The sulfate or sulphate ion is a polyatomic

anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...

with the

empirical formula In chemistry, the empirical formula of a chemical compound is the simplest whole number ratio of atoms present in a compound. A simple example of this concept is that the empirical formula of sulfur monoxide, or SO, would simply be SO, as is t ...

. Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are

salt Salt is a mineral composed primarily of sodium chloride (NaCl), a chemical compound belonging to the larger class of salts; salt in the form of a natural crystalline mineral is known as rock salt or halite. Salt is present in vast quanti ...

s of sulfuric acid and many are prepared from that acid.

Spelling

"Sulfate" is the spelling recommended by

IUPAC The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...

, but "sulphate" was traditionally used in

British English British English (BrE, en-GB, or BE) is, according to Lexico, Oxford Dictionaries, "English language, English as used in Great Britain, as distinct from that used elsewhere". More narrowly, it can refer specifically to the English language in ...

Structure

The sulfate anion consists of a central

sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formul ...

atom Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons. Every solid, liquid, gas ...

surrounded by four equivalent

oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as we ...

atoms in a

tetrahedral In geometry, a tetrahedron (plural: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular faces, six straight edges, and four vertex corners. The tetrahedron is the simplest of all the ...

arrangement. The symmetry is the same as that of methane. The sulfur atom is in the +6

oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. ...

while the four oxygen atoms are each in the −2 state. The sulfate ion carries an overall charge of −2 and it is the

conjugate base A conjugate acid, within the Brønsted–Lowry acid–base theory, is a chemical compound formed when an acid donates a proton () to a base—in other words, it is a base with a hydrogen ion added to it, as in the reverse reaction it loses a ...

of the bisulfate (or hydrogensulfate) ion, , which is in turn the conjugate base of , sulfuric acid. Organic

sulfate ester Organosulfates are a class of organic compounds sharing a common functional group with the structure R-O-SO3−. The SO4 core is a sulfate group and the R group is any organic residue. All organosulfates are formally esters derived from alcohols ...

s, such as

dimethyl sulfate Dimethyl sulfate (DMS) is a chemical compound with formula (CH3O)2SO2. As the diester of methanol and sulfuric acid, its formula is often written as ( CH3)2 SO4 or Me2SO4, where CH3 or Me is methyl. Me2SO4 is mainly used as a methylating agen ...

, are covalent compounds and

ester In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ...

s of sulfuric acid. The

tetrahedral molecular geometry In a tetrahedral molecular geometry, a central atom is located at the center with four substituents that are located at the corners of a tetrahedron. The bond angles are cos−1(−) = 109.4712206...° ≈ 109.5° when all four substituents are ...

of the sulfate ion is as predicted by

VSEPR theory Valence shell electron pair repulsion (VSEPR) theory ( , ), is a model used in chemistry to predict the geometry of individual molecules from the number of electron pairs surrounding their central atoms. It is also named the Gillespie-Nyholm t ...

Bonding

The first description of the bonding in modern terms was by Gilbert Lewis in his groundbreaking paper of 1916 where he described the bonding in terms of electron octets around each atom, that is no double bonds and a

formal charge In chemistry, a formal charge (F.C. or q), in the covalent view of chemical bonding, is the charge assigned to an atom in a molecule, assuming that electrons in all chemical bonds are shared equally between atoms, regardless of relative electrone ...

of +2 on the sulfur atom. Later,

Linus Pauling Linus Carl Pauling (; February 28, 1901August 19, 1994) was an American chemist, biochemist, chemical engineer, peace activist, author, and educator. He published more than 1,200 papers and books, of which about 850 dealt with scientific top ...

used

valence bond theory In chemistry, valence bond (VB) theory is one of the two basic theories, along with molecular orbital (MO) theory, that were developed to use the methods of quantum mechanics to explain chemical bonding. It focuses on how the atomic orbitals of ...

to propose that the most significant resonance canonicals had two

pi bond In chemistry, pi bonds (π bonds) are covalent chemical bonds, in each of which two lobes of an orbital on one atom overlap with two lobes of an orbital on another atom, and in which this overlap occurs laterally. Each of these atomic orbita ...

s involving d orbitals. His reasoning was that the charge on sulfur was thus reduced, in accordance with his principle of electroneutrality. The S−O bond length of 149 pm is shorter than the bond lengths in sulfuric acid of 157 pm for S−OH. The double bonding was taken by Pauling to account for the shortness of the S−O bond. Pauling's use of d orbitals provoked a debate on the relative importance of

pi bonding In chemistry, pi bonds (π bonds) are covalent chemical bonds, in each of which two lobes of an orbital on one atom overlap with two lobes of an orbital on another atom, and in which this overlap occurs laterally. Each of these atomic orbitals ...

and bond polarity ( electrostatic attraction) in causing the shortening of the S−O bond. The outcome was a broad consensus that d orbitals play a role, but are not as significant as Pauling had believed. A widely accepted description involving pπ – dπ bonding was initially proposed by Durward William John Cruickshank. In this model, fully occupied p orbitals on oxygen overlap with empty sulfur d orbitals (principally the d_''z''² and d_{''x''²–''y''²}). However, in this description, despite there being some π character to the S−O bonds, the bond has significant ionic character. For sulfuric acid, computational analysis (with natural bond orbitals) confirms a clear positive charge on sulfur (theoretically +2.45) and a low 3d occupancy. Therefore, the representation with four single bonds is the optimal Lewis structure rather than the one with two double bonds (thus the Lewis model, not the Pauling model). In this model, the structure obeys the

octet rule The octet rule is a chemical rule of thumb that reflects the theory that main-group elements tend to bond in such a way that each atom has eight electrons in its valence shell, giving it the same electronic configuration as a noble gas. The ...

and the charge distribution is in agreement with the

electronegativity Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the ...

of the atoms. The discrepancy between the S−O bond length in the sulfate ion and the S−OH bond length in sulfuric acid is explained by donation of p-orbital electrons from the terminal S=O bonds in sulfuric acid into the antibonding S−OH orbitals, weakening them resulting in the longer bond length of the latter. However, the bonding representation of Pauling for sulfate and other main group compounds with oxygen is still a common way of representing the bonding in many textbooks. The apparent contradiction can be cleared if one realizes that the

covalent A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atom ...

double bonds in the Lewis structure in reality represent bonds that are strongly polarized by more than 90% towards the oxygen atom. On the other hand, in the structure with a dipolar bond, the charge is localized as a

lone pair In chemistry, a lone pair refers to a pair of valence electrons that are not shared with another atom in a covalent bondIUPAC '' Gold Book'' definition''lone (electron) pair''/ref> and is sometimes called an unshared pair or non-bonding pair. L ...

on the oxygen.

Preparation

Methods of preparing metal sulfates include: *treating metal, metal hydroxide, metal carbonate or metal oxide with sulfuric acid : : : *oxidation of metal

sulfide Sulfide (British English also sulphide) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to chemical compounds l ...

s or

sulfite Sulfites or sulphites are compounds that contain the sulfite ion (or the sulfate(IV) ion, from its correct systematic name), . The sulfite ion is the conjugate base of bisulfite. Although its acid (sulfurous acid) is elusive, its salts are wide ...

Properties

There are numerous examples of ionic sulfates, many of which are highly

soluble In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution. The extent of the solub ...

water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as ...

. Exceptions include

calcium sulfate Calcium sulfate (or calcium sulphate) is the inorganic compound with the formula CaSO4 and related hydrates. In the form of γ-anhydrite (the anhydrous form), it is used as a desiccant. One particular hydrate is better known as plaster of Paris, ...

, strontium sulfate, lead(II) sulfate, and

barium sulfate Barium sulfate (or sulphate) is the inorganic compound with the chemical formula Ba SO4. It is a white crystalline solid that is odorless and insoluble in water. It occurs as the mineral barite, which is the main commercial source of barium ...

, which are poorly soluble. Radium sulfate is the most insoluble sulfate known. The barium derivative is useful in the

gravimetric analysis Gravimetric analysis describes a set of methods used in analytical chemistry Analytical chemistry studies and uses instruments and methods to separate, identify, and quantify matter. In practice, separation, identification or quantificati ...

of sulfate: if one adds a solution of most barium salts, for instance

barium chloride Barium chloride is an inorganic compound with the formula Ba Cl2. It is one of the most common water-soluble salts of barium. Like most other water-soluble barium salts, it is white, highly toxic, and imparts a yellow-green coloration to a flame. ...

, to a solution containing sulfate ions, barium sulfate will precipitate out of solution as a whitish powder. This is a common laboratory test to determine if sulfate anions are present. The sulfate ion can act as a ligand attaching either by one oxygen (monodentate) or by two oxygens as either a

chelate Chelation is a type of bonding of ions and molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a single central metal atom. These ligands are ...

or a bridge. An example is the complex or the neutral metal complex where the sulfate ion is acting as a bidentate ligand. The metal–oxygen bonds in sulfate complexes can have significant covalent character.

Uses and occurrence

Commercial applications

Objectes de la Sala Horta i Marjal (27190138015)

Sulfates are widely used industrially. Major compounds include: *

Gypsum Gypsum is a soft sulfate mineral composed of calcium sulfate dihydrate, with the chemical formula . It is widely mined and is used as a fertilizer and as the main constituent in many forms of plaster, blackboard or sidewalk chalk, and dr ...

, the natural mineral form of hydrated

, is used to produce

plaster Plaster is a building material used for the protective or decorative coating of walls and ceilings and for moulding and casting decorative elements. In English, "plaster" usually means a material used for the interiors of buildings, while "r ...

. About 100 million tonnes per year are used by the construction industry. *

Copper sulfate Copper sulfate may refer to: * Copper(II) sulfate Copper(II) sulfate, also known as copper sulphate, is an inorganic compound with the chemical formula . It forms hydrates , where ''n'' can range from 1 to 7. The pentahydrate (''n'' = 5), a brigh ...

, a common algaecide, the more stable form ( ) is used for galvanic cells as electrolyte *

Iron(II) sulfate Iron(II) sulfate (British English: iron(II) sulphate) or ferrous sulfate denotes a range of salts with the formula Fe SO4·''x''H2O. These compounds exist most commonly as the hepta hydrate (''x'' = 7) but several values for x are kno ...

, a common form of iron in mineral supplements for humans, animals, and soil for plants *

Magnesium sulfate Magnesium sulfate or magnesium sulphate (in English-speaking countries other than the US) is a chemical compound, a salt with the formula , consisting of magnesium cations (20.19% by mass) and sulfate anions . It is a white crystalline solid, ...

(commonly known as

Epsom salts Magnesium sulfate or magnesium sulphate (in English-speaking countries other than the US) is a chemical compound, a salt with the formula , consisting of magnesium cations (20.19% by mass) and sulfate anions . It is a white crystalline solid, ...

), used in therapeutic baths * Lead(II) sulfate, produced on both plates during the discharge of a lead–acid battery *

Sodium laureth sulfate Sodium laureth sulfate (SLES), an accepted contraction of sodium lauryl ether sulfate (SLES), also called sodium alkylethersulfate, is an anionic detergent and surfactant found in many personal care products (soaps, shampoos, toothpaste, etc.) an ...

, or SLES, a common

detergent A detergent is a surfactant or a mixture of surfactants with cleansing properties when in dilute solutions. There are a large variety of detergents, a common family being the alkylbenzene sulfonates, which are soap-like compounds that are m ...

in shampoo formulations * Polyhalite, , used as

fertiliser A fertilizer (American English) or fertiliser (British English; see spelling differences) is any material of natural or synthetic origin that is applied to soil or to plant tissues to supply plant nutrients. Fertilizers may be distinct from ...

Occurrence in nature

Sulfate-reducing bacteria, some anaerobic microorganisms, such as those living in sediment or near deep sea thermal vents, use the reduction of sulfates coupled with the oxidation of organic compounds or hydrogen as an energy source for chemosynthesis.

History

Some sulfates were known to alchemists. The vitriol salts, from the Latin ''vitreolum'', glassy, were so-called because they were some of the first transparent crystals known. Green vitriol is

iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in ...

(II) sulfate heptahydrate, ; blue vitriol is

copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkish ...

(II) sulfate pentahydrate, and white vitriol is zinc sulfate heptahydrate, .

Alum An alum () is a type of chemical compound, usually a hydrated double sulfate salt of aluminium with the general formula , where is a monovalent cation such as potassium or ammonium. By itself, "alum" often refers to potassium alum, with t ...

, a double sulfate of

potassium Potassium is the chemical element with the symbol K (from Neo-Latin '' kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosp ...

and

aluminium Aluminium (aluminum in AmE, American and CanE, Canadian English) is a chemical element with the Symbol (chemistry), symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately o ...

with the formula , figured in the development of the chemical industry.

Environmental effects

Sulfates occur as microscopic particles (

aerosols An aerosol is a suspension (chemistry), suspension of fine solid particles or liquid Drop (liquid), droplets in air or another gas. Aerosols can be natural or Human impact on the environment, anthropogenic. Examples of natural aerosols are fog o ...

) resulting from fossil fuel and

biomass Biomass is plant-based material used as a fuel for heat or electricity production. It can be in the form of wood, wood residues, energy crops, agricultural residues, and waste from industry, farms, and households. Some people use the terms biom ...

combustion. They increase the acidity of the

atmosphere An atmosphere () is a layer of gas or layers of gases that envelop a planet, and is held in place by the gravity of the planetary body. A planet retains an atmosphere when the gravity is great and the temperature of the atmosphere is low. ...

and form acid rain. The

anaerobic Anaerobic means "living, active, occurring, or existing in the absence of free oxygen", as opposed to aerobic which means "living, active, or occurring only in the presence of oxygen." Anaerobic may also refer to: *Adhesive#Anaerobic, Anaerobic ad ...

sulfate-reducing bacteria '' Desulfovibrio desulfuricans'' and '' D. vulgaris'' can remove the black sulfate crust that often tarnishes buildings.

Main effects on climate

The main direct effect of sulfates on the climate involves the scattering of light, effectively increasing the Earth's

albedo Albedo (; ) is the measure of the diffuse reflection of solar radiation out of the total solar radiation and measured on a scale from 0, corresponding to a black body that absorbs all incident radiation, to 1, corresponding to a body that refl ...

. This effect is moderately well understood and leads to a cooling from the negative

radiative forcing Radiative forcing (or climate forcing) is the change in energy flux in the atmosphere caused by natural or anthropogenic factors of climate change as measured by watts / metre2. It is a scientific concept used to quantify and compare the exter ...

of about 0.4 W/m² relative to pre-industrial values, partially offsetting the larger (about 2.4 W/m²) warming effect of

greenhouse gas A greenhouse gas (GHG or GhG) is a gas that absorbs and emits radiant energy within the thermal infrared range, causing the greenhouse effect. The primary greenhouse gases in Earth's atmosphere are water vapor (), carbon dioxide (), met ...

es. The effect is strongly spatially non-uniform, being largest downstream of large industrial areas. The first indirect effect is also known as the Twomey effect. Sulfate aerosols can act as

cloud condensation nuclei Cloud condensation nuclei (CCNs), also known as cloud seeds, are small particles typically 0.2 µm, or one hundredth the size of a cloud droplet. CCNs are a unique subset of aerosols in the atmosphere on which water vapour condenses. This c ...

and this leads to greater numbers of smaller droplets of water. Many smaller droplets can diffuse light more efficiently than a few larger droplets. The second indirect effect is the further knock-on effects of having more cloud condensation nuclei. It is proposed that these include the suppression of drizzle, increased cloud height, to facilitate

cloud In meteorology, a cloud is an aerosol consisting of a visible mass of miniature liquid droplets, frozen crystals, or other particles suspended in the atmosphere of a planetary body or similar space. Water or various other chemicals may ...

formation at low humidities and longer cloud lifetime. Sulfate may also result in changes in the particle size distribution, which can affect the clouds radiative properties in ways that are not fully understood. Chemical effects such as the dissolution of soluble gases and slightly soluble substances, surface tension depression by organic substances and accommodation coefficient changes are also included in the second indirect effect. The indirect effects probably have a cooling effect, perhaps up to 2 W/m², although the uncertainty is very large. Sulfates are therefore implicated in

global dimming Global dimming is the reduction in the amount of global direct irradiance at the Earth's surface that has been observed since systematic measurements began in the 1950s. The effect varies by location, but worldwide it has been estimated to be of ...

. Sulfate is also the major contributor to stratospheric aerosol formed by oxidation of sulfur dioxide injected into the stratosphere by impulsive volcanoes such as the

1991 eruption of Mount Pinatubo The 1991 eruption of Mount Pinatubo in the Philippines' Luzon Volcanic Arc was the second-largest volcanic eruption of the 20th century, behind only the 1912 eruption of Novarupta in Alaska. Eruptive activity began on April 2 as a series of ...

in the

Philippines The Philippines (; fil, Pilipinas, links=no), officially the Republic of the Philippines ( fil, Republika ng Pilipinas, links=no), * bik, Republika kan Filipinas * ceb, Republika sa Pilipinas * cbk, República de Filipinas * hil, Republ ...

. This aerosol exerts a cooling effect on climate during its 1-2 year lifetime in the stratosphere.

Hydrogensulfate (bisulfate)

The hydrogensulfate ion (), also called the bisulfate ion, is the

of sulfuric acid (). Sulfuric acid is classified as a strong acid; in aqueous solutions it ionizes completely to form

hydronium In chemistry, hydronium (hydroxonium in traditional British English) is the common name for the aqueous cation , the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid is di ...

() and hydrogensulfate () ions. In other words, the sulfuric acid behaves as a Brønsted–Lowry acid and is deprotonated to form hydrogensulfate ion. Hydrogensulfate has a

valency Valence or valency may refer to: Science * Valence (chemistry), a measure of an element's combining power with other atoms * Degree (graph theory), also called the valency of a vertex in graph theory * Valency (linguistics), aspect of verbs re ...

of 1. An example of a salt containing the ion is sodium bisulfate, . In dilute solutions the hydrogensulfate ions also dissociate, forming more hydronium ions and sulfate ions ().

Other sulfur oxyanions

Notes

References

{{Sulfates Particulates Sulfur oxyanions