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Author: Subject: Preparation of cyanides
mario840
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[*] posted on 2-12-2010 at 01:33


entropy51 good lord , holy mother of god , tell me and correct the recipe from Ledgard , tell me one thing that is just wrong in these recipe , of course if you don't have additional funnel you can add at one all mixture sulfuric acid , but you only bla bla bla bla so if you don't have any usefull information please be quiet , internet is full of people like you , it's just sad and make topic a big trash , yes myfan did it with phosphoric acid but he must added some water because mixture foamed .... but he did it , no heating about 50 - 60 just to boiling and the mixture don't change color to apple green but dark blue (shit i don't know it's beacuse he used phosphoric acid)
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entropy51
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[*] posted on 2-12-2010 at 07:15


So mario, is this prep as good as your hydrolysis of formamide?
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mario840
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[*] posted on 2-12-2010 at 07:49


no hydrolysis but DEHYDRATION of formamide with P2O5 or AlCl3 , men can you read ??? hydrolysis was idea of myfan this for the first point , the second you didn't even answer my question ... what is wrong with this recipe ?? tell me what exactly .. guys kmno4 did also like myfan successfully ! with procedures very similar like this but he mentioned about temperature lower (50 C) , i'm curious how many books you wrote ? tell me your title and then i will rate them , the third point is do you really belive that i say that i done these recipe and made highly toxic chemical withouth any papers (illegaly) ... i NEVER made any of highly watched chemical , so i'm waiting for your knowledge and correct of synthesis from Ledgard , did you ever made any of these chemical form his book ?? Jesus men stop spaming
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watson.fawkes
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[*] posted on 2-12-2010 at 09:55


Quote: Originally posted by mario840  
what is wrong with this recipe ?? tell me what exactly
Please understand. No one is under any obligation here to set you right. You posted information from a suspect source and others have called it out. There two purposes here. One is to protect other, future readers by declaiming the professed authority of your source. The other is to assist you, if you pay heed, from harming yourself. It's not all about you.

If you insist on making toxic chemicals with procedures from suspect sources, all I can bring myself to say is "Good bye, and good luck".
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mario840
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[*] posted on 2-12-2010 at 10:18


Quote: Originally posted by watson.fawkes  
Quote: Originally posted by mario840  


If you insist on making toxic chemicals with procedures from suspect sources


the best part is suspect sources ... these sources base on patent and inorganic preparatory not only in english, others country still has book in their languages :P , (the same amounts and the same concentration of H2SO4 which evolute hcn instead of cyan (CN)2 )... if you have brain and learn quick and read not only one book you can confirm "suspect" recipe , so guy enropy51 said these is crap , hmmmm very interesting so the patant and recipe from other books and work others member of these forum are also crap , i don't insist anybody to do ANY toxic chemical but the topic is about cyanide so i posted here in my opinion very good synthesis of it and confirming with others recipe it works, just read page nr. 4 (LD NaCl = 250 g so don't do NaCl !!!! :P)
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[*] posted on 2-12-2010 at 14:49


Just shut up and make it already mario please. If everyone is so full of shit then make it. Your main source is a book called into question and a kid who died while attempting the synthesis. So please by all means stop the trolling and get out and experiment a little will you.




Knowledge is useless to useless people...

"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story before."~Maynard James Keenan
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cyanureeves
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[*] posted on 2-12-2010 at 17:32


mario840 post your results if you try to do synthesis.i cooked urea with naoh today, it was hard as rock. i added charcoal and cooked some more. i extracted with water and got some dark koolaide stuff and added some ethanol but nothing happened. im going to go as far as the urea and naoh for now and store it.some literature says to fuse the ferrocyanides with the carbonates.i did this a couple of days ago but used the hydroxide because sodium carbonate needs way too much heat to melt and true to what i read the red(ferro stays on the bottom) and the supposedly kcn can be poured out.this did happen but i was experimenting by adding urea as well so it was contaminated.the literature states to use a ceramic or porcelain crucible to minimize ferrous contamination but it could be that ill reputable ledgard literature. but does makes some sense .i got a grey looking rock that doesnt fizz with vinegar. but i dont know what it is and had no plating solution value for me. at least this topic is up and going again.i'll see gold dissolving in cyanide if its the last thing i , i ,...AAaarrrhggg!
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[*] posted on 2-12-2010 at 20:38
red ferro


i made an error when i wrote the red is poured out along with the supposedly koh.i meant the red is the ferro and it does stay on the bottom.you can pour the clearer stuff but use a swiping motion as you pour because the red sediment also flows folllowing right after.
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Taoiseach
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[*] posted on 3-12-2010 at 00:15


There's a writeup on different synthesis routes on versuchschemie:

http://www.versuchschemie.de/topic,14106,-Bildung+des+Cyanid...

German only but with lots of pics and should be easy to understand with babelfish
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cyanureeves
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shocked.gif posted on 3-12-2010 at 05:30
kcn


holy moly taiosearch. that was the clearest synthesis ive ever seen. that site is awesome. hell its much like this one.so are the comments."enough kcn to send him and his family to the other world".hell ive got that grey stuff. ive had it many times. the one thing that differs is that mine has been oxygen saturated. love the german language .even though the translator doesnt do it justice i can make sense of it.i copied the whole thing with word pad but i had to copy the pics separate as it left them out.thank you for that hook up.hell i got that pasty,gummy precipitate right now. i think polverone is right then!
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cyanureeves
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biggrin.gif posted on 3-12-2010 at 05:32
taoiseach ,to each his own?


sorry for chopping your name
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madscientist
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[*] posted on 3-12-2010 at 15:31


How hot was the fire when you attempted the reduction with charcoal? Both components need to be finely divided and the fire has to be hot.



I weep at the sight of flaming acetic anhydride.
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cyanureeves
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[*] posted on 3-12-2010 at 16:24


i used regular propane in the blue bottle until my titanium cannister glowed. it wasnt a real synthesis by far.the charcoal was activated charcoal,whatever that means and it was lumpy.honestly i thought steel would melt with a super hot fire because i used to burn a hole through my cast iron pan with my cutting torch way before all the sodium carbonate even melted. i just found out right now that my urea did not turn blue with with iron sulfate yet all my other failed cyanide stuff does.i just assumed urea did beacause that is what had the cyanate.ive not been even close to real synthesis compared to the german fellow.everything ive made has decomposed immediately. also i think ive been automatically logged in on this site a couple of times.maybe im just tired.
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madscientist
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[*] posted on 3-12-2010 at 20:05


I don't think a propane burner is going to provide high enough temperatures. Try what I did - stick the can in a charcoal fire and blast it with a fan or hair dryer of some sort.

If you have any sort of success, try to precipitate the product in cold isopropyl alcohol. Then you can filter it and dry it quickly, reducing loss due to hydrolysis.




I weep at the sight of flaming acetic anhydride.
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cyanureeves
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[*] posted on 3-12-2010 at 20:37


madscientist in deed i will try your isopropyl.and most certainly will use charcoal fire and air. the propane burner not providing adequate heat was a proven fact.i will adhere to what has been written here and try not to variate with unfruitful results and write only until i succeed.but im sure i will be tempted to as soon as someone else puts in their most valuable two cents worth.
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mario840
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[*] posted on 4-12-2010 at 01:26


cyanureeves what can i say :D I HEARD this synthesis fucking rox , need low energy (boiling water bath !) no heating with gas burner beacuse hcn will soon decompse and water will be too much evoluting so yield will dramaticaly go down, sulfuric acid I HEARD the best concentration is 30 - 35%. why ? read some papers , and finnaly most important thing the pure ... hmmmmm .... over 99% , no other germans fellows can synthesis that pure chemical , the purest what i read is reduction of thiocyanate potassium (90%) , but it's a trick I HEARD when you use phosphoric acid yield will be higher, just read some paper men
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[*] posted on 9-2-2011 at 09:54



A few pages before, it has been told that Fe4(FeCN6)3 (Prussian blue) decomposes in contact with strong acids.

And a way to produce HCN (gaz) is by hydrolysing ferric ferrocyanide
from prussian blue with sulfuric acid (98% H2SO4 in a picture by grains4me).


Should be something like :
Fe7(CN)18(H2O)x + 9H2SO4 ==> 7FeSo4 + 18HCN (gaz) +(H2O)x



There's something i'd like to request.
Since strong acids do the job, would also HCl be able to do the job ?
(Or the reason why it wouldn't.)




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[*] posted on 9-2-2011 at 10:50


Given the facts that hydrogen cyanide is a toxic gas and half of the population are unable to smell it at low concentrations making it sounds like an excellent way to win a Darwin Award! :(
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[*] posted on 9-2-2011 at 14:01


I am sure that there are better references than this but fusion of ferrocyanides with alkali is a good route to alkali cyanides and I am probably repeating earlier posts but;

http://www.1911encyclopedia.org/Prussic_Acid

This chemistry seems a lot safer than acid treatment.
I have my doubts about the legality and safety of making alkali cyanides or hydrogen cyanide at home on more than a micro scale.
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[*] posted on 9-2-2011 at 19:22


thealchemist93000. dilute sulfuric acid definitely produces hcn. and if HCL acid liberates HCN, how do you propose to capture the gas?and what for(the gas)? i've bubbled HCN through ethanol and KOH, but either used too much OH or have used too much water/sulfuric acid and it turns to cyanate quick. mario840 would talk about appropriate KOH ratio but never told me how much or why not to use too much.mario840 has remained silent for a while and i dont know why because it seems to me that he is thought of as quite intelligent,just a little hot headed and stubborn perhaps.i've fused KOH with potassiumferrocyanide and just put it away in a crumbled up paper thinking nothing of it. i checked it a month later and the paper had black burnt holes all over it.
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[*] posted on 10-2-2011 at 04:03


Its seems that with HCl you get chlorine.



To capture the gas...
I was thinking about bubbling it through NaCO3.
It should produce NaCN crystals that you could collect with paper filtration.





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[*] posted on 10-2-2011 at 05:30


With HCl you don't get chlorine. You'll get HCN, but it is not easily separated.

HCN dissolves in water very well and it boils at 26 C. When you heat the solution, then HCN will be driven out, but also quite some HCl (and water vapor).

If you bubble HCN through an aqueous solution of Na2CO3, then it will be absorbed and you'll end up with NaHCO3 and NaCN in solution. Don't expect any NaCN to form crystals from such a solution. The salt is highly soluble and I would expect separation of NaHCO3 to occur before any NaCN precipitates.

There are also all kinds of other issues. HCN and NaCN are very prone to aerial oxidation, leading to formation of cyanate (OCN(-)), which in turn easily hydrolyses to carbonate and ammonia. Cyanides also tend to polymerize while being partially oxidized and so-called azulmic acid is formed, which is some brown goop, which is not interesting at all.

CN(-) also is such a weak acid, that boiling down a solution of this in water (e.g. the sodium salt) will lead to great losses of HCN while NaOH remains behind. You'll end up with a mix of NaOH and NaCN at best.

I think that the best method of isolating cyanide is to use alcoholic solutions of NaOH or KOH and bubble HCN through that.

Making cyanide in a safe way is not easy at all, not even if you have the ferro- or ferricyanides at hand. From your posts I get the impression that for the near future it is best that you leave this synthesis alone and first do some other more benign chemistry. If not, then indeed Darwin's selection criterion also may be applied to your set of genes :o.




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Want to wonder? Look at https://woelen.homescience.net
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[*] posted on 10-2-2011 at 06:22


I think the best approach could be to fuse potassium ferrocyanide on its own.
This will produce potassium cyanide and insoluble impurities. Adding water to the cold solid will give you a solution of potassium cyanide that can be carefully filtered and then reacted with whatever you want. The equipment and any remaining solution can be treated with bleach and then washed.
You have to be scrupulously careful with cyanide, it is extremely poisonous so great care must be exercised in making, handling and storing it.
If you want to do transition metal complex chemistry at home then oxalate or thiocyanate are both good ligands, form interesting and beautiful complexes and have only a fraction of the toxicity.

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[*] posted on 14-2-2011 at 09:05


Thanks Woelen for caring about my dna sample, but my darwinian's job is already done.
(i'm 41 since January 15th. i have 2 children, the youngest is yet 19 years old).


So, this week, i put 1g of prussian blue in H2SO4 (37%).
But, of course, did NOT heat the solution.
I noticed there was a black powder (that should be FeSO4) and the solution became less fluid and the glass was very cold.
Since the natural process is lowering the temperature, why heating to reach 26°C ?


HCN melting point is -13.4°C, i wonder whether there would be a way to get it by cooling.

Cause melting points are as thoses :
H2SO4 (65%) is -64°C
H2SO4 (37%) is lower than -64°C
FeSO4 is 57°C


By cooling (-14°C), is it possible to get a mix (solid) of FeSO4 and HCN ?
But if it is possible, it still requires to figure a way to split FeSO4 and HCN that is working at -14°C.





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[*] posted on 14-2-2011 at 12:21


Some time ago i was able to produce some potassium cyanide by dry safe method from potassium ferrocyanide (yellow prussiate of potash or potassium hexacyanidoferrate(II)). Process of it's thermal decomposition is however very complex, and gives completely different results depending on decomposition conditions. I will describe them below.

Properties of K4[Fe(CN)6]. In pure state salt is white crystalline substance, commercial product is actually trihydrate K4[Fe(CN)6]*3H2O and has yellow coloration. Molar mass: 368.35 g/mol (anhydrous); 422.388 g/mol (trihydrate). Density 1.85 g/cm3 (trihydrate). Trihydrate looses water at ~70C however is not completely dehydrated below ~110C. Soluble in water: Trihydrate 28.9 g/100 mL (20 °C), insoluble in ethanol, ether. Salt decomposes without melt at temperatures above ~350-400C (depending on conditions), stable to heating at the air to about ~200C, is oxidized by oxygen at higher temperatures.

It's very remarkable that salt decomposition depends greatly on reaction conditions. Major difference depend on access of oxygen and dehydration of the salt.

Decomposition at the air.

In presence of air thermal decomposition of salt results in formation of cyanate, iron oxides and cyanogen, as well as some small quantity of cyanide. At the top layers in the crucible reactions proceeds as follows:

1. 4K4Fe(CN)6 + 3O2 => 2Fe2O3 + 16KCN + 4(CN)2
2. 2KCN + O2 => 2KOCN

Experiment shown that decomposition according to equations above proceeds above ~350C at relatively fast heating (0C => 350C in ~45 min) and above ~400C on slow heating (~2C in 1 min). Potassium cyanate is produced in molten state and blocks reaction gases to evolve freely. Some part of cyanate decomposes further forming potassium carbonate, some cyanide and carbon monoxide witch is oxydated to carbon dioxide by ferric oxide present in reaction mixture:

3. 4KOCN => K2CO3 + 2KCN + CO + N2
4. 3Fe2O3 + CO => 2Fe3O4 + CO2

Reaction mixture forms two layers, black top layer and bottom gray layer. At 450C top layer composition shows that 50% of iron still exists as K4[Fe(CN)6], while other part exists as Fe2O3, major detected compounds: KOCN, Fe2O3, KOCN. At 580C iron is exists completely in form of Fe3O4, major detected compounds: Fe3O4, K2CO3, traces (~3%) of ferrocyanide. It's remarkable that Fe3O4, K4[Fe(CN)6] and K2CO3 exist in the top black layer of the mixture, while bottom gray one shows presence of K4[Fe(CN)6], K2CO3, Fe3C and KCN. It is thought that molten paste of cyanate & iron oxides prevents lower layer from air oxydation, so lower layers contains significant amount of unreacted ferrocyanide. Summary of air reactions gives following approximate reaction equation for decomposition in presence of oxygen:

A. 6K4Fe(CN)6 + 17.5O2 => 2Fe3O4 + 22KOCN + K2CO3 + 6(CN)2 + CO2 + N2 [around ~580C].

Decomposition out of air contact.

First thing to mention here is that decomposition at closed vessel gives completely different results depending on dehydration of source compound. It's known that thermal decomposition of hydrated salt in such conditions yields CO2, NH3 and HCN, while dehydrated salt melts little above red heat with formation of iron carbide and KCN:

1. K4[Fe(CN)6] => FeC2 + 4KCN + N2

However in this case process is no also such simple, since Fe3C is also formed. To explain it's formation following reactions are assumed to exist at some extent:

2. K4Fe(CN)6 => 4KCN + Fe + N2 + 2C
3. K4Fe(CN)6 => 4KCN + Fe + (CN)2
4. 6Fe + (CN)2 = 2Fe3C + N2

At 580C this reactions take place in lower part of crucible on heating on the air and in whole mass if process is carried out of air contact. Then heated further, above 630C melting of KCN occurs, blocking free evolution of gases from reaction mixture, what can cause mixture to escape reactor crucible. Summary of decomposition reactions out of air contact gives following approximate reaction equation:

B. 6K4Fe(CN)6 => 24 KCN + 2Fe3C + 6N2 + 5C

Right way to go

Experimentation with decomposition of pure salt as shown above is not completely suitable for simple and safe method of production of pure potassium cyanide. To overcome disadvantages of pure salt decomposition some methods have been developed long ago, those are classified as dry and wet ones. Wet methods require to work with highly dangerous gaseous HCN and will not be discussed here. Dry ways are in melting of ferrocyanide in presence of alkaline compounds such as K2CO3:

1. K4[Fe(CN)6] + K2CO3 => 6KCN + FeO + CO2

But under influence of the iron oxide formed a small quantity of cyanide is transformed to cyanate, so reaction is in reality as follows:

2. K4[Fe(CN)6] + K2CO3 => 5KCN + KOCN + Fe + CO2

Combination of reaction equations above gives more accurate equation:

C. 2K4[Fe(CN)6] + 2K2CO3 => 11KCN + KOCN + FeO + Fe + 2CO2

This process is known as Leibig's brocess, and has however disadvantage sine resulting product contains cyanate and is difficult to separate from formed FeO. To overcome this disadvantages one can use more sophisticated process proposed by Wagner, witch uses additive of charcoal to reduce any cyanate formed:

D. K4[Fe(CN)6] + K2CO3 + C => 6KCN + Fe + CO2 + CO

Advantage of this process is that formed product is free from cyanate, and that metal iron is easy to separate. One more advantage is that process generates gas with reducing nature witch then formed in closed vessel forms protective atmosphere preventing cyanide from oxidation.

Experimental results.

Dehydrated ferrocyanide was prepared by tempering on the air at 150C for 2 hours. Salt was finely ground in mortar and intimately mixed with K2CO3 and lampback (taken it quantities according eq. D above) by grounding in mortal all together. This reaction mixture was placed to the porcelain crucible, covered with tightly fit porcelain lid, and was placed into electric furnace with temperature controlling program. Mixture was heated from room temperature to 560C in one hour, and is allowed to sit at this temperature for one more hour to allow free gassing of formed CO2 and CO. On completion of this period mixture is heated further to 650C in 30 minutes and allowed to sit for one hour at this temperature, this resulted in melting of reaction product and separation of iron particles. Crucible is allowed to cool to room temperature and is broken down to obtain solidified KCN/Fe mixture. Product has shiny white appearance with gray spots of iron particles evidenced by ferromagnetic properties of the sample. Product has faint bitter almond smell. All process was carried out in room without efficient ventilation or effective fume hood, no cyanogen or other smells were detected.

:cool:

Method is suitable for obtaining relatively pure cyanide in safe dry way. Some details on ferrocyanide decomposition can be obtained from article attached to this message.

Attachment: Thermal Decomposition of Potassium Hexacyanoferrate (II) trihydrate.pdf (666kB)
This file has been downloaded 1258 times

[Edited on 14-2-2011 by Engager]




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