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Author: Subject: Preparation of Al(HSO4)3
EvlRenne
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[*] posted on 15-11-2018 at 13:56
Preparation of Al(HSO4)3


Hello everyone,

guys, I've been searching on web, and can't find how can I make aluminum hydrogen sulfate? I want to try it as a catalyst for organic synthesis as a lot of reference says about its efficiency.

[Edited on 15-11-2018 by EvlRenne]
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Metacelsus
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[*] posted on 16-11-2018 at 01:15


You could try mixing aluminum sulfate (Al2(SO4)3) with sulfuric acid.



As below, so above.
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EvlRenne
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[*] posted on 16-11-2018 at 04:03


Quote: Originally posted by Metacelsus  
You could try mixing aluminum sulfate (Al2(SO4)3) with sulfuric acid.

And evaporate at 200+ C? I tried, did not work.
Only 1 mention I found from one of the article:
Preparation of aluminum hydrogen sulfate
Anhydrous aluminum chloride (33.4 g, 0.25 mol) was placed into a 500 mL suction flask equipped with a constant-pressure dropping funnel. The gas outlet was connected to a vacuum system through an adsorbing solution (water) and an alkali trap. Concentrated sulfuric acid (98%, 73.5 g, 0.75 mol) was added drop-wise over a period of 1 h at room temperature during which HCl was evolved. After completion of the addition, the mixture was stirred for 30 min, while the residual HCl was eliminated by suction. Finally, a pale-brown solid material was obtained (77.0 g).

I will not be able to do it, because I have no equipment to prepare AlCl3.
I hope that there is the other way to make it.
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clearly_not_atara
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[*] posted on 16-11-2018 at 12:18


I think the "simplest" version is to add aluminium metal to concentrated sulfuric acid... obviously this will cause a very vigorous reaction, but it obviates the need to dry the product. I'm not sure how to contain the reaction -- even adding small pieces of aluminium to an excess of H2SO4 rapidly stirred on an oil bath is likely to be too vigorous. It might be possible to dilute the sulfuric acid with a sufficiently inert solvent - the only thing that comes to mind are fluorinated solvents, maybe PCBTF.

EDIT: above is wrong, Al will reduce H2SO4 to SO2

Another possibility is to replace aluminium chloride with another salt which is easier to dry and where the conjugate acid can be distilled off easily. One interesting possibility is aluminium borate, AlBO3, which would react like this:

AlBO3 + 3 H2SO4 >> H3BO3 + Al(HSO4)3

Boric acid will not vaporize at normal pressures but it can be vacuum distilled and IIRC it is significantly more volatile than sulfuric acid.

Quote:
And evaporate at 200+ C? I tried, did not work.


Can you describe what happened? Did you get a lot of SO2 release?

[Edited on 16-11-2018 by clearly_not_atara]




[Edited on 04-20-1969 by clearly_not_atara]
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[*] posted on 16-11-2018 at 12:23


Just get a big stainless steel trashcan(if stainless steel doesnt react with sulfuric acid of course) put some sulfuric acid at the bottom and dump some aluminum into it, then run.
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clearly_not_atara
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[*] posted on 16-11-2018 at 12:30


See my edit above: Al will reduce conc. H2SO4, which makes the procedure inapplicable.

It would be nice to find another volatile acid which is not dehydrated or oxidized by H2SO4. Aluminium triacetate might be obtained by dissolving aluminium metal in anhydrous acetic acid, although the reaction might need a catalyst to get started. Then you could add Al(OAc)3 to H2SO4 and distill off AcOH. We know H2SO4 won't dehydrate AcOH.




[Edited on 04-20-1969 by clearly_not_atara]
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EvlRenne
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[*] posted on 16-11-2018 at 14:14


Quote: Originally posted by clearly_not_atara  


Quote:
And evaporate at 200+ C? I tried, did not work.


Can you describe what happened? Did you get a lot of SO2 release?

[Edited on 16-11-2018 by clearly_not_atara]

It was a lot of Al2(SO4)3 as white crystals, SO2 was in moderate amount.
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kmno4
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[*] posted on 16-11-2018 at 15:51


Quote:

It was a lot of Al2(SO4)3 as white crystals, SO2 was in moderate amount.

No wonder:

al.bmp - 67kB


Al(HSO4)3 exists only in Iranian, Indian... etc "publications" and its existence has nothing to do with reality.
Procedure (and results) for its preparation, given above (J. Chem. Sci. Vol. 128, No. 3, March 2016, pp. 429–439. by Iranian team) , is copied from earlier article (Bull. Chem. Soc. Jpn., 76, 1863–1864 (2003), by another Iranian team).

ps.

"Finally, a pale-brown solid material was obtained in 77
g. Al(HSO4)3 was characterized by the determination of its H+
content by titration with NaOH (Calcd 0.95%, Found 0.96%)
and SO4 by..... "
I wonder, how they obtained this result by simple HaOH titration ??
And 73,5 g of 98% H2SO4 is not 0.75 mol but 0,735 mol.




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clearly_not_atara
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[*] posted on 16-11-2018 at 21:18


I'm surprised that the Bulletin of the Chemical Society of Japan could be so deceived. I would have hoped that the peer reviewers would object to the paper's use of a nonexistent compound!



[Edited on 04-20-1969 by clearly_not_atara]
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EvlRenne
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[*] posted on 17-11-2018 at 10:29


Thank you all for answers, now I'm a little bit confused, what are they use then instead of Al(HSO4)3?
https://link.springer.com/article/10.1007%2Fs00706-003-0083-...
https://link.springer.com/article/10.1007%2Fs12039-016-1036-...
https://link.springer.com/article/10.1134%2FS107036321505030...
https://link.springer.com/article/10.1134%2FS107036321606028...

[Edited on 17-11-2018 by EvlRenne]
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kmno4
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[*] posted on 18-11-2018 at 14:19


Iran, Iran, Iran and Iran :D
What is the catalyst ?
Who knows.... Reaction of AlCl3 and H2SO4 should be more investigated, with elemental analysis of the product.
It cannot be Al(HSO4)3 because it woud split into normal sulfate and H2SO4.
The procedure (and result) for "Al(HSO4)3" preparation is identical (with scaling) in each cited article - it is highly doubtful whether these articles have any scientific value.
Maybe islamic chemistry is different :o
الله أكبر




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[*] posted on 18-11-2018 at 18:27


Quote: Originally posted by kmno4  
Maybe islamic chemistry is different :o
الله أكبر

Despite all the weird languages that spambots speak in, I think you may actually be the first to use Arabic script here. I see you are a human. Carry on.

Though, in Iran, I suppose it would actually be Farsi. But for the purposes of this discussion, it makes no difference.




The first step in the process of learning something is admitting that you don't know it already.

I'm givin' the spam shields max power at full warp, but they just dinna have the power! We're gonna have to evacuate to new forum software!
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Gearhead_Shem_Tov
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[*] posted on 18-11-2018 at 21:06


Quote: Originally posted by kmno4  
Iran, Iran, Iran and Iran :D
...
Maybe islamic chemistry is different :o
الله أكبر


A: "What have Islamic chemists ever given us!"

B: "Mineral acids?"

A: "What?"

B: "Strong mineral acid."

A: "Oh, yeah, yeah, they did give us that. That's true."

C: "And alcohol distillation."

D: "Oh, yeah, distillation. Remember, Reg, what drinks used to be like?"

A: "Yeah, alright, I'll grant you, mineral acids and alcohol are two things the Islamic chemists have done."

E: "And the alkalis."

A: "Yeah, well, obviously the alkalis. I mean, the alkalis go without saying, don't they? But apart from mineral acids, alcohol, and alkalis—"

B: "Alembics?"

C: "Aludels?"

D: "Athanors?"

B: "Water baths."

C: "Sand baths."

A: "Right, yeah, well, apart from ..."







[Edited on 19-11-2018 by Gearhead_Shem_Tov]
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EvlRenne
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[*] posted on 19-11-2018 at 03:41


Okey, guys, all jokes aside.
So that kind of catalyst isn't exists?
How come Russian/Japanese/German/Iranian/Chinees (https://www.sciencedirect.com/science/article/pii/S100184170...)/Brazilin (http://www.scielo.br/scielo.php?script=sci_arttext&pid=S...) chemistry journals mentioned it?
All of it have no value?

[Edited on 19-11-2018 by EvlRenne]

[Edited on 19-11-2018 by EvlRenne]
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kmno4
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[*] posted on 19-11-2018 at 07:12


Quote: Originally posted by EvlRenne  

How come Russian/Japanese/German/Iranian/Chinees (https://www.sciencedirect.com/science/article/pii/S100184170...)/Brazilin (http://www.scielo.br/scielo.php?script=sci_arttext&pid=S...) chemistry journals mentioned it?
All of it have no value?

These articles also are produced by.... Iranian teams.
Journal name is just only a name. Some journals are more reliable, other journals are not. I have seen too many fake procedures and sentences "we were unable to obtain any reliable results following procedure given by (name) in (journal)". When I see "simple, efficient, microwaves, solvent-free.....etc " it means that it may not work at all. Sometime is very clear (as in Al(HSO4)3 case) that it must be something wrong.
But - I do not say it does not work at all.
I say that it cannot be Al(HSO4)3. Besides, it is described as "non hygroscopic". Do you know any non-hygroscopic Al salt, with simple, not chelating anion ? I do not know such one.
So - what it is ? Something highly acidic, that is all I can deduce from these articles. I heard about sulfonated alumina (by chlorolufonic acid), but if it has something to do with it - I do not know.
As they say - experiment is king ;)




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clearly_not_atara
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[*] posted on 19-11-2018 at 09:53


Is it possible that the rxn product of H2SO4 + AlCl3 is a useful catalyst? Sure. But is it "non-hygroscopic"? I can't believe that!

"Anhydrous aluminum chloride (3.34 g, 0.025 mol) was charged in the flask and concentrated sulfuric acid (98%, 7.35 g, 0.075 mol) was added dropwise over a period of 30 min at room temperature. HCl evolved immediately. After completion of the addition, the mixture was shaken for 30 min, while the residual HCl was eliminated by suction. Finally, a pale-brown solid material was obtained in 7.7 g."

NB. gas not characterized; weight not consistent with Al(HSO4)3; product not subject to elemental analysis. We expect 8 grams of aluminium bisulfate, we find 7.7. What else was lost? Water? From concentrated sulfuric acid under mere suction? Sure, you say, mechanical losses.

I have a question: why do the mechanical losses stay exactly the same when you make the system ten times larger? From EvilRenne's post, above:

"Anhydrous aluminum chloride (33.4 g, 0.25 mol) was placed into a 500 mL suction flask equipped with a constant-pressure dropping funnel. The gas outlet was connected to a vacuum system through an adsorbing solution (water) and an alkali trap. Concentrated sulfuric acid (98%, 73.5 g, 0.75 mol) was added drop-wise over a period of 1 h at room temperature during which HCl was evolved. After completion of the addition, the mixture was stirred for 30 min, while the residual HCl was eliminated by suction. Finally, a pale-brown solid material was obtained (77.0 g)"

That's right: precisely the same relative masses, within 1% error (i.e. amazing), just scaled up by a factor of ten. There are two possibilities:

- some mysterious aluminium-chloride-sulfate compound prepared with exquisite precision

- fakery and plagiarism

Guess what I'm betting on?




[Edited on 04-20-1969 by clearly_not_atara]
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[*] posted on 20-11-2018 at 12:21


This:
https://pubs.acs.org/doi/abs/10.1021/ja01172a002
lists a solid phase "Al2(SO4)3.3H2SO4.12H2O", which would rearrange as "Al(HSO4)3.6H2O"
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[*] posted on 23-11-2018 at 02:24


I have seen this paper already.
Quote:
"Al2(SO4)3.3H2SO4.12H2O", which would rearrange as "Al(HSO4)3.6H2O"

Rearranging chemical symbols on paper/editor is rather poor kind of chemistry.
Why not H3[Al(SO4)3]•6H2O, Al2(SO4)(HSO4)4•H2SO4•12H2O, or whatever ?
Because exact molecular structure of this compound is not known, such a "rearrangement" is pure speculation.

In mentioned paper, there is a reference (from Monatshefte für Chemie) about similar compounds ,2Al(HSO4)3•7H2O , as suggested by author it is a complex, with aluminosulfate anion. There is also given preparation of it, from conc. H2SO4 and aluminium sulfate (but it is not clear, at least for me).

The last publication about Al2(SO4)3-H2SO4-H2O system, is article from the Journal of Chemical Society (DOI: 10.1039/JR9520004431). They use much more sophisticated methods of analysis than given in earlier publications. The compound Al2(SO4)3•3H2SO4•12H2O is NOT detected in their experiments and - according to the authors - it is possibly Al2(S04)3•H2S04•8H20. They also report several other acid sulfates.
The paper is worth reading but.... date of its publication is 1952 year. So, the system Al2(SO4)3-H2SO4-H2O awaits for modern reinvestigation.
Anyway, there is no (so far) reported anhydrous acid aluminium sulfates.




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