:Lithium perchlorate
{{short description|Chemical compound}}
{{chembox
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 451153890
| Name = Lithium perchlorate
| ImageFile = Lithium Perchlorate.svg
| ImageSize = 180px
| ImageFile1 = Lithiumperchlorat.png
| ImageSize1 = 240px
| ImageCaption1 = __ Li+ __ Cl7+ __ O2−
Unit cell of lithium perchlorate.
| ImageAlt1 = The orthorhombic unit cell of lithium perchlorate under standard conditions.
| ImageName = Lithium perchlorate
| IUPACName = Lithium perchlorate
| OtherNames = Perchloric acid, lithium salt; Lithium Cloricum
| Section1 = {{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 133514
| InChI = 1/ClHO4.Li/c2-1(3,4)5;/h(H,2,3,4,5);/q;+1/p-1
| InChIKey = MHCFAGZWMAWTNR-REWHXWOFAR
| SMILES = [Li+].[O-]Cl(=O)(=O)=O
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/ClHO4.Li/c2-1(3,4)5;/h(H,2,3,4,5);/q;+1/p-1
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = MHCFAGZWMAWTNR-UHFFFAOYSA-M
| CASNo = 7791-03-9
| CASNo_Ref = {{cascite|correct|CAS}}
| UNII_Ref = {{fdacite|changed|FDA}}
| UNII = Q86SE98C9C
| PubChem = 23665649
}}
| Section2 = {{Chembox Properties
| Formula = {{chem|LiClO|4}}
| MolarMass = {{ubli
| 106.39 g/mol (anhydrous)
| 160.44 g/mol (trihydrate)
}}
| Appearance = White crystals
| Odor = Odorless
| Density = 2.42 g/cm3
| Solubility = {{ubli
| 42.7 g/100 mL (0 °C)
| 49 g/100 mL (10 °C)
| 59.8 g/100 mL (25 °C)
| 71.8 g/100 mL (40 °C)
| 119.5 g/100 mL (80 °C)
| 300 g/100 g (120 °C){{Cite web | url=http://chemister.ru/Database/properties-en.php?dbid=1&id=612 | title=Lithium perchlorate|website=chemister.ru}}
}}
| SolubleOther = Soluble in alcohols, ethyl acetate
| Solvent1 = acetone
| Solubility2 = {{ubli
| 182 g/100 g (CH3OH)
| 152 g/100 g (C2H5OH)
| 105 g/100 g (C3H7OH)
| 79.3 g/100 g (n-C4H9OH)
| 58 g/100 g (i-C4H9OH
}}
| Solvent2 = alcohols
|Solubility3= 95.2 g/100 g{{cite book|chapter=Lithium Perchlorate|title=AMCP 706-187 Military Pyrotechnics - Properties of Materials|chapter-url=https://archive.org/details/AMCP706187MilitaryPyrotechnicsPropertiesOfMaterials/page/n197|pages=181–182|date=October 1963|publisher=US Army Materiel Command}}
|Solvent3=ethyl acetate
|Solvent4=ethyl ether
| MeltingPtC = 236
| BoilingPtC = 430
| BoilingPt_notes =
decomposes from 400 °C
}}
| Section3 = {{Chembox Structure
| UnitCellFormulas = 4 formula per cell
| SpaceGroup = Pnma, No. 62
| LattConst_a = 865.7(1) pm
| LattConst_b = 691.29(9) pm
| LattConst_c = 483.23(6) pm
| Coordination = tetrahedral at Cl
}}
| Section4 = {{Chembox Thermochemistry
| DeltaHf = −380.99 kJ/mol
| DeltaHc =
}}
| Section7 = {{Chembox Hazards
| ExternalSDS = [http://www.sciencelab.com/msds.php?msdsId=9924516 MSDS]
| MainHazards = Oxidizer, irritant
| NFPA-H = 2 | NFPA-F = 0 | NFPA-R = 0 | NFPA-S = OX
| GHSPictograms = {{GHS03}}{{GHS07}}{{Sigma-Aldrich|id=431567|name=Lithium perchlorate|accessdate=2014-05-09}}
| GHSSignalWord = Danger
| HPhrases = {{H-phrases|272|315|319|335}}
| PPhrases = {{P-phrases|220|261|305+351+338}}
}}
| Section8 = {{Chembox Related
| OtherAnions = Lithium chloride
Lithium hypochlorite
Lithium chlorate
| OtherCations = Sodium perchlorate
Potassium perchlorate
Rubidium perchlorate
}}
}}
Lithium perchlorate is the inorganic compound with the formula LiClO4. This white or colourless crystalline salt is noteworthy for its high solubility in many solvents. It exists both in anhydrous form and as a trihydrate.
Applications
=Inorganic chemistry=
Lithium perchlorate is used as a source of oxygen in some chemical oxygen generators. It decomposes at about 400 °C, yielding lithium chloride and oxygen:{{cite journal|title=Lithium Perchlorate Oxygen Candle. Pyrochemical Source of Pure Oxygen|first1=M. M.|last1=Markowitz|first2=D. A.|last2=Boryta|first3=Harvey Jr.|last3=Stewart|journal=Industrial & Engineering Chemistry Product Research and Development|year=1964|volume=3|issue=4|pages=321–330
|doi=10.1021/i360012a016}}
: LiClO4 → LiCl + 2 O2
Over 60% of the mass of the lithium perchlorate is released as oxygen. It has both the highest oxygen to weight and oxygen to volume ratio of all practical perchlorate salts, and higher oxygen to volume ratio than liquid oxygen.{{cite book|author=Herbert Ellern|title=Military and Civilian Pyrotechnics|page=237|year=1968|publisher=Chemical Publishing Company|isbn=978-0-8206-0364-3|ol=OL37082807M}}
Lithium perchlorate is used as an oxidizer in some experimental solid rocket propellants, and to produce red colored flame in pyrotechnic compositions.{{cite book|author1=Basil T. Fedoroff|author2=Oliver E. Sheffield|title=Encyclopedia of explosives and related items|chapter=Lithium Perchlorate|date=January 1975 |chapter-url=https://archive.org/details/DTIC_ADA019502/page/45|volume=7|page=L45|publisher=Picatinny Arsenal|lccn=61-61759}}
=Organic chemistry=
LiClO4 is highly soluble in organic solvents, even diethyl ether. Such solutions are employed in Diels–Alder reactions, where it is proposed that the Lewis acidic Li+ binds to Lewis basic sites on the dienophile, thereby accelerating the reaction.Charette, A. B. "Lithium Perchlorate" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. {{doi|10.1002/047084289X}}.
Lithium perchlorate is also used as a co-catalyst in the coupling of α,β-unsaturated carbonyls with aldehydes, also known as the Baylis–Hillman reaction.[http://www.sigmaaldrich.com/catalog/search/ProductDetail/sigald/205281] Lithium Perchlorate Product Detail Page
Solid lithium perchlorate is found to be a mild and efficient Lewis acid for promoting cyanosilylation of carbonyl compounds under neutral conditions.{{cite journal
| author= N. Azizi, M.R. Saidi
| title = An improved synthesis of cyanohydrins in the presence of solid LiClO4 under solvent-free conditions
| journal = Journal of Organometallic Chemistry
| year = 2003
| volume = 688
| issue = 1–2
| pages = 283–285| doi = 10.1016/j.jorganchem.2003.09.014
}}
=Batteries=
Lithium perchlorate is also used as an electrolyte salt in lithium-ion batteries. Lithium perchlorate is chosen over alternative salts such as lithium hexafluorophosphate or lithium tetrafluoroborate when its superior electrical impedance, conductivity, hygroscopicity, and anodic stability properties are of importance to the specific application.{{cite journal|last=Xu|first=Kang|title=Nonaqueous liquid electrolytes for lithium-based rechargeable batteries|journal=Chemical Reviews|date=2004|volume=104|issue=10|pages=4303–4417|doi=10.1021/cr030203g|pmid=15669157|url=https://is.muni.cz/el/1431/podzim2006/C7780/um/Read/2659326/LiON_ellytes_ChRev04_4303.pdf|access-date=24 February 2014}} However, these beneficial properties are often overshadowed by the electrolyte's strong oxidizing properties, making the electrolyte reactive toward its solvent at high temperatures and/or high current loads. Due to these hazards the battery is often considered unfit for industrial applications.
=Biochemistry=
Concentrated solutions of lithium perchlorate (4.5 mol/L) are used as a chaotropic agent to denature proteins.
Production
Lithium perchlorate can be manufactured by reaction of sodium perchlorate with lithium chloride. It can be also prepared by electrolysis of lithium chlorate at 200 mA/cm2 at temperatures above 20 °C.Helmut Vogt, Jan Balej, John E. Bennett, Peter Wintzer, Saeed Akbar Sheikh, Patrizio Gallone "Chlorine Oxides and Chlorine Oxygen Acids" in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH. {{doi|10.1002/14356007.a06_483}}
Safety
Perchlorates often give explosive mixtures with organic compounds, finely divided metals, sulfur, and other reducing agents.
References
{{reflist}}
Fuerther reading
- {{Cite encyclopedia |title=Perchlorate Oxidizers |encyclopedia=Encyclopedia of Oxidizers |publisher=De Gruyter |last=Schmidt |first=Eckart W. |date=2022 |pages=3752–3761|doi=10.1515/9783110750294-028 |isbn=978-3-11-075029-4 |chapter=Alkali Metal Chlorates and Perchlorates}}
External links
- [https://webbook.nist.gov/cgi/cbook.cgi?ID=C7791039 WebBook page for LiClO4]
{{Lithium compounds}}
{{Perchlorates}}