Sciencemadness Discussion Board - Druken Aga Challenge (DAC) #3 - Closed (but open to discussion)

I am genuinely surprised to find that the submissions are so... um... nonexistant. There have been a large number of good ideas floated. None without certain difficulties, but that is the nature of the competition.

I wouldn't write off ol' WGTR just yet, haha! I've been slaving away, trying different configurations of this and that, probably spending way too much time working on this. One wouldn't believe how much effort it takes to make something simple and easily duplicable by the masses. If the goal was to find the most complex solution, I could have done that easily. In the end, a compromise will have to be reached. An easy design will be an expensive one. An inexpensive design will require more skill from the constructor. I'm not sure that both "cheap" and "easy" are possible at the same time, especially since both terms are relative to a person's resources and skill. The current design is reaching a point of sufficient compromise, I think.

I am going to school and working full time, so that has slowed me down quite a bit.

WGTR - 25-1-2015 at 09:01

I think that j_sum1's setup is quite clever. The first thing I noticed was how well his collection of random junk bits fit together. It might sound like I'm joking, but I'm really not.

aga - 26-1-2015 at 02:06

Woohoo !

I knew somebody would come up with something.

"The Winner will be the one who posts the Best overall solution"

Unless i'm mistaken j_sum1, yours is the Only solution, making you the Winner !

Does anybody disagree ?

plante1999 - 26-1-2015 at 03:59

I'd like to point the fact that even if his setup is remarkably well built for rubbish, there is NO WAY on earth it could be used to make any yield whatsoever by burning beans and peanuts.

Just my two cent

[Edited on 26-1-2015 by plante1999]

Fantasma4500 - 26-1-2015 at 11:00

browsing some older threads about today i got to the idea of reacting urea with ozone, cant say if this would work at all, but it would generate 2 moles NO3 per mole urea and one mole CO2 -- IF it could be done, im not a total wizard when it comes to figuring out whether reactions could take place

420MLGnOhEADsCOPEpro - 26-1-2015 at 12:58

i think j_sum1's method could work better if a microwave were used to heat the material while it's burning

Loptr - 26-1-2015 at 13:23

Must I remind you of the objective.

Objective: Make at least 100ml of 30w% Nitric Acid in the easiest and cheapest way possible.

This isn't over until someone has produced 100ml of 30% w/w of Nitric Acid.

I have a few papers describing the production of dichloramine as the dominant product in solution (never been isolated before), which can then be oxidized to various products, including nitrogen gas (N2), nitrates (NO3), nitrous oxide (N2O), nitric oxide (NO), and others not mentioned.

This is an existing problem within water purification plants where they have to remove the nitrates being formed (albeit biologically), but it is an oxidative process, so it should be able to be done synthetically.

I have also been reading into acid rain, of which, HNO3 is a constituent, so I am learning more about that process and to see if it can be scaled up.

[Edited on 26-1-2015 by Loptr]

aga - 26-1-2015 at 14:08

Well, i did say that i'd take the opinions of others into account ...

j_sum1 is the only entry though, so that kind of narrows it down a bit.

j_sum1 - 26-1-2015 at 15:10

I close my eyes for a bit and wake up in the midst of a controversy. I must admit to being somewhat flattered.

Quote: Originally posted by deltaH

I think you may have gotten tantalisingly close!

Quote: Originally posted by plante1999

there is NO WAY on earth it could be used to make any yield whatsoever by burning beans and peanuts.

The truth is undoubtedly somewhere between these two sentiments.

I never considered myself a serious contender here but thought it worth a shot. And the only reason I posted anything (after what I thought was a failure) is because I thought the challenge worthwhile in and of itself. It seemed silly to put the effort in and not show my findings to give others a leg up.

And plante1999, you are very correct on this. It all comes down to yield – whatever method is employed. All routes were going to be a struggle – whether one is burning beans, making sparks in the air, babysitting a pile of faeces or attempting to react urea with oxygen (with whatever pressure could be attained and without a Pt catalyst). I note that even commercially, this last method has ridiculously low yield and most of the feed has to be diverted back into the system again.

With my embryonic lab I knew that the 100mL 30% was likely out of reach. Hence work on a proof of concept. If HNO3 acid rain occurs naturally then at least my concept was feasible.

Thanks all for the comments on my junk assembly. I was pleasantly surprised at how well it all fitted together. What you can't tell from the photos is the thing seals quite well. I am going to keep the spray chamber for – something anyway. Maybe SO2 capture.
The efficiency of my junk assembly was really a shortcoming though. I overlooked a simpler solution that would have accommodated the gas flow much more easily. If this thread remains open or a new one spawns from it then I will post my idea. I am not done with this concept even if the deadline is passed.

Quote: Originally posted by Loptr

Must I remind you of the objective.
Objective: Make at least 100ml of 30w% Nitric Acid in the easiest and cheapest way possible.
This isn't over until someone has produced 100ml of 30% w/w of Nitric Acid.

Actually, I thought this was over on 24 January.

So, in terms of the comp, it really comes down to how rigorously aga defines "best solution" and "24 Jan". And that would be up to him. I am intrigued by the late ideas and hints at late submissions.
In terms of the challenge of making HNO3, I have learned a lot through reading this thread and researching ideas. (French method? Who knew?) There are still unexplored avenues here and I feel the challenge is an excellent one on its own merits.

So, back to you aga. It's been fun.

aga - 26-1-2015 at 16:03

From page 1 :-

"If January is too short a time, then there need be no Closing date.

If there are No entries before January, the challenge will stay open until the beer runs out, which doesn't look like anytime soon."

There is still Beer here, despite my best efforts, and j_sum1 seems to be onto something interesting, so we keep it going !

Edit:

Technically nobody Won per se, however j_sum1's approach is wonderful, and deserves at least some banana.

P.M me your paypal address please.

[Edited on 27-1-2015 by aga]

j_sum1 - 26-1-2015 at 17:03

Game on. Let's see what else comes up. I unfortunately won't be able to play for maybe three weeks. I am going to mull on my modifications for a while and see what transpires.

aga. PM coming your way.

Zombie - 26-1-2015 at 20:13

You guys are one giant bunch of goof balls. I say this with love in my heart, and a smile on my face.
This thread is wonderful, and Mr. Aga... I commend you on your humanity.

Mr. J.sum1... Fantastic! Burning beans. Who would have thunk it. I'm gonna have a look around the house to see what I can spark up.

Edit:
In looking around I did find some common Wallgreens ingredients to produce Nitric acid using simple gas generators or more complex distillation equipment. They are really nothing more than pour, and play. Too bad they don't fit the rule set. (Ice Pack/Hydrogen Peroxide/a few old pennies, and some hardware store battery acid) Easier than fermented pee for sure. :cool:

[Edited on 27-1-2015 by Zombie]

WGTR - 28-1-2015 at 18:40

To stave off the SM community's stomach pangs of unfulfilled expectations, I humbly present a preview of Project Dead Woodchuck. It's a work in progress, but hopefully it will prove to be more useful than its namesake.

Attachment: Rotating_Arc.avi (4.8MB)
This file has been downloaded 1185 times

The electrodes are water-cooled by means of a miniature submersible pump. The electrodes may look complicated, but they were made out of water pipe, tubing, copper wire, solder, and bits of copper sheet. One drill press offered its services, but otherwise only hand tools were used.

To fit the spirit of the competition, the power supply delivers 150V at 3A to the reactor, in series with a 30 ohm resistor. This type of power would be available by rectifying mains voltage. I noted that there is a pretty strong smell of ozone in the fume hood, but I haven't taken a sample yet to look for brown gas.

The arc rotates, but not as fast as I want it to. Note how far away the magnet is from the arc. As I bring it closer, the arc gets drawn to the center of the ring magnet, where it rotates so fast as to be a solid ring of light. This rapid rotation is desirable, as it greatly improves electrode life. With the current configuration, though, the magnetic field quickly blows out the arc when it is brought this close. The arc voltage needs to be higher, or the reactor geometry needs to change.

When the arc doesn't rotate fast enough, small travelling hot spots can develop on the electrodes. These are visible as bright strands of light present in the overall luminous arc. As the arc concentrates at various points on the electrode, it mildly etches the surface, actually making the problem worse. The arc gets noisier, and rotation begins to slow down. The arc keeps going, though. The video was recorded from a 30 minute long test.

Before starting the reactor, I do polish both electrodes and gap them carefully. With this kind of treatment the arc rotates smoothly through the air gap, delivering a solid luminous ring. Looking through welding lenses, the air gap glows bright orange, with slight tinges of green around the cathode.

Within a few minutes, however, very small hot spots begin developing around the imperfections on the electrodes. Arc rotation slows down, as the arc tends to linger in these areas a bit longer. Although the air gap still glows, there is more green coloration present. The electrodes themselves are not overheating, though. The water keeps them cool.

Anyway, I'll probably be working on this for quite a while. If anyone else wants to try their hand at it, feel free to jump in. I'm not doing this to actually win anything; that's why I don't mind sharing it.

j_sum1 - 28-1-2015 at 19:22

Ok. Colour me impressed.

plante1999 - 28-1-2015 at 22:43

To stave off the SM community's stomach pangs of unfulfilled expectations, I humbly present a preview of Project Dead Woodchuck. It's a work in progress, but hopefully it will prove to be more useful than its namesake.

Now, THATS something that has serious potential..

Good luck!

CuReUS - 28-1-2015 at 23:29

Quote: Originally posted by plante1999

Now, THATS something that has serious potential..

Good luck!

are you kidding ? that's freakin awesome ,tooooo goood
and WGTR says he is in school lol
I think he deserves the prize for just making a thing like that

also,for the burning beans idea ,instead of burning beans, could you mix melamine with some oxidising agent(bleach,permanganate ? ) and then burn that ?
http://en.wikipedia.org/wiki/Melamine

Zombie - 28-1-2015 at 23:33

Really guys. I get the outside the box thinking but how does any of this make it easy for joe blow to make nitric acid at home. I thought that was the point?

I posted 2-3 posts up that I found the stuff right in the house, and every corner store on the planet has the same stuff.

This is turning into a Rube Goldberg competition... It seems contrary to the original intent. BUT it's your game.

j_sum1 - 28-1-2015 at 23:59

I think the point is that some items are not available at every corner store. There are many places whee nitrates are restricted. Sulfuric acid is almost impossible to find otc where I live. And there are historically numerous novel routes to nitric acid.
Therefore to have a highly accessible method for nitric acid is a good idea. Something that is not dependent on certain supplies is also a good idea. I am not really expecting an armageddon or totalitarian state situation personally but the chemistry implications of such a situation are an interesting exploration.

plante1999 - 29-1-2015 at 00:55

Quote: Originally posted by CuReUS

Quote: Originally posted by plante1999

Now, THATS something that has serious potential..

Good luck!

are you kidding ?

I was not being sarcastic.

[Edited on 29-1-2015 by plante1999]

aga - 29-1-2015 at 01:10

a preview of Project Dead Woodchuck

That is totally AWESOME !

Brilliant work WGTR.

Truly Brilliant.

U2U please.

Zombie - 29-1-2015 at 15:17

I think the point is that some items are not available at every corner store. There are many places whee nitrates are restricted. Sulfuric acid is almost impossible to find otc where I live. And there are historically numerous novel routes to nitric acid.
Therefore to have a highly accessible method for nitric acid is a good idea. Something that is not dependent on certain supplies is also a good idea. I am not really expecting an armageddon or totalitarian state situation personally but the chemistry implications of such a situation are an interesting exploration.

Cold packs, hydrogen peroxide, copper and battery acid? Hard to find?

"An instant cold pack is a device that consists of two bags; one containing water, inside a bag containing ammonium nitrate, calcium ammonium nitrate or urea."

The reactions can be done in peanut butter jars. No offense meant gentlemen. Sorry if I distracted anyone.

Just sayin'

[Edited on 29-1-2015 by Zombie]

[Edited on 29-1-2015 by Zombie]

morganbw - 29-1-2015 at 15:28

Nitric acid has been around for hundreds of years. It will not go away because of some regulation.

So far I have seen no one reinventing the wheel on new ways to make it.
It would surely be nice if someone would come up with an efficient industrial process that fit nicely with the common home chemist. I just have not seen it yet.

For me I prefer to buy it, but I have made fuming nitric acid in the past.

Good luck guys, I hope to benefit from your hard work.

Zombie - 29-1-2015 at 15:31

Quote: Originally posted by morganbw

Nitric acid has been around for hundreds of years. It will not go away because of some regulation.

So far I have seen no one reinventing the wheel on new ways to make it.
It would surely be nice if someone would come up with an efficient industrial process that fit nicely with the common home chemist. I just have not seen it yet.

For me I prefer to buy it, but I have made fuming nitric acid in the past.

Good luck guys, I hope to benefit from your hard work.

https://www.youtube.com/watch?v=2yE7v4wkuZU

morganbw - 29-1-2015 at 16:24

Thanks Zombie,
I have seen that video, in a way it reinforces what I posted. Nothing new as it is touching on chemistry that has been around for a very long time.

I have used one of the methods outlined, which was the nitrate and H2SO4 method for some nitric acid I was needing a long time ago.

All of this is very old school, and is the main reason I posted that nitric acid is not going away from hobbyist.

[Edited on 30-1-2015 by morganbw]

Zombie - 29-1-2015 at 16:33

That's also what I am saying. The challenge goal seems to have fallen into a re-invention of the wheel contest.

Respectfully I admire the thinking... It's going miles from easy. I sure cant build some spinning thing that converts woodchucks or squirrels into anything acceptable by societal standards. I'm looking at the trees, not the forest.

morganbw - 29-1-2015 at 16:34

That's also what I am saying. The challenge goal seems to have fallen into a re-invention of the wheel contest.

Respectfully I admire the thinking... It's going miles from easy. I sure cant build some spinning thing that converts woodchucks or squirrels into anything acceptable by societal standards. I'm looking at the trees, not the forest.

Agree

j_sum1 - 29-1-2015 at 17:27

Ok.
In my town, auto parts places do not sell H2SO4. Neither do hardware stores. Neither does the specialist battery shop.
Cold packs are available from the pharmacy but are rather expensive. Also, it is far from clear what is in them. I know what I would like to be in them but I also know that there are a few different endothermic reactions used. It is just not a sensible source.
Nitrate fertilisers are available, but I haven't seen high percentage nitrates in garden supplies or hardware stores.

So, tell me about your method now.
As I see it, this thread fills a niche -- educational if nothing else.

Zombie - 29-1-2015 at 18:43

Wallmart, pharmacy, IGA groceries, 7-11 stores, Dollar stores all have cold packs.
Look at the side to be sure it is ammonium nitrate. You get two packs for about 20 bucks, and @ contains about 200gr.
Mix w/ enough distilled water to completely dissolve, and filter out the stuff that doesn't dissolve. It's some sort of drying agent or anti cake stuff.
Evaporate off the water, and you are good to go there.

The rest is in the video I posted... Go to the junk yard if needed, and empty a few batteries OR ace hardware for a 10 dollar gallon, and a half of sulfuric acid.

I use a filter flack, and an aquarium hose. Combine the ammonium nitrate, and sulfuric acid, in the flask (50/50 ratio) and stopper off. The hose side goes into a bottle of hydrogen peroxide (2 oz or so) in an ice bath. Heat the acid mix till it starts to react, and bubble thru the peroxide. You can test on an old penny.

I'm not versed at the lingo or method to properly explain it but I hope my explanation is clear enough to fit into the thread. Backyard nitric acid @ 30 bucks for 2-4 oz, and off the radar.

WGTR - 29-1-2015 at 19:09

If the concept of making an acid from air, water, and electricity doesn't excite you, then it doesn't. It won't appeal to everyone.

This is an international forum, and various people here have different levels of difficulty in procuring nitrates or nitric acid. Just because it is in your corner store, doesn't mean that it will be there next year. If you noticed Chuck Schumer's latest photo op, he was clutching an ammonium nitrate cold-pack in his fist. That silly rascal.

ny-senator-chuck-schumer-calls-bomb-making-homes-de.jpg - 56kB

Nitric acid is such a ubiquitous chemical for the lab that it is good to explore ways of ensuring that it remains available to the amateur chemist. Distilling it from cold packs is one way, making it from air is yet another. One method may work better than the other depending on one's local situation. Here in the U.S. it's not a problem right now. I currently have gallons of fuming nitric at my disposal (and have no use for it). If I need something, I can order it from Fisher and get it in a couple of days.

Anyway, I'm surprised by all the attention my short video received. It was intended as a status update on an incomplete project. It seemed like interest was waning in the thread, and there was some disappointment in the lack of submissions. I posted it then just to add some life to the thread, and inspire other interested competitors not to give up.

I put a couple months of evenings into simplifying this project. The concept began life as PWM converter that would run on a 12V battery. It would create a high frequency sine wave, which would then be stepped up by a home-made transformer to 50V. A separate high frequency unit would deliver 5000V, enough to fire the gap between the electrodes. As I went through various iterations of the design, I was nagged by the thought that even though I was designing the circuit to be simple, most people would still not be able to duplicate it. I eventually ended up with the current design, which is just some random bits of water pipe soldered together to form water-cooled electrodes. I even replaced the electromagnet design with a simple and cheap ceramic ring magnet. Every time I was tempted to go out back and turn something on a lathe, I waited until I could figure out a way to accomplish the same thing with hand tools and scrap bits.

The next phase is to introduce air flow into the reactor. I'm thinking tangential flow in the same direction as the arc rotation for starters. If the arc remains stable, then some effort will be spent collecting the gas, and if necessary, shielding the exposed parts to prevent corrosion by the product gasses.

Yes, I am going to school, but part time. I work full time in a research facility. Technically I'm a professional, but I'm an amateur at heart.

Zombie - 29-1-2015 at 19:44

Oh please Sir... Do not take any offense on your work. That is/ was by no means my intent. I'd shake your hand, and beg you to mentor me if we were face to face. Hell maybe even adopt me...

No No No... I just joined here, and am learning. Part of that process (for me) is joining in on threads that I can understand, and hopefully contribute to.

Odd thing about this thread... I live in a county of 2500 people, and can get these ingredients. BUT I would have to go 40 miles (each way) to get those cold pills they make Meth from. Those are not available here.

Perhaps I came on too strong.

I very much admire the work both on this thread, and all through the forum.
Respect!

WGTR - 29-1-2015 at 20:32

Oh, I didn't take any personal offence, don't worry. In fact, I was busy typing my reply before your post came up, so I wasn't directly responding to it. Certain attitudes get lost in the translation of the written word. Frankly, I was not the slightest bit annoyed or offended. I am naturally intense, and tend to state things very thoroughly without realizing it. If you can reread the entire thing with more humour added, it might come out more the way I intended it. Imagine if it was a trained squirrel that wrote it. Now imagine that Chuck Schumer is a trained squirrel.

At the same time, there are several threads here detailing how to get nitric acid from nitrates. It is pretty much the standard hobbyist way of making nitric acid. The challenge in this thread, though, is to synthesise nitric acid from non-nitrate sources. As mentioned earlier in the thread, there are valid reasons why people would want to do that. It would be nice if we don't stray too far from that in this thread.

[Edited on 1-30-2015 by WGTR]

Zombie - 29-1-2015 at 20:37

Understood.
I did see how the thread shifted from everyday to the exotic.

I'll put on my thinking cap, and keep the monkey away from the keyboard. Kudos!

deltaH - 30-1-2015 at 02:34

Very nice WGTR, loved the teaser trailer :cool:

This competition is hotting up nicely, for a moment I thought it kinda fizzled, but it appears not. Anyhow, experience tells these kinds of things take a long time to perfect and the goal here is no trivial matter!

I think in the end with the effort people are putting in, multiple routes will be made to work and that's really excellent because different solutions may suit different people's backgrounds better.

blogfast25 - 30-1-2015 at 07:33

WGTR:

Yours is the one to follow. That electrical arcs can combine nitrogen and oxygen into NO2 is well understood. In 1894 Argon was isolated by Lord Rayleigh and Sir William Ramsay using that principle:

http://en.wikipedia.org/wiki/Argon#History

Connecting a flow of air through the arc into NO2 scrubber will be the really interesting next step.

I did see how the thread shifted from everyday to the exotic.

I'll put on my thinking cap, and keep the monkey away from the keyboard. Kudos!

Define "exotic"?

And DO keep monkey away from keyboard or any semblance of a sane discussion.

[Edited on 30-1-2015 by blogfast25]

Darkstar - 30-1-2015 at 07:46

More like "novel."

Zombie - 30-1-2015 at 07:47

Quote: Originally posted by aga

Synthesis of Nitric Acid
(as proposed by WGTR)

Objective: Make at least 100ml of 30w% Nitric Acid in the easiest and cheapest way possible.

Prize €250 / $309 / £197 whatever the exchange rates are at the time

Reagents available:-

1. Any plants or rocks that you, or anybody else, can find in a 5 mile radius of your home.

2. Any product available from a supermarket.

3. Gasoline, Diesel, Vegetable Oils.

4. Common Bacteria or Fungii

5. Steel, Iron, Copper, Aluminium, Zinc ...

6. Anything an Animal ejects Voluntarily while living.

Prohibited Reagents: All chemicals that can be bought in their pure or pure-ish form. Nitric Acid in any form. Unicorn Extracts. Elf Dust/Leprechaun Powder.

Equipment available: Standard glassware, any household item, or improvised item(s) made from household item(s).
Anything that a non-chemist would have access to, like a Spoon, Drill, hammer, lathe ...

Prohibited Equipment: Advanced Glassware (not normally available to a home chemist), quartz tube & furnace, Any Voltage > (250 * 1.41) V.

'Standard Glassware' is What i have in my lab.
That's the Definition.
U2U me if you think what you need to use might not be what i have in my lab.

The Ideal is to make a useful quantity of Nitric Acid in a way that we all could make it, and be shown/described in a way that others could copy.

As it's a DAC, Violation of that Ideal will disqualify an entry that fits the rules, yet is not of any Use at all to others.

Submissions should be ONE POST ONLY in this thread (edit as needed) and include photos that can be seen without following links, chemical formulae and Amounts, and temperatures where relevant.
NOTE: the Single Post must show how it is done, in detail, so it can be copied, and verified.

Opening date : 1st January 2015.
DO NOT POST ENTRIES BEFORE THAT DATE.

Closing date for entries : 24th January 2015

The Winner will be the one who posts the Best overall solution, and i will take the opinions of others into account when judging.

Prize Winner(s) will be announced after Assessing, Judging and then Testing the procedures, likely before the end of Jan 2015.

The winner gets the stated Prize.

If any submissions look really great, and don't win, they could get a prize too.

All prizes paid by paypal.

As always, my inebriated word is final, unless it's not.

Edit:
Max Voltage changed to fit where i live as well (blush)

[Edited on 24-11-2014 by aga]

By exotic I meant shifting from Mr. Aga's statement of "easiest, and cheapest way possible" into building apparatus to achieve his goal. No disrespect.

I leashed the monkey...

aga - 30-1-2015 at 12:05

Inspired by j_sum1 and WGTR's astounding efforts so far, i think i'll try and enter this competition myself.

Despite being fascinated with the spinny sparky thing, i bought 3 bags of dried beans.

How about heating a 3-neck flask with the beans in it, an aquarium air pump gently blowing air into 1 neck (stopper off the middle neck) and lead the flow from the other neck through a copper tube, also heated, with the other end of the tube under water ?

Perhaps chuck some ammonia in the pot as well.

No, i have no idea what Chemistry i'm talking about, so i'll try it and see what happens.

Loptr - 30-1-2015 at 12:08

Here is a novel idea for the preparation of nitric acid for those lacking nitrate salts.

I will sell and ship sodium nitrate to anyone, anywhere, to allow them to produce nitric acid, either using sulfuric acid or the dry bisulfate distillation method.

If you can't buy it locally, then have it sent to you!

Just kidding. I am not trying to get myself or anyone else in trouble

Loptr - 30-1-2015 at 12:12

My attempts at preparing minute amounts of dichoramine made me think twice, especially with risk of forming nitrogen trichloride. Yes, I know NCl3 can be oxidized to HNO3, but just not worth it.

Also, I have redirected. I am attempting a micro-scale synthesis of HNO3 via the Ostwald process using Ammonia gas and hot copper wire, as seen at the following page.

http://digipac.ca/chemical/mtom/contents/chapter3/fritzhaber...

[Edited on 30-1-2015 by Loptr]

aga - 30-1-2015 at 12:13

That's the kind of Thinking i was hoping for - Outside the Box !

Nice try, but no banana.

Edit:

I can confirm that approx 50ml 30% ammonia solution in a vac flask keeps a suspended ring of 15mm copper pipe at high heat for a long long time.

I didn't collect any gasses, or see any noticeable brown gas.

I suspect that the ammonia gas would need to be completely oxidised to prevent the formation of ammonium nitrate absorbing the desired HNO3.

[Edited on 30-1-2015 by aga]

[Edited on 30-1-2015 by aga]

Loptr - 30-1-2015 at 12:41

Quote: Originally posted by aga

That's the kind of Thinking i was hoping for - Outside the Box !

Nice try, but no banana.

Edit:

I can confirm that approx 50ml 30% ammonia solution in a vac flask keeps a suspended ring of 15mm copper pipe at high heat for a long long time.

I didn't collect any gasses, or see any noticeable brown gas.

I suspect that the ammonia gas would need to be completely oxidised to prevent the formation of ammonium nitrate absorbing the desired HNO3.

[Edited on 30-1-2015 by aga]

[Edited on 30-1-2015 by aga]

Yeah, this has been something I have been thinking about. I was planning on using very dense copper wool stuffed into a horizontal connecting tube, which one one side is connected to the dry ammonia gas source, and the other leading to a test tube filled with water. Eventually, the copper will melt to the bottom of the connecting tube, which will allow ammonia gas to bypass the hot copper, and make it into the solution, which will form ammonium nitrate. (ammonia would always make it through, but ammonium nitrate would start to become the dominant product in the receiving test tube as the surface area of the copper decreased)

I think a way to determine how much NO2 can be produced before all the copper melts would be helpful in determining the amount of ammonia gas to provide.

What about bubbling ammonia through a pool of molten copper?

[Edited on 30-1-2015 by Loptr]

A quartz test tube might be able to contain molten copper. I am stepping outside my area of expertise, but copper melts at 1,085°C, whereas quartz tube's max working temp is 1200°C. Maybe wrap the quartz test tube with resistance wire to melt the copper, and maintain it in a molten state that way? Then figure out a way to bubble ammonia gas through the molten copper. Resistance wire could also be substituted with a propane torch.

This sounds dangerous, to say the least.

[Edited on 30-1-2015 by Loptr]

[Edited on 30-1-2015 by Loptr]

[Edited on 30-1-2015 by Loptr]

aga - 30-1-2015 at 14:23

Resistance is Futile (favourite Borg saying)

The main issue there would be the quartz tube, according to the rules.

Loptr - 30-1-2015 at 14:27

I believe you can buy a Quartz test tube off eBay for $25.

That's as off the shelf as any other glassware.

Besides, it's not the only container that could be used.

[Edited on 30-1-2015 by Loptr]

blogfast25 - 30-1-2015 at 15:53

aga (and j_sum1):

The idea of oxidising organic nitrogen (read amines, amides and other mainly nitrogen/hydrogen MO bearing materials) to NOx with traditional combustion methods is in fact beyond risible.

Way before the advent of the Haber and Ostwald processes wars were being fought over access to nitrate bearing resources:

http://en.wikipedia.org/wiki/War_of_the_Pacific

Do you really think no one would have thought of such a process already, considering it would make one as rich as Croesus in the case of success?

The N-O bond really doesn't form easily at all, see also the extraordinary forcing conditions applied in the Ostwald process.

Apart from the combination of N2 and O2 to NOx in an electrical arc, the only avenue worth investigating is the microbiological digestion of ammoniacal nitrogen to nitrates.

[Edited on 30-1-2015 by blogfast25]

j_sum1 - 30-1-2015 at 16:52

Better add deltaH to your list there blogfast.
I have to say that I really respect your thoughts and your knowledge base which well and truly eclipses mine. But it won't stop me experimenting and exploring some ideas for myself. Risible is a strong word.

I was thinking along the lines of the Ostwald process and then was daunted by the pressure requirements and the necessity to divert some of the stream back through the reactor. And that is before attempting to find some otc platinum that met the brief. I was also thinking along the lines of urea and milk protein as a starting material when deltaH suggested soy beans. I have not found any online evidence of anyone attempting this kind of process so it will either be a dismal failure as you predict or a novel method.

I think I have said a number of times that I don't consider myself a particularly competent competitor in this challenge. But I do love the experimental process -- enough to post what I considered a failure. I was genuinely stunned to be even considered for a prize. Given that I didn't get to see what I hoped, I am going to continue the experiment.

There is another possible route that has some similarities to mine and might be extremely simple. I am not going to attempt it but I offer it out there to be picked up by someone.
Why not rip the catalytic converter off your car and bubble the exhaust gases through water. That should produce something (or else what is the catalytic converter for?) I don't think the nitric acid would necessarily be cheap by this method. But the process would be simple and the necessary equipment ubiquitous.

blogfast25 - 30-1-2015 at 17:40

Risible is a strong word.

Nothing wrong with 'strong' words at all.

The idea that in this day and age and with the power of so much hindsight some would still entertain the idea of 'burning' (let's call a spade a spade) nitrogenous matter to nitrogen oxides just baffles me.

Had those entertaining that idea made it conditional to the use of some 'catalyst X' it would have gained minimum credibility in my eyes, even in the light of the enormous difficulty of developing/deploying such pixiedust. But that seems to have crossed no one's mind either (apologies if I've missed that part).

[Edited on 31-1-2015 by blogfast25]

j_sum1 - 30-1-2015 at 18:07

You are far more knowledgeable than I am -- both historically and chemically. You have the benefit of a lot more hindsight. And I am not aat all offended that you should choose strong words.
I can see that I am going to find out what it is about burning hydrocarbons in air at pressure that causes some N2 to oxidise.

Admittedly without any significant thermodynamic research I blended ideas about oxidising N2 in a combustion engine and oxidising NH3 in the Ostwald process and wondered what would happen if one attempted oxidation of urea or proteins.

I am more than open to the idea of catalysis but have no experience in selecting an appropriate catalyst.
And if you can point me to some thermodynamic data that indicates that it really is infeasible then I would welcome it. (In which case no catalyst is going to help anyway.) But I sure wouldn't ask you to do my research for me.

In the meantime, I am happy to put a bit of time into reading and have a couple of modifications that I would like to try. It sure can't hurt. Worst case scenario is that I buy some peanuts and end up making them into cookies.

[edit]
Blogfast, do you mind telling me what you think does happen to the nitrogen in proteins when they are combusted?

[Edited on 31-1-2015 by j_sum1]

Zombie - 30-1-2015 at 18:11

Can you make enough for all of us?

plante1999 - 30-1-2015 at 20:53

I'm on blogfast side here and I actually worked a bunch on this mater and put a lot of my money (and investor money) in the search for something viable and I have gained a fair amount of knowledge on the subject.

Like I said early in this thread, without quartz tube and or high voltage you are only going to piss in a dirt pile. Seriously, nitrates where a very rare material when it gained large use in Energetic and bullet propellant manufacture. Actually, the ONLY reason Germany was able to go in war was by inventing the Ostwald process. Arc process do work and is not that costly for amateur, but in industrial scale it is not worth it.

The point I'm making is that if there was another catalyst then platinum (which is already hard to work with), it would have gained mainstream industrial use.

Also, nitrogen is extremely unlikely to get oxidized, and thinking the mere burning of nitrogen material at atmospheric pressure without catalyst is beyond my understanding. Engines yield some NOx because of the extreme pressure and temperature, plus the radicals present during engine run (not to mention some metal oxide catalyst).

I would be A LOT more entertained to see the same exact challenge with allowed quartz tubing, platinum wire and or high voltage.

Zombie - 30-1-2015 at 20:59

http://www.ebay.com/itm/2-lb-Sodium-Nitrate-Gold-Scrap-Refin...

http://www.ebay.com/itm/Sulfuric-Acid-98-1000Ml-Poly-Bottle-...

[Edited on 31-1-2015 by Zombie]

j_sum1 - 30-1-2015 at 21:12

Right back at you zombie.

I think it was established fairly early on and clarified by aga that use of commercial nitrates was outside of the parameters of the competition. And I have pointed out a couple of times that they are not universally available anyway.

I am interested in what Plante1999 and blogfast have to say. Early on in the thread there was much vocalising of "it's impossible". Now there is a bit more "It's impossible because..."

Zombie - 30-1-2015 at 21:33

Not to bust stones here. It's your game fellas... Some guys can't get the acid, some guys can't get the nitrates, some guys can't get iron lungs for pressure, some can't get bat poo, Burning beans, and car exhaust are just not quick / easy, and No one want to ferment pee.

In essence it is a great exorcise for the brain but the reality is if two guys teamed up, and exchanged what they have... Cookie time.

I mean no offense, It just seems to outlandish to climb a mountain for a snow flake.

In MY humble opinion... The fella that burnt the beans won because he was the only fella to submit. The rest is all split milk, and soggy cookies. :cool:

j_sum1 - 30-1-2015 at 23:10

It's your game fellas...

It sure is. It is and always has been a competition and a challenge. Playing is optional. Constructive evaluation of ideas presented is welcome. Criticism of the competition parameters is less so.

I mean no offense, It just seems to outlandish to climb a mountain for a snow flake.

Mallory reportedly said when asked why he climbed mountains, "Because it is there." As one who also has a passion for mountaineering, I share the sentiment. It is more about the journey than the destination.
In terms of this thread, I have learned a lot about nitric acid and its production that I would never have known if I hadn't participated. For me it was always about the learning, about having a project for my new lab and the possible bonus of someone unearthing a cheap and simple otc source of a useful reagent. Even if that bonus proves elusive or impossible, it has been a worthwhile exercise.

deltaH - 31-1-2015 at 00:21

The attached paper studies the combustion of urea-formaldehyde re-inforced chipboard and investigates the use of air staging to lower the amount of NOx produced.[1]

This paper is interesting, because while wood doesn't contain much protein and hence nitrogenic matter, the urea-formaldehyde raises the nitrogen content to 3.58%, resulting in a big 'problem'

of making NOx during combustion. The theoretical maximum amount being some 12300ppm NOx as NO2, according to the paper.

If you look at figure 9 in the paper, you see that using a stoichiometric ratio of air above 2.5 when burning UF-chipboard results in a NOx content of a little over 1000ppm in their furnace... that's not too shabby.

No catalyst, no forcing conditions.

I suggest that it would be wise to pump ice water (perhaps in a closed loop from container with ice) through the absorber to maximise the stripping of NOx and concentration of the nitric acid that is ultimately yielded.

Still prefer soybeans though...

Blogfast, I quote from the introduction of the attached paper:

Quote:

The NOx emissions from biomass combustion are mainly caused by the nitrogen in the fuel.[2]

As for the why hasn't this been done before, quite simply because it doesn't work as well as burning ammonia over platinum (far from it), nevertheless, in the amateur context, it might work well enough.

As for the catalyst, I've already discussed it to death in aga's thread about ammonia oxidation, as well as suggestions for upping the activity of copper pixie dust

If one were inclined to incorporate a catalyst with bean burning, I'd suggest soaking the beans in a copper salt solution overnight to absorb (preferably not sulfate), then drying them in the sun. It's a complication and extra expense though...

Attachment: fuelstaging.pdf (243kB)
This file has been downloaded 2050 times

References:

[1] Salzmann, R. (2001). Fuel Staging for NOx Reduction in Biomass Combustion: Experiments and Modeling. Energy & Fuels. 15, pp. 575-582.

[2] Nussbaumer, T. (1989). Schadstoffbildung bei der Verbrennung von Holz. Ph.D. Thesis ETH No. 8838.

[Edited on 31-1-2015 by deltaH]

deltaH - 31-1-2015 at 03:14

According to the wiki on Schweizer's reagent, air can oxidise the copper tetraamine complex to ammonium nitrites (references copy pasta'ed from the article) at ?ambient conditions?

I found this intriguing. So far I've only seen 'exotic' reagents affect ammonia oxidation under mild conditions. We've seen copper discussed as a heterogeneous catalyst for this reaction, so here's the homogeneous version as well.

References:

Y. Cudennec, et al. (1995). "Etude cinétique de l'oxydation de l'ammoniac en présence d'ions cuivriques". Comptes Rendus Académie Sciences Paris, série II,Méca; phys. chim. astron. 320(6): 309–316.

Y. Cudennec, et al. (1993). "Synthesis and study of Cu(NO2)2(NH3)4 and Cu(NO2)2(NH3)2". European journal of solid state and inorganic chemistry. 30(1-2): 77–85.

[Edited on 31-1-2015 by deltaH]

CuReUS - 31-1-2015 at 04:00

Blogfast, do you mind telling me what you think does happen to the nitrogen in proteins when they are combusted?

depends on how you combust it
http://en.wikipedia.org/wiki/Dumas_method
http://en.wikipedia.org/wiki/Kjeldahl_method

what about my idea of burning melamine instead of beans.I am sure melamine contains more nitrogen pound per pound compared to beans

WGTR's arc method is the best,but the voltage input for that machine is going to be a limiting factor
if too high voltage is needed,the person who is running the machine might get raided by the cops,thinking that the person might be a drug cook

Mallory reportedly said when asked why he climbed mountains, "Because it is there."

mallory

,do you mean keith mallory,from guns of navarone by alistair MacLean
http://en.wikipedia.org/wiki/The_Guns_of_Navarone_(novel)#Pl...
I thought he was a fictitious character

j_sum1 - 31-1-2015 at 04:08

Mallory
http://en.wikipedia.org/wiki/George_Mallory

deltaH - 31-1-2015 at 04:17

Melamine powder? It's really hard to burn. Hexamine containing fuel tablets on the other hand...

The main reason I went with the 'crazy' idea of using soy is that its (1)really cheap, (2) available in most countries and (3), nobody would bat an eyelid if you buy 20kg of it... hell you can buy 100kg

(4)renewable.

Also, while the yield would probably be piss poor, if you build a 'rig' you could probably burn a lot quite quickly if you use a blower... which you should anyhow to get decent excess air in there.

The absorber could be more of a challenge than the combustion chamber I think. For one thing and also as j_sum suggested, volumetric flow rates are large and this can entrain the droplets significantly.

A packed absorber with random packing would work much better. Liquid needs to be pumped to the top and would trickle down. You use a wide range of small objects as random packing, no need for the sophisticated shapes used by industry. The idea is simply to have a film of liquid falling over objects where the objects increase the area of the film per volume of the absorber. The 'objects' need to be inert to the liquid and spread the falling film out nicely.

[Edited on 31-1-2015 by deltaH]

Loptr - 31-1-2015 at 06:37

I just got a quote of $30 for a 23mm OD, 20mm ID, 300mm L Quartz test tube.

Not too expensive and can be shipped anywhere in the world.

blogfast25 - 31-1-2015 at 08:12

Blogfast, do you mind telling me what you think does happen to the nitrogen in proteins when they are combusted?

I honestly don't know. A mixture of organics like nitriles et al, ammonia, some nitrogen and probably very small amounts of NOx, if I had to guess...

Etaoin Shrdlu - 31-1-2015 at 11:03

Blogfast, do you mind telling me what you think does happen to the nitrogen in proteins when they are combusted?

I honestly don't know. A mixture of organics like nitriles et al, ammonia, some nitrogen and probably very small amounts of NOx, if I had to guess...

Apparently amines do form NO_x when burned. http://cameochemicals.noaa.gov/react/7

I can't find much on this, probably hampered by the fact that most of my searches are turning up information on using amines to treat combustion gases.

EDIT: Source for ammonia. http://www.fs.fed.us/psw/publications/riggan/psw_1988_riggan...

Best source on fuel nitrogen conversion I can find for higher nitrogen content. https://books.google.com/books?id=tZYfa7vCJ_AC&lpg=PA93&...

[Edited on 1-31-2015 by Etaoin Shrdlu]

aga - 31-1-2015 at 11:59

Quote: Originally posted by Loptr

I just got a quote of $30 for a 23mm OD, 20mm ID, 300mm L Quartz test tube.

Not too expensive and can be shipped anywhere in the world.

It's more about lateral thinking really.

Try to imagine ways that you could make HNO3 on a desert island for example.

No electricity, no ebay, internet ... yet plenty of sunshine and saltwater.

And fish. Lots and lots of fish.

deltaH - 31-1-2015 at 12:37

Dry fish in sunshine then burn fish. Absorb NOx in seawater, then distil with solar still and more sunshine. Enjoy pina colada from coconut shell.

[Edited on 31-1-2015 by deltaH]

blogfast25 - 31-1-2015 at 13:42

Apparently amines do form NO_x when burned. http://cameochemicals.noaa.gov/react/7

Quote:

The combustion of amines yields noxious NOx gases.

Doesn't say much about yield though, does it?

Here's someone preparing cadaverine, a diamine. Doesn't look too hard. Burn and lets see?

http://www.sciencemadness.org/talk/viewthread.php?tid=61305

[Edited on 31-1-2015 by blogfast25]

aga - 31-1-2015 at 14:28

Does not Experimentation yield data ?

blogfast25 - 31-1-2015 at 15:32

Quote: Originally posted by aga

Does not Experimentation yield data ?

Specifically what experimentation are you referring to here?

blogfast25 - 31-1-2015 at 19:10

Going by one of Etaoin's links, chances are that much of the burnt organic N will be found in the ashes... as ammonium salts. Provided incineration temperatures aren't excessive. Quite a bit will escape as NH3.

[Edited on 1-2-2015 by blogfast25]

radiance88 - 31-1-2015 at 20:12

There seems to be two sides here in this thread - those who think it can be done, and try (even if the yield is inefficient), and those who think that it's impossible, and are persistent in telling us it's pointless for even trying for this goal.

The naysayers could be technically correct, and maybe in truth we really are screwed here and just spinning our wheels.

But personally, I'd rather see a bunch of novel attempts along with their write-ups, than to see everyone lose enthusiasm and heart over it and stop trying, and let it go dead.

As a hobbyist, I've never seen this kind of ingenuity before, and it makes me a little bit excited to even see what people manage to come up with.

Watching people do this on YouTube was what inspired me to get into this and start studying in the first place.

Sure - you can buy plaster at the hardware store for much cheaper than what it costs you to make it via calcium chloride and magnesium sulfate - but that's not entirely the point why someone does this at home.

Another reality here is we're not all here a bunch of pro chemists working in corporate labs, able to order any chemical we want to. We're a group of people working each in his own way, attempting to cope with the societal, legal and economical constraints in our own environments, to practice science as a hobby at home.

We can't always beat these said constraints - but we really don't have any choice but to keep on trying.

It's a challenge that obviously has amateur experimentalism at heart. It's fun and inspiring to see some folks just rig up something in their garage or backyard even if they don't hit the mark. For some folks it's impossible and for some it's just another fun challenge that gives them something to tinker around and have fun with.

I'd say let's see where this little road takes us, and just enjoy ourselves along the way.

plante1999 - 31-1-2015 at 21:51

Quote: Originally posted by radiance88

There seems to be two sides here in this thread - those who think it can be done, and try (even if the yield is inefficient), and those who think that it's impossible, and are persistent in telling us it's pointless for even trying for this goal.

I think you missed it, there is the ones which think they can find a gold ring at the beach with sticks (a very unlikely possibility). And the one that think if they wanted to look it would be way more practical to use a metal detector.

aga - 1-2-2015 at 01:20

... then there are those with dangerously little Knowledge, who failed to find the gold ring with the sticks and metal detector, and carried on trying.

One of those still trying to find the ring, might, by pure chance, discover a functioning Field Technology.

Very far fetched, of course, but the fact remains that people actually Doing Stuff stumble upon all sorts of things, probably unrelated to what they were trying to do.

j_sum1 - 1-2-2015 at 04:30

If I don't find out how to make nitric acid, I will find out what I do and don't know.
I don't think I should have to defend that notion.

blogfast25 - 1-2-2015 at 06:18

If I don't find out how to make nitric acid, I will find out what I do and don't know.
I don't think I should have to defend that notion.

Not in the slightest but its not a very effective way of conducting applied research.

Using low MM amines and amides as models and looking for catalysts that would improve NOx yield during their combustion would be more targeted, for instance.

[Edited on 1-2-2015 by blogfast25]

deltaH - 1-2-2015 at 07:49

Quote:

Using low MM amines and amides as models and looking for catalysts that would improve NOx yield during their combustion would be more targeted, for instance.

This has been suggested, including using hexamine containing fuel tablets (my favorite), urea and melamine. Amides have not, though urea is amide-like. Any ideas for OTC amides that could be useful for this? Ideally what you're burning should be easy to burn (something urea and melamine are not) with a reasonable heat of combustion.

blogfast25 - 1-2-2015 at 08:31

OTC amides: Nylon. One N for every six C.

[Edited on 1-2-2015 by blogfast25]

Etaoin Shrdlu - 1-2-2015 at 10:17

Apparently amines do form NO_x when burned. http://cameochemicals.noaa.gov/react/7

Quote:

The combustion of amines yields noxious NOx gases.

Doesn't say much about yield though, does it?

No, this was the problem with most of the links I turned up before I ran across the term "fuel nitrogen" and started hitting somewhat more significant information. I just felt it was a reasonable indication that burning nitrogen-containing compounds had a noticeable effect on NO_x generation.

Here's someone preparing cadaverine, a diamine. Doesn't look too hard. Burn and lets see?

Now that would have somebody kicking down my door. (Or! I'd get the whole neighborhood to myself for a while.) If I were going to attempt this I'd either use one of the amino acids that are readily available in bulk, or straight soy protein since legumes seem to be under consideration.

blogfast25 - 1-2-2015 at 10:39

Now that would have somebody kicking down my door.

Huh? Explain?

gdflp - 1-2-2015 at 11:00

Now that would have somebody kicking down my door.

Huh? Explain?

The smell of cadaverine in addition to burning and vaporizing it, some neighbors might not appreciate it.

deltaH - 1-2-2015 at 11:17

OTC amides: Nylon. One N for every six C.

blogfast25 - 1-2-2015 at 11:18

Quote: Originally posted by gdflp

The smell of cadaverine in addition to burning and vaporizing it, some neighbors might not appreciate it.

Boh. Depends on how you do things.

aga - 1-2-2015 at 12:22

Hmm. A Catalyst sounds great.

I've got Copper, so ill try that, hot.

Wife says NO to the use of her Platinum.

blogfast25 - 1-2-2015 at 16:54

Jokes aside, if I had to put money on a catalyst that could help oxidise amines/amides in fairly 'normal' combustion conditions, I'd be thinking of a transition metal oxide with oxidising properties like CuO, V2O5 or MnO2 (not an exhaustive list).

Catalyst would oxidise -NH2/-NH- to NO or NO2, itself being reduced to a lower oxidation state.

Air oxygen would regenerate the catalyst to its highest oxidation state.

j_sum1 - 1-2-2015 at 18:15

Thanks for the thought blogfast. there is no reason why I can't add some battery gunk MnO2 to my experiment and see if that doesn't help things along. There will be some iron oxides in there too as well in all likelihood. I will get rid of the ZnCl2 first though.
Selecting a catalyst is well outside my experience though. I have some CoO and NiO that I could try also, but that is getting beyond my third-world otc approach possibly.

deltaH - 2-2-2015 at 00:00

Here's a present for you j_sum1, "Manganese in the catalytic oxidation of ammonia" full text available here:
https://archive.org/details/manganeseincatal00piggrich
Break a beaker

[Edited on 2-2-2015 by deltaH]

blogfast25 - 2-2-2015 at 06:56

For this kind of heterogeneous catalysis a fluidised bed reactor would be ideal:

http://en.wikipedia.org/wiki/Fluidized_bed_reactor

[Edited on 2-2-2015 by blogfast25]

hyfalcon - 2-2-2015 at 07:26

Hey, my coffee roaster works on the same principle. Hmmm....

blogfast25 - 2-2-2015 at 09:58

I warmly recommend delta's last link: it's practically a guide to build-your-own-nitric-acid-plant but quite OTC.

deltaH - 2-2-2015 at 10:10

Yes, I would say Charles Snowden Piggot has won this competition posthumously 95 years ago.

blogfast25 - 2-2-2015 at 10:36

Quote: Originally posted by deltaH

Yes, I would say Charles Snowden Piggot has won this competition posthumously 95 years ago.

Right on the money, Delta.

deltaH - 2-2-2015 at 10:53

So sad to see the library stamps on the back page, only read twice in 1926 and 1928... very poignant

Bert, please consider adding this 17-page gem to the SM library for archival purposes, lest it is lost.

aga - 2-2-2015 at 11:44

+1

definitely worth archiving/preserving.

aga - 2-2-2015 at 12:02