Hydroxylamine, sulfate

An additional mole of ammonium sulfate per mole of final lactam is generated duting the manufacture of hydroxylamine sulfate [10039-54-0] via the Raschig process, which converts ammonia, air, water, carbon dioxide, and sulfur dioxide to the hydroxylamine salt. Thus, a minimum of two moles of ammonium sulfate is produced per mole of lactam, but commercial processes can approach twice that amount. The DSM/Stamicarbon HPO process, which uses hydroxylamine phosphate [19098-16-9] ia a recycled phosphate buffer, can reduce the amount to less than two moles per mole of lactam. Ammonium sulfate is sold as a fertilizer. However, because H2SO4 is released and acidifies the soil as the salt decomposes, it is alow grade fertilizer, and contributes only marginally to the economics of the process (145,146) (see Caprolactam). 

YeUowing of wool can occur during dyeing, depending on pH, temperature and time, and chlorinated wools ate especially sensitive. Bleaching agents that can be added to the dyebath have been developed based on sodium bisulfite and hydroxylamine sulfate (108). Addition of hydrogen peroxide to the dyebath after exhaustion can also be effective. 

Allied-Signal Process. Cyclohexanone [108-94-1] is produced in 98% yield at 95% conversion by liquid-phase catal57tic hydrogenation of phenol. Hydroxylamine sulfate is produced in aqueous solution by the conventional Raschig process, wherein NO from the catalytic air oxidation of ammonia is absorbed in ammonium carbonate solution as ammonium nitrite (eq. 1). The latter is reduced with sulfur dioxide to hydroxylamine disulfonate (eq. 2), which is hydrolyzed to acidic hydroxylamine sulfate solution (eq. 3). 

Hydroxylamine sulfate is produced by direct hydrogen reduction of nitric oxide over platinum catalyst in the presence of sulfuric acid. Only 0.9 kg ammonium sulfate is produced per kilogram of caprolactam, but at the expense of hydrogen consumption (11). A concentrated nitric oxide stream is obtained by catalytic oxidation of ammonia with oxygen. Steam is used as a diluent in order to avoid operating within the explosive limits for the system. The oxidation is followed by condensation of the steam. The net reaction is... 

The resulting mixture does not crystalize and is converted into a mixture of oximes by treatment of a solution of the mixture in 20 ml of ethanol with a solution of 1.8 g of hydroxylamine sulfate in 3 ml of water. 1.B g of sodium acetate In 5 ml of water is added, and the mixture is refluxed for 5 hours, then extracted with ethyl acetate, and the ethyl acetate solution is washed with a saturated aqueous sodium chloride solution and dried over Sodium sulfate. After evaporating the solvent, the residue is triturated with warm ether and 1.1 g of a crystalline oxime is obtained, MP 16B° to 171°C. 

Hydroxylamine sulfate, 5, 73 -Hydroxyphenylarsonic acid, 7, 4, 5 0-Hydroxy Propionic Acid, 7, 54, 55 Hypochlorous acid, 5, 31... 

Lustrous yel needles, mp 33° (Refs 2 3), prepd by the action of hydroxylamine (yield 50%), hydrazine (yield 20%), or Na azide on 2-naphtha-lenediazonium sulfate (Ref 3) or by the action of hydroxylamine sulfate on 2-naphthalene diazonium sulfate in sulfuric acid/glac acet ac (Ref 5)... 

Hydroxylamine [oxyammonium (NH2OH)], hydroxylamine sulfate [(NH20H)2-H2S04], other derivatives, and aminothanolamines were some of the earliest novel chemistry alternatives to hydrazine, but none have proved as useful as DEHA. 

Hydroxylamine, hydrochloride, 55,40 Hydroxylamine sulfate, 58, 32, 36 Hydroxylamine-O-sulfonic acid, 58, 32, 34, 36... 

Derelanko, M.J., Gad, S.C., Gavigan, F.A., Babich, P.C. and Rinehart, W.E. (1987). Toxicity of hydroxylamine sulfate following dermal exposure Variability with exposure method and... 

Workers exposed to hydroxylamine sulfate for 1 day at unspecified air levels showed blood methemoglobinemia concentrations of 25%. Dusts and mists of hydroxylamine sulfate are irritants of the mucous membranes and eyes. Although details are lacking, repeated exposure to the sulfate is reported to have caused respiratory sensitization with asthmalike symptoms. 

Hydroxylamine hydrochloride is highly irritating to the skin, eyes, and mucous membranes and has caused contact dermatitis in workers exposed for 2-60 days. Hydroxylamine itself is only moderately irritating to the skin. Hydroxylamine sulfate on the skin of rabbits was irritating at levels as low as a 10-mg dose. It is considered to be a potential skin sensitizer. 

Allied Corp. Hydroxylamine Sulfate Product Safety Data Sheet. Morristown, NJ, Allied Corporation, 1983... 

The acid, protonating the hydroxylamine, prevents the reverse reaction and thus causes rapid and complete hydrolysis distillation of the final solution then drives off the aldehyde or ketone, and the hydroxylamine sulfate remains behind. This method must be used with care, however, as the acid may cause a Beckmann rearrangement to occur. 

Treatment of 2-aminotriazoline with hydroxylamine sulfate at 70 °C for 1 h gave a mixture of 1,5- and 1,3-diaminotriazole <90JHC1109>. The relative amount of the 1,5-isomer increased at lower temperatures and times but the overall yield fell. 

Hydroxylamine sulfate may be prepared by mixing stoichiometric amounts of hydroxylamine and sulfuric acid. It also may be prepared by electrolytical-ly reducing an aqueous solution of ammonium sulfate. 

Elemental composition H 4.92%, N 17.06%, O 58.49%, S 19.59%. The concentration of hydroxylamine sulfate in aqueous solution may be measured by coulometric titration against a standard solution of oxidizing agent, such as bromine (See Hydroxylamine). Sulfate anion may be measured by ion chromatography. 

Mercury is most accurately determined by the cold vapor atomic absorption spectroscopic method. The instrument is set at the wavelength 253.7 nm. The metal, its salts and organic derivatives in aqueous solution can be measured by this method. The solution or the solid compounds are digested with nitric acid to convert into water-soluble mercury(ll) nitrate, followed by treatment with potassium permanganate and potassium persulfate under careful heating. The excess oxidants in the solution are reduced with NaCl-hydroxylamine sulfate. The solution is treated with stannous chloride and aerated. The cold Hg vapor volatdizes into the absorption cell where absorbance is measured. 

German workers have also isolated a novel spirocyclic 4(5/7)-oxazolone 96 in high yield by reaction of 95 with hydroxylamine sulfate (Scheme 6.25). This was part of an investigation of the synthesis and reactions of 95. 

This reaction yields HA in an anhydrous medium CH3 N02 +H2 S04 =HOS02 CCH NOH(I) (I)+2H20=H2S04+HC00H+NH20H or H2S04 + CO+NH2 OH (Ref 1), Hydroxylamine sulfate is highly toxic. Its uses are similar to those for the acid sulfate... 

Hydroxylamine Sulfate Diethylene Glycol Beta-Propiolactone Nitrogen Tetroxide Ethylene Oxide Benzophenone Benzophenone Diethylene Glycol Oxygen, Liquefied Dibenzoyl Peroxide Catechol Cresols... 

Hydroxylamine Sulfate — Fire Hazards Flash Point (deg. F) Not flammable Flammable Limits in Air (%) Not flammable Fire Extinguishing Agents Not pertinent Fire Extinguishing Agents Not To Be Used Not pertinent Special Hazards of Combustion Products Sulfuric acid fumes may form... 

Commercial hydroxylamine sulfate and chlorosulfonic acid, obtained from Eastman Kodak Company, were used directly. The checkers found that commercially available hydroxylamine-O-sulfonic acid is sometimes of low purity. Therefore, the use of freshly prepared reagent is recommended. 

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