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Sodium perborate

Sodium perborate is an , most commonly encountered as the tetrahydrate with the NaBO₃·4H₂O, appearing as a white, odorless crystalline powder that serves as a stable source of active oxygen for bleaching and oxidation applications. It exhibits limited in (approximately 21.5 g/L at 18°C), slowly decomposing to release (H₂O₂), which acts as the primary bleaching agent, and it melts with decomposition around 60°C. As a peroxygen , it is hydrolytically unstable due to its boron-oxygen-oxygen bonds, making it incompatible with strong reducing agents, acids, or , and it functions as an in aqueous solutions under alkaline conditions.

Properties and Structure

The tetrahydrate form, with a molecular weight of 153.86 g/mol, is the predominant commercial variant, containing about 10% available oxygen by weight, which is crucial for its efficacy in oxidative processes. Structurally, it can be represented as sodium metaperborate tetrahydrate, where the perborate anion ([B(O₂)(OH)₂]⁻) coordinates with molecules, enabling gradual release of H₂O₂ in :
NaBO₃·4H₂O → Na⁺ + [B(OH)₄]⁻ + H₂O₂. This decomposition is pH-dependent, accelerating in acidic media to liberate oxygen gas, while remaining stable in dry storage.

Production

Sodium perborate tetrahydrate is industrially synthesized by reacting disodium tetraborate pentahydrate () with in an alkaline medium, followed by from the resulting solution. The process typically involves:
  1. Dissolving in solution.
  2. Adding H₂O₂ to form the perborate complex.
  3. Cooling and crystallizing the tetrahydrate product. U.S. production volumes have varied, reaching approximately 4.8 million pounds in 2016, reflecting its steady demand in consumer and industrial sectors.

Uses

Primarily employed as a bleaching agent in detergents and products, sodium perborate provides an environmentally friendlier to chlorine-based bleaches by releasing H₂O₂ at lower temperatures (around 60°C), effective against stains on cotton, wool, and synthetic fabrics. It is also incorporated into dentifrices, denture cleaners, and pharmaceuticals for its , deodorizing, and mild properties, aiding in without excessive enamel wear. In , it serves as a mild oxidant for reactions like Baeyer-Villiger oxidations, epoxidations, and halogenations, often in eco-friendly aqueous media.

Safety and Environmental Considerations

Sodium perborate is classified as an oxidizer (GHS H272) and poses hazards including and eye irritation (H315, H318), respiratory (H335), and potential (H360FD), requiring handling with protective equipment to avoid dust inhalation or contact. It is toxic if ingested (H302) and decomposes in to release oxygen, potentially intensifying , though it is non-combustible itself. Environmentally, it biodegrades to borates, which are naturally occurring but can accumulate in water bodies; regulatory limits apply in detergents to mitigate boron pollution.

Structure and properties

Molecular structure

Sodium perborate exists primarily as hydrated salts with the general NaBO₃·nH₂O, where n = 0 (), 1 (monohydrate), or 4 (tetrahydrate). The compound is ionic in nature, consisting of sodium cations (Na⁺) and the peroxyborate dianion, represented as [Na⁺]₂[B₂O₄(OH)₄]²⁻·(H₂O)ₓ, where x denotes the variable level. The core structural feature is the peroxyborate anion, a cyclic dimer denoted as [(HO)₂B(O–O)B(OH)₂]²⁻, which incorporates a (O–O) bridge linking two atoms in a six-membered ring configuration: B–O–O–B–O–O. Each atom adopts a tetrahedral , coordinated to two hydroxy groups () and two oxygen atoms from the bridging peroxo groups. This dimeric structure, with its symmetric cyclic arrangement and two peroxo bridges, imparts the compound's oxidative properties while maintaining stability in the solid state. The tetrahydrate form, NaBO₃·4H₂O or equivalently Na₂H₄B₂O₈·4H₂O, appears as a crystalline solid and is the most common variant, featuring four water molecules of per . In contrast, the monohydrate, NaBO₃·H₂O or Na₂[B₂(O₂)₂(OH)₄]·2H₂O, incorporates two lattice water molecules associated with the dimeric anion, resulting in a more compact hydration shell and greater thermal stability compared to the tetrahydrate. The form is less stable and rarely isolated. These hydrate differences primarily affect the and but preserve the fundamental peroxyborate anion structure across forms.

Physical properties

Sodium perborate tetrahydrate is typically observed as a white to colorless, odorless, free-flowing crystalline powder. The monohydrate form appears as a white amorphous powder. It exhibits moderate in , dissolving at a rate of 2.3 g per 100 mL at 20°C to form an alkaline solution. increases with temperature. The compound is sparingly soluble in alcohols and insoluble in non-polar organic solvents such as acetone and hydrocarbons. The density of the tetrahydrate is 1.73 g/cm³. The tetrahydrate does not have a distinct melting point but dehydrates around 60°C to form the monohydrate without releasing oxygen or forming a liquid phase; further decomposition at higher temperatures (around 130°C) releases oxygen. Sodium perborate is hygroscopic, readily absorbing atmospheric moisture in humid conditions to form partial hydrates, which can affect its handling and storage. When stored in dry conditions away from heat and light, it remains stable for extended periods, though exposure to elevated temperatures above 60°C leads to dehydration. The tetrahydrate contains approximately 10.4% theoretical available oxygen (commercial products typically 9-11%), contributing to its physical characteristics as a solid oxygen source.

History and synthesis

Discovery and development

Sodium perborate was first synthesized in 1898 through independent efforts by Russian chemists Sebastian Tanatar and by P. Melikoff and L. Pissarjewski. Tanatar prepared it by reacting with sodium metaborate, while Melikoff and Pissarjewski obtained it via of a sodium borate solution. These discoveries marked the initial identification of the compound as a stable peroxyborate salt, highlighting its potential as an oxygen-releasing agent. Early commercial interest emerged in the early , driven by its bleaching properties. Henkel launched in 1907, the world's first self-acting detergent powder incorporating sodium perborate for stain removal and whitening without manual boiling. In 1903, German chemist Otto Liebknecht patented an improved production method involving the reaction of with under controlled conditions, facilitating scalable manufacturing. Shortly thereafter, in 1904, French chemist Marcel Jaubert described a process using and , leading to further patents for detergent applications. These innovations spurred industrial production, with companies like Degussa (now Evonik) recognizing its value as a safer alternative to liquid for textile bleaching. Key milestones in the included electrolytic production methods introduced in 1920, which enhanced efficiency and enabled mass-market penetration across . In , sodium perborate gained recognition as a stable solid source of , valued for its thermal stability and ease of handling in formulations compared to more volatile peroxides. Recent developments reflect regulatory pressures, with sodium perborate facing phase-out in the post-2010 due to classifications as a reproductive under cosmetics regulations, leading to bans in from December 2010. Despite this, it continues to be used in detergents and bleaching agents both in the (under boron content restrictions) and in non-EU markets, particularly in and other regions, supported by steady global market growth projected at 3.7% CAGR from 2025 through 2030.

Preparation methods

Sodium perborate is typically synthesized in the laboratory by first preparing sodium metaborate from and , followed by with under controlled conditions. The process involves dissolving 5 g of (Na₂B₄O₇·10H₂O) and 1 g of NaOH in water to form sodium metaborate, then adding 30% H₂O₂ while maintaining a of approximately 9 and temperature below 20°C to favor of the tetrahydrate. The balanced for the overall is: \mathrm{Na_2B_4O_7 \cdot 10H_2O + 2NaOH + 4H_2O_2 \rightarrow 4NaBO_3 \cdot 4H_2O + 11H_2O} The product is filtered, washed, and dried at room temperature, yielding white crystals suitable for small-scale applications. Industrial production primarily employs a continuous chemical process starting with the dissolution of borax pentahydrate in sodium hydroxide at 60–90°C to generate a sodium metaborate solution, which is then clarified by centrifugation. This solution is cooled to 20–30°C in a vacuum crystallizer, where 40% H₂O₂ is added slowly under stirring, stabilized with magnesium sulfate to prevent peroxide decomposition, leading to the precipitation of sodium perborate tetrahydrate. The reaction proceeds as: \mathrm{NaBO_2 + H_2O_2 + 3H_2O \rightarrow NaBO_3 \cdot 4H_2O} Yields exceed 95% for the tetrahydrate, with the crystals separated by centrifugation, washed to remove residual borates, and dried with warm air at around 35°C. An alternative electrolytic method involves the oxidation of borate electrolytes (containing borax, sodium carbonate, and stabilizers) in a cooled cell (10–15°C) using platinum or boron-doped diamond anodes at current densities of 1–3 kA/m², generating H₂O₂ in situ for reaction with borate ions; this achieves current efficiencies up to 41% but is less common due to higher energy demands (3–4 kWh/kg). The monohydrate form is obtained by dehydrating the tetrahydrate in a fluidized-bed dryer at 100–150°C under controlled airflow, removing three s of per mole of product while minimizing . The anhydrous form requires higher-temperature fusion above 200°C in specialized reactors to eliminate all , though this variant is rarely produced due to instability. Purification is achieved through recrystallization from aqueous solutions at low temperatures (5–10°C) to enhance crystal purity and size, followed by washing with cold water or dilute to exclude impurities such as chlorides from raw materials; the use of polycarboxylic polymers (50–300 ppm) during improves particle and density without introducing contaminants.

Chemical behavior

Hydrolysis and decomposition

Sodium perborate undergoes upon contact with water, yielding and sodium metaborate as primary products. The reaction can be represented by the equation: \mathrm{NaBO_3 + H_2O \rightarrow NaBO_2 + H_2O_2} This process is influenced by , proceeding more rapidly in acidic environments where the equilibrium shifts toward free rather than intact perborate species. In neutral to alkaline conditions, hydrolysis is slower, allowing perborate to persist longer in solution. At higher concentrations, aqueous solutions of sodium perborate feature mixtures that include various peroxoborate anions, such as the diperoxodihydroxodiborate [B₂O₄(OH)₄]²⁻ and the monohydroxodiperoxoborate [HOB(O₂)₂]⁻, alongside the products. These species contribute to the oxidative capacity of perborate solutions by stabilizing the functionality. Spectroscopic studies confirm the presence of such anions even in moderately dilute media. Thermal decomposition of sodium perborate occurs above 60°C, leading to the evolution of oxygen gas and formation of sodium metaborate. The overall is: $2\mathrm{NaBO_3 \rightarrow Na_2B_2O_4 + O_2} This mirrors aspects of decomposition but is moderated by the matrix, which influences the and rate. In biological systems, sodium perborate decomposition is catalyzed by the enzyme , which facilitates the breakdown into , oxygen, and . This interaction underpins perborate's utility in certain biochemical assays and highlights its peroxide-like behavior in enzymatic contexts.

Reactivity

Sodium perborate serves as a stable source of active oxygen, releasing upon in aqueous environments, which enables it to function as a mild akin to H₂O₂ but with superior thermal and storage stability in its solid form. This property allows it to selectively oxidize various substrates, including the conversion of sulfides to sulfoxides under controlled conditions. As a strong oxidizer, sodium perborate is incompatible with reducing agents, which can trigger exothermic reactions, as well as with acids that accelerate the of and certain metals or metal catalysts that promote catalytic breakdown. These interactions underscore the need for careful handling to prevent unintended reactivity. The compound exhibits activity primarily through the oxidative damage inflicted by released species on bacterial membranes, membrane-bound enzymes, and associated proteins. In practical formulations such as detergents, sodium perborate's stability is improved by incorporating stabilizers like magnesium silicates, which help maintain its integrity during storage and use.

Applications

Bleaching and cleaning

Sodium perborate serves as a primary oxygen-based bleaching agent in detergents, where it has been incorporated since the early to enhance and whitening. It typically comprises 10-20% of powder detergent formulations, releasing upon in water to oxidize organic stains such as those from , , and at temperatures of 40-60°C. This mechanism provides effective bleaching without the need for high heat, making it suitable for modern washing cycles. In textile processing, sodium perborate is employed for bleaching natural fibers like and , particularly to restore yellowed or discolored fabrics. It acts gently on these materials, avoiding the degradation and yellowing associated with chlorine-based bleaches, while effectively removing impurities through controlled oxidation. For household applications, sodium perborate is integrated into scouring powders and surface disinfectants, where it aids in removing tough residues and sanitizing areas like countertops and tiles by oxidizing and killing . It is also used in formulations for polishing and surfaces, helping to dissolve without abrasive damage. Compared to , sodium perborate offers superior stability in dry formulations, preventing premature decomposition and non-yellowing effects on fabrics, while being more environmentally benign as it breaks down into oxygen, , and borates rather than releasing byproducts.

Medical and dental uses

Sodium perborate is utilized in oral antiseptics, particularly as effervescent powders or rinses for treating mouth ulcers and , where it acts as an to reduce bacterial load. A double-blind crossover study from 1979 demonstrated that the released from sodium perborate formulations can prevent or retard colonization by through oxidation mechanisms. Formulations typically contain 68-70% sodium perborate monohydrate, often combined with to produce upon dissolution in water, enhancing cleaning action in the oral cavity. However, its use in cosmetic dental products is prohibited in the since 2019 due to concerns. In dental applications, sodium perborate serves as a bleaching agent for non-vital teeth, commonly applied as 10-15% solutions or pastes in intracoronal procedures to whiten discolored . Comparative studies show sodium perborate has efficacy similar to carbamide peroxide but lower than , often requiring multiple applications for effective whitening in primary and permanent non-vital teeth.

Organic synthesis

Sodium perborate serves as a mild and versatile oxidant in , particularly for selective oxygen-transfer reactions. It offers advantages over pure , including greater stability, ease of handling, and reduced risk of explosive decomposition, while being inexpensive and compatible with protic solvents such as acetic acid. Typically employed in 2-5 equivalents, it generates peroxy species for controlled oxidations. One key application is the oxidation of thioethers to or . For instance, phenyl methyl (PhSCH₃) is converted to methyl phenyl (PhS(O)CH₃) or further to the using sodium perborate in acetic acid at , providing high selectivity depending on the amount of oxidant used. This method is effective for both aliphatic and aromatic thioethers, yielding up to 90% for under mild conditions. Sodium perborate also facilitates the conversion of aryl halides to via a two-step process involving -catalyzed borylation followed by oxidation. In the first step, aryl halides (ArX) undergo Miyaura borylation with a catalyst to form arylboronic acids or esters; these are then oxidized with sodium perborate in aqueous media as a safe alternative to , yielding (ArOH) in good yields (e.g., 85% from iodobenzene). The overall transformation, ArX + H₂O → ArOH, proceeds under mild aqueous conditions without requiring harsh bases. As a mild oxidant, sodium perborate converts primary alcohols, especially benzylic ones, to aldehydes. Benzyl alcohol, for example, is oxidized to benzaldehyde in acetic acid at room temperature, achieving 80-95% yield while avoiding over-oxidation to carboxylic acids. This reaction leverages neutral aqueous polyethylene glycol media for enhanced selectivity and environmental compatibility. Additionally, sodium perborate promotes Baeyer-Villiger oxidation of ketones to esters or lactones. Cyclohexanone is transformed to ε-caprolactone using sodium perborate in acetic acid at 70-80°C, with yields around 75-85% and complete regioselectivity favoring migration of the more substituted group. Alternatively, in formic acid, it provides a safer substitute for peracids, as demonstrated in the synthesis of chloroketolactones (66% yield). \begin{align*} &\ce{PhSCH3 + NaBO3 ->[AcOH][\Delta] PhS(O)CH3} \\ &\ce{ArX ->[Cu cat., B source] ArB(OH)2 ->[NaBO3][H2O] ArOH} \\ &\ce{PhCH2OH + NaBO3 ->[AcOH][rt] PhCHO} \\ &\ce{(CH2)5CO + NaBO3 ->[AcOH][70-80°C] O(CH2)5CO} \end{align*}

Safety and regulation

Health effects

Sodium perborate demonstrates moderate acute oral toxicity, with an LD50 value of approximately 2567 mg/kg body weight in rats, based on Guideline 401 testing. It is classified as (Acute Category 4) under the Globally Harmonized System of Classification and Labelling of Chemicals (GHS). Dermal exposure shows low acute toxicity, with an LD50 greater than 2000 mg/kg in rabbits. The compound is a strong irritant to eyes, causing serious damage; it may cause mild skin irritation upon contact with moisture due to its hydrolysis and release of . Inhalation of sodium perborate dust or powder leads to irritation, classified as Specific Target Organ Toxicity (Single Exposure) Category 3, with symptoms including coughing, , and upper respiratory discomfort. Chronic exposure to sodium perborate results in accumulation in the body, which is associated with , including impaired and developmental effects on the unborn child. It is harmonized as a reproductive toxicant Category 1B (may damage or the unborn child) under GHS and REACH regulations, qualifying it as a (SVHC). studies have indicated weak but reproducible mutagenic potential in bacterial assays such as typhimurium strains TA100 and TA102, though it lacks a harmonized for mutagenicity or carcinogenicity. Primary exposure routes for sodium perborate include dermal contact during handling of cleaning products and of airborne particles from powdered formulations in industrial or household settings. Acute symptoms from encompass , , , and , while dermal exposure can provoke , characterized by redness, itching, and blistering upon repeated or prolonged contact. may exacerbate respiratory symptoms, potentially leading to chronic irritation with ongoing exposure. For first aid, immediate rinsing of eyes or skin with copious amounts of water for at least 15 minutes is recommended to minimize irritation and damage. In cases of inhalation, move the affected individual to fresh air and monitor for respiratory distress. For ingestion, rinse the mouth with water but do not induce vomiting; seek urgent medical attention, as borate compounds like sodium perborate have a fatal dose range of 100-500 mg/kg body weight in humans.

Environmental impact

Sodium perborate enters the primarily through its use in detergents and products, where it hydrolyzes to release borate ions and . The borate ions, derived from the content, are the primary long-term environmental concern due to their mobility and potential for accumulation in and systems. can bioaccumulate in , leading to that impairs growth and results in excessive uptake into plant tissues at elevated concentrations. In aquatic environments, borate ions pose toxicity risks to fish, invertebrates, and algae, with no-observed-effect concentrations (NOECs) for fish ranging from 0.75 to 18 mg B/L and a predicted no-effect concentration (PNEC) of 0.075 mg B/L based on the lowest NOEC. Acute toxicity data for sodium perborate indicate an LC50 of 51 mg/L (96-hour exposure) for the fish species Brachydanio rerio. Predicted environmental concentrations (PECs) from detergent releases can reach 0.18–0.6 mg B/L locally, often exceeding the PNEC and signaling potential harm to aquatic ecosystems. Wastewater from domestic and industrial sources represents a major pathway for sodium perborate discharge, accounting for nearly 100% of emissions in municipal effluents from applications. The moiety decomposes rapidly into oxygen and , exhibiting short-term effects with a PNEC of 10 μg/L, but the component persists in due to its , low to sediments, and limited , maintaining over extended periods. This persistence contributes to chronic exposure risks in receiving waters, though does not sorb strongly to or bioaccumulate significantly in most organisms. Mitigation efforts have focused on replacing sodium perborate with in environmentally friendly formulations, which eliminates release while providing similar bleaching efficacy and fully degrading to benign products like soda ash, water, and oxygen. This substitution has reduced loads in and runoff, aligning with broader industry trends toward sustainable alternatives to minimize ecological persistence.

Regulatory status

In the , sodium perborate has been classified as a substance toxic to in Category 1B under the , Labelling and Packaging ( since December 1, 2010, following its inclusion in VI of Regulation (EC) No 1272/2008 via the 31st ATP amendment. This classification stems from its potential to cause based on animal studies, leading to strict restrictions under REACH. Specifically, sodium perborate and related perboric acid salts are prohibited in cosmetic products at any concentration under II of Regulation (EC) No 1223/2009, with additional limits on boron content exceeding 0.1% in wash-off products where applicable, though the CMR status enforces a total ban. Furthermore, under REACH XVII (entry 72 and related borate restrictions), its use is curtailed in detergents and cleaning agents to minimize environmental release, effectively phasing it out in favor of less hazardous alternatives since the early . Despite EU restrictions, sodium perborate continues to be produced and used in detergents and other applications in regions like , with global market growth projected at 3.7% CAGR from 2025 to 2030. In the United States, sodium perborate is affirmed as (GRAS) for use as an indirect in contact substances, such as sanitizing solutions for , under 21 CFR Part 178, provided it complies with good practices and does not migrate into at levels posing risks. Occupational is regulated by the (OSHA), which sets a (PEL) of 15 mg/m³ as an 8-hour time-weighted average for total dust of borates, including sodium perborate, treating it under the general category for particulates not otherwise regulated (PNOR). Globally, regulatory approaches vary, with sodium perborate remaining permissible in non-EU regions for formulations, particularly in where markets like and continue production and use it as a bleaching agent without the stringent CMR bans, though subject to general chemical safety standards. The (WHO) has noted reproductive risks associated with borates, including sodium perborate, in its criteria for compounds, highlighting potential developmental toxicity at high exposure levels and recommending monitoring in occupational and environmental contexts. Various regions impose limits on in discharges to protect ecosystems, with some guidelines recommending levels below 1-2 mg/L depending on local standards.

Commercial products

Bocasan

Bocasan was an effervescent powder formulated as an oral wound cleanser primarily used in the for managing mouth sores, denture irritation, and gingival conditions such as acute or chronic . The product consisted of 68.635% w/w sodium perborate monohydrate and 29.415% w/w sodium bitartrate, with additional excipients including sodium, oil, , ginger, and to enhance flavor and solubility. It was supplied in single-dose sachets, typically 1.7 g each, designed to dissolve readily in warm to form an alkaline solution with oxidative properties suitable for oral . For use, one sachet of Bocasan was dissolved in 30 ml of warm water to prepare a solution, which was then swished around the and spat out without ; the regimen recommended three applications daily after meals, not exceeding 7 days of continuous use (or 14 days under professional guidance). Marketed initially by Knox Laboratories Ltd. of starting in the , it gained traction as an rinse for promoting in the oral cavity, particularly for adults and children over 12 years old, though it was contraindicated for those under 12. By the , during its peak availability, the product had been rebranded and distributed under the Laboratories name, reflecting its established role in dental routines. A 1992 clinical evaluation published in the Journal of Periodontology demonstrated the effectiveness of a peroxyborate rinse, such as Bocasan, in reducing plaque regrowth, outperforming saline and certain other commercial mouthwashes but showing lesser inhibition compared to . Despite its popularity for aiding and gingival cleansing, Bocasan was discontinued in the UK around 2003 amid growing regulatory scrutiny of compounds in consumer products. It was subsequently replaced by Bikosan, a reformulated version marketed by Bik & Bik that maintains a comparable cleansing profile in convenient mono-dose packaging. This phase-out occurred ahead of broader restrictions on borates, which intensified in the mid-2000s due to environmental and health concerns.

Amosan

Amosan is a powdered oral rinse primarily marketed in the United States for treating minor irritations, including sores, sores, ulcers, denture irritation, orthodontic discomfort, and post-dental wounds. The formulation consists of sodium perborate monohydrate as the active ingredient (1.2 g per 1.7 g envelope), buffered with L-tartaric acid, along with inactive components such as sodium saccharin and flavorings like or cherry. Each single-use envelope contains 1.7 grams of powder, designed to be dissolved in for immediate use up to four times daily after meals or as directed by a healthcare . The product was introduced prior to 2010 as an over-the-counter oral care aid but faced challenges following the European Union's ban on sodium perborate and related borates in cosmetics, effective December 1, 2010, due to classifications as carcinogenic, mutagenic, or toxic for reproduction. This regulation led to a temporary halt in production or distribution in affected markets, prompting a reformulation shift. In 2017, Vintage Brands Limited revived Amosan for the U.S. market, repositioning it as a non-cosmetic oral debriding agent to comply with regulatory distinctions, allowing continued availability without major changes to its core composition. Upon dissolution in warm , Amosan quickly releases nascent oxygen through the of sodium perborate, creating an effervescent that aids in debriding , removing debris, and providing mild oxygenation to promote healing. This mechanism exhibits antibacterial action by oxidizing bacterial cell membranes, enzymes, and proteins, inhibiting microbial growth and secondary infections in oral lesions. Clinical reviews and studies on sodium perborate-based rinses, including Amosan, demonstrate efficacy in reducing plaque, , and bacterial colonization, with one analysis noting its role in accelerating and limiting formation comparable to other oxidizing agents. As of November 2024 (latest labeling update), Amosan remains available over-the-counter in the through pharmacies, online retailers, and dental suppliers, with no significant reformulations since its revival. In the , it is restricted due to the ongoing borate prohibitions in cosmetic and certain oral care products, though limited imports may occur via third-party sellers; official distribution is not permitted.