Lithium hydroxide

Last updated
Lithium hydroxide
Lithiumhydroxide t.png
Lithium-hydroxide-xtal-3D-SF.png
Kristallstruktur Lithiumhydroxid.png
   Li +        O 2−        H +
Lithium hydroxide.jpg
Names
IUPAC name
Lithium hydroxide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.013.804 OOjs UI icon edit-ltr-progressive.svg
68415
PubChem CID
RTECS number
  • OJ6307070
UNII
UN number 2680
  • InChI=1S/Li.H2O/h;1H2/q+1;/p-1 Yes check.svgY
    Key: WMFOQBRAJBCJND-UHFFFAOYSA-M Yes check.svgY
  • InChI=1/Li.H2O/h;1H2/q+1;/p-1
    Key: WMFOQBRAJBCJND-REWHXWO
  • [Li+].[OH-]
Properties
LiOH
Molar mass
  • 23.95 g/mol (anhydrous)
  • 41.96 g/mol (monohydrate)
Appearance Hygroscopic white solid
Odor none
Density
  • 1.46 g/cm3 (anhydrous)
  • 1.51 g/cm3 (monohydrate)
Melting point 462 °C (864 °F; 735 K)
Boiling point 924 °C (1,695 °F; 1,197 K) (decomposes)
  • anhydrous:
  • 12.7 g/(100 mL) (0 °C)
  • 12.8 g/(100 mL) (20 °C)
  • 17.5 g/(100 mL) (100 °C)
  • monohydrate:
  • 22.3 g/(100 mL) (10 °C)
  • 26.8 g/(100 mL) (80 °C) [1]
Solubility in methanol
  • 9.76 g/(100 g) (anhydrous; 20 °C, 48 hours mixing)
  • 13.69 g/(100 g) (monohydrate; 20 °C, 48 hours mixing) [2]
Solubility in ethanol
  • 2.36 g/(100 g) (anhydrous; 20 °C, 48 hours mixing)
  • 2.18 g/(100 g) (monohydrate; 20 °C, 48 hours mixing) [2]
Solubility in isopropanol
  • 0 g/(100 g) (anhydrous; 20 °C, 48 hours mixing)
  • 0.11 g/(100 g) (monohydrate; 20 °C, 48 hours mixing) [2]
Acidity (pKa)14.4 [3]
Conjugate base Lithium monoxide anion
−12.3·10−6 cm3/mol
  • 1.464 (anhydrous)
  • 1.460 (monohydrate)
4.754  D [4]
Thermochemistry [5]
49.6 J/(mol·K)
Std molar
entropy (S⦵298)
42.8 J/(mol·K)
−487.5 kJ/mol
−441.5 kJ/mol
Enthalpy of fusion (ΔfH⦵fus)
20.9 kJ/mol (at melting point)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Corrosive
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
0
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
210 mg/kg (oral, rat) [6]
Safety data sheet (SDS) "ICSC 0913".
"ICSC 0914". (monohydrate)
Related compounds
Other anions
Lithium amide
Other cations
Related compounds
 Lithium oxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Lithium hydroxide is an inorganic compound with the formula LiOH. It can exist as anhydrous or hydrated, and both forms are white hygroscopic solids. They are soluble in water and slightly soluble in ethanol. Both are available commercially. While classified as a strong base, lithium hydroxide is the weakest known alkali metal hydroxide.

Contents

Production

The preferred feedstock is hard-rock spodumene, where the lithium content is expressed as % lithium oxide.

Lithium carbonate route

Lithium hydroxide is often produced industrially from lithium carbonate in a metathesis reaction with calcium hydroxide: [7]

Li2CO3 + Ca(OH)2 → 2 LiOH + CaCO3

The initially produced hydrate is dehydrated by heating under vacuum up to 180 °C.

Lithium sulfate route

An alternative route involves the intermediacy of lithium sulfate: [8] [9]

α-spodumene → β-spodumene
β-spodumene + CaO → Li2O + ...
Li2O + H2SO4 → Li2SO4 + H2O
Li2SO4 + 2 NaOH → Na2SO4 + 2 LiOH

The main by-products are gypsum and sodium sulphate, which have some market value.

Commercial setting

According to Bloomberg, Ganfeng Lithium Co. Ltd. [10] (GFL or Ganfeng) [11] and Albemarle were the largest producers in 2020 with around 25kt/y, followed by Livent Corporation (FMC) and SQM. [10] Significant new capacity is planned, to keep pace with demand driven by vehicle electrification. Ganfeng are to expand lithium chemical capacity to 85,000 tons, adding the capacity leased from Jiangte, Ganfeng will become the largest lithium hydroxide producer globally in 2021. [10]

Albemarle's Kemerton WA plant, originally planned to deliver 100kt/y has been scaled back to 50kt/y. [12]

In 2020 Tianqi Lithium's, plant in Kwinana, Western Australia is the largest producer, with a capacity of 48kt/y. [13]

Applications

Lithium ion batteries

Lithium hydroxide is mainly consumed in the production of cathode materials for lithium ion batteries such as lithium cobalt oxide (LiCoO2) and lithium iron phosphate. It is preferred over lithium carbonate as a precursor for lithium nickel manganese cobalt oxides. [14]

Grease

A popular lithium grease thickener is lithium 12-hydroxystearate, which produces a general-purpose lubricating grease due to its high resistance to water and usefulness at a range of temperatures.

Carbon dioxide scrubbing

Lithium hydroxide is used in breathing gas purification systems for spacecraft, submarines, and rebreathers to remove carbon dioxide from exhaled gas by producing lithium carbonate and water: [15]

2 LiOH·H2O + CO2 → Li2CO3 + 3 H2O

or

2 LiOH + CO2 → Li2CO3 + H2O

The latter, anhydrous hydroxide, is preferred for its lower mass and lesser water production for respirator systems in spacecraft. One gram of anhydrous lithium hydroxide can remove 450 cm3 of carbon dioxide gas. The monohydrate loses its water at 100–110 °C.

Precursor

Lithium hydroxide, together with lithium carbonate, is a key intermediates used for the production of other lithium compounds, illustrated by its use in the production of lithium fluoride: [7]

LiOH + HF → LiF + H2O

Other uses

It is also used in ceramics and some Portland cement formulations, where it is also used to suppress ASR (concrete cancer). [16]

Lithium hydroxide (isotopically enriched in lithium-7) is used to alkalize the reactor coolant in pressurized water reactors for corrosion control. [17] It is good radiation protection against free neutrons.

Price

In 2012, the price of lithium hydroxide was about $5-6/kg. [18]

In December 2020 it had risen to $9/kg [19]

On 18 March 2021 the price had risen to US$11.50/kg [20]

See also

Related Research Articles

<span class="mw-page-title-main">Hydroxide</span> Chemical compound

Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, a ligand, a nucleophile, and a catalyst. The hydroxide ion forms salts, some of which dissociate in aqueous solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per annum commodity chemical. The corresponding electrically neutral compound HO• is the hydroxyl radical. The corresponding covalently bound group –OH of atoms is the hydroxy group. Both the hydroxide ion and hydroxy group are nucleophiles and can act as catalysts in organic chemistry.

<span class="mw-page-title-main">Lithium carbonate</span> Chemical compound

Lithium carbonate is an inorganic compound, the lithium salt of carbonic acid with the formula Li
2CO
3. This white salt is widely used in processing metal oxides. It is on the World Health Organization's List of Essential Medicines for its efficacy in the treatment of mood disorders such as bipolar disorder.

<span class="mw-page-title-main">Base (chemistry)</span> Type of chemical substance

In chemistry, there are three definitions in common use of the word "base": Arrhenius bases, Brønsted bases, and Lewis bases. All definitions agree that bases are substances that react with acids, as originally proposed by G.-F. Rouelle in the mid-18th century.

<span class="mw-page-title-main">Potassium hydroxide</span> Inorganic compound (KOH)

Potassium hydroxide is an inorganic compound with the formula KOH, and is commonly called caustic potash.

<span class="mw-page-title-main">Potassium carbonate</span> Chemical compound

Potassium carbonate is the inorganic compound with the formula K2CO3. It is a white salt, which is soluble in water and forms a strongly alkaline solution. It is deliquescent, often appearing as a damp or wet solid. Potassium carbonate is mainly used in the production of soap and glass. Commonly, it can be found as the result of leakage of alkaline batteries.

<span class="mw-page-title-main">Magnesium carbonate</span> Chemical compound

Magnesium carbonate, MgCO3, is an inorganic salt that is a colourless or white solid. Several hydrated and basic forms of magnesium carbonate also exist as minerals.

<span class="mw-page-title-main">Barium hydroxide</span> Chemical compound

Barium hydroxide is a chemical compound with the chemical formula Ba(OH)2. The monohydrate (x = 1), known as baryta or baryta-water, is one of the principal compounds of barium. This white granular monohydrate is the usual commercial form.

Sodium oxide is a chemical compound with the formula Na2O. It is used in ceramics and glasses. It is a white solid but the compound is rarely encountered. Instead "sodium oxide" is used to describe components of various materials such as glasses and fertilizers which contain oxides that include sodium and other elements.

<span class="mw-page-title-main">Lithium hydride</span> Chemical compound

Lithium hydride is an inorganic compound with the formula LiH. This alkali metal hydride is a colorless solid, although commercial samples are grey. Characteristic of a salt-like (ionic) hydride, it has a high melting point, and it is not soluble but reactive with all protic organic solvents. It is soluble and nonreactive with certain molten salts such as lithium fluoride, lithium borohydride, and sodium hydride. With a molar mass of 7.95 g/mol, it is the lightest ionic compound.

<span class="mw-page-title-main">Telluric acid</span> Chemical compound (Te(OH)6)

Telluric acid, or more accurately orthotelluric acid, is a chemical compound with the formula Te(OH)6, often written as H6TeO6. It is a white crystalline solid made up of octahedral Te(OH)6 molecules which persist in aqueous solution. In the solid state, there are two forms, rhombohedral and monoclinic, and both contain octahedral Te(OH)6 molecules, containing one hexavalent tellurium (Te) atom in the +6 oxidation state, attached to six hydroxyl (–OH) groups, thus, it can be called tellurium(VI) hydroxide. Telluric acid is a weak acid which is dibasic, forming tellurate salts with strong bases and hydrogen tellurate salts with weaker bases or upon hydrolysis of tellurates in water. It is used as tellurium-source in the synthesis of oxidation catalysts.

<span class="mw-page-title-main">Lithium bromide</span> Chemical compound

Lithium bromide (LiBr) is a chemical compound of lithium and bromine. Its extreme hygroscopic character makes LiBr useful as a desiccant in certain air conditioning systems.

<span class="mw-page-title-main">Lithium sulfate</span> Chemical compound

Lithium sulfate is a white inorganic salt with the formula Li2SO4. It is the lithium salt of sulfuric acid.

Basic oxides are oxides that show basic properties, in opposition to acidic oxides. A basic oxide can either react with water to form a base, or with an acid to form a salt and water in a neutralization reaction.

<span class="mw-page-title-main">Lithium oxide</span> Chemical compound

Lithium oxide (Li
2O) or lithia is an inorganic chemical compound. It is a white solid. Although not specifically important, many materials are assessed on the basis of their Li2O content. For example, the Li2O content of the principal lithium mineral spodumene (LiAlSi2O6) is 8.03%.

<span class="mw-page-title-main">Lithium peroxide</span> Chemical compound

Lithium peroxide is the inorganic compound with the formula Li2O2. It is a white, nonhygroscopic solid. Because of its high oxygen:mass and oxygen:volume ratios, the solid has been used to remove CO2 from the atmosphere in spacecraft.

<span class="mw-page-title-main">Cadmium nitrate</span> Chemical compound

Cadmium nitrate describes any of the related members of a family of inorganic compounds with the general formula , the most commonly encountered form being the tetrahydrate. The anhydrous form is volatile, but the others are colourless crystalline solids that are deliquescent, tending to absorb enough moisture from the air to form an aqueous solution. Like other cadmium compounds, cadmium nitrate is known to be carcinogenic.

<span class="mw-page-title-main">Carbon dioxide scrubber</span> Device which absorbs carbon dioxide from circulated gas

A carbon dioxide scrubber is a piece of equipment that absorbs carbon dioxide (CO2). It is used to treat exhaust gases from industrial plants or from exhaled air in life support systems such as rebreathers or in spacecraft, submersible craft or airtight chambers. Carbon dioxide scrubbers are also used in controlled atmosphere (CA) storage. They have also been researched for carbon capture and storage as a means of combating climate change.

<span class="mw-page-title-main">Cobalt(II) hydroxide</span> Chemical compound

Cobalt(II) hydroxide or cobaltous hydroxide is the inorganic compound with the formula Co(OH)
2, consisting of divalent cobalt cations Co2+
 and hydroxide anions OH−
. The pure compound, often called the "beta form" is a pink solid insoluble in water.

Aluminium carbonate (Al2(CO3)3), is a carbonate of aluminium. It is not well characterized; one authority says that simple carbonates of aluminium are not known. However related compounds are known, such as the basic sodium aluminium carbonate mineral dawsonite (NaAlCO3(OH)2) and hydrated basic aluminium carbonate minerals scarbroite (Al5(CO3)(OH)13•5(H2O)) and hydroscarbroite (Al14(CO3)3(OH)36•nH2O).

Lithium thiocyanate is a chemical compound with the formula LiSCN. It is an extremely hygroscopic white solid that forms the monohydrate and the dihydrate. It is the least stable of the alkali metal thiocyanates due to the large electrostatic deforming field of the lithium cation.

References

  1. ↑ Lide, David R., ed. (2006). CRC Handbook of Chemistry and Physics (87th ed.). Boca Raton, FL: CRC Press. ISBN   0-8493-0487-3.
  2. 1 2 3 Khosravi J (2007). Production of Lithium Peroxide and Lithium Oxide in an Alcohol Medium. Chapter 9: Results. ISBN   978-0-494-38597-5.
  3. ↑ Popov K, Lajunen LH, Popov A, Rönkkömäki H, Hannu-Kuure H, Vendilo A (2002). "7Li, 23Na, 39K and 133Cs NMR comparative equilibrium study of alkali metal cation hydroxide complexes in aqueous solutions. First numerical value for CsOH formation". Inorganic Chemistry Communications. 5 (3): 223–225. doi:10.1016/S1387-7003(02)00335-0 . Retrieved 21 January 2017.
  4. ↑ CRC handbook of chemistry and physics : a ready-reference book of chemical and physical data. William M. Haynes, David R. Lide, Thomas J. Bruno (2016-2017, 97th ed.). Boca Raton, Florida. 2016. ISBN   978-1-4987-5428-6. OCLC   930681942.{{cite book}}: CS1 maint: location missing publisher (link) CS1 maint: others (link)
  5. ↑ CRC handbook of chemistry and physics : a ready-reference book of chemical and physical data. William M. Haynes, David R. Lide, Thomas J. Bruno (2016-2017, 97th ed.). Boca Raton, Florida. 2016. ISBN   978-1-4987-5428-6. OCLC   930681942.{{cite book}}: CS1 maint: location missing publisher (link) CS1 maint: others (link)
  6. ↑ Chambers M. "ChemIDplus – 1310-65-2 – WMFOQBRAJBCJND-UHFFFAOYSA-M – Lithium hydroxide anhydrous – Similar structures search, synonyms, formulas, resource links, and other chemical information". chem.sis.nlm.nih.gov. Retrieved 12 April 2018.
  7. 1 2 Wietelmann U, Bauer RJ (2000). Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a15_393. ISBN   978-3527306732.
  8. ↑ "Proposed Albemarle Plant Site" (PDF). Albemarle. Retrieved 4 December 2020.
  9. ↑ "Corporate presentation" (PDF). Nemaska Lithium. May 2018. Archived from the original (PDF) on 23 October 2021. Retrieved 5 December 2020.
  10. 1 2 3 "China's Ganfeng to Be Largest Lithium Hydroxide Producer". BloombergNEF. 10 September 2020. Retrieved 4 December 2020.
  11. ↑ "Ganfeng Lithium Group". Ganfeng Lithium . Retrieved 25 March 2021.
  12. ↑ Stephens, Kate; Lynch, Jacqueline (27 August 2020). "Slowing demand for lithium sees WA's largest refinery scaled back". www.abc.net.au.
  13. ↑ "Largest of its kind lithium hydroxide plant launched in Kwinana". Government of Western Australia. 10 September 2019. Archived from the original on 17 February 2023. Retrieved 4 December 2020.
  14. ↑ Barrera, Priscilla (27 June 2019). "Will Lithium Hydroxide Really Overtake Lithium Carbonate? | INN". Investing News Network. Retrieved 5 December 2020.
  15. ↑ Jaunsen JR (1989). "The Behavior and Capabilities of Lithium Hydroxide Carbon Dioxide Scrubbers in a Deep Sea Environment". US Naval Academy Technical Report. USNA-TSPR-157. Archived from the original on 2009-08-24. Retrieved 2008-06-17.{{cite journal}}: CS1 maint: unfit URL (link)
  16. ↑ Kawamura M, Fuwa H (2003). "Effects of lithium salts on ASR gel composition and expansion of mortars". Cement and Concrete Research. 33 (6): 913–919. doi:10.1016/S0008-8846(02)01092-X. OSTI   20658311 . Retrieved 2022-10-17.
  17. ↑ Managing Critical Isotopes: Stewardship of Lithium-7 Is Needed to Ensure a Stable Supply, GAO-13-716 // U.S. Government Accountability Office, 19 September 2013; pdf
  18. ↑ "Lithium Prices 2012". investingnews.com. Investing News Network. 14 June 2012. Archived from the original on 11 March 2018. Retrieved 12 April 2018.
  19. ↑ "London Metal Exchange: Lithium prices". London metal exchange. Retrieved 4 December 2020.
  20. ↑ "LITHIUM AT THE LME". LME The London Metal Exchange . 18 March 2021. Retrieved 22 March 2021.
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