Sciencemadness Discussion Board

Easy Isopropyl Nitrate

APO - 2-3-2013 at 13:51

I read that anhydrous Magnesium Nitrate can be added to nitric acid to bring the concentration past it's azetropic concentration. I thought maybe it could replace dangerous nitric acid for some reactions, and I got mixed answers on that post. I've heard that it's extremely reactive and very powerful. Then I remembered that on Megalomania, they used Isopropanol saturated with Urea and then added Nitric Acid to make Isopropyl Nitrate (along with other steps), so I thought maybe adding anhydrous Magnesium Nitrate to Isopropanol saturated with Urea could yield Isopropyl Nitrate in solution.

franklyn - 2-3-2013 at 14:54

You still need H2SO4 , and inexpensive NaNO3 will do.
Without nitric acid, urea serves no use.

.

kristofvagyok - 2-3-2013 at 18:10

Quote: Originally posted by APO  
it could replace dangerous nitric acid

HNO3 is not more dangerous than your life. If you would have wrote +95% HNO3 or something stronger like that, than I would say, maybe. But isopropyl-nitrate could be easily made with relative dilute solutions of nitric acid (50-60%), what is just only dangerous if you spill it on your face or drink it. If you work properly, than it's perfectly safe.
Quote: Originally posted by APO  
I thought maybe adding anhydrous Magnesium Nitrate to Isopropanol saturated with Urea could yield Isopropyl Nitrate in solution

And what would make the nitrate ester? If there is no acid present, nothing will happen. There will be a really awesome solution of Mg-nitrate, urea and alcohol. More than awesome, good for nothing!

There is a really simple rule: chemistry couldn't be made without chemicals. If you plan to make energetic compounds from air and soil, than you will have really hard time to produce anything. Unless you are afraid from every basic reagent I would suggest theorical chemistry. It won't harm your skin or cause accidents.

neptunium - 3-3-2013 at 06:46

which defeat the purpose of making energetics...lots of people out there interested in making those but wont mess with mineral acids!
its completly backward!
if you are willing to take the risk of loosing fingers (or worse) then you should be willing (you would think) to deal with concentrated acid...this whole thing is either a kewl signature or someone with limited access to chemicals and limited interest in real science...

APO - 3-3-2013 at 16:10

I'm fine with the thought of acids now.

AndersHoveland - 3-3-2013 at 23:08

Just remember that isopropyl alcohol is oxidized more easily than the other alcohols. Nitrations of isopropyl alcohol can be problematic. To give the short explanation, it is possible, but it can be difficult to get the reaction to work.

The C-H bond on the central carbon is more polar and is easily oxidized to the ketone. As soon as it is oxidized to acetone, the molecule immediately tautomerizes under the acidic conditions, and the resulting enol is easily oxidized by further nitric acid. Under some conditions, some trinitromethane can even be formed, as it can essentially become a modification of the Haloform reaction.

[Edited on 4-3-2013 by AndersHoveland]

APO - 3-3-2013 at 23:10

I know it's really freakin' hard, I think I'll have to get a procedure that is reliable in the first place.

AndersHoveland - 3-3-2013 at 23:14

Quote:

Isopropyl nitrate boils at 101-102°. It is easily inflammable, burning with a white lumious flame, and its superheated vapor explodes violently when ignited. Direct nitration of isopropyl alcohol is difficult due to oxidation of the carbon atom carrying the secondary hydroxyl group.

Direct nitration was found to yield mainly acetone due to the oxidation of the secondary alcoholic group. However a process for the continuous nitration of isopropyl alcohol in the presence of urea has been described in Imperial Chemical Industries patents (W.G.Allen and T.J. Tobin -British Patent 696489-1953;749734,749844-1956

iso-propyl alcohol and urea were introduced into nitric acid (over 40 % HNO3) at its boiling temperature
and a current of air stirred and removed unstable products.
According to Desseige (G.Desseigne, Mém.podres 37,97;1955) the method gave ca. 80% yield. He used nitric acid of over 50 % HNO3 at 108-110 C.
Quote:

Take 5 ml of 50%-65% nitric acid, add about 100 mg Urea, cool and add 5 ml isopropanol, NOT LESS!!! [Using the stoichiometric best amount of isopropanol, here about 2,5 ml, may cause too much heat generating and decomposion of the mixture.] When you cool the solution you prepared after 1-2 hours a isopropyl nitrate-Phase on the acidic solution should have formed.

put about 5 ml HNO3 55% in a test tube, then add urea until you find that it's enough.....you have to find out yourself....then add about 5 ml isopropyl alcohol and then let the test tube swim in cold water....at first the urea bubbles, ´reacting with the HNO3, and then, after a while, a thick layer of IPN forms on the acid mix.

mackolol - 7-1-2018 at 10:37

Let me bring this thread to live. Yesterday i tried to make IPN because it interested me. I did this on small scale so took 11ml of IPA 4,5ml of conc. h2so4 and 3 ml of water mixed it and put into freezer to cool it down as low as possible. Then i took around 12g of kno3 and dissolved in 45ml of h2o (i know i took to small amount of water and in further steps salt crystallised in my addition funnel). Then i put my flask with acid and ipa on cooling ice bath and with stirring i started adding solution of kno3 caring not to heat mixture over 2C. When some of kno3 had crystallised and blocked my funned i added a little of water and started to add it by simply pouring. Each pour temp rised by 1C so it wasnt very exothermic. When everything was added i left it on ice bath for an hour. When i poured it to separating funnel i havent seen any organic layer. I added ink and thought that maybe ipa is colourless and this will help but this did nothing. I can also say that mixture is still smelling like ipa. Maybe there was too much water that broke ester and this reaction has to be done without diluting acids. Can somebody help?

roXefeller - 16-1-2018 at 19:41

I haven't sat down and run the stoich with your numbers but you seem to be adding water where there shouldn't be. I would suggest you check your molar quantities for yourself. The purpose of the conc h2so4 is to draw water away from the nitric ester reaction occurring on the IPA. Diluting with water will bring the concentration to a point where water isn't being sufficiently drawn away. Adding the kno3 is merely to create hno3 in situ, therefore requiring more conc h2so4 to be consumed in hno3 creation. Reply back with your stoichiometric quantities to see for yourself.

LearnedAmateur - 17-1-2018 at 04:43

Yeah, the thing about esters is that they typically exist in equilibrium (here, iPrOH + HNO3 <-> iPrNO2 + H2O), so Le Chatelier’s principle comes into play. Like roXefeller said, (one of) the purposes of the sulphuric acid is to remove water to drive the reaction to the products side - by adding water, the reaction wants to act in a way which minimises the change, so the equilibrium is shifted to the reactant side. Since the sulphuric acid also acts as a catalyst, removing the protonated hydroxyl group of the alcohol as well as the ester hydrolysis, adding water will just cause this to occur faster. I’m not entirely sure on the solubilities, but adding iPrOH instead of water would be a more preferable option.

[Edited on 17-1-2018 by LearnedAmateur]