Chemistry: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
3D model (JSmol)
ChemSpider
UNII
Properties
CuI
Molar mass 190.45 g/mol
Appearance White solid
Odor odorless
Density 5.67 g/cm3 [1]
Melting point 606 °C (1,123 °F; 879 K)
Boiling point 1,290 °C (2,350 °F; 1,560 K) (decomposes)
0.000042 g/100 mL
1.27 x 10−12 [2]
Solubility soluble in ammonia and iodide solutions
insoluble in dilute acids
Vapor pressure 10 mm Hg (656 °C)
-63.0·10−6 cm3/mol
2.346
Structure
zincblende
Tetrahedral anions and cations
Hazards
Safety data sheet Sigma Aldrich
GHS pictograms GHS05: CorrosiveGHS07: HarmfulGHS09: Environmental hazard
GHS Signal word DANGER
H302, H315, H319, H335, H410
P261, P273, P305+351+338, P501
NFPA 704 (fire diamond)
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilHealth code 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no codeNFPA 704 four-colored diamond
1
1
0
Flash point Non-flammable
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 1 mg/m3 (as Cu)[3]
REL (Recommended)
 TWA 1 mg/m3 (as Cu)[3]
IDLH (Immediate danger)
 TWA 100 mg/m3 (as Cu)[3]
Related compounds
Other anions
Other cations
 silver iodide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☑Y verify (what is ☑Y☒N ?)
Infobox references

Copper(I) iodide is the inorganic compound with the 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.[4][5][6]

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.[7] Consistent with its covalency, CuI is a p-type semiconductor.[8]

Copper(I)-iodide-unit-cell-3D-balls.png 150px Copper(I)-iodide-(alpha)-unit-cell-3D-balls.png
γ-CuI β-CuI α-CuI

Preparation

Copper(I) iodide can be prepared by heating iodine and copper in concentrated hydriodic acid.[9]

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.[4]

Cu2+ + 2I− → CuI + 0.5 I2

Reactions

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

4 CuI + Hg → Cu2HgI4 + 2 Cu

This reaction can be used for the detection of mercury since the white (CuI) to brown (Cu2HgI4) color change is dramatic.

Copper(I) iodide is used in the synthesis of Cu(I) clusters such as Cu
6I−
7.[10]

Copper(I) iodide dissolves in acetonitrile, yielding diverse complexes. Upon crystallization, molecular[11] or polymeric[12][13] 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.[14]

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).[15]

CuI is used as a co-catalyst with palladium catalyst in the Sonogashira coupling.[16]

CuI is used in cloud seeding,[17] 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.[citation needed]

CuI is used as a source of dietary iodine in table salt and animal feed.[17]

References

  1. ↑ Lide, David R., ed (2006). CRC Handbook of Chemistry and Physics (87th ed.). Boca Raton, FL: CRC Press. ISBN 0-8493-0487-3. 
  2. ↑ John Rumble (June 18, 2018) (in English). CRC Handbook of Chemistry and Physics (99th ed.). CRC Press. pp. 4–47. ISBN 978-1138561632. 
  3. ↑ 3.0 3.1 3.2 NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/npg/npgd0150.html. 
  4. ↑ 4.0 4.1 George B. Kauffman, Lawrence W. Fang (1983). Copper(I) Iodide. Inorganic Syntheses. 22. p. 101. doi:10.1002/9780470132531.ch20. 
  5. ↑ "Verification". https://www.mindat.org/min-2580.html. 
  6. ↑ "List of Minerals". 21 March 2011. https://www.ima-mineralogy.org/Minlist.htm. 
  7. ↑ Structural Inorganic Chemistry (5th ed.). Oxford: Oxford University Press. 1984. 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. ↑ Inorganic Chemistry. San Diego: Academic Press. 2001. ISBN 0-12-352651-5. 
  10. ↑ Yu, Muxin; Chen, Lian; Jiang, Feilong; Zhou, Kang; Liu, Caiping; Sun, Cai; Li, Xingjun; Yang, Yan et al. (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. ↑ "Crystal structure of di-μ-iodido-bis-[bis(aceto-nitrile-κN)copper(I)"]. Acta Crystallographica Section E 71 (Pt 11): m189-90. November 2015. doi:10.1107/S2056989015018149. PMID 26594527. 
  12. ↑ "Lewis-Base Adducts of Group 11 Metal(I) Compounds. XL. Conformational Systematics of [(N-base)1(CuX)1]∞ Orthogonal' Stair' Polymers (N-base = 'One-Dimensional Aceto-nitrile, Benzo-nitrile Ligand)" (in en). Australian Journal of Chemistry 42 (1): 79. 1989. doi:10.1071/CH9890079. ISSN 0004-9425. 
  13. ↑ "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)2TaH[(μ2-H)Cu(μ2-I)2Cu(μ2-H)]2HTa(η5-C5H5)2, (η5-C5H4But)2TaH(μ2-H)2Cu(μ2-I)2Cu(μ2-H)2HTa(η5-C5H4But)2·CH3CN and {Cu(μ3-I)·P[N(CH3)2]3}4" (in en). Inorganica Chimica Acta 169 (1): 109–118. 1990. doi:10.1016/S0020-1693(00)82043-5. 
  14. ↑ "Copper(I) iodide ribbons coordinated with thiourea derivatives". Acta Crystallographica Section C 74 (Pt 12): 1650–1655. December 2018. doi:10.1107/S2053229618015620. PMID 30516149. 
  15. ↑ "Copper-catalyzed halogen exchange in aryl halides: an aromatic Finkelstein reaction". Journal of the American Chemical Society 124 (50): 14844–5. December 2002. doi:10.1021/ja028865v. PMID 12475315. 
  16. ↑ Sonogashira, K. (2002), "Development of Pd-Cu catalyzed cross-coupling of terminal acetylenes with sp2-carbon halides", J. Organomet. Chem. 653 (1–2): 46–49, doi:10.1016/s0022-328x(02)01158-0 
  17. ↑ 17.0 17.1 "Copper compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. June 2000. pp. 1–31. doi:10.1002/14356007.a07_567. ISBN 3527306730. 

Further reading

  • Dictionary of Inorganic Compounds. 3. London: Chapman and Hall. 1992. pp. 3103. 

External links

HI He
LiI BeI2 BI3 CI4 NI3 I2O4,
I2O5,
I4O9 		IF,
IF3,
IF5,
IF7 		Ne
NaI MgI2 AlI3 SiI4 PI3,
P2I4 		S ICl,
ICl3 		Ar
KI CaI2 Sc TiI4 VI3 CrI3 MnI2 FeI2 CoI2 NiI2 CuI ZnI2 Ga2I6 GeI2,
GeI4 		AsI3 Se IBr Kr
RbI SrI2 YI3 ZrI4 NbI5 Mo Tc Ru Rh Pd AgI CdI2 InI3 SnI4,
SnI2 		SbI3 TeI4 I Xe
CsI BaI2   HfI4 TaI5 W Re Os Ir Pt AuI Hg2I2,
HgI2 		TlI PbI2 BiI3 Po AtI Rn
Fr RaI2   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La Ce Pr Nd Pm SmI2 Eu Gd TbI3 Dy Ho Er Tm Yb Lu
Ac ThI4 Pa UI3,
UI4 		Np Pu Am Cm Bk Cf EsI3 Fm Md No Lr



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