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Rosco Bodine
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| Quote: | Originally posted by rogue chemist
Rosco, I tried a slight variation on your method of reacting the HCl and acetone. 26mL of HCl and 28mL of acetone were mixed at room temp (18C) in a
250mL flask. The flask was outfitted with a 2 hole stopper with a thermomehter in one hole and in the other hole was a 3' lenght of glass
tubing. Upon mixing the HCl and acetone in the flask the temperature shot up to 36C. THis was allowed to sit at room temperature for 1.5h, at the
end of which the solution was only very slightly yellow. Still mostly clear. What color was your solution after sitting at room temp for 1.5h,
Rosco? |
That is the same color I saw . The size of the batch is going to cause variations in the color
development because of the difference in conservation or radiation of the exotherm from the self-heating . A bigger batch would tend to develop a
higher temperature and react for a longer time from its own heat of reaction . The idea is simply to let the solution self-heat from its own reaction
, and when that self-heating diminishes to add gentle supplemental heating to sustain the reaction until the color is fully developed to that intense
deep ruby red color that sheets into a bright yellow film when it is swirled against the walls where a thin layer can be observed . There can be
exceptions , but often it is true that such an intense coloration is an indication of a high concentration of a particular compound , so this was
thought to be a likely visual indicator as a "marker" for the reaction point where there is substantially a single product in solution ,
hopefully the desired precursor . Experiments will show what is the exact point of color development which provides best yields , but my guess is
that this intense coloration is very close to that point if not perfect . | Quote: | | This flask was transfered to a hot water bath. Since I was doing this outside and had set up the bath earlier when the flask was put in the bath the
temp of the flask dropped to 15C. over a period of 20min the temp of the hotplate was adjusted to end up with a fairly constant temperature of
60-63C. Acetone condensing was noticed at around 60C in the piece of glass tubing. The acetone stopped condensing after around 20 min. Total
heating time was just under 2.5h( 30 min @ 55-65C +2h@60-63C). After this time The solution was an incredible deep red, like you Rosco, no tea like
color. If one swirls the flask the residue on the flask walls appear deep yellow. There was a very slight slick of oily substance on the surface.
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Your description matches what I saw . After removing from the heat , I allowed my mixture to stand
overnight at about 15 C and then refrigerated it . I
wanted to observe how much further the reaction would go over the next few hours without heating , to get an idea how close the timing of the
peroxidation
needs to be . It appears that the further reaction of the acetone and HCl slows down greatly once removed from the gentle heating of even a couple of
hours ,
following the initial self-heating , and the reaction virtually stops altogether when the mixture is refrigerated . This is good
because it allows for "taking a break" from the experiment or starting one batch of precursor and keeping it refrigerated to
resume the reaction later , being able to simply watch for and use the color development as an indicator of the reaction progress . | Quote: |
When peroxidizing this what is a good temp to keep it at maximum? I think I will try 0C or 10C. Any ideas? |
It depends on what method of stirring and how closely you control the addition rate of peroxide , what is your strategy . I
don't know what is the ideal so I just made a guess as to how I should proceed . I haven't yet peroxidized the
same mixture as we are discussing here .
My strategy will be to add 2 or 3 ml of HCl to the stirred precursor , in a container
sitting in a not yet filled water bath , and then to add by drops the peroxide , while
allowing the stirred mixture to heat up
slowly from its own exotherm , controlling
the heating by rate of addition to a peak of about 65 C , when about 10% of the
peroxide should have been added . Then
I would add the ice to the bath and allow the temperature in the stirred mixture to fall to 10 C before resuming addition of the peroxide at such a
rate as to not exceed 15 C for the mixture to the end of the addition , continuing the stirring for 30 minutes past the end of the addition .
The stirring is stopped and the suspended
crystals clump together in suspension looking similar to curdled milk which is not
yet separated into layers . After standing
the crystals should rise to the top as a floating raft . I simply dumped the entire
mixture into its melted cooling bath and then skimmed the crystals after a partial neutralization of the bath with the calculated amount of ammonia
water .
You need to calculate the neutralization equivalent because any great excess will start to decompose the DPPP . If you go to far with the ammonia ,
vinegar seems to be good for bringing the pH back to slight acidity . The crystals skimmed from the top are rinsed on the filter with distilled
water .
P.S. This is an interesting material , but I know already that its deficiency is going to be its odor and its irritating vapor . This shit
absolutely reeks of a capsacin like vapor which irritates the eyes , and generally fucks up your sense of smell and taste for a day after being near
the stuff . It is for damn certain physiologically active . Sprinkle some DPPP around any shrubbery you don't want dogs to frequent as a
place to pee and you can be guaranteed they will get the message ! This stuff would make a better fumigant than formaldehyde . It
first seems to have a sort of "light" odor
until you are near it for awhile and realize that it literally permeates everything . I personally don't like the odor of the stuff so my own
experiments will be dutifully scientific , but there will likely be no long term fascination with DPPP for me simply because of its disagreeable damn
shitty odor . It's in the same category with methylene chloride and formaldehyde and
some other unpleasant materials . So that is going to diminish interest in the material .
[Edited on 8-1-2005 by Rosco Bodine]
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Joeychemist
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that sqaures with me
Ok, it sounds as if every ones stories are squaring up pretty close, I agree with all of the above and will second that.
Rosco, you're right, this stuffs smell is by far its least appealing quality. Have you tested the product yet???Hmmm..???
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Rosco Bodine
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Other than to light off a small amount that was a residue on some still damp filter paper , I haven't fired any of the stuff . The damp material
did flash quite
energetically with the usual AP whoomp and a little bit of snap crackle pop included that was interesting
Chloramine could be what is causing the trouble with these reactions where ammonia is used for the neutralizer .
I'm going to use a basic sodium salt
next time and see if a lot of the "mysterious" irritant vapor will happily
not be a problem .
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Joeychemist
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I wish
Sadly to say I don't think that there is a way to fully get rid of that awful odor.
I can tell you that I have used ample sodium bi-carb and ammonia to wash this stuff and nothing, the smell still remains and I still cry every time I
get too close. The last batch I had was about 4 days ago and it still stinks in my laundry room still stinks of it.
The metal witness plates I used also still stinks of the DPPP smell too. Fucking fowl.
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Rosco Bodine
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So are you saying the eye and nose stinging "mace" like vapor is present even if you don't use any ammonia at all , but
neutralize with soda instead ?
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Joeychemist
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that's what I'm saying
Yeah, that's what I’m saying
I washed this stuff under countless portions of water and sodium bi-carb and it would still irritate my eyes and mucus glands and make me dizzy if I
was around it too much.
I also tried washing one batch with both ammonia then the bi-carb and there was no noticeable change in the odor or the manner in which I was affected
by it.
I really firmly believe that this stuff is dangerous and slightly if not very toxic. I think I'm going to go to the pet store and buy some rats
to test some things out. I wonder what the LD.50 for a rat would be?
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Rosco Bodine
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You know that's exactly what I was thinking is that DPPP may be a better poison than it is an explosive , and I plan
to introduce some ant mounds to the
saved filtrate to see how well they like it
The smell of DPPP has an uncanny similarity to some strong insecticide odors
like chlorodane or the fungicide orthenex .
In fact I have wondered if perhaps some
chlorinated byproduct may be responsible for the odor and effects , or if perhaps the
DPPP itself may not be accurately described by the patent , and there may
perhaps be a chlorine somewhere on the molecule .
I wonder if urea would have any reaction with DPPP or would be of any value in the rinsing .
[Edited on 8-1-2005 by Rosco Bodine]
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Pyroz
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I too had a serious problem with the smell. So I washed the DPPP crystals in pure water w/ bicarbonate (I tried sodium hydroxide and water and that
does seem to work well too)--- and then I allowed DPPP to air dry inside of a plastic bag filled with bicarbonate in a plastic container.
After 1 week the smell was less noticable when the product was fully dry. Right now DPPP product that I have made does not smell that much--- its much
weaker like mildly acidic Camphenol.
Is DPPP toxic?--- likely it is a very mild poison--- I doubt it could be used as a poison. It isn;t really corrosive either if you get it on your skin
like AP does nor does it seem to form metal peroxides with copper or most other metals--- fairly intert i think.
In fact I have wondered if perhaps some
chlorinated byproduct may be responsible for the odor and effects...
I have often wondered this myself--- it seems that the left over liquid in the DPPP product maybe resposable for causing the acidic smell.
[Edited on 8-1-2005 by Pyroz]
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Joeychemist
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Wait a second!
You may be onto something there pyroz.
There is air indeed trapped inside these crystals (that’s why they float) so there may indeed be chlorine or something becoming trapped in these
crystals as they are forming. I think I’m going to go buy some more desiccant and see if I can drive all the moisture out after I recrystallize in
acetone. This could also explain the crackling when it is burned.
[Edited on 8-1-2005 by Joeychemist]
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Matsumoto_Hideki
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Crackling when it burns? really?
I haven't noticed this when DPPP is fully dry!
I was also wondering if a small amount of chlorinated product was leftover, and I think I know what it might be "chloroxylitol" ? what ever
the substance is, it is a waxy gummy yellowish material and you will see it during your peroxidation sticking to the sides of the container. This
makes up the majority of the smell.
[Edited on 8-1-2005 by Matsumoto_Hideki]
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Rosco Bodine
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A urea solution rinse still seems like a good idea to me . Urea can complex
both chlorine and hydrogen peroxide .
But one of the first things I want try with
the fully dried DPPP is to make some putty .
A good binder syrup is 20 grams of Bullseye pistol powder allowed to gelatinize on long standing with 60 ml acetone in a sealed bottle . For AP
putty
about 1.5 to 1.75 parts by weight of the binder syrup to 1 part AP , mixed well
with a popsicle stick on a baggie seems
about right . The partially dried material can be shaped and then hardens into a rigid mass as the residual solvent evaporates after a couple of days
. But the AP putty , while powerful , doesn't really have the brisance
to make a good detonating composition and is more of a very noisy novelty than anything else . It seems almost , but not quite quick enough as a
detonator charge . So I am curious as to how DPPP might perform if substituted for AP in such a putty . Maybe a DPPP putty would be a more useful
composition .
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Pyroz
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| Quote: | Originally posted by Joeychemist
You may be onto something there pyroz.
There is air indeed trapped inside these crystals (that’s why they float) so there may indeed be chlorine or something becoming trapped in these
crystals as they are forming. I think I’m going to go buy some more desiccant and see if I can drive all the moisture out after I recrystallize in
acetone. This could also explain the crackling when it is burned.
[Edited on 8-1-2005 by Joeychemist] |
The DPPP that I made sinks like a stone in water. So it is quite dense. I think their is some gas left over in your product...
Rosco:
You are definetly on the right track with your DPPP putty! I'd like to try some too--- the NC, NG, HMTN binder present in rifle power could
certainly help. I've just made a length of DPPP detcord and we will see what comes of that. No new tests yet--- I'm under 1' of snow at
the moment and I'm making use of the low temperature outside for various exploding projects
[Edited on 8-1-2005 by Pyroz]
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Joeychemist
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what???
| Quote: | Originally posted by Pyroz
The DPPP that I made sinks like a stone in water--- it is also denser than vegetable canola oil. So it is quite dense. |
How can DPPP crystals have a higher density than a thick heavy viscous liquide like vetable oil?
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Pyroz
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sorry, that was an error... pls ignore it... it is heavy material. i put a compressed tube of 1 gram DPPP in ethyl alcohol it sunk, I placed it in
water---it sunk---, I place the same material in light vegtable oil and it appeared to sink--- and then bobbed up to the surface.
---sorry, i was mistaken.
i'm trying that whole density test thing--- humm ,what else can I use for a liquid medium?
[Edited on 8-1-2005 by Pyroz]
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Joeychemist
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The whole density thing?
| Quote: | Originally posted by Pyroz
i'm trying that whole density test thing |
You don’t know how to calculate the density?
Well then, I suppose it’s time you learn.
http://www.nyu.edu/pages/mathmol/textbook/density.html
[Edited on 8-1-2005 by Joeychemist]
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Rosco Bodine
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| Quote: | Originally posted by Pyroz
Rosco:
You are definetly on the right track with your DPPP putty! I'd like to try some too--- the NC, NG, HMTN binder present in rifle power could
certainly help. |
Bullseye pistol powder is what most folks use for AP putty because it is the highest
nitroglycerine content commercial powder that is commonly available just about anywhere . There are a couple of other brands that are similar . High
nitro content powders are usually pistol powders or maybe a few shotshell powders , not rifle powders which must burn much slower because of the
heavier powder charge and steep initial pressures .
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Pyroz
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hold on--- measurements coming. I was mearly testing the visable density.
now for the math: I did a calculation with acetone peroxide first. I got 1.192 gram/cc ---- makes sense right?
The DPPP product gives 1.836 gram/cc
hummm..maybe someone esle can varify my findings?
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Rosco Bodine
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| Quote: | Originally posted by Pyroz
hold on--- measurements coming. I was mearly testing the visable density. |
I wonder if DPPP sinks or floats in molten Erythritol Tetranitrate
If anyone cares to test that pleeeeeease only a very small sample for that experiment .
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The_Davster
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I did the peroxidation of the solution I prepared yesterday.
The deep red solution was left overnight(13h) in the garage at around 0C. It was then cooled to -12C via freezer. At the same time 50mL of 35% H2O2
was coolded in the same freezer for the same length of time(1h). 2mL of HCl was added to the dark red solution. The flask was placed in a slush
bath(salt, water, ice cubes, snow) and ther peroxide was added dropwise. Adding the first 10mL of peroxide dropwise caused the temp to increase to
around 8C. The flask was swirled a few times after the addition of each drop. Adding the next 20mL of peroxide was done by squirting a dropper of
peroxide in then swirling. The temperature increse was no where near as great per addition as during the addition of the first 10mLs. The remalining
20 mL of peroxide was added in 5mL increments with swirling in the bath. The temperature actually decreased during this. Over the entire course of
peroxidation the maximum temp reached was 8C. After the final addition the flask was allowed to sit in the slush bath for 30 min. The crystalls of
DPPP were everywher in the mother liquor,not floating or sinking. It was then filtered and the filtrate was removed before neutralizing because it
was still a deep yellow. The DPPP is now drying.
The yellow filtrate has been sitting aroud for a few hours and has gone completly clear. DPPP has floated to the surface, buoyed up by bubbles of
(probally) oxygen. The source of this oxygen is probally decomposition of H2O2 caused by Fe(II) and (III) impurities in the OTC HCl used.
[Edited on 9-1-2005 by rogue chemist]
[Edited on 9-1-2005 by rogue chemist]
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Rosco Bodine
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That sounds like it went very smoothly .
Did that reaction mixture stay pretty clean and free from droplets of insoluble goo ?
Were the crystals suspended throughout the mixture and clumping like curdled milk
with regions of light yellow liquid between the hanging chains of crystals sort of suspended in the liquid like dense growths of seaweed hanging
vertically in the ocean . A sort of Kelp-like crystal suspension ?
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 .
[Edited on 9-1-2005 by Rosco Bodine]
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The_Davster
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Quite smoothly. I wonder what causes the massive temp increase and vaporization of reactants that was reported a while back?
The reaction mix stayed quite clean, the red liquid( is this phorone dihydrochloride or pentachlorophorone?) had a slight oil slick on the surface,
reminiscent of a bit of gasoline on a wet road, but there was a very minor ammount of it and there were no signs of this after peroxidization. There
were a few balck bits of rubber but that is remanents from enlarging the stopper hole for the thermometer during the heating of the acetone/HCl.
I think that I understand what you are refering to here but I observed none of this. Perhaps it is caused by DPPP crystallizing upon some of the
insoluble oily droplets? My DPPP was freeflowing and spread equally throughout the mother liquor.
The yield will be weighed, but may not be completly accurate. I had done a trial testtube sized peroxidation of the dark red liquid before attempting
the entire batch. And a little(very little) of the DPPP was lost onto the table during filtering by accidently overfilling the funnel . And, of course, I could not resist a flame test of the damp DPPP. I estimate that at maximum 0.5g of DPPP was lost.
The origional patent did claim black smoke if I am not mistaken? I recieved some of this. Not large ammounts, but a black outline was visible on the
edge of the flame during deflagration and a few black carbonaceous particles were noticed floating out of the air soon after the deflagration.
[Edited on 9-1-2005 by rogue chemist]
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Rosco Bodine
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That temperature spike at the very start of peroxidation is what was causing the runaway reported for early experiments . According to the patent that
would be the formation of the pentachlorophorone from
the phorone dihydrochloride via HCl and H2O2 .
The intensely red liquid is phorone dihydrochloride . Conversion to pentachlorophorone which forms next is where the heat spike occurs .
I always start a reaction slowly so as to get an idea what kind of addition rate
can be used and still keep control of the exotherm . It was clear that the reaction has a rapid rate in that initial 10-15% of the peroxide addition
so that is where you
have to make the addition literally by drops , and watch the temperature to keep from getting trouble .
Probably the crystal clumping which I observed was related to a bit of the insoluble oily material and the action of the stirrer . The precursor
mixture for my
last peroxidation experiment was one I had used an excess of acid , and then balanced with some added acetone later in an effort to salvage the batch
. It was a darker mixture than the one I have in the cooler now that is like the ratio and color you used , which is evidently an improvement giving
a cleaner reaction mixture . I am a step behind you fellows who are doing new reactions working from information I just posted , plus I'm taking
a break while my last batch is still drying . It's okay if somebody else proves or disproves any theory I have , it just saves me work
[Edited on 9-1-2005 by Rosco Bodine]
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The_Davster
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Has anyone tried recrystalizing DPPP? I am wondering whether the cream color of DPPP is actually the color of the DPPP or could possibly be
attributed to unreacted phorone dihydrochloride or pentachlorophorone trapped within the crystall latice of the DPPP. Time permitting, I may have a
chance to dissolve DPPP in a solvent(acetone?) and add ammonia to destroy any phorone dihydrochloride or pentachlorophorone. I know from experiance
in failed DPPP reactions that ammonia does destroy phorone dihydrochloride and/or pentachlorophorone. Then crashing into water to precipitate the
DPPP.
EDIT: Damn, I will need concentrated ammonia or ammonia gas to try this, the commercial ammonia I have contains too much water for this.
[Edited on 9-1-2005 by rogue chemist]
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Mickhael
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I'm still letting mine dry, and hoping to get the MEKP made shortly, any thoughts yet on how much water the MEKP would expell from damp DPPP?
Also to comment on the fumes, I would recamend a good mask, I noticed how bad the fumes were right away, and since whenever I'm working around it
I wear my S10 gas mask, it seems to block everything out perfectly, plus gives some head protection...I got it off ebay for $70 cdn.
Ps:Is it possible for someone to get a close look at DPPP in a lab, to see finally what the thing looks like? Hexa? Penta? Phorone? Clorine??
[Edited on 9-1-2005 by Mickhael]
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Rosco Bodine
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The ammonia will also destroy the DPPP , at least at a certain pH . So activated charcoal would be a plan , or simply precipitating the DPPP slowly
by a dropwise addition of cold water to the
stirred acetone would purify it also . DPPP
is the least soluble component in water so it should crystallize out first in pure form . I tend to believe it is pure already
because the color is so even and the crystals are uniformly sized .
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