Calcium sulfate (or calcium sulphate) is the inorganic compound with the formula CaSO
4 and related
hydrate
In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
s. In the form of γ-
anhydrite
Anhydrite, or anhydrous calcium sulfate, is a mineral with the chemical formula CaSO4. It is in the orthorhombic crystal system, with three directions of perfect cleavage parallel to the three planes of symmetry. It is not isomorphous with the ...
(the
anhydrous
A substance is anhydrous if it contains no water. Many processes in chemistry can be impeded by the presence of water; therefore, it is important that water-free reagents and techniques are used. In practice, however, it is very difficult to achi ...
form), it is used as a
desiccant
A desiccant is a hygroscopic substance that is used to induce or sustain a state of dryness (desiccation) in its vicinity; it is the opposite of a humectant. Commonly encountered pre-packaged desiccants are solids that absorb water. Desiccants ...
. One particular hydrate is better known as
plaster of Paris
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 "re ...
, and another occurs naturally as the mineral
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 drywa ...
. It has many uses in industry. All forms are white solids that are poorly soluble in water.
[Franz Wirsching "Calcium Sulfate" in Ullmann's Encyclopedia of Industrial Chemistry, 2012 Wiley-VCH, Weinheim. ] Calcium sulfate causes
permanent hardness
Hard water is water that has high mineral content (in contrast with "soft water"). Hard water is formed when water percolates through deposits of limestone, chalk or gypsum, which are largely made up of calcium and magnesium carbonates, bic ...
in water.
Hydration states and crystallographic structures
The compound exists in three levels of hydration corresponding to different crystallographic structures and to minerals:
* (
anhydrite
Anhydrite, or anhydrous calcium sulfate, is a mineral with the chemical formula CaSO4. It is in the orthorhombic crystal system, with three directions of perfect cleavage parallel to the three planes of symmetry. It is not isomorphous with the ...
): anhydrous state. The structure is related to that of
zirconium orthosilicate
Zircon () is a mineral belonging to the group of nesosilicates and is a source of the metal zirconium. Its chemical name is zirconium(IV) silicate, and its corresponding chemical formula is Zirconium, ZrSilicate, SiO4. An empirical formula sh ...
(zircon): is 8-coordinate, is tetrahedral, O is 3-coordinate.
* (
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 drywa ...
and
selenite (mineral)
Selenite, satin spar, desert rose, gypsum flower are crystal habit varieties of the mineral gypsum.
All varieties of gypsum, including selenite and alabaster, are composed of calcium sulfate dihydrate (meaning that it has two molecules of w ...
): dihydrate.
* (
bassanite
Bassanite is a calcium sulfate mineral with formula CaSO4· H2O or 2CaSO4·H2O. In other words it has half a water molecule per CaSO4 unit, hence its synonym ''calcium sulfate hemihydrate''.
Bassanite was first described in 1910 for an occurrenc ...
): hemihydrate, also known as
plaster of Paris
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 "re ...
. Specific hemihydrates are sometimes distinguished: α-hemihydrate and β-hemihydrate.
[Taylor H.F.W. (1990) ''Cement Chemistry''. Academic Press, , pp. 186-187.]
Uses
The main use of calcium sulfate is to produce plaster of Paris and
stucco
Stucco or render is a construction material made of aggregates, a binder, and water. Stucco is applied wet and hardens to a very dense solid. It is used as a decorative coating for walls and ceilings, exterior walls, and as a sculptural and a ...
. These applications exploit the fact that calcium sulfate which has been powdered and
calcined
Calcination refers to thermal treatment of a solid chemical compound (e.g. mixed carbonate ores) whereby the compound is raised to high temperature without melting under restricted supply of ambient oxygen (i.e. gaseous O2 fraction of air), gener ...
forms a moldable paste upon
hydration Hydration may refer to:
* Hydrate, a substance that contains water
* Hydration enthalpy, energy released through hydrating a substance
* Hydration reaction, a chemical addition reaction where a hydroxyl group and proton are added to a compound
* ...
and hardens as crystalline calcium sulfate dihydrate. It is also convenient that calcium sulfate is poorly
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 solubi ...
in water and does not readily dissolve in contact with water after its solidification.
Hydration and dehydration reactions
With judicious heating, gypsum converts to the partially dehydrated mineral called
bassanite
Bassanite is a calcium sulfate mineral with formula CaSO4· H2O or 2CaSO4·H2O. In other words it has half a water molecule per CaSO4 unit, hence its synonym ''calcium sulfate hemihydrate''.
Bassanite was first described in 1910 for an occurrenc ...
or
plaster of Paris
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 "re ...
. This material has the formula CaSO
4·(''n''H
2O), where 0.5 ≤ ''n'' ≤ 0.8.
[ Temperatures between are required to drive off the water within its structure. The details of the temperature and time depend on ambient humidity. Temperatures as high as are used in industrial calcination, but at these temperatures γ-anhydrite begins to form. The heat energy delivered to the gypsum at this time (the heat of hydration) tends to go into driving off water (as water vapor) rather than increasing the temperature of the mineral, which rises slowly until the water is gone, then increases more rapidly. The equation for the partial dehydration is:
: CaSO4 · 2 H2O → CaSO4 · H2O + H2O↑
The ]endothermic
In thermochemistry, an endothermic process () is any thermodynamic process with an increase in the enthalpy (or internal energy ) of the system.Oxtoby, D. W; Gillis, H.P., Butler, L. J. (2015).''Principle of Modern Chemistry'', Brooks Cole. ...
property of this reaction is relevant to the performance of drywall
Drywall (also called plasterboard, dry lining, wallboard, sheet rock, gypsum board, buster board, custard board, and gypsum panel) is a panel made of calcium sulfate dihydrate (gypsum), with or without additives, typically extruded between thic ...
, conferring fire resistance to residential and other structures. In a fire, the structure behind a sheet of drywall will remain relatively cool as water is lost from the gypsum, thus preventing (or substantially retarding) damage to the framing (through combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
of wood
Wood is a porous and fibrous structural tissue found in the stems and roots of trees and other woody plants. It is an organic materiala natural composite of cellulose fibers that are strong in tension and embedded in a matrix of lignin ...
members or loss of strength of steel
Steel is an alloy made up of iron with added carbon to improve its strength and fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that are corrosion- and oxidation-resistan ...
at high temperatures) and consequent structural collapse. But at higher temperatures, calcium sulfate will release oxygen and act as an oxidizing agent
An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or " accepts"/"receives" an electron from a (called the , , or ). In other words, an oxi ...
. This property is used in aluminothermy
Aluminothermic reactions are exothermic chemical reactions using aluminum as the reducing agent at high temperature. The process is industrially useful for production of alloys of iron. The most prominent example is the thermite reaction between i ...
. In contrast to most minerals, which when rehydrated simply form liquid or semi-liquid pastes, or remain powdery, calcined gypsum has an unusual property: when mixed with water at normal (ambient) temperatures, it quickly reverts chemically to the preferred dihydrate form, while physically "setting" to form a rigid and relatively strong gypsum crystal lattice:
:CaSO4 · H2O + H2O → CaSO4 · 2 H2O
This reaction is exothermic
In thermodynamics, an exothermic process () is a thermodynamic process or reaction that releases energy from the system to its surroundings, usually in the form of heat, but also in a form of light (e.g. a spark, flame, or flash), electricity ...
and is responsible for the ease with which gypsum can be cast into various shapes including sheets (for drywall
Drywall (also called plasterboard, dry lining, wallboard, sheet rock, gypsum board, buster board, custard board, and gypsum panel) is a panel made of calcium sulfate dihydrate (gypsum), with or without additives, typically extruded between thic ...
), sticks (for blackboard chalk), and molds (to immobilize broken bones, or for metal casting). Mixed with polymers, it has been used as a bone repair cement. Small amounts of calcined gypsum are added to earth to create strong structures directly from cast earth, an alternative to adobe
Adobe ( ; ) is a building material made from earth and organic materials. is Spanish for '' mudbrick''. In some English-speaking regions of Spanish heritage, such as the Southwestern United States, the term is used to refer to any kind of ...
(which loses its strength when wet). The conditions of dehydration can be changed to adjust the porosity of the hemihydrate, resulting in the so-called α- and β-hemihydrates (which are more or less chemically identical).
On heating to , the nearly water-free form, called γ-anhydrite (CaSO4·''n''H2O where ''n'' = 0 to 0.05) is produced. γ-Anhydrite reacts slowly with water to return to the dihydrate state, a property exploited in some commercial desiccant
A desiccant is a hygroscopic substance that is used to induce or sustain a state of dryness (desiccation) in its vicinity; it is the opposite of a humectant. Commonly encountered pre-packaged desiccants are solids that absorb water. Desiccants ...
s. On heating above 250 °C, the completely anhydrous form called β-anhydrite or "natural" anhydrite
Anhydrite, or anhydrous calcium sulfate, is a mineral with the chemical formula CaSO4. It is in the orthorhombic crystal system, with three directions of perfect cleavage parallel to the three planes of symmetry. It is not isomorphous with the ...
is formed. Natural anhydrite does not react with water, even over geological timescales, unless very finely ground.
The variable composition of the hemihydrate and γ-anhydrite, and their easy inter-conversion, is due to their nearly identical crystal structures containing "channels" that can accommodate variable amounts of water, or other small molecules such as methanol
Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical and the simplest aliphatic alcohol, with the formula C H3 O H (a methyl group linked to a hydroxyl group, often abbreviated as MeOH). It is ...
.
Food industry
The calcium sulfate hydrates are used as a coagulant in products such as tofu
Tofu (), also known as bean curd in English, is a food prepared by coagulating soy milk and then pressing the resulting curds into solid white blocks of varying softness; it can be ''silken'', ''soft'', ''firm'', ''extra firm'' or ''super f ...
.
For the FDA, it is permitted in Cheese and Related Cheese Products; Cereal Flours; Bakery Products; Frozen Desserts; Artificial Sweeteners for Jelly & Preserves; Condiment Vegetables; and Condiment Tomatoes and some candies.
It is known in the E number
E numbers ("E" stands for "Europe") are codes for substances used as food additives, including those found naturally in many foods such as vitamin C, for use within the European Union (EU) and European Free Trade Association (EFTA). Commonly ...
series as E516, and the UN's FAO knows it as a firming agent, a flour treatment agent, a sequestrant, and a leavening agent.[
]
Dentistry
Calcium sulfate has a long history of use in dentistry. It has been used in bone regeneration as a graft material and graft binder (or extender) and as a barrier in guided bone tissue regeneration. It is a biocompatible material and is completely resorbed following implantation. It does not evoke a significant host response and creates a calcium-rich milieu in the area of implantation.
Other uses
When sold at the anhydrous state as a desiccant with a color-indicating agent under the name Drierite
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 ...
, it appears blue (anhydrous) or pink (hydrated) due to impregnation with cobalt(II) chloride
Cobalt(II) chloride is an inorganic compound of cobalt and chlorine, with the formula . The compound forms several hydrates ·''n'', for ''n'' = 1, 2, 6, and 9. Claims of the formation of tri- and tetrahydrates have not been confirmed.M. T. Saug ...
, which functions as a moisture indicator.
Up to the 1970s, commercial quantities of sulfuric acid
Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular fo ...
were produced in Whitehaven
Whitehaven is a town and port on the English north west coast and near to the Lake District National Park in Cumbria, England. Historically in Cumberland, it lies by road south-west of Carlisle and to the north of Barrow-in-Furness. It i ...
(Cumbria
Cumbria ( ) is a ceremonial and non-metropolitan county in North West England, bordering Scotland. The county and Cumbria County Council, its local government, came into existence in 1974 after the passage of the Local Government Act 1972. ...
, UK) from anhydrous calcium sulfate. Upon being mixed with shale
Shale is a fine-grained, clastic sedimentary rock formed from mud that is a mix of flakes of clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4) and tiny fragments (silt-sized particles) of other minerals, especiall ...
or marl
Marl is an earthy material rich in carbonate minerals, clays, and silt. When hardened into rock, this becomes marlstone. It is formed in marine or freshwater environments, often through the activities of algae.
Marl makes up the lower part ...
, and roasted, the sulfate liberates sulfur dioxide
Sulfur dioxide (IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic a ...
gas, a precursor in sulfuric acid
Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular fo ...
production, the reaction also produces calcium silicate
Calcium silicate is the chemical compound Ca2SiO4, also known as calcium orthosilicate and is sometimes formulated as 2CaO·SiO2. It is also referred to by the shortened trade name Cal-Sil or Calsil. It occurs naturally as the mineral larnite. ...
, a mineral phase essential in cement
A cement is a binder, a chemical substance used for construction that sets, hardens, and adheres to other materials to bind them together. Cement is seldom used on its own, but rather to bind sand and gravel (aggregate) together. Cement mixe ...
clinker
Clinker may refer to:
*Clinker (boat building), construction method for wooden boats
*Clinker (waste), waste from industrial processes
*Clinker (cement), a kilned then quenched cement product
* ''Clinkers'' (album), a 1978 album by saxophonist St ...
production.
: 2 CaSO4 + 2 SiO2 → 2 CaSiO3 + 2 SO2 + O2
The plant made sulfuric acid by the “Anhydrite Process” , in which cement clinker
200px, Typical clinker nodules
200px, Hot clinker
Cement clinker is a solid material produced in the manufacture of Portland cement as an intermediary product. Clinker occurs as lumps or nodules, usually to in diameter. It is produced by sinte ...
itself was a by-product. In this process, anhydrite (calcium sulfate) replaces limestone in a cement rawmix, and under reducing conditions, sulfur dioxide
Sulfur dioxide (IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic a ...
is evolved instead of carbon dioxide
Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is t ...
. The sulfur dioxide is converted to sulfuric acid by the Contact Process
The contact process is the current method of producing sulfuric acid in the high concentrations needed for industrial processes. Platinum was originally used as the catalyst for this reaction; however, as it is susceptible to reacting with arsenic ...
using a vanadium pentoxide
Vanadium(V) oxide (''vanadia'') is the inorganic compound with the formula V2 O5. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because o ...
catalyst
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
.
CaSO4 + 2 C → CaS + 2CO2
3 CaSO4 + CaS + 2 SiO2 → 2 Ca2SiO4 (belite
Belite is an industrial mineral important in Portland cement manufacture. Its main constituent is dicalcium silicate, Ca2SiO4, sometimes formulated as 2 CaO · SiO2 (C2S in cement chemist notation).
Etymology
The name was given by Törnebohm in ...
) + 4 SO2
3 CaSO4 + CaS → 4 CaO + 4 SO2
Ca2SiO4 + CaO → Ca3OSiO4 (alite
Alite is an impure form of tricalcium silicate, , sometimes formulated as ( in cement chemist notation), typically with 3-4% of substituent oxides. It is the major, and characteristic, phase in Portland cement. The name was given by Törnebohm i ...
)
2 SO2 + O2 → 2 SO3
(in the presence of the catalyst
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
vanadium pentoxide
Vanadium(V) oxide (''vanadia'') is the inorganic compound with the formula V2 O5. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because o ...
)
SO3 + H2O → H2SO4
Because of its use in an expanding niche market, the Whitehaven plant continued to expand in a manner not shared by the other Anhydrite Process plants. The anhydrite mine opened on 11/1/1955, and the acid plant started on 14/11/1955. For a while in the early 1970s, it became the largest sulfuric acid plant in the UK, making about 13% of national production, and it was by far the largest Anhydrite Process plant ever built.
Production and occurrence
The main sources of calcium sulfate are naturally occurring 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 drywa ...
and anhydrite
Anhydrite, or anhydrous calcium sulfate, is a mineral with the chemical formula CaSO4. It is in the orthorhombic crystal system, with three directions of perfect cleavage parallel to the three planes of symmetry. It is not isomorphous with the ...
, which occur at many locations worldwide as evaporite
An evaporite () is a water- soluble sedimentary mineral deposit that results from concentration and crystallization by evaporation from an aqueous solution. There are two types of evaporite deposits: marine, which can also be described as ocean ...
s. These may be extracted by open-cast quarrying or by deep mining. World production of natural gypsum is around 127 million tonnes per annum.
In addition to natural sources, calcium sulfate is produced as a by-product in a number of processes:
*In flue-gas desulfurization
Flue-gas desulfurization (FGD) is a set of technologies used to remove sulfur dioxide () from exhaust flue gases of fossil-fuel power plants, and from the emissions of other sulfur oxide emitting processes such as waste incineration.
Methods
...
, exhaust gases from fossil-fuel power station
A fossil fuel power station is a thermal power station which burns a fossil fuel, such as coal or natural gas, to produce electricity. Fossil fuel power stations have machinery to convert the heat energy of combustion into mechanical energy, wh ...
s and other processes (e.g. cement manufacture) are scrubbed to reduce their sulfur oxide content, by injecting finely ground limestone
Limestone ( calcium carbonate ) is a type of carbonate sedimentary rock which is the main source of the material lime. It is composed mostly of the minerals calcite and aragonite, which are different crystal forms of . Limestone forms w ...
:
:
Related sulfur-trapping methods use lime and some produces an impure calcium sulfite, which oxidizes on storage to calcium sulfate.
*In the production of phosphoric acid
Phosphoric acid (orthophosphoric acid, monophosphoric acid or phosphoric(V) acid) is a colorless, odorless phosphorus-containing solid, and inorganic compound with the chemical formula . It is commonly encountered as an 85% aqueous solution, w ...
from phosphate rock
Phosphorite, phosphate rock or rock phosphate is a non-detrital sedimentary rock that contains high amounts of phosphate minerals. The phosphate content of phosphorite (or grade of phosphate rock) varies greatly, from 4% to 20% phosphorus pento ...
, calcium phosphate is treated with sulfuric acid and calcium sulfate precipitates. The product, called phosphogypsum
Phosphogypsum (PG) is the calcium sulfate hydrate formed as a by-product of the production of fertilizer from phosphate rock. It is mainly composed of gypsum (CaSO4·2H2O). Although gypsum is a widely used material in the construction industry, p ...
is often contaminated with impurities making its use uneconomic.
*In the production of hydrogen fluoride
Hydrogen fluoride (fluorane) is an inorganic compound with the chemical formula . This colorless gas or liquid is the principal industrial source of fluorine, often as an aqueous solution called hydrofluoric acid. It is an important feedstock ...
, calcium fluoride
Calcium fluoride is the inorganic compound of the elements calcium and fluorine with the formula CaF2. It is a white insoluble solid. It occurs as the mineral fluorite (also called fluorspar), which is often deeply coloured owing to impurities.
...
is treated with sulfuric acid, precipitating calcium sulfate.
*In the refining of zinc
Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...
, solutions of zinc sulfate
Zinc sulfate is an inorganic compound. It is used as a dietary supplement to treat zinc deficiency and to prevent the condition in those at high risk. Side effects of excess supplementation may include abdominal pain, vomiting, headache, and ti ...
are treated with hydrated lime
Calcium hydroxide (traditionally called slaked lime) is an inorganic compound with the chemical formula Ca( OH)2. It is a colorless crystal or white powder and is produced when quicklime (calcium oxide) is mixed or slaked with water. It has ma ...
to co-precipitate heavy metals such as barium
Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element.
Th ...
.
*Calcium sulfate can also be recovered and re-used from scrap drywall at construction sites.
These precipitation processes tend to concentrate radioactive elements in the calcium sulfate product. This issue is particular with the phosphate by-product, since phosphate ores naturally contain uranium
Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
and its decay product
In nuclear physics, a decay product (also known as a daughter product, daughter isotope, radio-daughter, or daughter nuclide) is the remaining nuclide left over from radioactive decay. Radioactive decay often proceeds via a sequence of steps ( ...
s such as radium-226, lead-210 and polonium-210
Polonium-210 (210Po, Po-210, historically radium F) is an isotope of polonium. It undergoes alpha decay to stable 206Pb with a half-life of 138.376 days (about months), the longest half-life of all naturally occurring polonium isotopes. First ...
. Extraction of uranium from phosphorus ores can be economical on its own depending on prices on the uranium market
The uranium market, like all commodity markets, has a history of volatility, moving with the standard forces of supply and demand as well as geopolitical pressures. It has also evolved particularities of its own in response to the unique nature and ...
or the separation of uranium can be mandated by environmental legislation and its sale is used to recover part of the cost of the process.
Calcium sulfate is also a common component of fouling
Fouling is the accumulation of unwanted material on solid surfaces. The fouling materials can consist of either living organisms (biofouling) or a non-living substance (inorganic or organic). Fouling is usually distinguished from other surf ...
deposits in industrial heat exchangers, because its solubility decreases with increasing temperature (see the specific section on the retrograde solubility).
Retrograde solubility
The dissolution of the different crystalline phases of calcium sulfate in water is exothermic
In thermodynamics, an exothermic process () is a thermodynamic process or reaction that releases energy from the system to its surroundings, usually in the form of heat, but also in a form of light (e.g. a spark, flame, or flash), electricity ...
and releases heat
In thermodynamics, heat is defined as the form of energy crossing the boundary of a thermodynamic system by virtue of a temperature difference across the boundary. A thermodynamic system does not ''contain'' heat. Nevertheless, the term is ...
(decrease in Enthalpy
Enthalpy , a property of a thermodynamic system, is the sum of the system's internal energy and the product of its pressure and volume. It is a state function used in many measurements in chemical, biological, and physical systems at a constant ...
: ΔH < 0). As an immediate consequence, to proceed, the dissolution reaction needs to evacuate this heat that can be considered as a product of reaction. If the system is cooled, the dissolution equilibrium will evolve towards the right according to the Le Chatelier principle and calcium sulfate will dissolve more easily. Thus the solubility of calcium sulfate increases as the temperature decreases and vice versa. If the temperature of the system is raised, the reaction heat cannot dissipate and the equilibrium will regress towards the left according to Le Chatelier principle. The solubility of calcium sulfate decreases as temperature increases. This counter-intuitive solubility behaviour is called retrograde solubility. It is less common than for most of the salts whose dissolution reaction is endothermic
In thermochemistry, an endothermic process () is any thermodynamic process with an increase in the enthalpy (or internal energy ) of the system.Oxtoby, D. W; Gillis, H.P., Butler, L. J. (2015).''Principle of Modern Chemistry'', Brooks Cole. ...
(i.e., the reaction consumes heat: increase in Enthalpy
Enthalpy , a property of a thermodynamic system, is the sum of the system's internal energy and the product of its pressure and volume. It is a state function used in many measurements in chemical, biological, and physical systems at a constant ...
: ΔH > 0) and whose solubility increases with temperature. Another calcium compound, calcium hydroxide
Calcium hydroxide (traditionally called slaked lime) is an inorganic compound with the chemical formula Ca( OH)2. It is a colorless crystal or white powder and is produced when quicklime (calcium oxide) is mixed or slaked with water. It has ma ...
(Ca(OH)2, portlandite
Portlandite is a hydroxide-bearing mineral typically included in the oxide mineral class. It is the naturally occurring form of calcium hydroxide (Ca(OH)2) and the calcium analogue of brucite (Mg(OH)2).
Occurrence
Portlandite occurs in a variety ...
) also exhibits a retrograde solubility for the same thermodynamic reason: because its dissolution reaction is also exothermic and releases heat. So, to dissolve the maximum amount of calcium sulfate or calcium hydroxide in water, it is necessary to cool the solution down close to its freezing point instead of increasing its temperature.
The retrograde solubility of calcium sulfate is also responsible for its precipitation in the hottest zone of heating systems and for its contribution to the formation of scale in boiler
A boiler is a closed vessel in which fluid (generally water) is heated. The fluid does not necessarily boil. The heated or vaporized fluid exits the boiler for use in various processes or heating applications, including water heating, central ...
s along with the precipitation of calcium carbonate whose solubility
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 solubi ...
also decreases when CO2 degasses from hot water or can escape out of the system.
On planet Mars
2011 findings by the ''Opportunity'' rover on the planet Mars
Mars is the fourth planet from the Sun and the second-smallest planet in the Solar System, only being larger than Mercury. In the English language, Mars is named for the Roman god of war. Mars is a terrestrial planet with a thin at ...
show a form of calcium sulfate in a vein on the surface. Images suggest the mineral is 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 drywa ...
.
See also
* Calcium sulfate (data page)
*Alabaster
Alabaster is a mineral or rock that is soft, often used for carving, and is processed for plaster powder. Archaeologists and the stone processing industry use the word differently from geologists. The former use it in a wider sense that include ...
*Anhydrite
Anhydrite, or anhydrous calcium sulfate, is a mineral with the chemical formula CaSO4. It is in the orthorhombic crystal system, with three directions of perfect cleavage parallel to the three planes of symmetry. It is not isomorphous with the ...
*''Bathybius haeckelii
''Bathybius haeckelii'' was a substance that British biologist Thomas Henry Huxley discovered and initially believed to be a form of primordial matter, a source of all organic life. He later admitted his mistake when it proved to be just the prod ...
''
*Chalk
Chalk is a soft, white, porous, sedimentary carbonate rock. It is a form of limestone composed of the mineral calcite and originally formed deep under the sea by the compression of microscopic plankton that had settled to the sea floor. C ...
(calcium carbonate)
*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 drywa ...
*Gypsum 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 "re ...
*Phosphogypsum
Phosphogypsum (PG) is the calcium sulfate hydrate formed as a by-product of the production of fertilizer from phosphate rock. It is mainly composed of gypsum (CaSO4·2H2O). Although gypsum is a widely used material in the construction industry, p ...
*Selenite (mineral)
Selenite, satin spar, desert rose, gypsum flower are crystal habit varieties of the mineral gypsum.
All varieties of gypsum, including selenite and alabaster, are composed of calcium sulfate dihydrate (meaning that it has two molecules of w ...
*Flue-gas desulfurization
Flue-gas desulfurization (FGD) is a set of technologies used to remove sulfur dioxide () from exhaust flue gases of fossil-fuel power plants, and from the emissions of other sulfur oxide emitting processes such as waste incineration.
Methods
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References
External links
International Chemical Safety Card 1215
{{Authority control
Calcium compounds
Sulfates
Desiccants
Food additives
Pyrotechnic colorants
E-number additives