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Sodium ferrocyanide
Sodium ferrocyanide
Sodium ferrocyanide
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Sodium ferrocyanide[1]
Names
IUPAC name
Sodium [hexacyanoferrate(II)]
Other names
  • Yellow prussiate of soda (YPS)
  • Tetrasodium hexacyanoferrate
  • Gelbnatron
  • Ferrocyannatrium
  • sodium hexacyanoferrate(II)
  • Yellow blood salt[citation needed]
Identifiers
3D model (JSmol)
ChEBI
ECHA InfoCard 100.033.696 Edit this at Wikidata
EC Number
  • 237-081-9
E number E535 (acidity regulators, ...)
UNII
UN number 3077 (SODIUM FERROCYANIDE)
  • Key: GTSHREYGKSITGK-UHFFFAOYSA-N
  • InChI=1S/6CN.Fe.4Na/c6*1-2;;;;;/q6*-1;+2;4*+1
  • [Na+].[Na+].N#C[Fe-4](C#N)(C#N)(C#N)(C#N)C#N.[Na+].[Na+]
Properties
Na4[Fe(CN)6]
Molar mass 303.91 g/mol
Appearance pale yellow crystals
Odor odorless
Density 1.458 g/cm3
Melting point 435 °C (815 °F; 708 K) (anhydrous)
81.5 °C (178.7 °F; 354.6 K) (decahydrate) (decomposes)
10.2 g/100 mL (10 °C)
17.6 g/100 mL (20 °C)
39.7 g/100 mL (96.6 °C)
1.530
Structure
monoclinic
Related compounds
Other anions
 Sodium ferricyanide (Red prussiate of soda)
Other cations
 Potassium ferrocyanide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Sodium ferrocyanide is the sodium salt of the coordination compound of formula [Fe(CN)6]4−. In its hydrous form, Na4Fe(CN)6·10H2O (sodium ferrocyanide decahydrate), it is sometimes known as yellow prussiate of soda.[2] It is a yellow crystalline solid that is soluble in water and insoluble in alcohol. The yellow color is the color of ferrocyanide anion. Despite the presence of the cyanide ligands, sodium ferrocyanide has low toxicity (acceptable daily intake 0–0.025 mg/kg body weight[3]). The ferrocyanides are less toxic than many salts of cyanide, because they tend not to release free cyanide.[4] However, like all ferrocyanide salt solutions, addition of an acid or exposure to UV light can result in the production of hydrogen cyanide gas, which is extremely toxic.[5][6]

Uses

[edit]

When combined with a Fe(III) salt, it converts to a deep blue pigment called Prussian blue, Fe3+4[Fe2+(CN)6]3.[7] It is used as a stabilizer for the coating on welding rods. In the petroleum industry, it is used for removal of mercaptans.

In the EU, ferrocyanides (E 535–538) were, as of 2018, solely authorized as additives in salt and salt substitutes, where they serve as anticaking agents. The kidneys are the organ susceptible to ferrocyanide toxicity, but according to the EFSA, ferrocyanides are of no safety concern at the levels at which they are used.[8]

Production

[edit]

Sodium ferrocyanide is produced industrially from hydrogen cyanide, ferrous chloride, and calcium hydroxide, the combination of which affords Ca2[Fe(CN)6]·11H2O. A solution of this salt is then treated with sodium salts to precipitate the mixed calcium-sodium salt CaNa2[Fe(CN)6]2, which in turn is treated with sodium carbonate to give the tetrasodium salt.[9]

References

[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia

Sodium ferrocyanide

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from Grokipedia
Sodium ferrocyanide is an inorganic coordination with the Na₄[Fe(CN)₆]·10H₂O, consisting of sodium ions and the hexacyanoferrate(II) complex, and it is commonly known as prussiate of soda. This pale , odorless crystalline solid has a molecular weight of 303.91 g/mol () and a of 1.458 g/cm³, decomposing at 435 °C without . It is highly soluble in (approximately 17.6 g/100 mL at 25 °C) but insoluble in alcohol and , and it remains stable under normal conditions while slowly releasing gas upon exposure to strong acids or light. As a food additive designated E 535 in the , sodium ferrocyanide is primarily employed as an in table salt and salt substitutes at levels up to 20 mg/kg, preventing clumping by adsorbing . It is also approved by the for use in salt at a maximum of 13 ppm, and it finds industrial applications in the production of pigments, ore flotation processes, and photographic toning and fixing, as well as emerging uses in materials such as analogues. Additionally, it serves as an in road salts, particularly in regions like the and , where it enters the environment via runoff. Regarding safety, sodium ferrocyanide exhibits low due to the tight binding of to the iron center, resulting in minimal and no significant genotoxic, carcinogenic, or reproductive effects in available studies. The has established an of 0.03 mg/kg body weight per day for the , with dietary exposures from authorized uses estimated at up to 0.004 mg/kg body weight per day—well below levels of concern—and a of 4.4 mg/kg body weight per day based on renal effects in long-term studies. Environmentally, it persists in as a metallocyanide complex but degrades slowly, potentially releasing trace free under certain conditions like microbial action or photolysis.

Chemical identity

Molecular structure

Sodium ferrocyanide, with the chemical formula Na4[Fe(CN)6]Na_4[Fe(CN)_6], exists in an anhydrous form and is more commonly encountered as the decahydrate Na4[Fe(CN)6]⋅10H2ONa_4[Fe(CN)_6]\cdot 10H_2O. The anhydrous form has a molar mass of 303.91 g/mol, while the decahydrate has a molar mass of 484.1 g/mol. The structure features sodium cations paired with the ferrocyanide anion [Fe(CN)6]4−[Fe(CN)_6]^{4-}, a coordination complex in which the iron(II) ion adopts an octahedral geometry surrounded by six cyanide (CN−CN^-) ligands. The iron center maintains a low-spin d6d^6 electronic configuration, characteristic of strong-field ligands like cyanide that promote pairing of electrons in the t2gt_{2g} orbitals. The ligands bind tightly to the iron, conferring exceptional stability to the with a large formation constant and resistance to dissociation under normal conditions. This inertness arises from the high covalency and back-bonding interactions between the iron dd orbitals and the π∗\pi^* orbitals. In the decahydrate form, the compound crystallizes as a solid in a monoclinic lattice, where the molecules of hydration are incorporated into the structure, stabilizing the ionic assembly without directly coordinating to the iron center.

Physical properties

Sodium ferrocyanide typically appears as a pale yellow crystalline solid, often in the form of the decahydrate, Na₄[Fe(CN)₆]·10H₂O. This coloration arises from the coordination structure of the anion. The compound is odorless and presents as a or granules. It exhibits high solubility in , with approximately 10.2 g dissolving in 100 mL at around 1–10 °C, increasing to 17.6 g/100 mL at 25 °C, while remaining insoluble in alcohol and most organic solvents. The decahydrate form has a of 1.458 g/cm³. The decahydrate loses its at 81.5 °C, becoming , while the form decomposes at 435 °C into , iron, carbon, and . Under normal conditions, sodium ferrocyanide is stable and slightly efflorescent, with steady occurring above 50 °C for the .

History and nomenclature

Discovery and early uses

Sodium ferrocyanide, known historically as yellow prussiate of soda, traces its origins to the accidental discovery of in 1704 by the Berlin paint maker Johann Jacob Diesbach, who, while working in the laboratory of Johann Conrad Dippel and attempting to produce a red using contaminated with animal blood together with iron salts, accidentally synthesized the blue pigment through the in situ formation of . This breakthrough introduced the complex to chemistry, though the compound itself remained unidentified for decades. , chemically ferric ferrocyanide, quickly gained popularity as a stable, affordable alternative to natural blue pigments like , revolutionizing dyeing and painting in by the early . The first intentional preparation of soluble ferrocyanide salts, including the sodium variant, occurred in 1752 when French chemist Pierre Joseph Macquer treated with (soda), yielding the yellow crystalline sodium ferrocyanide, alongside the analogous potassium salt from treatment. Macquer's work demonstrated that these "prussiates" were derived directly from the blue pigment, establishing their chemical relationship and earning the sodium compound its early name due to its yellow hue and Prussian heritage. In the late 18th and early 19th centuries, sodium ferrocyanide found initial applications in processes, where it served as a precursor for producing pigments on textiles and canvases, enabling vibrant, lightfast s that were commercially exported across by the 1820s. Additionally, by the early , the compound was employed in as a for detecting iron ions, forming the characteristic blue precipitate that confirmed the presence of ferric iron in solutions.

Naming conventions

Sodium ferrocyanide is systematically named tetrasodium hexacyanidoferrate(II) according to , reflecting its coordination structure with iron in the +2 and six ligands. Commonly, it is referred to as sodium ferrocyanide or yellow prussiate of soda, the latter being a historical designation originating from its relation to pigments. In the , it is designated as the E535, authorizing its use as an under regulated conditions. Synonyms include sodium hexacyanoferrate(II) and the Na₄[Fe(CN)₆], which emphasize its ionic composition as the tetrasodium salt of the hexacyanoferrate(II) anion. The prefix "ferro-" in its name distinguishes it from sodium ferricyanide, where "ferri-" denotes iron in the +3 , corresponding to the [Fe(CN)₆]³⁻ anion.

Production methods

Industrial synthesis

Sodium ferrocyanide is produced industrially on a large scale through a multi-step process that begins with the reaction of (HCN) with ferrous chloride (FeCl₂) in the presence of (Ca(OH)₂). This initial reaction forms an insoluble calcium ferrocyanide intermediate, which precipitates out of the aqueous solution under controlled temperature and pH conditions to facilitate separation. The balanced for this step is: 6HCN+FeCl2+2Ca(OH)2→Ca2[Fe(CN)6]+2HCl+4H2O6 \mathrm{HCN} + \mathrm{FeCl_2} + 2 \mathrm{Ca(OH)_2} \rightarrow \mathrm{Ca_2[Fe(CN)_6]} + 2 \mathrm{HCl} + 4 \mathrm{H_2O} (Note: The HCl is neutralized under controlled pH to prevent cyanide release.) The process requires careful handling of HCN due to its high toxicity and volatility, typically involving enclosed reactors and neutralization systems to minimize risks during synthesis. The calcium ferrocyanide intermediate is then converted to sodium ferrocyanide by treatment with (Na₂CO₃) or (NaCl) in an aqueous medium, displacing the calcium ions through a double decomposition reaction. With , the balanced equation is: Ca2[Fe(CN)6]+2Na2CO3→Na4[Fe(CN)6]+2CaCO3\mathrm{Ca_2[Fe(CN)_6]} + 2 \mathrm{Na_2CO_3} \rightarrow \mathrm{Na_4[Fe(CN)_6]} + 2 \mathrm{CaCO_3} ( precipitates for separation.) This step produces the soluble sodium salt, which is subsequently purified via filtration, concentration, and to yield the decahydrate form, Na₄[Fe(CN)₆]·10H₂O, commonly used commercially. Byproducts include calcium salts such as or , which are managed through to comply with environmental regulations. Global production of sodium ferrocyanide occurs at a scale of thousands of tons annually, with major hubs in and driven by demand in and chemical industries. Chinese producers dominate due to abundant access and cost efficiencies, while European facilities emphasize sustainable practices in HCN sourcing and .

Laboratory preparation

Sodium ferrocyanide can be prepared in the laboratory through small-scale methods that emphasize controlled conditions for high purity, often starting from more readily available precursors like sodium cyanide or ferricyanide salts. These approaches contrast with industrial processes by focusing on simple apparatus and minimal reagents, suitable for educational or research settings. A standard laboratory method involves the reaction of ferrous sulfate (FeSO₄) with sodium cyanide (NaCN) in aqueous solution under inert atmosphere to prevent oxidation. The balanced equation is: FeSO4+6NaCN→Na4[Fe(CN)6]+Na2SO4\mathrm{FeSO_4} + 6 \mathrm{NaCN} \rightarrow \mathrm{Na_4[Fe(CN)_6]} + \mathrm{Na_2SO_4} In practice, ferrous sulfate is dissolved in water, and a solution of NaCN is added slowly with stirring at room temperature or slightly elevated temperature (20-40°C). The mixture is maintained at neutral to slightly alkaline pH, and the product forms as a soluble complex. The solution is filtered to remove any impurities, and the sodium ferrocyanide is isolated by evaporation or cooling to promote crystallization of the decahydrate form. An alternative preparation utilizes the reduction of sodium ferricyanide (Na₃[Fe(CN)₆]) in an alkaline medium. Sodium ferricyanide is dissolved in a sodium hydroxide solution (0.1-1 M), and a stoichiometric amount of a reducing agent such as sodium dithionite (Na₂S₂O₄) is added gradually under stirring at room temperature or slightly elevated temperature (20-40°C). The reductant reduces the Fe(III) center to Fe(II), forming the ferrocyanide complex: \ce[Fe(CN)6]3−+e−−>[Fe(CN)6]4−\ce{ [Fe(CN)6]^{3-} + e^- -> [Fe(CN)6]^{4-} } (with dithionite acting as the ). Excess reductant is quenched with air oxidation or mild , and the product is recovered by after pH adjustment. This route is particularly useful when precursors are accessible. Following synthesis by either method, purification is achieved through recrystallization from hot . The crude product is dissolved in minimal boiling (solubility ~40 g/100 mL at 100°C), filtered hot to remove impurities, and allowed to cool slowly to , yielding colorless, efflorescent crystals of the decahydrate Na₄[Fe(CN)₆]·10H₂O. Multiple recrystallizations may be employed for analytical-grade purity, with yields typically 70-85% based on starting material. All laboratory preparations involving compounds require strict safety protocols due to the presence of ligands, which pose risks if released under acidic conditions or heating. Procedures should be conducted in a well-ventilated , with appropriate including gloves, goggles, and lab coat; any spills must be neutralized with solution before cleanup.

Applications

Food and anticaking uses

Sodium ferrocyanide functions primarily as an anticaking agent in table salt, sea salt, and iodized salt, helping to maintain free-flowing properties by preventing clumping due to moisture exposure. In the European Union, it is designated as food additive E535 and authorized for use in these salts at maximum levels of 20 mg/kg (20 ppm), with typical application levels ranging from 10 to 20 mg/kg. In the United States, it is approved as yellow prussiate of soda (sodium ferrocyanide decahydrate) under 21 CFR 172.490, permitting its use in salt at a maximum of 13 ppm (calculated as anhydrous sodium ferrocyanide), in amounts not exceeding those reasonably required to achieve the intended effect. Globally, it is recognized as safe for similar applications in food-grade salts by regulatory bodies including Health Canada (up to 13 ppm, calculated as anhydrous sodium ferrocyanide) and Food Standards Australia New Zealand (up to 50 mg/kg as total ferrocyanides). The mechanism of action involves the ferrocyanide ions adsorbing onto the surface of crystals, where their negatively charged, multivalent structure creates a charge mismatch that inhibits further and bridging, thus reducing agglomeration without altering the salt's , color, or . This physical interference with moisture-induced recrystallization ensures the salt remains pourable even in humid conditions. From a nutritional perspective, sodium ferrocyanide imparts no caloric value and contributes negligibly to overall sodium , as exposure from typical salt consumption is estimated at up to 0.009 mg/kg body weight per day—far below levels of toxicological concern. Its adoption as an in table salt began in the mid-20th century, with widespread industrial use emerging in the to improve handling and storage of refined salts.

Industrial and chemical applications

Sodium ferrocyanide serves as a key precursor in the production of pigment, formed by reacting with ferric (Fe(III)) salts to yield ferric , a deep blue compound widely used in paints, inks, dyes, and blueprint paper. This application has historically dominated its industrial consumption, though demand has shifted toward other sectors in modern usage. In industrial processes, sodium ferrocyanide functions as a stabilizer in the coatings of welding rods, enhancing arc stability during welding operations. It also acts as a mercaptan scavenger in petroleum refining, where it removes odorous sulfur compounds to purify fuels and improve product quality. Additionally, in mining, it serves as a depressant agent in ore flotation, selectively inhibiting the floatability of certain minerals like galena to facilitate separation of valuable ores. It is also employed as an anticaking agent in road salts to prevent clumping during storage and application. In , sodium ferrocyanide is employed in qualitative tests for ferric ions (Fe³⁺), producing a characteristic blue precipitate of upon reaction, which confirms the presence of iron in solutions. It finds further use in for toning, bleaching, and fixing processes, where it helps develop and stabilize images by forming complex precipitates. Other applications include for the removal of through complexation, forming insoluble ferrocyanide precipitates that sequester ions like and . In the industry, it aids tanning processes by stabilizing metal salts and improving hide penetration during treatment.

Safety and regulation

Toxicity and health effects

Sodium ferrocyanide demonstrates low , with an oral LD50 in rats reported between 1,600 and 3,200 mg/kg body weight. The Joint FAO/WHO Expert Committee on Food Additives (JECFA) established an (ADI) of 0–0.025 mg/kg body weight, reflecting its limited absorption and rapid excretion primarily via urine. In humans and animals, much of an oral dose is excreted unchanged, with half-lives around 135 minutes in adults and minimal systemic effects at low exposures. The compound's cyanide ligands are strongly coordinated to the iron(II) center, preventing significant dissociation and cyanide release at neutral or physiological pH. Studies in rats show that even at doses up to 10 mg/kg body weight, free cyanide levels remain below 0.06 mg/kg, far under thresholds for toxicity. However, under specific conditions such as exposure to strong acids or ultraviolet radiation, hydrogen cyanide gas can form, posing a potential hazard in industrial or laboratory mishandling. Health effects primarily involve the kidneys as the target organ, where high doses lead to accumulation, increased urinary cell excretion, and tubular damage in s, with a (NOAEL) of 4.4 mg/kg body weight per day in chronic studies. No evidence of was found across bacterial, mammalian cell, and assays, and long-term studies showed no carcinogenicity. In dogs and humans, renal function remained unaffected at tested doses up to 1,000 ppm over weeks. Main exposure routes are oral from food sources and during industrial handling, where dust may irritate the . Overdose, though uncommon given the low toxicity, could produce symptoms resembling , such as , , , and respiratory discomfort, but such incidents are rare due to poor . The European Food Safety Authority's 2018 re-evaluation affirmed no safety concerns at authorised levels, supporting a group ADI of 0.03 mg/kg body weight per day (expressed as ferrocyanide ) with exposures well below this threshold in typical diets.

Regulatory approvals and limits

In the , sodium ferrocyanide is authorized as a under the designation E535, as specified in Commission Regulation (EU) No 231/2012, which lays down specifications for food additives listed in Annexes II and III to Regulation (EC) No /2008. It is permitted exclusively as an in salt and salt substitutes, with a maximum level of 20 mg/kg (expressed as anhydrous sodium ferrocyanide). The (EFSA) reaffirmed its safety in a 2018 re-evaluation, concluding no concern at these authorized levels and establishing a group (ADI) of 0.03 mg/kg body weight per day for ferrocyanides (E 535–538), based on low and absence of genotoxic or carcinogenic effects. In the United States, sodium ferrocyanide, known as yellow prussiate of soda, is regulated by the (FDA) as a direct under 21 CFR 172.490, rather than GRAS status. It is approved solely as an in table salt or as an adjuvant in dendritic salt crystal production, limited to a maximum of 13 parts per million (ppm), calculated as sodium ferrocyanide, to achieve its intended effect. The monitors compliance through good manufacturing practices, with no specified upper limits beyond this for human food use, though a separate provision under 21 CFR 573.1020 allows up to 13 ppm in animal feed salt. The Joint FAO/WHO Expert Committee on Food Additives (JECFA) has evaluated sodium ferrocyanide multiple times, most notably establishing an ADI of 0–0.025 mg/kg body weight in 1974 (Meeting 18), based on its low toxicity and rapid excretion without accumulation. This assessment supports its global acceptance as INS 535, an international numbering system additive permitted in over 100 countries for anticaking purposes in salt, aligning with standards that emphasize safe use levels without numerical restrictions beyond . In , sodium ferrocyanide is listed among permitted s under Canada's Food Additive Regulations, approved for use in salt at a maximum of 13 ppm (anhydrous basis) when used singly, or in combination with not exceeding this total. and authorize it as INS 535 under the Australia New Zealand Food Standards Code (Schedule 15), primarily as an anticaking agent in salt, with no explicit numerical limit but subject to (as needed) conditions for efficacy. However, restrictions apply in organic standards; for instance, the Organic Materials Review Institute () prohibits it in certified organic foods due to its synthetic nature, while some international organic regimes, like the , allow its limited use up to 20 mg/kg in organic salt production. As of November 2025, no major regulatory changes have altered approvals for use, with the 2018 EFSA opinion remaining the benchmark in the . For , EFSA affirmations in 2023 and 2024 supported authorizations, including Commission Implementing Regulation () 2025/708, maintaining safety at proposed levels up to 80 mg/kg (as anion) in feed salt for all animal . Ongoing monitoring focuses on potential impurities, such as free , to ensure compliance with purity criteria (e.g., ≤10 mg/kg insoluble matter and limits under and JECFA specifications), though no widespread revisions have been implemented.

References

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