Ral123
National Hazard
Posts: 735
Registered: 31-12-2011
Member Is Offline
Mood: No Mood
|
|
Effects of amines on C-NO2 bonds
We all know how stable nitromethane is, but this video http://www.youtube.com/watch?v=br-f1Ls9hZ0 shows it can be efficiently sensitised with DETA. The first question that comes to me is, if it
sensitises so well, how well can it store in mixed condition? Can this be used to sensitise other nitro compounds, for example mixture of DNT/HDN?
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
I am not entirely sure, but I think one of the reasons nitromethane is sensitized is because that these amines are basic, and promote a small portion
of the nitromethane converting into its aci- tautomer, which is much more sensitive.
In contrast, typically amines reduce sensitivity when they are in the same aromatic system as the nitro group, an example being TNTAB.
Another possible reason for the sensitization may be that the N-H is more easily oxidized than a C-H bond, due to its polar nature, despite the fact
that it is less energetic. So the barrier to reaction could be lower.
|
|
|
killswitch
Hazard to Others
Posts: 209
Registered: 8-7-2011
Location: is a relative concept
Member Is Offline
Mood: No Mood
|
|
What about hexamine? Does that dissolve in NM?
|
|
|
Dany
Hazard to Others
Posts: 482
Registered: 3-8-2013
Member Is Offline
Mood: No Mood
|
|
Addition of bases (not only DETA) increases the sensitivity of nitromethane (NM) towards shocks. Experiments shows [1] that addition of 0.05 wt% of
DETA to NM increase the detonation velocity and pressure and decreases the critical diameter of the explosive. Acids and water have similar but weaker
effect on failure diameter of this explosive.
it is not advisable to store sensitized nitromethane. The addition of amine to NM is performed on site. Indeed the addition, of bases to nitromethane
decreases the thermal stability of the mixture. other nitroaromatics (picric acid, tetryl and TNT) have similar effect (decreases of thermal
stability) when various bases are added which is obvious from their DSC (Differential Scanning Calorimetry) curves [2]. read the two paper below (and
references therein) for more information on sensitized nitromethane and nitroaromatics by the addition of amine.
[1] Zeman, S. Accounts of the New Aspects of Nitromethane Initiation Reactivity, Cent. Eur. J. Energ. Mater. 2009,
6(1), 119-133.
[2] C. P. Constantinou and M. M. Chaudhri, MEASUREMENT OF THE SENSITIZATION OF NITROCOMPOUNDS BY AMINES USING DIFFERENTIAL SCANNING CALORIMETRY,
J. Therm. Anal., 1995, 45, 1301-1311.
Dany.
Attachment: Accounts of the New Aspects of Nitromethane Initiation Reactivity.pdf (457kB)
This file has been downloaded 953 times
Attachment: MEASUREMENT OF THE SENSITIZATION OF NITROCOMPOUNDS BY AMINES USING DIFFERENTIAL SCANNING CALORIMETRY.pdf (516kB)
This file has been downloaded 465 times
[Edited on 20-9-2013 by Dany]
|
|
|
NeonPulse
Hazard to Others
Posts: 417
Registered: 29-6-2013
Location: The other end of the internet.
Member Is Offline
Mood: Isolated from Reality! For Real this time....
|
|
i have tried in the past and hexamine wont dissolve in
nitromethane. i think a solvent that is miscible with NM that also dissolves the hexamine may be the way to go.
|
|
|
Ral123
National Hazard
Posts: 735
Registered: 31-12-2011
Member Is Offline
Mood: No Mood
|
|
I've heard about NaOH sensitising TNT before. What's your opinion, can NM be sensitised with hydrazine(hydrate)? This would be elegant way if it
works, non corrosive and more powerful then the inert stuff.
|
|
|
PHILOU Zrealone
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
Member Is Offline
Mood: Bis-diazo-dinitro-hydroquinonic
|
|
Quote: Originally posted by Ral123  | | I've heard about NaOH sensitising TNT before. What's your opinion, can NM be sensitised with hydrazine(hydrate)? This would be elegant way if it
works, non corrosive and more powerful then the inert stuff. |
-Red ammonium picrate (vs the yellow one) (from NH4OH and TNP)
-Deep red TNT sodium nitronate (vs pale yellow one) (from TNT and concentrated NaOH)
-Brown methylnitronate of Na of NH3 or of N2H4 (from CH3-NO2 and NaOH, NH4OH or N2H5OH
All are based on nitro-nirtonic equilibrium; in basic media nitronic is more present and this sensitizes the stuff!
-For picric acid (I have left aside the uninvolved part of the aromatic ring in the equation)
HO-C=C-NO2 + NH4OH --> O=C-C=N(O)-ONH4 + NH4-C=C-NO2 + H2O
-For TNT (I have left aside the uninvolved part of the aromatic ring in the equation)
CH3-C=C-NO2 + NaOH --> CH2=C-C=N(O)-ONa + H2O
-For NM
CH3-NO2 + NaOH --> CH2=N(O)-ONa + H2O
CH3-NO2 + NH4OH --> CH2=N(O)-ONH4 + H2O
CH3-NO2 + N2H5OH --> CH2=N(O)-ON2H5 + H2O
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
Would that mean trinitrobenzene would not be sensitized by base?
|
|
|
killswitch
Hazard to Others
Posts: 209
Registered: 8-7-2011
Location: is a relative concept
Member Is Offline
Mood: No Mood
|
|
Forming the aci-nitro of TNB would introduce an sp3 carbon and destroy aromaticity.
|
|
|
Fantasma4500
International Hazard
Posts: 1677
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline
Mood: dangerously practical
|
|
there is this ''field manufactured explosives''
a scanned book, you probably know the kind
i remember reading that sawdust mixed with NM have been used, and the product was an actually functional secondary.. how about that?
|
|
|
Ral123
National Hazard
Posts: 735
Registered: 31-12-2011
Member Is Offline
Mood: No Mood
|
|
But who would do that, it's going to be weak, flammable, volatile and hard to set off.
Can someone suggest a practical way to sensitise NM with N2H4.H2O. I promise a test if the concept is good.
|
|
|
SherlockHolmes
Harmless
Posts: 44
Registered: 29-7-2012
Location: Bulgaria
Member Is Offline
Mood: No Mood
|
|
Wow, here discuss my test  Besides DETA I managed to sensitize nitromethane and
with 30% aluminum http://www.youtube.com/watch?v=tCcH8pmXShw
Obtained not only with a DETA and EDA, ethanolamine and others amines 
Sorry for my english. I am not from England. Thank you!
|
|
|
Ral123
National Hazard
Posts: 735
Registered: 31-12-2011
Member Is Offline
Mood: No Mood
|
|
I wonder how much dimethyl aniline would do the trick also
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
