Lithium perchlorate

Lithium perchlorate

Names
IUPAC name Lithium perchlorate
Other names Perchloric acid, lithium salt; Lithium Cloricum
Identifiers
CAS Number	7791-03-9
3D model (Jmol)	Interactive image
ChemSpider	133514
ECHA InfoCard	100.029.307
PubChem	23665649
UNII	Q86SE98C9C
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	ClLiO4
Molar mass	106.39 g·mol^−1
Appearance	white crystals
Odor	odorless
Density	2.42 g/cm^3
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]
Thermochemistry
Specific heat capacity (C)	105 J/mol·K[1]
Std molar entropy (S^o298)	125.5 J/mol·K[1]
Std enthalpy of formation (ΔfH^o298)	-380.99 kJ/mol
Gibbs free energy (ΔfG˚)	-254 kJ/mol[1]
Hazards
Main hazards	Oxidizer, irritant
Safety data sheet	MSDS
GHS pictograms	[2]
GHS signal word	Danger
GHS hazard statements	H272, H315, H319, H335[2]
GHS precautionary statements	P220, P261, P305+351+338[2]
EU classification (DSD)	O Xi
R-phrases	R8, R36/37/38
S-phrases	S17, S26, S36
NFPA 704	0 2 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).
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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, the latter being over 60% of its mass. It has both the highest oxygen to weight and oxygen to volume ratio of all perchlorates, except beryllium diperchlorate, which is expensive and highly toxic.

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.^[3]

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.^[4]

Batteries

Lithium perchlorate is also used as an electrolyte in lithium-ion batteries. Lithium perchlorate is chosen over alternative electrolytes 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.^[5] 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.^[5]

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.^[6]

Safety

Perchlorates often give explosive mixtures with organic compounds.^[6]

References

1. http://chemister.ru/Database/properties-en.php?dbid=1&id=612
2. Sigma-Aldrich Co., Lithium perchlorate. Retrieved on 2014-05-09.
3. Charette, A. B. "Lithium Perchlorate" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289.
4. Lithium Perchlorate Product Detail Page
5. 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.
6. 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

Salts and the ester of the perchlorate ion
HClO4																	He
LiClO4	Be(ClO4)2											B(ClO4)4^−	ROClO3	N(ClO4)3 NH4ClO4	O	FClO4	Ne
NaClO4	Mg(ClO4)2											Al(ClO4)3	Si	P	S	ClO4^− ClOClO3 Cl2O7	Ar
KClO4	Ca(ClO4)2	Sc(ClO4)3	Ti(ClO4)4	VO(ClO4)3	Cr(ClO4)3	Mn(ClO4)2	Fe(ClO4)3	Co(ClO4)2, Co(ClO4)3	Ni(ClO4)2	Cu(ClO4)2	Zn(ClO4)2	Ga(ClO4)3	Ge	As	Se	Br	Kr
RbClO4	Sr(ClO4)2	Y	Zr	Nb	Mo	Tc	Ru	Rh	Pd(ClO4)2	AgClO4	Cd(ClO4)2	In	Sn	Sb	Te	I	Xe
CsClO4	Ba(ClO4)2		Hf	Ta	W	Re	Os	Ir	Pt	Au	Hg2(ClO4)2, Hg(ClO4)2	Tl(ClO4)3	Pb(ClO4)2	Bi(ClO4)3	Po	At	Rn
Fr	Ra		Rf	Db	Sg	Bh	Hs	Mt	Ds	Rg	Cn	Nh	Fl	Mc	Lv	Ts	Og
		↓
		La	Ce(ClO4)x	Pr	Nd	Pm	Sm	Eu	Gd	Tb	Dy	Ho	Er	Tm	Yb	Lu
		Ac	Th	Pa	UO2(ClO4)2	Np	Pu	Am	Cm	Bk	Cf	Es	Fm	Md	No	Lr