SimpleChemist-238
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Nitrating Isopropyl Alcohol
I wanted to try to safely nitrate isotropy alcohol.
I was playing around with the idea and with my ventilation on I slowly add nitric acid to a reflux setup containing room temp sulfuric acid and
isotropy alcohol. Very very slowly, around a drop every 30 seconds I let the nitric acid react. The reaction was still too violent to control. It
scarred me just how violent it was. Plumes of NO2 flying out of the condenser and lots of heat. I recovered my acid from the pressure funnel and
stopped the reaction. Not some thing I will trying again for a few months. I have seen the videos on the net and was hoping to control it. It may not
be a bad test for nitric acid concentration.
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byko3y
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What procedure did you use?
"When it comes time to mix Solution A with Solution B, don't just dump the two together as Drone's notes may have inferred. Doing so will release a
quite impressive orange/red mushroom cloud that will send you running for cover. Instead, add B to A SLOWLY!", where solution A is sodium nitrite in
water and solution B is isopropyl alcohol in dilluted sulfuric acid.
The fumes of NO2 are okay, until it's too much of them. Also, you should add the IPA-H2SO4 solution to the bottom of HNO2 solution, because otherwise
a local drop of ph will decompose the HNO2 on the surface, leading to more NO+NO2 fumes.
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Amos
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Quote: Originally posted by byko3y  | What procedure did you use?
"When it comes time to mix Solution A with Solution B, don't just dump the two together as Drone's notes may have inferred. Doing so will release a
quite impressive orange/red mushroom cloud that will send you running for cover. Instead, add B to A SLOWLY!", where solution A is sodium nitrite in
water and solution B is isopropyl alcohol in dilluted sulfuric acid.
The fumes of NO2 are okay, until it's too much of them. Also, you should add the IPA-H2SO4 solution to the bottom of HNO2 solution, because otherwise
a local drop of ph will decompose the HNO2 on the surface, leading to more NO+NO2 fumes. |
You really should read the actual post. No one said anything about using nitrites; the OP is attempting to NITRATE isopropyl alcohol, not produce
isopropyl nitrite.
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SimpleChemist-238
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Isoproyl nitrite is very easy to make but Amos is right I am attempting to nitrate it. To make things clear and to repeat my self I added very slowly
the nitric acid to the isopropyl and sulfuric. I used equal volumes of nitric to sulfuric. My exact amounts were,
50ml of 90% isopropyl
30ml of 98% sulfuric acid
30ml of 90% nitric acid
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Tdep
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Did you use any method of cooling? IPN runaways are a very easy thing to do but a nice icebath and everything cooled down as low as possible should be
your first step in trying to control someone like this.
Adding just the nitric acid to the sulphuric produces a large amount of heat which would easily add to the runaway. I feel you'd have much more luck
mixing the mixed acids together first and adding the alcohol drop wise to the acids.
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byko3y
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Okay, now I understand what actually OP did, because I've got essentially the same results without cooling. This shit starts boiling like crazy and
gives off red fumes of NO2. This happened even when I've added a nitric acid into a beaker with residual IPA.
SimpleChemist-238, where do you suppose him to get the 90% nitric acid? I believe the reaction can be done with 34 weight parts of 70% HNO3 + 56 parts
of 95% H2SO4 + 10 parts of IPA.
https://www.google.com/patents/US2225893
https://www.google.com/patents/US2618650
PS: OMG, I'm so obliviuos, I've just realized that SimpleChemist-238 is the Original Poster of the thread.
So you are using 40:55:40 ratio for IPA:H2SO4:HNO3. I'd say it's definitely wrong.
Most of procedures for nitration using H2SO4+HNO3 tell that you need to prepare the acid mixture first, and then add your precursor. I'm sure your
problam lays in overheating.
[Edited on 2-6-2015 by byko3y]
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nn2
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adjust your drip to produce smaller drops and introduce strong stirring in the acid. You may have to cool significantly, but I do recommend using a
thermometer to see that a reaction is happening.. so if it jumps from -40 to -25 after you add a few drops.. you know to slow down.
dry ice + solvent to get a good temp bath (choose the solvent from a ice bath coolant mixture table), or perhaps salt ice will be enough.
I believe for many nitrations you need to chill your acids really good.
Are you sure that HNO3 is not getting hot when you add it to the H2SO4.. since its being further dehydration (you do not have anhydrous conditions).
Also, you are only using 90% iso. That water there is finding the concentrated sulfuric acid and reacting with it to produce heat.
and in this case you should chill your isopropyl alcohol too. this might be tricky, i suggest maybe an auto syringe (stepper motor) that pushes on the
actual syringe that is enclosed in some low temp bath.. might be tricky apparatus. i see a copper tube that fits the syringe snuggly, a thick end on
the non plunger side (with a thin thin hole in it to allow the neeedle to pass through it.. and have a coolant sleave around this. so basically the
droplet forms right at the end.. also having it fall a distance might allow the droplet of alcohol to penetrate deeper into the nitration bath (thats
being stirred hard), so the reaction happens under the surface of your mixture, allowing cooling to happen better.. if you just form a interface of
H2SO4/HNO3 and alcohol.. they will not mix that well because of density differences... so you have like, two puddles with a reaction happening between
them, so heat goes off into the air rather then being quickly absorbed by the surrounding liquid.
[Edited on 2-6-2015 by nn2]
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byko3y
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| Quote: Originally posted by nn2 | That water there is finding the concentrated sulfuric acid and reacting with it to produce heat...
if you just form a interface of H2SO4/HNO3 and alcohol.. they will not mix that well because of density difference... |
The water on reaction with 98% conc sulfuric acid will not produce heat, but it will produce a lot of heat, enough to boil the water.
You need to mix the acid mixture while adding the alcohol and add it slightly (one third) below the surface.
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clearly_not_atara
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If the alcohol is already mixed with the H2SO4 in the flask (as it should be) and then cooled, obviously the residual water can't heat the sol'n again
when HNO3 is added. The problem is that there's a runaway chain reaction when HNO3 starts to oxidize IPA to acetone, which produces heat, leading to
more oxidation, and eventually a big mess. Isopropyl nitrate (which is an explosive, duh) can oxidize itself so once things get hot it
doesn't matter if the nitrate had already reacted. The conditions will never be fully anhydrous because isopropanol + H2SO4 >> isopropylsulfuric
acid + H2O.
The solution is to make the reaction much colder, using an ice bath with ammonia, and making sure the temp. doesn't rise above -20C with
dropwise HNO3 and stirring. I don't think you have to go all the way down to dry ice/acetone (-78 C) but at room temp. you're not going to see
anything but oxidation no matter how slow your addition is. If this moves too slowly, prepare a mixture of HNO3/H2SO4 (concentrated) and add that
dropwise instead. And for the sake of not having tiny shards of glass embedded into your face, wear a mask and work with small amounts.
EDIT: adding isopropanol to HNO3 + H2SO4 does indeed make more sense than the reverse.
[Edited on 2-6-2015 by clearly_not_atara]
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SimpleChemist-238
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I'm trying to brake into organic chemistry but its difficult to find good procedures. I was thinking about bromating benzyl alcohol but its difficult
to find good info on the subject. I want to avoid benzene and I thought benzyl alcohol would be a good substitute. I thought about using salicylic
acid but it is insoluble in water so it would make reactions more difficult. A simple aromatic compound that's not to deadly is what I am looking for.
We are chemists , we bring light to the darkness. Knowledge to ignorant, excitement to the depressed and unknowing. we bring crops to broken fields
and water to the desert. Where there is fear we bring curiosity.
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DraconicAcid
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| Quote: Originally posted by SimpleChemist-238 | I'm trying to brake into organic chemistry but its difficult to find good procedures. I was thinking about bromating benzyl alcohol but its difficult
to find good info on the subject. I want to avoid benzene and I thought benzyl alcohol would be a good substitute. I thought about using salicylic
acid but it is insoluble in water so it would make reactions more difficult. A simple aromatic compound that's not to deadly is what I am looking for.
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If you want to do an aqueous-phase reaction of salicylic acid, do it in basic solution.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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SimpleChemist-238
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| Quote: Originally posted by DraconicAcid | | Quote: Originally posted by SimpleChemist-238 | I'm trying to brake into organic chemistry but its difficult to find good procedures. I was thinking about bromating benzyl alcohol but its difficult
to find good info on the subject. I want to avoid benzene and I thought benzyl alcohol would be a good substitute. I thought about using salicylic
acid but it is insoluble in water so it would make reactions more difficult. A simple aromatic compound that's not to deadly is what I am looking for.
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If you want to do an aqueous-phase reaction of salicylic acid, do it in basic solution. |
Won't the base lets say sodium hydroxide react with any acids used in the synthesis? If not why?
We are chemists , we bring light to the darkness. Knowledge to ignorant, excitement to the depressed and unknowing. we bring crops to broken fields
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kecskesajt
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This is all pain in ass,just add isopropyl-iodide to silver nitrate and BOOOM:You have IPNO3(hopefullynot BOOOm)
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kecskesajt
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This is all pain in ass,just add isopropyl-iodide to silver nitrate and BOOOM:You have IPNO3(hopefullynot BOOOm)
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kecskesajt
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This is all pain in ass,just add isopropyl-iodide to silver nitrate and BOOOM:You have IPNO3(hopefullynot BOOOm)
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