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 chemi ...

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, 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 A polymer (; Greek ''poly-'', "many" + '' -mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic and ...

to a

monomer In chemistry, a monomer ( ; ''mono-'', "one" + '' -mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or three-dimensional network in a process called polymerization. Classification ...

at mild temperature.

Structure

Anhydrous

adopts three structures, depending on the

temperature Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measured with a thermometer. Thermometers are calibrated in various temperature scales that historically have relied on ...

and the

state State may refer to: Arts, entertainment, and media Literature * ''State Magazine'', a monthly magazine published by the U.S. Department of State * ''The State'' (newspaper), a daily newspaper in Columbia, South Carolina, United States * '' Our ...

(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 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 Oxford () is a city in England. It is the county town and only city of Oxfordshire. In 2020, its population was estimated at 151,584. It is north-west of London, south-east of Birmingham and north-east of Bristol. The city is home to the Un ...

, United Kingdom. . Yttrium(III) chloride adopts the same structure, as do a range of other compounds. When aluminium trichloride is in its melted state, it exists as the dimer , with tetracoordinate 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 into

trigonal planar In chemistry, trigonal planar is a molecular geometry model with one atom at the center and three atoms at the corners of an equilateral triangle, called peripheral atoms, all in one plane. In an ideal trigonal planar species, all three ligands ...

, 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 describ ...

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 f ...

s such as

sodium chloride Sodium chloride , commonly known as salt (although sea salt also contains other chemical salts), is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. With molar masses of 22.99 and 35 ...

. Aluminium chloride monomer belongs to the

point group In geometry, a point group is a mathematical group of symmetry operations ( isometries in a Euclidean space) that have a fixed point in common. The coordinate origin of the Euclidean space is conventionally taken to be a fixed point, and every ...

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 conve ...

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 conve ...

() as

counterion 160px, cation-exchange_resin.html" ;"title="Polystyrene sulfonate, a cation-exchange resin">Polystyrene sulfonate, a cation-exchange resin, is typically supplied with as the counterion. In chemistry, a counterion (sometimes written as "counter ...

Hydrogen bond In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing ...

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

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 ...

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 m ...

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 intermedia ...

. 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-dioxoan ...

(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 ato ...

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, es ...

. 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 ...

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 sat ...

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 effectin ...

reaction is more widely used than the acylation 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 equ ...

quantities, because it complexes 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

zeolite Zeolites are microporous, crystalline aluminosilicate materials commonly used as commercial adsorbents and catalysts. They mainly consist of silicon, aluminium, oxygen, and have the general formula ･y where is either a metal ion or H+. These ...

s. 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 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 si ...

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 co-catalyst. : AlCl3 formylation

Other applications in organic and organometallic synthesis

Aluminium chloride finds a wide variety of other applications in

organic chemistry Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clay ...

. For example, it can catalyse the "

ene reaction In organic chemistry, the ene reaction (also known as the Alder-ene reaction by its discoverer Kurt Alder in 1943) is a chemical reaction between an alkene with an allylic hydrogen (the ene) and a compound containing a multiple bond (the enophile ...

", 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: : AlCl3 ene rxn

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, from certain metal halides via the so-called

Fischer Fischer is a German occupational surname, meaning fisherman. The name Fischer is the fourth most common German surname. The English version is Fisher. People with the surname A * Abraham Fischer (1850–1913) South African public official * ...

-Hafner synthesis. Dichlorophenylphosphine 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 a ...

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 base 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 ...

s such as benzophenone 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-trimethylbenze ...

. It forms tetrachloroaluminate () 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 s ...

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 t ...

and magnesium hydrides in

tetrahydrofuran Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water- miscible organic liquid with low viscosity. It is ...

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 complex 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 perchlora ...

es,

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 ...

is acidic owing to the ionization of the

aquo 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 perchl ...

s: : Aqueous solutions behave similarly to other

aluminium Aluminium (aluminum in AmE, American and CanE, Canadian English) is a chemical element with the Symbol (chemistry), symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately o ...

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 ...

containing hydrated ions, giving a gelatinous

precipitate In an aqueous solution, precipitation is the process of transforming a dissolved substance into an insoluble solid from a super-saturated solution. The solid formed is called the precipitate. In case of an inorganic chemical reaction leading ...

aluminium hydroxide Aluminium hydroxide, Al(OH)3, is found in nature as the mineral gibbsite (also known as hydrargillite) and its three much rarer Polymorphism (materials science), polymorphs: bayerite, doyleite, and nordstrandite. Aluminium hydroxide is Amphoter ...

upon reaction with dilute

sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly caustic base and alkal ...

: :

Synthesis

Aluminium chloride is manufactured on a large scale by the

exothermic In thermodynamics, an exothermic process () is a thermodynamic process or reaction that releases energy from the system to its surroundings, usually in the form of heat, but also in a form of light (e.g. a spark, flame, or flash), electricity ...

reaction of

metal with chlorine or

at temperatures between . : : Aluminium chloride may be formed via a single displacement reaction between copper(II) chloride 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 Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid. It is a component of the gastric acid in the dig ...

. 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.

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