Cerium(III) sulfide

Names
IUPAC name

Cerium(III) sulfide

Other names

* Cerium sulfide red
* Cerium sesquisulfide
* Cerous sulfide
* Dicerium trisulfide

Identifiers

CAS Number

* 12014-93-6 Y

3D model (JSmol)

* Interactive image

ChemSpider |

* 140174

EC Number |

* 234-603-7

PubChem CID

* 159394

InChI

* InChI=1S/2Ce.3S/q2*+3;3*-2

Key: MMXSKTNPRXHINM-UHFFFAOYSA-N

SMILES

* [S-2].[S-2].[S-2].[Ce+3].[Ce+3]

Properties

Chemical formula

| Ce2S3
Molar mass | 375.73 g/mol
Appearance  | Red/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)

Solubility in water

| insoluble
Solubility | soluble in warm formic or acetic acid
soluble in cold dil. HCl, HNO3 or H2SO4
Band gap | 2.06 eV (γ-Ce2S3)

Refractive index (nD)

| 2.77 (589 nm)
Structure

Crystal structure

| orthorhombic (α-Ce2S3)
tetragonal (β-Ce2S3)
cubic (γ-Ce2S3)
Thermochemistry

Heat capacity (C)

| 126.2 J·mol−1·K−1

Std enthalpy of
formation (ΔfH⦵298)

| -1260 kJ·mol−1

Gibbs free energy (ΔfG˚)

| -1230 kJ·mol−1
Hazards
GHS pictograms |
GHS Signal word | Warning

GHS hazard statements

| H315, H319, H335

GHS precautionary statements

| P261, P280, P305+351+338
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).

Infobox references

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]

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]

## Contents

* 1 Synthesis
* 2 Polymorphs
* 2.1 α polymorph
* 2.2 γ polymorph
* 3 Reactions
* 4 Applications
* 4.1 Refractory material
* 4.2 Pigment and other uses
* 5 References

## 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

This article's factual accuracy is disputed. Please help to ensure that disputed statements are reliably sourced. (September 2022) (Learn how and when to remove this template message)

|

Polymorphs of cerium(III) sulfide  Polymorph  | T of formation  | Colour  | Crystal system  | Space group  | Lattice constants

|
|
|
|
|

α-Ce2S3 | <900 °C  | burgundy | Othorhombic  | Pnma (No. 62)  | a=7.63 Å, b=4.12 Å, c=15.71 Å
β-Ce2S3 | 900–1200 °C  | red | Tetragonal  | I41/acd (No. 142)  | a=15.37 Å, c=20.35 Å
γ-Ce2S3 | >1200 °C  | black | Cubic  | I43d (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-Gd

3. 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-Ce

3[5] Cerium Ce1 coordination  | Cerium Ce2 coordination  | Sulfur S1 coordination  | Sulfur S2 coordination  | Sulfur S3 coordination

|
|
|
|

|  |  |  |

### γ polymorph

The γ polymorph of cerium(III) sulfide adopts a cation-deficient form of the Th

4 structure. 8 out the 9 metal positions in the Th

4 structure are occupied by cerium in γ-Ce

3, with the remainder as vacancies. This composition can be represented by the formula Ce
2.667□
0.333S
4. 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 ΔfG° 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.

## References

1. ↑ 1.0 1.1 1.2 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. https://doi.org/10.1021/ja01130a002.
2. ↑ 2.00 2.01 2.02 2.03 2.04 2.05 2.06 2.07 2.08 2.09 2.10 Hirai, Shinji; Shimakage, Kazuyoshi; Saitou, Yasushi; Nishimura, Toshiyuki; Uemura, Yoichiro; Mitomo, Mamoru; Brewer, Leo (1998). "Synthesis and Sintering of Cerium(III) Sulfide Powders" (in en). Journal of the American Ceramic Society 81 (1): 145–151. doi:10.1111/j.1151-2916.1998.tb02306.x. ISSN 1551-2916. https://ceramics.onlinelibrary.wiley.com/doi/abs/10.1111/j.1151-2916.1998.tb02306.x.
3. ↑ 3.0 3.1 3.2 3.3 3.4 Kariper, I. A. (2014). "Synthesis and characterization of cerium sulfide thin film" (in en). Progress in Natural Science: Materials International (Elsevier) 24 (6): 663–670. doi:10.1016/j.pnsc.2014.10.005. ISSN 1002-0071.
4. ↑ 4.0 4.1 Hadden, Gavin, ed (1946). "Chapter 11 - Ames Project". Manhattan District History. 4 - Auxiliary Activities. Washington, D.C.: US Army Corps of Engineers. https://www.osti.gov/opennet/manhattan_district.
5. ↑ 5.0 5.1 5.2 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. ↑ 6.0 6.1 Wells, A. F. (1984). Structural Inorganic Chemistry (5th ed.). Oxford University Press. pp. 766–767. ISBN 978-0-19-965763-6.
7. ↑ 7.0 7.1 Tanaka, Masashi; Nagao, Masanori; Matsumoto, Ryo; Kataoka, Noriyuki; Ueta, Ikuo; Tanaka, Hiromi; Watauchi, Satoshi; Tanaka, Isao et al. (2017-10-25). "Superconductivity and its enhancement under high pressure in "F-free" single crystals of CeOBiS2" (in en). Journal of Alloys and Compounds 722: 467–473. doi:10.1016/j.jallcom.2017.06.125. ISSN 0925-8388. https://www.sciencedirect.com/science/article/pii/S0925838817321254.

* v
* t
* e

Cerium compounds

Cerium(III)|

* CeBr3
* Ce2(CO3)3
* CeCl3
* CeF3
* CeI3
* Ce(OH)3
* Ce2O3
* Ce2(SO4)3
* Ce(NO3)3

| Organocerium(III)|

* Ce(acac)3
* Ce2(C2O4)3
* Ce(CH3SO3)3

|

Cerium(III,IV)|

* Ce3O4

Cerium(IV)|

* (NH4)4Ce(SO4)4•2 H2O
* (NH4)2Ce(NO3)6
* CeB6
* Ce(NO3)4
* CeO2
* Ce(SO4)2

* v
* t
* e

Sulfides

| H2S
H2S2 |  |  |  |  |  |  |  |  |  |  |  |  |  |  |  |  | He

|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|

Li2S | BeS |  |  |  |  |  |  |  |  |  |  | B2S3 | CS2
COS | (NH4)SH | O | F | Ne
Na2S
Na2Sx | MgS |  |  |  |  |  |  |  |  |  |  | Al2S3 | SiS
SiS2 | PxSy | S | Cl | Ar
K2S | CaS | Sc2S3 | TiS2 | V | CrS
Cr2S3 | MnS
MnS2 | FeS
Fe3S4 | CoS | NiS | Cu2S
CuS | ZnS | GaS
Ga2S3 | GeS
GeS2 | As2S3
As4S3 | SeS2 | Br | Kr
Rb2S | SrS | Y2S3 | ZrS2 | NbS2 | MoS2 | Tc | Ru | Rh2S3 | PdS | Ag2S | CdS | In2S3 | SnS
SnS2 | Sb2S3
Sb2S5 | TeS2 | I | Xe
Cs2S | BaS | *  | HfS2 | TaS2 | WS2
WS3 | ReS2
Re2S7 | Os | Ir2S3
IrS2 | PtS
PtS2 | Au2S
Au2S3 | HgS | Tl2S | PbS
PbS2 | Bi2S3 | Po | At | Rn
Fr | Ra | **  | Rf | Db | Sg | Bh | Hs | Mt | Ds | Rg | Cn | Nh | Fl | Mc | Lv | Ts | Og |  |  |  |  |  |  |  |
|  | ↓ |  |  |  |  |  |  |  |  |  |  |  |  |  |  |
| * | La2S3 | CeS
Ce2S3 | Pr2S3 | Nd2S3 | Pm2S3 | SmS
Sm2S3 | Eu2S3 | Gd2S3 | Tb2S3 | Dy2S3 | Ho2S3 | Er2S3 | Tm2S3 | Yb2S3 | Lu2S3 |
| ** | Ac | ThS2 | Pa | US2 | Np | Pu | Am | Cm | Bk | Cf | Es | Fm | Md | No | Lr |

0.00

(0 votes)

Original source: https://en.wikipedia.org/wiki/Cerium(III) sulfide. Read more

|

Retrieved from "https://handwiki.org/wiki/index.php?title=Chemistry:Cerium(III)_sulfide&oldid=555380"
*[CID]: Compound ID
*[H315]: Causes skin irritation
*[H319]: Causes serious eye irritation
*[H335]: May cause respiratory irritation
*[P261]: Avoid breathing dust/fume/gas/mist/vapours/spray
*[P280]: Wear protective gloves/protective clothing/eye protection/face protection
*[P305+351+338]: IF IN EYES: Rinse continuously with water for several minutes. Remove contact lenses if present and easy to do – continue rinsing
*[v]: View this template
*[t]: Discuss this template
*[e]: Edit this template