Cerium(III) sulfide

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Cerium(III) sulfide
Cerium(III)-sulfide-A-polymorph-unit-cell-3D-bs-17.png
Names
IUPAC name
Cerium(III) sulfide
Other names
  • Cerium sulfide red
  • Cerium sesquisulfide
  • Cerous sulfide
  • Dicerium trisulfide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.031.445 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 234-603-7
PubChem CID
  • InChI=1S/2Ce.3S/q2*+3;3*-2
    Key: MMXSKTNPRXHINM-UHFFFAOYSA-N
  • [S-2].[S-2].[S-2].[Ce+3].[Ce+3]
Properties
Ce2S3
Molar mass 375.73 g/mol
AppearanceRed/burgundy/black crystals (depending on polymorph)
Density 5.18 g/cm3
Melting point 1,840 to 1,940 °C (3,340 to 3,520 °F; 2,110 to 2,210 K)
Boiling point decomposes (at 2300 °C)
insoluble
Solubility soluble in warm formic or acetic acid
soluble in cold dil. HCl, HNO3 or H2SO4
Band gap 2.06 eV (γ-Ce2S3)
2.77 (589 nm)
Structure
orthorhombic (α-Ce2S3)
tetragonal (β-Ce2S3)
cubic (γ-Ce2S3)
Thermochemistry
126.2 J·mol−1·K−1
-1260 kJ·mol−1
-1230 kJ·mol−1
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H315, H319, H335
P261, P280, P305+P351+P338
Related compounds
Other anions
Cerium(III) oxide, Cerium(III) selenide, Cerium(III) oxyselenide
Other cations
Samarium(III) sulfide, Praseodymium(III) sulfide
Related compounds
Cerium(II) sulfide, Ce3S4, Cerium disulfide, Ce2O2S
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Cerium(III) sulfide, also known as cerium sesquisulfide, is an inorganic compound with the formula Ce2S3. It is the sulfide salt of cerium(III) and exists as three polymorphs with different crystal structures. [1] [2] [3]

Contents

Its high melting point (comparable to silica or alumina) and chemically inert nature have led to occasional examination of potential use as a refractory material for crucibles, but it has never been widely adopted for this application. [2]

The distinctive red colour of two of the polymorphs (α- and β-Ce2S3) and aforementioned chemical stability up to high temperatures have led to some limited commercial use as a red pigment (known as cerium sulfide red). [3]

Synthesis

The oldest syntheses reported for cerium(III) sulfide follow a typical rare earth sesquisulfide formation route, which involves heating the corresponding cerium sesquioxide to 900–1100 °C in an atmosphere of hydrogen sulfide: [1] [4]

Ce2O3 + 3 H2S → Ce2S3 + 3 H2O

Newer synthetic procedures utilise less toxic carbon disulfide gas for sulfurisation, starting from cerium dioxide which is reduced by the CS2 gas at temperatures of 800–1000 °C: [2]

6 CeO2 + 5 CS2 → 3 Ce2S3 + 5 CO2 + SO2

Polymorphs

Polymorphs of cerium(III) sulfide
PolymorphT of formationColourCrystal systemSpace groupLattice constants
α-Ce2S3<900 °CburgundyOthorhombicPnma (No. 62)a=7.63 Å, b=4.12 Å, c=15.71 Å
β-Ce2S3900–1200 °CredTetragonalI41/acd (No. 142)a=15.37 Å, c=20.35 Å
γ-Ce2S3>1200 °CblackCubicI43d (No. 220)a=8.63 Å

Ce2S3 exists in three polymorphic forms: α-Ce2S3 (orthorhombic, burgundy colour), β-Ce2S3 (tetragonal, red colour), γ-Ce2S3 (cubic, black colour). [1] [2] [3] They are analogous to the crystal structures of the likewise trimorphic Pr2S3 and Nd2S3. [2]

Following the synthetic procedures given above will yield mostly the α- and β- polymorphs, with the proportion of α-Ce2S3 increasing at lower temperatures (~700–900 °C) and with longer reaction times. [2] [3] The α- form can be irreversibly transformed into β-Ce2S3 by vacuum heating at 1200 °C for 7 hours. Then γ-Ce2S3 is obtained from sintering of β-Ce2S3 powder via hot pressing at an even higher temperature (1700 °C). [2]

α polymorph

The α polymorph of cerium(III) sulfide has the same structure as α-Gd2S3. It contains both 7-coordinate and 8-coordinate cerium ions, Ce3+, with monocapped and bicapped trigonal prismatic coordination geometry, respectively. The sulfide ions, S2−, are 5-coordinate. [5] Two thirds of them adopt a square pyramidal geometry and one third adopt a trigonal bipyramidal geometry. [6]

Coordination in α-Ce2S3 [5]
Cerium Ce1 coordinationCerium Ce2 coordinationSulfur S1 coordinationSulfur S2 coordinationSulfur S3 coordination
Cerium(III)-sulfide-A-polymorph-Ce1-coord-3D-bs-17.png Cerium(III)-sulfide-A-polymorph-Ce2-coord-3D-bs-17.png Cerium(III)-sulfide-A-polymorph-S1-coord-3D-bs-17.png Cerium(III)-sulfide-A-polymorph-S2-coord-3D-bs-17.png Cerium(III)-sulfide-A-polymorph-S3-coord-3D-bs-17.png

γ polymorph

The γ polymorph of cerium(III) sulfide adopts a cation-deficient form of the Th3P4 structure. 8 out the 9 metal positions in the Th3P4 structure are occupied by cerium in γ-Ce2S3, with the remainder as vacancies. This composition can be represented by the formula Ce2.6670.333S4. The cerium ions are 8-coordinate while the sulfide ions are 6-coordinate (distorted octahedral). [5] [6]

Reactions

Some reported reactions of cerium(III) sulfide are with bismuth compounds in order to form superconducting crystalline materials of the M(O,F)BiS2 family (for M=Ce). [7]

The reaction of Ce2S3 with Bi2S3 and Bi2O3 in a sealed tube at 950 °C gives the parent compound CeOBiS2:

3 Ce2S3 + Bi2S3 + 2 Bi2O3 → 6 CeOBiS2

This material is superconducting on its own, but the properties can be enhanced if it is doped with fluoride by including BiF3 in the reaction mixture. [7]

Applications

Refractory material

Cerium(III) and cerium(IV) sulfides were first investigated in the 1940s as part of the Manhattan project, where they were considered -but eventually not adopted- as advanced refractory materials. [2] Their suggested application was as the material in crucibles for the casting of uranium and plutonium metal. [2] [4]

Although the sulfide's properties (high melting point and large, large negative Δf and chemical inertness) are suitable and cerium is a relatively common element (66 ppm, about as much as copper), the danger of the traditional H2S-involving production route and the difficulty in controlling the formation of the resulting Ce2S3/CeS solid mixture meant that the compound was ultimately not developed further for such applications. [2]

Pigment and other uses

The main non-research use of cerium(III) sulfide is as a specialty inorganic pigment. [3] The strong red hues of α- and β-Ce2S3, non-prohibitive cost of cerium, and chemically inert behaviour up to high temperature are the factors which make the compound desirable as a pigment.

Regarding other applications, the γ-Ce2S3 polymorph has a band gap of 2.06 eV and high Seebeck coefficient, thus it has been proposed as a high-temperature semiconductor for thermoelectric generators. [2] A practical implementation thereof has not been demonstrated so far.

Related Research Articles

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<span class="mw-page-title-main">Lead(II) oxide</span> Chemical compound

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<span class="mw-page-title-main">Iron(II,III) oxide</span> Chemical compound

Iron(II,III) oxide, or black iron oxide, is the chemical compound with formula Fe3O4. It occurs in nature as the mineral magnetite. It is one of a number of iron oxides, the others being iron(II) oxide (FeO), which is rare, and iron(III) oxide (Fe2O3) which also occurs naturally as the mineral hematite. It contains both Fe2+ and Fe3+ ions and is sometimes formulated as FeO ∙ Fe2O3. This iron oxide is encountered in the laboratory as a black powder. It exhibits permanent magnetism and is ferrimagnetic, but is sometimes incorrectly described as ferromagnetic. Its most extensive use is as a black pigment (see: Mars Black). For this purpose, it is synthesized rather than being extracted from the naturally occurring mineral as the particle size and shape can be varied by the method of production.

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<span class="mw-page-title-main">Bismuth(III) oxide</span> Chemical compound

Bismuth(III) oxide is perhaps the most industrially important compound of bismuth. It is also a common starting point for bismuth chemistry. It is found naturally as the mineral bismite (monoclinic) and sphaerobismoite, but it is usually obtained as a by-product of the smelting of copper and lead ores. Dibismuth trioxide is commonly used to produce the "Dragon's eggs" effect in fireworks, as a replacement of red lead.

<span class="mw-page-title-main">Phosphorus sulfides</span>

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<span class="mw-page-title-main">Gallium(III) oxide</span> Chemical compound

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References

  1. 1 2 3 Banks, E.; Stripp, K. F.; Newkirk, H. W.; Ward, R. (1952). "Cerium(III) Sulfide and Selenide and Some of their Solid Solutions1". Journal of the American Chemical Society. 74 (10): 2450–2453. doi:10.1021/ja01130a002. ISSN   0002-7863.
  2. 1 2 3 4 5 6 7 8 9 10 11 Hirai, Shinji; Shimakage, Kazuyoshi; Saitou, Yasushi; Nishimura, Toshiyuki; Uemura, Yoichiro; Mitomo, Mamoru; Brewer, Leo (1998). "Synthesis and Sintering of Cerium(III) Sulfide Powders". Journal of the American Ceramic Society. 81 (1): 145–151. doi:10.1111/j.1151-2916.1998.tb02306.x. ISSN   1551-2916.
  3. 1 2 3 4 5 Kariper, I. A. (2014). "Synthesis and characterization of cerium sulfide thin film". Progress in Natural Science: Materials International. Elsevier. 24 (6): 663–670. doi: 10.1016/j.pnsc.2014.10.005 . ISSN   1002-0071.
  4. 1 2 Hadden, Gavin, ed. (1946). "Chapter 11 - Ames Project". Manhattan District History. Vol. 4 - Auxiliary Activities. Washington, D.C.: US Army Corps of Engineers.
  5. 1 2 3 Schleid, Thomas; Lauxmann, Petra (1999). "Röntgenstrukturanalysen an Einkristallen von Ce2S3 im A- und C-Typ". Z. Anorg. Allg. Chem. 625 (7): 1053–1055. doi:10.1002/(SICI)1521-3749(199907)625:7<1053::AID-ZAAC1053>3.0.CO;2-Z.
  6. 1 2 Wells, A. F. (1984). Structural Inorganic Chemistry (5th ed.). Oxford University Press. pp. 766–767. ISBN   978-0-19-965763-6.
  7. 1 2 Tanaka, Masashi; Nagao, Masanori; Matsumoto, Ryo; Kataoka, Noriyuki; Ueta, Ikuo; Tanaka, Hiromi; Watauchi, Satoshi; Tanaka, Isao; Takano, Yoshihiko (2017-10-25). "Superconductivity and its enhancement under high pressure in "F-free" single crystals of CeOBiS2". Journal of Alloys and Compounds. 722: 467–473. arXiv: 1706.03590 . doi:10.1016/j.jallcom.2017.06.125. ISSN   0925-8388. S2CID   119537216.