Indium(III) sulfate

Properties

In water solution, the indium ion forms a complex with water and sulfate, examples being and . Indium is unusual in forming a sulfate complex. The effect on the sulfate ion is revealed in the Raman spectrum. The proportion of sulfate complex increases with temperature showing the reaction that forms it is endothermic. The proportion also increases with concentration of the solution and can be over a half.

The Raman spectrum of the solution shows lines at 650, 1000 and due to a sulfur–oxygen bonds in sulfate bound to indium. A line at is due to the indium-oxygen bond to the sulfate. The water attached to the indium atom causes a band at about .

During extraction of indium, a sulfate solution of mixed metals, including indium sulfate, has trivalent metals partitioned into a kerosene solution of di-2-ethylhexyl hydrogen phosphate. Isododecylphosphetanic and diisooctylphosphinic acids can also be used for this function. The kerosene mixture is then backwashed with an acid to recover the metals in a water solution and regenerate the extracting fluid.

The heat capacity of anhydrous indium sulfate at standard conditions is 65.73 cal/deg/mole (1.651 J/g/deg). The heat capacity increases smoothly with temperature, indicating no crystal structure transitions.

Production

Indium metal reacts with cold concentrated sulfuric acid to produce Indium sulfate and hydrogen gas. If hot concentrated sulfuric acid is used indium will reduce the sulfuric acid to sulfur dioxide.

Indium sulfate can also be produced from a reaction of sulfuric acid on indium oxide, indium carbonate, or indium hydroxide.

Reactions

When heated to 710 K or above, indium sulfate decomposes by giving off sulfur trioxide vapour, yielding indium oxide.

:

Alkalis added to indium sulfate solutions precipitate basic salts. For example, potassium hydroxide produces either a basic sulfate, , or depending on pH. Sodium pyrophosphate causes a slimy precipitate of indium pyrophosphate, . Potassium periodate causes a precipitate of a basic indium periodate, . Oxalic acid causes a precipitate of indium oxalate, . Alkali oxalates cause a precipitate of the alkali dioxalatoindate to form , where M = Na, K or NH4.

Related compounds

Hydrogen sulfates

An acid sulfate, indium hydrogensulfate tetrahydrate with the formula crystallises in the orthorhombic system with unit cell dimensions a = , b = , c = , with four of the formula per cell. The density is . In the acid sulfate, two water molecules are linked to the indium atom and a hydronium ion takes care of the proton. This is part of an acid sulfate family that includes Al, Ga, In, Tl(III), Fe(III) and Ti(III). is made by evaporating an indium sulfate in 40% sulfuric acid solution or cooling indium sulfate in a 60% sulfuric acid solution. As the acid tetrahydrate is heated it gives off water yielding a trihydrate, monohydrate, and an anhydrous form at 370 K, 385 K and 482 K. Above 505 K it gives out more water and sulfur dioxide yielding the neutral indium sulfate. Indium hydrogensulfate is a proton conductor with conductivity .

Basic sulfates

A basic indium sulfate is made by adding ethanol to a water solution of indium sulfate. Crystals can be formed by using a 0.05 molar solution with twice the volume of ethanol, and waiting for several weeks for crystals to form. has monoclinic crystals with a= b= c= and β=107.5°. Cell volume is . This insoluble basic salt also forms if indium sulfate solution is diluted below 0.005 molar. So a precipitate forms from diluted solutions as well as from heated solutions.

Anhydrous double sulfates

Two different types of anhydrous double indium sulfates have been made. One is from the family M, with M being a large singly positive ion such as K, Rb, Cs, Tl or ; M is triply charged and can be Al, Ga, In, Tl, V, Cr, Fe, Sc and other rare earths; and X is S or Se. Most of these have a rhombohedral crystal structure. However, triammonium indium trisulfate, converts from rhombohedral to monoclinic as the temperature drops below 80 C, and converts back into a rhombohedral form with space group R3c as the temperature rises above 110 C.

Another series of anhydrous rhombohedral double salts in the same series of exists. These can be made by heating a mixture of anhydrous sulfates at 350 C, or by dehydrating hydrous double alum type salts at 300 C. The substances in this series are , , and . Although exists it has a different crystalline form.

Hydrated double sulfates

Hydrated double salts of indium in an alum structure exist with formula . All alums have a cubic crystal structure with space group Pa3. has molecular weight 656.0, unit cell width , cell volume and density . It has the β alum structure. The cesium alum can be used in the analysis of indium. It precipitates when cesium nitrate is added to indium sulfate solution with extra sulfuric acid added.

Indium ammonium alum is fairly unstable at room temperature and must be crystallised below 5 C. It decomposes at 36 C to a tetrahydrate. It changes to a ferroelectric phase below 127 K. The alum methyl ammonium indium sulfate dodecahydrate becomes ferroelectric below 164 K. Potassium indium alum has not been crystallised. Rubidum indium alum is highly efflorescent very easily losing its water.

Another series of monoclinic hydrated double salts have four water molecules , with five formulae per unit cell, where M is , K or Rb and the point group is P2/c. The prototype substance for the series is .

Cadmium can also form a double sulfate, .

Crystals with less water also exist like .

Organic double sulfates

Organic base double sulfates of indium include the guanidinium salt , which crystallises in a monoclinic system with space group P2/c a = , b = , c = , β = 93.39°, cell volume , 4 formulas per cell and density . [H(4,4'-bi-py)] crystallises in the triclinic system with a = , b = , c = , α = 107.61°, β = 98.79°, γ = 93.89°, cell volume , one formula per cell and density . [H(2,2'-bipy)], the hexamethylenediamine salt and also exist. Yet other organic derivatives include those of triethylenetetramine, and amylammonium. Tri-μ-sulfato-κ6O:O'-bis[aqua(1,10-phenanthroline-κ2N,N')indium(III)] dihydrate, , has a 1,10-phenanthroline molecule linked to each indium ion. Two indium ions are linked via three sulfate groups. It forms triclinic crystals with two formulas per unit cell. The density is .

Dimethylindium sulfate can be made by reacting trimethylindium with dry sulfuric acid.

Mixed

A double indium sulfate chloride salt has formula where n = .

Monovalent

Indium(I) sulfate, can be made in a solid state by heating indium metal with indium(III) sulfate, but when dissolving in water or sulfuric acid, reacts to produce hydrogen gas. The mixed valence salt is also made by heating indium metal with indium(III) sulfate.

Use

Indium sulfate is a commercially available chemical. It can be used to electroplate indium metal, as a hardening agent in gold electroplating or to prepare other indium containing substances such as copper indium selenide. It has been sold as a health supplement, even though there is no evidence of benefit to humans, and it is toxic.

The first high-frequency transistor was the surface-barrier germanium transistor developed by Philco in 1953, capable of operating up to . These were made by etching depressions into an N-type germanium base from both sides with jets of indium sulfate until it was a few ten-thousandths of an inch thick. Indium electroplated into the depressions formed the collector and emitter.

References

References

1. link. (10 February 2012 ''Indium Cooperation'')
2. (July 1933). "Indium Sulfate". Journal of the American Chemical Society.
3. (2015). "Handbook of Inorganic Substances 2015". Walter de Gruyter.
4. (2013). "Structural assessment of anhydrous sulfates with high field 33S solid state NMR and first principles calculations". CrystEngComm.
5. (1 January 1880). "On the Molecular Heat and Volume of the Rare Earths and Their Sulphates". Proceedings of the Royal Society of London.
6. "Sfety Data Sheet Indium sulfate anhydrous 99.99%". Pfaltz & Bauer, Inc..
7. "MSDS OF Indium Sulfate".
8. (September 1981). "An X-ray diffraction study of the structure of the aqua indium(III) ion in indium sulphate solution". Chemical Physics Letters.
9. (1966). "Advanced Inorganic Chemistry". John Wiley & Sons.
10. (1963). "Raman Spectra of Aqueous Solutions of Indium Sulfate, Nitrate, and Perchlorate". The Journal of Chemical Physics.
11. (22 October 2013). "The Analytical Chemistry of Indium". Elsevier.
12. (October 2004). "Extraction of indium(III) from sulfate solutions with organophosphorus acids". Russian Journal of Applied Chemistry.
13. (1969). "Thermodynamic Data for Ferric Sulfate and Indium Sulfate". U.S. Department of the Interior, Bureau of Mines.
14. (August 1944). "Indium". Journal of Chemical Education.
15. (April 1999). "Synthesis and structure of indium oxide nanoparticles dispersed within pores of mesoporous silica". Materials Research Bulletin.
16. (1984). "Chapter 4. Al, Ga, In, Tl". Annual Reports on the Progress of Chemistry, Section A.
17. (22 October 2013). "The Analytical Chemistry of Indium". Elsevier.
18. (22 October 2013). "The Analytical Chemistry of Indium". Elsevier.
19. (15 July 1979). "Structure cristalline du sulfate acide d'indium(III) hydraté". Acta Crystallographica Section B.
20. (January 2007). "Proton conduction in indium hydrogensulfate and hydrous zirconia composites". Russian Journal of Inorganic Chemistry.
21. (1961). "The Crystal Structure of InOHSO₄(H₂O)₂". Acta Chemica Scandinavica.
22. (1962). "The Crystal Structure of FeOHSO₄ and InOHSO₄". Acta Chemica Scandinavica.
23. (15 November 1980). "The low-temperature forms of some M1/3MIII(XO4)3 compounds: structure of triammonium indium(III) trisulfate". Acta Crystallographica Section B.
24. (July 1974). "Préparation et caractérisation cristallographique de quelques sulfates doubles d'indium(III) et de thallium(III), MI3MIII (SO4)3 (MI = Na, K, Rb et Cs)". Journal of the Less Common Metals.
25. (June 1972). "Preparation et caracterisation cristallographique des sulfates et seleniates doubles anhydres d'indium M¹In(XO₄)₂". Journal of the Less Common Metals.
26. (2004). "Indium(iii) hydration in aqueous solutions of perchlorate, nitrate and sulfate. Raman and infrared spectroscopic studies and ab-initio molecular orbital calculations of indium(iii)-water clusters". Physical Chemistry Chemical Physics.
27. (1981). "Structural studies on the caesium alums, CsM III [SO₄]₂{{Hydrate". Journal of the Chemical Society, Dalton Transactions.
28. (1997). "Chromium luminescence as a probe of site effects in the alum lattice". Journal of the Chemical Society, Dalton Transactions.
29. (22 October 2013). "The Analytical Chemistry of Indium". Elsevier.
30. (June 1936). "Some Double Salts of Indium and Organic Bases". Journal of the American Chemical Society.
31. (1 September 1987). "NMR and dielectric studies of NH4+ motion in some ammonium alums". Physica Scripta.
32. (1888). "The Encyclopædia Britannica: A Dictionary of Arts, Sciences, and General Literature".
33. (1973). "Nuclear quadrupole coupling of 115In in NH₄In(SO₄)₂{{Hydrate". The Journal of Chemical Physics.
34. (1 September 1975). "EPR of Cr3+ in Methyl Ammonium Indium Sulfate Dodecahydrate". Physica Status Solidi B.
35. (1 February 1963). "A STUDY ON THE PROBABLE EXISTENCE OF POTASSIUM INDIUM ALUM WITH RADIOACTIVE NUCLEI. PART I". Journal of the Indian Chemical Society.
36. (April 1999). "Vibrational spectra of hexaaqua complexes.". Vibrational Spectroscopy.
37. "inorganic Materials Database".
38. (May 2024). "Inorganic Materials Database".
39. (May 2024). "Inorganic Materials Database".
40. (November 1983). "[Study of zinc- and cadmium sulfates interaction with indium sulfate in aqueous solution at 25 deg C]". Zhurnal Neorganicheskoj Khimii.
41. (March 1979). "Crystal structure of KIn(SO4)₂{{Hydrate". Soviet Physics Doklady.
42. (November 2006). "Supramolecular compounds of indium sulfates with nitrogen-containing cations". Russian Journal of Coordination Chemistry.
43. (March 2009). "Solvothermal Synthesis and Characterization of One-dimensional Chained Indium-Sulfate". Chemical Journal of Chinese Universities.
44. (15 September 2010). "Tri-µ-sulfato-κ6O:O'-bis[aqua(1,10-phenanthroline- κ2N,N')indium(III)] dihydrate". Acta Crystallographica Section E.
45. (June 1973). "Bis(dialkylmetall)sulfate der elemente gallium, indium und thallium". Journal of Organometallic Chemistry.
46. (August 1977). "Double salts of indium trichloride with the alkali chlorides, with ammonium chloride, and with indium sulfate". Canadian Journal of Chemistry.
47. (September 1986). "Vzaimodejstvie metallicheskogo indiya s sul'fatom indiya(3)". Zhurnal Neorganicheskoj Khimii.
48. (May 1982). "Sul'fat odnovalentnogo indiya, ego sintez i svojstva". Zhurnal Obshchej Khimii.
49. (31 May 1993). "Chemistry of Aluminium, Gallium, Indium, and Thallium". Springer.
50. (14 March 2013). "Indium: Geology, Mineralogy, and Economics". Springer Science & Business Media.
51. "Indium Corp. In2(SO4)3 Indium Sulfate Anhydrous".
52. (2 July 2008). "Health Benefits of Indium".
53. (December 1953). "The Surface-Barrier Transistor: Part I-Principles of the Surface-Barrier Transistor". Proceedings of the IRE.
54. (4 December 1953). "Philco Claims Its Transistor Outperforms Others Now In Use". Wall Street Journal.
55. (January 1954). "Electroplated Transistors Announced". Electronics Magazine.