Chromium A. Properties Chromium is a transition metal with the chemical symbol Cr and atomic number 24.

Its name is derived from the Greek word "chrma", which means color, because many of its compounds are intensely colored. Its standard atomic weight is 51.9961 g/mol and it has an electronic configuration of [Ar] 3d5 4s1. It is a steel-gray, lustrous, hard metal that has a high melting point. It is also tasteless, odorless, and malleable. It has a high corrosion resistance and hardness. 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. Chromium is notable for its ability to form quintuple covalent bonds. B. Sources/ Occurence Chromium was discovered by Louis Nicolas Vauquelin in the mineral crocoite (lead chromate) in 1797. It is the 21st most abundant element in Earth's crust with an average concentration of 100 ppm. Its compounds are found in the environment, due to erosion of chromium-containing rocks and can be distributed by volcanic eruptions. The most useful source of chromium commercially is the ore chromite, FeCr2O4. 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. Oxidation of this ore by air in molten alkali gives sodium chromate, Na2CrO4 in which the chromium is in the +6 oxidation state. This is converted to the Cr(III) oxide Cr2O3 by extraction into water, precipitation, and reduction with carbon. The oxide is then further reduced with aluminium or silicon to

form chromium metal. Though native chromium deposits are rare, some native chromium metal has been discovered. The Udachnaya Pipe in Russia produces samples of the native metal. Naturally occurring chromium is composed of three stable isotopes; 52Cr, 53Cr and 54Cr with 52Cr being the most abundant (83.789% natural abundance). The most common oxidation states of chromium are +2, +3, and +6, with +3 being the most stable. +1, +4 and +5 are rare. The oxidation state 3+ is the most stable one and therefore a large number of chromium(III) compounds is known. Chromium(III) can be obtained by dissolving chromium in acids like hydrochloric acid or sulfuric acid. The second stable oxidation state is 6+, for example the chromate, which is produced in large scale by oxidative roasting of chromite ore with calcium or sodium carbonate. Chromate and dichromate are in an equilibrium, which is influenced in that case by the law of mass action and therefore by the pH of the solution. 2 CrO42- + 2 H3O+ Cr2O72- + 3 H2O The change in equilibrium is also visible by a change from yellow (chromate) to orange (dichromate) if an acid is added to a neutral solution of potassium chromate. At lower pH, further condensation to more complex oxyanions of chromium is possible. The chromate and dichromate are strong oxidizing reagents at low pH. Chromium, unlike metals such as iron and nickel, does not suffer from hydrogen embrittlement. It does suffer from nitrogen embrittlement - chromium reacts with nitrogen from air and forms brittle nitrides at temperatures necessary to work the metal parts. C. Important Compounds and their Uses/ Applications Weapons found in burial pits dating from the late 3rd century BC Qin Dynasty of the Terracotta Army near Xi'an, China have been analyzed by archaeologists. Although buried more than 2,000 years

ago, the ancient bronze tips of crossbow bolts and swords found at the site did not show any sign of corrosion because the bronze was coated with chromium. In 1797, Louis Nicolas Vauquelin received samples of crocoite ore. He produced chromium oxide (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. He was also able to detect traces of chromium in precious gemstones, such as ruby or emerald. 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 until 1848 when large deposits of chromite where found near Bursa, Turkey. 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. Metal alloys now account for 85% of the use of chromium. The remainder is used in the chemical industry and refractory and foundry industries. Because of its strengthening effect on steel and increased corrosion resistance, Chromium has been an important alloying material for steel. An important stainless steel is 18/10 stainless, made from iron with 10% nickel and 18% chromium, is widely used for cookware and cutlery. For these applications, ferrochromium is added to the molten iron. The relative high hardness and corrosion resistance of unalloyed chromium makes it a good surface coating. The mineral crocoite (lead chromate

PbCrO4) was used as a yellow pigment shortly after its discovery. After a synthesis method became available starting from the more abundant chromite, Chrome yellow was, together with cadmium yellow, one of the most used yellow pigments. The pigment does not degrade in the light and has a strong color. The signaling effect of yellow was used for school buses in the United States and for Postal Service in Europe. The use of chrome yellow declined due to environmental and safety concerns and was substituted by organic pigments or other lead-free alternatives. Other pigments based on chromium are, for example, the bright red pigment Chrome red, which is a basic lead chromate (PbCrO4Pb(OH)2). Chrome green is a mixture of Prussian blue and chrome yellow, while the Chrome oxide green is Chromium(III) oxide. Glass is colored green by the addition of chromium(III) oxide. This is similar to emerald, which is also colored by chromium.A red color is achieved by doping chromium(III) into the crystals of corundum, which are then called ruby. Therefore, chromium is used in producing synthetic rubies. The toxicity of chromium(VI) salts is used in the preservation of wood. For example, chromated copper arsenate (CCA) is used in timber treatment to prevent wood from decay fungi, wood attacking insects, including termites, and marine borers. The formulations contain chromium based on the oxide CrO3 between 35.3% and 65.5%. In the United States, 65,300 metric tons of CCA solution have been used in 1996. The use of chromium-containing dietary supplements is controversial due to the complex effects of the used supplements. The popular dietary supplement chromium picolinate complex generates chromosome damage in hamster cells. In the United States the dietary guidelines for daily chromium uptake were lowered from 50-200 g for an adult to 35 g (adult male) and to 25 g (adult female). Trivalent chromium (Cr(III) or Cr3+) is required in trace amounts for sugar and lipid metabolism in

humans, and its deficiency may cause a disease called chromium deficiency. In contrast, hexavalent chromium (Cr(VI) or Cr6+) is very toxic and mutagenic when inhaled. Cr(VI) has not been established as a carcinogen when in solution, though it may cause allergic contact dermatitis. As chromium compounds were used in dyes and paints and the tanning of leather, these compounds are often found in soil and groundwater at abandoned industrial sites, now needing environmental cleanup and remediation per the treatment of brownfield land. Primer paint containing hexavalent chromium is still widely used for aerospace and automobile refinishing applications. D. Reference http://webelements.com/ http://www.mindat.org/min-1037.html http://www.umm.edu/altmed/articles/chromium-000294.htm http://www.epa.gov/ttnatw01/hlthef/chromium.html

Mae Bernadette B. Bote BS ChE 1