Lithium perchlorate

Lithium perchlorate
	; __ Li+ __ Cl7+ __ O2− ; Unit cell of lithium perchlorate.
Names
	IUPAC name Lithium perchlorate
	Other names Perchloric acid, lithium salt; Lithium Cloricum
Identifiers
CAS Number	7791-03-9 ;
3D model (JSmol)	Interactive image;
ChemSpider	133514 ;
ECHA InfoCard	100.029.307
PubChem CID	23665649;
UNII	Q86SE98C9C ;
CompTox Dashboard (EPA)	DTXSID40872829 ;
	InChI InChI=1S/ClHO4.Li/c2-1(3,4)5;/h(H,2,3,4,5);/q;+1/p-1 Key: MHCFAGZWMAWTNR-UHFFFAOYSA-M ; InChI=1/ClHO4.Li/c2-1(3,4)5;/h(H,2,3,4,5);/q;+1/p-1 Key: MHCFAGZWMAWTNR-REWHXWOFAR;
	SMILES [Li+].[O-]Cl(=O)(=O)=O;
Properties
Chemical formula	LiClO; 4
Molar mass	106.39 g/mol (anhydrous); 160.44 g/mol (trihydrate)
Appearance	white crystals
Odor	odorless
Density	2.42 g/cm3
Melting point	236 °C (457 °F; 509 K)
Boiling point	430 °C (806 °F; 703 K) ; decomposes from 400 °C
Solubility in water	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)
Solubility	soluble in alcohol, ethyl acetate
Solubility in acetone	137 g/100 g
Solubility in alcohol	1.82 g/g (0 °C, in CH3OH); 1.52 g/g (0 °C, in C2H5OH); 1.05 g/g (25 °C, in C3H7OH); 0.793 g/g (0 °C, in C4H9OH)
Structure
Space group	Pnma, No. 62
Lattice constant	a = 865.7(1) pm, b = 691.29(9) pm, c = 483.23(6) pm
Formula units (Z)	4 formula per cell
Coordination geometry	tetrahedral at Cl
Thermochemistry
Heat capacity (C)	105 J/mol·K
Std molar; entropy (So298)	125.5 J/mol·K
Std enthalpy of; formation (ΔfH⦵298)	-380.99 kJ/mol
Gibbs free energy (ΔfG˚)	-254 kJ/mol
Hazards
Main hazards	Oxidizer, irritant
Safety data sheet	MSDS
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H272, H315, H319, H335
Precautionary statements	P220, P261, P305+P351+P338
NFPA 704 (fire diamond)	2 0 0 OX
Related compounds
Other anions	Lithium chloride; Lithium hypochlorite; Lithium chlorate
Other cations	Sodium perchlorate; Potassium perchlorate; Rubidium perchlorate
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	(what is ?)
	Infobox references

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:^[4]

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.

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.^[5]

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.^[6]

Solid lithium perchlorate is found to be a mild and efficient Lewis acid for promoting cyanosilylation of carbonyl compounds under neutral conditions.^[7]

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.^[8] 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.^[8]

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.^[9]

Safety[]

Perchlorates often give explosive mixtures with organic compounds.^[9]

References[]

^ ^a ^b ^c ^d ^e ^f ^g "Lithium perchlorate".
^ Wickleder, Mathias S. (2003). "Crystal Structure of LiClO4". Zeitschrift für Anorganische und Allgemeine Chemie. 629 (9): 1466–1468. doi:10.1002/zaac.200300114.
^ ^a ^b ^c Sigma-Aldrich Co., Lithium perchlorate. Retrieved on 2014-05-09.
^ M. M. Markowitz, D. A. Boryta, and Harvey Stewart, Jr. (1964). "Lithium Perchlorate Oxygen Candle. Pyrochemical Source of Pure Oxygen". Ind. Eng. Chem. Prod. Res. Dev. 3 (4): 321–330. doi:10.1021/i360012a016.CS1 maint: uses authors parameter (link)
^ 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.
^ [1] Lithium Perchlorate Product Detail Page
^ N. Azizi, M.R. Saidi (2003). "An improved synthesis of cyanohydrins in the presence of solid LiClO4 under solvent-free conditions". Journal of Organometallic Chemistry. 688 (1–2): 283–285. doi:10.1016/j.jorganchem.2003.09.014.
^ ^a ^b Xu, Kang (2004). "Nonaqueous liquid electrolytes for lithium-based rechargeable batteries" (PDF). Chemical Reviews. 104 (10): 4303–4417. doi:10.1021/cr030203g. PMID 15669157. Retrieved 24 February 2014.
^ ^a ^b 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

External links[]

WebBook page for LiClO4

HClO₄

He

LiClO₄

B(ClO
₄)⁻
₄

NH₄ClO₄

H₃OClO₄

FClO₄

Ne

NaClO₄

Mg(ClO₄)₂

Al(ClO
₄)⁻
₄

Al(ClO
₄)³⁻
₆

Si

P

S

ClO⁻
₄
ClOClO₃
Cl₂O₇

Ar

KClO₄

Ca(ClO₄)₂

Sc(ClO₄)₃

Ti(ClO₄)₄

VO(ClO₄)₃
VO₂(ClO₄)

Cr(ClO₄)₃

Fe(ClO₄)₂

,

Cu(ClO₄)₂

Ge

As

Se

Br

Kr

RbClO₄

Sr(ClO₄)₂

Zr(ClO₄)₄

Mo

Tc

Ru

Rh(ClO₄)₃

AgClO₄

Sb

I

Xe

CsClO₄

Ba(ClO₄)₂

W

Re

Os

Ir

Pt

Au

,

Po

At

Rn

Ra

Rf

Db

Sg

Bh

Hs

Mt

Ds

Rg

Cn

Nh

Fl

Mc

Lv

Ts

Og

↓

La

Pr

Nd

Pm

Ac

Pa

Np

Pu

Am

Cm

Bk

Cf

Es

Fm

Md

No

Lr

[chemister-1] ^ ^a ^b ^c ^d ^e ^f ^g "Lithium perchlorate".

[2] Wickleder, Mathias S. (2003). "Crystal Structure of LiClO4". Zeitschrift für Anorganische und Allgemeine Chemie. 629 (9): 1466–1468. doi:10.1002/zaac.200300114.

[sigma-3] Sigma-Aldrich Co., Lithium perchlorate. Retrieved on 2014-05-09.

[4] M. M. Markowitz, D. A. Boryta, and Harvey Stewart, Jr. (1964). "Lithium Perchlorate Oxygen Candle. Pyrochemical Source of Pure Oxygen". Ind. Eng. Chem. Prod. Res. Dev. 3 (4): 321–330. doi:10.1021/i360012a016.CS1 maint: uses authors parameter (link)

[5] 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.

[6] [1] Lithium Perchlorate Product Detail Page

[7] N. Azizi, M.R. Saidi (2003). "An improved synthesis of cyanohydrins in the presence of solid LiClO4 under solvent-free conditions". Journal of Organometallic Chemistry. 688 (1–2): 283–285. doi:10.1016/j.jorganchem.2003.09.014.

[Xu-8] Xu, Kang (2004). "Nonaqueous liquid electrolytes for lithium-based rechargeable batteries" (PDF). Chemical Reviews. 104 (10): 4303–4417. doi:10.1021/cr030203g. PMID 15669157. Retrieved 24 February 2014.

[Vogt-9] 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

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

v t Lithium compounds (list)
Inorganic (list)	Li₂ Dilithium LiAlCl₄ Aluminium chloride/LAC Li_1+xAl_xGe_2-x(PO₄)₃ Aluminium germanium phosphate/LAGP LiAlH₄ Aluminium hydride/LAH LiAlO₂ LiB(C₆F₅)₄ LiBF₄ LiBH₄ LiBO₂ LiB₃O₅ Triborate/LBO Li₂B₄O₇ Borate/Tetraborate LiBr Li₂C₂ LiCF₃SO₃ LiCH₃O LiCN Li₂CO₃ Li₂C₂O₄ LiCl LiClO LiClO₃ LiClO₄ LiCoO₂ CsLiB₆O₁₀ CLBO LiD LiF FLiBe LiFePO₄ Iron phosphate/LFP FLiNaK LiGaH₄ Li₂GeF₆ LiH LiHCO₃ LiHe LiI LiIO₃ Li₂IrO₃ Li₇La₃Zr₂O₁₂ Li₂MoO₄ Li_0.9Mo₆O₁₇ LiN₃ Azide Li₃N LiNH₂ Li₂NH LiNO₂ LiNO₃ LiNaNO₂ LiNbO₃ LiO⁻ LiO₂ Li₂O Li₂O₂ LiOH Li₃P LiPF₆ Li₂Po Li₂PtO₃ Li₂RuO₃ Li₂S Li₂SO₃ Li₂SO₄ Li₂Se Li₄SiO₄ Li₂SiO₃ Li₂Si₂O₅ LiTaO₃ Li₂TiO₃ Li₂WO₄ LiYF₄ Neodymium-doped
Organic (soaps)	Hemolithin (extraterrestrial protein) Organolithium reagents Gilman reagent CH₃COOLi Acetate C₄H₆LiNO₄ Aspartate LiC₂F₆NO₄S₂ LiTFSI LiN(SiMe₃)₂ LiHMDS Li₃C₆H₅O₇ Citrate C₅H₅Li Cyclopentadienide LiN(C₃H₇)₂ Diisopropylamide (C₆H₅)₂PLi Diphenylphosphide C₁₈H₃₅LiO₃ 12-Hydroxystearate C₆H₁₃Li n-Hexyllithium C₄H₉Li n-Butyllithium CH₃CHLiCH₂CH₃ sec-Butyllithium (CH₃)₃CLi tert-Butyllithium C₁₂H₂₈BLi L-selectride CH₃Li Methyllithium Li⁺C₁₀H₈⁻ Naphthalene C₅H₁₁Li Neopentyllithium C₅H₃LiN₂O₄ Orotate C₆H₅Li Phenyllithium LiC₂CH₃ Propynyllithium LiO₂C(CH₂)₁₆CH₃ Stearate C₄H₅LiO₄ Succinate LiEt₃BH Superhydride LiOC(CH₃)₃ tert-Butoxide C₉H₁₈LiN Tetramethylpiperidide LiC₂H₃ Vinyllithium
Minerals	Amblygonite Elbaite LiAlSiO₄ Eucryptite Faizievite Fluor-liddicoatite Hectorite LiNaSiB₃O₇OH Jadarite Li(AlSi₂O₆) Keatite Lepidolite LiMnPO₄ Lithiophilite Li₃PO₄ Lithiophosphate Nambulite Neptunite LiAlSi₄0₁₀ Petalite Cs(Be₂Li)Al₂Si₆O₁₈ Pezzottaite Saliotite LiAl(SiO₃)₂ Spodumene Sugilite Tourmaline LiFePO₄ Triphylite Li₂CO₃ Zabuyelite Zektzerite Zinnwaldite
Hypothetical	Li_xBe_y Lithium beryllide La_2/3-xLi_3xTiO₃He
Other Li-related	Aluminium–lithium alloys Heteroatom-promoted lateral lithiation LB buffer LiNi_xCo_yAl_zO₂ Lithium nickel cobalt aluminium oxides LiNi_xMn_yCo_zO₂ Lithium nickel manganese cobalt oxides Lithium soap Lucifer yellow Magnesium–lithium alloys NASICON

Names

__ Li⁺ __ Cl⁷⁺ __ O²⁻ Unit cell of lithium perchlorate.
IUPAC name Lithium perchlorate
Other names Perchloric acid, lithium salt; Lithium Cloricum
Identifiers
CAS Number	7791-03-9^Y
3D model (JSmol)	Interactive image
ChemSpider	133514^Y
ECHA InfoCard	100.029.307
PubChem CID	23665649
UNII	Q86SE98C9C^N
CompTox Dashboard (EPA)	DTXSID40872829
InChI InChI=1S/ClHO4.Li/c2-1(3,4)5;/h(H,2,3,4,5);/q;+1/p-1^Y Key: MHCFAGZWMAWTNR-UHFFFAOYSA-M^Y InChI=1/ClHO4.Li/c2-1(3,4)5;/h(H,2,3,4,5);/q;+1/p-1 Key: MHCFAGZWMAWTNR-REWHXWOFAR
SMILES [Li+].[O-]Cl(=O)(=O)=O
Properties
Chemical formula	LiClO ₄
Molar mass	106.39 g/mol (anhydrous) 160.44 g/mol (trihydrate)
Appearance	white crystals
Odor	odorless
Density	2.42 g/cm³
Melting point	236 °C (457 °F; 509 K)
Boiling point	430 °C (806 °F; 703 K) decomposes from 400 °C
Solubility in water	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)^[1]
Solubility	soluble in alcohol, ethyl acetate^[1]
Solubility in acetone	137 g/100 g^[1]
Solubility in alcohol	1.82 g/g (0 °C, in CH₃OH) 1.52 g/g (0 °C, in C₂H₅OH) 1.05 g/g (25 °C, in C₃H₇OH) 0.793 g/g (0 °C, in C₄H₉OH)^[1]
Structure
Space group	Pnma, No. 62
Lattice constant	a = 865.7(1) pm, b = 691.29(9) pm, c = 483.23(6) pm^[2]
Formula units (Z)	4 formula per cell
Coordination geometry	tetrahedral at Cl
Thermochemistry
Heat capacity (C)	105 J/mol·K^[1]
Std molar entropy (S^o₂₉₈)	125.5 J/mol·K^[1]
Std enthalpy of formation (Δ_fH^⦵₂₉₈)	-380.99 kJ/mol
Gibbs free energy (Δ_fG˚)	-254 kJ/mol^[1]
Hazards
Main hazards	Oxidizer, irritant
Safety data sheet	MSDS
GHS labelling:
Pictograms	^[3]
Signal word	Danger
Hazard statements	H272, H315, H319, H335^[3]
Precautionary statements	P220, P261, P305+P351+P338^[3]
NFPA 704 (fire diamond)	2 0 0 OX
Related compounds
Other anions	Lithium chloride Lithium hypochlorite Lithium chlorate
Other cations	Sodium perchlorate Potassium perchlorate Rubidium perchlorate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N (what is ^YN ?)
Infobox references