Sciencemadness Discussion Board

Tetrasulfur Tetranitride

Picric-A - 1-5-2008 at 08:42

Hey people,
I am kinda new to this branch of chemistry so if i am being stupid just tell me :P

I have used the search engine and there doesnt seem to be a post on this so here we go...
Has anyone had any sucsess in making this explosive?
i hear the synthesis is fairly simple and wikipedia even give you a step by step approach but is there aything else i should know?
all comments welcome!
thanks,

ScienceGeek - 1-5-2008 at 08:49

Check out this site:
http://www.roguesci.org/chemlab/energetics/nitrogen_sulfide....

After having read this, try to ask more detailed questions :)

Picric-A - 1-5-2008 at 09:29

thanks,
i will try to make my questions more detailed next time,

Axt - 1-5-2008 at 10:16

In all the years I've been around the forums I've never actually know anyone attempt it. Anyway I'm attaching what looks to be the most convenient preparation. They prefer the use of ether over benzene and CS2, saying the yield is not nealy as good when the later two are used. They also use sulphur monochloride rather then the most commonly mentioned dichloride.

Attachment: NITROGEN TETRASULFIDE AND NITROGEN TETRASELENIDE.pdf (280kB)
This file has been downloaded 1688 times

Picric-A - 1-5-2008 at 11:41

thanks for that. I think i will try it tommorow.
My only concern with this is using ether. I have hear that it can be pretty nasty solvent to use due to the volatility and the fact that it is a anasthetic!:o
am i being a bit over the top here?

ScienceGeek - 1-5-2008 at 16:35

I think you're being a bit over the top, yes :P, but one can never be too careful!

Diethyl Ether, as an anaesthetic, is not used anymore (except in third- world countries).

Diethyl Ether is very volatile, and you shouldn't breathe it, but if you get a couple of whiffs, it really isn't that dangerous! Only danger is its extreme flammability, which is why you should do this outside to prevent any buildup of explosive gases.
Also, if you do it outside or not, do not keep any open flames or the like nearby. Also, try to prevent a discharge of static electricity. One never thinks about it, because the conditions need to be perfect for something to go wrong with static electricity, but it actually happened to me once whilst working with Carbon Disulfide...

woelen - 1-5-2008 at 23:25

Ether is much less risky than CS2 and benzene. Ether is relatively non-toxic (unless you breathe so much that it numbs you), while CS2 is very toxic and benzene is a known carcinogen. I also would worry much more about the S2Cl2, which is a VERY noxious compound with an evil smell.

Formatik - 1-5-2008 at 23:38

Quote:
Originally posted by ScienceGeek
Check out this site:
http://www.roguesci.org/chemlab/energetics/nitrogen_sulfide....


Any suitable organic solvent will work, if not benzene then toluene, CHCl3, ether, CS2, or CCl4. From the sulfur chlorides, S4N4 forms from S2Cl2, SCl2 or SOCl2. The reaction with S2Cl2 is: 6 S2Cl2 + 16 NH3 = S4N4 + 12 NH4Cl + 8 S. Gmelin S [B], p. 1545 mentions that some preparations of authors were highly explosive due too strong of a drying of the reacting mixture and usage of SCl2 - which can impurify the nitride with NCl3.

Even in the absence of air, S4N4 is said to detonate at about 130 deg (though if heated slowly it burns in air). It explodes from a hammer blow, but it is less shock sensitive than Hg(ONC)2. This compound also hydrolyses slowly from cold water, rapidly so from hot water. 3 g S4N4 in 8 times the amount of cold water shaken for 24 hours causes it to solubilize forming NH3, H2S2O3, H2S3O6, H2SO3 and H2SO4. In air, S4N4 decomposes noticeably. Even pure S4N4 at normal pressures decomposes and forms S. Though another source (J.chem.Soc. 1936, 1645/9, 1648) claims it is stable in air and can be stored without decomposition.

ShadowWarrior4444 - 1-5-2008 at 23:53

Quote:
Originally posted by Schockwave
Quote:
Originally posted by ScienceGeek
Check out this site:
http://www.roguesci.org/chemlab/energetics/nitrogen_sulfide....


Any suitable organic solvent will work, if not benzene then toluene, CHCl3, ether, CS2, or CCl4. From the sulfur chlorides, S4N4 forms from S2Cl2, SCl2 or SOCl2. The reaction with S2Cl2 is: 6 S2Cl2 + 16 NH3 = S4N4 + 12 NH4Cl + 8 S. Gmelin S [B], p. 1545 mentions that some preparations of authors were highly explosive due too strong of a drying of the reacting mixture and usage of SCl2 - which can impurify the nitride with NCl3.

Even in the absence of air, S4N4 is said to detonate at about 130 deg (though if heated slowly it burns in air). It explodes from a hammer blow, but it is less shock sensitive than Hg(ONC)2. This compound also hydrolyses slowly from cold water, rapidly so from hot water. 3 g S4N4 in 8 times the amount of cold water shaken for 24 hours causes it to solubilize forming NH3, H2S2O3, H2S3O6, H2SO3 and H2SO4. In air, S4N4 decomposes noticeably. Even pure S4N4 at normal pressures decomposes and forms S. Though another source (J.chem.Soc. 1936, 1645/9, 1648) claims it is stable in air and can be stored without decomposition.


The differing reports for air stability may well be due to humidity at the time of the measurements, though one might hope that the scientists involved would consider the potential for hydrolysis and measure that. *does so hate blatantly contradictory reports*

Formatik - 2-5-2008 at 00:16

Quote:
Originally posted by ShadowWarrior4444
Quote:
Originally posted by Schockwave
Quote:
Originally posted by ScienceGeek
Check out this site:
http://www.roguesci.org/chemlab/energetics/nitrogen_sulfide....


Any suitable organic solvent will work, if not benzene then toluene, CHCl3, ether, CS2, or CCl4. From the sulfur chlorides, S4N4 forms from S2Cl2, SCl2 or SOCl2. The reaction with S2Cl2 is: 6 S2Cl2 + 16 NH3 = S4N4 + 12 NH4Cl + 8 S. Gmelin S [B], p. 1545 mentions that some preparations of authors were highly explosive due too strong of a drying of the reacting mixture and usage of SCl2 - which can impurify the nitride with NCl3.

Even in the absence of air, S4N4 is said to detonate at about 130 deg (though if heated slowly it burns in air). It explodes from a hammer blow, but it is less shock sensitive than Hg(ONC)2. This compound also hydrolyses slowly from cold water, rapidly so from hot water. 3 g S4N4 in 8 times the amount of cold water shaken for 24 hours causes it to solubilize forming NH3, H2S2O3, H2S3O6, H2SO3 and H2SO4. In air, S4N4 decomposes noticeably. Even pure S4N4 at normal pressures decomposes and forms S. Though another source (J.chem.Soc. 1936, 1645/9, 1648) claims it is stable in air and can be stored without decomposition.


The differing reports for air stability may well be due to humidity at the time of the measurements, though one might hope that the scientists involved would consider the potential for hydrolysis and measure that. *does so hate blatantly contradictory reports*


I'm also leaning more towards the report of it decomposing in air. In another report there was noted that the nitride loses its glance in moist air. Gmelin talks quite a bit about its hydrolysis. And yes, I hate those blatantly contradictory reports too. ;)

Picric-A - 2-5-2008 at 02:13

I have just finihsed making my TSTN.
I got about 30g of product which i presume contains traces of elemental sulphur but through research i have found it is a good thing to have this impurity as it stabilises the product. From the information Axt gave it says after the TSTN precipitates out you will be left with a red soloution. I think something went wrong becuase i was left with a more orangy yellow soloution:o
I will try detonating some later on. I will tell you how i get on.
Thanks for all your help so far

Axt - 2-5-2008 at 02:22

Thats wrong Picric-A, the precipitate is NH4Cl and S8, the N4S4 remains in solution, or is extracted from the crude precip with further ether. At least thats the way I read it.

Picric-A - 2-5-2008 at 05:27

well that could explain the fact it isnt even burning/detonating...!
soz for that mistaque. why is my soloution orange when it is supposed to be bright red?

Axt - 2-5-2008 at 06:16

Maybe the red colour is a result of an excess NH3, since the colour cant be reproduced by redisolving S4N4 in ether. So possibly the redness is instead some of the S4N4.2NH3 or a lower NH3 complex as shown in article as a red liquid. But really, it could be the result of a lot of things.

woelen - 2-5-2008 at 09:23

@Shockwave: Can S4N4 really be formed from SOCl2 and NH3 in a solvent like ether, CHCl3 or CH2Cl2? SOCl2 is a chemical which is not that hard to obtain (at least for EU-based people), so it could be something worth giving a try. Could you please elaborate on the procedure for using SOCl2?

Picric-A - 2-5-2008 at 11:10

That could probably be the reason Axt, i did use a slight exess in ammonia as i thought it would not make a big difference.
I have extracted my TSTN and i got it to detonate wonderfully. it is much more sensative than i expected, i manaed to make it detonate by hitting a small sample with a hammer and grinding it (only an extremly small amount..!) with a rock produced lots of small sharp cracks (small explosions)
What i am going to do next is test its lewis base properties and react it with SO3 and see if the product S4N4.SO3 is explosive.

Taoiseach - 3-5-2008 at 08:49

I have an old chemistry book that says N4S4 can be made by reacting S and dry liquid ammonia, a sideproduct being hydrogen sulfide tough no details are given. It should be possible to liquify NH3 in an ice + CaCl2*6H2O bath (2:3 ratio). N4S4 is soluble in benzene, chloroform, benzaldehyde and dry ammonia at -40°C, sublimes @135°C, melts at 178°C and detonates @ 207°C.
Bromine reacts with N4S4 to form red crystals of N4S4Br6. There are also nicely colored complexes with TiCl4, SbCl5, SnCl4 and MoCl5.

Pulverulescent - 3-5-2008 at 09:20

Quote:
Originally posted by woelen
SOCl2 is a chemical which is not that hard to obtain (at least for EU-based people)


I need thionyl chloride, woelen, and I'm in the EU (Ireland) but where can I get it?

If you know a company willing to sell it to individuals, please let us know?

'Fingers crossed!

P

ScienceGeek - 3-5-2008 at 09:32

Continuing off- topicness:
Same here, woelen. I actually think this doesn't just go for me and Pulverulescent...:)

woelen - 3-5-2008 at 10:15

Both of you, see your U2U box. Only thing is that Norway is not in the EU and then I have doubts about whether it is shipped to Norway. It will have to go through customs, and that may be a problem with stuff like thionyl chloride.

I do not post sources like this on a public forum, so please don't post it here. If other people are interested, then U2U and I _may_ give you the source ;)

[Edited on 3-5-08 by woelen]

Picric-A - 4-5-2008 at 00:45

could you give me more information on how i could liquify ammonia Taoiseach.
I have a good supply of ammonia heat NH4NO3 with NaOH (both very cheap and plentifull) to release ammonia gas which i then dry with CaCl2.
I have also heard heating urea works but thats a different topic.

How could i liquify the ammonia with a simple ice/ CaCl2 water bath?

not_important - 4-5-2008 at 01:01

Much better that CaCl2/ice mixtures is to use solid CO2 (dry ice). Ammonia gives off a lot of heat when condensing, you'll go through a lot of ice in liquefying more that a few ml of ammonia.

Picric-A - 4-5-2008 at 09:41

its hard to find dry ice around here (london)
do i make a saturated CaCl2 soloution and free it in my frezer?

Formatik - 5-5-2008 at 12:35

Quote:
Originally posted by woelen
@Shockwave: Can S4N4 really be formed from SOCl2 and NH3 in a solvent like ether, CHCl3 or CH2Cl2? SOCl2 is a chemical which is not that hard to obtain (at least for EU-based people), so it could be something worth giving a try. Could you please elaborate on the procedure for using SOCl2?


Gmelin says that the preparations in the literature consist of the reaction of NH3-gas onto a sulfur chloride and then mentions those solvents and sulfur chlorides, it only briefly mentions the SOCl2 - by addition of dry NH3 gas into SOCl2 (which is being cooled in water) gives a yellow-white mass, from which with boiling CS2 can S4N4 of a yield of 10% of the used SOCl2 be obtained (Jenaische Z.Med.Naturw. 6[1871]79/92, 80).
Quote:
Originally posted by Taoiseach
I have an old chemistry book that says N4S4 can be made by reacting S and dry liquid ammonia, a sideproduct being hydrogen sulfide tough no details are given.



The same thing is in Gmelin, they mention sulfur with reaction of liquid NH3 forms S4N4. They say the nitride is the form of its NH3-compound in solution. The S4N4 can be isolated if the S^2- is removed through AgI in the form of Ag2S, the filtrate is evaporated and the residue is heated for 2 hours at 100 deg. (this is risky because S4N4 explodes above 100 deg. according to various authors, although by some it was higher due to the rate of heating) and then in a vacuum over H2SO4 brought to permanence and then finally extract it with CS2, upon evaporation of the CS2, the S4N4 crystallizes out (Ber. 38 [1905] 2659/67, 2662). After S4N4 has been solubilized in liquid NH3, allowing the NH3 to evaporate leaves behind a brown-red mass. After losing more NH3 in air, this mass colors black and then orange-red. This orange-red product has a formula in between S4N4.2NH3 and S4N4.2.5 NH3. So likely only through such a extraction method can the NH3 be removed.



It's also mentioned further in COPAE (Davis), where there was also several patents which recommended it as filler for fuses, and primers, and detonators alone or in mixtures with an oxidizer like PbO2, Pb(NO3)2, KClO3, NaBrO3, KBrO3, or NaClO3. Though based on some of its hydrolysis products, mixing it with any chlorate or bromate is a bad idea, especially hygroscopic sodium salts.

franklyn - 5-5-2008 at 23:08

Another thread exits on this
http://www.sciencemadness.org/talk/viewthread.php?tid=851#pi...

From encyclopedia Britannica on its properties

Sulfur forms a variety of covalent binary nitrides, but the two most interesting ones are
tetrasulfur tetranitride, S4N4, and disulfur dinitride, S2N2, because they are precursors
to an unusual polymer called polythiazyl, (SN)x. This polymeric sulfur nitride is unusual
because, even though it is composed solely of two nonmetals, it exhibits some properties
normally associated only with metals. The best preparation of S4N4 involves bubbling NH3
into a heated (50° C) solution of S2Cl2 dissolved in CCl4 or C6H6.

6S2Cl2 + 16NH3 -> S4N4 + S8 + 12NH4Cl

Tetrasulfur tetranitride forms thermochromic crystals, which are crystals that change
colour with temperature. They are red at temperatures above 100° C, orange at 25° C,
and colourless at -190° C. The crystals are stable in air but will explode in response to
shock or friction. The compound has a cage structure with a plane of four nitrogen
atoms with two sulfur atoms above and below the plane (see Figure 15). When S4N4
vapour is pumped through silver wool at 250°–300° C and low pressure (less than 1.0
mm Hg), an unstable dimer, S2N2, can be condensed. This compound has an essentially
square structure with alternating sulfur and nitrogen atoms. Like S4N4, it is sensitive to
shock and can explode when heated to temperatures higher than 30° C. At 25° C, S2N2
slowly polymerizes through a ring opening mechanism to polythiazyl, (SN)x. This rather
amazing material has a bronze colour, a metallic lustre, and the electrical and thermal
conductivity of a metal. It becomes a superconductor at 0.26 kelvin.

.

mayko - 6-5-2023 at 07:53

I just ran across this, which elaborates on the selenium analog and gives a short blurb about the tellurium analog. From "Selenium, Tellurium, and Polonium", by K. W. Bagnall (a freestanding 1966 book and also chapter 24 of Comprehensive Inorganic Chemistry, 1973)

Attachment: Selenium_Tellurium_Nitrides.pdf (163kB)
This file has been downloaded 242 times

Can't wait for someone to make the polonium version!!

Lionel Spanner - 11-5-2023 at 15:07

Quote: Originally posted by mayko  
I just ran across this, which elaborates on the selenium analog and gives a short blurb about the tellurium analog. From "Selenium, Tellurium, and Polonium", by K. W. Bagnall (a freestanding 1966 book and also chapter 24 of Comprehensive Inorganic Chemistry, 1973)



Can't wait for someone to make the polonium version!!

There is in fact an experimental procedure for selenium nitride in Brauer p.435/436, one of many highly reactive compounds prepared by extraordinarily brave and/or foolish German chemists in the 1920s and 1930s.
When a procedure in Brauer starts with an explicit warning about how explosive it is (which for context, you don't get with e.g. hydrazoic acid or chlorine dioxide), you know it is not to be taken lightly at all. And the procedure finishes like this:

"Pure selenium nitride is best stored under benzene because of its explosive nature. The dry substance may not be placed in glass stoppered bottles since the contents generally explode when such bottles are opened. Cardboard boxes are the best containers."

There is no procedure for tellurium nitride; I can only imagine it's even less stable, and even if polonium nitride could be prepared and isolated, it would probably self-destruct due to its high radioactivity.

[Edited on 11-5-2023 by Lionel Spanner]