Sciencemadness Discussion Board

Preparation of cyanides

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mario840 - 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)

entropy51 - 2-12-2010 at 07:15

So mario, is this prep as good as your hydrolysis of formamide?

mario840 - 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

watson.fawkes - 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".

mario840 - 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)

Sedit - 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.

cyanureeves - 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!

red ferro

cyanureeves - 2-12-2010 at 20:38

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.

Taoiseach - 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

kcn

cyanureeves - 3-12-2010 at 05:30

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!

taoiseach ,to each his own?

cyanureeves - 3-12-2010 at 05:32

sorry for chopping your name

madscientist - 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.

cyanureeves - 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.

madscientist - 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.

cyanureeves - 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.

mario840 - 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

thealchemist93000 - 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.)





ScienceSquirrel - 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! :(

ScienceSquirrel - 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.

cyanureeves - 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.

thealchemist93000 - 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.






woelen - 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.

ScienceSquirrel - 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.


thealchemist93000 - 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.






Engager - 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 1431 times

[Edited on 14-2-2011 by Engager]

kmno4 - 14-2-2011 at 15:54

Long time ago I performed similar experiment.
My product was hard, crystalline grey mass, smeling like bitter ... + ferromagnetic particles (however much weaker than Fe)
But this "result" gives no information about what it is.
I took a sample of this product (after purification) as catalyst for benzoin condensation.
And I had to boil mixture for very long time to obtain visible amounts of benzoin :mad:
The same amount of pure KCN gave sudden formation of benzoin after 1/10 of time needed for "pyrolytical KCN" synth.

This:
K4[Fe(CN)6] + K2CO3 + C => 6KCN + Fe + CO2 + CO
is only theory (wishful thinking).
Have you tried to do some tests for your product (carbonates, KCN content, yield) ?

Engager - 14-2-2011 at 22:21




I have done only qualitive test for cyanide, without quantitative analysis of the sample, however i will do this some time later in the lab, because i don't want to work with cyanogen nasties at home conditions. Images above are from "Cyanide Industry". Pyrolityc method of cyanide production is known for the long time, it surely works and was even used in industry, only thing to ensure here is that time about ~3 hours is enough to complete conversion of source products.

Here is also a description of cyanide production by Leibig's method from "The Practical Metal-Worker's Assistant", by Oliver Byrne:

This substance may be prepared by exposing ferrocyanide of potassium (yellow prussiate of potash) to a red heat in an iron crucible; then pounding the mass, and boiling it in alcohol of about spec. grav. 0.900: cyanide of potassium crystallizes on cooling the resulting solution. It is now, however, almost universally prepared for electro-metallurgical purposes, by a process which was first suggested by Messrs. F. and E. Rodgers. but afterwards more fully explained by Professor Liebig, and hence called "Liebig's Process:" it is at once both simple and easy of performance.

Ferrocyanide of potassium rounded fine, is dried over a slow fire (we have found an iron plate, or clean shovel, to serve the purpose very well): it must be constantly stirred to prevent its forming a cake upon the hot iron; when perfectly free from moisture, 8 parts must be thoroughly well mixed with three parts of carbonate of potash, also well dried: put a cast-iron crucible into the fire, and, when it is red hot, nearly fill it with the mixture, and keep up the heat by occasional augmentations of fuel: the crucible should be kept covered as much as possible. In a short time the whole fuses into a beautiful liquid with the evolution of gas. It should be kept in this state for 10 or 15 minutes, being occasionally stirred with an iron rod: the portion adhering to the red should be examined from time to time, and when the liquid on it cools white, it is an indication that it is ready to be removed from the fire; but the first time a cast-iron crucible is used, this test will not be so accurate, the salt having then a light gray color. When the crucible is removed from the fire, it should be placed upon a stone, the mass stirred, and then allowed to settle for a short time, after which the clear, or liquid part, is to be poured off into a clean iron vessel. The sediment should be scraped clean out of the crucible while it is hot, as the crucible will do to use again several times; but if the mass at bottom be allowed to cool it will be difficult to remove it from the crucible afterwards. The clear liquid poured off is cyanide of potassium, having from 25 to 30 per cent, of cyanate of potash, and other impurities generally contained in commercial yellow prussiate of potash: 80 per cent. of cyanide of potassium is the greatest proportion that this process can give. We have occasionally obtained it at 78 per cent. from commercial materials, but more generally at 70 and 72 per cent; and we have found cyanide of potassium in the market containing as little as 49 per cent. of pure cyanide.

[Edited on 15-2-2011 by Engager]

Engager - 14-2-2011 at 22:44

Quote: Originally posted by kmno4  
Long time ago I performed similar experiment.
My product was hard, crystalline grey mass, smeling like bitter ... + ferromagnetic particles (however much weaker than Fe)
But this "result" gives no information about what it is.
I took a sample of this product (after purification) as catalyst for benzoin condensation.
And I had to boil mixture for very long time to obtain visible amounts of benzoin :mad:
The same amount of pure KCN gave sudden formation of benzoin after 1/10 of time needed for "pyrolytical KCN" synth.

This:
K4[Fe(CN)6] + K2CO3 + C => 6KCN + Fe + CO2 + CO
is only theory (wishful thinking).
Have you tried to do some tests for your product (carbonates, KCN content, yield) ?


What are exact conditions of your pyrolysis experiment? Have you added carbon to reduce cyanate? How much care was taken to protect mixture from the air? What is the temperature scheme used?

kmno4 - 15-2-2011 at 02:23

Quote:

What are exact conditions of your pyrolysis experiment? Have you added carbon to reduce cyanate? How much care was taken to protect mixture from the air? What is the temperature scheme used?

These data are not available :P
Just it was performed long time ago, in much simpler way than your experiment.
Synthesis via K4[Fe(CN)6] + K2CO3 + C methode is mentioned many times in books and even in this topic.
The most important to me is real amount of KCN prepared from given amount of K4[Fe(CN)6], not very nice looking equations.
If something is crystalline and sweet - it does not mean that it is pure sugar.

Random - 16-2-2011 at 06:02

What about the reaction of chloroform with amines to yield isocyanides?

CHCl3 + amine + base --> isocyanide

Now, if we use ammonia instead of amine?

CHCl3 + NH3(g) + base --> cyanide salt?

Picric-A - 16-2-2011 at 07:32

Quote: Originally posted by Random  
What about the reaction of chloroform with amines to yield isocyanides?

CHCl3 + amine + base --> isocyanide

Now, if we use ammonia instead of amine?

CHCl3 + NH3(g) + base --> cyanide salt?


This is a well documented reaction. The only drawback is the fact the NH3+base and CHCl3 are imiccible and so a PTC is required.

Random - 16-2-2011 at 10:13

Do you know some PTC which is easy available or easy to make? I think this route is a lot easier than those other high temperature reactions.

ScienceSquirrel - 16-2-2011 at 10:41

You have to use a very strong basis eg potassium hydroxide and it is hard to keep the ammonia in solution at normal pressure.
A lot of chloride is produced as well so it is hard to fish the potassium cyanide out of the reaction mixture at the end.
Balance the equation and allow for formate etc formed by hydrolysis and you will see how disgusting it is! :(

Picric-A - 16-2-2011 at 12:34

Quote: Originally posted by Random  
Do you know some PTC which is easy available or easy to make? I think this route is a lot easier than those other high temperature reactions.


It is no where as good as the other outlined methods.... yields are crap and as affore mentioned high pressures are needed for good yields....
benzyltrimethylammonium chloride should work fine!

Random - 16-2-2011 at 14:42

It sounds hard to do then. But, maybe cyanides could be made from organic isocyanides which could be made from amine+chloroform+base?

Also there is formamide decomposition route.

entropy51 - 16-2-2011 at 15:05

Quote: Originally posted by Random  
Also there is formamide decomposition route.
Please don't post random misinfformation before at least using the search function to see if it's already been randomly posted by random newbies:
Quote: Originally posted by Nicodem  
I think we should all wait our funny cyanide kewls to provide the reference for their illogical claim that alkali cyanides can be made by reacting formamide with alkali hydroxides. This patent is surely not what they had in mind (considering the required reaction conditions and all). It should not be so difficult telling us where they read about a reaction so kewl that goes against chemical theory and against experimental data confirming that formamide reacts with KOH and NaOH in the usual manner.
There's a whole frickn thread on this nonsense.

ScienceSquirrel - 16-2-2011 at 16:03

The ways of making potassium or sodium cyanide on a laboratory scale have been exhaustively explored and documented including detailed preparations.

The best way to go about it is to research the recipes, buy the reagents for your chosen method and then execute the preparation using the appropriate safety precautions and scale. Test your product and if it contains significant amounts of free cyanide anion store and use it with the appropriate precautions.

Making sodium thiosulphate by boiling up sodium metabisulphite, sodium hydroxide and sulphur is OK.
It is really not poisonous so making up your own recipe is OK, but DIY cyanide is nuts unless you have serious experience!

Random - 17-2-2011 at 04:16

I didn't say to use hydroxides, formamide on strong heating decomposes into water and HCN, on slow into ammonia and carbon monoxide.

Check more on wikipedia about Hydrogen Cyanide.

I also read on some page that HCN was successfully synthesized from formamide in history, just I don't remember who did it first..


Melgar - 17-2-2011 at 10:26

I haven't read the whole thread, but I was curious if sodium hydroxide/carbonate could be mixed with cyanuric acid, then heated to like 800C in a cast iron (or refractory clay) crucible to get sodium cyanide. I'm assuming it'd work with urea, which would give the cyanate first. And 800C is maybe too hot for me to get it to. I'm guessing 600 or 700 would probably work?

And dissolving in RT methanol then filtering and evaporating would give fairly pure NaCN, right? I'm guessing water could be used too, but it might be a little harder to evaporate away without decomposing the NaCN, right?

[Edited on 2/17/11 by Melgar]

Engager - 18-3-2011 at 16:31

Quote: Originally posted by kmno4  
Quote:

What are exact conditions of your pyrolysis experiment? Have you added carbon to reduce cyanate? How much care was taken to protect mixture from the air? What is the temperature scheme used?

These data are not available :P
Just it was performed long time ago, in much simpler way than your experiment.
Synthesis via K4[Fe(CN)6] + K2CO3 + C methode is mentioned many times in books and even in this topic.
The most important to me is real amount of KCN prepared from given amount of K4[Fe(CN)6], not very nice looking equations.
If something is crystalline and sweet - it does not mean that it is pure sugar.


Ok... May be this is not sugar. However, recently i made a larger batch of cyanide using method i've described. Although i haven't made precise analysis, i've observed mass loss and it was consistent with equation from the book. A batch of product was flushed with water, and filtered. Unsoluble impurities were metallic Fe and some carbon. Obtained solution was used for benzoin condensation. Procedure i've used was taken from http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0094, refluxing period was 1 hour instead of 30 min proposed by the procedure. Benzoin was obtained with 82% yield. :) So purity of product remain unknown, but it is proved to be useful for benzoin condensation.


[Edited on 19-3-2011 by Engager]

Rosco Bodine - 21-8-2011 at 11:47

Quote: Originally posted by Nicodem  
Wouldn't polyethylene start "cracking" at the temperature required? Most of it might escape in form of vapors of higher olefins.

If using pre-prepared tripotassium cyanurate the powder is fine enough (and chemicaly homogenous = as much as it can be) to form KOCN at lower temperatures (250-350°C).* This yields a highly homogenous and very fine product. Perhaps such product would be more ready to react with something like polyethylene at somewhat lower temperatures.
Perhaps the reduction would work even better with thoroughly homogenized crude KOCN with sugar:D, which then carbonizes to some fine carbon that should do the job. However, at the begining there would be a lot of annoying froating due to evolved H2O and CO2 from such a "caramel candy". Starch does not melt, so perhaps it would be more apropriate even though it would be less homogenous.

* This is how I once supposedly prepared some KOCN: I prepared "tripotassium cyanurate" (due to pKa3, I doubt one can prepare it stoichiometricaly pure from KOH) from cyanuric acid and 3 eq of KOH in IPA solution, vacuum filtered the white voluminous paste and while still wet (to avoid CO2 absorption) heated it on a hotplate well covered with alu-foil until up to some 250-350°C and left there for about 2h. There was some cracking of the powder at the beginning and later no more notable change. I haven't analyzed the product but given that no cyanuric acid precipitated after acidification with HCl of an aqueous solution of the product, I assume only KOCN could have formed. This was a modification based on GB710143 where Na2CO3 with cyanuric acid is used to produce NaOCN. If someone is terribly curious if this was truly KOCN, I might bother to check with IR (if someone is so kind to provide a reference spectra:P).


Pardon my digression concerning a parallel interest with regards to cyanuric acid possibly having other usefulness as well. I will go out on a limb here somewhat with speculation
since this seems possible but complete references are not available for having certainty about this possible scheme.

What would be more interesting for me than the IR spectra
would be an experiment to find out about the feasability of further reaction of the KOCN with additional KOH or NaOH either as a subsequent addition, or provided in excess sufficient from the beginning of the reaction, to accomplish the reaction described by Dreschel leading to the dibasic salt of cyanamide and a carbonate. This would be interesting not in regards to production of cyanides so much as it would be interesting as a path to guanidine and also to aminoguanidine.

3 KOCN + 3 KOH ------> K2CN2 + 2 K2CO3 + NH3

This is the reaction of Dreschel corrected to show the evolution of ammonia reported in the attached article, see page 11 of the pdf The Ammono Carbonic Acids Franklin, JACS 44

What I have thought about is the sum of the reactions

(HOCN)3 + 3 KOH ----> K3(OCN)3 + 3 HOH ---->

3 KOCN + 3 KOH ----> K2CN2 + 2 K2CO3 + NH3 =

--------------------------------------------------------------------

(HOCN)3 + 6 KOH ----> K2CN2 + 2 K2CO3 + NH3

Doubling the amount of hydroxide for the formation of the tripotassium cyanurate could then lead to dipotassium cyanamide. Curiosity exists whether or not this entire reaction sequence may occur in DMSO under reflux, so that byproduct H2O and NH3 is volatilized.

Subsequent treatment of the completed reaction mixture
with hydrazine sulfate could lead to aminoguanidine.
Nitrosation in situ could produce guanyl azide and cyclization to 5-aminotetrazole would seem convenient as a possible one pot synthesis.

Alternatively the completed reaction mixture might be acidified for isolation of cyanamide or cyanoguanidine
or be used as an intermediate for production of guanidine.

It remains unclear what sort of reaction condition is required for the Dreschel reaction to proceed, and with what efficiency does that described reaction occur. But the implications are certainly interesting for these other possible end products obtainable from cyanuric acid, under whatever reaction conditions, and most interesting if indeed such reactions can occur under relatively milder conditions of temperature than the pyrolytic decomposition schemes, especially if it would occur in DMSO.

Now there is a qualitative analysis approach that you know very well is more interesting than an IR spectrum :D

Dreschel article also attached see pae 13 of pdf

Attached also is some data about the level of hydration of
alkali cyanurates. Evidently the tripotassium cyanurate has been reported difficult. The disodium cyanurate and trisodium cyanurate reportedly crystallize in anhydrous form. So it may go equally well to work with the less expensive sodium salts.

GB710143 also attached

Attachment: The Ammono Carbonic Acids JACS.pdf (1.1MB)
This file has been downloaded 1150 times

Attachment: Dreschel article.pdf (1.9MB)
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Attachment: GB710143 Cyanates from Cyanurates.pdf (791kB)
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Attachment: Alkali Cyanurates thermochemical properties JOCS 70.pdf (214kB)
This file has been downloaded 1161 times

There is some additional discussion regarding the cyanate in a cyanate specific thread
http://www.sciencemadness.org/talk/viewthread.php?tid=9128

[Edited on 22-8-2011 by Rosco Bodine]

497 - 26-9-2011 at 21:48

Here's an idea I haven't seen, though it seems obvious.
Adding TCCA to an alkaline solution of amino acids has been shown to give high yields of the corresponding nitrile and CO2. Other sources indicate that glycine yields HCN from reacting with hypochlorite.
So why not just gradually add TCCA to the glycine solution, keeping glycine in excess in order to prevent the TCCA from destroying the cyanide?
Separation of cyanide from the cyanurates and chlorides shouldn't be hard right?
Doesn't get much easier than that...

[Edited on 27-9-2011 by 497]

S.C. Wack - 27-9-2011 at 14:53

Quote: Originally posted by Rosco Bodine  

Alternatively the completed reaction mixture might be acidified for isolation of cyanamide


Since you happen to mention GB710143 and an interest in cyanamide, perhaps I can mention here the amine version of cyanuric acid, melamine, and bell-ringer US2656253. Both patents are known here due to trying to find a use for it, since it's on hand (but not larger tubing, yet. Or the pressure apparatus for the GB).

slinky - 17-1-2012 at 15:52

Quote: Originally posted by Polverone  
YIKES! I found the following information on another site:

a patent on making metal cyanides from nitrates or nitrites and
carbon; US patent 579988.
KNO3 + 4C -> KCN + 3CO
KNO2 + 3C -> KCN + 2CO

I was unable to access the patent since I'm temporarily banned from the database for running too many queries (oops).

So I decided to try just forming a pyrotechnic mixture with the right ratios. 10 grams KNO3, 4.8 of charcoal, place in stainless steel vessel and ignite with gas heating from below...

As expected, the mass of what remained was much reduced, from loss of gas, solid particulates, things flung from the vessel by the reaction, etc. There was little material left in the bottom. I figured there had to be more to the method than this; after all, nobody talks about pyrotechnic formulas leaving cyanide lying around, and this is pretty much the same thing.

Anyway, not having an analytical method for detecting cyanides at hand and being too stupid to look one up (and also expecting failure), I added a bit of vinegar to the residue left in the bottom. It fizzed vigorously and I caught the distinct odor of almonds... At which point I backed the heck away from there. I now intend to find a method for assaying KCN that is not so suicidal, and also to try making some more and purifying it (I have no idea what purity I obtained with this first test.) This method seems to be a vastly superior route to cyanides for the home experimenter, compared to the laborious steps given in the PMJB and the 19th century texts from which they were derived. I hope to view that patent soon and see if it contains any additional refinements (compared to crude ignition).


I gave this a shot. It seemed to be the most simplistic method listed in this thread.

The reaction vessel I used was a small stainless steel camping pan 1/2 full with heavy duty foil over the top. The reagents occupied an approximate volume of 350 ml. The carbon was activated carbon from the pet store fish isle which I ground finely in a coffee grinder. The NaNO2 was free flowing and fine. I placed the reaction vessel over very low gas heat. Nothing happened for few mins as the mixture came up to temperature. A violent reaction occured. The foil lid blew off the small pan. It looked like a small volcano erupting. The reaction reminded me of gunpowder burning. It made a big mess. There were little black crystalline pebbles of the partially reacted mixture everywhere. A decent amount of smoke was created. It looked like there was a fire. The cleanup was painstaking because I didn't know if the reaction had succeed and there was potentially NaCN all over everything in a 5 foot radius from the cup. There was indeed a blackened crystalline fused mass in the bottom of the cup. I was so preoccupied with the mess and smoke I had made, I neglected to test the remaining product on some silver. I called it a day.

I'm interested in trying this again. This time, in a much less full heavy duty stainless steel pot with a weighted lid on top to keep the spatter down. After the reaction, do you suggest that I continue heating it? Should I just allow it to cool and go from there? It seems to me that any continued heating would be irrelevant because the mixture has already literally burned on it's own.


[Edited on 1.18.2012 by slinky]

Bot0nist - 17-1-2012 at 16:19

Quote: Originally posted by slinky  
Quote: Originally posted by Polverone  
YIKES! I found the following information on another site:

a patent on making metal cyanides from nitrates or nitrites and
carbon; US patent 579988.
KNO3 + 4C -> KCN + 3CO
KNO2 + 3C -> KCN + 2CO

I was unable to access the patent since I'm temporarily banned from the database for running too many queries (oops).

So I decided to try just forming a pyrotechnic mixture with the right ratios. 10 grams KNO3, 4.8 of charcoal, place in stainless steel vessel and ignite with gas heating from below...

As expected, the mass of what remained was much reduced, from loss of gas, solid particulates, things flung from the vessel by the reaction, etc. There was little material left in the bottom. I figured there had to be more to the method than this; after all, nobody talks about pyrotechnic formulas leaving cyanide lying around, and this is pretty much the same thing.

Anyway, not having an analytical method for detecting cyanides at hand and being too stupid to look one up (and also expecting failure), I added a bit of vinegar to the residue left in the bottom. It fizzed vigorously and I caught the distinct odor of almonds... At which point I backed the heck away from there. I now intend to find a method for assaying KCN that is not so suicidal, and also to try making some more and purifying it (I have no idea what purity I obtained with this first test.) This method seems to be a vastly superior route to cyanides for the home experimenter, compared to the laborious steps given in the PMJB and the 19th century texts from which they were derived. I hope to view that patent soon and see if it contains any additional refinements (compared to crude ignition).


I gave this a shot. It seemed to be the most simplistic method listed in this thread.

The reaction vessel I used was a small stainless steel camping pan 1/2 full with heavy duty foil over the top. The reagents occupied an approximate volume of 350 ml. The carbon was activated carbon from the pet store fish isle which I ground finely in a coffee grinder. The NaNO2 was free flowing and fine. I placed the reaction vessel over very low gas heat. Nothing happened for few mins as the mixture came up to temperature. All at once, a violent reaction happened. The foil lid blew off the small pan. It looked like a small volcano erupting. The reaction reminded me of gunpowder burning. It made a big mess. There were little black crystalline pebbles of the partially reacted mixture everywhere. A decent amount of smoke was created. It looked like there was a fire. The cleanup was painstaking because I didn't know if the reaction had succeed and there was potentially NaCN all over everything in a 5 foot radius from the cup. There was indeed a blackened crystalline fused mass in the bottom of the cup. I was so preoccupied with the mess and smoke I had made, I neglected to test the remaining product on some silver. I called it a day.

I'm interested in trying this again. This time, in a much less full heavy duty stainless steel pot with a weighted lid on top to keep the spatter down. After the reaction, do you suggest that I continue heating it? Should I just allow it to cool and go from there? It seems to me that any continued heating would be irrelevant because the mixture has already literally burned on it's own.

[Edited on 1.17.2012 by slinky]



Did you read the whole thread? What about the patent mentioned?

Quote: Originally posted by Polverone  


Oh, BTW, that patent I mentioned in the 2nd post in this thread? It involves using electrified carbon rods in molten KNO3/KNO2, so it's still not the easiest thing ever...


[Edited on 18-1-2012 by Bot0nist]

slinky - 17-1-2012 at 16:22

He himself didn't use electrified carbon rods. I did read the patent he cited a few times.

Bot0nist - 17-1-2012 at 16:31

I don't think his reaction lead to confirmed formation of metal cyanides either. He even implied that him smelling almonds was not conclusive, and no attempts where made to determine yield. Two things you have also not done.

I would love if it was that easy, but I have attempted to make NaNO<sub>2</sub> via C and NaNO<sub>3</sub> in a similar fashion, albeit with different proportions. Keep experimenting though. Try and find a way to accurately confirm the formation of metal cyanides and then isolate and quantify your yield. This would be the best place to focus efforts, IMHO.

[Edited on 18-1-2012 by Bot0nist]

seashell1982 - 31-1-2012 at 17:03

Here is the method I'm planning to follow:
Quote:

To convert the ferro to cyanide do this (please note that these instructions were for the potassium not sodium salt. I'm assuming that the ratios are similar for both); Mix thoroughly 8 parts of dry sodium ferrocyanide and 3 parts dry sodium carbonate (pool pH adjuster), heat them in a steel container (cleaned oil filter can works nicely), with constant stirring (use clothes hanger, straightened out), with a propane torch or other intense heat source till it melts into a clear liquid. Heating is continued until the mix no longer fizzes and the fluid portion is colorless. After a few minutes rest, to allow the contents to settle, the clear portion is poured from the heavy black sediment (iron) at the bottom of the crucible and onto to a clean slab or steel bowl. It's then broken up while still warm and stored in airtight bottles. This will be almost pure cyanide.

K4Fe(CN)6•3H2O + K2CO3 --> 6KCN + CO2 + FeO + 3H2O

Is the above possible in my backyard?

cyanureeves - 31-1-2012 at 18:20

i've done this but with sodium carbonate and never could tell the clear liquid from the rest of the fused stuff. i used a swiping motion when i poured the liquid in hopes that the liquid portion would run out first then the sediment would follow afterwards and so i could separate the solid from the liquid. what i got was a grey rocklike stuff. it made good prussian blue with iron sulphate but so did the ferrocyanide.i never got it to dissolve gold but did use it for a gold plating solution but it was not satisfactory. i think oxygen is absorbed to quickly when pouring the molten stuff out and turns to cyanate instead. i dont know but i want to try with potassium carbonate because it melts faster. this time i would cover it immediately with a huge pot with plumbers putty on the rim to make a seal so as to starve it of oxygen. this liquid hardens fast too but it can be done in the backyard,now to make the ferrocyanide or cyanide like the german site shows requires lots of heat,i had to use a leaf blower and tons of charcoal and still didnt get it hot enough to thoroughly fuse.i could'nt see crap because i had snot and tears running all the way down to my belly.

seashell1982 - 1-2-2012 at 18:02

Is there some way to turn wet potassium ferrocyanide into the dry version? Like this:

K4Fe(CN)6•3H2O --> K4Fe(CN)6 + 3H2O

Apparently I need the anhydrous, but the chemical supply stores seem only to sell the trihydrate version.

Engager - 3-2-2012 at 01:51

Yes. Actually you can use hydrate. Just heat it up on the frying pan, it looses water at about ~130C and became lighter in colour. You can as well control completeness of dehydration by measuring mass loss, just heat up on the pan until mass loss will become theoretical. Dry fusion of pure K4Fe(CN)6 is a bit tricky, if you will try to do this on air contact you will end with with cyanate and cyanogen beeing evolved. To prevent oxidation process must carried out out of air contact, that's why method witch K2CO3 and carbon works the best - you don't need protecting atmosphere you just must cover reaction vessel with lid to reduce free air flow, reaction products CO and CO2 will form protecting buffer of gas under the cover and prevent oxidation of product to cyanate, remember you don't need completely airtight vessel (reaction gases must evolve freely) just cover crucible with ceramic lid and heat it up in electric furnace. I made K4Fe(CN)6 + K2CO3 + C process for many times now and produced a lots of cyanide using this method, temperature program i've used ~30 min to 600C, then 1 hour at this temp, rise to 650 in 30 minutes, and one more hour at 650. If your crucible is high and you sit it long enough cyanide separates from Fe and carbon particles and solidifies as shiny snow white layer at the top layer, however if this has't happened and resulting mass is black and feromagnetic this is fine too, you can separate cyanide by dissolving and filtering. I've used such cyanide for the benzoin condensation 2 or 3 times, each time from new batch and always got good yields of benzoin.


[Edited on 3-2-2012 by Engager]

Ephoton - 3-2-2012 at 09:11

I have always thought that the reduction of cyanate to cyanide would need simuler conditions as the reduction
of nitrate too nitrite.

In the ionic nitrites thread taoiseach has posted a link too the german forum that describes the use
of calcium formate for the reduction of nitrate.

I was thinking of lead tartrate before but with this prep laid out for us I would think this would be an
easier task.

thread to taoiseach's post
http://www.sciencemadness.org/talk/viewthread.php?tid=52&...

german thread too nitrite synthesis with calcium formate
http://www.versuchschemie.de/topic,13865,-Herstellung+von+Ni...

seashell1982 - 3-2-2012 at 18:17

Quote: Originally posted by Engager  
I made K4Fe(CN)6 + K2CO3 + C process for many times now and produced a lots of cyanide using this method,
Will this carbon work? http://www.onlinesciencemall.com/carbon-lumps-15-grams.html

Quote: Originally posted by Engager  
resulting mass is black and feromagnetic this is fine too, you can separate cyanide by dissolving and filtering
How exactly do you do that?

[Edited on 4-2-2012 by RisingSun96815]

AJKOER - 3-2-2012 at 21:29

Here is a preparation for HCN or its salts that uses only household products (scary). The reference is a bit dated but I suspect basically accurate. Source: "The Pharmaceutical journal and transactions", by Pharmaceutical Society of Great Britain on December 24, 1887, page 530:

"When the ammonia and iodine are first mixed, an explosive compound, the so-called iodide of nitrogen, is precipitated, but soon splits up again and dissolves. Disregarding this reaction, the steps of the process may be made clear by the following equations, which are not given as an exact representation of what is probably a more complicated reaction, but rather as an explanation of the results detailed above. Schbnbein (Watts' 'Dictionary,' vol. iii., p. 297) has found that hypoiodite of ammonium is formed by the action of iodine on excess of ammonia. The reactions may, therefore, be represented as follows:—

1. Iodide and hypoiodite of ammonium are formed thus :—

6 NH4HO + 3 I2 = 3 NH4I + 3 NH2IO + 3 H2O

2. The hypoiodite reacts with the alcohol to form iodoform and iodide and formate of ammonium, thus:—

2C2H60 + 8NH4IO = CHI3 + 3 NH4CHO2 + 5 NH4I + 4H20

3. The iodoform reacts with the free ammonia to form iodide and formate of ammonium thus :—

CHI3 + 4 NH4HO = 3 NH4I + NH4CH02 + 2 H20, so that ultimately the tincture contains iodide and formate of ammonium, free ammonia and spirit.

http://books.google.com/books?pg=PA529&lpg=PA529&dq=...

Now, allow the tincture to evaporate leaving I2 and Ammonium formate, then followed the process outlined by Madscientist on page 1 of this thread , but allow the Iodine to collect at the top of the heated vessel by cooling that area. Per Madscientist:

"PREPARATION OF POTASSIUM CYANIDE (KCN):
The ammonium formate crystals are heated by flame in an environment containing as little oxygen gas as possible. The ammonium formate decomposes into formamide (HCONH2) which then decomposes into hydrogen cyanide.

[HCOO-][NH4+] --} HCONH2 + H2O
HCONH2 + H2O --} HCN + 2(H2O)

The gas given off is condensed in in a rubber, plastic, or, preferrably, glass tube that has one end immersed in a beaker containing a solution of potassium hydroxide (KOH). The tube should be positioned so that any liquids forming in it will run off into the beaker of potassium hydroxide. Some of the gas given off may not be condensed..."

If one effectively recycles the Iodine, then this process is relatively inexpensive consuming just NH3 and alcohol. However, a potential issue is the creation of any NI3 (from any residual Ammonia and/or a side reaction, per Wiki noted below, plus Iodine) from the heating of the Iodine/ammonium formate, which should be guarded against, as its detonation could spread deadly HCN gas.

Note, per wikipedia:
"When heated, ammonium formate eliminates water, forming formamide. Upon further heating it forms to HCN and H2O. A side reaction of this is the decomposition of formamide to CO and NH3."


[Edited on 4-2-2012 by AJKOER]

Ephoton - 4-2-2012 at 07:13

Why use iodine to make ammonium formate ?

I have made this before with just formic acid and ammonia gas.
The formic was made via oxalic acid and glycerol then turned to salt with sodium bicarbonate.

The formate can be made into an acid which is strong enough to be gassed with 80 too 85% sulfuric acid
if the formate is added to the acid when it is cooled below 0C. if the temp is above 0C it will crack your formic
acid and make carbon monoxide.

waist of iodine.

I would do my best not to work with HCN having had a dose of it in the past.
It was far from pleasent and ive been poisoned by quite a few of my stupid endevours when I was younger.
HCN was up there with the worst the post about it is probably here somewere.

I think you should listen to some of the warnings posted by the people here HCN is as bad as they say.



AJKOER - 4-2-2012 at 09:32

Ephoton:

I definitely agreed do not attempt this synthesis (in case it actually does work).

The positive aspect of the thread is letting kids known that Nitrogen tri-iodide, a novelty explosive, cannot safely be prepared adding ammonia to tincture of iodine and heating the product. This could, instead, lead to a tragic poisoning by way of Hydrogen Cyanide gas fumes.

So don't do it!

entropy51 - 4-2-2012 at 14:08

Quote: Originally posted by AJKOER  
The positive aspect of the thread is letting kids known that Nitrogen tri-iodide, a novelty explosive, cannot safely be prepared adding ammonia to tincture of iodine and heating the product. This could, instead, lead to a tragic poisoning by way of Hydrogen Cyanide gas fumes.

So don't do it!
Do you really believe that this reaction will make significant amounts of HCN?

AJKOER - 4-2-2012 at 16:03


OK, if we net these two reactions (per the source):

2C2H60 + 8NH4IO = CHI3 + 3 NH4CHO2 + 5 NH4I + 4H20
CHI3 + 4 NH4OH = 3 NH4I + NH4CH02 + 2 H20
-------------------------------------------------------------------------
2C2H60 + 8NH4IO + 4 NH4OH = 4 NH4CHO2 + 8 NH4I + 6 H20

or, dividing through by 2:

C2H60 + 4 NH4IO + 2 NH4OH = 2 NH4CHO2 + 4 NH4I + 3 H20

So, for each mole of alcohol, we form two moles of ammonium formate. Per its decomposition reaction, one mole of ammonium formate produces one mole of HCN. So, if we are not limited by the available Iodine & Ammonia (that is, plan the experiment with an excess of I2 and NH3), each mole of alcohol can produce 2 moles (or 44.8 liters) of HCN gas. However, there is a side reaction:

NH4CHOO ---Heat Secondary Reaction--> NH3 + H2O + CO

so if the yield is reduced by 40% (a significant side reaction), each mole of alcohol still produces over a mole of HCN (as .6 X 2 = 1.2 mole).

Also, it is perhaps not unusual to employ an excess of NH3 (it is cheap) and we are attempting to recycle the Iodine.





[Edited on 5-2-2012 by AJKOER]

entropy51 - 4-2-2012 at 16:47

Quote: Originally posted by AJKOER  
The reference is a bit dated but I suspect basically accurate. Source: "The Pharmaceutical journal and transactions", by Pharmaceutical Society of Great Britain on December 24, 1887, page 530:
I suspect it is hokum. And 1887 is more than "a bit dated". You can't believe everything you read. Unless you're an arm chair chemist who doesn't own any glssware or chemicals to verify what you read.

AJKOER - 6-2-2012 at 13:53

Quote: Originally posted by entropy51  
Quote: Originally posted by AJKOER  
The reference is a bit dated but I suspect basically accurate. Source: "The Pharmaceutical journal and transactions", by Pharmaceutical Society of Great Britain on December 24, 1887, page 530:
I suspect it is hokum. And 1887 is more than "a bit dated". You can't believe everything you read. Unless you're an arm chair chemist who doesn't own any glssware or chemicals to verify what you read.


Actually, if you know or even looked at some of the reactions, in light of today's knowledge, your comment "hokum' is really misplaced.

For your edification, the 1st reaction is based on the classic disproportionation of a halogen in water. For Iodine:

I2 + H2O <===> HI + HIO

and adding NH3 reacts forming NH4I and NH4IO, a reaction correctly referenced back to Watt's.

Next, the creation of Iodoform is also a classic reaction. For example per "Chemistry, inorganic and organic: with experiments' By Charles Loudon Bloxam, page 636:

"Iodoform, CHI3 or tri-iodo-methane, is a product of the action of iodine upon alcohol in an alkaline solution, the immediate agent being probably a hypo-iodite, whilst chloroform is produced by a hypo-chlorite. To prepare it, dissolve 32 parts of potassium carbonate in 80 parts of water, add 16 parts of alcohol of 95 per cent, and 32 parts of iodine; heat gently till the colour of the iodine has disappeared, when iodoform will be deposited on cooling.

CH3-CH2OH + 6KOH + I8 = CHI3 + HCOOK + 5KI + H2O.

To recover the iodine left as KI, the filtrate from the iodoform is mixed with 20 parts of HC1 and 2.5 parts of potassium dichromate, which liberates the iodine. The liquid is neutralised with potassium carbonate, and 32 parts more of that salt are added, together with 6 parts of iodine and 16 of alcohol; the operations of heating and cooling are then repeated.

Iodoform is deposited in yellow shining hexagonal plates, smelling of safi'ron. It fuses at 120° C, and may be sublimed with slight decomposition. It is insoluble in water, but dissolves in alcohol and ether. When boiled with potash, it is partly volatilised with the steam, and partly decomposed, yielding potassium iodide and formate. The production of CHI3, on adding iodine and dilute KOH and stirring, is a very delicate test for alcohol, but many other substances also yield it. "

link:
http://books.google.com/books?pg=PA662&dq=ammonia+and+et...
IvT4zQHcbv0gGxxJXnCg&id=ogtDAAAAIAAJ#v=onepage&q=ammonia%20and%20ethyl%20iodide&f=false

Also, another source:

"An introduction to chemical pharmacology: pharmacodynamics in relation to ....", page 7 of 30 by Hugh McGuigan:

"IODOFORM AND PHYSIOLOGICAL SUBSTITUTES

Iodoform, or triodomethane, was the first solid antiseptic known. It is prepared by the action of iodine upon alcohol or acetone, in the presence of an alkali or an alkaline carbonate. Its formation is also used to test for the presence of alcohol or acetone. A solution of I in KI is added to the solution of alcohol, or acetone, and warmed, then dilute NaOH or KOH is added, drop by drop until the color has disappeared. Iodoform is formed :

CH3COCH8 + 3KI0 = CH3COCI3 + 3K0H
CH3COCI3 + KOH = CH3COOK + CHI3

The potassium hypoiodite KIO is formed when dilute KOH is added to the I in KI solution : 2 KOH + I2 = KIO + KI + H2O. The hypoiodites are easily decomposed into iodides, and iodates:

3 KIO = KIO3 + 2KI.

Both the iodate and iodide are usually formed in the solution with the iodoform, even when KI has not been added. Strong alkalies cause the formation of the iodate; and, therefore, if a too strong alkali is added, it interferes with the reaction. For this reason, sodium carbonate or potassium carbonate instead of the hydrate is sometimes recommended in making the iodoform test. From alcohol, iodoform is prepared, possibly according to the following reaction:

C2H6OH+I8+6KHCO3 = CHI3+5KI + KCOOH+6CO2+5H2O

Ethyl iodide, acetic ether, and other compounds are probably also produced. The result appears to be greatly influenced by the temperature, and the relative amounts of the materials used."

Please note the last sentenced as I do not mean to say that careful attention to detail is not needed for a successful reaction here.

LINK:
http://www.ebooksread.com/authors-eng/hugh-mcguigan/an-intro...

With respect to the creation of any Ethyl iodide, which, per Bloxam, page 633:

"In a large number of cases the mere treatment of an alcohol with halogen hydride, particularly in the presence of a dehydrating agent, will produce the halogen substitution product, the reaction being of the type ROH + HX = EX + HOH." Note, we are not directly employing a dehydrating agent, but the overall reaction does consume water. To best understand how to proceed with these multi-step reactions, also note in the reaction:

I2 + H2O <===> HI + HIO

clearly having an excess of conc. NH3 to remove the HI and HIO would be good as otherwise a possible disproportionation into iodate (noted above as unfavorable):

3 HIO --> 2 HI + HIO3

Other factors, mild heat (say 90 C), KI to add to the solubility of the Iodine, and working in a sealed chamber (to prevent ammonia loss). Heat and water loss would also increase the reactivity of the HI in the creation of iodides.

----------------------------------------------

Per research, I also can across the Tollens Reagents test, which could also form NH4HCO2. In general, for an aldehyde, RCOH:

RCOH + 2 Ag2(NH3)2OH ---> 2 Ag(s) + NH4(+)RCO2(-) + H2O + 3 NH3

which, in our case of interest, R is a single hydrogen (H) and the synthesis is thus based on formaldehyde, H2CO.

LINK:
http://opencourseware.kfupm.edu.sa/colleges/cs/chem/chem303/files%5C3-Lecture_Notes_CHEM-303_(Classification_Tests).pdf

----------------------------------------------



[Edited on 6-2-2012 by AJKOER]

seashell1982 - 16-2-2012 at 09:22

I made the following attempt this morning: I heated wet potassium ferrocyanide until it was lighter in color, assuming it changed to anyhydrous. I then combined it with potassium carbonate and a little carbon, added a lid to the crucible, and heated it in my gas-powered fireplace for 2 hours. The result was a black solid with a few white crystals on the edge of the black mass. I'm assuming the white crystals are actually potassium carbonate. What am I doing wrong here? Is the temp of my fireplace too low? I checked periodically, and I never got any liquid.

Engager - 16-2-2012 at 09:32

Temperature schedule to be used in K4[Fe(CN)6] + K2CO3 + C: about 1 hour to 600C, 30 min to 650-700, and 1 hour at 650-700C. And actually yes, mixture should be liquid at this temp since KCN melts around 630C. Correctly prepared product after cooling is fused black ferromagnetic mass with smell of bitter almond. I guess that your temperature was too low for the process.

[Edited on 16-2-2012 by Engager]

Magpie - 16-2-2012 at 12:41

I would treat that black mass you took out of your fireplace with a lot of respect. Ie, there may be more cyanide there than you think. I suggest you test it using a Prussian Blue test as follows:

1.Place about 1 mL of water in a small test tube.
2. Add a smidgen (few mg) of FeSO4*7H20 or other soluble ferrous salt and stir until dissolved.
3. Acidify with a few drops of 1M HCl.
4. Add a smidgen of your product and stir.

An intense dark blue color indicates the presence of cyanide.

[Edited on 16-2-2012 by Magpie]

cyanureeves - 16-2-2012 at 16:51

i second magpie because i bubbled hcn into potassium hydroxide/ water solution by distilling potassium ferrocyanide with sulfuric acid.i then added cold ethanol to precipitate the salt and it all turned to ammonia in a day but to make a long story short,i mostly had cyanate because of the water or excess potassium hydroxide.i forgot about the salt which i stored in a jar with a dessicant but last month i took it out and added a bit of water and dropped a piece of gold in it and now i got a yellowish looking solution which i did never before could produce.i know gold cyanide is white but where is the gold color coming from.i think i always had cyanide in the mix because it plates out gold beautifully and boy had i been careless with the stuff.definitley wear a mask when you break the hard black mass.

S.C. Wack - 16-2-2012 at 17:13

Perhaps assumptions were made about the ease of completely dehydrating the salt?

cyanureeves - 16-2-2012 at 18:41

the salt is very very difficult to dry, it actually never did even in the texas summer heat. just when it was about to dry off it kept grabbing moisture from the air like a freaking gecko.this salt was stored with baked epsom salt in a jar for over six months. the little piece of gold is sitting at the bottom of a tiny jar covered in crystal clear salt covered by a spongy looking stuff then the yellow solution.i did the method engager is doing and also the urea,charcoal and carbonate method and got the salt to dissolve copper and silver but only when adding 3% hydrogen peroxide. the copper just melts like butter on the outside and bleeds off but the silver breaks up into particles.i should've weighed the gold before i dropped it in the salt.

seashell1982 - 21-2-2012 at 07:56

Today I replaced my thick-walled crucible with a steel soup can, and sure enough I got liquid. I let it cook for an hour, and had a black mass. So how exactly do I filter this to extract any KCN that is there?

madmanhere - 21-2-2012 at 23:31

Is it safe to buy Potassium Ferrocyanide? I mean the lab guys will ask a million questions as to why you need the compound, right? And what will you reply?

PS: I'm not interested in making this stuff. Just curious after seeing the amount of enthusiasm in here. :)

barley81 - 22-2-2012 at 10:58

Yes. Ferrocyanides/ferricyanides are not that toxic because the cyanide ligands are tightly bound to the iron core. Perfectly safe to buy, and not that expensive too.

cyanureeves - 22-2-2012 at 19:04

Quote: Originally posted by RisingSun96815  
Today I replaced my thick-walled crucible with a steel soup can, and sure enough I got liquid. I let it cook for an hour, and had a black mass. So how exactly do I filter this to extract any KCN that is there?
i think the next step is crush the mass to a powder and throw it in a container with warm water.swish it around and invert it totally over and flush on a filtered funnel that is taped to a jar or glass.as the stuff is pouring quickly cover the whole thing with plastic wrap and tape it tightly around the glass.when it is all poured out inject ice cold ethanol into the container through the plastic.you rapidly see the white precipitate out like a gel looking stuff and more so if you shake it.avoid oxygen is a key also. this precipitate is what dissolved copper and silver in my experiment when i added peroxide but as of yet it did not dissolve gold. this stuff is so hard to dry too.

cyanureeves - 22-2-2012 at 19:11

Quote: Originally posted by madmanhere  
Is it safe to buy Potassium Ferrocyanide? I mean the lab guys will ask a million questions as to why you need the compound, right? And what will you reply?

PS: I'm not interested in making this stuff. Just curious after seeing the amount of enthusiasm in here. :)
yes it is and i have bought some.its safe as heck because photographers use it also and i read that it is also added to food to keep it from caking up. ferrycyanide is also safe to buy but its more expensive.both can release hcn and become deadly though if acid is added to them but hell ,bullets are deadly.

madmanhere - 23-2-2012 at 08:26

Thanks for the replies.

I went through myfanwy's video on NaCN preparation and is intrigued by a few basic things. Searched on Google, but couldn't find an answer.

1. If room temperature is ~30'C, HCN will be in gaseous form. To convert into liquid, one should pass chilled water through the condenser. Assuming HCN indeed comes out in liquid form at the other end of the condenser, how do you ensure it is collected as a liquid? Should we immerse the receiving flask in chilled water too?

If yes, another question. If the climate is very humid- say 80%, atmospheric water vapour will condense on the inner walls of the receiving flask. Is there any problem if HCN mixes with this water?

2. Instead of using an empty receiving flask, why can't we just dip one end of the condenser tube into NaOH? Is it safe (bubbling)? Is there any chance for NaOH to get sucked up into the heating flask?

3. How is NaCN extracted from NaOH solution? Heating is not safe, right?

I don't plan to conduct the experiment any time soon (chemistry noob + know the dangers). Would love to do it after a while though.




[Edited on 23-2-2012 by madmanhere]

AirCowPeaCock - 23-2-2012 at 08:59

Its so viscous! Pretty :D

kotze - 23-2-2012 at 12:29

"If yes, another question. If the climate is very humid- say 80%, atmospheric water vapour will condense on the inner walls of the receiving flask. Is there any problem if HCN mixes with this water?"

It probably hydrolizes, so yes.

"Instead of using an empty receiving flask, why can't we just dip one end of the condenser tube into NaOH? Is it safe (bubbling)? Is there any chance for NaOH to get sucked up into the heating flask?"

One should never risk a suck-back when working with such awefully dangerous substances. If suckback happens and ice-cold NaOH solution is sucked back into the hot reaction vessel, chances are the glass will crack, releasing deadly HCN fumes.

"How is NaCN extracted from NaOH solution? Heating is not safe, right?"

Heating wet cyanide is one of the fastest ways to destroy it. It could be precipated with ice-cold ethanol but I would rather evaporate under vacuum at a low temperature until it starts to crystallize.

Personally I would not conduct this experiment even when someone offered me 1000$ to do it. There are much easier and far less dangerous ways to make cyanide which have been posted already. I would prefer decomposing dry potassium ferrocyanide in a charcoal furnace and then boil the resulting mass in MeOH to dissolve all cyanide. The MeOH is then filtered and destilled until dry canide is obtained.

ferro+carbonate+c method

expInfi - 24-2-2012 at 11:14

Yes. Actually you can use hydrate. Just heat it up on the frying pan, it looses water at about ~130C and became lighter in colour. You can as well control completeness of dehydration by measuring mass loss, just heat up on the pan until mass loss will become theoretical. Dry fusion of pure K4Fe(CN)6 is a bit tricky, if you will try to do this on air contact you will end with with cyanate and cyanogen beeing evolved. To prevent oxidation process must carried out out of air contact, that's why method witch K2CO3 and carbon works the best - you don't need protecting atmosphere you just must cover reaction vessel with lid to reduce free air flow, reaction products CO and CO2 will form protecting buffer of gas under the cover and prevent oxidation of product to cyanate, remember you don't need completely airtight vessel (reaction gases must evolve freely) just cover crucible with ceramic lid and heat it up in electric furnace. I made K4Fe(CN)6 + K2CO3 + C process for many times now and produced a lots of cyanide using this method, temperature program i've used ~30 min to 600C, then 1 hour at this temp, rise to 650 in 30 minutes, and one more hour at 650. If your crucible is high and you sit it long enough cyanide separates from Fe and carbon particles and solidifies as shiny snow white layer at the top layer, however if this has't happened and resulting mass is black and feromagnetic this is fine too, you can separate cyanide by dissolving and filtering. I've used such cyanide for the benzoin condensation 2 or 3 times, each time from new batch and always got good yields of benzoin. [Edited on 3-2-2012 by Engager]

1.Can porcelain crucible be used ?
2.Can carbon rode be used to stir the mass?
3.If not porcelain or iron , can regular stainless steel cooking ware can be used ?
4.How the temp. variation can be done in a domestic cooking gas range ?
5.The regular wook burnt will work or need to buy activated charcoal from amazon or so ?

I used first a regular cooking ware (stainless steel) and then a porcelain.None worked.But I didnt regulate the air and due to fear of toxic gas i had the windows open and exhaust fan on all the time.I didnt add carbon either.I should have made the ventilation clear but the pan kept closed it seems ?
Anyway what I ended up with is a dark ,dry sediment.Need to try next after getting ur response..
Thanks !

Magpie - 25-2-2012 at 18:23

Quote: Originally posted by Magpie  
I would treat that black mass you took out of your fireplace with a lot of respect. Ie, there may be more cyanide there than you think. I suggest you test it using a Prussian Blue test as follows:

1.Place about 1 mL of water in a small test tube.
2. Add a smidgen (few mg) of FeSO4*7H20 or other soluble ferrous salt and stir until dissolved.
3. Acidify with a few drops of 1M HCl.
4. Add a smidgen of your product and stir.

An intense dark blue color indicates the presence of cyanide.

[Edited on 16-2-2012 by Magpie]


I should also point out that it is necessary for some ferric ions be present also. So I add a drop or two of 0.5M FeCl3 to be sure.

An interesting paper I found shows that the ideal pH for the formation of Prussian Blue is 5.5 to 6.5 and that the Fe:CN ratio of 0.5 is best:

http://www.saimm.co.za/Journal/v092n01p017.pdf

Brewster also says that the addition of a little fluoride ion keeps the Prussian Blue in suspension thereby providing the best coloration. I have 0.5M NaF handy for this, but usually don't need it.

Some procedures also call for heating the test tube. For inorganic work anyway I have found this not to be necessary.

What are your experiences/preferences?

madmanhere - 26-2-2012 at 04:23

Finally!

Heated a pinch (may even less) of K. Ferrocyanide in a test tube. Once it became white, added excess of 88% phosphoric acid and heated the solution.

It started bubbling leaving water droplets at the side (also HCN?) and the solution turned blue suggesting the experiment was a success! The solution was not as blue as in myfanwy's experiment. Guess it's because the phosphoric acid was pure and colourless.

Sniffed the contents, but didn't get any bitter almond smell. Guess I am not genetically endowed. :(

entropy51 - 26-2-2012 at 10:50

Quote: Originally posted by madmanhere  
Finally!

Heated a pinch (may even less) of K. Ferrocyanide in a test tube. Once it became white, added excess of 88% phosphoric acid and heated the solution.

It started bubbling leaving water droplets at the side (also HCN?) and the solution turned blue suggesting the experiment was a success! The solution was not as blue as in myfanwy's experiment. Guess it's because the phosphoric acid was pure and colourless.

Sniffed the contents, but didn't get any bitter almond smell. Guess I am not genetically endowed. :(
Ferrocyanide when acidified and heated releases HCN. You may or may not have converted the ferrocyanide to cyanide; you will obtain HCN in either case.

You actually sniffed it huh? There are bold chemists and old chemists, but there are no old, bold chemists.

madmanhere - 26-2-2012 at 14:00

As I said the quantity was very small. Less than a pinch of ferro. And I didn't smell when the reaction was going on- only after removing the test tube from the flame.

It was too tempting. Other than that I was doing some pretty lame stuff- like heating NaOH crystals with H3PO4 and the likes. ;)

[Edited on 26-2-2012 by madmanhere]

cyanureeves - 26-2-2012 at 14:09

there is a german video on youtube where a guy heats potassium ferrocyanide and potassium carbonate in a test tube and cyanide forms on the side of the mass like a white beach. the test tube is angled at about 22.5 deg. so the cyanide will run away from the fused mass instead of mixing. i read that the cyanide actually forms on the bottom when done in an upright container.i would be tempted to sniff the dried product but not when its still warm and surely not when in gas form.

expInfi - 29-2-2012 at 17:11

Quote: Originally posted by RisingSun96815  
Today I replaced my thick-walled crucible with a steel soup can, and sure enough I got liquid. I let it cook for an hour, and had a black mass. So how exactly do I filter this to extract any KCN that is there?


I tried today morning with soup can.I added carbon as well.I saw liquid forming not enough to separate.And after an hour looks like it fused together to a molten mass.Does this mass has KCN ? If I add warm water to this ,will it dissolve Gold ?

cyanureeves - 29-2-2012 at 18:45

i doubt you will dissolve gold with all that charcoal still absorbing all the cyanide if you succeeded. i could not get the isolated white stuff to dissolve gold only copper but after i added peroxide too. silver just disintergrated into particles.why dont you crush the stuff and filter it?

[Edited on 1-3-2012 by cyanureeves]

expInfi - 29-2-2012 at 18:57

Quote: Originally posted by cyanureeves  
i doubt you will dissolve gold with all that charcoal still absorbing all the cyanide if you succeeded. i could not get the isolated white stuff to dissolve gold only copper but after i added peroxide too. silver just disintergrated into particles.why dont you crush the stuff and filter it?

[Edited on 1-3-2012 by cyanureeves]


You mean filter the way you mentioned with a precaution to prevent conversion to cyanate ?Its pretty tough to do so coz I m doing all these in my kitchen :P.I am thinking the 3 hour temp scheme (dont know how to establish it above a gas stove though) will melt it to liquid.Anyhow is this mass poisonous or would be harmless as ferrocyanide ?

expInfi - 29-2-2012 at 19:00

Did anyone try myfanwy94 ? Condensing HCN and neutralizing with NaOH ?

http://www.youtube.com/watch?v=K5NuqpdYDhE

cyanureeves - 29-2-2012 at 19:51

i havent tried condensing hcn. i got all the chemicals and glass and even bought two gas masks but i am really scared and havent mustered the guts yet. i think the charcoal canister russian mask will be best for this task. this summer i tried making nitric acid and all the nitric vapors leaked somewhere and never condensed.i cannot allow this to happen with hcn i got new kleck clips too. i will make nitric one more time then i will do the hcn.myfanwy did condense hcn but not with NaOH. honestly i think you need fire and a good blow dryer to get the heat up there.i believe you will get ferrocyanide if you start with ,potash and blood and iron shavings but it will stink your whole house and you need lots of heat.i used deer hooves instead of blood and did isolated the salt and did make prussian blue,i used a blue propane torch bottle i got from walmart

[Edited on 1-3-2012 by cyanureeves]

madmanhere - 29-2-2012 at 20:21

Bad post.

[Edited on 1-3-2012 by madmanhere]

[Edited on 1-3-2012 by madmanhere]

expInfi - 29-2-2012 at 20:26

Quote: Originally posted by madmanhere  
Quote: Originally posted by cyanureeves  
myfanwy did condense hcn but not with NaOH.

I still don't understand how he got crystallized NaCN out of the solution. Any idea? The video shows him mixing NaOH with HCN and then the crystals without mentioning how he got it.

As kotze said, one could use cold ethanol under vacuum. But I don't know how to create the vacuum..

@explnfi:
Conducting the experiment in a kitchen? :o

[Edited on 1-3-2012 by madmanhere]


He used ethanol to precipitate it.

expInfi - 29-2-2012 at 20:31

Quote: Originally posted by cyanureeves  
i havent tried condensing hcn. i got all the chemicals and glass and even bought two gas masks but i am really scared and havent mustered the guts yet. i think the charcoal canister russian mask will be best for this task. this summer i tried making nitric acid and all the nitric vapors leaked somewhere and never condensed.i cannot allow this to happen with hcn i got new kleck clips too. i will make nitric one more time then i will do the hcn.myfanwy did condense hcn but not with NaOH. honestly i think you need fire and a good blow dryer to get the heat up there.i believe you will get ferrocyanide if you start with ,potash and blood and iron shavings but it will stink your whole house and you need lots of heat.i used deer hooves instead of blood and did isolated the salt and did make prussian blue,i used a blue propane torch bottle i got from walmart

[Edited on 1-3-2012 by cyanureeves]


What apparatus you plan to use ? Fractional Distillation Apparutus ? Then it should be safe right ?If I try,I will not use anything less than that.It comes with an affordable price in amazon / ebay (around $200) But I am willing to take a risk if I can make this mostly unavailable species of Chemical Kingdom.But your post is scary.How did the nitric vapors leak ?Which apparatus you used ?

expInfi - 29-2-2012 at 20:37

Quote: Originally posted by expInfi  
Quote: Originally posted by cyanureeves  
i doubt you will dissolve gold with all that charcoal still absorbing all the cyanide if you succeeded. i could not get the isolated white stuff to dissolve gold only copper but after i added peroxide too. silver just disintergrated into particles.why dont you crush the stuff and filter it?

[Edited on 1-3-2012 by cyanureeves]


You mean filter the way you mentioned with a precaution to prevent conversion to cyanate ?Its pretty tough to do so coz I m doing all these in my kitchen :P.I am thinking the 3 hour temp scheme (dont know how to establish it above a gas stove though) will melt it to liquid.Anyhow is this mass poisonous or would be harmless as ferrocyanide ?



About this molten mass , do you think it is poisonous ? Or it is ferrocyanide still ? Coz I could successfully clear everything without falling dead:) . Just wanted to know if I was playing with a ghost without knowing :)

seashell1982 - 1-3-2012 at 09:31

Quote: Originally posted by expInfi  
Did anyone try myfanwy94 ? Condensing HCN and neutralizing with NaOH ?

http://www.youtube.com/watch?v=K5NuqpdYDhE[/url]


Can someone tell me what specific hardware this guy used, and maybe include some links to on-line sources where they can be purchased? Also, I didn't see where NaOH came in, and the use of ethanol wasn't very detailed. Can someone go into more detail about these two processes? Thanks.

madmanhere - 1-3-2012 at 10:53

Quote: Originally posted by RisingSun96815  

Can someone tell me what specific hardware this guy used, and maybe include some links to on-line sources where they can be purchased? Also, I didn't see where NaOH came in, and the use of ethanol wasn't very detailed. Can someone go into more detail about these two processes? Thanks.


NaOH was in the receiver flask.
HCN + NaOH -> NaCN + H2O
Ethanol is used to precipitate NaCN. I think the idea is to filter the salt after precipitation.

expInfi - 1-3-2012 at 15:21

Quote: Originally posted by RisingSun96815  
Quote: Originally posted by expInfi  
Did anyone try myfanwy94 ? Condensing HCN and neutralizing with NaOH ?

http://www.youtube.com/watch?v=K5NuqpdYDhE[/url]


Can someone tell me what specific hardware this guy used, and maybe include some links to on-line sources where they can be purchased? Also, I didn't see where NaOH came in, and the use of ethanol wasn't very detailed. Can someone go into more detail about these two processes? Thanks.


Its a distillation apparatus.It is not fractional ,but I think the safest would be to use the vacuum distillation apparatus.I ordered one from Amazon.I dont think air should be sucked up before it is boiled.But HCN can get into to you via skin.So a mask is a must and proper clothing as well. NaOH or KOH can be prepared by those flakes mixing with water(Experts : Correct me if I am wrong).Flakes are also available in ebay or amazon.I can see that he is using airtight receiver flask.But I would need someone here to say , if it is necessary to keep the vacuum in receiver to precipitate KCN using cold ethanol.

cyanureeves - 1-3-2012 at 17:18

i'll be darned myfanwy did use sodium hydroxide,i was about to do it without hydroxide.well i've done it with potassium hydroxide then because i did the same except i used too much hydroxide and i also used a tube and bubbled it directly into the mix.i'm sure it had condense hcn going into the mix but myfanwy's method is better because he used phosphoric acid and i used sulfuric.of course max was smarter and had precise temp control. my nitric distillation set up consists of a rb boiling flask.arm adaptor and a alhinn condensor going into an rb flask, all in 24/40. in my case ,having pro glassware did not make me a pro because my nitric did not condense,i dont know where it went all i got was mostly sulfuric acid.i need to learn more about securing the glassware.i'm used to using coffee pots and teflon tape.you know what they say"you can take the boy out of the ghetto,but what for?"i just made that up.

expInfi - 1-3-2012 at 17:22

Quote: Originally posted by cyanureeves  
i'll be darned myfanwy did use sodium hydroxide,i was about to do it without hydroxide.well i've done it with potassium hydroxide then because i did the same except i used too much hydroxide and i also used a tube and bubbled it directly into the mix.i'm sure it had condense hcn going into the mix but myfanwy's method is better because he used phosphoric acid and i used sulfuric.of course max was smarter and had precise temp control. my nitric distillation set up consists of a rb boiling flask.arm adaptor and a alhinn condensor going into an rb flask, all in 24/40. in my case ,having pro glassware did not make me a pro because my nitric did not condense,i dont know where it went all i got was mostly sulfuric acid.i need to learn more about securing the glassware.i'm used to using coffee pots and teflon tape.you know what they say"you can take the boy out of the ghetto,but what for?"i just made that up.


Well , I hope you wont use coffe pot to make HCN ! Would you think that vacuum distiller is a safe stuff to use ? And I am going to use KOH.
Could you pls answer , if vacuum is required to precipitate KCN using ethanol ?

entropy51 - 1-3-2012 at 17:36

Quote: Originally posted by cyanureeves  
having pro glassware did not make me a pro because my nitric did not condense,i dont know where it went
Quote: Originally posted by expInfi  
Could you pls answer , if vacuum is required to precipitate KCN using ethanol ?
You kids are playing with fire, trying to make HCN without having a clue as to the basics of this kind of chemistry.

This is what happens when you think you can learn a complicated subject by watching lame youtube videos.

[Edited on 2-3-2012 by entropy51]

expInfi - 1-3-2012 at 17:40

Quote: Originally posted by entropy51  
Quote: Originally posted by cyanureeves  
having pro glassware did not make me a pro because my nitric did not condense,i dont know where it went
Quote: Originally posted by expInfi  
Could you pls answer , if vacuum is required to precipitate KCN using ethanol ?
You kids are playing with fire, trying to make HCN without having a clue as to the basics of this kind of chemistry.

This is what happens when you think you can learn a complicated subject by watching lame youtube videos.

[Edited on 2-3-2012 by entropy51]


It would have been better if you could convey the answer instead of giving a blanket warning.And pls do not judge that all are 5th grade failed.

entropy51 - 1-3-2012 at 17:53

Quote: Originally posted by expInfi  
.And pls do not judge that all are 5th grade failed.
I see no evidence to the contrary.

expInfi - 1-3-2012 at 17:57

Quote: Originally posted by entropy51  
Quote: Originally posted by expInfi  
.And pls do not judge that all are 5th grade failed.
I see no evidence to the contrary.


Ok.Would you mind explaining how KCN can be prepared from the solution of condensed HCN in KOH ?

expInfi - 1-3-2012 at 17:58

And if possible precautions to be taken for the whole procedure ..

seashell1982 - 1-3-2012 at 17:59

What type of heat source is used in the video? Where can I buy one?

Is air pumped out of the apparatus using some type of vacuum?

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