Silver(II) sulfate
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3D model (JSmol) |
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| Properties | |
| AgSO4 | |
| Molar mass | 203.93 g/mol |
| Appearance | Black solid |
| Density | 4.46 g/cm3 |
| Melting point | 126 °C (259 °F; 399 K)[1] (decomposition) |
| Reacts[1][2] | |
| Solubility | Insoluble in sulfuric acid and organic solvents[1][3] |
| Related compounds | |
Other cations |
Copper(II) sulfate Gold(II) sulfate |
Related compounds |
Silver(I) sulfate |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Silver(II) sulfate is an inorganic chemical compound with the formula AgSO4. A lesser-known silver sulfate compared to the much more common silver(I) sulfate, it is a black solid that also forms the monohydrate, AgSO4·H2O, which is also a black solid.[2]
Preparation and structure
[edit]Silver(II) sulfate is prepared by the reaction of silver(II) fluoride and sulfuric acid:[2]
- AgF2 + H2SO4 → AgSO4 + 2 HF
Different reaction temperatures produce different polymorphs. The reaction at –35 °C produces the more common α form, while the reaction at 70 °C produces a mixture of the α and β forms.[2][4]
α-AgSO4 can also be produced electrochemically by the electrolysis of a solution of silver(I) sulfate in sulfuric acid. This method produces a purer product than the first method.[1]
The α polymorph, an antiferromagnet isostructural to a high-temperature polymorph of PdSO4, has square-planar AgO4 centers which are all linked by SO4 tetrahedra. This polymorph is relatively unchanged even at pressures up to 23 GPa. Above this pressure, it decomposes to silver pyrosulfate (Ag2S2O7) with the release of oxygen.[5][6]
The β polymorph, isostructural to CuSO4, has distorted AgO6 octahederas also linked by SO4 tetrahedra.[4]
Anhydrous silver(II) sulfate slowly absorbs moisture from air to produce the monohydrate, AgSO4·H2O, which converts back to the anhydrous form when heated to 90 °C. Its structural formula is [Ag(H2O)2][Ag(SO4)2], indicating the presence of two different silver atom environments which are linked by SO4 bridges.[7]
| Compound | α-AgSO4[6] | β-AgSO4[4] | AgSO4·H2O[7] |
|---|---|---|---|
| Crystal Structure | Monoclinic | Monoclinic | Triclinic |
| Space Group | C2/c | P21/n | P1 |
| Lattice constant a (Å) | 12.85 | 4.75 | 5.12 |
| Lattice constant b (Å) | 13.67 | 8.77 | 5.39 |
| Lattice constant c (Å) | 9.37 | 7.22 | 7.85 |
| α | 107.3° | ||
| β | 47.6° | 94.0° | 105.1° |
| γ | 92.4° | ||
| Z | 16 | 4 | 2 |
| Calculated density (g/cm3) | 4.46 | 4.51 | 3.72 |
Properties and reactions
[edit]Anhydrous silver(II) sulfate slowly hydrates in air to the monohydrate. The monohydrate is air-stable; however, any impurities catalyze the reduction to silver(I) sulfate. The monohydrate releases water, forming the anhydrous form (α polymorph) when heated to 90 °C, which in turn exothermically decomposes to silver pyrosulfate (Ag2S2O7) at 126 °C:[8][7]
- 2 AgSO4 → 2 Ag2S2O7 + O2
On the other hand, the β polymorph decomposes at 220 °C also to silver pyrosulfate. The resulting silver pyrosulfate decomposes at 344 °C to silver(I) sulfate with the release of sulfur trioxide:[4][2][1]
- Ag2S2O7 → Ag2SO4 + SO3
Applications
[edit]Silver(II) sulfate has no applications, but is being studied as an oxidizing agent in organic chemistry, such as in the C-C coupling of aromatic systems.[3]
References
[edit]- 1 2 3 4 5 Połczyński, Piotr; Gilewski, Tomasz E.; Gawraczyński, Jakub; Derzsi, Mariana; Leszczyński, Piotr Jerzy; Gadomski, Wojciech; Mazej, Zoran; Jurczakowski, Rafał; Grochala, Wojciech (2016). "Efficient Electrosynthesis of Ag II SO 4 : A Powerful Oxidizer and Narrow Band Gap Semiconductor". European Journal of Inorganic Chemistry. 2016 (35): 5401–5404. Bibcode:2016EJIC.2016.5401P. doi:10.1002/ejic.201601183. ISSN 1434-1948.
- 1 2 3 4 5 Malinowski, Przemysław J.; Derzsi, Mariana; Mazej, Zoran; Jagličić, Zvonko; Gaweł, Bartłomiej; Łasocha, Wiesław; Grochala, Wojciech (2010). "Ag II SO 4 : A Genuine Sulfate of Divalent Silver with Anomalously Strong One-Dimensional Antiferromagnetic Interactions". Angewandte Chemie International Edition. 49 (9): 1683–1686. Bibcode:2010ACIE...49.1683M. doi:10.1002/anie.200906863. ISSN 1433-7851. PMID 20084660.
- 1 2 Budniak, Adam K.; Masny, Michał; Prezelj, Kristina; Grzeszkiewicz, Mikołaj; Gawraczyński, Jakub; Dobrzycki, Łukasz; Cyrański, Michał K.; Koźmiński, Wiktor; Mazej, Zoran; Fijałkowski, Karol J.; Grochala, Wojciech; Leszczyński, Piotr J. (2017). "Reconnaissance of reactivity of an Ag(II)SO 4 one-electron oxidizer towards naphthalene derivatives". New Journal of Chemistry. 41 (19): 10742–10749. doi:10.1039/C7NJ02299A. ISSN 1144-0546.
- 1 2 3 4 Domański, Mateusz; Mazej, Zoran; Grochala, Wojciech (2022). "New CuSO 4 -related high-temperature polymorph of Ag II SO 4". Zeitschrift für anorganische und allgemeine Chemie. 648 (24) e202200252. Bibcode:2022ZAACh.648E0252D. doi:10.1002/zaac.202200252. ISSN 0044-2313.
- ↑ Köhler, Jürgen (2010). "Strong One-Dimensional Antiferromagnetic Interactions of Silver(II) Ions in Silver Sulfate". Angewandte Chemie International Edition. 49 (18): 3114–3115. Bibcode:2010ACIE...49.3114K. doi:10.1002/anie.201000448. ISSN 1433-7851. PMID 20229557.
- 1 2 Derzsi, Mariana; Budzianowski, Armand; Struzhkin, Viktor V.; Malinowski, Przemysław J.; Leszczyński, Piotr J.; Mazej, Zoran; Grochala, Wojciech (2013). "Redetermination of crystal structure of Ag( ii )SO 4 and its high-pressure behavior up to 30 GPa". CrystEngComm. 15 (1): 192–198. Bibcode:2013CEG....15..192D. doi:10.1039/C2CE26282G. ISSN 1466-8033.
- 1 2 3 Gilewski, Tomasz E.; Gawraczyński, Jakub; Derzsi, Mariana; Jagličić, Zvonko; Mazej, Zoran; Połczyński, Piotr; Jurczakowski, Rafal; Leszczyński, Piotr J.; Grochala, Wojciech (2017). "[Ag(OH 2 ) 2 ][Ag(SO 4 ) 2 ]: A Hydrate of a Silver(II) Salt". Chemistry – A European Journal. 23 (8): 1805–1813. Bibcode:2017ChEuJ..23.1805G. doi:10.1002/chem.201604179. ISSN 0947-6539. PMID 27862472.
- ↑ Malinowski, Przemyslaw Jan; Derzsi, Mariana; Budzianowski, Armand; Leszczyński, Piotr J.; Gaweł, Bartlomiej; Mazej, Zoran; Grochala, Wojciech (2011). "Unusual Thermal Decomposition of Ag II SO 4 Yielding Ag I 2 S 2 O 7 : Bending Hammond's Rule". Chemistry – A European Journal. 17 (38): 10524–10527. Bibcode:2011ChEuJ..1710524M. doi:10.1002/chem.201101952. ISSN 0947-6539. PMID 21853491.