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Author: Subject: Azides
Thraxx
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[*] posted on 17-1-2017 at 02:37


About the IP extract + IP nitrit method.
Schema of reaction:
HS Extract (3 times) + NaOH + IP nitrite == NaN3 + Na2SO4+IPA
1/8 mol=16g + 5g + 13ml == 7,5g

Extracted was 5 h at RT ,reaction was 24 h at -5C in freezer.Precipitated was with 3 vol. of ethanol(tech.)+aceton 1:1

Pictures: 1,2,3= extraction chemicals and extraction beaker
4=extract + NaOH solution in 40 ml IPalc.
5= extract with NaOH sol + IPnitrite=reaction mixture
6= the reaction mixture after 12 h.
7= reaction mixture after 24h.
8,9,10,11=filtration and amorph product
12=giving the product in the beaker before diluting
13 =product diluted in watter,very solubile
14=precipitation with alc./aceton mix
15=precipitation after 12 h. in freezer at -5C=ZERO
Conclusion: This reaction I did 13 x.Only one of these was with yield,all other reactions produced either dark liquid or ,like this -nothing.Does somebody knew what is wrong or what to do for to have some yield?

P1.JPG - 21kB 2.JPG - 149kB P3.JPG - 22kB P4.JPG - 18kB P5.JPG - 19kB P6.JPG - 17kB P7.JPG - 18kB P8.JPG - 18kB P9.JPG - 22kB P10.JPG - 27kB P11.JPG - 26kB P12.JPG - 21kB P13.JPG - 21kB P14.JPG - 20kB P15.JPG - 19kB

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]
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PHILOU Zrealone
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[*] posted on 18-1-2017 at 00:29


Quote: Originally posted by Theoretic  
Quote: Originally posted by PHILOU Zrealone  

If OH(-) eliminates nitrite from isopropyl nitrite it will be as NO2(-) and "isopropyl hydroxyde"

It won't! That's substitution you're talking about; it's not elimination. That's why I specifically said "Hydroxide E2 eliminates nitrite from IP nitrite". E2 elimination.
OH- won't displace nitrite to form isopropanol; OH- isn't a very good nucleophile and NO2 isn't a very good leaving group, with the C-N sigma* antibonding orbital at a too-high energy to react with hydroxide.
If hydroxide ever 'displaces' the nitrite, it happens by addition to the N center, then elimination of isopropoxide anion.

[Edited on 16-1-2017 by Theoretic]

Oh yes I understand now. I simply reused your "eliminates" without noticing the E2.
Yes I was speaking of substitution.
The case of nitrite esters is a hard one because into water they are extremely unstable...while they are very easily made from dilluted HONO (what is in strong opposition with most other esters that require concentrated acid and water scavenging to schift equilibrium to the right side of the reaction).
In fact the nitrous ester suffer from very easy retroconversion into the alcohol and nitrous acid...in fact as fast as it was done.
HO-N=O + Alk-OH <===> Alk-O-N=O + HO-H
The reaction is almost instantaneous and may go via several pathways:
-nitrosonium exchange with a proton form water (most probable)
-hydroxyl exchange with a nitrite anion (probably too slow)
-protonation of the alcohol, elimination of water to make carbocation and attack of the nitrite to leave a proton (probably too slow)

So nitrite esters are sensitive to base, to acid like most esters but also to neutral water; leave a nitrite ester for a few seconds into water and it has already reached decomposition/recomposition equilibrium.
This is the reason organic chemistry likes this reactant so much.
Easily done, easily collected and very reactive (fast reacting).




PH Z (PHILOU Zrealone)

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Thraxx
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[*] posted on 18-1-2017 at 13:00


Well,but what could be the strange liquid?Hydrazine is reducing. agent.Alcohol is not possible to be reducted,but what the HNO2?Could it be reduced into HNO azanone ? And is the azanone able to react with hydrazine or alcohol?
---
If the problem is in the lability of alcohol-nitrite,then it should be added either in drops,or it should be diluted.In the old methods they have a big part of diethylether.May be this is the reason-ether is a solvent for alcohol-nitrite.
From other point of view,in Urbanski,part III.under Baryum azid is described such method,where is ading of ethylnitrite during more hours and is freezed under -15C.
May be,that the IP extract/IPnitrite method need ether. Or an dropper.



[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]
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PHILOU Zrealone
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[*] posted on 19-1-2017 at 09:07


Quote: Originally posted by Thraxx  
Well,but what could be the strange liquid?Hydrazine is reducing. agent.Alcohol is not possible to be reducted,but what the HNO2?Could it be reduced into HNO azanone ? And is the azanone able to react with hydrazine or alcohol?
---
If the problem is in the lability of alcohol-nitrite,then it should be added either in drops,or it should be diluted.In the old methods they have a big part of diethylether.May be this is the reason-ether is a solvent for alcohol-nitrite.
From other point of view,in Urbanski,part III.under Baryum azid is described such method,where is ading of ethylnitrite during more hours and is freezed under -15C.
May be,that the IP extract/IPnitrite method need ether. Or an dropper.

No other idea. You have the product in hand so you can do a lot of testing on it...
Smell, evaporation (crystals?), pH, burning, explosion.

You have made so much experiments with a lot of variations on the amount of reactants and procedure. Usually less ingredients is the best to avoid side reactions --> KISS method (Keep It Short and Simple).

I think the ether may help the nitrite ester to solubilize (especially into the case of less volatile nitrite esters like n-butyl nitrite) and help the alkaline azide to precipitate from the media.

[Edited on 19-1-2017 by PHILOU Zrealone]




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Thraxx
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[*] posted on 19-1-2017 at 22:25


For the chemistry I am lover and fucker and from this position I feel me not competent,despite of 13 bad experiences, to tell about such important method like Thiele/Stolle's method is ,that it doesnt work.I will try to look at this method in its historic developement and connections.
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[*] posted on 22-1-2017 at 06:54



In the literature is citate the Thiele/Stolle method in relation to industry to the end of WWI.After only like method for labors.Simmilar method in the industry is citate by Urbanski.
This reaction has 2,59 mol of ethylnitrite and to this ethylnitrite is added during 24 h suspension of 1,8 mol Ba(OH)2 in 2 mol of 10% hydrazin hydrate.All freezed deep under OC.After they bubbled it with CO2 for to remove barium hydroxide.
This reaction should be theoretically 1:1:1 ,but they want to have surplus of etylnitrite and less of hydroxide.


bariumazid1.PNG - 41kBbariumazid4.PNG - 46kBbariumazid4.PNG - 46kB
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[*] posted on 22-1-2017 at 12:06


Precipitation of Ba(OH)2 happens as carbonate (BaCO3 is white precipitate).
Because
CO2 + H2O --> H2CO3
H2CO3 <--> H(+) + HCO3(-)
HCO3(-) <--> H(+) +CO3(2-)
and
Ba(OH)2 -aq-> Ba(2+) + 2 OH(-)
OH(-) + H(+) <--> H2O
finally
Ba(2+) + CO3(2-) <--> BaCO3(s)

Don't add to much CO2.
because
H2CO3 + Ba(N3)2 --> BaCO3(s) + 2 HN3
and
HN3 is very toxic (like cyanide) and volatile




PH Z (PHILOU Zrealone)

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Thraxx
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[*] posted on 23-1-2017 at 04:44


The Barium azide could be advantageously,because it seems be easier to purify.
In this moment I am doing other experiment-I converted the data from BaN6 manufacture to the NaN3:
2,59 mol of ethylnitrite=ekv. 2,59 mol of IPnitrite=265,22ml IPnitrite
1,8 mol of Barium hydroxide=ekv.3,6 mol of NaOH=144g NaOH
2 mol of Hydrazin hydrate=extrakt of 2 mol Hydrazine sulphate=260 g Hydraz.sulfate.
(The citation from Urbanski says nothing about solvent,but if it should be freezed to -15C,then it could be some alcohol.I take technical ethanol)

I gave one half of 1/10 of these amounts= 13ml IPnitrit + 7,2g NaOH(in 50ml tech.ethanol) + extraction of 13 g HS(in 50 ml tech.ethanol). To the IPnitrite I added yeasterday each one half of hour 5ml of extraction + hydroxide.Hydroxide I gave less than I should gave.And it was funny,I saw the ethylazid on the bottom there.

Now,after 24 h it is cloudy liquid and I am waiting until it will be clean.







[Edited on 15-10-2016 by Thraxx]
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[*] posted on 23-1-2017 at 06:25


If we knew the title of the book, we could read it ourselves and answer our own questions. Could you tell us what it is?
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[*] posted on 23-1-2017 at 10:25


Chemistry and Technology of Explosives
Vol. III.
by Tadeusz Urbanski
Pergamon press
Warszawa 1965
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[*] posted on 19-5-2018 at 05:06


Silver azide directly from hydrazine sulfate


Be very cautious with this reaction, don't scale this up without adaquate protective measures , do this outside or in a fumehood! It is unknown how much of the extremely toxic and explosive hydrazoic acid escapes the solution as a gas instead of being sequestered by Ag+, especially at the low pH utilized. Stability of the silver azide produced from this synthesis is also unknown and probably needs thorough washings to get rid of all traces of sulfuric acid and free hydrazoic, which may increase sensitivity of the end product. Silver azide is one of the most powerful primary explosives used commercially, with comparatively high sensitivities to friction and static

This was more of a small-scale-proof-of-principle experiment than an optimized synthesis, though the end result was positively identified as silver azide, others migh like to experiment further with this to maximize yield etc. :D

40 ml destilled water was added to a 50 ml erlenmeyer flask, together with 1 ml 98% sulfuric acid. About 100 mg of silver nitrate was added, which dissolved completely. Excess hydrazine sulfate was added in small increments until nothing dissolved further at room temperature (estimate 0.5 g or so).

To 10 ml of distilled water was added 0.2 g NaNO2 and dissolved. While at room temperature, the nitrite solution was added very slowly (1 drop every 10 sec or so) to the hydrazine sulfate/sulfuric/silver nitrate solution. Each drop of nitrite produced some fizzling, presumably nitrogen gas from side reactions of the hydrazine/hydrazoic with nitrous acid. After 10 minutes or so, a dense and pearl white precipitate started to form, which detonated with extreme vigor from flame in microscopic amounts.

The reaction of hydrazine and nitrous acid is mostly determined by pH and nitrite/hydrazium ion concentration. At low pH and excess hydrazinium, hydrazoic acid is the main product of the reaction (see attached articles). Apparently, silver azide itself is insoluble enough, even at such low pH, to precipitate from the reaction and reduce destruction by nitrous acid from solution. Minimizing the amount of sulfuric needed to keep at a pH <1 might work even better, in that the equilibrium between silver azide and free hydrazoic is as far to the silver azide as possible. Hydrazine nitrate/nitric might also work better due to the relative insolubility of the hydrazine sulfate in the solution, less OTC though.

[EDIT] If I got it right, a 1% solution of sulfuric should have a pH of ~1. With additions of nitrite, a 2% solution of SA seems more than enough to keep the pH at <1 during the reaction. Just checked the maximum solubility of hydrazine sulfate in a 50 ml solution of 2% sulfuric acid (1 g SA total), which seems about 0.65 g. (5 mmoles) at 25 C. If the reaction is taken as stoichoimetric, this would correspond to 0.849 g of silver nitrate and 0.345 g of sodium nitrite to form 0.749 g of silver azide (100% yield). In practice, an excess of hydrazine is probably needed, though 0.5 g of silver azide from 0.65 g hydrazine sulfate may be possible...the product also seems more dense than formed from NaN3/AgNO3 solutions...not bad! :D


Attachment: The kinetics of nitrite scavenging by hydrazine and hydrazoic acids at high acidities.pdf (269kB)
This file has been downloaded 58 times

Attachment: Is hydrazoic acid (HN3) an intermediate in the destruction of hydrazine by excess nitrous acid (659kB)
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[Edited on 20-5-2018 by nitro-genes]
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[*] posted on 22-5-2018 at 04:34


Attachment: Kinetic and product study of the reaction between nitrous acid and hydrazine.pdf (984kB)
This file has been downloaded 76 times

[Edited on 22-5-2018 by nitro-genes]
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[*] posted on 1-6-2018 at 01:02


2-Dimethylaminoethylazide

https://en.wikipedia.org/wiki/2-Dimethylaminoethylazide

Has anyone looked into this? Looks like a better UDMH
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