Cobalt(II) chloride refers to inorganic compounds with the formula . These compounds include anhydrous as well as several hydrates. The anhydrous form is a blue solid; the dihydrate is purple and the hexahydrate is pink. The hexahydrate is commonly used in the laboratory.
Properties Solid forms Anhydrous cobalt chloride has the cadmium chloride structure () (Rm) in which the cobalt(II) ions are octahedrally coordinated. At about 706 °C (20 degrees below the melting point), the coordination changes to tetrahedral. The vapor pressure has been reported as 7.6 mmHg at the melting point.Yuzo Saeki, Ryoko Matsuzaki, Naomi Aoyama (1977): "The vapor pressure of cobalt dichloride". Journal of the Less Common Metals, volume 55, issue 2, pages 289-291. The anhydrous salt, which is hygroscopic, sublimes under flowing hydrogen chloride. The dihydrate, CoCl2(H2O)2, is a coordination polymer. Each Co center is coordinated to four doubly bridging chloride ligands. The octahedron is completed by a pair of mutually trans aquo ligands.
Solid hexahydrate •6 contains the neutral molecule trans- and two molecules of water of crystallization. Claims of the formation of tri- and tetrahydrates have not been confirmed.M. T. Saugier, M. Noailly, R. Cohen-Adad, F. Paulik, and J. Paulik (1977): "Equilibres solide ⇄ liquide ⇆ vapeur du systeme binaire -" Journal of Thermal Analysis, volume 11, issue 1, pages 87–100. Note: the lowest point of fig.6 is inconsistent with fig.7; probably should be at -27.8 C instead of 0 C.
Solutions Cobalt chloride is fairly soluble in water. Under atmospheric pressure, the mass concentration of a saturated solution of in water is about 54% at the boiling point, 120.2 °C; 48% at 51.25 °C; 35% at 25 °C; 33% at 0 °C; and 29% at −27.8 °C.
Diluted aqueous solutions of contain the hexaaquo complex . Concentrated solutions are red at room temperature but become blue at higher temperatures.The Merck Index, 7th edition, Merck & Co, Rahway, New Jersey, USA, 1960.
Preparation The anhydrous compound can be prepared by heating the hydrated cobalt chlorides under flowing hydrogen chloride or by treating hydrated cobalt(II) acetate with acetyl chloride:
Aqueous solutions of cobalt chloride can be prepared from cobalt(II) hydroxide or cobalt(II) carbonate and hydrochloric acid according to this idealized equation:
Cooling saturated aqueous solutions yields the dihydrate between 120.2 °C and 51.25 °C, and the hexahydrate below 51.25 °C. Water ice, rather than cobalt chloride, will crystallize from solutions with concentration below 29%. The monohydrate and the anhydrous forms can be obtained by cooling solutions only under high pressure, above 206 °C and 335 °C, respectively.
On rapid heating or in a closed container, each of the 6-, 2-, and 1- hydrates partially melts into a mixture of the next lower hydrate and a saturated solution—at 51.25 °C, 206 °C, and 335 °C, respectively. On slow heating in an open container, so that the water vapor pressure over the solid is practically zero, water evaporates out of each of the solid 6-, 2-, and 1- hydrates, leaving the next lower hydrate, at about 40°C, 89°C, and 125°C, respectively. If the partial pressure of the water vapor is in equilibrium with the solid, as in a confined but not pressurized container, the decomposition occurs at about 115°C, 145°C, and 195°C, respectively.
Dehydration can also be effected with trimethylsilyl chloride: •6 + 12 → + 6 + 12 HCl
Reactions Cobalt(II) chloride is a precursor to many other cobalt compounds. The hexahydrate and the anhydrous salt are weak Lewis acids. The adducts are usually either octahedral or tetrahedral. It forms an octahedral complex with pyridine ():
With triphenylphosphine (), a tetrahedral complex results:
Salts of the anionic complex CoCl42− can be prepared using tetraethylammonium chloride: + 2 [(C2H5)4N]Cl → [(C2H5)4N)]2[CoCl4] The tetrachlorocobaltate ion [CoCl4]2− is the blue ion that forms upon addition of hydrochloric acid to aqueous solutions of hydrated cobalt chloride, which are pink.
Treating anhydrous cobalt chloride with hydrogen fluoride gives cobalt(II) fluoride:
Precursor to organocobalt derivatives
Reaction of the anhydrous compound with sodium cyclopentadienide gives cobaltocene . Reaction of 1-norbornyllithium with the ·THF produces tetrakis(1-norbornyl)cobalt(IV) — a rare example of a stable transition metal/saturated alkane compound, different products are obtained in other solvents.
Moisture indication
Cobalt chloride is a common visual moisture indicator due to its distinct colour change when hydrated. The colour change is from some shade of blue when dry, to a pink when hydrated, although the shade of colour depends on the substrate and concentration. It is impregnated into paper to make test strips for detecting moisture in solutions, or more slowly, in air/gas. Desiccants such as silica gel can incorporate cobalt chloride to indicate when it is "spent" (i.e. hydrated).
Health issues Cobalt is essential for most higher forms of life, but more than a few milligrams each day is harmful. Although poisonings have rarely resulted from cobalt compounds, their chronic ingestion has caused serious health problems at doses far less than the lethal dose. In 1966, the addition of cobalt compounds to stabilize beer foam in Canada led to a peculiar form of toxin-induced cardiomyopathy, which came to be known as beer drinker's cardiomyopathy. 11.1.5 The unusual type of myocardiopathy recognized in 1965 and 1966 in Quebec (Canada), Minneapolis (Minnesota), Leuven (Belgium), and Omaha (Nebraska) was associated with episodes of acute heart failure (e/g/, 50 deaths among 112 beer drinkers).
Furthermore, cobalt(II) chloride is suspected of causing cancer (i.e., possibly carcinogenic, IARC Group 2B) as per the International Agency for Research on Cancer (IARC) Monographs.[PDF
In 2005–06, cobalt chloride was the eighth-most-prevalent allergen in patch tests (8.4%).Zug KA, Warshaw EM, Fowler JF Jr, Maibach HI, Belsito DL, Pratt MD, Sasseville D, Storrs FJ, Taylor JS, Mathias CG, Deleo VA, Rietschel RL, Marks J. Patch-test results of the North American Contact Dermatitis Group 2005–2006. Dermatitis. 2009 May–Jun;20(3):149-60.
Other uses Invisible ink: when suspended in solution, cobalt(II) chloride can be made to appear invisible on a surface; when that same surface is subsequently exposed to significant heat (such as from a handheld heat gun or lighter) the ink reversibly changes to blue. Cobalt chloride is an established chemical inducer of hypoxia-like responses such as erythropoiesis. Cobalt supplementation is not banned and therefore would not be detected by current anti-doping testing. Cobalt chloride is a banned substance under the Australian Thoroughbred Racing Board. Cobalt chloride is one method used to induce pulmonary arterial hypertension in animals for research and evaluation of treatment efficacy.
References
External links
International Chemical Safety Card 0783 National Pollutant Inventory – Cobalt fact sheet IARC Monograph "Cobalt and Cobalt Compounds"