Lithium perchlorate

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Lithium perchlorate
Lithium perchlorate.png
Lithiumperchlorat.png
__ Li +     __ Cl 7+     __ O 2−
Unit cell of lithium perchlorate.
Names
IUPAC name
Lithium perchlorate
Other names
Perchloric acid, lithium salt; Lithium Cloricum
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.029.307 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/ClHO4.Li/c2-1(3,4)5;/h(H,2,3,4,5);/q;+1/p-1 Yes check.svgY
    Key: MHCFAGZWMAWTNR-UHFFFAOYSA-M Yes check.svgY
  • InChI=1/ClHO4.Li/c2-1(3,4)5;/h(H,2,3,4,5);/q;+1/p-1
    Key: MHCFAGZWMAWTNR-REWHXWOFAR
  • [Li+].[O-]Cl(=O)(=O)=O
Properties
LiClO
4
Molar mass
  • 106.39 g/mol (anhydrous)
  • 160.44 g/mol (trihydrate)
AppearanceWhite 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
  • 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 alcohols, ethyl acetate [1]
Solubility in acetone 137 g/100 g [1]
Solubility in alcohols
Solubility in ethyl acetate 95.2 g/100 g [2]
Solubility in ethyl ether 113.7 g/100 g [2]
Structure
Pnma, No. 62
a = 865.7(1) pm, b = 691.29(9) pm, c = 483.23(6) pm [3]
4 formula per cell
tetrahedral at Cl
Thermochemistry
105 J/mol·K [1]
Std molar
entropy
(S298)
125.5 J/mol·K [1]
−380.99 kJ/mol
−254 kJ/mol [1]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Oxidizer, irritant
GHS labelling:
GHS-pictogram-rondflam.svg GHS-pictogram-exclam.svg [4]
Danger
H272, H315, H319, H335 [4]
P220, P261, P305+P351+P338 [4]
NFPA 704 (fire diamond)
2
0
0
OX
Safety data sheet (SDS) MSDS
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).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

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.

Contents

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: [5]

LiClO4 → LiCl + 2 O2

Over 60% of the mass of the lithium perchlorate is released as oxygen. [2] 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. [6]

Lithium perchlorate is used as an oxidizer in solid rocket propellants, and to produce red colored flame in pyrotechnic compositions. [2] [7]

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. [8]

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. [9]

Solid lithium perchlorate is found to be a mild and efficient Lewis acid for promoting cyanosilylation of carbonyl compounds under neutral conditions. [10]

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. [11] 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. [11]

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. [12]

Safety

Perchlorates often give explosive mixtures with organic compounds, finely divided metals, sulfur, and other reducing agents. [12] [2]

Related Research Articles

<span class="mw-page-title-main">Chlorine</span> Chemical element, symbol Cl and atomic number 17

Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is a yellow-green gas at room temperature. It is an extremely reactive element and a strong oxidising agent: among the elements, it has the highest electron affinity and the third-highest electronegativity on the revised Pauling scale, behind only oxygen and fluorine.

<span class="mw-page-title-main">Carboxylic acid</span> Organic compound containing a –C(=O)OH group

In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group attached to an R-group. The general formula of a carboxylic acid is R−COOH or R−CO2H, with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic acids occur widely. Important examples include the amino acids and fatty acids. Deprotonation of a carboxylic acid gives a carboxylate anion.

<span class="mw-page-title-main">Electrolysis</span> Technique in chemistry and manufacturing

In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity".

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

Ammonium perchlorate ("AP") is an inorganic compound with the formula NH4ClO4. It is a colorless or white solid that is soluble in water. It is a powerful oxidizer. Combined with a fuel, it can be used as a rocket propellant called ammonium perchlorate composite propellant. Its instability has involved it in a number of accidents, such as the PEPCON disaster.

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

Perchloric acid is a mineral acid with the formula HClO4. Usually found as an aqueous solution, this colorless compound is a stronger acid than sulfuric acid, nitric acid and hydrochloric acid. It is a powerful oxidizer when hot, but aqueous solutions up to approximately 70% by weight at room temperature are generally safe, only showing strong acid features and no oxidizing properties. Perchloric acid is useful for preparing perchlorate salts, especially ammonium perchlorate, an important rocket fuel component. Perchloric acid is dangerously corrosive and readily forms potentially explosive mixtures.

The term chloride refers either to a chloride ion, which is a negatively charged chlorine atom, or a non-charged chlorine atom covalently bonded to the rest of the molecule by a single bond. Many inorganic chlorides are salts. Many organic compounds are chlorides. The pronunciation of the word "chloride" is.

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

Manganese dioxide is the inorganic compound with the formula MnO
2
. This blackish or brown solid occurs naturally as the mineral pyrolusite, which is the main ore of manganese and a component of manganese nodules. The principal use for MnO
2
is for dry-cell batteries, such as the alkaline battery and the zinc–carbon battery. MnO
2
is also used as a pigment and as a precursor to other manganese compounds, such as KMnO
4
. It is used as a reagent in organic synthesis, for example, for the oxidation of allylic alcohols. MnO
2
has an α-polymorph that can incorporate a variety of atoms in the "tunnels" or "channels" between the manganese oxide octahedra. There is considerable interest in α-MnO
2
as a possible cathode for lithium-ion batteries.

Iron(III) chloride describes the inorganic compounds with the formula FeCl3(H2O)x. Also called ferric chloride, these compounds are available both in anhydrous and hydrated forms which are both hygroscopic. They are common sources of iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while the hydrate is a mild oxidizing agent. It is used as a water cleaner and as an etchant for metals.

In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens (F2, Cl2, Br2, I2). Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

In organic chemistry, an aryl halide is an aromatic compound in which one or more hydrogen atoms, directly bonded to an aromatic ring are replaced by a halide. The haloarene are different from haloalkanes because they exhibit many differences in methods of preparation and properties. The most important members are the aryl chlorides, but the class of compounds is so broad that there are many derivatives and applications.

<span class="mw-page-title-main">Hypochlorite</span> Ion

In chemistry, hypochlorite is an anion with the chemical formula ClO. It combines with a number of cations to form hypochlorite salts. Common examples include sodium hypochlorite and calcium hypochlorite. The Cl-O distance in ClO is 1.69 Å.

<span class="mw-page-title-main">Thionyl chloride</span> Inorganic compound (SOCl2)

Thionyl chloride is an inorganic compound with the chemical formula SOCl2. It is a moderately volatile, colourless liquid with an unpleasant acrid odour. Thionyl chloride is primarily used as a chlorinating reagent, with approximately 45,000 tonnes per year being produced during the early 1990s, but is occasionally also used as a solvent. It is toxic, reacts with water, and is also listed under the Chemical Weapons Convention as it may be used for the production of chemical weapons.

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

Phosphorus pentachloride is the chemical compound with the formula PCl5. It is one of the most important phosphorus chlorides/oxychlorides, others being PCl3 and POCl3. PCl5 finds use as a chlorinating reagent. It is a colourless, water-sensitive solid, although commercial samples can be yellowish and contaminated with hydrogen chloride.

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

Sodium perchlorate is the inorganic compound with the chemical formula NaClO4. It is a white crystalline, hygroscopic solid that is highly soluble in water and in alcohol. It is usually encountered as the monohydrate. The compound is noteworthy as the most water-soluble of the common perchlorate salts.

<span class="mw-page-title-main">Gold(III) chloride</span> Chemical compound

Gold(III) chloride, traditionally called auric chloride, is an inorganic compound of gold and chlorine with the molecular formula Au2Cl6. The "III" in the name indicates that the gold has an oxidation state of +3, typical for many gold compounds. It has two forms, the monohydrate (AuCl3·H2O) and the anhydrous form, which are both hygroscopic and light-sensitive solids. This compound is a dimer of AuCl3. This compound has a few uses, such as an oxidizing agent and for catalyzing various organic reactions.

<span class="mw-page-title-main">Hexafluorophosphate</span> Anion with the chemical formula PF6–

Hexafluorophosphate is an anion with chemical formula of [PF6]. It is an octahedral species that imparts no color to its salts. [PF6] is isoelectronic with sulfur hexafluoride, SF6, and the hexafluorosilicate dianion, [SiF6]2−, and hexafluoroantimonate [SbF6]. In this anion, phosphorus has a valence of 5. Being poorly nucleophilic, hexafluorophosphate is classified as a non-coordinating anion.

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

Dichlorine hexoxide is the chemical compound with the molecular formula Cl
2
O
6
, which is correct for its gaseous state. However, in liquid or solid form, this chlorine oxide ionizes into the dark red ionic compound chloryl perchlorate [ClO
2
]+
[ClO
4
]
, which may be thought of as the mixed anhydride of chloric and perchloric acids.

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

Calcium perchlorate is classified as a metal perchlorate salt with the molecular formula Ca(ClO4)2. It is an inorganic compound that is a yellow-white crystalline solid in appearance. As a strong oxidizing agent, it reacts with reducing agents when heated to generate heat and products that may be gaseous. Calcium perchlorate has been categorized as having explosive reactivity. Ca(ClO4)2 is a common chemical on the soil of planet Mars, counting for almost 1% of the Martian dust, by weight.

Gallium compounds are compounds containing the element gallium. These compounds are found primarily in the +3 oxidation state. The +1 oxidation state is also found in some compounds, although it is less common than it is for gallium's heavier congeners indium and thallium. For example, the very stable GaCl2 contains both gallium(I) and gallium(III) and can be formulated as GaIGaIIICl4; in contrast, the monochloride is unstable above 0 °C, disproportionating into elemental gallium and gallium(III) chloride. Compounds containing Ga–Ga bonds are true gallium(II) compounds, such as GaS (which can be formulated as Ga24+(S2−)2) and the dioxan complex Ga2Cl4(C4H8O2)2. There are also compounds of gallium with negative oxidation states, ranging from -5 to -1, most of these compounds being magnesium gallides (MgxGay).

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

Acetyl hypochlorite, also known as chlorine acetate, is a chemical compound with the formula CH3COOCl. It is a photosensitive colorless liquid that is a short lived intermediate in the Hunsdiecker reaction.

References

  1. 1 2 3 4 5 6 7 "Lithium perchlorate". chemister.ru.
  2. 1 2 3 4 5 "Lithium Perchlorate". AMCP 706-187 Military Pyrotechnics - Properties of Materials. US Army Materiel Command. October 1963. pp. 181–182.
  3. Wickleder, Mathias S. (2003). "Crystal Structure of LiClO4". Zeitschrift für Anorganische und Allgemeine Chemie. 629 (9): 1466–1468. doi:10.1002/zaac.200300114.
  4. 1 2 3 Sigma-Aldrich Co., Lithium perchlorate. Retrieved on 2014-05-09.
  5. Markowitz, M. M.; Boryta, D. A.; Stewart, Harvey Jr. (1964). "Lithium Perchlorate Oxygen Candle. Pyrochemical Source of Pure Oxygen". Industrial & Engineering Chemistry Product Research and Development. 3 (4): 321–330. doi:10.1021/i360012a016.
  6. Herbert Ellern (1968). Military and Civilian Pyrotechnics. Chemical Publishing Company. p. 237. ISBN   978-0-8206-0364-3. OL   37082807M.
  7. Basil T. Fedoroff; Oliver E. Sheffield (January 1975). "Lithium Perchlorate". Encyclopedia of explosives and related items. Vol. 7. Picatinny Arsenal. p. L45. LCCN   61-61759.
  8. 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.
  9. Lithium Perchlorate Product Detail Page
  10. 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.
  11. 1 2 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.
  12. 1 2 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
HClO4 He
LiClO4 Be(ClO4)2 B(ClO4)4
B(ClO4)3
ROClO3 N(ClO4)3
NH4ClO4
NOClO4
H3OClO4 FClO4 Ne
NaClO4 Mg(ClO4)2 Al(ClO4)3
Al(ClO4)4
Al(ClO4)2−5
Al(ClO4)3−6
SiPS ClO4
ClOClO3
Cl2O7
Ar
KClO4 Ca(ClO4)2 Sc(ClO4)3 Ti(ClO4)4 VO(ClO4)3
VO2(ClO4)
Cr(ClO4)3 Mn(ClO4)2 Fe(ClO4)2
Fe(ClO4)3
Co(ClO4)2,
Co(ClO4)3
Ni(ClO4)2 Cu(ClO4)2 Zn(ClO4)2 Ga(ClO4)3 GeAsSeBrKr
RbClO4 Sr(ClO4)2 Y(ClO4)3 Zr(ClO4)4 Nb(ClO4)5 MoTcRu Rh(ClO4)3 Pd(ClO4)2 AgClO4 Cd(ClO4)2 In(ClO4)3 Sn(ClO4)4 Sb TeO(ClO4)2 IXe
CsClO4 Ba(ClO4)2   Lu(ClO4)3 Hf(ClO4)4 Ta(ClO4)5
TaO(ClO4)3
TaO2ClO4
WReOsIrPtAu Hg2(ClO4)2,
Hg(ClO4)2
Tl(ClO4),
Tl(ClO4)3
Pb(ClO4)2 Bi(ClO4)3 PoAtRn
FrClO4 Ra LrRfDbSgBhHsMtDsRgCnNhFlMcLvTsOg
La Ce(ClO4)x Pr(ClO4)3 Nd(ClO4)3 Pm Sm(ClO4)3 Eu(ClO4)3 Gd(ClO4)3 Tb(ClO4)3 Dy(ClO4)3 Ho(ClO4)3 Er(ClO4)3 Tm(ClO4)3 Yb(ClO4)3
Ac Th(ClO4)4 Pa UO2(ClO4)2 NpPuAmCmBkCfEsFmMdNo