Mercury(II) sulfate, commonly called mercuricsulfate, is the chemical compoundHgSO4. It is an odorless salt that forms white granules or crystalline powder. In water, it separates into an insoluble sulfate with a yellow color and sulfuric acid.[3]
Portion of structure of HgSO4 illustrating the distorted tetrahedral geometry at Hg (dark blue spheres).
The anhydrous compound features Hg2+ in a highly distorted tetrahedral HgO4 environment. Two Hg-O distances are 2.22 Å and the others are 2.28 and 2.42 Å.[5] In the monohydrate, Hg2+ adopts a linear coordination geometry with Hg-O (sulfate) and Hg-O (water) bond lengths of 2.179 and 2.228 Å, respectively. Four weaker bonds are also observed with Hg---O distances >2.5 Å.[6]
Historyedit
In 1932, the Japanese chemical company Chisso Corporation began using mercury sulfate as the catalyst for the production of acetaldehyde from acetylene and water. Though it was unknown at the time, methylmercury is formed as side product of this reaction. Exposure and consumption of the mercury waste products, including methylmercury, that were dumped into Minamata Bay by Chisso are believed to be the cause of Minamata disease in Minamata, Japan.[7]
Productionedit
Mercury sulfate can be produced by treating mercury with hot concentrated sulfuric acid:[8]
An acidic solution of mercury sulfate is known as Denigés' reagent. It was commonly used throughout the 20th century as a qualitative analysis reagent. If Denigés' reagent is added to a solution containing compounds that have tertiary alcohols, a yellow or red precipitate will form.[10]
The reaction scheme is provided below. The conversion of 2,5-dimethyhexyn-2,5-diol to 2,2,5,5-tetramethylte-trahydrofuran using aqueous mercury sulfate without the addition of acid.[12]
Conversion of 2,5-dimethyhexyn-2,5-diol to 2,2,5,5-tetramethylte-trahydrofuran-3-one
Health issuesedit
Inhalation of HgSO4 can result in acute poisoning: causing tightness in the chest, difficulties breathing, coughing and pain. Exposure of HgSO4 to the eyes can cause ulceration of conjunctiva and cornea. If mercury sulfate is exposed to the skin it may cause sensitization dermatitis. Lastly, ingestion of mercury sulfate will cause necrosis, pain, vomiting, and severe purging. Ingestion can result in death within a few hours due to peripheral vascular collapse.[1]
It was used in the late 19th century to induce vomiting for medical reasons. [1]
^Aurivillius, Karin; Stålhandske, Claes (1980). "A Reinvestigation of the Crystal Structures of HgSO4 and CdSO4". Zeitschrift für Kristallographie - Crystalline Materials. 153 (1–2): 121–129. Bibcode:1980ZK....153..121A. doi:10.1524/zkri.1980.0011.
^Stålhandske, C. (1980). "An X-ray and Neutron Diffraction Study of Mercury(II) Sulphate Monohydrate". Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry. 36: 23–26. doi:10.1107/s0567740880002361.
^Minamata Disease. Boston University. Retrieved 2016-11-10.
^Simon, Matthias; Jönk, Peter; Wühl-Couturier, Gabriele; Halbach, Stefan (2006). "Mercury, Mercury Alloys, and Mercury Compounds". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a16_269.pub2. ISBN3527306730.
^Robey, R. F.; Robertson, N. C. (May 1947). "Test for tert-Butyl and Isopropyl Alcohols with Deniges Reagent". Analytical Chemistry. 19 (5): 310–311. doi:10.1021/ac60005a007.
^Marks, E. M.; Lipkin, D. (1939). "Reaction of Aliphatic Ethers with Denigés' Reagent". J. Org. Chem. 3 (6): 598–602. doi:10.1021/jo01223a008.
^Vogt, R; Nieuwland, J (September 1921). "The role of mercury salts in the catalytic transformation of acetylene into acetaldehyde, and a new commercial process for manufacture of paraaldehyde". J. Am. Chem. Soc. 43 (9): 2071–81. doi:10.1021/ja01442a010.
^Wasacz, J. P.; Badding, V. G. (1982). "A hydration of an alkyne illustrating steam and vacuum distillation". Journal of Chemical Education. 59 (8): 694. Bibcode:1982JChEd..59..694W. doi:10.1021/ed059p694.
External linksedit
Wikimedia Commons has media related to Mercury(II) sulfate.
NIOSH Pocket Guide to Chemical Hazards
November 23, 2023
mercury, sulfate, commonly, called, mercuric, sulfate, chemical, compound, hgso4, odorless, salt, that, forms, white, granules, crystalline, powder, water, separates, into, insoluble, sulfate, with, yellow, color, sulfuric, acid, namesother, names, mercuric, s. Mercury II sulfate commonly called mercuric sulfate is the chemical compound HgSO4 It is an odorless salt that forms white granules or crystalline powder In water it separates into an insoluble sulfate with a yellow color and sulfuric acid 3 Mercury II sulfate NamesOther names Mercuric sulfate Mercurypersulfate Mercury Bisulfate 1 IdentifiersCAS Number 7783 35 9 Y3D model JSmol Interactive imageChemSpider 22950ECHA InfoCard 100 029 083EC Number 231 992 5PubChem CID 24544RTECS number OX0500000UNII J4L3PPG58I YUN number 1645CompTox Dashboard EPA DTXSID7064819InChI InChI 1S Hg H2O4S c 1 5 2 3 4 h H2 1 2 3 4 q 2 p 2Key DOBUSJIVSSJEDA UHFFFAOYSA LSMILES O S O O O Hg 2 PropertiesChemical formula HgSO4Molar mass 296 653 g molAppearance white monoclinic crystalsOdor odorlessDensity 6 47 g cm3 solidSublimationconditions 450 C dec 2 Solubility in water Decomposes in water to yellow mercuric subsulfate and sulfuric acidSolubility soluble in hot H2SO4 NaCl solution insoluble in alcohol acetone ammoniaMagnetic susceptibility x 78 1 10 6 cm3 molStructureCrystal structure rhombicThermochemistryStd enthalpy offormation DfH 298 707 5 kJ mol 1 3 HazardsGHS labelling 4 PictogramsSignal word DangerHazard statements H300 H310 H330 H373 H410Precautionary statements P260 P262 P264 P270 P271 P273 P280 P284 P301 P316 P302 P352 P304 P340 P316 P319 P320 P321 P330 P361 P364 P391 P403 P233 P405 P501NFPA 704 fire diamond 301Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox references Contents 1 Structure 2 History 3 Production 4 Uses 4 1 Deniges reagent 4 2 Production of acetaldehyde 4 3 Oxymercuration demercuration of alkenes 4 4 Hydration of alkynes 5 Health issues 6 References 7 External linksStructure edit nbsp Portion of structure of HgSO4 illustrating the distorted tetrahedral geometry at Hg dark blue spheres The anhydrous compound features Hg2 in a highly distorted tetrahedral HgO4 environment Two Hg O distances are 2 22 A and the others are 2 28 and 2 42 A 5 In the monohydrate Hg2 adopts a linear coordination geometry with Hg O sulfate and Hg O water bond lengths of 2 179 and 2 228 A respectively Four weaker bonds are also observed with Hg O distances gt 2 5 A 6 History editIn 1932 the Japanese chemical company Chisso Corporation began using mercury sulfate as the catalyst for the production of acetaldehyde from acetylene and water Though it was unknown at the time methylmercury is formed as side product of this reaction Exposure and consumption of the mercury waste products including methylmercury that were dumped into Minamata Bay by Chisso are believed to be the cause of Minamata disease in Minamata Japan 7 Production editMercury sulfate can be produced by treating mercury with hot concentrated sulfuric acid 8 Hg 2 H2SO4 HgSO4 SO2 2 H2OAlternatively yellow mercuric oxide reacts also with concentrated sulfuric acid 9 Uses editDeniges reagent edit An acidic solution of mercury sulfate is known as Deniges reagent It was commonly used throughout the 20th century as a qualitative analysis reagent If Deniges reagent is added to a solution containing compounds that have tertiary alcohols a yellow or red precipitate will form 10 Production of acetaldehyde edit As previously mentioned Hg S O4 was used as the catalyst for the production of acetaldehyde from acetylene and water 11 Oxymercuration demercuration of alkenes edit Mercury Compounds such as mercury sulfate and mercury II acetate are commonly used as catalysts in the oxymercuration demercuration a type of Electrophilic Addition reaction The hydration of an alkene results in an alcohol that follows regioselectivity that is predicted by Markovnikov s Rule citation needed Hydration of alkynes edit The reaction scheme is provided below The conversion of 2 5 dimethyhexyn 2 5 diol to 2 2 5 5 tetramethylte trahydrofuran using aqueous mercury sulfate without the addition of acid 12 nbsp Conversion of 2 5 dimethyhexyn 2 5 diol to 2 2 5 5 tetramethylte trahydrofuran 3 oneHealth issues editInhalation of HgSO4 can result in acute poisoning causing tightness in the chest difficulties breathing coughing and pain Exposure of HgSO4 to the eyes can cause ulceration of conjunctiva and cornea If mercury sulfate is exposed to the skin it may cause sensitization dermatitis Lastly ingestion of mercury sulfate will cause necrosis pain vomiting and severe purging Ingestion can result in death within a few hours due to peripheral vascular collapse 1 It was used in the late 19th century to induce vomiting for medical reasons 1 References edit a b Chemicalbook Retrieved 2 May 2011 Wu Shengji Uddin Md Azhar Nagano Saori Ozaki Masaki Sasaoka Eiji 2011 Fundamental Study on Decomposition Characteristics of Mercury Compounds over Solid Powder by Temperature Programmed Decomposition Desorption Mass Spectrometry Energy amp Fuels 25 1 144 153 doi 10 1021 ef1009499 a b Lide David R 1998 Handbook of Chemistry and Physics 87 ed Boca Raton Florida CRC Press pp 5 19 ISBN 0 8493 0594 2 Mercuric sulfate pubchem ncbi nlm nih gov Aurivillius Karin Stalhandske Claes 1980 A Reinvestigation of the Crystal Structures of HgSO4 and CdSO4 Zeitschrift fur Kristallographie Crystalline Materials 153 1 2 121 129 Bibcode 1980ZK 153 121A doi 10 1524 zkri 1980 0011 Stalhandske C 1980 An X ray and Neutron Diffraction Study of Mercury II Sulphate Monohydrate Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 36 23 26 doi 10 1107 s0567740880002361 Minamata Disease Boston University Retrieved 2016 11 10 Simon Matthias Jonk Peter Wuhl Couturier Gabriele Halbach Stefan 2006 Mercury Mercury Alloys and Mercury Compounds Ullmann s Encyclopedia of Industrial Chemistry doi 10 1002 14356007 a16 269 pub2 ISBN 3527306730 Robey R F Robertson N C May 1947 Test for tert Butyl and Isopropyl Alcohols with Deniges Reagent Analytical Chemistry 19 5 310 311 doi 10 1021 ac60005a007 Marks E M Lipkin D 1939 Reaction of Aliphatic Ethers with Deniges Reagent J Org Chem 3 6 598 602 doi 10 1021 jo01223a008 Vogt R Nieuwland J September 1921 The role of mercury salts in the catalytic transformation of acetylene into acetaldehyde and a new commercial process for manufacture of paraaldehyde J Am Chem Soc 43 9 2071 81 doi 10 1021 ja01442a010 Wasacz J P Badding V G 1982 A hydration of an alkyne illustrating steam and vacuum distillation Journal of Chemical Education 59 8 694 Bibcode 1982JChEd 59 694W doi 10 1021 ed059p694 External links edit nbsp Wikimedia Commons has media related to Mercury II sulfate National Pollutant Inventory Mercury and compounds Fact Sheet NIOSH Pocket Guide to Chemical Hazards Retrieved from https en wikipedia org w index php title Mercury II sulfate amp oldid 1163342757, wikipedia, wiki, book, books, library,
