Sodium Sulfate Resources

Sodium sulfate is an important industrial chemical. As recently as ten years ago it was produced and consumed in the United States in quantities exceeding 1 Mtpy. Since then, both its production and use have declined; however, approximately half the production still comes from natural sources. [Fig. 1] illustrates the history of production of natural sodium sulfate in the United States. Production of natural sodium sulfate from various types of deposits is the main source of this chemical in Canada and Mexico, and probably in Argentina, Chile, Iran, Spain, and the Russian Republics. MINERALOGY AND PHYSICAL PROPERTIES Sodium sulfate is widespread in occurrence and is a common constituent of many mineral waters, as well as seawater. Atmospheric precipitation contains sulfate; it is one of the major dissolved constituents of rain and snow (Davis and Dewiest, 1966). Many of the saline lakes throughout the world contain varying amounts of sodium sulfate. Because sodium is usually the dominant cation, some workers make an anionic distinction, referring to lakes containing predominantly sulfate as bitter lakes and those containing predominantly carbonate as alkali or soda lakes (Bateman, 1950). Sodium sulfate in its natural form is found in two principal minerals, mirabilite and thenardite. Mirabilite, the hydrous form, is commonly called Glauber's salt. It was discovered by the German chemist, J.R. Glauber (1603-1668), who derived its name from the Latin, sal mirabile, meaning wonderful salt. Thenardite, the anhydrous variety, was named for the French chemist, Louis Jacques Thenard (1777-1857) of the University of Paris (Mitchell, 1979). The largest quantities occur in the form of mirabilite. Sodium sulfate is found in varying degrees of purity, from theoretically pure efflorescent crystals of mirabilite to combinations and admixtures of other salts and impurities. It is a common constituent of some brines; from this source much is extracted commercially. Sodium sulfate also is found in compounds, such as the minerals glauberite, the double salt of anhydrous sodium and calcium sulfate, bloedite, the hydrous double-salt of sodium sulfate and magnesium sulfate, and burkeite, the anhydrous double-salt of sodium carbonate and sodium sulfate. Over 40 minerals contain sodium sulfate in varying proportions; many are of special interest because of their frequent occurrence. Table 1 lists some sodium-sulfate bearing minerals. The reader is referred to other publications (Cole, 1926, Dana, 1932, Grabau, 1920, and Dietrich, 1969) for descriptions of these minerals. Only mirabilite and thenardite will be described herein. Mirabilite Na$04.10H20, contains 55.9% water of crystallization. It is noted for its efflorescence or spontaneous loss of water. On dehydration it changes to the anhydrous form, Na2S0,. Mirabilite is an opaque to colorless, water-soluble mineral that tastes first cool, then slightly bitter. It has a specific gravity of 1.48. It frequently forms as efflorescent, needlelike monoclinic crystals, but generally is found in the massive form. Thenardite, the anhydrous mineral, Na2S04, contains 43.68% Na20 and 56.32% SO3. It ranges from colorless to white and may be tinted shades of gray or brown. It is a water soluble mineral with a slightly salty taste. Its specific gravity (2.67) and hardness (2.5 to 3) exceed those of mirabilite. It commonly occurs in the massive form without visible crystals. Its crystals are frequently tabular pyramids of the orthorhombic system. Sodium sulfate also occurs as a heptahydrate, containing seven molecules of water, but this is unstable and has not been found in the natural environment. The solubility of sodium sulfate has an important effect on the crystallization of the salt in nature, as well as in its production. Its solubility in water generally increases as a nonlinear function of temperature. Below 1.2°C, ice and mirabilite form. As the temperature is increased above O°C, increasing amounts of sodium sulfate become soluble. At 32.4°C, a transition point on the solubility curve is reached, as the decahydrate melts in its own water of crystallization and the anhydrous form crystallizes. With in- creasing temperatures, solubility decreases somewhat. The presence of other dissolved salts changes the transition temperature and solubility characteristics of sodium sulfate.