Aluminium chloride, also known as aluminium trichloride, is an

inorganic compound In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemistr ...

with the formula . It forms hexahydrate with the formula , containing six water molecules of hydration. Both are colourless crystals, but samples are often contaminated with

iron(III) chloride Iron(III) chloride is the inorganic compound with the formula . Also called ferric chloride, it is a common compound of iron in the +3 oxidation state. The anhydrous compound is a crystalline solid with a melting point of 307.6 °C. The colo ...

, giving a yellow color. The anhydrous material is important commercially. It has a low melting and boiling point. It is mainly produced and consumed in the production of aluminium metal, but large amounts are also used in other areas of the chemical industry. The compound is often cited as a

Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...

. It is an example of an

that reversibly changes from a polymer to a monomer at mild temperature.

Structure

Anhydrous

adopts three structures, depending on the temperature and the state (solid, liquid, gas). Solid has a sheet-like layered structure with cubic close-packed chloride ions. In this framework, the Al centres exhibit

octahedral coordination geometry In chemistry, octahedral molecular geometry, also called square bipyramidal, describes the shape of compounds with six atoms or groups of atoms or ligands symmetrically arranged around a central atom, defining the vertices of an octahedron. The oc ...

. In contrast, has a more molecular structure, with the centers occupying adjacent tetrahedral holes of the close-packed framework of ions. Wells, A. F. (1984) ''Structural Inorganic Chemistry'', Oxford Press, Oxford, United Kingdom. .

Yttrium(III) chloride Yttrium(III) chloride is an inorganic compound of yttrium and chloride. It exists in two forms, the hydrate (YCl3(H2O)6) and an anhydrous form (YCl3). Both are colourless solids that are highly soluble in water and deliquescent. Structure Solid ...

adopts the same structure, as do a range of other compounds. When aluminium trichloride is in its melted state, it exists as the

dimer Dimer may refer to: * Dimer (chemistry), a chemical structure formed from two similar sub-units ** Protein dimer, a protein quaternary structure ** d-dimer * Dimer model, an item in statistical mechanics, based on ''domino tiling'' * Julius Dimer ( ...

, with

tetracoordinate In chemistry, crystallography, and materials science, the coordination number, also called ligancy, of a central atom in a molecule or crystal is the number of atoms, molecules or ions bonded to it. The ion/molecule/atom surrounding the central io ...

aluminium. This change in structure is related to the lower density of the liquid phase (1.78 g/cm³) versus solid aluminium trichloride (2.48 g/cm³). dimers are also found in the vapour phase. At higher temperatures, the dimers

dissociate Dissociation in chemistry is a general process in which molecules (or ionic compounds such as salts, or complexes) separate or split into other things such as atoms, ions, or radicals, usually in a reversible manner. For instance, when an acid ...

into trigonal planar monomer, which is structurally analogous to . The melt conducts

electricity Electricity is the set of physical phenomena associated with the presence and motion of matter that has a property of electric charge. Electricity is related to magnetism, both being part of the phenomenon of electromagnetism, as described ...

poorly, unlike more ionic

halide In chemistry, a halide (rarely halogenide) is a binary chemical compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative (or more electropositive) than the halogen, to make a fluor ...

s such as sodium chloride. Aluminium chloride monomer belongs to the point group D_3h in its monomeric form and D_2h in its dimeric form.

Hexahydrate

The hexahydrate consists of

octahedral In geometry, an octahedron (plural: octahedra, octahedrons) is a polyhedron with eight faces. The term is most commonly used to refer to the regular octahedron, a Platonic solid composed of eight equilateral triangles, four of which meet at ea ...

cation An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...

centers and chloride

anions An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by con ...

() as

counterion 160px, Polystyrene sulfonate, a cation-exchange resin, is typically supplied with as the counterion.">cation-exchange_resin.html" ;"title="Polystyrene sulfonate, a cation-exchange resin">Polystyrene sulfonate, a cation-exchange resin, is typical ...

s. Hydrogen bonds link the cation and anions. The hydrated form of aluminium chloride has an octahedral molecular geometry, with the central aluminium ion surrounded by six

water ligand In chemistry, metal aquo complexes are coordination compounds containing metal ions with only water as a ligand. These complexes are the predominant species in aqueous solutions of many metal salts, such as metal nitrates, sulfates, and perch ...

molecules. Being coordinatively saturated, the hydrate is of little value as a

catalyst Catalysis () is the process of increasing the reaction rate, rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the ...

in Friedel-Crafts alkylation and related reactions.

Uses

Alkylation and acylation of arenes

is a common Lewis-acid

for Friedel-Crafts reactions, both acylations and alkylations. Important products are

detergent A detergent is a surfactant or a mixture of surfactants with cleansing properties when in dilute solutions. There are a large variety of detergents, a common family being the alkylbenzene sulfonates, which are soap-like compounds that are mor ...

s and

ethylbenzene Ethylbenzene is an organic compound with the formula . It is a highly flammable, colorless liquid with an odor similar to that of gasoline. This monocyclic aromatic hydrocarbon is important in the petrochemical industry as an reaction intermediat ...

. These types of reactions are the major use for aluminium chloride, for example, in the preparation of

anthraquinone Anthraquinone, also called anthracenedione or dioxoanthracene, is an aromatic organic compound with formula . Isomers include various quinone derivatives. The term anthraquinone however refers to the isomer, 9,10-anthraquinone (IUPAC: 9,10-dioxoa ...

(used in the

dye A dye is a colored substance that chemically bonds to the substrate to which it is being applied. This distinguishes dyes from pigments which do not chemically bind to the material they color. Dye is generally applied in an aqueous solution and ...

stuffs industry) from

benzene Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms ...

and

phosgene Phosgene is the organic chemical compound with the formula COCl2. It is a toxic, colorless gas; in low concentrations, its musty odor resembles that of freshly cut hay or grass. Phosgene is a valued and important industrial building block, esp ...

. In the general Friedel-Crafts reaction, an

acyl chloride In organic chemistry, an acyl chloride (or acid chloride) is an organic compound with the functional group . Their formula is usually written , where R is a side chain. They are reactive derivatives of carboxylic acids (). A specific example o ...

alkyl halide The haloalkanes (also known as halogenoalkanes or alkyl halides) are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely us ...

reacts with an

aromatic In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to satu ...

system as shown: : Benzene Friedel-Crafts alkylation-diagram

The

alkylation Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effecting al ...

reaction is more widely used than the

acylation In chemistry, acylation (or alkanoylation) is the chemical reaction in which an acyl group () is added to a compound. The compound providing the acyl group is called the acylating agent. Because they form a strong electrophile when treated with s ...

reaction, although its practice is more technically demanding. For both reactions, the aluminium chloride, as well as other materials and the equipment, should be dry, although a trace of moisture is necessary for the reaction to proceed. Detailed procedures are available for alkylation and acylation of arenes. A general problem with the Friedel-Crafts reaction is that the aluminium chloride catalyst sometimes is required in full

stoichiometric Stoichiometry refers to the relationship between the quantities of reactants and products before, during, and following chemical reactions. Stoichiometry is founded on the law of conservation of mass where the total mass of the reactants equal ...

quantities, because it

complex Complex commonly refers to: * Complexity, the behaviour of a system whose components interact in multiple ways so possible interactions are difficult to describe ** Complex system, a system composed of many components which may interact with each ...

es strongly with the products. This complication sometimes generates a large amount of

corrosive A corrosive substance is one that will damage or destroy other substances with which it comes into contact by means of a chemical reaction. Etymology The word ''corrosive'' is derived from the Latin verb ''corrodere'', which means ''to gnaw'', ...

waste. For these and similar reasons, the use of aluminium chloride has often been displaced by zeolites. Aluminium chloride can also be used to introduce

aldehyde In organic chemistry, an aldehyde () is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred to as an aldehyde but can also be classified as a formyl group ...

groups onto

rings, for example via the

Gattermann-Koch reaction The Gattermann reaction, (also known as the Gattermann formylation and the Gattermann salicylaldehyde synthesis) is a chemical reaction in which aromatic compounds are formylated by a mixture of hydrogen cyanide (HCN) and hydrogen chloride (HCl) ...

which uses

carbon monoxide Carbon monoxide (chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simpl ...

hydrogen chloride The compound hydrogen chloride has the chemical formula and as such is a hydrogen halide. At room temperature, it is a colourless gas, which forms white fumes of hydrochloric acid upon contact with atmospheric water vapor. Hydrogen chloride g ...

and a

copper(I) chloride Copper(I) chloride, commonly called cuprous chloride, is the lower chloride of copper, with the formula CuCl. The substance is a white solid sparingly soluble in water, but very soluble in concentrated hydrochloric acid. Impure samples appear gre ...

co-catalyst Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...

. :

Other applications in organic and organometallic synthesis

Aluminium chloride finds a wide variety of other applications in organic chemistry. For example, it can catalyse the " ene reaction", such as the addition of

3-buten-2-one Methyl vinyl ketone (MVK, IUPAC name: butenone) is the organic compound with the formula CH3C(O)CH=CH2. It is a reactive compound classified as an enone, in fact the simplest example thereof. It is a colorless, flammable, highly toxic liquid wi ...

(methyl vinyl ketone) to

carvone Carvone is a member of a family of chemicals called terpenoids. Carvone is found naturally in many essential oils, but is most abundant in the oils from seeds of caraway (''Carum carvi''), spearmint (''Mentha spicata''), and dill. Uses Both carvo ...

: :

It is used to induce a variety of hydrocarbon couplings and rearrangements. Aluminium chloride combined with aluminium in the presence of an arene can be used to synthesize bis(arene) metal complexes, e.g.

bis(benzene)chromium Bis(benzene)chromium is the organometallic compound with the formula Cr( η6-C6H6)2. It is sometimes called dibenzenechromium. The compound played an important role in the development of sandwich compounds in organometallic chemistry and is the ...

, from certain metal halides via the so-called Fischer-Hafner synthesis.

Dichlorophenylphosphine Dichlorophenylphosphine is an organophosphorus compound with the formula C6H5PCl2. This colourless viscous liquid is commonly used in the synthesis of organophosphines. Dichlorophenylphosphine is commercially available. It may be prepared by an ...

is prepared by reaction of

and

phosphorus trichloride Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic ...

catalyzed by aluminium chloride.

Reactions

Anhydrous aluminium chloride is a powerful

, capable of forming Lewis acid-base

adduct An adduct (from the Latin ''adductus'', "drawn toward" alternatively, a contraction of "addition product") is a product of a direct addition of two or more distinct molecules, resulting in a single reaction product containing all atoms of all co ...

s with even weak Lewis bases such as

benzophenone Benzophenone is the organic compound with the formula (C6H5)2CO, generally abbreviated Ph2CO. It is a white solid that is soluble in organic solvents. Benzophenone is a widely used building block in organic chemistry, being the parent diarylket ...

and

mesitylene Mesitylene or 1,3,5-trimethylbenzene is a derivative of benzene with three methyl substituents positioned symmetrically around the ring. The other two isomeric trimethylbenzenes are 1,2,4-trimethylbenzene (pseudocumene) and 1,2,3-trimethylbenzene ...

. It forms

tetrachloroaluminate Tetrachloroaluminate lCl4sup>− is an anion formed from aluminium and chlorine. The anion has a tetrahedral shape, similar to carbon tetrachloride where carbon is replaced with aluminium. Some tetrachloroaluminates are soluble in organic s ...

() in the presence of

chloride The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the element chlorine (a halogen) gains an electron or when a compound such as hydrogen chloride is dissolved in water or other polar solvents. Chloride salts ...

ions. Aluminium chloride reacts with

calcium Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar ...

and

magnesium hydride Magnesium hydride is the chemical compound with the molecular formula MgH2. It contains 7.66% by weight of hydrogen and has been studied as a potential hydrogen storage medium. Preparation In 1951 preparation from the elements was first reporte ...

s in tetrahydrofuran forming tetrahydroaluminates.

Reactions with water

Anhydrous aluminium chloride is

hygroscopic Hygroscopy is the phenomenon of attracting and holding water molecules via either absorption or adsorption from the surrounding environment, which is usually at normal or room temperature. If water molecules become suspended among the substance ...

, having a very pronounced affinity for water. It fumes in moist air and hisses when mixed with liquid water as the Cl⁻ ligands are displaced with H₂O molecules to form the hexahydrate . The anhydrous phase cannot be regained on heating the hexahydrate. Instead HCl is lost leaving aluminium hydroxide or alumina (aluminium oxide): : Like metal aquo complexes,

aqueous An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, or sodium chloride (NaCl), in water would be ...

is acidic owing to the ionization of the aquo ligands: : Aqueous solutions behave similarly to other

aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. It has ...

salts In chemistry, a salt is a chemical compound consisting of an ionic assembly of positively charged cations and negatively charged anions, which results in a compound with no net electric charge. A common example is table salt, with positively cha ...

containing hydrated

ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conv ...

s, giving a gelatinous precipitate of

aluminium hydroxide Aluminium hydroxide, Al(OH)3, is found in nature as the mineral gibbsite (also known as hydrargillite) and its three much rarer polymorphs: bayerite, doyleite, and nordstrandite. Aluminium hydroxide is amphoteric, i.e., it has both basic and ...

upon reaction with dilute sodium hydroxide: :

Synthesis

Aluminium chloride is manufactured on a large scale by the exothermic reaction of

metal with chlorine or

at temperatures between . : : Aluminium chloride may be formed via a

single displacement reaction A single-displacement reaction, also known as single replacement reaction or exchange reaction, is a chemical reaction in which one element is replaced by another in a compound. It can be represented generically as: :A + BC -> AC + B where eithe ...

between

copper(II) chloride Copper(II) chloride is the chemical compound with the chemical formula CuCl2. The anhydrous form is yellowish brown but slowly absorbs moisture to form a blue-green dihydrate. Both the anhydrous and the dihydrate forms occur naturally as the ve ...

and aluminium metal. : In the US in 1993, approximately 21,000 tons were produced, not counting the amounts consumed in the production of aluminium. Hydrated aluminium trichloride is prepared by dissolving aluminium oxides in hydrochloric acid. Metallic aluminium also readily dissolves in hydrochloric acid ─ releasing hydrogen gas and generating considerable heat. Heating this solid does not produce anhydrous aluminium trichloride, the hexahydrate decomposes to

when heated: : Aluminium also forms a lower

aluminium(I) chloride Aluminium monochloride, or chloridoaluminium is the metal halide with the formula AlCl. Aluminum monochloride as a molecule is thermodynamically stable at high temperature and low pressure only. This compound is produced as a step in the Alcan pr ...

(AlCl), but this is very unstable and only known in the vapour phase.

Natural occurrence

Anhydrous aluminium chloride is not found as a mineral. The hexahydrate, however, is known as the rare mineral chloraluminite. A more complex, basic and hydrated aluminium chloride mineral is

cadwaladerite Cadwaladerite is a rare aluminium halide mineral with formula: AlCl(OH)2·4(H2O). It was reported for an amorphous substance associated with sulfate minerals and embedded in a halite crystal cluster. Its status is uncertain due to inadequate data. ...

Safety

Anhydrous reacts vigorously with bases, so suitable precautions are required. It can cause irritation to the eyes, skin, and the respiratory system if inhaled or on contact.Aluminum Chloride
solvaychemicals.us

References

External links

International Chemical Safety Card 1125

Index of Organic Synthesis procedures that utilize AlCl₃

MSDS

Government of Canada Fact Sheets and Frequently Asked Questions: Aluminum Salts
{{Authority control Chlorides Metal halides Aluminium compounds Inorganic compounds Reagents for organic chemistry Deliquescent substances Acid catalysts