Sodium sulfate is mainly used for the manufacture of detergents and in the Kraft process of paper pulping. About two thirds of the world's production is from mirabilite, the natural mineral form of the decahydrate, and the remainder from by-products of chemical processes such as hydrochloric acid production.
In the 18th century, Glauber's salt began to be used as a raw material for the industrial production of soda ash (sodium carbonate), by reaction with potash (potassium carbonate). Demand for soda ash increased and supply of sodium sulfate had to increase in line. Therefore, in the nineteenth century, the Leblanc process, producing synthetic sodium sulfate as a key intermediate, became the principal method of soda ash production.
In fact, the equilibrium is very complex, depending on concentration and temperature, with other acid salts being present.
Sodium sulfate has unusual solubility characteristics in water. Its solubility rises more than tenfold between 0 °C to 32.4 °C, where it reaches a maximum of 49.7 g Na2SO4 per 100 g water. At this point the solubility curve changes slope, and the solubility becomes almost independent of temperature. In the presence of NaCl, the solubility of sodium sulfate is markedly diminished. Such changes provide the basis for the use of sodium sulfate in passive solar heating systems, as well is in the preparation and purification of sodium sulfate. This nonconformity can be explained in terms of hydration, since 32.4 °C corresponds with the temperature at which the crystalline decahydrate (Glauber's salt) changes to give a sulfate liquid phase and an anhydrous solid phase.
Sodium sulfate decahydrate is also unusual among hydrated salts in having a measureable residual entropy (entropy at absolute zero) of 6.32 J·K-1·mol-1. This is ascribed to its ability to distribute water much more rapidly compared to most hydrates.
Sodium sulfate displays a moderate tendency to form double salts. The only alums formed with common trivalent metals are NaAl(SO4)2 (unstable above 39 °C) and NaCr(SO4)2, in contrast to potassium sulfate and ammonium sulfate which form many stable alums. Double salts with some other alkali metal sulfates are known, including Na2SO4.3K2SO4 which occurs naturally as the mineral glaserite. Formation of glaserite by reaction of sodium sulfate with potassium chloride has been used as the basis of a method for producing potassium sulfate, a fertiliser. Other double salts include 3Na2SO4.CaSO4, 3Na2SO4.MgSO4 (vanthoffite) and NaF.Na2SO4.
Major producers of 200–1500 Mt/a in 2006 include Searles Valley Minerals (California, USA), Airborne Industrial Minerals (Saskatchewan, Canada), Química del Rey (Coahuila, Mexico), Criaderos Minerales Y Derivados and Minera de Santa Marta, also known as Grupo Crimidesa (Burgos, Spain), FMC Foret (Toledo, Spain), Sulquisa (Madrid, Spain), and in China Chengdu Sanlian Tianquan Chemical (Sichuan), Hongze Yinzhu Chemical Group (Jiangsu), Nafine Chemical Industry Group (Shanxi), and Sichuan Province Chuanmei Mirabilite (Sichuan), and Kuchuksulphat JSC (Altai Krai, Siberia, Russia).
Anhydrous sodium sulfate occurs in arid environments as the mineral thenardite. It slowly turns to mirabilite in damp air. Sodium sulfate is also found as glauberite, a calcium sodium sulfate mineral. Both minerals are less common than mirabilite.
The most important chemical sodium sulfate production is during hydrochloric acid production, either from sodium chloride (salt) and sulfuric acid, in the Mannheim process, or from sulfur dioxide in the Hargreaves process. The resulting sodium sulfate from these processes are known as salt cake.
The second major production of sodium sulfate are the processes where surplus sulfuric acid is neutralised by sodium hydroxide, as applied on a large scale in the production of rayon. This method is also a regularly applied and convenient laboratory preparation.
Formerly, sodium sulfate was also a by-product of the manufacture of sodium dichromate, where sulfuric acid is added to sodium chromate solution forming sodium dichromate, or subsequently chromic acid. Alternatively, sodium sulfate is or was formed in the production of lithium carbonate, chelating agents, resorcinol, ascorbic acid, silica pigments, nitric acid, and phenol.
Bulk sodium sulfate is usually purified via the decahydrate form, since the anhydrous form tends to attract iron compounds and organic compounds. The anhydrous form is easily produced from the hydrated form by gentle warming.
Major sodium sulfate by-product producers of 50–80 Mt/a in 2006 include Elementis Chromium (chromium industry, Castle Hayne, NC, USA), Lenzing AG (200 Mt/a, rayon industry, Lenzing, Austria), Addiseo (formerly Rhodia, methionine industry, Les Roches-Roussillon, France), Elementis (chromium industry, Stockton-on-Tees, UK), Shikoku Chemicals (Tokushima, Japan) and Visko-R (rayon industry, Russia).
Another formerly major use for sodium sulfate, notably in the USA and Canada, is in the Kraft process for the manufacture of wood pulp. Organics present in the "black liquor" from this process are burnt to produce heat, needed to drive the reduction of sodium sulfate to sodium sulfide. However, this process is being replaced by newer processes; use of sodium sulfate in the USA and Canadian pulp industry declined from 1.4 Mt/a in 1970 to only approx. 150,000 tonnes in 2006.
The glass industry provides another significant application for sodium sulfate, as second largest application in Europe. Sodium sulfate is used as a fining agent, to help remove small air bubbles from molten glass. It fluxes the glass, and prevents scum formation of the glass melt during refining. The glass industry in Europe has been consuming from 1970 to 2006 a stable 110,000 tonnes annually.
Sodium sulfate is important in the manufacture of textiles, particularly in Japan, where it is the largest application. Sodium sulfate helps in "levelling", reducing negative charges on fibres so that dyes can penetrate evenly. Unlike the alternative sodium chloride, it does not corrode the stainless steel vessels used in dyeing. This application in Japan and USA consumed in 2006 approximately 100,000 tonnes.
Other uses for sodium sulfate include de-frosting windows, in carpet fresheners, starch manufacture, and as an additive to cattle feed.
Lately, sodium sulfate has been found effective in dissolving very finely electroplated micrometre gold that is found in gold electroplated hardware on electronic products such as pins, and other connectors and switches. It is safer and cheaper than other reagents used for gold recovery, with little concern for adverse reactions or health effects.
At least one company makes a laptop computer chill mat using sodium sulfate decahydrate inside a quilted plastic pad. The material slowly turns to liquid as the heat from the laptop is transferred.