AJKOER
Radically Dubious
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Forming HE In Situ to Improve Stability
I recently came across the following comment (see http://www.guidechem.com/reference/dic-15333.html ), to quote:
"Heating a mixture of an ammonium salt with a nitrite salt causes a violent explosion on melting, owing to formation and decomposition of ammonium
nitrite. Salts of other nitrogenous bases behave similarly. Mixtures of ammonium chloride and sodium nitrite are used as commercial explosives."
My take on the reactions:
NH4Cl <--Heat--> NH3 + HCl
HCl + NaNO2 --> NaCl + HNO2 --Low pH,Heat--> NaCl + H2O + NO + NO2
2 NH3 + (2 NO2 + H2O) -->2 NH3 + (HNO2 + HNO3) --> NH4NO2 + NH4NO3
or, the action via dry NH3:
2 NO2 + 2 NO + 4 NH3 --> 2 NH4NO2 + 2 H2O + 2 N2 (see AndersHoveland comment at http://www.sciencemadness.org/talk/viewthread.php?tid=23807&... )
So the impractical high explosive ammonium nitrite is made seemingly more practical.
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Here is another simple example of how to address a highly explosive, but overly sensitive salt. For example, in the case of ammonium chlorate,
prepared, in part, in situ by mixing NH4Cl (or, more questionablely, NH4NO3, except at a low temperature where a dissociation into NH3 and HNO3
occurs, as an explosive decomposition of NH4NO3 occurs with high temperatures (see https://docs.google.com/viewer?a=v&q=cache:24T2OzVp9JsJ:... ) Expected reactions:
NH4Cl --Heat--> NH3 + HCl
KClO3 + HCl --> KCl + H2O + ClO2 + Cl2
2 ClO2 + H2O <--> HClO2 + HClO3
2 ClO2 + H2O + 2 NH3 --> NH4ClO3 + NH4ClO2 --> Explosion
With respect to dry ClO2 and NH3 reaction, given its explosive nature, it is hard to speculate on the intermediate products.
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Another example similar to the above adding CuO to NH4NO3 and mildly heating. Some possible reactions:
NH4NO3 --Mild Heat--> HNO3 + NH3
CuO + 2 HNO3 --> Cu(NO3)2 + H2O (vapor)
4 NH3 + Cu(NO3)2 --> Cu(NH3)4(NO3)2
that is, the possible formation and detonation of Copper ammonium nitrate.
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Also, in a similar vein to the first example but more complex, what if one heated a layer of NH4Cl mixed with a solid hypochlorite like Ca(OCl)2 or
perhaps even Lead hypochlorite, Pb(ClO)2, prepared as follows (see http://bcs.whfreeman.com/WebPub/Chemistry/ichem5e/Videos/Hyp... assuming it is stable enough:
"Initially, lead(II) ion reacts with hypochlorite ion to give a white precipitate of lead(II) hypochlorite:
Pb2++(aq) + 2 ClO-(aq) --> Pb(ClO)2(s)
The lead(II) hypochlorite is then oxidized to lead(IV) oxide. Reaction is slow at room temperature but much faster when the tube is placed in boiling
water.
Pb2+(aq) + 2 H2O(l) --> PbO2(s) + 4 H+(aq) + 2 e-
ClO-(aq) + 2 H+(aq) + 2 e- --> Cl-(aq) + H2O(l) "
Now, the action of HCl (from the sublimed NH4Cl) on the hypochlorite should generate Cl2, for example, with calcium hypochlorite:
4 HCl + Ca(OCl)2 --> CaCl2 + (2 HCl + 2 HOCl) --> CaCl2 + 2 Cl2 + 2 H2O
which could react as follows with the ammonia:
Cl2 + 2 NH3 --> NH2Cl + NH4Cl (see http://pubs.acs.org/doi/abs/10.1021/ja01644a010 )
Then, a layer of NaNO2 (over the hypochlorite) could be acted upon by the NH2Cl vapors would then either form NH2NO2 or detonate in the attempt:
NaNO2 (dry) + NH2Cl (g) --> NaCl (s) + NH2NO2 (or decompose energetically as is common in many failed Nitroamine synthesis)
Of course, some of the HCl could act on the NaNO2 forming HNO2 and then with NH3, as was noted above, result in NH4NO2.
Other possible side reactions:
Pb(ClO)2 + H2O (water vapor) + 2 NaNO2 --> PbCl2 + 2 NaNO3 + H2O (water vapor)
So this suggested setup may be capable of forming (and/or causing to detonate): NH2NO2, NH4NO2, NaNO3 or an unstable Lead salt.
[Edited on 2-4-2013 by AJKOER]
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Fantasma4500
International Hazard
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interesting.. would test the NaNO2 + NH4Cl out in milligram size if i had some nitrite..
perhaps as etn is sometimes initiated these mixtures could also be initiated by thermite like stuff, perhaps KNO3 + silicone powder?
perhaps even rocket candy? (i have seen a video with a guy stating he have used blasting caps with etn, folded in aluminium foil molten with rocket
candy)
perhaps even KNO3 and flour (stabilized with adding some sugar?)
if its properly put together with thin layers of materials seperating the components this should be possible..
but who knows if its a gas or the solids in the NaNO2 + NH4Cl itself that goes bang.. could be both..
perhaps these could even be put together as initiators for sensitive compounds (like etn or petn) to then not even have the risk of an actual primary,
perhaps for other sensitive secondaries that doesnt det. when heated?
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Trotsky
Hazard to Others
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Ammonium nitrite can't be that prone to exploding- it's used as a pesticide. If I understand correctly, it only detonates when it gets quite hot,
like 70C.
It's easy enough to generate that sort of temp- hardly a need for thermite.
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AJKOER
Radically Dubious
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Antiswat:
Some of my concerns on all of my cited preparations is the resulting power of the explosion. As long as a mild (or intense?) heating source is acting
as an exterior source to compensate for the total 'heat of formation' prior to decomposition of the HE, I believe, other than yield considerations,
that the explosion should be in line with the targeted HE. In fact, for some the reactions where more moles of gas are formed then in the original HE
decomposition, the power could even conceivably be larger.
Note, there is nothing free here. Design considerations have to be overcome (like having the NH4Cl heated sufficiently to sublime, but maintaining the
heat exposure, for example, to the HE to avoid decomposition before its full yield is obtained).
I am also aware of some paths to preparations which have been discarded or avoided due to inherent dangers of premature detonation of the HE. The
design consideration here would be to encapsulated the preparation with the anticipation of said detonation.
[Edited on 2-4-2013 by AJKOER]
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AJKOER
Radically Dubious
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Here is another related example using NH4Cl which has been saturated with high strength NaOCl and heated in a closed chamber. Possible reactions:
NH4Cl + NaOCl <--> NH4ClO + NaCl
and explodes due to the unstable Ammonium hypochlorite, or if the reaction proceeds:
2 NH4Cl --Heat--> 2 NH3 + 2 HCl
2 HCl + NaOCl --> NaCl + (HCl + HOCl) --> NaCl + Cl2 + H2O
Cl2 + 2 NH3 --> NH2Cl + NH4Cl
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Net so far:
NH4Cl + NaOCl --> NaCl + NH2Cl + H2O
Now, lets restart add a little vinegar (HAc) to the NH4Cl saturated with high strength NaOCl and heated in a closed chamber:
2 CH3COOH + 2 NaOCl --> 2 HOCl + 2 CH3COONa
HOCl + NH2Cl --> NHCl2 + H2O
HOCl + NHCl2 --> NCl3 + H2O
Now, our net reaction is:
NH4Cl + 3 NaOCl + 2 CH3COOH --> NaCl + 2 CH3COONa + NCl3 + 3 H2O
where the yellow oily Nitrogen trichloride HE has been created. However, the above solution of NaOCl is already dilute, as is the vinegar, so some
substitutions/additions may be necessary (Boric or Citric acid in place of Acetic acid and add anhydrous MgSO4 to remove some of the water, or scratch
the aqueous NaOCl altogether and use sodium dichloroisocyanurate, which is the active ingredient in the powderized cleanser Comet).
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AJKOER
Radically Dubious
Posts: 3026
Registered: 7-5-2011
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Here is another related example using NH4Cl which has been saturated with high strength NaOCl and heated in a closed chamber. Possible reactions:
NH4Cl + NaOCl <--> NH4ClO + NaCl
and explodes due to the unstable Ammonium hypochlorite, or if the reaction proceeds:
2 NH4Cl --Heat--> 2 NH3 + 2 HCl
2 HCl + NaOCl --> NaCl + (HCl + HOCl) --> NaCl + Cl2 + H2O
Cl2 + 2 NH3 --> NH2Cl + NH4Cl
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Net so far:
NH4Cl + NaOCl --> NaCl + NH2Cl + H2O
Now, lets restart add a little vinegar (HAc) to the NH4Cl saturated with high strength NaOCl and heated in a closed chamber:
2 CH3COOH + 2 NaOCl --> 2 HOCl + 2 CH3COONa
HOCl + NH2Cl --> NHCl2 + H2O
HOCl + NHCl2 --> NCl3 + H2O
Now, our net reaction is:
NH4Cl + 3 NaOCl + 2 CH3COOH --> NaCl + 2 CH3COONa + NCl3 + 3 H2O
where the yellow oily Nitrogen trichloride HE has been created. However, the above solution of NaOCl is already dilute, as is the vinegar, so some
substitutions/additions may be necessary (Boric or Citric acid in place of Acetic acid and add anhydrous MgSO4 to remove some of the water, or scratch
the aqueous NaOCl altogether and use sodium dichloroisocyanurate, which is the active ingredient in the powderized cleanser Comet).
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