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The_Davster
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| Quote: | Originally posted by Rosco Bodine
Are you going to weigh your yield and do the math to get the percentage ?
( 27.57 grams would be 100% of theoretical ) 24.8 grams would be 90% of theoretical .
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11.6 g of pale yellow DPPP + 1.2g pure white DPPP recovered from filtrate=12.8g
46.4% yield
Very little DPPP was lost during the procedure. At max a gram of DPPP. But even taking that into account a terrible yield for a procedure that is
reporting 90%. Is it possible that some DPPP sublimated during drying. Damn, and just when we think that a appropriate procedure has been worked
out.
Anyone else have yields using a procedure like Rosco's on p19?
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Pyroz
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i always get a good solid yield... you might want to let the reaction take place over a little longer period of time. keep you reaction temperature
stable around 2C-3C or less.
oh yeah--- you might want to see some damage for yourself. Remember these are .223 rifle shell cases filled with 1 gram of explosive. DPPP vs AP test.
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Rosco Bodine
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An experiment is in progress now regarding the reverse order of addition for the peroxidation step , that is to add the precursor very slowly by drops
to the well stirred H2O2 at -10 to 0 C . Presently about two thirds of the precursor have been added and the mixture is orange with almost zero
crystals , maybe an isolated few crystals but no massive precipitation as when using the other order of addition . No real noticeable fumes either ,
the entire dynamic of the reaction is quite different .
I plan on leaving the reaction mixture in the salted ice bath overnight when the addition is finished . Will update on the results when I have
anything further to report .
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Matsumoto_Hideki
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Suprise you are not getting a runaway ?
Well, I am officially letting the chem department in on this DPPP project of ours.
A collegue of mine thinks that the punjent smell is most defentlyMESITYLENE an aromatic hydrocarbon C9H12 and colour possibly by some crude Mestityl
oxide.
Now about adding your reactants in backwards, I tried this once never to repeat it again.. as the result was massive overheating ..think a
yellowstone national park geyser... This of course was partly to do with the reaction being done at room temp.
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Rosco Bodine
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Mesitylene and mesityl oxide are both colorless . They are irritants however , so that could be relevant .
Adding the precursor at about one drop every 2 to 3 seconds to the H2O2 in a beaker sitting in a salted ice bath on a magnetic stirrer and having a
thermometer in the mixture the entire time , the peak temperature I got was
- 2 C minus two degrees , and the average was about - 4 C , so you are simply not controlling the reaction closely if you got that sort of runaway .
There are crystals forming in the reaction now that the addition is finished , and the mixture is stable so far at - 4 C .
[Edited on 11-1-2005 by Rosco Bodine]
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Pyroz
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Very interesting...I wonder what those crystal might end up actually being? humm, curious to know.
I hope more people begin testing the power of supposed DPPP product so we can get an accurate depiction of what is going on here.
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Rosco Bodine
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Two hours after the end of the slow dropwise addition of the precursor , the reaction mixture is now a thick slurry of fine crystals , and the color
of the mixture
is bright yellow . A few globules of insoluble black goo are present , a small quantity perhaps a quarter gram total unreacted material from the 100
ml of precursor which was used for the reaction . One test which may shed light on the difference between samples is a side by side identical weight
sample , test for weight loss on heating for a fixed time .
I have some very accurate scales for the before and after weighing .
UPDATE :
Eight hours past the end of the addition , after standing overnight , the mixture in the beaker has set up to a semi-solid consistency of nearly white
cystals having a very pale yellowish green color . The ice bath is almost completely melted and the temperature of the mixture has risen to 5 C .
The pasty mixture is loosened by manually stirring it with the thermometer and is just barely fluid enough consistency to be stirred by the magnetic
stirrer set to maximum if given an assist with a little help to get the mixture moving with the thermometer . Some larger globules of insoluble black
goo have separated and accumulated on the bottom . Stirring was immediately stopped to avoid breaking up the separated insoluble material and
contaminating the crystals . The reaction mixture will be allowed to stand awhile longer in the melted bath and then dumped into a larger container of
icewater
to separate the crystals , and rinse them away from the insoluble black goo which separated during the crystallization . There appears to be a couple
of grams of the insoluble black material . I wish to dilute some of the separated goo with acetone and see if has a color , but simply appears black
as would some concentrated
portion of an intensely colored dyestuff . I am curious as to whether this separated material is the substance responsible for the red tinting of the
precursor mixture originally .
UPDATE : After another hour the color of the crystals is faded more and now the color of the crystals is pure white , the temperature is 10 C .
Update : The reaction mixture has been diluted to twice its volume with water and
the crystals have been decanted and rinsed away from the insoluble residue ,
nearly all of which is adhering to the stirbar . I overestimated the amount before and the quantity appears to be no more than a quarter gram to a
half gram of insoluble material , which is no longer globular but has solidified to a light brown solid , not really intensely colored as would be a
dyestuff but more caramel color of low intensity . The white crystals are very nearly the density of water , sink only slowly and some crystals float
or suspend at neutral buoyancy from adherent bubbles of oxygen from the peroxide . There is no noticeable smell except ( I hate to say it ) there is
a faint clear clean odor typical of AP , having none of the irritant effects of the product
from the other order of addition . It is too soon to be conclusive , but this stuff looks like AP and smells like AP . I'll know for sure after
filtering and drying and doing a weight loss on heating comparison with a sample of known AP made by the usual method .
[Edited on 11-1-2005 by Rosco Bodine]
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Joeychemist
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Nice!
Good work Rosco!
So it would appear that reversing the process will also work, but may produce AP  .Hmmm......
Also as i have mentioned before, that brown insoluble junk burns producing a thick black smoke, it is highly flamable but does not deflagrate. I would
suggest you try burning a sample.Just to be sure we are on the same page.  
[Edited on 11-1-2005 by Joeychemist]
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Rosco Bodine
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Is "DPPP" for real or only "tinted" AP ?
That is the page we are on about right now . And I intend to get to the bottom of this with some no bullshit analysis and sample comparisons that
will nail this down by instrumental measurements and
scientific method which won't leave any wiggle room for opinions or high hopes .
I have rectangular crystals right now from the sublimation overnight of the side by side samples of AP and "DPPP" and the crystals from
sublimation of the "DPPP" look just like AP .
The most interesting thing to me at this point is the extreme exotherm that occurs upon the very initial part of the peroxidation when the peroxide is
added to the precursor in the usual order of addition , and the irritant byproduct . Both of these things tend to strongly suggest that a quite
different reaction mechanism is at work when the reaction order of addition is done that way . I am not yet ready to give up on the idea that DPPP is
indeed for real , but there are some good reasons for the skepticisms expressed by Axt and others , even though these would seem to be disproven by
the witness plate tests .
I have also wondered if DPPP may actually be AP but occurring as an unusal and unidentified polymer , not the trimer nor the tetramer , but perhaps a
"hexamer" form . Sometimes a specific polymer form and crystal form can demonstrate quite different properties from other forms . There are
a lot of angles to look at in studying "DPPP" to discover the real story on exactly just what it is , and that could turn out to be
different from what Mackowiak says . Let's reserve our conclusions until we do and interpret the results of various experiments which may shed
some light on what are valid questions about the curiosity which we are calling DPPP , and which may well not even be DPPP but may not be garden
variety AP either .
[Edited on 11-1-2005 by Rosco Bodine]
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Joeychemist
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Cursed!
A different version of AP is a possability. (Maybe we'll get the patent on it) As of now I don't know. As I have said Under a microscope I can clearly see 3 different crystal forms, they appear to me to be
DCAP,TCAP and what I thought were "DPPP" crystals. maybe I was wrong in asuming it was "DPPP",maybe you're right, maybe their
is somthing else happeing. Does it smell like "funky AP" or plain old runofthemill AP?
Maybe we should let Hideki bring it to his school lab, better his ass than ours right?
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Rosco Bodine
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About the smell now it is on the filter I can't tell because I neutralized it by flooding it on the filter with 2% ammonium hydroxide , let it
drain through and then flooded it again with distilled water , drained and rinsed again with distilled water , leaving a slight odor of ammonia on the
still damp crystals which is the only smell I can detect . But before the rinsing and neutralization it smelled like plain AP and looks like AP in
every respect but one , it doesn't glitter like AP even though it is snow white in color .
The possibility of a different isomer of AP seems likely . The tetrameric AP is something which looks and smells very close to trimeric AP but has
slightly greater power and way less volatility . I haven't quantified the volatility but the terameric sits happily in storage in a loosely
covered container for *years* without dissipating greatly , while a like sample of the trimer sitting right beside it and stored exactly the same way
is 90% evaporated away . So it is entirely possible to have different forms of AP which generally look and smell the same but most definitely do not
behave identically otherwise .
UPDATE : The crystals are very nearly dry and strangely enough the crystals seem to have almost no detectable odor at all ,
not the distinct AP odor that they had when wet . I'll know more when the crystals are completely dry , but as I recall AP has a very slight
odor all the time , wet or dry , and these white crystals are at this point of drying nearly odorless which may or may not change when they are dried
completely . To my nose regular AP has a slight aromatic odor which is similar to the immediate smell of the discharge of a firearm using ammunition
loaded with double base smokeless powder , which could itself be an odor related to traces of acetone used in the manufacture of the cordite .
AP ( in the unburned condition ) smells very similar to that transient smell of fresh gunsmoke which is slightly fragrant and dissipates in a second
or two to a heavier smoky odor . Does anyone else detect this , any shooters out there ?
The material is basically dry now and it does have a very faint AP like odor barely discernable to smell by getting the nose right down to a half inch
away from a paper plate covered with crystals in a layer 3 mm thick . The smell still seems fainter to me than regular AP , but it has been awhile
since I made a batch of AP and what I have on hand is a saved sample . I will let the crystals continue to air out overnight and see if there is any
further decrease of the odor before I weigh the product and transfer it to a container for keeping . There is plenty for further testing against the
existing sample of "DPPP" which I have already .
I may take the remaining half of the refrigerated precursor and subject it to the conventional order of addition at the same temperature and slow
rates as were used for producing this sample to
observe what differences occur using the same batch of precursor both ways .
[Edited on 12-1-2005 by Rosco Bodine]
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Matsumoto_Hideki
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So if colour isn't coming from Mesityl oxide ?
Well, why would one say mesityl oxide perhaps this person ment mesityl oxide interating with chlorine
forming a benzene chloride ???
Again i am having the university figure this stuff out for us/// we will soon get some resuts.
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PainKilla
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Mesytil Oxide itself is a ketone and can (I would assume) form peroxides....having discussed this with mumbles eariler, I think it's been
concluded (others have doubts as well) that this is NOT DPPP, but possibly even TCAP... which would not surprise me, since every thing seems about the
same. Benzene can form peroxides too, so it could be that we are getting some wierd benzene peroxide. I can't pretend to know though as I am
still a super novice in chem. What does puzzle me however is where exactly this colour is actaully coming from, as mesitylene and methyl isobutynel
ketone (mesytyl oxide) are both basically clear or pale yellow. I can't imagine any Cl compound making a deep deep red, but where else could the
answer lie..... I am expecting some intersting results soon from a certain someone .
Also, I am sure SOME phorone is formed, but I think it plays little or even no role in foming this compound. They have disticnt melting and
decompostion point, so if anyone would like to test this out.... Also, is there crystals (I dont remeber...thread is a WEE bit too long) when the
"DCP" is frozen.....because there SHOULD be assuming phorone IS actually formed..... from what I recall there is not and this further leads
me to believe that no actual phorone is made. With "DCP" I think its melting point would be lower, but nontheless still achievable with
freezer temperatures, again, I am not the most advanced person in the field (translates to I suck) but it should be tested as much mroe conclusive
results may be obtained whenwe actually know what we are working with....
This could be some derative of chloroacetone too, speaking of which if phorone is not a byproduct... then you better watch how you handle this as
neither benzene (or benzene/zyl?l chloride) are pleasent things to be working around, and neither is chloroacetone or mesytilene compounds in
general... basicallly be careful ....
What are more proficeint in chemistry peoples' input on this? Also, does chloroacetone form peroxides of any kind?
[Edited on 12-1-2005 by PainKilla]
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Rosco Bodine
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The focus at this point is as I understand it is to rule in or out that what we have been calling DPPP , may be a form of AP , either regular AP
contaminated or coordinated with some other substance , or possibly AP in some unknown state of polymerization . The side by side sublimation
experiment with parallel samples sitting in the same bath in identical culture tubes were producing
identical results when I checked a few hours ago . In effect I am slowly distilling
the solid samples from the bottom of the culture tubes and condensing and crystallizing the vapor on the colder upper
inside surfaces of the tubes . The accumulation of crystals from sublimation are depositing at the same rate and look identical , both white
rectangular crystals .
A melting point on each respective type of the sublimed crystals , followed by a melting point on a mixed sample of the two will be revealing . If all
three melting points are the same , the two samples of sublimate are the same substance .
I just happen to have on hand some melting point capillary tubes .
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Pyroz
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--they certainly don't act the same when detonated.. they may appear to be the same crystal- wise but they must have different densities.
[Edited on 12-1-2005 by Pyroz]
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PainKilla
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Yes but this could also result in different cooling techniques....when I left my AP in subzero temps, I got crystals nearly impossible to see, and it
was very dense and detonated seemingly stronger....it just turned it it was standard TCAP/DCAP with small crystals.... try making AP exactly the same
minus the heating and then test the results. I have a feeling this is just regular AP, at least for some of us.
[Edited on 12-1-2005 by PainKilla]
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Rosco Bodine
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The tests certainly suggest something is different about the two substances explosive power . But why ? Suppose that what is being identified as DPPP
is actually a binary compound or composite of AP along with something else which is an unknown volatile explosive substance , or a substance which
acts as a detonation catalyst for AP , and possibly for other substances as well . The unknown material being responsible for the apparent power of
DPPP might be an effective additive for other explosives .
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The_Davster
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I personally feel that "DPPP" is different from regular CTAP. Whether the structure of diphorone pentaperoxide is correct in the patent or
if this is some AP varaint( >trimer), Just from what I have observed this does not seem to be the plain old garden variety of AP.
In any case I am eagerly awaiting the results from Matsumoto_Hideki's university.
Unfortunatly my experimentation is on hold for a few weeks due to exams. I do not experiment too close to exam time after an incident in which I got
a bad mark on an essay as a result of ( I believe) exposure to chloroform fumes the night before(Oh, and because I must study ).
[Edited on 12-1-2005 by rogue chemist]
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Pyroz
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strange
The "DPPP" product was tested against 1gram of cold formed AP (made at -2C) not warm flakey stuff. I'm all too familar with the
difference between cold formed AP and AP formed at 10C+. So this is why I'm thinking something else is going on here. I have done test after test
and each time ---"DPPP" looks if it has at least double the power of the 1gram AP charge, if not, more.
I am finding all of this truely bizarre.
------------------------------------------
*news flash* I just finished baking some AP in my oven on 110F. The AP is gone--- completely vapoured off while the DPPP has formed a white crust
which smell like the inside of a pingpong ball---reminds me of an acidic camphor. Its still very explosive after heating. Interesting you may want to try this out for yourself.
[Edited on 12-1-2005 by Pyroz]
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Rosco Bodine
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Indeed it is a thought provoking line of investigation which we are about here .
The "melting point analysis" which I mentioned above is a very old but reliable tool for analysis , and I hope it will be one of the
conventional tests done by others at the decently equipped laboratories where this sort of testing is pursued .
It seems every idea I have involves more work for me . And since I don't have a regular melting point apparatus I have to do each of such tests
absolutely manually . Such tasks are so easy with all the right equipment .
I believe I will run the synthesis again on the other half of the precursor , using the more conventional order of addition of adding the peroxide to
the precursor , so I can compare the product from the different methods run at identical temperatures . Then I need to take a break because of other
business which requires my time . The followup tests can be done later with the samples in hand .
[Edited on 12-1-2005 by Rosco Bodine]
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PainKilla
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Well it seems that tradional AP is not formed but i still thing SOME sort of AP is formed... perhaps some chloroacetone derative, with the Cl acting
as an extra catalyst or something, maybe its tetrarameric AP, or maybe even pentameric? It's late but I will do the stiochimetry tommorow and see
if it works out relative to the ratios for DPPP....
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Rosco Bodine
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Tetrameric is a more dense and reflective material than the trimer which is as refective as frost itself . Tetramer crystals are heavier and more
coarse granulation than the trimer . This material we are calling DPPP is very close to density of water , at least the unrecrystallized material is
fairly low density near 1 g / cc for the crude material , and it does not have that reflective crystalline glitter , but has a more matte white
appearance . Now the sublimate from the sample of DPPP does glitter like frost in sunlight .
So go figure .
[Edited on 12-1-2005 by Rosco Bodine]
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The_Davster
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| Quote: | Originally posted by Pyroz
*news flash* I just finished baking some AP in my oven on 110F. The AP is gone--- completely vapoured off while the DPPP has formed a white crust
which smell like the inside of a pingpong ball---reminds me of an acidic camphor. Its still very explosive after heating. Interesting you may want to try this out for yourself.
[Edited on 12-1-2005 by Pyroz] |
Yay, acidic camphor, also known as chlorobutanol. The smells of camphor and chlorobutanol are very close. So now we know that the same variety of "DPPP" can be produced by heating the pale yellow variety of
"DPPP" as can be by allowing the reaction mix to stand overnight after peroxidization.
| Quote: | Originally posted by Rosco Bodine
and it does not have that reflective crystalline glitter , but has a more matte white appearance .
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The "DPPP" I recieved after allowing to stand overnight did have a reflective crystalline glitter and was not as powdery as the pale yellow
"DPPP", some very small crystalls were visible.
EDIT: I keep spelling "pale" as "paly"
[Edited on 12-1-2005 by rogue chemist]
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Rosco Bodine
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Yeah that's one of the reasons I need to repeat the synthesis at the same temperatures and see if the crystals
would look more similar in size and reflectivity . The slower crystals form ,
generally the better their appearance .
I'm really mostly interested in purity ,
not so much focused on appearances
because I know that can vary greatly
even for the same pure substance .
Color however is another matter entirely
and since my existing sample of DPPP is
slightly tinted yellowish , I want to try to
get a sample of the white product from
the next synthesis .
[Edited on 12-1-2005 by Rosco Bodine]
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Matsumoto_Hideki
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So this verifies the formation of Phorone as well !
In order for chlorobutanol C4H7Cl30 to be produced it has to be forming around the cracking of acetone to phorone.
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