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Iron(II) sulfate
Encyclopedia
Iron sulfate (Br.E. iron(II) sulphate) or ferrous sulfate is the chemical compound
with the formula Fe
SO4
. Known since ancient times as copperas and as green vitriol, the blue-green heptahydrate is the most common form of this material. All iron sulfates dissolve in water to give the same aquo complex
[Fe(H2O)6]2+, which has octahedral molecular geometry
and is paramagnetic.
, and several of these forms exist in nature.
At 90 °C, the heptahydrate loses water to form the colorless monohydrate. In its anhydrous, crystalline state, its standard enthalpy of formation
is ΔfH°solid = -928.4 kJ·mol-1 and its standard molar entropy
is S°solid = 107.5 J·K−1·mol−1.
All mentioned mineral forms are connected with oxidation zones of Fe-bearing ore beds (pyrite
, marcasite
, chalcopyrite
, etc.) and related environments (like coal fire sites). Many undergo rapid dehydration and sometimes oxidation.
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.
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:
and the original green crystals are converted into a dirty-yellow anhydrous solid. When further heated, the anhydrous material releases sulfur dioxide
and white fumes of sulfur trioxide
, leaving a reddish-brown iron(III) oxide. Decomposition of iron(II) sulfate begins at about 480 °C.
Like all iron(II) salts, iron(II) sulfate is a reducing agent. For example, it reduces nitric acid to nitrogen oxide and chlorine to chloride:
Upon exposure to air, it oxidizes to form a corrosive brown-yellow coating of basic ferric sulfate, which is an adduct of ferric oxide and ferric sulfate:
, mostly for the reduction of chromate
in cement
.
anemia
. Constipation is a frequent and uncomfortable side effect associated with the administration of oral iron supplements. Stool softeners often are prescribed to prevent constipation.
s, most notably iron gall ink, which was used from the middle ages
until the end of the eighteenth century. It also finds use in wool
dye
ing 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 eighteenth century and remained in use well into the nineteenth 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. Sometimes, it is included in canned black olives as an artificial colorant.
Ferrous sulfate can also be used to stain concrete and some limestones and sandstones a yellowish rust color.
Woodworkers use ferrous sulfate solutions to color maple wood a silvery hue.
it is used for treating iron chlorosis. Although not as rapid-acting as iron chelate, its effects are longer-lasting. It can be mixed with compost and dug into to the soil to create a store which can last for years. It is also used as a lawn
conditioner, and moss killer.
In the second half of the 19th century, ferrous sulfate was also used as a photographic developer for collodion process
images.
Ferrous sulfate is sometimes added to the cooling water flowing through the brass tubes of a turbine condenser. It forms a corrosion-resistant, protective coating on the inside of the tube.
It has been applied for the purification of water by flocculation
and for phosphate
removal in municipal and industrial sewage
treatment plants to prevent eutrophication
of surface water bodies.
It is used as a traditional method of treating wood panel on houses, either alone, dissolved in water, or as a component of water-based paint.
Green vitriol is also a useful reagent in the identification of mushrooms.
Chemical compound
A chemical compound is a pure chemical substance consisting of two or more different chemical elements that can be separated into simpler substances by chemical reactions. Chemical compounds have a unique and defined chemical structure; they consist of a fixed ratio of atoms that are held together...
with the formula Fe
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...
SO4
Sulfate
In inorganic chemistry, a sulfate is a salt of sulfuric acid.-Chemical properties:...
. Known since ancient times as copperas and as green vitriol, the blue-green heptahydrate is the most common form of this material. All iron sulfates dissolve in water to give the same aquo complex
Metal aquo complex
Metal aquo complexes are coordination compounds containing metal ions with only water as a ligand. These complexes are the predominant species in aqueous solutions of many metal salts, such as metal nitrates, sulfates, and perchlorates. They have the general stoichiometry [Mn]z+. Their behavior...
[Fe(H2O)6]2+, which has octahedral molecular geometry
Octahedral molecular geometry
In chemistry, octahedral molecular geometry describes the shape of compounds where in six atoms or groups of atoms or ligands are symmetrically arranged around a central atom, defining the vertices of an octahedron...
and is paramagnetic.
Hydrates
Iron(II) sulfate can be found in various states of hydrationHydrate
Hydrate is a term used in inorganic chemistry and organic chemistry to indicate that a substance contains water. The chemical state of the water varies widely between hydrates, some of which were so labeled before their chemical structure was understood....
, and several of these forms exist in nature.
- FeSO4·H2O (mineral: szomolnokite, relatively rare)
- FeSO4·4H2O (mineral: rozeniteRozeniteRozenite is an uncommon hydrous iron sulfate mineral, Fe2+SO4•4.It occurs as a secondary mineral, formed under low humidity at less than 21 °C as an alteration of copper-free melanterite which is a post mine alteration product of pyrite or marcasite. It also occurs in lacustrine sediments and coal...
, white, relatively common, may be dehydratation product of melanterite) - FeSO4·5H2O (mineral: siderotilSiderotilSiderotil is an iron sulfate hydrate mineral with formula: FeSO4·5H2O which forms by the dehydration of melanterite. Copper commonly occurs substituting for iron in the structure. It typically occurs as fibrous or powdery encrustations, but may also occur as acicular triclinic crystals.It was...
, relatively rare) - FeSO4·6H2O (mineral: ferrohexahydrite, relatively rare)
- FeSO4·7H2O (mineral: melanteriteMelanteriteMelanterite is a mineral form of hydrous iron sulfate: FeSO4·7H2O. It is the iron analogue of the copper sulfate chalcanthite. It alters to siderotil by loss of water. It is a secondary sulfate mineral which forms from the oxidation of primary sulfide minerals such as pyrite and marcasite in the...
, blue-green, relatively common)
At 90 °C, the heptahydrate loses water to form the colorless monohydrate. In its anhydrous, crystalline state, its standard enthalpy of formation
Standard enthalpy change of formation
The standard enthalpy of formation or standard heat of formation of a compound is the change of enthalpy that accompanies the formation of 1 mole of a substance in its standard state from its constituent elements in their standard states...
is ΔfH°solid = -928.4 kJ·mol-1 and its standard molar entropy
Standard molar entropy
In chemistry, the standard molar entropy is the entropy content of one mole of substance, under standard conditions ....
is S°solid = 107.5 J·K−1·mol−1.
All mentioned mineral forms are connected with oxidation zones of Fe-bearing ore beds (pyrite
Pyrite
The mineral pyrite, or iron pyrite, is an iron sulfide with the formula FeS2. This mineral's metallic luster and pale-to-normal, brass-yellow hue have earned it the nickname fool's gold because of its resemblance to gold...
, marcasite
Marcasite
The mineral marcasite, sometimes called white iron pyrite, is iron sulfide with orthorhombic crystal structure. It is physically and crystallographically distinct from pyrite, which is iron sulfide with cubic crystal structure. Both structures do have in common that they contain the disulfide...
, chalcopyrite
Chalcopyrite
Chalcopyrite is a copper iron sulfide mineral that crystallizes in the tetragonal system. It has the chemical composition CuFeS2. It has a brassy to golden yellow color and a hardness of 3.5 to 4 on the Mohs scale. Its streak is diagnostic as green tinged black.On exposure to air, chalcopyrite...
, etc.) and related environments (like coal fire sites). Many undergo rapid dehydration and sometimes oxidation.
Production and reactions
In the finishing of steelSteel
Steel is an alloy that consists mostly of iron and has a carbon content between 0.2% and 2.1% by weight, depending on the grade. Carbon is the most common alloying material for iron, but various other alloying elements are used, such as manganese, chromium, vanadium, and tungsten...
prior to plating or coating, the steel sheet or rod is passed through pickling baths
Pickling (metal)
Tarnision is a metal surface treatment used to remove impurities, such as stains, inorganic contaminants, rust or scale from ferrous metals, copper, and aluminum alloys. A solution called Tarnision liquor, which contains strong acids, is used to remove the surface impurities...
of sulfuric acid. This treatment produces large quantities of iron(II) sulfate as a by-product.
- Fe + H2SO4 → FeSO4 + H2
Another source of large amounts results from the production of titanium dioxide
Titanium dioxide
Titanium dioxide, also known as titanium oxide or titania, is the naturally occurring oxide of titanium, chemical formula . When used as a pigment, it is called titanium white, Pigment White 6, or CI 77891. Generally it comes in two different forms, rutile and anatase. It has a wide range of...
from ilmenite
Ilmenite
Ilmenite is a weakly magnetic titanium-iron oxide mineral which is iron-black or steel-gray. It is a crystalline iron titanium oxide . It crystallizes in the trigonal system, and it has the same crystal structure as corundum and hematite....
via the sulfate process.
Ferrous sulfate is also prepared commercially by oxidation of pyrite:
- 2 FeS2 + 7 O2 + 2 H2O → 2 FeSO4 + 2 H2SO4
Reactions
On heating, iron(II) sulfate first loses its water of crystallizationWater of crystallization
In crystallography, water of crystallization or water of hydration or crystallization water is water that occurs in crystals. Water of crystallization is necessary for the maintenance of crystalline properties, but capable of being removed by sufficient heat...
and the original green crystals are converted into a dirty-yellow anhydrous solid. When further heated, the anhydrous material releases sulfur dioxide
Sulfur dioxide
Sulfur dioxide is the chemical compound with the formula . It is released by volcanoes and in various industrial processes. Since coal and petroleum often contain sulfur compounds, their combustion generates sulfur dioxide unless the sulfur compounds are removed before burning the fuel...
and white fumes of sulfur trioxide
Sulfur trioxide
Sulfur trioxide is the chemical compound with the formula SO3. In the gaseous form, this species is a significant pollutant, being the primary agent in acid rain. It is prepared on massive scales as a precursor to sulfuric acid.-Structure and bonding:Gaseous SO3 is a trigonal planar molecule of...
, leaving a reddish-brown iron(III) oxide. Decomposition of iron(II) sulfate begins at about 480 °C.
- 2 FeSO4 → Fe2O3 + SO2 + SO3
Like all iron(II) salts, iron(II) sulfate is a reducing agent. For example, it reduces nitric acid to nitrogen oxide and chlorine to chloride:
- 6 FeSO4 + 3 H2SO4 + 2 HNO3 → 3 Fe2(SO4)3 + 4 H2O + 2 NO
- 6 FeSO4 + 3 Cl2 → 2 Fe2(SO4)3 + 2 FeCl3
- 12 FeSO4 + 3 O2 → 4 Fe2(SO4)3 + 2 Fe2O3
Uses
Industrially, ferrous sulfate is mainly used as a precursor to other iron compounds. It is a reducing agentReducing agent
A reducing agent is the element or compound in a reduction-oxidation reaction that donates an electron to another species; however, since the reducer loses an electron we say it is "oxidized"...
, mostly for the reduction of chromate
Chromate
Chromate salts contain the chromate anion, CrO42−. Dichromate salts contain the dichromate anion, Cr2O72−. They are oxyanions of chromium in the oxidation state +6. They are moderately strong oxidizing agents.- Chemical properties :...
in cement
Cement
In the most general sense of the word, a cement is a binder, a substance that sets and hardens independently, and can bind other materials together. The word "cement" traces to the Romans, who used the term opus caementicium to describe masonry resembling modern concrete that was made from crushed...
.
Nutritional supplement
Together with other iron compounds, ferrous sulfate is used to fortify foods and to treat iron-deficiencyIron deficiency (medicine)
Iron deficiency is one of the most common of the nutritional deficiencies. Iron is present in all cells in the human body, and has several vital functions...
anemia
Anemia
Anemia is a decrease in number of red blood cells or less than the normal quantity of hemoglobin in the blood. However, it can include decreased oxygen-binding ability of each hemoglobin molecule due to deformity or lack in numerical development as in some other types of hemoglobin...
. Constipation is a frequent and uncomfortable side effect associated with the administration of oral iron supplements. Stool softeners often are prescribed to prevent constipation.
Colorant
Ferrous sulfate was used in the manufacture of inkInk
Ink is a liquid or paste that contains pigments and/or dyes and is used to color a surface to produce an image, text, or design. Ink is used for drawing and/or writing with a pen, brush, or quill...
s, most notably iron gall ink, which was used from the middle ages
Middle Ages
The Middle Ages is a periodization of European history from the 5th century to the 15th century. The Middle Ages follows the fall of the Western Roman Empire in 476 and precedes the Early Modern Era. It is the middle period of a three-period division of Western history: Classic, Medieval and Modern...
until the end of the eighteenth century. It also finds use in wool
Wool
Wool is the textile fiber obtained from sheep and certain other animals, including cashmere from goats, mohair from goats, qiviut from muskoxen, vicuña, alpaca, camel from animals in the camel family, and angora from rabbits....
dye
Dye
A dye is a colored substance that has an affinity to the substrate to which it is being applied. The dye is generally applied in an aqueous solution, and requires a mordant to improve the fastness of the dye on the fiber....
ing as a mordant
Mordant
A mordant is a substance used to set dyes on fabrics or tissue sections by forming a coordination complex with the dye which then attaches to the fabric or tissue. It may be used for dyeing fabrics, or for intensifying stains in cell or tissue preparations. The term mordant comes from the Latin...
. Harewood
Harewood (material)
Harewood is wood that has been treated with mineral substances to alter its color. Unlike dyeing processes, making harewood involves a chemical change, rather than simply superimposing color on the material....
, a material used in marquetry
Marquetry
Marquetry is the art and craft of applying pieces of veneer to a structure to form decorative patterns, designs or pictures. The technique may be applied to case furniture or even seat furniture, to decorative small objects with smooth, veneerable surfaces or to freestanding pictorial panels...
and parquetry
Parquetry
Parquetry is a geometric mosaic of wood pieces used for decorative effect. The two main uses of parquetry are as veneer patterns on furniture and block patterns for flooring. Parquet patterns are entirely geometrical and angular—squares, triangles, lozenges. The most popular parquet flooring...
since the 17th century, is also made using ferrous sulfate.
Two different methods for the direct application of indigo dye
Indigo dye
Indigo dye is an organic compound with a distinctive blue color . Historically, indigo was a natural dye extracted from plants, and this process was important economically because blue dyes were once rare. Nearly all indigo dye produced today — several thousand tons each year — is synthetic...
were developed in England in the eighteenth century and remained in use well into the nineteenth 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. Sometimes, it is included in canned black olives as an artificial colorant.
Ferrous sulfate can also be used to stain concrete and some limestones and sandstones a yellowish rust color.
Woodworkers use ferrous sulfate solutions to color maple wood a silvery hue.
Other uses
In horticultureHorticulture
Horticulture is the industry and science of plant cultivation including the process of preparing soil for the planting of seeds, tubers, or cuttings. Horticulturists work and conduct research in the disciplines of plant propagation and cultivation, crop production, plant breeding and genetic...
it is used for treating iron chlorosis. Although not as rapid-acting as iron chelate, its effects are longer-lasting. It can be mixed with compost and dug into to the soil to create a store which can last for years. It is also used as a lawn
Lawn
A lawn is an area of aesthetic and recreational land planted with grasses or other durable plants, which usually are maintained at a low and consistent height. Low ornamental meadows in natural landscaping styles are a contemporary option of a lawn...
conditioner, and moss killer.
In the second half of the 19th century, ferrous sulfate was also used as a photographic developer for collodion process
Collodion process
The collodion process is an early photographic process. It was introduced in the 1850s and by the end of that decade it had almost entirely replaced the first practical photographic process, the daguerreotype. During the 1880s the collodion process, in turn, was largely replaced by gelatin dry...
images.
Ferrous sulfate is sometimes added to the cooling water flowing through the brass tubes of a turbine condenser. It forms a corrosion-resistant, protective coating on the inside of the tube.
It has been applied for the purification of water by flocculation
Flocculation
Flocculation, in the field of chemistry, is a process wherein colloids come out of suspension in the form of floc or flakes by the addition of a clarifying agent. The action differs from precipitation in that, prior to flocculation, colloids are merely suspended in a liquid and not actually...
and for phosphate
Phosphate
A phosphate, an inorganic chemical, is a salt of phosphoric acid. In organic chemistry, a phosphate, or organophosphate, is an ester of phosphoric acid. Organic phosphates are important in biochemistry and biogeochemistry or ecology. Inorganic phosphates are mined to obtain phosphorus for use in...
removal in municipal and industrial sewage
Sewage
Sewage is water-carried waste, in solution or suspension, that is intended to be removed from a community. Also known as wastewater, it is more than 99% water and is characterized by volume or rate of flow, physical condition, chemical constituents and the bacteriological organisms that it contains...
treatment plants to prevent eutrophication
Eutrophication
Eutrophication or more precisely hypertrophication, is the movement of a body of water′s trophic status in the direction of increasing plant biomass, by the addition of artificial or natural substances, such as nitrates and phosphates, through fertilizers or sewage, to an aquatic system...
of surface water bodies.
It is used as a traditional method of treating wood panel on houses, either alone, dissolved in water, or as a component of water-based paint.
Green vitriol is also a useful reagent in the identification of mushrooms.
See also
- Iron(III) sulfateIron(III) sulfateIron sulfate , is the chemical compound with the formula Fe23, the sulfate of trivalent iron. Usually yellow, it is a rhombic crystalline salt and soluble in water at room temperature. It is used in dyeing as a mordant, and as a coagulant for industrial wastes. It is also used in pigments, and in...
, the other common simple sulfate of iron. - Mohr's saltMohr's saltAmmonium iron sulfate, or Mohr's Salt, is the inorganic compound with the formula 2Fe2·6H2O. Containing two different cations, Fe2+ and NH4+, it is classified as a double salt of ferrous sulfate and ammonium sulfate. It is a common laboratory reagent...
(Ammonium iron(II) sulfate), a common double salt of ammonium sulfateAmmonium sulfateAmmonium sulfate , 2SO4, is an inorganic salt with a number of commercial uses. The most common use is as a soil fertilizer. It contains 21% nitrogen as ammonium cations, and 24% sulfur as sulfate anions...
with iron(II) sulfate.