Copper: Wikis

  
  
  
  
  

Note: Many of our articles have direct quotes from sources you can cite, within the Wikipedia article! This article doesn't yet, but we're working on it! See more info or our list of citable articles.

Did you know ...


More interesting facts on Copper

Include this on your site/blog:

Encyclopedia

From Wikipedia, the free encyclopedia

nickelcopperzinc
-

Cu

Ag
Appearance
reddish/orange metallic luster

Native copper (~4 cm in size)
General properties
Name, symbol, number copper, Cu, 29
Element category transition metal
Group, period, block 114, d
Standard atomic weight 63.546(3)g·mol−1
Electron configuration [Ar] 3d10 4s1
Electrons per shell 2, 8, 18, 1 (Image)
Physical properties
Phase solid
Density (near r.t.) 8.94 g·cm−3
Liquid density at m.p. 8.02 g·cm−3
Melting point 1357.77 K, 1084.62 °C, 1984.32 °F
Boiling point 2835 K, 2562 °C, 4643 °F
Heat of fusion 13.26 kJ·mol−1
Heat of vaporization 300.4 kJ·mol−1
Specific heat capacity (25 °C) 24.440 J·mol−1·K−1
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 +1, +2, +3, +4
(mildly basic oxide)
Electronegativity 1.90 (Pauling scale)
Ionization energies
(more)
1st: 745.5 kJ·mol−1
2nd: 1957.9 kJ·mol−1
3rd: 3555 kJ·mol−1
Atomic radius 128 pm
Covalent radius 132±4 pm
Van der Waals radius 140 pm
Miscellanea
Crystal structure face-centered cubic
Magnetic ordering diamagnetic
Electrical resistivity (20 °C) 16.78 nΩ·m
Thermal conductivity (300 K) 401 W·m−1·K−1
Thermal expansion (25 °C) 16.5 µm·m−1·K−1
Speed of sound (thin rod) (r.t.) (annealed)
3810 m·s−1
Young's modulus 110–128 GPa
Shear modulus 48 GPa
Bulk modulus 140 GPa
Poisson ratio 0.34
Mohs hardness 3.0
Vickers hardness 369 MPa
Brinell hardness 874 MPa
CAS registry number 7440-50-8
Most stable isotopes
Main article: Isotopes of copper
iso NA half-life DM DE (MeV) DP
63Cu 69.15% 63Cu is stable with 34 neutrons
65Cu 30.85% 65Cu is stable with 36 neutrons


Copper (pronounced /ˈkɒpər/, KOP-ər) is a chemical element with the symbol Cu (Latin: cuprum) and atomic number 29. It is a ductile metal with very high thermal and electrical conductivity. Pure copper is rather soft and malleable, and a freshly-exposed surface has a pinkish or peachy color. It is used as a thermal conductor, an electrical conductor, a building material, and a constituent of various metal alloys.

A copper disc made by continuous casting and etching.

Copper metal and alloys have been used for thousands of years. In the Roman era, copper was principally mined on Cyprus, hence the origin of the name of the metal as Cyprium, "metal of Cyprus", later shortened to Cuprum. There may be insufficient reserves to sustain current high rates of copper consumption.[1] Some countries, such as Chile and the United States, still have sizable reserves of the metal which are extracted through large open pit mines.

Copper compounds are known in several oxidation states, usually 2+, where they often impart blue or green colors to natural minerals such as turquoise and have been used historically widely as pigments. Copper as both metal and pigmented salt, has a significant presence in decorative art. Copper 2+ ions are soluble in water, where they function at low concentration as bacteriostatic substances and fungicides. For this reason, copper metal can be used as an anti-germ surface that can add to the anti-bacterial and antimicrobial features of buildings such as hospitals.[2] In sufficient amounts, copper salts can be poisonous to higher organisms as well. However, despite universal toxicity at high concentrations, the 2+ copper ion at lower concentrations is an essential trace nutrient to all higher plant and animal life. In animals, including humans, it is found widely in tissues, with concentration in liver, muscle, and bone. It functions as a co-factor in various enzymes and in copper-based pigments.

Contents

History

Copper Age

Copper, as native copper, is one of the few metals to occur naturally as an un-compounded mineral. Copper was known to some of the oldest civilizations on record, and has a history of use that is at least 10,000 years old. Some estimates of copper's discovery place this event around 9000 BC in the Middle East.[3] A copper pendant was found in what is now northern Iraq that dates to 8700 BC.[4] It is probable that gold and meteoritic iron were the only metals used by humans before copper.[5] By 5000 BC, there are signs of copper smelting: the refining of copper from simple copper compounds such as malachite or azurite. Among archaeological sites in Anatolia, Çatal Höyük (~6000 BC) features native copper artifacts and smelted lead beads, but no smelted copper. Can Hasan (~5000 BC) had access to smelted copper but the oldest smelted copper artifact found (a copper chisel from the chalcolithic site of Prokuplje in Serbia) has pre-dated Can Hasan by 500 years. The smelting facilities in the Balkans appear to be more advanced than the Turkish forges found at a later date, so it is quite probable that copper smelting originated in the Balkans. Investment casting was realized in 4500–4000 BC in Southeast Asia.[3]

Ancient Copper ingot from Zakros, Crete is shaped in the form of an animal skin typical for that era.

Copper smelting appears to have been developed independently in several parts of the world. In addition to its development in the Balkans by 5500 BC, it was developed in China before 2800 BC, in the Andes around 2000 BC, in Central America around 600 AD, and in West Africa around 900 AD.[6] Copper is found extensively in the Indus Valley Civilization by the 3rd millennium BC. In Europe, Ötzi the Iceman, a well-preserved male dated to 3300–3200 BC, was found with an axe with a copper head 99.7% pure. High levels of arsenic in his hair suggest he was involved in copper smelting. Over the course of centuries, experience with copper has assisted the development of other metals; for example, knowledge of copper smelting led to the discovery of iron smelting.

In the Americas production in the Old Copper Complex, located in present day Michigan and Wisconsin, was dated back to between 6000 to 3000 BC.[7][8]

Bronze Age

Alloying of copper with zinc or tin to make brass or bronze was practiced soon after the discovery of copper itself. There exist copper and bronze artifacts from Sumerian cities that date to 3000 BC,[9] and Egyptian artifacts of copper and copper-tin alloys nearly as old. In one pyramid, a copper plumbing system was found that is 5000 years old.[10] The Egyptians found that adding a small amount of tin made the metal easier to cast, so copper-tin (bronze) alloys were found in Egypt almost as soon as copper was found. Very important sources of copper in the Levant were located in Timna valley (Negev, now in southern Israel) and Faynan (biblical Punon, Jordan).[11]

By 2000 BC, Europe was using bronze.[9] The use of bronze became so widespread in Europe approximately from 2500 BC to 600 BC that it has been named the Bronze Age. The transitional period in certain regions between the preceding Neolithic period and the Bronze Age is termed the Chalcolithic ("copper-stone"), with some high-purity copper tools being used alongside stone tools. Brass (copper-zinc alloy) was known to the Greeks, but only became a significant supplement to bronze during the Roman empire.

During the Bronze Age, one copper mine at Great Orme in North Wales, extended for a depth of 70 meters.[12] At Alderley Edge in Cheshire, carbon dates have established mining at around 2280 to 1890 BC (at 95% probability).[13]

Antiquity and Middle Ages

In alchemy the symbol for copper, perhaps a stylized mirror, was also the symbol for the goddess and planet Venus.
Chalcolithic copper mine in Timna Valley, Negev Desert, Israel.

In Greek the metal was known by the name chalkos (χαλκός). Copper was a very important resource for the Romans, Greeks and other ancient peoples. In Roman times, it became known as aes Cyprium (aes being the generic Latin term for copper alloys such as bronze and other metals, and Cyprium because so much of it was mined in Cyprus). From this, the phrase was simplified to cuprum, hence the English copper. Copper was associated with the goddess Aphrodite/Venus in mythology and alchemy, owing to its lustrous beauty, its ancient use in producing mirrors, and its association with Cyprus, which was sacred to the goddess. In astrology, alchemy the seven heavenly bodies known to the ancients were associated with seven metals also known in antiquity, and Venus was assigned to copper.[14]

Britain's first use of brass occurred around the 3rd–2nd century BC. 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.[15]

Copper metallurgy was flourishing in South America, particularly in Peru around the beginning of the first millennium AD. Copper technology proceeded at a much slower rate on other continents. Africa's major location for copper reserves is Zambia. Copper burial ornamentals dated from the 15th century have been uncovered, but the metal's commercial production did not start until the early 1900s. Australian copper artifacts exist, but they appear only after the arrival of the Europeans; the aboriginal culture apparently did not develop their own metallurgical abilities.

Crucial in the metallurgical and technological worlds, copper has also played an important cultural role, particularly in currency. Romans in the 6th through 3rd centuries BC used copper lumps as money. At first, just 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 a copper-zinc alloy, while Octavianus Augustus Caesar's coins were made from Cu-Pb-Sn alloys.

The gates of the Temple of Jerusalem used Corinthian bronze made by depletion gilding. Corinthian bronze was most prevalent in Alexandria, where alchemy is thought to have begun.[16] In ancient India (before 1000 BC), 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 as time passed, (~1500 BC) for headaches, burns, and itching. Hippocrates (~400 BC) used copper to treat leg ulcers associated with varicose veins. Ancient Aztecs fought sore throats by gargling with copper mixtures.

Copper is also the part of many rich stories and legends, such as that of Iraq's Baghdad Battery. Copper cylinders soldered to lead, which date back to 248 BC to 226 AD, resemble a galvanic cell, leading people to believe this may have been the first battery. This claim has so far not been substantiated.

The Bible also refers to the importance of copper: "Men know how to mine silver and refine gold, to dig iron from the earth and melt copper from stone" (Job. 28:1–2).

Modern period

The Great Copper Mountain was a mine in Falun, Sweden, that operated for a millennium from the 10th century to 1992. It produced as much as two thirds of Europe's copper needs in the 17th century and helped fund many of Sweden's wars during that time. It was referred to as the nation's treasury; Sweden had a copper backed currency.

Throughout history, copper's use in art has extended far beyond currency. Vannoccio Biringuccio, Giorgio Vasari and Benvenuto Cellini are three Renaissance sculptors from the mid 1500s, notable for their work with bronze. From about 1560 to about 1775, thin sheets of copper were commonly used as a canvas for paintings. Silver plated copper was used in the pre-photograph known as the daguerreotype. The Statue of Liberty, dedicated on October 28, 1886, was constructed of copper thought to have come from French-owned mines in Norway.

Plating was a technology that started in the mid 1600s in some areas. One common use for copper plating, widespread in the 1700s, was the sheathing of ships' hulls. Copper sheathing could be used to protect wooden hulled ships from algae, and from the shipworm "Teredo navalis", a saltwater clam. The ships of Christopher Columbus were among the earliest to have this protection.[17] The Norddeutsche Affinerie in Hamburg was the first modern electroplating plant starting its production in 1876.[18]

In 1801 Paul Revere established America's first copper rolling mill in Canton, Massachusetts. In the early 1800s, it was discovered that copper wire could be used as a conductor, but it wasn't until 1990 that copper, in oxide form, was discovered for use as a superconducting material. The German scientist Gottfried Osann invented powder metallurgy of copper in 1830 while determining the metal's atomic weight. Around then it was also discovered that the amount and type of alloying element (e.g. tin) would affect the tones of bells, allowing for a variety of rich sounds, leading to bell casting, another common use for copper and its alloys.

Flash smelting, was developed by Outokumpu in Finland and first applied at the Harjavalta plant in 1949. The process makes smelting more energy efficient and is today used for 50% of the world’s primary copper production.[19]

Copper has been pivotal in the economic and sociological worlds, notably disputes involving copper mines. The 1906 Cananea Strike in Mexico dealt with issues of work organization. The Teniente copper mine (1904-1951) raised political issues about capitalism and class structure. Japan's largest copper mine, the Ashio mine, was the site of a riot in 1907. The Arizona miners' strike of 1938 dealt with American labor issues including the "right to strike".

Characteristics

Color

Copper just above its melting point keeps its pink luster color when enough light outshines the orange incandescence color.

Copper has a reddish, orangish, or brownish color because a thin layer of tarnish (including oxides) gradually forms on its surface when gases (especially oxygen) in the air react with it. But pure copper, when fresh, is actually a pinkish or peachy metal. Copper, caesium and gold are the only three elemental metals with a natural color other than gray or silver.[20] The usual gray color of metals depends on their "electron sea" that is capable of absorbing and re-emitting photons over a wide range of frequencies. Copper has its characteristic color because of its unique band structure. By Madelung's rule the 4s subshell should be filled before electrons are placed in the 3d subshell but copper is an exception to the rule with only one electron in the 4s subshell instead of two. The energy of a photon of blue or violet light is sufficient for a d band electron to absorb it and transition to the half-full s band. Thus the light reflected by copper is missing some blue/violet components and appears red. This phenomenon is shared with gold which has a corresponding 5s/4d structure.[21] In its liquefied state, a pure copper surface without ambient light appears somewhat greenish, a characteristic shared with gold. When liquid copper is in bright ambient light, it retains some of its pinkish luster. When copper is burnt in oxygen it gives off a black oxide.

Group 11 of the periodic table

Copper occupies the same family of the periodic table as silver and gold, since they each have one s-orbital electron on top of a filled electron shell which forms metallic bonds. This similarity in electron structure makes them similar in many characteristics. All have very high thermal and electrical conductivity, and all are malleable metals. Among pure metals at room temperature, copper has the second highest electrical and thermal conductivity, after silver.[22]

Occurrence

Native copper, ca. 4×2 cm.

Copper can be found as native copper in mineral form (for example, in Michigan's Keewenaw Peninsula). It is a polycrystal, with the largest single crystals measuring 4.4×3.2×3.2 cm.[23] Minerals such as the sulfides: chalcopyrite (CuFeS2), bornite (Cu5FeS4), covellite (CuS), chalcocite (Cu2S) are sources of copper, as are the carbonates: azurite (Cu3(CO3)2(OH)2) and malachite (Cu2CO3(OH)2) and the oxide: cuprite (Cu2O).[22]

Mechanical properties

Copper is easily worked, being both ductile and malleable. The ease with which it can be drawn into wire makes it useful for electrical work in addition to its excellent electrical properties. Copper can be machined, although it is usually necessary to use an alloy for intricate parts, such as threaded components, to get really good machinability characteristics. Good thermal conduction makes it useful for heatsinks and in heat exchangers. Copper has good corrosion resistance, but not as good as gold. It has excellent brazing and soldering properties and can also be welded, although best results are obtained with gas metal arc welding.[24]

Copper is normally supplied, as with nearly all metals for industrial and commercial use, in a fine grained polycrystalline form. Polycrystalline metals have greater strength than monocrystalline forms, and the difference is greater for smaller grain (crystal) sizes. The reason is due to the inability of stress dislocations in the crystal structure to cross the grain boundaries.[25]

Electrical properties

Copper electrical busbars distributing power to a large building

At 59.6×106 S/m copper has the second highest electrical conductivity of any element, just after silver. This high value is due to virtually all the valence electrons (one per atom) taking part in conduction. The resulting free electrons in the copper amount to a huge charge density of 13.6×109 C/m3. This high charge density is responsible for the rather slow drift velocity of currents in copper cable (drift velocity may be calculated as the ratio of current density to charge density). For instance, at a current density of 5×106 A/m2 (typically, the maximum current density present in household wiring and grid distribution) the drift velocity is just a little over ⅓ mm/s.[26]

Corrosion

Contact with other metals

Copper should not be in direct mechanical contact with metals of different electropotential (for example, a copper pipe joined to an iron pipe), especially in the presence of moisture, as the completion of an electrical circuit (for instance through the common ground) will cause the juncture to act as an electrochemical cell (like a single cell of a battery). The weak electrical currents themselves are harmless but the electrochemical reaction will cause the conversion of the iron to other compounds, eventually destroying the functionality of the union. This problem is usually solved in plumbing by separating copper pipe from iron pipe with some non-conducting segment (usually plastic or rubber).

Solutions

Copper does not react with water, but it slowly reacts with atmospheric oxygen forming a layer of brown-black copper oxide. In contrast to the oxidation of iron by wet air, this oxide layer stops the further, bulk corrosion. A green layer of copper carbonate, called verdigris, can often be seen on old copper constructions, such as the Statue of Liberty.

Copper reacts with hydrogen sulfide- and sulfide-containing solutions, forming various copper sulfides on its surface. In sulfide-containing solutions, copper is less noble than hydrogen and will corrode. This is observed in everyday life when copper metal surfaces tarnish after exposure to air containing sulfur compounds.

Copper is slowly dissolved in oxygen-containing ammonia solutions because ammonia forms water-soluble complexes with copper. Copper reacts with a combination of oxygen and hydrochloric acid to form a series of copper chlorides. Copper(II) chloride (green/blue) when boiled with copper metal undergoes a symproportionation reaction to form white copper(I) chloride.

Germicidal effect

Copper is germicidal, via the oligodynamic effect. For example, brass doorknobs disinfect themselves of many bacteria within a period of eight hours.[27] Antimicrobial properties of copper are effective against MRSA,[28] Escherichia coli[29] and other pathogens.[30][31][32] In colder temperature, longer time is required to kill bacteria.

Copper has the intrinsic ability to kill a variety of potentially harmful pathogens. On February 29, 2008, the United States EPA registered 275 alloys, containing greater than 65% nominal copper content, as antimicrobial materials[33]. Registered alloys include pure copper, an assortment of brasses and bronzes, and additional alloys. EPA-sanctioned tests using Good Laboratory Practices were conducted in order to obtain several antimicrobial claims valid against: methicillin-resistant Staphylococcus aureus (MRSA), Enterobacter aerogenes, Escherichia coli O157: H7 and Pseudomonas aeruginosa. The EPA registration allows the manufacturers of these copper alloys to legally make public health claims as to the health effects of these materials. Several of the aforementioned bacteria are responsible for a large portion of the nearly two million hospital-acquired infections contracted each year in the United States[34]. Frequently touched surfaces in hospitals and public facilities harbor bacteria and increase the risk for contracting infections. Covering touch surfaces with copper alloys can help reduce microbial contamination associated with hospital-acquired infections on these surfaces.

Isotopes

Copper has 29 distinct isotopes ranging in atomic mass from 52 to 80. Two of these, 63Cu and 65Cu, are stable and occur naturally, with 63Cu comprising approximately 69% of naturally occurring copper.[35]

The other 27 isotopes are radioactive and do not occur naturally. The most stable of these is 67Cu with a half-life of 61.83 hours. The least stable is 54Cu with a half-life of approximately 75 ns. Unstable copper isotopes with atomic masses below 63 tend to undergo β+ decay, while isotopes with atomic masses above 65 tend to undergo β decay. 64Cu decays by both β+ and β.[35]

68Cu, 69Cu, 71Cu, 72Cu, and 76Cu each have one metastable isomer. 70Cu has two isomers, making a total of 7 distinct isomers. The most stable of these is 68mCu with a half-life of 3.75 minutes. The least stable is 69mCu with a half-life of 360 ns.[35]

Production

Chuquicamata is the largest open pit copper mines in the world.
Copper output in 2005

Output

Most copper ore is mined or extracted as copper sulfides from large open pit mines in porphyry copper deposits that contain 0.4 to 1.0% copper. Examples include: Chuquicamata in Chile and El Chino Mine in New Mexico. The average abundance of copper found within crustal rocks is approximately 68 ppm by mass, and 22 ppm by atoms. In 2005, Chile was the top mine producer of copper with at least one-third world share followed by the USA, Indonesia and Peru, reports the British Geological Survey.[22]

Reserves

World production trend
Copper Prices 2003 - 2008 in USD

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. As with many natural resources, total amount of copper on Earth is vast (around 1014 tons just in the top kilometer of Earth's crust, or about 5 million years worth at the current rate of extraction). However, only a tiny fraction of these reserves is economically viable, given present-day prices and technologies. Various estimates of existing copper reserves available for mining vary from 25 years to 60 years, depending on core assumptions such as the growth rate.[36]

Copper is a finite resource, but it can be recycled. Recycling is a major source of copper in the modern world. As consumption in India and China increases, copper supplies are becoming scarcer.[37] The copper price has quintupled from the 60-year low in 1999, rising from US$0.60 per pound (US$1.32/kg) in June 1999 to US$3.75 per pound (US$8.27/kg) in May 2006, where it dropped to US$2.40 per pound (US$5.29/kg) in February 2007 then rebounded to US$3.50 per pound (US$7.71/kg = £3.89 = 5.00) in April 2007.[38] By early February 2009, however, weakening global demand and a steep fall in commodity prices since the previous year's highs had left copper prices at US$1.51 per pound.[39]

The Intergovernmental Council of Copper Exporting Countries (CIPEC), defunct since 1992, once tried to play a similar role for copper as OPEC does for oil, but never achieved the same influence, not least because the second-largest producer, the United States, was never a member. Formed in 1967, its principal members were Chile, Peru, Zaire, and Zambia.

Methods

Applications

Copper is malleable and ductile and is a good conductor of both heat and electricity.

The purity of copper is expressed as 4N for 99.99% pure or 7N for 99.99999% pure. The numeral gives the number of nines after the decimal point when expressed as a decimal (e.g. 4N means 0.9999, or 99.99%). Copper is often too soft for its applications, so it is incorporated in numerous alloys. For example, brass is a copper-zinc alloy, and bronze is a copper-tin alloy.[40]

It is used extensively, in products such as:

Piping

Assorted copper fittings
  • including water supply.
  • used extensively in refrigeration and air conditioning equipment because of its ease of fabrication and soldering, as well as high conductivity to heat.

Electrical applications

Copper roof on the Minneapolis City Hall, coated with patina

Architecture and industry

Old copper utensils in a Jerusalem restaurant
  • Copper is used to prevent a building being directly struck by lightning. High above the roof, copper spikes (lightning rods) are connected to a very thick copper cable which leads to a large metal plate underneath the ground. The voltage is dispersed throughout the ground harmlessly, instead of destroying the main structure.[42]

Household products

Coinage

Biomedical applications

Chemical applications

Miscellanea

  • Musical instruments, especially brass instruments and timpani.
  • Class D fire extinguisher, used in powder form to extinguish lithium fires by covering the burning metal and performing similar to a heat sink.
  • Textile fibers to create antimicrobial protective fabrics.[48]
  • Weaponry
    • Small arms ammunition commonly uses copper as a jacketing material around the bullet core.
    • Copper is also commonly used as a case material, in the form of brass.
    • Copper is used as a liner in shaped charge armor-piercing warheads and demolition explosives (blade).
  • Copper is frequently used in electroplating, usually as a base for other metals such as nickel.

Alloys

Numerous copper alloys exist, many with important historical and contemporary uses. Speculum metal and bronze are alloys of copper and tin. Brass is an alloy of copper and zinc. Monel metal, also called cupronickel, is an alloy of copper and nickel. While the metal "bronze" usually refers to copper-tin alloys, it also is a generic term for any alloy of copper, such as aluminium bronze, silicon bronze, and manganese bronze. Copper is one of the most important constituents of carat silver and gold alloys and carat solders used in the jewelry industry, modifying the color, hardness and melting point of the resulting alloys.[49]

Compounds

Copper(I) oxide powder

Common oxidation states of copper include the less stable copper(I) state, Cu+; and the more stable copper(II) state, Cu2+, which forms blue or blue-green salts and solutions. Under unusual conditions, a 3+ state and even an extremely rare 4+ state can be obtained. Using old nomenclature for the naming of salts, copper(I) is called cuprous, and copper(II) is cupric. In oxidation copper is mildly basic.

Copper(II) carbonate is green from which arises the unique appearance of copper-clad roofs or domes on some buildings. Copper(II) sulfate forms a blue crystalline pentahydrate which is perhaps the most familiar copper compound in the laboratory. It is used as a fungicide, known as Bordeaux mixture.

There are two stable copper oxides, copper(II) oxide (CuO) and copper(I) oxide (Cu2O). Copper oxides are used to make yttrium barium copper oxide (YBa2Cu3O7-δ) or YBCO which forms the basis of many unconventional superconductors.

  • Copper(III) compounds, rare: potassium hexafluorocuprate (K3CuF6)
  • Copper(IV) compounds, extremely rare: caesium hexafluorocuprate (Cs2CuF6)

Tests for copper(II) ion

Adding an aqueous solution of sodium hydroxide will form a blue precipitate of copper(II) hydroxide. The ionic equation is:

Cu2+ (aq) + 2 OH (aq) → Cu(OH)2 (s)

The full equation shows that the reaction is due to hydroxide ions deprotonating the hexaaquacopper(II) complex:

[Cu(H2O)6]2+ (aq) + 2 OH(aq) → Cu(H2O)4(OH)2 (s) + 2 H2O (l)

Adding ammonium hydroxide (aqueous ammonia) causes the same precipitate to form. Upon adding excess ammonia, the precipitate dissolves, forming a deep blue ammonia complex, tetraamminecopper(II):

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

A more delicate test than ammonia is potassium ferrocyanide, which gives a brown precipitate with copper salts.

Biological role

Rich sources of copper include oysters, beef or lamb liver, Brazil nuts, blackstrap molasses, cocoa, and black pepper. Good sources include lobster, nuts and sunflower seeds, green olives, avocados and wheat bran.

Copper is essential in all plants and animals. The human body normally contains copper at a level of about 1.4 to 2.1 mg for each kg of body weight.[50] Copper is distributed widely in the body and occurs in liver, muscle and bone. Copper is transported in the bloodstream on a plasma protein called ceruloplasmin. When copper is first absorbed in the gut it is transported to the liver bound to albumin. Copper metabolism and excretion is controlled delivery of copper to the liver by ceruloplasmin, where it is excreted in bile.

Copper is found in a variety of enzymes, including the copper centers of cytochrome c oxidase and the enzyme superoxide dismutase (containing copper and zinc). In addition to its enzymatic roles, copper is used for biological electron transport. The blue copper proteins that participate in electron transport include azurin and plastocyanin. The name "blue copper" comes from their intense blue color arising from a ligand-to-metal charge transfer (LMCT) absorption band around 600 nm.

Most molluscs and some arthropods such as the horseshoe crab use the copper-containing pigment hemocyanin rather than iron-containing hemoglobin for oxygen transport, so their blood is blue when oxygenated rather than red.[51]

It is believed that zinc and copper compete for absorption in the digestive tract so that a diet that is excessive in one of these minerals may result in a deficiency in the other. The RDA for copper in normal healthy adults is 0.9 mg/day. On the other hand, professional research on the subject recommends 3.0 mg/day.[52] Because of its role in facilitating iron uptake, copper deficiency can often produce anemia-like symptoms. Conversely, an accumulation of copper in body tissues are believed to cause the symptoms of Wilson's disease in humans.

Chronic copper depletion leads to abnormalities in metabolism of fats, high triglycerides, non-alcoholic steatohepatitis (NASH), fatty liver disease and poor melanin and dopamine synthesis causing depression and sunburn. Food rich in copper should be eaten away from any milk or egg proteins as they block absorption.

Reference ranges for blood tests, comparing blood content of copper (shown in gray) with other constituents.

Toxicity

Toxicity can occur from eating acidic food that has been cooked with copper cookware. Cirrhosis of the liver in children (Indian Childhood Cirrhosis) has been linked to boiling milk in copper cookware. The Merck Manual states that recent studies suggest that a genetic defect is associated with this cirrhosis.[53] Since copper is actively excreted by the normal body, chronic copper toxicosis in humans without a genetic defect in copper handling has not been demonstrated.[50] However, large amounts (gram quantities) of copper salts taken in suicide attempts have produced acute copper toxicity in normal humans. Equivalent amounts of copper salts (30 mg/kg) are toxic in animals[54]

Miscellaneous hazards

The metal, when powdered, is a fire hazard. At concentrations higher than 1 mg/L, copper can stain clothes and items washed in water.

Recycling

Copper is 100% recyclable without any loss of quality whether in a raw state or contained in a manufactured product. Copper is the third most recycled metal after iron and aluminium. It is estimated that 80% of the copper ever mined is still in use today.[55] Common grades of copper for recycling are:

  • Bare bright - very clean and pure copper wire usually 12 AWG (2.05 mm) or larger that has insulation and any tarnish removed
  • #1 copper - pipe with a new appearance and free of any foreign material
  • #2 copper - pipe with corrosion or foreign material and small gauge wire with no insulation

Insulated wire is also commonly recycled once the insulation is stripped off.

High purity copper scrap is directly melted in a furnace and the molten copper is deoxidized and cast into billets, or ingots. Lower purity scrap is usually refined to attain the desired purity level by an electroplating process in which the copper scrap is dissolved into a bath of sulfuric acid and then electroplated out of the solution.[56]

See also

References

  1. ^ "Earth's Limited Supply of Metals Raises Concern". http://www.livescience.com/strangenews/060119_scarce_metals.html. Retrieved 2008-03-16. 
  2. ^ Barnaby J. Feder (March 26, 2008). "Regulators Stamp Copper as a Germ Killer". New York Times. http://www.nytimes.com/2008/03/26/business/26microbes.html?_r=1&scp=2&sq=copper&st=nyt&oref=slogin. 
  3. ^ a b "CSA - Discovery Guides, A Brief History of Copper". Csa.com. http://www.csa.com/discoveryguides/copper/overview.php. Retrieved 2008-09-12. 
  4. ^ Rayner W. Hesse (2007). Rayner W. Hesse. Greenwood Publishing Group. p. 56. ISBN 0313335079. 
  5. ^ "Copper". Elements.vanderkrogt.net. http://elements.vanderkrogt.net/element.php?sym=Cu. Retrieved 2008-09-12. 
  6. ^ R. Cowen. "Essays on Geology, History, and People, Chapter 3: "Fire and Metals: Copper". http://www.geology.ucdavis.edu/~cowen/~GEL115/115CH3.html. Retrieved 2009-07-07. 
  7. ^ Thomas C. Pleger, "A Brief Introduction to the Old Copper Complex of the Western Great Lakes: 4000-1000 BC", Proceedings of the Twenty-seventh Annual Meeting of the Forest History Association of Wisconsin, Oconto, Wisconsin, October 5, 2002, pp. 10-18.
  8. ^ Thomas E. Emerson, Dale L. McElrath, Archaic Societies: Diversity and Complexity Across the Midcontinent, SUNY Press, 2009 ISBN 1438427018.
  9. ^ a b Ian McNeil (2002). Encyclopaedia of the History of Technology. London ; New York: Routledge. pp. 13;48–66. ISBN 0203192117. 
  10. ^ "The History of Plumbing - Egypt". The plumber. http://www.theplumber.com/egypt.html. Retrieved 2009-05-05. 
  11. ^ J.M. Tebes (2007). "A Land whose Stones are Iron, and out of whose Hills You can Dig Copper: The Exploitation and Circulation of Copper in the Iron Age Negev and Edom". DavarLogos 6 (1). http://dialnet.unirioja.es/servlet/articulo?codigo=2314512. 
  12. ^ O’Brien, W. (1997). Bronze Age Copper Mining in Britain and Ireland. Shire Publications Ltd. ISBN 0747803218. 
  13. ^ Timberlake, S. and Prag A.J.N.W. (2005). The Archaeology of Alderley Edge: Survey, excavation and experiment in an ancient mining landscape. Oxford: John and Erica Hedges Ltd.. p. 396. 
  14. ^ T. A. Rickard (1932). "The Nomenclature of Copper and its Alloys". The Journal of the Royal Anthropological Institute of Great Britain and Ireland 62: 281. doi:10.2307/2843960. http://www.jstor.org/pss/2843960. 
  15. ^ Susan R. Martin (1995). "The State of Our Knowledge About Ancient Copper Mining in Michigan". The Michigan Archaeologist 41 (2-3): 119. http://www.ramtops.co.uk/copper.html. 
  16. ^ Jacobson, D. M. (2000). Corinthian Bronze and the Gold of the Alchemists. 33. p. 60. http://www.goldbulletin.org/downloads/JACOB_2_33.PDF. 
  17. ^ "Copper History". http://www.copperinfo.com/aboutcopper/history.html. Retrieved 2008-09-04. 
  18. ^ Stelter, M.; Bombach, H. (2004). "Process Optimization in Copper Electrorefining". Advanced Engineering Materials 6: 558. doi:10.1002/adem.200400403. 
  19. ^ "Outokumpu Flash Smelting". Outokumpu. p. 2. http://www.outokumpu.com/files/Technology/Documents/Newlogobrochures/FlashSmelting.pdf. 
  20. ^ Chambers, William; Chambers, Robert (1884). Chambers's Information for the People. L (5th ed.). W. & R. Chambers. p. 312. ISBN 0665469128. http://books.google.com/books?id=eGIMAAAAYAAJ. .
  21. ^ M. Razeghi (2006). Fundamentals of Solid State Engineering. Birkhäuser. pp. 154–156. ISBN 0387281525. 
  22. ^ a b c C. R. Hammond (2004). The Elements, in Handbook of Chemistry and Physics 81st edition. CRC press. ISBN 0849304857. 
  23. ^ P. C. Rickwood (1981). "The largest crystals". American Mineralogist 66: 885. http://www.minsocam.org/ammin/AM66/AM66_885.pdf. 
  24. ^ Joseph R. Davis (2001). Copper and Copper Alloys. ASM International. pp. 3–6,266. ISBN 0871707268. 
  25. ^ William F. Smith, Javad Hashemi (2003). Foundations of Materials Science and Engineering. McGraw-Hill Professional. p. 223. ISBN 0072921943. 
  26. ^ J. Seymour (1972). Physical Electronics. Pitman Publishing. pp. 25–27,53–54. ISBN 0273411764. 
  27. ^ P. J. Kuhn (1983). "Doorknobs: A Source of Nosocomial Infection?". http://members.vol.at/schmiede/MsgverSSt.html. Retrieved 2007-08-15. 
  28. ^ Noyce JO, Michels H, Keevil CW (2006). "Potential use of copper surfaces to reduce survival of epidemic meticillin-resistant Staphylococcus aureus in the healthcare environment". J. Hosp. Infect. 63 (3): 289. doi:10.1016/j.jhin.2005.12.008. PMID 16650507. 
  29. ^ Noyce JO, Michels H, Keevil CW (2006). "Use of copper cast alloys to control Escherichia coli O157 cross-contamination during food processing". Appl. Environ. Microbiol. 72 (6): 4239. doi:10.1128/AEM.02532-05. PMID 16751537. 
  30. ^ Mehtar S, Wiid I, Todorov SD (2008). "The antimicrobial activity of copper and copper alloys against nosocomial pathogens and Mycobacterium tuberculosis isolated from healthcare facilities in the Western Cape: an in-vitro study". J. Hosp. Infect. 68 (1): 45. doi:10.1016/j.jhin.2007.10.009. PMID 18069086. 
  31. ^ Gant VA, Wren MW, Rollins MS, Jeanes A, Hickok SS, Hall TJ (2007). "Three novel highly charged copper-based biocides: safety and efficacy against healthcare-associated organisms". J. Antimicrob. Chemother. 60 (2): 294. doi:10.1093/jac/dkm201. PMID 17567632. 
  32. ^ Noyce JO, Michels H, Keevil CW (2007). "Inactivation of influenza A virus on copper versus stainless steel surfaces". Appl. Environ. Microbiol. 73 (8): 2748. doi:10.1128/AEM.01139-06. PMID 17259354. 
  33. ^ "EPA registers copper-containing alloy products". US Environmental Protection Agency. http://www.epa.gov/pesticides/factsheets/copper-alloy-products.htm. Retrieved 2009-06-06. 
  34. ^ "Center for Decease Control and Prevention". http://www.cdc.gov/ncidod/eid/vol7no2/pdfs/peterson.pdf. Retrieved 2009-06-06. 
  35. ^ a b c Audi, G (2003). "Nubase2003 Evaluation of Nuclear and Decay Properties". Nuclear Physics A (Atomic Mass Data Center) 729: 3. doi:10.1016/j.nuclphysa.2003.11.001. 
  36. ^ Brown, Lester (2006). Plan B 2.0: Rescuing a Planet Under Stress and a Civilization in Trouble. New York: W.W. Norton. p. 109. ISBN 0393328317. 
  37. ^ Andrew Leonard (2006-03-02). "Peak copper?". Salon - How the World Works. http://www.salon.com/tech/htww/2006/03/02/peak_copper/index.html. Retrieved 2008-03-23. 
  38. ^ "Copper Trends: Live Metal Spot Prices". http://metalspotprice.com/copper-trends/. 
  39. ^ R. Ackerman (02-04-2009). "A Bottom In Sight For Copper". Forbes. http://www.forbes.com/2009/02/04/copper-frontera-southern-markets-equity-0205_china_51.html. 
  40. ^ "Copper". American Elements. 2008. http://www.americanelements.com/cu.html. Retrieved 2008-07-12. 
  41. ^ Berg, Jan. "Why did we paint the library's roof?". http://www.deforest.lib.wi.us/FAQS.htm. Retrieved 2007-09-20. 
  42. ^ Physics 1, Jacaranda Science. 3rd Ed.. 2009. 
  43. ^ a b c "Coinage". Copper and copper alloys. ISBN 9780871707260. http://books.google.com/books?id=sxkPJzmkhnUC&pg=PA167. 
  44. ^ a b "Coin Specifications". United States Mint. 2008. http://www.usmint.gov/about_the_mint/index.cfm?flash=yes&action=coin_specifications. Retrieved 2008-07-12. 
  45. ^ "FAQ Royal Mint". The Royal Mint. 2008-07-01. http://www.royalmint.com/home/frequentlyaskedquestions.aspx. Retrieved 2010-03-11. 
  46. ^ "Circulating Coin Designs". Royal Australian Mint. http://www.ramint.gov.au/designs/products/circulating.cfm. Retrieved 2010-03-11. 
  47. ^ "Questions and answers". Change for the Better. Reserve Bank of New Zealand. http://www.newcoins.govt.nz/1570749.html. Retrieved 2008-07-13. 
  48. ^ "Antimicrobial Products that Shield Against Bacteria and Fungi". Cupron, Inc.. 2008. http://www.cupron.com/. Retrieved 2008-07-13. 
  49. ^ "Gold Jewellery Alloys". World Gold Council. http://www.utilisegold.com/jewellery_technology/colours/colour_alloys/. Retrieved 2009-06-06. 
  50. ^ a b "Amount of copper in the normal human body, and other nutritional copper facts". http://www.copper.org/consumers/health/papers/cu_health_uk/cu_health_uk.html. Retrieved April 3, 2009. 
  51. ^ "Fun Facts". Horseshoe Crab. University of Delaware. http://www.ocean.udel.edu/horseshoecrab/funFacts.html. Retrieved 2008-07-13. 
  52. ^ Copper. In: Recommended Dietary Allowances. Washington, D.C.: National Research Council, Food Nutrition Board, NRC/NAS. 1980. pp. 151–154. 
  53. ^ "Merck Manulas -- Online Medical Library: Copper". Merck. November 2005. http://www.merck.com/mmpe/sec01/ch005/ch005c.html?qt=copper%20and%20milk&alt=sh. Retrieved 2008-07-19. 
  54. ^ "Pesticide Information Profile for Copper Sulfate". Cornell University. http://pmep.cce.cornell.edu/profiles/extoxnet/carbaryl-dicrotophos/copper-sulfate-ext.html. Retrieved 2008-07-10. 
  55. ^ "International Copper Association". http://www.copperinfo.com/environment/recycling.html. 
  56. ^ "Overview of Recycled Copper" Copper.org.

Further reading

External links


1911 encyclopedia

Up to date as of January 14, 2010

From LoveToKnow 1911

COPPER (symbol Cu, atomic weight 63.1, H =1, or 63.6, O =16), a metal which has been known to and used by the human race from the most remote periods. Its alloy with tin (bronze) was the first metallic compound in common use by mankind, and so extensive and characteristic was its employment in prehistoric times that the epoch is known as the Bronze Age. By the Greeks and Romans both the metal and its alloys were indifferently known as xaXxos and aes. As, according to Pliny, the Roman supply was chiefly drawn from Cyprus, it came to be termed aes cyprium, which was gradually shortened to cyprium, and corrupted into cuprum, whence comes the English word copper, the French cuivre, and the German Kupfer. Copper is a brilliant metal of a peculiar red colour which assumes a pinkish or yellowish tinge on a freshly fractured surface of the pure metal, and is purplish when the metal contains cuprous oxide. Its specific gravity varies between 8.91 and 8.95, according to the treatment to which it may have been subjected; J. F. W. Hampe gives 8.945 (V) for perfectly pure and compact copper. Ordinary commercial copper is somewhat porous and has a specific gravity ranging from 8.2 to 8.5. It takes a brilliant polish, is in a high degree malleable and ductile, and in tenacity it only falls short of iron, exceeding in that quality both silver and gold. By different authorities its melting-point is stated at from 1000° to 1200° C.; C. T. Heycock and F. H. Neville give 1080° 5; P. Dejean gives 1085° as the freezingpoint. The molten metal is sea-green in colour, and at higher temperatures (in the electric arc) it vaporizes and burns with a green flame. G. W. A. Kahlbaum succeeded in subliming the metal in a vacuum, and H. Moissan (Compt. rend., 1905, 141, p. 853) distilled it in the electric furnace. Molten copper absorbs carbon monoxide, hydrogen and sulphur dioxide; it also appears to decompose hydrocarbons (methane, ethane), absorbing the hydrogen and the carbon separating out. These occluded gases are all liberated when the copper cools, and so give rise to porous castings, unless special precautions are taken. The gases are also expelled from the molten metal by lead, carbon dioxide, or water vapour. Its specific heat is o 0899 at 0° C. and 0.0942 at 10o; the coefficient of linear expansion per 1° C. is o o01869. In electric conductivity it stands next to silver; the conducting power of silver being equal to loo, that of perfectly pure copper is given by A. Matthiessen as 96.4 at 13° C.

Copper is not affected by exposure in dry air, but in a moist atmosphere, containing carbonic acid, it becomes coated with a green basic carbonate. When heated or rubbed it emits a peculiar disagreeable odour. Sulphuric and hydrochloric acids have little or no action upon it at ordinary temperatures, even when in a fine state of division; but on heating, copper sulphate and sulphur dioxide are formed in the first case, and cuprous chloride and hydrogen in the second. Concentrated nitric acid has also very little action, but with the dilute acid a vigorous action ensues. The first products of this reaction are copper nitrate and nitric oxide, but, as the concentration of the copper nitrate increases, nitrous oxide and, eventually, free nitrogen are liberated.

Many colloidal solutions of copper have been obtained. A reddish-brown solution is obtained from solutions of copper chloride, stannous chloride and an alkaline tartrate (Lottermoser, Anorganische Colloide, 1901).

Table of contents

Occurrence

Copper is widely distributed in nature, occurring in most soils, ferruginous mineral waters, and ores. It has been discovered in seaweed; in the blood of certain Cephalopoda and Ascidia as haemocyanin, a substance resembling the ferruginous haemoglobin, and of a species of Limulus; in straw, hay, eggs, cheese, meat, and other food-stuffs; in the liver and kidneys, and, in traces, in the blood of man and other animals (as an entirely adventitious constituent, however); it has also been shown by A. H. Church to exist to the extent of 5.9% in turacin, the colouring-matter of the wing-feathers of the Turaco.

Native copper, sometimes termed by miners malleable or virgin copper, occurs as a mineral having all the properties of the smelted metal. It crystallizes in the cubic system, but the crystals are often flattened, elongated, rounded or otherwise distorted. Twins are common. Usually the metal is arborescent, dendritic, filiform, moss-like or laminar. Native copper is found in most copper-mines, usually in the upper workings, where the deposit has been exposed to atmospheric influences. The metal seems to have been reduced from solutions of its salts, and deposits may be formed around mine-timber or on iron objects. It often fills cracks and fissures in the rock. It is not infrequently found in serpentine, and in basic eruptive rocks, where it occurs as veins and in amygdales. The largest known deposits are those in the Lake Superior region, near Keweenaw Point, Michigan, where masses upwards of 400 tons in weight have been discovered. The metal was formerly worked by the Indians for implements and ornaments. It occurs in a series of amygdaloidal dolerites or diabases, and in the associated sandstones and conglomerates. Native silver occurs with the copper, in some cases embedded in it, like crystals in a porphyry. The copper is also accompanied by epidote, calcite, prehnite, analcite and other zeolitic minerals. Pseudomorphs after calcite are known; and it is notable that native copper occurs pseudomorphous after aragonite at Corocoro, in Bolivia, where the copper is disseminated through sandstone.

Ores

The principal ores of copper are the oxides cuprite and melaconite, the carbonates malachite and chessylite, the basic chloride atacamite, the silicate chrysocolla, the sulphides chalcocite, chalcopyrite, erubescite and tetrahedrite. Cuprite occurs in most cupriferous mines, but never by itself in large quantities. Melaconite was formerly largely worked in the Lake Superior region, and is abundant in some of the mines of Tennessee and the Mississippi valley. Malachite is a valuable ore containing about 56% of the metal; it is obtained in very large quantities from South Australia, Siberia and other localities. Frequently intermixed with the green malachite is the blue carbonate chessylite or azurite, an ore containing when pure 55.16% of the metal. Atacamite occurs chiefly in Chile and Peru. Chrysocolla contains in the pure state 30% of the metal; it is an abundant ore in Chile, Wisconsin and Missouri. The sulphur compounds of copper are, however, the most valuable from the economic point of view. Chalcocite, redruthite, copper-glance or vitreous copper (Cu 2 S) contains about 80% of copper. Copper pyrites, or chalcopyrite, contains 34.6% of copper when pure; but many of the ores, such as those worked specially by wet processes on account of the presence of a large proportion of iron sulphide, contain less than 5% of copper. Cornish ores are almost entirely pyritic; and indeed it is from such ores that by far the largest proportion of copper is extracted throughout the world. In Cornwall copper lodes usually run east and west. They occur both in the " killas " or clay-slate, and in the " growan " or granite. Erubescite, bornite, or horseflesh ore is much richer in copper than the ordinary pyrites, and contains 56 or 57% of copper. Tetrahedrite, fahlerz, or grey copper, contains from 30 to 48% of copper, with arsenic, antimony, iron and sometimes zinc, silver or mercury. Other copper minerals are percylite (PbCuC1 2 (OH) 2), boleite (3PbCuC1 2 (OH) 2j AgCI), stromeyerite {(Cu, Ag) 2 S}, cubanite (CuS, Fe 2 S 3), stannite (Cu 2 S, FeSnS3), tennantite (3Cu 2 S, As2S3), emplectite (Cu 2 S, Bi 2 S 3), wolfsbergite (Cu 2 S, Sb2S3), famatinite (3Cu 2 S, Sb 2 S 5) and enargite (3Cu2S, As2S5). For other minerals, see Compounds of Copper below.

Metallurgy

Copper is obtained from its ores by three principal methods, which may be denominated - (r) the pyro-metallurgical or dry method, (2) the hydro-metallurgical or wet method, and (3) the electro-metallurgical method.

The methods of working vary according to the nature of the ores treated and local circumstances. The dry method, or ordinary smelting, cannot be profitably practised with ores containing less than 4% of copper, for which and for still poorer ores the wet process is preferred.

Copper Smelting

We shall first give the general principles which underlie the methods for the dry extraction of copper, and then proceed to a more detailed discussion of the plant used. Since all sulphuretted copper ores (and these are of the most economic importance) are invariably contaminated with arsenic and antimony, it is necessary to eliminate these impurities, as far as possible, at a very early stage. This is effected by calcination or roasting. The roasted ore is then smelted to a mixture of copper and iron sulphides, known as copper " matte " or " coarse-metal," which contains little or no arsenic, antimony or silica. The coarse-metal is now smelted, with coke and siliceous fluxes (in order to slag off the iron), and the product, consisting of an impure copper sulphide, is variously known as " blue-metal," when more or less iron is still present, " pimplemetal," when free copper and more or less copper oxide is present, or " fine " or " white-metal," which is a fairly pure copper sulphide, containing about 75% of the metal. This product is re-smelted to form " coarse-copper," containing about 95% of the metal, which is then refined. Roasted ores may be smelted in reverberatory furnaces (English process), or in blast-furnaces (German or Swedish process). The matte is treated either in reverberatory furnaces (English process), in blast furnaces (German process), or in converters (Bessemer process). The " American process " or " Pyritic smelting " consists in the direct smelting of raw ores to matte in blast furnaces. The plant in which the operations are conducted varies in different countries. But though this or that process takes its name from the country in which it has been mainly developed, this does not mean that only that process is there followed.

The " English process " is made up of the following operations: (i) calcination; (2) smelting in reverberatory furnaces to form the matte; (3) roasting the matte; and (4) subsequent smelting in reverberatory furnaces to fineor white-metal; (5) treating the fine-metal in reverberatory furnaces to coarseor blistercopper, either with or without previous calcination; (6) refining of the coarse-copper. A shorter process (the so-called " direct process ") converts the fine-metal into refined copper directly. The " Welsh process " closely resembles the English method; the main difference consists in the enrichment of the matte by smelting with the rich copper-bearing slags obtained in subsequent operations. The " German or Swedish process " is characterized by the introduction of blast-furnaces. It is made up of the following operations: (z) calcination, (2) smelting in blast-furnaces to form the matte, (3) roasting the matte, (4) smelting in blast-furnaces with coke and fluxes to " black- " or " coarse-metal," (5) refining the coarse-metal. The " AngloGerman Process " is a combination of the two preceding, and consists in smelting the calcined ores in shaft furnaces, concentrating the matte in reverberatory furnaces, and smelting to coarse-metal in either.

The impurities contained in coarse-copper are mainly iron, lead, zinc, cobalt, nickel, bismuth, arsenic, antimony, sulphur, selenium and tellurium. These can be eliminated by an oxidizing fusion, and slagging or volatilizing the products resulting from this operation, or by electrolysis (see below). In the process of oxidation, a certain amount of cuprous oxide is always formed, which melts in with the copper and diminishes its softness and tenacity. It is, therefore, necessary to reconvert the oxide into the metal. This is effected by stirring the molten metal with a pole of green wood (" poling "); the products which arise from the combustion and distillation of the wood reduce the oxide to metal, and if the operation be properly conducted " tough-pitch " copper, soft, malleable and exhibiting a lustrous silky fracture, is obtained. The surface of the molten metal is protected from oxidation by a layer of anthracite or charcoal. " Bean-shot " copper is obtained by throwing the molten metal into hot water; if cold water be used, " feathered-shot " copper is formed.

Rosette " copper is obtained as thin plates of a characteristic dark-red colour, by pouring water upon the surface of the molten metal, and removing the crust formed. " Japan " copper is purple-red in colour, and is formed by casting into ingots, weighing from six ounces to a pound, and rapidly cooling by immersion in water. The colour of these two varieties is due to a layer of oxide. " Tile " copper is an impure copper, and is obtained by refining the first tappings. " Best-selected " copper is a purer variety.

Calcination or Roasting and Calcining Furnaces

The roasting should be conducted so as to eliminate as much of the arsenic and antimony as possible, and to leave just enough sulphur as is necessary to combine with all the copper present when the calcined ore is smelted. The process is effected either in heaps, stalls, shaft furnaces, reverberatory furnaces or muffle furnaces. Stall and heap roasting require considerable time, and can only be economically employed when the loss of the sulphur is of no consequence; they also occupy much space, but they have the advantage of requiring little fuel and handling. Shaft furnaces are in use for ores rich in sulphur, and where it is desirable to convert the waste gases into sulphuric acid. Reverberatory roasting does not admit of the utilization of the waste gases, and requires fine ores and much labour and fuel; it has, however, the advantage of being rapid. Muffle furnaces are suitable for fine ores which are liable to decrepitate or sinter. They involve high cost in fuel and labour, but permit the utilization of the waste gases.

Reverberatory furnaces of three types are employed in calcining copper ores: (I) fixed furnaces, with either hand or mechanical rabbling; (2) furnaces with movable beds; (3) furnaces with rotating working chambers. Hand rabbling in fixed furnaces has been largely superseded by mechanical rabbling. Of mechanically rabbling furnaces we may mention the O'Harra modified by Allen-Brown, the Hixon, the KellerGaylord-Cole, the Ropp, the Spence, the Wethey, the Parkes, Pearce's " Turret " and Brown's " Horseshoe " furnaces. Blake's and Brunton's furnaces are reverberatory furnaces with a movable bed. Furnaces with rotating working chambers admit of continuous working; the fuel and labour costs are both low.

In the White-Howell revolving furnace with lifters - a modification of the Oxland - the ore is fed and discharged in a continuous stream. The Bruckner cylinder resembles the Elliot and Russell black ash furnace; its cylinder tapers slightly towards each end, and is generally 18 ft. long by 8 ft. 6 in. in its greatest diameter. Its charge of from 8 to 12 tons of ore or concentrates is slowly agitated at a rate of three revolutions a minute, and in from 24 to 36 hours it is reduced from say 40 or 35% 'to' 7% of sulphur. The ore is under better control than is possible with the continuous feed and discharge, and when sufficiently roasted can be passed red-hot to the reverberatory furnace. These advantages compensate for the wear and tear and the cost of moving the heavy dead-weight.

Shaft calcining furnaces are available for fine ores and permit the recovery of the sulphur. They are square, oblong or circular in section, and the interior is fitted with horizontal or inclined plates or prisms, which regulate the fall of the ore. In the Gerstenhoffer and Hasenclever-Helbig furnaces the fall is retarded by prisms and inclined plates. In other furnaces the ore rests on a series of horizontal plates, and either remains on the same plate throughout the operation (0111vier and Perret furnace), or is passed from plate to plate by hand (Maletra), or by mechanical means (Spence and M`Dougall).

The M`Dougall furnace is turret-shaped, and consists of a series of circular hearths, on which the ore is agitated by rakes attached to revolving arms and made to fall from hearth to hearth. It has been modified by Herreshoff, who uses a large hollow revolving central shaft cooled by a current of air. The shaft is provided with sockets, into which movable arms with their rakes are readily dropped. The Peter Spence type of calcining furnace has been followed in a large number of inventions. In some the rakes are attached to rigid frames, with a reciprocating motion, in others to cross-bars moved by revolving chains. Some of these furnaces are straight, others circular. Some have only one hearth, others three. This and the previous type of furnace, owing to their large capacity, are at present in greatest favour. The M`Dougall-Herreshoff, working on ores of over 30% of sulphur, requires no fuel; but in furnaces of the reverberatory type fuel must be used, as an excess of air enters through the slotted sides and the hinged doors which open and shut frequently to permit of the passage of the rakes. The consumption of fuel, however, does not exceed i of coal to io of ore. The quantity of ore which these large furnaces, with a hearth area as great as 2000 ft. and over, will roast varies from 40 to 60 tons a day. Shaft calcining furnaces like the Gerstenhoffer, Hasenclever, and others designed for burning pyrites fines have not found favour in modern copper works.

The Fusion of Ores in Reverberatory and Cupola Furnaces

After the ore has been partially calcined, it is smelted to extract its earthy matter and to concentrate the copper with part of its iron and sulphur into a matte. In reverberatory furnaces it is smelted by fuel in a fireplace, separate from the ore, and in cupolas the fuel, generally coke, is in direct contact with the ore. When Swansea was the centre of the copper-smelting industry in Europe, many varieties of ores from different mines were smelted in the same furnaces, and the Welsh reverberatory furnaces were used. To-day more than eight-tenths of the copper ores of the world are reduced to impure copper bars or to fine copper at the mines; and where the character of the ore permits, the cupola furnace is found more economical in both fuel and labour than the reverberatory.

The Welsh method finds adherents only in Wales and Chile. In America the usual method is to roast ores or concentrates so that the matte yielded by either the reverberatory or cupola furnace will run from 45 to 50% in copper, and then to transfer to the Bessemer converter, which blows it up to 99%. In Butte, Montana, reverberatories have in the past been preferred to cupola furnaces, as the charge has consisted mainly of fine roasted concentrates; but the cupola is gaining ground there. At the Boston and Great Falls (Montana) works tilting reverberatories, modelled after open hearth steel furnaces, were first erected; but they were found to possess objectionable features. Now both these and the egg-shaped reverberatories are being abandoned for furnaces as long as 43 ft. 6 in. from bridge to bridge and of a width of 15 ft. 9 in. heated by gas, with regenerative checker work at each end, and fed with ore or concentrates, red-hot from the calciners, through a line of hoppers suspended above the roof. Furnaces of this size smelt 200 tons of charge a day. But even when the old type of reverberatory is preferred, as at the Argo works, at Denver, where rich goldand silver-bearing copper matte is made, the growth of the furnace in size has been steady. Richard Pearce's reverberatories in 1878 had an area of hearth of 15 ft. by 9 ft. 8 in., and smelted 12 tons of cold charge daily, with a consumption of 1 ton of coal to 2.4 tons of ore. In 1900 the furnaces were 35 ft. by 16 ft., and smelt 50 tons daily of hot ore, with the consumption of 1 ton of coal to 3.7 tons of ore.

The home of cupola smelting was Germany, where it has never ceased to make steady progress. In Mansfeld brick cupola furnaces are without a rival in size, equipment and performance. They are round stacks, designed on the model of iron blast furnaces, 29 ft. high, fed mechanically, and provided with stoves to heat the blast by the furnace gases. The low percentage of sulphur in the roasted ore is little more than enough to produce a matte of 40 to 45%, and therefore the escaping gases are better fitted than those of most copper cupola furnaces for burning in a stove. But as the slag carries on an average 46% of silica, it is only through the utmost skill that it can be made to run as low on an average as 0.3% in copper oxide. As the matte contains on an average o. 2% of silver, it is still treated by the Ziervogel wet method of extraction, the management dreading the loss which might occur in the Bessemer process of concentration, applied as preliminary to electrolytic separation. Blast furnaces of large size, built of brick, have been constructed for treating the richest and more silicious ores of Rio Tinto, and the Rio Tinto Company has introduced converters at the mine. This method of extraction contrasts favourably in time with the leaching process, which is so slow that over io,000,000 tons of ore are always under treatment on the immense leaching floors of the company's works in Spain. In the United States the cupola has undergone a radical modification in being built of water-jacketed sections. The first water-jacketed cupola which came into general use was a circular inverted cone, with a slight taper, of 36 inches diameter at the tuyeres, and composed of an outer and an inner metal shell, between which water circulated. As greater size has been demanded, oval and rectangular furnaces - as large as 180 in. by 56 in. at the tuyereshave been built in sections of cast or sheet iron or steel. A single section can be removed and replaced without entirely emptying the stack, as a shell of congealed slag always coats the inner surface of the jacket. The largest furnaces are those of the Boston & Montana Company at Great Falls, Montana, which have put through soo tons of charge daily, pouring their melted slag and matte into large wells of io ft. in diameter. A combined brickand water-cooled furnace has been adopted by the Iron Mountain Company at Keswick, Cal., for matte concentration. In it the cooling is effected by water pipes, interposed horizontally between the layers of bricks. The Mt. Lyell smelting works in Tasmania, which are of special interest, will be referred to later. (See Pyritic Smelting below.) Concentrating Matte to Copper in the Bessemer Converter. - As soon as the pneumatic method of decarburizing pig iron was accepted as practicable, experiments were made with a view to Bessemerizing copper ores and mattes. One of the earliest and most exhaustive series of experiments was made on Rio Tinto ores at the John Brown works by John Hollway, with the aim of both smelting the ore and concentrating the matte in the same furnace, by the heat evolved through the oxidation of their sulphur and iron. Experiments along the same lines were made by Francis Bawden at Rio Tinto and Claude Vautin in Australia. The difficulty of effecting this double object in one operation was so great that in subsequent experiments the aim was merely to concentrate the matte to metallic copper in converters of the Bessemer type. The concentration was effected without any embarrassment till metallic copper commenced to separate and chill in the bottom tuyeres. To meet this obstacle P. Manhes proposed elevated side tuyeres, which could be kept clear by punching through gates in a wind box. His invention was adopted by the Vivians, at the Eguilles works near Sargues, Vaucluse, France, and at Leghorn in Italy. But the greatest expansion of this method has been in the United States, where more than 400,000,000 lb. of copper are annually made in Bessemer converters. Vessels of several designs are used - some modelled exactly after steel converters, other barrelshaped, but all with side tuyeres elevated about io in. above the level of the bottom lining. Practice, however, in treating copper matte differs essentially from the treatment of pig iron, inasmuch as from 20 to 30% of iron must be eliminated as slag and an equivalent quantity of silica must be supplied. The only practical mode of doing this, as yet devised, is by lining the converter with a silicious mixture. This is so rapidly consumed that the converters must be cooled and partially relined after 3 to 6 charges, dependent on the iron contents of the matte. When available, a silicious rock containing copper or the precious metals is of course preferred to barren lining. The material for lining, and the frequent replacement thereof, constitute the principal expense of the method. The other items of cost are labour, the quantity of which depends on the mechanical appliances provided for handling the converter shells and inserting the lining; and the blast, which in barrel-shaped converters is low and in vertical converters is high, and which varies therefore from 3 to is lb to the square inch. The quantity of air consumed in a converter which will blow up about 35 tons of matte per day is about 3000 cub. ft. per minute. The operation of raising a charge of so % matte to copper usually consists of two blows. The first blow occupies about 25 minutes, and oxidizes all but a small quantity of the iron and some of the sulphur, raising the product to white metal. The slag is then poured and skimmed, the blast turned on and converter retilted. During the second blow the sulphur is rapidly oxidized, and the charge reduced to metal of 99% in from 30 to 40 minutes. Little or no slag results from the second blow. That from the first blow contains between 1% and 2% of copper, and is usually poured from ladles operated by an electric crane into a reverberatory, or into the settling well of the cupola. The matte also, in all economically planned works, is conveyed, still molten, by electric cranes from the furnace to the converters. When lead or zinc is not present in notable quantity, the loss of the precious metals by volatilization is slight, but more than 5% of these metals in the matte is prohibitive. Under favourable conditions in the larger works of the United States the cost of converting a 50% matte to metallic copper is generally understood to be only about 1 o to iw of a cent per lb. of refined copper.

Pyritic Smelting

The heat generated by the oxidation of iron and sulphur has always been used to maintain combustion in the kilns or stalls for roasting pyrites. Pyritic smelting is a development of the Russian engineer Semenikov's treatment (proposed in 1866) of copper matte in a Bessemer converter. Since John Hollway's and other early experiments of Lawrence Austin and Robert Sticht, no serious attempts have been made to utilize the heat escaping from a converting vessel in smelting ore and matte either in the same apparatus or in a separate furnace. But considerable progress has been made in smelting highly sulphuretted ores by the heat of their own oxidizable constituents. At Tilt Cove, Newfoundland, the Cape Copper Company smelted copper ore, with just the proper proportion of sulphur, iron and silica, successfully without any fuel, when once the initial charge had been fused with coke. The furnaces used were of ordinary design and built of brick. Lump ore alone was fed, and the resulting matte showed a concentration of only 3 into i. When, however, a hot blast is used on highly sulphuretted copper ores, a concentration of 8 of ore into i of matte is obtained, with a consumption of less than one-third the fuel which would be consumed in smelting the charge had the ore been previously calcined. A great impetus to pyritic smelting was given by the investigations of W. L. Austin, of Denver, Colorado, and both at Leadville and Silverton raw ores are successfully smelted with as low a fuel consumption as 3 of coke to zoo of charge.

Two types of pyritic smelting may be distinguished: one, in which the operation is solely sustained by the combustion of the sulphur in the ores, without the assistance of fuel or a hot blast; the other in which the operation is accelerated by fuel, or a hot blast, or both. The largest establishment in which advantage is taken of the self-contained fuel is at the smelting works of the Mt. Lyell Company, Tasmania. There the blast is raised from 600° to 700° F. in stoves heated by extraneous fuel, and the raw ore smelted with only 3% of coke. The ore is a compact iron pyrites containing copper 2.5%, silver 3.83 oz., gold 0.139 oz. It is smelted raw with hot blast in cupola furnaces, the largest being 2 10 in. by 40 in. The resulting matte runs 25%. This is reconcentrated raw in hot-blast cupolas to 55%, and blown directly into copper in converters. Thus these ores, as heavily charged with sulphur as those of the Rio Tinto, are speedily reduced by three operations and without roasting, with a saving of 97.6% of the copper, 93.2% of the silver and 93.6% of the gold.

Pyritic smelting has met with a varying economic success. According to Herbert Lang, its most prominent chance of success is in localities where fuel is dear, and the ores contain precious metals and sufficient sulphides and arsenides to render profitable dressing unnecessary.

The Nicholls and James Process

Nicholls and James have applied, very ingeniously, well-known reactions to the refining of copper, raised to the grade of white metal. This process is practised by the Cape Copper and Elliot Metal Company. A portion of the white metal is calcined to such a degree of oxidation that when fused with the unroasted portion, the reaction between the oxygen in the roasted matte and the sulphur in the raw VII. 4 a material liberates the metallic copper. The metal is so pure that it can be refined by a continuous operation in the same furnace.

Wet Methods for Copper Extraction

Wet methods are only employed for low grade ores (under favourable circumstances ore containing from 4 to i % of copper has admitted of economic treatment), and for gold and silver bearing metallurgical products.

The fundamental principle consists in getting the ore into a solution, from which the metal can be precipitated. The ores of any economic importance contain the copper either as oxide, carbonate, sulphate or sulphide. These compounds are got into solution either as chlorides or sulphates, and from either of these salts the metal can be readily obtained. Ores in which the copper is present as oxide or carbonate are soluble in sulphuric or hydrochloric acids, ferrous chloride, ferric sulphate, ammoniacal compounds and sodium thiosulphate. Of these solvents, only the first three are of economic importance. The choice of sulphuric or hydrochloric acid depends mainly upon the cost, both acting with about the same rapidity; thus if a Leblanc soda factory is near at hand, then hydrochloric acid would most certainly be employed. Ferrous chloride is not much used; the Douglas-Hunt process uses a mixture of salt and ferrous sulphate which involves the formation of ferrous chloride, and the new Douglas-Hunt process employs sulphuric acid in which ferrous chloride is added after leaching.

Sulphuric acid may be applied as such on the ores placed in lead, brick, or stone chambers; or as a mixture of sulphur dioxide, nitrous fumes (generated from Chile saltpetre and sulphuric acid), and steam, which permeates the ore resting on the false bottom of a brick chamber. When most of the copper has been converted into the sulphate, the ore is lixiviated. Hydrochloric acid is applied in the same way as sulphuric acid; it has certain advantages of which the most important is that it does not admit the formation of basic salts; its chief disadvantage is that it dissolves the oxides of iron, and accordingly must not be used for highly ferriferous ores. The solubility of copper carbonate in ferrous chloride solution was pointed out by Max Schaffner in 1862, and the subsequent recognition of the solubility of the oxide in the same solvent by James Douglas and Sterry Hunt resulted in the " Douglas-Hunt " process for the wet extraction of copper. Ferrous chloride decomposes the copper oxide and carbonate with the formation of cuprous and cupric chlorides (which remain in solution), and the precipitation of ferrous oxide, carbon dioxide being simultaneously liberated from the carbonate. In the original form of the Douglas-Hunt process, ferrous chloride was formed by the interaction of sodium chloride (common salt) with ferrous sulphate (green vitriol), the sodium sulphate formed at the same time being removed by crystallization. The ground ore was stirred with this solution at 7 C. in wooden tubs until all the copper was dissolved. The liquor was then filtered from the iron oxides, and the filtrate treated with scrap iron, which precipitated the copper and reformed ferrous chloride, which could be used in the first stage of the process. The advantage of this method rests chiefly on the small amount of iron required; but its disadvantages are that any silver present in the ores goes into solution, the formation of basic salts, and the difficulty of filtering from the iron oxides. A modification of the method was designed to remedy these defects. The ore is first treated with dilute sulphuric acid, and then ferrous or calcium chloride added, thus forming copper chlorides. If calcium chloride be used the precipitated calcium sulphate must be removed by filtration. Sulphur dioxide is then blown in, and the precipitate is treated with iron, which produces metallic copper, or milk of lime, which produces cuprous oxide. Hot air is blown into the filtrate, which contains ferrous or calcium chlorides, to expel the excess of sulphur dioxide, and the liquid can then be used again. In this process (" new Douglas-Hunt ") there are no iron oxides formed, the silver is not dissolved, and the quantity of iron necessary is relatively small, since all the copper is in the cuprous condition. It is not used in the treatment of ores, but finds application in the case of calcined argentiferous lead and copper mattes.

The precipitation of the copper from the solution, in which it is present as sulphate, or as cuprous and cupric chlorides, is generally effected by metallic iron. Either wrought, pig, iron sponge or iron bars are employed, and it is important to notice that the form in which the copper is precipitated, and also the time taken for the separation, largely depend upon the condition in which the iron is applied. Spongy iron acts most rapidly, and after this follow iron turnings and then sheet clippings. Other precipitants such as sulphuretted hydrogen and solutions of sulphides, which precipitate the copper as sulphides, and milk of lime, which gives copper oxides, have not met with commercial success. When using iron as the precipitant, it is desirable that the solution should be as neutral as possible, and the quantity of ferric salts present should be reduced to a minimum; otherwise, a certain amount of iron would be used up by the free acid and in reducing the ferric salts. Ores in which the copper is present as sulphate are directly lixiviated and treated with iron. Mine waters generally contain the copper in this form, and it is extracted by conducting the waters along troughs fitted with iron gratings.

The wet extraction of metallic copper from ores in which it occurs as the sulphide, may be considered to involve the following operations: (r) conversion of the copper into a soluble form, (2) dissolving out the soluble copper salt, (3) the precipitation of the copper. Copper sulphide may be converted either into the sulphate, which is soluble in water; the oxide, soluble in sulphuric or hydrochloric acid; cupric chloride, soluble in water; or cuprous chloride, which is soluble in solutions of metallic chlorides.

The conversion into sulphate is generally effected by the oxidizing processes of weathering, calcination, heating with iron nitrate or ferric sulphate. It may also be accomplished by calcination with ferrous sulphate, or other easily decomposable sulphates, such as aluminium sulphate. Weathering is a very slow, and, therefore, an expensive process; moreover, the entire conversion is only accomplished after a number of years. Calcination is only advisable for ores which contain relatively much iron pyrites and little copper pyrites. Also, however slowly the calcination may be conducted, there is always more or less copper sulphide left unchanged, and some copper oxide formed. Calcination with ferrous sulphate converts all the copper sulphide into sulphate. Heap roasting has been successfully employed at Agordo, in the Venetian Alps, and at Majdanpek in Servia. Josef Perino's process, which consists in heating the ore with iron nitrate to 50 0 -150° C., is said to possess several advantages, but it has not been applied commercially. Ferric sulphate is only used as an auxiliary to the weathering process and in an electrolytic process.

The conversion of the sulphide into oxide is adopted where the Douglas-Hunt process is employed, or where hydrochloric or sulphuric acids are cheap. The calcination is effected in reverberatory furnaces, or in muffle furnaces, if the sulphur is to be recovered. Heap, stall or shaft furnace roasting is not very satisfactory, as it is very difficult to transform all the sulphide into oxide.

The conversion of copper sulphide into the chlorides may be accomplished by calcining with common salt, or by treating the ores with ferrous chloride and hydrochloric acid or with ferric chloride. The dry way is best; the wet way is only employed when fuel is very dear, or when it is absolutely necessary that no noxious vapours should escape into the atmosphere. The dry method consists in an oxidizing roasting of the ores, and a subsequent chloridizing roasting with either common salt or Abraumsalz in reverberatory or muffle furnaces. The bulk of the copper is thus transformed into cupric chloride, little cuprous chloride being obtained. This method had been long proposed by William Longmaid, Max Schaffner, Becchi and Haupt, but was only introduced into England by the labours of William Henderson, J. A. Phillips and others. The wet method is employed at Rio Tinto, the particular variant being known as the " Dotsch " process. This consists in stacking the broken ore in heaps and adding a mixture of sodium sulphate and ferric chloride in the proportions necessary for the entire conversion of the iron into ferric sulphate. The heaps are moistened with ferric chloride solution, and the reaction is maintained by the liquid percolating through the heap. The liquid is run off at the base of the heaps into the precipitating tanks, where the copper is thrown down by means of metallic iron. The ferrous chloride formed at the same time is converted into ferric chloride which can be used to moisten the heaps. This conversion is effected by allowing the ferrous chloride liquors slowly to descend a tower, filled with pieces of wood, coke or quartz, where it meets an ascending current of chlorine.

The sulphate, oxide or chlorides, which are obtained from the sulphuretted ores, are lixiviated and the metal precipitated fn the same manner as we have previously described.

The metal so obtained is known as " cement " copper. If it contains more than 55% of copper it is directly refined, while if it contains a lower percentage it is smelted with matte or calcined copper pyrites. The chief impurities are basic salts of iron, free iron, graphite, and sometimes silica, antimony and iron arsenates. Washing removes some of these impurities, but some copper always passes into the slimes. If much carbonaceous matter be present (and this is generally so when iron sponge is used as the precipitant) the crude product is heated to redness in the air; this burns out the carbon, and, at the same time, oxidizes a little of the copper, which must be subsequently reduced. A similar operation is conducted when arsenic is present; basic-lined reverberatory furnaces have been used for the same purpose.

Electrolytic Refining

The principles have long been known on which is based the electrolytic separation of copper from the certain elements which generally accompany it, whether these, like silver and gold, are valuable, or, like arsenic, antimony, bismuth, selenium and tellurium, are merely impurities. But it was not until the dynamo was improved as a machine for generating large quantities of electricity at a very low cost that the electrolysis of copper could be practised on a commercial scale. To-day, by reason of other uses to which electricity is applied, electrically deposited copper of high conductivity is in everincreasing demand, and commands a higher price than copper refined by fusion. This increase in value permits of copper with not over £2 or $to worth of the precious metals being profitably subjected to electrolytic treatment. Thus many million ounces of silver and a great deal of gold are recovered which formerly were lost.

The earliest serious attempt to refine copper industrially was made by G. R. Elkington, whose first patent is dated 1865. He cast crude copper, as obtained from the ore, into plates which were used as anodes, sheets of electro-deposited copper forming the cathodes. Six anodes were suspended, alternately with four cathodes, in a saturated solution of copper sulphate in a cylindrical fire-clay trough, all the anodes being connected in one parallel group, and all the cathodes in another. A hundred or more jars were coupled in series, the cathodes of one to the anodes of the next, and were so arranged that with the aid of side-pipes with leaden connexions and india-rubber joints the electrolyte could, once daily, be made to circulate through them all from the top of one jar to the bottom of the next. The current from a Wilde's dynamo was passed, apparently with a current density of 5 or 6 amperes per sq. ft., until the anodes were too crippled for further use. The cathodes, when thick enough, were either cast and rolled or sent into the market direct. Silver and other insoluble impurities collected at the bottom of the trough up to the level of the lower side-tube, and were then run off through a plug in the bottom into settling tanks, from which they were removed for metallurgical treatment. The electrolyte was used until the accumulation of iron in it was too great, but was mixed from time to time with a little water acidulated by sulphuric acid. This process is of historic interest, and in principle it is identical with that now used. The modifications introduced have been chiefly in details, in order to economize materials and labour, to ensure purity of product, and to increase the rate of deposition.

The chemistry of the process has been studied by Martin Kiliani (Bergand Hiittenmdnnische Zeitung, 1885, p. 2 49), who found that, using the (low) current-density of 1 . 8 ampere per sq. ft. of cathode, and an electrolyte containing qlb of copper sulphate and z lb of sulphuric acid per gallon, all the gold, platinum and silver present in the crude copper anode remain as metals, undissolved, in the anode slime or mud, and all the lead remains there as sulphate, formed by the action of the sulphuric acid (or S04 ions); he found also that arsenic forms arsenious oxide, which dissolves until the solution is saturated, and then remains in the slime, from which on long standing it gradually dissolves, after conversion by secondary reactions into arsenic oxide; antimony forms a basic sulphate which in part dissolves; bismuth partly dissolves and partly remains, but the dissolved portion tends slowly to separate out as a basic salt which becomes added to the slime; cuprous oxide, sulphide and selenides remain in the slime, and very slowly pass into solution by simple chemical action; tin partly dissolves (but in part separates again as basic salt) and partly remains as basic sulphate and stannic oxide; zinc, iron, nickel and cobalt pass into solution - more readily indeed than does the copper. Of the metals which dissolve, none (except bismuth, which is rarely present in any quantity) deposits at the anode so long as the solution retains its proper proportion of copper and acid, and the current-density is not too great. Neutral solutions are to be avoided because in them silver dissolves from the anode and, being more electro-negative than copper, is deposited at the cathode, while antimony and arsenic are also deposited, imparting a dark colour to the copper. Electrolytic copper should contain at least 99.92% of metallic copper, the balance consisting mainly of oxygen with not more than o oi % in all of lead, arsenic, antimony, bismuth and silver. Such a degree of purity is, however, unattainable unless the conditions of electrolysis are rigidly adhered to. It should be observed that the free acid is gradually neutralized, partly by chemical action on certain constituents of the slime, partly by local action between different metals of the anode, both of which effect solution independently of the current, and partly by the peroxidation (or aeration) of ferrous sulphate formed from the iron in the anode. At the same time there is a gradual substitution of other metals for copper in the solution, because although copper plus other (more electro-positive) metals are constantly dissolving at the anode, only copper is deposited at the cathode. Hence the composition and acidity of the solution, on which so much depends, must be constantly watched.

The dependence of the mechanical qualities of the copper upon the current-density employed is well known. A very weak current gives a pale and brittle deposit, but as the current-density is increased up to a certain point, the properties of the metal improve; beyond this point they deteriorate, the colour becoming darker and the deposit less coherent, until at last it is dark brown and spongy or pulverulent. The presence of even a small proportion of hydrochloric acid imparts a brown tint to the deposit. Baron H. v. Hiibl (Mittheil. des k. k. militiir-geograph. Inst., 1886, vol. vi. p. 51) has found that with neutral solutions a 5% solution of copper sulphate gave no good result, while with a 20% solution the best deposit was obtained with a current-density of 28 amperes per sq. ft.; with solutions containing 2% of sulphuric acid, the 5% solution gave good deposits with current-densities of 4 to 7.5 amperes, and the 20% solution with 11.5 to 37 amperes, per sq. ft. The maximum current-densities for a pure acid solution at rest were: for 15% pure copper sulphate solutions 14 to 21 amperes, and for 20% solutions 18.5 to 28 amperes, per sq. ft.; but when the solutions were kept in gentle motion these maxima could be increased to 21 -28 and 28-37 amperes per sq. ft. respectively. The necessity for adjusting the current-density to the composition and treatment of the electrolyte is thus apparent. The advantage of keeping the solution in motion is due partly to the renewal of solution thus effected in the neighbourhood of the electrodes, and partly to the neutralization of the tendency of liquids undergoing electrolysis to separate into layers, due to the different specific gravities of the solutions flowing from the opposing electrodes. Such an irregular distribution of the bath, with strong copper sulphate solution from the anode at the bottom and acid solution from the cathode at the top, not only alters the conductivity in different strata and so causes irregular current-distribution, but may lead to the current-density in the upper layers being too great for the proportion of copper there present. Irregular and defective deposits are therefore obtained. Provision for circulation of solution is made in the systems of copper-refining now in use. Henry Wilde, in 1875, in depositing copper on iron printing-rollers, recognized this principle and rotated the rollers during electrolysis, thereby renewing the surfaces of metal and liquid in mutual contact, and imparting sufficient motion to the solution to prevent stratification; as an alternative he imparted motion to the electrolyte by means of propeller blades. Other workers have followed more or less on the same lines; reference may be made to the patents of F. E. and A. S. Elmore, who sought to improve the character of the deposit by burnishing during electrolysis, of E. Dumoulin, and Sherard Cowper-Coles (Engineering Review, 1905, vol. xiii. p. 392), who prefers to rotate the cathode at a speed that maintains a peripheral velocity of at least woo ft. per minute. Certain other inventors have applied the same principle in a different way. H. Thofehrn in America and J. C. Graham in England have patented processes by which jets of the electrolyte are caused to impinge with considerable force upon the surface of the cathode, so that the renewal of the liquid at this point takes place very rapidly, and current-densities per sq. ft. of 50 to too amperes are recommended by the former, and of 300 amperes by the latter. Graham has described experiments in this direction, using a jet of electrolyte forced (beneath the surface of the bath) through a hole in the anode upon the surface of the cathode. Whilst the jet was playing, a good deposit was formed with so high a current-density as 280 amperes per sq. ft., but if the jet was checked, the deposit (now in a still liquid) was instantaneously ruined. When two or more jets were used side by side the deposit was good opposite the centre of each, but bad at the point where two currents met, because the rate of flow was reduced. By introducing perforated shields of ebonite between the electrodes, so that the full current-density was only attained at the centres of the jets, these ill effects could be prevented. One of the chief troubles met with was the formation of arborescent growths around the edges of the cathode, due to the greater current-density in this region; this, however, was also obviated by the use of screens. By means of a very brisk rotation of cathode, combined with a rapid current of electrolyte, J. W. Swan has succeeded in depositing excellent copper at currentdensities exceeding moo amperes per sq. ft. The methods by which such results are to be obtained cannot, however, as yet be practised economically on a working scale; one great difficulty in applying them to the refining of metals is that the jets of liquid would be liable to carry with them articles of anode mud, and Swan has shown that the presence of solid particles in the electrolyte is one of the most fruitful causes of the well-known nodular growths on electrodeposited copper. Experiments on a working scale with one of the jet processes in America have, it is reported, been given up after a full trial.

In copper-refining practice, the current-density commonly ranges from 7.5 to 12 or 15, and occasionally to 18, amperes per sq. ft. The electrical pressure required to force a current of this intensity through the solution, and to overcome a certain opposing electromotive force arising from the more electro-negative impurities of the anode, depends upon the composition of the bath and of the anodes, the distance between the electrodes, and the temperature, but under the usual working conditions averages o-3 volt for every pair of electrodes in series. In nearly all the processes now used, the solution contains about 12 to 2 lb of copper sulphate and from 5 to to oz. of sulphuric acid per gallon of water, and the space between the electrodes is from II. to 2 in., whilst the total area of cathode surface in each tank may be 200 sq. ft., more or less. The anodes are usually cast copper plates about (say) 3 ft. by 2 ft. by or t in. The cathodes are frequently of electro-deposited copper, deposited to a thickness of about 3 1 in. on black-leaded copper plates, from which they are stripped before use. The tanks are commonly constructed of wood lined with lead, or tarred inside, and are placed in terrace fashion each a little higher than the next in series, to facilitate the flow of solution through them all from a cistern at one end to a well at the other. Gangways are left between adjoining rows of tanks, and an overhead travelling-crane facilitates the removal of the electrodes. The arrangement of the tanks depends largely upon the voltage available from the electric generator selected; commonly they are divided into groups, all the baths in each group being in series. In the huge Anaconda plant, for example, in which 150 tons of refined copper can be produced daily by the Thofehrn multiple system (not the jet system alluded to above), there are 600 tanks about 84 ft. by 41 ft. by 34 ft. deep, arranged in three groups of 200 tanks in series. The connexions are made by copper rods, each of which, in length, is twice the width of the tank, with a bayonet-bend in the middle, and serves to support the cathodes in the one and the anodes in the next tank. Selfregistering voltmeters indicate at any moment the potential difference in every tank, and therefore give notice of short circuits occurring at any part of the installation. The chief differences between the commercial systems of refining lie in the arrangement of the baths, in the disposition and manner of supporting the electrodes in each, in the method of circulating the solution, and in the current-density employed. The various systems are often classed in two groups, known respectively as the Multiple and Series systems, depending upon the arrangement of the electrodes in each tank. Under the multiple system anodes and cathodes are placed alternately, all the anodes in one tank being connected to one rod, and all the cathodes to another, and the potential difference between the terminals of each tank is that between a single pair of plates. Under the series system only the first anode and the last cathode are connected to the conductors; between these are suspended, isolated from one another, a number of intermediate bi-polar electrode plates of raw copper, each of these plates acting on one side as a cathode, receiving a deposit of copper, and on the other as an anode, passing into solution; the voltage between the terminals of the tank will be as many times as great as that between a single pair of plates as there are spaces between electrodes in the tank. In time the original impure copper of the plates becomes replaced by refined copper, but if the plates are initially very impure and dissolve irregularly, it may happen that much residual scrap may have to be remelted, or that some of the metal may be twice refined, thus involving a waste of energy. Moreover, the high potential difference between the terminals of the series tank introduces a greater danger of shortcircuiting through scraps of metal at the bottom of the bath; for this reason, also, lead-lined vats are inadmissible, and tarred slate tanks are often used instead. A valuable comparison of the multiple and series systems has been published by E. Keller (see The Mineral Industry, New York, 1899, vol. vii. p. 229). G. Kroupa has calculated that the cost of refining is 8s. per ton of copper higher under the series than it is under the multiple system; but against this, it must be remembered that the new works of the Baltimore Copper Smelting and Rolling Company, which are as large as those of the Anaconda Copper Mining Company, are using the Hayden process, which is the chief representative of the several series systems. In this system rolled copper anodes are used; these, being purer than many cast anodes, having flat surfaces, and being held in place by guides, dissolve with great regularity and require a space of only a in. between the electrodes, so that the potential difference between each pair of plates may be reduced to 0.15 - o-2 volt.

J. A. W. Borchers, in Germany, and A. E. Schneider and O. Szontagh, in America, have introduced a method of circulating the solution in each vat by forcing air into a vertical pipe communicating between the bottom and top of a tank, with the result that the bubbling of the air upward aspirates solution through the vertical pipe from below, at the same time aerating it, and causing it to overflow into the top of the tank. Obviously this slow circulation has but little effect on the rate at which the copper may be deposited. The electrolyte, when too impure for further use, is commonly recrystallized, or electrolysed with insoluble anodes to recover the copper.

The yield of copper per ampere (in round numbers, t oz. of copper per ampere per diem) by Faraday's law is never attained in practice; and although 98% may with care be obtained, from 94 to 96% represents the more usual current-efficiency. With too % currentefficiency and a potential difference of 0.3 volt between the electrodes, t lb of copper should require about o-154 electrical horse-power hours as the amount of energy to be expended in the tank for its production. In practice the expenditure is somewhat greater than this; in large works the gross horse-power required for the refining itself and for power and lighting in the factory may not exceed 0.19 to 0.2 (or in smaller works 0.25) horse-power hours per pound of copper refined.

Many attempts have been made to use crude sulphide of copper or matte as an anode, and recover the copper at the cathode, the sulphur and other insoluble constitutents being left at the anode. The best known of these is the Marchese process, which was tested on a working scale at Genoa and Stolberg in Rhenish Prussia. As the operation proceeded, it was found that the voltage had to be raised until it became prohibitive, while the anodes rapidly became honeycombed through and, crumbling away, filled up the space at the bottom of the vat. The process was abandoned, but in a modified form appears to be now in use in Nijni-Novgorod in Russia. Siemens and Halske introduced a combined process in which the ore, after being part-roasted, is leached by solutions from a previous electrolytic operation, and the resulting copper solution electrolysed. In this process the anode solution had to be kept separate from the cathode solution, and the membrane which had in consequence to be used, was liable to become torn, and so to cause trouble by permitting the two solutions to mix. Modifications of the process have therefore been tried.

Modern methods in copper smelting and refining have effected enormous economy in time, space, and labour, and have consequently increased the world's output. With pyritic smelting a sulphuretted copper ore, fed into a cupola in the morning, can be passed directly to the converter, blown up to metal, and shipped as 99% bars by evening - an operation which formerly, with heap roasting of the ore and repeated roasting of the mattes in stalls, would have occupied not less than four months. A large furnace and a Bessemer converter, the pair capable of making a million pounds of copper a month from a low-grade sulphuretted ore, will not occupy a space of more than 25 ft. by ioo ft.; and whereas, in making metallic copper out of a low-grade sulphuretted ore, one day's labour used to be expended on every ton of ore treated, to-day one day's labour will carry at least four tons of ore through the different mechanical and metallurgical processes necessary to reduce them to metal. About 7 o % of the world's annual copper output is refined electrolytically, and from the 461,583 tons refined in the United States in 1907, there were recovered 13,995,436 oz. of silver and 272,150 oz. of gold. The recovery of these valuable metals has contributed in no small degree to the expansion of electrolytic refining.

Production

The sources of copper, its applications and its metallurgy, have undergone great changes. Chile was the largest producer in 1869 with 54,867 tons; but in 1899 her production had fallen off to 25,000 tons. Great Britain, though she had made half the world's copper in 1830, held second place in 1860, making from native ores 15,968 tons; in 190o her production was 777 tons, and in 1907, 711 tons. The United States made only S72 tons in 1850, and 12,600 tons in 1870; but she today makes more than 60% of the world's total. In 1879, Spain was the largest producer, but now ranks third.

Country.

1895.

1900.

1905.

1907.

United States

175,294

2 74,933

397, 00 3

398,736

Spain and Portugal

55,755

53,7 18

45,5 2 7

50,470

Japan. .. .

18,725

28,285

3 6 ,4 8 5

49,718

Chile

22,428

26,016

29,632

27,112

Germany.. .

16,799

20,635

22,492

20,818

Australasia. .

Io,160

2 3,3 68

34,4 8 3

41,910

Mexico .

12,806

22,473

70,010

61,127

Russia. ... .

5,364

8,128

8,839

15,240

World's production .

339,994

496,819

6 99,5 1 4

723,807

The estimated total production for each decade of the 19th century in metric tons is here shown: 1801-1810 -1811-1820 1821-1830 -1831-1840 1841-1850 -1851-1860 1861-1870 -1871-1880 1881-1890 -1891-1900 The following table gives the output of various countries and the world's production for the years 1895, 1900, 1905, 907 As the stock on hand rarely exceeds three months' demand, and is often little more than a month's supply, it is evident that consumption has kept close pace with production.

The large demand for copper to be used in sheathing ships ceased on the introduction of iron in shipbuilding because of the difficulty of coating iron with an impervious layer of copper; but the consumption in the manufacture of electric apparatus and for electric conductors has far more than compensated.

Alloys of Copper.-Copper unites with almost all other metals, and a large number of its alloys are of importance in the arts. The principal alloys in which it forms a leading ingredient are brass, bronze, and German or nickel silver; under these several heads their respective applications and qualities will be found.

Compounds of Copper.-Copper probably forms six oxides, viz. Cu 4 0, Cu 3 0, Cu20, CuO, Cu 2 0 3 and Cu0 2. The most important are cuprous oxide, Cu 2 0, and cupric oxide, CuO, both of Oxides which give rise to well-defined series of salts. The other and hy- oxides do not possess this property, as is also the case droxides. of the hydrated oxides Cu30 2 2H 2 O and Cu 4035H 2 O, described by M. Siewert.

Cuprous oxide, Cu 2 0, occurs in nature as the mineral cuprite (q.v.). It may be prepared artificially by heating copper wire to a white heat, and afterwards at a red heat, by the atmospheric oxidation of copper reduced in hydrogen, or by the slow oxidation of the metal under water. It is obtained as a fine red crystalline precipitate by reducing an alkaline copper solution with sugar. When finely divided it is of a fine red colour. It fuses at red heat, and colours glass a ruby-red. The property was known to the ancients and during the middle ages; it was then lost for several centuries, to be rediscovered in about 1827. Cuprous oxide is reduced by hydrogen, carbon monoxide, charcoal, or iron, to the metal; it dissolves in hydrochloric acid forming cuprous chloride, and in other mineral acids to form cupric salts, with the separation of copper. It dissolves in ammonia, forming a colourless solution which rapidly oxidizes and turns blue. A hydrated cuprous oxide, (4Cu 2 O, H 2 0), is obtained as a bright yellow powder, when cuprous chloride is treated with potash or soda. It rapidly absorbs oxygen, assuming a blue colour. Cuprous oxide corresponds to the series of cuprous salts, which are mostly white in colour, insoluble in water, and readily oxidized to cupric salts.

Cupric oxide, CuO, occurs in nature as the mineral melaconite (q.v.), and can be obtained as a hygroscopic black powder by the gentle ignition of copper nitrate, carbonate or hydroxide; also by heating the hydroxide. It oxidizes carbon compounds to carbon dioxide and water, and therefore finds extensive application in analytical organic chemistry. It is also employed to colour glass, to which it imparts a light green colour. Cupric hydroxide, Cu(OH) 2, is obtained as a greenish-blue flocculent precipitate by mixing cold solutions of potash and a cupric salt. This precipitate always contains more or less potash, which cannot be entirely removed by washing. A purer product is obtained by adding ammonium chloride, filtering, and washing with hot water. Several hydrated oxides, e.g. Cu(OH)2.3CuO,Cu(OH)2.6H20,6CuO H20,have been described. Both the oxide and hydroxide dissolve in ammonia to form a beautiful azure-blue solution (Schweizer's reagent), which dissolves cellulose, or perhaps, holds it in suspension as water does starch; accordingly, the solution rapidly perforates paper or calico. The salts derived from cupric oxide are generally white when anhydrous, but blue or green when hydrated.

Copper quadrantoxide, Cu 4 0, is an olive-green powder formed by mixing well-cooled solutions of copper sulphate and alkaline stannous chloride. The trientoxide, Cu 3 0, is obtained when cupric oxide is heated to 1500 0 -2000° C. It forms yellowish-red crystals, which scratch glass, and are unaffected by all acids except hydrofluoric; it also dissolves in molten potash. Copper dioxide, CuO 2 H 2 O, is obtained as a yellowish-brown powder, by treating cupric hydrate with hydrogen peroxide. When moist, it decomposes at about 6° C., but the dry substance must be heated to about 180°, before decomposition sets in (see L. Moser, Abst. J.C.S., 1907, ii. p. 549).

Cuprous hydride, (CuH) n, was first obtained by Wurtz in 1844, who treated a solution of copper sulphate with hypophosphorous acid, at a temperature not exceeding 70° C. According to E. J. Bartlett and W. H. Merrill, it decomposes when heated, and gives cupric hydride, CuH 21 as a reddish-brown spongy mass, which turns to a chocolate colour on exposure. It is a strong reducing agent.

Cuprous fluoride, CuF, is a ruby-red crystalline mass, formed by heating cuprous chloride in an atmosphere of hydrofluoric acid at I g oo°-1200° C. It is soluble in boiling hydrochloric acid, but it is not reprecipitated by water, as is the case with cuprous chloride. Cupric fluoride, CuF 2, is obtained by dissolving cupric oxide in hydrofluoric acid. The hydrated form, (CuF 21 2H 2 O, 5HF),is obtained as blue crystals, sparingly soluble in cold water; when heated to 100° C. it gives the compound CuF(OH), which, when heated with ammonium fluoride in a current of carbon dioxide, gives anhydrous copper fluoride as a white powder.

Cuprous chloride, CuCl or Cu 2 Cl 21 was obtained by Robert Boyle by heating copper with mercuric chloride. It is also obtained by burning the metal in chlorine, by heating copper and cupric oxide with hydrochloric acid, or copper and cupric chloride with hydrochloric acid. It dissolves in the excess of acid, and is precipitated as a white crystalline powder on the addition of water. It melts at below red heat to a brown mass, and its vapour density at both red and white heat corresponds to the formula Cu 2 C1 2. It turns dirty violet on exposure to air and light; in moist air it absorbs oxygen and forms an oxychloride. Its solution in hydrochloric acid readily absorbs carbon monoxide and acetylene; hence it finds application in gas analysis. Its solution in ammonia is at first colourless, but rapidly turns blue, owing to oxidation. This solution absorbs acetylene with the precipitation of red cuprous acetylide, Cu 2 C 2, a very explosive compound. Cupric chloride, CuC1 2, is obtained by burning copper in an excess of chlorine, or by heating the hydrated chloride, obtained by dissolving the metal or cupric oxide in an excess of hydrochloric acid. It is a brown deliquescent powder, which rapidly forms the green hydrated salt CuC1 21 2H 2 0 on exposure. The oxychloride Cu 3 0 2 C1 2.4H 2 O is obtained as a pale blue precipitate when potash is added to an excess of cupric chloride. The oxychloride Cu 4 O 3 C1 2 ,4H 2 0 occurs in nature as the mineral atacamite. It may be artificially prepared by heating salt with ammonium copper sulphate to Poo°. Other naturally occurring oxychlorides are botallackite and tallingite. " Brunswick green," a light green pigment, is obtained from copper sulphate and bleaching powder.

The bromides closely resemble the chlorides and fluorides. Cuprous iodide, Cu 2 l 21 is obtained as a white powder, which suffers little alteration on exposure, by the direct union of its components or by mixing solutions of cuprous chloride in hydrochloric acid and potassium iodide; or, with liberation of iodine, by adding potassium iodide to a cupric salt. It absorbs ammonia, forming the compound Cu 2 I 2r 4NH 3. Cupric iodide is only known in combination, as in Cu12, 4NH 31 H 2 O, which is obtained by exposing Cu 2 I 2 ,4NH 3 to moist air.

Cuprous sulphide, Cu 2 S, occurs in nature as the mineral chalcocite or copper-glance, and may be obtained as a black brittle mass by the direct combination of its constituents. (See above, Metallurgy.) Cupric sulphide, CuS, occurs in nature as the mineral covellite. It may be prepared by heating cuprous sulphide with sulphur, or triturating cuprous sulphide with cold strong nitric acid, or as a dark brown precipitate by treating a copper solution with sulphuretted hydrogen. Several polysulphides, e.g. Cu2S5, Cu 2 S 6, Cu4S5, Cu 2 S 3, have been described; they are all unstable, decomposing into cupric sulphide and sulphur. Cuprous sulphite, CuS0 3 H 2 O, is obtained as a brownish-red crystalline powder by treating cuprous hydrate with sulphurous acid. A cuproso-cupric sulphite, Cu2S03, CuSO 3 ,2H 2 0, is obtained by mixing solutions of cupric sulphate and acid sodium sulphite.

Cupric sulphate or " Blue Vitriol," CuSO 4, is one of the most important salts of copper. It occurs in cupriferous mine waters and as the minerals chalcanthite or cyanosite, CuSO 4.5H 2 O, and boothite, CuSO 4.7H 2 O. Cupric sulphate is obtained commercially by the I 91,000 96,000 1 35 ,000 218,400 291,000 900,000 oxidation of sulphuretted copper ores (see above, Metallurgy; wet methods), or by dissolving cupric oxide in sulphuric acid. It was obtained in 1644 by Van Helmont, who heated copper with sulphur and moistened the residue, and in 1648 by Glauber, who dissolved copper in strong sulphuric acid. (For the mechanism of this reaction see C. H. Sluiter, Chem. Weekblad, 1906, 3, p. 63, and C. M. van Deventer, ibid., 1906, 3, p. 515.) It crystallizes with five molecules of water as large blue triclinic prisms. When heated to Poo°, it loses four molecules of water and forms the bluish-white monohydrate, which, on further heating to 250°-260°, is converted into the white CuSO 4. The anhydrous salt is very hygroscopic, and hence finds application as a desiccating agent. It also absorbs gaseous hydrochloric acid. Copper sulphate is readily soluble in water, but insoluble in alcohol; it dissolves in hydrochloric acid with a considerable fall in temperature, cupric chloride being formed. The copper is readily replaced by iron, a knife-blade placed in an aqueous solution being covered immediately with a bright red deposit of copper. At one time this was regarded as a transmutation of iron into copper. Several basic salts are known, some of which occur as minerals; of these, we may mention brochantite, CuS04, 3Cu (OH 2), langite, CuSO 4, 3Cu(OH) 2, H 2 O, lyellite (or devilline), warringtonite; woodwardite and enysite are hydrated copperaluminium sulphates, connellite is a basic copper chlorosulphate, and spangolite is a basic copper aluminium chlorosulphate. Copper sulphate finds application in calico printing and in the preparation of the pigment Scheele's green.

A copper nitride, Cu 3 N, is obtained by heating precipitated cuprous oxide in ammonia gas (A. Guntz and H. Bassett, Bull. Soc. Chim., 1906, 35, p. 201). A maroon-coloured powder, of composition CuN02, is formed when pure dry nitrogen dioxide is passed over finelydivided copper at 25 0 -30 0. It decomposes when heated to 900; with water it gives nitric oxide and cupric nitrate and nitrite. Cupric nitrate, Cu(NO 3) 2, is obtained by dissolving the metal or oxide in nitric acid. It forms dark blue prismatic crystals containing 3, 4, or 6 molecules of water according to the temperature of crystallization. The trihydrate melts at 114.5°, and boils at 170 0, giving off nitric acid, and leaving the basic salt Cu(NO 3) 2.3Cu(OH) 2. The mineral gerhardtite is the basic nitrate Cu2(OH)3N03.

Copper combines directly with phosphorus to form several compounds. The phosphide obtained by heating cupric phosphate, Cu 2 H 2 P 2 O 81 in hydrogen, when mixed with potassium and cuprous sulphides or levigated coke, constitutes " Abel's fuse," which is used as a primer. A phosphide, Cu 3 P 2, is formed by passing phosphoretted hydrogen over heated cuprous chloride. (For other phosphides see E. Heyn and 0. Bauer, Rep. Chem. Soc., 1906, 3, p. 39.) Cupric phosphate, Cu 3 (PO 4) 2, may be obtained by precipitating a copper solution with sodium phosphate. Basic copper phosphates are of frequent occurrence in the mineral kingdom. Of these we may notice libethenite, Cu 2 (OH)PO 4; chalcosiderite, a basic copper iron phosphate; torbernite, a copper uranyl phosphate; andrewsite, a hydrated copper iron phosphate; and henwoodite, a hydrated copper aluminium phosphate.

Copper combines directly with arsenic to form several arsenides, some of which occur in the mineral kingdom. Of these we may mention whitneyite, Cu 9 As, algodonite, Cu 6 As, and domeykite, Cu3As. Copper arsenate is similar to cupric phosphate, and the resemblance is to be observed in the naturally occurring copper arsenates, which are generally isomorphous with the corresponding phosphates. Olivenite corresponds to libethenite; clinoclase, euchroite, cornwallite and tyrolite are basic arsenates; zeunerite corresponds to torbernite; chalcophyllite (tamarite or " copper-mica ") is a basic copper aluminium sulphato-arsenate, and bayldonite is a similar compound containing lead instead of aluminium. Copper arsenite forms the basis of a number of once valuable, but very poisonous, pigments. Scheele's green is a basic copper arsenite; Schweinfurt green, an aceto-arsenite; and Casselmann's green a compound of cupric sulphate with potassium or sodium acetate.

Normal cupric carbonate, CuCO 3, has not been definitely obtained, basic hydrated forms being formed when an alkaline carbonate is added to a cupric salt. Copper carbonates are of wide occurrence in the mineral kingdom, and constitute the valuable ores malachite and azurite. Copper rust has the same composition as malachite; it results from the action of carbon dioxide and water on the metal. Copper carbonate is also the basis of the valuable blue to green pigments verditer, Bremen blue and Bremen green. Mountain or mineral green is a naturally occurring carbonate.

By the direct union of copper and silicon, cuprosilicon, consisting mainly of Cu 4 Si, is obtained (Lebeau, C.R., 1906; Vigouroux, ibid.). Copper silicates occur in the mineral kingdom, many minerals owing their colour to the presence of a cupriferous element. Dioptase and chrysocolla (q.v.) are the most important forms.

Detection

Compounds of copper impart a bright green coloration to the flame of a Bunsen burner. Ammonia gives a characteristic blue coloration when added to a solution of a copper salt; potassium ferrocyanide gives a brown precipitate, and, if the solution be very dilute, a brown colour is produced. This latter reaction will detect one part of copper in 500,000 of water. For the borax beads and the qualitative separation of copper from other metals, see Chemistry: Analytical. For the quantitative estimation, see Assaying: Copper.

Medicine

In medicine copper sulphate was employed as an emetic, but its employment for this purpose is now very rare, as it is exceedingly depressant, and if it fails to act, may seriously damage the gastric mucous membrane. It is, however, a useful superficial caustic and antiseptic. All copper compounds are poisonous, but not so harmful as the copper arsenical pigments.

References

. - See generally H. J. Steven's Copper Handbook (annual), W. H. Weld, The Copper Mines of the World (1907), The Mineral Industry (annual), and Mineral Resources of the United States (annual). For the dry metallurgy, see E. D. Peters, Principles of Copper Smelting (New York, 1907); for pyritic smelting, see T. A. Rickard, Pyrite Smelting (1905); for wet methods, see Eissler, Hydrometallurgy of Copper (London, 1902); and for electrolytic methods, see T. Ulke, Die electrolytische Raffination des Kupfers (Halle, 1904). Reference should also be made to the articles Metallurgy and ELECTROMetallurgy. For the chemistry of copper and its compounds see the references in the article Chemistry: Inorganic. Toxicologic and hygienic aspects are treated in Tschirsch's Das Kupfer vom Standpunkt der gerichtlichen Chemie, Toxikologie and Hygiene (Stuttgart, 1893).


<< Henry Coppee

Copperas >>


Bible wiki

Up to date as of January 23, 2010

From BibleWiki


derived from the Greek kupros (the island of Cyprus), called "Cyprian brass," occurs only in the Authorized Version in Ez 8:27. Elsewhere the Hebrew word (nehosheth) is improperly rendered "brass," and sometimes "steel" (2 Sam 22:35; Jer 15:12). The "bow of steel" (Job 20:24; Ps 1834) should have been "bow of copper" (or "brass," as in the R.V.). The vessels of "fine copper" of Ez 8:27 were probably similar to those of "bright brass" mentioned in 1 Kg 7:45; Dan 10:6.

Tubal-cain was the first artificer in brass and iron (Gen 4:22). Hiram was noted as a worker in brass (1 Kg 7:14). Copper abounded in Palestine (Deut 8:9; Isa 60:17; 1Chr 22:3, 14). All sorts of vessels in the tabernacle and the temple were made of it (Lev 6:28; Num 16:39; 2Chr 4:16; Ez 8:27); also weapons of war (1Sam 17:5, 6, 38; 2 Sam 21:16). Iron is mentioned only four times (Gen 4:22; Lev 26:19; Num 31:22; 35:16) in the first four books of Moses, while copper (rendered "brass") is mentioned forty times. (See BRASS.)

We find mention of Alexander (q.v.), a "coppersmith" of Ephesus (2 Tim 4:14).

This entry includes text from Easton's Bible Dictionary, 1897.

what mentions this? (please help by turning references to this page into wiki links)

This article needs to be merged with COPPER (Jewish Encyclopedia).

Simple English

File:Cu,
Some small pieces of copper in a tube. New copper is a pink color. The color changes to the more orange colour that many people have seen soon when new copper is left in air.

Copper is a chemical element. It is the 29th element on the periodic table. It has 29 protons. Its mass number is 63.55. It is a transition metal. It is in the middle of the periodic table. The symbol for copper is "Cu", which comes from the Latin word cuprum, which, in turn, came from the Latin word for the island of Cyprus, where copper was found. [1]

Contents

Properties

Physical properties

[[File:|thumb|copper disc, acid etched, you see the normally invisible crystalline structure]] It is a reddish-coloured metal. It is pink when new and turns red when it is put in air. It is very flexible and ductile. It can be stretched into wires easily. It is one of the few colored metals. Most metals are gray or silver. Gold, copper, and osmium are the only three colored metals. It conducts electricity and heat very well.

Chemical properties

It is more pink when pure and turns reddish when exposed to air. The reddish color is a thin layer of corrosion on the copper (copper(I) oxide). Copper can also turn black when heated. This is because of a coating of copper(II) oxide. It can also turn green. This is because of a coating of copper(II) carbonate and copper(II) hydroxide. Copper corrodes in solutions having sulfides. It reacts with solutions of hydrochloric acid or ammonia containing oxygen. It can also dissolve in a mixture of hydrogen peroxide and hydrochloric acid. This makes copper(II) chloride. It does not dissolve in plain acids. It can dissolve in nitric acid to make copper(II) nitrate and nitrogen dioxide or nitric oxide.

Compounds

It forms chemical compounds. Copper in these compounds has two normal oxidation states. +2 is most common. Most +2 copper compounds are blue. +1 copper compounds can be white. Copper compounds are weak oxidizing agents. They corrode many metals. This corrosion takes the metal and puts it in the chemical compound, leaving the copper behind. An example would be iron and copper(II) sulfate reacting to make copper and iron(II) sulfate. +1 copper compounds are reducing agents when in air. They are normally made by reduction of +2 compounds.

Copper compounds can be black, green, reddish, white, blue, or yellow.

Occurrence

[[File:|thumb|100px|Copper as a metal in the ground]]

File:Min
Chalcopyrite

Copper can be found as a metal in the ground. Normally it is green on the outside. Most copper is not as a metal but in chemical compounds. Chalcopyrite is the most common copper ore. It is a mixture of pyrite and copper sulfide. Copper is found in small amounts in living things. Some mollusks and arthropods have blue blood because they have copper in their blood. Animals such as humans and other mammals have red blood because it contains iron.

Preparation

Copper is sometimes just taken out of the ground and shaped into objects. But most copper is not in a metal form in the ground. Chalcopyrite is the main copper ore. It is heated with air to separate the iron as iron(II) oxide. Some copper(I) oxide is made. Sulfur dioxide is also made. Then silicon dioxide is added, which reacts with the iron(II) oxide to make a liquid which is drained. Now only copper and sulfide are left. The copper sulfide reacts with air to make copper metal and sulfur dioxide. Some copper sulfide reacts with the copper(I) oxide to make copper and sulfur dioxide. This makes impure copper.

Copper is made pure by electrolyzing it. A thin sheet of pure copper is put on the cathode and a thick sheet of impure copper is put on the anode. The electrolyte is copper sulfate. The impure copper gets dissolved in the solution. It then coats the thin sheet of pure copper. This makes the copper pure.

Large amounts of copper are recycled because of it's high value and the increasing depletion of worldwide copper reserves.

Uses

As an element

Copper may be the oldest metal in use, as very old copper tools have been found. Copper is used in electrical wiring. It can also be shaped into various parts. It can be used in a heat sink. The Statue of Liberty is made of copper. It is also used in pipes carrying water, because it does not corrode.

When people mix copper with tin, bronze is made. Bronze is an important metal, because it can be shaped into useful things, but it was more important before the use of iron. When zinc is mixed with copper, brass is made. It can be alloyed with nickel to make cupronickel.

As chemical compounds

Copper is important in the human body. If a person does not get enough copper, the molecules in the body might not work. Having too much copper, though, can be a problem. Humans get most of the copper they need from food, and vitamins also contain copper to make sure we get enough. Copper compounds are also used to kill fungi and algae.

Safety

Copper is not toxic as a metal. Copper compounds are toxic though, although small amounts are needed to live. Copper is expelled from the body easily, so it does not build up in toxic effects.

See also

References

koi:Ыргӧн








Got something to say? Make a comment.
Your name
Your email address
Message