Sciencemadness Discussion Board - HCl via vitriole + NaCl

HCl via vitriole + NaCl

chief - 25-9-2008 at 15:39

Has anyone tried this:
Alchemists made HCl by distillig NaCl with vitriole, source:
http://www.retrobibliothek.de/retrobib/seite.html?id=103403

Probably Iron- or Copper-sulfate ...
Does it mean: FeSO4, CuSO4, or is another Fe-sulfate meant ?
==> Maybe the FeSO4 can just be made by electrolytically dissolving Fe in Na2SO4 ?

Then a cycle would be possible:
==> FeSO4 * xH2O (?) + 2 NaCl ==> 2 HCl + Na2SO4 + H2O (???)
==> Fe electrolyzing in Na2SO4-solution
==> fresh NaCl from the shop, and again ...

Probably the H2O in the vitriole is necessary, but what would happen when thermally decomposing gypsum (CaSO4) with NaCl (probably above 1000 [Celsius]), maybe with 2 buried-in welding-graphite- electrodes, that give any temperature ...

Maybe the vitriole could be made from the gypsum somehow ??

chief - 25-9-2008 at 15:48

And maybe the Fe could dissolve in the Na2SO4-solution by it's own galvanic potential/energy, just by connecting it to eg. a copper-electrode in the same bath ...
That could be so easy: Using the chemical energy of the iron-scrap ..

And Na2SO4 coasts below 100 $/ton, and is sold for thermal-storage, because it has some phase-transition at 32 [Celsius](with water), that makes it ideal for floor-heating ...

Probably the HCl from gypsum will not work, since at the high-CaSO4-decomposition-temp the
(SO3 <==> SO2)-equilibrium is too far o the SO2-side ; so how could someone with no Na2SO4-access make the FeSO4 from Fe + CaSO4 ?

chemoleo - 25-9-2008 at 17:45

I imagine this was done with iron sulfate (which is commonly referred to as vitriol, as in the distillation of SO3 from FeSO4), due to the crystal water the free acid (H2SO4/HSO4-) formed can liberate the HCl from NaCl, and the HCl then reacts with the Fe(II/III+) to form FeCl2/3. The latter decomposes with heat, giving HCl/Cl2 gas. Not sure how well it would work with CuSO4, because the resultant Cu chlorides are more stable than the Fe chloride hydrates...

If you react CaSO4 with NaCl you'd get some sort of odd thermitic reaction. Likely it needs an enormous activation energy, and wouldn't work without a booster (oxidant/reductants such as KClO3/ sulfur, Al powder etc)

PS Please merge your double posts into one, we have an editing function here.

chemrox - 25-9-2008 at 22:21

I thought vitriol was sulfuric acid. Maybe I'm thinking of "oil of vitriol." If it is sulfuric, I've done it and it works! That is the way I make HCl since I rarely use it and don't need much when I do.

not_important - 25-9-2008 at 23:15

Quote:

Originally posted by chief
And maybe the Fe could dissolve in the Na2SO4-solution by it's own galvanic potential/energy, just by connecting it to eg. a copper-electrode in the same bath ...
That could be so easy: Using the chemical energy of the iron-scrap ..
...
so how could someone with no Na2SO4-access make the FeSO4 from Fe + CaSO4 ?

Try writing a balanced equation for reacting aqueous Na2SO4 with metallic iron and get iron sulfate out of it; that sodium has to go somewhere. You can react iron with water containing certain salts, you get iron hydroxides/hydrated oxides plus hydrogen.

As for the other

CaSO4 + C => CaCO3 + SO2 + CaO @1200 C, not balanced

2SO2 + 2Fe(OH)3 (moist) => FeSO4 + FeSO3 + 3 H2O

not terribly practical.

Klute - 26-9-2008 at 02:34

I'm also convinced Vitriol refers to sulfuric acid, which would make sense. In france, we even have a term for people who have been (intentionally) disfigured with conc. H2SO4: "Vitriolés", the vitriol-ized. And there is also the verb "to vitriolize".

And it would make sense, H2SO4 and NaCl was (is?) a very common way of producing dry HCl gas in the lab.

[Edited on 26-9-2008 by Klute]

chief - 26-9-2008 at 02:47

In German: "VitriolOel == H2SO4", "Eisenvitriol == Fe-salt of H2SO4", etc. .
"Oil of vitriol" == H2SO4, maybe vitri-ole(-um) lead to the term of oleum.

Anyhow: It seems, that some Fe-vitriole may be one of the most worthy challenges, since
==> it gives H2SO4, if thermally decompositioned
==> HNO3 if decompositioned with some Saltpeter
==> HCl if decompositioned with NaCl
==> and who knows what else !!

Fe-vitriole as one way to different mineral-acids. Maybe there is some more easy way to make it from one of the fertilizers: MgSO4/K2SO4-mixture etc .. Also Mg(OH)2 etc. might be less soluble than one of the (vitriole-giving)-Metals hydroxides ... which might help ...

not_important - 26-9-2008 at 03:16

In English, using "the google"

Quote:

vitriol

n.

1.
a. See sulfuric acid.
b. Any of various sulfates of metals, such as ferrous sulfate, zinc sulfate, or copper sulfate.
2. Bitterly abusive feeling or expression.

tr.v., -oled or -olled, -ol·ing or -ol·ling, -ols or -ols.

To expose or subject to vitriol.

[Middle English, from Old French, from Medieval Latin vitriolum, from Late Latin vitreolum, neuter of vitreolus, of glass, from Latin vitreus. See vitreous.]

You're not going to make iron sulfate from other soluble sulfates as you suggest, Fe(OH)2 has low solubility and is quickly oxidised by air to Fe(OH)3 &| hydrated ferric oxides which is even less soluble.

You can make iron sulfates by heating ammonium sulfate with iron oxide to several hundred degrees C, as ammonium salts of strong acids tend to function as that heat when heated. Ammonium sulfate breaks down into NH3 and (NH4)HSO4, then NH3, H2O, and SO3, when heated under reduced pressure; if somewhat enclosed the sulfate or SO3 oxidises some of the ammonia to N2 and more H2O along with SO2, S, and even H2S.

All you are doing is taking an old method of making sulfuric acid and combining it with standard methods of making more volatile mineral acids.

Picric-A - 26-9-2008 at 11:16

FeSO4 is cheaply available form most garden stores (around £11 for 25kg). Otherwise Electrolosis of a Na2SO4 with iron electrodes and a suitable diaphram (porous pot) will yield NaOH and FeSO4. Finally as not important suggests heating (NH4)HSO4 with FeOx or steel wool in a tin can will yield impure FeSO4 wich may require purification.

chemrox - 26-9-2008 at 11:48

Hey Klute,
are there so many people in France disfigured by H2SO4 that you have a specific word? (Or was this a fun day at the acadamy?) How in the world does this happen to folks there? Anyway, I thought the goal was to make HCl not metal sulfates.

chloric1 - 26-9-2008 at 14:37

De re metallica usually suggest mixtures of aluminum sulfate and ferrous sulfate with potassium nitrate for Nitric acid or with rocksalt for HCl. The water of hydration should be suffient for aqueous HCl distillate I would think.

ScienceSquirrel - 26-9-2008 at 15:15

Quote:

Originally posted by chemrox
Hey Klute,
are there so many people in France disfigured by H2SO4 that you have a specific word? (Or was this a fun day at the acadamy?) How in the world does this happen to folks there? Anyway, I thought the goal was to make HCl not metal sulfates.

The throwing or spraying of acid in people's faces, particularly young women, was a common crime at one time.
The French have a word for it and it is documented in early nineteenth British writing.

Klute - 26-9-2008 at 20:30

Indeed, just like ScienceSquireel said, it was common enough to haev a specific verb... Unfortuanly, it still happens nowdays (although much less I hope), especially wives that are acuused of cheating on their husbands, or refluse the marry the man chosen by their family... Very sad.

watson.fawkes - 27-9-2008 at 14:41

Historically, vitriol is the sulphate of iron. Oil of vitriol is the acid. It's first attested to in the 14<sup>th</sup> century, right at the time when Arab science was arriving at the beginning of the Renaissance.

benzal - 27-9-2008 at 15:40

there is a video of it on you tube, http://uk.youtube.com/watch?v=gUGBV8Pa9SM