect against barnacles and mussels. It was originally used pure, but has since been superseded by Muntz metal and copper-based paint. Similarly, as discussed in copper alloys in aquaculture, copper alloys have become important netting materials in the aquaculture industry because they are antimicrobial and prevent biofouling, even in extreme conditions^[142] and have strong structural and corrosion-resistant^[143] properties in marine environments.

Antimicrobial

Copper-alloy touch surfaces have natural properties that destroy a wide range of microorganisms (e.g., E. coli O157:H7, methicillin-resistant Staphylococcus aureus (MRSA), Staphylococcus, Clostridium difficile, influenza A virus, adenovirus, SARS-Cov-2, and fungi).^[144][145] Indians have been using copper vessels since ancient times for storing water, even before modern science realized its antimicrobial properties.^[146] Some copper alloys were proven to kill more than 99.9% of disease-causing bacteria within just two hours when cleaned regularly.^[147] The United States Environmental Protection Agency (EPA) has approved the registrations of these copper alloys as «antimicrobial materials with public health benefits»;^[147] that approval allows manufacturers to make legal claims to the public health benefits of products made of registered alloys. In addition, the EPA has approved a long list of antimicrobial copper products made from these alloys, such as bedrails, handrails, over-bed tables, sinks, faucets, door knobs, toilet hardware, computer keyboards, health club equipment, and shopping cart handles (for a comprehensive list, see: Antimicrobial copper-alloy touch surfaces#Approved products). Copper doorknobs are used by hospitals to reduce the transfer of disease, and Legionnaires’ disease is suppressed by copper tubing in plumbing systems.^[148] Antimicrobial copper alloy products are now being installed in healthcare facilities in the U.K., Ireland, Japan, Korea, France, Denmark, and Brazil, as well as being called for in the US,^[149] and in the subway transit system in Santiago, Chile, where copper-zinc alloy handrails were installed in some 30 stations between 2011 and 2014.^{[150][151][152]}
Textile fibers can be blended with copper to create antimicrobial protective fabrics.^{[153][unreliable source?]}

Speculative investing

Copper may be used as a speculative investment due to the predicted increase in use from worldwide infrastructure growth, and the important role it has in producing wind turbines, solar panels, and other renewable energy sources.^[154][155] Another reason predicted demand increases is the fact that electric cars contain an average of 3.6 times as much copper as conventional cars, although the effect of electric cars on copper demand is debated.^[156][157] Some people invest in copper through copper mining stocks, ETFs, and futures. Others store physical copper in the form of copper bars or rounds although these tend to carry a higher premium in comparison to precious metals.^[158] Those who want to avoid the premiums of copper bullion alternatively store old copper wire, copper tubing or American pennies made before 1982.^[159]

Folk medicine

Copper is commonly used in jewelry, and according to some folklore, copper bracelets relieve arthritis symptoms.^[160] In one trial for osteoarthritis and one trial for rheumatoid arthritis, no differences is found between copper bracelet and control (non-copper) bracelet.^[161][162] No evidence shows that copper can be absorbed through the skin. If it were, it might lead to copper poisoning.^[163]

Compression clothing

Recently, some compression clothing with inter-woven copper has been marketed with health claims similar to the folk medicine claims. Because compression clothing is a valid treatment for some ailments, the clothing may have that benefit, but the added copper may have no benefit beyond a placebo effect.^[164]

Degradation

Chromobacterium violaceum and Pseudomonas fluorescens can both mobilize solid copper as a cyanide compound.^[165] The ericoid mycorrhizal fungi associated with Calluna, Erica and Vaccinium can grow in metalliferous soils containing copper.^[165] The ectomycorrhizal fungus Suillus luteus protects young pine trees from copper toxicity. A sample of the fungus Aspergillus niger was found growing from gold mining solution and was found to contain cyano complexes of such metals as gold, silver, copper, iron, and zinc. The fungus also plays a role in the solubilization of heavy metal sulfides.^[166]

Biological role

Biochemistry

Copper proteins have diverse roles in biological electron transport and oxygen transportation, processes that exploit the easy interconversion of Cu(I) and Cu(II).^[167] Copper is essential in the aerobic respiration of all eukaryotes. In mitochondria, it is found in cytochrome c oxidase, which is the last protein in oxidative phosphorylation. Cytochrome c oxidase is the protein that binds the O₂ between a copper and an iron; the protein transfers 8 electrons to the O₂ molecule to reduce it to two molecules of water. Copper is also found in many superoxide dismutases, proteins that catalyze the decomposition of superoxides by converting it (by disproportionation) to oxygen and hydrogen peroxide:

• Cu²⁺-SOD + O₂⁻ → Cu⁺-SOD + O₂ (reduction of copper; oxidation of superoxide)
• Cu⁺-SOD + O₂⁻ + 2H⁺ → Cu²⁺-SOD + H₂O₂ (oxidation of copper; reduction of superoxide)

The protein hemocyanin is the oxygen carrier in most mollusks and some arthropods such as the horseshoe crab (Limulus polyphemus).^[168] Because hemocyanin is blue, these organisms have blue blood rather than the red blood of iron-based hemoglobin. Structurally related to hemocyanin are the laccases and tyrosinases. Instead of reversibly binding oxygen, these proteins hydroxylate substrates, illustrated by their role in the formation of lacquers.^[169] The biological role for copper commenced with the appearance of oxygen in earth’s atmosphere.^[170] Several copper proteins, such as the «blue copper proteins», do not interact directly with substrates; hence they are not enzymes. These proteins relay electrons by the process called electron transfer.^[169]

A unique tetranuclear copper center has been found in nitrous-oxide reductase.^[171]

Chemical compounds which were developed for treatment of Wilson’s disease have been investigated for use in cancer therapy.^[172]

Nutrition

Copper is an essential trace element in plants and animals, but not all microorganisms. The human body contains copper at a level of about 1.4 to 2.1 mg per kg of body mass.^[173]

Absorption

Copper is absorbed in the gut, then transported to the liver bound to albumin.^[174] After processing in the liver, copper is distributed to other tissues in a second phase, which involves the protein ceruloplasmin, carrying the majority of copper in blood. Ceruloplasmin also carries the copper that is excreted in milk, and is particularly well-absorbed as a copper source.^[175] Copper in the body normally undergoes enterohepatic circulation (about 5 mg a day, vs. about 1 mg per day absorbed in the diet and excreted from the body), and the body is able to excrete some excess copper, if needed, via bile, which carries some copper out of the liver that is not then reabsorbed by the intestine.^[176][177]

Dietary recommendations

The U.S. Institute of Medicine (IOM) updated the estimated average requirements (EARs) and recommended dietary allowances (RDAs) for copper in 2001. If there is not sufficient information to establish EARs and RDAs, an estimate designated Adequate Intake (AI) is used instead. The AIs for copper are: 200 μg of copper for 0–6-month-old males and females, and 220 μg of copper for 7–12-month-old males and females. For both sexes, the RDAs for copper are: 340 μg of copper for 1–3 years old, 440 μg of copper for 4–8 years old, 700 μg of copper for 9–13 years old, 890 μg of copper for 14–18 years old and 900 μg of copper for ages 19 years and older. For pregnancy, 1,000 μg. For lactation, 1,300 μg.^[178] As for safety, the IOM also sets tolerable upper intake levels (ULs) for vitamins and minerals when evidence is sufficient. In the case of copper the UL is set at 10 mg/day. Collectively the EARs, RDAs, AIs and ULs are referred to as Dietary Reference Intakes.^[179]

The European Food Safety Authority (EFSA) refers to the collective set of information as Dietary Reference Values, with Population Reference Intake (PRI) instead of RDA, and Average Requirement instead of EAR. AI and UL defined the same as in United States. For women and men ages 18 and older the AIs are set at 1.3 and 1.6 mg/day, respectively. AIs for pregnancy and lactation is 1.5 mg/day. For children ages 1–17 years the AIs increase with age from 0.7 to 1.3 mg/day. These AIs are higher than the U.S. RDAs.^[180] The European Food Safety Authority reviewed the same safety question and set its UL at 5 mg/day, which is half the U.S. value.^[181]

For U.S. food and dietary supplement labeling purposes the amount in a serving is expressed as a percent of Daily Value (%DV). For copper labeling purposes 100% of the Daily Value was 2.0 mg, but as of May 27, 2016 it was revised to 0.9 mg to bring it into agreement with the RDA.^[182][183] A table of the old and new adult daily values is provided at Reference Daily Intake.

Deficiency

Because of its role in facilitating iron uptake, copper deficiency can produce anemia-like symptoms, neutropenia, bone abnormalities, hypopigmentation, impaired growth, increased incidence of infections, osteoporosis, hyperthyroidism, and abnormalities in glucose and cholesterol metabolism. Conversely, Wilson’s disease causes an accumulation of copper in body tissues.

Severe deficiency can be found by testing for low plasma or serum copper levels, low ceruloplasmin, and low red blood cell superoxide dismutase levels; these are not sensitive to marginal copper status. The «cytochrome c oxidase activity of leucocytes and platelets» has been stated as another factor in deficiency, but the results have not been confirmed by replication.^[184]

Toxicity

Gram quantities of various copper salts have been taken in suicide attempts and produced acute copper toxicity in humans, possibly due to redox cycling and the generation of reactive oxygen species that damage DNA.^[185][186] Corresponding amounts of copper salts (30 mg/kg) are toxic in animals.^[187] A minimum dietary value for healthy growth in rabbits has been reported to be at least 3 ppm in the diet.^[188] However, higher concentrations of copper (100 ppm, 200 ppm, or 500 ppm) in the diet of rabbits may favorably influence feed conversion efficiency, growth rates, and carcass dressing percentages.^[189]

Chronic copper toxicity does not normally occur in humans because of transport systems that regulate absorption and excretion. Autosomal recessive mutations in copper transport proteins can disable these systems, leading to Wilson’s disease with copper accumulation and cirrhosis of the liver in persons who have inherited two defective genes.^[173]

Elevated copper levels have also been linked to worsening symptoms of Alzheimer’s disease.^[190][191]

Human exposure

In the US, the Occupational Safety and Health Administration (OSHA) has designated a permissible exposure limit (PEL) for copper dust and fumes in the workplace as a time-weighted average (TWA) of 1 mg/m³.^[192] The National Institute for Occupational Safety and Health (NIOSH) has set a recommended exposure limit (REL) of 1 mg/m³, time-weighted average. The IDLH (immediately dangerous to life and health) value is 100 mg/m³.^[193]

Copper is a constituent of tobacco smoke.^[194][195] The tobacco plant readily absorbs and accumulates heavy metals, such as copper from the surrounding soil into its leaves. These are readily absorbed into the user’s body following smoke inhalation.^[196] The health implications are not clear.^[197]

See also

• Copper in renewable energy
• Copper nanoparticle
• Erosion corrosion of copper water tubes
  • Cold water pitting of copper tube
• List of countries by copper production
• Metal theft
  • Operation Tremor

• Anaconda Copper
• Antofagasta PLC
• Codelco
• El Boleo mine
• Grasberg mine

References

Notes

Pourbaix diagrams for copper

in pure water, or acidic or alkali conditions. Copper in neutral water is more noble than hydrogen.	in water containing sulfide	in 10 M ammonia solution	in a chloride solution

Further reading

• Massaro, Edward J., ed. (2002). Handbook of Copper Pharmacology and Toxicology. Humana Press. ISBN 978-0-89603-943-8.
• «Copper: Technology & Competitiveness (Summary) Chapter 6: Copper Production Technology» (PDF). Office of Technology Assessment. 2005.
• Current Medicinal Chemistry, Volume 12, Number 10, May 2005, pp. 1161–1208(48) Metals, Toxicity and Oxidative Stress
• William D. Callister (2003). Materials Science and Engineering: an Introduction (6th ed.). Wiley, New York. Table 6.1, p. 137. ISBN 978-0-471-73696-7.
• Material: Copper (Cu), bulk, MEMS and Nanotechnology Clearinghouse.
• Kim BE; Nevitt T; Thiele DJ (2008). «Mechanisms for copper acquisition, distribution and regulation». Nat. Chem. Biol. 4 (3): 176–85. doi:10.1038/nchembio.72. PMID 18277979.

External links

• Copper at The Periodic Table of Videos (University of Nottingham)
• Copper and compounds fact sheet from the National Pollutant Inventory of Australia
• Copper.org – official website of the Copper Development Association with an extensive site of properties and uses of copper
• Price history of copper, according to the IMF

(лат. Cuprum-от назв. о. Кипр, где в древности добывали медную руду) Сu, хим. элемент I гр. периодич. системы, ат. н. 29, ат. м. 63,546. Прир. М. состоит из смеси двух стабильных изотопов ⁶³ Сu (69,09%) и ⁶⁵ Сu (30,91%). Поперечное сечение захвата тепловых нейтронов для прир. смеси 3,77^.10^-28 м ². Конфигурация внеш. электронной оболочки атома 3d¹⁰4s¹; степени окисления + 1, +2, редко +3, + 4; энергии ионизации Сu⁰Сu⁺Сu^{2 +} Сu³⁺ соотв. равны 7,7264, 20,2921, 36,83 эВ; сродство к электрону 1,8 эВ; электроотрицательность по Полингу 1,9; атомный радиус 0,128 нм, ионные радиусы (в скобках указаны координац. числа) Сu⁺ 0,060 нм (2), 0,074 нм (4), 0,091 нм (6), Сu²⁺ 0,071 нм (2), 0,079 нм (5), 0,087 нм (6); работа выхода электрона 4,36 эВ.

Содержание М. в земной коре (4,7^.5,5)^.10^-3% по массе. Для М. характерны месторождения гидротермального происхождения. В морской воде содержание М. 3^.10^-7% по массе, в речной Ч1^.10^-7%; ионы М., поступающие в бассейны морей и океанов, сорбируются донными отложениями, поэтому содержание М. в них достигает 5,7^.10^-3%. Ионы М. участвуют во многих физиол. процессах, среднее содержание М. в живых организмах 2^.10^-4% по массе, в крови человека ок. 0,001 мг/л.

В земной коре М. встречается в осн. в виде соед. с S (св. 90% мировых запасов и добычи М.) и в виде кислородсодержащих соединений. Среди многочисл. минералов М. (более 250) наиб. важны: халькопирит CuFeS₂, ковеллин CuS, халькозин Cu₂S, борнит Cu₅FeS₄, куприт Сu₂ О, малахит CuCO₃^.Cu(OH)₂, хризоколла CuSiO₃^.2H₂O др. Редко встречается самородная М. Медные руды по минера-логич. составу м. б. подразделены на сульфидные, оксидные и смешанные (30-40% Си в форме оксидных минералов). По текстурным особенностям различают медные руды массивные, или сплошные (колчеданные, медно-никелевые, по-лиметаллич.), и прожилково-вкрапленные (медистые песчаники и сланцы). Медные руды полиметаллич., помимо М., они содержат Fe, Zn, Pb, Ni, Au, Ag, Mo, Re, Se, Fe, платиновые металлы и др. Осн. мировые запасы М. (кроме СССР) сосредоточены в Сев. Америке (США, Канада, Мексика)-32%, Юж. Америке (Чили, Перу)-30%, Африке (Замбия, Заир)-15%. Мировые запасы медных руд (без СССР) составляют 847,6 млн. т, в т. ч. доказанные 447,4 млн. т.

Свойства. М.-пластичный, розовато-красный металл с характерным металлич. блеском, тонкие пленки М. при просвечивании-зеленовато-голубого цвета. Кристаллич. решетка гранецентрированная кубич., а = 0,36150 нм, 2 = 4, пространств. группа Fт З т. Т. пл. 1083,4 ⁰ С, т. кип. 2567 °С; плотн. 8,92 г/см ³, жидкой при 1100 ⁰ С-8,36 г/см ³, при 200°С-8,32 г/см ³, рентгеновская плотн. 8,9331 г/см ³; C⁰ _р 24,44 ДжДмоль Х К), ур-ние температурной зависимости в интервале 248-1356,9 К: С ⁰ _р = >4,187(5,41 + 1,4^.7^.10^-3 Т)ДжДмоль ^. К); DH⁰ _пл 13,02 кДж/моль, скрытая DH _пл 205 кДж/молъ, DH⁰ _исп 304,8 кДж/моль; 0₂₉₈ 33,15 ДжДмоль ^. К); ур-ние температурной зависимости давления пара над жидкой М.: lgp(Па) = -17650/T + 1 l,27^.l,273lg Т(1356,9-2870 К). Даже при 1900 К давление пара над М. не превышает 133,32 Па. Температурный коэф. линейного расширения 1,7^.10^-5 К ^-1 (273-323 К), ур-ние температурной зависимости линейного расширения: t = l₀(1 + 1,67^.10^-5t + +>3,8^.10^-9t² + 1,5^.10^-12t³) м, где l₀ -длина образца при 25 °С; объемная усадка при кристаллизации-4,1%. Наиб. важные и широко используемые св-ва М.-ее высокая теплопроводность и малое электрич. сопротивление:

Температурный коэф. r 4,3-10~³ К ^-1 (273-373 К). М. диамагнитна, уд. магн. восприимчивость -0,66^.10^-6. Для жидкой М. у (в мН/м): 1120 (1413 К), 1160 (1473 К), 1226 (1573 К); h (в мПа ^. с): 4,0 (1356,9 К), 8,6 (1373 К), 3,41 (1418 К).

М.-мягкий, ковкий металл; твердость по Моосу 3,0; твердость по Бринеллю 370-420 МПа; s _раст 220 МПа; относит. удлинение 60%, относит. уменьшение поперечного сечения 70%; модуль продольной упругости 112 ГПа; модуль сдвига 49,25 ГПа; коэф. Пуассона 0,34. После обработки давлением в связи с наклепом предел прочности М. возрастает до 400-450 МПа, уменьшаются на 1-3% удлинение и электрич. проводимость; последствия наклепа устраняются после отжига металла при 900-1000 К. Под действием нейтронного облучения (373 К, поток 5^.10¹⁹ n/см ²) предел текучести М. возрастает почти в 2,7 раза, сопротивление разрыву-в 1,26 раза, удлинение уменьшается в 1,35 раза. Небольшие примеси Bi, Pb вызывают красноломкость М., S, О ₂ — хладноломкость, примеси Р, As, Al, Fe заметно уменьшают электрич. проводимость М.

М. растворяет Н ₂, к-рый существенно ухудшает ее мех. св-ва («водородная болезнь»). Р-римость Н ₂ при 0,1 МПа (в см ³ на 1 кг М.):

Стандартный электродный потенциал для р-ции Сu²⁺ + + 2е Сu равен 0,339 В, для р-ции Cu⁺ + eСu 0,515 В. Хим. активность М. невелика. В сухом воздухе при комнатной т-ре М. почти не окисляется. При нагр. тускнеет из-за образования пленки меди оксидов. Заметное взаимод. с О ₂ воздуха начинается ок. 200 °С по схеме: СuСu₂ О СuО. Сначала при т-ре до 377 °С образуется Сu₂ О, а выше 377 °С- двухслойная окалина, внутр. слой к-рой состоит из Сu₂ О, внешний-из СuО. Во влажном воздухе в присут. СО ₂ на пов-сти М. образуется зеленоватая пленка Cu(OH)₂ x х СuСО ₃, в присут. SO₂ -пленка CuSO₄ Х 3Cu(OH)₂, в среде H₂S-черная пленка сульфида CuS.

М. не реагирует с Н ₂, N₂, С, Si. При пропускании NH₃ над раскаленной М. образуется Cu₃N, в аналогичных условиях при контакте с парами S, Se, H₂S, оксидами азота на пов-сти М. образуются соотв. сульфиды, селениды, оксиды. При сплавлении с S М. дает Cu₂S, с Se и Те -соотв. селениды и теллуриды. М. активно реагирует с галогенами, образуя соответствующие соли (см. Меди хлориды). С соляной к-той, разб. H₂SO₄, СН ₃ СООН M. взаимод. только в присут. окислителей, образуя соответствующие соли Cu(II). В HNO₃

М. раств. с образованием Cu(NO₃)₂ и оксидов азота, в горячей конц. H₂SO₄-c образованием CuSO₄ и SO₂ ,в конц. р-рах цианидов — давая комплекс состава [Cu(CN)₂]^—.

Соли Cu(I) бесцв., практически не раств. в воде, легко окисляются; Cu(I) склонна к диспропорционированию: 2Cu⁺ Cu²⁺ + Сu⁰. Соли Cu(II), напротив, хорошо раств. в воде, в разб. р-рах полностью диссоциированы. Аквака-тионы [Сu(Н ₂ О)₄]^{2 +} придают водному р-ру голубой цвет. При введении NaOH в р-ры солей Cu(II) сначала выпадает Сu(ОН)₂ (см. Меди гидроксиды), а в очень конц. р-рах NaOH образуется Na₂[Cu(OH)₄]. В р-рах соед. Cu(II) при действии Na₂CO₃ или К ₂ СО ₃ осаждаются основные карбонаты mCuCO₃^.Cu(OH)₂ (см. Меди карбонаты), при избытке оса-дителя они раств. с образованием комплексов, напр. К ₂[Сu(СО ₃)₂]^. ЗН ₂ О. При обработке аммиачных р-ров солей М. ацетиленом получают карбид СuС ₂. Ионы М. количественно восстанавливаются до металла др. более электроотрицат. металлами.

Соли Cu(I) и Cu(II) с рядом молекул и ионов (NH₃, CN^—, Сl^— и др.) образуют устойчивые комплексные соед., напр. (NH₄)₂[CuBr₃], K₃[Cu(CN)₄], K₂[CuCl₄], аммиакаты; коор-динац. числа для Сu(I)-2, 3, 4, для Сu(II)-3, 4, 6. Путем образования комплексных соед. можно перевести в р-р многие нерастворимые соли М. Известны соед. Cu(III)- неустойчивые, сильные окислители, примеры-KCuO₂, K₃[CuF₆]. Наиб. важным соед. М. посвящены отдельные статьи, см., напр., Меди ацетаты, Меди нитрат, Меди сульфат, Медь-органические соединения.

Получение. Осн. сырье для получения М.-сульфидные, реже-смешанные руды. Большое значение приобретает переработка вторичного сырья, из к-рого в ряде развитых стран получают до 30-60% производимой М. В связи с невысоким содержанием М. в рудах (0,5-1,2%) и их много-компонентностью руды подвергают флотационному обогащению, получая попутно, помимо медного, и др. концентраты, напр. цинковый, никелевый, молибденовый, пиритный, свинцовый. Содержание М. в медных концентратах достигает 18-45%.

Осн. кол-во М. (85-88%) получают по пирометаллургич. схемам, к-рые, как правило, включают след. последовательные стадии: обжиг концентрата, плавку, конвертирование, рафинирование. Обжиг проводят при переработке высокосернистых и полиметаллич. концентратов. При обжиге удаляют избыточное кол-во S в форме газов, содержащих 5-8% SO₂ и используемых для произ-ва H₂SO₄, и переводят часть примесей (Fe, Zn, As, Pb и др.) в формы, переходящие при послед. плавке в шлак. Обжиг проводят в печах «кипящего слоя» с применением дутья, обогащенного О ₂ (24-26% О ₂), без затрат углеродистого топлива. Продукт обжига — огарок -плавят в печах отражательного типа, реже — электропечах. Богатые М. руды плавили в шахтных печах, в настоящее время этот способ имеет подчиненное значение. Перечисл. способы плавки связаны с расходом (10-18% от массы шихты) углеродистого топлива (прир. газ, мазут, кокс) или электроэнергии (350-450 кВт ^. ч на 1 т шихты).

В процессе плавки образуются 2 жидкие фазы-сплав сульфидов М., Fe, цветных металлов (штейн; 22-45% Сu) и сплав оксидов металлов и силикатов (шлак; 0,4-0,7% Сu), к-рые не смешиваются друг с другом. Шлаки складируют или используют при произ-ве строит. материалов. Осваиваются автогенные процессы плавки, использующие тепло экзотермич. р-ций окисления сульфидов; концентраты обрабатывают в атмосфере О ₂, воздуха, обогащенного О ₂, или подогретого воздуха. Высокая производительность, получение богатых М. штейнов (до 75% Сu) и концентрированных по SO₂ газов, миним. расход углеродистого топлива-достоинства, определяющие автогенные процессы как перспективное направление в развитии пирометаллургии М. Важнейшие способы автогенной плавки-кислородно-факельная, взвешенная, отражательная, электроплавка, плавка в жидкой ванне, процессы «Норанда», «Мицубиси».

Расплав штейна (в осн. Cu₂S Х FeS) направляют на кон-вертирование — продувку сжатым воздухом с целью количеств. окисления FeS и его ошлакования в присут. кварцевого флюса (первая стадия процесса), окисления Cu₂S и макс. удаления S и большинства примесей (вторая стадия):

При конвертировании используют тепло экзотермических р-ций окисления, конечный продукт-черновая М. (98,5-99,3% Сu).

Черновую М. рафинируют огневым, а затем электрохим. способом. Огневое рафинирование основано на большем, чем у М., сродстве большинства металлов-примесей к кислороду, что позволяет при продувке расплава воздухом окислить и ошлаковать количественно Fe, S, Zn, Pb и, частично, Ni, As, Sb, Bi. Для удаления кислорода расплав М. обрабатывают восстановителем (прир. конверсир. газ, сырая древесина). Готовый металл (>=99,5% Сu) разливают в формы, удобные для проведения электролиза. Полученные отливки служат анодами. Электролитич. рафинирование проводят в сернокислых р-рах при наложении постоянного тока; в процессе электролиза осуществляется непрерывная циркуляция подогреваемого (57-67°С) р-ра, М. осаждают на катодных основах, получаемых также электролизом в спец. матричных ваннах при условиях, обеспечивающих осаждение чистого металла. Для получения ровного катодного осадка требуемой текстуры в электролит вводят ПАВ. Катодную М. (>=99,94% Сu) переплавляют и разливают в формы, удобные для послед. обработки прокаткой, волочением. При растворении анодов ряд примесей (As, Fe, Ni, Sb) накапливается в электролите, поэтому часть его выводят из циркуляц. цикла (заменяя равным объемом р-ра H₂SO₄) и направляют на переработку для получения техн. сортов медного и никелевого купоросов. Нерастворимые включения анода образуют дисперсный продукт — шлам, в к-ром концентрируются благородные и редкие металлы. Этот продукт специально перерабатывают в шламовом цикле. Анодные остатки (выход их 15-18% от массы анода) возвращают на переплавку в цикл огневого рафинирования.

При пирометаллургич. переработке медного концентрата извлекают до 96-98% М. и благородных металлов, однако степень извлечения сопутствующих элементов (S, Zn, Ni, Pb) гораздо ниже, a Fe полностью теряется со шлаком.

Многие проблемы пирометаллургич. произ-ва М. (экологическая из-за повыш. тепло-, пыле- и газовыделения, взры-воопасность в случае контакта расплава штейна с водой и др.) устраняются при использовании гидрометаллургич. технологии. Она включает: селективное выщелачивание М. из сырья, чаще всего р-ром H₂SO₄ или NH₃; очистку р-ра от примесей и извлечение сопутствующих ценных элементов (Zn, Co, Ni, Cd и др.); выделение М. При переработке бедных р-ров (0,5-12,0 г/л М.) используют цементацию на железном скрапе и экстракцию с послед. электрохим. осаждением М. Из богатых р-ров (30-40 г/л М.) М. извлекают чаще электролизом или автоклавным осаждением водородом (127-197 °С, давление Н ₂ 1,5-2,5 МПа). В последнем случае М. получают в форме порошка (>=99,6% М.). Гидрометаллургич. схемы эффективны при извлечении М. из бедных руд методами подземного, кучного, чанового выщелачивания, в т. ч. с использованием биохим. окисления сульфидов; остатки от выщелачивания смешанных руд обогащают флотацией. Рациональна переработка полиметаллич. концентратов, вторичного сырья, особенно при небольшом объеме произ-ва. В этом случае весьма перспективно автоклавное выщелачивание при повыш. т-рах (137-197 °С) и давлении кислородсодержащего газа-окислителя (давление О ₂ 0,2-1,0 МПа), обеспечивающее значит. интенсификацию процесса, получение более чистых р-ров и элементной S при окислении сульфидов. Гидрометаллургич. схемы позволяют более комплексно использовать сырье, проще обеспечить экологич. и пром. санитарию. Внедрение их сдерживается из-за недостаточной интенсивности, повыш. эксплуатац. затрат и др.

Определение. Соед. М. в смеси с содой и углем в пламени горелки образуют красный металлич. королек, р-римый в HNO₃. Р-ры, содержащие ионы Сu²⁺ , при добавлении NH₃ приобретают синюю окраску (чувствительность 0,007 мг/л); при добавлении K₄[Fe(CN)₆] выпадает красно-коричневый осадок (чувствительность 0,0001 мг/л); при взаимод. с Na₂S или (NH₄)₂S образуется черный осадок CuS. Для количеств. определения М. используют гравиметрич., объемный, комплексонометрич., амперометрич., кондуктометрич., по-лярографич., потенциометрич., радиоактивац., эмиссионный, спектральный методы анализа. При повыш. содержании М. ее определяют объемным иодометрич. или более точным электрогравиметрич. методом. Для определения малых кол-в М. используют фотометрич. метод с дити-зоном, купфероном, диэтилдитиокарбаматом Na (чувствительность 0,02-0,002 мг/л), атомно-абсорбционный (кислородно-водородное пламя, l = 324,7 нм, чувствительность 0,01-0,0015 мг/л). При определении содержания М. в сточных водах дополнительно используют флуоресцентный (чувствительность 0,002 мг/л), спектральный (0,002-0,003 мг/л), хроматографич. (0,07 мг/л) методы анализа.

Применение. Широкое применение М. в пром-сти обусловлено рядом ее ценных св-в и прежде всего высокой электрич. проводимостью, пластичностью, теплопроводностью. Более 50% М. используется для изготовления проводов, кабелей, шин, токопроводящих частей электрич. установок. Из М. изготовляют теплообменную аппаратуру (вакуум-испарители, подогреватели, холодильники). Более 30% М. применяют в виде сплавов, важнейшие из к-рых — бронзы, латуни, мельхиор и др. (см. Меди сплавы). М. и ее сплавы используют также для изготовления художеств. изделий. В виде фольги М. применяют в радиоэлектронике. Значит. кол-во М. (10-12%) применяют в виде разл. соед. в медицине (антисептич. и вяжущие ср-ва), для изготовления инсектофунгицидов, в качестве медных удобрений, пигментов, катализаторов, в гальванотехнике и т. д.

Мировое произ-во М. (без СССР) ок. 7,5 млн. т, в т. ч. из вторичного сырья-1,15 млн. т/год (1985). Осн. страны-производители рафинированной М. (1985): США (1,7 млн. т), Япония (1,1), Чили (0,9), Канада (0,8), Замбия (0,53), Заир (0,5).

Все соли М. ядовиты; раздражают слизистые, поражают желудочно-кишечный тракт, вызывают тошноту, рвоту, заболевание печени и др. При вдыхании пыли М. развивается хронич. отравление. ПДК для аэрозолей М. 1 мг/м ³, питьевой воды 1,0 мг/л, для рыбных водоемов 0,01 мг/л, в сточных водах до биол. очистки 0,5 мг/л.

М. известна человечеству с глубокой древности. М. и ее сплавы сыграли заметную роль в развитии цивилизации.

Лит.: Набойченко С. С., Смирнов В. И., Гидрометаллургия меди, М., 1974; Металлургия меди, никеля, кобальта, 2 изд., ч. 1, М., 1977; Онаев И. А., Жакибаев Б. К., Медь в истории цивилизации, А.-А., 1983; Ванюков А. В., Уткин Н. И., Комплексная переработка медного и никелевого сырья, М., 1988; Ванюков А. В. [и др.], Плавка в жидкой ванне, М., 1988; Подчайно-ва В. Н., Симонова Л. Н., Медь, М., 1990. С. С. Набойченко.

Медь

1. Положение меди в периодической системе химических элементов
2. Электронное строение меди
3. Физические свойства
4. Нахождение в природе
5. Способы получения
6. Качественные реакции
7. Химические свойства

Оксид меди (II)

• Способы получения
• Химические свойства

Оксид меди (I)

• Химические свойства

Гидроксид меди (II)

• Химические свойства

Соли меди

Медь

Положение в периодической системе химических элементов

Медь расположена в 11 группе  (или в  побочной подгруппе II группы в короткопериодной  ПСХЭ) и в четвертом периоде периодической системы химических элементов Д.И. Менделеева.

Электронное строение меди

Электронная конфигурация  меди в основном состоянии:

+29Cu 1s²2s²2p⁶3s²3p⁶3d¹⁰4s¹ 1s  2s 2p

3s   3p    4s     3d

У атома меди уже в основном энергетическом состоянии происходит провал (проскок) электрона с 4s-подуровня на 3d-подуровень.

Физические свойства 

Медь – твердый металл золотисто-розового цвета (розового цвета при отсутствии оксидной плёнки). Медь относительно легко поддается механической обработке.  В природе встречается в том числе в чистом виде и широко применяется в различных отраслях науки, техники и производства.

Изображение с портала zen.yandex.com/media/id/5d426107ae56cc00ad977411/uralskaia-boginia-liubvi-5d6bcceda660d700b075a12d

Температура плавления 1083,4^оС, температура кипения 2567^оС, плотность меди 8,92 г/см³.

Медь — ценный металл в сфере вторичной переработки. Сдав лом меди в пункт приема, Вы можете получить хорошее денежное вознаграждение. Подробнее про прием лома меди.

Нахождение в природе

Медь встречается в земной коре (0,0047-0,0055 масс.%), в речной и морской воде. В природе медь встречается как в соединениях, так и в самородном виде. В промышленности используют халькопирит CuFeS₂, также известный как медный колчедан, халькозин Cu₂S и борнит Cu₅FeS₄. Также распространены и другие минералы меди: ковеллин CuS, куприт Cu₂O, азурит Cu₃(CO₃)₂(OH)₂, малахит Cu₂(OH)₂CO₃. Иногда медь встречается в самородном виде, масса которых может достигать 400 тонн.

Способы получения меди

Медь получают из медных руд и минералов. Основные методы получения меди — электролиз, пирометаллургический и гидрометаллургический.

• Гидрометаллургический метод: растворение медных минералов в разбавленных растворах серной кислоты, с последующим вытеснением металлическим железом.

Например, вытеснение меди из сульфата железом:

CuSO₄ + Fe = Cu + FeSO₄

Видеоопыт взаимодействия сульфата меди (II) с железом можно посмотреть здесь.

• Пирометаллургический метод: получение меди из сульфидных руд. Это сложный процесс, который включает большое количество реакций. Основные стадии процесса:

1) Обжиг сульфидов:

2CuS + 3O₂ = 2CuO + 2SO₂

2) восстановление меди из оксида, например, водородом:

CuO + H₂ = Cu + H₂O

• Электролиз растворов солей меди:

2CuSO₄ + 2H₂O → 2Cu + O₂ + 2H₂SO₄

Качественные реакции на ионы меди (II)

Качественная реакция на ионы меди +2 – взаимодействие солей меди (II) с щелочами. При этом образуется голубой осадок гидроксида меди(II).

Например, сульфат меди (II) взаимодействует с гидроксидом натрия:

CuSO₄   +   2NaOH   →   Cu(OH)₂   +  Na₂SO₄

Соли меди (II) окрашивают пламя в зеленый цвет.

Химические свойства меди

В соединениях медь может проявлять степени окисления +1 и +2.

1. Медь — химически малоактивный металл. При нагревании медь может реагировать с некоторыми неметаллами: кислородом, серой, галогенами.

1.1. При нагревании медь реагирует с достаточно сильными окислителями, например, с кислородом, образуя CuО, Cu₂О в зависимости от условий:

4Cu  +  О₂ → 2Cu₂О

2Cu  +  О₂ → 2CuО

1.2. Медь реагирует с серой с образованием сульфида меди (II):

Cu  +  S  → CuS

Видеоопыт взаимодействия меди с серой можно посмотреть здесь.

1.3. Медь взаимодействует с галогенами. При этом образуются галогениды меди (II):

Cu  +  Cl₂  =  CuCl₂

Сu  +  Br₂  =  CuBr₂

Но, обратите внимание: 

2Cu + I₂ = 2CuI

Видеоопыт взаимодействия меди с хлором можно посмотреть здесь.

1.4. С азотом, углеродом и кремнием медь не реагирует:

Cu   +  N₂    ≠  

Cu   +  C    ≠  

Cu   +  Si    ≠  

1.5. Медь не взаимодействует с водородом.

Cu   +  H₂    ≠  

1.6. Медь взаимодействует с кислородом с образованием оксида:

2Cu  +  O₂  →  2CuO

2. Медь взаимодействует и со сложными веществами:

2.1. Медь в сухом воздухе и при комнатной температуре не окисляется, но во влажном воздухе, в присутствии оксида углерода (IV) покрывается зеленым налетом карбоната гидроксомеди (II):

2Cu   +  H₂O  +  CO₂  + O₂ =  (CuOH)₂CO₃

2.2. В ряду напряжений медь находится правее водорода и поэтому не может вытеснить водород из растворов минеральных кислот (разбавленной серной кислоты и др.).

Например, медь не реагирует с разбавленной серной кислотой:

Cu   +  H₂SO₄ (разб.)    ≠  

Видеоопыт взаимодействия меди с соляной кислотой можно посмотреть здесь.

2.3. При этом медь реагирует при нагревании с концентрированной серной кислотой. При нагревании реакция идет, образуются оксид серы (IV), сульфат меди (II) и вода:

Cu  +  2H₂SO_4(конц.) →  CuSO₄  +  SO₂  +  2H₂O

2.4. Медь реагирует даже при обычных условиях с азотной кислотой.

С концентрированной азотной кислотой:

Cu  +  4HNO_3(конц.)  =  Cu(NO₃)₂  +  2NO₂  +  2H₂O

С разбавленной азотной кислотой:

3Cu  +  8HNO_3(разб.)  =  3Cu(NO₃)₂  +  2NO  +  4H₂O

Реакция меди с азотной кислотой

2.5. Растворы щелочей на медь практически не действуют.

2.6. Медь вытесняет металлы, стоящие правее в ряду напряжений, из растворов их солей.

Например, медь реагирует с нитратом ртути (II) с образованием нитрата меди (II) и ртути:

Hg(NO₃)₂   +  Cu  =   Cu(NO₃)₂   +  Hg

2.7. Медь окисляется оксидом азота (IV) и солями  железа (III)

2Cu   +   NO₂   =   Cu₂O   +  NO

2FeCl₃   +   Cu  =  2FeCl₂  +  CuCl₂

Оксид меди (II)

Оксид меди (II) CuO – твердое кристаллическое вещество черного цвета.

Способы получения оксида меди (II)

Оксид меди (II) можно получить различными методами:

1. Термическим разложением гидроксида меди (II) при 200°С: 

Cu(OH)₂   →   CuO   +  H₂O

2. В лаборатории оксид меди (II) получают окислением меди при нагревании на воздухе при 400–500°С:

2Cu   +   O₂      2CuO           

 3. В лаборатории оксид меди (II) также получают прокаливанием солей (CuOH)₂CO₃, Cu(NO₃)₂:

(CuOH)₂CO₃     2CuO   +   CO₂   +   H₂O

2Cu(NO₃)₂       2CuO    +   4NO₂   +   O₂

Химические свойства оксида меди (II)

Оксид меди (II) – основный оксид (при этом у него есть слабо выраженные амфотерные свойства). При этом он является довольно сильным окислителем.

1. При взаимодействии оксида меди (II) с сильными и растворимыми кислотами образуются соли.

Например, оксид меди (II) взаимодействует с соляной кислотой:

СuO  +  2HBr  =  CuBr₂  +  H₂O

CuO  +  2HCl  =  CuCl₂  +  H₂O

Видеоопыт взаимодействия оксида меди (II) с серной кислотой можно посмотреть здесь.

2. Оксид меди (II) вступает в реакцию с кислотными оксидами. 

Например, оксид меди (II) взаимодействует с оксидом серы (VI) с образованием сульфата меди (II):

CuO  + SO₃  → CuSO₄

3. Оксид меди (II) не взаимодействует с водой.

4. В окислительно-восстановительных реакциях соединения меди (II) проявляют окислительные свойства:

Например, оксид меди (II) окисляет аммиак:

3CuO + 2NH₃ → 3Cu + N₂ + 3H₂O

Оксид меди (II) можно восстановить углеродом, водородом или угарным газом при нагревании:

СuO + C  → Cu + CO

Видеоопыт взаимодействия оксида меди (II) с водородом можно посмотреть здесь.

Более активные металлы вытесняют медь из оксида.

Например, алюминий восстанавливает оксид меди (II):

3CuO + 2Al = 3Cu + Al₂O₃

Оксид меди (I)

Оксид меди (I) Cu₂O – твердое кристаллическое вещество коричнево-красного цвета.

Способы получения оксида меди (I)

В лаборатории оксид меди (I) получают восстановлением свежеосажденного гидроксида меди (II), например, альдегидами или глюкозой:

CH₃CHO   +  2Cu(OH)₂  → CH₃COOH   +   Cu₂O↓   +   2H₂O

CH₂ОН(CHOН)₄СНО   +  2Cu(OH)₂   →  CH₂ОН(CHOН)₄СООН  +   Cu₂O↓   +   2H₂O

Химические свойства оксида меди (I)

1. Оксид меди (I) обладает основными свойствами.

При действии на оксид меди (I) галогеноводородных кислот получают галогениды меди (I) и воду:

Например, соляная кислота с оксидом меди (I) образует хлорид меди (I):

Cu₂O  +  2HCl   =   2CuCl↓   +  H₂O

2. При растворении Cu₂O в концентрированной серной, азотной кислотах образуются только соли меди (II):

Cu₂O  +  3H₂SO_4(конц.)   =  2CuSO₄  +  SO₂  + 3H₂O

Cu₂O  +  6HNO_3(конц.)  =  2Cu(NO₃)₂  +  2NO₂  +  3H₂O

5Cu₂O  +  13H₂SO₄   +  2KMnO₄   =  10CuSO₄  +  2MnSO₄  +   K₂SO₄  + 13H₂O

3. Устойчивыми соединениями меди (I) являются нерастворимые соединения (CuCl, Cu₂S) или комплексные соединения [Cu(NH₃)₂]⁺. Последние получают растворением в концентрированном растворе аммиака оксида меди (I), хлорида меди (I):

Cu₂O  +  4NH₃  +  H₂O  =  2[Cu(NH₃)₂]OH

CuCl   +  2NH₃   =  [Cu(NH₃)₂]Cl

Аммиачные растворы солей меди (I) взаимодействуют с ацетиленом:

СH ≡ CH + 2[Cu(NH₃)₂]Cl    →   СuC ≡ CCu  +  2NH₄Cl + 2NH₃

4. В окислительно-восстановительных реакциях соединения меди (I) проявляют окислительно-восстановительную двойственность:

Например, при взаимодействии с угарным газом, более активными металлами или водородом оксид меди (II) проявляет свойства окислителя:

Cu₂O  +  CO  =  2Cu  +  CO₂

Cu₂O  +  H₂  =  2Cu  + H₂O

 3Cu₂O  +  2Al  =  6Cu  +  Al₂O₃

А под действием окислителей, например, кислорода — свойства восстановителя:

2Cu₂O  +  O₂  =  4CuO

Гидроксид меди (II)

Способы получения гидроксида меди (II)

1. Гидроксид меди (II) можно получить действием раствора щелочи на соли меди (II).

Например, хлорид меди (II) реагирует с водным раствором гидроксида натрия с образованием гидроксида меди (II) и хлорида натрия:

CuCl₂  +  2NaOH   →   Cu(OH)₂  +  2NaCl

Химические свойства

Гидроксид меди (II) Сu(OН)₂ проявляет слабо выраженные амфотерные свойства (с преобладанием основных).

1. Взаимодействует с кислотами.

Например, взаимодействует с бромоводородной кислотой с образованием бромида меди (II) и воды:

Сu(OН)₂  +  2HBr  =  CuBr₂  +  2H₂O

Cu(OН)₂  +  2HCl  =  CuCl₂  +  2H₂O

2. Гидроксид меди (II) легко взаимодействует с раствором аммиака, образуя сине-фиолетовое комплексное соединение:

Сu(OH)₂  +  4(NH₃ · H₂O)   =  [Cu(NH₃)₄](OH)₂   +  4H₂O

Cu(OH)₂  +  4NH₃  =  [Cu(NH₃)₄](OH)₂

3. При взаимодействии гидроксида меди (II) с концентрированными (более 40%) растворами щелочей образуется комплексное соединение:

Cu(OH)₂  + 2NaOH_(конц.)  =  Na₂[Cu(OH)₄]

Но этой реакции в ЕГЭ по химии пока нет!

4. При нагревании гидроксид меди (II) разлагается:

Сu(OH)₂ → CuO  +  H₂O

Соли меди

Соли меди (I)

В окислительно-восстановительных реакциях соединения меди (I) проявляют окислительно-восстановительную двойственность. Как восстановители они реагируют с окислителями.

Например, хлорид меди (I) окисляется концентрированной азотной кислотой:

CuCl  +  3HNO_3(конц.)  =  Cu(NO₃)₂  +  HCl  +  NO₂  +  H₂O

Также хлорид меди (I) реагирует с хлором:

2CuCl   +  Cl₂   =  2CuCl₂

 Хлорид меди (I) окисляется кислородом в присутствии соляной кислоты:

4CuCl   +  O₂  +  4HCl   =   4CuCl₂   +  2H₂O

Прочие галогениды меди (I) также легко окисляются другими сильными окислителями:

2CuI  +  4H₂SO₄  +  2MnO₂  =  2CuSO₄  +  2MnSO₄  +  I₂  +  4H₂O

Иодид меди (I)  реагирует с концентрированной серной кислотой:

4CuI   +   5H₂SO_{4(конц.гор.)}  =  4CuSO₄   +  2I₂   +   H₂S   +  4H₂O

Сульфид меди (I) реагирует с азотной кислотой. При этом образуются различные продукты окисления серы на холоде и при нагревании:

Cu₂S  +  8HNO_{3(конц.хол.)}   =  2Cu(NO₃)₂  +  S  +  4NO₂  +  4H₂O

Cu₂S  +  12HNO_{3(конц.гор.)}   =  Cu(NO₃)₂  +  CuSO₄   +  10NO₂  +  6H₂O

Для соединений меди (I) возможна реакция диспропорционирования:

2CuCl  =  Cu   +  CuCl₂

Комплексные соединения типа [Cu(NH₃)₂]⁺ получают растворением в концентрированном растворе аммиака:

CuCl  +  3NH₃  +  H₂O  →   [Cu(NH₃)₂]OH  +  NH₄Cl

Соли меди (II)

В окислительно-восстановительных реакциях соединения меди (II) проявляют окислительные свойства.

Например, соли меди (II) окисляют иодиды и сульфиты:

2CuCl₂  +  4KI = 2CuI  +  I₂  +  4KCl

2CuCl₂  +  Na₂SO₃  +  2NaOH  =  2CuCl  +  Na₂SO₄  +  2NaCl  +  H₂O

Бромиды и иодиды меди (II) можно окислить перманганатом калия:

5CuBr₂  +  2KMnO₄  +  8H₂SO₄  =  5CuSO₄  +  K₂SO₄  +  2MnSO₄  +  5Br₂  +  8H₂O

Соли меди (II) также окисляют сульфиты:

2CuSO₄  +  Na₂SO₃   +  2H₂O   =  Cu₂O   +  Na₂SO₄     +  2H₂SO₄

 Более активные металлы вытесняют медь из солей.

Например, сульфат меди (II) реагирует с железом:

CuSO₄  +  Fe  =  FeSO₄  +  Cu

Cu(NO₃)₂   + Fe  =  Fe(NO₃)₂   +  Cu

Сульфид меди (II) можно окислить концентрированной азотной кислотой. При нагревании возможно образование сульфата меди (II):

CuS  +  8HNO_{3(конц.гор.)}   =   CuSO₄   +   8NO₂   +  4H₂O

Еще одна форма этой реакции:

CuS  +  10HNO_3(конц.)     =  Cu(NO₃)₂  +  H₂SO₄  +    8NO₂↑ +  4H₂O

При горении сульфида меди (II) образуется оксид меди (II)  и диоксид серы:

2CuS  +  3O₂    2CuO  +  2SO₂↑

Соли меди (II) вступают в обменные реакции, как и все соли.

Например, растворимые соли меди (II) реагируют с сульфидами:

CuBr₂  +  Na₂S  =  CuS↓  +  2NaBr

 При взаимодействии солей меди (II) с щелочами образуется голубой осадок гидроксида меди (II):

CuSO₄  +  2NaOH  =  Cu(OH)₂↓  +  Na₂SO₄

Электролиз раствора нитрата меди (II):

2Cu(NO₃)₂    +   2Н₂О →  2Cu   +   O₂  +  4HNO₃

Некоторые соли меди при нагревании разлагаются, например, нитрат меди (II):

2Cu(NO₃)₂ → 2CuO  +  4NO₂  +  O₂

Основный карбонат меди разлагается на оксид меди (II), углекислый газ и воду:

(CuOH)₂CO₃ →  2CuO  +  CO₂  +  H₂O

При взаимодействии солей меди (II) с избытком аммиака образуются аммиачные комплексы:

CuCl₂  + 4NH₃  =   [Cu(NH₃)₄]Cl₂

При смешивании растворов солей меди (II) и карбонатов происходит гидролиз и по катиону слабого основания, и по аниону слабой кислоты:

2CuSO₄  +  2Na₂CO₃  +  H₂O  =  (CuOH)₂CO₃↓  +  2Na₂SO₄  +  CO₂

Медь и соединения меди

1) Через раствор хлорида меди (II) с помощью графитовых электродов пропускали постоянный электрический ток. Выделившийся на катоде продукт электролиза растворили в концентрированной  азотной кислоте. Образовавшийся при этом газ собрали  и пропустили через раствор гидроксида натрия. Выделившийся на аноде газообразный продукт электролиза пропустили через горячий раствор гидроксида натрия. Напишите уравнения описанных реакций.

2) Вещество, полученное на катоде при электролизе расплава хлорида меди (II), реагирует с серой. Полученный продукт обработали концентрированной азотной кислотой, и выделившийся газ пропустили  через раствор гидроксида бария. Напишите уравнения описанных реакций.

3) Неизвестная соль бесцветна и окрашивает пламя в желтый цвет. При легком нагревании этой соли с концентрированной серной кислотой отгоняется жидкость, в которой растворяется медь; последнее превращение сопровождается выделением бурого газа и образованием соли меди. При термическом распаде обеих солей одним из продуктов разложения является кислород. Напишите уравнения описанных реакций.

4) При взаимодействии раствора соли А со щелочью было получено студенистое нерастворимое в воде вещество голубого цвета, которое растворили в бесцветной жидкости Б с образованием раствора синего цвета. Твердый продукт, оставшийся после осторожного выпаривания раствора, прокалили; при этом выделились два газа, один из которых бурого цвета, а второй входит в состав атмосферного воздуха, и осталось твердое вещество черного цвета, которое растворяется в жидкости Б с образованием вещества А. Напишите уравнения описанных реакций.

5) Медную стружку растворили в разбавленной азотной кислоте, и раствор нейтрализовали едким кали. Выделившееся вещество голубого цвета отделили, прокалили (цвет вещества изменился на черный), смешали с коксом и повторно прокалили. Напишите уравнения описанных реакций.

6) В раствор нитрата ртути (II) добавили медную стружку. После окончания реакции раствор профильтровали, и фильтрат по каплям прибавляли к раствору, содержащему едкий натр и гидроксид аммония. При этом наблюдали кратковременное образование осадка, который растворился с образованием раствора ярко-синего цвета. При добавлении в полученный раствор избытка раствора серной кислоты происходило изменение цвета. Напишите уравнения описанных реакций.

7) Оксид меди (I) обработали концентрированной азотной кислотой, раствор осторожно выпарили и твердый остаток прокалили. Газообразные продукты реакции пропустили через большое количество воды и в образовавшийся раствор добавили магниевую стружку, в результате выделился газ, используемый в медицине. Напишите уравнения описанных реакций.

Твердое вещество, образующееся при нагревании малахита, нагрели в атмосфере водорода. Продукт реакции обработали концентрированной серной кислотой, внесли в раствор хлорида натрия, содержащий медные опилки, в результате образовался осадок. Напишите уравнения описанных реакций.

9) Соль, полученную при растворении меди в разбавленной азотной кислоте, подвергли электролизу, используя графитовые электроды. Вещество, выделившееся на аноде, ввели во взаимодействие с натрием, а полученный продукт реакции поместили в сосуд с углекислым газом. Напишите уравнения описанных реакций.

10) Твердый продукт термического разложения малахита растворили при нагревании в концентрированной азотной кислоте. Раствор осторожно выпарили, и твердый остаток прокалили, получив вещество черного цвета, которое нагрели в избытке аммиака (газ). Напишите уравнения описанных реакций.

11) К порошкообразному веществу черного цвета добавили раствор разбавленной серной кислоты и нагрели. В полученный раствор голубого цвета приливали раствор едкого натра до прекращения выделения осадка. Осадок отфильтровали и нагрели. Продукт реакции нагревали в атмосфере водорода, в результате чего получилось вещество красного цвета. Напишите уравнения описанных реакций.

12) Неизвестное вещество красного цвета нагрели в хлоре, и продукт реакции растворили в воде. В полученный раствор добавили щелочь, выпавший осадок голубого цвета отфильтровали и прокалили. При нагревании продукта прокаливании, который имеет черный цвет, с коксом было получено исходное вещество красного цвета. Напишите уравнения описанных реакций.

13) Раствор, полученный при взаимодействии меди с концентрированной азотной кислотой, выпарили и осадок прокалили. Газообразные продукты полностью поглощены водой, а над твердым остатком пропустили водород. Напишите уравнения описанных реакций.

14) Черный порошок, который образовался при сжигании металла красного цвета в избытке воздуха, растворили в 10%-серной кислоте. В полученный раствор добавили щелочь, и выпавший осадок голубого цвета отделили и растворили в избытке раствора аммиака. Напишите уравнения описанных реакций.

15) Вещество черного цвета получили, прокаливая осадок, который образуется при взаимодействии гидроксида натрия и сульфата меди (II). При нагревании этого вещества с углем получают металл красного цвета, который растворяется в концентрированной серной кислоте. Напишите уравнения описанных реакций.

16) Металлическую медь обработали при нагревании йодом. Полученный продукт растворили в концентрированной серной кислоте при нагревании. Образовавшийся раствор обработали раствором гидроксидом калия. Выпавший осадок прокалили. Напишите уравнения описанных реакций.

17) К раствору хлорида меди (II) добавили избыток раствора соды. Выпавший осадок прокалили, а полученный продукт нагрели в атмосфере водорода. Полученный порошок растворили в разбавленной азотной кислоте. Напишите уравнения описанных реакций.

18)  Медь растворили в разбавленной азотной кислоте. К полученному раствору добавили избыток раствора аммиака, наблюдая сначала образование осадка, а затем – его полное растворение с образованием темно-синего раствора. Полученный раствор обработали серной кислотой до появления характерной голубой окраски солей меди. Напишите уравнения описанных реакций.

19) Медь растворили в концентрированной азотной кислоте. К полученному раствору добавили избыток раствора аммиака, наблюдая сначала образование осадка, а затем – его полное растворение с образованием темно-синего раствора. Полученный раствор обработали избытком соляной кислоты. Напишите уравнения описанных реакций.

20) Газ, полученный при взаимодействии железных опилок с раствором соляной кислоты, пропустили над нагретым оксидом меди (II) до полного восстановления металла. полученный металл растворили в концентрированной азотной кислоте. Образовавшийся раствор подвергли электролизу с инертными электродами. Напишите уравнения описанных реакций.

21)  Йод поместили в пробирку с концентрированной горячей азотной кислотой. Выделившийся газ пропустили через воду в присутствии кислорода. В полученный раствор добавили гидроксид меди (II). Образовавшийся раствор выпарили и сухой твердый остаток прокалили. Напишите уравнения описанных реакций.

22)  Оранжевый оксид меди поместили в концентрированную серную кислоту и нагрели. К полученному голубому раствору прилили избыток раствора гидроксида калия. выпавший синий осадок отфильтровали, просушили и прокалили. Полученное при этом твердое черное вещество в стеклянную трубку, нагрели и пропустили над ним аммиак. Напишите уравнения описанных реакций.

23) Оксид меди (II) обработали раствором серной кислоты. При электролизе образующегося раствора на инертном аноде выделяется газ. Газ смешали с оксидом азота (IV) и поглотили с водой. К разбавленному раствору полученной кислоты добавили магний, в результате чего в растворе образовалось две соли, а выделение газообразного продукта не происходило. Напишите уравнения описанных реакций.

24)  Оксид меди (II) нагрели в токе угарного газа. Полученное вещество сожгли в атмосфере хлора. Продукт реакции растворили в в воде. Полученный раствор разделили на две части. К одной части добавили раствор иодида калия, ко второй – раствор нитрата серебра. И в том, и в другом случае наблюдали образование осадка. Напишите уравнения описанных реакций.

25) Нитрат меди (II) прокалили, образовавшееся твердое вещество растворили в разбавленной серной кислоте. Раствор полученной соли подвергли электролизу. Выделившееся на катоде вещество растворили в концентрированной азотной кислоте. Растворение протекает с выделением бурого газа. Напишите уравнения описанных реакций.

26) Щавелевую кислоту нагрели с небольшим количеством концентрированной серной кислоты. Выделившийся газ пропустили через раствор гидроксида кальция. В котором выпал осадок. Часть газа не поглотилась, его пропустили над твердым веществом черного цвета, полученным при прокаливании нитрата меди (II). В результате образовалось твердое вещество темно-красного цвета. Напишите уравнения описанных реакций.

27)   Концентрированная серная кислота прореагировала с медью. Выделившийся при газ полностью поглотили избытком раствора гидроксида калия. Продукт окисления меди смешали с расчетным количеством гидроксида натрия до прекращения выпадения осадка. Последний растворили в избытке соляной кислоты. Напишите уравнения описанных реакций.

Ответы и решения

1.

CuCl₂       Cu      +      Сl₂

           на катоде    на аноде

Cu   +   4HNO_3(конц.)   =  Cu(NO₃)₂  +  2NO₂↑  +  2H₂O

2Cu(NO₃)₂  =2CuO   +  4NO₂↑   +  O₂↑

6NaOH_(гор.)  +  3Cl₂  =  NaClO₃  +  5NaCl  +  3H₂O

2.

CuCl₂  = Cu        +       Сl₂

           на катоде        на аноде

Cu   +   S  =  CuS

CuS  +  8HNO_{3(конц.гор.)}     =  CuSO₄  +  8NO₂↑  +  4H₂O

или CuS  +  10HNO_3(конц.)     =  Cu(NO₃)₂  +  H₂SO₄  +    8NO₂↑ +  4H₂O

4NO₂  +  2Ba(OH)₂  =  Ba(NO₃)₂  +  Ba(NO₂)₂  +  2H₂O

3.

NaNO_3(тв.)  +  H₂SO_4(конц.)  =  HNO₃  +  NaHSO₄

Cu   +   4HNO_3(конц.)   =  Cu(NO₃)₂  +  2NO₂↑  +  2H₂O

2Cu(NO₃)₂  = 2CuO   +  4NO₂↑ +  O₂↑

2NaNO₃  = 2NaNO₂  +  O₂↑

4.

Cu(NO₃)₂ +  2NaOH  =  Cu(OH)₂↓  +  2NaNO₃

Cu(OH)₂  +  2HNO₃  =  Cu(NO₃)₂  +  2H₂O

2Cu(NO₃)₂  = 2CuO   +  4NO₂↑   +  O₂↑

CuO  +  2HNO₃  =  Cu(NO₃)₂  +  H₂O

5. 3Cu   +   8HNO_3(разб.)   =  3Cu(NO₃)₂  +  2NO₂↑  +  4H₂O

Cu(NO₃)₂  +  2КOH  =  Cu(OH)₂↓  +  2КNO₃

Cu(OH)₂ =  CuO   +  H₂O

CuO  +  C  Cu  +  CO

6. Hg(NO₃)₂ +  Cu  =   Cu(NO₃)₂   +  Hg

Cu(NO₃)₂   +  2NaOH  =  Cu(OH)₂↓ +  2NaNO₃

Сu(OH)₂  +  4(NH₃ · H₂O)   =  [Cu(NH₃)₄](OH)₂   +  4H₂O

[Cu(NH₃)₄](OH)₂   +  5H₂SO₄   =   CuSO₄   +  4NH₄HSO₄  +  2H₂O

7. Cu₂O +  6HNO_3(конц.)  =  2Cu(NO₃)₂  +  2NO₂  +  3H₂O

2Cu(NO₃)₂  = 2CuO   +  4NO₂↑   +  O₂↑

4NO₂   +  O₂  +   2H₂O  =  4HNO₃

10HNO₃  +  4Mg  =  4Mg(NO₃)₂  +  N₂O  +  5H₂O

8. (CuOH)₂CO₃  =  2CuO  +  CO₂  +  H₂O

CuO  +  H₂  = Cu  +  H₂O

Cu  +  2H₂SO_4(конц.)  =  CuSO₄  +  SO₂  +  2H₂O

CuSO₄  +  Cu  +  2NaCl  =  2CuCl↓  +  Na₂SO₄

9.

3Cu   +   8HNO_3(разб.)   =  3Cu(NO₃)₂  +  2NO₂↑  +  4H₂O

2Cu(NO₃)₂     +  2H₂O  =   2Cu           +   O₂          +     4HNO₃

                                        на катоде        на аноде

2Na  +  O₂  =  Na₂O₂

2Na₂O₂  +  CO₂  =  2Na₂CO₃  +  O₂

10.

(CuOH)₂CO₃  = 2CuO  +  CO₂  +  H₂O

CuO  +  2HNO₃   =  Cu(NO₃)₂  +  H₂O

2Cu(NO₃)₂  = 2CuO   +  4NO₂↑   +  O₂↑

3CuO  +  2NH₃ = 3Cu  +  N₂  +  3H₂O

11.

CuO  +  H₂SO₄  = CuSO₄  +  H₂O

CuSO₄  +  2NaOH  =  Cu(OH)₂  +  Na₂SO₄

Cu(OH)₂  = CuO  +  H₂O

CuO  +  H₂  =  Cu  +  H₂O

12.

Cu  +  Cl₂  = CuCl₂

CuCl₂  +  2NaOH  =  Cu(OH)₂↓  +  2NaCl

Cu(OH)₂  = CuO  +  H₂O

CuO  +  C  = Cu  +  CO

13.

Cu +   4HNO_3(конц.)   =  Cu(NO₃)₂  +  2NO₂↑  +  2H₂O

2Cu(NO₃)₂  = 2CuO   +  4NO₂↑   +  O₂↑

4NO₂  +  O₂  +  2H₂O  =  4HNO₃

CuO  +  H₂  = Cu  +  H₂O

14.

2Cu   +   O₂   =   2CuO

CuO    +    H₂SO₄   =   CuSO₄  +  H₂O

CuSO₄    +   NaOH    =    Cu(OH)₂↓  +  Na₂SO₄

Сu(OH)₂   +  4(NH₃ · H₂O)   =  [Cu(NH₃)₄](OH)₂   +  4H₂O

15.

СuSO₄ +  2NaOH  =  Cu(OH)₂  +  Na₂SO₄

Cu(OH)₂  = CuO  +  H₂O

CuO  +  C =  Cu  +  CO

Cu  +  2H₂SO_4(конц.)  =  CuSO₄  +  SO₂  +  2H₂O

16.      

2Cu  +  I₂   =  2CuI

2CuI   +  4H₂SO₄   =  2CuSO₄  +  I₂  +  2SO₂  +  4H₂O

СuSO₄  +  2KOH  =  Cu(OH)₂  +  K₂SO₄

Cu(OH)₂ = CuO  +  H₂O

17.

 2CuCl₂  +  2Na₂CO₃  +  H₂O  =  (CuOH)₂CO₃  +  CO₂  +  4NaCl

(CuOH)₂CO₃   =  2CuO   +  CO₂  +  H₂O

CuO  +  H₂  = Cu  +  H₂O

3Cu   +   8HNO_3(разб.)   =  3Cu(NO₃)₂  +  2NO₂↑  +  4H₂O

18.

 3Cu   +   8HNO_3(разб.)   =  3Cu(NO₃)₂  +  2NO₂↑  +  4H₂O

Сu(NO₃)₂  +  2NH₃· H₂O   =  Cu(OH)₂↓  +  2NH₄NO₃

Cu(OH)₂   +   4NH₃· H₂O   =  [Cu(NH₃)₄](OH)₂   +  4H₂O

[Cu(NH₃)₄](OH)₂   +   3H₂SO₄    =  CuSO₄   +   2(NH₄)₂SO₄    +  2H₂O

19)       Cu   +   4HNO_3(конц.)   =  Cu(NO₃)₂  +  2NO₂↑  +  2H₂O

Сu(NO₃)₂  +  2NH₃· H₂O   =  Cu(OH)₂↓  +  2NH₄NO₃

Cu(OH)₂   +   4NH₃· H₂O   =  [Cu(NH₃)₄](OH)₂   +  4H₂O

[Cu(NH₃)₄](OH)₂   +   6HCl    =  CuCl₂   +   4NH₄Cl    +  2H₂O

20.

Fe   +   2HCl    =    FeCl₂   +   H₂

CuO    +  H₂   =   Cu   +   H₂O

Cu   +   4HNO_3(конц.)   =  Cu(NO₃)₂  +  2NO₂↑  +  2H₂O

2Cu(NO₃)₂     +  2H₂O  =     2Cu   +   O₂  +  4HNO₃

21.

 I₂   +   10HNO₃    =   2HIO₃   +   10NO₂   +   4H₂O

4NO₂   +   2H₂O  +  O₂    =    4HNO₃

Cu(OH)₂  +  2HNO₃  = Cu(NO₃)₂  +  2H₂O

2Cu(NO₃)₂  = 2CuO   +  4NO₂↑   +  O₂↑

22.       

Cu₂O   +  3H₂SO₄   =  2CuSO₄   +   SO₂   +   3H₂O

СuSO₄  +  2KOH  =  Cu(OH)₂  +  K₂SO₄

Cu(OH)₂  = CuO  +  H₂O

3CuO  +  2NH₃ = 3Cu  +  N₂  +  3H₂O

23.

CuO   +  H₂SO₄  =  CuSO₄  +  H₂O

2CuSO₄    +   2H₂O =  2Cu   +   O₂  +  2H₂SO₄

4NO₂   +  O₂   +   2H₂O  =  4HNO₃

10HNO₃   +   4Mg    =    4Mg(NO₃)₂   +   NH₄NO₃  +   3H₂O

24.      

CuO    +   CO =  Cu   +   CO₂

Cu   +   Cl₂   =  CuCl₂

2CuCl₂   +   2KI   =   2CuCl↓   +   I₂   +   2KCl

CuCl₂    +   2AgNO₃   =   2AgCl↓    +   Cu(NO₃)₂

.

25.      

2Cu(NO₃)₂  = 2CuO   +  4NO₂↑   +  O₂↑

CuO   +  H₂SO₄  =  CuSO₄  +  H₂O

2CuSO₄    +   2H₂O =  2Cu   +   O₂  +  2H₂SO₄

Cu   +   4HNO_3(конц.)   =  Cu(NO₃)₂  +  2NO₂↑  +  2H₂O

26.     

 H₂C₂O₄    =   CO↑   +   CO₂↑   +   H₂O

CO₂   +   Ca(OH)₂   =   CaCO₃  +  H₂O

2Cu(NO₃)₂  =2CuO   +  4NO₂↑   +  O₂↑

CuO    +   CO  = Cu   +   CO₂

27.      

Cu  +  2H₂SO_4(конц.)  =  CuSO₄  +  SO₂  +  2H₂O

SO₂   +   2KOH   =   K₂SO₃   +   H₂O

СuSO₄  +  2NaOH  =  Cu(OH)₂  +  Na₂SO₄

Cu(OH)₂  +  2HCl = CuCl₂  +  2H₂O