Aluminium chloride

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Alum inium chloride (AlCl3), also know n as alum inium trichloride , describe compounds w ith the f ormula AlCl3(H2O) n (n = 0 or
Aluminium chloride
6). They consist of aluminium and chlorine atoms in a 1:3 ratio, and one f orm also contains six w aters of hydration. Both are w hite
solids, but samples are of ten contaminated w ith 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. [7] The compound is of ten cited
as a Lew is acid. It is an example of an inorganic compound that reversibly changes f rom a polymer to a monomer at mild
temperature.

Contents [hide]
1 Uses
1.1 Alkylation and acylation of arenes
1.2 Other applications in organic and organometallic synthesis
2 Structure
2.1 Anhydrous
2.2 Hexahydrate
3 Reactions
Names
3.1 Reactions with water
IUPAC name
4 Synthesis
aluminium chloride
5 Natural occurrence Other names
6 Safety aluminium(III) chloride
7 See also aluminum trichloride

8 References Identifiers

9 External links CAS Number 7446-70-0 (anhy drous)

10124-27-3 (hy drate)
7784-13-6 (hexahy drate)

Uses [ edit ]
3D model (JSmol) monomer: Interactiv e
image
Alkylation and acylation of arenes [ edit ]
dimer: Interactiv e image
AlCl3 is a common Lew is-acid catalyst f or Friedel–Craf ts reactions, both acylations and alkylations.[8] Important products are ChEBI CHEBI:30114
detergents and ethylbenzene. These types of reactions are the major use f or aluminium chloride, f or example, in the preparation of ChemSpider 22445
anthraquinone (used in the dyestuf f s industry) f rom benzene and phosgene.[9] In the general Friedel–Craf ts reaction, an acyl chloride ECHA Inf oCard 100.028.371
or alkyl halide reacts w ith an aromatic system as show n:[8] EC Number 231-208-1
Gmelin Ref erence 1876
PubChem CID 24012
RTECS number BD0530000
UNII LIF1N9568Y
CompTox DTXSID6029674
The alkylation reaction is more w idely used than the acylation reaction, although its practice is more technically demanding. For both
Dashboard (EPA)
reactions, the aluminium chloride, as w ell as other materials and the equipment, should be dry, although a trace of moisture is
InChI [show]
necessary f or the reaction to proceed.[citation needed] Detailed procedures are available f or alkylation[10] and acylation[11][12] of arenes.
SMILES [show]
A general problem w ith the Friedel–Craf ts reaction is that the aluminium chloride catalyst sometimes is required in f ull stoichiometric Properties
quantities, because it complexes strongly w ith the products. This complication sometimes generates a large amount of corrosive Chemical f ormula AlCl3
w aste. For these and similar reasons, the use of aluminium chloride has of ten been displaced by zeolites.[7] Molar mass 133.341 g/mol (anhy drous)
241.432 g/mol
Aluminium chloride can also be used to introduce aldehyde groups onto aromatic rings, f or example via the Gattermann-Koch
(hexahy drate)[1]
reaction w hich uses carbon monoxide, hydrogen chloride and a copper(I) chloride co-catalyst.[13]
Appearance white or pale y ellow solid,
hy groscopic
Density 2.48 g/cm 3 (anhy drous)
2.398 g/cm 3
(hexahy drate)[1]
Melting point 192.6 °C (378.7 °F;
465.8 K)
(anhy drous)[1]
100 °C (212 °F; 373 K)
Other applications in organic and organometallic synthesis [ edit ]
(hexahy drate, dec.)[1]
Aluminium chloride f inds a w ide variety of other applications in organic chemistry.[14] For example, it can catalyse the "ene reaction", Boiling point 180 °C (356 °F; 453 K)
such as the addition of 3-buten-2-one (methyl vinyl ketone) to carvone:[15] (sublimes)[1]
Solubility in water 439 g/l (0 °C)
449 g/l (10 °C)
458 g/l (20 °C)
466 g/l (30 °C)
473 g/l (40 °C)
481 g/l (60 °C)
486 g/l (80 °C)
490 g/l (100 °C)
It is used to induce a variety of hydrocarbon couplings and rearrangements.[16][17] Solubility soluble in hy drogen
chloride, ethanol,
Aluminium chloride combined w ith aluminium in the presence of an arene can be used to synthesize bis(arene) metal complexes, e.g.
chlorof orm, carbon
bis(benzene)chromium, f rom certain metal halides via the so-called Fischer-Haf ner synthesis. Dichlorophenylphosphine is prepared tetrachloride
by reaction of benzene and phosphorus trichloride catalyzed by aluminium chloride.[18] slightly soluble in benzene
Vapor pressure 133.3 Pa (99 °C)
Structure [ edit ] 13.3 kPa (151 °C)[2]
Viscosity 0.35 cP (197 °C)
Anhydrous [ edit ] 0.26 cP (237 °C)[2]
Structure
AlCl3 adopts three structures, depending on the temperature and the state (solid, liquid, gas). Solid AlCl3 is a sheet-like layered cubic Cry stal structure Monoclinic, mS16
close packed layers. In this f ramew ork, the Al centres exhibit octahedral coordination geometry.[19] When aluminium trichloride is in its Space group C12/m1, No. 12[3]
melted state, it exists as the dimer Al2Cl6, w ith tetracoordinate aluminium. This change in structure is related to the low er density of Lattice constant a = 0.591 nm, b = 0.591
the liquid phase (1.78 g/cm3) versus solid aluminium trichloride (2.48 g/cm3). Al2Cl6 dimers are also f ound in the vapour phase. At nm, c = 1.752 nm [3]
Lattice v olume (V) 0.52996 nm 3
higher temperatures, the Al2Cl6 dimers dissociate into trigonal planar AlCl3, w hich is structurally analogous to BF3. The melt conducts
Formula units (Z) 6
electricity poorly,[9] unlike more-ionic halides such as sodium chloride.
Coordination Octahedral (solid)
Aluminium chloride monomer belongs to the point geometry Tetrahedral (liquid)
group D3h in its monomeric f orm and D2h in its dimeric Molecular shape Trigonal planar
f orm. (monomeric v apour)
Thermochemistry
Hexahydrate [ edit ] Heat capacity (C) 91.1 J/mol·K[4]
Std molar 109.3 J/mol·K[4]
The hexahydrate consists of octahedral [Al(H2O) 6]3+
entropy (So298)
centers and chloride counterions. Hydrogen bonds
Std enthalpy of −704.2 kJ/mol[4]
link the cation and anions.[20] The hydrated f orm of f ormation
aluminium chloride has an octahedral molecular geometry, w ith the central aluminum ion surrounded by six w ater ligand molecules. (ΔfH⦵298)
Being coordinatively saturated, the hydrate is of little value as a catalyst in Friedel-Craf ts alkylation and related reactions. Gibbs f ree energy -628.8 kJ/mol[4]
(ΔfG˚)
Pharmacology
Reactions [ edit ]
ATC code D10AX01 (WHO )
Anhydrous aluminium chloride is a pow erf ul Lew is acid, capable of f orming Lew is acid-base adducts w ith even w eak Lew is bases Hazards
such as benzophenone and mesitylene.[8] It f orms tetrachloroaluminate (AlCl4−) in the presence of chloride ions. Saf ety data sheet See: data page
GHS pictograms
Aluminium chloride reacts w ith calcium and magnesium hydrides in tetrahydrof uran f orming tetrahydroaluminates. [5]

Reactions with water [ edit ] GHS Signal word Danger

GHS hazard H314[5]
Anhydrous aluminium chloride is hygroscopic, having a very pronounced af f inity f or w ater. It f umes in moist air and hisses w hen
statements
mixed w ith liquid w ater as the Cl− ligands are displaced w ith H2O molecules to f orm the hexahydrate [Al(H2O) 6]Cl3 . The anhydrous GHS P280, P310,
phase cannot be regained on heating the hexahydrate. Instead HCl is lost leaving aluminium hydroxide or alumina (aluminium oxide): precautionary P305+351+338[5]
statements
Al(H2O) 6Cl3 → Al(OH) 3 + 3 HCl + 3 H2O NFPA 704
Like metal aquo complexes, aqueous AlCl3 is acidic ow ing to the ionization of the aquo ligands: (f ire diamond) 0
3 2
[Al(H2O) 6]3+ ⇌ [Al(OH)(H2O) 5]2+ + H+

Aqueous solutions behave similarly to other aluminium salts containing hydrated Al3+ ions, giving a gelatinous precipitate of aluminium Lethal dose or concentration (LD, LC):
hydroxide upon reaction w ith dilute sodium hydroxide: LD 50 (median anhydrous:
dose) 380 mg/kg, rat (oral)
AlCl3 + 3 NaOH → [Al(OH) 3] + 3 NaCl
hexahydrate:
3311 mg/kg, rat (oral)
Synthesis [ edit ]
NIOSH (US health exposure limits):
Aluminium chloride is manuf actured on a large scale by the exothermic reaction of aluminium metal w ith chlorine or hydrogen chloride PEL none[6]
(Permissible)
at temperatures betw een 650 to 750 °C (1,202 to 1,382 °F). [9]
REL 2 mg/m 3[6]
2 Al + 3 Cl2 → 2 AlCl3 (Recommended)

2 Al + 6 HCl → 2 AlCl3 + 3 H2 IDLH N.D. [6]

(Immediate
Aluminum chloride may be f ormed via a single displacement reaction betw een copper chloride and aluminum metal. danger)
Related compounds
2 Al + 3 CuCl2 → 2 AlCl3 + 3 Cu
Other anions Aluminium f luoride
In the US in 1993, approximately 21,000 tons w ere produced, not counting the amounts consumed in the production of aluminium. [7] Aluminium bromide
Aluminium iodide
Hydrated aluminium trichloride is prepared by dissolving aluminium oxides in hydrochloric acid. Metallic aluminum also readily
Other cations Boron trichloride
dissolves in hydrochloric acid ─ releasing hydrogen gas and generating considerable heat. Heating this solid does not produce Gallium trichloride
anhydrous aluminium trichloride, the hexahydrate decomposes to aluminium hydroxide w hen heated: Indium(III) chloride
Magnesium chloride
Al(H2O) 6Cl3 → Al(OH) 3 + 3 HCl + 3 H2O
Related Lewis Iron(III) chloride
Aluminium also f orms a low er chloride, aluminium(I) chloride (AlCl), but this is very unstable and only know n in the vapour phase. [9] acids Boron trif luoride
Supplementary data page
Natural occurrence [ edit ] Structure and Ref ractiv e index (n),
properties Dielectric constant (εr), etc.
Anhydrous compound is now unknow n among the minerals. The hexahydrate, how ever, is know n as the rare mineral chloraluminite. Thermody namic Phase behav iour
[21][22] A more complex, basic and hydrated mineral is cadw aladerite.[23][24] data solid–liquid–gas
Spectral data UV, IR, NMR, MS
Safety [ edit ] Except where otherwise noted, data are giv en
f or materials in their standard state (at 25 °C
Anhydrous AlCl3 reacts vigorously w ith bases, so suitable precautions are required. It can cause irritation to the eyes, skin, and the [77 °F], 100 kPa).

respiratory system if inhaled or on contact.[25] v erif y (what is ?)

Inf obox ref erences

See also [ edit ]

aluminium monochloride

References [ edit ]

1. ^ a b c d e Hay nes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd 4. ^ a b c d Hay nes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.).
ed.). Boca Raton, FL: CRC Press. p. 4.45. ISBN 1439855110. Boca Raton, FL: CRC Press. p. 5.5. ISBN 1439855110.

2. ^ a b Aluminum chloride Archiv ed 2014-05-05 at the Way back Machine. Chemister.ru 5. ^ a b c Sigma-Aldrich Co., Aluminum chloride
. Retriev ed on 2014-05-05.
(2007-03-19). Retriev ed on 2017-03-17. 6. ^ a b c NIOSH Pocket Guide to Chemical Hazards. "#0024" . National Institute f or
3. ^ a b Ketelaar, J. A. A. (1935). "Die Kristallstruktur der Aluminiumhalogenide II". Zeitschrift für Occupational Saf ety and Health (NIOSH).
Kristallographie – Crystalline Materials. 90 (1–6). doi:10.1524/zkri.1935.90.1.237 .
S2CID 100796636 .
 7. ^ a b c Helmboldt, Otto; Keith Hudson, L.; Misra, Chanaky a; Wef ers, Karl; Heck, Wolf gang; 15. ^ Snider, B. B. (1980). "Lewis-acid cataly zed ene reactions". Acc. Chem. Res. 13 (11): 426.
Stark, Hans; Danner, Max; Rösch, Norbert (2007). "Aluminum Compounds, Inorganic". doi:10.1021/ar50155a007 .
Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley -VCH. 16. ^ Reuben D. Rieke; Stephen E. Bales; Phillip M. Hudnall; Timothy P. Burns; Graham S.
doi:10.1002/14356007.a01_527.pub2 . Poindexter (1979). "Highly Reactiv e Magnesium f or the Preparation of Grignard Reagents:
8. ^a b c Olah, G. A., ed. (1963). Friedel-Crafts and Related Reactions. 1. New York City : 1-Norbornanecarboxy lic Acid". Organic Syntheses. 59: 85. doi:10.15227/orgsy n.059.0085 .
Interscience. 17. ^ Sami A. Shama; Carl C. Wamser (1983). "Hexamethy l Dewar Benzene". Organic
9. ^ a b c d Greenwood, Norman N.; Earnshaw, Alan (1984). Chemistry of the Elements . Syntheses. 61: 62. doi:10.15227/orgsy n.061.0062 .
Oxf ord: Pergamon Press. ISBN 978-0-08-022057-4. 18. ^ B. Buchner; L. B. Lockhart, Jr. (1951). "Pheny ldichlorophosphine". Organic Syntheses. 31:
10. ^ Jonathan T. Reev es1, Zhulin Tan, Daniel R. Fandrick, Jinhua J. Song, Nathan K. Yee, Chris 88. doi:10.15227/orgsy n.031.0088 .
H. Senanay ake (2012). "Sy nthesis of Trif luoromethy l Ketones f rom Carboxy lic Acids: 19. ^ In contrast, AlBr3 has a more molecular structure, with the Al3+ centers occupy ing adjacent
4-(3,4-Dibromopheny l)-1,1,1-trif luoro-4-methy lpentan-2-one" . Organic Syntheses. 89: 210. tetrahedral holes of the close-packed f ramework of Br− ions. Wells, A. F. (1984) Structural
doi:10.15227/orgsy n.089.0210 . Inorganic Chemistry, Oxf ord Press, Oxf ord, United Kingdom. ISBN 0198553706.
11. ^ Kamil Paruch; Libor Vy klicky ; Thomas J. Katz (2003). "Preparation of 9,10- 20. ^ Andress, K.R.; Carpenter, C. (1934). "Kristallhy drate II. Die Struktur v on Chromchlorid- und
Dimethoxy phenanthrene and 3,6-Diacety l-9,10-Dimethoxy phenanthrene". Organic Syntheses. Aluminiumchloridhexahy drat". Zeitschrift für Kristallographie – Crystalline Materials. 87.
80: 227. doi:10.15227/orgsy n.080.0227 . doi:10.1524/zkri.1934.87.1.446 .
12. ^ Alexander J. Seed; Vaishali Sonpatki; Mark R. Herbert (2002). "3-(4-Bromobenzoy l)propanoic 21. ^ https://www.ima-mineralogy.org/Minlist.htm
Acid". Organic Syntheses. 79: 204. doi:10.15227/orgsy n.079.0204 . 22. ^ https://www.ima-mineralogy.org/Minlist.htm
13. ^ Wade, L. G. (2003) Organic Chemistry, 5th edition, Prentice Hall, Upper Saddle Riv er, New 23. ^ https://www.mindat.org/min-845.html
Jersey, United States. ISBN 013033832X. 24. ^ https://www.ima-mineralogy.org/Minlist.htm
14. ^ Galatsis, P. (1999) Handbook of Reagents for Organic Synthesis: Acidic and Basic 25. ^ Aluminum Chloride . solv ay chemicals.us
Reagents, H. J. Reich, J. H. Rigby (eds.) Wiley, New York City. pp. 12–15.
ISBN 978-0-471-97925-8.

External links [ edit ]

International Chemical Saf ety Card 1125

Index of Organic Synthesis procedures that utilize AlCl3
The period 3 chlorides
MSDS
Government of Canada Fact Sheets and Frequently Asked Questions: Aluminum Salts

V·T ·E Alum inium com pounds [hide]

Al(I) AlBr · AlCl · AlF · AlI · Al2O

Al(II) AlB2 · AlB12 · AlO · K2Al2B2O7

AlAs · Al(BH 4)3 · AlBr3 · AlCl 3 · AlF 3 · AlH 3 · AlI 3 · AlN · Al(NO3)3 · Al2(CO3)3 · Al(OH)3 · Al(OH)2OAc · Al(OH)(OAc)2 · Al(OAc)3 · Al2SO4(OAc)4 · AlP · AlPO4 · AlSb · Al(C 5H 7O2)3 · Al(MnO4)3 ·
Al2(MoO4)3 · Al2O3 · Al2S3 · Al2(SO4)3 · Al2Se3 · Al2Te3 · Al2SiO5 · Al4C 3 · AlOHO · Al(OH)2CO2C 17H 5 · NaAlH 2(OC 2H 4OCH 3)2 · LiAlH 2(OC 2H 4OCH 3)2
Al(III)
Alums (NH 4)Al(SO4)2 · KAl(SO4)2 · NaAl(SO4)2

Organoaluminium(III) compounds (Al(CH 3)3)2 · (Al(C 2H 5)3)2 · Al(CH 2CH(CH 3)2)3 · Al(C 2H 5)2Cl · Al(C 2H 5)2CN · Al(CH 2CH(CH 3)2)2H · Al(C 2H 5)2Cl2C 2H 5Cl · Ti(C 5H 5)2CH 2ClAl(CH 3)2