Chemistry:Lithium carbonate

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Lithium carbonate
Lithium-carbonate-xtal-1979-Mercury-3D-sf.png
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Lithium carbonate A.jpg
Names
IUPAC name
Lithium carbonate
Other names
Dilithium carbonate, Carbolith, Cibalith-S, Duralith, Eskalith, Lithane, Lithizine, Lithobid, Lithonate, Lithotabs Priadel, Zabuyelite
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
KEGG
RTECS number
  • OJ5800000
UNII
Properties
Li2CO3
Molar mass 73.89 g/mol
Appearance Odorless white powder
Density 2.11 g/cm3
Melting point 723 °C (1,333 °F; 996 K)
Boiling point 1,310 °C (2,390 °F; 1,580 K)
Decomposes from ~1300 °C
  • 1.54 g/100 mL (0 °C)
  • 1.43 g/100 mL (10 °C)
  • 1.29 g/100 mL (25 °C)
  • 1.08 g/100 mL (40 °C)
  • 0.69 g/100 mL (100 °C)[1]
8.15×10−4[2]
Solubility Insoluble in acetone, ammonia, alcohol[3]
−27.0·10−6 cm3/mol
1.428[4]
Viscosity
  • 4.64 cP (777 °C)
  • 3.36 cP (817 °C)[3]
Thermochemistry
97.4 J/mol·K[3]
90.37 J/mol·K[3]
−1215.6 kJ/mol[3]
−1132.4 kJ/mol[3]
Hazards
Main hazards Irritant
Safety data sheet ICSC 1109
GHS pictograms GHS07: Harmful[5]
GHS Signal word Warning
H302, H319[5]
P305+351+338[5]
Flash point Non-flammable
Related compounds
Other cations
 Sodium carbonate
Potassium carbonate
Rubidium carbonate
Caesium carbonate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references
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Lithium carbonate is an inorganic compound, the lithium salt of carbonic acid with the formula Li2CO3. This white salt is widely used in processing metal oxides. It is on the World Health Organization's List of Essential Medicines[6] for its efficacy in the treatment of mood disorders such as bipolar disorder.[7][6]

Uses

Lithium carbonate is an important industrial chemical. Its main use is as a precursor to compounds used in lithium-ion batteries.

Glasses derived from lithium carbonate are useful in ovenware. Lithium carbonate is a common ingredient in both low-fire and high-fire ceramic glaze. It forms low-melting fluxes with silica and other materials. Its alkaline properties are conducive to changing the state of metal oxide colorants in glaze, particularly red iron oxide (Fe2O3). Cement sets more rapidly when prepared with lithium carbonate, and is useful for tile adhesives. When added to aluminium trifluoride, it forms LiF which yields a superior electrolyte for the processing of aluminium.[8]

Rechargeable batteries

Lithium carbonate-derived compounds are crucial to lithium-ion batteries. Lithium carbonate may be converted into lithium hydroxide as an intermediate. In practice, two components of the battery are made with lithium compounds: the cathode and the electrolyte. The electrolyte is a solution of lithium hexafluorophosphate, while the cathode uses one of several lithiated structures, the most popular of which are lithium cobalt oxide and lithium iron phosphate.

Lithium prices

Medical uses

Main page: Chemistry:Lithium (medication)

In 1843, lithium carbonate was used to treat stones in the bladder. In 1859, some doctors recommended a therapy with lithium salts for a number of ailments, including gout, urinary calculi, rheumatism, mania, depression, and headache.

In 1948, John Cade discovered the anti-manic effects of lithium ions.[9] This finding led to lithium carbonate's use as a psychiatric medication to treat mania, the elevated phase of bipolar disorder. Prescription lithium carbonate from a pharmacy is suitable for use as medicine in humans but industrial lithium carbonate is not since it may contain unsafe levels of toxic heavy metals or other toxicants. After ingestion, lithium carbonate is dissociated into pharmacologically active lithium ions (Li+) and (non-therapeutic) carbonate, with 300 mg of lithium carbonate containing approximately 8 mEq (8 mmol) of lithium ion.[7] According to the Food and Drug Administration (FDA), 300–600 mg of lithium carbonate taken two to three times daily is typical for maintenance of bipolar I disorder in adults,[7] where the exact dose given varies depending on factors such as the patient's serum lithium concentrations, which must be closely monitored by a physician to avoid lithium toxicity and potential kidney damage (or even kidney failure) from lithium-induced nephrogenic diabetes insipidus.[10][7] Dehydration and certain drugs, including NSAIDs such as ibuprofen, can increase serum lithium concentrations to unsafe levels whereas other drugs, such as caffeine, may decrease concentrations. In contrast to the elemental ions sodium, potassium, and calcium, there is no known cellular mechanism specifically dedicated to regulating intracellular lithium. Lithium can enter cells through epithelial sodium channels.[11] Lithium ions interfere with ion transport processes (see "Sodium pump") that relay and amplify messages carried to the cells of the brain.[12] Mania is associated with irregular increases in protein kinase C (PKC) activity within the brain. Lithium carbonate and sodium valproate, another drug traditionally used to treat the disorder, act in the brain by inhibiting PKC's activity and help to produce other compounds that also inhibit the PKC.[13] Lithium carbonate's mood-controlling properties are not fully understood.[14]

Health risks

Taking lithium salts has risks and side effects. Extended use of lithium to treat mental disorders has been known to lead to acquired nephrogenic diabetes insipidus.[15] Lithium intoxication can affect the central nervous system and renal system and can be lethal.[16] Over a prolonged period, lithium can accumulate in the principal cells of the collecting duct and interfere with antidiuretic hormone (ADH), which regulates the water permeability of principal cells in the collecting tubule.[11] The medullary interstitium of the collecting duct system naturally has a high sodium concentration and attempts to maintain it. There is no known mechanism for cells to distinguish lithium ions from sodium ions, so damage to the kidney's nephrons may occur if lithium concentrations become too high as a result of dehydration, hyponatremia, an unusually low sodium diet, or certain drugs.

Red pyrotechnic colorant

Lithium carbonate is used to impart a red color to fireworks.[17]

Properties and reactions

Unlike sodium carbonate, which forms at least three hydrates, lithium carbonate exists only in the anhydrous form. Its solubility in water is low relative to other lithium salts. The isolation of lithium from aqueous extracts of lithium ores capitalizes on this poor solubility. Its apparent solubility increases 10-fold under a mild pressure of carbon dioxide; this effect is due to the formation of the metastable lithium bicarbonate, which is more soluble:[8]

Li2CO3 + CO2 + H2O ⇌ 2 LiHCO3

The extraction of lithium carbonate at high pressures of CO2 and its precipitation upon depressurizing is the basis of the Quebec process.

Lithium carbonate can also be purified by exploiting its diminished solubility in hot water. Thus, heating a saturated aqueous solution causes crystallization of Li2CO3.[18]

Lithium carbonate, and other carbonates of group 1, do not decarboxylate readily. Li2CO3 decomposes at temperatures around 1300 °C.

Production

Lithium is extracted from primarily two sources: spodumene in pegmatite deposits, and lithium salts in underground brine pools. About 82,000 tons were produced in 2020, showing significant and consistent growth.[19]

From underground brine reservoirs

In the Salar de Atacama in the Atacama desert of Northern Chile, lithium carbonate and hydroxide are produced from brine.[20][21]

The process pumps lithium rich brine from below ground into shallow pans for evaporation. The brine contains many different dissolved ions, and as their concentration increases, salts precipitate out of solution and sink. The remaining supernatant liquid is used for the next step. The sequence of pans may vary depending on the concentration of ions in a particular source of brine.

In the first pan, halite (sodium chloride or common salt) crystallises. This has little economic value and is discarded. The supernatant, with ever increasing concentration of dissolved solids, is transferred successively to the sylvinite (sodium potassium chloride) pan, the carnalite (potassium magnesium chloride) pan and finally a pan designed to maximise the concentration of lithium chloride. The process takes about 15 months. The concentrate (30-35% lithium chloride solution) is trucked to Salar del Carmen. There, boron and magnesium are removed (typically residual boron is removed by solvent extraction and/or ion exchange and magnesium by raising the pH above 10 with sodium hydroxide)[22] then in the final step, by addition of sodium carbonate, the desired lithium carbonate is precipitated out, separated, and processed.

Some of the by-products from the evaporation process may also have economic value.

There is considerable attention to the use of water in this water poor region. SQM commissioned a life-cycle analysis (LCA) which concluded that water consumption for SQM's lithium hydroxide and carbonate is significantly lower than the average consumption by production from the main ore-based process, using spodumene. A more general LCA suggests the opposite for extraction from reservoirs.[23]

The majority of brine based production is in the "lithium triangle" in South America.

From 'geothermal' brine

A potential source of lithium is the leachates of geothermal wells, carried to the surface.[24] Recovery of lithium has been demonstrated in the field; the lithium is separated by simple precipitation and filtration.[25] The process and environmental costs are primarily those of the already-operating well; net environmental impacts may thus be positive.[26]

The brine of United Downs Deep Geothermal Power project near Redruth is claimed by Cornish Lithium to be valuable due to its high lithium concentration (220 mg/L) with low magnesium (<5 mg/L) and total dissolved solids content of <29g/L,[27] and a flow rate of 40-60l/s.[23]

From ore

α-spodumene is roasted at 1100 °C for 1h to make β-spodumene, then roasted at 250 °C for 10 minutes with sulphuric acid.[28][20]

As of 2020, Australia was the world's largest producer of lithium intermediates,[29] all based on spodumene.

In recent years mining companies have begun exploration of lithium projects throughout North America, South America and Australia to identify economic deposits that can potentially bring new supplies of lithium carbonate online to meet the growing demand for the product.[30]

From clay

In 2020 Tesla Motors announced a revolutionary process to extract lithium from clay in Nevada using only salt and no acid. This was met with scepticism.[31]

From end-of-life batteries

A few small companies are recycling spent batteries, focusing on recovering copper and cobalt. Some recover lithium carbonate alongside the compound Li2Al4(CO3)(OH)12⋅3H2O also.[32][33][34][35]

Other

In April 2017 MGX Minerals reported it had received independent confirmation of its rapid lithium extraction process to recover lithium and other valuable minerals from oil and gas wastewater brine. [36]

Electrodialysis has been proposed to extract lithium from seawater, but it is not commercially viable.[37]

Natural occurrence

Natural lithium carbonate is known as zabuyelite.[38] This mineral is connected with deposits of some salt lakes and some pegmatites.[39]

References

  1. ↑ Seidell, Atherton; Linke, William F. (1952). Solubilities of Inorganic and Organic Compounds. Van Nostrand. 
  2. ↑ John Rumble (June 18, 2018) (in English). CRC Handbook of Chemistry and Physics (99 ed.). CRC Press. pp. 5–188. ISBN 978-1-138-56163-2. 
  3. ↑ 3.0 3.1 3.2 3.3 3.4 3.5 "lithium carbonate". 2007-03-19. http://chemister.ru/Database/properties-en.php?dbid=1&id=608. 
  4. ↑ Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN:0-07-049439-8
  5. ↑ 5.0 5.1 5.2 Sigma-Aldrich Co., Lithium carbonate. Retrieved on 2014-06-03.
  6. ↑ 6.0 6.1 "WHO Model List of Essential Medicines" (PDF). World Health Organization. October 2013. http://apps.who.int/iris/bitstream/10665/93142/1/EML_18_eng.pdf?ua=1. 
  7. ↑ 7.0 7.1 7.2 7.3 "Lithium Carbonate Medication Guide". https://www.accessdata.fda.gov/drugsatfda_docs/label/2018/017812s031,018421s031,018558s026lbl.pdf. 
  8. ↑ 8.0 8.1 Ulrich Wietelmann; Richard J. Bauer (2005). "Lithium and Lithium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a15_393. ISBN 3-527-30673-0. 
  9. ↑ Cade, J. F. (2000). "Lithium salts in the treatment of psychotic excitement. 1949.". Bulletin of the World Health Organization 78 (4): 518–520. ISSN 0042-9686. PMID 10885180. 
  10. ↑ Amdisen A. (1978). "Clinical and serum level monitoring in lithium therapy and lithium intoxication". J. Anal. Toxicol. 2 (5): 193–202. doi:10.1093/jat/2.5.193. 
  11. ↑ 11.0 11.1 Lerma, Edgar V.. "Renal toxicity of lithium". UpToDate. https://www.uptodate.com/contents/renal-toxicity-of-lithium. 
  12. ↑ "lithium, Lithobid: Drug Facts, Side Effects and Dosing". 2016-06-17. http://www.medicinenet.com/lithium/article.htm. 
  13. ↑ Yildiz, A; Guleryuz, S; Ankerst, DP; Ongür, D; Renshaw, PF (2008). "Protein kinase C inhibition in the treatment of mania: a double-blind, placebo-controlled trial of tamoxifen". Archives of General Psychiatry 65 (3): 255–63. doi:10.1001/archgenpsychiatry.2007.43. PMID 18316672. http://mediatum.ub.tum.de/doc/1185490/document.pdf. [yes|permanent dead link|dead link}}]
  14. ↑ Lithium Carbonate at PubChem
  15. ↑ Richard T. Timmer; Jeff M. Sands (1999-03-01). "Lithium Intoxication". Journal of the American Society of Nephrology 10 (3): 666–674. doi:10.1681/ASN.V103666. PMID 10073618. http://jasn.asnjournals.org/content/10/3/666.short. Retrieved 2017-01-02. 
  16. ↑ Simard, M; Gumbiner, B; Lee, A; Lewis, H; Norman, D (1989). "Lithium carbonate intoxication. A case report and review of the literature". Archives of Internal Medicine 149 (1): 36–46. doi:10.1001/archinte.149.1.36. PMID 2492186. http://archinte.highwire.org/cgi/reprint/149/1/36.pdf. Retrieved 2010-09-11. 
  17. ↑ "Chemistry of Fireworks". https://fireworks.com/education-and-safety/chemistry-compounds. 
  18. ↑ Caley, E. R.; Elving, P. J. (1939). "Purification of Lithium Carbonate". Inorganic Syntheses. Inorganic Syntheses. 1. pp. 1–2. doi:10.1002/9780470132326.ch1. ISBN 978-0-470-13232-6. 
  19. ↑ "Global lithium production 2020". https://www.statista.com/statistics/606684/world-production-of-lithium/. 
  20. ↑ 20.0 20.1 "Sustainability of lithium production in Chile". SQM. https://www.sqm.com/wp-content/uploads/2020/09/SQM_-_Sustainable_Lithium_-_English.pdf. 
  21. ↑ Telsnig, Thomas; Potz, Christian; Haas, Jannik; Eltrop, Ludger; Palma-Behnke, Rodrigo (2017). "Opportunities to integrate solar technologies into the Chilean lithium mining industry – reducing process related GHG emissions of a strategic storage resource". Solarpaces 2016: International Conference on Concentrating Solar Power and Chemical Energy Systems. 1850. p. 110017. doi:10.1063/1.4984491. Bibcode: 2017AIPC.1850k0017T. 
  22. ↑ Dry, Mike. "Extraction of Lithium from Brine – Old and New Chemistry". http://downloads.aqsim.com/Extraction%20of%20Lithium%20from%20Brine%20%2013%20Old%20and%20New%20Chemistry.pdf. 
  23. ↑ 23.0 23.1 Early, Catherine (25 Nov 2020). "The new 'gold rush' for green lithium". BBC. https://www.bbc.com/future/article/20201124-how-geothermal-lithium-could-revolutionise-green-energy. 
  24. ↑ Parker, Ann. Mining Geothermal Resources . Lawrence Livermore National Laboratory
  25. ↑ Patel, P. (16 November 2011) Startup to Capture Lithium from Geothermal Plants. technologyreview.com
  26. ↑ Wald, M. (28 September 2011) Start-Up in California Plans to Capture Lithium, and Market Share . The New York Times
  27. ↑ "Cornish Lithium Releases Globally Significant Lithium Grades". 17 September 2020. https://cornishlithium.com/company-announcements/cornish-lithium-releases-globally-significant-lithium-grades/. 
  28. ↑ Meshram, Pratima; Pandey, B. D.; Mankhand, T. R. (1 December 2014). "Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation: A comprehensive review". Hydrometallurgy 150: 192–208. doi:10.1016/j.hydromet.2014.10.012. Bibcode: 2014HydMe.150..192M. https://www.sciencedirect.com/science/article/abs/pii/S0304386X14002278. Retrieved 2 Dec 2020. 
  29. ↑ Jaskula, Brian W. (January 2020). "Mineral Commodity Summaries 2020". https://pubs.usgs.gov/periodicals/mcs2020/mcs2020-lithium.pdf. 
  30. ↑ "Junior mining companies exploring for lithium". https://www.juniorminingnetwork.com/news-topics/topic/lithium.html. 
  31. ↑ Scheyder, Ernest (24 Sep 2020). "Tesla's Nevada lithium plan faces stark obstacles on path to production". Reuters. https://www.reuters.com/article/tesla-batteryday-lithium/teslas-nevada-lithium-plan-faces-stark-obstacles-on-path-to-production-idINL2N2GK2E1. 
  32. ↑ Serna-Guerrero, Rodrigo (5 November 2019). "A Critical Review of Lithium-Ion Battery Recycling Processes from a Circular Economy Perspective". Batteries 5 (4): 68. doi:10.3390/batteries5040068. 
  33. ↑ Dolotko, Oleksandr; Gehrke, Niclas; Malliaridou, Triantafillia; Sieweck, Raphael; Herrmann, Laura; Hunzinger, Bettina; Knapp, Michael; Ehrenberg, Helmut (March 28, 2023). "Universal and efficient extraction of lithium for lithium-ion battery recycling using mechanochemistry". Communications Chemistry (Springer Science and Business Media LLC) 6 (1). doi:10.1038/s42004-023-00844-2. ISSN 2399-3669. 
  34. ↑ Kropachev, Andrey; Kalabskiy, Igor (2020). "Hydrometallurgical preparation of lithium aluminum carbonate hydroxide hydrate, Li2Al4(CO3)(OH)12·3H2O from aluminate solution". Minerals Engineering (Elsevier BV) 155: 106470. doi:10.1016/j.mineng.2020.106470. ISSN 0892-6875. 
  35. ↑ Dave Borlace (15 May 2023). Battery recycling just got a whole lot better (YouTube video). London: Just Have a Think. Retrieved 15 May 2023.
  36. ↑ "MGX Minerals Receives Independent Confirmation of Rapid Lithium Extraction Process". 20 April 2017. https://www.juniorminingnetwork.com/junior-miner-news/press-releases/28-cse/xmg/31459-mgx-minerals-receives-independent-confirmation-of-rapid-lithium-extraction-process.html. 
  37. ↑ Martin, Richard (2015-06-08). "Quest to Mine Seawater for Lithium Advances". https://www.technologyreview.com/s/538036/quest-to-mine-seawater-for-lithium-advances/. 
  38. ↑ David Barthelmy. "Zabuyelite Mineral Data". Mineralogy Database. http://webmineral.com/data/Zabuyelite.shtml. 
  39. ↑ mindat.org

Wilkinson

External links

Carbonates
H2CO3 He
Li2CO3,
LiHCO3 		BeCO3 B C (NH4)2CO3,
NH4HCO3 		O F Ne
Na2CO3,
NaHCO3,
Na3H(CO3)2 		MgCO3,
Mg(HCO3)2 		Al2(CO3)3 Si P S Cl Ar
K2CO3,
KHCO3 		CaCO3,
Ca(HCO3)2 		Sc Ti V Cr MnCO3 FeCO3 CoCO3 NiCO3 CuCO3 ZnCO3 Ga Ge As Se Br Kr
Rb2CO3 SrCO3 Y Zr Nb Mo Tc Ru Rh Pd Ag2CO3 CdCO3 In Sn Sb Te I Xe
Cs2CO3,
CsHCO3 		BaCO3   Hf Ta W Re Os Ir Pt Au Hg Tl2CO3 PbCO3 (BiO)2CO3 Po At Rn
Fr Ra   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La2(CO3)3 Ce2(CO3)3 Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac Th Pa UO2CO3 Np Pu Am Cm Bk Cf Es Fm Md No Lr



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