Sodium sulfate
Sodium sulfate is the sodium salt of sulfuric acid. When anhydrous, it is a white crystalline solid of formula Na2SO4 known as the mineral thenardite; the decahydrate Na2SO4·10H2O has been known as Glauber's salt or, historically, sal mirabilis since the 17th century. Another solid is the heptahydrate, which transforms to mirabilite when cooled. With an annual production of 6 million tonnes, it is a major commodity chemical and one of the most damaging salts in structure conservation: when it grows in the pores of stones it can achieve high levels of pressure, causing structures to crack.
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.
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.
The hydrate of sodium sulfate is known as Glauber's Salt after the Dutch/German chemist and apothecary Johann Rudolf Glauber (1604–1670), who discovered it in 1625 in Austrian spring water. He named it sal mirabilis (miraculous salt), because of its medicinal properties: the crystals were used as a general purpose laxative, until more sophisticated alternatives came about in the 1900s.[1][2]
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 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.[
Sodium sulfate is chemically very stable, being unreactive toward most oxidising or reducing agents at normal temperatures. At high temperatures, it can be reduced to sodium sulfide:[4]
Sodium sulfate is a typical ionic sulfate, containing Na+ ions and SO42− ions. Aqueous solutions can produce precipitates when combined with salts of Ba2+ or Pb2+, which form insoluble sulfates
- Na2SO4 + 2 C → Na2S + 2 CO2(g)
- Na2SO4(aq) + H2SO4(aq) ⇌ 2 NaHSO4(aq)
Sodium sulfate is a typical ionic sulfate, containing Na+ ions and SO42− ions. Aqueous solutions can produce precipitates when combined with salts of Ba2+ or Pb2+, which form insoluble sulfates
- Na2SO4(aq) + BaCl2(aq) → 2 NaCl(aq) + BaSO4(s)
Sodium sulfate has unusual solubility characteristics in water.[7] Its solubility in water rises more than tenfold between 0 °C to 32.384 °C, where it reaches a maximum of 497 g/L. At this point the solubility curve changes slope, and the solubility becomes almost independent of temperature. This temperature at 32.384 °C, corresponding to the release of crystal water and melting of the hydrated salt, serves as an accurate temperature reference for thermometer calibration.
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.[8]
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.[9] 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.[10] Other double salts include 3Na2SO4·CaSO4, 3Na2SO4·MgSO4 (vanthoffite) and NaF·Na2SO4.[11]
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.[8]
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.[9] 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.[10] Other double salts include 3Na2SO4·CaSO4, 3Na2SO4·MgSO4 (vanthoffite) and NaF·Na2SO4.[11]
The world production of sodium sulfate, mostly in the form of the decahydrate amounts to approximately 5.5 to 6 million tonnes annually (Mt/a). In 1985, production was 4.5 Mt/a, half from natural sources, and half from chemical production. After 2000, at a stable level until 2006, natural production had increased to 4 Mt/a, and chemical production decreased to 1.5 to 2 Mt/a, with a total of 5.5 to 6 Mt/a.[12][13][14][15] For all applications, naturally produced and chemically produced sodium sulfate are practically interchangeable.
Major producers of 200,000–1,500,000 tonnes/a in 2006 include Searles Valley Minerals (California, US), 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).[12][14] In Saskatchewan, one of the major miners is Saskatchewan Minerals.
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.
In the laboratory it can also be synthesized from the reaction between sodium bicarbonate and magnesium sulfate.
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, US), 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).[12]
[edit] Natural sources
Two thirds of the world's production of the decahydrate (Glauber's salt) is from the natural mineral form mirabilite, for example as found in lake beds in southern Saskatchewan. In 1990, Mexico and Spain were the world's main producers of natural sodium sulfate (each around 500,000 tonnes), with Russia, US and Canada around 350,000 tonnes each.[13] Natural resources are estimated as over 1 billion tonnes.[12][13]Major producers of 200,000–1,500,000 tonnes/a in 2006 include Searles Valley Minerals (California, US), 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).[12][14] In Saskatchewan, one of the major miners is Saskatchewan Minerals.
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.
[edit] Chemical industry
About one third of the world's sodium sulfate is produced as by-product of other processes in chemical industry. Most of this production is chemically inherent to the primary process, and only marginally economical. By effort of the industry, therefore, sodium sulfate production as by-product is declining.
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.[16][17] The resulting sodium sulfate from these processes are known as salt cake.- Mannheim: 2 NaCl + H2SO4 → 2 HCl + Na2SO4
- Hargreaves: 4 NaCl + 2 SO2 + O2 + 2 H2O → 4 HCl + 2 Na2SO4
In the laboratory it can also be synthesized from the reaction between sodium bicarbonate and magnesium sulfate.
- 2NaHCO3 + MgSO4 → Na2SO4 + Mg(OH)2 + 2CO2
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, US), 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).[12]
Commodity industries
With US pricing at $30 per tonne in 1970, in 2006 up to $90 per tonne for salt cake quality and $130 for better grades, sodium sulfate is a very cheap material. The largest use is as filler in powdered home laundry detergents, consuming approx. 50% of world production. This use is waning as domestic consumers are increasingly switching to compact or liquid detergents that do not include sodium sulfate.[12]Another formerly major use for sodium sulfate, notably in the US 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 US and Canadian pulp industry declined from 1.4 Mt/a in 1970 to only approx. 150,000 tonnes in 2006.[12]
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.[12]
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 US consumed in 2006 approximately 100,000 tonnes.[12]
[edit] Thermal storage
The high heat storage capacity in the phase change from solid to liquid, and the advantageous phase change temperature of 32 °C (90 °F) makes this material especially appropriate for storing low grade solar heat for later release in space heating applications. In some applications the material is incorporated into thermal tiles that are placed in an attic space while in other applications the salt is incorporated into cells surrounded by solar–heated water. The phase change allows a substantial reduction in the mass of the material required for effective heat storage (the heat of fusion of sodium sulfate decahydrate is 25.53 kJ/mol or about 19 cal/gm), with the further advantage of a consistency of temperature as long as sufficient material in the appropriate phase is available.
[edit] Small-scale applications
In the laboratory, anhydrous sodium sulfate is widely used as an inert drying agent, for removing traces of water from organic solutions.[18] It is more efficient, but slower-acting, than the similar agent magnesium sulfate. It is only effective below about 30 °C, but it can be used with a variety of materials since it is chemically fairly inert. Sodium sulfate is added to the solution until the crystals no longer clump together; the two video clips (see above) demonstrate how the crystals clump when still wet, but some crystals flow freely once a sample is dry.Glauber's salt, the decahydrate, was historically used as a laxative. It is effective for the removal of certain drugs such as acetaminophen from the body, for example, after an overdose.[19][20]
In 1953, sodium sulfate was proposed for heat storage in passive solar heating systems. This takes advantage of its unusual solubility properties, and the high heat of crystallisation (78.2 kJ/mol).[21]
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.[citation needed]
At least one company, ThermalTake, makes a laptop computer chill mat (iXoft Notebook Cooler) using sodium sulfate decahydrate inside a quilted plastic pad. The material slowly turns to liquid and recirculates, equalizing laptop temperature and acting as an insulation.
[edit] Safety
Although sodium sulfate is generally regarded as non-toxic,[22] it should be handled with care. The dust can cause temporary asthma or eye irritation; this risk can be prevented by using eye protection and a paper mask. Transport is not limited, and no Risk Phrase or Safety Phrase apply.[23][edit] References
- ^ Szydlo, Zbigniew (1994). Water which does not wet hands: The Alchemy of Michael Sendivogius. London-Warsaw: Polish Academy of Sciences.
- ^ Westfall, Richard S. (1995). "Glauber, Johann Rudolf". The Galileo Project. http://galileo.rice.edu/Catalog/NewFiles/glauber.html.
- ^ Aftalion, Fred (1991). A History of the International Chemical Industry. Philadelphia: University of Pennsylvania Press. pp. 11–16. ISBN 0-8122-1297-5.
- ^ Linke, W.F.; A. Seidell (1965). Solubilities of Inorganic and Metal Organic Compounds (4th ed.). Van Nostrand. ISBN 0841200971.
- ^ Brodale, G.; W.F. Giauque (1958). "The Heat of Hydration of Sodium Sulfate. Low Temperature Heat Capacity and Entropy of Sodium Sulfate Decahydrate". Journal of the American Chemical Society 80 (9): 2042–2044. doi:10.1021/ja01542a003.
- ^ Lipson, Henry; C.A. Beevers (1935). "The Crystal Structure of the Alums". Proceedings of the Royal Society of London Series A 148 (865): 664–80. doi:10.1098/rspa.1935.0040.
- ^ Garrett, Donald E. (2001). Sodium sulfate : handbook of deposits, processing, properties, and use. San Diego: Academic Press. ISBN 9780122761515.
- ^ Mellor, Joseph William (1961). Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry. Volume II (new impression ed.). London: Longmans. pp. 656–673. ISBN 0582462770.
- ^ a b c "Statistical compendium Sodium sulfate". Reston, Virginia: US Geological Survey, Minerals Information. 1997. http://minerals.usgs.gov/minerals/pubs/commodity/sodium_sulfate/stat. Retrieved 2007-04-22.
- ^ Cocchetto, D.M.; G. Levy (1981). "Absorption of orally administered sodium sulfate in humans". J Pharm Sci 70 (3): 331–3. doi:10.1002/jps.2600700330. PMID 7264905.
- ^ Prescott, L.F.; J.A.J.H. Critchley (1979). "The Treatment of Acetaminophen Poisoning". Annual Review of Pharmacology and Toxicology 23: 87–101. doi:10.1146/annurev.pa.23.040183.000511. PMID 6347057.
- ^ "Sodium sulfate (WHO Food Additives Series 44)". World Health Organization. 2000. http://www.inchem.org/documents/jecfa/jecmono/v44jec07.htm. Retrieved 2007-06-06.
- ^ "MSDS Sodium Sulfate Anhydrous". James T Baker. 2006. http://hazard.com/msds/mf/baker/baker/files/s5022.htm. Retrieved 2007-04-21.
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