Sciencemadness Discussion Board - from a secret admirer

from a secret admirer

Polverone - 21-2-2003 at 14:18

Quote:

From: Anonymous
To: (my e-mail address)
Subject: nitration catalysts patent GB501034

There have been no experiments by me to determine if the information is reliable, but this patent GB501034 may be of interest to your online discussion group . Another patent of interest concerning several nitrations, including a nitration for producing TNT using dilute acid and mild temperatures, is US2435314 . An interesting organic peroxide patent is GB620498 . An experiment I have done related to that patent is as follows : Mix 105ml of acetone and 105ml of methyl ethyl ketone, in a quart jar having a plastic lid. Pre-chill in a freezer the mixed ketones, and in separate containers 310ml of Baquacil 27 percent peroxide and 40ml 31.45 percent HCl . When everything is sub-freezing cold , pour into the cold ketones mixture the cold peroxide and swirl to mix . Prepare a bowl of ice cubes and water large enough to serve as a cooling bath for the quart jar . Then add the HCl incrementally in four portions every fifteen minutes and swirl to mix and allow to cool in the ice bath between additions . Place the lid on the jar loosely at first and leave it in the melting ice for twenty-four hours . The lid should be just snug enough to prevent evaporation but not so tight as to prevent a slow leaking of any overpressure. A layer of mixed organic peroxides will separate as a clear viscous oil , yield about 145 grams . This can be pipetted off or a decantation followed by use of a separatory funnel can be used to get the product which is the bottom layer . This mixed peroxide solution consists of predominately 50 percent acetone peroxide trimer , and 50 percent methyl ethyl ketone peroxide dimer , with smaller percentages of different isomers of each . Because of the MEKP content , the liquid is incompatible with metals and reactive towards many things , but seems safe in contact with teflon , polypropylene and polyethylene. A tiny droplet of the stuff soaked into a small ball of cotton , smaller than a BB if you value your ears , gives a very loud report when place upon iron and whacked by a hammer . A bit of paper towel works too . The liquid ketones peroxides mix could be used an active plasticizer and densifier for crystalline peroxides to improve their performance , or used as a sensitizer and fuel component similarly as is nitromethane used for the two component Kinepak type explosives based on ammonium nitrate . Plastic containers would be an imperative for this composition . While it may well be flame sensitive , the highest performance would probably be realized if it was cap initiated . HMTD for example or AP caps should be entirely adequate . Such compositions by weight would be about 1:5 ratio for CO balance and greatest brisance to about 1:8.4 for CO2 balance and greatest utilization of fuel value of the organic peroxides.

GB501034 is very, mmm, interesting. It claims that special transition metal catalysts can improve nitration operations. This is not so surprising. What is surprising is that the patent claims these special catalysts make the resulting explosives both more powerful and more stable.

Quote:

A special phenomenon takes place when nitrating glycerine. A nitrating substance of reduced shock-sensibleness, but of increased explosive action than in the case of the usual nitrating process, is produced when using a molybdenum catalyser.
The substance produced with the catalyser detonated at a height of fall of 14 cm, while nitroglycerine produced without catalyser detonates in the drop-press at a height of fall of 6 to 7 cm.
Iron plates of a thickness of 8 mm are pierced by 32 g of commonly prepared nitroglycerine, while the substance prepared with the catalyser pierced already by 1 g an iron plate of the same quality and of a thickness of 4.4 mm.

These claims smell very fishy to me, particularly with regard to power. Why couldn't the applicant compare his super-nitroglycerine and ordinary nitroglycerine using plates of the same thickness?

GB620498 is another curious patent. It has a "special process" (didn't look all that unusual to me) for reacting acetone, H2O2, and a mineral acid to produce explosive peroxides. It is claimed that the peroxide produced by said process is different from acetone peroxide in that it is more stable, more powerful, and has a different molecular weight and melting point from acetone peroxide. I am again very suspicious, given how close the preparation detailed is to common improvised preparations of acetone peroxide. One perhaps interesting thing is that the patent suggests that other organic solvents may be added to the reaction mixture to retard the formation of large crystals. I don't see how Mr. Anonymous's experiments with mixed liquid organic peroxides are related to this patent, BTW.

US2435314 breaks the trend and appears to present a useful modification of nitration, but I'll let you look and judge for yourselves.

[Edited on 23-2-2003 by Polverone]

BASF - 22-2-2003 at 13:38

The last one eems to me like a heavy case of "holy grail-peroxide"

Would be interesting what the main peroxide in GB620498 is......maybe our ominous DPPP?

However, as the patent serves a detailed description of the process and the product was tested comparatively to TNT (exactly the same lead-block-expansion as TNT, while being less sensitive than trimeric AP.......about 17cm for 2kg fall-hammer) this is again one of the most interesting high explosives a backyard chemist would ever get its hands on.....

BTW, i may have missed it while reading, but it seems that the inventor did not list the density of the product.......

HLR

P.S. Would´nt this patent fit very well to our library?

Blind Angel - 22-2-2003 at 13:46

if that was true why wouldn't we have heard of it before?

BASF - 22-2-2003 at 14:10

I don´t want to offend you, but isn´t the fact that we didn´t hear about it so far the thing that MAKES it that interesting??!!

However........NOW anyone has heard of it.

Maybe it still has AP´s tendency to sublimate, which would make it commercially fairly unattractive.

The claimed storage stability may apply to good chemical stability, and not to sublimation.

Blind Angel - 22-2-2003 at 14:14

Yeah true BASF, sorry

Anonymous responds

Polverone - 22-2-2003 at 16:48

Quote:

From: Anonymous <nobody@nox.lemuria.org>
To: (my e-mail address)
Subject: Mr. Anonymouss experimental relevancy

Regarding GB620498, line 62 complete specification, references obtaining the organic peroxide product in the form of a liquid by addition of a solvent to the reaction mixture, for example using ether ....which would also likely produce ether peroxide and possibly have an adverse effect on the stability of the product. I knew that MEKP was a decent solvent for AP, and also quite stable, although reactive. So I got the bright idea of combining two high yield syntheses which can occur under identical conditions, hoping that the product would precipitate as a liquid solution, or eutectic mixture of organic peroxides, more convenient for moistening ammonium nitrate to obtain an intimate mixture, like Kinepak. The patent contains a lot of useful general information and food for thought, and observations about the free radical sensitizing effect mentioned in later patents which cite the organic peroxides as being useful sensitizers/enhancers for other explosives . The nitration catalyst patent GB501034 mentions production of higher nitronaphthalenes, penta and tetranitronaphtalenes under milder conditions than those usually required for such higher nitrations. The effect possibly could be caused by an active intermediate in which the metal compound is a componenet formed and then decomposed, similarly to the mercury intermediate in the so called "catalytic" process which forms picric acid from benzene, and trinitrocresol from toluene under relatively mild conditions for nitration. Often part of the claims in a patent may be inventers euphoria, as many patents tend to oversell the invention, but then there is often something useful there too. Just thought you guys may want to look at this stuff. I have solutions from my own experiments for some of your problems with things like picramic acid via the polysulfide/Zinin reaction. I will pass along the info. But I wont post in the clear given the witch hunt underway in our world today, and the misunderstandings about science experiments which can get ugly with the authorities.

I will continue to act as an intermediary for the time being. However, as I stated in an e-mail reply, I am not sure why this individual does not trust any anonymizing proxies if he trusts anonymous remailers.

[Edited on 23-2-2003 by Polverone]

Polverone - 23-2-2003 at 12:20

From the material you provided from PATR 2700, it is apparent that the peroxide patent given above was for preparing trimeric acetone peroxide, and the basis for comparison was the dimeric form.

the mail keeps coming

Polverone - 23-2-2003 at 12:42

Quote:

From: Anonymous
To: (my e-mail address)
Subject: more patents of interest ect.

Thanks for giving me the opportunity to share. Please fell free to edit these different topic related informations so that I do not disturb the forum categories organization with multiple topic information shared by e-mail. Ill try to prove worthy of the trouble, and prove I am worth my salt or multiple salt.

Regarding the acetone peroxide topic, the tetrameric isomer is much less volatile and more stable than the other isomers. It is also slightly more powerful when detonated, and would be a better initiator. It is also an OTC synthetic via SnCl produced from tin fishing sinkers dissolved in hot HCl and boiled down to a gooey precipitate which hardens on cooling. Store in airtight container. Small portions of SnCl for immediate use may be dissolved in water for use, but the solution deteriorates from hydrolysis on keeping after some days to weeks passage of time.

A direct link for the tetrameric AP pdf is here http://www.rsc.org/CFCart/displayarticlefree.cfm?article=82D....
If that doesnt work try this for the article page and link for the pdf
http://www.rsc.org/CFmuscat/intermediate_abstract.cfm?FURL=/... or try the main page here and scroll down to article 288 follow from main text link http://www.rsc.org/is/journals/current/jcr/jc999004.htm

As promised, there is some info I can share regarding the polysulfide route to picramic acid. I will preface by saying there are better, more efficient uses for picric acid, from what I have observed about the usefulness of DDNP, which is what I presume is the ultimate object.

A good quality of deep red crystalline sodium picramate in good yields is possible via the sodium polysulfide reduction of sodium picrate. Several times I have repeated the experiments and found that slight adjustments in reaction conditions can improve the results, so I have not yet determined what conditions are optimum.

Please feel free to tweak the general process, if you want to do the work. The polysulfide reduction is quite similar to the synthesis described in your library. The problem that I have seen in the online descriptions of the polysulfide reduction, is a lack of detail about the correct method of preparation for the sodium polysulfide reagent. A thorough, intimate mixing of the correct proportions of NaOH and sulfur, being first thoroughly mixed as DRY ingredients, which absorb moisture from the air very gradually, darken in color, and initiate a spontaneous highly exothermic reaction while being stirred is the required approach for producing a good polysulfide reagent. If atmospheric moisture is low, a trigger mister can be used to get things going. The idea is to get the reaction going from a stirred dry powder which becomes crumbly as it warms and darkens and then a drop or two of water is added, the mixture stirred very well and a few more drops of water added, whereupon the reaction then proceeds on its own to form the polysulfide very quickly as a dark red but transparent liquid which looks bright yellow in thin layers. The stoichiometry for reactions involving polysulfides is not fully known. The goal is to get a good reduction without a great precipitation of elemental sulfur as a contaminant. My own theory is that if the alkalinity is just right, the higher polysulfide which is decomposed in the reduction can be converted to a lower polysulfide and remain in solution, instead of precipitating free sulfur. The polysulfide may possibly even reform from its fragments after acting as an unstable intermediate compound in the reduction. I am uncertain that the actual mechanism for the reaction involving polysulfide is even known, beyond the knowing that it just works somehow.

The following is from my old lab notes, with commentary ideas included.

Experimental:

On a hotplate stirrer is placed an 800ml beaker and with stirring, 22.9 grams, (.1 mole) picric acid is dissolved in 400ml boiling water. Heating is stopped. To the stirred still hot solution is added a solution of 4.2grams NaOH (.105 moles) in 25ml water.

comment: easy solution was noted so less water may be useful in subsequent syntheses.

While the slightly alkaline sodium picrate solution is cooling, a sodium polysulfide reagent is prepared as follows:

NOTE: All of the following procedures should be done with good ventilation, toxic gas is produced.

Into a 100ml beaker is placed 13 grams NaOH fine prills and 10.1 grams powdered sulfur (flowers of sulfur USP) Using a glass stirring rod the granular materials were manually mixed dry as thoroughly as posssible, and as the stirring was continued the mixture began to take up moisture from the air and darken in color slightly, and the physical texture changed as the mixture became stiffer and more difficult to stir. The particles become adherent to each other and the mixture begins to warm.

A couple of drops of water are fed from an eyedropper onto the stirring rod and stirred into the mixture, then two drops more, and stirring is assertively done between dropwise additions to blend the very gradually increasing moisture into the reactants. The induction of a highly exothermic reaction occurs concurrently with the slight dampening of the mixture which may need to be stirred yet a little more if any "dry lumping" is observed. The pasty mixture gets really hot and darkens quite rapidly, with an evolution of intense "sulfur fumes" from the melting and reacting sulfur. Hold the beaker by the upper rim where it is cool and do not get burned by touching the walls of the beaker near the reaction mixture. The addition of water two or three drops only, in each addition may be continued portionwise, with stirring between these small additions, in order to maintain the heat by reaction and heat of dilution, until a dark red transparent solution results. The hot reaction mixture should become a thin and mobile enough liquid that further mixing and dilution can be done by manually swirling the beaker lightly.

Once the pasty mixture has cleared to a hot solution (melt would probably be more accurate description), then gradual additions of water in increasing amounts should be made by the eyedropperfull until the volume of the resulting solution is about 40ml volume. If a dark red melt clear of solids fails to form completely on its own heat of reaction, at this point DO NOT add a lot more water and "boil" or a partly crystallized failed to complete reaction mixture will probably result.

If 1 or 2 ml of added water is insufficient to "kick" the reaction by heat of dilution, then supplemental heat will be required to drive the reaction to completion, before further dilution to a volume of 40 ml. This dilution should be sufficient to prevent the reagent from crystallizing upon cooling. Keep the polysulfide reagent from contact with the air after it is prepared. Air may degrade and cause precipitation of elemental sulfur from the polysulfide reagent if it is left standing uncovered. The prepared reagent is put into a separatory funnel and supported over the still warm sodium picrate solution prepared earlier. A piece of plastic wrap is secured over the top of the beaker with a rubber band and the plastic wrap is puntured in the center to admit the tip of the separatory funnel. This is done to exclude air from circulating freely around the surface of the solution in the beaker during the addition of the polysulfide solution. A seal is not needed here, a loose covering is sufficient.

To the stirred sodium picrate solution at 44 degrees centigrade, was added the sodium polysulfide at a rate of one drop per second to one drop per two seconds, with stirring continued for one hour. The mixture was then covered to the complete exclusion of air, and allowed to stand in the cold overnight, chilled to 5 degrees centigrade, filtered and the crystals of sodium picramate and the filter paper and filter cake were further dried by placing on a stack of paper blotters. The crystals were dark red prismatic and very fine granulation, and were used without further purification for the diazotation reaction.

Perhaps one of the more interesting things about DDNP is its formation of a 50/50 eutectic (density 1.75) with picric acid, which will melt below 100 degrees centigrade. See US1428011. Another potential use is the coprecipitation of DDNP with nitrated polyhydric alcohols, which does result in granular form materials that can function as decent intitiators. See GB568109

Disadvantages with DDNP are its light sensitivity and its difficulty to produce in a decent crystalline form having good density. That pretty much requires a Soxhlet extraction using an acetone/naptha solvent mix running in a darkroom, and what you end up with is still shit compared to the performance and stability of the basic lead picrate clathrates that are really the best use for lead azide. OTC methods for the "azo-clathrates" (my term) are more productive of an entirely satisfactory initiator. In my opinion the most advanced technology for lead azide is disclosed in US3431156, example compound 5 produces yields that are quantitative in my own tests, and the performance is excellent in all ways. A similar process can be used to provide enrichment to the properties of the compound in example 4 of US3293091.

A most exceptional igniting composition which also results from a synthesis providing quantitative yields is US2175249. This is a fine material for the initial fire in a firing train, for either fuse or electric.

Now my comments. The preparation of sodium polysulfide given strikes me as odd if Anonymous truly intended to exclude it from air, but even if the procedure followed is questionable it apparently gave good results. I do appreciate his idea of using the polysulfide under strongly alkaline conditions, so that sulfur freed by the reaction will dissolve once more.

I have seen that tetrameric acetone peroxide PDF before. I notice that the authors did not record yields for SnCl2 as opposed to SnCl4, saying only that they were lower. Would other Lewis acids work?

[Edited on 23-2-2003 by Polverone]

Anonymous provides useful urea nitrate method

Polverone - 23-2-2003 at 13:06

Quote:

From: Anonymous
To: (my e-mail address)
Subject: Urea Nitrate OTC optimized synthesis

Urea Nitrate is OTC quick and easy, nearly a kilo at a time in a one gallon pickle jar is a trivial procedure. Accurate measures of weights and volumes should be used for this optimized synthesis to obtain a good result. Prepare two separate solutions, 540 grams of feed grade urea in 700 ml water, and a second solution of 790 grams of ammonium nitrate in 500 ml water. Filter each solution to remove any cloudiness if desired. Mix the two solutions in a one gallon wide mouth pickle jar and place the jar into a hot water bath until the mixture reaches 80 degrees centigrade. Then remove the jar from the bath, drop in a three inch stirring bar and place the jar onto a magnetic stirrer. Add precisely 1000 ml of 31.45 per cent HCl in a fairly rapid stream, about 200 ml per minute is fine, to the rapidly stirred hot mixture. An exothermic reaction will occur over the course of the addition and the mixture will almost reach the boiling point. Allow the stirred hot mixture to steam freely to the air while it remains very hot. The moisture loss is beneficial to cooling and to crystallization which follows.

Vigorous stirring is continued, as the solution is allowed to slowly cool. After a few minutes of air cooling, the precipitation of well formed, dense crystals of urea nitrate will begin. The stirring is continued to keep the crystals in suspension for a couple of hours of additional slow air cooling. The container is loosely sealed once the mixture has ceased steaming and cooled somewhat. The further cooling is then hastened by next placing the jar into a plain water bath for an hour, followed by a cold water bath for an hour, stirring up the crystals from time to time to break up the mass of crystals. The jar then goes into the deep freeze overnight to complete the precipitation. The mixture should get cold enough to form frost on the jar when it is removed from the freezer. The crystals are stirred up a final time and the cold mixture is filtered. A method which works well is to first decant 500 ml of the cold supernatant liquid into a wash bottle, and then use this cold solution to rinse the residual crystals from the jar onto the filter. A half meter square of fify-fifty polyester cotton from an old dress shirt placed into a large funnel drained into a gallon jug is a good setup. The corners of the cloth may be gathered together, and the material twisted down tightly to squeeze a lot of residual liquid from the mass of cold crystals. The tightly compressed ball of crystals can then be placed upon a terry cloth towel to wick out most of the remaining liquid. Then the crystal cake is broken up and spread out in a layer in a heated glass tray for air drying. Yield is 935 grams of dried crystals of urea nitrate, which is 84.4 per cent of theory.

[discussion of use of urea nitrate as explosive snipped]

Urea Nitrate is stable but highly corrosive even to stainless steels, so plastic charge containers are required. Its advantage is that it is cheap, storable, not hygroscopic, odorless, has good energy and is OTC.

Anonymous, whoever you may be, thank you for a very useful and simple synthesis of urea nitrate. I am interested in this compound mostly because you can prepare nitrourea from it and then reduce that to produce semicarbazide. It also looks like it might help me get rid of some of the large quantities of fertilizers I have lying around :-). But I snipped the part where you discussed its use as an explosive because I want this board to remain primarily about chemistry. Sometimes I let practical information about explosives applications slip through, other times I don't. I realize it can seem rather arbitrary. But for the most part I would be happiest if chemistry information is propagated here, and the discussion of explosives use takes place elsewhere.

Say, do you want to try your hand at giving us a simple prep of guanidine nitrate? I seem to recall somebody found information on making it with ammonium nitrate, urea, and a silica catalyst, but I don't know that anybody ever reported first-hand experience with the procedure.

[Edited on 23-2-2003 by Polverone]

Nick F - 23-2-2003 at 14:50

Urea is indeed a useful chemical:

Urea --> Guanidine nitrate, UN

UN --> NU

NU --> Semicarbazide, nitramide, DPT

Semicarbazide --> NaN3, NTO

Nitramide --> K-RDX, probably loads of things I can't remember.

DPT --> RDX, HMX

Guanidine nitrate --> nitroguanidine

Nitroguanidine --> aminoguanidine

Aminoguanidine --> tetrazene, aminotetrazole

These are just a few of the great things that can be made with it! Such a versatile starting point...

I was thinking of making GN from urea and AN, I found some information on it and posted it over at Roguesci. I came to the conclusion that the route going through calcium cyanamide would be the safest, rather than silica catalysed urea + AN. I never got round to doing very much testing though, I concentrated my efforst on getting a GN sample instead. But it didn't work, maybe one day I will try and make it...
Anyway, those that are interested should check Roguesci (HE's and Links & Literature sections), there's plenty of info to get you started - including several working procedures, although technically we have a working procedure for WP...!

BASF - 23-2-2003 at 17:02

Quote:

From the material you provided from PATR 2700, it is apparent that the peroxide patent given above was for preparing trimeric acetone peroxide, and the basis for comparison was the dimeric form.

I have not read PATR 2700 nor do i know this piece of text, but i´d say let the patent speak for its own.....

As opposed to the vagueness of the Mackowiak-patent(DPPP-synth) it serves very detailed info, especially on calorimetric data, trauzl tests, brisance tests.

TNT was used as a reference, and the peroxide exhibits similar trauzl expansion volume and a high value for the heat of explosion.

It has to be considered that the peroxide herein refered to has a Mw of only about 130g/mol while TNT has a Mw of 227g/mol.

This means that the Trauzl test with its 10g standard load favours the peroxide, which in addition, would have an inferior density(1.3g/ccm; TNT has 1.6g/ccm).

On the other hand, trimeric AP has a 250ccm lead-block expansion as opposed to the 320ccm(318 for TNT) for the patent´s peroxide which is definitely worth discussion...

HLR

[Edited on 24-2-2003 by BASF]

[Edited on 24-2-2003 by BASF]

another piping hot plateful of patents

Polverone - 23-2-2003 at 19:13

Quote:

From: Anonymous
To: (my e-mail address)
Subject: semicarbazide and guanidine nitrate ect.

Apologies for any breach of decorum for observations regarding detonabilty properties of urea nitrate however such properties are valid physical data pertaining to materials of crystalline form which is often peculiar to the conditions under which that material is produced. The same compound produced by a different method may have differing senstivity, stability, density, crystal modification, and since the method I devised is novel, there is no published data for comparison regarding a form of urea nitrate made by this method. I included the information because it seemed relevant to describing the product which is an energetic material..I knew I should have evaluated the merit of this materials applications in hydroponics, but it slipped my mind :-). Hey I know the score, in some places big brother is so bad that even test tubes and microscope slides are watched items. This forum is your house, so edit away where you may need.

Other interesting urea related patents include GB839078, GB597717, GB1014071 and US2817581.

Anyway, the guanidine nitrate patents are GB923272 and US3043878, but I havent done experiments with these. The nitroguanidine which is easily made by dehydration of guanidine nitrate is useful for producing nitroaminoguanidine, by reaction with hydrazine sulfate. And from the nitroaminoguanidine can be produced a series of heavy metal salts which are initiators, primary er uh "energetic materials". See US2251101, US2617826, US2456583, GB553406, GB593878. I have wondered if a parallel reaction may be possible between nitrourea and hydrazine, which may result in a "nitroaminourea" being the product, and possibly a series of associated metal salts which correspond with the already known salts of nitroaminoguanidine. I have seen no reports or information regarding experiments attempting to produce any such "nitroaminourea"....... so Philou Zrealone where are you :-) We have an experiment, yeah baby..... a science experiment made just for you :-) nitroaminourea, does it even exist??

There are other ways to make semicarbazide that may be easier. A variation on the method I use for hydrazine sulfate, can be used to make the semicarbazide directly from urea. See GB1063893 and US5241117. The hydrazine sulfate synthesis which I have done successfully many times is a slightly modified procedure based on the method described by GB392845. Everything is OTC ingredient optimized and the yields are high, the hydrazine is freebased into methanol by a modified procedure similar to GB876038. This results in hydrazine hydrate in methanol. However, if the methanol contains sufficient sodium methoxide or potassium methoxide, by methods such as US2278550 or US4267396, then anhydrous hydrazine in methanol is the result :-). Good yields of alkali azides may be obtained by reaction of the methanolic hydrazine with isopropyl nitrite. See US1628380, US5098597, US5208002. Small scale syntheses for alkali
azides are favored by anhydrous methods in my experience.

There are two azide patents which seem to be a dead end on the patent servers. I wish that anyone having access to a hard copy archives of British patents would get and scan and post copies of GB128014 and GB129152.

When I first started receiving these e-mail messages, I thought they might be coming from a paranoid teenager who had plenty of time to dig around patent databases. I no longer believe this to be the case. Mr. Anonymous possesses (or at least feigns remarkably well) considerable hands-on experience with that of which he speaks. If he wishes to continue sharing information I will not be inclined to strike out anything, even that relating to practical application/initiation of explosives.

Now, about the hydrazine sulfate synthesis. This is one of those many "I will get around to it one day when I have more spare time" reactions that I have always wanted to try. Very brief summary of GB392845 for those who don't want to look it up and read it: urea, NaOH, and sodium hypochlorite are reacted in the presence of glue or gelatin to form hydrazine, which is precipitated as the sulfate. The patent specifies 37 grams of sodium hypochlorite dissolved in 250 mL of water (when making a small batch of 370 mL liquid total). This corresponds to a considerably higher concentration of sodium hypochlorite than one will find in household liquid bleaches or even pool bleaches. When performing this reaction with OTC materials, does one just substitute a greater quantity of the dilute household/pool bleach, or prepare a stronger hypochlorite solution from solid calcium or lithium hypochlorite?

It has been some time since I have talked to Philou Zrealone or he has posted here. However, I will attempt to contact him and see if we can tempt that wily Belgian to contemplate nitroaminourea and other such things.

hydrazine sulfate

Polverone - 24-2-2003 at 11:31

Quote:

From: Anonymous
To: (my e-mail address)
Subject: hydrazine sulfate OTC optimized synthesis

The key to OTC adaptation of many described industrial reactions is to not look at the concentrations of various solutions being put into a reaction mixture as necessarily being critical, but rather to evaluate the total water present in the reaction zone described, and then reverse engineer the reagents you will use adaptively to obtain the closest approximation to the same described reaction zone conditions using OTC materials.

For example, If you start with 10 per cent pool hypochlorite, and first get it freezing cold, then you can add your solid NaOH to the hypochlorite with stirring, in two separate additions with a rechilling of the basified hypochlorite after the additions. If the urea is dissolved in a minimum amount of hot water, and the gelatine added to the hot urea solution, it will require some periodic shaking in a sealed container, but the gelatine will dissolve. It requires way less gelatine than the patent describes anyway. By applying the strategy I described, the reaction zone conditions of the patent can be very closely matched by use of OTC materials. Everything gets mixed together in the reaction anyway right?

There is no problem using OTC materials if you compensate the approach and adjust for total water, and keep to the molar proportions. I could write up the details for Hydrazine Sulfate OTC optimized quick and easy. The reaction is a bit complicated by foaming at a point, so a lot of empty space in the reaction vessel is required, as headroom for preventing overflows. This constraint places the yield limit to about 140 grams of hydrazine sulfate for a "pickle jar" sized reaction vessel. Actually I do the reaction in a 4 liter erlenmeyer equipped with a 4 liter foam overflow return reservoir. A 6 liter flat bottomed florence flask would be better. The oxidation of urea proceeds just fine in the cold and I prechill the basified hypochlorite to 10 below 0 degrees centigrade. Get it stirring with a large stirbar, and pour the warm urea/gelatine solution into the vortex of the mixture. I let the reaction proceed on its own gentle exotherm for about 1 and one half hours, and through to a point of 75 per cent subsiding of foaming, before applying any supplemental heating to finish the oxidation. The foaming can get wild when the heat is applied if the reaction has not proceeded far enough towards completion before the heating is applied. This synthesis goes through some interesting color changes which help to track the progress of the reaction towards completion.

About two minutes after pouring in the warm urea/gelatine solution the mixture changes from light yellowish green to white and the mixture foams to double its volume. After ten minutes the stiff foam begins to break free under the influence of the stirbar and slowly subsides while becoming more mobile and stirrable. After one hour the foam has subsided to about two thirds its initial highpoint. A slight orange color is noted. The foam continues to fall and then heat is applied very gradually, because just a small heating will kick the reaction back into a vigorous foaming, and this is when the overflow may occur. The idea is to just nudge the reaction rate a bit, and then let it proceed to run on its own energy again. The orange color will become very pronounced and darker at this stage of the reaction, as the foaming subsides nearly completely. At this point it is safe to increase the temperature rapidly up about 85 or 90 degrees centigrade to drive the reaction to completion. At the endpoint of the reaction the dark orange color will dissipate almost completely, and the solution color will suddenly fade to a very pale slight yellow tint, almost clear. When you see that color change, the reaction is complete. Peak the temperature, and then discontinue heating. Immediately remove the flask to a cool water bath.

Hydrazine Sulfate OTC optimized, Experimental:

1500 ml of 10 per cent sodium hypochlorite is placed into a 2 liter glass jar, lightly sealed with a lid, and placed into the freezer overnight to chill to 15 below 0 degrees centigrade. Into the prechilled 1500 ml of "liquid pool chlorinator" is dropped a stirbar and while stirring, 194 grams of fine prilled NaOH is added into the vortex at a rate as fast as it will dissolve and not accumulate on the bottom. Because of the exotherm, the addition must be done in two portions in order to prevent excessive warming and thermal decomposition of the hypochlorite. The first portion of the NaOH should be about 110 grams, and then the solution should be rechilled in the freezer to about 0 degrees centigrade before adding in the same manner the remaining 84 grams of NaOH. The basified hypochlorite is then returned to the freezer for keeping, and to rechill to 15 below 0 degrees centigrade for its use later in the hydrazine synthesis.

In a separate half liter jar having a lid, 132 grams of urea is dissolved in 70 ml of hot distilled water.

In yet another half liter jar having a lid, 1.8 (one and eight tenths gram) grams of gelatine is dissolved in 70 ml of hot distilled water.

Shaking of these containers will facilitate the solution, and supplemental warming of the containers in a hot water bath will also be required. After these warm solutions are prepared, and all solids are dissolved, the two solutions are combined just before use, and the combined solutions are kept standing in a bowl of warm water to mainatain everything in solution and prevent the mixture from congealing, which will occur if the mixture is allowed to cool.

A 4 liter Erlenmeyer flask is placed upon a stirrer hotplate and a three inch stirbar is placed in the flask. The heat remains off. Into the neck of the flask is placed a wide mouth plastic funnel of one gallon capacity, the neck of the funnel is enlarged with a bushing cut from a two inch length of one and five eighths OD, one and one quarter ID, tygon vinyl tubing, for a snug fit in the neck of the flask. The plastic funnel serves as an overflow reservoir and return path for any foaming which may exceed the capacity of the flask during the reaction.

The previously prepared, cold basified hypochlorite solution is poured into the flask and the stirrer started without any heating. The previously prepared, warm combined solution of urea and gelatine is poured
through the funnel into the well stirred hypochlorite.

After a couple of minutes the reaction will initiate, and after fifteen minutes the foaming mixture will occupy twice the original volume, and the foam will temporarily be very rigid and motionless, but this will not persist for more than a few minutes. The foam will begin to very slowly disintegrate and stir down. The foam is viscous enough to cause uncoupling of the stirbar on the stirplate, at speed settings above 40 per cent, so it is better to have it stir successfully at a conservative setting.

About one hour after the reaction is begun, supplemental heat is applied, cautiously at first, because about ten minutes later a renewed episode of foaming will occur. This is a very transient and less viscous foaming which dissipates quickly. The onset of this foaming will be indicated by a dark orange color about the reaction mixture. When this episode of foaming occurs the reaction is nearing completion, and with increasing heating of the mixture to about 90 degrees centigrade, the reaction is complete at about one and one half hours from the beginning.

I do not even measure the temperature endpoint, but establish the endpoint by observing the color shift from orange to a very pale yellow, almost clear......very light tint to the solution. When the mixture has become hot enough, and all the foaming has subsided, the moisture will begin to reflux on the walls of the flask above the liquid and in the neck area of the flask. This happens when a mixture
is nearing the boiling point, which is plenty hot enough for this reaction. So when the refluxing moisture and color change have occured, the heating is stopped and the flask is removed to a cooling bath. After the mixture has cooled down, it is acidified by the dropwise addition of dilute sulfuric acid, with stirring, and using the same overflow funnel setup as before. 1100 ml of density 1.260 new battery electrolyte, which is 35 per cent sulfuric acid, is added at a rate of 3 or 4 drips per second to the stirred solution, and an exotherm is evident during the neutralization / acidification. The acidified mixture is cooled to about 10 to 15 degrees centigrade
for precipitation of the hydrazine sulfate, and allowed to stand for several hours to complete the precipitation. Do not chill the
mixture very cold or huge amounts of Glaubers Salt (hydrated sodium sulfate) will settle out along with the hydrazine sulfate.

The hydrazine sulfate is filtered and dried, yield is 159 grams.

In the previous communication about the usefulness of urea, I failed to mention a patent which shows the usefulness of urea in synthesis of methylamine. EP 0037862 discloses a high yield synthesis for methylamine nitrate. Also see GB1548827 for a closely related synthesis. It is my guess that paraformaldehyde would react with a diluted urea/ammonium nitrate eutectic. There was a mention of the nitrate process at the Hive, but no details or followup information was posted in the methylamine FAQ. Also see GB168333. Urea can also form clathrate salts with hydrocarbon fuels, preventing their migration in oxidizer mixtures. See US3135637.
It seems possible that urea nitrate might form a complex salt with basic lead picrate, but no experiments have been done by me to confirm this. Urea nitrate is reported to form a double salt with basic calcium nitrate (See GB349301 example 3) So the inference may be drawn that other basic metal salts may also form double salts with urea nitrate.

The possibility of forming salts of nitrourea is briefly mentioned and an equation shown on the front page of US2263289.

I wish to remind anyone who experiments with straight lead azide that it is slowly decomposed by carbon dioxide, carbonic acid in combination with moisture from the air, creating free hydrazoic acid by that decomposition, so the material must be treated accordingly with caution. See GB196593, and GB304144. Other good to know patents are GB160953, US1914530.

In another matter , there has been discussion of how to convert nitrates to nitrites. See US792515.
Many years ago I bought the smallest bag of Sodium Nitrite which I could obtain at the time, and that was a one hundred pound bag of DuPont food grade nitrite which cost a whopping twelve dollars, at the cash and carry counter sales at a meat packing plant. So I have a lifetime supply for preserving sausages and such :-).

One more patent which is of possible interest is US3066139. I think the reaction on line 33 should read 2HNO3, probably a typo.

Edit: the first version I received was incomplete. This method seems excellent and I will be reposting the hydrazine sulfate portion of this document (along with other relevant information that comes this way) on the Hive with attribution to Anonymous. Mr. Anonymous, as long as your fingers do not tire and your attention does not flag, continue to distill and pass on the lore of what seems to be considerable time spent in recreational chemistry.

[Edited on 24-2-2003 by Polverone]

nitroaminoguanidine related

KABOOOM(pyrojustforfun) - 2-3-2003 at 18:55

it might be possible to react with HNO2
click here

[Edited on 3-3-2003 by KABOOOM(pyrojustforfun)]

madscientist - 2-3-2003 at 22:50

I think it would form a mixture of azide from reacting with the NHNH2 group and nitroso from reacting with the RNHR' group. Do you have references that indicate otherwise?

KABOOOM(pyrojustforfun) - 11-3-2003 at 19:49

<a href="http://www.angelfire.com/rnb/pjff/Tetracene_PJFF.gif">mechanism in which tetracene is made</a>

PHILOU Zrealone - 24-3-2003 at 02:57

I think Mr Anonymous did a good job but I'm a bit annoyed because starting from one tread, you end up with many and if we continue that way, this forum will end to look terrible!
I strongly suggest to Mr Anonymous to try to separate more its tread sothat Polverone can open defined tread!
You clearly see that here are discussed:
-tetracene
-Aminoguanidine
-NH2-NH3HSO4
-nitroguanidine
-nitrourea
-aminonitroguanidine
-urea nitrate
-guanidine nitrate
-semicarbazide
-aceton/butanone mixed peroxyde
-CTetraAP
-picramic acid
-DDNP
-and very poor info on the very subject of this tread, the assisted nitration of aromatics with the help of transition metal nitrates!

So this tread even if interesting turn to be a messy mix!

Anyway:
R-NH-NH2 + HNO2 --> R-N3 and if there is a way to interact with a -NH2 or a =NH and make a cyclisation it will occure!It is the case in tetracene!So possible intermediary is an azide!

Guanidine nitrate is stable at the T of reaction!And you get amino, diamino and triamino guanidine nitrate!
NH2-C(=NH)-NH3NO3 + 3NH2-NH2 -100°C-> NH2-C(=NH)-NH-NH3NO3 + NH2-C(=N-NH2)-NH-NH3NO3 + NH2-NH-C(=N-NH2)-NH-NH3NO3 +NH3(g)

nitroguanidine is also a stable towards heat HE so it will survive the fusing with NH2-NH3HSO4 to yield aminonitroguanidine!

Urea nitrate might be also a good idea but it is less stable than guanidine nitrate and there are risk of troubles; better make direct neutralisation in the cold of semicarbazide!

nitrourea is way to unstable to survive the heating; you will more than certainly free NOx that will oxydise NH2-NH2 into HN3, N2O, N2 and NO!The HN3 will not make urea azide or nitrourea azide because they are too acidic!
One possible by product is a sort of tetracene
NH2-CO-NH-NO2 + NH2-NH2 -?-> NH2-CO-NH-N(OH)-N(OH)-NH2 -?->
NH2-CO-N=N-N=NH +2H2O -?-> H2N-C°(OH)-N=N-N=N-° (CYCLISATION AT THE °) -?->
HN=C°-N=N-N=N-°

PHILOU Zrealone - 24-3-2003 at 03:01

I forgot to say that maybe nitroaminoguanidine and nitroaminourea might be done by dehydration from the original nitrate salt as it is done for the nitoguanidine and nitrourea; but care must be taken with the second one!
:cool:

my fault

Polverone - 24-3-2003 at 10:28

Our anonymous friend may jump around within his messages, but part of the fault is mine as I initially stuffed all of his communications into one thread. I won't be doing so in the future.

PHILOU Zrealone - 24-3-2003 at 11:20

No problemo!
As soon as he knows we encounter problems and help us to solve it by separating and making more concise/specific posts; it would help us not to do that extra work!And it will be much more simple for him to read a specific tread and the repplies of interest!

Zelot - 12-4-2008 at 17:52

In the interests of making urea nitrate using ammonium nitrate and hydrochloric acid, would a ~10% HCL solution be able to be used without trouble? That is all I have available at this point in time. And also, what purity does 'feed' grade mean?

Sauron - 12-4-2008 at 23:29

The short answer is NO.

Why did you revive a dead thread from 2003?

Your question is not even on topic.

Can you make urea nitrate from ammonium nitrate and dilute HCl?

No.

Can you make urea nitrate from ammonium nitrate and anything? Not that I know of. Other than urea itself of course.

If you want to make urea nitrate use urea and nitric acid. Urea is OTC. Nitric acid is too in most places. If not, react KNO3 with H2SO4 and distill.

Urea nitrate prep is in Davis book in forum library freely downloadable.

[Edited on 14-4-2008 by Sauron]

Rosco Bodine - 13-4-2008 at 02:34

Hey Sauron , life is for learning .

The urea nitrate synth from Mr. A above works ,
I'll personally vouch for him

It would give lower yield using 10% HCl and would have
to go a modified addition sequence , probably using 3 liters
of the 10%HCl and first dissolving the NH4NO3 into it
as a solid addition , followed by the urea as a rapid solid addition and maybe a second crystallization of an evaporated and concentrated residual filtrate ,
but it could surely work .

And about "feed grade" urea , "food grade" high purity
for a dietary supplement for ruminants , but less pure urea would certainly work also .

Sauron - 13-4-2008 at 04:24

Quote:

Originally posted by Zelot
In the interests of making urea nitrate using ammonium nitrate and hydrochloric acid, would a ~10% HCL solution be able to be used without trouble? That is all I have available at this point in time. And also, what purity does 'feed' grade mean?

Roscoe, Zelot did not mention urea as a reactant. And I only read the first post at top of thread, which had no mention of urea nitrate.

If Zelot has said "urea, NH4NO2 and HCl -> urea nitrate" it would have made sense. Or, if I had bothered to read the thread, it would have still made sense. But I didn't and he didn't. All I saw was a 2003 dead thread, an apparently non-sequitur post and something about AN + HCl -> urea nitrate.

So sorry. I guess the AN is serving as a source of nitrate and the HCl is just liberating that th react with urea. Byproduct NH4Cl.

However, as AN does not grow on trees and is often more restrricted than HNO3, would it not made more sense just to nitrate urea per Davis? I mean, it seems like the long way round the block.

Pulverulescent - 14-4-2008 at 03:40

Quote:

Originally posted by Sauron
However, as AN does not grow on trees and is often more restrricted than HNO3.

'Guess it depends on where you are, Sauron!
I can just about afford to lose AN, but HN03 is a different matter.

P

Sauron - 14-4-2008 at 06:06

Where I am, AN requires a permit from the Ministry of Industry to buy, while nitric acid is unrestricted.

Almost 20 years ago I wanted to blue some steel (firearms related) and the traditional recipe for bueing salts is a mixture of AN and lye (caustic soda NaOH) - quite concentrated and at a high temperature. But I could not buy the AN to do this. If I had been in the USA I could have just ordered a fiber drum of the blueing salys from Brownells but here, other side od the Pacific, I just wanted to mix my own. No dice.

Obviously this restriction is based on security concerns over diversion of AN to prepare improvised explosives.

I can probably buy AR grade NH4NO3 in Kg quantities, I am not sure, as I have never tried. But obviously that would be inappropriate and uneconomical for a technical process like blueing steel. Buying a 25 Kg sack, simply was not on.

A similar situation exists in this part of the world viz KClO3. It is used to increase the yield of certain tropical fruit by commercial growers but the government restricts imports over security concerns similar to AN. So growers smuggle it in through Laos from Yunnan, Cina. I mean, by the multi-ton load. Occasionally illegal stocks of chlorate go off and people get killed. Also occasionally, terrorists divert chlorate from agricultural stocks (legal or not) and use it to make bombs. The bomb(s) in Bali a few years ago were principally chlorate mixtures.

Zinc - 14-4-2008 at 06:55

This is the first time I read that KClO3 is used in agriculture. Where could I find more information about it?

Sauron - 14-4-2008 at 07:05

Perhaps the FAO (UN) or the USDA or the EU equivalent.

The application I know of is to up the yield of lamyai (longan) which is a small tropical fruit related to lychee.

Try this Google link, I just did a search on chlorate agriculture and got a lot of pertinent hits.

http://www.google.co.th/search?hl=en&q=chlorate+agricult...

[Edited on 14-4-2008 by Sauron]

Pulverulescent - 14-4-2008 at 09:56

I knew (from my halcyon weed-cultivation days, curtailed by "legalised" state interference!) that chlorates can boost plant growth but I didn't know they can explode spontaneously in storage.
For that to occur I'd imagine there'd be some organic contamination present---or lots of anode-debris (just joking).
I found NaCl03 great fun though, back in its weedkilling days!
Even green-grocers stocked it, and selling by weight (the salt being wet) was a nice little earner!
Nostalgia imminent. . .

P

Sauron - 14-4-2008 at 11:38

I'm sure it was a matter of an unfortunate admixture with some sort of fuel. You are correct, it would not have been spontaneous. And it was not a minor explosion. If memory serves more than a hundred people were killed. This occured in Chian Mai province, Thailand.

E-tech - 18-4-2008 at 11:31

The Bali bombings were chlorate and aluminum powder.
Wouldn't potassium nitrate work just as well as ammonium nitrate in the urea nitrate reaction?

-=HeX=- - 29-7-2008 at 00:48

The urea nitrate reaction here took me a lot of lost sleep to find.... But I dont mid that, for it is completely OTC

many thanks to Roscoe (Mr. Anon.) For providing me with a method to make several kilos of high explosive. I have a question though: would 95% sulphuric acid work in place of the hydrochloric acid? Over here we do not have food stores and I only managed to smuggle over 1 litre of 23% this time. I think sulphuric would work, just how much should I use?

Picric-A - 29-7-2008 at 06:52

It looks like mr. annonomous got that hydrazine sulphate sythesis straight off this site, unless of course he wrote the site himself:
http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/h...

a_bab - 29-7-2008 at 07:53

Or unless the stoned people ripped the article of this site. It happends, you know...

Picric-A - 29-7-2008 at 08:17

nope the article was published before the thread was posted...
If you check out my thread on making soidum azide via hydrazine wich is about 10 threads below this one cobrasniper555 wrote he knows the person who wrote that article.... hmmm!

[Edited on 29-7-2008 by Picric-A]

Rosco Bodine - 29-7-2008 at 09:27

I wouldn't trust that Mr. A fellow any further than I could throw him, and would definitely make subject to good verification anything that either he or that equally suspicious Rosco Bodine character might say

IIRC the use of sulfuric instead of HCl for the urea nitrate reaction is complicated by a suspected double salt formation
or is otherwise just not as clean and straightforward. The
HCl method as described works better of the two from trying it both ways, and the HCl is cheaper.

[Edited on 29-7-2008 by Rosco Bodine]

Formatik - 31-7-2008 at 13:26

Quote:

Originally posted by Rosco Bodine
Hey Sauron , life is for learning .

The urea nitrate synth from Mr. A above works ,
I'll personally vouch for him

Then it's kind of like GB1429282 which uses 35% HCl , NaClO4 and urea to get urea perchlorate. They don't test it, but also claim KClO4 or NH4ClO4, and H2SO4 or HNO3 could work. Extraction is kind of a pain though.

a_bab - 1-8-2008 at 06:32

A friend of mine told me long ago something about a possible link between Mr. A and someone else on this thread. Double personality... for a nobile goal.

-=HeX=- - 1-8-2008 at 08:08

Ah now a_bab... Dont we all know who it is that has schizophrenia :p *Taps nose* but Damn Roscoe, I really like the azo clathrates, however I have not had the time, or stirring hotplate, to try them yet. Soon I will though and I will also be trying a silver variant too. I posed on roguesci about that a while back. Thanks for the advice on the sulphuric forming a double salt, I will source some more HCl soon. I sense a rather large bang on its way

Rosco Bodine - 1-8-2008 at 09:37

The silver probably won't form the lattice crystal like the basic lead salt will do. If you want a hotter azo-clathrate
just try the chlorate or perchlorate variant.