Cobalt(III) chloride

Cobalt(III) chloride or cobaltic chloride is an unstable and elusive compound of cobalt and chlorine with formula CoCl
3. In this compound, the cobalt atoms have a formal charge of +3.[1]

Cobalt(III) chloride
Names
IUPAC name
Cobalt(III) chloride
Other names
Cobaltic chloride
Cobalt trichloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.030.509
EC Number
  • 233-574-8
Properties
CoCl3
Molar mass 165.2913 g/mol (anhydrous)
Melting point Solid decomposes over −60°C
Solubility soluble in ethanol, diethyl ether
Hazards
GHS pictograms
GHS Signal word Danger
H300, H330
P260, P264, P270, P271, P284, P301+310, P304+340, P310, P320, P321, P330, P403+233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

The compound has been reported to exist in the gas phase at high temperatures, in equilibrium with cobalt(II) chloride and chlorine gas.[2][3] It has also been found to be stable at very low temperatures, dispersed in a frozen argon matrix.[4]

Some articles from the 1920s and 1930s claim the synthesis of bulk amounts of this compound in pure form;[5][6] however, those results do not seem to have been reproduced, or have been attributed to other substances like the hexachlorocobaltate(III) anion CoCl3−
6.[1] Those earlier reports claim that it gives green solutions in anhydrous solvents such as ethanol and diethyl ether, and that it is stable only a very low temperatures (below −60 °C).[7]

Structure and properties

The infrared spectrum of the compound in frozen argon indicates that the isolated CoCl
3 molecule is planar with D3h symmetry.[4]

A theoretical study of the stability of this and other metal trihalides at 25 °C was published by Nelson and Sharpe in 1966.[8]

Thermodynamic properties for the gas phase have been determined by the Glushko Thermocenter of the Russian Academy of Sciences.[9]

Preparation

Cobalt trichloride was detected in 1952 by Schäfer and Krehl in the gas phase when cobalt(II) chloride CoCl
2 is heated in an atmosphere of chlorine Cl
2. The trichloride is formed through the equilibrium

2CoCl
2 + Cl
2 ↔ 2 CoCl
3

At 918 K (below the melting point of CoCl
2, 999 K), the trichloride was the predominant cobalt species in the vapor, with partial pressure of 0.72 mm Hg versus 0.62 for the dichloride. However, equilibrium shifts to the left at higher temperatures. At 1073 K, the partial pressures were 7.3 and 31.3 mm Hg, respectively.[2][10][3]

Cobalt trichloride, in amounts sufficient to study spectroscopically, was obtained by Green and others in 1983, by sputtering cobalt electrodes with chlorine atoms and trapping the resulting molecules in frozen argon at 14 K.[4]

A report from 1969 claims that treatment of solid cobalt(III) hydroxide CoOOH·H
2O with anhydrous ether saturated with HCl at −20 °C produces a green solution (stable at −78 °C) with the characteristic spectrum of CoCl
3.[1]

In a 1932 report, the compound was claimed to arise in the electrolysis of cobalt(II) chloride in anhydrous ethanol.[7]

The hexachlorocobaltate(III) anion CoCl3−
6 has been identified in preparations of cobalt(III) salts and hydrochloric acid HCl in glacial acetic acid.[1]

In solutions of cobalt(III) salts with chloride ions, the anionic complexes (H
2O)
5Cl2+
 and (H
2O)
4(OH)Cl+
 are present.[11]

Trichlorides of cobalt(III) complexed with various ligands, such as organic amines, can be quite stable. In particular, hexamminecobalt(III) chloride Co(NH
3)
6Cl
3 is the archetypal Werner complex and has uses in biological research. Another classical example is tris(ethylenediamine)cobalt(III) chloride Co(H
2N–C
2H
4–NH
2)
3Cl
3.

References
  1. Arthur W. Chester, El-Ahmadi Heiba, Ralph M. Dessau, and William J. Koehl Jr. (1969): "The interaction of cobalt(III) with chloride ion in acetic acid". Inorganic and Nuclear Chemistry Letters, volume 5, issue 4, pages 277-283. doi:10.1016/0020-1650(69)80198-4
  2. Harald Schäfer and Kurt Krehl (1952): "Das gasförmige Kobalt(III)‐chlorid und seine thermochemischen Eigenschaften". Zeitschrift für anorganische und allgemeine Chemie, volume 268, issue 1‐2, pages 25-34. doi:10.1002/zaac.19522680105
  3. W. D. Halstead (1975): "A review of saturated vapour pressures and allied data for the principal corrosion products of iron, chromium, nickel and cobalt in flue gases". Corrosion Science, volume 15, issues 6–12, pages 603-625. doi:10.1016/0010-938X(75)90027-X
  4. David W. Green, Dana P. McDermott, and Adelle Bergman (1983): "Infrared spectra of the matrix-isolated chlorides of iron, cobalt, and nickel." Journal of Molecular Spectroscopy, volume 98, issue 1, pages 111-124. doi:10.1016/0022-2852(83)90206-0
  5. C. Schall and H. Markgraf (1924). Transactions of the American Electrochemical Society, volume 45, page 161.
  6. D. Hibert and C. Duval (1937): Comptes rendues, volume 204, page 780.
  7. C. Schall (1932): "Zur anodischen Oxydation von Co und Ni‐Dichlorid (Nachtrag)." Zeitschrift für Elektrochemie, volume 38, page 27.
  8. P. G. Nelson and A. G. Sharpe (1966): "The variations in the thermal stabilities of the trichlorides, tribromides, and tri-iodides of the metals of the first transition series at 25 °C". Journal of the Chemical Society A: Inorganic, Physical, Theoretical, volume 1966,pages 501-511 doi:10.1039/J19660000501
  9. Scientific Group Thermodata Europe (2001): "Thermodynamic Properties of Compounds, CoCl
    3     to {[chem|NpCl|3}}". In: Landolt-Börnstein - Group IV Physical Chemistry, Part 3: Compounds from CoCl
    3    g to Ge
    3    N
    4    ; volume 19 A3. doi:10.1007/10551582_3 ISBN 978-3-540-66796-4
  10. Harald Schäfer and Günther Breil (1956): "Über die Neigung zur Bildung gasförmiger Trichloride bei den Elementen Cr, Mn, Fe, Co, Ni, untersucht mit der Reaktion MeCl
    2     gas + 1/2 Cl
    2     = MeCl
    3     gas". Zeitschrift für anorganische und allgemeine Chemie, volume 283, issue 1‐6, pages 304-313. doi:10.1002/zaac.19562830130
  11. T. J. Conocchioli, G. H. Nancollas, and N. Sutin (1965): "The kinetics of the formation and dissociation of the monochloro complex of cobalt(III)". Inorganic Chemistry, volume 5, issue 1, pages 1-5. doi:10.1021/ic50035a001
Salts and covalent derivatives of the chloride ion
HCl He
LiCl BeCl2 BCl3
B2Cl4		 CCl4 NCl3
ClN3		 Cl2O
ClO2
Cl2O7		 ClF
ClF3
ClF5		 Ne
NaCl MgCl2 AlCl
AlCl3		 SiCl4 P2Cl4
PCl3
PCl5		 S2Cl2
SCl2
SCl4		 Cl2 Ar
KCl CaCl
CaCl2		 ScCl3 TiCl2
TiCl3
TiCl4		 VCl2
VCl3
VCl4
VCl5		 CrCl2
CrCl3
CrCl4		 MnCl2 FeCl2
FeCl3		 CoCl2
CoCl3		 NiCl2 CuCl
CuCl2		 ZnCl2 GaCl2
GaCl3		 GeCl2
GeCl4		 AsCl3
AsCl5		 Se2Cl2
SeCl4		 BrCl KrCl
RbCl SrCl2 YCl3 ZrCl3
ZrCl4		 NbCl3
NbCl4
NbCl5		 MoCl2
MoCl3
MoCl4
MoCl5
MoCl6		 TcCl3
TcCl4		 RuCl3 RhCl3 PdCl2 AgCl CdCl2 InCl
InCl2
InCl3		 SnCl2
SnCl4		 SbCl3
SbCl5		 Te3Cl2
TeCl4		 ICl
ICl3		 XeCl
XeCl2
XeCl4
CsCl BaCl2   HfCl4 TaCl5 WCl2
WCl3
WCl4
WCl5
WCl6		 Re3Cl9
ReCl4
ReCl5
ReCl6		 OsCl4 IrCl2
IrCl3
IrCl4		 PtCl2
PtCl4		 AuCl
AuCl3		 Hg2Cl2,
HgCl2		 TlCl PbCl2,
PbCl4		 BiCl3 PoCl2,
PoCl4		 AtCl RnCl2
FrCl RaCl2   RfCl4 Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
LaCl3 CeCl3 PrCl3 NdCl2,
NdCl3		 PmCl3 SmCl2,
SmCl3		 EuCl2,
EuCl3		 GdCl3 TbCl3 DyCl2,
DyCl3		 HoCl3 ErCl3 TmCl2
TmCl3		 YbCl2
YbCl3		 LuCl3
AcCl3 ThCl4 PaCl5 UCl3
UCl4
UCl5
UCl6		 NpCl4 PuCl3 AmCl2
AmCl3		 CmCl3 BkCl3 CfCl3 EsCl3 Fm Md No LrCl3
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