Chromium - Wikipedia, the free encyclopedia

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Chromium
From Wikipedia, the free encyclopedia

Chromium is a chemical element which has the symbol Cr and atomic number 24. It is the first element in Group 6. It is a steely-gray, lustrous, hard and brittle metal [2] which takes a high polish, resists tarnishing, and has a high melting point. The name of the element is derived from the Greek word '( )+, chr!ma, meaning colour,[3] because many of its compounds are intensely coloured. Chromium oxide was used by the Chinese in the Qin dynasty over 2,000 years ago to coat metal weapons found with the Terracotta Army. Chromium was discovered as an element after it came to the attention of the western world in the red crystalline mineral crocoite (lead(II) chromate), discovered in 1761 and initially used as a pigment. Louis Nicolas Vauquelin first isolated chromium metal from this mineral in 1797. Since Vauquelin's first production of metallic chromium, small amounts of native (free) chromium metal have been discovered in rare minerals, but these are not used commercially. Instead, nearly all chromium is commercially extracted from the single commercially viable ore chromite, which is iron chromium oxide (FeCr2O4). Chromite is also now the chief source of chromium for chromium pigments. Chromium metal and ferrochromium alloy are commercially produced from chromite by silicothermic or aluminothermic reactions, or by roasting and leaching processes. Chromium metal has proven of high value due to its high corrosion resistance and hardness. A major development was the discovery that steel could be made highly resistant to corrosion and discoloration by adding metallic chromium to form stainless steel. This application, along with chrome plating (electroplating with chromium) currently comprise 85% of the commercial use for the element, with applications for chromium compounds forming the remainder.

Chromium
24Cr
! Mo vanadium " chromium # manganese Chromium in the periodic table

Cr

Appearance silvery metallic

General properties Name, symbol, number Pronunciation Element category chromium, Cr, 24 / kro mi$m/ KROH-mee- m transition metal

Group, period, block 6, 4, d Standard atomic weight Electron configuration 51.9961(6) [Ar] 3d5 4s1 2, 8, 13, 1

Physical properties Phase Density (near r.t.) Liquid density at m.p. Melting point Boiling point Heat of fusion solid 7.19 gcm%3 6.3 gcm%3 2180 K, 1907 &C, 3465 &F 2944 K, 2671 &C, 4840 &F 21.0 kJmol%1 23.35 Jmol%1K%1 4 ! 2: 4 5 29/03/21 # Vapor pressure

Heat of vaporization 347 kJmol%1 Molar heat capacity

1 9 01 Trivalent chromium (Cr(III)) ion is possibly PDF created with Pro for trial version www.pdffactory.com required in pdfFactory trace amounts sugar and lipid

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remainder. Trivalent chromium (Cr(III)) ion is possibly required in trace amounts for sugar and lipid metabolism, although the issue remains in debate.[4] In larger amounts and in different forms, chromium can be toxic and carcinogenic. The most prominent example of toxic chromium is hexavalent chromium (Cr(VI)). Abandoned chromium production sites often require environmental cleanup.

Heat of vaporization 347 kJmol Molar heat capacity 23.35 Jmol%1K%1

Vapor pressure P (Pa) 1 10 100 1k 10 k 100 k

at T (K) 1656 1807 1991 2223 2530 2942 Atomic properties Oxidation states Electronegativity Ionization energies 6, 5, 4, 3, 2, 1, -1, -2 (strongly acidic oxide) 1.66 (Pauling scale) 1st: 652.9 kJmol%1 2nd: 1590.6 kJmol%1 3rd: 2987 kJmol%1 Atomic radius Covalent radius 128 pm 139,5 pm Miscellanea Crystal structure body-centered cubic

Contents
1 Characteristics 1.1 Physical 1.1.1 Passivation 1.2 Occurrence 1.3 Isotopes 2 Compounds 2.1 Chromium(III) 2.2 Chromium(VI) 2.3 Chromium(V) and chromium(IV) 2.4 Chromium(II) 2.5 Chromium(I) 2.6 Chromium(0) 3 History 4 Production 5 Applications 5.1 Metallurgy 5.2 Dye and pigment 5.2.1 Synthetic ruby and the first laser 5.3 Wood preservative 5.4 Tanning 5.5 Refractory material 5.6 Catalysts 5.7 Other use 6 Biological role 7 Precautions 7.1 Cr(VI) 7.2 Environmental issues 8 Notes 9 References 10 External links

(more)

Magnetic ordering Electrical resistivity

antiferromagnetic (rather: SDW [1]) (20 &C) 125 n-m (25 &C) 4.9 mm%1K%1

Thermal conductivity 93.9 Wm%1K%1 Thermal expansion Speed of sound (thin (20 &C) 5940 ms%1 rod) Young's modulus Shear modulus Bulk modulus Poisson ratio Mohs hardness Vickers hardness Brinell hardness 279 GPa 115 GPa 160 GPa 0.21 8.5 1060 MPa 1120 MPa

CAS registry number 7440-47-3 History Discovery First isolation Louis Nicolas Vauquelin (1797) Louis Nicolas Vauquelin (1798)

Characteristics
Physical
2 9 01

Most stable isotopes Main article: Isotopes of chromium 4 ! 2: 4 5 29/03/21 #

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Physical
Chromium is remarkable for its magnetic properties: it is the only elemental solid which shows antiferromagnetic ordering at room temperature (and below). Above 38 &C, it transforms into a paramagnetic state.[1] Passivation
iso
50

Most stable isotopes Main article: Isotopes of chromium NA half-life DM DE

(MeV)

DP
50

Cr 4.345%

>1.3.1018 (/+/+) 1.167 y 0 1

Ti

51

Cr

syn

27.7025 d

0.320

51

52 Cr 83.789% 52Cr is stable with 28 neutrons Chromium metal left standing in air is passivated by oxygen, forming a thin 53 Cr 9.501% 53Cr is stable with 29 neutrons protective oxide surface layer. This layer is a 54 Cr 2.365% 54Cr is stable with 30 neutrons spinel structure only a few atoms thick. It is very dense, and prevents the diffusion of Decay modes in parentheses are predicted, but oxygen into the underlying material. This have not yet been observed barrier is in contrast to iron or plain carbon steels, where the oxygen migrates into the underlying material and causes rusting.[5] The passivation can be enhanced by short contact with oxidizing acids like nitric acid. Passivated chromium is stable against acids. The opposite effect can be achieved by treatment with a strong reducing agent that destroys the protective oxide layer on the metal. Chromium metal treated in this way readily dissolves in weak acids.[6]

Chromium, unlike metals such as iron and nickel, does not suffer from hydrogen embrittlement. However, it does suffer from nitrogen embrittlement, reacting with nitrogen from air and forming brittle nitrides at the high temperatures necessary to work the metal parts.[7]

Occurrence
See also category: Chromium minerals Chromium is the 22nd most abundant element in Earth's crust with an average concentration of 100 ppm.[8] Chromium compounds are found in the environment, due to erosion of chromium-containing rocks and can be distributed by volcanic eruptions. The concentrations range in soil is between 1 and 300 mg/kg, in sea water 5 to 800 g/liter, and in rivers and lakes 26 g/liter to 5.2 mg/liter.[9] Chromium is mined as chromite (FeCr2O4) ore.[10] About two-fifths of the chromite ores and concentrates in the world are produced in South Africa, while Kazakhstan, India, Russia, and Turkey are also substantial producers. Untapped chromite deposits are plentiful, but geographically concentrated in Kazakhstan and southern Africa.[11]

Crocoite (PbCrO4)

Although rare, deposits of native chromium exist.[12][13] The Udachnaya Pipe in Russia produces samples of the native Chromite ore metal. This mine is a kimberlite pipe, rich in diamonds, and the reducing environment helped produce both elemental 3 9 01 4 ! 2: 4 5 29/03/21 # [14] PDF created withand pdfFactory Pro trial version www.pdffactory.com chromium diamond.

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Chromite ore

Udachnaya Pipe in Russia produces samples of the native metal. This mine is a kimberlite pipe, rich in diamonds, and the reducing environment helped produce both elemental

chromium and diamond.[14] The relation between Cr(III) and Cr(VI) strongly depends on pH and oxidative properties of the location, but in most cases, the Cr(III) is the dominating species,[9] although in some areas the ground water can contain up to 39 g/liter of total chromium of which 30 g/liter is present as Cr(VI).[15]

Isotopes
Main article: Isotopes of chromium Naturally occurring chromium is composed of three stable isotopes; 52Cr, 53Cr and 54Cr with 52Cr being the most abundant (83.789% natural abundance). 19 radioisotopes have been characterized with the most stable being 50Cr with a half-life of (more than) 1.8 . 1017 years, and 51Cr with a half-life of 27.7 days. All of the remaining radioactive isotopes have half-lives that are less than 24 hours and the majority of these have half-lives that are less than 1 minute. This element also has 2 meta states.[16]
53

Cr is the radiogenic decay product of 53Mn. Chromium isotopic contents are typically combined with manganese isotopic contents and have found application in isotope geology. Mn-Cr isotope ratios reinforce the evidence from 26Al and 107Pd for the early history of the solar system. Variations in 53Cr/52Cr and Mn/Cr ratios from several meteorites indicate an initial 53Mn/55Mn ratio that suggests Mn-Cr isotopic composition must result from in-situ decay of 53Mn in differentiated planetary bodies. Hence 53Cr provides additional evidence for nucleosynthetic processes immediately before coalescence of the solar system.[17] The isotopes of chromium range in atomic mass from 43 u (43Cr) to 67 u (67Cr). The primary decay mode before the most abundant stable isotope, 52Cr, is electron capture and the primary mode after is beta decay.[16] 53Cr has been posited as a proxy for atmospheric oxygen concentration.[18]

Compounds
See also category: Chromium compounds Chromium is a member of the transition metals, in group 6. Oxidation Chromium(0) has an electronic configuration of 4s13d5, owing to the states[note 1][19] lower energy of the high spin configuration. Chromium exhibits a wide range of possible oxidation states, where the +3 state is most stable %2 Na2[Cr(CO)5] energetically; the +3 and +6 states are most commonly observed in %1 Na2[Cr2(CO)10] chromium compounds, whereas the +1, +4 and +5 states are rare.[19] 0 Cr(C6H6)2 The following is the Pourbaix diagram for chromium in pure water, +1 K3[Cr(CN)5NO] perchloric acid or sodium hydroxide:[9][20]
4 9 01

+2 CrCl 2

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perchloric acid or sodium hydroxide:[9][20]

+1 K3[Cr(CN)5NO] +2 CrCl 2 +3 CrCl 3 +4 K2CrF6 +5 K3CrO8 +6 K2CrO4

Chromium(III)
A large number of chromium(III) compounds are known. Chromium(III) can be obtained by dissolving elemental chromium in acids like hydrochloric acid or 3+ sulfuric acid. The Cr ion has a 3+ similar radius (63 pm) to the Al Anhydrous chromium(III) ion (radius 50 pm), so they can chloride (CrCl3) replace each other in some compounds, such as in chrome alum and alum. When a trace 3+ 3+ amount of Cr replaces Al in corundum (aluminium oxide, Al2O3), the red-colored ruby is formed.

Chromium(III) chloride hexahydrate ([CrCl2(H2O)4]Cl2H2O)

Chromium(III) ions tend to form octahedral complexes. The colors of these complexes is determined by the ligands attached to the Cr centre. The commercially available chromium(III) chloride hydrate is the dark green complex [CrCl2(H2O)4]Cl. Closely related compounds have different colours: pale green [CrCl(H2O)5]Cl 2 and the violet [Cr(H2O)6]Cl3. If water-free green chromium(III) chloride is dissolved in water then the green solution turns violet after some time, due to the substitution of water by chloride in the inner coordination sphere. This kind of reaction is also observed with solutions of chrome alum and other water-soluble chromium(III) salts. Chromium(III) hydroxide (Cr(OH)3) is amphoteric, dissolving in acidic solutions to form 3% [Cr(H2O)6]3+, and in basic solutions to form [Cr(OH)6] . It is dehydrated by heating to form the green chromium(III) oxide (Cr2O3), which is the stable oxide with a crystal structure identical to that of corundum.[6]

Chromium(VI)
5 9 01 Chromium(VI) compounds are powerful oxidants at low or PDF created with pdfFactory Pro trial version www.pdffactory.com 4 ! 2: 4 5 29/03/21 #

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Chromium(VI)
Chromium(VI) compounds are powerful oxidants at low or 2% neutral pH. Most important are chromate anion (CrO4 ) and dichromate (Cr2O72-) anions, which exist in equilibrium: 2 [CrO4]2- + 2 H+ [Cr2O7]2- + H2O

Chromium(VI) halides are known also and include the hexafluoride CrF6 and chromyl chloride (CrO2Cl 2).[6]

Chromium(VI) oxide

Sodium chromate is produced industrially by the oxidative roasting of chromite ore with calcium or sodium carbonate. The dominant species is therefore, by the law of mass action, determined by the pH of the solution. The change in equilibrium is visible by a change from yellow (chromate) to orange (dichromate), such as when an acid is added to a neutral solution of potassium chromate. At yet lower pH values, further condensation to more complex oxyanions of chromium is possible. Both the chromate and dichromate anions are strong oxidizing reagents at low pH:[6] Cr2O7 + 14 H3O + 6 e% # 2 Cr
2% + 3+

+ 21 H2O (00 = 1.33 V)

They are, however, only moderately oxidizing at high pH:[6] CrO4 + 4 H2O + 3 e% # Cr(OH)3 + 5 OH (00 = %0.13 V)
2% %

Chromium(VI) compounds in solution can be detected by adding an acidic hydrogen peroxide solution. The unstable dark blue chromium(VI) peroxide (CrO5) is formed, which can be stabilized as an ether adduct CrO5OR2.[6]

Sodium chromate (Na2CrO4)

Chromic acid has the hypothetical formula H2CrO4. It is a vaguely described chemical, despite many well-defined chromates and dichromates being known. The dark red chromium(VI) oxide CrO3, the acid anhydride of chromic acid, is sold industrially as "chromic acid".[6] It can be produced by mixing sulfuric acid with dichromate, and is a strong oxidizing agent.

Chromium(V) and chromium(IV)

The oxidation state +5 is only realized in few compounds but are intermediates in many reactions involving oxidations by chromate. The only binary compound is the volatile chromium(V) fluoride (CrF5). This red solid has a melting point of 30 &C and a boiling point of 117 &C. It can be synthesized by treating chromium metal with fluorine at 400 &C and 200 bar pressure. The peroxochromate(V) is another example of the +5 oxidation state. Potassium peroxochromate (K3[Cr(O2)4]) is made by reacting potassium chromate with hydrogen peroxide at low temperatures. This red brown compound is stable at room temperature but decomposes spontaneously at 1502170 &C.[21] Compounds of chromium(IV) (in the +4 oxidation state) are slightly more common than those of chromium(V). The tetrahalides, CrF4, CrCl4, and CrBr4, can be produced by treating the trihalides (CrX3) with the corresponding halogen at elevated temperatures. 6 9 01 Such compounds are susceptible to disproportionation reactions and are not stable 4 ! 2: 4 5 29/03/21 # in PDF created with pdfFactory Pro trial version www.pdffactory.com

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those of chromium(V). The tetrahalides, CrF4, CrCl4, and CrBr4, can be produced by treating the trihalides (CrX3) with the corresponding halogen at elevated temperatures. Such compounds are susceptible to disproportionation reactions and are not stable in water.

Chromium(II)
Many chromium(II) compounds are known, including the water-stable chromium(II) chloride, CrCl2, which can be made by reduction of chromium(III) chloride with zinc. The resulting bright blue solution is only stable at neutral pH.[6] Many chromous carboxylates are also known, most famously, the red chromous acetate (Cr2(O2CCH3)4), which features a quadruple bond.

Chromium(I)
Most Cr(I) compounds are obtained by oxidation of electron-rich, octahedral Cr(0) complexes. Other Cr(I) complexes contain cyclopentadienyl ligands. As verified by X-ray diffraction, a Cr-Cr quintuple bond (length 183.51(4) pm) has also been described.[22] Extremely bulky monodentate ligands stabilize this compound by shielding the quintuple bond from further reactions.

Chromium(0)
Main article: Organochromium chemistry Many chromium(0) compounds are known. Most are derivatives of chromium hexacarbonyl or bis(benzene)chromium.

History
Weapons found in burial pits dating from the late 3rd century B.C. Qin Dynasty of the Terracotta Army near Xi'an, China have been analyzed by archaeologists. Chromium compound determined Although buried more than 2,000 years ago, the experimentally to contain a Cr-Cr ancient bronze tips of crossbow bolts and swords quintuple bond found at the site showed unexpectedly little corrosion, possibly because the bronze was deliberately coated with a thin layer of chromium oxide.[23] However, this oxide layer was not chromium metal or chrome plating as we know it. Chromium minerals as pigments came to the attention of the west in the 18th century. On 26 July 1761, Johann Gottlob Lehmann found an orange-red mineral in the Beryozovskoye mines in the Ural Mountains which he named Siberian red lead. Though misidentified as a lead compound with selenium and iron components, the mineral was in fact crocoite (lead chromate) with a formula of PbCrO4.[24] In 1770, Peter Simon Pallas visited the same site as Lehmann and found a red lead mineral that had useful properties as a pigment in paints. The use of Siberian red lead as a paint pigment then developed rapidly. A bright yellow pigment made from crocoite also became fashionable.[24]
7 9 01

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a paint pigment then developed rapidly. A bright yellow pigment made from crocoite also became fashionable.[24] In 1797, Louis Nicolas Vauquelin received samples of crocoite ore. He produced chromium trioxide (CrO3) by mixing crocoite with hydrochloric acid. In 1798, Vauquelin discovered that he could isolate metallic chromium by heating the oxide in a charcoal oven, making him the discoverer of the element.[25] Vauquelin was also able to detect traces of chromium in precious gemstones, such as ruby or emerald.[24][26] During the 1800s, chromium was primarily used as a component of paints and in tanning salts. At first, crocoite from Russia was the main source, but in 1827, a larger chromite deposit was discovered near Baltimore, United States. This made the United States the largest producer of chromium products till 1848 when large deposits of chromite were found near Bursa, Turkey.[10]
The red colour of rubies is from a small amount of chromium.

Chromium is also known for its luster when polished. It is used as a protective and decorative coating on car parts, plumbing fixtures, furniture parts and many other items, usually applied by electroplating. Chromium was used for electroplating as early as 1848, but this use only became widespread with the development of an improved process in 1924.[27] Metal alloys now account for 85% of the use of chromium. The remainder is used in the chemical industry and refractory and foundry industries.

Production

Piece of chromium produced with aluminothermic reaction World production trend of chromium

Approximately 4.4 million metric tons of marketable chromite ore were produced in 2000, and converted into ~3.3 million tons of ferro-chrome with an approximate market value of 2.5 billion United States dollars.[28] The largest producers of chromium ore have been South Africa (44%) India (18%), Kazakhstan Chromium, remelted in a horizontal (16%) Zimbabwe (5%), Finland (4%) Iran (4%) and arc zone-refiner, showing large Brazil (2%) with several other countries producing the visible crystal grains rest of less than 10% of the world production.[28] 8 9 01 4 ! 2: 4 5 29/03/21 # PDF created with pdfFactory Pro trial version www.pdffactory.com

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Chromium, remelted in a horizontal arc zone-refiner, showing large visible crystal grains

(16%) Zimbabwe (5%), Finland (4%) Iran (4%) and Brazil (2%) with several other countries producing the rest of less than 10% of the world production.[28]

The two main products of chromium ore refining are ferrochromium and metallic chromium. For those products the ore smelter process differs considerably. For the production of ferrochromium, the chromite ore (FeCr2O4) is reduced in large scale in electric arc furnace or in smaller smelters with either aluminium or silicon in an aluminothermic reaction.[29] For the production of pure chromium, the iron has to be separated from the chromium in a two step roasting and leaching process. The chromite ore is heated with a mixture of calcium carbonate and sodium carbonate in the presence of air. The chromium is oxidized to the hexavalent form, while the iron forms the stable Fe2O3. The Chromium ore output in 2002[28] subsequent leaching at higher elevated temperatures dissolves the chromates and leaves the insoluble iron oxide. The chromate is converted by sulfuric acid into the dichromate.[29] 4 FeCr2O4 + 8 Na2CO3 + 7 O2 # 8 Na2CrO4 + 2 Fe2O3 + 8 CO2 2 Na2CrO4 + H2SO4 # Na2Cr2O7 + Na2SO4 + H2O The dichromate is converted to the chromium(III) oxide by reduction with carbon and then reduced in an aluminothermic reaction to chromium.[29] Na2Cr2O7 + 2 C # Cr2O3 + Na2CO3 + CO Cr2O3 + 2 Al # Al2O3 + 2 Cr

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