3D model (JSmol)
CompTox Dashboard (EPA)
|Molar mass||134.45 g/mol (anhydrous)|
170.48 g/mol (dihydrate)
|Appearance||yellow-brown solid (anhydrous)|
blue-green solid (dihydrate)
|Density||3.386 g/cm3 (anhydrous) |
2.51 g/cm3 (dihydrate)
|Melting point|| 498 °C (928 °F; 771 K) (anhydrous) |
100 °C (dehydration of dihydrate)
|Boiling point||993 °C (1,819 °F; 1,266 K) (anhydrous, decomposes)|
|70.6 g/100 mL (0 °C) |
75.7 g/100 mL (25 °C)
107.9 g/100 mL (100 °C)
68 g/100 mL (15 °C)
|distorted CdI2 structure|
|H301, H302, H312, H315, H318, H319, H335, H410, H411|
|P261, P264, P270, P271, P273, P280, P301+P310, P301+P312, P302+P352, P304+P340, P305+P351+P338, P310, P312, P321, P322, P330, P332+P313, P337+P313, P362, P363, P391, P403+P233, P405, P501|
|NFPA 704 (fire diamond)|
|NIOSH (US health exposure limits):|
|TWA 1 mg/m3 (as Cu)|
|TWA 1 mg/m3 (as Cu)|
IDLH (Immediate danger)
|TWA 100 mg/m3 (as Cu)|
|Safety data sheet (SDS)||Fisher Scientific|
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
what is ?)(
Both the anhydrous and the dihydrate forms occur naturally as the very rare minerals tolbachite and eriochalcite, respectively.
Anhydrous CuCl2 adopts a distorted cadmium iodide structure. In this motif, the copper centers are octahedral. Most copper(II) compounds exhibit distortions from idealized octahedral geometry due to the Jahn-Teller effect, which in this case describes the localization of one d-electron into a molecular orbital that is strongly antibonding with respect to a pair of chloride ligands. In CuCl2·2H2O, the copper again adopts a highly distorted octahedral geometry, the Cu(II) centers being surrounded by two water ligands and four chloride ligands, which bridge asymmetrically to other Cu centers.
Properties and reactions
Aqueous solution prepared from copper(II) chloride contain a range of copper(II) complexes depending on concentration, temperature, and the presence of additional chloride ions. These species include blue color of [Cu(H2O)6]2+ and yellow or red color of the halide complexes of the formula [CuCl2+x]x−.
Copper(II) hydroxide precipitates upon treating copper(II) chloride solutions with base:
- CuCl2 + 2 NaOH → Cu(OH)2 + 2 NaCl
Partial hydrolysis gives dicopper chloride trihydroxide, Cu2(OH)3Cl, a popular fungicide.
- 2 CuCl2 → 2 CuCl + Cl2
Copper(II) chloride (CuCl2) reacts with several metals to produce copper metal or copper(I) chloride (CuCl) with oxidation of the other metal. To convert copper(II) chloride to copper(I) chloride, it can be convenient to reduce an aqueous solution with sulfur dioxide as the reductant:
- 2 CuCl2 + SO2 + 2 H2O → 2 CuCl + 2 HCl + H2SO4
CuCl2 reacts with HCl or other chloride sources to form complex ions: the red CuCl3− (it is a dimer in reality, Cu2Cl62−, a couple of tetrahedrons that share an edge), and the green or yellow CuCl42−.
2 + Cl−
2 + 2 Cl−
Some of these complexes can be crystallized from aqueous solution, and they adopt a wide variety of structures.
- CuCl2 + 2 C5H5N → [CuCl2(C5H5N)2] (tetragonal)
- CuCl2 + 2 (C6H5)3PO → [CuCl2((C6H5)3PO)2] (tetrahedral)
Copper(II) chloride is prepared commercially by the action of chlorination of copper. Copper at red heat (300-400°C) combines directly with chlorine gas, giving (molten) copper (II) chloride. The reaction is very exothermic.
- Cu(s) + Cl2(g) → CuCl2(l)
- CuO + 2NH4Cl → CuCl2 + 2NH3 + H2O
Once prepared, a solution of CuCl2 may be purified by crystallization. A standard method takes the solution mixed in hot dilute hydrochloric acid, and causes the crystals to form by cooling in a Calcium chloride (CaCl2)-ice bath.
There are indirect and rarely used means of using copper ions in solution to form copper(II) chloride. Electrolysis of aqueous sodium chloride with copper electrodes produces (among other things) a blue-green foam that can be collected and converted to the hydrate. While this is not usually done due to the emission of toxic chlorine gas, and the prevalence of the more general chloralkali process, the electrolysis will convert the copper metal to copper ions in solution forming the compound. Indeed, any solution of copper ions can be mixed with hydrochloric acid and made into a copper chloride by removing any other ions.
Copper(II) chloride occurs naturally as the very rare anhydrous mineral tolbachite and the dihydrate eriochalcite. Both are found near fumaroles and in some Cu mines. More common are mixed oxyhydroxide-chlorides like atacamite Cu2(OH)3Cl, arising among Cu ore beds oxidation zones in arid climate (also known from some altered slags).
In organic synthesis
Co-catalyst in Wacker process
A major industrial application for copper(II) chloride is as a co-catalyst with palladium(II) chloride in the Wacker process. In this process, ethene (ethylene) is converted to ethanal (acetaldehyde) using water and air. During the reaction, PdCl2 is reduced to Pd, and the CuCl2 serves to re-oxidize this back to PdCl2. Air can then oxidize the resultant CuCl back to CuCl2, completing the cycle.
- C2H4 + PdCl2 + H2O → CH3CHO + Pd + 2 HCl
- Pd + 2 CuCl2 → 2 CuCl + PdCl2
- 4 CuCl + 4 HCl + O2 → 4 CuCl2 + 2 H2O
The overall process is:
- 2 C2H4 + O2 → 2 CH3CHO
Other organic synthetic applications
Copper(II) chloride has some highly specialized applications in the synthesis of organic compounds. It affects chlorination of aromatic hydrocarbons—this is often performed in the presence of aluminium oxide. It is able to chlorinate the alpha position of carbonyl compounds:
CuCl2, in the presence of oxygen, can also oxidize phenols. The major product can be directed to give either a quinone or a coupled product from oxidative dimerization. The latter process provides a high-yield route to 1,1-binaphthol:
Such compounds are intermediates in the synthesis of BINAP and its derivatives.
In inorganic synthesis
Catalyst in production of chlorine
Copper(II) chloride is used as a catalyst in a variety of processes that produce chlorine by oxychlorination. The Deacon process takes place at about 400 to 450 °C in the presence of a copper chloride:
- 4 HCl + O2 → 2 Cl2 + 2 H2O
Copper(II) chloride is used in the Copper–chlorine cycle in which it splits steam into a copper oxygen compound and hydrogen chloride, and is later recovered in the cycle from the electrolysis of copper(I) chloride.
In humidity indicator cards (HICs), cobalt-free brown to azure (copper(II) chloride base) HICs can be found on the market. In 1998, the European Community (EC) classified items containing cobalt(II) chloride of 0.01 to 1% w/w as T (Toxic), with the corresponding R phrase of R49 (may cause cancer if inhaled). As a consequence, new cobalt-free humidity indicator cards have been developed that contain copper.
This section needs expansion. You can help by adding to it. (August 2021)
- NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH).
- Marlene C. Morris, Howard F. McMurdie, Eloise H. Evans, Boris Paretzkin, Harry S. Parker, and Nicolas C. Panagiotopoulos (1981) Copper chloride hydrate (eriochalcite), in Standard X-ray Diffraction Powder Patterns National Bureau of Standards, Monograph 25, Section 18; page 33.
- Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN 0-19-855370-6.
- Peter Baláž (2008). Mechanochemistry in Nanoscience and Minerals Engineering. Springer. p. 167. ISBN 978-3-540-74854-0.
- Marina Brustolon (2009). Electron paramagnetic resonance: a practitioner's toolkit. John Wiley and Sons. p. 3. ISBN 978-0-470-25882-8.
- Greenwood, N. N. and Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4.
- Naida S. Gill; F. B. Taylor (1967). Tetrahalo Complexes of Dipositive Metals in the First Transition Series. Inorganic Syntheses. Vol. 9. pp. 136–142. doi:10.1002/9780470132401.ch37. ISBN 978-0-470-13240-1.
- S. H. Bertz, E. H. Fairchild, in Handbook of Reagents for Organic Synthesis, Volume 1: Reagents, Auxiliaries and Catalysts for C-C Bond Formation, (R. M. Coates, S. E. Denmark, eds.), pp. 220-3, Wiley, New York, 1738.
- W. L. F. Armarego; Christina Li Lin Chai (2009-05-22). Purification of Laboratory Chemicals (Google Books excerpt) (6th ed.). Butterworth-Heinemann. p. 461. ISBN 978-1-85617-567-8.
- "List of Minerals". 21 March 2011.
- C. E. Castro; E. J. Gaughan; D. C. Owsley (1965). "Cupric Halide Halogenations". Journal of Organic Chemistry. 30 (2): 587. doi:10.1021/jo01013a069.
- J. Brussee; J. L. G. Groenendijk; J. M. Koppele; A. C. A. Jansen (1985). "On the mechanism of the formation of s(−)-(1, 1'-binaphthalene)-2,2'-diol via copper(II)amine complexes". Tetrahedron. 41 (16): 3313. doi:10.1016/S0040-4020(01)96682-7.
- Chandrasekhar, M.; Kusum L. Chandra; Vinod K. Singh (2003). "Total Synthesis of (+)-Boronolide, (+)-Deacetylboronolide, and (+)-Dideacetylboronolide". Journal of Organic Chemistry. 68 (10): 4039–4045. doi:10.1021/jo0269058. PMID 12737588.
- Krishna, Palakodety Radha; G. Dayaker (2007). "A stereoselective total synthesis of (−)-andrachcinidine via an olefin cross-metathesis protocol". Tetrahedron Letters. Elsevier. 48 (41): 7279–7282. doi:10.1016/j.tetlet.2007.08.053.
- H.Wayne Richardson, "Copper Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim, doi:10.1002/14356007.a07_567
- Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
- Lide, David R. (1990). CRC handbook of chemistry and physics: a ready-reference book of chemical and physical data. Boca Raton: CRC Press. ISBN 0-8493-0471-7.
- The Merck Index, 7th edition, Merck & Co, Rahway, New Jersey, USA, 1960.
- D. Nicholls, Complexes and First-Row Transition Elements, Macmillan Press, London, 1973.
- A. F. Wells, 'Structural Inorganic Chemistry, 5th ed., Oxford University Press, Oxford, UK, 1984.
- J. March, Advanced Organic Chemistry, 4th ed., p. 723, Wiley, New York, 1992.
- Fieser & Fieser Reagents for Organic Synthesis Volume 5, p158, Wiley, New York, 1975.
- D. W. Smith (1976). "Chlorocuprates(II)". Coordination Chemistry Reviews. 21 (2–3): 93–158. doi:10.1016/S0010-8545(00)80445-2.
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