Sciencemadness Discussion Board

HELP(sulfuric acid)

Korialstrasz69 - 24-9-2015 at 01:50

Hey everyone.New member here.
I have some questions :
1-
how to synthesis a small amount of sulfuric acid from Ammonium sulfate without the use of any acids ?
please suggest your method in details with description of every case of things going wrong(as far as you know)
i don't have any acids and i cannot buy them nor online nor offline(Welcome to syria)
but i have some lead to be used as an electrode.(No i can't get platinum)
Now i have a lil questions:what other materials than pyrex resist Corrosive acids/bases ?and conducts heat good ?it's not necessary to resist high temperatures.
Thanks anyways :3

Sulaiman - 24-9-2015 at 02:07

If there is no Sulphuric acid available,
what do you use in lead-acid batteries ?

Electrolysis

100PercentChemistry - 24-9-2015 at 02:54

https://m.youtube.com/watch?v=5dUSF9Gl0xE this way uses copper sulphate. I will keep looking for an ammonium sulfate method.

[Edited on 24-9-2015 by 100PercentChemistry]

sorry

100PercentChemistry - 24-9-2015 at 03:06

Most methods use hcl. https://m.youtube.com/watch?v=_RglgJQ8vIg. This uses sodium bi sulphate or ph down. Is this available in Syria? After you are done, just boil it to the concentration you want and titrate.

[Edited on 24-9-2015 by 100PercentChemistry]

100PercentChemistry - 24-9-2015 at 03:12

I guess borosilicate glass resists heat good. I've only had one temperature related breakage. That was when it was really hot and I added ice cold water, it shattered. It also resists common acids except HF. Regular glass will work against most acids, but is not for heating.

Korialstrasz69 - 24-9-2015 at 07:35

Sulfuric acid is only provided to battery repairing specialists and these are watched by the government,and if you ask one of them for some sulfuric acid you will probably be arrested for terrorism since you know what "Sulfuric" means.
And i need a renewable source like i can always buy NH4SO4 but i can't afford 80$ battery for each batch of acid.
anyways the copper sulfate seems good,but can i by any way transform ammonium sulfate to copper sulfate ?maybe melting the salt with copper wire would work ?
i saw like most of them videos by NurdRage and as i said,no acids available here.And i highly suspect the bisulfate is available or even provided to the public.And i have no idea where to search and no one to ask for a "Pool chemical supplier".
anyway thanks for all the responses,looking forward for my first batch.
btw does anyone around suffer the same shit as here ?

100PercentChemistry - 24-9-2015 at 12:29


"btw does anyone around suffer the same shit as here ?"

I live in the U.S. it is not as bad here. But slowly it is getting harder. Some stores have stopped selling sulfuric acid drain cleaner. Also iodine became a list 1 chemical in th east couple of years.

aga - 24-9-2015 at 14:28

Where are you Korialstrasz69 ?

zed - 24-9-2015 at 16:41

Well, apply a vacuum to it, while heating in a microwave oven.

Should be in the search engine somewhere. I'll look.

http://www.google.com/patents/US20040234441
US5951831.Condensation.Polymerization.Phosphoric.Acid.pdf

[Edited on 25-9-2015 by zed]

[Edited on 25-9-2015 by zed]

Korialstrasz69 - 24-9-2015 at 23:40

aga Lattakia-Syria,why ?
Zed i do know the pattern and it gives me hope in dark nights,but i need one little batch to start off the production.
what are you talking about,vacuuming and heating ?i can't vacuum.my tools are as simple as a cookware but if you're talking about transforming the ammonium => copper sulfate i can maybe get a teflon pan,or i don't even mind ruining an aluminum can for that purpose,it's a one time process and then i can apply the pattern.
besides what are you talking about phosphoric acid and polymerization and shit ?

macckone - 25-9-2015 at 06:36

Simple method of converting ammonium sulfate to copper sulfate.
Requires copper carbonate.
This is a double displacement reaction.
Mix ammonium sulfate with an excess of copper carbonate.
Mix enough water to form paste.
Then heat it while stirring with good ventilation.
The ammonium carbonate will decompose and leave the
mixture. This requires high heat and teflon is not advised.
Repeat with more water until you have a nice blue.
Then dissolve your copper sulfate and recrystallize.

Sodium bisulfate can be decomposed to make sulfur trioxide
as can ferrous or ferric sulfate and copper sulfate.
These are relatively low heat.
But require a distillation apparatus or ceramic retort.
If you have access to pottery supplies then a ceramic retort
should be relatively easy to make.

Magnesium sulfate aka epsom salt (which should be readily
available) can be electrolized in a diaphram cell.

Both calcium sulfate and magnesium sulfate give off
sulfur trioxide and sulfur dioxide at very high temperature.

The lead chamber method is workable for a home chemist.
There is a thread on here about that method.

Finally there is also a thread on burning sulfur and
using vanadium pentoxide to produce sulfur trioxide.

Last method, get some lead acid batteries and pour
the sulfuric acid out. Then heat to concentrate the
sulfuric acid. It may be contaminated with lead
but the solution to that is to dilute it to 10% then
filter as lead and lead sulfate are less soluble at
that concentration. Then reconcentrate it.

If you only need a small amount the last method
is probably your best bet.

Korialstrasz69 - 25-9-2015 at 06:48

macckone,You're god mate ! thanks !

zed - 25-9-2015 at 12:36

The method used to convert Ammonium Phosphate to Phosphoric Acid and Poly-Phosphoric acid...may be applied to Ammonium Sulfate, to produce Sulfuric Acid. Heat a little Ammonium Sulfate in a microwave. If you smell Ammonia, the reaction is Working. Sulfuric Acid is a high boiler. It is possible to boil off Ammonia and Water vapor, while leaving the Sulfuric Acid behind.

Think about it.

Since you are in Syria, what the hell do you need Sulfuric Acid for? Seems to me, there has been a war raging, and unauthorized possession of such an item might result in serious punishment.

Just assuming access to Microwave ovens. Where I live, folks sometimes discard working units, with their trash. But, it is a big world, and conditions vary.
Guys from the UK, have reported difficulty in obtaining regular ice. While, Dry Ice, is something they can only dream about.

[Edited on 25-9-2015 by zed]

Korialstrasz69 - 25-9-2015 at 13:27

Pretty sure it will be no more than ammonium bisulfate,plus i cannot afford to fuck our microwave up with ammounia :3 Am thinking melting the salt and decomposing it then separate the bisulfate with alcohol and then reheat it with copper,maybe it works.
Now imagine your lab without acids.the only reaction you can do is probably hot ice ._. .from sulfuric i can get hydrochloric and might get my hand on some nitrate.from that point i can have some fun and do real reactions.Since i started i made sure no one suspects it,i don't go around asking stores for nitric acid and i never order big supply and never online and never mail delivery.And please,ammonium sulfate is the most "unsuspectable"material and it seems i can access everything from it.so pretty safe i assume.

ave369 - 25-9-2015 at 23:16

1. Heat ammonium sulfate in a microwave oven to produce ammonium bisulfate. Nothing can go wrong here, except some stench of ammonia, but this is expected.

2. Dissolve this in water, add bicarbonate of soda, and boil. The stench of ammonia will appear again. Ammonium will be removed, you will have a solution of sodium bisulfate. Crystallize it.

3. Melt and calcine sodium bisulfate, it will turn into pyrosulfate. Use a porcelain cup instead of a crucible, if you have no access to proper crucibles. Stop the calcination when you see persistent, corrosive white fumes emerging instead of common water steam. This is your sulfuric acid escaping.

4. Put sodium pyrosulfate in sacrificial glassware (or, better, a tube made of some corrosion-resistant metal) and heat it like hell on a gas burner. Evolving SO3 should be directed into sulfuric acid (this results in oleum), but since you have no sulfuric acid at start, try to just condense it. Be careful: this anhydride is extremely hazardous! Do this outside, wear goggles and a respirator or, better, a gas mask! (obtaining one of those in Syria should be easy; with all those gas attack scares, you should have a lot of these distributed among the civilians as civil defense). White, extremely corrosive fumes will escape the apparatus, and they will also emerge when you VERY CAREFULLY drip the anhydride into water. Do it only after you put the water on the bottom of a large round-bottom flask, so the flask walls will protect you from any acid sprays and sprinkles!!! Do not, under any conditions, drip water into pure SO3!!! But you only have to deal with the pure pandemonium trioxide the first time, later you will have some sulfuric acid to be turned to oleum.

You can also pyrolyze the halfway calcined bisulfate which still has some water in it. This way, you will condense oleum instead of pure sulfur trioxide. This should be preferable if you have no sulfuric acid to absorb the trioxide.

5. I have some unverified info that adding magnesium sulfate (sold in drugstores under the name of Epsom salt, calcine it beforehand to make sure it's anhydrous!) to sodium pyrosulfate makes the pyrolysis easier. I'll check it out soon.

6. When you have prepared oleum, be extremely careful when diluting it to 98% sulfuric. Normally, you dilute oleum with 70-80% sulfuric (the boiled-down Bat), such a dilution is calm and does not produce any spectacular and destructive special effects. Since you don't have that, pour your oleum on a bottom of a large round-bottom flask and carefully, drop by drop, drip water. Oleum will spray and sprinkle, water will flash-boil. However, any sprays and sprinkles of acid will be stopped by the flask walls. Continue to do this until the oleum no longer fumes.



You can make a retort for pyrolysis out of steel plumbing and a thin steel tube as the "nose". It should be all-steel, because steel is passivated by conc. sulfuric. Buy a lot of plumbing parts of different sizes and threads in a hardware shop and assemble a retort from them. Bottles can be substituted for flasks if the process does not involve heating them. Small round-bottom flasks can be made out of lighting bulbs.



[Edited on 26-9-2015 by ave369]

j_sum1 - 26-9-2015 at 00:02

I just watched a youtube video on making sulfuric acid using magnesium sulfate and oxalic acid. It is a simple precipitation reaction. If you have access to these, it might be an eaay route.
Search for "sulfuric acid new method".

ave369 - 26-9-2015 at 00:10

j_sum1, nice find! This way, it seems, one can make dilute sulfuric acid, a substitute for the Bat, in any amounts. However, one still needs to boil it down, and boiling down to 98% is a huge mess. I boiled the Bat many times but never got above 94% (even that required tricks and perversions). If one needs 98%, pyrosulfate pyrolysis is the way to go.



I think, the Zintl-Karyakin method also deserves an honourable mention. This is a method for purifying boiled-down Bat or similar low-grade concentrated sulfuric acid. You add potassium dichromate into it and distill. This requires a retort you are ready to lose, and should be done outdoors (hexavalent chromium is a carcinogen, you don't want it to be sprayed in your home in case of glassware failure). The retort or boiling flask should be thermally insulated with rockwool or a similar material. Discard the first, dilute grams of distillate, and you will get high-grade 99% sulfuric acid (chromium trioxide, AFAIK, is an azeotrope breaker).


You can prepare dilute sulfuric acid by the method with oxalic acid, then boil it down as much as possible, then purify it using the Zintl-Karyakin method. And use this acid to absorb SO3 to get oleum.

I think that a "Plumber's Nightmare" steel retort is ideal for Zintl-Karyakin, since it is immune to thermal cracking and not corroded by conc. sulfuric. In it, you probably can do the process even at your home. One hurdle: for this retort, your boiled-down acid must be as strong as possible (94+%). Halfway-boiled acid (80%) produces dilute sulfuric acid vapors when distilled, and these slowly attack the steel pipe instead of passivating it.


[Edited on 26-9-2015 by ave369]

ave369 - 26-9-2015 at 01:57



Here is a crude drawing of a DIY oleum still. Substitute pyrosulfate for sulfuric + dichromate for Zintl-Karyakin distillation.





[Edited on 26-9-2015 by ave369]

oleum still.png - 22kB

j_sum1 - 26-9-2015 at 02:26

Out of interest, would copper pipe work for the retort? Is Cu resistent to SO3 or oleum?

ave369 - 26-9-2015 at 03:20

Quote: Originally posted by j_sum1  
Out of interest, would copper pipe work for the retort? Is Cu resistent to SO3 or oleum?


I doubt it. Hot concentrated sulfuric acid oxidizes copper, but passivates iron. Nota bene: iron is only completely passivated by cold sulfuric acid, but hot acid does slowly attack it. However, if the apparatus is robust enough, it won't eat through it. You'll at most get a minor contamination of green vitriol in the resulting distillate.



[Edited on 26-9-2015 by ave369]

Korialstrasz69 - 26-9-2015 at 05:24

Thank you all folks.i think i'l try to get a crucible and try the pyrosulfate way.
btw how does one get oxalic acid?i think it's sold in pharmacies ?
and i don't think i need that much concentration,90~95 is good enough to cook more with ammounium sulfate i think.but thank you all,great gods of chemistry :3

ave369 - 26-9-2015 at 05:26

Oxalic acid is sold in hardware stores, as cleaning powder to wipe off insoluble salts from hard water.

And more concentration is always better than less. You can skip the calcining step and put sodium bisulfate directly into the iron retort. This way you will make (theoretically) 100% sulfuric acid, but in fact a weaker solution because part of SO3 will escape. And, at one point, dilute H2SO4 will be condensing in the steel pipe, damaging it and fouling your distillate with green vitriol. So it's better to use half-calcined bisulfate/pyrosulfate mixture and distill oleum.

Don't forget the respirator or gas mask! SO3 is vile shit!


[Edited on 26-9-2015 by ave369]

j_sum1 - 27-9-2015 at 16:11

For the record, I intend to attempt the oxalic acid + epsom salt route to H2SO4 some time soon. It looks to be a bit more expensive than electrolysing copper sulfate but a whole lot faster. About the same amount of boiling down will be required.
I intend to have the OA in slight excess. I don't want to have stray Mg in my final product. A bit of research suggests that oxalic acid decomposes at moderate temperatures in concentrated H2SO4. Reported by Gay Lussac in 1832 no less!

I may attempt Ave's concentration methodology using pyrosulfate but it is probably overkill for me. I doubt that I really need to play with SO3. When I actually need 98%+ in large quantities, I will simply bite the bullet and pay for dangerous goods shipping from a reputable supplier.

Korialstrasz69 - 28-9-2015 at 00:46

Fuck this.clay is absence since a year because it all comes from another city and steel god knows.
i wanna ask what plastics resist SO3 ?i saw the plastic resistance sheet but it only tells about 2% and 5% sulfuric acid..does that mean none resist more than that ?because PVC is available...

ave369 - 28-9-2015 at 04:40

Plastics do not resist heat. And pyrosulfate pyrolysis occurs at 500-600 Celsius. Any plastic will burn at these temperatures. Ditto with plain boiling down: this requires 300 Celsius, which no plastic can survive either.

Korialstrasz69 - 29-9-2015 at 13:56

Well i was planning to do the pyrolysis in a porcelain cup and the condensing in a plastic tube or an iron tube (doesn't seem wise to me at least)but let's see if every two bisulfate molecules released two molecule of water and every pyrosulfate released 2 SO3 it will make 100% sulfuric acid which seems to burn PVC...

Korialstrasz69 - 29-9-2015 at 14:18

Umm...fuck...
SO2 if much less corrosive than SO3 and both 20% H2O2 and elemental sulfur is available...i just discovered this method ._.
uhm... sorry ._.

macckone - 29-9-2015 at 15:11

You probably have access to lead there as well. You may need to get a car battery and
drain the sulfuric acid and then melt the lead plates but I am certain lead acid batteries
are available. You may also be able to get wheel balancing weights. Lead is easily melted
and molded. It is also pretty resistant to sulfur dioxide, sulfur vapor, sulfur trioxide and
sulfuric acid. It makes an ideal material for the collection and condensation apparatus.

Leads melting point (620C) is only slightly above(60C) copper sulfate's decomposition
temperature (560C). But it is significantly above(160C) that of sodium pyrosulfate's
decomposition temperature (460C).

Steel will not be significantly corroded by DRY sulfur dioxide or trioxide but is corroded
somewhat by sulfur both as the liquid and the vapor. And even slight traces of water
and all bets are off.

Of course lead and steel can be unwanted contaminants in your sulfuric acid.
If your reactions can't tolerate them you have to go with glass or ceramics.


[Edited on 29-9-2015 by macckone]

ave369 - 29-9-2015 at 22:35

Quote: Originally posted by Korialstrasz69  
Umm...fuck...
SO2 if much less corrosive than SO3 and both 20% H2O2 and elemental sulfur is available...i just discovered this method ._.
uhm... sorry ._.


If you want to make dilute sulfuric acid, you'd better use MgSO4 + oxalic acid method. Both reagents are cheaper and more common than H2O2.

Korialstrasz69 - 30-9-2015 at 02:56

i can't get both probably because of my lack of knowledge,and lead batteries are available but way too expensive for me,and anyway can't i concentrate it as far as 90% with boiling ?also i saw on wikipedia that SO2 is lever 0 oxidizer while SO3 is lever 3 oxidizer ,so i can burn sulfur in a tin can and bubble it through H2O2 (Which is easly available,only a little expensive) and that's how i'l get my first batch and what follows will be prepared with this neat formula : http://www.google.com/patents/US20040234441

j_sum1 - 30-9-2015 at 03:41

Quote: Originally posted by Korialstrasz69  
i can't get both probably because of my lack of knowledge,and lead batteries are available but way too expensive for me,and anyway can't i concentrate it as far as 90% with boiling ?also i saw on wikipedia that SO2 is lever 0 oxidizer while SO3 is lever 3 oxidizer ,so i can burn sulfur in a tin can and bubble it through H2O2 (Which is easly available,only a little expensive) and that's how i'l get my first batch and what follows will be prepared with this neat formula : http://www.google.com/patents/US20040234441

Yee-Ouch!
Andd you think this is going to be cheaper?
By the time you invest in enough high temp equipment to do this safely and deal with your hot gas stream, you are certainly going to be out of pocket.

It's an interesting idea, but
1. Patents have a way of not disclosing everything and so, be prepared for some surprises (including the possibility that it won't work at all.)
2. Dealing with two hazardous chemicals simultaneously at close to 300 degrees is not for the faint-hearted and is certainly not something a beginner should attempt. (I would count myself a beginner in this case.)
3. I am going to be lazy here and not look up the thermodynamics. It would not surprise me in the slightest if it was infeasibe. Check it out before proceeding. It seems to me that if it was a workable process then it would be one that would be done on an industrial scale long ago.
4. Even if it does work, I think you will be in for quite a bit of experimenting before you get a setup that works reliably. Just a hunch.

Seriously, I recommend electrolysis of copper sulfate. Slow but effective. CuSO4 is not too hard to obtain. You can do it in a plastic container with a piece of lead, a strip of copper and an old phone charger. You can get good quality acid this way. What's not to like?

macckone - 30-9-2015 at 07:01

Oxidation of sulfur dioxide by hydrogen peroxide is pretty effective.
There are a number of youtube videos that use this method but you really
need 30% or higher hydrogen peroxide to get a decent yield and sulfur dioxide
is not very soluble so you need much more sulfur than the equations would indicate.
Concentrating hydrogen peroxide is also relatively easy, just tedious and you get
a good amount of loss.

Korialstrasz69 - 30-9-2015 at 07:09

Copper sulfate's unavailability.i got both ammonium sulfate and sulfur by chance since both are fertilizers.but i can't get that shit i don't even know where.

j_sum1 - 30-9-2015 at 15:33

Let's see if I have this right.
* You live in Syria, which is probably not the easiest place to do amateur chemistry.
* You have access to sulfur, ammonium sulfate and hydrogen peroxide. (Unusual mix.)
* You don't have easy access to any other reagents. (I wonder if you have exhausted all possibilities though.)
* In particular you cannot get copper sulfate, copper carbonate (which can be made fairly easily btw), oxalic acid or epsom salts.
* You are relatively inexperienced as a chemist (implied, not stated.)
* You have been provided with probably the most concise list of routes to H2SO4 that I have ever seen. Twelve methods plus variations by my count.
And you are gravitating towards the methods that require SO3 or evolve high temperature ammonia.

Just exactly what do you need 98% sulfuric acid for anyway?

I am not really trying to discourage you, but I do think, walk before you run. I am all for experimentation and think that adapting a method to suit your own particular local constraints is a great idea. I am just confused by the whole scenario where you have almost no basic reagents but need concentrated sulfuric for... something. I am also confused as to why you want to attempt the ambitious before attempting to purchase some epsom salts and a flower pot. (Both available from a garden supply store.)

100PercentChemistry - 30-9-2015 at 16:08

To make copper carbonate use
Materials:
50 ml Beaker
100 ml Beaker
25 ml sodium bicarbonate
12V 2A switching power supply
Water
Copper wire, 12 gauge
Evaporating dish
Electrical or Duct tape
Small Glass Jar
Stirrer
Acetic acid (vinegar)


Procedure:
1. Gather materials
2. Measure 50 ml of hot water in the 100 ml beaker
3. Measure 25 ml sodium bicarbonate into the 50 ml beaker
4. Add water to 50 ml beaker
5. Bend copper wires and attach to power supply wires with power supply still unplugged
6. Tape power supply wires down
7. Insert wires into 50 ml beaker with the bent parts over the lip
8. Observe beaker
9. Plug in power supply
10. Observe reaction, taking note every thirty seconds for five minutes
11. Take note every 5 minutes until 30 minutes
12. Record final observation at 1 hour
13. Add 80 ml of boiling water to 100 ml beaker
14. Filter out water from from electrolyzing beaker and scrape resulting solids into 100 ml beaker
15. Stir 100 ml beaker contents
16. Re-filter mixture
17. Scrape solids into evaporating dish
18. Wait until solids dry
19. Crush resulting material with mortar and pestle until a fine powder
20. Store resulting powder in jar. To test material, add acetic acid, if the material bubbles and becomes a green solution the material is copper carbonate.

[Edited on 1-10-2015 by 100PercentChemistry]

[Edited on 1-10-2015 by 100PercentChemistry]

100PercentChemistry - 30-9-2015 at 16:13

Do you have a power supply like a computer fan, powerful battery(lantern batteries are usually 9v 1am0), or a dc power supply?
Again what do you want to synthesize?
What type of stores do you have?


[Edited on 1-10-2015 by 100PercentChemistry]

[Edited on 1-10-2015 by 100PercentChemistry]

Korialstrasz69 - 30-9-2015 at 16:38

First of all,really sorry for the long post and mind fuck and insisting on getting the acid and all,but that's that.we got a few good methods for everybody anyway so nothing went to waste.
I can get epsom salt,first of all.oxalic acid i cannot go around asking for it but still a i might find it.Hydrogen peroxide is available as a tooth whitener and sulfur is available for tomato fertilizing,and ammonium sulfate is a regular fertilizer very well so yes not so unusual.don't wanna brag but am not inexperienced,maybe i am actually,i have just been reading for years now and saw a whole lot of videos(NerdRage,NileRed,ChemPayer)and read a whole fucking lot of wikipedia,so i know at least basics in working with chemicals.
this part you can skip,but i have a good cause for every single method:
1-i don't know where to get copper sulfate and don't want attention since i already said chemistry means explosive here(If it's only used by chemists).
2-i don't have HCl and here we clean drains with NaOH.
3-A dollar costs 300 Syrian pond and i can't afford a 28k S.P battery.
4-i already left a piece of copper to rot into carbonate,need time.
5-i lack knowledge about diaphram cell i must admit.
6-since the first few methods and am looking and asking around for steel pipes or raw clay but both are not used,hardware stores sell pure iron pipes and my city isn't getting any clay since people have been hiding weapons in clay jars(still can't get the logic here really but it's a fact).
7-and vanadium pentoxide...you guessed it.
8-ave369's method seemed great,but as i said no means available to withstand SO3 or oleum.
9-still looking for oxalic acid.
10-that's it(please kill me).
i feel like a shit.
anyway am planning to use our vacuum cleaner to make sulfuric acid from sulfur's SO2.i have already dealt with hot ammonia in my fucking kitchen,and the experiment will be done outside anyway.and no SO3 is involved in the patent.
"Just exactly what do you need 98% sulfuric acid for anyway?"
Please stop asking this,you can't run a lab without oxidizing agents and acids and especially sulfuric acid since it's needed in equilibrium reactions that release water.i don't have much time now but tomorrow i'l come with a bunch of reactions that i can't preform due to lack of acids.
Sorry everybody for the long post and for bothering you all with searching,especially you j_sum1,but i never realized how hard is it to be an amature chemist in a war situation.Also sorry for turning this post from chemistry to personal problems.

j_sum1 - 30-9-2015 at 16:47

Quote: Originally posted by Korialstrasz69  

Sorry everybody for the long post and for bothering you all with searching,especially you j_sum1,but i never realized how hard is it to be an amature chemist in a war situation.Also sorry for turning this post from chemistry to personal problems.

No offense taken. In any case, this has turned out to be a worthwhile thread since it summarises in one place so many different methods for obtaining an essential reagent.
And I am sure that being an amateur chemist in a war zone is fraught with difficulty.
For the record, it has taken me a year to incrementally build up my lab and I am still making my own acids (except HCl). The truth is though that you can do a lot of chemistry at small scale and don't need a large quantity of anything.

[edit]
Copper sulfate may be available as a fungicide or as an agent for preventing root growth in drains etc. ("Rooto" in the US.) I got mine from a pottery supplier. You can probably order it online. It is unlikely to raise any suspicions. (You could always spray some on your tomatoes.) And if you have copper wire and a soluble sulfate salt (which you do) then you can make it easily enough through a number of different routes.
This might be exactly what you want. An alternative is to use an unglazed terracotta flower pot inside a bucket to act as a membrane and separate the two half cells. It might be a more reliable and robust setup than a suspended coffee filter.
Alternatively, by use of an inert electrode you could go directly from magnesium sulfate to sulfuric acid dropping a Mg(OH)2 precipitate. (Although I have no actual experience of this method.)


[Edited on 1-10-2015 by j_sum1]

NedsHead - 30-9-2015 at 19:21

Quote: Originally posted by j_sum1  

Copper sulfate may be available as a fungicide or as an agent for preventing root growth in drains etc. ("Rooto" in the US.) I got mine from a pottery supplier.


[Edited on 1-10-2015 by j_sum1]


I get mine from the garden section at a hardware store, it says on the container that it is used for correcting copper deficiency, it can also be called Bluestone

Little_Ghost_again - 4-10-2015 at 11:43

I found a list but it seems the site has now gone!! I dont think the Op has any chance of getting copper sulphate, it was on the embargo list I saw. I think also its really easy to under estimate just how much of a risk he is taking buying some of these things.
I am not going to get political but I feel for the guy, its a terrible situation over there, seems like 3 sides all fighting and anybody remotely buying something that could be turned into something is probably not going to fair well. The other thing is human rights, lets face it if he is suspected of something it isnt likely he is going to get anywhere near a trial let alone a fair one.
Clay.....
I no nothing of your country but I do know most countries have clay somewhere below the subsoil, if it was me I would find where people hate growing things because the soil is hard to work, I would then go and grow things there ;).
Clay from my own experience normally comes up pretty clean once you get a couple feet down. A computer fan and decent wood fire with a mud surround might just get your clay baked enough to use as a retort. I appreciate this isnt ideal but somewhere not too far from you there is surely some clay to dig up :D.
This might be utter crap but maybe a ceramic mug with a homemade clay retort top from clay you dig and fire might do the job for you.
I dont know the chemistry but seeing as you can get sodium hydroxide and copper wire maybe there is a way to copper sulphate from that? others will need to guide on this as my knowledge is zero.
Keep us informed and carry on being careful, I watch the news alot and seeing as they are bombing the shit out of hospitals with foreign civilians in them that are phoning up and pleading to stop and yet just because they think the bad guys are there they continue. Keep safe my friend chemistry isnt worth dying for.
I salute you for having the balls to attempt this.
One other thought I had was maybe if you could get lead sheet like used on roofs you could line some steel with this to try and cut down on the attacking from the weaker acid. If I could get away with it I would send you the 250g of copper sulphate I have, but my worry would be it might cause you problems receiving it.
One thing I might be able to do for you is return a favor that someone kindly did for me on here, I got sent some MMO electrodes, I cant spare much but I am more than happy to cut some bits off and send them. I doubt a couple of small bits would raise suspicion. Let me know if its possible to get post from the uk.

Little_Ghost_again - 4-10-2015 at 11:52

I know you want sulphuric acid but this might help as well. you can get hydrochloric acid from baking soda and table salt

NaCl + NaHCO3 ® HCl­ + Na2CO3
Also you have access to PVC, on here is a thread or two and one where aga pyrolized PVC and bubble the gas into water to make hydrochloric acid. I am just trying to think of some ways to get you acids, maybe hydrochloric would be safer and easier to start with??

j_sum1 - 4-10-2015 at 12:00

Are you sure?
I would have thought that reaction would go in the other direction.

Little_Ghost_again - 4-10-2015 at 12:06

Quote: Originally posted by j_sum1  
Are you sure?
I would have thought that reaction would go in the other direction.

No i am not sure I thought it had posted the link I will try again sorry http://amedleyofpotpourri.blogspot.co.uk/2011/12/making-hydr...
Looks like I didnt paste the link last time :o, I havnt got a clue if it works but maybe the link will help answer some questions, I just skimmed through to be honest, I was hoping to help as the thought of someone with little equipment trying to mess with some of the reactions is pretty scary.
I bitch about living in the middle of no where and not having pool shock local to me, reading this kind of thread really puts things in perspective. I am also kinda impressed that despite everything going on over there people are trying to have a life and do a hobby that carries some serious risks for them. It just hit a nerve with me and made me think that maybe I am not as bad off as I thought

[Edited on 4-10-2015 by Little_Ghost_again]

j_sum1 - 4-10-2015 at 12:17

Ok, so it is heated to drive the reaction to the right.
The products look like the standard acid + carbonate reaction: resulting in salt plus water plus CO2. What prevents this from occurring?

Little_Ghost_again - 4-10-2015 at 13:32

Quote: Originally posted by j_sum1  
Ok, so it is heated to drive the reaction to the right.
The products look like the standard acid + carbonate reaction: resulting in salt plus water plus CO2. What prevents this from occurring?

I only skimmed it to be honest, but I have some bicarb I found today lurking in a box, so I could give it a go after school if it helps?

Little_Ghost_again - 4-10-2015 at 13:39

I read it to mean heat the salt and sodium carbonate to make the HCL, where is the acid apart from the HCL? I am just guessing but the heating drives the gas out the tube. Sorry j_sum1 I dont know anything about this but will try with the bicarb tomorrow and see what happens.
Somehow though it might be easier for him to use PVC and heat that. Some HCL would at least give him a few other options for now

ave369 - 4-10-2015 at 14:07

Also, pure iron pipes will do. Maybe a bit more green vitriol impurity, but it will work.

Korialstrasz69 - 5-10-2015 at 01:53

First of all,thank you very much Little_Ghost_again,it's really helpful to have someone feeling for you :)
well now,all good grade clay for pottery comes from the city of Hama,witch stopped coming even for arts students because they've been hiding weapons in it,but i don't think i need that anymore.
check this out:
http://imgur.com/UpDHrfh
can you guess what that color is?it's copper ions bruh!
as i mix and heat i believe i will get a nice batch of Copper sulfate ready for electrolysis,and anyone would prefer the wet chemical way on the high temp way.and as i get my first batch i think il be using the patent and get going :)
thanks you very much for your offer bro,but i prefer not,i think carbon electrodes will work good enough,and i might be a little suspected already.
like we were talking about breaking bad and chemistry in college other day when that old man came asking for some money.as he walked be we looked back and he disappeared,another man came and said something to us about him.i think i might be watched.
nonetheless,i think am in a relatively safe area.
thank you all for responses,if this one idea fails i think i'll attempt the PVC method,Thanks again all !

Little_Ghost_again - 5-10-2015 at 06:45

Quote: Originally posted by Korialstrasz69  
First of all,thank you very much Little_Ghost_again,it's really helpful to have someone feeling for you :)
well now,all good grade clay for pottery comes from the city of Hama,witch stopped coming even for arts students because they've been hiding weapons in it,but i don't think i need that anymore.
check this out:
http://imgur.com/UpDHrfh
can you guess what that color is?it's copper ions bruh!
as i mix and heat i believe i will get a nice batch of Copper sulfate ready for electrolysis,and anyone would prefer the wet chemical way on the high temp way.and as i get my first batch i think il be using the patent and get going :)
thanks you very much for your offer bro,but i prefer not,i think carbon electrodes will work good enough,and i might be a little suspected already.
like we were talking about breaking bad and chemistry in college other day when that old man came asking for some money.as he walked be we looked back and he disappeared,another man came and said something to us about him.i think i might be watched.
nonetheless,i think am in a relatively safe area.
thank you all for responses,if this one idea fails i think i'll attempt the PVC method,Thanks again all !


Not being funny but probably best to say nothing to nobody where you are. I lived in another part of UK that was full of clay, I now live in Scotland and there is no clay just peat. Funny thing is when I was in Devon I wanted peat for some aquarium fish, the clay was a pain. Now I live in Scotland the fish are happy but I could do with some clay for an oven lol.
Congrats on the copper, the PVC should give you hydrochloric and from there you are away!!
Keep things low key no such thing as a safe place, ask those that were working in the hospital :mad:.

AJKOER - 20-1-2016 at 06:01

Just found this "Acceleration of Sulfurous Acid Oxidation by Freezing of Aqueous Solution", by Kazuhiro, link: https://www.researchgate.net/publication/244692896_Accelerat... , to quote from abstract:

"Oxidation of sulfurous acid (H2SO3) to sulfuric acid (H2SO4 by dissolved oxygen (O2) in an aqueous solution was remarkably enhanced by freezing. The concentration of sulfurous acid in a sample solution which froze in a - 10°C refrigerant for 60 min decreased by about 50%, and three freeze/thaw cycles resulted in perfect conversion into sulfuric acid. The difference of reaction rates in -20°C and -10°C refrigerants indicated that the rate-determining step of the reaction was the growth rate of ice formation in the sulfurous acid in an aqueous solution. The yield of sulfurous acid oxidation in a -10°C refrigerant was higher than that in a - 20°C refrigerant."
-----------------------------------

My speculation on the pathway is the presence of a transition metal impurity, low pH, and dissolved oxygen that resulted in the formation of some Fenton products. The hydrolysis of two such products is:

.OH + -OH = .O- + H2O

My recent research indicates at standard conditions the reaction equilibrium is actually favored to move more to the right with the formation of the so called hydroxyl radical anion .O- (see, for example, http://pubs.acs.org/doi/abs/10.1021/j100087a022 ). But, somewhat problematic is that low pH moves the equilibrium to the left. However, the formation of ice effectively removes water along with increased viscosity arguably could move the reaction back to the right.

Assuming the hydroxyl radical anion is created, I do recall the following reaction with it and oxygen ([Edit] Found a reference, see page 182, equations R36, R37 and R38 in "Plasma Kinetics in Atmospheric Gases", by M. Capitelli, et al., link:
https://books.google.com/books?id=2ofqCAAAQBAJ&pg=PA182&...):

R37 .O- + O2 = O3 + e

R38 .O- + O2 = O + O2 + e

Or, possibly as:

.O- + O2 = .O3-

where I suspect the .O3- radical anion, or whatever products per above, would certainly be a stronger oxidizer than O2. The speculated reaction could then be:

H2SO3 + .O3- = H2SO4 + .O2-

More background on .O3- radical anion, please see https://books.google.com/books?id=7B8KwVVZRPEC&pg=PA85&a... and this reference referring to it as the ozonid anion at https://books.google.com/books?id=qyN6_83vz2MC&pg=PA472&... . Note, the last reference notes O3 + e- = .O3- and the former, O3 + e- = .O- + O2, which appears to support my cited equilibrium formation reaction of the ozonid radical anion stated above.

More associated reactions:

2 .O2- + 2 H+ = H2O2 + O2

where the oxygen could be partially recycled, and the hydrogen peroxide likely consumed in a Fenton reaction, or with Sulfurous acid:

H2SO3 + H2O2 = H2SO4 + H2O

Interestingly, some reactive oxygen species (like Singlet oxygen, for example) are best formed at low temperatures (and also, preferably at neutral to high pH conditions).
---------------------------------

[Edit] I would be remiss not to cite a well documented path by passing air/O2 through H2SO3 in the presence of a hydroxyl radical source (like by action of sunlight on aqueous N2O, or aqueous nitrite or nitrate salt, or a Fenton-like reaction with a transition metal oxide like Cu2O, FeO.Fe2O3, TiO2,..).

For example, per one source: "Rate Constants for Reactions of Inorganic Radicals in Aqueous Solution" by P. Neta and Robert E. Huie, to quote:

"3.11. Sulfite Radical
The .SO3− radical is most commonly produced by the reaction of .OH with sulfite or bisulfite.
.OH + SO3(2−) → OH− + .SO3−"

And further:
"3.13. Peroxomonosulfate Radical
The SO5.− radical is produced by the reaction of .SO3− with O2.
.SO3− + O2 → SO5.−"

Also:
"The SO5.− radical is a stronger oxidant than .SO3−, with an estimated redox potential of 1.1 V at pH 7.39. It is still quite selective in its reactions, oxidizing hydroxybenzenes at high pH rapidly but only slowly or not at all at low pH. The radical possibly also reacts by oxygen-atom transfer with sulfite or bisulfite.

SO5.− + SO3(2−) → SO4.− + SO4(2−)

In such a case, the SO4.− would react rapidly with the SO3(2−), regenerating .SO3−, and thus making it difficult to distinguish this reaction from an electron transfer path. "

Link: https://www.google.com/url?sa=t&source=web&rct=j&...
------------------------------------

Bottom line, try adding, for example, KNO3 ([Edit] better KNO3 plus sea salt or employ NaNO3/NaBr for more efficiency, see http://pubs.acs.org/doi/abs/10.1021/jp109560j?src=recsys&... ) to very cold H2SO3 and aerate in sunlight.

[Edited on 21-1-2016 by AJKOER]

hissingnoise - 20-1-2016 at 06:18

'Worth remembering, perhaps, that SO3 does not dissolve in water but causes boiling at the interface which produces a non-condensible acid mist which is very corrosive!

It does dissolve readily in concentrated acid to produce oleum . . .