Sciencemadness Discussion Board

Copper Picrate?

quicksilver - 29-9-2005 at 18:20

I have a series of questions that I am hoping some can answer or point me in the right direction.
Certainly copper picrates are possible....
The questions I have are of metalic energetic compositons and their sensitivity. Realizing that certain heavier metalic molecules (lead, mercury) are used in energetic materials, why is it that on occation when lighter metals are used (silver, copper) they exhibit greater sensivity in certain compostions (azides, fulminates)?
In other instances copper & silver acyitide has been used with some success but often their sensitivity in other energetic materials are so high that they are not employed for industrrial uses.
Could copper, nickel, and silver be utilized as picrates without undue sensitivity? Testing (Federoff, Urbanski) has noted that temprature for ignition is within range of heavier metals. Experimentors have nitrated everything under the sun. At such a time of experimentation with energetic materials, certainly work was done with metalic compostions....(?) Yet less toxic metals have been shown to have too great a sensitivity in some materials and not others. Has there been greater experimentation with these materials than is commonly known?
What is it that makes some metalic elements impart greater sensitivity to certain energetic materials and yet to others they can play a productive role?
My purpose for asking is my curiosity about less toxic metalic elements in energetic materials and their possable roles in everyday industrial uses (airbags, etc, etc) - I know this is a lengthy query; & I appologize. I just thought that someone has some commentary or experience with this subject greater than my own.

Thank you for any light you may shed on this subject.

Sickman - 29-9-2005 at 22:28

QuickSilver,

First I'd like to say that I haven't the foggiest idea as to why the more heavy metal salts seem to be more sensitive or why for example silver salts tend to degrade in sunlight. My best explanation is that it's just the way it is.

To answer your questions about copper picrate and the others about their sensitivity and industrial uses I can quote The Chemistry of Powder and Explosives by Davis in a drop test of a 2-kilo weight (in inches) on various substances causing explosion in one or more instances in ten trials.

Mercury Fulminate 2"
Tetryl 8"
TNT 14"
Picric Acid 14"
Copper Picrate 12"
Zinc Picrate 12"
Ferrous Picrate 14"

Anyway, you get the idea that most of the picrates are very stable. Nickel picrate seems to be more sensitive with a drop of 4".

In the patent US5392713 a hydrated(making it less sensitive and probably less powerful) metal picrate is used as a substitute for lead azide. In the British patent GB191123493 potassium picrate is used as a substitute for potassium chlorate in bullet primers. It also appears in the patents quite regularly that ferrous picrate is used as a fuel additive for automobiles for better gas mileage.

In my own experiance with metal picrates I have found basic lead picrate to be the most useful. It can be used in place of lead styphnate to initiate Lead azide in a firing train; it can also be used in bullet primers.

As far as getting good Vod rates and reliability for the initiation of high explosives, picrates just don't cut it at all.
Which is the main reason they are not used too much for such purposes commercially, militarily, or otherwise. In other words even the best picrates such as basic lead picrate can't detonate TNT, Picric Acid, RDX or other significant HE's in a reasonable amount and with any degree of reliability at all whatsoever. Which makes them quite useless in that regard, unless you are using the picrates as simple ignition compounds to initate some primary explosive as lead azide mercury fulminate even DDNP which tends to suck in my own trials with it.

P.S. All the attempts in the literature to move away from lead azide to create a "safer" detonating cap just leads to a less reliable, less economical "placebo" style detonator which only serves to make the inviromentalists happier and in light of all the rest of the crap polluting the world, an INSIGNIFICANT compromise! Dido with the airbag! I like my sodium Azide just were it is!:P

quicksilver - 1-10-2005 at 07:13

Quote:
Originally posted by Sickman

-=snipped for brevity=-

In my own experiance with metal picrates I have found basic lead picrate to be the most useful. It can be used in place of lead styphnate to initiate Lead azide in a firing train; it can also be used in bullet primers.

As far as getting good Vod rates and reliability for the initiation of high explosives, picrates just don't cut it at all.
Which is the main reason they are not used too much for such purposes commercially, militarily, or otherwise. In other words even the best picrates such as basic lead picrate can't detonate TNT, Picric Acid, RDX or other significant HE's in a reasonable amount and with any degree of reliability at all whatsoever. Which makes them quite useless in that regard, unless you are using the picrates as simple ignition compounds to initate some primary explosive as lead azide mercury fulminate even DDNP which tends to suck in my own trials with it.

P.S. All the attempts in the literature to move away from lead azide to create a "safer" detonating cap just leads to a less reliable, less economical "placebo" style detonator which only serves to make the inviromentalists happier and in light of all the rest of the crap polluting the world, an INSIGNIFICANT compromise! Dido with the airbag! I like my sodium Azide just were it is!:P


Thank you for the info and the patents. I continue to wonder about this and I suppose it's not as simple a question as it looks on the surface.....
I only wish I could work with the British patents more effectivly; espacenet is a real pain; and there is such a good deal of information there.;)

Sickman - 1-10-2005 at 08:57

quicksilver,

"espacenet is a real pain"

You've got that right. What I don't understand is why they don't have a more relative search engine. For example when I type in a chemical name and search I would like it to bring up patents that tell me exactly how to manufacture it or a better way to recrystallize it. Instead I get thousands of results that just mention it in passing and I have to search for hours to find anything.

Also when it comes to non-english patents such as japanese and german or russian I wish they would have an option to translate into english for english users. Another thing that is really annoying with the search option is that it doesn't seem to bring up early patents like 1920's 1930's when alot of significant and original explosives were being developed.

quicksilver - 2-10-2005 at 08:47

Quote:
Originally posted by Sickman
quicksilver,

"espacenet is a real pain"
. Another thing that is really annoying with the search option is that it doesn't seem to bring up early patents like 1920's 1930's when alot of significant and original explosives were being developed.


That is -=EXACTLY=- where I was going with the under-current of my question on metalic energetic materials......During the time frame of the mid 19th century onward, there has been SO MUCH EXPERIMENTAION that the answers to questions such as this most likly exist. But getting to the meat of the thing usually involves access to a great library or national patents. Espacenet is a treasure of information: I have seen some of the stuff folks on forums here gotten from there. Really useful stuff! But they will be the first people to tell you that it's a real hassle; indeed actual work, to get the material that SHOULD be available to the public.
I honestly wouldn't put it past them (ESPACENET) to have a censoring element within their site.
And so I won't go too far off topic here, I would say at this point that I am working with cupric picrates now and believe that I have a usable sample. I work with extremely small samples when doing experiments of this nature (sub-gram). What I have is a green material that needs to finish it's time in the desicator (I dry slowly) so that I would maintain crystal shape for the microscope. It appears promising: I simply subsituted anhydrous copper nitrate for lead nitrate in a standard proceedure.

Rosco Bodine - 3-10-2005 at 05:38

The formation of undesirable hydrates and low density crystal forms is what hinders the potential usefulness of copper and other metallic picrates . Even the anhydrous salts of the metals which are known to form useful initiators can form as crystals which do not have useful explosive properties , except when the salts are made under a specific condition for their formation which produces the crystal form which does have the desired properties . It requires very special conditions of temperature and concentration of reactants , pH and rate of reaction , and the vigorousness of the agitation during mixing has bearing on the sort of crystals which will result . So it is known that there are many reaction conditions which greatly influence the product , aside from the chemical equations which apply . The product is governed by many variables which have bearing , so what is the result may differ very much simply from changing one of the variables about the reaction condition . A simple chemical reaction like A + B = ( A + B ) + or - n ( HOH ) can produce a dozen different materials varying with the conditions for the reaction , with only one , or NONE of the dozen having any useful explosive properties . The physical chemistry , crystalline form of the product has enormous bearing on explosive properties , and this is a general rule for energetic materials which is even more applicable to primary explosives where the density and crystal form are especially critical , definitive actually , for what will be the explosive properties for the sample .

The mathematics applicable to energetic materials is very highly algebraic more than arithmetical , so you may find surprises which seem not to make sense ,
compounds which by arithmetical logic would seem to be or should be expected to be more explosive or less explosive , and yet to confound your expectation , the compound will manifest its own identity as it pleases , being what it will be according to its true nature , without any deference to prediction or expectation of what it " ought to be " .

Barium Styphnate is one of the few materials which I have seen mentioned as having usefulness , other than the lead salts which are well known . The usefulness of most of the energetic metal salts occurs when the salt is a component of a complementary mixture with other similar salts . This is because generally no single compound itself has all the desirable properties present to perform the task required , so composite mixtures are used to embody the desirable properties of each components contribution to a " hybrid " mixed composition . Multiple salts and clathrates have the advantage for this reason , and are most interesting for experimentation . It is unlikely that any
single " simple salt " intitiator will be found which demonstrates the combination of desirable properties of a complex salt " hybrid " . That search has already been made by many different researchers who pretty much never discovered any single compound simple salt , " perfect initiator " ......but did find a few complex salts and complementary mixtures which are very close to perfection . The complex salts are then really where the focus of experiments should be if the interest is in advanced technology for initiators . And with regards to " getting the lead out " , well possibly that can be done , and the silver , copper , nickel , possibly cobalt , and barium combinations are likely candidates in that quest , but as mixtures or complexes ....and beyond picrates , involving styphnates and tetrazoles ,
and possibley some of the hydrazine derived complexes of nitroguanidine or DDNP . It would be my guess that is the
direction your experiments will go when things dead end on any single simple salt picrates , because that ground has already been covered , more than likely ,
and if anything satisfactory had been found , then it would already be in common use .

quicksilver - 3-10-2005 at 17:14

Quote:
Originally posted by Rosco Bodine
Even the anhydrous salts of the metals which are known to form useful initiators can form as crystals which do not have useful explosive properties , except when the salts are made under a specific condition for their formation which produces the crystal form which does have the desired properties . It requires very special conditions of temperature and concentration of reactants , pH and rate of reaction , and the vigorousness of the agitation during mixing has bearing on the sort of crystals which will result . So it is known that there are many reaction conditions which greatly influence the product , aside from the chemical equations which apply . The product is governed by many variables which have bearing , so what is the result may differ very much simply from changing one of the variables about the reaction condition . A simple chemical reaction like A + B = ( A + B ) + or - n ( HOH ) can produce a dozen different materials varying with the conditions for the reaction , with only one , or NONE of the dozen having any useful explosive properties .


Could this be why copper does not respond to the "fulminate process" as does Hg?
Both copper nitrate and nickel nitrate are so damn hygroscopic that they must be prepped (dryed out extreamly well) to even begin to work with their proper weights. The water they hold is unbelievable.
I have been working with both and believe that I have a nickel picrate now. It is emerald prismatic in color and shape. Response to flame is lack-luster as wet lead styphnate but it does respond.
My sideline is hobby rocketry and I found a wonderful concept in the development of bridgless ignitors....at issue is not only the resistance and eletrical conductivity but also the "pop"...it must be continuous and possess a strong flame. - You got me hooked on patents for my information and I have found some of the BEST US patents on bridgeless ignitors (US3320104, US4968364) but therein the inventor used lead styphnate. The conductivity of picrates is better suited to the needs of a bridgeless ignitor; the need for a carrier and a resisance component (graphite) may not be needed. But lead picrate "pops" when used in such a fashon, while nickel picrate may not...it appears thus far I have found the component, that being nickel picrate. Using Nickel nitrate (anhydrous) and applying the the basic (sodium hydroxide) picrate synth previously discussed, I think this will work. And true enough, I have had little luck using copper nitrate. [A simple test with a multi-meter reviels the conductivity of picrates, regardless of crystal shape, etc.]
The fulminates (being almost kitchen chemistry) have proven fruitless in any attempt at the introduction of copper during the standard Hg synth. Even though I ahd found the correct time for introduction of copper during the production of mercury fulminate (the only way I know to make copper fulminate), the product not only lacks conductivity but is totally inconsistent from one batch to another. No matter how carefully I monitor temp and time. Oh, I have gotten product but from one batch to another; the consistency is terrible....
Once again what you say has rung true....ruefully I have given up on fulminates as being much too filled with unknowns to extrapolate the use of other metalic materials for a usefull energetic material. Picrates are at least predictable.
- Sorry about jumping from picrates to fulminates here but what is being discussed appears to ring true for both.

Rosco Bodine - 4-10-2005 at 05:59

Silver powder or precipitaed silver has been used to make conductive compositions . For one variant IIRC , silver azide can be treated in such away as to reduce the surface of the crystals in suspension to metallic silver , which makes them conductive .

Bright aluminum dust of the extremely fine mesh airfloat variety , and possibly zinc dust or other fine metal powders could also give conductive mixtures .

Potassium picrate of a very specific crystal variety which is made by a patent process has also found usefulness in primer igniter compositions while other more usual forms of potassium picrate are not useful .

It would seem to me that a clathrate of
precisely intended burn rate could be easily made which would work well as a single compound igniter , enhanced as to conductivity and flame temperature by mixture with a metal powder .

There have been developed a good many different bridgewire " bead " compositions
which are deposited as a paste or slurry and then harden to a pellet adhering to the bridgewire . Some of these are probably adaptable to use as conductive compositions . Actually , in high reliability firing trains , there can be redundancy achieved by using a conductive composition even though a bridgewire is present , and then firing with a high enough voltage that it is guaranteed the
device will function , whether the bridgewire functions or not . High enough voltage and current even eliminates the essential need for the primary , as the base charge can be fired by the thermal shock and impulse from the sudden pop of the arc as a last redundancy in a device having about four independant paths which simultaneously provide different possible paths to detonation . You might find something like this scheme applied in a missile warhead where it is desired to be absolutely damn sure a dud is avoided with an expensive munition , so they use layered redundancy to guarantee functioning , multi-detonators each having multi-path to detonation capability .

Axt - 4-10-2005 at 06:34

I realise your after a single compound for the igniters, but also have a look at US2970047 & US3090310, I've been meaning to try replacing graphite bridgewireless igniters with PbO2. Which can both provide the required resistance and act as an oxidiser. Perhaps in combination with Ti for its low conductivity & hot splattering thermite reaction.

quicksilver - 4-10-2005 at 07:12

Quote:
Originally posted by Rosco Bodine

Potassium picrate of a very specific crystal variety which is made by a patent process has also found usefulness in primer igniter compositions while other more usual forms of potassium picrate are not useful .

It would seem to me that a clathrate of
precisely intended burn rate could be easily made which would work well as a single compound igniter , enhanced as to conductivity and flame temperature by mixture with a metal powder .

There have been developed a good many different bridgewire " bead " compositions
which are deposited as a paste or slurry and then harden to a pellet adhering to the bridgewire . Some of these are probably adaptable to use as conductive compositions . Actually , in high reliability firing trains , there can be redundancy achieved by using a conductive composition even though a bridgewire is present , and then firing with a high enough voltage that it is guaranteed the
device will function , whether the bridgewire functions or not . High enough voltage and current even eliminates the essential need for the primary , as the base charge can be fired by the thermal shock and impulse from the sudden pop of the arc as a last redundancy in a device having about four independant paths which simultaneously provide different possible paths to detonation . You might find something like this scheme applied in a missile warhead where it is desired to be absolutely damn sure a dud is avoided with an expensive munition , so they use layered redundancy to guarantee functioning , multi-detonators each having multi-path to detonation capability .


Aluminum has the capasity to lubricate as well. Fitting a friction sensitive compound in a tube or other assembly is made easier and safer by the application of flake Al to the area or component. It is a wonderful asset in construction of ignitors (as is graphite) but the added benefit of Al is that it continues the flame. In the rocketry hobby the final rocket and altimeter can cost several hunderd dollars if not more so. So I really want to make sure that both initial stage and booster-'cute deployment fires. The main issue is that one must depend on battery power for all seconday issues. Therefore an ignitor MUST funtion (to deploy a recovery 'cute or a seconday stage) with low voltage and moderate current; yet it must not be static sensitive. The added bridge-wire is a great insurance policy. The problem, of course is soldering a human hair size wire.
The clathrate idea is something I have not had not yet really experimented with. I don't know if it is as conductive as picrates / styphnate compounds. There exists the caged lattice (of which you know better than I) and superficially I believe that may offer some electrical resistence. Which is often a good thing; creating a source of heat when current is applied.
With picrates / styphnate compounds the use of graphite and a "carrier" is employed to this end and the correct ratios must be found. It's a time consuming agenda. Generally one is looking for 1-5 ohms w/ a battery assembly. With a cap-discharge unit one may go as high as 12 ohms.
The standing formula for a bridgless ignitor is:
KCLO3 55%
graphite/ conductive lampblack 25%
Al 5%
lead dioxide 9%
Mg 5%
Manganese dioxide 1%
Carrier agent or binder is NC Laquer
This will work very well but it's quite complex to adjust to a specif electrical charge.

While the patent US 4968364 uses a very simple approach:
lead styphnate (or one may use picrates) 95% + /- 1-2%
graphite 5% + /- .35%
Cellulose acetate & acetone as binder.

Adjusted by milligrams to fit most anything;
you can see that it's a dream come true but the use of lead picrate creates a pop, while another metal may result in a surge of flame; perfect for an ignitor.
Now the clathrate concept is an important consideration because if a clathrate is not completly dry it flames (then pops). If a carrier agent such as cellulose acetate / acetone were used to hold the mixture togehter it may be much more cost effective.
The most important issue is how it conducts.....if there is resistence, that can be worked out via a streight conductor metal or graphite. If it is a strong conductor then resistence must be applied via a binder.
Have you seen any (non-US) patents in this regard on ESPACENET? If so, let me know so I can try once more to get their stuff....I am hooked on patents and I want to make that site useful for me finally.

Thanks again.

Sickman - 4-10-2005 at 21:13

Dear Rosco Bodine,

It seems that I remember you mentioning something about adding a chlorate to an azo-clathrate solution to change the characteristics of the final complex.

Anyway I wasn't sure if it was concluded in US3431156 that only a lead salt could be used to entrap additional amounts of lead azide. What I'm wondering here is would it be possible to come up with a way of trapping lead azide in copper picrate or some other picrate besides the basic lead picrate of the patent. It seems like first the lead azide would be made in a solution and then picric acid, sodium hydroxide and a copper salt would be added to that to make copper picrate, which would hopefully trap large amounts of lead azide in it's crystal lattice as the copper picrate crystallizes in the lead azide solution. Would any of this be possible or worth the experiments? If you think a basic copper picrate- lead azide clathrate is not possible please explain your reasons for thinking this.

As always thank you for your replies.:)

[Edited on 5-10-2005 by Sickman]

[Edited on 5-10-2005 by Sickman]

Rosco Bodine - 5-10-2005 at 05:49

Copper can form so many different azides that have the potential for sensitivity dangers , that it would probably not be one of my first choices for experimentation with azide containing clathrates . Bismuth is a metal rarely mentioned and might be worth considering as a possible analogue for lead , however what may be its usefulness for clathrate formation I don't know . Igniter compositions are not where you would want to form an azide containing clathrate because the azide makes those compositions detonating instead of igniting compositions . The slower burning clathrates like the dibasic or tribasic compounds would be likely candidates for an igniter squib for a rocket engine , where a long duration burning match composition is what is desired . The inclusion of chlorate or perchlorate in a clathrate tends to make it
burn faster and hotter than similar clathrates which only contain nitrate as the oxidizer , so in that regard it is similar as with mixtures . The basic lead picrate / lead nitrate based clathrates obey the rules for proportional composition described by the patent for the lead compounds . It may be that if different metal basic lead picrates do form that they will follow the same pattern , or they may follow a different rule for their formation . I haven't experimented with all of the possible lead compounds and none at all with efforts at clathrates based on other metal basic picrates than lead . Just because the basic lead picrate can form clathrates in no way assures that the same is possible for other basic metal picrates . There may be a few other basic metal picrates which behave the same way ....or none of the others except for lead . There are also many possible double or multiple salts which are not clathrates , but have similar value .

One of the possibilities which has crossed my mind about the clathrates is to attempt introduction of mercury fulminate into the basic lead picrate / lead nitrate matrix . It is a little known fact that Mercury Fulminate is significantly soluble without decompositon in boiling water , from which it may be recrystallized as salt like white crystals which deposit on cooling . So it seems possible that a similar fulminate-clathrate series of compounds could form in analogous fashion as do the azo-clathrates . This could be an interesting line of experimentation for possibly useful fulminate complexes never before described and possibly unknown altogether . The storage stability and performance and physical properties of such a theoretical fulminate-clathrate could possibly be superior to fulminate alone . If such a clathrate is possible and has good properties , it sure would bring new value and usefulness to the good old original initiator , mercury fulminate . So does this sound like a worthwhile experiment ? :D

[Edited on 5-10-2005 by Rosco Bodine]

quicksilver - 5-10-2005 at 06:49

Quote:
Originally posted by Axt
I realise your after a single compound for the igniters, but also have a look at US2970047 & US3090310, I've been meaning to try replacing graphite bridgewireless igniters with PbO2. Which can both provide the required resistance and act as an oxidiser. Perhaps in combination with Ti for its low conductivity & hot splattering thermite reaction.


Good stuff...thanks. I think that US 4968364 does present some info on PbO2 but I don't remember if it was from a conductive, adjuntive perspective or what.....I think I may have some Ti fines around here for that purpose, I imagine I would need -325 mesh or finer. The good thing about oxides is that they will generally be conductive and mix well. While metal powders can be hard to find as fine grain (except Al of course). I just happen to have a ridiclous amount of Cu powder, the coursest is -425 (some at sub-sieve level!) & the usual Al (Ekhart 5413, etc).
The nickel picrate is all dried now and really did come out pretty good considering that both nickel nitrate and copper nitrate are as hygroscopic as I have yet seen! About a third their weight is water and that will throw off any chem synth to the point of failure.

quicksilver - 5-10-2005 at 07:17

Quote:
Originally posted by Rosco Bodine
One of the possibilities which has crossed my mind about the clathrates is to attempt introduction of mercury fulminate into the basic lead picrate / lead nitrate matrix . It is a little known fact that Mercury Fulminate is significantly soluble without decompositon in boiling water , from which it may be recrystallized as salt like white crystals which deposit on cooling . So it seems possible that a similar fulminate-clathrate series of compounds could form in analogous fashion as do the azo-clathrates . This could be an interesting line of experimentation for possibly useful fulminate complexes never before described and possibly unknown altogether . The storage stability and performance and physical properties of such a theoretical fulminate-clathrate could possibly be superior to fulminate alone . If such a clathrate is possible and has good properties , it sure would bring new value and usefulness to the good old original initiator , mercury fulminate . So does this sound like a worthwhile experiment ? :D

[Edited on 5-10-2005 by Rosco Bodine]


My dear Roscoe, if you could find a method of making fulminates consistent from batch to batch I would eat my hat! I had once thought that Picric Acid was a finicky little devil but in my opinion it doesn't hold a candle to the damnable fulminates!
Curse them for the kitchen-chemisrty that they be! Damn the fulminates....and damn their 19th century "formulas".
I have made my share of Hg fulminate and have yet to KNOW that the batch will turn out with full, well shaped crystaline structure OR heavy amounts of mercury nitrate fine powder clogging up the batch. I keep a accurate lab, and watch my measurments; but I give you my word on this....I can't predict from one batch to another if my Hg fulminate will duplicate itself well enough to be used in a proper synth involving other compounds. If you figure a method to control reaction temp/time from the moment the alcohol goes in, my hats off to you. I say this in humor of course, but really....I have a real bitch of a time with it; no kidding.
What I have determined is that, at the point that the alcohol is placed into the mercuric nitrate/HNO3...there is an uncontrolable time lag before the reaction....and it's this time lag upon which the fulminate result hinges. Even if kept at one consistent temp there exist variables that seem to me to be uncontrolable.....I get very frustrated with making fulminate. Sometimes I have made fulminate that has the best look and response I could have ever wanted and at others, using the same ratios and temps, I get crap......damn mercury fulminate!:mad:

Rosco Bodine - 5-10-2005 at 13:39

The trick is that you have to add the alcohol to the mercuric nitrate and HNO3
solution while it is still very warm from the dissolution of the mercury , and still contaminated with nitric oxides . Both the elevated temperature and the presence of the nitric oxides are necessary for the reaction to start quickly with the alcohol .

If you are using pre-made mercuric nitrate
and experiencing trouble , it is because of the lack of nitric oxides . Add a little sodium nitrite or perhaps a bit of starch or paraformaldehyde and warm to initiate some decomposition of the nitric acid before adding alcohol to the warm mixture , and then the reaction should start quickly and run hot as it is supposed to do . Use a flask large enough to accommodate the violently boiling reaction and provide enough surface area to allow refluxing on the inside walls which
are air cooled . I am no expert on mercury fulminate so I can't give you an optimized synthesis , but I can look through my notes and see what references I have which may be useful .
I have made it a few times , but haven't gotten great yields , probably for not using pure ethanol , but used instead the denatured variety , which is not recommended , and tends to reduce the yields .

There's a pretty good discussion on fulminates in the following old thread at E&W

http://www.roguesci.org/theforum/showthread.php?t=297&pa...

[Edited on 6-10-2005 by Rosco Bodine]

quicksilver - 5-10-2005 at 22:32

Quote:
Originally posted by Rosco Bodine
The trick is that you have to add the alcohol to the mercuric nitrate and HNO3
solution while it is still very warm from the dissolution of the mercury , and still contaminated with nitric oxides . Both the elevated temperature and the presence of the nitric oxides are necessary for the reaction to start quickly with the alcohol .


There's a pretty good discussion on fulminates in the following old thread at E&W

http://www.roguesci.org/theforum/showthread.php?t=297&pa...


You may just have hit it on the bean with that one - I'll give it a try this weekend. I actually use the name quicksilver as a reminder to myself to stay humble with my feeble attempts @ my hobby. For as much as I have done a fair job at somethings, an old-time quirky thing like fulminates gives me a challenge I have yet to say I can reliably reproduce the results thereof (always my goal).
I _DID_ work with the hcl purification you had mentined and damn it, if it wasn't the more productive thing I had worked w/ in quite some time. I had kept some "orange-ish" picric acid I had made many moons ago and I got myself a half pound of really good looking PA!
Now the patent you posted was VERY interesting....I too have studied the COPAE ('till she was dog eared) and I seem to remember something about the catalytic form of PA production (I -=think=- it was in the COPAE....) and wondered if anyone actually tryed it. Now here I see an actual patent mentioning the mercuric nitrate format for PA production!
The facinating thing is that when looking at the formulation written down (I am not the best at that as my chem was undergrad level) It does not seem to make sence (no benzene, etc). But yet it must work and I would bet it has a scalability that is more flexable then that of direct nitration of clean phenol.
I only wish that this type of dicussion was available when I was in school. How valuable it must be to those who are and are reading these threads right now.
That is one reason I copy many of the discussions here and in E&W, you just can't get this info or the amount of input from so many varied sources and so many folks who share the same hobby. Not to mention the appliciablity of the material to such a vast venue.....pretty cool stuff.

MERCURY PICRATE...

quicksilver - 6-10-2005 at 16:43

Roscoe, I read with interest your posts on E&W....you did just what I had done. You used denatured industrial alcohol...that MAY be the issue here (due to impurities, etc). I think that since our results were the same (tan fine crystal, poor yield, etc) that the ethanol source is a major problem. I will be addressing that soon. The other thing you spoke of was the use of the poorly made fulminate turned into a mercury picrate (or, I thought; styphnate). But as we see the nesessity for the (mercury fulminate) solution to be 7.5 grams to one liter of 100C H2O is problematic for the synth of a picrate without wasting PA.....Or at least I get that from what I have read thus far.

How would one go about generating a mercury picrate (using imperfect Hg fulminate) if our solution was that high in H2O? Could styphnic acid be a more efficient choice? I think there is something here.....could a crystaline lattice be generated? Has this even been attempted previously and what might be the pitfalls or dangers (aside from toxicty, etc)? Would a teflon stir-bar generate too much friction in this synth? It _has_ in silver fulminate: a good friend ruined some glassware dextrinating same some time ago. What do you think could be done here?

Rosco Bodine - 6-10-2005 at 19:25

Mercury picrate is news to me .....

You must have misread something or
misunderstood .

BTW ......

I have an experiment underway now where I am attempting to recover any residual picric acid remaining in the distilled water which I have saved from final recrystallizations . I found that if I stirred in small portions of washing soda and observed for effervescence I could manage a rough titration , neutralizing the
residual acidity to form the soluble sodium salt . I observed that not only does the effervescence subside from appearing as
vigorously with each new portion of sodium carbonate added to indicate the approaching neutralization point , but there is also a sudden color shift to a darker color right at the equivalence point , so the sodium picrate solution is in effect its own color indicator for titration ....how convenient :D .

To the solution of sodium picrate is added by portions and with stirring to dissolve , potassium nitrate , which reacts with the
sodium picrate by double decomposition and precipitates the only slightly soluble potassium picrate , leaving a residual solution of mostly sodium nitrate .

This appears to be a valid method for recovery of picric acid as its potassium salt from relatively dilute solutions which might otherwise be simply discarded .

The solubility variation for the potassium picrate is much greater than the variation for picric acid itself , in terms of the reduced solubility at room temperature compared to the solubility at the boiling point , and this along with the salting out effect of the sodium nitrate byproduct , makes the precipitation of the potassium picrate proceed to a significant degree of completion . So don't throw away those
leftover solutions from recrystallization , if you have a liter or more .....you should try this simple recovery method . The precipitated potassium picrate is very fine mesh , but can be dissolved on heating and then cooled slowly to get larger crystals . The potassium picrate can be used for different purposes , or converted to picric acid with HCl .

Useless MF discussion

pdb - 7-10-2005 at 05:03

Quicksilver, I think this discussion about MF is meaningless. If you had more knowledge of chemistry in general and fulminates synthesis in particular, you would be aware that some reactions, such as this one, are intrinsically extremely complex, involving not less than 8 subsequent and/or simultaneous sub-reactions from only 3 initial components, to lead eventually to the MF precipitation. This is a first explanation for the variability you observed in MF preparation. Second, with such a complex chemical train, involving very exothermic reactions, one can easily understand that its performance will depend a lot on the preparation circumstances that may affect heat exchanges, and thus temperature. Depending on your apparatus, the quantities of chemicals, the shape of the vessel (which affects the ratio surface/volume on the one hand, and the condensation of volatile by-products on the other hand, both effects having an impact on heat exchange), HNO3 concentration, alcohol purity, ambient temperature, etc etc, sometimes you will have to heat the vessel to start the reaction, some other times you will need to add fresh alcohol to reduce its pace, MF precipitation will require a few minutes, a few dozens of minutes… or never happen (which is actually quite exceptional). Third, the literature is full with studies and report dealing with the "brown", "grey", "white", "white-grey", "brownish", and so on… MF, all these compounds being 95% and more of pure MF, but contaminated either with Mercury, or some polymerised by-products or other chemicals like the ones used to denature commercial alcohol, or all them together. For a hobbyist usage, that makes almost no difference and you can use any of them. For the sake of purity, you can dissolve your crop in concentrated NH4OH and then recrystallise MF as a white powder… Last, if you are dissatisfied with MF because of the variety of factors that intervene in its synthesis, don't even think about silver fulminate, whose reaction is even more chaotic and difficult to control ! (after many crops, I still sometimes end up with no precipitate at all). Not to mention that the extreme sensitivity of SM would not go well with your lack of familiarisation with such stuff.

quicksilver - 7-10-2005 at 07:22

Quote:
Originally posted by pdb
Last, if you are dissatisfied with MF because of the variety of factors that intervene in its synthesis, don't even think about silver fulminate, whose reaction is even more chaotic and difficult to control ! (after many crops, I still sometimes end up with no precipitate at all). Not to mention that the extreme sensitivity of SM would not go well with your lack of familiarisation with such stuff.


It is EXACTLY that element of inconsistency that makes any discussion of the process meaningful.
Think about what you just said....after understanding (and I asume you do) all the variables you still have trouble with reproduction of a consistent end-result.

Come on....relax.....this is no big deal....we are simply talking about hypothetical stuff: what's to be so uptight about?
I apprieciate that you may be concerned that I know less than yourself; and I may. But I do know the basic concepts of fulminating compounds. I am simply not afraid to say that something doesn't make sence to me or I don't understand fully certain issues. I just don't have to know everything; that's why I ask questions. And why I listen and read... You make a point that a discussion is meaningless because a reaction is complex. And that complexities are somehow either mastered or not discussed...????? Sir, that does not make sence in the light of a discussion board on chemistry.
You make a further point that MF can maintain itself in various forms and that from a hobbyiest perspective it makes no difference. But yet it does. As you certainly know some forms are non-reactive, some yields are so low as to be inappropriate to the time invested, and some may be perfect for the application. What in Heaven's name is wrong with discussing the idiocyncracies of that individuation?
Why are you angry? It seems odd to be angry or even bothered by someone's questions.....If you don't like something on TV do keep watching? I just turn it off. If I am so damn offensive just stop reading anything I write & assume I am a knave and dull and I have nothing that would interest you. On the other hand, if you really have an outstanding education and communication skills and you find it entertaining to help folks with less knowlege than yourself you might want to clearify areas wherein I might learn more...and I would certainly be greatful.
But you need not discribe in detail Edward Howard's work as I am quite familiar. Nor Brugnatelli's for I know that well also.
However, I do apprieciate your concern for my well being and if that was the thrust of your diatribe, I certainly applogise for misinterpreting your remarks.

quicksilver - 7-10-2005 at 07:44

Quote:
Originally posted by Rosco Bodine
Mercury picrate is news to me .....

You must have misread something or
misunderstood .


I certainly could have misunderstood, or even snipped it out of context but I kept the textfile of the whole discussion....

I don't remember if it was you or the other fellow you were speaking with, within that series of posts in E&W but toward the end of the dialog...and I quote directly from there:
"The solubility of the mercury fulminate in hot water is something I keep thinking about
in terms of how this could be useful . One idea that has occurred to me is that perhaps
mercury fulminate may form a double salt with mercury or basic mercury picrate and
if it does , then this material could have useful properties."

Does that ring a bell? Was it you who spoke of the solubility factors; as they seem to be a insurmountable issue.
But be that as it may: it was a great dialog and I kept the whole of it as therein you discussed exactly the issues I had encountered. I am glad you remembered that diaglog to begin with.

pdb - 7-10-2005 at 08:15

Quicksilver, I didn't mean to be arrogant or whatsoever. I just meant that trying to secure on a small or micro-scale a process to obtain certain reproductibility in MF preparation is not far from impossible, and almost pointless, as in most instances you will effectively succeed your synthesis. To me, it's much more important to secure a regular process for preparing NG for instance, since this nitration can be repeated very precisely, with same conditions and same yield than try to "streamline" MF manufacture, given the intrinsic chaotic aspect of this particular reaction.

In other terms, if your goal is to prepare MF, this discussion is not required, and if it is to make MF synthesis (on lab scale) 100% predictable, it is very likely out of reach. In my opinion, a clue that this reaction cannot be streamlined lies in the great number of recipes you can find in the literature. Not talking of amateur' recipes, but industrial processes, that varied from a country to another one, and along time also.

Rosco Bodine - 7-10-2005 at 15:27

@quicksilver

Right , mercury picrate and basic mercury picrate ..... I remember now as an earlier thought about possible complex or multiple salts with mercury fulminate ,
analogous to the basic lead picrate , lead
nitrate complexes with lead azide .

What I was getting at there in that old thread , is that possibly a mixture of mercuric nitrate with sodium picrate could form a basic mercuric picrate which could be held in suspension in boiling hot water as mercury fulminate was sprinkled into the suspension , and that possibly a multiple salt would form , like basic mercury picrate / mercury nitrate / mercury fulminate triple salt . Such a reaction would be analogous to what is done with lead salts and lead azide .

Another possibility is to form the basic lead picrate / lead nitrate double salt which is the matrix former for the lead multiple salt clathrates , but to see if mercury fulminate itself could be adsorbed into the lead compounds matrix .

quicksilver - 7-10-2005 at 17:06

Quote:
Originally posted by Rosco Bodine

BTW ......

I have an experiment underway now where I am attempting to recover any residual picric acid remaining in the distilled water which I have saved from final recrystallizations . I found that if I stirred in small portions of washing soda and observed for effervescence I could manage a rough titration , neutralizing the
residual acidity to form the soluble sodium salt . I observed that not only does the effervescence subside from appearing as
vigorously with each new portion of sodium carbonate added to indicate the approaching neutralization point , but there is also a sudden color shift to a darker color right at the equivalence point , so the sodium picrate solution is in effect its own color indicator for titration ....how convenient


I don't remember if it was in this contextual agenda that you had once addressed this before but I seem to remember something you were once talking about that was close....
I think it was in the context of mercury fulminate (I'm getting fuzzy now with both compounds). Using a solution of sodium carbonate (or bicarb) and given the solubility factor to precipitate mercury carbonate. Continuing to add (in drops) the carbonate as further mercury fulminate dissolves, continuing a reaction to the completion of sodium fulminate.
I'm digging this up from memory so forgive me....The thrust was to initially employ sodium chloride within a solution of MF so as to precipitate sodium fulminate, which then could be used to precipitate many differing fulminates in a cold process by mixing w/ a solution of metalic nitrates. acetates, etc. But there was the idea of using carbonate (I don't remember the reason as to why, however) rather than the sodium chloride. I'll bet it was a solubility issue, but I don't remember....did you ever do that experiment?

-=OK...let's forget the damn fulminates for a second=-

However you are now activly doing an experiment; viewing a rough titration with PA somewhat similarly. And if this is successful the result would be [elimination (or great reduction) of residual acidity to form a soluble sodium salt]: to utilize color indictors where they did not exist (or to any great extent). This then would give you guidlines where none had previously existed. Yes?

Damn baking soda goes a long way!

In the offing one gets to stop wasting PA (the baby and the bathwater or wash-water as it were). Have you tried this as of this writing....??
In-so-far as the recovery method you mentioned: you bet I'm going to try it. If I were to really dig up all the bottles of nitrated phenols that were less than what I wanted for personal usage (I keep 'em) I think I have a seriously LARGE amount to work with. I used the simple HCl re-crystalization on one bottle and got about 250 grams of really good looking product where the PA was too "orange" for me.
I also want to try it with styphnic acid (can't think of a reason not to) as I have a bunch that was left over from experimenting with nitrites....
Very cool idea.

quicksilver - 7-10-2005 at 17:34

Quote:
Originally posted by pdb
Quicksilver, I didn't mean to be arrogant or whatsoever. I just meant that trying to secure on a small or micro-scale a process to obtain certain reproductibility in MF preparation is not far from impossible, and almost pointless, as in most instances you will effectively succeed your synthesis. To me, it's much more important to secure a regular process for preparing NG for instance, since this nitration can be repeated very precisely, with same conditions and same yield than try to "streamline" MF manufacture, given the intrinsic chaotic aspect of this particular reaction.

In other terms, if your goal is to prepare MF, this discussion is not required, and if it is to make MF synthesis (on lab scale) 100% predictable, it is very likely out of reach. In my opinion, a clue that this reaction cannot be streamlined lies in the great number of recipes you can find in the literature. Not talking of amateur' recipes, but industrial processes, that varied from a country to another one, and along time also.



Agreed. I doubt very much that industrial scale predicability could be achieved w/ MF by us working in our labs; make-shift or otherwise, for so many reasons. I think I even remember reading that when those great "balloons" were in use, there were continual changes that had to be implimented. I imagine that the simple change in temperature of a door being open or the ethanol being cooler, or God knows what, would throw off that bastard.
My point however is that any discussion where "thinking out of the box" is implimented is a productive one as it gets the wheels turning of those who may know something more or perceive something differently than oneself. This "thinking out of the box" is how the clathrate concept was developed I believe. If memory serves, originally a Nun had worked w/ clathrates but I do not believe she was the one to apply it toward energetic materials.....
So let's say you dream up an idea or ponder a problem that seems to turn you around in circles.....Often by discussing it with others they may invision something from their personal experience that will have an effect, or not, or may effect the way you invision the problem itself. In any event I really do believe that there is no such thing as a wasted experiment; only additional data.

I just love the idea of "thinking out of the box".

Rosco Bodine - 7-10-2005 at 18:30

Quote:
Originally posted by quicksilver
However you are now activly doing an experiment; viewing a rough titration with PA somewhat similarly. And if this is successful the result would be [elimination (or great reduction) of residual acidity to form a soluble sodium salt]: to utilize color indictors where they did not exist (or to any great extent). This then would give you guidlines where none had previously existed. Yes?

Damn baking soda goes a long way!

In the offing one gets to stop wasting PA (the baby and the bathwater or wash-water as it were). Have you tried this as of this writing....??


Yes it works and it appears to be useful method of recovering the residual content of dissolved picric acid from the supernatant solutions remaining from the final crystallization from distilled water .
the potassium picrate can be used in synthesis or for other purposes . You get a few grams of a useful material that would otherwise go down the drain .

quicksilver - 9-10-2005 at 17:47

Quote:
Originally posted by Rosco B. You get a few grams of a useful material that would otherwise go down the drain .


I apprieciate your input in this, a rather diverse thread. Tying all together what you had spoken of helped a great deal. I kept some simple notes regarding some hobby stuff I did....and had a lot of fun.

Picric Acid Synth using "Color Indicators" to Produce Higher Yield

Having nitrated phenols from various sources and using various techniques I have found that modern chemistry need not overlook what was perhaps a lost art of nitration. It has been mentioned by others more astute than myself that color changes and solution clarity (a "cloudy" appearance) may be used as proper indicators of the various stages of both preparation and nitration. I have noticed that when I use such indicators I am now able to produce a crop of picric acid crystals that match both mp and purity of the "store bought" reagent material. I have been able to reproduce these results with most any quantity and basic ingredients. I have been surprised that when I use the methods of color change as indicators rather than precise time and temperature management; the results prove themselves to be best for my efforts. As mentioned previously, perhaps this is a lost art; I will say that it does hold promise.

With Picric Acid, I used the following:

Format followed basic methodology (Similar to Davis method) but using ASA (Aspirin)
Pure ASA was obtained [In this instance I use a mix of alcohol & acetone at room temperature to extract same]
Sulphonization was as follows:
Example: 25 grams of H2SO4 was used for every 25 grams ASA as per Davis, the initial sulphonization is equal acid for phenol.
Example: 100 grams Phenol is sulphonated w/ 56ml H2SO4 if one is using "drain cleaner" (93%) acid - a simple method of
volume was utilized as 14 mil of H2SO4 is 25 grams; so one may extrapolate
a "quick and dirty" method of finding the volume of acid for one's
initial sulphonization.
However in this synth I used a bit of a twist as I wanted to maintain the acidic acid as much as I could prior to nitration. So I mixed equal parts H2SO4 w/ the ASA and let the material sit for 6 hours @ 20 C yielding a very thick cream of pink acidic sulfate (I have used this with Styphic Acid with excellent results). After which I utilized a weight equal amount of 72% H2SO4 and applied heat (80 C) to form a complete sulphonization which from past experience would be a ruby red solution. I found this method in a very old patent on styphnic acid and it works every time. I have used it with Indigo and the results were outstanding. A note on color: what I wanted was a deep scarlet solution from the creamy pink sulfate, which was my starting point. The color became my road map in a sense.
[In this instance I had 42 grams ASA to work with and did the arithmetic necessary]
The nitration was simple and I used 70% HNO3; only because I had it available and did not want to go to the trouble of working with prills of NaNO3 or KNO3 (which are coated with wax / clay, as are fertilizer grade AN). I wanted to maintain purity and the only time I have had really unacceptable products I traced the impurity back to the prill. If I use the common sources of KNO3 prill from "Stump Remover" or the NaNO3 from the 40 lbs bags of "Nitre of Soda", they are all coated prills. Some to a lesser degree; some much more. I had found this to be a very common additive to prill nitrates due to the manufacturing process adopted in both the United States and in northern Europe.
After HNO3 was applied via sep funnel I heated @ 100 C for 2 hours noticing that color was light-orange cloudy with very bright yellow crystal formation on surface edge of vessel. Solution was removed from heat and set up to crystallize on it's own for 12 hours. No cooling was applied, In fact insulation was applied to vessel via fiber-glass and it cooled very slowly yielding crystals approx 2mm in length. Care was taken not to stir of shake the vessel to minimize the crystals from "shaving" themselves against one another. These is an issue here that a "crust" forms during the time the nitrated solution is allowed to set up. This proved to be no problem as in the past the mp of the crust material was the same as the beautiful crystals beneath. However, it should be noted that I did not use a mechanical stir bar during this process. had I done so the crystal size would have suffered due to the "shaving" of the crystals just prior to the elimination of heat. IMO the crystals form that fast when sulphonation is as complete as it was utilizing the above technique.
Using Buchner funnel and glass filter the initial crop was 79 grams totally dry. The mother liquor was retained but unfortunately it was not voluminous enough and of course much too acidic to work with. It was added to a corresponding amount of ice and water. A further crop of crystals was yielded. Then added to it was common sodium bicarbonate; as discussed previously in this thread, another crop of crystals was observed. What I did was add, portion wise very small amounts observing the reaction. These crystals need to be dried and weighed, however there was definatly some material recovered. I can’t estimate at this time what it weighs.
I started with 42 grams of ASA and ended with 79 grams initially (and with harvesting from the solution...perhaps as much as 90+ grams), I believe. I could outline the same synth with specific time-table and temps of course but as I have worked with much larger amounts and smaller I find that the slight changes will occur and by using COLOR as an indicator, the results reproduce themselves uniquely well. While I have had an opportunity to duplicate this with appropriate measurement tools and precision; the result varies. These variables are diverse; they include issues related to the temp, time, weight, & purity of the chemicals, thus the synth as a whole. When I used PHYSICAL INDICATORS despite the variables, the results were excellent and repeatable.

Rosco Bodine - 10-10-2005 at 06:00

There are some numbers which need to be considered and applied to the process which you are reporting . When you are translating from one method to another and substituting different precursors , generally what you must do is work on a molar basis so that the stoichiometry and molar proportions are the same .

For example , mole weights of

phenol = 94.11 grams
aspirin = 180.16 grams

picric acid = 229.11 grams

To maintain the same molar proportions for a reaction involving aspirin substituted for phenol , requires almost doubling the amount of aspirin used in the same reaction as would be the amount of phenol , 180.16 / 94.11 = 1.914 , so
1.914 grams of aspirin substitutes for 1 gram of phenol in a reaction where aspirin is substituted directly for phenol , in order to preserve the molar proportions .

Also with regards to maximum yields ,
the theoretical maximum yield from aspirin
with 100% coversion to picric acid is
229.11 / 180.16 = 1.27 , or 1.27 grams of picric acid for each 1 gram of aspirin .

Reaction temperatures are very important for controlling the nitration so that it proceeds at a good rate without surging problems or accumulation of unreacted material , and reduces the problem with undesired byproducts .

The numbers which apply are as critical to the success of such syntheses as are any visual observations . A nitration is generally not a process which can be safely or efficiently conducted with any repeatability and predictabilty , except when it is worked out how to do it " by the numbers " which apply . These reactions are so sensitive to variables that for safety and for the efficiency of the process , there has to be a reasonable precision about conducting the reactions in a very well measured and regulated set of conditions , particulary as the batch size is scaled upwards .

quicksilver - 10-10-2005 at 06:41

Quote:
Originally posted by Rosco Bodine

Reaction temperatures are very important for controlling the nitration so that it proceeds at a good rate without surging problems or accumulation of unreacted material , and reduces the problem with undesired byproducts .

The numbers which apply are as critical to the success of such syntheses as are any visual observations . A nitration is generally not a process which can be safely or efficiently conducted with any repeatability and predictabilty , except when it is worked out how to do it " by the numbers " which apply . These reactions are so sensitive to variables that for safety and for the efficiency of the process , there has to be a reasonable precision about conducting the reactions in a very well measured and regulated set of conditions , particulary as the batch size is scaled upwards .


I know it doesn't present an equal molar weight but what I ended up with was fantastic. And while I wouldn't recommend anyone continue in that manner in times past, that must have been the technique to a greater degree. What I ended up with was good stuff. Of couse as actual science goes the whole thing I posted was a rant; but it did produce decient results....
I hate to "back-peddle" but I should have waited before I posted that thing......
Well, the truth is while I was delighted with the initial yield and busily clapping my hands I think that my initial impression of the total was a poor one. BUT it was still up there! (...Seems what I thought was totally dry could still use some drying, etc). I have to toss out the numbers as it really needs a desicator to dry properly. In addition the fact is, I should never have even mentioned the recovered material as it was very fluffy.... But it appears that differing methods of initial sulphonization have a vast difference in end yield. I have no idea what the ratio (as related to phenol) is with Indego but there again the result is very similar. The starting product being in varience from one batch of indego to another (some are "whispy", while others are grainular).
I knew seconds after I pressed the "POST" button I should have left off the initial numbers. But, DAMN, the yield WAS great as well as very good looking in form. What can I say? It was fun.

Rosco Bodine - 10-10-2005 at 07:41

The problem with unmeasured physical observations is they can often be deceiving . The same thing happened to me when I was evaluating methyl salicylate as a precursor for picric acid , and there was a huge volume of low density crystals which to visual inspection appeared to be a fine yield . But as the material was filtered and purified and dried the amount kept getting smaller and smaller , and upon weighing ( the scales don't lie ) ....it was known with no uncertainty that the yield was only about a third what would have been gotten from aspirin . You can't really trust your eyes when it comes to tracking these reactions because the density of the product can cause huge variations in the apparent amount of end product , so only weight tells the true tale on what you have goten from a synthesis . At certain stages of course visual observations are important , but not necessarily definitive of what is occurring , so don't place undue emphasis on what you see compared with what you actually measure . Sometimes your estimates will prove out to be true , but often there will be discrepancies , in which case you have to trust the measurements as being what is accurate even if the measurements are not what you hoped or estimated .

quicksilver - 10-10-2005 at 13:07

Well...you simply have to look at these snaps....I tried to use a camera that would capture the crystals. The first is the direct yield and next is the total yield...please check them out. It's really something.

But what I thought of is "what do I really have here?" Di & Ttrinotrophenol are both light yellow....is it possible that a great yield could come from a lower nitration????? I won't know until I run up to the Univ. and have a friend do a really professional mp on it. But the yield IS prretty big. (It's now in the desicator)

picric-asa-10-7.jpg - 50kB

quicksilver - 10-10-2005 at 13:09

Here is a picture of the total yield...-- I believe even if there is some serious water inside the crystals; I still got a good yield for a "kitchen synth"..... I will know the truth in a day or so....

[Edited on 10-10-2005 by quicksilver]

picric-asa-total.jpg - 60kB

Rosco Bodine - 15-10-2005 at 05:35

If you started with 42 grams of ASA ,
then by my experience the best you will get is 42 X 1.27 X .9 = 48 grams total
picric acid .

Okay , truth time , tell us what the scales say you got :D

quicksilver - 15-10-2005 at 06:29

Quote:
Originally posted by Rosco Bodine
If you started with 42 grams of ASA ,
then by my experience the best you will get is 42 X 1.27 X .9 = 48 grams total
picric acid .

Okay , truth time , tell us what the scales say you got :D


Oh God.....I wanted to put this off as long as I could. 46 ..... I started with 42 (ASA) It LOOKED like I had about twice that but it was not only fluffy, there was what seemed like water within the crystal itself. I noticed it when I actually moved it about the table when taking pics of it. :( All I can say is that it IS Trinitrophenol and very good looking under the microscope. It's mp is 123 on the nose. I know that from a quality MP machine at the Univ. and was actually suprised. I thought it was a mix but it's right on the number.
I thought I could "Kitchen Waltz" my way into turning animal asprin into a 500gr bottle of Spectrum's best......When I used a real desicator I just kept watching the numbers on the scale drop and drop....

Rosco Bodine - 15-10-2005 at 06:46

Hehehe .....

We all know the disappointing feeling of having to keep moving those counterweights on the triple beams into the next notches going in the wrong direction to get that beam level :D .

But what you are getting there is actually about optimal according to my own experience . I can usually predict within
2% of exactly what I am going to get , and if the result varies beyond that , then I start looking hard for the cause of the anomaly .