Calcium sulfate hemihydrate

Description

Calcium sulfate hemihydrate (CaSO4 • 0.5H2O) is the dehydrated product of gypsum, calcium sulfate dihydrate (CaSO4•2H2O). It is obtained by heating gypsum to approximately 150°C. It is known as gypsum plaster or plaster of Paris (POP). On adding water, it solidifies by an exothermic reaction into hydrated calcium sulphate. It is commonly used to precast and hold parts of ornamental plasterwork placed on ceilings and cornices. Plaster of Paris casts can be used as a treatment of fractures to immobilize the limb. It is also used as a desiccant, and in medicine as a tablet excipient.

Chemical Properties

white or slightly off-white powder or granules

Occurrence

Gypsum originates from a supersaturated aqueous solution in the shallow sea, which first evaporates and deposits carbonates, then sulphates and finally chlorides. Gypsum and anhydrite are almost always found in the Permian, Triassic, and Tertiary formations. The Permian includes the Upper Permian (Zechstein deposits, Germany). The Triassic consists of Lower (Buntsandstein), Middle (Muschelkalk), and Upper Triassic (Keuper). The Tertiary deposits include the Eocene (Spain, Persia, Near East), the Oligocene (Paris), and the Miocene deposits (Mediterranean area, North africa). The Jurassic and Cretaceous formations, which lie between the Triassic and Tertiary, are almost devoid of useful gypsum deposits, as are the older pre-Permian formations – at least in the Old World – as, for example, the Carboniferous formation. The accepted view is that gypsum, CaSO4 · 2 H2O, was formed upon initial crystallization. The best known deposits of primary gypsum are those of the Paris Basin and the areas around the Mediterranean. Under increased pressure and thus temperature, anhydrite could have developed locally from the original gypsum. However, uptake of surface water can convert the anhydrite back into gypsum. This gypsum is therefore a secondary rock, especially in formations older than the Middle Tertiary.
The various gypsum and anhydrite deposits differ in purity, structure, and color. The major impurities are calcium carbonate (limestone), dolomite, marl, clay; less frequently, silica, bitumen, glauberite, syngenite, and polyhalite. Gypsum can be pure white. If it contains iron oxide, it is reddish to yellowish. If clay and/or bitumen is present, it is gray to black. Very pure anhydrite is bluish white, but usually it is gray with a bluish tinge. The white veins sometimes found on the boundary between gypsum and anhydrite consist largely of glauberite (CaSO4 · Na2SO4) or Glauber’s salt (Na2SO4 · 10 H2O).

Definition

ChEBI: Calcium sulfate hemihydrate is a calcium salt and a hydrate.

General Description

Gypsum is a naturally hydrated calcium sulfate. It can also be easily synthesized in a partially hydrated or anhydrous form. The partially hydrated form is called hemihydrate calcium sulfate, while the anhydrous form is called anhydrite (Jorgensen 1994). In the past, a gypsum fiber product made of long, strong, and thin fibers that had good reinforcing properties was used. These fibers were nonabrasive and stable up to a temperature of 1,000°C. They were also stable in mild acids and bases (Virta 1994).

Industrial uses

Gypsum is the most common sulfate mineral,characterized by the chemical formulaCaSO₄ · 2H₂O; it shows little variation from thiscomposition.
Gypsum is one of the several evaporite minerals.This mineral group includes chlorides,carbonates, borates, nitrates, and sulfates. Theseminerals precipitate in seas, lakes, caves, andsalt flats due to concentration of ions by evaporation.When heated or subjected to solutionswith very large salinities, gypsum converts tobassanite (CaSO₄.H₂O) or anhydrite (CaSO₄).Under equilibrium conditions, this conversionto anhydrite is direct. The conversion occursabove 42°C in pure water.
Gypsum is used for making building plaster,wallboard tiles, as an absorbent for chemicals,as a paint pigment and extender, and forcoating papers. Natural gypsum of California,containing 15 to 20% sulfur, is used for producingammonium sulfate for fertilizer. Gypsumis also used to make sulfuric acid by heatingto 1093°C in an air-limited furnace. Theresultant calcium sulfide is reacted to yield limeand sulfuric acid. Raw gypsum is also used tomix with portland cement to retard the set.Compact massive types of the mineral are usedas building stones.

Solubility in water

Gypsum is slightly soluble in water. Gypsum is readily soluble in glycerol and sugar solutions and in aqueous solutions of chelating agents, such as EDTA.

Purification Methods

Its solubility in H2O is 0.2parts/100 at 18.75o. It dehydrates completely >650o. Dry it below 300o to give a solid with estimated pore size ca 38% of volume. Anhydrous CaSO4 (Drierite) has a high affinity for H2O and will absorb 6.6% of its weight of H2O to form the hemihydrate (gypsum). It sets to a hard mass with H2O; hence it should be kept in a tightly sealed container. The solubility of gypsum in H2O is unusual: 0.176% at 0o, 0.209% at 30o, 0.210 at 40o, 0.204 at 50o and 0.200 at 60o. [Hulett J Am Chem Soc 27 49 1905, James & Partington J Chem Soc 107 1019 1915, Namba J Soc Chem Ind 40 2797 1920.]