View Full Version : Improvised distillation apparatus
NoltaiR
April 1st, 2002, 01:35 AM
Well crap.. I just hate starting new topics.. but anyways maybe you guys can help out.
For the longest time I have used an 'evolved' method of the old IM handbook procedure for distilling HNO3 out of H2SO4 and KNO3 (because I am too cheap to buy real distilling apparatus). The handbook says to take two glass coke bottles and to connect them together at the mouths with paper or cloth. One bottle should have a 2:1 mix of KNO3:H2SO4 and the other bottle should be empty.. it will be the recieving 'flask'. The first bottle is heated by gently applying an open flame to it and while occasionally pouring cool water over the recieving bottle.
Well my evolved method uses two gallon-sized wine bottles (which can stand a great amount of heat) that are duct taped together at the mouth. The first bottle is suspended in the air by being balanced on lumber (2x4) in the following fasion:
<pre>
.------.
: :::
: ::: <--sucky drawing of a winebottle
: ______.
|| ||
|| || <--2x4
</pre>
The recieving bottle (not pictured) has a large ice pack over it.
It takes a little while but I usually can get a fairly good amount of HNO3.
Anyways, tonight I was going to try to distill the H2SO4 alone to make fuming H2SO4. It looks like it is working although it is going EXTREMELY slow! Are there any other ways I can make it work better/faster or are there other methods other than distillation that can be used to purify the H2SO4 (basically I am trying to separate the H2SO4 from the additives that are mixed with it because I buy the drain cleaner stuff).
rikkitikkitavi
April 1st, 2002, 02:14 AM
A:
the reason why it is so slow is probably because the heating is not enough.
80 % acid boils at around 190 C , and it rises steeply up to 338 C when the acid hits 98 % (cant go further, fuming sulfuric acid is impossible to produce by distillation)
When heating diluted sulfuric acid, below 80 % only thing vapourized is water, but above that an increasing amount of sulfuric acid is going away to. that is why it fumes so much.
but if you have a reciever flask , that will of course condensate everything to a more dilute acid.(not entirely)
when distilled in open aprox. 50 % of the acid is lost in vapour.
If using normal glass for this, take it very very slowly with the heating. Normal soda glas is very temperature chock sensitive at high temperatures. Cracks easily. And 300 C hot sulfuric acid is NASTY!
If you had access to platinum or tantal a
metall, electrolysis could be tried, but it will also be slow , since the conductivity of the acid
drops a lot when concentration goes up.
Frezzing ? Only if you had a very coold freezer.
80-90 % freezes below -30 C. But if you have 98 % acid it does freeze at not much below 0 C.
Q1:
you guys who have access to drain cleaner acid ,
have tou noticed that the additives are oxidizer at high tempereratures? I mean if the additives are stable enough to withstand 300 C sulfuric acid, they are probably not of a nusiance when making H.E ?
Q2:
Could someone with a vaccum setup try to concentrate sulfuric under vaccum ? Then the end point is lowered to about 200 C instead of 338 C. This is how it is done in the industry, mostly because distillation at 338 C takes special equipment. OTherwise it is the same.
/rickard
<small>[ April 01, 2002, 01:21 AM: Message edited by: rikkitikkitavi ]</small>
Azazel
April 1st, 2002, 06:44 AM
wouldnt you need a suitable catalyst for this to happen rather than vacuum... like u learn that kinda stuff in high school chem i think
Lagen
April 1st, 2002, 07:13 AM
I'm sure you meant H2SO4 synthesis, not H2SO4 distillation.
And you should have read rickard's profile before flaming him...
10fingers
April 1st, 2002, 06:34 PM
It takes a lot of heat to distill sulfuric acid. The type of glass you are using will probably break. This is dangerous, one of the worst things you would want to get on you is boiling sulfuric acid. Maybe some type of stainless steel apparatus would work better.
Also, if you just heat up your sulfuric acid enough it may reduce the impurities into carbon/gas which would boil off or settle to the bottom.
EventHorizon
April 1st, 2002, 08:20 PM
Improvised methods are great in a pinch, even good to just experiment with BUT do youself a favor and get a good glassware setup. Yes they are expensive if you just go on Kimbles site and order a whole setup, but go on ebay and get pieces here and there and see the difference it makes. I went from choking my self to death on SOx fumes, fu*king around with insanely hot glassware trying to pour the distilled H2SO4 in pyrex bottles, then worrying about breaking the bottle cause of the vacuum the hot product produces, to distilling 98%+ H2SO4 with almost insane ease. No fumes and incredibly good product. My setup is a 2L Kontes RBBF, 24/40 adapter to a Friedricks(sp) condenser, a graduated erlynmier receiving flask, and a 24/40 stopcock. Put in a measured amount of the dilute acid, boil out the calculated amount of water (+ ~50-100ml extra), remove the 24/40 adapter and put in the stopcock. When cool, open the stopcock to releive the vacuum and viola.
Pu239 Stuchtiger
April 1st, 2002, 08:46 PM
Rickard, I think the reason drain opener H2SO4 is an oxidizer at higher temperatures is because hot concentrated sulfuric acid is a strong oxidizer, not because of the presence of other oxidizing chemicals. I believe the reason drain opener H2SO4 is usually brownish is because of high selenium content.
NoltaiR
April 1st, 2002, 09:16 PM
Well I abandoned the H2SO4 idea after about 4 hours of work to get my H2SO4 only slightly more concentrated (although it was enough that the AP I made earlier today only required half of the usual amount of acid).
Anyways I am going to try a better way of distilling the HNO3 from the H2SO4/KNO3 mix because my wine bottles may take a hell of a lot of heat before breaking... but they are so large that they are almost impossible to use as a recieving flask because it is very hard to keep a low temperature within such a large area.
Azazel
April 2nd, 2002, 03:34 AM
sorry i didnt mean to seem like a meanie.... sorry
im not flaming... just stating what i read... i think im confused
vulture
April 2nd, 2002, 03:42 AM
According to me 98% sulfuric freezes at around 15C, that's what happens with my sulfuric in the basement where it's around 15.
da man
April 2nd, 2002, 03:56 AM
I use drain cleaner H2SO4 and i never purify it. Mine is "mo-flow" brand and is 98.5% sulphuric acid. It is also a browny black colour, but seeing that it is 98.5% i think there must not be very much of the added "corrosion resister". I have used this to make nitroglycerine, picric acid (asprin method) and cellulose hexanitrate without purifying and each has worked fine! if it is reasonably concentrated, don't bother with the purification.
The Great Milenko
April 2nd, 2002, 11:18 AM
I was thinking of trying the IM method for a while now, and I "borrowed" a really strange bit of glassware from school recently, and I dont know quite what it's called, but I thought that it would be great for this purpose, anyway I have a picture of what the basic method I would use instead of two bottles taped together(sorry for the shitty illustration, but it's not one of my strong points), I also thought that why not use an oil bath to heat the KNO3/H2SO4 mix instead of using fire, as this would eliminate hot spots, right?
<a href="http://au.photos.yahoo.com/shaolin_tf" target="_blank">Click here, then click on "My Photo's" and then open nitric acid.jpg</a>
I'd have an ice jacket thing around the pipe bit on the left to cool it down also even though it is'nt in the pic, so would this work? or should I just go lo-tek all the way and just use a couple glass bottles taped together?
And about how hard would either of these two methods be? would it be worth it? I was also going to ring up a photo supplier shop and ask if they sell etching fluid, or aquatis fortis, would they be onto me as to why I wanted it? Has anyone else who lives in Aus found a good place to get HN03 that is near melbourne or perhaps ships to melbourne?
<small>[ April 02, 2002, 10:58 AM: Message edited by: The Great Milenko ]</small>
rikkitikkitavi
April 2nd, 2002, 11:28 AM
pu 239...
of course youre right. my typo
I meant to say that wouldnt the hot sulfuric acid OXIDIZE the impurities. but if they already are in a
maximum oxidized state, they cant do much harm can they? Anyway both my questions have been fully answered but of course keep the topic alive. Concentration or rather reconcentrating sulfuric acid are of greatest interest.
for the record. Only compounds withstanding boiling 98% (338 C @ 1 atm ) sulfuric acid
are silica iron (12-15 % Si, rest Fe) , boronoxide glass (pyrex f e x) and similar ACID-composition ceramics/glass, tantal. teflone to of course but only below 250 C. but I have probably overseen a few :)
stainless steel is corroded even at low temperatures. Carbon steel withstand COLD conc sulfuric acid at 20 C, but already at 30-40 signs of heavy corrosion appears.
/rickard
<small>[ April 02, 2002, 10:32 AM: Message edited by: rikkitikkitavi ]</small>
mongo blongo
April 2nd, 2002, 12:18 PM
vulture - that happened to my H2SO4 too. I think it's more around 9C. Have a look in the thread "WTF happened to my H2SO4?" if you haven't already. :)
Milenko- It would be better to use sand rather than oil (less mess to clean up) but it will work. You also need to use a receiving flask because you will loose a lot of HNO3 with an open beaker.
Zambosan
April 2nd, 2002, 01:15 PM
Milenko: the glassware you pinched is called a "retort". Incidentally, they're nice 'n expensive. If you can cool the vapors in the neck *very* quickly, you may be able to get away with a collection dish... but a receiving flask is much better. You don't want NOx vapors floating around you.
CyclonitePyro
April 2nd, 2002, 05:17 PM
I have a United glass tech 24/40 distillation setup: <a href="http://www.unitedglasstech.com/distillation.htm" target="_blank">http://www.unitedglasstech.com/distillation.htm</a>
I didn't like working with my drain opener dark brown acid so I tried to distill it so it would be nice and clear, it was already 98% by boiling. Even under vacuum, it took long to heat and boil, and when it did it wasn't smooth, it bumped a lot.
It would sit there like it wasn't boiling and then rise as if it was increasing it's own volume and even got high enough to pour out of the 1000mL boiling flask and pour down the condenser, there was about 500mL of H2SO4. I tried it again, but this time I put broken pieces of glass in the boiling flask to act as boiling stones to smooth the boiling but it still bumped.
I thought if I could boil it whatever made it brown would be left behind in the boiling flask.
Now I have another brand of drain opener acid and it is clear but slighty yellowish, and if I stir it with a glass rod bubbled form, it's sudsy, has anyone used this acid with these properties? Did it interfere with any reactions?
DBSP
April 2nd, 2002, 06:34 PM
When I concentrate H2SO4 I boil down the 37% H2SO4 wich is clear but when it's allmost done it gets a bit brownish. I looked at some 30ml I concentrated some time ago and it was allost black. Why does the color change when it gets concentrated.
Anthony
April 2nd, 2002, 09:44 PM
I *believe* that it's organic impurities in the H2SO4 that decompose to carbon during the concentration process, the carbon giving the H2SO4 a brown/black colour.
EventHorizon
April 2nd, 2002, 10:36 PM
I boil down battery acid bought in bulk. Does a wonderful job and the end product is water clear. The only thing is that at the end of the boiling while the acid is ~300°C there is an alomst crystaline "puffy" precipitate that forms but after the acid has cooled there is nothing. Anyone know what that is?
Zambosan
April 3rd, 2002, 02:07 PM
Yeah, H2SO4 bumps BADLY when boiling. Once the concentration/temp. gets high enough, it'll just sit there doing nothing, then BAM... a humongous bubble will explode out. Some good ceramic boiling chips should help to tame that down.
nbk2000
April 3rd, 2002, 03:20 PM
Or you could have a capillary tube going down into the acid with a constant stream of dried air going through it. That'd prevent bumping too.
I believe in prior discussion that the crystalline material in the acid is a meta-hydrate of SO<sub>3</sub>.
The Great Milenko
April 4th, 2002, 07:20 AM
Well what could I use to maybe attach a flask to the side bit, or is there any type of piping or such that I could use? I take it that I could'nt just use some metal pipe? :rolleyes:
mongo blongo
April 4th, 2002, 08:27 AM
PVC pipe works I think. Metals and acids don't go well together!
DBSP
April 4th, 2002, 08:34 AM
Wouldn't the HNO3 liquify the plastic??
rikkitikkitavi
April 4th, 2002, 10:59 AM
only plastics withstanding 100 % HNO3 are PTFE and similar polyfluorinated polymers.
PVC har shorttime resistance to COLD conc sulfuric acid, but is agressivly attacked by HNO3 at high conc.
/rickard
mongo blongo
April 4th, 2002, 12:51 PM
What plastic is the one you find inside aresol cans (the pipe)? It looks transparent but a little misty. Sorry I thought it was PVC but the stuff I'm talking about resists HNO3 fine! I use it in my improvised still (much wider tubing than the tube in the aresol cans though).
rikkitikkitavi
April 4th, 2002, 01:03 PM
it is probably not , but can be PTFE. Non coloured PTFE is milky in apperance. '
PTFE has the lowest coefficeint of friction , so it is very slippery .
Put it in a flame , if it catches fire readily it isnt PTFE- beware
PTFE gives of HF when strongly heated.
If it works, good. But dont be surprised if 100 % HNO3 burns away your plastic all of a sudden :)
/rickard
DBSP
April 4th, 2002, 02:31 PM
I have some meassuring cylinders made of plastic wich fit the discription of PTFE. I've had conc H2SO4 in it short times and I've had no problems with it. Could it be PTFE?
Zambosan
April 4th, 2002, 02:37 PM
Most plasticv labware is made of fluorinated polymers so that they're able to resist most common lab chemicals, including acids. Nalgene is a trade name for this material, and they tend to stamp it into the equipment made with it.
mongo blongo
April 4th, 2002, 03:10 PM
I just found a 100ml beaker that I nicked from college a few years back. I think it's made from the same stuff as my pipe. It has "labplex" and "pp 135C Max" printed on it.
DBSP
April 4th, 2002, 04:11 PM
I just had a look at my cylinders the only thing I found on them was "made in west germany" no company name or anything else.
Anthony
April 4th, 2002, 04:22 PM
I thought the "PP" on plastic labware was an acronym for Poly Propelene.
Zambosan
April 4th, 2002, 05:05 PM
That would be consistent with the stated max temperature, since the melting point for polypropylene is 160-170 deg. C, and it starts becoming plastic before becoming completely fluid.
DBSP
April 4th, 2002, 05:55 PM
I saw an ad in the paper today, they sell 50kg of Ca(NO3)2 for 17,5$
and I remembered an old topic called calsuim nitrate I think. There the uses of it is discussed and it came out that CN is very good for use in H2SO4+xNO3 reactions. Since it formes the insuluble CaSO4 you could just filter it and you'll be left with a decent nitric. The problem is that i don't have any acid proof filters I'll have to remove the CaSO4 by dest. The retort could be useful but I don't know if I can find it. I've thought about buying a real still but if I can get away with something simpler and chaper that would be nice.
Do you have any suggestions of sutible tools for just stripping the acid out?
This probably a very stupid question though. :o
Pu239 Stuchtiger
April 4th, 2002, 06:25 PM
Glass filters do exist, those can be used. Unless you're willing to use a great excess of Ca(NO3)2, you're always going to have a fair amount of sulfuric acid contamination in your nitric acid.
mongo blongo
April 4th, 2002, 06:38 PM
Glass wool = glass filter.
nbk2000
April 5th, 2002, 03:37 AM
Calcium sulphate is soluble in sulfuric acid, so you're not going to be able to filter it out.
Pu239 Stuchtiger
April 5th, 2002, 03:49 AM
What matters in this case is CaSO4's solubility in HNO3. I don't know how soluble CaSO4 is in HNO3, but I don't think it would dissolve well at all.
DBSP
April 5th, 2002, 04:50 AM
Read this topic: <a href="http://www.roguesci.org/cgi-bin/ewforum/ultimatebb.cgi?ubb=get_topic;f=1;t=000209" target="_blank">calcium nitrate</a>
In that topic some people say CaSO4 is unsuluble in acids.
I have no idea myself I've just read the posts.
Pu239 Stuchtiger
April 5th, 2002, 04:57 AM
Hrm, I just looked up solubility data for CaSO4. According to my sources, it is "sparingly soluble in water but soluble in acids".
The Great Milenko
April 6th, 2002, 06:34 AM
Oh! I have a few nalgene bottles, you can get them in pretty much all camping stores in Aus, if you can tape together a couple glass bottles when using the IM method and the HN03 does'nt melt the tape, then could'nt I just cut the tops and bottoms off a few bottles and tape them together? I'd overlap them of course, but would this work?
I need to be sure that the HN03 would'nt dissolve the nalgene bottles?
rikkitikkitavi
April 6th, 2002, 09:20 AM
calcium sulfate is more soluble in acid than in water because of the
equlibrium:
SO42- + H+ = HSO4- thus CaSO4 dissolves in the form of CaHSO4
CaHSO4 is supposed to be more soluble than CaSO4 but I havent found any references so far.
Anyway, I have used this method to produce diluted (about 20-30 %) HNO3 with Ca(NO3)2 and H2SO4 with fairly good results.
Dissolving the Ca(NO3)2 in water seemed essential, mixing solid
Ca(NO3)2 with conc acid didnt make anything. Probably the solid is covered with CaSO4 instantly preventing further reaction.
One problem is that the preciptated CaSO4 is extremely fine thus forming a porrigde more than a preciptate, very difficult to filter + that is adsorbs a lot of liquid and hence increasing losses. I just let it sit for a few days and the decanted the top liquid.
Eventually I started to distill the mixture to get higher conc HNO3, but it didnt work out so good. Probably because of the CaSO4 forming again. Better results with NaNO3
Fertilizer Ca(NO3)2 (a k a kalksalpeter in swedish, norweigan salpeter ) has following formula:
Ca(NO3)2NH4NO3*10 H2O.
Drying it in a oven (100C) removes water and cranking up the temp to 200 C decomposes the NH4NO3 (careful, good ventilation!)
Anhydrous Ca(NO3)2 is very hygroscopic.
I rectrystallised it at first to remove impurities and then dried it.
I plan to setup a HNO3 vaccum concentrator working with Mg(NO3)2 as a waterabsorbant instead of sulfuric acid. Anyone tried this ?
Nowadays I make HNO3 from (NH4)2SO4 + Ca(NO3)2
/rickard
<small>[ April 06, 2002, 08:23 AM: Message edited by: rikkitikkitavi ]</small>
DBSP
April 6th, 2002, 09:40 AM
Rikki where do you find the (NH4)2SO4. And has it got any synonyms.(di-ammonium-sulphate)?
<small>[ April 06, 2002, 08:53 AM: Message edited by: DBSP ]</small>
kingspaz
April 6th, 2002, 06:41 PM
(NH4)2SO4 + Ca(NO3)2 ----> 2HNO3 + CaSO4 + 2NH3 ?????
wouldn't the NH3 react with the HNO3? ---> NH4NO3?(
(NH4)2SO4 is called ammonium sulphate, can;t think fo anyother names, thats the proper name anyways.
can be made from 2NH4NO3 + H2SO4 ----> 2HNO3 + (NH4)2SO4
rikkitikkitavi
April 7th, 2002, 10:49 AM
ammonium sulfate is sold as fertilizer under the name ammonsulfat in sweden.
<a href="http://www.lantmannen.se/vaxtodling/vaxtodlaren/lantmannen/vaxtnar/sortiment/godselsortiment.html" target="_blank">http://www.lantmannen.se/vaxtodling/vaxtodlaren/lantmannen/vaxtnar/sortiment/ godselsortiment.html</a>
I was lucky to find half a sack full of some old one, which I still use.
1)[NH4]2SO4 + heat 150 C => NH4HSO4 + NH3 @150C
careful lots of NH3 is produced and it is very toxic. I made it in a special oven , gas fired where the NH3 produced was sucked into the
gas flame and incinerated, with myself about 10 m away, upwind. If cought in a cloud of NH3 you are in deep trouble. I also had a gasmask covering my eyes to with a NH3 filter. But it still smelled strongly to the point of nauseous in the air, why I made it in a small house far from neighbours. Large amounts of NH3 released causes heavy damage to green plants, it simply turns yellow and dies, so that has also to considered.
2) NH4HSO4 + Ca[NO3]2 => NH4NO3 + HNO3 + CaSO4
diluted to about 20 % HNO3 , se my previous post. Distillation concentrates the HNO3 to about 65 %
I have a small distillation setup made of a cooking pot covered with nonstick and the distillation column made of stainless steel, wich is resistant to HNO3 < 90 %. Same column has uses in making of alcohol!
And it has never been cleaner!
Stainless steel is attacked by the mixture of NH4HSO4, Ca[NO3]2, HNO3 and CaSO4 though, hence the pot covered with nonstick.
Its messy and takes a good lab to perform because of the large amounts of NH3 formed, which is very toxic both to humans and nature.
A rainy day is good , because the NH3 is quickly absorbed by the rain.
I know is is a ridiculously akward way on getting hands on nitric, but in sweden you cant buy it and neither sulfuric acid in any concentration without lots of permits... but it is a cheap way to make it. Cost about 1,5 US$ / liter 65 % .
/rickard
<small>[ April 07, 2002, 09:52 AM: Message edited by: rikkitikkitavi ]</small>
DBSP
April 7th, 2002, 01:49 PM
Ammonium sulphate,hmm the formula did seem a bit familiar.
I'm going up north this summer and I've got plans to go to Norway to get some acids, the orwegian border cant be to difficult to get through. I shuld be esier than the danish border.
Rickard haven't you got any source of sulfuric acid?
I thought about something to do with the NH3, couldn't you leed the NH3 through some tubing from the oven straight into some water to get rid of the NH3?
Pu239 Stuchtiger
April 7th, 2002, 04:43 PM
Rickard, wouldn't it be Ca(HSO4)2 instead of CaHSO4?
rikkitikkitavi
April 7th, 2002, 05:08 PM
should be of course since calcium is 2+ and I think most people with some knowledge in chemistry understands it that :)
anyway, back to topic. DBSP:
absorbing the NH3 could probably be feasible, but even if 99% is absorbed that last 1 % is going to smell a LOT which has to be taken in account.
You really need to be careful, like I wrote I used a gas mask all the time.
Unfortunately I dont have access to a remote place anymore, so I have run out of HNO3 :( .
/rickard
DBSP
April 7th, 2002, 06:14 PM
I can say one thing for shure I'm getting myself some H2SO4 from a place I know of and I'll hold on to it tightly. When I can't get anything more there I'll start emtying old car batterys. Better than getting NH3 poisoned!! And I'm definately going to our neighbor cuntries.
About the absorbing thing, what if you had lets say 3 or 4 water containers linked together so that all NH3 would get absorbed. Then it could work. But thats a hell of alot work, I'd rather put that work into getting some H2SO4.
da man
May 17th, 2002, 09:36 PM
Sorry to bring up an old topic, but i have a question relating to distilling nitric acid.
Does anyone know the proper amounts for distilling nitric acid from sulphuric acid and ammonium nitrate? I searched everywhere but couldn't find anything, i could only find the quantities for doing it with KNO3 or NaNO3, but i'm sure it can be done with NH4NO3.
mongo blongo
May 17th, 2002, 11:15 PM
Yes it can!
Give a man a fish and he will feed his family for one day. Give him a net and he will fish for the rest of his life.(or until the net breaks or something). :)
I will give you the net:(stuff may be a bit wrong coz I'm pissed)
First get the equation you need.
XNO3+H2SO4--->HNO3+ XHSO4 (X being most popular- K, Na or NH4)
As you can see to make 1 molecule of HNO3 you need to react 1 mol of XNO3 with 1mol of H2SO4.
Now you need a periodic table to find the relative atomic masses of each compound.
For you
NH4NO3: N=14.01 H=1 O=16.00
So total RAM for NH4NO3 =14.01 +(1*4)+14.01+(16*3)= 80
for H2SO4: H=1 S=32.07 O=16
So RAM for H2SO4=(2*1)+32.07+(16*4)= 98.07
So now if you react 80g of NH4NO3 with 98g H2SO4 you will get:
HNO3-H=1 N=14 O=16
Total RAM for HNO3=63
Theoretical yield = 63g HNO3 + the other shit which you don't need :)
I don't know if I have made any mistakes coz I'm out of it. I will check it again tomorrow.
I hope you can make good use of this stuff so that you can work out amounts for other reactions. :) If you have any questions about this then just ask. :)
C-ya
<small>[ May 17, 2002, 10:18 PM: Message edited by: mongo blongo ]</small>
da man
May 18th, 2002, 02:26 AM
Mongo blongo, it seems you always drunk or stoned. :D
Thanks for the help, i'm purifying my ammonium nitrate now, and i'll be starting distillation tommorow!
mongo blongo
May 18th, 2002, 02:53 PM
Yea,I do like to get fucked up once in a while. :D
I think it all looks ok now (I'm sober now, but not for long :D )
Good luck.
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