Sciencemadness Discussion Board - Experimental explosives

Experimental explosives

a nitrogen rich explosive - 10-4-2016 at 06:39

Scientific Trigger Warning: All compounds/syntheses described in this thread are PURELY THEORETICAL.

I just had an idea: if hexametethylene diamine peroxide, why not HMD nitrate? I can't find anything on the web...

PHILOU Zrealone - 10-4-2016 at 07:57

I also thought about it...since HMDP contains two tertiary amine, maybe that it can catch a proton and its anion.
--> hexametethylene diamine peroxide mono salts and di-salts
HMDP nitrate
HMDP dinitrate
HMDP perchlorate
HMDP diperchlorate
HMDP nitroformiate
HMDP dinitroformiate
I suspect it has to do with the poor basicity induced by the nearby oxygen atoms (see electronic attraction for the sequence N->-CH2->->-O-) but maybe with a very strong acid...

Also
Teriary amines upon exposure to peroxydes do form N-oxydes
so why not...
--> hexametethylene diamine peroxide di-N-oxyde
O=N(CH2-O-O-CH2)3N=O
HMDP-di-N-oxydes --> HMDPDNO
or
-->hexametethylene diamine peroxide-N-oxyde
N(CH2-O-O-CH2)3N=O
HMDP-N-oxyde --> HMDPNO

And such N-oxydes of ternary amines also do form salts...
so maybe with a very strong acid
-->hexametethylene diamine peroxide-N-oxyde mono salts and di-salts
HMDPNO nitrate
HMDPNO dinitrate
HMDPNO perchlorate
HMDPNO diperchlorate
HMDPNO nitroformiate
HMDPNO dinitroformiate
and
--> hexametethylene diamine peroxide di-N-oxyde mono salts and di-salts
HMDPDNO nitrate
HMDPDNO dinitrate
HMDPDNO perchlorate
HMDPDNO diperchlorate
HMDPDNO nitroformiate
HMDPDNO dinitroformiate

But all this is for sure a wild dream

I have already made a year ago a predictive density calculations for all of those molécules and if they existed, they would be very powerful HE...but probably way too sensitive for any practical use.

[Edited on 10-4-2016 by PHILOU Zrealone]

a nitrogen rich explosive - 10-4-2016 at 08:32

That's the thing I was worried about - the 999 out of 1000 very high explosives that are too sensitive for practical use (some tetrazoles in particular)

Anyway, thanks for your help.

EDIT:

Hexamethylene dinitrate DOES exist on the Dortmund Data Bank...

http://ddbonline.ddbst.com/DDBSearch/onlineddboverview.exe?s...

[Edited on 10-4-2016 by a nitrogen rich explosive]

a nitrogen rich explosive - 10-4-2016 at 09:11

Although this wasn't the primary purpose of this thread, have you heard of the highly explosive hexanitroethane/boron mixtures? Archived by the UK explosives authorities:
https://web.archive.org/web/20070930200122/http://stinet.dti...
I assume that this would also work with hexanitroethane/nanomagnesium and
tetranitromethane/fuel... The oxygen balance looks very good.

Aurium - 10-4-2016 at 09:32

New energetics are always an interesting topic for sure!
People have nitrated (or tried) about everything. Even random starch and petrol. Results vary xD.

Nitrocellulose is a macro-molecule. Like a plastic, like PE.
It can be condensed to a plastic ball and detonated that way. However, NC can't be said to be a HE like RDX or TNT at all, it's much less brisant.

Polyethylene glycol (PEG). It's easily found as an OTC laxative (I had a bad week).
Researching the molecule I found it's nitrated form was used as a binder on a solid-fuel composition for the Trident II missile.
I wasn't able to find any more info on the properties of PEG.
EG however is a well-known liquid explosive, so PEG's synthesis shouldn't be much different.

I wonder what other macro-molecule energetics can be found. These could have very different, and interesting properties.

a nitrogen rich explosive - 10-4-2016 at 10:33

Other macromolecule EMs could be very interesting...

From what I could guess, it would turn into polyethylene glycol dinitrate. Polyvinyl nitrate is also a thing, although there isn't much about it.

The problem is sensitivity.

a nitrogen rich explosive - 10-4-2016 at 11:00

Other macromolecule EMs could be very interesting...

From what I could guess, it would turn into polyethylene glycol dinitrate. Polyvinyl nitrate is also a thing, although there isn't much about it.

The problem is sensitivity.

a nitrogen rich explosive - 10-4-2016 at 11:04

Scientific Trigger Warning

This synthesis has not been attempted and is PURELY THEORETICAL.

Synthesis of heptanitropentane:
My initial impressions are that 2-nitro 3-acetoxy 1-propene and nitroform would react to form heptanitropentane. OB looks about zero, although it is again highly sensitive.
I have access to a university laboratory, although I doubt that they would sanction a chemistry student to attempt to synthesise a very experimental extremely violent he...

PHILOU Zrealone - 10-4-2016 at 13:52

Quote: Originally posted by a nitrogen rich explosive

That's the thing I was worried about - the 999 out of 1000 very high explosives that are too sensitive for practical use (some tetrazoles in particular)

Anyway, thanks for your help.

EDIT:

Hexamethylene dinitrate DOES exist on the Dortmund Data Bank...

http://ddbonline.ddbst.com/DDBSearch/onlineddboverview.exe?s...

[Edited on 10-4-2016 by a nitrogen rich explosive]

Hexamethylene DIAMINE dinitrate is only:
O2NOH.H2N-CH2-CH2-CH2-CH2-CH2-CH2-NH2.HONO2
Normal it forms a disalt, the two amino groups are far enough not to interfere and those are primary alkyl amines thus quite basic.
This has nothing to do with HMTDP...

a nitrogen rich explosive - 10-4-2016 at 14:33

Sorry, I haven't researched (or had any need) to do anything with hexamethylene, and I assumed that the diamine was there anyway...

Mistakes like that can cost lives.

PHILOU Zrealone - 12-4-2016 at 02:46

Quote: Originally posted by a nitrogen rich explosive

Although this wasn't the primary purpose of this thread, have you heard of the highly explosive hexanitroethane/boron mixtures? Archived by the UK explosives authorities:
https://web.archive.org/web/20070930200122/http://stinet.dti...
I assume that this would also work with hexanitroethane/nanomagnesium and
tetranitromethane/fuel... The oxygen balance looks very good.

All those per-nitro-alcanes (all H replaced by NO2) / fuel mixes are powerful, brisant and sensitive HE...this is due to the easy lability of vicinal -NO2 and conversion into nitrite (-O-N=O) --> easy evolution of NO and NO2 with further exothermic reaction with the fuel --> runnaway and D2D transition.

If you can make a high energy fuel miscible with the per-nitro-alcane, then you would get a super-HE (very sensitive).
The idea of per-cyano-compounds has been proposed by Franklyn and I.

OB balanced binary mixes of TNM and HNE containing not a single H atom with tetracyanomethane, hexacyanoethane, hexacyanobenzene or tricyano-sym-triazene (cyanuric cyanide) for example should be quite interesting.

PHILOU Zrealone - 12-4-2016 at 02:57

Quote: Originally posted by Aurium

Polyethylene glycol (PEG). It's easily found as an OTC laxative (I had a bad week).
Researching the molecule I found it's nitrated form was used as a binder on a solid-fuel composition for the Trident II missile.
I wasn't able to find any more info on the properties of PEG.
EG however is a well-known liquid explosive, so PEG's synthesis shouldn't be much different.

PEG is a polymer of ethene-epoxyde...
n cyclo(*-CH2-CH2-O-*) --> (-CH2-CH2-O-)n
thus a long chain of -CH2-CH2-O-CH2-CH2-O-CH2-CH2-O...
with groups at the end like HO-.
It is NOT explosive, even if you put a O2N-O at each of the two ends.
EG is NOTa well-known liquid explosive...you probably thought about EG dinitrate (EGDN)...

Please think twice and reread/do a critical relecture before/prior posting.

PHILOU Zrealone - 12-4-2016 at 03:12

Quote: Originally posted by a nitrogen rich explosive

Synthesis of heptanitropentane:
My initial impressions are that 2-nitro 3-acetoxy 1-propene and nitroform would react to form heptanitropentane. OB looks about zero, although it is again highly sensitive.
I have access to a university laboratory, although I doubt that they would sanction a chemistry student to attempt to synthesise a very experimental extremely violent he...

Let's look at you reaction...
2-nitro 3-acetoxy 1-propene would be CH3-CO-O-CH2-C(NO2)=CH2
So
CH3-CO-O-CH2-C(NO2)=CH2 + HC(NO2)3 --> CH3-CO-O-CH2-CH(NO2)-CH2-C(NO2)3
By virtue of the molecular conformation and EWG effects of both trinitromethyl and nitro, one may expect elimination of acetic acid (if it doesn't happen spontaneously, then first hydrolysis to the alcohol that will dehydrate) to make a new alcene...
2,4,4,4-tetranitro-1-butene
CH3-CO-O-CH2-CH(NO2)-CH2-C(NO2)3 --> CH2=C(NO2)-CH2-C(NO2)3 + CH3-CO2H
or
CH3-CO-O-CH2-CH(NO2)-CH2-C(NO2)3 + H2O --> HO-CH2-CH(NO2)-CH2-C(NO2)3 + CH3-CO2H
HO-CH2-CH(NO2)-CH2-C(NO2)3 --> CH2=C(NO2)-CH2-C(NO2)3

Then finally:
CH2=C(NO2)-CH2-C(NO2)3 + HC(NO2)3 -->(O2N)3C-CH2-CH(NO2)-CH2-C(NO2)3
1,1,1,3,5,5,5-heptanitropentane

Nice.
You can now do it and report scientific results here

James Ikanov - 12-4-2016 at 12:52

I'm interested in a few things, one rather tame. A panclastite of N2O and a solid or liquid fuel. I think it would be very insensitive and probably even wimpy, but I also think it would by nature be very dense if it used liquid Dinitrogen Oxide.

The other is the nitrate of REB A, which I'm not sure is possible or plausible. My very shitty napkin math said it could hold some absurd number of nitro groups in it's structure, but that would require that it be capable of surviving exposure to a strong acid in the first place, which I doubt somewhat. My napkin math said it could hold something like 24 nitro groups at a time, but I could be WAY off on that.

a nitrogen rich explosive - 12-4-2016 at 15:35

Rebauside A would probably be able to react to form rebauside a 24-nitrate. From what I can tell, your napkin math is correct...

a nitrogen rich explosive - 13-4-2016 at 03:19

@PHILOU Zrealone:

1) Would you expect that heptanitropentane be a highly flammable liquid, or a very high explosive?

2) Am I right in thinking that nitration of the pyridine salt of HNP would form octonitropentane?

Thanks in advance

PHILOU Zrealone - 13-4-2016 at 10:52

Quote: Originally posted by a nitrogen rich explosive

@PHILOU Zrealone:

1) Would you expect that heptanitropentane be a highly flammable liquid, or a very high explosive?

2) Am I right in thinking that nitration of the pyridine salt of HNP would form octonitropentane?

Thanks in advance

1) a HE solid
2) depends if HNP is acid enough to form a pyridine salt and what nitration media...

PHILOU Zrealone - 13-4-2016 at 10:57

Quote: Originally posted by James Ikanov

I'm interested in a few things, one rather tame. A panclastite of N2O and a solid or liquid fuel. I think it would be very insensitive and probably even wimpy, but I also think it would by nature be very dense if it used liquid Dinitrogen Oxide.

The other is the nitrate of REB A, which I'm not sure is possible or plausible. My very shitty napkin math said it could hold some absurd number of nitro groups in it's structure, but that would require that it be capable of surviving exposure to a strong acid in the first place, which I doubt somewhat. My napkin math said it could hold something like 24 nitro groups at a time, but I could be WAY off on that.

Reb A or Rebaudioside A (Stevia ose) count 14 free hydroxy groups, so you would be a chemical master if you can put 24 on it. Also there is a carboxylic ester in the structure so one of the cyclic ose might split off the molecule --> only 10 remaining in the biggest part of the molecule and 5 in the tiniest.

PHILOU Zrealone - 13-4-2016 at 10:58

Quote: Originally posted by James Ikanov

N2O is endothermic and a provider of activated O, so the fuel will burn very hot. N2O/butane goes above 2200°C.

Dornier 335A - 13-4-2016 at 11:24

I ran a quick calculation for a mixture of liquid N2O and nitrobenzene. Ratio 81.7% N2O to 18.3% C5H5NO2 and density 1.22 g/cm³.
D_CJ: 6630 m/s
P_CJ: 165 kbar
Energy of detonation: 5.57 MJ/kg

As a comparison, here is liquid NO with the same fuel:
Ratio 75.3/24.7, density 1.27 g/cm³.
D_CJ: 7380 m/s
P_CJ: 200 kbar
Energy of detonation: 7.78 MJ/kg

Bert - 13-4-2016 at 11:26

Hey, if you have a lot of questions, no lab work to report and no references/links to sources?

Please use the "short question/ quick answer" thread!

I am going to collect all of these nitrogen rich threads that lack useful references/links or any lab report and merge them into this thread:

https://www.sciencemadness.org/whisper/viewthread.php?tid=26...

PHILOU Zrealone - 14-4-2016 at 08:53

Quote: Originally posted by Dornier 335A

I ran a quick calculation for a mixture of liquid N2O and nitrobenzene. Ratio 81.7% N2O to 18.3% C5H5NO2 and density 1.22 g/cm³.
D_CJ: 6630 m/s
P_CJ: 165 kbar
Energy of detonation: 5.57 MJ/kg

As a comparison, here is liquid NO with the same fuel:
Ratio 75.3/24.7, density 1.27 g/cm³.
D_CJ: 7380 m/s
P_CJ: 200 kbar
Energy of detonation: 7.78 MJ/kg

Nice program/calculator you have there Dornier 335A,
Would be good to calculate also for NO2(g) and/or N2O4(l or s) thus for the real panclastite stuff.

[Edited on 14-4-2016 by PHILOU Zrealone]

Dornier 335A - 15-4-2016 at 04:41

Alright, here is liquid N2O4 and nitrobenzene (70/30):
Density 1.36 g/cm³

D_CJ: 7360 m/s
P_CJ: 212 kbar
Energy of detonation: 7.10 MJ/kg

PHILOU Zrealone - 29-4-2016 at 09:14

Quote: Originally posted by Dornier 335A

I ran a quick calculation for a mixture of liquid N2O and nitrobenzene. Ratio 81.7% N2O to 18.3% C5H5NO2 and density 1.22 g/cm3.
DCJ: 6630 m/s
PCJ: 165 kbar
Energy of detonation: 5.57 MJ/kg

As a comparison, here is liquid NO with the same fuel:
Ratio 75.3/24.7, density 1.27 g/cm3.
DCJ: 7380 m/s
PCJ: 200 kbar
Energy of detonation: 7.78 MJ/kg

Quote: Originally posted by Dornier 335A

Alright, here is liquid N2O4 and nitrobenzene (70/30):
Density 1.36 g/cm³

D_CJ: 7360 m/s
P_CJ: 212 kbar
Energy of detonation: 7.10 MJ/kg

Are you sure for this last? I would have thought it to be more powerful owing to an overal denser mix...

Here are some datas:
N2O
d(l) at -89°C = 1.23 g/cm³
H°f(g) = +82.05 kJ/mol
H°vap = +16.53 kJ/mol
--> H°f(l) = +98,58 kJ/mol

NO
d(l) at -151.8°C = 1.30 g/cm³
H°f(l) = +87.7 kJ/mol
H°vap = +13.83 kJ/mol
--> H°f(g) = +73,87 kJ/mol

N2O3
d(l) at 3.5°C = 1.447 g/cm³
H°f(g) = +91.2 kJ/mol

N2O4
d(l) at 20°C = 1.45 g/cm³
H°f(l) = +9.16 kJ/mol
H°vap = +38.12 kJ/mol
--> H°f(g) = -28.96 kJ/mol

NO2
H°f(g) = +34.0 kJ/mol
H°r (N2O4 --> 2 NO2) = +57.23 kJ/mol

N2O5
d(s) at 20°C = 1.642 g/cm³ (T°f=30°C)
H°f(s) = -43.1 kJ/mol
H°f(g) = +11.3 kJ/mol (must be wrong since H°vap and H°fusion or H°sublim are >0 and increasing with MW) so should be << -43.1...)

specialactivitieSK - 1-5-2016 at 00:28

Would be possible to bring liquid explosives to detonate by Sonoluminescence ?

a nitrogen rich explosive - 1-5-2016 at 01:14

Sonoluminescence? Please explain - I have never come across that before.

Dornier 335A - 1-5-2016 at 06:35

Wikipedia does give a higher value for N2O4 and nitrobenzene. The article does contain errors though, so it's maybe not the most reliable source. My program replicates their VoD for the similar mixture TNM/nitrobenzene and N2O4/nitrobenzene is a lot less dense so I think my valule is closer to the reality.

XeonTheMGPony - 1-5-2016 at 08:01

Quote: Originally posted by a nitrogen rich explosive

Sonoluminescence? Please explain - I have never come across that before.

If you use a pair of matched ultrasonic transducer at 180 degrees of each other and fire them with a liquid in the center, it creates a plasma bubble that emits lights as it rapidly expands and implodes due to irredecent temps built up in the core of the bubble.

I do not recall the frequency needed, they used it as a FX trick in the movie (Chain Reaction)

https://en.wikipedia.org/wiki/Sonoluminescence

So I'd have to say odds are very good it would trigger a liquid HE

[Edited on 1-5-2016 by XeonTheMGPony]

mayko - 1-5-2016 at 08:20

Quote: Originally posted by XeonTheMGPony

Quote: Originally posted by a nitrogen rich explosive

Sonoluminescence? Please explain - I have never come across that before.

I (and StackExchange) am under the impression that cavitation (the process which causes sonoluminescence) is the mechanism responsible for the shock sensitivity of nitroglycerine.

There is also a species of shrimp which uses cavitation as a weapon to stun its prey:

https://www.youtube.com/watch?v=s-puNYSVCCc
https://www.youtube.com/watch?v=XC6I8iPiHT8

a nitrogen rich explosive - 1-5-2016 at 09:14

And also MEKP? So the bubble expands until the heat is too great, at which point it collapses in on itself to create a shockwave. That's very interesting.

XeonTheMGPony - 1-5-2016 at 09:22

it is the implosion that creates the heat.

it is very similar to cavitation.

PHILOU Zrealone - 1-5-2016 at 09:42

Assuming the very big T° and pressure in a cavitation bubble under quasi adiabatic conditions, I would say that any liquid (with a high to medium volatility) explosive should detonate.

Sonication also makes the media heat up.

a nitrogen rich explosive - 1-5-2016 at 09:48

Sonication?

PHILOU Zrealone - 1-5-2016 at 11:48

Quote: Originally posted by a nitrogen rich explosive

Sonication?

S-O-Ni(3+) --> SONi-cation
No kidding.

Sonication from the verb to sonicate...to submit something to the action of sound...here ultrasounds...

Do me and us a favor, do first a Google search on sonochemistry, ultrasounds and Titanium horn...eventually search into the forum before asking such questions.

[Edited on 1-5-2016 by PHILOU Zrealone]

specialactivitieSK - 13-5-2016 at 02:55

It would be possible to produce organic perchlorates from Pentaerythritol and Erythritol through hydrochloride + NaClO4 and should be of practical use ?

[Edited on 13-5-2016 by specialactivitieSK]

Microtek - 13-5-2016 at 03:10

If you are thinking of perchlorate esters, they are very powerful and incredibly sensitive, at least for high substituent to substrate ratios. Not even remotely practical, and you would probably lose important bodily appendages in the process of making these compounds.

ecos - 13-5-2016 at 06:17

Quote: Originally posted by Microtek

If you are thinking of perchlorate esters, they are very powerful and incredibly sensitive, at least for high substituent to substrate ratios. Not even remotely practical, and you would probably lose important bodily appendages in the process of making these compounds.

would you please give examples of perchlorate esters?

PHILOU Zrealone - 13-5-2016 at 07:33

Quote: Originally posted by specialactivitieSK

It would be possible to produce organic perchlorates from Pentaerythritol and Erythritol through hydrochloride + NaClO4 and should be of practical use ?

[Edited on 13-5-2016 by specialactivitieSK]

I know an european guy who attempted propantriol triperchlorate ester and pentaerythritol tetraperchlorate ester at one of his French friend's house...despite my warning he did it and it resulted in a devastative indoor explosion (apparently involving a visite of the police, confiscation of material and financial penalty)...I don't know if he (or someone else) was hurt (or worst)...and I didn't got the whole story because he was apparently so ashamed and not proud of it to tell the full story.
He did his experiment following a successful but riskful procedure involving the making of Cl2O7 and 100% HClO4 to esterifiate glycol (1,2-ethandiol) and glycerol (1,2,3-propantriol).

Examples of perchloric esters are methyl, ethyl and trichloromethyl perchlorates. All 3 have bad reputation.
One of the famous members of this forum did some with extreme caution and cold distillation/condensation (do a search).

Sensitivity (towards heat, shock or friction) of perchloric esters is much higher than that of parent nitric esters.

Main reason must be the following equation that holds true for hypochlorous esters and responsible for their explosive unstability...
CH3-O-Cl(l) --> CH2=O(g) + HCl(g) + heat
(CH3)2CH-O-Cl(l) --> (CH3)2C=O(l) + HCl(g) + heat

by analogy
CH3-O-ClO3 (l) --> CH2=O (g) + HO-ClO2 (l) + heat
2 HO-ClO2 (l) --> H2O (l) + 1/2O2(g) + 2 ClO2(g)
Note that ClO2 is an explosive when brought into contact with organic materials and formaldehyde is extermely oxydable
--> spontaneous heating and deflagro-detonation --> CO2 + Cl2 + H2O
Isopropyl perchlorate should behave the same!

--> Any primary or secondary alcohols will behave like that upon the slightest stimulus.
Erythritol or pentaerythritol tetraperchlorates would be very bad news because holding only primary and secondary alcoholic functions just like methanol, ethanol, glycol, propantriol whose perchloric esters are hyper sensitive...

Now as a light through the dark (?) tertiary alcohols do form stable hypochlorous esters...
Typical example is terbutyl hypochlorite used in some organic chemical reactions and available as a reactant via common chemical product resellers.
--> (CH3)3C-O-Cl exist and is stable

Then by analogy:
--> Maybe (CH3)C-O-ClO3 (tertbutyl perchlorate) might be of value and display some practical use (stability).
If this holds the preparation test phase it should remain relatively stable because
(CH3)3C-O-ClO3 <---> (CH3)3C(+) + ClO4(-)
(CH3)3C-O-ClO3 <---> (CH3)2C=CH2 + HClO4
This last step is stil critical because 100% HClO4 in contact with organic matter is prompt for heating, fire, deflagration and detonation...

If t-butyl ester is proven to be stable enough, then:
Even better would be to test bicyclo(2,2,2)octane-1,4-diol diperchlorate... because it should be denser and with a better OB
O3Cl-O-C(-CH2-CH2-)3C-O-ClO3

Then taking the adamantane structure, it can hold 4 tertiary alcohol positions --> adamantane tetrol tetraperchlorate with the 4 alcohol positions as far of each other as possible to avoid stress of the external perchlorate groups.

Cubane might also be interesting assuming that all summits could hold a ternary alcohol
--> cubane octa-ol octaperchlorate
C8(-O-ClO3)8
But this might be a little too pushed because octanitrocubane has already a hard time to get all its -NO2 unstressed and -O-ClO3 will be much larger group...
--> So more realistic but stil very powerfully potent HE, with 4 tops of the cubane holding 4 alcohol functions as far as possible of each other
--> cubane tetrol tetraperchlorate C8H4(O-ClO3)4 (C₈H₄Cl₄O₁₆)
--> Perfect OB --> 8 CO2(g) + 4 HCl(g)

The idea to use 1,1,2,2-tetramethyl-ethan-1,2-diol (tetramethyl-glycol obtainable via reduction of propanone (aceton)--> pinacole) to make a diperchloric ester will be risky since it tends to rearrange into pinacolone in acidic media...so this viccinal tertiary alcohol might be a source of troubles in the case of perchloric esters...

[Edited on 13-5-2016 by PHILOU Zrealone]

Eosin Y - 13-5-2016 at 10:57

Ethyl perchlorate was responsible for the famous 'spoon shot' wasn't it?
My problem with organic perchlorates is that something like methyl perchlorate would easily score 4-4-4 for H&S (toxicity ~phosgene, highly explosive, highly reactive.) Also, when distilling HClO4 to anyhdrous, does it all turn to Cl2O7 or does only some of that form?