Copper
Copper | |||||||||||||||||||||||||||||||||
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Appearance | Red-orange metallic luster | ||||||||||||||||||||||||||||||||
Standard atomic weight Ar°(Cu) | |||||||||||||||||||||||||||||||||
Copper in the periodic table | |||||||||||||||||||||||||||||||||
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kJ/mol | |||||||||||||||||||||||||||||||||
Heat of vaporization | 300.4 kJ/mol | ||||||||||||||||||||||||||||||||
Molar heat capacity | 24.440 J/(mol·K) | ||||||||||||||||||||||||||||||||
Vapor pressure
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Atomic properties | |||||||||||||||||||||||||||||||||
9000 BC) | |||||||||||||||||||||||||||||||||
Symbol | "Cu": from Latin cuprum | ||||||||||||||||||||||||||||||||
Isotopes of copper | |||||||||||||||||||||||||||||||||
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Copper is a
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 c. 8000 BC. Thousands of years later, it was the first metal to be smelted from sulfide ores, c. 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.[8]
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.[9]
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
Copper is essential to all living organisms as a trace
Characteristics
Physical
Copper,
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.[14] 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.[12] The maximum possible current density of copper in open air is approximately 3.1×106 A/m2, above which it begins to heat excessively.[15]
Copper is one of a few metallic elements with a natural color other than gray or silver.
As with other metals, if copper is put in contact with another metal in the presence of an electrolyte, galvanic corrosion will occur.[18]
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[19] and the Statue of Liberty.[20] Copper tarnishes when exposed to some sulfur compounds, with which it reacts to form various copper sulfides.[21]
Isotopes
There are 29
Cu
with a half-life of 61.83 hours.[22] Seven metastable isomers 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.[23]
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.[24]
Occurrence
Copper is produced in massive stars
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.[29]
Production
Most copper is mined or
Reserves and prices
Copper has been in use for at least 10,000 years, but more than 95% of all copper ever mined and smelted has been extracted since 1900.[33] 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.[34] Recycling is a major source of copper in the modern world.[33]
The price of copper is volatile.[35] After a peak in 2022 the price unexpectedly fell.[36]
Methods
The great majority of copper ores are sulfides. Common ores are the sulfides chalcopyrite (CuFeS2), bornite (Cu5FeS4) and, to a lesser extent, covellite (CuS) and chalcocite (Cu2S).[37] These ores occur at the level of <1% Cu. Concentration of the ore is required, which begins with comminution followed by froth flotation. The remaining concentrate is the smelted, which can be described with two simplified equations: [38]
- 2 Cu2S + 3 O2 → 2 Cu2O + 2 SO2
Cuprous oxide reacts with cuprous sulfide to convert to blister copper upon heating
- 2 Cu2O + Cu2S → 6 Cu + 2 SO2
This roasting gives matte copper, roughly 50% Cu by weight, which is purified by electrolysis. Depending on the ore, sometimes other metals are obtained during the electrolysis including platinum and gold.
Aside from sulfides, another family of ores are oxides. Approximately 15% of the world's copper supply derives from these oxides. The beneficiation process for oxides involves extracton with sulfuric acid solutions followed by electrolysis. In parallel with the above method for "concentrated" sulfide and oxide ores, copper is recovered from mine tailings and heaps. A variety of methods are used including leaching with sulfuric acid, ammonia, ferric chloride. Biological methods are also used.[38][39]
A significant source of copper is from recycling. Recycling is facilitated because copper is usually deployed in its metallic state. In 2001, a typical automobile contained 20–30 kg of copper. Recycling usually begins with some melting process using a blast furnace.[38]
A potential source of copper is polymetallic nodules, which have an estimated concentration 1.3%.[40][41]
Recycling
Like aluminium, 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
Environmental impacts
The environmental cost of copper mining was estimated at 3.7 kg
Copper mining waste in Valea Şesei, Romania, has significantly altered nearby water properties. The water in the affected areas is highly acidic, with a pH range of 2.1–4.9, and shows elevated electrical conductivity levels between 280 and 1561 mS/cm.[49] These changes in water chemistry make the environment inhospitable for fish, essentially rendering the water uninhabitable for aquatic life.
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.[52] Some lead-free solders consist of tin alloyed with a small proportion of copper and other metals.[53]
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,[54] 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.[55] 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.[56] Alloys of copper with aluminium (about 7%) have a golden color and are used in decorations.[26] 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.[57]
Compounds
Copper forms a rich variety of compounds, usually with oxidation states +1 and +2, which are often called cuprous and cupric, respectively.[58] Copper compounds promote or catalyse numerous chemical and biological processes.[59]
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,[60] important examples include copper(I) sulfide (Cu2S) and copper monosulfide (CuS).[61]
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.[58]
- 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.[62]
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
Copper(III) and copper(IV)
Copper(III) is most often found in oxides. A simple example is potassium
Some copper proteins form
Complexes of copper(III) are also found as intermediates in reactions of organocopper compounds, for example in the Kharasch–Sosnovsky reaction.[80][81][82]
History
A timeline of copper illustrates how this metal has advanced human civilization for the past 11,000 years.[83]
Prehistoric
Copper Age
Copper occurs naturally as
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.
Production in the
Bronze Age
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.
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.[102]
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
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.[105]
In North America, native copper is known to have been extracted from sites on Isle Royale with primitive stone tools between 800 and 1600 AD.[106] Copper annealing was being performed in the North American city of Cahokia around 1000–1300 AD.[107] There are several exquisite copper plates, known as the Mississippian copper plates that have been found in North America in the area around Cahokia dating from this time period (1000–1300 AD).[107] The copper plates were thought to have been manufactured at Cahokia before ending up elsewhere in the Midwest and southeastern United States like the Wulfing cache and Etowah plates.
In South America a copper mask dated to 1000 BC found in the Argentinian Andes is the oldest known copper artifact discovered in the Andes.[108] Peru has been considered the origin for early copper metallurgy in pre-Columbian America, but the copper mask from Argentina suggests that the Cajón del Maipo of the southern Andes was another important center for early copper workings in South America.[108] 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.[109][110]
The gates of the
Modern
The
Copper is used in roofing,
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.[116] 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 Southwest 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.[117]
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.[118]
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.[119]
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).[26] For more than two centuries, copper paint has been used on boat hulls to control the growth of plants and shellfish.[120] A small part of the copper supply is used for nutritional supplements and fungicides in agriculture.[62][121] 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
For a short period from the late 1960s to the late 1970s, copper wiring was replaced by
Electric motors
Copper's superior
Renewable energy production
Copper plays an important role in these renewable energy systems.
When choosing electrical conductors, facility planners and engineers factor capital investment costs of materials against operational savings due to their electrical energy efficiencies over their useful lives, plus maintenance costs. Copper often fares well in these calculations. A factor called "copper usage intensity,” is a measure of the quantity of copper necessary to install one megawatt of new power-generating capacity.
When planning for a new renewable power facility, engineers and product specifiers seek to avoid supply shortages of selected materials. According to the United States Geological Survey, in-ground copper reserves have increased more than 700% since 1950, from almost 100 million tonnes to 720 million tonnes in 2017, despite the fact that world refined usage has more than tripled in the last 50 years.[143] Copper resources are estimated to exceed 5,000 million tonnes.[144][145]
Bolstering the supply from copper extraction is the more than 30 percent of copper installed from 2007 to 2017 that came from recycled sources.[146] Its recycling rate is higher than any other metal.[147]Architecture
Copper has been used since ancient times as a durable,
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.[152][153][154] It can be a mixture of carbonate and sulfate compounds in various amounts, depending upon environmental conditions such as sulfur-containing acid rain.[155][156][157][158] 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.[159]
Copper has excellent
Antibiofouling
Copper is
Antimicrobial
Copper demand
Total world production in 2023 is expected to be almost 23 million
For some purposes, other metals can substitute,
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
Folk medicine
Copper is commonly used in jewelry, and according to some folklore, copper bracelets relieve arthritis symptoms.[184] In one trial for osteoarthritis and one trial for rheumatoid arthritis, no differences were found between copper bracelet and control (non-copper) bracelet.[185][186] No evidence shows that copper can be absorbed through the skin. If it were, it might lead to copper poisoning.[187]
Degradation
Chromobacterium violaceum and Pseudomonas fluorescens can both mobilize solid copper as a cyanide compound.[188] The ericoid mycorrhizal fungi associated with Calluna, Erica and Vaccinium can grow in metalliferous soils containing copper.[188] 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.[189]
Biological role
Biochemistry
- 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
A unique tetranuclear copper center has been found in nitrous-oxide reductase.[194]
Chemical compounds which were developed for treatment of Wilson's disease have been investigated for use in cancer therapy.[195]
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.[196]
Absorption
Copper is absorbed in the gut, then transported to the liver bound to albumin.[197] 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.[198] 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.[199][200]
Dietary recommendations
The
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.[203] 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.[204]
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[update], it was revised to 0.9 mg to bring it into agreement with the RDA.[205][206] 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.[207]
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
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.[196]
Elevated copper levels have also been linked to worsening symptoms of Alzheimer's disease.[213][214]
Human exposure
In the US, the
Copper is a constituent of
See also
- Copper in renewable energy
- Copper nanoparticle
- Erosion corrosion of copper water tubes
- List of countries by copper production
- Metal theft
- Anaconda Copper
- Antofagasta PLC
- Codelco
- El Boleo mine
- Grasberg mine
- Copper foil
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Notes
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. 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
- International Copper Association and the Copper Alliance, a business interest group
- Copper.org – official website of the Copper Development Association, a North American industry association with an extensive site of properties and uses of copper
- Price history of LME Copper, according to the IMF