Sciencemadness Discussion Board - Nitration with Anhydrous Copper Nitrate

Mixed acids won't work to form Nitramines.

Generally that is correct, but there are numerous exceptions. Urea and guanidine being the most obvious. The condensation product between acetamide and formaldehyde can also be nitrated with mixed acids. Even for hexamine, it is not entirely impossible for it to undergo a mixed acid nitration, although the product is a lesser nitramine compound:
http://www.sciencemadness.org/talk/viewthread.php?tid=19103

Quote: Originally posted by virgilius1979

Is it possible to react 1,1-2,2 tetrachloroetylene with AgNO3 ? or other similar product ? what solvent is best suited for this ?

Again, the answer to this question is not a clear yes or no. The rate of reaction for the displacement of chlorine from organic compounds is generally too negligible to be practical. Bromine or iodine atoms displace off much more easily. Indeed, bromomethane has been used as a fumigrant because of its poisonous alkylating properties.

Putting two nitrate groups on the same carbon is not practical. Methylene dinitrate, for example, is not even stable at room temperature. You would not get any useful product from your proposed reaction, or variant thereof. If you want to know exactly what would form, I am not entirely sure but I would guess they would include various byproducts such as oxalic acid, carbon monoxide, carbon dioxide, dichloroacetic acid.

There are quite a few different reasons your proposed reaction has no hope of producing anything useful. It is a complex subject, and I am not going to thoroughly go into all the details. I think it has been adequately covered in various other threads in this forum.

70% will turn skin yellow instantaneously !

If you get concentrated nitric acid burns, they should be immediately be rinsed with water, but then afterwards the skin should be repeatedly rubbed with a piece of cotton soaked in bleach, until most of the yellow discoloration has been washed off. Otherwise the nitrated proteins will act as allergens and hinder the healing process.

Hmm... Is there a concentration of nitric acid that won't burn skin?

Nitric acid below around 12% concentration generally does not have oxidizing properties. There is actually no clear point where it is no longer an oxidizer, but a lower concentrations the oxidizing reaction rate decreases exponentially. At much lower concentrations nitric acid will essentially behave like any other strong acid. 2% nitric acid failed to dissolve a piece of copper foil after 24 hours. You could probably dip your hand in 2% nitric acid if you quickly rinsed it off with plenty of water afterwards.

Be sure to wear long gloves when pouring 70% nitric acid. Even when one is very careful, there are always little micro droplets that splash upwards. Likely you will not see any splashing, but you can feel the tiny droplets when they get on your skin.

Quote: Originally posted by virgilius1979

I could reflux acetone with Ca metal to dehydrate it, i guess.

I think acetone might condense into a resin in the presence of a strong base.

[Edited on 19-2-2013 by AndersHoveland]

Motherload - 18-2-2013 at 23:00

I know about urea and guanidine.
But the question wasn't about them.
It was about a hexamine type derivative.
Tetraminetetramine.

[Edited on 19-2-2013 by Motherload]

APO - 19-2-2013 at 00:12

If I have a respirator, goggles, gloves, a lab coat, and a solution of sodium bicarbonate on hand, will that be enough safety to work with 70% or white fuming nitric acid? Also are there any gloves that are invunerable to nitric acid?

APO - 19-2-2013 at 00:13

Also I'm gonna ask my teacher if any nitrate salt can be used to run a nitration.

AndersHoveland - 22-2-2013 at 02:24

Also I'm gonna ask my teacher if any nitrate salt can be used to run a nitration.

I doubt he would know. This specific subject is not really a basic area in chemistry.

bahamuth - 22-2-2013 at 02:45

70% will turn skin yellow instantaneously !

Hmm, I find that nitrated skin works like a very good "band aid" until new bright pink skin forms underneath the burn until the yellow patch of nitrated skin easily sheds by itself. But then again I'd never had really large patches of skin nitrated..

KonkreteRocketry - 22-2-2013 at 05:25

Or maybe like this..

Thermal decomp of Cu(NO3)2(H2O)3.

Get 3 H2O, 4 NO2, 1 O2, and 2CuO.

Collect the gas, the NO2 and O2.
Collect the CuO left over.

Pass the NO2 and O2 gas into a glass of distilled water.

NO2 + H2O = HNO3.

Put CuO into HNO3.

Get Anhydrous copper nitrate

NO2 + H2O Get HNO3.

AndersHoveland - 22-2-2013 at 06:33

Putting CuO into HNO3 will not make anyhydrous copper nitrate.

CuO + 2 HNO3 --> Cu(NO3)2 · H2O

Motherload - 22-2-2013 at 07:06

CuO + N2O4 should work or 2X NO2
I don't know how vigorously the reaction would take place. Probably try it with a 100 mg of CuO with lots of cooling to keep the N2O4 liquid as I am certain the reaction will be exothermic and will need lots of ventilation.

DraconicAcid - 22-2-2013 at 10:45

Putting CuO into HNO3 will not make anyhydrous copper nitrate.

CuO + 2 HNO3 --> Cu(NO3)2 · H2O

Not to mention that the nitric acid itself is rarely anhydrous (the concentrated stuff we use in the lab is 70% nitric acid, the rest water).

Cite: Aldrich Catalogue, 2012-2014, p 1901-1902.

KonkreteRocketry - 22-2-2013 at 12:05

Quote: Originally posted by DraconicAcid

Putting CuO into HNO3 will not make anyhydrous copper nitrate.

CuO + 2 HNO3 --> Cu(NO3)2 · H2O

Not to mention that the nitric acid itself is rarely anhydrous (the concentrated stuff we use in the lab is 70% nitric acid, the rest water).

Cite: Aldrich Catalogue, 2012-2014, p 1901-1902.

Quote:

Putting CuO into HNO3 will not make anyhydrous copper nitrate. CuO + 2 HNO3 --> Cu(NO3)2 · H2O

Uummmm ok, but pure HNO3 does give Anhydrous Cu(NO3)2 right ?

Copper, silver compounds have a lot of reactions :p

DraconicAcid - 22-2-2013 at 12:09

Quote: Originally posted by KonkreteRocketry

Uummmm ok, but pure HNO3 does give Anhydrous Cu(NO3)2 right ?

Copper, silver compounds have a lot of reactions

Probably not, because one of the products of the reaction is water. Whether or not anhydrous nitric acid would be sufficiently hygroscopic to absorb that water is beyond me, but I have my doubts that your plans of passing NO2 through a glass of distilled water will give you the anhydrous result you crave.

[Edited on 22-2-2013 by DraconicAcid]

plante1999 - 22-2-2013 at 16:57

Here is my unscusceful try at making anhydrous copper nitrate. I also tested liquid nitrogen oxide dissolution in conc. nitric acid, as a preparation for my Ostwald reactor project.

Here is my set-up at making liquid nitrogen oxides. I used a snow/ conc. HCl mixture to make the cooling bath, it dropped to -40 Celsius. The NOx generator contain copper, 40% HNO3 and is quite cold at -5 degree Celsius. As you can see I now have ground glass!

Here is the liquid NOx:

Just after adding the copper, but it didn't reacted:

Because it didn't reacted, I dessided to test nitrogen oxide solubility, I added 1 ml of 70%+ nitric acid to the liquid NOx, you can see the nitric acid in the round bottom flask next to the beaker:

And this is my extremly concentrated nitric acid and the copper piece (I only have one ground glass stopper, and it was used for the nitric acid):

I may re-try this, but using gaseous NOx on hot copper.

DraconicAcid - 22-2-2013 at 18:16

Cool (or cold). The intense blue of the NOx is presumably due to N2O3, which Cotton and Wilkinson assured me was blue (NO2 being red-brown and N2O4 being colourless). I made it once by holding a chunk of dry ice over some copper reacting with nitric acid- it was soon covered in a blue frost.

Motherload - 22-2-2013 at 22:25

As far as I understand .... Any nitrations involving cupric nitrate require acetic anhydride.
They can only mono nitrate a deactivated aromatic ring.
What is the expected outcome for using cupric nitrate .... That would be better than conventional nitration for synthesizing energetics ?

KonkreteRocketry - 22-2-2013 at 23:13

I got an idea, get the NO2 gas from the decomp, then cool it down to -11 degree to get N2O4, then put the dry CuO to get Copper nitrate

AndersHoveland - 23-2-2013 at 01:25

As far as I understand .... Any nitrations involving cupric nitrate require acetic anhydride.

Unless you can manage to prepare anhydrous Cu(NO3)2 in the absence of water, which is not a simple thing to do.

They can only mono nitrate a deactivated aromatic ring.
What is the expected outcome for using cupric nitrate .... That would be better than conventional nitration for synthesizing energetics ?

Do not quote me on this, but I think I remember reading that nitrations with Cu(NO3)2 on aromatic rings give a higher ratio yield of the para- isomer, as the case may be, and are also less likely to oxidize any vulnerable functional groups.

Motherload - 23-2-2013 at 07:37

Quote: Originally posted by KonkreteRocketry

I got an idea, get the NO2 gas from the decomp, then cool it down to -11 degree to get N2O4, then put the dry CuO to get Copper nitrate

I have mentioned that a couple of times in your copper nitrate synthesis thread.

@Anders
I know that ... I am posting in the "Nitration with Anhydrous Nitrate" thread regarding nitration with Acetic anhydride present.

[Edited on 23-2-2013 by Motherload]

[Edited on 23-2-2013 by Motherload]

AndersHoveland - 23-2-2013 at 13:55

Quote: Originally posted by KonkreteRocketry

I got an idea, get the NO2 gas from the decomp, then cool it down to -11 degree to get N2O4, then put the dry CuO to get Copper nitrate

I think it would probably work, but I am not completely sure. CuO might be too weak of a base in the absence of water. (Even if the gas is absorbed, you might only get some sort of double nitrate/nitrite salt, if the initial nitrite that forms is not in ionic form then further NO2 would then not be able to oxidize it to the pure nitrate.) For the reaction to proceed, you would also need some sort of liquid solvent that could dissolve either the initial solid reactant or the product, I am not sure what exactly that might be.

Edit: Woelen says the reaction does work...

Quote: Originally posted by woelen

But in the 1960's the anhydrous salt was prepared by reaction of metallic copper with a solution of thoroughly dried NO2 in ethyl acetate at low temperature.

Makes me wonder how the reaction can produce nitric oxide without the copper nitrate just oxidizing it.

[Edited on 23-2-2013 by AndersHoveland]

APO - 5-5-2013 at 22:16

Excuse me, but I've already obtained the Anhydrous Copper Nitrate. Can we get back to nitration?

killswitch - 11-5-2013 at 20:32

Excuse me, but I've already obtained the Anhydrous Copper Nitrate. Can we get back to nitration?

So, you wanted a nitramine, correct? And I'm assuming you want to eschew acetic anhydride?

What substrates are you considering?

And political or nationalist signatures of any kind are a tendentious topic here. We post for the science, not the drama.

[Edited on 12-5-2013 by killswitch]

APO - 11-5-2013 at 21:55

Signature... Taken care of.

I would like to make Picric Acid from it, Anders said I could use it to nitrate phenol. Also Methenamine would be fun. I haven't maid any Acetic Anhydride yet, so that's not currently an option until I get Phosphorus Trichloride.

chemcam - 11-5-2013 at 22:21

Come on APO, you have listed in the last week that you want to make just about every single high powered explosive. Do you know the chemistry behind them that will prevent you from killing yourself? Why start so huge? Have you even done a nitration before? I'm guessing not since you ask if there is a nitric acid that won't burn your skin, you should wonder how HE's will rip your skin off, and figure out a blast shield/loading mechanism.

Do some acid-base extractions, make nitrocellulose for damn sakes. Everyone here is concerned about your wants and needs man can you not take a hint? Tell me ONE experiment you have done pertaining to basic knowledge of any energetic.

There are fun things you can do other than risking your life with these compounds. What chemicals are in your possession right now and I'll tell you something k3wl you ran reasonably do to improve your skills. Do you even own a beaker, a Flask..? what do you have in your lab, maybe a GC-MS unit?

EDIT 1: Fixed errors.

EDIT 2: This just happened today, here is a picture of my thumb after a tiny drop of 70% nitric acid got on me, I didn't notice until it was hurting and at that time I could see some meat was eaten under the yellow stain. After I washed my hands the yellow skin fell off and now I have this little hole.

[Edited on 5-12-2013 by chemcam]

APO - 12-5-2013 at 14:46

That's not so bad.

chemcam - 12-5-2013 at 14:56

That's not so bad.

Yeah, nothing to be afraid of, just respect it and it will respect you. I was being lazy and didn't put my gloves on while filling up my 250mL reagent bottle from a large 2.5L bottle. The drop got me when I took the funnel out.

APO - 12-5-2013 at 16:26

Ever work with fuming nitric acid?

chemcam - 12-5-2013 at 16:34

Yes I have made it many times. I haven't spilled it though, I always wear gloves with WFNA and RFNA. The ACS 70% that I have even fumes quite a bit.

APO - 12-5-2013 at 20:41

Do you use a respirator?

chemcam - 12-5-2013 at 21:19

Do you use a respirator?

No I dont use a respirator only use very nice goggles. When I do a reaction that fumes heavily like NO3 or similar I have 2 large fans that push the vapors out of the garage. Never have fans suck the vapor or you will have problems. I also have a fume hood but at the moment it needs repairs, I ran the fan solid for a long time with no speed regulation and it burnt out.

EDIT: Hey APO with these kind of questions that nobody else benefits from why don't you just u2u them to me instead. I'm not an asshole or anything, but a smart-ass sometimes.

[Edited on 5-13-2013 by chemcam]

woelen - 13-5-2013 at 02:40

Signature... Taken care of.

I would like to make Picric Acid from it, Anders said I could use it to nitrate phenol. Also Methenamine would be fun. I haven't maid any Acetic Anhydride yet, so that's not currently an option until I get Phosphorus Trichloride.

What are you talking about? Please be realistic. A 13 year old boy getting phosphorus trichloride?
Are you really interested in chemistry or do you just want to boast about dangerous and hard to obtain chemicals to impress others?

Could you post a list of chemicals you have now and as others asked, could you also tell what kind of equipment you have? You know? Stuff like PCl3 is not for little kids.

plante1999 - 13-5-2013 at 02:57

He was saying that President Obama "sucks".

Simply quoting, not saying my opinion.

APO - 13-5-2013 at 13:51

First of all Woelen, Phosphorus Trichloride can be made from slow addition of gaseous Chlorine to elemental Phosphorus, and second of all, I'm truly interested in chemistry and I'm editing a lab tour video as we speak to silence some of my critics.

Bot0nist - 13-5-2013 at 16:27

APO, I can tell ytou are very interested in chemistry, but I really doubt wha you have is anhydrous copper nitrate under argon. I know thats what the seller said it was, but I am 99.99% sure it is a hydrate.

Good luck friend.

APO - 13-5-2013 at 16:56

Damn.

chemcam - 13-5-2013 at 16:59

Damn.

Can you post a picture of what you have, in the bag.

APO - 13-5-2013 at 17:03

Will do in my lab tour.

chemcam - 13-5-2013 at 21:30