Cadmium sulfide

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Cadmium sulfide
3D model of the structure of hawleyite
3D model of the structure of greenockite
Cadmium sulfide.jpg
Names
Other names
Cadmium(II) sulfide,
Greenockite
Hawleyite
Identifiers
1306-23-6 YesY
ChemSpider 7969586 YesY
EC Number 215-147-8
Jmol 3D model Interactive image
PubChem 14783
RTECS number EV3150000
UNII 057EZR4Z7Q YesY
UN number 2570
  • InChI=1S/Cd.S/q+2;-2 YesY
    Key: FRLJSGOEGLARCA-UHFFFAOYSA-N YesY
  • InChI=1/Cd.S/q+2;-2
    Key: FRLJSGOEGLARCA-UHFFFAOYAL
  • [S-2].[Cd+2]
Properties
CdS
Molar mass 144.47 g·mol−1
Appearance Yellow-orange to brown solid.
Density 4.826 g/cm3, solid.
Melting point 1,750 °C (3,180 °F; 2,020 K) 10 MPa
Boiling point 980 °C (1,800 °F; 1,250 K) (sublimation)
insoluble[1]
Solubility soluble in acid
very slightly soluble in ammonium hydroxide
2.529
Structure
Hexagonal, Cubic
Thermochemistry
65 J·mol−1·K−1[2]
−162 kJ·mol−1[2]
Vapor pressure {{{value}}}
Related compounds
Other anions
Cadmium oxide
Cadmium selenide
Other cations
Zinc sulfide
Mercury sulfide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
YesY verify (what is YesYN ?)
Infobox references

Cadmium sulfide is the inorganic compound with the formula CdS. Cadmium sulfide is a yellow solid.[3] It occurs in nature with two different crystal structures as the rare minerals greenockite and hawleyite, but is more prevalent as an impurity substituent in the similarly structured zinc ores sphalerite and wurtzite, which are the major economic sources of cadmium. As a compound that is easy to isolate and purify, it is the principal source of cadmium for all commercial applications.[3] Its vivid yellow color led to its adoption as a pigment for the yellow paint "cadmium yellow" in the 18th century.

Production

Cadmium sulfide can be prepared by the precipitation from soluble cadmium(II) salts with sulfide ion. This reaction has been used for gravimetric analysis and qualitative inorganic analysis.[4]
The preparative route and the subsequent treatment of the product, affects the polymorphic form that is produced (i.e., cubic vs hexagonal). It has been asserted that chemical precipitation methods result in the cubic zincblende form[5]

Pigment production usually involves the precipitation of CdS, the washing of the solid precipitate to remove soluble cadmium salts followed by calcination (roasting) to convert it to the hexagonal form followed by milling to produce a powder.[6] When cadmium sulfide selenides are required the CdSe is co-precipitated with CdS and the cadmium sulfoselenide is created during the calcination step.[6]

Cadmium sulfide is sometimes associated with sulfate reducing bacteria.[7][8]

Routes to thin films of CdS

Special methods are used to produce films of CdS as components in some photoresistors and solar cells. In the chemical bath deposition method, thin films of CdS have been prepared using thiourea as the source of sulfide anions and an ammonium buffer solution to control pH:[9]

Cd2+ + H2O + (NH2)2CS + 2 NH3 → CdS + (NH2)2CO + 2 NH4+

Cadmium sulfide is the inorganic compound with the formula CdS. Cadmium sulfide is a yellow solid. It occurs in nature with two different crystal structures as the rare minerals greenockite and hawleyite, but is more prevalent as an impurity substituent in the similarly structured zinc ores sphalerite and wurtzite, which are the major economic sources of cadmium. As a compound that is easy to isolate and purify, it is the principal source of cadmium for all commercial applications. Its vivid yellow color led to its adoption as a pigment for the yellow paint "cadmium yellow" in the 18th century.Cadmium sulfide can be produced using metalorganic vapour phase epitaxy and MOCVD techniques.[10] This process requies volatile cadmium and sulfur precursors. A common example is the reaction of dimethylcadmium with diethyl sulfide:[10]

Cd(CH3)2 + Et2S → CdS + CH3CH3 + C4H10

Many other methods have been reported.

Other methods to produce films of CdS include

Reactions

Cadmium sulfide is soluble in (actually degraded by) acids, and this conversion has been investigated as a method of extracting the pigment from waste polymers e.g. HDPE pipes:[16]

CdS + 2 HCl → CdCl2 + H2S

When solutions of sulfide solutions containing dispersed CdS particles are irradiated with light hydrogen gas is generated:[17]

H2S → H2 + S ΔHf = +9.4 kcal/mol

The proposed mechanism involves the electron/hole pairs created when incident light is absorbed by the cadmium sulfide[18] followed by these reacting with water and sulfide:[17]

Production of an electron hole pair
CdS +  → e + hole+
Reaction of electron
2e + 2H2O → H2 + 2OH
Reaction of hole
2hole+ + S2− → S

Structure and physical properties

Cadmium sulfide has, like zinc sulfide, two crystal forms. The more stable hexagonal wurtzite structure (found in the mineral Greenockite) and the cubic zinc blende structure (found in the mineral Hawleyite). In both of these forms the cadmium and sulfur atoms are four coordinate.[19] There is also a high pressure form with the NaCl rock salt structure.[19]

Cadmium sulfide is a direct band gap semiconductor (gap 2.42 eV[18]). The magnitude of its band gap means that it appears coloured.[3]
As well as this obvious property others properties result:

Thin films of Cadmium Sulfide can be piezoelectric and have been used as transducers which can operate at frequencies in the GHz region.

Applications

Pigment

Yellow cadmium sulfide- pigment

Synthetic cadmium pigments based on cadmium sulfide are valued for their good thermal stability, light and weather fastness, chemical resistance and high opacity.[6] As a pigment, CdS is known as cadmium yellow.[3] (CI pigment yellow 37)[29]).About 2000 tons are produced annually as of 1982, representing about 25% of the cadmium processed commercially.[30] CdS is used as pigment in plastics.[6]

Historical use in art

The general commercial availability of cadmium sulfide from the 1840s led to its adoption by artists, notably Van Gogh, Monet (in his London series and other works) and Matisse (Bathers by a river 1916–1919).[31] The presence of cadmium in paints has been used to detect forgeries in paintings alleged to have been produced prior to the 19th century.[32]

CdS-CdSe solutions

CdS and CdSe form solid solutions. Increasing amounts of cadmium selenide, gives pigments verging toward red, for example CI pigment orange 20 and CI pigment red 108.[29]
Such solid solutions are components of photoresistors (light dependent resistors) sensitive to visible and near infrared light.[citation needed]

Safety

Cadmium sulfide is toxic, especially when inhaled as dust, and cadmium compounds general are classified as carcinogenic.[33] Problems of biocompatibility have been reported when CdS is used as colors in tattoos[34]).

References

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  2. 2.0 2.1 Lua error in package.lua at line 80: module 'strict' not found.
  3. 3.0 3.1 3.2 3.3 Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier ISBN 0-12-352651-5
  4. Fred Ibbotson (2007), The Chemical Analysis of Steel-Works' Materials,Read Books, ISBN 1-4067-8113-4
  5. Paul Klocek (1991), Handbook of Infrared Optical Materials, CRC Press ISBN 0-8247-8468-5
  6. 6.0 6.1 6.2 6.3 Lua error in package.lua at line 80: module 'strict' not found.
  7. Larry L. Barton 1995 Sulfate reducing bacteria, Springer, ISBN 0-306-44857-2
  8. Lua error in package.lua at line 80: module 'strict' not found.
  9. Lua error in package.lua at line 80: module 'strict' not found.
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  13. Lua error in package.lua at line 80: module 'strict' not found.
  14. U.S. Patent 4,086,101 Photovoltaic cells, J.F. Jordan, C.M. Lampkin Issue date: April 25, 1978
  15. U.S. Patent 3,208,022, High performance photoresistor, Y.T. Sihvonen, issue date: September 21, 1965
  16. Lua error in package.lua at line 80: module 'strict' not found.
  17. 17.0 17.1 Mario Schiavello (1985) Photoelectrochemistry, Photocatalysis, and Photoreactors: Fundamentals and Developments Springer ISBN 90-277-1946-2
  18. 18.0 18.1 18.2 D. Lincot, Gary Hodes Chemical Solution Deposition of Semiconducting and Non-Metallic Films: Proceedings of the International Symposium The Electrochemical Society, 2006 ISBN 1-56677-433-0
  19. 19.0 19.1 Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications ISBN 0-19-855370-6
  20. Antonio Luque, Steven Hegedus, (2003), Handbook of Photovoltaic Science and Engineering John Wiley and Sons ISBN 0-471-49196-9
  21. Lua error in package.lua at line 80: module 'strict' not found.
  22. C. Fouassier,(1994), Luminescence in Encyclopedia of Inorganic Chemistry, John Wiley & Sons ISBN 0-471-93620-0
  23. Lua error in package.lua at line 80: module 'strict' not found.
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  27. H. Zhao et al, "The effect of impurities on the doping and VOC of CdTe/CdS thin film solar cells", Thin Solid Films, Vol. 517, No. 7 (2009) pp. 2365-2369, [1] doi:10.1016/j.tsf.2008.11.041
  28. P.K. Weimar, "The TFT a new thin-film transistor", Proc. IRE, Vol. 50, No. 6 (1962) pp. 1462-1469, [2] doi:10.1109/JRPROC.1962.288190
  29. 29.0 29.1 R. M. Christie 2001 Colour Chemistry, p. 155 Royal Society of Chemistry ISBN 0-85404-573-2
  30. Karl-Heinz Schulte-Schrepping, Magnus Piscator "Cadmium and Cadmium Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, 2007 Wiley-VCH, Weinheim. doi:10.1002/14356007.a04_499.
  31. Sidney Perkowitz, 1998, Empire of Light: A History of Discovery in Science and Art Joseph Henry Press, ISBN 0-309-06556-9
  32. W. Stanley Taft, James W. Mayer, Richard Newman, Peter Kuniholm, Dusan Stulik (2000) The Science of Paintings, Springer, ISBN 0-387-98722-3
  33. CDC International Chemical Safety Card - Cadmium Sulfide
  34. Lua error in package.lua at line 80: module 'strict' not found.

External links