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Aluminum Chloride

AlCl3 salt

Properties

StateSolid (powder, hygroscopic)
ColorYellowish-white (anhydrous); colorless (hexahydrate)
SolubilityReacts with water (anhydrous); hexahydrate freely soluble
Melting Point192.4°C (at 2.5 atm; sublimes at 180°C at 1 atm)
Boiling Point180°C (sublimes)

About Aluminum Chloride

Aluminum chloride is the Lewis acid that organic chemists reach for whenever a reaction needs an electrophile activated by halide abstraction — the canonical example being Friedel–Crafts alkylation and acylation, where AlCl3 strips chloride off an alkyl or acyl halide to generate the carbocation or acylium ion that attacks the aromatic ring. The activation works because aluminum's empty p-orbital is hungry enough for electron density that even a weakly basic chloride donates lone-pair electrons readily, and the resulting [AlCl4]⁻ counterion is stable enough that the carbocation is genuinely free to react. Beyond the Friedel–Crafts reactions, AlCl3 catalyzes Diels–Alder cycloadditions (where it activates the dienophile carbonyl), various rearrangements, and the Gattermann–Koch formylation. The structural curiosity of the molecule is that it dimerizes — solid AlCl3 has a layered ionic structure, but in the gas phase or in non-coordinating solvents it forms Al2Cl6 with two bridging chlorines, a textbook example of a halide-bridged dimer with three-coordinate geometry filled out by donation from a neighbor's lone pair. The handling reality is that anhydrous AlCl3 reacts with water with an aggressive exotherm, releasing HCl gas and generating a corrosive solution — which is why bottles arrive with desiccant, get opened in a dry box or under a flow of nitrogen, and never sit on the bench longer than they have to.

Where you'll encounter it

If you've done a Friedel–Crafts acylation or alkylation in undergraduate organic chemistry, AlCl3 was the catalyst — it's the standard reagent for installing acetyl groups on benzene rings or branching alkyl groups onto aromatic systems. In industry, the same chemistry feeds production of detergent alkylbenzenes, anthraquinone dye precursors, and a long list of pharmaceutical intermediates. The other place it shows up is in antiperspirants, where the related compound aluminum chlorohydrate (Al2(OH)5Cl) is the sweat-blocking active ingredient — the aluminum ions form a temporary plug in eccrine sweat ducts. The fume hood encounter most chemists remember is opening an old AlCl3 bottle: the trapped HCl from slow hydrolysis vents immediately and the cap rim is usually crusted with corrosion product.

Common Uses

  • Friedel–Crafts alkylation and acylation catalyst
  • Lewis acid for Diels–Alder and Mukaiyama aldol reactions
  • Petroleum-refining isomerization and alkylation catalyst
  • Aluminum chlorohydrate (related salt) as antiperspirant active
  • Pharmaceutical and dye intermediate synthesis

Safety Information

Reacts violently with water — exotherm and HCl release happen the moment the anhydrous solid contacts moisture. Causes severe skin and eye burns; vapor and dust irritate the airways. Always handle under a glove-bag or in a dry inert atmosphere; quench spills with limited additions of dry sodium carbonate before any aqueous wash. GHS H290, H302, H314.

This safety summary is for educational reference only and may not be complete. It is not a substitute for Safety Data Sheets (SDS), medical advice, or professional chemical safety guidance. Always consult appropriate SDS and qualified professionals before handling chemicals.

Constituent Elements

Frequently Asked Questions

What is the molar mass of aluminum chloride?
133.341 g/mol. Sum 26.982 for the aluminum and 3(35.453) for the three chlorines, giving 133.34. The hexahydrate form (AlCl3·6H2O) weighs 241.43 g/mol — worth checking the bottle label, since the hydrate is the form that's commonly available for cosmetic and water-treatment applications while the anhydrous form is the one needed for Lewis-acid catalysis.
Why is aluminum chloride important in organic chemistry?
It's the Lewis acid that pulls chloride off alkyl and acyl halides cleanly enough to generate the carbocation or acylium that attacks an aromatic ring — the reactive species at the heart of Friedel–Crafts alkylation and acylation. The empty 3p orbital on aluminum is electrophilic enough to coordinate even a weakly basic chloride, and the resulting [AlCl4]⁻ is a soft, non-nucleophilic counterion, so the carbocation has time to find the arene rather than collapsing back.
Why does aluminum chloride react with water?
Anhydrous AlCl3 has Al(III) in a coordinately unsaturated electron-poor environment. Water is both a nucleophile and a proton source — it coordinates to the aluminum, then deprotonates to release HCl, then repeats until the aluminum ends up as Al(OH)3 and three equivalents of HCl have been released. The reaction is exothermic enough that a dropwise addition of water to AlCl3 will spit; the standard quench protocol is to add the AlCl3 slowly to a large excess of crushed ice, never the other way around.