Iron(II) sulfate (British English: iron(II) sulphate) or ferrous sulfate denotes a range of salts with the formula FeSO4·xH2O. These compounds exist most commonly as the heptahydrate (x = 7) but several values for x are known. The hydrated form is used medically to treat or prevent iron deficiency, and also for industrial applications. Known since ancient times as copperas and as green vitriol (vitriol is an archaic name for sulfate), the blue-green heptahydrate (hydrate with 7 molecules of water) is the most common form of this material. All the iron(II) sulfates dissolve in water to give the same aquo complex [Fe(H2O)6]2+, which has octahedral molecular geometry and is paramagnetic. The name copperas dates from times when the copper(II) sulfate was known as blue copperas, and perhaps in analogy, iron(II) and zinc sulfate were known respectively as green and white copperas.[18]
Industrially, ferrous sulfate is mainly used as a precursor to other iron compounds. It is a reducing agent, and as such is useful for the reduction of chromateincement to less toxic Cr(III) compounds. Historically ferrous sulfate was used in the textile industry for centuries as a dye fixative. It is used historically to blacken leather and as a constituent of iron gall ink.[22] The preparation of sulfuric acid ('oil of vitriol') by the distillation of green vitriol (iron(II) sulfate) has been known for at least 700 years.
Iron(II) sulfate is sold as ferrous sulfate, a soil amendment[23] for lowering the pH of a high alkaline soil so that plants can access the soil's nutrients.[24]
Inhorticulture it is used for treating iron chlorosis.[25] Although not as rapid-acting as ferric EDTA, its effects are longer-lasting. It can be mixed with compost and dug into the soil to create a store which can last for years.[26] Ferrous sulfate can be used as a lawn conditioner.[26] It can also be used to eliminate silvery thread moss in golf course putting greens.[27]
Ferrous sulfate was used in the manufacture of inks, most notably iron gall ink, which was used from the Middle Ages until the end of the 18th century. Chemical tests made on the Lachish letters (c. 588–586 BCE) showed the possible presence of iron.[30] It is thought that oak galls and copperas may have been used in making the ink on those letters.[31] It also finds use in wooldyeing as a mordant. Harewood, a material used in marquetry and parquetry since the 17th century, is also made using ferrous sulfate.
Two different methods for the direct application of indigo dye were developed in England in the 18th century and remained in use well into the 19th century. One of these, known as china blue, involved iron(II) sulfate. After printing an insoluble form of indigo onto the fabric, the indigo was reduced to leuco-indigo in a sequence of baths of ferrous sulfate (with reoxidation to indigo in air between immersions). The china blue process could make sharp designs, but it could not produce the dark hues of other methods.
In the second half of the 1850s ferrous sulfate was used as a photographic developer for collodion process images.[32]
The tetrahydrate is stabilized when the temperature of aqueous solutions reaches 56.6 °C (133.9 °F). At 64.8 °C (148.6 °F) these solutions form both the tetrahydrate and monohydrate.[5]
Mineral forms are found in oxidation zones of iron-bearing ore beds, e.g. pyrite, marcasite, chalcopyrite, etc. They are also found in related environments, like coal fire sites. Many rapidly dehydrate and sometimes oxidize. Numerous other, more complex (either basic, hydrated, and/or containing additional cations) Fe(II)-bearing sulfates exist in such environments, with copiapite being a common example.[41]
In the finishing of steel prior to plating or coating, the steel sheet or rod is passed through pickling baths of sulfuric acid. This treatment produces large quantities of iron(II) sulfate as a by-product.[42]
Fe + H2SO4 → FeSO4 + H2
Another source of large amounts results from the production of titanium dioxide from ilmenite via the sulfate process.
Ferrous sulfate is also prepared commercially by oxidation of pyrite:[43]
2 FeS2 + 7 O2 + 2 H2O → 2 FeSO4 + 2 H2SO4
It can be produced by displacement of metals less reactive than Iron from solutions of their sulfate:
Its mild reducing power is of value in organic synthesis.[44] It is used as the iron catalyst component of Fenton's reagent.
Ferrous sulfate can be detected by the cerimetric method, which is the official method of the Indian Pharmacopoeia. This method includes the use of ferroin solution showing a red to light green colour change during titration.[45]
^World Health Organization (2019). World Health Organization model list of essential medicines: 21st list 2019. Geneva: World Health Organization. hdl:10665/325771. WHO/MVP/EMP/IAU/2019.06. License: CC BY-NC-SA 3.0 IGO.
^Koenig, Rich and Kuhns, Mike: Control of Iron Chlorosis in Ornamental and Crop Plants. (Utah State University, Salt Lake City, August 1996) p.3
^ abHandreck K (2002). Gardening Down Under: A Guide to Healthier Soils and Plants (2nd ed.). Collingwood, Victoria: CSIRO Publishing. pp. 146–47. ISBN0-643-06677-2.
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Fe2O3 + SO2 + SO3
