Chromium 101
Chromium (
/ˈkroʊmiəm/ KROH-mee-əm) is a chemical element which has the symbol Cr and atomic number 24, first element in Group 6. It is a steely-gray, lustrous, hard metal that takes a high polish and has a high melting point. It is also odorless, tasteless, and malleable. The name of the element is derived from the Greek word “chrōma” (χρώμα), meaning colour,[2] because many of its compounds are intensely coloured. It was discovered by Louis Nicolas Vauquelin in the mineral crocoite (lead chromate) in 1797. Crocoite was used as a pigment, and after the discovery that the mineral chromite also contains chromium this latter mineral was used to produce pigments as well.
Chromium was regarded with great interest because of 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 chromium to form stainless steel. This application, along with chrome plating (electroplating with chromium) are currently the highest-volume uses of the metal. Chromium and ferrochromium are produced from the single commercially viable ore, chromite, by silicothermic or aluminothermic reaction or by roasting and leaching processes. Although trivalent chromium (Cr(III)) is required in trace amounts for sugar and lipid metabolism, few cases have been reported where its complete removal from the diet has caused chromium deficiency. In larger amounts and 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.
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Characteristics
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
Chromium metal left standing in air is passivated by oxygen, forming a thin protective oxide surface layer. This layer is a spinel structure only a few atoms thick. It is very dense, and prevents the diffusion of oxygen into the underlying material. This barrier is in contrast to iron or plain carbon steels, where the oxygen migrates into the underlying material and causes rusting.[3] 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 reactant that destroys the protective oxide layer on the metal. Chromium metal treated in this way readily dissolves in weak acids.[4]
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.[5]
Occurrence
Chromium is the 21st most abundant element in Earth’s crust with an average concentration of 100 ppm.[6] 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 3000 mg/kg, in sea water 5 to 800 µg/liter, and in rivers and lakes 26 µg/liter to 5.2 mg/liter.[7]
Crocoite (PbCrO4)
Chromite ore
Chromium is mined as chromite (FeCr2O4) ore.[8] 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.[9]
Although rare, deposits of native chromium exist.[10][11] The 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.[12]
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,[7] although in some areas the ground water can contain up to 39 µg of total chromium of which 30 µg is present as Cr(VI).[13]
Isotopes
Naturally occurring chromium is composed of three stable isotopes; 52Cr, 53Cr and 54Cr with 52Cr being the most abundant (83.789% natural abundance). Nineteen 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.[14]
53Cr 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.[15]
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.[14] 53Cr has been posited as a proxy for atmospheric oxygen concentration.[16]
Compounds
| Oxidation states[note 1][17][18] |
|
|---|---|
| −2 | Na2[Cr(CO)5] |
| −1 | Na2[Cr2(CO)10] |
| 0 | Cr(C6H6)2 |
| +1 | K3[Cr(CN)5NO] |
| +2 | CrCl2 |
| +3 | CrCl3 |
| +4 | K2CrF6 |
| +5 | K3CrO8 |
| +6 | K2CrO4 |
Chromium is a member of the transition metals, in group 6. Chromium(0) has an electronic configuration of 4s13d5, owing to the lower energy of the high spin configuration. Chromium exhibits a wide range of possible oxidation states, where the +3 state is most stable energetically; the +3 and +6 states are most commonly observed in chromium compounds, whereas the +1, +4 and +5 states are rare.[17][18]
The following is the Pourbaix diagram for chromium in pure water, perchloric acid or sodium hydroxide:[7][19] 
Chromium(III)
Chromium(III) chloride hexahydrate ([CrCl2(H2O)4]Cl·2H2O)
Anhydrous chromium(III) chloride (CrCl3)
The oxidation state +3 is the most stable, and a large number of chromium(III) compounds are known. Chromium(III) can be obtained by dissolving elemental chromium in acids like hydrochloric acid or sulfuric acid. The Cr3+ ion has a similar radius (63 pm) to the Al3+ ion (radius 50 pm), so they can replace each other in some compounds, such as in chrome alum and alum. When a trace amount of Cr3+ replaces Al3+ in corundum (aluminium oxide, Al2O3), the red-colored ruby is formed.
Chromium(III) ions in water are invariably octahedrally coordinated with water molecules and anions. The commercially available chromium(III) chloride hydrate is the dark green complex [CrCl2(H2O)4]Cl, but two other forms are known: pale green [CrCl(H2O)5]Cl2, 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 for chloride in the inner coordination sphere. This kind of reaction is also observed in chrome alum solutions and other water-soluble chromium(III) salts. The reverse reaction may be induced by heating the solution.
Chromium(III) hydroxide (Cr(OH)3) is amphoteric, dissolving in acidic solutions to form [Cr(H2O)6]3+, and in basic solutions to form [Cr(OH)6]3−. 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.[4]
Chromium(VI)
Chromium(VI) oxide
Chromium(VI) compounds are powerful oxidants at low or neutral pH, and, except the hexafluoride, contain oxygen as a ligand, such as the chromate anion (CrO2−
4) and chromyl chloride (CrO2Cl2).[4]
Chromium(VI) is most commonly encountered in the chromate (CrO2−
4) and dichromate (Cr2O2−
7) anions. Chromate is produced industrially by the oxidative roasting of chromite ore with calcium or sodium carbonate. The chromate and dichromate anions are in equilibrium:
- 2 CrO2−
4 + 2 H3O+ → Cr2O2−
7 + 3 H2O
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:[4]
