Calcium sulfate

Calcium sulfate occurs at three levels of hydration with different crystallographic structures: anhydrous, dihydrate, and hemihydrate. The anhydrous (anhydrite) crystallizes as an tightly-bound orthohombic lattice with space group Pnma, in which each is 8-coordinated, or surrounded, by 8 oxygen atoms from tetrahedral . It is similar in topology to zircon. The dihydrate (gypsum) forms a monoclinic crystal with space group C2/c. Its structure consists of alternating layers: one with coordinated with tetrahedral and another with interstitial water molecules. The hemihydrate (bassanite) is also known as plaster of Paris. Specific hemihydrates are sometimes distinguished between α-hemihydrate and β-hemihydrate. ==Uses==

The main use of calcium sulfate is to produce plaster of Paris and stucco. These applications exploit the fact that calcium sulfate which has been powdered and calcined forms a moldable paste upon hydration and hardens as crystalline calcium sulfate dihydrate. It is also convenient that calcium sulfate is poorly soluble 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 or plaster of Paris. This material has the formula CaSO4·(nH2O), where 0.5 ≤ n ≤ 0.8. 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 series as E516, and the UN's FAO knows it as a firming agent, a flour treatment agent, a sequestrant, and a leavening agent. 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. Desiccant When sold at the anhydrous state as a desiccant with a color-indicating agent under the name Drierite, it appears blue (anhydrous) or pink (hydrated) due to impregnation with cobalt(II) chloride, which functions as a moisture indicator. Sulfuric acid production Up to the 1970s, commercial quantities of sulfuric acid were produced from anhydrous calcium sulfate. Upon being mixed with shale or marl, and roasted at 1400°C, the sulfate liberates sulfur dioxide gas, a precursor to sulfuric acid. The reaction also produces calcium silicate, used in cement clinker production. : Some component reactions pertaining to calcium sulfate: : : : : ==Production and occurrence==

The main sources of calcium sulfate are naturally occurring gypsum and anhydrite, which occur at many locations worldwide as evaporites. 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, exhaust gases from fossil-fuel power stations and other processes (e.g. cement manufacture) are scrubbed to reduce their sulfur dioxide content, by injecting finely ground limestone: : 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 from phosphate rock, calcium phosphate is treated with sulfuric acid and calcium sulfate precipitates. The product, called phosphogypsum is often contaminated with impurities making its use uneconomic. • In the production of hydrogen fluoride, calcium fluoride is treated with sulfuric acid, precipitating calcium sulfate. • In the refining of zinc, solutions of zinc sulfate are treated with hydrated lime to co-precipitate heavy metals such as barium. • 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 and its decay products such as radium-226, lead-210 and polonium-210. Extraction of uranium from phosphorus ores can be economical on its own depending on prices on the uranium market 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 deposits in industrial heat exchangers, because its solubility decreases with increasing temperature (see the specific section on the retrograde solubility). ==Solubility==

The solubility of calcium sulfate decreases as temperature increases. This behaviour ("retrograde solubility") is uncommon: dissolution of most of the salts is endothermic and their solubility increases with 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 boilers along with the precipitation of calcium carbonate whose solubility also decreases when CO2 degasses from hot water or can escape out of the system. ==See also==