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Sodium aluminosilicate
Sodium aluminosilicate
Sodium aluminosilicate
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Sodium aluminosilicate
Names
IUPAC name
aluminum sodium dioxido(oxo)silane
Other names
  • Aluminosilicic acid
  • aluminum sodium silicate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.014.259 Edit this at Wikidata
EC Number
  • 215-684-8
E number E554 (acidity regulators, ...)
UNII
  • InChI=1S/Al.Na.2O3Si/c;;2*1-4(2)3/q+3;+1;2*-2 checkY
    Key: URGAHOPLAPQHLN-UHFFFAOYSA-N checkY
  • [O-] [Si](=O)[O-].[O-] [Si](=O)[O-].[Na+].[Al+3]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Sodium aluminosilicate refers to compounds which contain sodium, aluminium, silicon and oxygen, and which may also contain water. These include synthetic amorphous sodium aluminosilicate, a few naturally occurring minerals and synthetic zeolites. Synthetic amorphous sodium aluminosilicate is widely used as a food additive, E 554.

Amorphous sodium aluminosilicate

[edit]

This substance is produced with a wide range of compositions and has many different applications. It is encountered as an additive E 554 in food where it acts as an anticaking (free flow) agent. As it is manufactured with a range of compositions it is not strictly a chemical compound with a fixed stoichiometry.[1] One supplier quotes a typical analysis for one of their products as 14SiO2·Al2O3·Na2O·3H2O,(Na2Al2Si14O32·3H2O).[2]

The US FDA has as of April 1, 2012 approved sodium aluminosilicate (sodium silicoaluminate) for direct contact with consumable items under 21 CFR 182.2727.[3] Sodium aluminosilicate is used as molecular sieve in medicinal containers to keep contents dry.

Sodium aluminosilicate may also be listed as:

  • aluminium sodium salt
  • sodium silicoaluminate
  • aluminosilicic acid, sodium salt
  • sodium aluminium silicate
  • aluminum sodium silicate
  • sodium silico aluminate
  • sasil

As a problem in industrial processes

[edit]

The formation of sodium aluminosilicate makes the Bayer process uneconomical for bauxites high in silica.[citation needed]

Minerals sometimes called sodium aluminosilicate

[edit]

Naturally occurring minerals that are sometimes given the chemical name sodium aluminosilicate include albite (NaAlSi3O8, an end-member of the plagioclase series) and jadeite (NaAlSi2O6).[citation needed]

Synthetic zeolites sometimes called sodium aluminosilicate

[edit]

Synthetic zeolites have complex structures and examples (with structural formulae) are:

  • Na12Al12Si12O48·27H2O, zeolite A (Linde type A sodium form, NaA), used in laundry detergents[4]
  • Na16Al16Si32O96·16H2O, Analcime, IUPAC code ANA[4]
  • Na12Al12Si12O48·q H2O, Losod[5]
  • Na384Al384Si384O1536·518H2O, Linde type N

References

[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia

Sodium aluminosilicate

View on Grokipedia
from Grokipedia
Sodium aluminosilicate, also known as sodium silicoaluminate, is an inorganic compound with the general formula Na₂O·Al₂O₃·2SiO₂·xH₂O (where x varies depending on hydration), consisting of sodium, aluminum, silicon, and oxygen atoms arranged in a crystalline or amorphous structure. It typically appears as an odorless, fine white powder or beads that is insoluble in water and organic solvents but partially soluble in strong acids and alkalis at elevated temperatures. This material is widely utilized as an anticaking agent (E 554 in the European Union) in food products such as table salt, powdered spices, and grated cheeses to prevent clumping by absorbing moisture; it is authorized as a carry-over up to 20 mg/kg in foods per EU regulations. Beyond food, it serves as a molecular sieve for drying applications in pharmaceuticals, a bulking agent in cosmetics, and an absorbent or flow aid in various industrial processes. Chemically, it is generally unreactive and non-flammable but can act as a catalyst in certain reactions; upon strong heating, it may emit toxic fumes such as disodium oxide. Safety assessments indicate low acute toxicity and irritancy, though its aluminum content raises concerns for chronic exposure, with dietary intake from additives potentially exceeding the tolerable weekly intake (TWI) of 1 mg/kg body weight for aluminum in some populations (e.g., children using supplements), as of the 2020 EFSA evaluation, prompting calls for further toxicological data.

Overview and chemistry

Definition and composition

Sodium aluminosilicates are a class of inorganic compounds composed primarily of sodium (Na), aluminum (Al), silicon (Si), and oxygen (O) atoms, frequently incorporating water molecules in their structure. These materials form three-dimensional framework structures where aluminum and silicon are tetrahedrally coordinated to oxygen, with sodium ions serving to balance the negative charge arising from the substitution of silicon by aluminum. The general stoichiometric formula for sodium aluminosilicates can be represented as Na₂O · Al₂O₃ · nSiO₂ · xH₂O, where n typically ranges from 2 to higher values depending on the specific variant, and x denotes the degree of hydration, often around 4.5 in synthetic forms. This composition reflects a molar of Na₂O:Al₂O₃:SiO₂ that varies but is commonly approximately 1:1:2 in basic hydrated structures, allowing for flexibility in synthesis and application. Unlike aluminosilicates balanced by other cations such as calcium or , sodium aluminosilicates are distinguished by the presence of sodium as the principal exchangeable cation, which influences their ion-exchange and in alkaline conditions. Historically, these compounds have been referred to by synonyms including sodium aluminum silicate, sodium silicoaluminate, and aluminum sodium silicate, reflecting variations in based on their perceived or aluminate dominance. Many sodium aluminosilicates belong to the subclass due to their porous frameworks.

Structure and bonding

Sodium aluminosilicates consist of a three-dimensional framework constructed from corner-sharing SiO₄ and AlO₄ tetrahedra, where the oxygen atoms form bridging linkages between and aluminum cations. This tetrahedral arrangement creates a rigid lattice in crystalline forms, with sodium ions (Na⁺) occupying extra-framework positions to maintain overall charge neutrality. A fundamental aspect of this structure is isomorphous substitution, in which trivalent aluminum (Al³⁺) replaces tetravalent silicon (Si⁴⁺) within the tetrahedral sites, generating a net negative charge on the framework due to the charge difference. These negatively charged sites are balanced by monovalent sodium cations, which reside in the interstices of the lattice and can migrate within it. The extent of substitution influences the framework's overall composition and properties, with higher aluminum content leading to more sodium ions per unit cell. Bonding within the aluminosilicate framework is predominantly covalent, characterized by strong Si–O and Al–O bonds that hold the tetrahedra together through shared oxygen bridges. In contrast, the interaction between the negatively charged framework and the sodium ions is primarily ionic, allowing for electrostatic attraction that stabilizes the structure while permitting ion mobility. This hybrid bonding scheme contributes to the material's stability and versatility. In crystalline sodium aluminosilicates, the tetrahedral framework often incorporates open channels or pores, which arise from the specific arrangement of the polyhedral units and facilitate the of ions and small molecules. These voids enable ion-exchange capabilities, as sodium ions can be reversibly replaced by other cations of similar size without disrupting the framework integrity.

Physical and chemical properties

Physical characteristics

Sodium aluminosilicate typically appears as a , fine or crystalline , often in the form of odorless and tasteless beads or pellets depending on the preparation method. The density of sodium aluminosilicate varies with its form, ranging from approximately 2.1 to 2.5 g/cm³ for crystalline and amorphous variants, reflecting its compact aluminosilicate framework. Bulk densities for powdered forms are lower, typically around 0.35–0.5 g/cm³. Regarding solubility, sodium aluminosilicate is insoluble in , alcohol, and most organic solvents, though it exhibits limited dispersibility in alkaline solutions where it can form suspensions without fully dissolving. Hydrated forms of sodium aluminosilicate undergo at temperatures between 100 and 300°C, releasing molecules from their while maintaining overall framework integrity up to higher temperatures. This thermal behavior is influenced by the open framework , which contributes to its as described in the structure and bonding section. The material decomposes upon further heating, potentially emitting fumes.

Reactivity and stability

Sodium aluminosilicates exhibit significant ion-exchange capacity, primarily through the replacement of sodium ions (Na⁺) with other cations such as calcium (Ca²⁺) or (H⁺). This property arises from the framework structure, particularly in crystalline forms like zeolite A, where exchangeable cations balance the negative charge of aluminum-substituted tetrahedral sites. Synthetic amorphous variants demonstrate base exchange capacities of at least 200 mg CaCO₃ per gram, with some achieving up to 282 mg CaCO₃/g, enabling efficient softening of by sequestering Ca²⁺ ions. Amorphous aluminosilicates with Si/Al ratios between 1 and 5 often surpass the of synthetic mordenite (Si/Al = 9.5) or natural zeolites (Si/Al ≈ 4.6), making them effective for removing and other cations from aqueous solutions. These materials display high stability in alkaline environments, where they are typically synthesized and maintain structural integrity due to the compatibility of their framework with high conditions (e.g., 12–14). In such settings, dissolution rates of and aluminum are controlled, supporting applications requiring resistance to caustic solutions. However, exposure to strong acids leads to decomposition via of Al-O-Si bonds, resulting in the release of (H₄SiO₄) and aluminum species, which progressively weakens the framework and reduces mechanical properties like tensile strength. This acid sensitivity is evident in sodium aluminosilicate hydrates (N-A-S-H), where sodium leaching initiates surface degradation, forming microscopic fissures and lowering degrees (e.g., Q⁴ sites from 79% to 73%). Reversible hydration and dehydration are characteristic of many sodium aluminosilicate structures, especially zeolitic forms, where water molecules occupy pores and can be removed by heating without permanent structural collapse, enhancing adsorptive capabilities. This process involves the expulsion of zeolitic water at elevated temperatures (e.g., 473 K), allowing framework contraction while preserving overall topology for rehydration. Solubility is highly pH-dependent, with low solubility and precipitation favored in neutral to basic solutions containing aluminum and silicon ions; for instance, amorphous sodium aluminum silicate forms readily at pH 7.5–8.5, with precipitation intensifying at higher pH due to increased aluminosilicate anion concentrations.

Natural forms

Associated minerals

Sodium aluminosilicates are represented in nature primarily by zeolite minerals within the natrolite subgroup, including natrolite, thomsonite, and gonnardite, each characterized by hydrated frameworks of aluminum and silicon tetrahedra linked by sodium and other cations. Natrolite, with the ideal composition Na₂Al₂Si₃O₁₀·2H₂O, is the most common member and exhibits acicular to fibrous crystal habits, often forming radiating sprays or slender prisms up to several centimeters long. Minor substitutions occur, such as calcium replacing up to 35% of sodium, leading to intermediate compositions. It is relatively widespread and typically found in cavities within basaltic rocks, with notable localities including Hohentwiel in Germany and the Watchung Mountains in New Jersey, USA. Thomsonite, formulated as NaCa₂Al₅Si₅O₂₀·6H₂O, displays prismatic or radiating fibrous habits, sometimes forming masses with a vitreous luster. It accommodates minor sodium-calcium variations but remains distinct in its higher aluminum content relative to . Thomsonite is less common than and occurs in similar zeolite-bearing environments, such as altered basalts in the and the in . Gonnardite, a rarer variant with composition (Na,Ca)₂Al₂Si₃O₁₀·2H₂O, features acicular or fibrous crystals akin to but with more pronounced calcium substitution for sodium, often approaching NaCaAl₂Si₃O₁₀·2H₂O in end-member forms. Its habits are typically slender needles in radiating aggregates. Gonnardite is uncommon and restricted to specific sites, including the type locality at Gignat in and vugs in alkaline rocks at , , .

Geological occurrence

Sodium aluminosilicates, such as and , primarily form in low-temperature hydrothermal environments, typically below 200°C, where they precipitate as secondary minerals in cavities and veins of volcanic rocks. These zeolites develop through the alteration of primary silicates like or feldspars by circulating fluids, often in vesicular basalts where fluids deposit silica, alumina, and sodium in open spaces. They are commonly associated with alkaline igneous rocks, such as basalts and syenites, as well as sedimentary deposits enriched in silica and alumina from volcanic detritus. In these settings, sodium-rich alkaline fluids ( >9) play a crucial role in the precipitation process, facilitating the transformation of precursor minerals like feldspars into hydrated frameworks during or low-grade . For instance, often arises from the burial alteration of volcanic materials in saline-alkaline lakes or closed sedimentary basins. Globally, these minerals are widespread in regions of extensive volcanism, such as the in , where and similar zeolites fill amygdules in basaltic flows through post-eruptive hydrothermal activity. They also occur prominently along the , including basaltic terrains in and the sequences of , reflecting the influence of sodium-bearing fluids in tectonically active zones.

Synthetic forms

Production methods

Sodium aluminosilicate is primarily synthesized through hydrothermal methods, where solutions of sodium aluminate and sodium silicate are mixed to form an amorphous aluminosilicate gel, which is then subjected to elevated temperatures and pressures in an autoclave to induce crystallization. This process typically operates at temperatures between 75°C and 200°C, with reaction times ranging from 3 to 8 hours, depending on the desired phase formation. The hydrothermal conditions facilitate the condensation of silicate and aluminate species into ordered framework structures, often under alkaline conditions provided by added NaOH. Precipitation methods involve the direct mixing of soluble silicates and aluminates in caustic soda solutions, leading to the rapid formation of a sodium aluminosilicate precipitate without the need for prolonged heating in some cases. In these approaches, the solutions are combined under high shear at temperatures of 40°C to 90°C, resulting in an initial or that precipitates due to . This technique is particularly suited for continuous industrial operations, where the precipitate is aged briefly before further processing. Crystallization is controlled through seeding with pre-formed and precise management of gradients to direct the formation of specific phases while minimizing unwanted amorphous material. Seeding enhances rates, achieving efficiencies up to 65% with concentrations below 20 g/L, and allows for tailored morphology by influencing growth kinetics. during aging prevents phase impurities, ensuring high-purity products. Industrial scale-up employs continuous flow reactors for mixing and , enabling high-volume production with yields approaching 1 of product from approximately 300 kg each of silica and alumina precursors. Energy requirements for the process average around 22,400 MJ per of , primarily from hydrothermal heating and drying steps at 80°C. These methods prioritize through of mother liquors, reducing waste and operational costs in large-scale facilities.

Common synthetic variants

Synthetic sodium aluminosilicates encompass a range of crystalline and amorphous forms, with the most prominent crystalline variants being zeolites characterized by ordered microporous frameworks. These structures enable selective molecular sieving based on pore dimensions and cation exchange capacities influenced by sodium content and silicon-to-aluminum ratios. , possessing the LTA (Linde Type A) , is a low-silica with the Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]·27H₂O. This variant features an Si/Al ratio of 1, resulting in a high density of sodium cations that balance the framework's negative charge, and its cubic contains sodalite cages connected by double four-rings, forming an alpha cage with a pore aperture of approximately 4 . The small pore size restricts access to molecules smaller than 4 , distinguishing it from larger-pore zeolites. In contrast, adopt the (FAU) framework, consisting of cages linked by double six-rings to form hexagonal prisms and larger supercages accessible via 12-ring windows with a pore size of about 7.4 . X has a lower Si/Al ratio (typically 1–1.5), leading to more aluminum atoms and thus a higher sodium cation content for charge compensation, while Y exhibits a higher Si/Al ratio (greater than 2, often up to 3 or more), reducing the aluminum content and sodium density, which enhances thermal stability. These differences in Si/Al ratios result in larger internal cages suitable for accommodating bigger guest molecules compared to A. Amorphous synthetic sodium aluminosilicates, lacking the long-range crystalline order of zeolites, are typically produced through rapid precipitation methods such as mixing and aluminate solutions under controlled and temperature conditions. These variants feature short-range networks with variable Si/Al ratios and sodium incorporation, but without defined pores, relying instead on surface area and disordered channels for functionality; their cation content varies based on synthesis parameters, often providing higher initial exchange capacities than crystalline forms in certain contexts.

Applications and uses

Detergent and water treatment

Sodium aluminosilicate, particularly in the form of synthetic (also known as 4A ), serves as a key builder in formulations by sequestering calcium and magnesium ions from through ion-exchange processes. This material exchanges its sodium ions for divalent calcium (Ca²⁺) and magnesium (Mg²⁺) ions, preventing the formation of insoluble salts that cause scaling and reduce cleaning efficiency. The ion-exchange property arises from the crystalline structure of sodium aluminosilicate, which features a network of pores and channels that selectively bind hardness ions, as established in its reactivity profile. Developed in the 1970s by companies such as and , sodium aluminosilicate emerged as an environmentally superior alternative to phosphate-based builders like sodium tripolyphosphate (STPP), which contribute to by promoting excessive algal growth in water bodies. Unlike phosphates, do not release into waterways, with over 96% of zeolite particles being removed during , thereby minimizing and oxygen depletion in aquatic ecosystems. This shift addressed growing concerns about phosphate-induced , leading to widespread adoption in phosphate-free detergents across and . In typical detergent formulations, is incorporated at loadings of 10–50% by weight, depending on the product type, with higher concentrations in compact powders to enhance performance in conditions. is optimized for effective dispersion, often with a mean of around 3.5 μm and rounded edges to reduce fabric abrasion and improve suspension in wash solutions. The material demonstrates strong effectiveness in , boasting an ion-exchange capacity of approximately 200–300 meq/100 g, which enables efficient removal even at low temperatures and short wash cycles.

Industrial catalysis and adsorption

Synthetic sodium aluminosilicates, particularly zeolite variants such as type 5A, are widely employed in for the separation of hydrocarbons through molecular sieving mechanisms. These materials, derived from sodium aluminosilicate frameworks with effective pore openings of approximately 5 Å, selectively adsorb linear paraffins while excluding branched isomers, enabling efficient purification of streams and production of high-purity normal paraffins for chemical feedstocks. This process operates via kinetic and thermodynamic selectivity, where rates and interaction strengths dictate molecule discrimination, achieving separation efficiencies exceeding 99% in simulated moving bed (SMB) configurations. In gas adsorption applications, sodium aluminosilicates like 3A and 4A excel at removing (H₂O) from industrial gas streams, including , air, and olefins, through temperature swing adsorption (TSA) processes that achieve dew points below -100°C. These s also facilitate CO₂ capture in air pre-purification units and (PSA) systems for upgrading and , leveraging strong interactions with CO₂ for selectivities over CH₄ and N₂ up to 100:1 under ambient conditions. Their microporous structure ensures reversible adsorption without degradation, supporting large-scale operations in petrochemical plants. For catalytic cracking, sodium aluminosilicates in the form of zeolite Y (faujasite) serve as the core component in (FCC) units, where initial sodium content is exchanged with rare earth cations (e.g., La³⁺, Ce³⁺) to generate Brønsted sites essential for cracking heavy gas oils into and light olefins. This stabilizes the framework against hydrothermal deactivation, increasing catalytic activity by over 100-fold compared to amorphous silica-alumina precursors, and enables processing of over 500 million tons of feedstocks annually across global refineries. The acidity, tuned to a Si/Al ratio of 5–15, promotes carbocation-mediated reactions with selectivities favoring yields up to 15 wt%. In nuclear waste treatment, sodium aluminosilicates such as and synthetic A are utilized for the ion-exchange removal of cesium (Cs⁺) and (Sr²⁺) from radioactive aqueous effluents, achieving factors greater than 100 through selective coordination with the lattice. For Cs⁺, adsorption capacities reach 89 mg/g at 8, following pseudo-second-order kinetics dominated by , while Sr²⁺ removal efficiencies exceed 90% via similar ion-exchange mechanisms, with capacities up to 69 mg/g in batch systems. These applications are critical for treating streams, reducing concentrations to below regulatory limits before or disposal.

Food and other applications

Sodium aluminosilicate is approved as a (E 554) in the and used as an in products like table salt, powdered spices, and grated cheeses to absorb moisture and prevent clumping. Authorized levels are up to 20 mg/kg in certain applications, such as cheese surface treatment, with safety assessments indicating low but ongoing monitoring of aluminum . In pharmaceuticals, it functions as a for drying applications in medicinal containers. In , it acts as a controller and bulking agent. Industrially, it serves as an absorbent and flow aid in processes involving textiles, , and composites.

Industrial challenges

Formation in processes

Sodium aluminosilicate precipitates as an unwanted byproduct in high-temperature alkaline aqueous systems, such as those in the for alumina refining and geothermal extraction systems, where silica and alumina concentrations are elevated due to raw material impurities or fluid chemistry. This occurs under alkaline conditions with greater than 9 and temperatures exceeding 200°C, where the of silica decreases sharply, leading to when combined with dissolved alumina. In such environments, the compound forms adherent scales on surfaces, exacerbating operational inefficiencies. In power plant boilers, formation is occasional and requires significant alumina contamination from sources like fly ash leaching. The mechanism begins with supersaturation of silicic acid and aluminate ions in the alkaline liquor, promoting rapid of amorphous sodium aluminosilicate gels or colloids within seconds to minutes. These initial amorphous deposits then undergo aging and transformation into crystalline phases, such as or cancrinite, through solution-mediated dissolution and reprecipitation, influenced by the Si/Al ratio and prolonged exposure to heat. This progression from amorphous to crystalline structures results in denser, more adherent scales that insulate metal surfaces, significantly reducing efficiency by up to 30% or more in affected equipment. Such formations are prevalent in plants, where hot, alkaline fluids (often 8–10) ascend rapidly, causing in pipelines and reinjection wells, as documented in mid-20th-century industrial surveys of fields like those in and . In the , scaling is a persistent issue in heat exchangers and evaporators due to caustic soda digestion of . These issues have been noted in assessments of geothermal and alumina refining operations. The impacts include severe equipment fouling, with scale thicknesses reaching several millimeters over operational cycles, leading to localized overheating, reduced thermal conductivity, and frequent shutdowns for . In extreme cases, such deposits have caused forced outages in geothermal facilities and reduced efficiency in alumina plants, with economic losses estimated in millions annually based on 1970s–1990s refinery and plant data, underscoring the need for vigilant impurity control in these processes.

Prevention and control

In industrial operations prone to sodium aluminosilicate scaling, such as the in alumina refining, geothermal systems, and alkaline process streams in boilers, water treatment strategies often incorporate chelants and dispersants to inhibit and . Chelating agents, including phosphonates like 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), complex with aluminum and ions in solution, preventing their assembly into scale-forming structures under geothermal or high-temperature conditions. Dispersants, such as polymeric additives with silyl-functional groups, maintain particles in suspension by adsorbing onto nascent crystals, reducing adhesion to surfaces and thereby minimizing in evaporators and heat exchangers. These treatments are typically dosed at low concentrations (e.g., 1-10 ppm) to achieve threshold inhibition without promoting alternative precipitation. Effective monitoring of and silica levels is essential for proactive control, as sodium aluminosilicate formation accelerates above 9 and silica concentrations exceeding limits. In systems, maintaining dissolved silica below 100 ppm as SiO₂ at >7.5 helps suppress and aluminosilicate deposition, with continuous online analysis using colorimetric or methods to guide adjustments. is regulated between 10-11 using or coordinated treatments to balance silica volatility and scale risk, particularly in high-pressure cycles where carryover to turbines must be limited to <0.02 ppm SiO₂. Operational controls, including and the application of synthetic inhibitors, provide robust management of scaling propensity. removes concentrated silica and aluminum from the , typically at rates of 1-5% of feedwater volume, to maintain silica below critical thresholds and prevent during load changes. Since the , synthetic inhibitors such as / polymers have been widely adopted for internal treatment, forming protective films or distorting crystal lattices to inhibit scale at temperatures up to 250°C. These all-organic programs replaced earlier phosphate-based methods, offering improved compatibility with demineralized feedwater and reducing formation. Advanced methods like magnetic treatment and zeolite seeding offer non-chemical or hybrid alternatives to redirect precipitation away from critical surfaces. Magnetic water treatment devices, employing permanent magnets (0.1-1 Tesla fields) on feed lines, alter hydration shells to promote softer, less adherent scales that can be easily flushed, with reported reductions in deposition by 50-80% in trials. seeding involves adding preformed crystals, such as sodalite-cancrinite mixtures (1-5 g/L), to process s in plants, which acts as sites to accelerate bulk and reduce surface by up to 90% under controlled . These techniques are particularly valuable in retrofitting existing systems, though efficacy depends on liquor composition and flow dynamics.

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