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Sulfamic acid

Sulfamic acid is a colorless, odorless, crystalline solid and a strong, non-oxidizing inorganic with the molecular H₃NO₃S and a of 97.09 g/. It appears as a white powder, is highly soluble in (up to 21.3 g/100 mL at 20 °C), and has a of 205 °C, decomposing shortly thereafter at 209 °C. First synthesized in the late through the reaction of with , sulfamic acid features a tetrahedral sulfur atom covalently bonded to an amino group (-NH₂), a hydroxyl group (-OH), and two double-bonded oxygen atoms, often adopting a zwitterionic form ([H₃N⁺-SO₃⁻]) in the solid state. Industrially, it is primarily produced by treating with (a mixture of and ) at controlled temperatures below 40 °C to form urea bisulfate, followed by further reaction to yield the acid. As a versatile compound with a pKa of approximately 1.0, sulfamic acid exhibits strong acidity (pH ~1.2 in 1% solution) but lacks the oxidizing power of , making it suitable for applications where must be minimized. Its key industrial uses include descaling and cleaning in boilers, heat exchangers, and dairy equipment to remove deposits; acting as a catalyst in such as Biginelli reactions for dihydropyrimidinones; stabilizing in swimming pools; and serving as a in production, herbicides, and flame retardants. Additionally, it functions as a regulator in and a in baths, highlighting its role in enhancing efficiency across chemical manufacturing and maintenance processes.

History and discovery

Early synthesis

Sulfamic acid was first reported in the late through laboratory-scale reactions involving sulfur-containing compounds and sources. The compound was initially synthesized by the direct reaction of with gas, a method described by chemist Ernst Berglund in , who prepared a relatively pure form of the acid for the first time. This marked the beginning of systematic study of sulfamic acid, though earlier impure preparations may have occurred as byproducts in related reactions. The primary reaction identified in Berglund's work is the combination of sulfur trioxide and ammonia to form sulfamic acid: \mathrm{SO_3 + NH_3 \rightarrow H_3NSO_3} This straightforward gas-phase or solution-based process yielded the compound but required careful control to avoid side reactions leading to ammonium sulfate or other impurities. An alternative early synthesis, developed by German chemist Friedrich Raschig in 1887, involved treating urea with fuming sulfuric acid, which generates sulfur trioxide in situ and facilitates the hydrolysis of an intermediate urea-sulfamic acid adduct to produce sulfamic acid alongside ammonium bisulfate and carbon dioxide. This method offered improved yields and purity for laboratory preparation compared to the direct ammonia route. Raschig's procedure, detailed in his seminal paper, emphasized the reaction's simplicity and enabled broader chemical exploration of the acid. Initial efforts to isolate sulfamic acid encountered significant difficulties due to its highly hygroscopic nature, causing the crystalline solid to deliquesce rapidly in humid air and complicating storage and purification. Additionally, the compound exhibited thermal instability, decomposing above approximately 200 °C into , , , and other gases, which hindered handling during early experiments. These properties limited immediate applications but spurred refinements in techniques that paved the way for 20th-century scalability.

Industrial development

The industrial development of sulfamic acid accelerated in the mid-20th century with the introduction of cost-effective large-scale production methods, shifting from earlier laboratory-scale syntheses dating back to the . In the 1940s, pioneered a key process involving the reaction of with fuming (), which enabled economical by producing sulfamic acid in high yields while generating byproducts like and . The reaction proceeds as follows: (\ce{NH2})2\ce{CO} + \ce{H2SO4} \text{(fuming)} \rightarrow \ce{H3NSO3} + \ce{CO2} + \ce{H2O} This innovation, detailed in a 1948 U.S. patent, addressed previous limitations in scalability and cost, positioning sulfamic acid as a viable alternative to stronger acids like hydrochloric acid in various applications. Following World War II, production expanded rapidly to meet rising demand from the cleaning and chemical industries, where sulfamic acid's non-corrosive properties made it ideal for descaling, herbicides, and flameproofing agents. The first commercial plant, established by DuPont, began operations in 1946, marking the onset of widespread industrial adoption. This post-war growth was driven by postwar economic recovery and industrial diversification, with sulfamic acid's use in household cleaners and industrial formulations fueling market expansion. Global consumption reached approximately 160,000 metric tons by amid steady growth. This evolution underscores sulfamic acid's transition from a niche compound to a cornerstone of modern chemical , supported by ongoing refinements for purity and .

Properties

Physical properties

Sulfamic acid appears as a , crystalline, odorless . Its molecular weight is 97.09 g/mol. The of sulfamic acid is 2.15 g/cm³ at 25 °C. It has a of 205 °C, with . Sulfamic acid exhibits high in , approximately 17.6 g per 100 mL at 20 °C, moderate solubility in , and is insoluble in non-polar solvents such as . The is non-hygroscopic, remaining stable and free from moisture absorption in typical storage conditions, though finely powdered forms may occasionally appear clumped. This pronounced enables effective dissolution in aqueous media.

Chemical properties

Sulfamic acid has the molecular formula H₃NSO₃, also represented as NH₂SO₃H. It behaves as a strong acid in , with a of approximately 0.99, leading to into H⁺ and H₂NSO₃⁻ ions. This acidity profile positions it as a moderately strong inorganic acid, with distinct reactivity due to its sulfamate structure. Sulfamic acid demonstrates good thermal stability, remaining intact up to around 200 °C, beyond which it decomposes into , , , and . Unlike more volatile mineral acids such as HCl or H₂SO₄, sulfamic acid exhibits low as a solid, minimizing vapor-related hazards during handling and storage. The acid readily forms stable sulfamate salts upon reaction with bases, such as sodium sulfamate (NaH₂NSO₃), which are water-soluble and widely used in various applications. These salts maintain the structural integrity of the sulfamate anion, contributing to the compound's utility in non-volatile acid systems.

Production

Laboratory synthesis

Sulfamic acid can be prepared in the laboratory through the reaction of urea with fuming sulfuric acid, typically at temperatures between 80 and 100 °C to form urea bisulfate as an intermediate, followed by further processing to yield the product. This method involves slowly adding urea to fuming sulfuric acid while maintaining controlled heating to manage the exothermic nature of the reaction and minimize decomposition. Yields of 90–98% are achievable with precise temperature regulation, as higher temperatures can promote side reactions leading to ammonium sulfate as a byproduct. An alternative laboratory approach involves the direct reaction of gaseous with in a well-ventilated to produce , which is then hydrolyzed to sulfamic acid. This gas-phase method requires careful control of gas flow rates to ensure efficient combination and avoid excessive heat buildup. Following synthesis by either method, the crude product is purified by recrystallization from hot water, where it is dissolved in near-boiling water and then cooled to precipitate pure crystals, effectively removing impurities such as unreacted or salts. Laboratory procedures demand the use of appropriate protective equipment, including gloves, goggles, and fume hoods, due to the highly exothermic reactions and the corrosive, irritating nature of the reagents involved.

Industrial production

Sulfamic acid is primarily produced on an industrial scale through a continuous reaction of urea with oleum, which consists of 20–65% sulfur trioxide (SO₃) in sulfuric acid (H₂SO₄), conducted in specialized reactors. The process begins with the controlled addition of urea to oleum under agitation to facilitate the sulfonation, generating sulfamic acid along with carbon dioxide (CO₂) as a byproduct; the reaction mixture is then cooled to promote crystallization, followed by separation, washing, and drying to yield the final product. This method, building on foundational processes developed by DuPont in the mid-20th century, allows for high throughput and consistent output suitable for commercial demands. Byproduct management is integral to the process efficiency, with CO₂ typically vented or captured for in other industrial applications to minimize emissions, while excess is recycled to reduce impurities in the final product. Purification steps, such as recrystallization, ensure levels remain below 0.1%, enhancing product quality for downstream uses. Global production is concentrated among key manufacturers in , , and , with major players including Shandong Mingda Chemical and Yazhong Chemical in , Nuchem Ltd. and Acuro Organics in , and SE and in , largely driven by demand for sulfamic acid in and descaling applications. In the 2020s, advancements have focused on improving and purity through optimized reactor designs and process controls, as well as better heat recovery systems. Cost factors favor this production route, as raw material averages around $370 per ton as of November 2025, making sulfamic acid more economical than (HCl) alternatives for descaling due to lower handling and mitigation expenses.

Structure and reactivity

Molecular structure

Sulfamic acid, with the H₃NSO₃, consists of a central atom tetrahedrally coordinated to an amino group (NH₂), a hydroxyl group (OH), and two oxygen atoms via double bonds (S=O). The zwitterionic structure, [H₃N⁺-SO₃⁻], is the predominant form in the solid state. Spectroscopic and computational studies indicate that the zwitterionic form is also favored over the neutral form in (for undissociated molecules) and in the gas phase. This zwitterionic configuration is stabilized by intramolecular hydrogen bonding between the hydrogens and the oxygens. X-ray crystallographic studies reveal the sulfur atom maintains tetrahedral geometry in the zwitterion, with the S–N bond length measured at approximately 1.77 Å and the S–O bond lengths around 1.44 Å, indicative of partial double-bond character in the S–O linkages consistent with sulfonate resonance. The N–S–O bond angles are about 106°, while O–S–O angles are roughly 113°, further supporting the tetrahedral arrangement around sulfur. Neutron diffraction confirms these dimensions and highlights the positions of hydrogen atoms involved in bonding. The crystal structure of solid sulfamic acid is orthorhombic, belonging to the space group Pbca, with lattice parameters a ≈ 8.07 Å, b ≈ 8.12 Å, and c ≈ 9.26 Å. Within the lattice, zwitterionic units form extensive hydrogen-bonded networks, where each ammonium group donates three N–H···O hydrogen bonds to sulfonate oxygens of neighboring molecules, creating a three-dimensional framework that contributes to the compound's stability. Spectroscopic techniques corroborate the structural features: infrared (IR) spectroscopy shows a characteristic S–N stretching vibration at approximately 1050 cm⁻¹ in the solid state, reflecting the single-bond nature of the S–N linkage in the zwitterion. Nuclear magnetic resonance (NMR) spectroscopy, particularly ¹H and ¹⁵N NMR, confirms the proton environments and nitrogen hybridization, with the ammonium protons appearing as a broad signal around 7–8 ppm in ¹H NMR spectra of solid samples.

Acid–base reactions

Sulfamic acid behaves as a moderately strong monoprotic acid in aqueous solutions, dissociating via the equilibrium \ce{H3NSO3 ⇌ H+ + H2NSO3-} with an K_a = 0.101 (or \mathrm{p}K_a \approx 1.0) at 25 °C. This value positions sulfamic acid as significantly weaker than , which has a first \mathrm{p}K_a \approx -3 for complete dissociation of its initial proton, but stronger than acetic acid with a \mathrm{p}K_a = 4.76. The relatively low \mathrm{p}K_a reflects the enhanced acidity due to the electron-withdrawing sulfonyl group adjacent to the protonated amino functionality, facilitating proton release. In acid–base reactions, sulfamic acid readily forms sulfamate salts upon neutralization with s or metals. For instance, its reaction with yields sodium sulfamate (monosodium sulfamate) according to \ce{H3NSO3 + NaOH → NaH2NSO3 + H2O}, a double displacement process commonly employed in titrations for standardizing solutions. Analogous reactions with other metals, metals, or organic s produce the corresponding sulfamates, which are stable ionic compounds soluble in water and used in various chemical syntheses. The stable \mathrm{p}K_a of sulfamic acid enables its use in buffer systems for precise pH adjustment, particularly in acidic ranges (pH 1–3), where it helps maintain consistent proton concentrations in industrial processes such as textile dyeing, electroplating baths, and water treatment. These applications leverage its moderate strength to avoid excessive acidity while providing effective control over reaction environments, outperforming weaker acids like acetic in scenarios requiring lower pH stability.

Hydrolysis

Sulfamic acid undergoes in , decomposing to and according to the reaction \ce{H3NSO3 + H2O -> H2SO4 + NH3} This process occurs slowly at but accelerates significantly at temperatures exceeding 100 °C. The of hydrolysis follow dependence on the concentration of sulfamic acid, with the rate constant increasing with temperature. At 35 °C, the half-life is approximately 260 hours, reflecting the relative stability of dilute solutions under ambient conditions. The mechanism proceeds via nucleophilic attack by on the sulfur atom of the sulfamic acid , resulting in cleavage of the S–N bond and formation of the products. This hydrolytic instability restricts the long-term storage of sulfamic acid in aqueous media, necessitating dry handling or short-term use in solution-based applications. A thermal variant of hydrolysis occurs upon heating sulfamic acid to around 260 °C, where it decomposes to , , and .

Other reactions

Sulfamic acid reacts with to form nitrososulfamic acid as an intermediate, which decomposes to nitrogen gas, , and , according to the overall equation: \mathrm{H_3NSO_3 + HNO_2 \rightarrow H_2SO_4 + N_2 + H_2O} This reaction is rapid and selective, making sulfamic acid a common reagent for scavenging excess in diazotization processes during synthesis, where it prevents over-nitrosation of aromatic amines without interfering with the primary reaction. With , sulfamic acid undergoes a similar oxidative , producing instead of gas: \mathrm{H_3NSO_3 + HNO_3 \rightarrow H_2SO_4 + N_2O + H_2O} This process is utilized in to generate or to neutralize residues in metal recovery operations. Sulfamic acid reacts with ions, such as from , to form N-chlorosulfamic acid, a chloramine-like : \mathrm{H_3NSO_3 + NaOCl \rightarrow Na^+ + ClHNSO_3^- + H_2O} This product exhibits biocidal activity similar to chloramines and is employed in disinfection formulations and pulp bleaching, where it provides controlled release of active chlorine while reducing the volatility and corrosiveness of free hypochlorite. Further chlorination can yield N,N-dichlorosulfamic acid under excess hypochlorite conditions. In the presence of alcohols and acid catalysts, sulfamic acid undergoes esterification to produce alkyl sulfamates: \mathrm{H_3NSO_3 + ROH \rightarrow ROSO_2NH_2 + H_2O} where R represents an . This reaction, often facilitated by activating agents like triphenylphosphine ditriflate, yields O-alkyl sulfamates used as intermediates in pharmaceutical synthesis, such as inhibitors, and in production. Yields are typically high for primary alcohols, with reaction conditions optimized at elevated temperatures to drive water removal. Sulfamic acid also interacts with silver surfaces or oxides to form soluble silver sulfamate complexes, enabling its use in polishing and cleaning tarnished silver by dissolving layers without aggressive etching. This application appears in commercial silver cleaners and electrochemical recovery processes.

Applications

Cleaning and descaling

Sulfamic acid serves as an effective in both household and industrial cleaning by reacting with calcium and magnesium carbonates in deposits, forming soluble sulfamates and releasing . The primary reaction with is: \mathrm{CaCO_3 + 2 H_3NSO_3 \rightarrow Ca(H_2NSO_3)_2 + H_2O + CO_2} This chelation mechanism dissolves scale without requiring mechanical abrasion, enabling thorough removal from surfaces like pipes and appliances. Compared to hydrochloric acid, sulfamic acid offers key advantages in descaling, including non-volatility to prevent fuming and reduced corrosiveness toward metals such as steel, copper, and brass. It performs efficiently in 5–10% aqueous solutions, often heated to 50–70°C for optimal speed without excessive material degradation. In practical applications, sulfamic acid features prominently in toilet cleaners to eliminate and urinary deposits, ensuring hygienic surfaces. It is also employed for and descaling in settings, preventing efficiency losses from mineral buildup. Additionally, it aids in metal polishing by removing , , and from surfaces like silver. Commercial formulations typically incorporate to improve wetting and penetration, enhancing overall cleaning performance on vertical or porous surfaces. These solutions maintain a of 1–2 to ensure reactivity while minimizing handling risks. As of , sulfamic acid is increasingly used in eco-friendly cleaners due to its biodegradable profile and lower environmental impact relative to harsher acids; industrial cleaning remains the largest application segment, accounting for over 40% of . Its low further supports safe use in consumer products.

Chemical synthesis

Sulfamic acid serves as a key precursor in the of sulfamates, particularly through its with primary amines to form N-substituted derivatives. For instance, the of sulfamic acid with yields cyclamic acid, which is subsequently neutralized with to produce sodium , a non-caloric artificial . This process involves heating the reactants in , followed by basification, achieving high yields due to the direct sulfonamidation. As a mild Brønsted acid , sulfamic acid facilitates esterification reactions, such as the conversion of free s to fatty acid alkyl esters for . In these transformations, sulfamic acid promotes the reaction between carboxylic acids and alcohols under solvent-free conditions at moderate temperatures (around 80–100°C), offering advantages over traditional catalysts by minimizing and enabling easy recovery through . Its role extends to polymerization processes, where it acts as an efficient for the synthesis of polyesters via esterification of diols and dicarboxylic acids, providing control over molecular weight and polydispersity in green polymer manufacturing. In pharmaceutical synthesis, sulfamic acid derivatives, particularly sulfamates, are employed in the development of inhibitors. These inhibitors feature a sulfamate group (–OSO₂NH₂) that mimics the of the enzyme's , with synthesis typically involving sulfamoylation of or alcoholic moieties using reagents derived from sulfamic acid. Sulfamate-based CAIs have shown potent inhibition (Kᵢ values in the nanomolar range) and are researched for treating conditions including by reducing . Sulfamic acid plays an essential role in dye production as an intermediate in the diazotization step for azo dyes, where it eliminates excess ions after diazonium formation to prevent unwanted side reactions and stabilize the component. This application is particularly valuable in the synthesis of acid and reactive azo dyes, allowing for controlled coupling with aromatic amines or to yield vibrant colorants with high purity. In , addition of sulfamic acid (typically 0.5–2 equivalents) to the diazo mixture at 0–5°C ensures efficient conversion and reduces waste. Sulfamic acid is used in green synthesis routes for through sulfation of alcohols and ethoxylated alcohols, such as fatty alcohols, to form ammonium-neutralized . This method avoids hazardous , promotes sustainability, and demonstrates high with minimal byproducts (primarily ). Such approaches align with eco-friendly chemical manufacturing principles, enabling reduced environmental impact in production for detergents and emulsifiers.

Other uses

Sulfamic acid finds application in processes, particularly as a regulator and in cooling systems, where it helps maintain optimal chemistry and prevents scale formation on equipment surfaces. Typical dosages range from 50 to 200 , depending on system conditions and hardness, allowing for effective control without excessive acidity. Its high in facilitates uniform distribution in aqueous environments, supporting these roles in cooling towers. In , sulfamic acid is a key precursor to , which serves as a component in formulations designed for , targeting woody plants, stumps, herbaceous perennials, and broadleaf weeds. acts systemically, translocating through plants to roots for comprehensive eradication, and is often applied in dilute solutions for selective control in turf and non-crop areas. While commonly used standalone for tough species like and brambles, it can be incorporated into mixed blends, such as those enhancing efficacy with compounds like , to broaden spectrum control in agricultural settings. Sulfamic acid contributes to materials through the formation of sulfamate salts, such as , which are integrated as additives in polymers to enhance resistance. These salts decompose during to release non-flammable gases and form protective char layers, improving the limiting oxygen index and reducing heat release rates in materials like , , and fabrics. For instance, guanidine sulfamate combined with polyphosphate has been shown to achieve V-0 ratings in UL-94 tests for polyamide 6 composites at loadings of 20-25 wt%. In , sulfamic acid functions as a for acid-base titrations, enabling precise determination of base concentrations due to its non-hygroscopic nature, high purity, and complete dissociation as a strong acid (pKa ≈ 1.0). It is typically dissolved in water to prepare standard solutions that are titrated against bases like , providing accurate equivalence points via potentiometric or indicator methods. This application is particularly valuable in protocols where stability and ease of handling are essential. Niche applications of sulfamic acid include its use as a and in breweries, where it effectively removes beer stone, protein deposits, and scale from equipment like vats, pipelines, and heat exchangers, while providing action through acidification. Additionally, as of 2025, highlights its role in electrolytes; for example, sulfamic acid-caprolactam mixtures inhibit evolution in proton batteries, improving and efficiency in aqueous systems.

Safety and environmental impact

Health hazards

Sulfamic acid is a and eye irritant, with solutions exceeding 10% concentration acting as corrosive agents that can cause severe burns upon contact. Inhalation of its dust or mist leads to irritation, including coughing, throat discomfort, and potential at high exposures. Ingestion may result in gastrointestinal distress, such as and . Chronic exposure to sulfamic acid is associated with potential damage to the liver and kidneys, and it exhibits moderate oral toxicity with an LD50 of approximately 2,000 mg/kg in rats. Prolonged inhalation can exacerbate lung irritation and contribute to mucous membrane toxicity. Safe handling requires personal protective equipment, including chemical-resistant gloves, safety goggles, and protective clothing to prevent skin and eye contact. Adequate ventilation is essential to minimize dust exposure, with a permissible exposure limit (PEL) of 15 mg/m³ for total dust as a general guideline for particulate not otherwise regulated. In case of exposure, first aid measures include immediate flushing of affected or eyes with copious amounts of for at least 15 minutes; for inhalation, move to and seek medical attention if breathing difficulties persist; and for , rinse the and do not induce vomiting, followed by medical evaluation. Neutralization with may be used for spills but not directly on . Under regulations, sulfamic acid is classified as a skin irritant (H315) and causes serious eye damage (H318), reflecting its hazardous nature while demonstrating lower overall toxicity compared to due to reduced corrosivity and similar but contextually milder acute effects.

Ecological considerations

Sulfamic acid is not readily biodegradable but hydrolyzes slowly in aqueous solutions to form ((NH₄)HSO₄), which further breaks down into naturally occurring and ions that integrate into environmental cycles. In environments, sulfamic acid poses a moderate risk to , with an LC50 of 70.3 mg/L for fathead minnows (Pimephales promelas) over 96 hours, though effects are limited due to its low bioaccumulation potential (log Kow ≈ 0 to -4.34). Despite its minimal persistence from , untreated releases of sulfamic acid into can contribute to acidification, lowering and potentially harming ecosystems if not neutralized prior to discharge. As a greener alternative in cleaning applications, sulfamic acid reduces reliance on , thereby lowering emissions of corrosive HCl vapors and associated environmental hazards during descaling processes. Under U.S. regulations, the Environmental Protection Agency classifies sulfamic acid as a low-concern chemical through its Safer Choice program, based on experimental and modeled data showing reduced risks to human health and the . In the European Union, sulfamic acid is registered under REACH without specific restrictions as of 2025, supporting its use over more hazardous strong acids in evaluated applications. From a sustainability perspective, sulfamic acid is recyclable in certain industrial cleaning and catalytic processes, where spent solutions can be regenerated, and its lower corrosivity compared to alternatives like minimizes metal dissolution in treatment effluents, aiding management.