Cobalt(II) chloride

Chemical compound From Wikipedia, the free encyclopedia

Cobalt(II) chloride refers to inorganic compounds with the formula CoCl2·(H2O)n. These compounds include anhydrous CoCl2 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.[4]

Quick facts Names, Identifiers ...
Cobalt(II) chloride
Hexahydrate
Anhydrous
Names
IUPAC name
Cobalt(II) chloride
Other names
Cobaltous chloride
Cobalt dichloride
Muriate of cobalt[1]
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.028.718 Edit this at Wikidata
EC Number
  • 231-589-4
RTECS number
  • GF9800000
UNII
UN number 3288
  • InChI=1S/2ClH.Co/h2*1H;/q;;+2/p-2 checkY
    Key: GVPFVAHMJGGAJG-UHFFFAOYSA-L checkY
  • InChI=1/2ClH.Co/h2*1H;/q;;+2/p-2
    Key: GVPFVAHMJGGAJG-NUQVWONBAU
  • anhydrous: Cl[Co]Cl
  • hexahydrate: Cl[Co-4](Cl)([OH2+])([OH2+])([OH2+])[OH2+].O.O
Properties
CoCl2
Molar mass 129.839 g/mol (anhydrous)
165.870 g/mol (dihydrate)
237.931 g/mol (hexahydrate)
Appearance blue crystals (anhydrous)
violet-blue (dihydrate)
rose red crystals (hexahydrate)
Density 3.356 g/cm3 (anhydrous)
2.477 g/cm3 (dihydrate)
1.924 g/cm3 (hexahydrate)
Melting point 726 °C (1,339 °F; 999 K) ±2 (anhydrous)[2]
140 °C (monohydrate)
100 °C (dihydrate)
86 °C (hexahydrate)
Boiling point 1,049 °C (1,920 °F; 1,322 K)
43.6 g/100 mL (0 °C)
45 g/100 mL (7 °C)
52.9 g/100 mL (20 °C)
105 g/100 mL (96 °C)
Solubility 38.5 g/100 mL (methanol)
8.6 g/100 mL (acetone)
soluble in ethanol, pyridine, glycerol
+12,660·10−6 cm3/mol
Structure
CdCl2 structure
hexagonal (anhydrous)
monoclinic (dihydrate)
Octahedral (hexahydrate)
Hazards
GHS labelling:
GHS06: Toxic GHS08: Health hazard GHS09: Environmental hazard
NFPA 704 (fire diamond)
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
80 mg/kg (rat, oral)
Safety data sheet (SDS) ICSC 0783
Related compounds
Other anions
Cobalt(II) fluoride
Cobalt(II) bromide
Cobalt(II) iodide
Other cations
Rhodium(III) chloride
Iridium(III) chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Properties

Solid forms

Anhydrous cobalt chloride has the cadmium chloride structure (CdCl
2
) (R3m) in which the cobalt(II) ions are octahedrally coordinated. At about 706 °C (20 degrees below the melting point), the coordination change to tetrahedral.[2] The vapor pressure has been reported as 7.6 mmHg at the melting point.[5] The anhydrous salt, which is hygroscopic, sublimes under flowing hydrogen chloride.[6] 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.[7]

Anhydrous
Dihydrate
Hexahydrate
Structures of the forms of cobalt(II) chloride

Solid hexahydrate CoCl2•6H
2
O
contains the neutral molecule trans-CoCl
2
(H
2
O)
4
and two molecules of water of crystallization.[8] Claims of the formation of tri- and tetrahydrates have not been confirmed.[9]

Solutions

Cobalt chloride is fairly soluble in water. Under atmospheric pressure, the mass concentration of a saturated solution of CoCl
2
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.[9]

Diluted aqueous solutions of CoCl
2
contain the hexaaquo complex [Co(H2O)6]2+. Concentrated solutions are red at room temperature but become blue at higher temperatures.[10]

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:[6]

Co(O2CCH3)2·(H2O)4 + 6 CH3COCl → CoCl2 + 6 CH3CO2H + 4 HCl

Aqueous solutions of cobalt chloride can be prepared from cobalt(II) hydroxide or cobalt(II) carbonate and hydrochloric acid according to this idealized equation:

CoCO3 + 2 HCl + 3 H2O → CoCl2·(H2O)4 + CO2

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.[9]

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.[9] 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.[9]

Dehydration can also be effected with trimethylsilyl chloride:[11]

CoCl
2
•6H
2
O
+ 12 (CH
3
)
3
SiCl
CoCl
2
+ 6[(CH
3
)
3
SiCl]
2
O
+ 12 HCl

Reactions

Cobalt(II) chloride is a precursor to many other cobalt compounds.[12] 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 (C
5
H
5
N
):[13]

CoCl2·6(H2O) + 4 C5H5N → CoCl2(C5H5N)4 + 6 H2O

With triphenylphosphine (P(C
6
H
5
)
3
), a tetrahedral complex results:

CoCl2·6(H2O) + 2 P(C6H5)3 → CoCl2[P(C6H5)3]2 + 6 H2O

Salts of the anionic complex CoCl42− can be prepared using tetraethylammonium chloride:[14]

CoCl
2
+ 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:[15]

CoCl2 + 2 HF → CoF2 + 2 HCl

Precursor to organocobalt derivatives

The structure of a cobalt(IV) coordination complex with the norbornyl anion

Reaction of the anhydrous compound with sodium cyclopentadienide gives cobaltocene Co(C
5
H
5
)
2
. Reaction of 1-norbornyllithium with the CoCl
2
·THF produces tetrakis(1-norbornyl)cobalt(IV)[16][17] — a rare example of a stable transition metal/saturated alkane compound,[4] different products are obtained in other solvents.[18]

Moisture indication

The deep blue colour of this moisture indicating silica gel is due to cobalt chloride. When hydrated the colour changes to a light pink/purple.

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).[19]

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.[20][21][22]

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.[23]

In 2005–06, cobalt chloride was the eighth-most-prevalent allergen in patch tests (8.4%).[24]

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.[25]
  • Cobalt chloride is an established chemical inducer of hypoxia-like responses such as erythropoiesis.[citation needed] Cobalt supplementation is not banned and therefore would not be detected by current anti-doping testing.[26] Cobalt chloride is a banned substance under the Australian Thoroughbred Racing Board.[27]
  • Cobalt chloride is one method used to induce pulmonary arterial hypertension in animals for research and evaluation of treatment efficacy.

References

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