Hydroxylammonium sulfate

Hydroxylammonium sulfate
Names
Other names
Hydroxylamine sulfate
Identifiers
CAS Number
  • 10039-54-0 checkY
3D model (JSmol)
  • Interactive image
ChEMBL
  • ChEMBL3183215
ChemSpider
  • 23229 checkY
ECHA InfoCard 100.030.095 Edit this at Wikidata
EC Number
  • 233-118-8
PubChem CID
  • 24846
RTECS number
  • NC5425000
UNII
  • 49KP498D4O checkY
UN number 2865
CompTox Dashboard (EPA)
  • DTXSID2025424 Edit this at Wikidata
InChI
  • InChI=1S/2H4NO.H2O4S/c2*1-2;1-5(2,3)4/h2*2H,1H3;(H2,1,2,3,4)/q2*+1;/p-2 checkY
    Key: VGYYSIDKAKXZEE-UHFFFAOYSA-L checkY
  • InChI=1/2H4NO.H2O4S/c2*1-2;1-5(2,3)4/h2*2H,1H3;(H2,1,2,3,4)/q2*+1;/p-2
    Key: VGYYSIDKAKXZEE-NUQVWONBAN
  • [O-]S([O-])(=O)=O.O[NH3+].O[NH3+]
Properties
Chemical formula
H8N2O6S
Molar mass 164.14 g/mol
Appearance white crystalline to fine product, slightly hygroscopic
Density 1.88 g/cm3
Melting point 120 °C (248 °F; 393 K) decomposes
Solubility in water
58.7 g/100 ml (20 °C)
Structure[1]
Crystal structure
Monoclinic
Space group
P21/c
Lattice constant
a = 7.932±0.002 Å, b = 7.321±0.002 Å, c = 10.403±0.003 Å
α = 90°, β = 106.93±0.03°, γ = 90°
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Hazards
GHS labelling:
GHS05: CorrosiveGHS07: Exclamation markGHS08: Health hazardGHS09: Environmental hazard
Warning
H290, H302, H312, H315, H317, H319, H351, H373, H400, H412
P201, P202, P234, P260, P261, P264, P270, P272, P273, P280, P281, P301+P312, P302+P352, P305+P351+P338, P308+P313, P312, P314, P321, P322, P330, P332+P313, P333+P313, P337+P313, P362, P363, P390, P391, P404, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
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1
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Safety data sheet (SDS) External MSDS
Related compounds
Other anions
Hydroxylammonium nitrate
Hydroxylammonium chloride
Other cations
Ammonium sulfate
Hydrazinium sulfate
Related compounds
Hydroxylamine
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
Chemical compound

Hydroxylammonium sulfate [NH3OH]2SO4, is the sulfuric acid salt of hydroxylamine. It is primarily used as an easily handled form of hydroxylamine, which is explosive when pure.

Synthesis

Hydroxylammonium sulfate is prepared industrially via the Raschig hydroxylamine process, which involves the reduction of nitrite with bisulfite. This initially gives hydroxylamine disulfonate, which is hydrolysed to hydroxylammonium sulfate:[2] It can also be obtained by the acid-base reaction of hydroxylamine with sulfuric acid:

2 NH2OH(aq) + H2SO4(aq) → (NH3OH)2SO4(aq)

Applications

Hydroxylammonium sulfate is used in organic synthesis to convert aldehydes and ketones to oximes, carboxylic acids and their derivatives (e.g. esters) to hydroxamic acids, isocyanates to N-hydroxyureas and nitriles to amidoximes. Hydroxylammonium sulfate is also used to generate hydroxylamine-O-sulfonic acid from oleum or chlorosulfuric acid.

Hydroxylammonium sulfate is used in the production of anti-skinning agents, pharmaceuticals, rubber, textiles, plastics and detergents. It is a radical scavenger that terminates radical polymerization reactions and serves as an antioxidant in natural rubber. (NH3OH)2SO4 is a starting material for some insecticides, herbicides and growth regulators. It is used in photography as a stabiliser for colour developers and as an additive in photographic emulsions in colour film.

Decomposition

At 120 °C, hydroxylammonium sulfate begins to decompose to sulfur trioxide, nitrous oxide, water, and ammonia[dubious – discuss]:

2 (NH3OH)2SO4 → 2 SO3 + N2O + 2 NH3 + 5 H2O

The reaction is exothermic above 138 °C, and is most exothermic at 177 °C.[3] Metals (especially copper, its alloys and its salts) catalyse the decomposition of hydroxylammonium sulfate. The instability of this compound is mainly due to the hydroxylammonium ion's weak nitrogen to oxygen single bond.

References

  1. ^ Mirceva, A.; Golic, L. (15 May 1995). "Hydroxylammonium Sulfate". Acta Crystallographica Section C Crystal Structure Communications. 51 (5): 798–800. doi:10.1107/S0108270194013351.
  2. ^ Oblath, S. B.; Markowitz, S. S.; Novakov, T.; Chang, S. G. (December 1982). "Kinetics of the initial reaction of nitrite ion in bisulfite solutions" (PDF). The Journal of Physical Chemistry. 86 (25): 4853–4857. doi:10.1021/j100222a005.
  3. ^ BASF hydroxylammonium sulfate product page[permanent dead link]
  • International Chemical Safety Card 0898
  • v
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Compounds containing the sulfate group (SO2−4)
H2SO4 He
Li2SO4 BeSO4 B2S2O9
-BO3
+BO3
esters
ROSO3
(RO)2SO2
+CO3
+C2O4
(NH4)2SO4
[N2H5]HSO4
(NH3OH)2SO4
NOHSO4
+NO3
H2OSO4 +F Ne
Na2SO4
NaHSO4
MgSO4 Al2(SO4)3
Al2SO4(OAc)4
Si +PO4 SO2−4
HSO3HSO4
(HSO4)2
+SO3
+Cl Ar
K2SO4
KHSO4
CaSO4 Sc2(SO4)3 TiOSO4 VSO4
V2(SO4)3
VOSO4
CrSO4
Cr2(SO4)3
MnSO4 FeSO4
Fe2(SO4)3
CoSO4
Co2(SO4)3
NiSO4
Ni2(SO4)3
CuSO4
Cu2SO4
[Cu(NH3)4(H2O)]SO4
ZnSO4 Ga2(SO4)3 Ge As +SeO3 Br Kr
RbHSO4
Rb2SO4
SrSO4 Y2(SO4)3 Zr(SO4)2 Nb2O2(SO4)3 MoO(SO4)2
MoO2(SO4)
Tc Ru(SO4)2 Rh2(SO4)3 PdSO4 Ag2SO4
AgSO4
CdSO4 In2(SO4)3 SnSO4
Sn(SO4)2
Sb2(SO4)3 Te I2(SO4)3
(IO)2SO4
+IO3
Xe
Cs2SO4
CsHSO4
BaSO4 * Lu2(SO4)3 Hf Ta WO(SO4)2 Re2O5(SO4)2 OsSO4
Os2(SO4)3
Os(SO4)2
IrSO4
Ir2(SO4)3
Pt2(SO4)54– AuSO4
Au2(SO4)3
Hg2SO4
HgSO4
Tl2SO4
Tl2(SO4)3
PbSO4
Pb(SO4)2
Bi2(SO4)3 PoSO4
Po(SO4)2
At Rn
Fr RaSO4 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
 
* La2(SO4)3 Ce2(SO4)3
Ce(SO4)2
Pr2(SO4)3 Nd2(SO4)3 Pm2(SO4)3 Sm2(SO4)3 EuSO4
Eu2(SO4)3
Gd2(SO4)3 Tb2(SO4)3 Dy2(SO4)3 Ho2(SO4)3 Er2(SO4)3 Tm2(SO4)3 Yb2(SO4)3
** Ac2(SO4)3 Th(SO4)2 Pa U2(SO4)3
U(SO4)2
UO2SO4
Np(SO4)2 Pu(SO4)2 Am2(SO4)3 Cm2(SO4)3 Bk Cf2(SO4)3 Es Fm Md No