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Author: Subject: Small scale production of H2SO4 in the amateur lab
Sulaiman
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[*] posted on 25-8-2020 at 07:12
Deleted post


I deleted a method that was inappropriate for this thread
Sorry.

[Edited on 25-8-2020 by Sulaiman]




CAUTION : Hobby Chemist, not Professional or even Amateur
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Fulmen
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[*] posted on 25-8-2020 at 07:22


That sounds exceedingly complicated and dangerous compared to simple electrolysis of CuSO4.



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[*] posted on 27-8-2020 at 22:26


I'm not 100% sure if I'm going to be able to find and unpack everything I need to do a trial run of oleum generation this weekend... my chemicals and equipment are packed in boxes and totes. The chemicals are well organized, but the equipment is not....

So anyway, I was putting together a list of what I would need earlier, and I drew a blank at gloves... what kind of gloves do people use for handling oleum? I would expect it to destroy almost any gloves immediately, perhaps setting them on fire.

Butyl rubber gloves are recommended for sulfuric acid according to: https://www.augusta.edu/services/ehs/chemsafe/PDF%20files/gl...

I've seen nitrile gloves recommended for sulfuric acid by other sources. I typically just wear latex gloves for sulfuric acid, but it does slowly attack them, so I try not to let any chemicals get on them, and I change gloves often.

Of course, oleum is in a whole different echelon than regular sulfuric acid. I wouldn't consider wearing latex, butyl, or nitrile gloves to handle oleum.

Viton gloves would be ideal, but they are extremely expensive, and I don't have time for shipping....
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[*] posted on 28-8-2020 at 04:03


Shoot me down if you like but don’t bother wearing gloves

I didn’t when I made SO3/oleum from pyrolysis of sodium bisulphate in some quantity

Nothing encourages careful handling better than exposed flesh

As you say the stuff destroys most glove materials

Keep a bucket of water and ice handy - It is quite unexciting pouring oleum onto ice - I know I’ve done it

If the stuff was toxic rather than corrosive - yes I would wear gloves
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[*] posted on 28-8-2020 at 06:25


Thanks Woelen for creating this thread, as you said in the U2U it would be awesome if this can lead to a workable and practical method.

I collected previous threads on the topic (and related threads such as SO3 production)

This is the first part.
The most important and extensive threads:

Axehandle posted this thread (2004)
H2SO4 by the Lead Chamber Process - success
https://www.sciencemadness.org/whisper/viewthread.php?tid=28...

garage chemist posted this in Prepublication (2008):
Sulfur trioxide from sodium hydrogen sulfate
https://www.sciencemadness.org/whisper/viewthread.php?tid=10...
And
Sulfur trioxide Oleum: the ferric sulfate method
https://www.sciencemadness.org/whisper/viewthread.php?tid=10...

len1 posted this in prepublication (2008):
Subject: Sulphur Trioxide and Oleum Using a Box Oven - Illustarted Practical Guide
http://www.sciencemadness.org/talk/viewthread.php?tid=10332

Microtek posted this thread (2017):
Lab scale contact process for H2SO4 (report)
https://www.sciencemadness.org/whisper/viewthread.php?tid=72...


Other useful and related threads:

Subject: oleum & SO3
http://www.sciencemadness.org/talk/viewthread.php?tid=727


Subject: SO3 from CaSO4 is it possible ?
http://www.sciencemadness.org/talk/viewthread.php?tid=15285


Subject: SO3 from pyrosulfate and H2SO4
http://www.sciencemadness.org/talk/viewthread.php?tid=63569


Subject: Sulfur Trioxide by m-Phosphoric Acid route (success)
http://www.sciencemadness.org/talk/viewthread.php?tid=65358





[Edited on 29-8-2020 by Belowzero]
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macckone
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[*] posted on 28-8-2020 at 09:28


This thread covers oxalate methods previously mentioned.
www.sciencemadness.org/talk/viewthread.php?tid=18963

They are much simpler than other methods if you have access to oxalic acid.

The easiest ways to get oxalic acid are as wood bleach (likely to be impacted by REACH), nitric acid oxidation of sucrose (birkeland-eyde reactor for nitric acid), oxidation of ethylene glycol (pick your oxidizer), and rhubarb leaves
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[*] posted on 28-8-2020 at 16:50


Quote: Originally posted by plastics  
Shoot me down if you like but don’t bother wearing gloves...


Nothing encourages careful handling better than exposed flesh...

... If the stuff was toxic rather than corrosive - yes I would wear gloves


Right on about exposed flesh!! I sometimes think that one can get careless/over-confidant with too much personal protective equipment (PPE). Personally, when handling corrosive material, I would wear proper safety goggles and/or a face shield before I would worry about gloves.
And after seeing too many videos with people in short pants and short sleeves, that is certainly "exposed flesh". A lab coat is cheap PPE.

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[*] posted on 28-8-2020 at 23:50


From Gyps and Lead and HCL.

http://dingler.culture.hu-berlin.de/article/pj139/ar139070

The invention of removing the sulfuric acid from the gypsum consists in using an intermediate body for this purpose, the sulfuric acid lead oxide, which gives off its sulfuric acid against hydrochloric acid with great ease, thereby transforming itself into chlorine lead, which then again with the help of finely ground gypsium is converted into sulfuric acid lead oxide.

If you pour over 1 1/4 equivalent of sulfuric acid lead oxide with 1 equivalent of hydrochloric acid at 21 ° Baumé, and heat both with stirring to about 50 to 60 ° Reaumur, the liquid is almost completely transformed into sulfuric acid after a short time. If you use e.g. 6 equivalents of sulfuric acid lead oxide and if 5 equivalents of hydrochloric acid at 21 ° Baumé are added, an acid is obtained in which the ratio of sulfuric acid to hydrochloric acid is 5: 1.

The more concentrated the hydrochloric acid with which one works, the more favorable this relationship is.

The exchange of hydrochloric acid for sulfuric acid takes place in quite different proportions, depending on how the hydrochloric acid is allowed to act in different strengths on the sulfuric acid lead oxide. Since the chlorine lead takes up a much larger space than the sulfuric acid lead oxide; as this salt generally retains a large part of the sulfuric acid obtained like a sponge, this fact provides a means of separating large masses of the sulfuric acid obtained from the lead chloride without filtration.

My method of making these facts useful in practice consists in setting up a wooden vessel lined with lead, depending on the scale in which the work is to be carried out, and which can be heated by means of steam through lead pipes. In this vessel, regardless of the shape, I put a certain amount | 284 | sulfuric acid lead oxide, which is then poured over with a mixture of sulfuric acid and hydrochloric acid or sulfuric acid alone from 18 ° Baumé until the salt is saturated or soaked with it. This weak acid is then always recovered in the course of the work, as will be shown below. It has no other purpose than to soak the lead salt with a liquid which does not change it and enables me to draw off the same quantity of acid which I give up. With diligent stirring and warming, as much hydrochloric acid of 21 ° Baumé is added as calculated for the first operation. After a while the liquid is left to stand still, to settle, and then just as much weak sulfuric acid is drawn off as hydrochloric acid was added to the measure. Furthermore, about half of the hydrochloric acid previously used is poured on for the second time, proceeding as the first, whereby all the sulfuric acid lead oxide is then converted into chlorine lead. After this acid has also been drawn off from the residue and combined with the first obtained, it is evaporated in vaulted lead pans up to 60 ° Baumé; but the escaping hydrochloric acid is collected by means of known apparatus.

By means of these operations, as a rule 3/4 of the sulfuric acid contained in the lead oxide sulfuric acid is immediately obtained for evaporation. If the correct quantity of water is now added to the chlorine lead, the quantity of weak acid which had to be artificially produced during the first operation is restored. When the lead salt settles, this weak acid is pumped onto a higher standing vessel and stored for further use. Further washing once or twice removes as much acid as possible from the lead chlorine; But so that this weak acid is not lost, it is suggested instead of ordinary water in the preparation of Glauber's salt and is saturated again with hydrochloric acid gas.

After the chlorine lead has been sufficiently washed out, the calculated quantity of Gyps is added in a very finely ground state with such a quantity of water that no stronger lye than 2 1/2 to 3 ° Baumé can arise. If the water is heated up to 60 ° Reaumur, the lead chlorine is converted back into lead oxide sulfuric acid in a short time. If one sees that the calcium chloride solution was not stronger than indicated above, and that it is not acidic, then, if the decomposition of gypsum has been conducted correctly, there must be no lead in solution. If this were the case, however, it is knocked out with a little lime. The newly recovered sulfuric acid lead oxide is ready for new decomposition after being washed out several times.

| 285 |
If this sulfuric acid, obtained from hydrochloric acid and gypsum, is to be brought on the market, it must be concentrated and cooked white by one of the known methods up to 66 ° Baumé, or treated according to my invention No. II.

II.
At that time, for the concentration of sulfuric acid, lead pans were first used, in which the acid was evaporated up to 60 ° Baumé; from there it came either in glass or platinum vessels, and then added up to 66 ° Baumé
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[*] posted on 29-8-2020 at 02:55


DUDE! That's a great find, if I read it correctly the reaction only consumes gypsum and hydrochloric acid.



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[*] posted on 29-8-2020 at 08:18


Fulmen, don't get to excited until you get it working.
These older journals are not always reliable.
The method seems plausible though.
The question remains if you can get it to work.
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[*] posted on 29-8-2020 at 09:16


True, true. It does look kinda messy and crude, and can only produce dilute acid. But it has potential as it uses only cheap OTC ingredients.

I wonder if I should start by making a lead beaker that could handle a bit of acid.




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[*] posted on 29-8-2020 at 12:50


So the basic reaction is something like this:

1. PbCl2 + CaSO4 => PbSO4 + CaCl2
2. PbSO4 + 2HCl => PbCl2 + H2SO4

But the devil is usually in the details, and I think we need a better translation.




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[*] posted on 30-8-2020 at 10:09


Fulmen,
Yes and neither one of those reactions looks like it would proceed very well.
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[*] posted on 30-8-2020 at 11:40


Lunge of course mentions this.

Attachment: gb18542161.pdf (3.1MB)
This file has been downloaded 65 times





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[*] posted on 31-8-2020 at 08:32


Macckone: It's the second one that has me puzzled. The first one should go to completion if given enough time, but the second is somewhat counter to common knowledge. However, the text does stress the need for strong HCl, so it might be some special conditions at play.



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[*] posted on 31-8-2020 at 08:50


S. C. Wack,
But does it work?
We all know there are patents and working patents.

The first step PbCl2 + CaSO4 -> PbSO4 + CaCl2
The reactants are practically insoluble.
One of the products is very soluble so in theory could be washed away to drive the reaction but that is going to take a lot of water.
The second step PbSO4 + 2HCl -> PbCl2 + H2SO4 would follow the same procedure, repeated washing with HCl to give a mixed product.

This is very cheap but it was never used in practice.
The only substantial cost is water and boiling it off.
For home use this is probably not prohibitive.
Commercially this is not practical of course.
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[*] posted on 31-8-2020 at 08:55


One thought, because of the nature of the reaction,
this should be possible with a sohxlet extractor.
I don't own one so I can't try it but that would give the driving force.
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[*] posted on 31-8-2020 at 09:10


Fulmen,
If you use a soxhlet, the HCl will boil as an ~20% constant temperature.
This would allow repeated extraction of the PbSO4 with 20% HCl
It will give a mixed product but the H2SO4 would be sequestered as it would not boil. My guess is that the equilibrium is somewhere around 1 to 2% H2SO4.
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[*] posted on 31-8-2020 at 14:01


Quote: Originally posted by macckone  
S. C. Wack,
But does it work?


I don't really care since it seems impractical and I can still get battery acid by the gallon at the hardware store...a better translation was asked for and provided...

The hint was, if you want to know old patented methods, read the old literature google and scihub have, and the highest authority is Lunge, although in retrospect his accuracy is not the best. I may have mentioned in the SO3 thread that Wolters is one of very few of the many etc.-method patents that Lunge sticks his neck out for. The early and late editions are literally voluminous, and this lead process is given short shrift within short shrift. Obviously if the process was ever used, he never heard of it.




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[*] posted on 31-8-2020 at 14:56


S C Wack,
I think the soxhlet method would work.
The europeans are limiting sulfuric acid, hence this thread.
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[*] posted on 31-8-2020 at 16:52


Like I'm not aware of this? Or like that makes this practical? Not long ago the Europeans had limited sulfuric acid and a love for working with lead. They did use lots of lead, not for this. I would assess the conversions separately and suspect one or both do not go well.



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[*] posted on 31-8-2020 at 19:22


Just a note on the oxalic acid process, it seems that iron (II) sulfate is not super ideal. The iron oxalate produced is a pain to filter, and some of the particles are fine enough to persist through multiple filtrations. It seems to mostly settle out as the acid is concentrated, but it still doesnt seem particularly great for acid production.
Magnesium sulfate is likely a better option, although magnesium oxalate has a slight solubility in water, especially when hot.




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[*] posted on 4-9-2020 at 14:11


Sulfuric acid by reaction of Sulfamic acid with nitric acid (wikipedia Sulfamic acid )

HNO3 + H3NSO3 → H2SO4 + N2O + H2O

The Nitric acid can be generated insitu from calcium nitrate

Ca(NO3)2 + 2 H3NSO3 → H2SO4 + CaSO4 + 2 N2O + 2 H2O

The CaSO4 is filtered out and almost pure solution of sulfuric acid is obtained.
Sulfamic acid is OTC cleaning agent, calcium nitrate is commonly available fertilizer.
Did anybody try?
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[*] posted on 4-9-2020 at 19:33


If I were to guess, this is made possible because the ionic reactions are like this:

PbCl2 (Ksp 1.7e-5) + CaSO4 (Ksp 4.9e-5) >> PbSO4 (Ksp 2.1e-8) + Ca2+ (aq) + 2 Cl- (aq)

PbSO4 + HCl + Cl- >> PbCl2 + HSO4- (aq)

That is, the sulfate ions are protonated in the acidic hydrochloric acid solution, but not in the neutral solution. The success of the calcium-to-lead metathesis thus depends on a neutral pH, while the lead sulfate-to-chloride metathesis happens at acidic pH, where the sulfate ion is protonated to bisulfate (pKa ~2).





[Edited on 04-20-1969 by clearly_not_atara]
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[*] posted on 5-9-2020 at 06:35


Adding methanol to a potassium hydrogen sulfate solution works and is nearly quantitative.

http://www.sciencemadness.org/talk/viewthread.php?tid=79548&...
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