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Cobalt(II) chloride

From Wikipedia, the free encyclopedia

Cobalt(II) chloride
anhydrous (left) and hexahydrate (right)
Cobalt(II) chloride Cobalt(II) chloride hexahydrate
General
Systematic name Cobalt(II) chloride
Cobalt dichloride
Other names Cobaltous chloride
Molecular formula CoCl2
Molar mass 129.84 g/mol (anhydrous)
Appearance see text
CAS number [7646-79-9] (anhydrous)
Properties
Density and phase 3.356 g/cm³, solid
Solubility in water 45 g/100 ml (7 °C)
53 g/100ml (20 °C)
Melting point 735°C
Boiling point 1049°C (1322 K)
Structure
Coordination
geometry
Octahedral
Crystal structure CdCl2 structure
Hazards
MSDS External MSDS
EU classification Toxic (T)
Carc. Cat. 2
Dangerous for
the environment (N)
NFPA 704
R-phrases R49, R22, R42/43, R50/53
S-phrases S2, S22, S53, S45,
S60, S61
Flash point non flammable
RTECS number  ?
Supplementary data page
Structure and
properties
n, εr, etc.
Thermodynamic
data
Phase behaviour
Solid, liquid, gas
Spectral data UV, IR, NMR, MS
Related compounds
Other anions Cobalt(II) fluoride
Cobalt(II) bromide
Cobalt(II) iodide
Cobalt(II) oxide
Other cations Rhodium(III) chloride
Iridium(III) chloride
Except where noted otherwise, data are given for
materials in their standard state (at 25 °C, 100 kPa)
Infobox disclaimer and references

Cobalt(II) chloride is the chemical compound with the formula CoCl2, although the term is used also to refer to the hydrate, which is a different chemical compound. CoCl2 is blue and CoCl2(H2O)6 is deep magenta. Because of this dramatic color change and the ease of the hydration/dehydration reaction, "cobalt chloride" is used as an indicator for water. The magenta hexahydrate is probably the most familiar cobalt compound in the laboratory:

CoCl2(H2O)6 in the solid state and in aqueous solution consists of the species trans-CoCl2(H2O)4. Two of the six molecules of water molecules in its formula unit are water of crystallization, four are bonded to the metal. This species dissolves readily in water and alcohol. It has the interesting property that a concentrated aqueous solution is red at room temperature, but becomes blue when heated.[1] CoCl2(H2O)6 salt is deliquescent.

The anhydrous salt CoCl2 is hygroscopic, readily converting to CoCl2(H2O)6.

Contents

[edit] Chemical properties

CoCl2(H2O)6 and CoCl2 are weak Lewis acids that convert to many other complexes. These cobalt (II) complexes are usually either octahedral, some of which are tetrahedral. Examples:

CoCl2(H2O)6 + C5H5N → CoCl2(C5H5N)4 + 6 H2O
CoCl2(H2O)6 + P(C6H5)3| → CoCl2[P(C6H5)3]2 + 6 H2O
CoCl2 + 2 (C2H5)4NCl → (C2H5)4N)2[CoCl4]

Otherwise, aqueous solutions of cobalt(II) chlorides behave like other cobalt(II) salts, such as the precipitaton of CoS upon treatment with H2S

[edit] Co(III) derivatives

In the presence of ammonia or amines, cobalt(II) is readily oxidised by oxygen in the air to give a variety of cobalt(III) complexes, for example:

4 [Co(H2O)6]Cl2 + 4 NH4Cl + 20 NH3 + O2 → 4 [Co(NH3)6]Cl3 + 26 H2O

The reaction is often performed in the presence of charcoal as a catalyst or hydrogen peroxide is employed in place of air. Other highly basic ligands induce the formation of Co(III) derivatives including carbonate, acetylacetonate, and oxalate. Simple carboxylates and halides do not.

Unlike Co(II) complexes, Co(III) complexes are very slow to exchange ligands, so they are said to be kinetically inert. The German chemist Alfred Werner was awarded the Nobel prize in 1913 for his studies on a series of these cobalt(III) compounds, work that led to an understanding of the structures of such coordination compounds.

[edit] CoCl3?

Regarding the existence of a simple cobalt(III) chloride, CoCl3, the literature is contradictory. The CRC 71 ed[2] describes such a compound as known, but Greenwood & Earnshaw [3] (which is more recent) states, "Apart from ...CoF3, ....the only known halides of cobalt are the dihalides."

[edit] Preparation

Cobalt(II) chloride may be prepared in its anhydrous form from cobalt metal and chlorine gas:

Co(s) + Cl2(g) → CoCl2(s)

The hydrated form can be prepared from cobalt(II) hydroxide or cobalt(II) carbonate with hydrochloric acid.

[edit] Uses

A popular use for cobalt(II) chloride is for the detection of moisture, for example in drying agents such as silica gel. In the US calcium sulfate is sold as a drying agent under the trade name Drierite. When cobalt(II) chloride is added as an indicator, the drying agent is blue when still active, pink when exhausted, corresponding to the anhydrous and hydrated forms of CoCl2, respectively. Cobalt chloride paper is likewise used to detect the presence of water.

In the laboratory, cobalt(II) chloride serves as a starting point for the synthesis of a variety of cobalt compounds. For example, the reaction of 1-norbonyllithium with CoCl2 produces a brown, thermally stable cobalt(IV) tetralkyl[4]—the only compound of its kind for which the detailed structure is fully known[3]:

Reaction of anhydrous CoCl2 with cyclopentadienylsodium in THF to give dark-purple cobaltocene, which can readily be oxidised to a Co(III) compound, the cobaltacenium cation which is isoelectronic with ferrocene. CoCl2 also reacts with ligands such as pyridine to produce tetrahedral metal complexes:

CoCl2 + 2 C5H5N → [CoCl2(C5H5N)2]

[edit] Suppliers/Manufacturers

[edit] References

  1.   The Merck Index, 7th edition, Merck & Co, Rahway, New Jersey, USA, 1960.
  2.   Handbook of Chemistry and Physics, 71st edition, CRC Press, Ann Arbor, Michigan, 1990.
  3.    Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.). Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4.
  4.   E. K. Byrne, D. S. Richeson, K. H. Theopold, Journal of the Chemical Society, Chemical Communications, 1491-2 (1986).
  5.   A. F. Wells, Structural Inorganic Chemistry, 5th ed., Oxford University Press, Oxford, UK, 1984. ISBN 0-19-855370-6.
  6.   Hill, Petrucci, McCreary, Perry, General Chemistry, 4th ed., Pearson/Prentice Hall, Upper Saddle River, New Jersey, USA. ISBN 0-13-140283-8.

[edit] External links

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