Copper(I) oxide
Copper(I) oxide or cuprous oxide is the inorganic compound with the formula Cu2O. It is one of the principal oxides of copper, the other being copper(II) oxide or cupric oxide (CuO). Cuprous oxide is a red-coloured solid and is a component of some antifouling paints. The compound can appear either yellow or red, depending on the size of the particles.[3] Copper(I) oxide is found as the reddish mineral cuprite.
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| IUPAC name Copper(I) oxide | |
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| ECHA InfoCard | 100.013.883 |
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| Properties | |
| Cu2O | |
| Molar mass | 143.09 g/mol |
| Appearance | brownish-red solid |
| Density | 6.0 g/cm3 |
| Melting point | 1,232 °C (2,250 °F; 1,505 K) |
| Boiling point | 1,800 °C (3,270 °F; 2,070 K) |
| Insoluble | |
| Solubility in acid | Soluble |
| Band gap | 2.137 eV |
| −20×10−6 cm3/mol | |
| Structure | |
| cubic | |
| Pn3m, #224 | |
a = 4.2696 | |
| Thermochemistry | |
Std molar entropy (S⦵298) | 93 J·mol−1·K−1 |
Std enthalpy of formation (ΔfH⦵298) | −170 kJ·mol−1 |
| Hazards | |
| GHS labelling: | |
| Danger | |
| H302, H318, H332, H410 | |
| P273, P305+P351+P338[1] | |
| NFPA 704 (fire diamond) | |
| NIOSH (US health exposure limits): | |
PEL (Permissible) | TWA 1 mg/m3 (as Cu)[2] |
REL (Recommended) | TWA 1 mg/m3 (as Cu)[2] |
IDLH (Immediate danger) | TWA 100 mg/m3 (as Cu)[2] |
| Safety data sheet (SDS) | SIRI.org |
| Related compounds | |
Other anions | Copper(I) sulfide Copper(II) sulfide Copper(I) selenide |
Other cations | Copper(II) oxide Silver(I) oxide Nickel(II) oxide Zinc oxide |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
Preparation edit
Copper(I) oxide may be produced by several methods.[4] Most straightforwardly, it arises via the oxidation of copper metal:
- 4 Cu + O2 → 2 Cu2O
Additives such as water and acids affect the rate of this process as well as the further oxidation to copper(II) oxides. It is also produced commercially by reduction of copper(II) solutions with sulfur dioxide.
Alternatively, it may be prepared via the reduction of Copper (II) Hydroxide with hydrogen peroxide during "a complex mechanism with the participation of three different reaction pathways is involved." with the final reducing reaction being:[5]
2 CuOOH+ → 2Cu(I) + H2O2 + O2
2Cu 2+ + OH- + H2O2 → 2Cu + + O2 + H2O [6]
Reactions edit
Aqueous cuprous chloride solutions react with base to give the same material. In all cases, the color is highly sensitive to the procedural details.
Formation of copper(I) oxide is the basis of the Fehling's test and Benedict's test for reducing sugars. These sugars reduce an alkaline solution of a copper(II) salt, giving a bright red precipitate of Cu2O.
It forms on silver-plated copper parts exposed to moisture when the silver layer is porous or damaged. This kind of corrosion is known as red plague.
Little evidence exists for copper(I) hydroxide CuOH, which is expected to rapidly undergo dehydration. A similar situation applies to the hydroxides of gold(I) and silver(I).
Properties edit
The solid is diamagnetic. In terms of their coordination spheres, copper centres are 2-coordinated and the oxides are tetrahedral. The structure thus resembles in some sense the main polymorphs of SiO2, but cuprous oxide's lattices interpenetrate.
Copper(I) oxide dissolves in concentrated ammonia solution to form the colourless complex [Cu(NH3)2]+, which is easily oxidized in air to the blue [Cu(NH3)4(H2O)2]2+. It dissolves in hydrochloric acid to give solutions of CuCl−
2. Dilute sulfuric acid and nitric acid produce copper(II) sulfate and copper(II) nitrate, respectively.[7]
Cu2O degrades to copper(II) oxide in moist air.
Structure edit
Cu2O crystallizes in a cubic structure with a lattice constant al = 4.2696 Å. The copper atoms arrange in a fcc sublattice, the oxygen atoms in a bcc sublattice. One sublattice is shifted by a quarter of the body diagonal. The space group is Pn3m, which includes the point group with full octahedral symmetry.
Semiconducting properties edit
In the history of semiconductor physics, Cu2O is one of the most studied materials, and many experimental semiconductor applications have been demonstrated first in this material:
- Semiconductor
- Semiconductor diodes[8]
- Phonoritons ("a coherent superposition of exciton, photon, and phonon")[9][10]
The lowest excitons in Cu2O are extremely long lived; absorption lineshapes have been demonstrated with neV linewidths, which is the narrowest bulk exciton resonance ever observed.[11] The associated quadrupole polaritons have low group velocity approaching the speed of sound. Thus, light moves almost as slowly as sound in this medium, which results in high polariton densities. Another unusual feature of the ground state excitons is that all primary scattering mechanisms are known quantitatively.[12] Cu2O was the first substance where an entirely parameter-free model of absorption linewidth broadening by temperature could be established, allowing the corresponding absorption coefficient to be deduced. It can be shown using Cu2O that the Kramers–Kronig relations do not apply to polaritons.[13]
Applications edit
Cuprous oxide is commonly used as a pigment, a fungicide, and an antifouling agent for marine paints. Rectifier diodes based on this material have been used industrially as early as 1924, long before silicon became the standard. Copper(I) oxide is also responsible for the pink color in a positive Benedict's test.
In December 2021, Toshiba announced the creation of a transparent cuprous oxide (Cu2O) thin-film solar cell. The cell achieved an 8.4% energy conversion efficiency, the highest efficiency ever reported for any cell of this type as of 2021. The cells could be used for high-altitude platform station applications and electric vehicles.[14]
Similar compounds edit
An example of natural copper(I,II) oxide is the mineral paramelaconite, Cu4O3 or CuI
2CuII
2O3.[15][16]
See also edit
References edit
- ^ https://www.nwmissouri.edu/naturalsciences/sds/c/Copper%20I%20oxide.pdf[dead link]
- ^ a b c NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH).
- ^ N. N. Greenwood, A. Earnshaw, Chemistry of the Elements, 2nd ed., Butterworth-Heinemann, Oxford, UK, 1997.
- ^ H. Wayne Richardson "Copper Compounds in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim. doi:10.1002/14356007.a07_567
- ^ Perez-Benito, Joaquin F. (2004-03-01). "Reaction pathways in the decomposition of hydrogen peroxide catalyzed by copper(II)". Journal of Inorganic Biochemistry. 98 (3): 430–438. doi:10.1016/j.jinorgbio.2003.10.025. ISSN 0162-0134. PMID 14987843.
- ^ Yener, Ersin (September 2017). "Improvement of Stability of Hydrogen Peroxide using Ethylene Glycol".
- ^ D. Nicholls, Complexes and First-Row Transition Elements, Macmillan Press, London, 1973.
- ^ L. O. Grondahl, Unidirectional current carrying device, Patent, 1927
- ^ Hanke, L.; Fröhlich, D.; Ivanov, A. L.; Littlewood, P. B.; Stolz, H. (1999-11-22). "LA Phonoritons in Cu2O". Physical Review Letters. 83 (21): 4365–4368. Bibcode:1999PhRvL..83.4365H. doi:10.1103/PhysRevLett.83.4365.
- ^ L. Brillouin: Wave Propagation and Group Velocity, Academic Press, New York City, 1960 ISBN 9781483276014.
- ^ Brandt, Jan; Fröhlich, Dietmar; Sandfort, Christian; Bayer, Manfred; Stolz, Heinrich; Naka, Nobuko (2007-11-19). "Ultranarrow Optical Absorption and Two-Phonon Excitation Spectroscopy of Cu2O Paraexcitons in a High Magnetic Field". Physical Review Letters. American Physical Society (APS). 99 (21): 217403. Bibcode:2007PhRvL..99u7403B. doi:10.1103/physrevlett.99.217403. ISSN 0031-9007. PMID 18233254.
- ^ J. P. Wolfe and A. Mysyrowicz: Excitonic Matter, Scientific American 250 (1984), No. 3, 98.
- ^ Hopfield, J. J. (1958). "Theory of the Contribution of Excitons to the Complex Dielectric Constant of Crystals". Physical Review. 112 (5): 1555–1567. Bibcode:1958PhRv..112.1555H. doi:10.1103/PhysRev.112.1555. ISSN 0031-899X.
- ^ Bellini, Emiliano (2021-12-22). "Toshiba claims 8.4% efficiency for transparent cuprous oxide solar cell". pv magazine. Retrieved 2021-12-22.
- ^ "Paramelaconite".
- ^ "List of Minerals". 21 March 2011.
External links edit
- Chemical Land21 Product Information page
- Copper oxides project page 2011-07-25 at the Wayback Machine