Gallium(III) sulfate

Gallium(III) sulfate refers to the chemical compound, a salt, with the formula Ga2(SO4)3, or its hydrates Ga2(SO4)3·xH2O. Gallium metal dissolves in sulfuric acid to form solutions containing [Ga(OH2)6]3+ and SO42− ions. The octadecahydrate Ga2(SO4)3·18H2O crystallises from these solutions at room temperature. This hydrate loses water in stages when heated, forming the anhydrate Ga2(SO4)3 above 150 °C[3] and completely above 310 °C.[1] Anhydrous Ga2(SO4)3 is isostructural with iron(III) sulfate, crystallizing in the rhombohedral space group R3.[4]

Gallium(III) sulfate
Names
Other names
  • Digallium trisulfate
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • (anhydrous): 236-816-0
  • InChI=1S/2Ga.3H2O4S/c;;3*1-5(2,3)4/h;;3*(H2,1,2,3,4)/q2*+3;;;/p-6
    Key: UXLRWZBQRAWBQA-UHFFFAOYSA-H
  • (octadecahydrate): InChI=1S/2Ga.3H2O4S.18H2O/c;;3*1-5(2,3)4;;;;;;;;;;;;;;;;;;/h;;3*(H2,1,2,3,4);18*1H2/q2*+3;;;;;;;;;;;;;;;;;;;;;/p-6
    Key: RBIKSELZKJNPFC-UHFFFAOYSA-H
  • (anhydrous): [O-]S(=O)(=O)[O-].[O-]S(=O)(=O)[O-].[O-]S(=O)(=O)[O-].[Ga+3].[Ga+3]
  • (monohydrate): O.[O-]S(=O)(=O)[O-].[O-]S(=O)(=O)[O-].[O-]S(=O)(=O)[O-].[Ga+3].[Ga+3]
  • (octadecahydrate): O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[O-]S(=O)(=O)[O-].[O-]S(=O)(=O)[O-].[O-]S(=O)(=O)[O-].[Ga+3].[Ga+3]
Properties
Ga2(SO4)3
Molar mass 445.7 g/mol
Appearance White solid[1]
Density 3.86 g/cm3[2]
Melting point 680 °C (1,256 °F; 953 K)[1] (decomposes)
Slightly soluble[2]
Hazards
GHS labelling:
GHS07: Exclamation mark
Warning
H315, H319, H335
P302+P352, P305+P351+P338
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
0
0
1
Related compounds
Other cations
 Aluminium sulfate, Indium(III) sulfate,
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Preparation

Gallium(III) sulfate is prepared from the reaction of hydroxygallium diacetate and sulfuric acid. The two reactants were mixed at 90 °C and left for 2 days which produced the octadecahydrate. Then, it was dried in a vacuum for 2 hours which created the extremely hygroscopic anhydrous form. The overall reaction is below:

2Ga(CH3COO)2OH + 3H2SO4 → Ga2(SO4)3 + 4CH3COOH + 2H2O

After the production, it was confirmed to be the simple salt, Ga2(SO4)3, by x-ray diffraction.[1]

Properties

When heated over 680 °C, gallium sulfate gives off sulfur trioxide, yielding gallium(III) oxide.[1] A gallium sulfate solution in water mixed with zinc sulfate can precipitate ZnGa2O4.[5]

Derivatives

Basic gallium sulfate is known with the formula (H3O)Ga3(SO4)2(OH)6.[6]

Double gallium sulfates are known with composition NaGa3(SO4)2(OH)6, KGa3(SO4)2(OH)6, RbGa3(SO4)2(OH)6, NH4Ga3(SO4)2(OH)6. These compounds are isostructural with jarosite and alunite. Jarosite and alunite can contain a small amount of gallium substituted for iron or aluminium.[6] Organic base double gallium sulfates can contain different core structures, these can be chains of [Ga(SO4)3]3-, [Ga(OH)(SO4)2]2- or [Ga(H2O)2(SO4)2]− or sheets of [Ga(H2O)2(SO4)2]− units.[7]

formula mw crystal
system		 space
group		 unit cell Å volume density properties reference
(H3O)Ga3(SO4)2(OH)6 R3m a=7.18 c=17.17 z=1.5 766 [8]
Ga4(OH)10SO4 [9]
NH4Ga3(SO4)2(OH)6 [7]
trisodium gallium sulfate Na3Ga(SO4)3 tetragonal a = 9.451 c = 7.097 [10]
NaGa3(SO4)2(OH)6 [7]
KGa3(SO4)2(OH)6 [7]
RbGa3(SO4)2(OH)6 [7]
Caesium gallium sulfate dodecahydrate CsGa(SO4)2•12H2O cubic Pa3 Z=4 2.127 refractive index=1.461 [11]
dimethylammonium gallium sulfate hexahydrate (CH3)2NH2Ga(SO4)2·6H2O ferroeelastic [12][13]
guanidinium gallium sulfate [C(NH2)3]Ga(SO4)2·6H2O hexagonal P31m a=11.82 c=9.13 ferroelectric [14]
Ethylenediammonium acid gallium sulfate [C2H10N2][H3O][Ga(SO4)3] [7]
Ethylenediammonium basic gallium sulfate [C2H10N2][Ga(OH)(SO4)2]·H2O [7]
Tetramethylenediammonium gallium sulfate [C4H14N2][Ga(H2O)2(SO4)2]2 [7]
Hexamethylenediammonium gallium sulfate [C6H18N2][Ga(H2O)2(SO4)2]2 [7]

References
  1. V.Yu. Proydakova; S.V. Kuznetsov; V.V. Voronov; P.P. Fedorov (2017). "СИНТЕЗ СУЛЬФАТА ГАЛЛИЯ" [SYNTHESIS OF GALLIUM SULFATE]. Fine Chemical Technologies (in Russian). 12 (3): 52–57. doi:10.32362/2410-6593-2017-12-3-52-57.
  2. "Gallium(III) sulfate hydrate". Alfa Aesar. Retrieved 11 May 2021.
  3. A. J. Downs, ed. (2012). Chemistry of Aluminium, Gallium, Indium and Thallium. Springer. p. 153. ISBN 9789401049603.
  4. Krause, M.; Gruehn, R. (1995). "Contributions on the thermal behaviour of sulphates XVII.1 Single crystal structure refinements of In2(SO4)3 and Ga2(SO4)3". Z. Kristallogr. 210 (6): 427–431. Bibcode:1995ZK....210..427K. doi:10.1524/zkri.1995.210.6.427.
  5. Hirano, Masanori; Okumura, Shiro; Hasegawa, Yasunori; Inagaki, Michio (October 2002). "Direct Precipitation of Spinel-Type Zn(Fe, Ga)2O4 Solid Solutions from Aqueous Solutions at 90°C: Influence of Iron Valence of Starting Salt on Their Crystallite Growth". Journal of Solid State Chemistry. 168 (1): 5–10. Bibcode:2002JSSCh.168....5H. doi:10.1006/jssc.2002.9662.
  6. Rudolph, Wolfram W.; Schmidt, Peer (July 2011). "Studies on synthetic galloalunites AGa3(SO4)2(OH)6: Synthesis, thermal analysis, and X-ray characterization". Thermochimica Acta. 521 (1–2): 112–120. CiteSeerX 10.1.1.881.3389. doi:10.1016/j.tca.2011.04.013.
  7. Kaufman, Elizabeth A.; Zeller, Matthias; Norquist, Alexander J. (2010-10-06). "A Slow Leak Synthetic Route to Organically Templated Gallium Sulfates". Crystal Growth & Design. 10 (10): 4656–4661. doi:10.1021/cg1009412. ISSN 1528-7483.
  8. Kydon, D. W.; Pintar, M.; Petch, H. E. (1968-06-15). "NMR Evidence of H 3 O + Ions in Gallium Sulfate". The Journal of Chemical Physics. 48 (12): 5348–5351. Bibcode:1968JChPh..48.5348K. doi:10.1063/1.1668226. ISSN 0021-9606.
  9. Kang, Bong Kyun; Lim, Hyeong Dae; Mang, Sung Ryul; Song, Keun Man; Jung, Mong Kwon; Kim, Sang-Woo; Yoon, Dae Ho (2015-01-20). "Synthesis and Characterization of Monodispersed β-Ga 2 O 3 Nanospheres via Morphology Controlled Ga 4 (OH) 10 SO 4 Precursors". Langmuir. 31 (2): 833–838. doi:10.1021/la504209f. ISSN 0743-7463. PMID 25539482.
  10. Fedorov, P. P.; Proidakova, V. Yu.; Kuznetsov, S. V.; Voronov, V. V. (November 2017). "Phase equilibria in systems of gallium sulfate with lithium or sodium sulfate". Russian Journal of Inorganic Chemistry. 62 (11): 1508–1513. doi:10.1134/S0036023617110067. ISSN 0036-0236. S2CID 103985885.
  11. Howard E. Swanson, Nancy T. Gilfrich, Marlene I. Cook, Roger Stinchfield, and Paul C. Parks (1 April 1959). "Standard X-ray Diffraction Powder Patterns" (PDF).{{cite web}}: CS1 maint: multiple names: authors list (link)
  12. Yasuda, Naohiko; Kaneda, Akio; Czapla, Zbigniew (March 1999). "Pressure effects in dimethylammonium gallium sulfate (DMAGaS)". Ferroelectrics. 223 (1): 71–78. Bibcode:1999Fer...223...71Y. doi:10.1080/00150199908260555. ISSN 0015-0193.
  13. Völkel, G; Böttcher, R; Michel, D; Czapla, Z; Banys, J (2005-07-20). "Dimethylammonium gallium sulfate hexahydrate and dimethylammonium aluminium sulfate hexahydrate—members of a crystal family with exceptional commensurate/incommensurate phase sequences". Journal of Physics: Condensed Matter. 17 (28): 4511–4529. Bibcode:2005JPCM...17.4511V. doi:10.1088/0953-8984/17/28/010. ISSN 0953-8984. S2CID 98806133.
  14. Geller, S.; Booth, D.P. (1959-01-01). "The crystal structure of guanidinium gallium sulfate hexahydrate, [C(NH2)3]Ga(SO4)2·6H2O". Zeitschrift für Kristallographie - Crystalline Materials. 111 (1–6): 117–128. doi:10.1524/zkri.1959.111.16.117. ISSN 2196-7105. S2CID 201840778.
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