Generating Oxygen Gas for the Production of Nitric Acid - Archive File

[megalomania]

Dhzugasvili
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Posts: 64
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Registered: APR 2001
posted 06-17-2001 04:59 PM
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I am using the process that I have read that works in the industrial method to produce Nitric Acid. I am bubbling NO2 through 70% nitric acid cooled to 5 degrees celcius. After a shitload of fumes were bubbled through, nitric acid became yellow, then dark yellow, then fucking really dark green and vigorously fuming NO2. From another of my posts I learned that this could be HNO2 instead of HNO3.
Well, down to the point. I also read in another post that by bubbling O2 through this weird nitric that I have now, I could obtain very highly concentrated nitric acid, again, at five degrees. I was just wondering how the hell to produce oxygen, pure oxygen other than by this method:

obtain 30% hydrogen peroxide and add chunks of manganese dioxide. Attach piping to erlhenmeyer flask and place tubing in solution to be oxygenated.

Any methods of generating OXYGEN other than this? Or otherwise generating pure nitric acid other than by vacuum distillation?





kingspaz
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Posts: 347
From: UK
Registered: SEP 2000
posted 06-17-2001 05:04 PM
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H2O2 and, liver, potato and yeast also work but a hell of alot better. also electrolysis of water producer oxygen (and hydrogen another useful gas )


Dhzugasvili
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Posts: 64
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Registered: APR 2001
posted 06-17-2001 05:25 PM
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Kingspaz, you mean H202 with yeast, potato, liver, etc? Sounds a little wierd, please clarify.


ALENGOSVIG1
Moderator
Posts: 766
From: Vancouver, Canada
Registered: NOV 2000
posted 06-17-2001 05:43 PM
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you could always just purchase a oxygen tank from a harware store. if that is not pure enough, try getting your hands on some medicinal oxygen. You'd most likely have to steal it out of the back of hospital supply truck. Tese are usually just pickup trucks with the tanks in the back. Medicinal oxygen is usually a green tank. Mabe if you worked in a home for the elderly you could steal one. Although i dont see whats wrong with the H2O2 + MnO2 method. just run the gas out of of the reaction vessel through water to clean it.
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Explosives Archive



CragHack
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Posts: 618
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Registered: DEC 2000
posted 06-17-2001 06:23 PM
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i don't know about yeast or liver, but potatos contain the enzyme catalase, this is a very efficient liberator of O2 in H2O2. I read online that it can produce 200,000 reactions per second. Human Blood also contains this enzyme.
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DarkAngel
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Posts: 592
From: ?
Registered: SEP 2000
posted 06-17-2001 06:44 PM
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Look at this site for some info about it:
http://www.chem.leeds.ac.uk/delights/texts/Demonstration_12.htm
I saw on a episode of David Letterman ones that someone blended some liver and than poured H2O2 to it,it started to foam for a long time something like this:

http://www.chem.leeds.ac.uk/delights/photos/H2O2_cat/thumb_3.jpg
http://www.chem.leeds.ac.uk/delights/photos/H2O2_cat/thumb_4.jpg
http://www.chem.leeds.ac.uk/delights/photos/H2O2_cat/thumb_5.jpg



For explosives and stuff go to Section1 http://www.section1.f2s.com And http://run.to/section1
sendtosection1@hotmail.com

[This message has been edited by DarkAngel (edited June 17, 2001).]



Anthony
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Posts: 2306
From: England
Registered: SEP 2000
posted 06-17-2001 07:03 PM
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I haven't used yeast for the catalase/H2O2 reaction but liver works about 10 times better than potato. Liver is really packed with catalase.


Dhzugasvili
Frequent Poster
Posts: 64
From:
Registered: APR 2001
posted 06-18-2001 01:40 PM
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Ok, Far out! I got the oxygen, bubbled it through my green shit acid with apparently alot of HNO2 and NO2 dissolved in it. After about 15 minutes or more of bubbling O2 in profuse quantities through it, it still remains the same fucking green color, and I seriously doubt that this is >95% nitric acid.
Lemme get to the real actual point about my topic, the burning, frustrating question I have... HAS ANYONE MANAGED TO MAKE CONCENTRATED RED FUCKING >95% NITRIC ACID WITHOUT A FUCKN' VACUUM PUMP?? IF SO, *PLEASE* TELL ME HOW THE HELL YOU DID IT AND I WILL LOOK AT YOU AS A GOD... please understand I am *very* frustrated that I haven't got this shit to work.

[vulture]

MnO2 as a solid is hard to administer at a constant rate without supervision. A separatory funnel or burette filled with a fairly diluted KMnO4 solution dripping it's contents into H2O2.

BTW, the oxygen needs to be administered to the NO2 before reacting it with water, because the 2 gases have very different solubilities in water.

Furthermore, simply bubbling NO2 into H2O will not yield much HNO2 as it is highly unstable in solution.

[Ziqquratu]

As a possible alternative to pure oxygen, all the oxidations I've ever done using oxygen as the oxidant (such as oxidation of metal complexes) have simply involved bubbling compressed air through the solution to be oxidised. I mean, the only things in air (in significant percentages) are nitrogen (inert), oxygen (what you're after) and carbon dioxide (not that much of it, really, and probably reasonably inert under the conditions). The oxygen doesnt need to dissolve too much - just enough to act as an oxidant, and you just keep bubbling so that as some oxygen is 'used up', some more is added.
It's certainly easier/cheaper than making or purchasing pure oxygen, and it should work in theory, so it's worth a try, wouldn't you say?

[vulture]

BTW, the oxygen needs to be administered to the NO2 before reacting it with water, because the 2 gases have very different solubilities in water.


Why do I need to requote myself?

Any HNO2 in solution will be fairly dissociated, so oxygen will not attack it to a noticeable extent.
Directly oxidizing the NO in solution isn't very useful either because you still need more oxygen to be added before you'll get HNO3.
And then ofcourse you all have different kinds of gasses in solution with different solubility and different partial pressures on the surface which makes it a mess equilibriumwise.

NO2 + H2O does not yield HNO3.

[yt2095]

as another possible alternative, and it is ONLY an idea, the EXact chemistry of which will require a little research on your part to get exact details.

I`ve had partial succes in making very dilute nitric acid, with the use of high voltage discharges.
a relatively simple peice of kit that can be made from things around your home, it`s called an Ozonator.
it consists of a jam jar with 2 pipes through the lid and 2 wires through the lid, the lid then being sealed with a glue gun so the wires and pipes done come out or leak gas.
the solid core wires on the inside of the jar are placed half way down and seperated by about an inch. and electical arc is passed between these two wire using the flyback transformer from an old portable TV.
a fish pump it attatched to one of the pipes so that air is passing through the arc and then out of the other tube as Ozone (O3) and various other NOx gasses, these gasses are then bubbled through a glass of water over night, the water will be quite acidic the next day.
it`s the same reason that large display Jacobs ladders are always enclosed in a polycarb or glass with the top left open, it`s not just for safety, but to provide the veiwers from inhaling large quantities of Ozone and brown NOx gasses.
well considering that even Flourine comes second to O3 as an oxidiser, perhaps that MAY be an alternative method for attatching your extra Oxygen?
if not, there`s nothing lost as it makes a great stain removing aparatus :)
i`m sure someone else may provide the correct chemistry for this writeup. but the theory seems sound enough, and it does make nitric acid albeit dilute.

all the best :)

[blindreeper]

yt2095, the chemistry has been pointed out http://www.roguesci.org/theforum/showthread.php?s=&threadid=1919 - a thread about making HNO3 from air using the electrical arc. It's funny how you just came up with the idea of using a flyback transformer from a tv, and I guote from that thread by Alchemist:

and I really do think a good vacuum and better arc (maybe a computer or TV flyback tranformer) would work much better.

It seems ironic that you came up with that idea...any one else get my gist?
Thats OT

Now down to the O3, there are some things worth trying and some things that will never be tried. As I don't think anyone wants to try distilling HF with a platinum rrtort in their home the same case with O3, it's not realistic. Although making NO2 with an arc is feasable and is effective if it is running right, as mega has worked it out to be somthing like 94c for 1L of 68% HNO3 which I would pay for any day. But I am not going to get into anything on this thread thats what the other one is for!

[yt2095]

blindreeper,

i REALLY don`t know what your issue is with me, but sort it out will you.
my email address is in my stats, as here is not the place to get arsey or debate personal issues.

if you`de have read my reply thouroughly you`de have seen that i mention that there are other places to obtain further information. i never mentioned that i invented this method!
and the point of interest was the O3, the NOx was just a bonus.

this thread is Oxygen rellated, with regards to Nitric acid.
i considered my post quite apt.
Yes Ozone can be quite nasty in large doses, but be sure, it is quite safe with correct precautions, and is not a contact poison that Flourine is! i fail to see your comparison.

i may add "does anyone get my gist" but that would be incitement :)

94c in a country where this readily obtainable is great, but for here and someone with the apropriate liscence, you may as well ask for horse feathers.
and it wasn`t presented as a feasable way to generate HNO3 but as a way to get Oxygen to react with his NOx radical

mail me, we`ll chat :)

[vulture]

well considering that even Flourine comes second to O3 as an oxidiser, perhaps that MAY be an alternative method for attatching your extra Oxygen?


Not true. Fluorine is a more powerful oxidizer than ozone, as reacting water with fluorine will yield ozone. Ozone does not react as violently with most materials either, PVC tubing can be used to transport it, IIRC.

The formation of O3 in your apparatus is only a sidereaction and not really necessary, as NO reacts spontaneously with O2 to give NO2.

BTW, reacting O3 with NH3 will directly yield HNO3, but this is a rather dangerous and impractical way. Should be a high yielding reaction though...:D

[yt2095]

Vulture,
yeah, i tried NH4OH 15% in the bottom of the jam jar as a test, the product stunk to high heaven of nitric!
the only change i noticed was the arc color was a little wider than with plain old air.
good stuff though :)
the copper electrodes became pitted as well and needed replacing after an over night session.
the water i bubbled this mix through crystalised on evaporation, i stongly suspect AN may have been a side product with a heavy NA doping.
O3 is more reactive on the pauling scale than Flourine IIRC, i`m almost positive of this (no pun intended) :)
if i can find the URL`s on the Ozone sires i looked at, i`m sure there`s about 3 or 4 different refernces worded to this effect, all different sites and beleive 2 of them were .gov sites (ok .gov is`nt alway beleivable to me either, with all the bullsh!t they come out with over simple things) but indeed you maybe 100% correct. if this thread is still going, and i have the time, i`ll try dig out these ref`s for you, and would welcome your opinion again.

and Vulture, never forget our new discovery... Cat Piss Chloride :)

all the best :)

[Marvin]

I'm interested to know how long the chopper transistor lasts, and the multiplier from the TV, unless these have been replaced.

Sparks dont produce much ozone at all though. Ozonators use silent electric discharges, usually high frequency between insulated plates.

I think absorbtion of oxygen by the solution will be very slow, and isnt being helped by the cooling. You want to speed the equilibrium conditions, not attempt to retard decomposition. I dont think this will be useful without pressureised oxygen left for long periods in sealed containers.

I dont like NO2 at all, and I think this method is impractical for high concentration nitric acid. Certainly for mid 90's without pressurised acid proof containers.

Distilling az acid twice from equal volumes of conc sulpuric is supposed to produce something like 95+% vacuum optional. This has been mentioned elsewhere.

As I understand it, adding MnO2 to the peroxide continually shouldnt be required as its action is supposed to be catalyctic. Last time I tried this, the oxygen died away very quickly, but I assumed this was because I was using 3% peroxide and it was simply exhausted.

[vulture]

According to Pauling:
electronegativity of oxygen: 3,5
electronegativity of fluorine: 4,0

If you react an oxidizer with a reducer, the weaker oxidizer will always be liberated.
Therefore, if reacting water with fluorine yields ozone, fluorine is a stronger oxidizer.
Fluorine also reacts with noble gases, which oxygen doesn't. With oxygen I mean oxygen in all it's forms, as the oxidation stage does not affect electronegativity.

Standard reduction potential for ozone: +2.076V
for fluorine: +2.87V

Convinced?

[densest]

a couple of comments:

the commercial synthesis of HNO3 is explained in some detail in the US EPA publications - google for them.

According to Merck, Cotton's "Inorganic Chemistry", etc.,
2 NO + O2 at STP -> NO2
NO2 + H2O -> HNO3 + NO (g)

According to something else that showed up on google, H2SO4 in (relatively) small proportions moves
the negative azeotrope equilibrium of HNO3 + H2O towards 100% HNO3
H2SO4 has a much higher affinity for H2O than HNO3

So, according to these authorities,
make NO by some means (say, electric discharge)
mix with air - NO2 should form (brown gas)
bubble through water
take gas remaining & mix with air again to form brown gas & recycle through water
take water mixture & distill to 70% HNO3
optionally, mix HN03 (70%) with H2SO4 (93+%) and redistill -> 95%+ HNO3

Details are available in the various references - please read them!
If you don't have the Merck Index and a few chemistry textbooks it would be a
very good thing to get them. A famous chemist once (reportedly) said:

A month in the laboratory can save as much as an hour in the library.

He's right ;-)

[yt2095]

Vulture,

yes, your quite right, my mistake.
i re-read the links again (after taking an hour to find them again) and i obviously misread them the 1`st time round several years ago.
sorry about that.
i supose to futher back your argument, it would be logical that if i was correct, then flourine in CFC`s wouldn`t break down our Ozone layer, and it clearly does.

Marvin, i use the "dafodil" cap that connects directly to the tube through a 10MOhm resitor to chassis. i`ve never had a problem with it so far. but your quite right, the yeilds for power used are quite low and not really worth bothering with except for experiments sake.
also your idea about high frequency silent discgarge, am i correct in thinking that would similar apparatus to an Air Ioniser?

[kingspaz]

'then flourine in CFC`s wouldn`t break down our Ozone layer, and it clearly does.' actually the CF bond doesn't usually break. its usually the catalytic effect of Cl* radicals produced by the homolytic fission of bonds due to light and UV hitting the CFC's in the upper atmosphere that is responsible for destroying ozone.

[yt2095]

i stand corrected again :)
it`s all good science tho, and hopefully of beneffit to others that MAY have thought as i did, thnx Kingspaz :)

[Marvin]

Silent electric discharge has been the accepted method for over a hundred years I think. Usually concentric glass tubes, with the inner surface of the inner tube, and the outer surface of the outer tube being coated with foil, or immersed in sulphuric acid. High frequency EHT at often around 20kv in modern systems but of old by an induction coil provides a silent discharge over the whole volume at low ion density.

This does ionise the gas without a spark breakdown, but a home ioniser is typically very different. Here they are just a 20 stage cockroft walton ladder with a few (very large) resistors on the end. The live mains input being the isolated side of the ladder. Produces a DC voltage of about 6kv below (I think for negative ions) ground and is sprayed into the air by sharp terminals. I dont see any part of this being useful for ozone and the power is far too low anyway.

I'm not sure if this is what you meant by 'similar aperatus to an air ioniser' so take this post as you find it.

NO gets liberated very readily when water is treated with NO2 but as the acid concentration rises this stops.

[Mendeleev]

The easiest way to get oxygen is to buy it at Home Depot or Lowes. They sell 40.1 gram, blow torch oxygen tanks for about $8.00. The tanks are used in the oxygen-Mapp gas blow torch (which burns like 2,800 degrees Celsius!), which they sell for $50 (it comes with both tanks). All of the gas blow torches sold at hardware stores are made by a company called bernzomatic, and they are located in the tools section. To release oxygen you need a valve. I would get the "jumbo torch valve" because it is the simplest one, it's just a short nozzle. Screw it on, turn the clamp and you've got about 6-8 minutes of oxygen at max flow, which should be enough for your purposes.


:D

[Mendeleev]

The oxygen-Mapp gas torch they sell has both oxygen and Mapp gas valves, so that is a good bet, plus you will have a very hot torch, I use it to ignite thermite :D.

[Dhzugasvili]

Well, evolution in this field has now taken me to higher places:cool:...long ago I managed the synthesis of density 1.52 nitric acid using simple distillation of 75% Nitric with H2SO4 (98%). Also I succeeded with metal nitrates and H2SO4 simple distillations. My product was sufficient and produced many HE's such as HMX and RDX, and others requiring high conc nitric. The HE's were produced with decent yields. I stopped making anything for about a year, but now im back in business. Now I want to set up a vacuum distillation (some of the diagrams in another Nitric Acid thread for building an aspirator are helpful) and carry out distillation of H2SO4 and Nitric (75%) in order to get white nitic acid for fabrication of PETN and other explos. BTW, how do you guys think that my red fuming nitric might have affected my HE prod in the past? What exactly does presence of NOx fumes in nitric do to an rdx reaction? I did treat it with urea but it didn't seem to do much help of ridding the acid of NOx. Im assuming white nitric acid as pure as you can get it can result in larger yields and a purer product, a safer reaction, w/out too much risk of runaway.......any thoughts?

[megalomania]

I am reviving this old thread because I caught a tidbit here about the reaction between ozone and ammonia. I did an Internet search and all I could find was mention of the reaction yielding ammonium nitrite. Does anyone happen to have any specifics about this reaction like what are the conditions? Nitrite salts are pretty valuable in their own right, and if all it takes is an ozone generator in an ammonia atmosphere this could be a useful reaction.

[megalomania]

I am reviving this old thread because I caught a tidbit here about the reaction between ozone and ammonia. I did an Internet search and all I could find was mention of the reaction yielding ammonium nitrite. Does anyone happen to have any specifics about this reaction like what are the conditions? Nitrite salts are pretty valuable in their own right, and if all it takes is an ozone generator in an ammonia atmosphere this could be a useful reaction.

[DONMAN]

Would it work to bubble H2 through a solution of nitric salt to get nitric acid?

[Alexires]

No, it wouldn't work Donovan.

1. You would need to have a nitric salt that was less stable than Nitric Acid and

2. H2 is relatively stable. For it to even begin to work you would need a reaction vessel capable of many atmosphere and high temperatures, as well as some kind of catalyst that is capable of storing the H2 as monatomic hydrogen.

Or thats how I think it works.

See, the only reason that H2SO4 and a metal nitrate works (with distillation) to make nitric is because sulphuric acid is a stronger acid than nitric, hence the equilibrium favours the nitric acid side of the equation.

The only thing you will get from bubbling H2 through a solution of a nitric salt would be an explosion hazard.

[DONMAN]

Thanks for the help, I am just learning chemistry. All help is appreciated greatly. Does any one have any good recommendations for chem that are intermediate references?

[rayman]

I am reviving this old thread because I caught a tidbit here about the reaction between ozone and ammonia.
I seen that as well, Did you find any more information on that mega ?

[FUTI]

Ammonium nitrite? Isn't that so labile under that condition that should decompose to N2 and H2O? Interesting anyway...

[10fingers]

Perhaps someone already mentioned it but why not make O2 by electrolysis of water? I would think that's the easiest and cheapest method.

[sbovisjb1]

Why dont you get one of those suba diving tanks? Or paintball tanks. Take it to a suba diving shop and you can get it filled up. Say you are going deep sea diving. But tell them to fill it up with pure oxygen and to leave out all the other gasses (nitrogen).

[festergrump]

You could get it filled at a scuba shop, but they'll probably not give you anything but the regular mix. They wouldn't want to be responsible for you getting high deep beneath the surface of the water from the tank they filled for you. It's a liability issue should something tragic happen.

Chances are they dispense it from a premixed bulk tank and couldn't help you out, anyway...

[sbovisjb1]

Festergump if you go past (I think) 50feet, oxygen becomes poisionous, so they add a mixture of pure oxygen and other gasses. It wont just be taken out of the air then.

[Dawg]

I haven't seen anyone mention the use of medical oxygen concentrators here. They are capable of producing ~ 90-95% pure O2 at 1-5 LPM. On Lab-X they just offered a palletload of 'em [used] for a $295 opening bid [min of 6/pallet]-there were no takers. I emailed the seller asking if they'd sell 2 of 'em and yesterday received them via UPS. I really only need one...


http://www.labx.com/v2/adsearch/detail3.cfm?adnumb=314398
http://www.portableoxygen.org/july.html

[Al Sheik Yerbuti]

Or paintball tanks. (nitrogen).

I'm pretty sure those are CO2, since CO2 can be kept liquid at ambient temperatures; thus significant volumes of safe propellant can be stored in those little tanks. :)

I'm thinking that everyone's best bet if you can afford it is to get an oxy-acetylene setup from your local welding supply. Besides, learning to use one of those torches is a great skill for us experimental types. Oh, and the acetylene can be used instead of calcium carbide when making (silver) double salts.

[nbk2000]

The gases used for pressurizing paintball guns are (in order of commonality) CO2, compressed air, and high-pressure Nitrogen.

[chembio]

You could try heating potassium permanganate crystals. It usually provides a source of oxygen gas. Just use a delivery tube to channel the O2 from the heated KMnO4 into whatever solution you need to.

[Nitric-producer]

The post above about obtaining fuming Nitric from the reaction between Ozone and Ammonia interested me. However is it right? My google search only indicated that it formed Ammonium Nitrate? However like so many things these days the information on the net is censored. Can anyone back this up from a textbook or the like?

[hydra]

Yes, that O3/NH3 route to nitric caught my eye too. Would very much like to see more info on this one.

By the way, the ozone-generators work by what's known as "Corona effect".

Any surface charged to a high enough voltage -gradient- will ionize the atoms surrounding it. Note the emphasis on GRADIENT...which is the variation in field strength =per unit distance=. I.e., so many megavolts per meter....or kilovolts per centimeter....or volts per micron.

Very high gradients are most often achieved via sharp points and surfaces. The point of a needle gets VERY small right at the tip...so even with relatively low voltages (e.g. 2-3kv) the 'gradient' becomes enormous.

By using a 'field' of such points; and a nice high voltage like 10-25kv (bw monitor to color-TV flyback output levels), you can get a pretty good production volume of ozone.

The same effect can also be gotten from bare wires of very small diameter. The very tight curvature of such a small radius produces a large gradient.

If you scrap out any old copiers, you'll find 1-3 of these "corona wires", almost always in pull-out mountings (since they attract dust/dirt, they need to be cleaned regularly).


This corona process is interesting for other ions too, for that matter. The technique has potential application in enhancing (or allowing in the first place) various chem reactions...via making the reactants more 'energetic', and producing various radicals via ionization.

[Alexires]

For those talking about the Corona effect, is this (http://jnaudin.free.fr/html/s_gdp1.htm) it?

Mega, might I suggest amalgamating this thread along with the "Nitric Acid from Air and Water" as well as the "A new take on HNO3 production"?

If hydra and the others are, in fact talking about glow discharge, then it shows that if these three threads were amalgamated, it wouldn't have been missed.

[hydra]

Alexires; just to be clear, my own plans involve low voltage, high current, arc plasmas; rather than high voltage, low current glow-discharge.

Either type of plasma can dissociate molecules and ionize atoms; but I believe there are a number of advantages (in this application) to using the LV/HC arc plasma; so that's what I'm focusing on.


As far as merging threads goes....I'm just a greenhorn here, so my take doesn't carry any weight; but I'd much rather see Oxygen Production as its own thread; not even related to HNO3 specifically. O2 is useful in many other processes as well.

The other hno3-via-plasma threads might be amalgamated into one....but the arc-method and glow-method are rather distinct. The equipment -surrounding- either method (e.g. weak acid recirculation etc) is probably quite similar tho.