Mercury(II) sulfate

Mercury(II) sulfate
Names
Other names
Mercuric sulfate, Mercurypersulfate, Mercury Bisulfate[1]
Identifiers
ECHA InfoCard 100.029.083
Properties
HgSO4
Molar mass 296.653 g/mol
Appearance white monoclinic crystals
Odor odorless
Density 6.47 g/cm³, solid
450 °C (dec.)[2]
Decomposes in water to yellow mercuric subsulfate and sulfuric acid
Solubility soluble in hot H2SO4, NaCl solution
insoluble in alcohol, acetone, ammonia
−78.1·10−6 cm3/mol
Structure
rhombic
Thermochemistry
−707.5 kJ mol−1[3]
Hazards
NFPA 704
Flammability code 0: Will not burn. E.g., water Health code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gas Reactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g., calcium Special hazards (white): no codeNFPA 704 four-colored diamond
0
3
1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Mercury(II) sulfate, commonly called mercuric sulfate, is the chemical compound HgSO4. 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, HgSO4 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 reactions. 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]

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 has, however, been successfully used in the late 19th century to induce vomiting for medical reasons.

References

  1. 1 2 "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.
  3. 1 2 Lide, David R. (1998). Handbook of Chemistry and Physics (87 ed.). Boca Raton, FL: CRC Press. pp. 5–19. ISBN 0-8493-0594-2.
  4. ↑ Minamata Disease. Boston University. Retrieved on 2016-11-10.
  5. ↑ Mercury in Your Environment | US EPA. Epa.gov (2016-10-04). Retrieved on 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.
  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.
Salts and esters of the sulfate ion
H2SO4 He
Li2SO4 BeSO4 B esters
ROSO3−
(RO)2SO2		 (NH4)2SO4
[N2H5]HSO4
(NH3OH)2SO4
NOHSO4		 HOSO4 F Ne
Na2SO4
NaHSO4		 MgSO4 Al2(SO4)3
Al2SO4(OAc)4		 Si P SO42−
HSO3HSO4
(HSO4)2		 Cl Ar
K2SO4
KHSO4		 CaSO4 Sc2(SO4)3 Ti(SO4)2
TiOSO4		 VSO4
V2(SO4)3
VOSO4		 CrSO4
Cr2(SO4)3		 MnSO4
Mn2(SO4)3		 FeSO4
Fe2(SO4)3		 CoSO4
Co2(SO4)3		 NiSO4 CuSO4
Cu2SO4
[Cu(NH3)4(H2O)]SO4		 ZnSO4 Ga2(SO4)3 Ge As Se Br Kr
RbHSO4
Rb2SO4		 SrSO4 Y2(SO4)3 Zr(SO4)2 Nb Mo Tc Ru Rh PdSO4 Ag2SO4 CdSO4 In2(SO4)3 SnSO4 Sb2(SO4)3 Te I Xe
Cs2SO4 BaSO4   Hf Ta W Re Os Ir Pt Au Hg2SO4
HgSO4		 Tl2SO4
Tl2(SO4)3		 PbSO4 Bi2(SO4)3 Po At Rn
Fr Ra   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La Ce2(SO4)3
Ce(SO4)2		 Pr2(SO4)3 Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb2(SO4)3 Lu
Ac Th Pa U(SO4)2
UO2SO4		 Np Pu Am Cm Bk Cf Es Fm Md No Lr

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