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quicksilver
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| Quote: | Originally posted by Quince
Thanks, that made it all clear.
Why do people seem to prefer the long needle-like crystals? Wouldn't they be more sensitive, due to breakage when moving and packing them?
Also, during boiling down for the second batch, it seems some picric acid is evaporating along with the water, as a cool surface above the boiling
liquid accumulates a yellowish condensate from just the steam, without there being any spray (even if I remove from the heat so boiling stops).
In regards to storage, is alcohol as effective a desensitizer as water? I ask as it's much faster to dry alcohol.
[Edited on 27-9-2005 by Quince] |
I don't know if you could determine if you are loosing material if the PA is still is in solution; it is a dye after all and yellow solution will
be everywhere. Measuring weight when dry is the only sure method to know if you are actually loosing material in evaporation (I think it's
doubtful if we are only speaking of evaperation).
Allowing PA to remain moist and off of any threads or frictional surfaces on the final container would maintain a safe environment for the most part
regardless of size or shape. Some compounds [primaries and secondaries] would be problematic with crystals of size but TNP, TNR, or TNPG don't
present that issue and especially when moist. But even so, the sensitivity of nitrated phenols or benzenes is not that high especially in comparison
to the nitramines as a group) On that note the nitrate ester nitramines such as Dinitrooxydiethylamine Nitrate (DNAN) is famous for being detonated
from impact, etc as a secondary. But it's not that pretty or useful in a variety of areas like TNP.
The use of a solution of greater solubility such as alcohol would possabily retain more of the product in solution. But for the purpose of simply
drying it and using same, it's perhaps a more convienient way to go. But for myself I would be hesitant only because I may loose some of the
better looking crystals when it reforms (no big deal to most folks). However, that is with nitrated phenols....there are some compounds that it has
been said, could form larger crystaline structures via alcohol and it would become a danger (i.e. lead azide).
[Edited on 27-9-2005 by quicksilver]
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Rosco Bodine
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| Quote: | Originally posted by Quince
Is there any advantage to using HNO3 instead of nitrates? |
Using nitric acid results in a thinner mixture due to the absence of bisulfate byproduct from the reaction of the nitrate and the sulfuric acid , and
a lesser amount of sulfuric acid is required since that amount which would be reacted with the nitrate to produce nitric acid in situ is not needed
when the nitric acid is supplied externally . The additional amount of sulfuric acid needed as a solvent an / or liquid carrier for the solids in the
nitration mixture so that the mixture remains stirrable is also reduced when the nitric acid is supplied externally .
But all things considered , it may not be as efficient to use nitric acid as to use the solid nitrate , or nitrate solution in nitric acid or water ,
and sulfuric acid in the increased amount required .
The usual opinion which has been expressed is that nitric acid has a higher nitrating effect than solid nitrate mixed with sulfuric acid , but for
nitrations of certain materials it has been observed by experiment that higher yields are produced by the solid nitrate and sulfuric acid mixture than
for similar molar strength nitrating mixtures using fuming nitric acid d. 1.5 . Urbanski supports this observation about the evident higher nitrating
effect of solid nitrates mixed with sulfuric acid as a generality , but in my own experiments it tends to be somewhat reaction specific and depends on
what thing is being nitrated , whether it is nitrated better by solid nitrate with sulfuric acid , or a mixed acid nitrating scheme using nitric and
sulfuric acids in
whatever sequence or proportions .
Different solid nitrates have different nitration strengths or activity in combination with sulfuric acid . See the attached file for a comparison of
various solid nitrates activity as nitrating agents increasing above nitric acid .
In my opinion it is evident that some amount of nitrosylsulfuric acid is formed in the nitrating mixture when solid sodium nitrate is used for the
nitration of sulfonated ASA in 92% sulfuric acid .
When the completed nitration mixture is allowed to cool to about 92C and cautiously diluted with water streamed onto the inside walls of the flask ,
stirred into the mixture , hydrolysis of the nitrosysulfuric acid occurs and a steady evolution of NO2 and perhaps some nitric acid vapors appears .
This hydrolysis is
exothermic and the products have oxidizing properties , which is likely the mechanism responsible for unexpected
" runaway reactions " which sometimes are observed in nitration mixtures which are near or at completion of the nitration .
In nitration mixtures where the water content is low , the nitrosylsulfuric acid accumulates , and the stability of the mixture depends upon the
temperature and the water content , so the nitration process completion temperature and the composition of the spent acids must be deliberately
controlled to enable the hydrolysis to be done by manual dilution of the finished nitration mixture , instead of occurring spontaneously at some
unfavorable temperature and water content in an unfinished nitration mixture , resulting in a final nitration stage runaway . It requires some trial
and error process engineering to establish the proportions of safe and efficient mixtures and determine the reaction temperatures and times which are
optimum for nitrations of specific materials .
With regards to the mixed nitrates eutectics which I mentioned earlier in connection with the possible salting effect that produces anomalous
increases in solubility , I found one tertiary eutectic in Urbanski 3 , page 257 .
66.5% NH4NO3
21% NaNO3
12.5% KNO3 f.p. 118.5 C
I am uncertain if this mixture exhibits the salting effect for increased water solubility in the same proportions as for the effect on lowered melting
point for the eutectic . The proportions for the salting effect are posssibly different and
I have no idea where such solubility anomalies are charted for reference , but such mixtures do exist .
Attachment: Page 46 from Urbanski vol. 1.pdf (8kB)
This file has been downloaded 2649 times
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Rosco Bodine
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| Quote: | Originally posted by Quince
Why do people seem to prefer the long needle-like crystals? |
Purity , and identification , ease of filtration and drying , bulk density , and sensitivity to initiation are all favored by production of the picric
acid in a very pure and crisply crystalline form . The crystals of picric acid first appear as rhombic plates which then lengthen into elongated flat
hexagonal blades which can reach 40 mm in length by 2 mm wide in thirty minutes . The crystals are thin and brittle and fragile , and settle to a
layer which forms an acicular mass of porcupine like blades growing in all directions . The open structure will occupy a third the volume of the
aqueous supernatant solution after slow cooling undisturbed of a boiling saturated solution . The action of a stirbar will break up the crystals into
a freely pourable form , and a tinkling sound will be made by the breakup of the crystals as if one was stirring a jar full of thin glass fragments
from broken cover slips or slivers of glass from shattered Christmas tree ornaments . If the stirring is continued for too long , the broken up
crystals will actually be wet milled into a fluffy and low density powder , so to obtain a good bulk density the disturbing and breakage of the
crystals must be carefully watched and limited in extent , and stopped when the desired aggregate density for the material is reached .
| Quote: |
Wouldn't they be more sensitive, due to breakage when moving and packing them? |
That's the whole idea , but there is no danger of initiation of picric acid from anything less than a hammer blow like impact . Normal handling
of picric acid will not generate sufficient impact to initiate it accidentally . Like TNT , picric acid is a very safe explosive and very difficult
to detonate unintentionally .
| Quote: |
Also, during boiling down for the second batch, it seems some picric acid is evaporating along with the water, as a cool surface above the boiling
liquid accumulates a yellowish condensate from just the steam, without there being any spray (even if I remove from the heat so boiling stops).
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Picric acid has a very slight volatility at elevated temperatures . More than likely
the carryover you have observed is due to microscopic particles of the solution , than from actual vapors of picric acid , but in either case it would
be only a few milligrams , escaping from even boiling away several liters of solution . The intensity of the dye effect is such that even the
smallest particle will cause a tint to be observable wherever it lands on a moist surface .
| Quote: |
In regards to storage, is alcohol as effective a desensitizer as water? I ask as it's much faster to dry alcohol. |
I am not certain , but I doubt it . The water relates to reducing flammability also , which of course alcohol would do just the opposite , and for
that reason would seem not to offer any advantage ,
probably being counterproductive in terms of overall safety .
In my own opinion it is unnecessary to store picric acid wet with 20% water .
This was probably something developed as a recommendation for the safer shipment of the material , since the forces generated by transportation
accidents are much higher than any forces generated by dropping a bottle onto the floor . Now when it comes to
" accidentally " tossing a jar out a fourth story window , maybe 20% moisture would be a wise precaution  But for ordinary handling , picric acid is not likely to be any significant
danger in any usual scenario . Nothing however is ever completely idiot proof
So this is one of those matters where it is a matter of discerning , personal discretion and situational awareness .
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quicksilver
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| Quote: | Originally posted by Rosco Bodine[
Purity , and identification , ease of filtration and drying , bulk density , and sensitivity to initiation are all favored by production of the picric
acid in a very pure and crisply crystalline form . The crystals of picric acid first appear as rhombic plates which then lengthen into elongated flat
hexagonal blades which can reach 40 mm in length by 2 mm wide in thirty minutes . The crystals are thin and brittle and fragile , and settle to a
layer which forms an acicular mass of porcupine like blades growing in all directions . The open structure will occupy a third the volume of the
aqueous supernatant solution after slow cooling undisturbed of a boiling saturated solution . The action of a stirbar will break up the crystals into
a freely pourable form , and a tinkling sound will be made by the breakup of the crystals as if one was stirring a jar full of thin glass fragments
from broken cover slips or slivers of glass from shattered Christmas tree ornaments . If the stirring is continued for too long , the broken up
crystals will actually be wet milled into a fluffy and low density powder , so to obtain a good bulk density the disturbing and breakage of the
crystals must be carefully watched and limited in extent , and stopped when the desired aggregate density for the material is reached .
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When I first noticed the actual vibration of crystals within the flask; it's amazing. I realized that an enourmous format of crystal forms could
be developed with PA. And I think one of the major authors mentioned that there was a sensitivity element dicovered during WWI in this regard: an
alteration of crystal shape and sensitivity. I posted a little picture of a asprin-PA synth in another thread wherein there is a fairly clear shot of
the rhombic plates (one needs to enlarge the photograph, in a browser it doesn't look as good as it could). They almost appear as mica and
reflect intensly. At first glance they do look like tiny pieces of broken glass. I have heard and read differing views on the subject of
temperature's influence on crystal growth and size. Does anyone have any experience with nitrated phenols in that regard?
[Generalized concept, that of lead azide being too sensitive in a needle crystal format & thus the use of cold water during a synth and
dextrine]
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Rosco Bodine
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From everything which I have observed in my own experiments with picric acid crystallizations , the two factors which are consistently critical to the
formation of excellent crystals are high purity of the crude product and significant batch size or
provisions to reduce the cooling rate of
smaller batches .
The thermal mass of batches at half mole scale or larger is required for good crystal formation , due to the slowed radiational cooling of reaction
vessels . If work with smaller batches is being conducted , then insulation must be wrapped around the hot solutions of picric acid , in order to
slow the heat loss and enable the formation and growth of good crystals .
Recently I have performed a repetition of my own previously developed and described synthesis for picric acid which has always produced a very pure
product from purified aspirin , using for each 1 gram of ASA , 4 ml of 92% H2SO4 , and 1.8 grams of NaNO3 . Typically the synthesis total yields are
about 90% of the theoretical , of recrystallized picric acid , based on ASA .
My most recent synthesis was done on a slightly more than 1 mole scale , 1.04 moles of ASA used as the precursor . The crude picric acid obtained
after a 5 hour nitration procedure and then a 1.5 hour dilution and cooling , was *very* light in color and the diluted reaction mixture was so pale
in color and free from any dark colored impurity that upon filtration it did not even stain the filter paper yellow ! This is the first time I have
ever seen this occur .
The crystals direct from the diluted nitration mixture were very uniform hard gritty fine mesh material which had the free draining easily filtering
physical consistency of fine quartz beach sand found in the surf line . It is the sort of material which is semi-fluidized by a small amount of water
to form a mobile slurry , which behaves as a liquid suspension for a few seconds following agitation , but then settles quickly to a dense mass from
which the water rapidly drains .
The crude picric acid after filtering , required 5200 ml of boiling distilled water for its dissolution . The solution was performed in a 6000 ml
Erlenmeyer flask resting upon a 12" square Cimarec hotplate stirrer . Upon cooling overnight to ambient temperature the excellent crystals were
filtered and dried , 198 grams of extremely pure picric acid obtained from the first recrystallization , 83% of theoretical based on ASA . The color
and crystal appearance is consistent with that of the finest reagent grade obtainable from pharmaceutical manufacturers .
The bulk density of the loosely poured untamped crystals is 0.7 .
The five liters of filtered solution from the first crystallization was boiled down to 1300 ml , and allowed to cool for a second crop of crystals .
No color change was noted , not a trace of orange nor any precipitation of impurity occurred during this reduction of the original 5200 ml of
solution to one fourth its volume for the second crop of crystals , which are identical in color to the first crystals . The physical form is
inferior for the second crop of crystals which are fine needles , a felt like mat of fine soft crystals , which are more typical for smaller volumes
of hot solution which cool too rapidly to permit the growth of the larger and more dense crystals . 16 grams obtained from the second crop of
crystals .
Just for the purpose of seeing what might precipitate , the filtered 1300 ml of solution was boiled down to 300 ml for a third crop of crystals .
There was still no color change nor precipitate of impurity , even at this extreme of concentration to a small residue of the original volume of the
solution , and it appears there may be one or two grams at most of powder form precipitate of picric acid as the third crop ,
and the very pale yellow color is unchanged from that of the original solution which has been reduced to one seventeenth , 5.7% of its original volume
......so it was most definitely a very " clean " nitration producing a very pure product directly from nitration of the sulfonated ASA .
Total yields are right on the predictable 90% based on ASA from
" Rosco's Good Old Country Recipe for Picric Acid " , and I don't ever complain because the purity is always so excellent and the
reaction so predictable . But every time I wonder , where is my other 10% ?
It seems like there is just some invisible
" wall " for the reaction efficiency , where the invisible little " loss gremlins " always
get their damn 10% 
Anybody else get this problem with picric acid , where it seems 10% simply vanishes into space with no explanation ?
During the course of the sulfonation and nitration , the physical observations indicated that the conversion was occurring to a high degree of
completion and as I watched the reactions , it appeared to me that the process is very close to a quantitaive conversion having no observable
indication of byproducts or loss . Yet no matter how clean or complete the reactions appear while in progress , and no matter how consistent the form
and color of the end product , 90% yield by the numbers * always * seems to be the result . So what I am beginning to wonder seriously is if the mole
weight of aspirin given in the literature as 180.16 is correct , or if aspirin is actually a hydrate having 10% greater mole weight . But the ASA
which I use is recrystallized from alcohol , so it would seem likely that if there is a hydrate of aspirin , then it is molecular water , and not
merely water of crystallization . The same thing could apply to resorcinol , where it seems a
similar yield limitation is observed for
conversion to the nitrated derivative .
If the mole weights being used for calculation are not on the mark for the actual precursor being used , then the discrepancy would be explained for
how a reaction which looks like it is quantitative , never seems to add up that way when running the final numbers .
I really hate to question the numbers provided by authoritative sources in the literature , but when my experiments continue to point to such a
possible discrepancy regarding molecular weights ,
the implication is inescapable that the numbers given in the literature just could be in error .
I suppose simple titration of a sample of ASA using a good color indicator would be a good place to start trying to see if the published mole weight
of 180.16 seems correct or not .
[Edited on 15-10-2005 by Rosco Bodine]
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quicksilver
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I am making an assumption that your synthesis is not done in a sealed situation.....Perhaps it is that we are not operating in a vacume & that is
a possible explanation for the "missing 10%" ?
Do not large chemical plants use most every production operation (especially nitrations) in a vacume for environmental reasons as well as reactive
ones...?
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Rosco Bodine
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At one time I thought that possibly there was initial loss from volatility during sulfonation of the ASA , but have ruled that out by doing the
sulfonation in a loosely glass stoppered flask . I have good ground jointed glassware and I would notice anything obvious in the way of a side
reaction . I study and monitor reactions very carefully and make time and temperature notes , keep log sheets of timed observations and notes of any
changes that attract attention .
For example :
I just recently in this last experiment have pegged the fact that nitrosylsulfuric acid is present in the nitration mixture and accounts for the red
fumes which appear when the finished nitration mixture is diluted . Nowhere have I ever seen this reported , but I'll guarantee you that what I
am observing is a fact .
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quicksilver
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| Quote: | Originally posted by Rosco Bodine
I just recently in this last experiment have pegged the fact that nitrosylsulfuric acid is present in the nitration mixture and accounts for the red
fumes which appear when the finished nitration mixture is diluted . Nowhere have I ever seen this reported , but I'll guarantee you that what I
am observing is a fact . |
This is interesting stuff......
Indeed; often I miss items that SHOULD be noted (as the above) because I believe that such a thing is not an anomly. Principally because I have
nothing to compare it to. If I were to have a classic example of this or that nitration (visually, etc) , I could note a unique issue. {I don't
mean to harp on the "visual" thing, it's just an example} however.... I too have had this (red fumes arise during dilution).
phenominon. The finished product in that instance (it was some weeks back) lacked the purity I had gotten previously. What issues contribute to
nitrosylsulfuric acids' creation at that point in the synthisis? Or is that a moot point and other factors over-ride the existence of
nitrosylsulfuric acid? - As I have seen this with other nitrations as well.
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Quince
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That's interesting. The only reddish fumes I've noticed are when squirting water from the wash bottle into the foam during late nitration.
I was under the impression they were just NO2 trapped by the foam being released when the water broke through it.
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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Rosco Bodine
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The first mention of this was made in the earlier post where I attached the file for the page from Urbanski describing the nitration activity series
for common nitrates .
My most recent nitration was one where I refined some temperatures , reaction rates and holding times by a very gradual adjustment of the conditions
which I have always generally followed with good success . The nitration went more smoothly and produced a more pure product than any picric acid
from ASA synthesis I have ever done , and absolutely no red fumes were produced from the beginning to the completion of the nitration , when most of
the picric acid had already precipitated as fine crystals in the spent acid mixture .
Only after the nitration was completed and cooled somewhat , when the mixture was being diluted for the precipitation of any not yet precipitated
product dissolved in the spent acid mixture , did red fumes suddenly appear during that stage commonly called the quenching or drowning of the spent
nitration mixture .
It was very evident that water was the trigger for the evolution of the red fumes ,
the mixture boiling on contact with the stream from a wash bottle , as the dilution was cautiously performed by sheeting the water down the inner
walls of the flask . There was a fair amount of the red fumes evolved when the mixture was diluted , and I have seen the same thing occur when spent
nitration mixtures are dumped over ice , so it is indeed the water and not the temperature which is causing the hydrolysis . The diluted nitration
mixture smells strongly of nitrous acid and I believe some of the acid is also trapped in the crude crystals , which accounts for more water being
required than should be required for the dissolution of the crude picric acid . The presence of the residual acidity lowers the solubility of the
crude product below what would be the solubility of the pure picric acid after being freed from the nitrous acid impurity .
I believe that nitrosylsulfuric acid is an unavoidable component of the nitration mixture when it is a low water content mixture using solid nitrate
and sulfuric acid . It is accumulating in the nitration mixture over the course of the nitration ,
and it may even be essential to the nitration . Knowing it is there helps in avoiding the conditions for its decomposition in an uncontrolled
fashion
which could cause a late nitration stage runaway .
There are different strategies which could be applied to exploit the usefulness of the nitrosylsulfuric acid * if * it is found to be a desirable
component in the nitration process , perhaps such as using an added nitrite as well as the nitrate , in some combination of proportions or sequence .
Or on the other hand if the nitrosylsulfuric acid proves to be an undesirable byproduct , then there are some combinations of temperature and water
content which would tend to cause decomposition of the material and limit its formation .
Which of these findings or strategies has validity is too early for me to know , and would require further experiments . This is likely " old
news " and is another aspect of the " lost art " specifics which were probably once common knowledge about picric acid , in the long
lost details of manufacture done a hundred years ago .
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quicksilver
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| Quote: | Originally posted by Rosco Bodine
There are different strategies which could be applied to exploit the usefulness of the nitrosylsulfuric acid * if * it is found to be a desirable
component in the nitration process , perhaps such as using an added nitrite as well as the nitrate , in some combination of proportions or sequence .
Or on the other hand if the nitrosylsulfuric acid proves to be an undesirable byproduct , then there are some combinations of temperature and water
content which would tend to cause decomposition of the material and limit its formation .
Which of these findings or strategies has validity is too early for me to know , and would require further experiments . This is likely " old
news " and is another aspect of the " lost art " specifics which were probably once common knowledge about picric acid , in the long
lost details of manufacture done a hundred years ago . |
The length and legibility of my notes needs to increase many fold as this question is something I am familiar with but did not have enough noted down
at the time of the experiment. First off, I have seen this phenominon in the ice quencing of distilled 90+ % HNO3, however at the time I thought
nothing of it. The yield was high albiet less pure than previous. But here this leads me to a speciific question of terminology. When the expression
"run-a-way" is used in a nitration we assume that to mean an uncontrolable reaction. Is it possable that a run-a-way reaction may occur that
simply results in oxcidation of the product to a greater or lesser extent and does not threaten a catostophic end result?
Where I am going with this is; could a run-a-way occur on a tiny scale, yielding inconsistent results, etc?
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Rosco Bodine
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Some nitrosylsulfuric acid is even produced in the mixture of nitrate and sulfuric acid from which nitric aicd is distilled , and it can be seen
decomposing when water is added to rinse the residue from the flask , producing a roiling cloud of NO2 from the decomposition of the nitrosylsulfuric
acid when the water contacts the material . The origin of the material is from the natural decomposition of some of the nitric acid , and this
decomposition is catalyzed by direct sunlight . Sunlight by itself can cause an
autocatalytic decomposition runaway oxidation to initiate in a nitration mixture .
Direct sunlight is your friend if you are intending to get a fulminate sort of reaction going . But that is not what you want to see in a nitration
mixture , so direct sunlight should be avoided .
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Quince
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Regarding red fumes appearing during distillation, I have a question. I have not observed the evolving of fumes when water is added, but when I
notice orange fumes appearing during VACUUM distillation (which seems to me must mean I've heated too fast), if I momentarily let air in, the
fumes disappear. At first I thought the inrush of air was simply pushing the NO2 back to the boiling flask, but on a closer look they actually become
white/clear. Now, I can't think of what in air would change the NO2 to something else.
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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Rosco Bodine
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2 HOH + O2 + 4 NO2 -----> 4 HNO3
Airborne water vapor and oxygen is the clarifier .
Nitric acid is found in rainwater after
thunderstorms .
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Rosco Bodine
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| Quote: | Originally posted by quicksilver
On another note I have used a process wherein picric acid is prepared by nitration of a nitrosophenol intermediate by preparing the phenol with sodium
hydroxide and sodium NITRITE. The resulting nitrosophenol intermediate is then nitrated by a standard nitration process using strong HNO3 - and in
this instance methlene chloride / HNO3 may not be exposed to much heat. Or a H2SO4 / solid nitrate mix may work. In any instance it is ment to be
processed a much lower temp.
Unfortunatly it comes from a UK patent application (#365, 208 David Salter, 1973) so I am having trouble getting a PDF file.... |
The patent you mentioned is GB1278576
describing the conversion of phenols to a nitrosophenol intermediate , and then nitrating to produce the normal nitro compound .
I tried to upload the file , but it is over
1 MB and the server won't allow the upload saying the file is too large .
I thought we had some bandwidth now ,
so what's up with that stuff ?
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quicksilver
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| Quote: | Originally posted by Rosco Bodine
The patent you mentioned is GB1278576
describing the conversion of phenols to a nitrosophenol intermediate , and then nitrating to produce the normal nitro compound .
I tried to upload the file , but it is over
1 MB and the server won't allow the upload saying the file is too large .
I thought we had some bandwidth now ,
so what's up with that stuff ? |
Thank you for hasseling that.
I want to know how you can actually get the whole thing from Espacenet......I have a terrible time with that site.
Now, the reason I was so damn off on that patent number is that it came from THE PREPRETORY MANUAL OF EXPLOSIVES, which, in another thread I
continually blast for being inaccurate. Almost EVERY DAMN patent # is wrong. Some off by one number, some wildly off like this one. The synth was fine
so I kept it in my notebook but the number was -=no where=- close or related. I just remembered when I read your post. --- Wow that book is so full of
typos and inaccuracys, I can't tell you all of them. I'll even bet that some of the stuff is dangerously mis-directed. I always double check
things from there with someone else or try to find the patent .
Thanks for trying however, I really enjoy the stuff you find and make good use of it.
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Rosco Bodine
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That " manual " is a complete fraud based on my impression of excerpts mentioned by others who reference it ....another crap book of
misinformation written by some asshole who doesn't know WTF he is talking about , but pretends that he does , just to make a buck , while
endangering the lives of anyone who trusts the information .... a real slimy kind of lowlife is what such authors are
I'll give away better information for free , and accurately provide references and explanations as best I can , along with some unpublished stuff
of my own invention as a bonus ...all for free
You just can't beat the price folks !
Maybe I should write an e-book and call it
Rosco's Good Old Country Recipes for Pyros , with patent references and lab notes .....guaranteed penis enlargement / mind expanding formulas
which even dullard dickheads can follow and see results in only thirty days ! Oh God , she blinded me with SCIENCE !  
Hmmm.....about ESPACENET , the wrapper for the pdf's has to be handled in an awkward way in order to recompile a standard pdf . First you have
to reset the document security setting for each saved page to " no security " , close and save changes . Reopen each page and delete the
" ghost pages " which contain no images so that each page is an image that is only " page 1 of 1 " instead of
" page whatever of some other number of total pages " , by deleting any preceding or following " ghost pages " which contain no
images . Close and save changes to each page . Now you should have security removed from actual single page saved files , and rename the files
according to their actual page numbers ,
for example ,
GB####### ( decriptive title ) ,
GB####### ( page 2 ) ,
and so on ......
Then insert the pages one at a time to the document first page , in the correct sequence , advancing the page view to each new page just saved , and
when the final page is added and viewed , close the assembled document and save changes . Simple huh ?
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Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
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She Blinded Me With SCIENCE
A real classic ........
Romy And Michele's High School Reunion: More Music Soundtrack Lyrics
--------------------------------------------------------------------------------
Artist: Thomas Dolby
( Lyrics ) Song :
She Blinded Me With Science .......
It's poetry in motion
She turned her tender eyes to me
As deep as any ocean
As sweet as any harmony
Mmm - but she blinded me with science
"She blinded me with science!"
And failed me in biology
When I'm dancing close to her
"Blinding me with science - science!"
I can smell the chemicals
"Blinding me with science - science!"
"Science!"
"Science!"
Mmm - but it's poetry in motion
And when she turned her eyes to me
As deep as any ocean
As sweet as any harmony
Mmm - but she blinded me with science
And failed me in geometry
When she's dancing next to me
"Blinding me with science - science!"
"Science!"
I can hear machinery
"Blinding me with science - science!"
"Science!"
It's poetry in motion
And now she's making love to me
The spheres are in commotion
The elements in harmony
She blinded me with science
"She blinded me with science!"
And hit me with technology
"Good heavens Miss Sakamoto - you're beautiful!"
I -I don't believe it!
There she goes again!
She's tidied up, and I can't find anything!
All my tubes and wires
And careful notes
And antiquated notions
But! - it's poetry in motion
And when she turned her eyes to me
As deep as any ocean
As sweet as any harmony
Mmm - but she blinded me with science
"She blinded me with - with science!"
She blinded me with
Attachment: blinded.mid (27kB)
This file has been downloaded 1457 times
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Sickman
Hazard to Self
Posts: 98
Registered: 9-5-2004
Member Is Offline
Mood: Icy and I see!
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Right on with Quicksilver; Rosco Bodine's posts are priceless. Also dido with the Preperatory Manual of Explosives. If I'm not mistaken
Rosco warned me about that book years ago.
He is right, it's a crap book. When I read through the pages I feel like the author is victimizing all of his customers by not telling them
upfront where he got the info and that it's not been tested by him and how dangerous it may be based on that fact.
As far as ESpnet is concerned I use it along with other search engines, but when I find a US patent I want, I go to Patent Fetcher cause it's just a quick and free PDF download.
[Edited on 19-10-2005 by Sickman]
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quicksilver
International Hazard
Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline
Mood: ~-=SWINGS=-~
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| Quote: | Originally posted by Sickman
As far as ESpnet is concerned I use it along with other search engines, but when I find a US patent I want, I go to Patent Fetcher cause it's just a quick and free PDF download.
[Edited on 19-10-2005 by Sickman] |
Good call...seems like a winner.
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quicksilver
International Hazard
Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline
Mood: ~-=SWINGS=-~
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| Quote: | Originally posted by Rosco Bodine
That " manual " is a complete fraud based on my impression of excerpts mentioned by others who reference it ....another crap book of
misinformation written by some asshole who doesn't know WTF he is talking about , but pretends that he does , just to make a buck , while
endangering the lives of anyone who trusts the information .... a real slimy kind of lowlife is what such authors are
I'll give away better information for free , and accurately provide references and explanations as best I can , along with some unpublished stuff
of my own invention as a bonus ...all for free
You just can't beat the price folks !
Maybe I should write an e-book and call it
Rosco's Good Old Country Recipes for Pyros , with patent references and lab notes .....guaranteed penis enlargement / mind expanding formulas
which even dullard dickheads can follow and see results in only thirty days ! Oh God , she blinded me with SCIENCE !
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GOD....You can't see how much I am smiling because that song IS my little quirk song.....it buzzes in my head when I start getting nuts with all
sorts of crazy crap around my house. My wife thinks I have "unique hobbies" and asks that I never share my interests with our friends (Like
I am going to discuss acid distilltion with an asst. American History prof. who always calls her classes "HER-STORY".
You know that Lagard has published some very seriously dangerious garbage. The other one I remember (but did not buy, of course) was some crap about
chem-weapons! No BS! The guy had stuff in there about seriously deadly poisons (real WMDs). And undoubtly he documented them as well as he did his
work on energetics. That is a time-bomb waiting to have some tragic repercussions. The whole thing with him that really ticked me off is that one
needs to actually have the book in one's possession to find the discrepencies, the typos, and the omissions. Thus paying money for the privlege
of frustration and annoyance. The damnist thing about it is that it doesn't seem like a crap book from a casual glance. That's the nastiest
thing. - Confession time... - I actually bought it when it first came out.
No bullshit stroke here but you DO have some strong background and commumication skills. That is what leads to success in both writting and teaching.
---- Lord knows you know your shit. But you can communicate. THAT, is a rare thing. I know a bunch of folks with Grad and Post-grad backgrounds that
can't communicate. Maybe you -should- write.
- - And actually I don't mean some "explosives_book" ( you could actually write an "explainitory-explosives" book detailing
all the pitfalls of other authors; that would be a help; as well as entertaining)......I mean a money maker like a high school chemistry book that
pulls kids in. That makes them not only understand but enjoy reading & practicing chemistry. A "Tutor text", not a text book per
se'. We know that all the lab shit that was done when I went to school (70's) can't be done now, so a lot of kids find chem dull. If
you could find stuff that intregues them using examples that would get past a school board you could pull down about a hundred grand for essentially
writting a thesis if the publisher pushes the book to a big school system.
Hell when I was in high school we had a teacher that blew crap up in class and no one thought a thing about it. He grew crystals (all sorts of toxic
stuff) and was a great communicator. And even jocks past his class because it was fun. Or you COULD do some antithisis-of-the-explosives book
genre'.....it would certainly sell as much as Lagard's stuff after folks find all the holes in the work.
Anyway, my Email is on the board, if you EVER want to bounce an idea around I would be very happy to check out what you're cookin' up.
[Edited on 19-10-2005 by quicksilver]
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Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
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picric acid from ASA , NaNO3 and 92% H2SO4
The most recent synthesis is one where some temperatures were closely watched and refined , and the nitration went very smoothly with absolutely no
surging nor red fume production , resulting in an exceptionally pure end product in 90% yield based on ASA . So the conditions are a good baseline
reference for any fine tuning of the process in efforts to get a little better efficiency . I believe it may be ultimately possible to get yields up
around 98% using some adjustments , but a 90% yield process provides a good place to start .
The synthesis followed my rule of thumb proportions which have always produced a good result , for each 1 gram purified ASA , 4 ml 92% H2SO4 , 1.8
grams purified NaNO3 .
In a 1 liter Erlenmeyer 24/40 flask was placed a 10 X 35 mm stirbar and 750 ml of
92% H2SO4 heated with stirring to 80 C .
187.5 grams of purified ASA was added in small portions as fast as it would dissolve in the stirred mixture over the course of 45 minutes , the
temperature gradually rising to about 105 C by the heat of reaction as the ASA dissolved . The flask was loosely stoppered with a hollow glass 24/40
stopper . Supplemental heating gradually raised the temperature to 118 C at the end of 90 minutes and the heating was discontinued . After standing
overnight the sulfonated ASA mixture had cooled and solidified to a dark colored transparent gel filled with small tan cubical? crystals of sulfonated
ASA . The mixture had to be reheated to 115 C to melt and with stirring redissolve so the mixture could be poured into the nitration flask .
Into a 4,000 ml Erlenmeyer flask was placed a heavy ( 62 gram ) 3 inch oval stirbar , and was set upon an old Type 1000 Thermolyne 7.5 X 7.5 stirrer
hotplate . Dry , sifted free of lumps , NaNO3 , 339 grams total was divided into three equal 113 gram portions in preparation for the nitration and
kept in sealed containers .
The hot sulfonated ASA mixture was poured into the 4L Erlenmeyer , the 900 ml of hot liquid not quite deep enough to completely cover the stirbar .
An 18 inch thermometer , 260 C 75 mm immersion , was leaned diagonally in the flask with its tip sitting in the curved bottom outer edge inside the
flask . A 4 inch flexible ventilation duct mounted in an extension ring was positioned next to the flask opening for removal of any fumes by the
remotely located blower whose intake air is drawn through the 4 inch hose and discharged outdoors . A second larger fan was situated next to the low
workbench to pull a gentle draft in the same general direction as the higher velocity intake adjacent the opening of the flask . These sorts of
precautions are essential for safely conducting a nitration on a molar scale . The nitration was conducted outdoors in an area shaded from direct
sunlight .
The stirrer was started and run just below the speed where splashing of the shallow liquid occurred , with portions of nitrate begun with the mixture
at 95 C ,
the decarboxylation foaming occurring instantly on contact from the first addition of nitrate . The additions were made steadily in portions using a
teaspoon ,
adding the nitrate in heavy sprinkles into the vortex , the reaction temperature rising and maintained in the range of 100 to 103 C by regulating the
rate of additions of the solid nitrate . The effervescence of CO2 from decarboxylation
occurred freely with no persistent foaming through the end of the addition of the first of the three portions of nitrate , and midway into the second
portion at 1 hour from the beginning of the nitration . At this midpoint , the effervescence becomes more sluggish and the viscosity of the mixture
is increased , the foaming from decarboxylation causes a volume increase for the mixture , and the additions must be slowed considerably . At the end
of the addition of the second portion , the heat of reaction alone is insufficient and very gentle supplemental heating is added to maintain 103 C .
About 15 grams into the final portion of nitrate , the time from the beginning of nitration will be 1 hour 45 minutes and some picric acid will begin
to precipitate in the thickening mixture , greatly slowing the remaining additions . The stirring speed is increased and the heating is raised to 106
C by 2 hours from the beginning of nitration . The remaining nitrate additions go very slowly and will require as much time as all of the nitrate
previously added . The temperature is very gradually allowed to increase over the remaining additions of nitrate , the following observations were
made for
reference concerning the elapsed times from the beginning of nitration , and the total amount of the third portion of nitrate having been added .
@ 2 hours 15 minutes , 30 grams ,
107-108 C
@ 2 hours 30 minutes , 40 grams ,
109 C
@ 2 hours 45 minutes , 45 grams ,
111 C
@ 3 hours , 55 grams , 113-114 C
@ 3 hours 10 minutes , 60 grams , 114 C
At this point the mixture has become a very thick slurry and additions are suspended for a time . There is an accumulation of solids upon the walls
of the flask and the thermometer is used to scrape the material into the vortex so the mixing can be accomplished . This manual assistance is
required several times during the course of the remaining nitration . Close temperature control is essential to limit temperature to 114 C , as there
are indications of an induction point for decomposition at about 116 C .
@ 3 hours 30 minutes , nitrate additions cautiously resumed , 113 C reaction temperature
@ 3 hours 45 minutes , 70 grams , 112 C
@ 4 hours , 85 grams , 112 C
@ 4 hours 30 minutes , 113 grams completion of addition 110 C , Supplemental heating very slightly reduced , reaction allowed to continue
@ 5 hours , slowly finishing reaction has cooled to 100 C and reaction appears complete , the temperature is subsiding
and the mixture is thinning as the temperature falls . Supplemental heating discontinued completely .
@ 5 hours 10 minutes , 97 C , mixture is now much thinner and is a free stirring smooth slurry with no foam whatsoever ,
a suspension of fine yellow reflective crystals of picric aicd suspended in a water clear colorless supernatant liquid of spent acid and bisulfate in
solution
@ 5 hours 20 minutes , 92 C , cautious and gradual dilution of the stirred mixture was begun by streaming water from a wash bottle onto the inner
walls of the flask and allowing the stirred mixture to be gradually diluted , limiting the temperature rise to 100 C , a total of about 1 liter of
water was added . The dilution was accompanied by a fair amount of red fumes being evolved , believed to be the result of decomposition of
nitrosylsulfuric aicd present in the spent nitration mixture .
The total volume of the diluted mixture was at the 2,000 ml graduation on the flask .
@ 6 hours , 74 C , ice is added to bring volume of diluted mixture to 2800 ml ,
and to speed cooling .
@ 6 hours 15 minutes , 23 C
Flask is placed in refrigerator to complete the precipitation .
The crude picric acid is filtered and blottered , and the still damp crystals are redissolved in 5200 ml boiling distilled water . On slow cooling ,
excellent crystals are formed , which after filtering and drying , are obtained 198 grams from the first crystallization , 83% yield based upon ASA ,
of exceptional quality picric acid .
An additional second crop of crystals ,
16 grams is obtained by boiling down the filtered liquid from the first crystallization to a volume of 1300 ml , and allowing to cool .
Yet a third crop of maybe 2 grams can be obtained by concentrating to 300 ml and cooling .
There was absolutely no dark colored impurity produced to tint the solutions or to precipitate and contaminate the product . The picric acid produced
was
absolutely free from any contamination byproducts .
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ordenblitz
Hazard to Others
Posts: 259
Registered: 18-7-2004
Location: Northwest
Member Is Offline
Mood: Bohr'd
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Thank you very much...
I was wondering when you were going to post:
Rosco's Good Old Country Recipe for TNP
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Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
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@ordenblitz
You are very welcome , as is everyone
who has also been interested in PA from ASA by way of the modern variation on the ancient process using NaNO3 and the
sulfonation mixture .
It's overdue that I paid close attention to the temps and times and set forth the details for a clean nitration . I will probably experiment
further in refining the process . The possibility of increasing the amount of H2SO4 by 10% or so may
have merit for yields and safety . This
process which I have worked out is still very much EXPERIMENTAL , even though it has produced the results I have described , it is possible the
reaction may not * always * follow exactly the same course every time for me or for others .
I will emphasize that those temps are already " pushing " the reaction to cut down on the time requirement , and are
not far below safe limits , but at the same time are about right for what is needed to get the job done . Sorry there's not more headroom
allowed for getting sloppy with the additions , but such is the reality for the thermodynamics of this particular nitration . You need to be familiar
with the heating response of your hotplate and not overshoot the mark , because the mixture absolutely won't forgive it ,
and may require the expansion room afforded by a large reaction flask .
A minor error * may * result in a foaming which itself lowers the concentration of the reaction mixture and self regulates the reaction to oppose a
potential runaway , so that the reaction subsides on its own and the nitration can be resumed . However , this is not guaranteed and depends on just
how
" minor " is the error outside of the window conditions . I am not about to deliberately cause a runaway out of curiosity to explore the
parameters of such a scenario , not without remote manipulation and a good solid bunker
from where I can watch what happens on a video monitor
There are inherent dangers in all nitrations , but this one appears to be reasonably predictable and safe , if the process is carefully done .
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quicksilver
International Hazard
Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline
Mood: ~-=SWINGS=-~
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| Quote: | Originally posted by Rosco Bodine
There are inherent dangers in all nitrations , but this one appears to be reasonably predictable and safe , if the process is carefully done .
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I have not heard much about runaway reactions w/ nitration of phenols, I have heard about it w/ amines and the typical nitric-ester issues. but not
with Phenols. I know it's possable w/ any nitration but yet I have heard little spoken of it.
You have been on these boards a long time; have you ever heard about someone having a runaway w/ PA?
The reason I ask is that during the "red-goo" issue I heard many people push the limit with phenol nitrations and the runaway / safety issue
was rarely discussed.
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