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Bismuth chloride

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(Redirected from Bismuth(III) chloride)
Bismuth chloride
Bismuth chloride
Names
IUPAC name Bismuth chloride
Other names Bismuth trichloride, Trichlorobismuth, Trichlorobismuthine, Bismuth(III) chloride
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.029.203 Edit this at Wikidata
PubChem CID
RTECS number
  • EB2690000
UNII
CompTox Dashboard (EPA)
InChI
  • InChI=1S/Bi.3ClH/h;3*1H/q+3;;;/p-3Key: JHXKRIRFYBPWGE-UHFFFAOYSA-K
  • InChI=1/Bi.3ClH/h;3*1H/q+3;;;/p-3Key: JHXKRIRFYBPWGE-DFZHHIFOAJ
SMILES
  • Cl(Cl)Cl
Properties
Chemical formula BiCl3
Molar mass 315.34 g/mol
Appearance hygroscopic white to yellow crystals
Density 4.75 g/cm
Melting point 227 °C (441 °F; 500 K)
Boiling point 447 °C (837 °F; 720 K)
Solubility in water Soluble,hydrolyses
Solubility soluble in methanol, diethyl ether, acetone
Magnetic susceptibility (χ) -26.5·10 cm/mol
Structure
Crystal structure cubic
Thermochemistry
Heat capacity (C) 0.333 J/(g K)
Std molar
entropy
(S298)
82.9 J/(K mol)
Std enthalpy of
formation
fH298)
-1.202 kJ/g
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2 0 0
Lethal dose or concentration (LD, LC):
LD50 (median dose) 3324 mg/kg, oral (rat)
Safety data sheet (SDS) JT Baker
Related compounds
Other anions bismuth fluoride, bismuth subsalicylate, bismuth trioxide
Other cations iron(III) chloride, manganese(II) chloride, cobalt(II) chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒verify (what is  ?) Infobox references
Chemical compound

Bismuth chloride (or butter of bismuth) is an inorganic compound with the chemical formula BiCl3. It is a covalent compound and is the common source of the Bi ion. In the gas phase and in the crystal, the species adopts a pyramidal structure, in accord with VSEPR theory.

Preparation

Bismuth chloride can be synthesized directly by passing chlorine over bismuth.

2 Bi + 3 Cl2 → 2 BiCl3

or by dissolving bismuth metal in aqua regia, evaporating the mixture to give BiCl3·2H2O, which can be distilled to form the anhydrous trichloride.

Alternatively, it may be prepared by adding hydrochloric acid to bismuth oxide and evaporating the solution.

Bi2O3 + 6 HCl → 2 BiCl3 + 3 H2O

Also, the compound can be prepared by dissolving bismuth in concentrated nitric acid and then adding solid sodium chloride into this solution.

Bi + 6 HNO3 → Bi(NO3)3 + 3 H2O + 3 NO2
Bi(NO3)3 + 3 NaCl → BiCl3 + 3 NaNO3

Structure

In the gas phase BiCl3 is pyramidal with a Cl–Bi–Cl angle of 97.5° and a bond length of 242 pm. In the solid state, each Bi atom has three near neighbors at 250 pm, two at 324 pm and three at a mean of 336 pm, the image above highlights the three closest neighbours. This structure is similar to that of AsCl3, AsBr3, SbCl3 and SbBr3.

Chemistry

Bismuth chloride is hydrolyzed readily to bismuth oxychloride, BiOCl:

Bi
(aq) + Cl
(aq) + H
2O(l) ⇌ BiOCl (s) + 2 H
(aq)

This reaction can be reversed by adding an acid, such as hydrochloric acid.

Reaction of solid BiCl3 with water vapour below 50 °C has been shown to produce the intermediate monohydrate, BiCl3·H2O.

Bismuth chloride is an oxidizing agent, being readily reduced to metallic bismuth by reducing agents.

Chloro complexes

In contrast to the usual expectation by consistency with periodic trends, BiCl3 is a Lewis acid, forming a variety of chloro complexes such as that strongly violates the octet rule. Furthermore, the octahedral structure of this coordination complex does not follow the predictions of VSEPR theory, since the lone pair on bismuth is unexpectedly stereochemically inactive. The dianionic complex does however adopt the expected square pyramidal structure.

Cs3 Cs3

Organic catalysis

Bismuth chloride is used as a catalyst in organic synthesis. In particular, it catalyzes the Michael reaction and the Mukaiyama aldol reaction. The addition of other metal iodides increases its catalytic activity.

References

  1. Godfrey, S. M.; McAuliffe, C. A.; Mackie, A. G.; Pritchard, R. G. (1998). Nicholas C. Norman (ed.). Chemistry of arsenic, antimony, and bismuth. Springer. p. 90. ISBN 0-7514-0389-X.
  2. Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0-07-049439-8
  3. Töke, Orsolya, and Magdolna Hargittai. "Molecular structure of bismuth trichloride from combined electron diffraction and vibrational spectroscopic study." Structural Chemistry 6.2 (1995): 127–130.
  4. Wells A.F. (1984) Structural Inorganic Chemistry 5th edition, pp. 879–884, Oxford Science Publications, ISBN 0-19-855370-6
  5. Joel Henry Hildebrand (2008). Principles of Chemistry. BiblioBazaar, LLC. p. 191. ISBN 978-0-559-31877-1.
  6. Frank Welcher (2008). Chemical Solutions. READ BOOKS. p. 48. ISBN 978-1-4437-2907-9.
  7. Wosylus, Aron; Hoffmann, Stefan; Schmidt, Marcus; Ruck, Michael (2010). "In-situ Study of the Solid-Gas Reaction of BiCl3 to BiOCl via the Intermediate Hydrate BiCl3·H2O". European Journal of Inorganic Chemistry. 2010 (10): 1469–1471. doi:10.1002/ejic.201000032. ISSN 1434-1948.
  8. Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  9. Hitomi Suzuki; Yoshihiro Matano (2001). Organobismuth chemistry. Elsevier. pp. 403–404. ISBN 0-444-20528-4.
Bismuth compounds
Bismuth(III)
Organobismuth(III)
Bismuth(V)
Organobismuth(V)
Salts and covalent derivatives of the chloride ion
HCl He
LiCl BeCl2 B4Cl4
B12Cl12
BCl3
B2Cl4
+BO3
C2Cl2
C2Cl4
C2Cl6
CCl4
+C
+CO3
NCl3
ClN3
+N
+NO3
ClxOy
Cl2O
Cl2O2
ClO
ClO2
Cl2O4
Cl2O6
Cl2O7
ClO4
+O
ClF
ClF3
ClF5
Ne
NaCl MgCl2 AlCl
AlCl3
Si5Cl12
Si2Cl6
SiCl4
P2Cl4
PCl3
PCl5
+P
S2Cl2
SCl2
SCl4
+SO4
Cl2 Ar
KCl CaCl
CaCl2
ScCl3 TiCl2
TiCl3
TiCl4
VCl2
VCl3
VCl4
VCl5
CrCl2
CrCl3
CrCl4
MnCl2
MnCl3
FeCl2
FeCl3
CoCl2
CoCl3
NiCl2 CuCl
CuCl2
ZnCl2 GaCl
GaCl3
GeCl2
GeCl4
AsCl3
AsCl5
+As
Se2Cl2
SeCl2
SeCl4
BrCl Kr
RbCl SrCl2 YCl3 ZrCl2
ZrCl3
ZrCl4
NbCl3
NbCl4
NbCl5
MoCl2
MoCl3
MoCl4
MoCl5
MoCl6
TcCl3
TcCl4
RuCl2
RuCl3
RuCl4
RhCl3 PdCl2 AgCl CdCl2 InCl
InCl2
InCl3
SnCl2
SnCl4
SbCl3
SbCl5
Te3Cl2
TeCl2
TeCl4
ICl
ICl3
XeCl
XeCl2
XeCl4
CsCl BaCl2 * LuCl3 HfCl4 TaCl3
TaCl4
TaCl5
WCl2
WCl3
WCl4
WCl5
WCl6
ReCl3
ReCl4
ReCl5
ReCl6
OsCl2
OsCl3
OsCl4
OsCl5
IrCl2
IrCl3
IrCl4
PtCl2
PtCl4
AuCl
(Au)2
AuCl3
Hg2Cl2
HgCl2
TlCl
TlCl3
PbCl2
PbCl4
BiCl3 PoCl2
PoCl4
AtCl Rn
FrCl RaCl2 ** LrCl3 RfCl4 DbCl5 SgO2Cl2 BhO3Cl 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
** AcCl3 ThCl3
ThCl4
PaCl4
PaCl5
UCl3
UCl4
UCl5
UCl6
NpCl3 PuCl3 AmCl2
AmCl3
CmCl3 BkCl3 CfCl3
CfCl2
EsCl2
EsCl3
FmCl2 MdCl2 NoCl2
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