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Mr Cool
December 2nd, 2002, 03:08 PM
My interest in preparing this substance was re-ignited during my moments of boredom when I would normally check for new posts here at the Forum... so I had a try, taking inspiration from US patent #4,535,185, in which urea and ammonium nitrate are fused together with a suitable catalyst.
Read the patent for more info, but I thought I'd post my experiences so far. I used:

30g of urea (dried),
80g of ammonium nitrate (dried),
15g (roughly) of calcium sulphate.

The calcium sulphate was used in place of the silica gel in the patent. I made it from calcium nitrate and sulphuric acid, washed it and dried it at a few hundred *C for about an hour, in a shallow pan over a coal fire. So it was very dry, but might not have had all the water of crystalisation removed.
The mixture was fused in a hot oil bath, although a small proportion of the ammonium nitrate remained solid. I then poured it into a shallow dish, and put it in the oven on gas mark 1.5 (around 150*C) for 90 minutes. After this time it was removed and allowed to cool.

Unfortunately, no guanidine nitrate was produced this time (at least it didn't blow up, hey?). I'm picking up a load of silica gel this week, after which I will be able to follow the patent exactly, with reduced quantities.
I think the possible reasons for failure are:

1) A combination of slightly too low temperature and too short a reaction time. A longer reaction time or a higher temperature might have succeeded (the patent mentions between 2 and 3 hours, at between 180*C and 195*C).
2) Still too much moisture in the reactants. I dried these in a warm, dry environment overnight, but they might still have had enough moisture in them to render the calcium sulphate useless.
3) Unsuitable dehydrating agent. Maybe it wasn't anhydrous enough, or maybe there's something about silica gel that is required, such as a porous structure for a high surface area? What I mean is, I think it's just there to suck up water, but maybe its surface actually catalyses the reaction as well?

I will try again with more care when I get the silica gel, ie. I will make the ammonium nitrate and urea anhydrous in a dessicator, I will thoroughly dessicate the silica gel, I will get an oven thermometer for better temperature control, and I will give it longer to react. And if it still fails, then I really don't know what's going wrong, I can see absolutely no reason why it shouldn't.

If it doesn't work, I will try bubbling dry ammonia gas through a mixture of molten urea and silica gel to form free base guanidine. I assume this would work better, since I believe the reaction relies upon an equilibrium between ammonium nitrate and ammonia and nitric acid, the ammonia then condensing with the carbonyl's oxygen and the nitric acid forming a salt with the guanidine produced.
Using gaseous ammonia won't be as convenient, but it might work and would at least be safer.

The results of my next test will be up by the end of next weekend at the latest.

kingspaz
December 2nd, 2002, 05:15 PM
i think i'm definately going to add this to the to do list :)
of course the patent could just be wrong :confused: ....i don't think the how dry the reactants are should affect it too much. so long as they are very dry i don't think they need be super dry. i say this because its likely alot of H2O will escape at 150<sup>o</sup>C anyway. i think the main reason is the reaction time. how did you test for guanidine nitrate by the way? if there was only about 10% of the expected yield had been made when you took it out the oven then you may not have detected it.
good find though :)

VasiaPupkin
December 2nd, 2002, 05:39 PM
Unfortunately silica-gel could not be replaced by CaSO4.
Because silica-gel is not only dehydrating agent but specific catalyst in this reaction.
I read in some article that this method lead to ~40% yeild in atmospheric pressure.
Surface of this melt must to be covered by gasous reaction products (use a lid, but sure dont close).
We tried to check this method but there was a little explosion after ~2 hours of heating.
I know only one safe method with calcium cyanamide (CaNCN) and ammonium nitrate...
Other methods may be dangerous for local overheat.

Mr Cool
December 2nd, 2002, 06:08 PM
The patent states a much higher yield. Although 40% would be fine for me :)
Yes, I was thinking silica gel might catalyse the reaction, as well as shift the equilibrium. The trouble is, there are different silica gels... I'll just have to see if the stuff I get works.
I thought an oven, which heats using the hot air all around the reaction, with the melt in a thin layer, would help prevent local over heating, so hopefully this won't be too much of a problem. Although I don't plan on scaling up the process much above a yield of around 25g at a time anyway, just in case.
I don't want to have to go via calcium cyanamide, the yield and purity of that when I made it from calcium cyanate (calcium carbonate plus urea, heat to around 300*C, then to around 700*C) was I think dubious at best, though maybe if I did it in a ceramic reaction vessel it would be better, the tin cans I used aren't ideal! Although calcium cyanamide would be useful for making cyanoguanidine.

Thanks for the info!

kingspaz
December 2nd, 2002, 07:00 PM
VasiaPupkin, can you please give some details about the explosion? it could be very beneficial for me to learn from your mistakes....and save my mums kitchen :p

metafractal
December 3rd, 2002, 07:44 AM
Why couldn't you just use silica gel? Theres no need to get it from a lab or anything (although doing so would not arouse much suspicion at all), it is one of the most available chemicals around. Maybe its just in my country, but whenever I buy a pair of shoes, a pair of socks, or anything, they put a little packet of silica gel in with it. I have had it given to me on request by a shoe shop before, it is as innocent as soap. Nonetheless, it may or may not make a difference. Its hard to tell. Good luck, I'll be interested to see how it goes, if it works well, it could become the next Acetone Peroxide!
&gt;&gt;Metafractal

nbk2000
December 3rd, 2002, 01:11 PM
It may be that pore size and particle density has varying effectiveness as catalysts.

However, given the benign nature of silica (asides from "dusties" <img border="0" title="" alt="[Wink]" src="wink.gif" /> ), it shouldn't be at all difficult to sample scam some manufacturers for various types to test out.

VasiaPupkin
December 3rd, 2002, 02:21 PM
Maybe they mean 40% yeild per AN... :/
I think all sorts of silica gel are possible.
We used crushed silica gel granules from shoes and scanner boxes. :)
A little jar with chemicals (~50g except catalyst) placed in sand bath on cooking range and heated.
Reaction zone (source of bubbling) was generally on silica gel surface and melt's surface must to be covered by NH3 atmosphere. Therefore thin layer reaction is not convenient way.
The jar was covered with glass lid for NH3 delaying. Temperature measured 160-180C from time to time by thermometer (higher temp. tends to foaming). Sure there was a strong smell of NH3.
I payed very much attention and care only in first time. I'm fed up with it because reaction seems stable <img border="0" title="" alt="[Wink]" src="wink.gif" /> And I began to go out into room for few minutes.
First time all was ok but when I went out again I heard a deaf and ringing sound. When I came back. Kitchen was in smoke and NH3 smell was everywere. Jar turned into glass pieces laying in smoked sand bath.
All nearest things (even ceiling and window) was in drops of solid melt and silica-gel pieces. And in window there was a crack - surprise for my Mom :/. Probably this f..ckin lid was striking into window.
I recall it with fun now. But I avoid to deal with GN since that case :D ... Sure it was not detonation but flash and explosion.
Later I read that this processes has exothermic nature and some local overheating possible. This method is dangerous only in final stadium when guanidin nitrate accumulated.
What do you think to use similar process with Ammonium sulphate instead of AN with more amount of catalyst?
Its also works but I did not try to do it.
And then to try to mix it with hot Ca(NO3)2 solution to precipitate CaSO4...

GN could not become next AP because it has unsatisfactory combination between explosive properties and preparing.
But it may be the next step in turn of chem. practice learning :p

Mr Cool
December 3rd, 2002, 04:34 PM
Thanks for that info, it's very helpful.
I wondered about using ammonium sulphate, I've even tried it before but didn't use a catalyst. I'll try it properly soon. I can't remember what happened when I tried it, but ammonium sulphate has a high melting point doesn't it? Around 300*C IIRC, so unless it dissolves in the molten urea it might not work as well. In which case, gaseous ammonia could be tried. And if I can't get it to work at all I'll go back to trying calcium cyanamide!
You say it's dangerous only when GN has accumulated in the reaction melt... interestingly the patent says that a maximum of three hours was used for the reaction time, maybe this is roughly the point at which it becomes dangerous? Can you recall how much time elapsed before the explosion in your experiment? This is one thing I don't want to find out by experimentation!

kingspaz
December 3rd, 2002, 06:01 PM
thanks for the info vasia!
why must it be covered in an NH3 atmosphere? i thought just using an excess of AN would be sufficient.
ok, melting points are as follows:
170<sup>o</sup>C for NH<sub>4</sub>NO<sub>3</sub>
133<sup>o</sup>C for Urea
so i would guess an optimum temperature to be somewhere between the two, 150<sup>o</sup>C?

edit: guanidine nitrate melts at 214<sup>o</sup>C so the mixture should become more or less solid as the reaction nears completion.

<small>[ December 03, 2002, 05:06 PM: Message edited by: kingspaz ]</small>

VasiaPupkin
December 3rd, 2002, 06:26 PM
Dont worry about melting point because all salt mixtures usually has lower MP than own components (eutectic mixtures).
If this problem would occur you can use some variation - for example add some NH4NO3 to mix for lowering M.P.
Be sure not so much amount :D

But some other problem is possible: I suppose a more rapid bubbling than with NH4NO3. Because since 147C (NH4)2SO4 tends to form NH3 and NH4HSO4. May be something else :/
This patent foresee a complete reaction because troubles is a rare chance in industry. (Theres no urea in final product)
They use better equipment, stirring and temperature control than you can provide. For example they can control reaction temperature continiously
but I can measure only from time to time (I must cover jar with lid) etc. My temperature change in sufficiently wide range :/
My friend-chemist said that 10C overheating from normal temperature usually lead to explosion when dicyandiamide reacted with AN to form GN. I thing its a similar case.
When urea concentration are lowering and GN goncentration is rising, mixture turns more and more sensitive for overheating. And it grows into uncontrolled exothermic process. Results you know :D .
You know that many industrial methods is very difficult in home lab even if you have all chemicals for similar causes.
Therefore the best choice is to find out other alternative and safe way.
I have wrote that it was approx. 2 hours of reaction. But take into account that I used doubtful temperature control and therefore this time is useless.
I dont know why it must be covered in an NH3 atmosphere. Its one of the conditions. May be because it rises NH3 conc. in melt. And soluted NH3 adsorbs on silica gel and initiate reaction...

kingspaz
December 3rd, 2002, 07:02 PM
i thought the NH3 that adsorbs to the SiO<sub>2</sub> came from the equilibrium of NH<sub>4</sub>NO<sub>3</sub> &lt;=&gt; HNO<sub>3</sub> + NH<sub>3</sub>

i thought if i start the reaction at 140<sup>o</sup>C in the oven then i can check how its going every now and then. if the reaction was stopped as soon as the mixture began to get lumpy you could have a worse yield but avoid the chance of an explosion.
vasia, when you say 'one of the conditons' as stated by who/where? i've read the patent and it doesn't mention an NH3 atmosphere over the reactants surface.

<small>[ December 03, 2002, 06:02 PM: Message edited by: kingspaz ]</small>

VasiaPupkin
December 5th, 2002, 07:21 AM
Thing about NH3 was in scanned article from chem. journal or book.
I have tried to find this pages, but it seems lost :(. I have found only article about CaNCN and AN method.
Lower temperatures lead to time losing and lower yeild I think. And you have to use more catalyst. But sure its more preferable process from safety viewpoint.

Mr Cool
December 8th, 2002, 07:07 AM
OK, thinking about the method with AN and calcium cyanamide now:
Does anyone know how hot you can get water in a normal pressure cooker? Because it would be very much safer to put the AN and cyanamide into water, enough to dissolve all soluble material, and then put this into a pressure cooker with a few inches of water at the bottom. The mixture is obviously unlikely to explode if it's 50% water. Then filter it while still warm, allow it to cool, and the GN should crystalise out and leave the unreacted AN in solution.
This wouldn't work with the AN and urea method I don't think, but since the cyanamide method isn't affected by water as far as I know, it could work well enough if you give it long enough to react. It just depends on the temperature you could get up to, I know the temperature normally used when the reactants are fused together is around 160*C, but maybe this temperature is only used to fuse the reactants and allow them to react?
Time for me to go and look at pressure cooker capabilities and prices...

VasiaPupkin
December 9th, 2002, 06:13 PM
This is a little translation from one article.
It look like patent description or lab manual dated 1962, IREA. I dont know what its mean.

Guanidine Nitrate

Reaction scheme summary: CaNCN +3NH4NO3 =&gt; GN + Ca(NO2)3 + 2NH3

Mix 53ml of water, 532g AN and 72g CC* in jar.
Mixture was heated for melting at 95C (10-15min in water bath). Then 0.5ml sunflower oil** was added with stirring.
Then 144g of CC was added continuously for 2 hours with first 1 hour stirring. Temperature was kept 90-95C.
Then 300 ml of boiling water was added. And still 600 ml hot water with 5g of activated carbon with 10-15 min stirring at 95C..
Solution was filtered and cooled to 2-3C. Mixture was held for an additional 1 hour at this temperature.
GN precipitated into white needles. Yeild 128-135g.
After recrystallisation from water they got GN 97% pure. m.p.211-212C.
As you see its one of the most safe and convinient GN method for water bath using.
If you try it in kitchen don't forget about good ventilation for strong ammonium smell.

*- calcium cyanamide technical grade 56% CaCN2. You would obtain much better yeild if CaCN2 is pure.
**- Its not joke. They wrote that it was the most effective thing to prevent foaming.

Mr Cool
December 10th, 2002, 01:26 PM
Thank you! That's exactly the kind of thing I've been looking for.

I didn't get a chance to buy any silica gel, so I couldn't try the other method. I like this last one more though.

nbk2000
December 10th, 2002, 09:55 PM
You're not going to find any pressure cooker capable of 160C. They usually only go up to 110-120C MAX.

<a href="http://www.indpipe.com/images/PDF/steam_temperature_pressure_table.pdf" target="_blank">http://www.indpipe.com/images/PDF/steam_temperature_pressure_table.pdf</a>

IPN
December 23rd, 2002, 02:44 PM
Unless you haven’t noticed there is process mentioned in the KIBC (Chapter 20: Nitroguanidine) about the production of GN
I will just copy it down:

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> NITROGUANIDINE

DETONATION VELOCITY 5630 M/sec. @ 1.0 G/cc.
7650 M/sec. @ 1.5 G/cc.

FRICTION SENSITIVITY Very insensitive

BEHAVIOR TO FLAME Melts with sublimation and decomposition.

Nitroguanidine is a powerful explosive. First made from bat guano, by extraction and formation of guanidine nitrate and subsequent treatment of this nitrate with sulfuric acid
(95% +) and filtration of the product. This explosive is similar in performance to picric acid and T.N.T.. While not being quite as brisant as these two explosives the ease of
manufacture and lack of friction sensitivity make nitroguanidine an attractive choice for a blasting cap base charge explosive. It is a cool explosive and does not give a high
temperature of detonation but gives a larger volume of gases upon detonation. This base charge explosive, should be loaded in the caps with the density not exceeding
1.35 G./cc. Excess loading densities will render the base charge undetonatable with 1.5 G. charges of H.M.T.D.. This explosive will work and work well and is very storage
stable. Larger diameter cap containers (3/8" +) should be used to ensure propagation of the detonation through the entire cap. Given below is the manufacture techniques
for production of nitroguanidine. This procedure will work well but is rather lengthy and labor intensive.

MANUFACTURE:
Obtain two clay flower pots with a small hole in their bottoms. Fitted to one of these is stainless steel tubing. A refractory made from "firebrick" and fired by charcoal should
be built. The flower pots will need to fit into this refractory and have ample room around them to pack the charcoal. An air blower (e.g. hairdryer, vacuum cleaner is hooked
up to blow air through the coal to generate the heat needed. In the bottom flower-pot, a stainless steel screen will be needed to keep from clogging the stainless steel tubing
from the ammonia inlet tube. Place 200 grams of calcium carbonate (Limestone, chalk) in the bottom flower pot, with, the stainless tubing attached. Place the other
flowerpot upside down directly on top of the bottom pot. Place this in the refractory furnace and place a pyrometer or high temperature thermometer into the hole in
the top clay flower pot. Start the furnace and blow air through the burning charcoal until the temperature inside the pots reaches 700 degrees C.. At this time begin to pass
ammonia gas through the stainless tubing into the lime inside. The temperature should never go over 820 degrees C. as the lime will decompose. The ammonia generator
the gas generator in the TACC section. The amounts needed in the generator are 170 G. ammonium nitrate fertilizer, 100 G. sodium hydroxide and adding 100 ml water to
the mixture. This water addition would be done in small portions to ensure the absorption of the gas by the calcium carbonate. This gas needs to be generated slowly! When
all the ammonium nitrate has been added and the gas ceases to generate from the generator deprive the charcoal of oxygen to extinguish the flame. Let the refractory
furnace cool and remove the flowerpots from it. The black material in the bottom is calcium cyanamide.

Place 216 grams of urea in a stainless steel pan. Heat until it begins to melt. Add in small portions 1300 grams ammonium nitrate.
CAUTION: This is dangerous and extreme care should be used in this step. This mixture could explode if allowed to burn. Water should be used if a fire does break out by
immediate dilution and quenching of the reaction mixture!!
Keep the temperature of the melt at 120 degrees centigrade. When the addition of the ammonium nitrate is complete and the mixture is liquid and at 120 degrees C. the
calcium cyanamide from above is added in portions over a twenty minute period. This mixtures temperature is held at 120 degrees C. for two hours and then diluted with
720 ml water. This liquid is heated to 95 degrees C. and then filtered through several coffee filters or a "fast" filter paper. The liquid thus obtained is allowed to cool to 25
degrees C. and then the crystals formed are filtered out. The liquid is reduced to 1/2 its volume by boiling. It is cooled and filtered and the crystals obtained are added to
those from the first filtration. These crystals are washed with 40 ml cold water. They are then dried in a shallow pyrex dish while heated in a hot oil bath at 110 degrees C.
for two hours. These crystals are guanidine nitrate (90% purity).

Immerse a one liter flask, containing 500 ml. concentrated sulfuric acid, in cracked ice. This acid is stirred until the temperature drops to 10 degrees C. or less. In small
portions, add 400 grams of dry guanidine nitrate to the acid with stirring to keep the temperature below 11 degrees C.. When all the guanidine nitrate is dissolved, pour the
now milky liquid into three liters of cracked ice and water. Let this stand until the nitroguanidine is completely crystallized out of the liquid. Filter these crystals out and
dissolve in four liters of boiling water (distilled if possible). Allow to cool by standing overnight and filter the crystals out. Dry these crystals by heating gently in a container
placed in a pan of boiling water. This dried material is then ready to store in a plastic container or to load into finished caps. </font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">

kabooom
January 20th, 2003, 11:13 PM
I think if semicarbazide is used instead of urea the yeald will be aminoguanidine nitrate which then can be used for tetracene synth and other compounds

<small>[ January 20, 2003, 10:27 PM: Message edited by: KABOOOM [pyrojustforfun] ]</small>

densest
August 6th, 2003, 02:17 PM
Looking at US patent 5,041,662 for making GN from AN and urea, it seems that there are three interesting points:<br>
Stirring the reaction mixture is essential - the patent shows a pump. A stainless steel stirrer would probably work for small batches.<br>
The reaction should take place in a closed container. Any oxygen in the reactor could cause a fire or explosion. A large quantity of NH3 and CO2 are emitted which should be captured to form ammonium carbamate, which is very useful as an ammonia source.
<br>The size of the silica gel particles can be deduced from the filter size used: between 3 and 8 micron, probably about 5 micron.
<p>
A stainless steel pressure cooker could be adapted to this purpose with a few modifications.
<br>
Replace the gasket with a PTFE ring.
<br>
Make a stirrer from a stainless steel cooking whisk. Attach it to a stainless rod which goes through the center of the lid. Make a rotating seal (called a gland by plumbers) with PTFE tape inside for low friction.
<br>
Remove the overpressure/overtemperature plug and replace it with a pipe to recover NH3.
This could be connected to a bubbler, cold chamber, or other recovery mechanism.
<p>
Comments in the patent suggest that the silica gel should be fully dehydrated before use. Baking it at 300C for several hours might work.
<p>
Comments?

Mr Cool
August 8th, 2003, 08:09 AM
Well, personally I think that aqueous method with CaNCN that Vasia posted is the most attractive. It doesn't have the elegant simplicity of the urea/AN method, but I think it is safer and perhaps even easier in practice. The only semi-hard bit is calcining the Ca(CNO)2 to form CaNCN, because it needs high temperatures for a long time, but it's easy enough really with a metal bin full of charcoal with some air holes at the bottom. The last time I tried it, everything went wrong because without thinking I used an aluminium pan to heat the Ca(CNO)2 in, and it melted. I'll have another go one day...

Kerrupt
August 12th, 2003, 11:26 AM
Is the patented method for making guanidine nitrate the only known way? I have around 100g of guanidine hydrochloride, could this be used to make gn? Anyone know the process for this and if it is feasible?

Mr Cool
August 20th, 2003, 04:04 PM
Reacting it with aqueous lead nitrate will ppte PbCl2. Filter this off, concentrate the remaining solution by boiling, cool, filter off GN crystals, purify by recrystalisation. It is perfectly feasable if you have lead nitrate, or lead and nitric acid.
Other nitrate salts will work, but Pb(NO3)2 is convenient since PbCl2 has a very low solubility. Other chlorides are often quite soluble, as is GN.

There is a method in which GN can be made from cyanoguanidine and AN in "practically theoretical" yields (HN=C(NH2)NHCN + 2 NH4NO3 --> 2 C(NH2)3NO3), and I have found a source of cyanoguanidine. Its use is related to epoxy resins (you might want to try searching for CG's synonyms as well). Trouble is, it comes in 25kg bags, ~£100/bag. However, I am actually almost tempted to get a bag; it could make 72kg of GN!!

I might ask if they know of somewhere where I could buy a little less, I think. Or ask if I could buy half a bag, for "testing."

Not_Osama
February 6th, 2004, 01:37 AM
While on the subject of GN, I would just like to tell you all that i found an incredibly cheapsupplier for the normally impossible to synthesize DICYANODIAMIDE! only 18 FREAKIN BUCKS A KILO!

Search and you will find. There are several small dealers who will not ask many questions and ship 2-3 weeks UPS ANYWHERE in USA.

Mine wil be arriving in under 2 weeks. I will upload my pics of materials and probably demo vids too. It'll probably be about a half kilo from 2-300 feet away. I got a new 6X Zoom Digital Vid Cam for Hanukkah so they should be real good quality!

Bert
February 6th, 2004, 03:15 PM
OK, give me at least one more hint. And did you spell it DICYANDIAMIDE? I just tried to buy guanidine nitrate for a blue strobe formulation. Even with an ATFE license, no one seemed intersted in selling me any, particularly in less than truckload quantities.

NightStalker
February 7th, 2004, 04:19 AM
"DICYANDIAMIDE" is mentioned as an ecetutic (SP?) component for making castable AN explosives in KIFE2.

Rosco Bodine
February 7th, 2004, 05:09 AM
While you fellows are doing chemistry involving cyanamide
and related materials , there are several interesting
compounds that are "in the neighborhood" , which
you should also keep in mind . The compounds
are useful for primary explosives .

Tetracene is the first such material which comes to mind .
Mix mildly warm solutions of Sodium or Calcium Cyanamide
with Hydrazine Sulfate and treat with Sodium Nitrite and
Tetracene precipitates .

GB308179 describes the details .

Another compound of interest but more difficult , would
be nitroaminoguanidine , the lead salt of which is a primary
of value .

GB553406
GB593878
US2251101
US2617826

Not_Osama
February 7th, 2004, 07:28 AM
My favorite Supplier is Spectrum Chemical. They generally are pretty easy going, unless you're buying like nitric acid, sulphuric acid, and glycerine.
Im not gonna give you their URL because if you're too stupid to find THAT then you have no business making GN!
They stock just about EVERYTHING here is only a sample of what i found:

Acetic Acid, Glacial
Acetic Anhydride, Reagent, ACS
Sodium Methoxide, Powder
Methenamine, Granular
Paraformaldehyde, Purified
Benzene, Anhydrous
Dicyanodiamide
Pentaerythritol, Reagent
1-Aminoguanidinium Hydrogen Carbonate (Aminoguanidine Bicarbonate)

and THATS just a list of the hard to find ones!

Not_Osama
February 7th, 2004, 09:54 AM
>Tetracene is the first such material which comes to mind .
>Mix mildly warm solutions of Sodium or Calcium Cyanamide
>with Hydrazine Sulfate and treat with Sodium Nitrite and
>Tetracene precipitates .

ok...First of all RB, have you recently checked the PRICES on hydrazine lately?! Not to mention the fact that nitrogen distilltion equipmint is a tad pricey for some. It is not worth Expulsion or prosecution to attempt this in the college labs, so it its tough for most to get ahold of.

I cannot understand why you would ever want to use pricey, dangerous hydrazine to make simple Tetracene! It is highly impracticle, and comes out to about 5X more expensive and takes at least 10X as long!

However, This Nitroaminoguanidine intrigues me. I found lots if info in it being used as an ingredient in rocket propellent, however unfortunately very little on this lead salt. You should start a discussion on it in a new thread! Im sure lots of people would be interested.

Rosco Bodine
February 7th, 2004, 12:44 PM
Okay , first of all Not_Osama , where exactly did I say to use hydrazine ???

If you carefully read my post , you would see I said hydrazine sulfate ,
which is dirt cheap and easy to make .

I make every effort not to say stupid shit in this forum .

Sure wish some other folks would do the same .

megalomania
February 7th, 2004, 02:27 PM
You are misinformed Not_Osama, hydrazine is not used, rather it is hydrazine sulfate. Hydrazine sulfate is made from unpurified dilute hydrazine made by mixing ammonia and bleach. This is well within the means of amateur experimentors and is quite inexpensive. It requires no nitrogen distillation equipment or exotic equipment of any kind.

EDIT: you beat me to it Rosco...

Not_Osama
February 17th, 2004, 11:45 AM
Okay , first of all Not_Osama , where exactly did I say to use hydrazine ???

If you carefully read my post , you would see I said hydrazine sulfate ,
which is dirt cheap and easy to make .

I make every effort not to say stupid shit in this forum .

Sure wish some other folks would do the same .

From here on out I promise never to post at 4 in the morning. Sleep deprivation can drain intelligenge like a mosquito swarm at a Blood Drive.

BTW Nightstalker...I highly reccomed NEVER trying to OPENLY PURCHASE guanidine nitrate or ANY other such highly restricted chemicals. It will immediately put your name on a government "WATCH LIST", and it could cause an ugly situation; Such as being forcefully interrogated at gunpoint by men with shiny badges.

It's much safer albeit more time consuming to synthesize that acetic anhydride or hydrazine than to purchase it from a supplier.

kingspaz
January 1st, 2005, 03:07 PM
I think some new information has come to light which warrents the revival of this thread. I've dug up a patent which prepares guanidine from thiourea, H2O2 and ammonia. The patent itself is supposed to use amines, and substituted thiourea forming substituted guanidines. If the substituent is hydrogen then it greatly simplifies things and gives the product that we want :)

Thiourea is available at photography shops.

http://l2.espacenet.com/espacenet/viewer?PN=AU520839&CY=ch&LG=en&DB=EPD

mongo blongo
January 1st, 2005, 06:16 PM
Nice find Kingspaz :)
Thiourea is also used for cleaning silver. In the UK you can find it as "Silver Dip" from Tesco, Asda and Sainsburys. ;)

FUTI
January 4th, 2005, 08:04 AM
be carefull thiourea is cancerogenic AFAIR:(
but I agree it is good post!

Mr Cool
January 4th, 2005, 12:40 PM
Bah, what isn't carcinogenic these days? We're not going to be eating it :).

I had a look at various polishes in Wilko's and Sainsbury's yesterday. Mostly they were the wadding type, which I assume to be basically just cloth soaked in solvent and hence useless, but there were a few creams which I suppose could be the thiourea type. However, none stated any ingredients, and it'd be an expensive way to get the struff anyway! But it would have been nice to test the method out.

A typical photography supplier will sell thiourea, 500g, for £11.81 incl. VAT.

mongo blongo
January 4th, 2005, 02:33 PM
The Thiourea I have is a saturated solution. I can't remember the price but it was about £2.00 for 500ml.

Mr Cool
January 4th, 2005, 03:54 PM
Hmmm, that isn't too bad....

Bert
January 4th, 2005, 04:24 PM
Has anyone doped out a pilot procedure for this yet? I've been looking at a blue strobe formula from Pyrotechnica for years that uses guanidine nitrate. You can't make a safe blue strobe with Copper sulfate/ammonium perchlorate/magnesium systems analogous to the Strontium and Barium sulfate/AP/Mg red and green strobes. Good, storeable blue strobe is kind of a holy grail thing to pyros- And none of the pyro suppliers carry guanidine nitrate.

kingspaz
January 4th, 2005, 06:51 PM
For the thiourea source I've had most success in typing 'silver dip' into google. Silver dip is an acidified solution of thiourea. Thiourea has water solubility of 1-5g in 100g water according to chemfinder. My 'plan' was to neutralise the silver dip with ammonia and then boil down to 1/6 its original volume and allow to cool hopefully precipitating thiourea. As this was boiling down I would also be boiling some 9% peroxide solution down to 1/5 of its original volume in an effort to improve its concentration.
As to an actual reaction procedure, the oxidation of the thiourea by the peroxide should be exothermic so should simply be a case of mixing the reactants and controling temperature. Then it should simply be a matter of mixing ammonia water with the solution, possibly applying heat, which should liberate the guanidine. If ammonia water is too weak then an ammonia generator could easily be made to bubble ammonia through the solution.

Ricky
August 20th, 2006, 03:43 PM
I belive this could be interested, the manufacture of triaminoguanidine and triaminoguanidium nitrate.
Maybe i didn't explain this right, a method to obtain triaminoguanidine is not simple. You could try bubbling ammonia through a hot solution of 6 g aminoguanidinum bicarbonate and some ml of 96% H2SO4 in 500 ml distilled water or a hot solution of 6 g aminoguanidinum bicarbonate in 500 ml of 25 % ammonium hydroxyde/some ml of 96% H2SO4 is stirred for several hours in a flask and the water is vaporized to collect the result, so that could give 1,3-diaminoguanidine.
Maybe that will work when the solution is boiled for several hours under pressure and triaminoguanidine is obtained.
Does anyone have infos to this or a way to obtain triaminoguanidine from guanidinuim hydrochloride or 1-aminoguanidinium sulfate ?

Chris The Great
August 20th, 2006, 06:51 PM
Get guanidine hydrochloride. Mixing a cold saturated solution of it with a cold saturated solution of ammonium nitrate immediately precipitates a large amount of white guanidine nitrate. Rinse it with ice cold water after filtering out. I got ~90g of it from 80g AN, which is roughly 75%. I would probably get more if I concentrated the filtrate, since the nitrate is somewhat soluble in water.
The final product needs recystallization, it seems to have a bit of ammonium chloride in it, but that is quite trivial.

AFAIK GuHCl is not watched or suspicious at all. Probably cheaper than thiourea and all that.

Triaminoguanidine is made by simply reacting 1mol guanidine nitrate with slightly less than 2 mol hydrazine hydrate in alcohol, filtering out the impurities, and then reacting the dissolved diaminoguanidine nitrate with a bit more than 1 mol hydrazine, to give triaminoguanidine nitrate which readily precipitates from the solution. There is a US patent which describes this in greater detail, with exact amounts, temperatures, times and yields (which are good).

Ricky
August 21st, 2006, 03:26 PM
I`ve never read about the patent, interesting and somewhat toxic. I belive that will work when ammonia is bubbled through a solution of 250 g guanidinium carbonate in 500 ml distilled water and some ml of 96 % H2SO4, 117 g guanidinium carbonate per 500 ml 25 % ammonium hydroxide or 145 g guanidinium carbonate per 500 ml 32 % ammonium hydroxide and some ml of 96 % H2SO4 to obtain 1,3-diaminoguanidine and triaminoguanidine.

patrick.mclachlan
October 30th, 2006, 08:31 AM
Ammonium Carbamate precipitates on cool items. In the AN and urea reaction be very careful with pipes that might get blocked with ammonium carbamate. Rather heat the pipes and equipment! Collect all the ammonia produced in water and analyse the water for ammonia content. By comparison to the theoretical content one can see how far the reaction has proceeded.