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Hydroxylamine

Hydroxylamine is an inorganic compound with the chemical formula NH₂OH, representing the simplest member of the hydroxylamine class, where a hydroxy group is substituted onto an ammonia molecule.^[1] It exists as a white, odorless, hygroscopic crystalline solid that is highly unstable at room temperature, readily decomposing in the presence of moisture or carbon dioxide, and is therefore most commonly handled in the form of stable salts such as the hydrochloride or sulfate.^[2] The compound has a melting point of 33 °C and a boiling point of 70 °C at reduced pressure (60 mm Hg), with high solubility in water and methanol but limited solubility in diethyl ether.^[2] Hydroxylamine is primarily produced industrially through the Raschig process, which involves the reduction of ammonium nitrite with bisulfite and sulfur dioxide in ammoniacal solution, though electrolytic reduction of ammonium chloride or nitric acid and catalytic hydrogenation methods are also employed.^[3] In laboratory settings, it can be generated from hydroxylamine hydrochloride by treatment with sodium methoxide or other bases, but purification to the free base requires careful handling due to its instability. As a versatile reducing agent, hydroxylamine plays a critical role in organic synthesis, notably in the production of oximes from carbonyl compounds, which serve as precursors for caprolactam—the key monomer for nylon-6—and in the manufacture of pharmaceuticals, pesticides, and antioxidants.^[4] It is also utilized in the semiconductor industry for photoresist stripping, in water treatment as a corrosion inhibitor, and in analytical chemistry for the determination of metals like iron and copper through complex formation.^[5] Despite its utility, hydroxylamine poses significant safety hazards due to its strong reducing properties and thermal instability; it can decompose explosively above 70 °C or upon contact with oxidizers, heavy metals, or acids, releasing toxic nitrogen oxides and ammonia.^[6] It is classified as corrosive to skin and eyes, potentially carcinogenic, and harmful if ingested or inhaled, with risks of methemoglobinemia and damage to aquatic life, necessitating strict handling protocols including storage under inert atmospheres and use of protective equipment.

History

Discovery

Hydroxylamine was first synthesized in 1865 by the German chemist Wilhelm Clemens Lossen while working in the laboratory of Wilhelm Heinrich Heintz at the University of Halle. Lossen prepared the compound as hydroxylammonium chloride by reducing ethyl nitrate with tin and hydrochloric acid, marking the initial identification of hydroxylamine as a stable chemical entity.^[7] The structure of hydroxylamine was proposed by Lossen as NH₂OH, based on its chemical behavior as an ammonia derivative with a hydroxy substituent, which allowed it to form oximes with aldehydes and ketones. This proposal was supported by early characterizations of its salts and reactivity patterns. Pure anhydrous hydroxylamine was isolated in 1891 by the Dutch chemist Cornelis Adriaan Lobry de Bruyn and the Belgian chemist Léon Maurice Crismer, who characterized its coordination complex with zinc chloride, ZnCl₂(NH₂OH)₂, providing further evidence for the structural formula.^[8] In the late 19th century, the structure was confirmed through a series of chemical reactions and derivative studies, including the formation of hydroxylammonium salts, with contributions from chemists such as H. Goldschmidt who observed properties of these salts around 1898. These efforts established hydroxylamine's role as a key reducing agent and intermediate in organic synthesis.

Industrial Development

The industrial development of hydroxylamine began with the invention of the Raschig process by German chemist Friedrich Raschig, who patented a method for its synthesis in 1887 through the reduction of nitrite with bisulfite to form hydroxylamine disulfonate, followed by hydrolysis.^[9] This breakthrough transformed hydroxylamine from a laboratory compound, first prepared by Wilhelm Lossen in 1865, into a viable industrial chemical by providing an economical route based on readily available inorganic materials. The process quickly gained traction for commercial applications, particularly in the production of oximes for organic synthesis. Following World War II, hydroxylamine production saw significant expansions in Europe and the United States, driven by its essential role in manufacturing caprolactam, the monomer for nylon 6, as well as in pharmaceutical intermediates.^[9] In Europe, companies like BASF restarted and scaled up caprolactam operations postwar, leveraging hydroxylamine in integrated processes to support the burgeoning synthetic fiber industry.^[10] Similarly, in the US, the demand for nylon materials spurred investments in domestic production capacities during the 1950s economic boom, with firms adapting Raschig-based methods to meet industrial needs. These developments marked a shift toward large-scale, continuous operations optimized for yield and cost-efficiency. A pivotal milestone occurred in 1956 when BASF introduced a catalytic hydrogenation process for hydroxylamine from nitric oxide and hydrogen, which enhanced the cost-effectiveness of caprolactam synthesis and reduced reliance on traditional Raschig variants.^[10] In the 2000s, further refinements emphasized sustainability, including direct catalytic routes using ammonia and hydrogen peroxide proposed in the 1990s and optimized thereafter, aiming to minimize waste and energy use while maintaining high atomic economy.^[5] These advancements continue to underpin hydroxylamine's role in modern chemical manufacturing.

Properties

Physical Properties

Hydroxylamine has the molecular formula NH₂OH and a molar mass of 33.03 g/mol.^[1] It appears as a hygroscopic, colorless crystalline solid, often in the form of needles or flakes.^[1] The compound melts at 33 °C but decomposes above this temperature, rendering a standard boiling point inapplicable under normal conditions; it sublimes or decomposes instead.^[1] Its density is 1.21 g/cm³ at 20 °C.^[1] Hydroxylamine is miscible with water and moderately soluble in alcohols such as methanol.^[11] Its vapor pressure is approximately 9 mm Hg at 40 °C.^[11] The standard enthalpy of formation (ΔH_f°) for solid hydroxylamine is -114 kJ/mol.^[12] Common salts of hydroxylamine, such as hydroxylammonium chloride (NH₃OHCl), are typically white, hygroscopic powders or colorless crystals with a density of 1.67 g/cm³ at 17 °C and a melting point of 151 °C (with decomposition).^[13] This salt is highly soluble in water (94 g/100 mL at 25 °C)^[14] and moderately soluble in alcohols like ethanol (4.4 g/100 mL).^[15]

Chemical Properties

Hydroxylamine exhibits amphoteric properties, functioning as a weak base with a pK_b of 8.06 and as a weak acid via its protonated form, the hydroxylammonium ion (NH₃OH⁺), which has a pK_a of 5.94 at 25 °C.^[1]^[16] This dual behavior arises from the nitrogen atom's ability to accept a proton and the oxygen atom's capacity to donate one in its protonated state. In aqueous solution, hydroxylamine predominantly exists in the neutral tautomeric form NH₂OH, with the zwitterionic tautomer ⁺NH₃O⁻ present in minor amounts (equilibrium constant K_T ≈ 2.6 × 10⁻²).^[17] The compound is thermally unstable, decomposing above 70 °C into nitrogen gas (N₂), water (H₂O), and ammonia (NH₃) via the reaction 3 NH₂OH → N₂ + NH₃ + 3 H₂O.^[18] This decomposition is exothermic and can lead to explosive hazards if confined. Hydroxylamine is also sensitive to light, which accelerates its degradation, and it reacts violently with certain metals, potentially causing explosive polymerization or detonation.^[18] Additionally, it is hygroscopic and unstable in the presence of atmospheric moisture or carbon dioxide, necessitating careful storage conditions.^[1] As a reducing agent, hydroxylamine participates in redox processes, with its position in the electrochemical series enabling electron donation in various reactions.^[1] Basic spectroscopic characterization includes infrared absorption bands, notably the N-O stretching vibration at approximately 920 cm⁻¹, which confirms the presence of the N-OH functionality.^[19]

Production

Industrial Processes

The primary industrial method for producing hydroxylamine remains the Raschig process, which involves the catalytic oxidation of ammonia to nitric oxide, followed by the formation of ammonium nitrite and its subsequent reduction using sulfur dioxide in the presence of ammonia to yield hydroxylamine disulfonate, which is then hydrolyzed to hydroxylamine sulfate.^[20] The key steps include the air oxidation of ammonia (4 NH₃ + 5 O₂ → 4 NO + 6 H₂O), oxidation of NO to NO₂, absorption into ammonium carbonate to form ammonium nitrite (NO + NO₂ + (NH₄)₂CO₃ → 2 NH₄NO₂ + CO₂), reduction to the disulfonate ((NH₄NO₂ + 2 SO₂ + NH₃ + H₂O → HON(SO₃NH₄)₂ + NH₄HSO₄), and hydrolysis (HON(SO₃NH₄)₂ + 2 H₂O → NH₂OH + NH₄HSO₄ + H₂SO₄). This process operates continuously in large-scale plants, with the overall simplified reaction often represented as 2 NH₃ + 3 HNO → 2 NH₂OH + HNO₃, achieving hydroxylamine sulfate of 90-95% purity after purification and distillation.^[20] A modern alternative is the catalytic hydrogenation of nitrates or nitrites, typically ammonium nitrate in phosphoric acid, using hydrogen gas over supported metal catalysts such as palladium on carbon (Pd/C).^[21] This HPO (hydroxylamine-phosphate-oxime) process maintains nitrate concentrations below 1.0 mol/kg, with ammonia-to-nitrate ratios of 2.2-7, temperatures of 20-70°C, and hydrogen pressures of at least 0.5 MPa (up to 200 atm in some configurations for enhanced selectivity), yielding hydroxylamine concentrations up to 1.5 mol/kg in the reaction mixture with high efficiency and minimal byproducts.^[21] It is favored in contemporary facilities for its cleaner operation and integration with downstream oxime production, such as for caprolactam synthesis. Another route involves the catalytic reduction of nitromethane or nitroethane, often via acid-catalyzed hydrolysis in the presence of catalysts like strong acids or metal promoters, producing hydroxylamine alongside formaldehyde or other fragments. This method is employed in select plants for high-purity hydroxylamine hydrochloride, though it is less dominant than the Raschig or hydrogenation processes due to raw material costs. Global production of hydroxylamine, primarily as stable salts like sulfate or hydrochloride for transport and use, is estimated at around 200,000 tons per year in the 2020s, driven by demand in chemical manufacturing.^[22]

Laboratory Preparation

One common laboratory method for preparing hydroxylamine involves the reduction of nitrous acid (HNO₂) generated in situ from sodium nitrite in acidic medium using zinc or tin as the reducing agent. This approach, historically developed by Divers in 1883, utilizes metals such as zinc dust or tin foil in the presence of sulfuric or hydrochloric acid to selectively reduce the nitrite to hydroxylamine while minimizing over-reduction to ammonia. The reaction proceeds according to the simplified equation:

\text{HNO}_2 + 2[\text{H}] \rightarrow \text{NH}_2\text{OH} + \text{H}_2\text{O}

where the nascent hydrogen ([H]) is provided by the metal-acid interaction. Typically, sodium nitrite is dissolved in dilute sulfuric acid, and zinc dust is added gradually with stirring and cooling to control the exothermic reaction; the mixture is then filtered to remove metal residues, and hydroxylamine is isolated as its sulfate salt by evaporation or precipitation. This method yields considerable quantities of hydroxylamine salts suitable for small-scale research, though exact yields depend on reaction conditions and purification steps.^[9] Another established laboratory route employs the hydrolysis of sodium hydroxylamine disulfonate, prepared by reacting sodium nitrite with sodium bisulfite and sulfur dioxide in aqueous solution. Sodium nitrite is dissolved in water with sodium bisulfite, and sulfur dioxide is bubbled through the solution at controlled pH (around 8-9) to form sodium hydroxylamine disulfonate (Na₂[ON(SO₃)₂]) as an intermediate. Hydrolysis of this disulfonate with dilute sulfuric acid under reflux for several hours liberates hydroxylamine as the sulfate salt:

$2\text{Na}_2[\text{ON}(\text{SO}_3)_2] + 4\text{H}_2\text{O} \rightarrow (\text{NH}_2\text{OH})_2 \cdot \text{H}_2\text{SO}_4 + 2\text{Na}_2\text{SO}_4 + \text{H}_2\text{SO}_4

The reaction mixture is neutralized, filtered to remove sodium sulfate, and concentrated to crystallize the product, offering high purity for analytical applications with reported yields exceeding 80% based on nitrite input. This method is favored in laboratories for its accessibility using common reagents and avoidance of high-pressure equipment.^[23] Electrochemical reduction of nitrate solutions provides a modern, controlled alternative for laboratory synthesis of hydroxylamine, typically conducted in an undivided cell using metal cathodes such as zinc, tin, or gold in acidic electrolytes like 0.1 M HNO₃. Nitrate ions are reduced at potentials around -0.5 to -1.0 V vs. RHE, with selective electron transfer favoring hydroxylamine over further reduction to ammonia or nitrite; for instance, zinc cathodes achieve faradaic efficiencies up to 70-80% under optimized conditions with current densities of 10-50 mA/cm². The product is extracted from the catholyte and purified by fractional distillation under vacuum (e.g., at 50-60°C and 10-20 mmHg) to prevent thermal decomposition above 70°C, yielding anhydrous or aqueous solutions of high purity (>95%) suitable for sensitive experiments. This technique emphasizes safety through ambient conditions and scalability for batch processes.^[24]^[25]

Chemical Reactions

Reduction Reactions

Hydroxylamine functions as a mild reducing agent in several chemical transformations, owing to its ability to donate electrons while being oxidized to products such as N₂O or N₂. Its standard reduction potential for the NH₂OH/N₂O couple is approximately 0.73 V vs. SHE, enabling selective reductions under controlled conditions. In organic synthesis, hydroxylamine and its derivatives facilitate the deoxygenation of sulfoxides to the corresponding sulfides. This reaction proceeds through the interaction of the sulfoxide with hydroxylamine-O-sulfonic acid or similar derivatives, where the nitrogen lone pair likely initiates a nucleophilic attack on the sulfur atom, displacing the oxygen as a leaving group and forming an intermediate that collapses to the sulfide and oxidized nitrogen species. For example, dimethyl sulfoxide is converted to dimethyl sulfide in 77% yield when treated with hydroxylamine-O-sulfonic acid at elevated temperatures (55–145°C) in solvents like ethanol or DMF, using 2–3 equivalents of the reducing agent. The mechanism involves the formation of a transient S-N bond, followed by elimination of water and nitrogen extrusion, ensuring high selectivity without affecting other functional groups. This method is particularly useful for preparing sulfides from sulfoxides in pharmaceutical intermediates.^[26] In analytical chemistry, hydroxylamine hydrochloride is commonly employed to reduce Fe³⁺ to Fe²⁺ prior to spectrophotometric or titrimetric determination. The reaction occurs quantitatively in acidic media according to 2NH₂OH + 4Fe³⁺ → N₂O + 4Fe²⁺ + H₂O + 4H⁺, allowing the total iron content to be measured after complete reduction. The resulting Fe²⁺ is then titrated with potassium permanganate in the standard redox reaction: MnO₄⁻ + 5Fe²⁺ + 8H⁺ → Mn²⁺ + 5Fe³⁺ + 4H₂O. This approach is preferred over other reductants like ascorbic acid because hydroxylamine does not interfere with the formation of colored complexes, such as the Fe²⁺-o-phenanthroline complex used for colorimetric analysis at 510 nm. Optimal conditions involve adding 1–2 mL of 10% hydroxylamine hydrochloride solution to the sample, heating briefly to ensure complete reduction, and performing the titration immediately to avoid reoxidation. This method achieves high accuracy, with errors typically below 0.5% in iron determinations from ores or environmental samples.^[27]^[28]

Oxidation and Other Reactivities

Hydroxylamine undergoes oxidation by molecular oxygen, yielding nitrous acid as a primary product according to the stoichiometry 2NH₂OH + 2O₂ → 2HNO₂ + 2H₂O under controlled conditions, though further decomposition to nitrogen gas (N₂) can occur depending on environmental factors such as pH and catalysts.^[29] This process is often autocatalytic, initiated by trace nitrous acid that accelerates the reaction through radical intermediates like the aminoxyl radical (NH₂O•), leading to enhanced rates in aqueous solutions.^[30] Autocatalytic decomposition pathways of hydroxylamine involve bimolecular isomerization to ammonia oxide (NH₂O-NH₂) as the initial step, with an activation barrier of approximately 16 kcal/mol in aqueous media, promoting instability in concentrated solutions and contributing to explosive risks in industrial handling.^[31] In nitrosation reactions, hydroxylamine reacts with nitrous acid to produce nitrous oxide gas via the equation NH₂OH + HNO₂ → N₂O + 2H₂O, a process that proceeds through electrophilic attack by the nitrosonium ion (NO⁺) on the oxygen atom of protonated hydroxylamine, followed by migration to nitrogen and elimination.^[32] This reaction exhibits pH dependence, with optimal rates in mildly acidic conditions (pH ~4-5) where the conjugate acid form predominates, and isotopic labeling confirms the symmetric intermediate hyponitrous acid (HON=NOH) as a key transient species.^[33] Hydroxylamine acts as a nucleophile in reactions with carbonyl compounds, forming oximes through condensation: R₂C=O + NH₂OH → R₂C=NOH + H₂O. This addition is pH-dependent, accelerating under slightly acidic conditions (pH 4-6) due to protonation of the carbonyl oxygen, which enhances electrophilicity, while alkaline media slow the process by favoring the free base form of hydroxylamine.^[34] The resulting oximes exhibit E/Z stereochemistry, with the Z isomer often predominant for aldehydes due to steric interactions during dehydration of the tetrahedral intermediate, though selective synthesis can favor either isomer by adjusting temperature or additives like pyridine.^[35] As a ligand in coordination chemistry, hydroxylamine coordinates to metal ions such as Cu²⁺ primarily through its nitrogen and oxygen donors, forming chelate complexes like [Cu(NH₂OH)₂(H₂O)₂]²⁺ in aqueous solutions. With Cu²⁺, deprotonation of the hydroxyl group leads to hydroximato (–NHO⁻) binding modes, often bidentate and equatorial in square-planar or octahedral geometries, influencing redox potentials and stabilizing Cu(II)/Cu(I) couples for catalytic applications.^[36]

Applications

Industrial Uses

The primary industrial application of hydroxylamine is in the production of caprolactam, the monomer for nylon-6, where it reacts with cyclohexanone to form cyclohexanone oxime, an essential intermediate that undergoes Beckmann rearrangement to yield caprolactam.^[1] This process accounts for over 95% of global hydroxylamine consumption, underscoring its critical role in the polymer industry, with annual worldwide caprolactam production approximately 7 million metric tons as of 2023 primarily driven by textile, automotive, and engineering plastic sectors.^[37]^[38] Hydroxylamine and its salts also serve as antioxidants and vulcanization accelerators in the rubber industry, stabilizing natural rubber viscosity and acting as short-stoppers in synthetic rubber polymerization to control molecular weight and prevent over-polymerization.^[39] In photography, hydroxylamine sulfate functions as a reducing agent and stabilizer in color developers, enhancing image quality by preventing oxidation and fogging during film processing.^[11]^[40] Derivatives of hydroxylamine, such as diethylhydroxylamine, are employed as corrosion inhibitors in boiler water treatment systems, where they act as reducing agents to scavenge dissolved oxygen and mitigate metal degradation in high-pressure environments. It plays an intermediate role in hydrazine production, serving as a precursor to hydroxylamine-O-sulfonic acid (HOSA), which reacts with ammonia or amines to generate hydrazines used in rocket fuels, pharmaceuticals, and agrochemicals.^[41]

Laboratory Applications

In laboratory organic synthesis, hydroxylamine reacts with aldehydes and ketones to form oximes, which serve as effective protecting groups for carbonyl functionalities during multi-step reactions. These oximes can be deprotected under mild conditions, allowing selective manipulation of other parts of the molecule. Furthermore, oximes derived from hydroxylamine undergo the Beckmann rearrangement under acidic or catalytic conditions to yield amides, a transformation widely employed for constructing peptide bonds and lactams in synthetic routes.^[42] Hydroxylamine's reducing properties enable its use in selective transformations, particularly in peptide synthesis where it participates in the α-ketoacid-hydroxylamine (KAHA) ligation to couple unprotected peptide segments chemoselectively, forming native amide linkages without epimerization. In pharmaceutical synthesis, controlled reduction of nitro groups to N-arylhydroxylamines using hydroxylamine intermediates or related conditions provides key building blocks for drug candidates, avoiding over-reduction to amines.^[43] For analytical purposes, hydroxylamine facilitates the detection of carbonyl compounds by forming oximes, which can be quantified colorimetrically through subsequent reactions or sensor arrays, offering high sensitivity for trace analysis in complex mixtures.^[44] Post-2020 developments have integrated hydroxylamine derivatives into click chemistry analogs, such as oxime-based bioorthogonal ligations, to enable precise bioconjugation and library screening in drug discovery.^[45]

Biochemical Roles

In bacterial nitrification, hydroxylamine functions as a crucial intermediate in the oxidation of ammonia to nitrite by ammonia-oxidizing bacteria, such as those in the genus Nitrosomonas. Ammonia monooxygenase (AMO), a multicomponent enzyme complex encoded by the amoCAB operon, catalyzes the initial oxidation of ammonia (NH₃) to hydroxylamine (NH₂OH), providing energy for the bacteria through subsequent electron transport.^[46] This step is highly conserved across ammonia-oxidizing organisms and is sensitive to inhibitors like acetylene, which specifically target AMO without affecting downstream processes.^[47] Following its production, hydroxylamine is rapidly oxidized to nitrite (NO₂⁻) by hydroxylamine oxidoreductase (HAO), a multiheme cytochrome c protein encoded by the hao gene, which facilitates the transfer of electrons to the respiratory chain while generating nitric oxide as a byproduct in some cases.^[48] In Nitrosomonas europaea, HAO ensures minimal accumulation of free hydroxylamine under normal conditions, maintaining process efficiency in nitrogen-cycling ecosystems like soils and aquatic environments.^[46] Disruption of this pathway, such as through genetic mutations in HAO, leads to hydroxylamine buildup and cessation of ammonia oxidation, underscoring its transient but essential role.^[47] Despite its biological utility, hydroxylamine is toxic to nitrifying bacteria at low concentrations, inhibiting ammonia oxidation, which complicates its management in wastewater treatment systems where it can suppress microbial activity and elevate effluent ammonia levels.^[49] This sensitivity has been exploited in studies to assess nitrification resilience, revealing that hydroxylamine addition can temporarily halt or reduce oxidation rates, prompting research into detoxification strategies like enzymatic conversion.^[50] In mammalian metabolism, hydroxylamine arises as a reactive intermediate through the N-hydroxylation of primary aromatic amines by cytochrome P450 enzymes, notably CYP1A2, which activates certain xenobiotics into mutagenic N-hydroxy arylamines capable of forming DNA adducts.^[51] This bioactivation pathway contributes to the carcinogenicity of compounds like arylamines, with CYP1A2's anionic mechanism favoring proton transfer to generate the hydroxylamine product, as supported by density functional theory modeling of reaction energetics.^[51] Inhibition studies demonstrate that hydroxylamine and its derivatives can modulate cytochrome P450 activity, altering drug metabolism and toxicity profiles in liver microsomes.^[52]

Safety and Environmental Aspects

Health Hazards

Hydroxylamine is acutely toxic and acts as a skin and eye irritant upon contact, causing redness, pain, and potential severe damage.^[1] It is harmful if ingested, with an oral LD₅₀ in rats of 516 mg/kg, indicating moderate toxicity via this route. Inhalation or dermal exposure can also lead to systemic effects, including the formation of methemoglobinemia through oxidation of hemoglobin in red blood cells, which impairs oxygen delivery and may result in cyanosis, headache, and dizziness.^[1]^[53] Chronic exposure to hydroxylamine is suspected of causing cancer based on limited animal data, though it lacks a formal IARC classification.^[6] The compound exhibits genotoxic potential by reacting with DNA, including alkylation that can lead to mutations and is implicated in reproductive toxicity, such as developmental effects observed in animal models.^[54] Safe handling of hydroxylamine requires using it primarily as stable salts or dilute aqueous solutions to reduce reactivity and toxicity risks.^[55] Storage should occur under an inert atmosphere in tightly sealed containers at cool temperatures to prevent decomposition and potential explosive hazards from instability.^[55] For exposure incidents, immediate first aid includes flushing skin or eyes with water, seeking medical attention for ingestion or inhalation, and for methemoglobinemia, primary treatment with methylene blue (1-2 mg/kg IV); ascorbic acid (typically 200-500 mg/day oral for mild or chronic cases) may be used as an alternative if methylene blue is contraindicated.^[56]

Environmental Impact

Hydroxylamine exhibits rapid degradation in environmental compartments, primarily through both abiotic and biotic mechanisms, limiting its long-term persistence but posing short-term risks during release. In surface waters, abiotic degradation via reaction with photochemically produced peroxy radicals proceeds with a half-life of approximately 2 hours under typical conditions.^[57] In soils and aerobic waters, microbial communities, particularly nitrifying bacteria, rapidly oxidize hydroxylamine to nitrite and subsequently to nitrate, resulting in half-lives under 1 day. This process follows first-order kinetics and is enhanced under oxygenated conditions, though anoxic environments may slow transformation and favor alternative pathways like nitrous oxide production.^[57] Despite its short persistence, hydroxylamine disrupts microbial nitrification in aquatic systems by selectively inhibiting nitrite-oxidizing bacteria more strongly than ammonia-oxidizing bacteria, leading to ammonia accumulation. Elevated ammonia levels from this inhibition exacerbate eutrophication risks, promoting algal blooms and subsequent oxygen depletion in affected water bodies. These effects are particularly concerning in wastewater-impacted or industrial discharge zones where hydroxylamine concentrations may transiently exceed natural levels. The U.S. Environmental Protection Agency tracks hydroxylamine under various regulatory frameworks due to its ecotoxicity, classifying it as very toxic to aquatic life with potential for long-lasting effects. It is also designated as a highly hazardous chemical by the Occupational Safety and Health Administration, requiring stringent reporting for releases exceeding specified thresholds.^[58] Potential risks from releases include localized oxygen depletion through heightened microbial respiration and chemical reactivity, underscoring the need for containment measures to mitigate ecological harm.

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The addition of hydroxylamine hydrochloride to carbon- yls to yield oximes is not only one of the best understood examples of a nonenzymatic addition- ...<|separator|>
[36]
Coordination modes of hydroxamic acids in copper(II), nickel(II) and ...
Formal redox potentials in aqueous solution were determined for copper(II) complexes with ligands having oxygen and nitrogen as donor atoms.
[37]
Electrocatalytic Synthesis of Nylon-6 Precursor at Almost 100 % Yield
Jul 24, 2023 · Synthesis of cyclohexanone oxime via the cyclohexanone-hydroxylamine process is widespread in the caprolactam industry, which is an upstream ...
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hydroxylamine production - Rest-of-World - ecoQuery - Ecoinvent
The Raschig process leads initially to an oxime; acid hydrolysis, removal of the ketone, and subsequent crystallization give the solid salt. With the ...
[39]
2021 Caprolactam Market Development Report - Echemi
Apr 26, 2021 · Among them, the cyclohexanone-hydroxylamine method accounts for more than 70% of the world's total production capacity, occupying an absolute ...
[40]
Fine Chemicals | UBE Corporation
Hydroxylamine sulfate (HAS). HAS is used as a viscosity stabilizer for natural rubber, and as a non-contaminating short-stopper for synthetic rubber.Missing: statistics | Show results with:statistics
[41]
HYDROXYLAMINE SULFATE - Ataman Kimya
Hydroxylamine Sulfate finds application as an antioxidant in natural rubber. Hydroxylamine Sulfate is also used in photography as a stabilizer for color ...
[42]
Synthesis of hydrazines from hydroxylamine-o-sulphonic acid
This process involves hydroxylamine-O-sulfonic acid (HOSA) as amine agent. This compound has a low polluting character since the various operations are carried ...
[43]
The Mechanochemical Beckmann Rearrangement: An Eco-efficient ...
Jan 27, 2021 · Aldehydes and ketones underwent one-pot oxime formation and elimination or Beckmann rearrangement reactions with hydroxylamine hydrochloride ...
[44]
Reduction of Nitroarenes into Aryl Amines and N-Aryl ... - NIH
Mar 22, 2016 · Scheme 1. ... Chemoselective reduction of nitroarenes (1–12) into aryl amines (1a–12a) and N-aryl hydroxylamines (1b–12b) catalyzed by 4% Ag/MTA ...
[45]
Improved Hydroxylamine Method for the Determination of Aldehydes ...
Improved Hydroxylamine Method for the Determination of Aldehydes and Ketones. ... A colorimetric chemosensor for heptanal with selectivity over ...
[46]
Discovery of a Hydroxylamine-Based Brain-Penetrant EGFR ...
We report the discovery of a selective, orally bioavailable, epidermal growth factor receptor (EGFR) inhibitor, 9, that exhibits high brain penetration and ...
[47]
Hydroxylamine as an intermediate in ammonia oxidation by globally ...
The ammonia-oxidizing archaea have recently been recognized as a significant component of many microbial communities in the biosphere.Missing: Heintz 1854
[48]
Loss of Ammonia Monooxygenase Activity in Nitrosomonas ... - NIH
Ammonia oxidation by Nitrosomonas europaea is mediated by two enzymes, ammonia monooxygenase (AMO), which catalyzes the oxidation of NH3 to hydroxylamine (NH2OH) ...
[49]
Is there a pathway for N2O production from hydroxylamine ... - NIH
Dec 13, 2016 · The first step of this process is catalyzed by ammonia monooxygenase, producing hydroxylamine (NH2OH). Hydroxylamine oxidoreductase (HAO) then ...
[50]
Hydroxylamine addition impact to Nitrosomonas europaea activity in ...
N. europaea maintained ammonia oxidizing activity when hydroxylamine was added before complete ammonia oxidation cessation. The impact could not be accounted ...
[51]
Efficient detoxication of hydroxylamine and nitrite through ...
Apr 17, 2023 · The accumulation of gaseous nitrogen in the form of NO was improved (0 → 0.23 ... Ev represents the nitrogen removal rate, and C1, C2 and ...
[52]
Theoretical studies of the mechanism of N-hydroxylation of primary ...
Feb 17, 2014 · The major event of the mechanism of their mutagenicity is N-hydroxylation by P450 enzymes, primarily P450 1A2 (CYP1A2), which leads to the ...Missing: hydroxylamine mammalian
[53]
Human Family 1-4 cytochrome P450 enzymes involved in the ... - NIH
This is an overview of the metabolic activation of drugs, natural products, physiological compounds, and general chemicals by catalytic activity of cytochrome ...
[54]
[PDF] HYDROXYLAMINE - CAMEO Chemicals
9.3 Boiling Point at 1 atm: 133.7°F = 56.5°C = 329.7°K 22 mm 158°F = 70°C ... 9.14 Heat of Decomposition: Currently not available. 9.15 Heat of Solution ...Missing: melting | Show results with:melting
[55]
Developmental toxicity of hydroxylamine: an example of a ... - PubMed
Several chemical derivatives of HA are potent developmental toxicants, whereas HA has been reported to cause no developmentally toxic effects. Since HA and its ...Missing: alkylation | Show results with:alkylation
[56]
hydroxylamine with deoxyguanosine in DNA - NIH
The International Agency for Research on Cancer (IARC) has classified o-anisidine as a group 2B carcinogens (IARC, 1982), which is possibly carcinogenic to ...<|separator|>
[57]
Storage and Use of Hydroxylamine Free Base (NH2OH) - Lessons
The energy density for the pure free base hydroxylamine, NH2OH, decomposing as NH2OH --> 1/2N2 + 1/2H2 + H2O is 1,240 cal/g for pure hydroxylamine. This is ...
[58]
HYDROXYLAMINE HYDROCHLORIDE - CAMEO Chemicals - NOAA
STORAGE PRECAUTIONS: You should keep this material in a tightly closed container under an inert atmosphere, and store it at refrigerated temperatures. (NTP ...
[59]
Ascorbic acid and chemically induced methemoglobinemias
In human red cell suspensions 5.0 mm ascorbate significantly attenuated the methemoglobinemic response to tested concentrations of sodium nitrite, hydroxylamine ...
[60]
Methemoglobinemia Treatment & Management - Medscape Reference
Dec 7, 2023 · The ascorbic acid dosage is 200-500 mg/day; unfortunately, long-term oral ascorbic acid therapy can promote the formation of sodium oxalate ...