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ave369
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SO3 from pyrosulfate and H2SO4
In my topic "A safer procedure of mineral acid synthesis", one of the users suggested that heating a pyrosulfate with conc. sulfuric acid can yield
SO3 at a much lower temperature then with pyrolysis.
Today, I tried to check it and boiled a small amount of sodium pyrosulfate with 80% sulfuric acid (I didn't have any stronger at hand). I think I
managed to produce some SO3, but only some. Here is the detailed description of my experiment.
A retort was mounted on a tripod. The retort's nose was put into a small flask containing 80% sulfuric acid, to make any evolving gas bubble through
this acid. In the retort was pyrosulfate and more 80% sulfuric acid. I started to heat the retort with a gas burner.
Early on, some kind of gas started to bubble from the retort's nose, and make white smoke on contact with outside air. I think it was SO3. Soon, the
evolution of smoke from the receiving flask ceased, but that same smoke started to form inside the retort. Soon, the inside of the retort turned milky
white. This milky white fog continued to bubble through the receiving flask, and made no further smoke with outside air. I think it was H2SO4: I've
driven all possible SO3 from the liquid inside the retort, all of the other SO3 combined with water present in the 80% sulfuric and start to form
H2SO4 mist. If the acid in the retort was stronger to begin with, I would get more SO3.
Am I right?
Smells like ammonia....
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gdflp
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Garagechemist has experimented with this method quite a bit, you can see his results here. He mentions that : Quote: | Any water is very detrimental to the yield | So yes, your explanation sounds quite plausible. It might be
worth trying again, but instead use the acid you produced from this experiment as the catalytic acid, instead of the 80% acid.
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ave369
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The tiny amount of SO3 I've made only managed to increase the concentration by a percent or two, if even that.
Smells like ammonia....
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clearly_not_atara
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The way to concentrate H2SO4 is to simply boil it long enough to remove all of the water. According to Wikipedia (shut up, you use it too) 98.3%
concentration forms at the boiling point (due to partial thermal decomposition). Sulfuric acid boils at 337º C, so there won't be an azeotrope.
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Magpie
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This may be useful:
http://www.sciencemadness.org/talk/viewthread.php?tid=10332
The single most important condition for a successful synthesis is good mixing - Nicodem
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ave369
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Quote: Originally posted by clearly_not_atara | The way to concentrate H2SO4 is to simply boil it long enough to remove all of the water. According to Wikipedia (shut up, you use it too) 98.3%
concentration forms at the boiling point (due to partial thermal decomposition). Sulfuric acid boils at 337º C, so there won't be an azeotrope.
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337º C is where the azeotrope boils. The azeotrope is 98,3%. But that's not what I mean.
What I mean is:
Have you really tried to boil battery acid? I mean, ever? Are you aware of the "white mist threshold" at 70-80%? Have you ever caught a whiff of that
mist, which, even rarefied to the point of invisibility, will burn your lungs? Have you ever lost a piece of glassware to thermal cracking, because
the difference between 337º C and whatever's outside is too large? Have you ever been frustrated at the fact that the goddamn white mist carries away
as much acid as water, and the concentration does not want to grow beyond 90%, despite the World War I level gas attack around your boiling vessel?
I've boiled more battery acid down to the 80% threshold than brewed coffee in the morning. But very rarely I was fortunate enough to reach 90%. THAT's
why I'm looking for other ways to boost it up to 98% and beyond.
[Edited on 10-9-2015 by ave369]
Smells like ammonia....
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Deathunter88
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DISTILL!!!!DISTILL!!!!DISTILL!!!!
No doubt you were excited when you distilled your first liquid, either water or ethanol. (or something else) Now apply that skill to sulfuric acid.
To get 98% sulfuric acid, distilling is both cost efficient, easy, safe(relatively) and feasible. Take your 80% acid and add 300ml to a 500ml RBF. Use
a ring stand and metal clamp to hold it 5mm above the top of the hotplate/radiator (air-bath), then attach a a 300mm vigreux column as an air
condenser. I think you can also use a actual air condenser or a Liebig condenser without water. Turn up the hotplate/radiator to full power and wait
for the acid to boil. This is when you have to experiment with the power setting of the hotplate/radiator. Not high enough and you get very little
distillate, too high and it overpowers the condenser and you get the WW1 fumes from the sulfuric acid vapors touching the air. Let it distill into a
beaker and every 2 minutes hold a paper towel above the receiving beaker and let a drop of the distillate fall on it. At the start nothing will
happen. But after a while the distillate will burn through the tissue. At this point change the receiving beaker and start collect acid at around 80%.
Let this distill until you get a further 50-100ml of acid.(After a while you will get good at determining the exact amount here) Then change the
beaker again to get your 98% acid. I distilled 1500ml of 96% drain cleaner in 3 hours. Got 1250ml of 98% acid.
[Edited on 11-9-2015 by Deathunter88]
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ave369
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I would be very glad to try this, but I'm a bit equipment-deficient. My distillation setup is a retort, and I'm unsure if it can survive distillation
of sulfuric acid without thermal cracking. I don't have another retort, after all.
Next time I order something on AntrazoXrom, however, I'll try to add some simple modern distillation setup to the list.
[Edited on 11-9-2015 by ave369]
Smells like ammonia....
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AJKOER
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There may be safer ways to obtain SO3, at least in very small amounts.
For example, start with a naturally occurring process, the formation of acid rain. To quote Wikipedia ( https://en.m.wikipedia.org/wiki/Acid_Rain ) on acid rain:
"In the gas phase sulfur dioxide is oxidized by reaction with the hydroxyl radical via an intermolecular reaction:[5]
SO2 + OH· → HOSO2·
which is followed by:
HOSO2· + O2 → HO2· + SO3
In the presence of water, sulfur trioxide (SO3) is converted rapidly to sulfuric acid:
SO3 (g) + H2O (l) → H2SO4 (aq)"
Now, there is a convenient path to the hydroxyl radical via the action of either sunlight or pulse radiation on N2O in the presence of water, for
example, as I have documented previously on SM. Or even possibly, a damp nitrate or nitrite for a path to hydroxyl radical generation via the aqueous
photochemical reaction:
NO3-(aq) + hv → •NO2 + •OH (see http://pubs.acs.org/doi/abs/10.1021/ja073609 )
Also, NO2-(aq) + hv → NO + •OH (actually, more complex, see, for example, discussion on page 2 at
https://www.google.com/url?url=http://scholar.google.com/sch... )
An alternate path in place of the hydroxyl radical, is via the contact of SO2 with fumes of decomposing strong HNO2 as, per Atomistry (link: http://nitrogen.atomistry.com/nitrous_acid.html ) on the oxidizing ability of Nitrous acid, to quote:
"Stannous chloride is converted into stannic chloride, sulphuretted hydrogen into sulphur, sulphur dioxide into sulphur trioxide. Iodine is liberated
from potassium iodide"
together with the comments:
"The decomposition of a cold dilute solution follows the reaction
3HNO2 ⇔ HNO3 + 2NO + H2O,
whereas stronger solutions at higher temperatures decompose according to the equations
2HNO2 ⇔ N2O3 + H2O ⇔ NO + NO2 + H2O"
And, the following gas phase reaction:
SO2 (g) + NO2 (g) = SO3 (g) + NO (g) (see discussion on the 5th page at this link address https://www.google.com/url?sa=t&source=web&rct=j&... )
And:
N2O3 + SO2 = N2O4 + SO3
Source, see for example, https://books.google.com/books?id=EvsbBQAAQBAJ&pg=PA209&... which also notes:
.HO2 + .NO → .NO2 + OH· (for another source, see http://www2.nau.edu/~doetqp-p/courses/env440/env440_2/lectur... )
where the HO2 radical formed from HOSO2· + O2 → HO2· + SO3 above, can help address the presence of Nitric oxide.
[Edited on 11-9-2015 by AJKOER]
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ave369
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Instead of unnecessary fiddling to make nitrous acid, I can just toss a copper coin into nitric acid and direct the resulting foxtail into a stream of
SO2. But I doubt that this will be useful in producing highly concentrated sulfuric acid: the industrialized version of this process produced chamber
grade acid, which was weaker than the result of my boiling experiments.
But so far, making metric craptons of pyrosulfate and distilling it with conc. sulfuric appears to be the most promising method to me.
[Edited on 11-9-2015 by ave369]
Smells like ammonia....
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CuReUS
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recently I learnt that SO3 can be made by heating ferric sulphate
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ave369
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I know that. But by dissolving nails in battery acid, you get ferrous sulfate. Where do I get ferric sulfate?
Smells like ammonia....
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Pumukli
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Ferric sulfate is used in my vicinity in waste water treatment plants to make Fe-hydroxy-flakes to help in the water clearing process. They use it by
the ton, so it should be a relativley cheap (and perhaps available) industrial chemical, even where you live. I don't know your circumstances but if
you have friends around such plants it would worth asking.
On the other hand when I opened some old ferrous sulfate bags I always found it partly oxidized (yellow). So O2 from air surely can do the
oxidation, speed is in question though. :-)
Maybe a ferrous sulfate solution, an aquarium pump, bubble stone, sort of heating setup, and maybe a catalitic ammount of something (redox
catalysator, Cu2+, Mn2+, etc) in an acidic solution would do the trick.
I've never tried such a reaction just thinking aloud. And assuming that getting ferrous sulfate is not nearly as problematic as getting ferric of
course.
[Edited on 11-9-2015 by Pumukli]
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ave369
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I live in a little town where all industry died out back in the days of the fall of the Soviet Union. Thank you very much, capitalism. Ferrous sulfate
and copper sulfate, they are easy to get because they are used in agriculture.
Smells like ammonia....
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AJKOER
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Quote: Originally posted by ave369 | Instead of unnecessary fiddling to make nitrous acid, I can just toss a copper coin into nitric acid and direct the resulting foxtail into a stream of
SO2. But I doubt that this will be useful in producing highly concentrated sulfuric acid: the industrialized version of this process produced chamber
grade acid, which was weaker than the result of my boiling experiments.
But so far, making metric craptons of pyrosulfate and distilling it with conc. sulfuric appears to be the most promising method to me.
[Edited on 11-9-2015 by ave369] |
Please note, my citations of SO3 formation is particular to a gas (not aqueous) phase reaction at low pH.
So, heating a dry nitrate salt (as a path to NO2 or N2O3) in the presence of SO2 is one possible route to test (akin to the Lead Chamber process
absence water). Adding CaSO3 to nearly boiling strong HNO2 (which I would also test in strong sunlight as the Nitrous acid can produce NO and OH
radicals) may form a mist containing SO3, or just some aqueous H2SO4.
My favorite (which I may get around to testing) is the simply safe photolysis of water vapor, SO2, N2O and O2 in a closed vessel allowing uv exposure
and see if any solid SO3 is created.
Another experiment (which I plan on performing) is saturating a solution with some SO2 and lots of N2O, and then treating the mix in the presence of
added O2 to photolysis or pulse radiation from a microwave. The expected product could include the aqueous HSO5- anion, or H2SO5 (assuming it has not
otherwised reacted, see https://books.google.com/books?id=vVvrCAAAQBAJ&pg=PA143&... ), which can be used to create persulfate salts. Reference, see discussion on the
sulfite radical on page 6 and the middle of page 7 at https://www.google.com/url?sa=t&source=web&rct=j&... and also http://pubs.acs.org/doi/abs/10.1021/jp011255h .
[Edited on 11-9-2015 by AJKOER]
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CuReUS
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Quote: Originally posted by ave369 |
I know that. But by dissolving nails in battery acid, you get ferrous sulfate. Where do I get ferric sulfate? |
like everything in life,you will get it if you search for it
like pumukli said,it is used in waste water treatment.It is also used as a pickling bath for Al and steel.
Quote: Originally posted by Pumukli |
Maybe a ferrous sulfate solution, an aquarium pump, bubble stone, sort of heating setup, and maybe a catalitic ammount of something (redox
catalysator, Cu2+, Mn2+, etc) in an acidic solution would do the trick.
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the wiki method mentions heating an acidic solution of FeSO4 with an oxidising agent to get ferric sulphate.
you could also make it using electrochemistry
https://books.google.co.in/books?id=vSsBCAAAQBAJ&pg=PA13... (pg-137,138)
[Edited on 13-9-2015 by CuReUS]
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Marvin
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Len has some cool stuff about Oleum from Sodium Pyrosulphate in his book.
Starting with distilling Sodium Hydrogen Sulphate, at the point it reaches 500C 90% of the water has left but only 10% of the potential
SO3. So starting to collect at 500C produces a 90% yield of Oleum containing 86% free SO3.
Starting to collect at 580C produces a 65% yeild of Oleum containing 94% free SO3. Almost pure SO3 coming off.
His end point is 820C which leaves the neutral sulphate as residue and he used a Quartz distilling flask with side arm. This is disappointing. Prior
to this and in previous discussions I'd rather hoped the reaction would be over by 500C and it really hasn't even started.
A rather cool and whip smart observation he makes is that adding neutral Sodium Sulphate to Sulphuric Acid effectively breaks the Water - Sulphur
Trioxide azeotrope.
I'm still looking for evidence that cooling the acid mixture precipitates neutral Sodium Sulphate, which might potentially lead to much lower
temperatures for production. Realistically even precipitating the Acid Sulphate would result in a concentration. I can't currently try the reaction
myself.
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ave369
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I've found a very interesting tidbit from a list of long-obsolete industrial technologies:
Na2S2O7+MgSO4=Na2Mg(SO4)2+SO3
An entry in an early XX century encyclopedia claims that adding magnesium sulfate to sodium pyrosulfate significantly lowers the temperature of its
decomposition.
Anybody knows more about this reaction? I've got a big fat jar of magnesium sulfate and will probably try this ASAP, but it would be good if anyone
knows any hidden problems.
[Edited on 13-9-2015 by ave369]
Smells like ammonia....
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AJKOER
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Quote: Originally posted by ave369 | In my topic "A safer procedure of mineral acid synthesis", one of the users suggested that heating a pyrosulfate with conc. sulfuric acid can yield
SO3 at a much lower temperature then with pyrolysis.
Today, I tried to check it and boiled a small amount of sodium pyrosulfate with 80% sulfuric acid (I didn't have any stronger at hand). I think I
managed to produce some SO3, but only some. Here is the detailed description of my experiment....
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Actually, just discovered that heating Ammonium sulfate can, at one stage in its thermal decomposition, forms the pyrosulfate. Here is a reference: http://onlinelibrary.wiley.com/doi/10.1002/jctb.5010200408/a... . To quote the abstract:
"The thermal decomposition and vaporisation of ammonium sulphate, (NH4)2SO4, is shown to take place via two distinct sets of reactions. In the first,
ammonium pyrosulphate, (NH4)2S2O7, is the primary condensed phase product: 2(NH4)2SO4 =(NH4)2S2O7+2NH3+H2O
The second stage concerns the decomposition of the pyrosulphate. Ammonia, sulphur dioxide, nitrogen and water are the major products, the dominant
reaction being 3(NH4)2S2O7 =2NH3+6SO2+2N2+9H2O"
Apparently, the formation of the pyrosulfate has been employed as a basis for a US patent 2,004,023,441to manufacture (or, possibly concentrate)
Sulfuric acid. See, "Chemical and thermal decomposition of ammonium sulphate into ammonia and sulphuric acid", US 20040234441 A1. Here is the
abstract:
"A method is described for manufacturing ammonia and sulphuric acid by decomposition of ammonium sulphate by a chemical and thermal handling process
The method concerns mixing of ammonium sulphate with concentrated sulphuric acid, where the mixture is heated to a temperature above 235° C., whereby
ammonium sulphate is melted, and thereafter by heating the mixture to above 280° C. but below the boiling point of concentrated sulphuric acid. It is
hereby achieved to decompose ammonium sulphate into ammonia gas and sulphuric acid liquid simultaneously, where the produced sulphuric acid during the
reaction time is mixed ideally with the concentrated sulphuric acid from the initial basis mixture."
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IrC
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Simpler to just post the patent so the process can be studied, plus a few more that appear to be useful.
Attachment: US20040234441A1.pdf (18kB) This file has been downloaded 594 times
Attachment: US20080056983A1.pdf (159kB) This file has been downloaded 527 times
Attachment: US7632479B2.pdf (190kB) This file has been downloaded 550 times
Attachment: WO2008025166A1.pdf (617kB) This file has been downloaded 532 times
Also informative:
Attachment: US4212855.pdf (277kB) This file has been downloaded 531 times
Attachment: US4490347.pdf (225kB) This file has been downloaded 530 times
Attachment: US5500098.pdf (493kB) This file has been downloaded 497 times
"Science is the belief in the ignorance of the experts" Richard Feynman
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AJKOER
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Here is a reference I just noticed, in my cited patent, that states the formation of oleum, in particular, requires pyrolyzing in the presence of
added O2, to quote:
"U.S. Pat. No. 4,490,347 (Gelblum) describes the production of oleum (sulfuric acid containing sulfur trioxide) from a mixture of ammonium bisulfate
and sulfuric acid, by pyrolyzing the mixture in the presence of oxygen. The production of oleum is not desirable in the recovery of ammonia and
sulfuric acid from ammonium sulfate."
where some sources claim the formation of ammonium bisulfate (see, for example, http://pubs.acs.org/doi/abs/10.1021/i260036a001 ) as one of the initial products on heating ammonium sulfate.
Said Patent (link http://www.google.com/patents/US4490347 ) from a safety perspective (explosion hazard), further notes:
"A first aspect to achieving the above objects is to feed oxygen-enriched air, i.e., air that is enriched with oxygen, into the furnace. Since the
ratio of oxygen to inerts in oxygen-enriched air is higher, less inerts are introduced into the process per mole of oxygen consumed. Thus less fuel is
needed to heat gases in the furnace. The degree of enrichment of the air with oxygen has practical limitations. As the concentration of oxygen is
increased, the burner temperature increases, flame profiles change, and more sophisticated burners and controls are needed to attain efficient
combustion, long equipment life, and to minimize the potential for explosion. Oxygen-Enriched air containing 22 to 40% oxygen by volume can be used in
conventional sulfuric acid regeneration (SAR) furnaces with a reasonable amount of control instrumentation."
[Edited on 14-9-2015 by AJKOER]
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aga
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Quote: Originally posted by ave369 | I've got a big fat jar of magnesium sulfate and will probably try this ASAP, but it would be good if anyone knows any hidden problems
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None of us know дерьмо about it really.
Googling and quoting is never as exciting as Doing and Finding Out. удача !
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ave369
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Today I tried this synthesis but failed it on the stage of making pyrosulfate. I chose a bad vessel for calcination and fouled the entire yield.
However, it seems that I made an interesting discovery. I'm still unsure if I understand correctly what happened, but I'll describe.
I had a small flask filled with a mixture of H2SO4 and HCl standing on a shelf in my lab for a long time. It was made by bubbling hydrogen chloride
gas through 80% sulfuric acid. Today I tried to purify this acid by distilling HCl out of it.
I did it, and here's what I found: an addition of HCl completely suppresses the formation of the infamous white mist! Instead of it, azeotropic HCl
vapors come out, which are easily absorbed by poking the retort's nose in water or even just condensed and dripped down, if the speed of distillation
is slow enough. When all HCl was distilled away from the mixture, in the retort was 95% sulfuric acid! When I opened the retort's tubulus while it
was still hot, it started fuming profusely and the retort filled itself with white mist, but while closed, no SOx at all emerged!
[Edited on 15-9-2015 by ave369]
Smells like ammonia....
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UC235
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Quote: Originally posted by ave369 | When I opened the retort's tubulus while it was still hot, it started fuming profusely and the retort filled itself with white mist, but while closed,
no SOx at all emerged! |
You do know that the white mist is SO3 vapor absorbing water from the air to form a mist of sulfuric acid (a known carcinogen, by the way, if
inhaled). If the vessel is closed, there is no moisture to do this even if you are forming SO3 vapor (which you were)
How do you know that the product was 95%? It sounds like you're just pulling a number out of your ass.
With regards to the original post, you did not produce any quantifiable SO3. If there was water present, there isn't any SO3 except traces in
equilibrium (no more than the fumes from regular hot sulfuric acid). The bubbles produced are air being forced out of the apparatus as it's heated and
the air expands. If you want to test the other poster's suggestion, you need to distill 98% sulfuric with the pyrosulfate in it and see if you can
condense any sulfur trioxide.
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ave369
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Quote: Originally posted by UC235 | If the vessel is closed, there is no moisture to do this even if you are forming SO3 vapor (which you were)
How do you know that the product was 95%? It sounds like you're just pulling a number out of your ass.
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When I did this before, the mist did form even in a closed retort. Because when sulfuric acid boils, it evaporates its own water along with SO3 AND
the water that it was diluted with (that's the very point of boiling it down. If there wasn't more water than SO3 in the vapors, boiling down wouldn't
work at all). There were times when the inside of the retort turned milky white.
I determined the concentration of the acid by measuring its density. However, my scale isn't particularly precise, so I used another method to confirm
that: by measuring the time required for charring wooden sticks of different size and composition (such as matchstick, toothpick, long thin chip of
firewood) with this acid.
Quote: Originally posted by UC235 | The bubbles produced are air being forced out of the apparatus as it's heated and the air expands. |
I've been living in this world for a long time and have seen many wonders. But air that fumes on contact with air - that's a miracle and a mystery!
BTW, thanks for warning about carcinogens, but I'm already a chain smoker. A little SOxes won't do any more harm.
[Edited on 15-9-2015 by ave369]
Smells like ammonia....
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