havarti_gouda
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Ammonium Nitrate with recent regulations in mind
I am exploring the process of turning primary and secondary alcohols into their respective aldehydes or ketones (e.g. isopropyl alcohol into acetone,
etc.) and am trying to obtain a small quantity of ammonium nitrate for the oxidation reaction. I've read about using dichromium/trichromium as well,
but would prefer to allocate the materials OTC. I'd also like to get some ammonium nitrate for reactions down the road, so it seemed like a good time
to investigate it.
I've read a few posts on here regarding Ammonium Nitrate in fertilizers and also further read in recent news articles about an extreme difficulty in
obtaining it due to its use in explosives. I'm starting to doubt that my local home depot would be stocking the usual 40lbs bags that have been
mentioned in various posts and in other places.
What are the most common sources of Ammonium Nitrate in fertilizers or other forms? Would they be available at a large chain hardware store, or would
it be better to go to a local gardening/lawn care type of business? I'd like to avoid cold packs due to the expense, but that may be the route I go if
purifying and isolating AN from another mixture is less realistic or cost efficient since I don't need very much. I imagine a couple of kgs would be
sufficient for years to come.
Sorry to ask this question being that it has been discussed at length in other posts, but it seemed most of the previous discussions were a year ago
and beyond and I imagine with law enforcement being so gung-ho about shutting down aspiring amateur chemists things have likely changed regarding its
availability in the usual places. Just like lye -- I can purchase sodium hydroxide crystals at local hardware stores, but not at any major chains such
as home depot, lowes, or ace hardware. I'm guessing a similar situation with AN.
Any information or links I may have overlooked would be greatly appreciated! Thanks!
[Edited on 26-1-2010 by havarti_gouda]
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bbartlog
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Probably easier to source some other nitrate (like KNO3) and turn it into ammonium nitrate. If you did want to buy in bulk I'd think rural feed stores
still carry the stuff. Home Depot so far as I can tell no longer sells any fertilizer that is mostly nitrate, though you can get urea there (and I
could be wrong, because there is a lot of seasonal adjustment in their stock). Kind of funny when you consider that you can pick up ten pound
canisters of black powder at some chain stores...
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havarti_gouda
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I still have like 9kg of NH4Cl left, maybe I should just get some nitric acid. I just didn't feel like waiting for a mail order. It's a form of
reverse laziness!
I was going to take a trip in the next day or two and do some investigation. A friend of mine's family actually runs a gardening/landscaping company,
so hopefully I can tap their supplies. We'll see.
What exactly would I do with urea? I've been reading a few things regarding going from urea to urea nitrate via urea, a nitrate salt, and sulfuric
acid, and breaking urea into NH3 and CO2. I have plenty of NH4Cl. Is nitric acid OTC anywhere?
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bbartlog
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So far as I know nitric acid is not OTC anywhere. I haven't had occasion to use urea for anything myself, just noticed it while scoping out
possibilities at Home Depot; some things off the top of my head are heating it to produce ammonia gas (via the reaction you describe, though the
reality of pyrolysis is messier), using it to make hydrazine sulfate (via a reaction described in detail in a thread elsewhere on this board), and in
the manufacture of barbituric acid.
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hissingnoise
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| Quote: | | So far as I know nitric acid is not OTC anywhere. . |
It depends on location bbartlog, but then you can buy BP!
http://www.growell.co.uk/g/98/Nitric-Acid-pH-Down
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havarti_gouda
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Seems like the local hydroponic store doesn't carry nitric acid, just phosphoric acid. I will keep looking though, that's a good suggestion, the HP
store.
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havarti_gouda
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So, I was going to order some NH4NO3, but I have to order it from a separate place from all the other stuff I was getting along with an additional
hazmat fee (ugh), so I'm wondering, could I generate NH4NO3 from Fe(NO3)3 and NH4Cl? I'd like to avoid generating nitric acid as I don't have enough
distillation equipment of pyrex, just glass. Is Fe(NO3)3 as powerful of an oxidizing agent as NH4NO3? Would I be able to use that for oxidizing
primary/secondary alcohols?
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havarti_gouda
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I ended up just ordering KNO3 instead.
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hissingnoise
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A metathetical reaction between (NH4)2SO4 and KNO3 might work.
Would K2SO4 precipitate? Hmmm. . .
[Edited on 29-1-2010 by hissingnoise]
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entropy51
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Rather than go thru all that, I would just buy some cold packs at the pharmacy. I know you said you didn't want to, but that avoids all hazardous
shipping fees and so my not be so expensive when all is said and done.
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aonomus
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The most you will have to do is likely dissolve and filter, then recrystallize to get rid of the anti caking agent, and increase purity. I usually do
this with pretty much anything that isn't reagent grade or higher.
Again, probably the safest bet to not go and buy huge amounts.
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havarti_gouda
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Well, I already placed the order for KNO3, and a few other things.
Was going to react H2SO4 w/ NH4Cl to yield NH4SO4. Then boil NH4SO4 w/ KNO3 in water and then let them cool. Apparently the KSO4 will precipitate out.
I can get a little extra from cold packs if necessary.
NH4SO4 + KNO3 + H2O = NH4NO3 + KSO4 + H2O
There's no anti-caking agent in this KNO3, I just got straight granules.
I only got 100 gms, so big brother is perfectly aware that I'm not using it for explosives. At 1:1, yield should be around equal.
KNO3 = 101.2g/mol, NH4SO4 114.2g/mol
KSO4 = 135.2g/mol, NH4NO3 80.1g/mol
So, that's equal, about. I should yield about 78-79 gms.
I imagine I'll only need like 10 gms per oxidation, if that. So, assuming I fail two or three times, I'll still have enough to get it right a few
times. I'll order more later if I need it or get it from cold packs in a pinch.
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per.y.ohlin
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It appears to me as though you are having difficulty writing the chemical formulae for a few compounds.
NH<sub>4</sub>SO<sub>4</sub> should be (NH<sub>4</sub> <sub>2</sub>SO<sub>4</sub> etc. See Chemistry 101 for more info.
The balanced equation comes out to:
(NH<sub>4</sub><sub>2</sub>SO<sub>4</sub> +
2KNO<sub>3</sub> ==> 2NH<sub>4</sub>NO<sub>3</sub> + K<sub>2</sub>SO<sub>4</sub>
1 mol               2 mol
           2 mol
            1 mol
132g/mol       101g/mol      80.0g/mol     174g/mol
132g               202g
            160g
             174g
That's 160g 2NH<sub>4</sub>NO<sub>3</sub> per 202g KNO<sub>3</sub>. Given 100g KNO<sub>3</sub>, you
get 79g of 2NH<sub>4</sub>NO<sub>3</sub>. Your result was correct, but your calculations were a bit lacking.
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havarti_gouda
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Oh, whoops. Yea, no wonder I thought it was a 1:1 molar ratio. :-)
So, I'd be doing it on a 0.5M:1M ratio. I see what I did too. I was wondering how I had the yield right, but it's because I wasn't taking into account
the correct number of molecules and doing it on a half mole level. I guess in this case, two wrongs *did* make a right. :-) j/k.
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bbartlog
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Just a note, while K2SO4 is not especially soluble it's hardly insoluble either, maybe 11-12g per 100ml of water. It won't all precipitate out just
like that. Adding some ethanol would help precipitate more of it but you still won't have a completely clean separation. But if you add an amount of
ethanol equal to the amount of water you should reduce the solubility of the K2SO4 by 95% or so.
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per.y.ohlin
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The solubility of K<sub>2</sub>SO<sub>4</sub> in mixed solvent systems
@bbartlog
An equal amount of ethanol does indeed reduce the solubility by ~95%. Did you know this from some theoretical understanding, or empirical data?
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JohnWW
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Reacting (NH4)2SO4 with Ca(NO3)2 metathetically would be MUCH better, due to the only very slight solubility of CaSO4.
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bbartlog
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Empirical data in the form of an old book by Atherton Seidell. I wish I had a better understanding of the theory behind solubility, but I always end
up looking things up.
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havarti_gouda
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Would other alcohols work in a similar fashion or only ethanol? What about isopropyl?
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per.y.ohlin
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According to the link I gave, isopropanol works just as well.
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havarti_gouda
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Oh, I didn't realize it was a link, I thought it was the topic of the message when skimming over the message. That's fantastic though. I prefer
working with isopropyl because while the cost of 99% is roughly equal to grain alcohol, it's significantly less laborious for me to prepare anhydrous
isopropyl than abs. ethanol.
I've been doing some experimenting with different alcohols lately. In fact, a friend of mine (who, unbelievably, has a masters degree in chemistry)
had told me "denatured alcohol" was straight methanol. It wasn't until doing various research that I found out "denatured alcohol" is actually ethanol
contaminated with methanol as well as a cocktail of other rubbish. It's just by sheer luck that a number of reactions I had attempted which used
methanol as a solvent, could use ethanol as well. But more than likely, the yields were consistently low because of lower solubility with ethanol.
I've since been using Heet for my source of OTC methanol. I'm not sure how homogeneous it is supposed to be, so I've been distilling it to yield pure
methanol and usually there's only a small amount of "whatever" (probably just water) remaining in the boiling flask. I'm not aware of any azeotrope
with methanol and water, as there is with isopropyl and ethanol. Isopropyl is easy to dry 99%, or just salting out the last 1% of water and then
distilling the isopropyl out of the isopropyl/salt mixture, thus side-stepping the azeotrope.
This is when I learned that even though someone has a degree in chemistry, they still might be completely incapable of providing any sort of valid
information. I originally took a lot of his information as gospel since I really didn't know any better, but have since realized that about 90% of
everything that comes out of his mouth is complete and utter bullshit. Fortunately, my journey with chemistry has encouraged a few life lessons. :-)
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grndpndr
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Quote: Originally posted by JohnWW  | | Reacting (NH4)2SO4 with Ca(NO3)2 metathetically would be MUCH better, due to the only very slight solubility of CaSO4. |
And much cheaper,about a buck a lb shipped. .1%insoluble/ uncoated. Ca(NO3)2+(NH4)2SO4 -> 2(NH4NO3)+CaSO4.
[Edited on 1-2-2010 by grndpndr]
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