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Sulaiman
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Which nitrate to buy?
I want to experiment with nitrations, I already have 96% sulphuric acid, glassware etc.
the classic nitrate to use is potassium nitrate, but now it is seen as a 'terrorist' chemical
from eBay, in order of increasing cost, I can buy;
Calcium nitrate
Strontium nitrate
Sodium nitrate
Barium nitrate
and off the affordability chart, Silver nitrate
I would like to choose the one that has the most usefulness for general chemistry
Which one should I buy and why?
[Edited on 12-4-2015 by Sulaiman]
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Deathunter88
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Quote: Originally posted by Sulaiman  | I want to experiment with nitrations, I already have 96% sulphuric acid, glassware etc.
the classic nitrate to use is potassium nitrate, but now it is seen as a 'terrorist' chemical
from eBay, in order of increasing cost, I can buy;
Calcium nitrate
Strontium nitrate
Sodium nitrate
Barium nitrate
and off the affordability chart, Silver nitrate
I would like to choose the one that has the most usefulness for general chemistry
Which one should I buy and why?
[Edited on 12-4-2015 by Sulaiman] |
I would go with calcium nitrate, because quote sciencemadness wiki: Because of its hygroscopicity, it is unsuitable for use as an oxidizer in
energetic mixtures; however, due to the insolubility of many calcium salts, the nitrate ion in calcium nitrate can easily be used to prepare other
more useful nitrates as well as other calcium compounds. Examples of this include the addition of sodium carbonate to precipitate calcium carbonate
and leave sodium nitrate in solution, or the addition of potassium sulfate to generate potassium nitrate in solution, precipitating calcium sulfate.
Virtually any nitrate compound can be produced by addition of a sulfate or carbonate solution in this manner.
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ISCGora
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Only thing with Ca(NO3)2 is if you were planning to make nitric acid from it,it will be pretty painful to remove the remaining CaSO4
Since it is not soluble in water only 0,24 g/100ml at 20 °C.
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hissingnoise
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| Quote: | | . . . the classic nitrate to use is potassium nitrate, but now it is seen as a 'terrorist' chemical from eBay. |
How so ─ ebay has massed ranks of sellers of this salt and calcium nitrate being very hygroscopic is practically useless for pyro or nitric acid
distillation.
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subsecret
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I don't recommend calcium nitrate. It's like having copper (II) in the form of the carbonate; it's pretty tough to work with when you have to prepare
other compounds in order to use it.
Fear is what you get when caution wasn't enough.
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gdflp
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Out of all the nitrates you listed, the best one to use for nitrations by far is sodium nitrate. The rest will precipitate sulfates on contact with
sulfuric acid which will then make workup a pain. Yields will likely also be very low because the nitrate particles will get coated in sulfate which
will prevent further reaction. Barium or strontium nitrate may be useful if you want to prepare other nitrates as sodium nitrate will not be able to
accomplish this in most cases(a metathesis reaction may work in some cases but yields will still be rather low).
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Bert
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Ammonium nitrate, you can make all the others from this one (plus nitric acid...) Or use it straight up for various propellants & explosives.
Of course, check your local laws first!
Rapopart’s Rules for critical commentary:
1. Attempt to re-express your target’s position so clearly, vividly and fairly that your target says: “Thanks, I wish I’d thought of putting it
that way.”
2. List any points of agreement (especially if they are not matters of general or widespread agreement).
3. Mention anything you have learned from your target.
4. Only then are you permitted to say so much as a word of rebuttal or criticism.
Anatol Rapoport was a Russian-born American mathematical psychologist (1911-2007).
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gdflp
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| Quote: Originally posted by Bert | Ammonium nitrate, you can make all the others from this one (plus nitric acid...) Or use it straight up for various propellants & explosives.
Of course, check your local laws first! |
Well, if potassium nitrate is banned because of it's possible use in terrorist applications, I would be very surprised if ammonium nitrate wasn't.
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bolbol
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If you really want KNO3 but don't want to order it from Ebay you can get stump removers and perform recrystallization to get a pure sample. There are
videos on youtube about this as well
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Etaoin Shrdlu
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EDIT: Oh damn, you're in England.
[Edited on 4-12-2015 by Etaoin Shrdlu]
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Sulaiman
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since Sept. 2014 EU explosive precursors laws
even if I find a supplier for potassium (or ammonium) nitrate I think I'd be breaking the law by buying it,
I can keep stuff on the list until 2016 then just possessing it will be illegal.
I've downloaded the license application forms and I may apply.
I'm not worried about small amounts synthesised or refined at home,
so I'll look at other routes.
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woelen
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The law you refer to does not apply to KNO3, or NaNO3. I live in NL and we have exactly the same law since Sept. 1, 2014. The new law applies to the
following 7 chemicals:
HNO3 (3% or more concentrated)
CH3NO2 (30% or more concentrated)
H2O2 (12% or more concentrated)
KClO3
KClO4
NaClO3
NaClO4
NH4NO3 already was hard to obtain before Sept. 1 , 2014, due to the regulation which came into effect after Breivik's terrorist attack in 2011.
KNO3 actually is one of the more benign chemicals and it can still be purchased without raising too much suspicion. NaNO3 is similar. Both can be
purchased from eBay.
Ca(NO3)2 is a pain in the ass to work with. It forms layers of gypsum with sulfates, which are very hard to remove from glassware. The thick solid
layers also may lead to hot spots, excessive bumping or even cracking of glassware when used in a distillation setup.
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Kitsune1
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I wouldn't bother using the Calcium salt, it is more trouble than it is worth in most cases; I like using Ammonium Nitrate, it is very versatile and
if it is available, it is cheap. You can make the group 1 metal nitrates from it and at the same time make Ammonium Hydroxide (if you want), Nitric
Acid can be made from it too. (It is available in high quantities in Equine instant cold packs in the UK).
I really wonder how much effect these laws will have against would be terrorists; after all if someone wants something bad enough, has enough money
and the wrong contacts, they will be able to. Just can't help but feel that these regulations will do little to help in the war against terror but
cause disruption in small industry and amateur chemistry, In the UK I really struggle to get hold of any compound that contains Iodine due to it's use
in the illicit production of Meth-amphetamine and yet the meth labs will still have a route to get it. Citric Acid is difficult to get due to it
sometimes being used by heroin addicts to acidify heroin before injection, but if they can't get that, they will use vitamin c or vinegar (I don't see
them banning or restricting that any time soon); instead of stopping drug abuse, it penalises people who make wine and cordials at home.
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bolbol
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Honestly none of the regulations really make much of a difference to people who use it for illegal stuff, only makes it a pain in the ass for the
people who have non-illegal uses. If you really really want it you can obtain it, stuff like safrole, ephedrine, iodine, phosphorus, or even lab grade
HI. Getting caught is the pain in the ass though,,
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AJKOER
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I still have access to relatively high purity KNO3 sold locally as stomp remover.
-------------------------------------------------------------------------------
However, if I did not, and wanted to prepare a nitrite/nitrate mix, an interesting new route which I may decide to test sometime in the future for
feasibility/efficiency would be as as follows:
1. React a small amount of Cu, dilute aqueous ammonia and dilute H2O2 in the presence of sea salt (serves as a good electrolyte) and NaOH (or possibly
Na2CO3) to maintain the pH over 7. The primary electrochemical reaction has associated side reactions including the formation of a small amount of
NH4NO2, hopefully stabilized by the presence of the NaOH.
2. The nitrite created will serve as a source generator of hydroxyl radicals under photolysis in this second step (but if this fails, maintaining a
H2O2 presence may work). Add more aqueous NH3 as the dilute ammonia is attacked by the OH radicals and eventually transformed into NH4NO2 and NH4NO3
under the action of sunlight.
3. Stop when the amount of dilute ammonia added and reacted under photolysis in the presence of the nitrite catalyst brings you to your total target
yield. Then, add for example, Na2CO3 or NaOH, to extract by heating NaNO3. Caution: never attempt to work with a concentrated ammonium nitrite
solution, or one that is acidified, as even such aqueous solutions have been reported to present an explosion hazard!
I already known the reference sources, which I will present when (and if) I post and have verified this potentially slow, but endless low cost nitrate
path from common chemicals and sunlight.
Here, however, is one of the key references, see http://www.researchgate.net/publication/23495784_Removal_of_... , to quote from the abstract:
"In this research work, H2O2 was selected as *OH precursor. The removal of ammonia under 253.7 nm irradiation from low-pressure mercury lamp in the
presence of H2O2 was studied to investigate the ammonia removal efficiency by *OH. Results show that the *OH, generated by H2O2 photolysis, could
oxidize NH3 to NO2- and further to NO3-. Removal efficiencies of ammonia were low and were affected by initial pH value and ammonia concentration.
Laser flash photolysis technique with transient absorption spectra of nanosecond was used to investigate the oxidation pathway and kinetics of ammonia
oxidation by *OH. Results illustrate that *OH could oxidize NH3 to form *NH2 with a second-order rate constant of (1.0 +/- 0.1) x 10(8) M(-1) s(-1)
(20 degrees C). *NH2, the main product of *OH with NH3, would further react with H2O2 to yield *NHOH. Since *NHOH could not stay stable in solution,
it would rapidly convert to NH2O2- and consequently NO2- and NO3-. "
The body of the paper appears to suggest that ammonia conversion was highest at pH 9.3 where molecular ammonia concentration as NH3 equals the cation
NH4+ concentration. Further, increase initial ammonia concentration increases the amount of nitrate formation, whose rate of formation declines as the
solution becomes more acidic (thereby implying the need for periodic addition of ammonia, H2O2 and NaOH to target pH 9.3 to maximize yield, which may,
nevertheless, be low).
Source: Environ Sci Technol. 2008 Nov 1;42(21):8070-5, "Removal of ammonia by OH radical in aqueous phase", by Huang L1, Li L, Dong W, Liu Y, Hou H.
[Edited on 13-4-2015 by AJKOER]
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aga
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The UK seems to apply each insane EU ruling with great Gusto.
Probably the UK's EU discount is involved.
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Bert
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Given the choice between Potassium, Sodium or Calcium nitrates as the only ones not requiring a permit?
Sodium nitrate if I intended to make nitric acid or perform a Sulfuric acid/nitrate nitration, such as synthesizing picric acid from aspirin.
Potassium nitrate if I had an interest in pyrotechnics.
Calcium nitrate if I wished to be able to manufacture either of the above nitrates easily from OTC materials, and also provide my tomato and pepper
plants a nice water soluble fertilizer to boost vegetative growth and inhibit blossom end rot (caused by low Calcium after a heavy rain)
Rapopart’s Rules for critical commentary:
1. Attempt to re-express your target’s position so clearly, vividly and fairly that your target says: “Thanks, I wish I’d thought of putting it
that way.”
2. List any points of agreement (especially if they are not matters of general or widespread agreement).
3. Mention anything you have learned from your target.
4. Only then are you permitted to say so much as a word of rebuttal or criticism.
Anatol Rapoport was a Russian-born American mathematical psychologist (1911-2007).
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jock88
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You can purchase 'Calcium Ammonium Nitrate' , aka CAN , or '27% straight Nitrogen' or '27.5% straight Nitrogen' from any farm store by the cwt.
It's a mixture of Ammonium Nitrate + Lime of some sort (insoluble).
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woelen
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This product, called KAS where I live, cannot be purchased anymore by people without a license. Only farmers who can show that they need it as
fertilizer can still buy this, but it requires paperwork. I as a plain consumer cannot buy KAS (kalk ammon salpeter, translated as chalc ammonium
saltpeter) anymore since four years ago.
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Sulaiman
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I've decided, I ordered calcium nitrate as I want to have a go at synthesising other nitrates
from a simple source, and I can use it as a fertiliser ... thanks Bert
a workmate gave me 15.22g KNO3 he had left over so enough for a trial run.
Thanks for all of the info.
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Texium
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The calcium sulfate formed is actually not a bad thing as long as you can stir the contents of the flask. Because it precipitates out all of the
sulfate, you'll generally get a better yield than using the soluble ones, and calcium sulfate is also hygroscopic, so it will also sequester some of
the water.
Praxichys has a video explaining all of this in greater detail. He used calcium ammonium nitrate, but the same principle applies when using normal
calcium nitrate: https://www.youtube.com/watch?v=7akk5ppJjEw
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Blunotte
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This route is too hard?
First:
Ca(NO3)2 + K2CO3 --(acq)--> CaCO3 (prec) + 2KNO3
Second:
filter and evaporate the solution
Et voilà, KNO3 without troubles 
If you work at 20°C, you will need about 420 gr of K2CO3 and 500 gr of
Ca(NO3)2 for every liter of water:
320g/l is the solubility in water at 20° of the KNO3, but the other reagents are much more soluble
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woelen
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I am afraid that it will be a terrible mess. Do not expect to obtain a nice clear liquid with a compact precipitate in it. At those high
concentrations you most likely get a white viscous mud, which will be very hard to handle. If you do this, you need much more dilute solutions, but
that has the disadvantage of having a lot of water to evaporate.
If you perform this reaction, then I would take a small excess amount of K2CO3. The KNO3 you obtain then contains some K2CO3, but you can separate
that fairly easily by means of recrystallization.
Keep in mind that K2CO3 is hygroscopic and the commercial material may contain quite some water, even if it looks dry. You may have to dry it in a hot
oven before using it in an experiment like this if you want accurate weight measurements.
Ca(NO3)2 is available as the tetrahydrate and anhydrous. Test this before doing the experiment. Heat some of the solid in a test tube and see how much
water vapor (which forms big drops of water higher up in the test tube) is formed. The anhydrous salt hardly produces any water, the hydrated salt
forms quite a lot of big drops of water.
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Blunotte
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Mmm...
Yes, it's right 
In these days I will want to buy some calcium nitrate and some potassium carbonate, so I will try to make it
For the eavporation, I don't think that somebody need tons of reagents, but much less than a kilo, I hope, so there is not a trouble for it 
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Blunotte
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Potassium nitrate is perfect for recrystallization: 
Solubility in water:
133 g/l (0 °C)
320 g/l (20 °C)
2470 g/l (100 °C)
So, just boil the solution, to evaporate some of the water, and then put in the freezer.
I think it is better to repeat this process several times, rather than do it in one go 
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