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Copper(I) iodide

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Copper(I) iodide
Copper(I) iodide
Names
IUPAC name Copper(I) iodide
Other names Cuprous iodide, marshite
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.028.795 Edit this at Wikidata
PubChem CID
UNII
CompTox Dashboard (EPA)
InChI
  • InChI=1S/Cu.HI/h;1H/q+1;/p-1Key: LSXDOTMGLUJQCM-UHFFFAOYSA-M
  • InChI=1/Cu.HI/h;1H/q+1;/p-1Key: LSXDOTMGLUJQCM-REWHXWOFAV
SMILES
  • I
Properties
Chemical formula CuI
Molar mass 190.450 g·mol
Appearance White solid
Odor odorless
Density 5.67 g/cm
Melting point 606 °C (1,123 °F; 879 K)
Boiling point 1,290 °C (2,350 °F; 1,560 K) (decomposes)
Solubility in water 0.000042 g/100 mL
Solubility product (Ksp) 1.27 x 10
Solubility soluble in ammonia and iodide solutions
insoluble in dilute acids
Vapor pressure 10 mm Hg (656 °C)
Magnetic susceptibility (χ) −63.0·10 cm/mol
Refractive index (nD) 2.346
Structure
Crystal structure zincblende
Coordination geometry Tetrahedral anions and cations
Hazards
GHS labelling:
Pictograms GHS05: CorrosiveGHS07: Exclamation markGHS09: Environmental hazard
Signal word Danger
Hazard statements H302, H315, H319, H335, H410
Precautionary statements P261, P273, P305+P351+P338, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
1 1 0
Flash point Non-flammable
NIOSH (US health exposure limits):
PEL (Permissible) TWA 1 mg/m (as Cu)
REL (Recommended) TWA 1 mg/m (as Cu)
IDLH (Immediate danger) TWA 100 mg/m (as Cu)
Safety data sheet (SDS) Sigma Aldrich
Related compounds
Other anions
Other cations
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkverify (what is  ?) Infobox references
Chemical compound

Copper(I) iodide is an inorganic compound with the chemical formula CuI. It is also known as cuprous iodide. It is useful in a variety of applications ranging from organic synthesis to cloud seeding.

Copper(I) iodide is white, but samples often appear tan or even, when found in nature as rare mineral marshite, reddish brown, but such color is due to the presence of impurities. It is common for samples of iodide-containing compounds to become discolored due to the facile aerobic oxidation of the iodide anion to molecular iodine.

Structure

Copper(I) iodide, like most binary (containing only two elements) metal halides, is an inorganic polymer. It has a rich phase diagram, meaning that it exists in several crystalline forms. It adopts a zinc blende structure below 390 °C (γ-CuI), a wurtzite structure between 390 and 440 °C (β-CuI), and a rock salt structure above 440 °C (α-CuI). The ions are tetrahedrally coordinated when in the zinc blende or the wurtzite structure, with a Cu-I distance of 2.338 Å. Copper(I) bromide and copper(I) chloride also transform from the zinc blende structure to the wurtzite structure at 405 and 435 °C, respectively. Therefore, the longer the copper–halide bond length, the lower the temperature needs to be to change the structure from the zinc blende structure to the wurtzite structure. The interatomic distances in copper(I) bromide and copper(I) chloride are 2.173 and 2.051 Å, respectively. Consistent with its covalency, CuI is a p-type semiconductor.

γ-CuI β-CuI α-CuI

Preparation

Copper(I) iodide can be prepared by heating iodine and copper in concentrated hydroiodic acid.

In the laboratory however, copper(I) iodide is prepared by simply mixing an aqueous solution of potassium iodide and a soluble copper(II) salt such as copper(II) sulfate.

2 Cu + 4 I → 2 CuI + I2

Reactions

Copper(I) iodide reacts with mercury vapors to form brown copper(I) tetraiodomercurate(II):

4 CuI + Hg → (Cu)2[HgI4] + 2 Cu

This reaction can be used for the detection of mercury since the white CuI to brown Cu2[HgI4] color change is dramatic.

Copper(I) iodide is used in the synthesis of Cu(I) clusters such as [Cu6I7].

Copper(I) iodide dissolves in acetonitrile, yielding diverse complexes. Upon crystallization, molecular or polymeric compounds can be isolated. Dissolution is also observed when a solution of the appropriate complexing agent in acetone or chloroform is used. For example, thiourea and its derivatives can be used. Solids that crystallize out of those solutions are composed of hybrid inorganic chains.

Uses

In combination with 1,2- or 1,3-diamine ligands, CuI catalyzes the conversion of aryl, heteroaryl, and vinyl bromides into the corresponding iodides. NaI is the typical iodide source and dioxane is a typical solvent (see aromatic Finkelstein reaction).

CuI is used as a co-catalyst with palladium catalyst in the Sonogashira coupling.

CuI is used in cloud seeding, altering the amount or type of precipitation of a cloud, or their structure by dispersing substances into the atmosphere which increase water's ability to form droplets or crystals. CuI provides a sphere for moisture in the cloud to condense around, causing precipitation to increase and cloud density to decrease.

The structural properties of CuI allow CuI to stabilize heat in nylon in commercial and residential carpet industries, automotive engine accessories, and other markets where durability and weight are a factor.

CuI is used as a source of dietary iodine in table salt and animal feed.

References

  1. Lide, David R., ed. (2006). CRC Handbook of Chemistry and Physics (87th ed.). Boca Raton, Florida: CRC Press. ISBN 0-8493-0487-3.
  2. John Rumble (June 18, 2018). CRC Handbook of Chemistry and Physics (99th ed.). CRC Press. pp. 4–47. ISBN 978-1138561632.
  3. ^ NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH).
  4. ^ George B. Kauffman, Lawrence W. Fang (1983). Copper(I) Iodide. Inorganic Syntheses. Vol. 22. p. 101. doi:10.1002/9780470132531.ch20.
  5. "Verification".
  6. "List of Minerals". 21 March 2011.
  7. Wells AF (1984). Structural Inorganic Chemistry (5th ed.). Oxford: Oxford University Press. pp. 410 and 444.
  8. Bidikoudi, Maria; Kymakis, Emmanuel (2019). "Novel approaches and scalability prospects of copper based hole transporting materials for planar perovskite solar cells". Journal of Materials Chemistry C. 7 (44): 13680–13708. doi:10.1039/c9tc04009a.
  9. Holleman AF, Wiberg E (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
  10. Yu M, Chen L, Jiang F, Zhou K, Liu C, Sun C, Li X, Yang Y, Hong M (2017). "Cation-Induced Strategy toward an Hourglass-Shaped Cu6I7– Cluster and its Color-Tunable Luminescence". Chemistry of Materials. 29 (19): 8093–8099. doi:10.1021/acs.chemmater.7b01790.
  11. Barth ER, Golz C, Knorr M, Strohmann C (November 2015). "Crystal structure of di-μ-iodido-bis-[bis(aceto-nitrile-κN)copper(I)]". Acta Crystallographica Section E. 71 (Pt 11): m189-90. doi:10.1107/S2056989015018149. PMC 4645014. PMID 26594527.
  12. Healy PC, Kildea JD, Skelton BW, White AH (1989). "Lewis-Base Adducts of Group 11 Metal(I) Compounds. XL. Conformational Systematics of ∞ Orthogonal' Stair' Polymers (N-base = 'One-Dimensional Aceto-nitrile, Benzo-nitrile Ligand)". Australian Journal of Chemistry. 42 (1): 79. doi:10.1071/CH9890079. ISSN 0004-9425.
  13. Arkhireeva TM, Bulychev BM, Sizov AI, Sokolova TA, Belsky VK, Soloveichik GL (1990). "Copper(I) complexes with metal-metal (d10–d10) bond. Crystal and molecular structures of adducts of tantalocene trihydride with copper(I) iodide of composition: (η5-C5H5)2TaH2HTa(η5-C5H5)2, (η5-C5H4But)2TaH(μ2-H)2Cu(μ2-I)2Cu(μ2-H)2HTa(η5-C5H4But)2·CH3CN and {Cu(μ3-I)·P3}4". Inorganica Chimica Acta. 169 (1): 109–118. doi:10.1016/S0020-1693(00)82043-5.
  14. Rosiak D, Okuniewski A, Chojnacki J (December 2018). "Copper(I) iodide ribbons coordinated with thiourea derivatives". Acta Crystallographica Section C. 74 (Pt 12): 1650–1655. doi:10.1107/S2053229618015620. PMID 30516149. S2CID 54615309.
  15. Klapars A, Buchwald SL (December 2002). "Copper-catalyzed halogen exchange in aryl halides: an aromatic Finkelstein reaction". Journal of the American Chemical Society. 124 (50): 14844–5. doi:10.1021/ja028865v. PMID 12475315. S2CID 11338218.
  16. Sonogashira, K. (2002), "Development of Pd-Cu catalyzed cross-coupling of terminal acetylenes with sp-carbon halides", J. Organomet. Chem., 653 (1–2): 46–49, doi:10.1016/s0022-328x(02)01158-0
  17. ^ Zhang J, Richardson HW (June 2000). "Copper compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. pp. 1–31. doi:10.1002/14356007.a07_567. ISBN 3527306730.

Further reading

  • Macintyre J (1992). Dictionary of Inorganic Compounds. Vol. 3. London: Chapman and Hall. p. 3103.

External links

Copper compounds
Cu(0,I)
Cu(I)
Cu(I,II)
Cu(II)
Cu(III)
Cu(IV)
Salts and covalent derivatives of the iodide ion
HI
+H
He
LiI BeI2 BI3
+BO3
CI4
+C
NI3
NH4I
+N
I2O4
I2O5
I2O6
I4O9
IF
IF3
IF5
IF7
Ne
NaI MgI2 AlI
AlI3
SiI4 PI3
P2I4
+P
PI5
S2I2 ICl
ICl3
Ar
KI CaI2 ScI3 TiI2
TiI3
TiI4
VI2
VI3
CrI2
CrI3
CrI4
MnI2 FeI2
FeI3
CoI2 NiI2
-Ni
CuI ZnI2 GaI
GaI3
GeI2
GeI4
+Ge
AsI3
As2I4
+As
Se IBr
IBr3
Kr
RbI
RbI3
SrI2 YI3 ZrI2
ZrI3
ZrI4
NbI4
NbI5
MoI2
MoI3
TcI3 RuI3 RhI3 PdI2 AgI CdI2 InI
InI3
SnI2
SnI4
SbI3
+Sb
TeI4
+Te
I
I
3
Xe
CsI
CsI3
BaI2   LuI3 HfI3
HfI4
TaI4
TaI5
WI2
WI3
WI4
ReI3
ReI
4
OsI
OsI2
OsI3
IrI3
IrI
4
PtI2
PtI4
AuI
AuI3
Hg2I2
HgI2
TlI
TlI3
PbI2 BiI3 PoI2
PoI4
AtI Rn
Fr RaI2   Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
LaI2
LaI3
CeI2
CeI3
PrI2
PrI3
NdI2
NdI3
PmI3 SmI2
SmI3
EuI2
EuI3
GdI2
GdI3
TbI3 DyI2
DyI
3
HoI3 ErI3 TmI2
TmI3
YbI2
YbI3
AcI3 ThI2
ThI3
ThI4
PaI4
PaI5
UI3
UI4
NpI3 PuI3 AmI2
AmI3
CmI3 BkI
3
CfI
2

CfI
3
EsI2
EsI3
Fm Md No
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