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Hydrogen selenide

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(Redirected from Hydroselenic acid)
Hydrogen selenide
Structural diagram of the hydrogen selenide molecule
Ball-and-stick model of hydrogen selenide molecule
Ball-and-stick model of hydrogen selenide molecule
Space-filling model of the hydrogen selenide molecule
Space-filling model of the hydrogen selenide molecule
  Selenium, Se  Hydrogen, H
Names
IUPAC name Hydrogen selenide
Other names Hydroselenic acid
selane
selenium hydride
Identifiers
CAS Number
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.029.071 Edit this at Wikidata
EC Number
  • 231-978-9
KEGG
PubChem CID
RTECS number
  • X1050000
UNII
UN number 2202
CompTox Dashboard (EPA)
InChI
  • InChI=1S/H2Se/h1H2Key: SPVXKVOXSXTJOY-UHFFFAOYSA-N
  • InChI=1/H2Se/h1H2Key: SPVXKVOXSXTJOY-UHFFFAOYAF
SMILES
Properties
Chemical formula H2Se
Molar mass 80.98 g/mol
Appearance Colorless gas
Odor decayed horseradish
Density 3.553 g/dm
Melting point −65.73 °C (−86.31 °F; 207.42 K)
Boiling point −41.25 °C (−42.25 °F; 231.90 K)
Solubility in water 0.70 g/100 mL
Solubility soluble in CS2, phosgene
Vapor pressure 9.5 atm (21°C)
Acidity (pKa) 3.89
Conjugate acid Selenonium
Conjugate base Selenide
Structure
Molecular shape Bent
Hazards
Occupational safety and health (OHS/OSH):
Main hazards Extremely toxic and flammable
GHS labelling:
Pictograms GHS02: FlammableGHS06: ToxicGHS09: Environmental hazard
Signal word Danger
Hazard statements H220, H330, H410
Precautionary statements P210, P260, P271, P273, P284, P304+P340, P310, P320, P377, P381, P391, P403, P403+P233, P405, P410+P403, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
4 4 0
Flash point flammable gas
Lethal dose or concentration (LD, LC):
LCLo (lowest published) 0.3 ppm (guinea pig, 8 hr)
5.9 ppm (rat, 1 hr)
NIOSH (US health exposure limits):
PEL (Permissible) TWA 0.05 ppm (0.2 mg/m)
REL (Recommended) TWA 0.05 ppm (0.2 mg/m)
IDLH (Immediate danger) 1 ppm
Safety data sheet (SDS) ICSC 0284
Related compounds
Other anions H2O
H2S
H2Te
H2Po
Other cations Na2Se
Ag2Se
Related compounds Arsine
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒verify (what is  ?) Infobox references
Chemical compound

Hydrogen selenide is an inorganic compound with the formula H2Se. This hydrogen chalcogenide is the simplest and most commonly encountered hydride of selenium. H2Se is a colorless, flammable gas under standard conditions. It is the most toxic selenium compound with an exposure limit of 0.05 ppm over an 8-hour period. Even at extremely low concentrations, this compound has a very irritating smell resembling that of decayed horseradish or "leaking gas", but smells of rotten eggs at higher concentrations.

Structure and properties

H2Se adopts a bent structure with a H−Se−H bond angle of 91°. Consistent with this structure, three IR-active vibrational bands are observed: 2358, 2345, and 1034 cm.

The properties of H2S and H2Se are similar, although the selenide is more acidic with pKa = 3.89 and the second pKa = 11, or 15.05 ± 0.02 at 25 °C.

Preparation

Industrially, it is produced by treating elemental selenium at T > 300 °C with hydrogen gas. A number of routes to H2Se have been reported, which are suitable for both large and small scale preparations. In the laboratory, H2Se is usually prepared by the action of water on Al2Se3, concomitant with formation of hydrated alumina. A related reaction involves the acid hydrolysis of FeSe.

Al2Se3 + 6 H2O ⇌ 2 Al(OH)3 + 3 H2Se

H2Se can also be prepared by means of different methods based on the in situ generation in aqueous solution using boron hydride, Marsh test and Devarda's alloy. According to the Sonoda method, H2Se is generated from the reaction of H2O and CO on Se in the presence of Et3N. H2Se can be purchased in cylinders.

Reactions

Elemental selenium can be recovered from H2Se through a reaction with aqueous sulfur dioxide (SO2).

2 H2Se + SO2 ⇌ 2 H2O + 2 Se + S

Its decomposition is used to prepare the highly pure element.

Applications

H2Se is commonly used in the synthesis of Se-containing compounds. It adds across alkenes. Illustrative is the synthesis of selenoureas from cyanamides:

Selenourea reaction

H2Se gas is used to dope semiconductors with selenium.

Safety

Hydrogen selenide is hazardous, being the most toxic selenium compound and far more toxic than its congener hydrogen sulfide. The threshold limit value is 0.05 ppm. The gas acts as an irritant at concentrations higher than 0.3 ppm, which is the main warning sign of exposure; below 1 ppm, this is "insufficient to prevent exposure", while at 1.5 ppm the irritation is "intolerable". Exposure at high concentrations, even for less than a minute, causes the gas to attack the eyes and mucous membranes; this causes cold-like symptoms for at least a few days afterwards. In Germany, the limit in drinking water is 0.008 mg/L, and the US EPA recommends a maximum contamination of 0.01 mg/L.

Despite being extremely toxic, no human fatalities have yet been reported. It is suspected that this is due to the gas' tendency to oxidise to form red selenium in mucous membranes; elemental selenium is less toxic than selenides are.

See also

References

  1. ^ NIOSH Pocket Guide to Chemical Hazards. "#0336". National Institute for Occupational Safety and Health (NIOSH).
  2. "Hydrogen selenide". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  3. ^ http://www.epa.gov/ttnatw01/hlthef/selenium.html, US Environmental Protection Agency, Air Toxins website
  4. ^ "CDC - Immediately Dangerous to Life or Health Concentrations (IDLH): Hydrogen selenide (as Se) - NIOSH Publications and Products". www.cdc.gov. 2018-11-02. Retrieved 2023-01-09.
  5. ^ https://www.cdc.gov/niosh/docs/81-123/pdfs/0336.pdf Occupational Health Guideline for Hydrogen Selenide, The National Institute for Occupational Safety and Health, 1978
  6. ^ William M. Haynes; David R. Lide; Thomas J. Bruno, eds. (2017). CRC handbook of chemistry and physics : a ready-reference book of chemical and physical data (97th ed.). Boca Raton, Florida. ISBN 978-1-4987-5429-3. OCLC 957751024.{{cite book}}: CS1 maint: location missing publisher (link)
  7. Levy, Daniel E.; Myers, Rollie J. (1990). "Spectroscopic determination of the second dissociation constant of hydrogen selenide and the activity coefficients and spectral shifts of its ions". The Journal of Physical Chemistry. 94 (20): 7842–7847. doi:10.1021/j100383a020.
  8. ^ Bernd E. Langner "Selenium and Selenium Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi:10.1002/14356007.a23_525.
  9. Féher, F. In "Handbook of Preparative Inorganic Chemistry"; Brauer, E., Ed.; Academic: New York, 1963; 1, p 418.
  10. Sonoda, N.; Kondo K.; Nagano, K.; Kambe, N.; Morimoto, F. Angewandte Chemie International Edition English 1980, vol. 19, page 308
  11. Cohen, V.I. (1980). "A Convenient Synthesis of Mono-, N,N′-Di-, and Trisubstituted Selenoureas from Methyl Carbamimidothioates (S-Methylpseudothioureas)". Synthesis. 1980: 60–63. doi:10.1055/s-1980-28927. S2CID 96314420.
  12. https://www.osha.gov/dts/chemicalsampling/data/CH_246700.html Archived 2017-05-02 at the Wayback Machine, OSHA GENERAL INDUSTRY PEL: 0.05 ppm, 0.2 mg/m3, OSHA CONSTRUCTION INDUSTRY PEL: 0.05 ppm, 0.2 mg/m3 TWA

External links

Hydrogen compounds
Selenium compounds
Se(−II)
Se(0,I)
Se(I)
Se(II)
Se(IV)
Se(VI)
Se(IV,VI)
Salts and covalent derivatives of the selenide ion
H2Se
H2Se2
+H
-H
He
Li2Se Be SexByOz CSe2
OCSe
(CH3)2Se
(NH4)2Se O F Ne
Na2Se MgSe Al2Se3 Si PxSey
-P
+S Cl Ar
K2Se CaSe Sc2Se3 TiSe2 V CrSe
Cr2Se3
MnSe
MnSe2
FeSe CoSe NiSe CuSe ZnSe GaSe
Ga2Se3
-Ga
GeSe
GeSe2
-Ge
As2Se3
As4Se3
Se
n
Br Kr
Rb2Se SrSe Y2Se3 Zr NbSe2
NbSe3
MoSe2 Tc Ru Rh Pd Ag2Se CdSe In2Se3 SnSe
SnSe2
-Sn
Sb2Se3 Te +I Xe
Cs2Se BaSe * LuSe
Lu2Se3
Hf TaSe2 WSe2
WSe3
ReSe2 Os Ir PtSe2 Au HgSe Tl2Se PbSe Bi2Se3 Po At Rn
Fr Ra ** Lr Rf Db Sg Bh Hs Mt Ds Rg CnSe Nh Fl Mc Lv Ts Og
 
* LaSe
La2Se3
CeSe
Ce2Se3
PrSe
Pr2Se3
NdSe
Nd2Se3
Pm SmSe
Sm2Se3
EuSe
Eu2Se3
GdSe
Gd2Se3
TbSe
Tb2Se3
DySe
Dy2Se3
HoSe
Ho2Se3
ErSe
Er2Se3
TmSe
Tm2Se3
YbSe
Yb2Se3
** Ac ThSe2 Pa USe2 Np PuSe Am Cm Bk Cf Es Fm Md No
Binary compounds of hydrogen
Alkali metal
(Group 1) hydrides
Alkaline
(Group 2)
earth hydrides
Monohydrides
Dihydrides
Group 13
hydrides
Boranes
Alanes
Gallanes
Indiganes
Thallanes
Nihonanes (predicted)
  • NhH
  • NhH3
  • Nh2H6
  • NhH5
Group 14 hydrides
Hydrocarbons
Silanes
Silenes
Silynes
Germanes
Stannanes
Plumbanes
Flerovanes (predicted)
  • FlH
  • FlH2
  • FlH4
Pnictogen
(Group 15) hydrides
Azanes
Azenes
Phosphanes
Phosphenes
Arsanes
Stibanes
Bismuthanes
Moscovanes
Hydrogen
chalcogenides
(Group 16 hydrides)
Polyoxidanes
  • H2O
  • H2O2
  • H2O3
  • H2O4
  • H2O5
  • more...
  • Polysulfanes
    Selanes
    Tellanes
    Polanes
    Livermoranes
    Hydrogen halides
    (Group 17 hydrides)
  • HF
  • HCl
  • HBr
  • HI
  • HAt
  • HTs (predicted)
  • Transition metal hydrides
    Lanthanide hydrides
    Actinide hydrides
    Exotic matter hydrides
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