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aga
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Falsch.
People with a bit of Common Sense can enjoy (!) a bungee jump, but they check the Fall distance, extensibility and length of the bungee and their own
weight before leaping off a bridge, hurtling towards the ground.
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Zombie
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Yet brilliant people will figure a way out of the dilemma before hitting the ground.
Who do you think had more fun?
Sorry... wrong thread.
They tried to have me "put to sleep" so I came back to return the favor.
Zom.
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WGTR
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Just for fun, I tried something different. No pictures or videos this time; I was just doing a quick test to see what would happen with a certain
procedure.
As derived from this reference, I tried electrolysing ammonia to see if it would oxidise at the anode. A nickel cathode and platinum anode were used for the test.
The electrolysis cell was simply two 25mL beakers connected via a glass salt bridge. This configuration provided a separate anode and cathode
compartment. 1g of NaOH was added to each beaker in 30mL of DI water. A few 10's of mg of CuSO4 was dissolved in 3.5mL of 30% ammonia,
and the deep blue solution was added to the anode compartment. The electrodes were inserted, and electrolysis was maintained at 100mA for
approximately 3 hours. Cell voltage was high, around 30V, due to the resistance caused by the salt bridge. No gasses were collected, but it appeared
that the production of cathode gasses was very much greater than that of the anode gasses.
The cell was left in operation overnight, but the anolyte level dipped below the anode, breaking the connection. I estimate that the cell operated
for a few hours. In the morning, the previously deep blue anolyte was clear, and the copper was precipitated as a black film at the bottom of the
anode compartment. The nickel cathode was still bright and clean, with no obvious contamination. The pH was not measured in this test.
The anolyte was poured into an evaporation tray, and gently evaporated down on a hot plate. The resulting moist slush was added to a 20mL test tube,
rinsed to the bottom with a small amount of DI water, and acidified with 98% H2SO4. The initial drop or two of acid caused a
violent release of gasses, almost ejecting material from the tube. Further drops had little comparative effect. There was no noticeable color to the
gasses.
Phosphorous-de-oxidized copper was filed into a fine powder, and a small amount was added to the test tube solution. Gentle heating was applied with
a propane torch. The copper powder immediately began reacting, producing copious amounts of gas. Further heating was not necessary. The solution
began turning blue, and significant amounts of brown gas filled the test tube. Strong bubbling continued for about 10 minutes.
It appears that nitrate was produced by the electrolytic oxidation of ammonia. A strong positive result for nitrates was given by the copper turning
test. A nickel cathode was used due to its low over-potential for hydrogen production. A bright platinum anode was used in order to duplicate the
original experiment. Also, it has a high over-potential for oxygen production, and is dimensionally stable under the cell conditions. It is possible
that a different material, such as steel, could be used. This may be verified at a later time.
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j_sum1
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Wow! Cool result.
I like this approach. Worth investigating further.
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NWS
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So I stumbled on this thread while looking for a way to make nitric acid after having used up all my OTC nitrates, and I have to say it's very
impressive. Concerning the electrolysis, I actually happen to have some information that may or may not be helpful. The 8th edition of quantitative
chemical analysis give the following reactions and E not values in volts.
HN3 +3H+ 2e- <--> N2 + NH4+ at 2.079 V (Avoid the reverse reaction at all costs!)
N2O(g)+ 2H+ + 2e- <-->N2(g) +h2O at 1.769 V
(laughing gas from nitrogen and water)
2NO(g) + 2H+ + 2e- <--> N2O+ H2O at 1.587 V
(reverse this and make NO from laughing gas?)
NO+ + e- <--> NO(g) at 1.46
(if someone finds a use for this then good for them)
HNO2 + H+ e- <--> NO(g) + H2O at 0.984 V
(same here)
NO3- + 4H+ + 3e- <--> NO(g)+ H2O at .955 V
(more or less useless because it'd probably be easier to oxidise NO to NO2)
NO3- + 3H+ +2e- <--> HNO2 + H2O at .940 V
(same here)
NO3- + 2H+ +e- <--> 1/2 N2O4 +H2O .798 V
(so avoid this because you'll just waste your precious nitrate)
N2+ 8H+ +6e- <--> 2NH4+ at 0.274 V
(a good way to get rid of ammonium if you need to)
N2+ 5H+ +4e- <--> N2H5+ at -0.214
(I don't like the looks of N2H5+)
3/2N2 + H+ + e- HN3 at -3.334
(avoid this one like the plague
and then for water
H2O + e- <--> 1/2H2 + OH- at -0.828 V
1/2O2 + 2H+ + 2e- <--> H2O at 1.229 V
It says nothing about ammonia/um to nitrate, but It might still be possible.
[Edited on 12-6-2015 by NWS]
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blogfast25
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Of course it's possible, see e.g. nitrogen fixation:
https://en.wikipedia.org/wiki/Nitrogen_fixation
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etoxiran
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Hmmm, you said no Pt allowed. But remember that almost every car in EU/USA/Australia produced after 2007 must have DPF/FAP filter. Main principle of
it's work was oxidizing soot to carbon dioxide, by NOx produced from exhaust gases over Pt catalyst.
High Pt load catalyst to be precise.
Cost of this part is about 50-250 euro, if you don't want disassemble your own vehicle, why not buy this part from ebay or local muffler shop?
It works (I don't have to use ideas like that because in my country I can buy HNO3 55% as cheap as 1 euro/dm3), but here you have ready to use
apparatus (need only reconfigure a bit and add heating unit).
Virtually can be running using only heat & air. Adding to air inlet additional oxygen (welding store), will make more NOx.
http://www.ecovehicletuning.co.uk/images/dpf-overview.jpg
Before i forget - catalytic converter is unsuitable - because can consist rhodium particle which are reducing NOx to N2 & O2.
[Edited on 13-6-2015 by etoxiran]
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NWS
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http://digipac.ca/chemical/mtom/contents/chapter3/fritzhaber... Is this too good to be true? modify this so the copper is partially submerged in the ammonia, vaporizing more and preventing the copper from
melting, Oxidize the NO to NO2, then store in silica or bubble though water?
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gatosgr
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What kind of apparratus do you need for this?
[Edited on 13-6-2015 by gatosgr]
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NWS
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I'd imagine one could redneck it pretty easy, suspend the copper wire over a 250 ml flask, use a stopper with a hole and then either some tubing to
bubble your hot gas mix through water or perhaps run it though a condenser
edit- Household ammonia doesn't work, I'm going to try and prepare something a bit stronger by nutralizing some of the ammonia into ammonium chloride,
drying, adding back to "regular" ammonia, adding a little NaOH and then distilling ammonia off the mix.
[Edited on 13-6-2015 by NWS]
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gatosgr
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You need 33% ammonia for this reaction. Nitric acid destroys rubber doesnt it?
[Edited on 13-6-2015 by gatosgr]
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NWS
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It does, however HDPE is fairly resistant to it, plus the extra ammonia fumes will probably offer some small protection.
Edit- where did you find that you needed 33%?
[Edited on 13-6-2015 by NWS]
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blogfast25
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Too vague. Many, even affordable elastomers resist nitric acid very well. Ethylene propylene copolymers (EPR, also EPDM) for instance are comparable
to (HD or LD)PE in their resistance to nitric acid. Peroxide-cured EPR is very resistant to it, even concentrated NA.
Hydrogenated nitrile rubber and hydrogenated SBS (SEBS) thermoplastic copolymer elastomers also exhibit good resistance to NA.
Make that 'very', instead of 'fairly'. 75 w% HNO3 (and higher) is routinely packaged in HDPE containers. The one I buy is. There's nothing in NA that
can oxidise the paraffinic structure of PE.
[Edited on 13-6-2015 by blogfast25]
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gatosgr
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From youtube search for the ostwald reaction.
[Edited on 13-6-2015 by gatosgr]
If anyone wants to participate you can make nitrogen by:
Nitrogen may be prepared from air by passing the air through a solution of caustic soda to remove carbon dioxide.
2 NaOH + CO2 ==> Na2CO3 + H2O
Then the gas stream is passed over heated copper turnings which removes the oxygen.
Cu + O2 ==> 2 CuO
Although I don't know what other steps you can take for making HNO3
[Edited on 13-6-2015 by gatosgr]
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NWS
Harmless
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Wait, when did we go from ammonia to nitrogen? What is the nitrogen being used for?
also I stand corrected on the rubber and HDPE.
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gatosgr
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nitrogen and a kite for high voltage
http://link.springer.com/article/10.1007%2FBF00764903#page-1
to make ammonia since you can't buy it can you? or other nitrates e.t.c.
here dont ask again:
https://www.youtube.com/watch?v=CnhAnhK7U18
[Edited on 13-6-2015 by gatosgr]
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NWS
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So it looks like we're back to electricity/ distilling urine XD
and gotcha
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j_sum1
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******************************************************************
Interesting that this thread is resurrected and gaining some new interest. It would be beneficial to newcomers to read it through. There is much
discussion that has gone on in the preceding pages. A huge number of ideas have been thrashed out. Some still hold potential and some have been
rejected. Here is a bit of a summary.
******************************************************************
1. As far as I know, the competition is still open. Better check with aga though.
2. Even for those who live in places where nitric acid and nitrates are difficult to procure, the simplest and cheapest method is still to purchase it
somehow. Nothing posted in this threat has threatened that position.
3. I am not aware of anyone actively working on the project currently. I believe that there are a few shelved projects that have not been given up
on.
4. To my knowledge there are two half completed projects that hold some potential:
(a) my own project based on the burning of plant proteins (lentils) to produce NOx which can then be absorbed by water to produce a very dilute acid
that can be boiled down. I have redesigned my furnace and flue and am confident of getting something but expect yields to be very low and for it to
be very time and energy consuming. My aim is scrap heap/ third world technology with zero dollars on consumables. But I have added copper +
manganese catalyst.
(b) WGTR's variation of the Birkeland-Eyde process. He has built some impressive equipment but is yet to sort out the air flow. I expect yields
again to be low. His is a lot more sophisticated than mine.
5. Other options
(a) the Ostwald process (ammonia + oxygen --> nitric acid) and variations thereof have to be rejected as outside the scope of the competition. The
necessity for (i) high pressure, (ii) high temperature (iii) a platinum-rhodium catalyst and (iv) refeeding 95% of the product stream back through the
process to lift yield above marginal values all combine to this being a highly technical approach. And that is before you consider the ammonia source
material. (Of course if you can design a suitcase sized "black box" that you can feed ammonia in and get a trickle of nitric acid out, you will
generate some interest and probably some sales.)
(b) The French method for producing nitrates and variations of that method are problematic due to the fact that these are (i) long-term projects (ii)
requiring large volumes of material to be workable, (iii) taking up considerable space (ie, not an urban back yard), and (iv) having considerable
smell. To my knowledge no one is currently working on this although If they had started back when the competition started they would well and truly
have the jump on everyone else by now.
(c) Other novel ideas have been presented including using urea as feedstock, but no viable routes have been devised.
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NWS
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Well what I've been spit balling for a few days now is a modified otswald processes with copper as a catalyst, the only thing holding me back from
actually trying is the need to make .880 ammonia, and yea, I've read pretty thoroughly looking for the magic bullet to make some nitric acid XD
edit- it may or may not end up that it simply makes ammonium nitrate, but I'd still be happy as can be if I got that far
[Edited on 14-6-2015 by NWS]
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WGTR
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I was thinking about this project yesterday. I haven't given up on it, but the realitites of life are such that I've had to focus on other things
lately. The basic design was working, although there are still a few bugs to work out of it. Ironically, one thing that has slowed me down is that
I've tried to make this a very simple design. I'm going to readjust my design a bit, and it may end up becoming more sophisticated than most people
would like. I think this is necessary just in the interest of me actually finishing the project. We can always simplify things later.
I don't recall an announcement from aga stating that he had run out of beer, so I assume the competition is still going. I took myself out of the
running for the prize, so I'm just doing this for the challenge.
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deltaH
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To expand on the electrolysis idea, earlier in the thread, I've mentioned a thesis that demonstrates that manganese dioxide is a functional low-cost
ammonia oxidation catalyst. Fortuitously, MnO2 can also be used to make cheap amateur-friendly anodes (albeit not very durable) since it is an
electrically conductive oxide. So...
BTW when run under basic conditions, you need added electrolyte (e.g. NaOH/KOH) because the ammonia does not ionise enough for good electrical
conductivity, so sodium/potassium nitrate would be the product generated if successful
EDIT: Nurdrage's method for making MnO2 anodes:
https://www.youtube.com/watch?v=nvMVlhBmv7M
[Edited on 19-6-2015 by deltaH]
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deltaH
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I've just remembered an odd experiment I've done many years ago. I've dissolved some melamine (the chemical, not the plastic) in water (can't dissolve
much, but slurry works), then slowly added spatula full amounts of calcium hypochlorite (as pool dry chlorine granules) with mixing and waiting for
the hypochlorite to react between additions . The solution initially turned yellow, then on further addition turns a very beautiful intense cherry
red, then if you continue even more additions, VIOLENTLY oxidises to generate copious amounts of a noxious NO2 smelling gas and turns clear again.
This experiment is maybe worth a revisit in light of this challenge as I think this may have been oxidising fully to make CO2 and NOx or nitrates.
Feel free to do so, I cannot do it in my current circumstances. Perhaps melamine can be substituted for another readily available nitrogen source?
Since melamine is made from urea, urea might work as well. Although I don't suspect urea would form the beautifully coloured intermediates that
melamine did. Be warned that this can potentially generate toxic and dangerous compounds besides the nitrogen oxides.
Urea granules + pool chlorine granules + a little water + induction period = CO2 + NO2 + crud + woosh?!
sounds a little too good to be true and dangerous
Ok, since this is a science forum, I had probably write that equation a little better (hope it's balanced):
2(NH2)2CO(s) + 7Ca(OCl)2(s) => 4NO2(g) + 2CO2(g) + 4H2O(g) + 7CaCl2(s) + heat
Bear in mind though that pool chlorine granules are only sixty something percent hypochlorite, 68% AFAIK?
Due to the potential violence of the reaction, I'd say passing the gasses directly through crushed ice is the best way to condense it as I think it
would be evolved so rapidly that ordinary water-cooled condensers wouldn't cope with the required heat transfer rate. Also, be warned, this might
explode (or do nothing or do nothing, then explode!).
Much of the carbon dioxide generated may well form calcium carbonate as commercial calcium hypochlorites probably contain significant amounts of lime
AFAIK? Anyhow, goodness only knows what will really go on in this soup of a reaction (if anything).
[Edited on 20-6-2015 by deltaH]
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aga
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Nice one deltaH.
Great to see that i'ts not only me that posts when drunk
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deltaH
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I'm hoping someone with urea can confirm if calcium hypochlorite is capable of oxidising it like I observed with melamine.
If that could work, it's game over for nitric acid production, well almost
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j_sum1
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deltaH, you always come up with good ideas. And it is good to see you back around here.
I have both urea and calcium hypochlorite in large quantities. As I recall, my Ca(OCl)2 is 100% which might be a bonus. I might just get some time
to experiment in a week's time. I will grind up a 10g batch according to the stoichiometry you stated (after checking it first) and see what happens.
I rather suspect it will be a dud. But that is based on the notion that, if it was that easy, someone would have stumbled on this idea before.
Still, that it what experimentation is for.
I will report back when done.
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