Mercury(II) sulfate

Mercury(II) sulfate
Names
	Other names Mercuric sulfate, Mercurypersulfate, Mercury Bisulfate[1]
Identifiers
CAS Number	7783-35-9 ;
ECHA InfoCard	100.029.083
PubChem CID	24544;
UNII	J4L3PPG58I ;
CompTox Dashboard (EPA)	DTXSID7064819 ;
Properties
Chemical formula	HgSO4
Molar mass	296.653 g/mol
Appearance	white monoclinic crystals
Odor	odorless
Density	6.47 g/cm³, solid
Sublimation; conditions	450 °C (dec.)[2]
Solubility in water	Decomposes in water to yellow mercuric subsulfate and sulfuric acid
Solubility	soluble in hot H2SO4, NaCl solution ; insoluble in alcohol, acetone, ammonia
Magnetic susceptibility (χ)	−78.1·10−6 cm3/mol
Structure
Crystal structure	rhombic
Thermochemistry
Std enthalpy of; formation (ΔfH⦵298)	−707.5 kJ mol−1[3]
Hazards
NFPA 704 (fire diamond)	0 3 1
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	verify (what is ?)
	Infobox references

Mercury(II) sulfate, commonly called mercuric sulfate, is the chemical compound Hg S O₄. It is an odorless solid that forms white granules or crystalline powder. In water, it separates into an insoluble sulfate with a yellow color and sulfuric acid.[3]

History

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.[4]

Production

Mercury sulfate, HgSO₄, can be produced by heating concentrated H₂SO₄ with elemental mercury:[5]

Hg + 2 H₂SO₄ → HgSO₄ + SO₂ + 2 H₂O

Or by dissolving solid yellow mercuric oxide in concentrated sulfuric acid and water. [6]

Uses

Denigés' reagent

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.[7]

Production of acetaldehyde

As previously mentioned, Hg S O₄ was used as the catalyst for the production of acetaldehyde from acetylene and water.[8]

Oxymercuration-demercuration of alkenes

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.

Hydration of alkynes

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.[9]

Conversion of 2,5-dimethyhexyn-2,5-diol to 2,2,5,5-tetramethylte-trahydrofuran-3-one

Health issues

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.

References

"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 & Fuels. 25 (1): 144–153. doi:10.1021/ef1009499.
Lide, David R. (1998). Handbook of Chemistry and Physics (87 ed.). Boca Raton, Florida: CRC Press. pp. 5–19. ISBN 0-8493-0594-2.
Minamata Disease. Boston University. Retrieved 2016-11-10.
Mercury in Your Environment | US EPA. Epa.gov (4 October 2016). Retrieved 2016-11-04.
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. doi:10.1021/ed059p694.

External links

This article is issued from Wikipedia. The text is licensed under Creative Commons - Attribution - Sharealike. Additional terms may apply for the media files.

[chembook-1] "Chemicalbook". Retrieved 2 May 2011.

[2] 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 & Fuels. 25 (1): 144–153. doi:10.1021/ef1009499.

[hand-3] Lide, David R. (1998). Handbook of Chemistry and Physics (87 ed.). Boca Raton, Florida: CRC Press. pp. 5–19. ISBN 0-8493-0594-2.

[4] Minamata Disease. Boston University. Retrieved 2016-11-10.

[5] Mercury in Your Environment | US EPA. Epa.gov (4 October 2016). Retrieved 2016-11-04.

[6] 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.

[7] 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-8] 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.

[9] Wasacz, J. P.; Badding, V. G. (1982). "A hydration of an alkyne illustrating steam and vacuum distillation". Journal of Chemical Education. 59 (8): 694. doi:10.1021/ed059p694.