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Magnesium phosphate
Magnesium phosphate
from Wikipedia
Magnesium phosphate monobasic
Magnesium phosphate dibasic
Magnesium phosphate tribasic

Magnesium phosphate is a general term for salts of magnesium and phosphate appearing in several forms and several hydrates:[1]

Amorphous magnesium phosphate is also claimed.[2]

Trimagnesium phosphate.

Safety

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Magnesium phosphates are listed on the U.S. FDA's Generally recognized as safe (GRAS) list of substances.[3]

See also

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References

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Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
Magnesium phosphates are a family of inorganic salts of magnesium and , including monomagnesium phosphate (Mg(H₂PO₄)₂), dimagnesium phosphate (MgHPO₄), and (Mg₃(PO₄)₂ · xH₂O), where x varies (commonly 0, 4, 5, or 8). The tribasic form, Mg₃(PO₄)₂, is a , odorless powder with low in (approximately 0.026 g/100 mL at 20°C) but higher in dilute acids and salt solutions. Its molecular weight is 262.86 g/mol, and it decomposes at around 1,184 °C without a distinct . These compounds occur naturally as minerals such as newberyite and bobierrite and are synthesized by reacting magnesium salts with phosphates. They serve multiple roles across industries, primarily as nutrient supplements providing essential magnesium and , and are approved by the U.S. (FDA) as (GRAS) for use in products such as baked , cereals, and beverages, functioning as a control agent, stabilizer, and thickener under 21 CFR 184.1434. In pharmaceuticals and , they act as antacids, opacifying agents, and polishing ingredients. A key application is in magnesium phosphate cements (MPCs) for rapid-setting binders in construction and biocompatible materials for repair. Variants such as dibasic magnesium phosphate share similar properties and uses, including as dietary supplements and in pharmaceutical tablets, while tribasic forms are used in fertilizers and flame retardants due to stability. The versatility stems from their ionic structures, enabling applications in , , and .

Overview

Definition and nomenclature

Magnesium phosphates constitute a family of inorganic salts formed by the combination of magnesium cations (Mg²⁺) and various phosphate anions, including the fully deprotonated (PO₄³⁻), the (HPO₄²⁻), and the dihydrogen phosphate ion (H₂PO₄⁻). These compounds arise from the reaction of magnesium sources with (H₃PO₄), which can exist in different states, leading to neutral and acidic variants. The neutral form, , has the general Mg₃(PO₄)₂, representing the stoichiometric balance where three magnesium ions neutralize two . Nomenclature for these salts reflects the degree of protonation in the phosphate component and the magnesium-to-phosphate ratio. Monomagnesium phosphate, or magnesium dihydrogen phosphate, corresponds to the formula Mg(H₂PO₄)₂, where the dihydrogen phosphate anion retains two protons. Dimagnesium phosphate, also known as magnesium hydrogen phosphate, is MgHPO₄, featuring the anion with one proton. , or , is Mg₃(PO₄)₂, with fully deprotonated anions. This naming convention—mono-, di-, and tri—directly parallels the acidity levels of derivatives, distinguishing the acid salts from the neutral salt. These compounds commonly occur in hydrated forms, incorporating water molecules into their crystal structures, such as the octahydrate Mg₃(PO₄)₂·8H₂O, known mineralogically as bobierrite. In regulatory contexts, is designated as E343 (specifically E343(iii) for the tribasic form) by the and as a , reflecting its longstanding use under this standardized naming for safety and labeling purposes.

Importance and applications

Magnesium phosphates play a vital role in biological systems, particularly through the interactions of magnesium and ions. In bone health, magnesium is essential for mineralization and development, as it stimulates activity and enzymes involved in reactions, while is crucial for formation, the primary mineral component of . deficiency can lead to conditions like or due to impaired formation, while is primarily associated with , reduced bone density, and secondary effects on mineralization. Additionally, magnesium-phosphate complexes are integral to cellular processes, serving as cofactors for metabolic enzymes and facilitating energy transfer. In biochemistry, magnesium ions interact directly with the phosphate groups of adenosine triphosphate (ATP), forming the Mg-ATP complex that is the active substrate for numerous enzymes involved in energy metabolism, protein synthesis, and signal transduction. These interactions enhance the electrophilicity of the phosphorus atom in ATP, enabling efficient phosphate transfer reactions essential for cellular functions. Magnesium also stabilizes the phosphate backbone of DNA and RNA, aiding in nucleic acid structure and replication processes. Commercially, magnesium phosphates are widely used as dietary supplements to address magnesium deficiencies, which are linked to symptoms such as muscle cramps, and as components in fertilizers to enhance uptake in crops. In , they form the basis of magnesium phosphate cements employed as bone void fillers in orthopedic and dental applications, with biomedical uses expanding since the due to their and rapid setting . The global market for magnesium phosphates has grown steadily, valued at approximately $1.4 billion in 2021 and projected to reach $2.0 billion by 2030, driven by demand in food, , and healthcare sectors. Magnesium phosphates hold (GRAS) status from the for use as direct human food ingredients, supporting their incorporation in supplements and fortified foods. Supplementation helps prevent magnesium deficiency-related issues, including muscle cramps caused by impaired neuromuscular function.

Chemical forms

Trimagnesium phosphate

Trimagnesium phosphate is the neutral form of magnesium phosphate, represented by the chemical formula \ceMg3(PO4)2nH2O\ce{Mg3(PO4)2 \cdot nH2O}, where nn can vary as 0 (anhydrous), 5 (pentahydrate), 8 (octahydrate), or 22 (22-hydrate). This compound features an ionic lattice structure consisting of \ceMg2+\ce{Mg^{2+}} cations and \cePO43\ce{PO4^{3-}} anions, with the magnesium ions occupying both octahedral and pentacoordinate sites. It is isostructural with cobalt(II) phosphate, sharing a similar crystalline arrangement that contributes to its stability. The form of has a of 262.86 g/mol and can be prepared by heating its hydrated variants to 400 °C, which drives off the water of hydration without decomposing the lattice. This treatment is a standard method to isolate the water-free compound, which exhibits enhanced stability suitable for high-temperature applications. Hydrated forms, particularly the octahydrate \ceMg3(PO4)28H2O\ce{Mg3(PO4)2 \cdot 8H2O}, occur naturally as the bobierrite, typically formed through the chemical alteration of deposits in environments like lava tubes or phosphate-rich sediments. The octahydrate can be synthesized in the laboratory by mixing solutions of disodium hydrogen phosphate (\ceNa2HPO4\ce{Na2HPO4}) and (\ceMgSO4\ce{MgSO4}) at an initial of 6.4–7.0, often with additives such as or to promote , followed by heating at 80–90 °C for 2–48 hours. This process yields bobierrite in monoclinic crystal phases, highlighting the compound's polymorphism under controlled conditions. Alternatively, hydrated forms from reactions involving magnesium salts and phosphate ions in aqueous solutions at neutral to slightly basic , leading to of the desired hydrate. is generally insoluble in , consistent with its ionic nature and low product.

Dimagnesium phosphate

Dimagnesium phosphate, with the MgHPO₄, consists of magnesium cations (Mg²⁺) paired with hydrogen phosphate anions (HPO₄²⁻) to achieve charge balance. It commonly occurs as a , particularly the trihydrate form MgHPO₄·3H₂O, which is the mineral newberyite found in phosphate-rich environments such as deposits. This monohydrogen variant distinguishes itself from other magnesium s by the partial of the phosphate group, influencing its stability and reactivity. The of dimagnesium phosphate trihydrate adopts an orthorhombic system in the Pbca , with lattice parameters a = 1.0203 nm, b = 1.067 nm, and c = 1.0015 nm. In this arrangement, the structure features infinite chains of corner-sharing HPO₄ tetrahedra connected by MgO₆ octahedra, where the magnesium ions coordinate with oxygen atoms from both the groups and water molecules. This configuration results in a more open packing compared to , primarily due to the lower of the HPO₄²⁻ anions from partial , which requires adjusted electrostatic interactions to maintain lattice integrity. Dimagnesium phosphate exhibits higher in than , with a solubility product constant (pKsp) of 5.83 ± 0.01, reflecting its greater dissolution tendency attributed to the hydrogen phosphate ion's ability to participate in acid-base equilibria. This enhanced supports its utility in dental applications, where magnesium phosphate cements incorporating dimagnesium phosphate demonstrate strong dentin bonding and properties, promoting in restorative materials.

Monomagnesium phosphate

Monomagnesium phosphate, with the chemical formula Mg(H₂PO₄)₂·nH₂O (where n = 0–4, often the tetrahydrate), consists of a magnesium cation (Mg²⁺) and two dihydrogen phosphate anions (H₂PO₄⁻). This ionic structure renders it highly acidic, as it derives directly from phosphoric acid, retaining two ionizable protons per phosphate group. Like other magnesium phosphates, its hydration state can vary, influencing solubility and stability. The compound is typically prepared through partial neutralization of with , followed by drying to yield the desired hydrate. The reaction proceeds as MgO + 2H₃PO₄ → Mg(H₂PO₄)₂ + H₂O, allowing control over the level to form this dihydrogen variant. It functions as a versatile precursor for synthesizing dimagnesium and trimagnesium phosphates by further adjustment of the acid-base ratio. Solutions of monomagnesium phosphate are markedly acidic, with a of approximately 4.5–5.5 in 1% aqueous concentration, due to the dissociation of its H₂PO₄⁻ anions. This property underscores its role as an acidity regulator in various applications. Notably, it serves as a primary component in magnesium phosphate cements, where its acidic reactivity enables rapid setting and strong bonding with .

Properties

Physical properties

Magnesium phosphates, encompassing (Mg₃(PO₄)₂), dimagnesium phosphate (MgHPO₄), and monomagnesium phosphate (Mg(H₂PO₄)₂), typically appear as white, odorless, and tasteless crystalline powders in their or hydrated forms. The is notably soft and bulky, while hydrated variants, such as the octahydrate of , form iridescent solids or rhombic plates. These physical characteristics contribute to their utility in applications requiring fine, non-reactive particulates. Thermal properties vary by form and hydration state. exhibits a high of 1,184 °C, reflecting its thermal stability in form. Hydrated magnesium phosphates, including the pentahydrate of and the trihydrate of dimagnesium phosphate, undergo , losing water molecules around 400 °C, which can lead to structural changes or decomposition upon further heating. Densities differ modestly across forms: the octahydrate of has a of 2.19 g/cm³, the trihydrate of dimagnesium phosphate approximately 2.12 g/cm³, and the dihydrate of monomagnesium phosphate about 2.4 g/cm³. These values indicate compact crystalline structures suitable for solid-state applications. Solubility in is generally low across all forms, underscoring their insolubility as a class, though they dissolve readily in dilute and certain salt solutions like salts. shows negligible , approximately 0.0023 g/L at 25 °C, equivalent to less than 0.0003 g/100 mL. Dimagnesium phosphate trihydrate is slightly more soluble at about 0.025 g/100 mL at 20 °C, while monomagnesium phosphate dihydrate exhibits around 0.014 g/100 mL, often accompanied by partial in aqueous environments. This limited , combined with , influences their in physiological and industrial contexts.

Chemical properties and reactivity

Magnesium phosphates exhibit low in , consistent with their physical properties, rendering them stable under neutral aqueous conditions. The solubility product constant (Ksp) for , Mg₃(PO₄)₂, is 1.04 × 10⁻²⁴ at 25°C, indicating extremely low dissociation into ions. This low Ksp underscores the compound's insolubility, with solubility increasing markedly in acidic environments due to of the ions, which shifts the equilibrium toward more soluble species like H₃PO₄. Hydrated forms of magnesium phosphate, such as Mg₃(PO₄)₂·8H₂O, undergo dehydration starting at lower temperatures, with significant loss of water occurring between 40°C and 200°C, leading to the phase. Further heating to temperatures exceeding 400°C completes the process, enhancing the thermal stability of the compound. At higher temperatures, around 1165°C, Mg₃(PO₄)₂ undergoes incongruent melting, potentially decomposing into (MgO) and (P₂O₅) under specific conditions in the MgO-P₂O₅ system. In terms of reactivity, magnesium phosphate demonstrates acid , as illustrated by the reaction: Mg3(PO4)2+6H+3Mg2++2H3PO4\mathrm{Mg_3(PO_4)_2 + 6H^+ \rightarrow 3Mg^{2+} + 2H_3PO_4} This protonation-driven dissolution highlights its -dependent behavior, where rises below 6 due to the formation of weaker acids. Additionally, magnesium phosphate can form coordination complexes with biomolecules containing groups, such as in interactions, where Mg²⁺ ions bridge moieties.

Production and occurrence

Natural occurrence

Magnesium phosphates occur naturally as rare , primarily in deposits and associated rock formations. Bobierrite (Mg₃(PO₄)₂·8H₂O) is a hydrated typically found as colorless to white crystals or nodules in bat within caves and lava tubes. It has been documented in locations such as the district of , Mejillones Island in , Marlborough in , and near Edgerton in Pipestone County, , . Newberyite (MgHPO₄·3H₂O), a dimagnesium , appears as light gray to colorless, dull crystals in similar environments, notably in Australian sites including Moorba Cave near , and the Skipton Lava Tubes in Victoria. Variants of bobierrite, often associated with other magnesium phosphates like schertelite, form through the alteration of under specific humidity and -rich conditions. These are scarce globally, reflecting the limited geochemical settings where magnesium and concentrations align naturally. In biological contexts, magnesium phosphates serve as minor components in various tissues and structures. In bone apatite, magnesium ions are incorporated into the lattice (Ca₁₀(PO₄)₆(OH)₂), substituting for calcium and influencing crystal formation and stability, with concentrations typically ranging from 0.5% to 1% by weight in and bones. They are also present in plant seeds, where magnesium-phosphate complexes aid in and metabolic processes, and in animal soft tissues, contributing to phosphate buffering. A prominent example is (NH₄MgPO₄·6H₂O), which forms in urinary stones in humans and animals, often as a result of urease-producing bacterial infections that alkalinize and precipitate the mineral rapidly. Struvite stones, also known as infection stones, can comprise up to 15% of all urinary calculi and are characterized by their staghorn morphology. These compounds contribute to sedimentary phosphate deposits, particularly in ancient -derived layers within rock, where magnesium phosphates like bobierrite and newberyite occur alongside dominant calcium phosphates such as . Such deposits are abundant in sedimentary basins influenced by biological accumulation, including marine phosphorites and terrestrial guano accumulations, providing a natural reservoir for cycling. Key regions include phosphate-rich sedimentary formations in and the western United States, where these minerals enhance the overall magnesium content of the rock.

Synthesis and preparation

Magnesium phosphates can be synthesized in laboratories through methods involving the reaction of soluble magnesium salts with sources. For instance, is commonly prepared by mixing (MgCl₂) with sodium or solutions, such as 3MgCl₂ + 2Na₃PO₄ → Mg₃(PO₄)₂ + 6NaCl, under controlled conditions at for 24 hours, followed by filtration, washing, and drying. This approach yields hydrated forms like Mg₃(PO₄)₂·5H₂O, with particle sizes in the nanoscale range when using equimolar concentrations of 10 mM solutions. Acid-base reactions provide another route, particularly for monomagnesium phosphate, where reacts with : MgO + 2H₃PO₄ → Mg(H₂PO₄)₂ + H₂O. Neutralization of with or hydroxide at varying ratios produces dimagnesium or other forms, with partial neutralization favoring dibasic magnesium phosphate. These reactions occur in aqueous media, often requiring stirring to ensure complete dissolution and . Industrial production typically employs the neutralization of with or oxide slurries to generate magnesium phosphates on a large scale, particularly for applications like fertilizers. The process involves precise control of (around 5 for dimagnesium phosphate forms) and (25–90°C) to selectively form specific hydrates, such as or trihydrated variants, while avoiding unwanted byproducts. This wet-process method is scalable, leveraging inexpensive raw materials like wet from rock , and supports high-volume output for agricultural uses without significant waste generation.

Uses

Nutritional and pharmaceutical uses

Magnesium phosphate, particularly in the form of , serves as a to address , which can manifest as muscle cramps, , and impaired bone health. Supplementation helps prevent these symptoms by supporting muscle function and , as magnesium is essential for over 300 enzymatic reactions, including those involved in energy production and neuromuscular conduction. Recommended daily dosages for elemental magnesium typically range from 310 to 420 mg for adults, though therapeutic doses for deficiency treatment may reach 500–1,000 mg per day under medical supervision to replenish stores without exceeding safe upper limits. As a food additive, (E343) is authorized for use in various processed foods, functioning as an acidity regulator, nutrient source, and stabilizer. It is commonly added to cereals, flours, batters, noodles, , and beverages to maintain levels, enhance by providing bioavailable magnesium and , and prevent caking or separation. The U.S. has affirmed its (GRAS) status since 1979, allowing its use at levels without specified maximums in most applications. In the , it is permitted in up to 65 food categories, including infant formulae at levels up to 1,000 mg/L expressed as P₂O₅, with a group for phosphates of 40 mg/kg body weight. In pharmaceutical applications, magnesium phosphate acts as a non-systemic to neutralize , though its efficacy is considered low and its use is infrequent compared to other magnesium salts. It is occasionally incorporated into oral powder formulations for acid relief. studies indicate that magnesium from phosphate forms is absorbed at approximately 30% in the intestine, influenced by factors such as dietary and gastrointestinal , with clinical trials demonstrating serum magnesium increases of up to 8% within hours of supplementation. Magnesium phosphate cements (MPCs) are widely utilized in orthopedic applications as bone void fillers and repair materials due to their rapid setting and . These cements form through an acid-base reaction between (MgO) and (NH₄H₂PO₄), producing struvite-like phases such as MgNH₄PO₄·6H₂O, as shown in the following equation: MgO+NH4H2PO4+5H2OMgNH4PO46H2O\text{MgO} + \text{NH}_4\text{H}_2\text{PO}_4 + 5\text{H}_2\text{O} \rightarrow \text{MgNH}_4\text{PO}_4 \cdot 6\text{H}_2\text{O} This reaction enables MPCs to set quickly, typically within 3–15 minutes, which aligns with clinical requirements for minimally invasive procedures and provides advantages over traditional cements, including faster hardening and higher early compressive strengths that exceed those of apatitic calcium phosphates at short reaction times (e.g., 1 hour). Development of MPCs for biomedical implants, including orthopedic fillers, gained traction from early studies around 2003, such as those modeling dissolution-precipitation mechanisms and evaluating degradation in animal models.

Industrial and construction applications

Magnesium phosphate cements (MPCs) are employed in for rapid repair of structures, including pavements, bridges, and runways, owing to their fast setting times of 3–15 minutes, high early compressive strengths up to 45 MPa, and low , which ensure durable bonds and minimal shrinkage in demanding environments. In , magnesium phosphates facilitate the precipitation of (MgNH₄PO₄·6H₂O) to remove and other contaminants from , achieving removal efficiencies up to 98% under optimal conditions like 8.5 and controlled magnesium dosing via sacrificial anodes. Additionally, magnesium phosphate compounds serve as inhibitors by forming protective coatings on metal surfaces, such as pipes, through chemical precipitation of iron phosphates and alkaline stabilization (around 10.6), which enhances resistance to saline environments for over 2400 hours without visible rust. Beyond and treatment, magnesium phosphates find industrial applications in flame retardants and ceramics. MPC-based coatings, incorporating fibers for crack resistance, exhibit excellent fire-retardancy by dissipating heat through bound water release, achieving bonding strengths above 0.6 MPa and initial setting times over , making them suitable for non-toxic, inorganic protective layers. As chemically bonded ceramics, MPCs offer high-temperature resistance and are used in materials, leveraging their rapid hardening and structural integrity for durable industrial components.

Other applications

Magnesium phosphate serves as a supplement in , delivering essential magnesium and to while aiding in management and promoting growth. Studies have shown that magnesium-fortified , including forms of magnesium phosphate, enhance uptake in like soybeans without compromising availability, leading to improved yields in acid . Typical application rates range from 50 to 200 kg/ha, depending on conditions and needs, to optimize magnesium and delivery while controlling acidity. In and , dimagnesium phosphate functions as a mild in toothpastes, helping to polish teeth without excessive wear, and as a stabilizer in formulations like lotions to maintain balance and prevent ingredient separation. Its insolubility contributes to stability in these applications, ensuring consistent product performance. Regulatory listings confirm its use in oral care and skincare items at low concentrations for these purposes. Commercial applications of magnesium phosphate in batteries and electronics include its use as a phosphate source in cathode materials, such as lithium iron magnesium phosphate variants that offer enhanced stability in lithium-ion systems. Studies post-2020 have also investigated its integration into biodegradable polymers, like incorporating amorphous magnesium phosphate into () via for biomedical scaffolds, promoting controlled degradation and bioactivity. These applications leverage its chemical stability for sustainable, high-performance materials in and transient electronics.

Safety and regulation

Health and toxicity

Magnesium phosphates exhibit low acute oral toxicity, with an estimated LD50 greater than 2000 mg/kg body weight in rats, indicating minimal risk from single high-dose ingestion. At elevated doses, they may cause gastrointestinal irritation, such as , , and , due to the laxative effects of magnesium salts, which are poorly absorbed in the gut. These compounds show no evidence of carcinogenicity or based on available toxicological assessments. Exposure to magnesium phosphate dust via can lead to irritation, including coughing and , particularly in occupational settings without proper ventilation; however, respiratory protection is generally not required under normal handling conditions. As a (E 343), magnesium phosphates are considered safe within the group (ADI) for phosphates of 40 mg per kg body weight per day, though exposures in certain populations like children may approach or exceed this limit from combined sources. Overdose of magnesium phosphates can result in , characterized by symptoms such as , , , and in severe cases, cardiac arrhythmias or respiratory depression, especially in individuals with impaired renal function. Additionally, magnesium phosphates may interact with certain antibiotics, including tetracyclines and quinolones, by forming insoluble complexes that reduce absorption and if taken concurrently.

Environmental considerations

Magnesium phosphate compounds, particularly insoluble forms such as magnesium hydrogen phosphate (MgHPO₄), exhibit low in water, which significantly minimizes their leaching into and under typical environmental conditions. This property reduces the mobility of ions in , limiting their transport to aquatic systems compared to more soluble fertilizers. However, when magnesium phosphate-based fertilizers are over-applied in agricultural settings, excess release can contribute to , promoting algal blooms and oxygen depletion in receiving water bodies. As a naturally occurring , magnesium phosphate can be solubilized primarily through microbial action in environments, where phosphate-solubilizing facilitate the conversion into bioavailable forms for uptake. This process enhances nutrient cycling without persistent accumulation, as evidenced by its use in stabilizing contaminated soils to promote degradation. Due to its inorganic nature and low solubility, magnesium phosphate demonstrates low potential in aquatic organisms, with ecotoxicity tests on marine species showing no significant uptake or magnification in food chains. Under EU regulations, magnesium phosphate is registered pursuant to REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals), ensuring assessment of its environmental risks prior to market placement. The revised Urban Waste Water Treatment Directive (Directive (EU) 2024/3019, entered into force on 24 December 2024) imposes stricter phosphorus discharge limits for wastewater treatment plants to mitigate eutrophication risks. For plants serving 150,000 population equivalents (p.e.) or more, total phosphorus must be below 0.5 mg/L or achieve at least 90% removal. For plants serving 10,000–150,000 p.e., the limits are below 0.7 mg/L or 87.5% removal. These tertiary treatment requirements apply to plants discharging into sensitive areas and are phased in, with 60% of applicable agglomerations required to comply by 31 December 2039 and full implementation by 31 December 2045; member states must transpose the directive by 24 December 2027. Sustainable sourcing of phosphate for magnesium phosphate production has faced increasing scrutiny since the 2010s due to mining impacts, including water contamination from phosphogypsum waste and heavy metal runoff, prompting calls for circular recovery strategies to reduce ecological footprints.

References

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