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Ammonium phosphate

Ammonium phosphate refers to a family of inorganic salts formed by the reaction of ammonia with phosphoric acid, including monoammonium phosphate (NH₄H₂PO₄), diammonium phosphate ((NH₄)₂HPO₄), and triammonium phosphate ((NH₄)₃PO₄), with the general formula (NH₄)ₙH₃₋ₙPO₄ where n = 1, 2, or 3. Ammonium phosphates were developed in the early 20th century as efficient fertilizers, with significant advancements by the Tennessee Valley Authority (TVA) in the production of high-analysis forms like mono- and diammonium phosphates. These compounds are typically white, odorless or faintly ammoniacal crystalline solids that are highly soluble in water, making them versatile for agricultural and industrial applications. The most prevalent forms, monoammonium and diammonium phosphates, serve as essential fertilizers providing nitrogen and phosphorus to plants, with monoammonium phosphate offering an N-P-K analysis of 11-52-0 and diammonium phosphate at 18-46-0. They are also key components in flame retardants, particularly in wildfire suppression agents and dry chemical fire extinguishers, where monoammonium phosphate acts by releasing phosphoric acid upon heating to form a char layer that inhibits combustion. Additionally, these salts find use as food additives for pH control and leavening in baked goods, as well as in fireproofing treatments for wood, paper, and textiles. Physically, monoammonium phosphate has a molecular weight of 115.03 g/, a of 1.80 g/cm³, and decomposes at 190 °C, while weighs 132.06 g/, has a of 1.619 g/cm³, and decomposes around 155 °C with loss of . Triammonium phosphate, with a molecular weight of 149.09 g/, is less stable and tends to hydrolyze in solution, limiting its standalone use but contributing to formulations in fertilizers and as a buffering agent. All forms exhibit mild acidity or basicity depending on the ratio—monoammonium is acidic ( ~4.2), diammonium is near-neutral to basic ( ~8)—and they are generally non-toxic at low concentrations but can irritate and eyes.

Overview

Definition and forms

Ammonium phosphates constitute a family of inorganic salts derived from the neutralization reaction between (NH₃) and (H₃PO₄), where the specific form depends on the extent of of the . These compounds are ionic in nature, comprising cations (NH₄⁺) and various anions such as dihydrogen phosphate (H₂PO₄⁻), (HPO₄²⁻), or (PO₄³⁻). The primary variants are monoammonium phosphate (MAP, (NH₄)H₂PO₄), which features one ion per molecule; diammonium phosphate (DAP, (NH₄)₂HPO₄), with two ions; and triammonium phosphate ((NH₄)₃PO₄), the fully neutralized form. While MAP and DAP are stable and widely utilized, the triammonium phosphate is inherently unstable, decomposing readily into and other products, which complicates its production and isolation. These salts play roles in diverse industries due to their nutrient content and chemical properties, notably as components in fertilizers to supply and to crops.

Historical development and importance

Ammonium phosphate compounds were first synthesized in the early through the reaction of with , with monoammonium phosphate () notably reported in 1821 by French chemist for its potential in fire-resistant treatments. Although initial applications were limited, the compound's recognition as a stable salt grew alongside advancements in production during the mid-1800s, driven by the expanding mining in regions like , where high-grade deposits were discovered in 1881. These early developments laid the groundwork for broader industrial exploration, though widespread adoption awaited technological refinements in the . The first industrial production of ammonium phosphate for fertilizers emerged in the early , with granular forms introduced by in 1930, marking a shift toward efficient, compound-based delivery for . Key milestones included the development of monoammonium phosphate (MAP) and diammonium phosphate (DAP) in the mid-20th century, with the (TVA) pioneering commercial DAP production in 1955 and both forms becoming staples by the 1960s due to their high content and ease of handling. Post-World War II, ammonium phosphates expanded into fire retardants, with research from the confirming their efficacy and leading to the introduction of long-term formulations like in the 1960s for . Today, phosphates, particularly and DAP, play a pivotal role in global , with annual exceeding 50 million metric tons, primarily as phosphorus-based fertilizers that enhance crop yields and support for billions. This scale underscores their economic and environmental significance, as they constitute a major portion of the 50 million nutrient tons applied worldwide in phosphate fertilizers, enabling sustainable intensification amid growing population demands.

Chemical composition

Molecular formulas and nomenclature

Ammonium phosphate refers to a family of inorganic salts formed by the reaction of with , resulting in three primary variants distinguished by the degree of on the . The monoammonium phosphate, also known as , has the molecular (NH_4)H_2PO_4. , or ammonium hydrogen phosphate, is represented by (NH_4)_2HPO_4. The fully neutralized form, triammonium phosphate, corresponds to (NH_4)_3PO_4. In IUPAC , these compounds are systematically named based on the cation (azanium) and the anion's protonation state. Monoammonium is termed azanium dihydrogen , diammonium is diazanium hydrogen , and triammonium is triazanium . Common synonyms include primary ammonium for the monobasic form and secondary ammonium for the dibasic form. Each variant is uniquely identified by its : 7722-76-1 for monoammonium , 7783-28-0 for , and 10361-65-6 for triammonium . The stoichiometry of these salts reflects the stepwise neutralization of phosphoric acid (H_3PO_4), a triprotic acid capable of donating up to three protons. In monoammonium phosphate, one ammonium ion (NH_4^+) replaces a single proton, leaving the dihydrogen phosphate anion (H_2PO_4^-). Diammonium phosphate incorporates two ammonium ions, forming the hydrogen phosphate anion (HPO_4^{2-}) with one remaining proton. Triammonium phosphate features three ammonium ions, fully deprotonating the phosphate to PO_4^{3-}. This progression determines the compounds' acidity and reactivity profiles.

Structural characteristics

Ammonium dihydrogen phosphate, commonly known as monoammonium phosphate (MAP), exhibits a tetragonal crystal structure in the space group I̅42d, characterized by an ionic lattice where tetrahedra (PO₄³⁻) are coordinated with NH₄⁺ cations, forming a framework stabilized by electrostatic interactions and hydrogen bonds. In this arrangement, each NH₄⁺ ion is surrounded by four oxygen atoms from the phosphate groups in a tetrahedral , contributing to the overall rigidity of the crystalline structure. Diammonium hydrogen phosphate (DAP) adopts a monoclinic crystal structure in the space group P2₁/c, featuring a similar ionic of anions and NH₄⁺ cations, where the tetrahedra are linked through corner-sharing and cation coordination to maintain structural integrity. Hydrogen bonding plays a crucial role in both MAP and DAP, with N-H···O interactions between ammonium groups and oxygen atoms providing additional stabilization, particularly evident in the dihydrogen phosphate form where O-H···O bonds further reinforce the . In contrast, triammonium phosphate displays inherent instability due to weaker ionic interactions between the highly charged PO₄³⁻ anions and NH₄⁺ cations, which promote rapid in aqueous environments and prevent the formation of a crystalline . This structural vulnerability arises from the reduced electrostatic balance compared to the protonated forms like and DAP.

Physical properties

Appearance and phase behavior

Ammonium phosphate, particularly in its common forms monoammonium phosphate (MAP) and diammonium phosphate (DAP), appears as a white, crystalline powder or granules that are typically odorless or exhibit only a faint ammonia scent. These forms often present as brilliant white tetrahedral crystals for MAP or as free-flowing granules for commercial DAP, though impurities can impart gray, tan, or brown hues in industrial products. Both and DAP are hygroscopic, readily absorbing from the air, which can lead to clumping or caking during storage and handling. This property arises from their ionic structures, contributing to their stability as solids under standard conditions but requiring sealed packaging to prevent degradation. The density of MAP is approximately 1.80 g/cm³, while DAP has a slightly lower value of about 1.62 g/cm³, reflecting differences in their molecular packing. Neither compound exhibits a distinct ; instead, they decompose upon heating before liquefaction, with MAP beginning decomposition around 190 °C and DAP at approximately 155 °C. In terms of phase behavior, phosphates remain in the crystalline phase at and standard pressure, with no liquid or gas transitions under ambient conditions; heating induces rather than phase changes like or . This behavior is linked to their crystal structures (tetragonal for monoammonium phosphate and monoclinic for ), which maintain integrity until volatile components are released.

Solubility and thermal stability

Ammonium phosphate's solubility in varies significantly among its common forms. Monoammonium phosphate (NH₄H₂PO₄, or MAP) is highly soluble, dissolving at approximately 37 g/100 mL at 20°C. Diammonium phosphate ((NH₄)₂HPO₄, or DAP) exhibits even greater solubility, around 58 g/100 mL at 20°C, although this can be influenced by conditions. In contrast, the triammonium phosphate form ((NH₄)₃PO₄) is extremely unstable in water, rapidly decomposing due to its inherent chemical instability. The of aqueous solutions also differs by form. solutions are acidic, typically with a of about 4.5, reflecting its dihydrogen content. solutions, however, are near-neutral to slightly , with a ranging from 7.5 to 8. Thermal stability of ammonium phosphates is limited, with endothermic decomposition beginning at temperatures of 150–200°C, primarily through the release of gas. This process absorbs heat without resulting in ignition, instead facilitating char formation that enhances non-flammable residue.

Production

Laboratory synthesis

Ammonium phosphates are prepared in the laboratory through the controlled neutralization of with , allowing for the synthesis of specific forms such as monoammonium phosphate ((NH₄)H₂PO₄) or ((NH₄)₂HPO₄) by adjusting the reactant and reaction . The process is typically conducted at or slightly elevated conditions to manage the exothermic nature of the reaction and prevent excessive volatilization. The basic reaction for monoammonium phosphate involves partial neutralization: \text{H}_3\text{PO}_4 + \text{NH}_3 \rightarrow (\text{NH}_4)\text{H}_2\text{PO}_4 This is achieved by maintaining the reaction between 4.2 and 4.6 to favor the monobasic form. For , additional is added to reach a of 7.5 to 8.0: \text{H}_3\text{PO}_4 + 2\text{NH}_3 \rightarrow (\text{NH}_4)_2\text{HPO}_4 pH monitoring ensures the desired product, as deviations can lead to mixtures of phosphate species. A standard step-by-step procedure for monoammonium phosphate begins with determining the stoichiometric ratio via . Pipette 10 cm³ of 1 mol dm⁻³ into a conical flask, add a few drops of indicator, and titrate with 1 mol dm⁻³ until the color changes from yellow to red, recording the acid volume required for neutralization. In an evaporating basin, pipette 10 cm³ of the and slowly add the equivalent volume of while stirring gently at to maintain the temperature below 50°C and avoid ammonia loss. Heat the mixture on a with over a , evaporating to about one-fifth the original volume without boiling to promote concentration. Cool the solution to to induce . For , the procedure is similar but uses 20 cm³ of with the acid volume from the of 10 cm³ , ensuring complete neutralization. The same and cooling steps apply, with adjustment if needed to confirm the dibasic form. Purification involves filtering the crystals through in a , washing with cold water if impurities are present, and drying at between filter papers or under to remove residual moisture without decomposition. Yield is calculated by weighing the dried product against the theoretical amount based on the limiting reactant. Safety precautions include wearing and working in a well-ventilated area, as both and are irritants to skin, eyes, and respiratory systems.

Industrial manufacturing processes

The primary industrial manufacturing process for ammonium phosphate involves the continuous reaction of wet-process with anhydrous in specialized reactors to produce monoammonium phosphate (, NH₄H₂PO₄) or (, (NH₄)₂HPO₄), depending on the molar ratio of to acid—typically 1:1 for and 2:1 for . This method, which accounts for the majority of global output, utilizes derived from phosphate rock treated with , ensuring scalability for production. The process is conducted in brick-lined acid reactors where partial neutralization occurs, forming a with approximately 22% . Key process steps include mixing the with a small amount of (about 93% concentration) in a , followed by ammoniation: roughly 70% of the is introduced in the for initial neutralization, while the remaining 30% is sparged directly into a rotary granulator to complete the and initiate formation. The resulting is then processed in a rotary ammoniator-granulator, where it is dried using hot air at inlet temperatures up to 300–350°C, with product exiting at 75–100°C, cooled, and screened to produce granules sized 1–4 mm for optimal handling and application. Oversized and undersized particles are recycled back into the granulator to maximize yield, with overall process efficiency enhanced through continuous operation and emission controls like wet scrubbers using and pond water to capture fluorides and particulates. Byproducts primarily consist of -rich off-gases, (HF), silicon (SiF₄), and particulate matter, which are managed via scrubbing systems to minimize environmental release. Global production of ammoniated phosphates, including MAP and DAP, averaged approximately 65 million metric tons annually from 2018–2022, with and the as leading producers— accounting for over one-third of output and the US contributing around 8–10 million tons as of 2023. As of 2024, global production reached approximately 66.8 million metric tons, with continued growth projected. focuses on energy optimization, with consumption for , , and screening averaging about 0.05 kWh per kg of product, while or provides heat for , generating export as a secondary . Yield optimizations, such as precise dosing and concentration control, achieve product purities of 95–98% P₂O₅ equivalent, reducing waste and supporting economic viability in large-scale plants using the (TVA) rotary drum process, which dominates 95% of US facilities.

Chemical reactivity

Decomposition reactions

Ammonium phosphate undergoes primarily through the loss of , with the specific pathway depending on the form of the compound and the temperature applied. For monoammonium phosphate ((NH₄)H₂PO₄), decomposition begins around 200°C, yielding gas (NH₃) and (H₃PO₄) in an described by the equation: (\ce{NH4})H2PO4 \rightarrow \ce{NH3} + \ce{H3PO4} at approximately 200°C. Further heating of the resulting leads to and formation of polys, as orthophosphate ions condense by removing . ((NH₄)₂HPO₄), on the other hand, starts decomposing at lower temperatures, around 70°C, initially converting to monoammonium phosphate and : (\ce{NH4})2HPO4 \rightarrow \ce{NH3} + (\ce{NH4})H2PO4 with dissociation pressure reaching about 5 mmHg at 100°C. At higher temperatures, such as 155°C, it releases phosphorus oxides, nitrogen oxides, and additional ammonia. These reactions are relevant in applications like fire retardants, where the released non-flammable gases dilute combustibles and the phosphoric acid promotes char formation. Hydrolytic decomposition occurs in aqueous solutions, particularly for the triammonium phosphate form ((NH₄)₃PO₄), which is unstable and readily hydrolyzes to diammonium and , driven by pH-dependent favoring the more stable acid salts: \ce{(NH4)3PO4 + H2O ⇌ (NH4)2HPO4 + NH3} This process is influenced by the solution's , with higher shifting the equilibrium toward the triammonium form, though it remains prone to dissociation due to the weak basicity of ammonium hydroxide compared to metal hydroxides. The releases , contributing to the compound's volatility in water. The kinetics of these decomposition reactions vary with conditions, including heating rate and additives. For thermal decomposition of diammonium phosphate, studies show time-dependent behavior where higher heating rates increase the onset temperature, indicating a dependence on and phase transitions. Activation energies for related ammonium phosphate systems, such as in self-generated atmospheres, are influenced by impurities, which can lower barriers and accelerate rates; for instance, certain metal ions act as catalysts in fire-retardant contexts by facilitating release and char promotion at lower temperatures. In fire-retardant applications, ammonium phosphate additives reduce the activation energy of in early stages, enhancing flame inhibition efficiency.

Interactions with other substances

Ammonium phosphate exhibits acid-base reactivity typical of its ionic composition, consisting of cations and anions. When treated with strong acids such as , it undergoes a displacement reaction, liberating and forming : (NH_4)_3PO_4 + 3HCl \rightarrow 3NH_4Cl + H_3PO_4. Similarly, reaction with leads to and formation of mixed phosphate-sulfate salts, such as ammonium phosphate sulfate (NH_4)_2(H_2PO_4)(HSO_4), which arises from the addition of one equivalent of to ammonium phosphate. In the presence of strong bases like sodium hydroxide, ammonium phosphate releases ammonia gas through deprotonation of the ammonium ions, yielding the corresponding alkali metal phosphate: (NH_4)_3PO_4 + 3NaOH \rightarrow Na_3PO_4 + 3NH_3 + 3H_2O. This reaction highlights the basic nature of the phosphate anion in facilitating ammonia displacement under alkaline conditions. Ammonium phosphate forms complexes and precipitates with various metal ions due to the low of metal phosphates. For instance, it reacts with calcium ions to precipitate phases, such as or , when solutions of ammonium phosphate and calcium salts are mixed at neutral to alkaline . With magnesium ions, it forms (magnesium ammonium phosphate hexahydrate, MgNH_4PO_4 \cdot 6H_2O), a sparingly soluble that precipitates readily in the presence of and phosphate at 7–11. Other divalent metals like , , and also form insoluble ammonium metal phosphates through similar precipitation mechanisms. The behavior of is generally limited, as is already in its highest (+5) in the anion, rendering it a weak incapable of significant electron acceptance./Qualitative_Analysis/Properties_of_Select_Nonmetal_Ions/Phosphate_Ion_(PO%25E2%2582%2584%25C2%25B3%25E2%2580%25BC)) It shows incompatibility with strong oxidants, such as , leading to rapid decomposition and release of toxic fumes including , oxides, and nitrogen oxides. In high-temperature environments, ammonium phosphate undergoes oxidation primarily through decomposition, releasing non-toxic gases like and that dilute the without substantial alteration of the core structure.

Applications

Agricultural uses

Ammonium phosphate, primarily in the forms of monoammonium phosphate (MAP) and (DAP), serves as a key fertilizer in by delivering essential nitrogen (N) and (P) to crops. MAP typically contains 11% N and 48-61% P₂O₅ equivalent, while DAP provides 18% N and 46% P₂O₅, making them highly concentrated sources that support plant energy transfer, , and overall vigor. These nutrients are vital for root development, as promotes early root formation and elongation, enhancing nutrient and water uptake in phosphorus-deficient soils. Application methods for ammonium phosphate fertilizers vary by crop and soil conditions to optimize nutrient efficiency. Granular forms are commonly broadcast across fields or placed in concentrated bands near seed rows to ensure direct access to roots, while liquid formulations, often derived from MAP, are suitable for drip irrigation or fertigation systems in row crops like corn and vegetables. MAP's acidic nature (pH 4-4.5) makes it preferable for to alkaline soils, where it temporarily lowers pH around the granule to improve phosphorus solubility, whereas DAP's higher pH (7.5-8) suits acidic soils to avoid excessive acidification. The use of MAP and DAP significantly boosts availability in deficient soils, leading to improved yields and quality. Adequate application has been shown to significantly increase growth in low-P environments, resulting in higher production, better stalk strength, and earlier maturity for cereals and . Together, these s contribute to a major share, accounting for around 70% of global production as of 2024, underscoring their role in sustaining food production amid growing demand.

Industrial and safety applications

Ammonium phosphate, particularly (DAP), serves as an effective in non-agricultural industrial applications, including Class A extinguishers and wood treatments, where it promotes char formation to inhibit . Upon to heat, DAP decomposes to release gas and , which blanket the and create a protective barrier on combustible surfaces like wood or materials. This mechanism enhances suppression by reducing oxygen access and , as briefly referenced in its behavior. In coatings for buildings and , ammonium polyphosphate (APP), a polymeric form of ammonium phosphate, expands when heated to form an insulating layer, providing fire resistance for up to four hours and protecting underlying materials from ignition. For applications such as plastics and textiles, incorporation of ammonium phosphate at concentrations of 10-20% by weight achieves significant retardancy, often meeting standards like V-0 by promoting intumescence and reducing peak heat release rates. Beyond fire safety, ammonium phosphate finds roles in other manufacturing sectors. In electronics etching, monoammonium phosphate (MAP) acts as a buffering to control pH during the cleaning and etching of printed boards and components, ensuring precise removal without excessive . It also functions as a yeast nutrient in processes, supplying essential and to support yeast and dough development in commercial bread . Additionally, in , stabilizes pH levels in industrial wastewater streams, preventing fluctuations that could impair downstream purification or efforts.

Safety and environmental aspects

Health hazards and handling

Ammonium phosphate compounds, such as monoammonium phosphate (MAP) and (DAP), act as irritants to the eyes, , and upon exposure. Contact with the eyes can cause serious , including redness, , and potential corneal damage if not promptly flushed. Skin exposure may result in mild to moderate , dryness, or , particularly with prolonged contact. Inhalation of dust particles leads to respiratory , manifesting as coughing, , and throat discomfort; higher concentrations can exacerbate these effects and potentially cause in severe cases. Additionally, thermal decomposition of ammonium phosphate can release gas, which is highly irritating and corrosive, potentially causing burns to the , eyes, and upon exposure. The (OSHA) sets a (PEL) for ammonium phosphate dust at 15 mg/m³ as an 8-hour time-weighted average for total dust and 5 mg/m³ for the respirable fraction, treating it as particulates not otherwise regulated. The American Conference of Governmental Industrial Hygienists (ACGIH) recommends a (TLV) of 10 mg/m³ for inhalable particles. However, ammonium phosphate is not classified as a by OSHA, the National Toxicology Program (NTP), or the International Agency for Research on Cancer (IARC). Safe handling of ammonium phosphate requires the use of (PPE), including chemical-resistant gloves, safety goggles or face shields, protective clothing, and NIOSH-approved respirators with particulate filters when levels may exceed exposure limits. It should be stored in cool, dry, well-ventilated areas in tightly sealed containers to prevent moisture absorption and decomposition, away from incompatible materials such as strong acids or bases. In case of spills, the area should be evacuated, suppressed with spray if safe, and the material collected using non-sparking tools for disposal; dilute residues with large amounts of to neutralize and prevent generation. , such as local exhaust ventilation, are recommended to minimize airborne during handling and processing.

Ecological impacts and regulations

Ammonium phosphate fertilizers pose significant ecological risks primarily through nutrient runoff and volatilization processes. The phosphate component, when applied to agricultural fields, can leach into waterways via or subsurface drainage, exacerbating in freshwater and coastal ecosystems. This nutrient enrichment promotes excessive algal growth, which subsequently leads to oxygen depletion—known as —creating "dead zones" that harm aquatic life, including populations and . For instance, studies on ammonium phosphate-based applications have documented increased stream , altering microbial communities and reducing overall . The ammonium fraction introduces additional environmental concerns via ammonia volatilization, where gaseous (NH₃) is released into the atmosphere, particularly under warm, moist conditions following fertilizer application. This volatilized contributes to by forming fine (PM₂.₅) and secondary aerosols, which deposit far from the source, leading to , in sensitive habitats, and indirect contributions to . In agricultural soils, residual can persist, potentially enhancing long-term availability but also increasing the risk of further emissions if not managed. These impacts are amplified in regions, where ammonium phosphate use is common. Regulatory frameworks aim to mitigate these ecological effects through targeted emission controls and best management practices. In the , the National Emission Ceilings Directive (Directive 2016/2284/EU) sets national reduction commitments for emissions, requiring member states to achieve decreases of 2% to 32% by 2030 compared to 2005 levels (varying by country), with linear interim trajectories from 2020 and promotion of agricultural best practices like precision fertilization to curb volatilization. Complementing this, the (Directive 2000/60/EC) establishes environmental quality standards for in surface waters to combat , requiring member states to implement measures such as reduced application rates near water bodies. In the United States, the Environmental Protection Agency (EPA) provides guidelines under the Clean Water Act, emphasizing vegetative buffer zones—strips of grass or along edges—to intercept runoff, with recommendations for widths of 10-50 feet depending on and to protect adjacent . These policies collectively drive adoption of sustainable practices to minimize ammonium phosphate's environmental footprint.

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