Witherite crystallizes in the orthorhombic system. The crystals are invariably twinned together in groups of three, giving rise to pseudo-hexagonal forms somewhat resembling bipyramidal crystals of quartz, the faces are usually rough and striated horizontally. It transforms into an hexagonal phase at 1084 K that changes into a cubic phase at 1254 K.
The mineral is named after William Withering, who in 1784 recognized it to be chemically distinct from barytes. It occurs in veins of lead ore at Hexham in Northumberland, Alston in Cumbria, Anglezarke, near Chorley in Lancashire and a few other localities. Witherite is readily altered to barium sulfate by the action of water containing calcium sulfate in solution and crystals are therefore frequently encrusted with barytes. It is the chief source of barium salts and is mined in considerable amounts in Northumberland. It is used for the preparation of rat poison, in the manufacture of glass and porcelain, and formerly for refining sugar. It is also used for controlling the chromate to sulfate ratio in chromium electroplating baths.
In the soda ash process, solid or dissolved sodium carbonate is added to barium sulfide solution, and the barium carbonate precipitate is filtered, washed and dried.
Barium carbonate is widely used in the ceramics industry as an ingredient in glazes. It acts as a flux, a matting and crystallizing agent and combines with certain colouring oxides to produce unique colours not easily attainable by other means. Its use is somewhat controversial since some claim that it can leach from glazes into food and drink. To provide a safe means of use, BaO is often used in fritted form.