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Author: Subject: HNO3????
12AX7
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[*] posted on 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




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Pyrovus
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[*] posted on 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.




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Levi
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[*] posted on 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 NCl<sub>3</sub> 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 NCl<sub>3</sub> in cold concentrated H<sub>2</sub>O<sub>2</sub> behind a blast shield :D




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[*] posted on 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.
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Filemon
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[*] posted on 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...?:o


Sure? I Believed that it produced N2.



[Edited on 28-4-2007 by Filemon]
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[*] posted on 29-4-2007 at 11:20


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...?:o


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
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Filemon
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[*] posted on 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.
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Filemon
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[*] posted on 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?
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