Cadmium sulfide

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Cadmium sulfide
3D model of the structure of hawleyite Hawleyite-3D-balls.png
3D model of the structure of hawleyite
3D model of the structure of greenockite Greenockite-3D-balls.png
3D model of the structure of greenockite
Cadmium sulfide.jpg
Names
Other names
cadmium(II) sulfide
greenockite
hawleyite
cadmium yellow
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.013.771 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 215-147-8
13655
PubChem CID
RTECS number
  • EV3150000
UNII
UN number 2570
  • InChI=1S/Cd.S/q+2;-2 Yes check.svgY
    Key: FRLJSGOEGLARCA-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/Cd.S/q+2;-2
    Key: FRLJSGOEGLARCA-UHFFFAOYAL
  • monomer:[S-2].[Cd+2]
  • hawleyite:[SH+2]12[CdH2-2] [SH+2]3[CdH2-2] [SH+2]([CdH-2]14)[CdH-2]1[S+2]5([CdH-2]38)[Cd-2]26[SH+2]2[CdH-2]([S+2]4)[SH+2]1[CdH2-2] [SH+2]3[CdH-2]2[S+2] [CdH-2]([SH+2]6[CdH-2]([SH+2])[SH+2]68)[SH+2]([CdH2-2]6)[CdH-2]35
  • greenockite:[CdH2-2]1[S+2]47[CdH-2]2[S+2] [CdH-2]3[S+2]8([CdH2-2] [SH+2]([CdH2-2]4)[CdH2-2]6)[CdH-2]4[S+2] [CdH-2]5[S+2]6([CdH2-2]6)[Cd-2]78[S+2]78[CdH-2]([SH+2]69)[SH+2]5[CdH2-2] [SH+2]4[CdH-2]7[SH+2]3[CdH2-2] [SH+2]2[CdH-2]8[SH+2]1[CdH2-2]9
  • greenockite:[CdH2-2]1[SH+2]([CdH2-2]6)[CdH2-2] [SH+2]7[CdH-2]2[S+2] [Cd-2]3([S+2] [CdH-2]9[S+2]5)[S+2]18[Cd-2]45[S+2] [CdH-2]5[SH+2]6[Cd-2]78[S+2]78[CdH2-2] [SH+2]5[CdH2-2] [S+2]4([CdH2-2] [SH+2]9[CdH2-2]4)[CdH-2]7[S+2]34[CdH2-2] [SH+2]2[CdH2-2]8
Properties
CdS
Molar mass 144.47 g·mol−1
AppearanceYellow-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
Band gap 2.42 eV
-50.0·10−6 cm3/mol
2.529
Structure
Hexagonal, Cubic
Thermochemistry
Std molar
entropy (S⦵298)
65 J·mol−1·K−1 [2]
−162 kJ·mol−1 [2]
Hazards
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg
Danger
H302, H341, H350, H361, H372, H413
P201, P202, P260, P264, P270, P273, P281, P301+P312, P308+P313, P314, P330, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
0
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
7080 mg/kg (rat, oral)
NIOSH (US health exposure limits):
PEL (Permissible)
[1910.1027] TWA 0.005 mg/m3 (as Cd) [3]
REL (Recommended)
Ca [3]
IDLH (Immediate danger)
Ca [9 mg/m3 (as Cd)] [3]
Safety data sheet (SDS) ICSC 0404
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).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Cadmium sulfide is the inorganic compound with the formula CdS. Cadmium sulfide is a yellow salt. [4] 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. [4] Its vivid yellow color led to its adoption as a pigment for the yellow paint "cadmium yellow" in the 18th century.

Contents

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. [5]
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. [6]

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. [7] When cadmium sulfide selenides are required the CdSe is co-precipitated with CdS and the cadmium sulfoselenide is created during the calcination step. [7]

Cadmium sulfide is sometimes associated with sulfate reducing bacteria. [8] [9]

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: [10]

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

Cadmium sulfide can be produced using metalorganic vapour phase epitaxy and MOCVD techniques by the reaction of dimethylcadmium with diethyl sulfide: [11]

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

Other methods to produce films of CdS include

Reactions

Cadmium sulfide can be dissolved in acids. [17]

CdS + 2 HCl → CdCl2 + H2S

When solutions of sulfide containing dispersed CdS particles are irradiated with light, hydrogen gas is generated: [18]

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 [19] followed by these reacting with water and sulfide: [18]

Production of an electron–hole pair
CdS + hν → e− + h+
Reaction of electron
2e− + 2H2O → H2 + 2OH−
Reaction of hole
2h+ + 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. [20] There is also a high pressure form with the NaCl rock salt structure. [20]

Cadmium sulfide is a direct band gap semiconductor (gap 2.42 eV). [19] The proximity of its band gap to visible light wavelengths gives it a coloured appearance. [4]
As well as this obvious property other properties result:

Applications

Pigment

Yellow cadmium sulfide- pigment Cadmiumgelb- Pigment.JPG
Yellow cadmium sulfide- pigment

CdS is used as pigment in plastics, showing good thermal stability, light and weather fastness, chemical resistance and high opacity. [7] As a pigment, CdS is known as cadmium yellow (CI pigment yellow 37). [4] [31] About 2000 tons are produced annually as of 1982, representing about 25% of the cadmium processed commercially. [32]

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). [33] The presence of cadmium in paints has been used to detect forgeries in paintings alleged to have been produced prior to the 19th century. [34]

CdS-CdSe solutions

CdS and CdSe form solid solutions with each other. Increasing amounts of cadmium selenide, gives pigments verging toward red, for example CI pigment orange 20 and CI pigment red 108. [31]
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 dangerous when inhaled as dust, and cadmium compounds in general are classified as carcinogenic. [35] Problems of biocompatibility have been reported when CdS is used as colors in tattoos. [36] CdS has an LD50 of approximately 7,080 mg/kg in rats - which is higher than other cadmium compounds due to its low solubility. [37]

Related Research Articles

<span class="mw-page-title-main">Cadmium</span> Chemical element, symbol Cd and atomic number 48

Cadmium is a chemical element; it has symbol Cd and atomic number 48. This soft, silvery-white metal is chemically similar to the two other stable metals in group 12, zinc and mercury. Like zinc, it demonstrates oxidation state +2 in most of its compounds, and like mercury, it has a lower melting point than the transition metals in groups 3 through 11. Cadmium and its congeners in group 12 are often not considered transition metals, in that they do not have partly filled d or f electron shells in the elemental or common oxidation states. The average concentration of cadmium in Earth's crust is between 0.1 and 0.5 parts per million (ppm). It was discovered in 1817 simultaneously by Stromeyer and Hermann, both in Germany, as an impurity in zinc carbonate.

<span class="mw-page-title-main">Indium</span> Chemical element, symbol In and atomic number 49

Indium is a chemical element; it has symbol In and atomic number 49. Indium is the softest metal that is not an alkali metal. It is a silvery-white metal that resembles tin in appearance. It is a post-transition metal that makes up 0.21 parts per million of the Earth's crust. Indium has a melting point higher than sodium and gallium, but lower than lithium and tin. Chemically, indium is similar to gallium and thallium, and it is largely intermediate between the two in terms of its properties. Indium was discovered in 1863 by Ferdinand Reich and Hieronymous Theodor Richter by spectroscopic methods. They named it for the indigo blue line in its spectrum. Indium was isolated the next year.

<span class="mw-page-title-main">Organic electronics</span> Field of materials science

Organic electronics is a field of materials science concerning the design, synthesis, characterization, and application of organic molecules or polymers that show desirable electronic properties such as conductivity. Unlike conventional inorganic conductors and semiconductors, organic electronic materials are constructed from organic (carbon-based) molecules or polymers using synthetic strategies developed in the context of organic chemistry and polymer chemistry.

<span class="mw-page-title-main">Cadmium pigments</span> Class of pigments that have cadmium as one of the chemical components

Cadmium pigments are a class of pigments that contain cadmium. Most of the cadmium produced worldwide has been for use in rechargeable nickel–cadmium batteries, which have been replaced by other rechargeable nickel-chemistry cell varieties such as NiMH cells, but about half of the remaining consumption of cadmium, which is approximately 2,000 tonnes annually, is used to produce colored cadmium pigments. The principal pigments are a family of yellow, orange and red cadmium sulfides and sulfoselenides, as well as compounds with other metals.

<span class="mw-page-title-main">Zinc sulfide</span> Inorganic compound

Zinc sulfide is an inorganic compound with the chemical formula of ZnS. This is the main form of zinc found in nature, where it mainly occurs as the mineral sphalerite. Although this mineral is usually black because of various impurities, the pure material is white, and it is widely used as a pigment. In its dense synthetic form, zinc sulfide can be transparent, and it is used as a window for visible optics and infrared optics.

<span class="mw-page-title-main">Cadmium arsenide</span> Chemical compound

Cadmium arsenide (Cd3As2) is an inorganic semimetal in the II-V family. It exhibits the Nernst effect.

A selenide is a chemical compound containing a selenium with oxidation number of −2. Similar to sulfide, selenides occur both as inorganic compounds and as organic derivatives, which are called organoselenium compound.

<span class="mw-page-title-main">Cadmium telluride</span> Semiconductor chemical compound used in solar cells

Cadmium telluride (CdTe) is a stable crystalline compound formed from cadmium and tellurium. It is mainly used as the semiconducting material in cadmium telluride photovoltaics and an infrared optical window. It is usually sandwiched with cadmium sulfide to form a p–n junction solar PV cell.

<span class="mw-page-title-main">Cadmium selenide</span> Chemical compound

Cadmium selenide is an inorganic compound with the formula CdSe. It is a black to red-black solid that is classified as a II-VI semiconductor of the n-type. It is a pigment but applications are declining because of environmental concerns

Hybrid solar cells combine advantages of both organic and inorganic semiconductors. Hybrid photovoltaics have organic materials that consist of conjugated polymers that absorb light as the donor and transport holes. Inorganic materials in hybrid cells are used as the acceptor and electron transporter in the structure. The hybrid photovoltaic devices have a potential for not only low-cost by roll-to-roll processing but also for scalable solar power conversion.

<span class="mw-page-title-main">Cadmium oxide</span> Inorganic compound with the formula CdO

Cadmium oxide is an inorganic compound with the formula CdO. It is one of the main precursors to other cadmium compounds. It crystallizes in a cubic rocksalt lattice like sodium chloride, with octahedral cation and anion centers. It occurs naturally as the rare mineral monteponite. Cadmium oxide can be found as a colorless amorphous powder or as brown or red crystals. Cadmium oxide is an n-type semiconductor with a band gap of 2.18 eV at room temperature.

<span class="mw-page-title-main">Zinc phosphide</span> Chemical compound

Zinc phosphide (Zn3P2) is an inorganic chemical compound. It is a grey solid, although commercial samples are often dark or even black. It is used as a rodenticide. Zn3P2 is a II-V semiconductor with a direct band gap of 1.5 eV and may have applications in photovoltaic cells. A second compound exists in the zinc-phosphorus system, zinc diphosphide (ZnP2).

Indium(III) sulfide (Indium sesquisulfide, Indium sulfide (2:3), Indium (3+) sulfide) is the inorganic compound with the formula In2S3.

<span class="mw-page-title-main">Quantum dot solar cell</span> Type of solar cell based on quantum dot devices

A quantum dot solar cell (QDSC) is a solar cell design that uses quantum dots as the captivating photovoltaic material. It attempts to replace bulk materials such as silicon, copper indium gallium selenide (CIGS) or cadmium telluride (CdTe). Quantum dots have bandgaps that are adjustable across a wide range of energy levels by changing their size. In bulk materials, the bandgap is fixed by the choice of material(s). This property makes quantum dots attractive for multi-junction solar cells, where a variety of materials are used to improve efficiency by harvesting multiple portions of the solar spectrum.

<span class="mw-page-title-main">Cadmium telluride photovoltaics</span> Type of solar power cell

Cadmium telluride (CdTe) photovoltaics is a photovoltaic (PV) technology based on the use of cadmium telluride in a thin semiconductor layer designed to absorb and convert sunlight into electricity. Cadmium telluride PV is the only thin film technology with lower costs than conventional solar cells made of crystalline silicon in multi-kilowatt systems.

<span class="mw-page-title-main">Thin-film solar cell</span> Type of second-generation solar cell

Thin-film solar cells are made by depositing one or more thin layers of photovoltaic material onto a substrate, such as glass, plastic or metal. Thin-film solar cells are typically a few nanometers (nm) to a few microns (µm) thick–much thinner than the wafers used in conventional crystalline silicon (c-Si) based solar cells, which can be up to 200 µm thick. Thin-film solar cells are commercially used in several technologies, including cadmium telluride (CdTe), copper indium gallium diselenide (CIGS), and amorphous thin-film silicon.

Chemical Bath Deposition, also called Chemical Solution Deposition and CBD, is a method of thin-film deposition, using an aqueous precursor solution. Chemical Bath Deposition typically forms films using heterogeneous nucleation, to form homogeneous thin films of metal chalcogenides and many less common ionic compounds. Chemical Bath Deposition produces films reliably, using a simple process with little infrastructure, at low temperature (<100˚C), and at low cost. Furthermore, Chemical Bath Deposition can be employed for large-area batch processing or continuous deposition. Films produced by CBD are often used in semiconductors, photovoltaic cells, and supercapacitors, and there is increasing interest in using Chemical Bath Deposition to create nanomaterials.

<span class="mw-page-title-main">CZTS</span> Chemical compound

Copper zinc tin sulfide (CZTS) is a quaternary semiconducting compound which has received increasing interest since the late 2000s for applications in thin film solar cells. The class of related materials includes other I2-II-IV-VI4 such as copper zinc tin selenide (CZTSe) and the sulfur-selenium alloy CZTSSe. CZTS offers favorable optical and electronic properties similar to CIGS (copper indium gallium selenide), making it well suited for use as a thin-film solar cell absorber layer, but unlike CIGS (or other thin films such as CdTe), CZTS is composed of only abundant and non-toxic elements. Concerns with the price and availability of indium in CIGS and tellurium in CdTe, as well as toxicity of cadmium have been a large motivator to search for alternative thin film solar cell materials. The power conversion efficiency of CZTS is still considerably lower than CIGS and CdTe, with laboratory cell records of 11.0 % for CZTS and 12.6 % for CZTSSe as of 2019.

Quantum dots (QDs) are semiconductor nanoparticles with a size less than 10 nm. They exhibited size-dependent properties especially in the optical absorption and the photoluminescence (PL). Typically, the fluorescence emission peak of the QDs can be tuned by changing their diameters. So far, QDs were consisted of different group elements such as CdTe, CdSe, CdS in the II-VI category, InP or InAs in the III-V category, CuInS2 or AgInS2 in the I–III–VI2 category, and PbSe/PbS in the IV-VI category. These QDs are promising candidates as fluorescent labels in various biological applications such as bioimaging, biosensing and drug delivery.

Zinc cadmium phosphide arsenide (Zn-Cd-P-As) is a quaternary system of group II (IUPAC group 12) and group V (IUPAC group 15) elements. Many of the inorganic compounds in the system are II-V semiconductor materials. The quaternary system of II3V2 compounds, (Zn1−xCdx)3(P1−yAsy)2, has been shown to allow solid solution continuously over the whole compositional range. This material system and its subsets have applications in electronics, optoelectronics, including photovoltaics, and thermoelectrics.

References

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  36. ↑ Bjornberg, A (Sep 1963). "Reactions to light in yellow tattoos from cadmium sulfide". Arch Dermatol. 88 (3): 267–71. doi:10.1001/archderm.1963.01590210025003. PMID   14043617.
  37. ↑ "Sicherheitsdatenblatt" (PDF). Archived from the original (PDF) on 24 July 2015.
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