SULFUR

also spelled Sulphur (S), nonmetallic chemical element belonging to the oxygen family (Group VIa of the periodic table), one of the most reactive of the elements. Known to the ancients (in Genesis it is called brimstone), sulfur was first classified as an element in 1777 by Antoine Lavoisier. It is estimated to be the ninth most abundant element in the universe. In the form of sulfides, sulfates, and elemental sulfur, the element constitutes about 0.03 percent of the Earth's crust. After oxygen and silicon, it is the most abundant constituent of minerals. Occurrence, properties, and uses. Native or free sulfur occurs chiefly in volcanic or sedimentary deposits. The former are located throughout the world; the latter are especially common along the U.S. coastal region of Texas and Louisiana. Coal, petroleum, and natural gas contain sulfur compounds. Sulfur-containing ores include such sulfides as pyrite (iron disulfide), galena (lead sulfide), cinnabar (mercury sulfide), sphalerite (zinc sulfide), and chalcopyrite (copper iron sulfide), as well as such sulfates as gypsum (calcium sulfate) and barite or heavy spar (barium sulfate). Where deposits of sulfur are located in salt domes, as they are along the coast of the Gulf of Mexico, the element is recovered by the Frasch process (q.v.). This process has made sulfur of a high purity (up to 99.9 percent pure) available in large quantity and has helped establish sulfur as one of the four most important basic chemical commodities. Wells are drilled from 60 to 600 m (200 to 2,000 feet) into the sulfur formation and then lined with a 6-inch (15-centimetre) pipe in which an air pipe and a water pipe of smaller diameter are concentrically placed. Superheated water, injected into the circular space between three- and six-inch pipes, penetrates the cap rock through holes on the bottom of the pipe. As the sulfur melts, it settles to the bottom of the deposit. From there it is pumped to the surface by applying air pressure through the central pipe. Several such wells operate under the ocean floor in the Gulf of Mexico. The sulfur is collected in reservoirs, or sumps, and from there transferred to vats or bins to solidify for storage and stockpiling. Vats may contain as much as 300,000 tons of sulfur. About 4,000,000 tons of sulphur are recovered in the United States each year from natural gas, petroleum refinery gases, pyrites, and smelter gases from the processing of copper, zinc, and lead ores. In most cases sulfur is separated from other gases as hydrogen sulfide and then converted to elemental sulfur by the Claus process, which involves the partial burning of hydrogen sulfide to sulfur dioxide, with subsequent reaction between the two to yield sulfur. Another important source is the sulfur dioxide emitted into the atmosphere by coal-fired steam power plants. In the early 1970s techniques to collect this sulfur dioxide and convert it into usable sulfur were developed. Pure sulfur is a tasteless, odourless, brittle solid that is pale yellow in colour, a poor conductor of electricity, and insoluble in water. The element exists in several different forms, the two most important being the orthorhombic (often called rhombic) and monoclinic crystalline modifications. Rhombic sulfur, which is stable at room temperature, includes the common roll sulfur (or brimstone), flowers of sulfur (a finely divided form obtained by sublimation of vapour directly to a solid upon cooling), and much natural sulfur. Monoclinic, or prismatic, sulfur, which is obtained when liquid sulfur is cooled slowly, consists of long, needlelike crystals. It is stable between 96 C (205 F) and 119 C (246 F), but at room temperature it changes slowly to the rhombic form. When hot molten sulfur is cooled suddenly (as by pouring it into cold water), it forms a soft, sticky, elastic, noncrystalline mass called amorphous, or plastic, sulfur. Although the rhombic and monoclinic forms are highly soluble in carbon disulfide, amorphous sulfur is not.