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HNO3????

menchaca - 30-3-2003 at 15:57

i dont know what i did when i was child or how i did it but this is what happened to me:

i took a large bottle and i added quantity of ammonia and a large quantity of comercial H2O2(3%) suddenly it´s colour turned red and white fumes appeard in the mouth of the bottle. Could that generate nitric acid? i dont know what to to think because nitric acid isnt easy to obtain oxidying ammnia but this was what happened to me and.........
well that´s all, i hope somebody can help me

thanks again!

DeusExMachina - 30-3-2003 at 17:02

no, that's not the way it works. You make HNO3 from ammonia with electrolisys. With platinum wires that is. I made a topic on this (I think it was me

)

menchaca - 31-3-2003 at 14:11

can you tell mi more about this?

about production of HNO3 electroliticly i mean......

Darkfire - 31-3-2003 at 15:10

H2SO4 + (X) NO3 = HNO3 + ....

You will need to distill of the nitric acid under low temps to avoid decomposition.

CTR

DeusExMachina - 31-3-2003 at 15:59

there has been a topic on this I have been told it is nearly impossible to do this with a home lab.

Darkfire - 31-3-2003 at 16:11

No way, its not hard at all with even a basic lab.

CTR

Rhadon - 31-3-2003 at 16:19

DeusExMachina: If you are referring to what I said in another topic: I was talking about the oxidation of ammonia back then (which I do now think should be possible to do at home as well, after BASF gave me details about the process to convince me

). What Darkfire is talking about will be possible to do at home, although a considerable amount of the HNO3 will decompose if you distil at atmospheric pressure. I'd suggest extracting the HNO3 with CH2Cl2 instead and avaporating the latter (b.p. of CH2Cl2 is only about 40 °C), that should be possible to do with hardly any decomposition of the HNO3. This method has already been covered well, at least in an older thread on the E&W forum. You might check this out when it's back up. There is also a patent about this process which should be worth reading. It's on the FTP in Xoo's Folder.

[Edited on 1-4-2003 by Rhadon]

[Edited on 1-4-2003 by Rhadon]

menchaca - 1-4-2003 at 11:22

will electrolitic oxidation of NH3 only posible with platinum electrodes? if other materials can be used what materials?

thanks again!

Cappy - 2-4-2003 at 16:34

My guess is that platinum is used because it is not very reactive with HNO3. Gold could probably be used, but still cost a lot. Aluminum could probably be used, but would lose more energy as heat (higher resistivity).

I'm not positive. Could someone confirm or deny this?

[Edited on 4/3/2003 by Cappy]

Theoretic - 2-10-2003 at 07:27

An answer on the original question: H2O2 reacts with ammonia to give NH4NO2:
2NH3+3H2O2=>NH4NO2+4H2O.
The red probably was NOx evolved from a side reaction. The white...?

Blind Angel - 2-10-2003 at 07:33

NH4NO2, wouldn't this be usefull to form nitrite (Sodium Nitrite and all)

NaCl + NH<subb>4NO2 -> NH4Cl + NaNO2
NaOH + NH<subb>4NO2 -> NH4OH + NaNO2

?
Any of those reaction possible (yes i'm pretty tired)

BASF - 3-10-2003 at 02:53

NH4NO2? - Sounds too good to be true.

Anodical oxidation of NH3 ? This would be very cool. Maybe there is a patent on this?

BTW, platinum wire is not that expensive.
The bigger problem is that the electrodes have to have a big surface to get the desired current density.( if the current density is too high, only tiny gas bubbles are generated)

BASF - 3-10-2003 at 02:59

I was once thinking of making my own platinum-coated electrodes by dissolving it in aqua regia, then just let it dispose on a less noble metal.

This is also a cool way of detecting noble metals: for example, you can take a coin of copper(has to be pre-cleaned, of course), then place a drop of silver- quicksilver- or maybe also platinum- solution on it. After 5 mins or so, the coin turns silver.

Theoretic - 3-10-2003 at 04:19

Getting nitrites via the chloride route is impossible, NH4NO2 decomposes at low temperatures (hot water). The alkali route seems all right to me, don't see why it might not work.

Mephisto - 3-10-2003 at 05:53

The NH4NO2 decomposes at 20 °C. So maybe it’s possible to make it at 5 °C and get then the alkali nitrites by mixing with other alkali salts (like Blind Angel said).

[Edited on 3-10-2003 by Mephisto]

Theoretic - 10-11-2003 at 09:13

So, anyway, I think the white fumes were fumes of H2O2/concentrated NH3 solution/whatever - the heat of reaction is supposed to be considerable.
Now, THAT helped, didn't it?

Blind Angel - 10-11-2003 at 11:15

If the heat of the reation was considerable then NH4NO2 would decompose instantly...
By cooling we would be able to get some NH4NO2 in H2O2 and water (considering that Peroxyde was used in excess to oxyde all the NH3

then you could catalyst the H2O2 decomposition in water with Zn, Mg or another metal which you would be able to filter off to get a solution of Water and NH4NO2 add NaOH and you got NH4OH and NaNO2 solution. NaNO2 melt a 271ºC so you can boil off the water, NH4OH will simply decompose into NH3 and water at high temp. Sodium Nitrite from Household ammonia and Hydrogen Peroxyde, someone to try it (my peroxyde stock is a bit low lol

) ?

It´s worth trying

Mephisto - 10-11-2003 at 16:03

Unfortunately I haven’t enough time for more exact tests with bigger amounts, now. But I tried to do this just with some millilitres, some months ago. I’ve add 27.3 g (0.2 mol) of ice-cold NH3 (25%) to 68 g (0.3 mol) ice-cold H2O2 (30%). Both liquids had a temperature of -8 °C. During the mixing, there wasn’t any fume-evoltution or rising of temperature noticeable. Then I added 8 g NaOH in ~30 ml distilled water and heated the whole mixture for 45 minutes at 60 °C with continuously magnetic stirring. A lot of bubbles evolved and NH3-smell was noticeable, but no nitrous fumes have been formed.

To test the presence of NO2- or NO3- I added a mixture of sulfanilacid and alpha-naphthylamine (in German “Lunges Reagenz”). The test was positive. But it is very very sensitive, so maybe just some milligrams of NaNO2 have formed. I don’t know. I let the liquid dry, but never tested the residue.

But even if this give only bad yields, it could be possible to synthesise a nitrite, by passing nitrous fumes from H2O2 and NH3 (see first post) through a NaOH solution.

… start on research

Theoretic - 29-12-2003 at 03:30

Hmm... The reaction of H2O2 and ammonia can lead to different outcomes, depending on the stochiometry. The main reaction that probably happened at such low temperatures was the formation of HYDRAZINE! The hydrazine could probably go to hydrazoic acid if there was enough H2O2 present. If there was more H2O2 and more vigorous reaction conditions, nitrogen could have been evolved. And of course, yet more H2O2 yields nitrite and nitrate. Just like chlorine, going in order from smaller to bigger amounts of chlorine in the stochiometry, the products of its reaction with ammonia are:
Hydrazine
Chloramine
Nitrogen
Dichloramine
Nitrogen trichloride.
Going back to NH3/H2O2... More vigorous reaction conditions are required, in my opinion.

Hydrazine From Peroxides?

Acid Test - 6-1-2004 at 16:44

Hydrazine from ammonia and H2O2.It sounds to good to be true!!!

The formula would have to be
2NH3 + H2O2

That is two parts ammonia to one part of hydrogen peroxide.Hydrazine requires 2 Nitrogen and four hydrogen.The extreme reactions are caused by the excess hydrogen and oxygen being released from the reaction

Hmmm...

Theoretic - 7-1-2004 at 01:33

Mephisto: how do you expect nitrous fumes (acidic) evolve after you've added strong alkali? Hydrochloric acid might be a better test. I even think that ammonium chloride could be used, so as to remove nitrous fumes from the reaction zone as soon as formed

[Edited on 9-1-2004 by Theoretic]

Acid Test - 7-1-2004 at 11:12

Actually in the presence of a ketone you
would probably get indole.This of course
will set the way for psychedelic chemistry.
Indole is the main component to all
tryptamines including 5-MT(serotonin)
I have always wanted to try to synthesis
5-MT and take a dose of it

Levi - 23-4-2007 at 20:42

I wonder whether or not nitrogen trichloride and peroxide will form nitric acid. Working with NCl3 isn't a good idea on a large scale, but if it works it would be a tempting route to nitrates. I don't have a fume hood so I won't be trying this, has anyone else been brave (read: stupid) enough?

Assuming this method works, are the following equations correct?

NH3 (aq) + 3HCl (aq) --> NCl3 + 3H2
2NCl3 + 5H2O2 --> + 2HNO3 + 3Cl2 (g) + 4H2O

The_Davster - 23-4-2007 at 21:06

My only experiance involving NCl3 was accidental and mildly amusing...
The first reaction will not work, the following will happen.
NH3 +HCl -->NH4Cl

IIRC, NCl3 is prepared by bubbling chlorine into an ammonium nitrate solution, or electrolysis of ammonium chloride.

The second reaction I really could not say...

Levi - 23-4-2007 at 21:31

Quote:

Originally posted by The_Davster
My only experiance involving NCl3 was accidental and mildly amusing...
The first reaction will not work, the following will happen.
NH3 +HCl -->NH4Cl

Ah, thanks for pointing that out! NH4Cl in a solution of HCl in excess should form NCl3 when NaOCl is added. Without the bleach nothing happens.

I guess what the question boils down to is will hydrogen peroxide oxidize nitrogen trichloride from +3 to +5?

[Edited on 24-4-2007 by Levi]

12AX7 - 24-4-2007 at 12:40

More pertinent would be to make NCl3, transiently so as not to handle it, and oxidize it to "NCl5" (which probably can not exist due to steric hinderance) and hydrolyse to "N(OH)5", which obviously prefers to form NO3- in solution. I don't know that you can chlorinate AND oxidate the nitrogen in the same vessel.

Is there a catalyst that might allow NH3 + 3OCl- = NCl3 + 3OH-, while promoting NCl3 + 2H2O + OCl- + Cl- = (NCl5 + 2OH- + H2O) = NO3- + 5Cl- + 4H+. (Is that balanced? I *think* it is...)

Tim

Pyrovus - 25-4-2007 at 00:35

The trouble is though that NCl3 hydrolyses to ammonia and hypochlorite, consistent with nitrogen being in the -3 state, as opposed to the hydrolysis to N(OH)3 and HCl, which would be expected were it in the +3.

The only plausible structure for NCl5 would be as the salt, tetrachloroammonium chloride, NCl4+Cl-. To form this from NCl3, you'd have to have the lone pair of the nitrogen act as a Lewis base towards the delta(+) chlorine of the hypochlorite, and I'm not sure that the lone pair on the nitrogen is terribly easily donated in NCl3. In addition, even if you do manage to form the NCl4+ cation, it seems reasonable to expect that it would hydrolyse in much the same way as NCl3 - i.e. to hypochlorite and ammonia, as the oxidation number of nitrogen will probably still be -3. The analogous NF4+ cation could be expected to hydrolyse to HNO3, however, as the nitrogen is definitely in the +5 state in that cation.

So, sadly I don't see this idea working.

Levi - 25-4-2007 at 01:21

Quote:

Originally posted by Pyrovus
The trouble is though that NCl3 hydrolyses to ammonia and hypochlorite, consistent with nitrogen being in the -3 state, as opposed to the hydrolysis to N(OH)3 and HCl, which would be expected were it in the +3.

Warning: I have no idea what I'm talking about ahead. Read with caution and skepticism.

Can NCl3 be oxidized with persulfuric acid and would this produce the nitrate ion? Perhaps since the nitrogen isn't +3 it might be better to start with ammonia... Anyhow, as I said before I have no idea what molecular forces are at work here so I'm really just talking out of my arse.

I'm still tempted to try a drop of NCl3 in cold concentrated H2O2 behind a blast shield

not_important - 25-4-2007 at 04:59

From

The constitution of the so-called nitrogen iodide.
Frederick D. Chattaway, J. Chem. Soc., Trans., 1896, 1572-1583

reacting NCl3 with base gives nitrate :
(not balanced) NCl3 + NaOH => NaCl + [ N(OH)3 ] => HNO3 + N2 + H2O

Most likely not the true reactions, some of the NCl3 must be oxidising intermediates up to N(V), and a rather dangerous way to get to nitrate.

Another less dangerous and inefficient route to nitrates is treating lead dioxide with aqueous ammonia, resulting in lead nitrate and Pb(OH)2.

Filemon - 28-4-2007 at 03:57

Quote:

Originally posted by Theoretic
An answer on the original question: H2O2 reacts with ammonia to give NH4NO2:
2NH3+3H2O2=>NH4NO2+4H2O.
The red probably was NOx evolved from a side reaction. The white...?

Sure? I Believed that it produced N2.

[Edited on 28-4-2007 by Filemon]

Filemon - 29-4-2007 at 11:20

Quote:

It is bad the reaction. It should be:

2NH3 + 2H2O2 => NH4NO2 + 2H2O

Where you have seen it?

It is possible that it is certain that you can synthesize NaNO2:

NH3 + H2O2 => NH2OH + H2O

NH2OH + H2O2 => NH4NO2 + H2O?? Does somebody know it?

There are colateral reactions:

3NH2OH => NH3 + N2 + 3H2O

Filemon - 29-4-2007 at 11:54

Yes it is possible:

http://en.wikipedia.org/wiki/Ammonium_nitrite

But it was probably oxidized NaNO2 with H2O2.

Filemon - 14-6-2007 at 16:21

A better way to make nitrite is this way:

3Fe(OH)2 (s) + 2NO3 - (ac) => Fe3O4 (s) + 2NO2 - (ac) + 3H2O

As I can distinguish a nitrate of a nitrite easily?