Sciencemadness Discussion Board

Silver azide synthesis question?

Trinitrophenol - 16-2-2014 at 06:19

Hello i have some very pure silver nitrate and sodium azide but not any lead nitrate. But i realy want to try out some azides instead of just the "poor" silver acetylide.

So the question is if its possible to synthesise silver azide by just adding aqueous soulutions of silver nitrate and sodium azide to precipitate usable silver azide.
Is there something thats needed to stabilze it? Such as whit lead azide witch needs dextrin to be stablized.

I have als had alot of troble finding a "good" silver azide synthesis, just so anyone wont complain about me not trying to do my own Research.

Dornier 335A - 16-2-2014 at 07:06

Quick answer: yes!
A dense precipitate forms when the two solutions are combined.
Silver azide will slowly decompose under light, but it's stable at room temperature in the dark.

Trinitrophenol - 16-2-2014 at 07:25

Quote: Originally posted by Dornier 335A  
Quick answer: yes!
A dense precipitate forms when the two solutions are combined.
Silver azide will slowly decompose under light, but it's stable at room temperature in the dark.


Have you tried this yourself? If not do you have any Sources on that it realy is this easy to make silver azide?

[Edited on 16-2-2014 by Trinitrophenol]

DubaiAmateurRocketry - 16-2-2014 at 07:41

Can copper II azide be used as primary ? How sensitive is it ?

Trinitrophenol - 16-2-2014 at 07:58

Quote: Originally posted by DubaiAmateurRocketry  
Can copper II azide be used as primary ? How sensitive is it ?


As far as i know, that compound is the reason azides shouldn't come into contact whit copper metal.
I dont know how sensitive it is, but its probly to sensitive to be handled safely.

Dornier 335A - 16-2-2014 at 11:30

A friend of mine did it. You can check any source - they will all say that AgNO3 and NaN3 solutions are the way to go.

Copper II azide is a very potent primary, but it's too friction sensitive to remove from a filter paper according to Encyclopedia of Explosives and Related Items by Fedoroff.

Turner - 16-2-2014 at 13:00

Is silver azide better or worse overall than Lead Azide?

Is it any better than silver acetylide DS?

Silver acetylide by itself is not a good primary (weak and sensitive), but the double salt has very good sensitivity qualities, and even though not the most powerful, this can be offset by just using more of it.

Dornier 335A - 16-2-2014 at 14:11

Silver azide has great initiating properties. Less silver azide is required than lead azide to initiate the same secondary.

Bert - 16-2-2014 at 16:59
Quote:

I have als had alot of troble finding a "good" silver azide synthesis, just so anyone wont complain about me not trying to do my own Research.


It took me litterally seconds to find patents and descriptions of the process, along with several previous threads right here you could have posted this question to. So someone WILL probably complain about you not trying.

If made by haphazardly adding a solution of NaN3 to a solution of AgNO3, you will most likely end up with a very fluffy, low density and difficult to handle/load product.

The methods used industrially yield a denser, free flowing powder as the product. A common method is to react the Silver nitrate and Sodium azide in a large volume of strong ammonia/water, which can dissolve the Silver azide- Then heating the solution, driving off the ammonia and causing the azide to crystalize relatively slowly out of solution, giveing larger, more dense crystals. A further refinement is to produce "seed crystals" by adding Silver acetate solution as the Silver azide begins to crystalize.

Process for producing Silver azide

Be VERY aware that the sensitivity to static electricity of AgN3 is much higher than that of Pb(N3)2: .01J for Lead azide vs .007J for Silver azide- I learned that the HARD way, years ago, when I made some special effect devices with Silver azide that would spontaneously explode when handled in dry cold weather by people wearing synthetic clothing that generated static.

Some primary explosives and their properties


[Edited on 17-2-2014 by Bert]

The_Davster - 16-2-2014 at 17:25

Bert: The ammonia method is interesting. I have used the method from the book in the azide sticky thread, which is essentially hot solutions of azide and silver nitrate with controlled, slow addition. Do you know of any studies comparing the properties of the two methods in terms of crystal size/morphology, and impact/friction and ESD sensitivity? If the ammonia method gives larger crystals, static sensitivity would be decreased, although sensitivity to impact would be increased. Likely a sweet spot in crystal size.

Hot additions of the two gives a very microcrystalline precipitate, you can see the shine of crystal faces, but not make out individual crystals with the naked eye. Never had any issues when handled properly, but you can see how glorious of a primary it is when ignited. The material on the tip of a spatula detonates when ignited with such violence the tip of the spatula was bent at 45o. Even puts silver nitrotetrazolate to shame, under approximately controlled conditions.

And no lead fumes when it goes off. Much healthier to play with than the lead flavour.

[Edited on 17-2-14 by The_Davster]

Bert - 16-2-2014 at 17:36

It's very snappy, and also scary sensitive. I don't use it anymore- Although no one was injured and we finished the film project OK, it wasn't a good day at work. Sure did make the film crew and actors respect the safety lines for the rest of the shoot!

The_Davster - 16-2-2014 at 17:48

If you do not mind me asking, what were you doing with a film crew and silver azide? Sounds like a good time.

Ral123 - 16-2-2014 at 22:44

Isn't mixing silver salts with ammonia potentially going to yield Ag3N(very dangerous)? I didn't know there was primary that would readily explode from static. I can hardly set of my AP with a stun gun.

Peroksit - 17-2-2014 at 01:56

dextrin can be used for modification of crystallization?

Rosco Bodine - 17-2-2014 at 07:31

Quote: Originally posted by Bert  

Quote:

I have als had alot of troble finding a "good" silver azide synthesis, just so anyone wont complain about me not trying to do my own Research.


It took me litterally seconds to find patents and descriptions of the process, along with several previous threads right here you could have posted this question to. So someone WILL probably complain about you not trying.


Yes, I had the same experience with a search turning up many references, which tends to put the topic of the OP in the realm of a request for spoonfeeding. There is an azides sticky thread which contains some attachments and links to entire books on azides and specifically lists exhaustive references to silver azide, so anyone doing enough reading would find what they are needing for basic background for any experimentation. The sticky azide thread hasn't evolved to the point of having dedicated sections for lead azide and for silver azide, but the reference sources are certainly found there, if anyone was doing a genuine search.
Quote:

If made by haphazardly adding a solution of NaN3 to a solution of AgNO3, you will most likely end up with a very fluffy, low density and difficult to handle/load product.


Yes the simplest approach of simply mixing the precursor solutions yields the colloidal microcrystalline low solubility precipitate which has low bulk density, and is parallel to what occurs for lead azide when the precursor solutions are simply mixed in a lump immediately and the precipitate allowed to settle and filtered. This can similarly occur for many other energetic materials where the most basic unrefined process method of simply pouring together "in a lump" the precursor solutions with mixing and reacting en masse, allows no time for crystal growth or provides no specific modification of the crystal size or type which is the end result for a modified reaction where solubility is altered slowly by changing tempertaure or the pH and solvent properties for crystal formation of particles that enter and reside and finally precipitate from a reaction zone in flux over a delayed period of time where the gradual change is controlled and favors a modified end product having altered properties. The method of reaction and how the manipulations are achieved in the reaction zone provided by the medium is an engineered process deliberately designed to produce a certain mesh size and form of crystals having differing properties and the difference can be significant for the type of product produced as the end result, even though it may be chemically identical with the material gotten by a different method. Different physical forms of the same material can have different performance when ultimately used in actual tests of uses anticipated for the material. The physical form can be definitively important for an energetic material so process chemistry and manipulations can be definitive about whether the end result is actually a useful form of the material, and the case may arise where two samples are chemically identical but one is useless for any practical purpose while the other sample may be entirely useful but simply a different physical form of the exact same compound.
Quote:

The methods used industrially yield a denser, free flowing powder as the product. A common method is to react the Silver nitrate and Sodium azide in a large volume of strong ammonia/water, which can dissolve the Silver azide- Then heating the solution, driving off the ammonia and causing the azide to crystalize relatively slowly out of solution, giveing larger, more dense crystals. A further refinement is to produce "seed crystals" by adding Silver acetate solution as the Silver azide begins to crystalize.

Process for producing Silver azide

Be VERY aware that the sensitivity to static electricity of AgN3 is much higher than that of Pb(N3)2: .01J for Lead azide vs .007J for Silver azide- I learned that the HARD way, years ago, when I made some special effect devices with Silver azide that would spontaneously explode when handled in dry cold weather by people wearing synthetic clothing that generated static.

Some primary explosives and their properties


The most unnerving property about static sensitivity that I have observed is that precipitations themselves and filtering manipulations do generate static electricity and charge continues to reside in the mass of precipitated material, so the idea that a source of static must be an external influence somehow is entirely erroneous. The static charge is resident in the material that is precipitated as much as lightning is attendant to the rain falling from the clouds of a thunderstorm. For some materials the effect is particularly evident as a physical effect and I think everyone should be aware of the phenomenon of innate static charge that may be quite significant and residing in a pile a precipitated crystals, from which as the moisture is leaving, the charge is building, just like is the case when rain is departing from a cloud. There are various strategies for bleeding off the static charge that can accumulate, but I have never seen the matter given much attention in the literature. Using conductive plastics that are aluminized or graphited or carbon containing seems to aid the dissipation of charge that seems to take forever if clear plastics are used, and virgin teflon and glass materials are not helpful, however
maintaining a high relative humidity generally also seems helpful for avoiding the danger. Static electricity can be scary unpredictable because it is an insidious danger and there is nothing really to indicate its potential presence except an intuitive general situational awareness that may even be a bit of healthy paranoia for the person handling some sensitive material, and colloidal form preciptates are much worse risks than are the larger grist materials. So one risk is traded for another for those who think a colloidal form is safer due to lowered impact sensitivity when it may be the safety that they thought was being achieved for the one danger, creates another greater danger that has made their strategy counterintuitive and ultimately counterproductive.
Where energetic materials are concerned and involves primary explosives, it has always been my thinking that the colloidal form materials are better handled damp or wet, not allowed to dry in clumps and then attempt made to sieve those adherent particles after they are dried. Every little lump becomes its own little electrostatic "battery" and it is unpredictable if the intensity of charge in the mass crosses the danger threshhold or not with colloidal materials. Is this another "all I did was touch it" scenario waiting to occur? Who wants to be the next statistic for an improbable scenario for purely dumb luck?

I would believe that the compaction on drying to a higher density pellet for a wet dextrin solution paste of a colloidal form primary is static related and the same effect as the breaking of a breath mint in the dark showing a burst of light emitted from the static electricity between the particles torn apart at the interface, or the ripping quickly of a strip of friction tape from a roll, bursting light from the separation point shows the adhesion forces of the mutual attraction of like particles, that is the innate static electricity present in the mass of particles. Better to know that force is there than to be deceived that it isn't present and isn't a factor, and to later learn the hard way it was.

[Edited on 17-2-2014 by Rosco Bodine]

Bert - 17-2-2014 at 09:28

Quote: Originally posted by Ral123  
I didn't know there was primary that would readily explode from static. I can hardly set of my AP with a stun gun. [/


You need to do some searching and reading. Here's a place to start:

http://www.springer.com/cda/content/document/cda_downloaddoc...

Don't EVER assume you can generalize a physical behavior from one material to another, or even from one sample to another of (chemicaly identical) same material in a different form. Just changing particle size or crystal geometry can have a large effect- there is a good reason Rosco spends so much time here discussing crystallization methods and modifiers, the gross chemistry is often less than 1/2 the story on the behavior of an explosive.


Trinitrophenol - 17-2-2014 at 10:11

Quote: Originally posted by Bert  

Quote:

I have als had alot of troble finding a "good" silver azide synthesis, just so anyone wont complain about me not trying to do my own Research.


It took me litterally seconds to find patents and descriptions of the process, along with several previous threads right here you could have posted this question to. So someone WILL probably complain about you not trying.

If made by haphazardly adding a solution of NaN3 to a solution of AgNO3, you will most likely end up with a very fluffy, low density and difficult to handle/load product.

The methods used industrially yield a denser, free flowing powder as the product. A common method is to react the Silver nitrate and Sodium azide in a large volume of strong ammonia/water, which can dissolve the Silver azide- Then heating the solution, driving off the ammonia and causing the azide to crystalize relatively slowly out of solution, giveing larger, more dense crystals. A further refinement is to produce "seed crystals" by adding Silver acetate solution as the Silver azide begins to crystalize.


The reason why i had trouble is because some suggest using nitric acid and even sodium hydroxide in these synths. And btw wouldn't ammonia and silver nitrate react to form silver nitride witch is highly sensitive.

Doesn't lead and silver azide become very sensitive when they are prepared with a larger crystal size. I thought that a colloidal form was desired when making them.

Bert - 17-2-2014 at 11:01

Read the patent literature I posted in first response. It specifies a mesh size range, and a crystalization profile to achieve it.

Look at other patent literature regarding the preparation of colloidal forms.

http://www.google.com/patents/US3264150

That patent includes a range of formulations and procedures, along with particle size and data on sensitivities, performance and loading characteristics- Engineers do a lot of work to turn chemistry into a good reliable product.

Keep digging, ask questions that show you're working at trying to learn. Someone will probably be able to answer.

Peroksit - 17-2-2014 at 12:18

"The most unnerving property about static sensitivity that I have observed is that precipitations themselves and filtering manipulations do generate static electricity and charge continues to reside in the mass of precipitated material, so the idea that a source of static must be an external influence somehow is entirely erroneous"

How can I eliminate this ? What I need to do ? it isn't enought simply grounding myself and static sensitive explosive ? do not allow humidity too low ? do not wear synthetic What do I need More ? Static confuses me very much



[Edited on 17-2-2014 by Peroksit]

Rosco Bodine - 17-2-2014 at 13:06

I don't think you can eliminate entirely the static from crystals since it is the static that holds the atoms and molecules together as crystals in the first place. And there is some sympathetic attraction at a distance that is the mutual attraction of like materials as if they would like to be merging and continuing growth as a larger crystal if a solvent was present, but they are discrete nuggets having the close field of electrostatic attraction stretched across the airspace between themselves. The effect will weaken over time in the presence of humidity and the differences in static charges gradually will equalize. But I have seen loose materials tend to "recharge" and spontaneously exhibit static effects for no apparent reason whatever, just sitting there in open air, so I don't really know what are all the nuances involved with static charge and particulate materials, except to be aware the effect is there to greater or lesser extent, and it is affected in intensity by ambient humidity and by the type of surface the material is resting on, and the amount of material present. It is like a big unknown when dealing with precipitates exactly what you may see. It would not be any surprise for me that this has been a source of accidents identified as some other cause, when it likely was indigenous innate static residing in the sample itself and not just a body charge on a technician that was an external charge. It may be more likely that the sample shocked / delivered charge to the technician than vice versa. A day when you have fog is a safer time for handling particulates. I keep a mister bottle with distilled water handy. Those conductive apparently aluminzed or graphited mylar films like are used for antistatic packaging computer parts are a good item to have on hand also. You can't really eliminate entirely the static but you can work around it and minimize its danger.

If you have used a clothes dryer you will observe that if the dryer is stopped just before the clothes are dry and removed while still steaming ......there is no static cling, but continue for five minutes longer till the clothes or other material is completely dry and you have extreme static. It works the same way for drying particulates. There is usually a point where the drying is not yet quite complete, when the material separates easily and falls apart into a loose powder without static and lumps as it finishes drying the last few percent. But if allowed for the drying to go to completion, then you see the static charge build up. Why ? I don't know but that is what occurs. Probably certain surfactants can help eliminate the issue just like anti cling sheets can be used in a clothes dryer.


[Edited on 17-2-2014 by Rosco Bodine]

Peroksit - 18-2-2014 at 10:07

Thank you Rosco

Thraxx - 7-12-2016 at 11:31

Today I did this reaction:
Into 1000 ml bottle I did 500 ml of 4,7% NaClO and in to ice bath I added there 32 g NaOH.In other baker I diluted in 100 ml watter 1g of gelatine/or may be KMnO4/ with 22g urea.After dilution I mixed both solutions and 2 h stirred.After I did the bottle into boiling watter for 20 min. There was too much foam,I should take there KMnO4.After I cooled in ice bath 1 hour and after I gave there 100 ml of 50%H2SO4.I waited 1 h. and filtered.
A piece of wet product(Hydrazine sulfate) I did into the bottle and give there ammonia and watter until was all dissolved.Ph was light acid.Then I gave there solution of NaNO2 and after solution of AgNO3 and the white AgN3 was there like milk.Filtration,washing and mixing with mercury fulminate to Astryl.

[Edited on 15-10-2016 by Thraxx]

Bert - 7-12-2016 at 20:47

Dr. Blechta's Astryl?

https://books.google.com/books?id=wfJHAAAAQBAJ&pg=PA4&am...

http://www.sellier-bellot.cz/en/company/history-overview/

Ca. 1924, Sellier & Bellot... Old school indeed.


Thraxx - 7-12-2016 at 22:28

Blechtas idea was to mix into the reaction beaker with silver azid synthesis crystals of aromatic nitro compounds .
The Astryl I associate with inventor Turek.(I will try to find the patent numbers)
Stettbacher did simmilar primer mixing merc.fulminate with 10% lead azide.
--
Until now I didnt find patent of Astryl,I found only Trademark Nr 115914 from year 1930 owner f.Sellier Bellot where was Blechta Director.
second I found patent of Turek Nr. 37577 from y. 1927 which is about Trinitrotriazidobenzene and its use like primer.
(I am looking for.....)
----------
Back to the Silver azide:
I worked in acording to Hodkinson patent from y. 1918(which was outgoing from work of Angelo 1893)
Angelo: Hydr.sulfate+AgNO2==AgN3 +2H2O +sulf.acid
Hodkinson:Hydr.sulfate + AgNO3+NaNO2==AgN3+2H2O+NaNO3+sulf.acid
Retions counted from Hodkinsons patent:
1 Step:130 g Hdr.Sulfate(1mol) diluted in 500 ml watter with help of added NH4OH to the weak acidity.
Discussion-is this the "hydrazine ammonium sulphate"?
could help more NH4 ? (Costain pat. 3943235,Taylor pat. 781440 GB.)
2 Step : 70g NaNO2(1 mol) diluted in 500 ml watter
3.Step: 170 g AgNO3 diluted in 1000 ml watter and acidified with 1ml of 70%HNO3.
After I put it together was it nice milk and after 10 min it turned pink and then after 10 min was all black black and black with metallic stains on surface.




[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

Bert - 8-12-2016 at 00:37

Mix Mercury fulminate with Lead azide, then you can't use either Cu or Al for container? What would you load that mix in?

90:3 Mercury fulminate:Silver azide allowed reduction of primary weight of S&B compound blasting caps from 250mg to 60, from litterature I just looked at. As percussion primer mix for cartridge use? It seems it would be too brissant.

Or does the word "primer" in your country = "blasting cap" in USA?

Thraxx - 8-12-2016 at 02:03

Quote: Originally posted by Bert  
Mix Mercury fulminate with Lead azide, then you can't use either Cu or Al for container? What would you load that mix in?

90:3 Mercury fulminate:Silver azide allowed reduction of primary weight of S&B compound blasting caps from 250mg to 60, from litterature I just looked at. As percussion primer mix for cartridge use? It seems it would be too brissant.

Or does the word "primer" in your country = "blasting cap" in USA?


In my country assignet the word "primer "the initiating stuff in the blasting cap .And the HE brizant in blasting cap is then "secondary".The percussion primer is assignet like "fuse".

The mixture of lead azide + merc.fulminate is used by Stettbacher for his lectures.Alfred Stettbacher was more university speaker than man of praxis.Verry funny was his work abbout "Langzeitzünders".

XeonTheMGPony - 8-12-2016 at 09:45

In reference to the metal issue here is my solution for the issue.

for my caps I use a paper wound tube about 1/8 diameter to press the comp delay into.

But since using peroxides as of late (I Do not have the necessities to make azids atm glass wear wise)

for safety reasons and using smaller amounts I started to press the peroxides into the paper tube first, then I load delay comp, this assembly then gets pressed into the preloaded metal tube with the 500mg etn, since this takes much less pressure to assemble

This has the added advantage of guiding the det wave down wards due to the higher confinement, the delay comp leaves a ash matrix above providing downward confinement, and due to the thick paper wrapping has much stronger axial confinement.

the added safety benefit of this system is all so the fact that if it goes off while pressing you have confetti and not shrapnel, and depending on your paper choice no issues with the bulk of primers out there.

[Edited on 9-12-2016 by XeonTheMGPony]

Thraxx - 8-12-2016 at 11:35

To Silver Azide:

I worked in acording to Hodgkinson patent from y. 1918(which was outgoing from work of Angelo 1893)Angelo:

Hydr.sulfate+AgNO2==AgN3 +2H2O + H2SO4

Hodgkinson:
Hydr.sulfate + AgNO3+NaNO2==AgN3+2H2O+NaNO3+H2SO4

Rations counted from Hodgkinsons patent:
1 Step:130 g Hdr.Sulfate(1mol) diluted in 500 ml watter with

help of added NH4OH to the weak acidity.Discussion-is this the

"hydrazine ammonium sulphate"?could help more NH4 ?

(Costain pat. 3943235,Taylor pat. 781440 GB.)

2 Step : 70g NaNO2(1 mol) diluted in 500 ml watter

3.Step: 170 g AgNO3 diluted in 1000 ml watter and acidified with 1ml of 70%HNO3.

After I put it together was it nice milk and after 10 min it turned pink and then after 10 min was all black black and black with metallic stains on surface.

This manner of manufacture AgN3 was described in patent of Hodgkinson GB 128014.

I did it many times and saw,that the reaction is in the reality white poridge of insoluble AgNO2 with metallic silver and big bubbles H2(?).Is here somebody who can do this patent?

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

Attachment: GB128014 (Hodgison silver azide from hydrazine).pdf (184kB)
This file has been downloaded 425 times

[Edited on 15-10-2016 by Thraxx]

Etanol - 10-12-2016 at 07:54

Quote: Originally posted by Thraxx  
To Silver Azide:

1 Step:130 g Hdr.Sulfate(1mol) diluted in 500 ml watter with



Try to increase the amount of water to 3 000 ml and not add ammonia.
Under alkaline environment there is a reaction
(Ag+) +N2H4 = Ag + N2

Under acid environment AgN3 is formed for a few hours.
T=20...30C

Thraxx - 10-12-2016 at 08:40

Quote: Originally posted by Etanol  
Quote: Originally posted by Thraxx  
To Silver Azide:

1 Step:130 g Hdr.Sulfate(1mol) diluted in 500 ml watter with



Try to increase the amount of water to 3 000 ml and not add ammonia.
Under alkaline environment there is a reaction
(Ag+) +N2H4 = Ag + N2

Under acid environment AgN3 is formed for a few hours.
T=20...30C

Thank you Etanol,,I found comentary of Rosco Bodine to this patent :

"After many careful experiments have been done without success
at reproducing the results described by GB128014 , I am reasonably
sure the method described by the patent is BOGUS and unworkable .

I used pure chemicals , accurately measured and controlled
conditions of pH in different experiments , in increments of
two tenths of a pH across the range from pH 5 to pH 7.2 .

I tried following the patents process description exactly ,
and I tried variations of every sort I could contemplate ,
with no joy in producing azides except in useless trace quantity
mixed with inert undesired by products .

On rare occasion I have encountered this scenario before ,
where a patent makes disclosure of a technology which does
not withstand scrutiny . There is no way of being sure about
the validity of what is reported by a patent except to experiment
and thereby put the matter to the test , which I have done .

My "finding" regarding GB128014 is that the information it
discloses is either incorrect or incomplete , and the process
it describes is *NOT* a straightforward nor valid method for
the synthesis of azides ."

It seems me that this patent is lie like many others.