Hydroxylammonium sulfate

Last updated
Hydroxylammonium sulfate
Hydroxylammonium-sulfate-2D-A.png
Hydroxylammonium-sulfate-unit-cell-3D-balls.png
Hydroxylammonium-sulfate-xtal-3D-vdW.png
Names
Other names
Hydroxylamine sulfate
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.030.095 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 233-118-8
PubChem CID
RTECS number
  • NC5425000
UNII
UN number 2865
  • InChI=1S/2H4NO.H2O4S/c2*1-2;1-5(2,3)4/h2*2H,1H3;(H2,1,2,3,4)/q2*+1;/p-2 Yes check.svgY
    Key: VGYYSIDKAKXZEE-UHFFFAOYSA-L Yes check.svgY
  • 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
H8N2O6S
Molar mass 164.14 g/mol
Appearancewhite crystalline to fine product, slightly hygroscopic
Density 1.88 g/cm3
Melting point 120 °C (248 °F; 393 K) decomposes
58.7 g/100 ml (20 °C)
Structure [1]
Monoclinic
P21/c
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°
4
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
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.svgHealth 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
3
1
2
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).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

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.

Contents

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.

Related Research Articles

<span class="mw-page-title-main">Sulfuric acid</span> Chemical compound (H₂SO₄)

Sulfuric acid or sulphuric acid, known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, and hydrogen, with the molecular formula H2SO4. It is a colorless, odorless, and viscous liquid that is miscible with water.

<span class="mw-page-title-main">Aqua regia</span> Mixture of nitric acid and hydrochloric acid in a 1:3 molar ratio

Aqua regia is a mixture of nitric acid and hydrochloric acid, optimally in a molar ratio of 1:3. Aqua regia is a fuming liquid. Freshly prepared aqua regia is colorless, but it turns yellow, orange or red within seconds from the formation of nitrosyl chloride and nitrogen dioxide. It was so named by alchemists because it can dissolve noble metals like gold and platinum, though not all metals.

<span class="mw-page-title-main">Ammonium</span> Chemical compound

Ammonium is a modified form of ammonia that has an extra hydrogen atom. It is a positively charged (cationic) molecular ion with the chemical formula NH+4 or [NH4]+. It is formed by the addition of a proton to ammonia. Ammonium is also a general name for positively charged (protonated) substituted amines and quaternary ammonium cations, where one or more hydrogen atoms are replaced by organic or other groups. Not only is ammonium a source of nitrogen and a key metabolite for many living organisms, but it is an integral part of the global nitrogen cycle. As such, human impact in recent years could have an effect on the biological communities that depend on it.

<span class="mw-page-title-main">Sulfurous acid</span> Chemical compound

Sulfuric(IV) acid, also known as sulfurous (UK: sulphurous) acid and thionic acid, is the chemical compound with the formula H2SO3.

<span class="mw-page-title-main">Hydroxylamine</span> Inorganic compound

Hydroxylamine is an inorganic compound with the chemical formula NH2OH. The compound is in a form of a white hygroscopic crystals. Hydroxylamine is almost always provided and used as an aqueous solution. It is consumed almost exclusively to produce Nylon-6. The oxidation of NH3 to hydroxylamine is a step in biological nitrification.

<span class="mw-page-title-main">Neutralization (chemistry)</span> Chemical reaction in which an acid and a base react quantitatively

In chemistry, neutralization or neutralisation is a chemical reaction in which acid and a base react with an equivalent quantity of each other. In a reaction in water, neutralization results in there being no excess of hydrogen or hydroxide ions present in the solution. The pH of the neutralized solution depends on the acid strength of the reactants.

The Raschig process for the production of hydroxylamine is one of three chemical processes developed by German chemist Friedrich Raschig. The main step in this process, patented by Raschig in 1887, is the reduction of nitrite with bisulfite towards hydroxylamine disulfonate, which is hydrolysed to hydroxylammonium sulfate. Most of the hydroxylamine produced is used in the manufacture of caprolactam, the precursor to the polymer Nylon 6.

<span class="mw-page-title-main">Ammonium sulfate</span> Chemical compound

Ammonium sulfate (American English and international scientific usage; ammonium sulphate in British English); (NH4)2SO4, is an inorganic salt with a number of commercial uses. The most common use is as a soil fertilizer. It contains 21% nitrogen and 24% sulfur.

In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation state. The reverse of disproportionation, such as when a compound in an intermediate oxidation state is formed from precursors of lower and higher oxidation states, is called comproportionation, also known as symproportionation.

<span class="mw-page-title-main">Nitrosation and nitrosylation</span> Process of converting organic compounds into nitroso derivatives

Nitrosation and nitrosylation are two names for the process of converting organic compounds or metal complexes into nitroso derivatives, i.e., compounds containing the R−NO functionality. The synonymy arises because the R-NO functionality can be interpreted two different ways, depending on the physico-chemical environment:

<span class="mw-page-title-main">Dimethyl sulfate</span> Chemical compound

Dimethyl sulfate (DMS) is a chemical compound with formula (CH3O)2SO2. As the diester of methanol and sulfuric acid, its formula is often written as (CH3)2SO4 or Me2SO4, where CH3 or Me is methyl. Me2SO4 is mainly used as a methylating agent in organic synthesis. Me2SO4 is a colourless oily liquid with a slight onion-like odour. Like all strong alkylating agents, Me2SO4 is toxic. Its use as a laboratory reagent has been superseded to some extent by methyl triflate, CF3SO3CH3, the methyl ester of trifluoromethanesulfonic acid.

<span class="mw-page-title-main">Sodium dithionite</span> Chemical compound

Sodium dithionite is a white crystalline powder with a sulfurous odor. Although it is stable in dry air, it decomposes in hot water and in acid solutions.

<span class="mw-page-title-main">Iodine clock reaction</span> Experiment to show chemical kinetics in action

The iodine clock reaction is a classical chemical clock demonstration experiment to display chemical kinetics in action; it was discovered by Hans Heinrich Landolt in 1886. The iodine clock reaction exists in several variations, which each involve iodine species and redox reagents in the presence of starch. Two colourless solutions are mixed and at first there is no visible reaction. After a short time delay, the liquid suddenly turns to a shade of dark blue due to the formation of a triiodide–starch complex. In some variations, the solution will repeatedly cycle from colorless to blue and back to colorless, until the reagents are depleted.

A nitrate test is a chemical test used to determine the presence of nitrate ion in solution. Testing for the presence of nitrate via wet chemistry is generally difficult compared with testing for other anions, as almost all nitrates are soluble in water. In contrast, many common ions give insoluble salts, e.g. halides precipitate with silver, and sulfate precipitate with barium.

<span class="mw-page-title-main">Hydroxylammonium chloride</span> Chemical compound, [NH3OH]Cl

Hydroxylammonium chloride is a chemical compound with the formula [NH3OH]+Cl. It is the hydrochloric acid salt of hydroxylamine. Hydroxylamine is a biological intermediate in nitrification and in anammox which are important in the nitrogen cycle in soil and in wastewater treatment plants.

<span class="mw-page-title-main">Calcium bisulfite</span> Chemical compound

Calcium bisulfite is an inorganic compound which is the salt of a calcium cation and a bisulfite anion. It may be prepared by treating lime with an excess of sulfur dioxide and water. As a food additive it is used as a preservative under the E number E227. Calcium bisulfite is an acid salt and behaves like an acid in aqueous solution. It is used in the sulfite process for producing paper from wood chips.

In chemistry, the amino radical, ·NH2, also known as the aminyl or azanyl, is the neutral form of the amide ion. Aminyl radicals are highly reactive and consequently short-lived, like most radicals; however, they form an important part of nitrogen chemistry. In sufficiently high concentration, amino radicals dimerise to form hydrazine. While NH2 as a functional group is common in nature, forming a part of many compounds, the radical cannot be isolated in its free form.

Hydroxylamine-<i>O</i>-sulfonic acid Chemical compound

Hydroxylamine-O-sulfonic acid (HOSA) or aminosulfuric acid is the inorganic compound with molecular formula H3NO4S that is formed by the sulfonation of hydroxylamine with oleum. It is a white, water-soluble and hygroscopic, solid, commonly represented by the condensed structural formula H2NOSO3H, though it actually exists as a zwitterion and thus is more accurately represented as +H3NOSO3. It is used as a reagent for the introduction of amine groups (–NH2), for the conversion of aldehydes into nitriles and alicyclic ketones into lactams (cyclic amides), and for the synthesis of variety of nitrogen-containing heterocycles.

<span class="mw-page-title-main">Ammonium iodate</span> Chemical compound

Ammonium iodate is an inorganic salt which is sparingly soluble in cold, and moderately soluble in hot water, like all iodate salts, it is a strong oxidizer.

<span class="mw-page-title-main">Sulfoxylic acid</span> Chemical compound

Sulfoxylic acid (H2SO2) (also known as hyposulfurous acid or sulfur dihydroxide) is an unstable oxoacid of sulfur in an intermediate oxidation state between hydrogen sulfide and dithionous acid. It consists of two hydroxy groups attached to a sulfur atom. Sulfoxylic acid contains sulfur in an oxidation state of +2. Sulfur monoxide (SO) can be considered as a theoretical anhydride for sulfoxylic acid, but it is not actually known to react with water.

References

  1. Mirceva, A.; Golic, L. (15 May 1995). "Hydroxylammonium Sulfate". Acta Crystallographica Section C Crystal Structure Communications. 51 (5): 798–800. Bibcode:1995AcCrC..51..798M. 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 ]