Anhydrous Aluminum Chloride prepration

Quote: Originally posted by 12AX7

Why does it not form CuCl2?

Because its subliming away, the melting point of CuCl2 is 500c, so I suppose its plausible that there could be a bit of cucl2 contamination. The AlCl3 sublimes at 200c, way before the CuCl2 even melts.

Not to mention it would turn water blue if it was contaminated with CuCl2 (and it did not seem to do so in my test). Not to mention you can vacuum sublime the AlCl3 to purify it if you want to

Additionally you can easily use a thin steel pipe (like say a broom stick) instead.



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copper does not react with HCl
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[Edited on 26-7-2010 by Chainhit222]

Quote: Originally posted by 12AX7

Ok, so if nothing else, you're doing thermal seperation. Like distilling TiCl4 from FeCl3 and etc. That works, and as a bonus, aluminum reacts with CuCl2 and most others, so if you have an excess of metal, you should get excellent results. Does steel passivate to hot HCl? FeCl3 is more volatile, though still not as much as AlCl3. Not that that's a big deal, most of the time AlCl3 and FeCl3 can be substituted as Lewis acids. If used as a long-term apparatus, I wonder if there would be any erosion of the pipe (steel or copper). Meh, can probably get more than a few pounds of AlCl3 out of it by then. Tim

Quote: Originally posted by chemrox

everybody except me already knew that a "barby" is a gas-fired barbecue oven? where have I been? I must however protest the substitution of the plural of an British/American volume unit for the conmon term for pure silica glass. Having got my little barns in, why do this, AlCl3 is cheap. It does need to be pure for most purposes ....

Wow that's a really good setup, even if the yields aren't the best who cares, it costs a few dollars to set up.
I'm definitely giving that a shot once we get a new gas cylinder for the BBQ

Quote: Originally posted by Chainhit222

i was running around my yard with a leaf blower in a gas mask shooing clouds of alcl3 away so my neighbors would not get suspicious if the cloud traveled into their yard :x I hope they did not see me [Edited on 28-7-2010 by Chainhit222]

Quote: Originally posted by chemrox

everybody except me already knew that a "barby" is a gas-fired barbecue oven? where have I been? I must however protest the substitution of the plural of an British/American volume unit for the conmon term for pure silica glass. Having got my little barns in, why do this, AlCl3 is cheap. It does need to be pure for most purposes ....

Jumpin' jelly beans! You didn't realize a barby was a BBQ. Shit....

As chainhit says, the anhydrous salt is not at all easily available without accounts.

I agree that FeCl3 etc contaminated Lewis acid will function for a lot of things. But, when it's being used for experimentals where I don't know what colours or changes to look for, they do not help at all. E.g. My commcercial grade acid stained my solvents of choice so dark brown I couldn't see through them with it held up to a light. That instantly increases the chances of incorrectly identifying something as intractable tar.

As I've said on other forums, I can order a huge number of things from genuine suppliers. I wouldn't mind if they spontaneously phoned me or asked to visit if they were bothered about an order, but I hate the idea of them closing the road off, getting their suits out and smashing the door down at 3am because I'm a member of the public and they think I'm churning out drugs or bombs.

It's also part of the fun, seeing what I can make at home better than the lab suppliers. It's not all that hard to surpass what gets passed off at CP grade, and it can be done for not a lot of effort and similar or lower price.

The AlCl3 depositing in my amber bottle was pure white. The CP grade was yellow, after weeks of rinsing the near opaque brown shit off it. I'd make it at home even if it was more expensive than the CP grade to be sure of what I had.

If we just ordered what we liked form suppliers, this forum wouldn't exist.

[Edited on 28-7-2010 by peach]

I seem to have alot of hydrate in my product. I vacuum sublimed some, and the left behind stuff is not particularly reactive with water. I might just have to do the iodine method

It must be reacting with the atmosphere during production. I wonder if pumping a mixture of argon and hcl would help. There is also some FeCl3 in my product (nice yellow color), I assume this means the pipe is impure.

Any idea what else is in aluminum foil or copper pipe? What kind of contaminants am I dealing with?

[Edited on 30-7-2010 by Chainhit222]

I am trying the 1,4-dmb with glyoxylic acid route for now, but I want to do gatterman too and compare them. Aparrantly it works much better with 2-bromo-1,4-dmb, but I don't really want the bromine atom there

My pipe is 1 inch ID.
I suggest you use something thicker then a 24/40 liebig condenser to condense the AlCl3, it clogs up WAY too easily. I was thinking a 300mm glass 24/40 tube, then put a liebig on the end of that, hopefully it would be a more even distribution and not clog so much. Then you could simply use a pipe cleaning brush to get your AlCl3 out. When a clog forms its pretty hard to unclog...

[Edited on 13-8-2010 by Chainhit222]

Given the level 4 rating it scores on the NFPA 704 fire diamond, coupled with it being controlled under the chemical weapons acts, I would recommend you don't use thionyl chloride.

You can dry FeCl3 hexahydrate (the dark yellow) with heat under a stream of hydrogen chloride gas.

A number of lewis acids behave this way with regards to drying by heat, they start fuming off hydrogen chloride gas as you try to dry them. By running them under that gas, they don't.

Lewis acids are roughly grouped into hard and soft. The hard and soft groups alone aren't perfect definitions, there are difference between the acids within those groups in terms of how aggressively they seek out electron pairs.

To produce clean, anhydrous lewis acid by thermally drying the damp veriations, you'll need to produce a clean, dry stream of hydrogen chloride gas. If you've not done this before, I would suggest practicing first, bubbling it into water to make up some hydrochloric acid. And starting with small amounts.

The gas isn't systemically toxic, but it's beyond 'a bit reactive' or 'a bit smelly'. It'll rot stainless and chrome fittings, normal keck clips fall to bits when exposed to very tiny leaks through the tapers, tubing goes 'funny', tubes tend to block up as things react at their ends and so on.

Drip some concentrated sulphuric acid on some table salt in a tiny test tube, then have a deep sniff and see if it's something you want to make a lot of. Be prepared for a 30 second long, involuntary coughing seizure.

[Edited on 30-8-2010 by peach]

Well put, Peach. Your description of HCl is spot-on.

Quote: Originally posted by White Yeti

I'd like to carry out a Friedel–Crafts very soon, so I'd like to give this a shot. I don't have a gas grill, instead I have a charcoal grill that can definitely get up to temperature, I've melted aluminium in it once upon a time, and steel can glow red hot if I force air into it, so temperature is not a problem. I also have some sodium bisulphate that I can mix with salt to generate HCl. However, I'm wondering if I can use a glass condenser for re-condensing aluminium chloride vapours. Won't soda lime glass crack under the temperature gradient? I mean, one side is at 400C+ and the rest is at 20C. Could I use a copper tube instead?

I am also planning on trying this soon. The Bisulphate sounds like a nice way to generate dry HCl, although according to wiki, the reaction proceeds at 200C. I suppose you could do it all in the BBQ .

I planned on having the copper tube exiting straight into an old jar surrounded by ice water. Dunno if this will be sufficient though.

"I am also planning on trying this soon. The Bisulphate sounds like a nice way to generate dry HCl, although according to wiki, the reaction proceeds at 200C. I suppose you could do it all in the BBQ .

I planned on having the copper tube exiting straight into an old jar surrounded by ice water. Dunno if this will be sufficient though."

Sounds like a nice idea, however the jar with the ice water sounds like a failed venture from the start. There's a reason why the OP used room temperature water. If you use ice water any water that was present in the tube would re-condense and contaminate your anhydrous aluminium chloride.

Quote: Originally posted by White Yeti

Sounds like a nice idea, however the jar with the ice water sounds like a failed venture from the start. There's a reason why the OP used room temperature water. If you use ice water any water that was present in the tube would re-condense and contaminate your anhydrous aluminium chloride.

Quote: Originally posted by White Yeti

To bbartlog & Thor. I understand. But how were you planning on attaching the jar to the copper tube and putting a vent without letting atmospheric humidity contaminate the condensed aluminium chloride? My reasoning is that you need to have some kind of tube between the copper tube and whatever condenser you plan to use (since the temperature gradient would crack any kind of glass, including boro). Also, you can't attach the jar hermetically because you need some kind of vent for the hydrogen gas that is evolved. The problem: once the HCl generator stops producing hydrogen chloride, the gases inside the copper tube are still very hot. When the temperature goes down, the gasses contract, reducing the pressure and causing humid air to get sucked in through the hydrogen vent. Since the jar the air would be entering into would be at 0C, it's only logical to think that atmospheric water would condense on its sides and contaminate the product. If air doesn't get sucked in, the tube or the jar would implode, making a mess, and wasting your time. How would you deal with this problem? The OP has an argon tank, but what would normal people use?

Quote: Originally posted by peach

Given the level 4 rating it scores on the NFPA 704 fire diamond, coupled with it being controlled under the chemical weapons acts, I would recommend you don't use thionyl chloride. [Edited on 30-8-2010 by peach]

Thought to give a hit for this one.

How about this kind of reactor:

Steel body, with ceramic clay inner and nicr heater wire
Quartz or boro tube blowing dry chlorine gas
Melt aluminium at 650-700C
Blow chlorine into it
AlCl3 will form and distill up to tube
The tube is heated too
Tube goes into cooled receiver where alcl3(FIXDED) should accumulate

Any ideas how to effectively prevent clogging the tube? Planning of using at least 3/4" or 1" steel tube.



[Edited on 10-7-2013 by testimento]



[Edited on 10-7-2013 by testimento]

Quote: Originally posted by testimento

How about this kind of reactor

Actually, I already obtained the material for both of them, but Im still waiting for the nichrome wire and glass tube. I'll be pleased to post pics of the process soon when the stuff comes. I've got several other things to do at the moment, including the furnace, so not today.

Quote: Originally posted by Cheddite Cheese

Yes, but from the perspective of the amateur chemist, why? It's much easier to make anhydrous AlCl3 than it is to make SOCl2. Quote: Originally posted by peach   Given the level 4 rating it scores on the NFPA 704 fire diamond, coupled with it being controlled under the chemical weapons acts, I would recommend you don't use thionyl chloride. [Edited on 30-8-2010 by peach]

I used 120gr(AlCl3.6H2O) and 350gr(SOCl2).I have to say nothing happened after adding resulting powder to water.No heat No vapor no gas.
I dont think SOCl2 is effective substance for dehydrating Aluminium Chloride Hexahydrate

Dehydration AlCl3.6H2O by Thionyl Chloride







[Edited on 10-9-2013 by Waffles SS]

Quote: Originally posted by Chainhit222

I just made anhydrous aluminum chloride. You will need: -aluminum foil -a barby -chlorine or hcl gas source -a piece of metal pipe (i used copper) -some way to connect it all together (i afro rigged it) my setup was: 1) flask connected to a addition funnel (ground glass 24/40) 2) a hose (i used tygon, vinyl is fine) leading from the hose barb on the flask to a ground glass vacuum take off thing wrapped in electrical tape and wedged into a copper tube filled with aluminum foil from the food store laid across the barby 3) a liebig condenser cooled with room temp water with one end wrapped in electrical tape wedged into the end of the pipe I preheated the barby as high as it would go (seems to be like 450c) (take off the flame guard if it has one) and then laid the pipe on it. At this point the pipe was being flooded with argon gas so the aluminum would not oxidize (i dont think it was necessary, but why not if you got a tank). After I was confident that the pipe and reactants were hot enough I switched the hose from argon to the hcl gas generator and turned it on. AlCl3 began to sublime and condense in the liebig. Once I ran out of hcl gas I took the liebig off and put it over a container. I then took a clean plastic glassware brush and pushed/twisted it through the liebig, which caused the alcl3 to fall out into my container. Id recommend a large chlorine gas generator, I ran out of chlorine so I just got a few grams of AlCl3 which is very slightly contaminated with burnt electrical tape. If you actually wanna do this, I would recommend adding a drying tube for the chlorine or HCl gas, and using some kind of heat resistant material (maybe muffler tape?) to make a connection between your glassware and the copper pipe. http://img807.imageshack.us/img807/241/thugfurnace.jpg (picture of setup) http://www.youtube.com/watch?v=bpi7cX5d0iw (youtube video of reaction) Why not use a quarts tube you ask? Because I cannot afford a quarts tube or a tube furnace. I have 12$ in my wallet. [Edited on 26-7-2010 by Chainhit222] [Edited on 26-7-2010 by Chainhit222]

Could gallium be used to amalgamate aluminum and make it more reactive towards chlorine or HCl gas? Gallium makes aluminum react as if it has no oxide. If gallium is useful in this case, it would possibly make the reaction go quicker and only be a matter of avoiding the use of aluminum tubing and using proper equipment.

Quote: Originally posted by Brain&Force

Aluminum reacts with HCl on contact

I'm so funking pissed after reading about how it is easy to perform anhydrous AlCl3, while they have no idea about the reaction, and I'm so tired after spending few days building actual devices and trying different modes, yet my only success was something like 20-30 g of AlCl3 and a lot of HCl smoke all over the room, because I have no idea how to perform the reaction without massive HCl leakage and AlCl3 hydrolysis having no special equipment.
I want to pinpoint some problems/mistakes:
- you can't do a straightforward Al+HCl or Al+Cl2 - they won't react at all (anhydrous!);
- and even heating to 100°C is not enough, reaction starts somewhere at 200°C, but optimally is run at 300-800°C;
- the reaction is exothermic, that's why you can actually see the aluminium burning (glowing red) in the HCl/Cl2 flow, if it flows fast enough, this can make your reactor crack;
- this crap obliterated everything that is colder than 180°C, inlets, outlets, walls, and you condenser is usually a big vessel with flat walls, which is a bad condenser in fact, that's why the AlCl3 easily makes its way to HCl outlet, clogging it and making you breath a life-given hydrogen chloride;
- producing 50 g of AlCl3 via HCl method can make a nice hydrogen explosion, destroying the room, until you properly dispose it (fume hood, draw it outside, burn, catalytically oxidize);
- I see no way to make appreciable amount of AlCl3 without complex heating of reactor part of the system, because you need to keep the very end of the reactor outlet hot, while condenser right next to it should be cold;
- simax/duran/etc bottle as a condenser is capable of processing not more than 20 g of AlCl3 without disassembing the apparatus (it has polypropylene blue or polybutyleneterephthalate red ring which are relatively heat-labile);
- you need to pass the HCl/Cl2 through a lot of aluminium, otherwise most of the gas will pass unreacted, because aluminium does not readily reacts with those gases.
Here's brauer's device that worked for me, until had been clogged.


Aluminium amalgam is a known catalyst of Friedel-Crafts, most likely reacting with chlorine in-situ. Maybe some other alloy will work (copper?) or even a bare aluminium:
"AlCl3 prepd. according to Radzivanovskii [Ber. 28, 1135(1895)] from Al and HCl is an active Friedel-Crafts catalyst.
C6H6 (200 g.) and 4 g. Al shavings treated with dry HCl until a brown coating covered the catalyst, then with 100 g. EtBr, and let stand 48 hrs. at 10-12°, followed by refluxing 2 hrs., gave 73% EtPh, b. 132-4°, d*° 0.8703, nD20 1.4950, 16-18% Et2C6H4" - The activity of aluminum chloride prepared by the method of Radzivanovskii (benzene alkylation) 000505318-Chem_Abs_45_Friedel_Crafts_with_Al_catalyst.pdf
Also see this thread http://www.sciencemadness.org/talk/viewthread.php?tid=5799
And those guys http://pubs.acs.org/doi/abs/10.1021/ed066p176 claim they've managed to perform Friedel-Crafts with a bare aluminium metal (reaction of secondary alkyl halide with toluene, aluminium wire activated by polishing it right before addition to the reaction mixture).
Tell me I can't use TFSE and the problems I state are already solved, thus every amatuer chemists can easily make AlCl3 on 1 mole scale.

Anhydrous AlCl3 from ZnCl2

Quote: Originally posted by ChemPlayer

byko3y, I certainly feel your pain (or rather, I did) because a lot of these preparations only seem to work give reasonable yield / purity if you've got the right sizes of flask, gaps, cooling mechanism, set them up just right etc. I recently spent quite a lot of time tweaking and have figured out a way of using what equipment i have and can boast a 40% yield of AlCl3 using the Zinc Chloride and aluminium powder reaction. And it's decent quality - works a treat for F-C acylations and some demethylations too. I reckon 60% is possible too with some more time. Video on the process and explanation is here: https://www.youtube.com/watch?v=g7sS69fQMsk

Quote: Originally posted by Magpie

Maybe it could be bubbled into an anhydrous solvent like chloroform. Thr chloroform could then be removed by distillation with the vacuum adapter connected to a moisture guard tube.

Thanks for the kind comments

You've all got me thinking about various improvements now, and I'm itching to try a couple of variations using slower heating, excess Al powder, and possibly using a quantity of a low bp inert (to AlCl3 and flame anyway) in the receiving container. DCM may be a first choice.

I like the idea that the solvent quickly heating and even boiling off will effectively act as a 'one-shot' rapid efficient heat exchanger for the hot vapours to condense in the receiver, just so long as it doesn't cause a jet coming out of the container expelling all the product with it!

Thursday is my window of opporunity to test so I will let you know...

(Btw had technical issues with original 'ChemPlayer' user so I had to start a new one 'ChemPlayer_').

Quote: Originally posted by Magpie

As you say the ZnCl2 liquifies before the reaction takes off. So this is really a liquid-solid reaction - a great improvement over a solid-solid reaction.

Quote: Originally posted by blogfast25

The external heating is weak, reaction enthalpy low and a gaseous reaction product carries away quite a bit of enthalpy.

Quote: Originally posted by Magpie

How can you say that the external heating is weak. Didn't ChemPlayer say that the RBF had to be intensely heated for 45 minutes before the reaction takes off? If the AlCl3 is a liquid when formed it looks like it quickly forms a solid in the form of smoke.

Quote: Originally posted by ChemPlayer_

So I sneaked in the time quickly to do another run, this time using 100g of anhydrous zinc chloride and 25g of aluminium powder (~25% molar excess). [snip] 3. I saw the liquid mentioned refluxing back into the flask (which didn't violently react with anything, hence I assume you must be right and this is AlCl3 or ZnCl3 as opposed to anything aqueous in nature - not that I imagine water can survive long in those conditions anyway). [snip] I can only conclude that a lot of the product must be retained in the reaction flask (or the reaction didn't go to completion). Ok so now I've got the basic set-up nailed (I think) my thoughts on next steps are to see if I can grind up the ZnCl2 into a finer powder (at the risk of atmospheric moisture absorption however) and hence a better surface area with the Al (and maybe slightly greater excess of Al to temper the likely faster reaction a bit). I have to replenish my ZnCl2 stocks first however as this is quite an 'expensive' process unoptimised! I do have a beautiful 100g+ of AlCl3 collected now though and I may do some more FC experimentation in the interim.

Quote: Originally posted by byko3y

Considering you can obtain at least 60% yield using a regular chlorine-foil method, I doubt the ZnCl2 way is viable. Pretty much the only major problem is to move the product all the way through the tube to the receiving vessel and stop it right there. I'm sure this was a major issue in your case.

I’ve been curious as to if loss of the alcl3 can be mitigated using anhydrous ethanol or methanol. Per US1647446A, the patent states that solvents can be used to suppress the powder alcl3



I’ve been finding a mix of information. Some sources say that ethanol reacts with alcl3 at room temperature. I can’t find anything about the recovery of alcl3 from anhydrous solutions of ethanol

[Edited on 30-6-2020 by Opylation]

I just completed a successful reaction of Aluminum with Chlorine gas. The first go-around worked but got ruined due to blowback from the chlorine trap. The second go worked but was ruined because I did not continue the chlorine generation. The third and final go worked perfectly.

I started by getting a chlorine generator ready, hooked it up with a short path condenser, and had it empty into a flask with small chips of aluminum foil. The vacuum adapter was then hooked up to a base scrubber to capture excess Cl2 gas. The aluminum was heated with a large propane torch set to almost closed (very weak stream, lower temp), which equated to roughly 700 degrees celsius. It was held away from glass (I have broken so many flasks because of heat shock) and slowly warmed. When it was too hot to touch, I then heated it much more rapidly and waited until I saw reddish-pink coloring of the glass. I stopped and shook the flask as best I could, and within seconds, it flashed and rapidly sublime out white substance. Once settled, it was exactly the consistency expected from the literature. I am very surprised I did not break my glassware during this reaction. That propane torch can reach 2000C if I opened it to full.

I must note that there should be catalyst added in future to help heat and begin the reaction. I have read about FeO2/CuCl2 mixture, like a powder that can be mixed. I will probably invest in a coffee grinder to help increase the surface area of the aluminum. If I was to require more however, more than 5-10g, then I would use some of the methods already posted here, as they seem to be geared towards larger amounts. Quartz tube was suggested, and maybe a doped quartz wool (FeCu/C) would be nice. Maybe a Fe-Fe(CN)6 complex would work?

Quote: Originally posted by Mateo_swe

Doesnt the chlorine generator and quartz tube with al-foil procedure work ok? Below is a procedure i saved from somewhere. I add a pdf with another variant that i also found somewhere. Concentrated (37%) hydrochloric acid (20 mL, 658 mmol) was added dropwise to hydrated calcium hypochlorite (22.0 g, 102 mmol) generating a steady stream of chlorine gas. The chlorine gas was passed through a glass column filled with aluminium foil (1.00 g, 37.1 mmol) and then into a water trap. Once the apparatus had been filled with chlorine gas the aluminium foil was heated with a bunsen burner to facilitate the reaction. Upon sufficient heating, the aluminium foil burnt with a bright white light signifying the reaction had commenced. At this point the bunsen burner was removed and the reaction self propagated along the column with occasional flickers of red-orange embers. When the vigorous reaction had subsided, a black residue remained in the column and a yellow powder (AlCl3) was deposited in the receiving flask. Yield: 4.05 g (82%).