AP Yields

[wymanthescienceman]

HI, I'm new to the forum and after much searching I could not find anywhere about how much yield one is to expect when making AP. I have been trying synths of some things have only made a few things so far (IE NC and SA), and I have yet to try and make AP mostly because of it's instability but now feel relatively confident in my abilities. The only H2O2 I currently have access to is 3%, but I have the rest of the chemicals at hand and was wondering what would be the best acid to use and how much. I have 98% H2SO4 and 31.45% HCl so which is better? The formula I was going to use is:

30ml 3% H2O2
6ml Acetone - (I've heard 1/5 acetone to H2O2 when using 3%)

So what type and amount of acid would be best and what kind of yields would I expect to get? Should I concentrate the H2O2? Is there a specific ratio to how much AP I get based on amounts of acetone/H2O2? Also, does being too cold change/slow down the synthesis? I was going to leave it outside covered between -5C and +5C. I mostly want to know how much yield is to be expected so I know how much I have to dispose of afterward as I don't want to store it at all until I get a feel for its power and stability issues, and even then I probably won't store it anyway, it's mostly for curiosity purposes. When I feel comfortable with its properties I will try my own tests as to see what acid I like and how much etc. and report my findings to share. :)

I am soon to try Nitric distillation as well as I don't like nitration with nitrates. :(

P.S. If I broke rules about posting let me know. Sorry, my bad.

[megalomania]

Yields will vary depending on technique. To my knowledge I have not seen any hard and fast reproducible yields being reported in the literature. You may find some members on the Forum who reported yields, but most will not have accurate analytical balances to give any results.

For my part, I can direct you to my website 'http://www.roguesci.org/megalomania/explo/acetoneperoxide.html' where I describe some of your questions.

My information is the published Picatinny Arsenal procedure, which uses sulfuric acid. I have never found a published procedure that uses hydrochloric acid, but there are enough people out there who swear by it.

I planned to do a study with controlled concentrations of hydrogen peroxide, different mineral and organic acids, and different reactions temperatures to determine % yields. This is no simple undertaking since I would have to do three replicate trials of some 15 variables to be tested for, or about 360 separate experiments.

In this situation I think you are best suited to answer your own question: Record the volumes of your reactants and weigh your product.

[Red Beret]

Hydrochloric acid works fine, it's all I've ever used and I never have a problem with it. The concentration of your H2O2 will greatly affect the yield, and in my experience this is the major factor upon which yield is dependant.

Don't waste 98% Sulfuric acid on this (unless it's very cheap and easy to obtain for you), save it for Nitric acid manufacture or Nitrate/H2SO4 nitrations.

In regard to yield, most people have moved away from large quantities of explosive peroxides, for a number of reasons, stability and storage being the main ones. You don't need much AP for making a couple of caps, depending on your cap size, you may need as little as 1g per cap, especially when used with a base charge such as PETN or Picric acid.

As mega said, run a few trials with what you have available, using the more common ratios out there, and weigh your product. If you are happy with the results continue what you are doing. If not, try another method. But I would seriously reccomend getting more concentrated H2O2

[wymanthescienceman]

Thanks, I guess I should use just the HCl then. The H2SO4 I got was from some supplier online and it was $22.00US per 500ml and that's way too spendy for me to be using on AP with HCl 31.45% being about $5-$7/gal.

I at last tried AP, although I did use H2SO4 for my first run. It's been almost a full day and with a pint of 3%H2O2 and 60ml acetone I have what looks like fumed silica (Cab-o-sil) very sparingly floating throughout the near clear solution with very little precipitate on the bottom. I can't imagine it to weigh any more than 100mg. How long could this possibly take, more than a week? Should there be more precip than this? Is it too cold at -5C?

I also tried to distill Nitric today but since I was using such a small test sample (10g H2SO4 8g AN) I didn't get more than a drop in my collection vessel using larger equipment than required. I'm guessing since it was done in the cold (about 0C) it couldn't get thru the condensor and would instead collect in the condensor neck and fall back into the reaction vessel. I'm using a 500ml florence flask heated in a water bath at about 80-85C, and a water jacket cooled Liebig condensor but I don't have it under vacuum. All joints are ground glass 24/40, but my collector vessel is not, it just has the end of the condensor in it. Is this a problem? I got no red fumes at any time, the distillate came out clear and it tested Ph 0 or less. Any suggestions/comments?

[Red Beret]

I would leave your solution for around three days when using 3% Peroxide. Thats what I used to do and I found that leaving it longer provided no extra product. Really, to get decent yields you need stronger peroxide.

With your nitric acid distillation, what I have found, is, it is'nt really worth doing such tiny batches, you need a fair amount of reactants to get a decent quantity of nitric acid. I can't comment on your setup a great deal, as mine was a very crude "old school setup" and wasn't terribly reliable. That's why I just use the H2SO4 with nitrate for my nitrations. Bit of a pain, but at the moment it's the best I have.

Your setup, although basic should be OK but it won't be THE most efficient out there. Don't quote me but I think you are correct on the condensor. It should be a little warmer to allow the gas to actually get into the condensor. Obviously, if it's not getting there (to the condensor) it can't go through and pass to the collecting vessel.

I believe mega has done an awful lot of work on nitric acid distillation, hence refer to his site or ask the man himself. As I said, my experience with the afore mentioned procedure is limited. Good luck.;)

[wymanthescienceman]

Where can I get Conc. H2O2? The only place I've found it so far is online from places like "Guardian of Eden" but it runs almost $55USD/gal with shipping. I can get it by the pint/quart but it's not worth it at over $30/qt. Is this the price to expect to pay for 35%? And even if I get 10x the output of AP this doesn't justify the price at all according to what I'm getting now at less than a gram per pint of 3%. That price seems a little high at about $1 per gram of AP, which is what it costs anyway with 3%. Where do you guys get your H2O2 from and at what concentrations?

[c.Tech]

I got my H2O2 from a pool chemical supply shop, $50 AUS for 5L of 10-20%

Then another forum member I’ve been chatting to (jetz) found it for approx. $34.

:mad: I got ripped off. Moral of the story, shop around.

EDIT: Forgot to add it was for spa's

[wymanthescienceman]

I keep hearing it can be at pool supply shops. I've been looking online and can't seem to find any. What's the name for it or what is it for/what does it do in pools/spas?

UPDATE - I have tried concentrating the H2O2. I boiled it to about 1/4 of its original volume, about 12% or so. I was getting impatient after boiling it for almost an hour (it was only 80ml) that I did the synthesis with slightly warm (about 50-60C) peroxide and room temp Acetone/HCl. It turned light white within 5 min when I put it outside at -11C. and about 10min later it had a layer of white stuff on top. I scooped a tiny amount out and held it over flame and it poofed. No odor no smoke just a clear poof. I didnt do any exact ratio. I just added about 15ml Acetone to 20ml warm H2O2 and about 2-5ml HCl 31.45. As I said I was IMPATIENT and it was such a small amount I wasn't worried about it being the dimer. I think I have success! I will do more experiments and tests with it to check its stability and report my final yield and any findings later, after it completes precipitation.

[Red Beret]

I believe it's called baquacil in the US. $55 per gallon is fairly pricey, but remember, it will last you a while. You can always half the batch size so you don't make more than you need.

c.Tech- You got done as well! I paid around $25 for a litre of %15 back in the day. Now I go to the pool store. ;)

[wymanthescienceman]

I have found Baquacil Shock & Oxidizer online at about $60 for 4 gallons incl. shipping, and it has to be bought by the 4 gallon case, but that works out to about $15/gal. That's the kinda price I was looking for. The problem is I don't want 4 gal! I saw another product called Baquaspa Shock & Oxidizer and since its for spas its sold by the quart at about $7.50. Has anybody had any experience with this product? I belive they are made by the same company so I don't see what the difference would be. But I can't find an MSDS for either to see what's in it. Anyone?

PS - What is the percentage in Baquacil?

[Cobalt.45]

If you've calculated the cost of your AP correctly, it would appear that your yields are very low.

Looking at old notes, I see that 4g yields were achieved using 220ml of 3% H2O2. This was after nearly 60 hours @ 5 degrees C.

Using 35% H2O2 that costs $25/quart, HCl @ $5.50/gallon and acetone around $5.00/ quart, AP costs $0.04/g, give or take.

My advice would be to use 35% H2O2, and to keep your reaction temperature at 5 degrees C.

[nmp2]

According to
www.poolspaforum.com
"...Baquaspa shock is 7.5% concentration and Baquacil shock is 27%..."

[Alexires]

C.Tech, talk to me about H2O2. I shall point you in the right direction.

I have found in the past that if you are making AP, two things that help (alot) is the amount of acid you put in, and the concentration of your H2O2.

I have always had excellent yields following Mega's directions but using 10-15mL of HCl instead of H2SO4.

You should concentrate your H2O2 to at least 30%. When I concentrate my H2O2 I try to keep the temp below 80*C, but I don't know if that really matters in regards to the decomposition of the H2O2.

I cool the Acetone and the H2O2, then add them together. Then add the HCl (all of this in a salt/ice/water bath) and keep it below 0*C as I add the acid.

When the acid has been added, it goes into the fridge for a few hours (where it is about -6*C or so), then used.

If your going to be storing it (even for a few hours) make sure to neutralize and clean it.

[rayman]

I guess this is where I should post this picture, but first the method

Ap

50 ml HYDROCHLORIC ACID ( H C l )
50ml ACETONE
100 ml H2O2 (35%)
2000 ml H2O
Sodium bicarbonate ( Baking soda )

Mix 50 ml HCI With 50 ml ACETONE ( you will need more for filtering process), in a 500ml jar ( I use a thick freezer bag under the lid to protect it from the acid ) Let sit in warm area for several days ( one week on avg in my experience) giving it a quick swirl every day to keep it mixed, Once it forms in to a dark redish black oily looking liquid place in the fridge for a day or so until you are ready for the next step, At this time also place your 100ml H2O2 in to the fridge

Place ice in a large ( salad bowl size with flat bottom ) bowl. place the HCI-Acetone mix jar into the ice ( I like to leave some ice under the jar to promote water flow and even cooling all around the jar as long as the base of the jar is stable) add some water into the bowl to about half again the level of the mixture in the jar.

once every thing is stable take your H2O2 and drip wise add 5 ml to the jar, stir it around ( I use wooded skewers ), The temprature of this mix WILL JUMP IF YOU ADD H2O2 TO FAST AND WILL CAUSE BOILING IN THE JAR RELEASEING GAS'S THAT WILL BURN YOUR EYES AND THROAT I KNOW THIS FOR FACT IT HAS HAPPENED TO ME, But that might have been HCI not used in the reaction with ACETONE

Wait some time ( I wait at least 5 min before adding my next 5 ml ) stiring every few minutes, DO NOT LEAVE THE MIXING JAR UNTIL IT IS COLD NOT EVEN TO PISS AT ANY TIME DURING THIS PART OF THE EXPERIMENT,

Every 5 min or so there after I add 5 ml until the temprature does not climb any more at this time I double the amount of H2O2 I add. Also remember to replenish the ice as needed to keep the mixture cool ie .. if the skewer feels warm do not add any H2O2 until the tempratiure has droped but keep stirring, Once all the H2O2 is used you will have noticed little flakes ( AP crystals ) forming on your skewer, Add Bicarbonate a little at a time stiring it in, it will fizz and bubble, keep adding until the fizzing and foaming stops.

Add several parts Water while stirring until the jar is nearly full , Filter ( I use a second jar and 2 coffee filters ( pre wet the filters with water)) into a second jar, Once the first jar once its empty give it a quick rinceing out, Place the AP crystals on the filter back into the first jar and rince out the second jar, Fill the first jar apx half full with water and give it some light stiring for a min or so to get all the AP in the water several times to wash it, Repeat the filtering twice more, Once with acetone then with water

Store in Actone or water if you are not planing on using in the next few days, It seems to take 2 - 4 days to dry out fairly well, If stored in water maybe a week or if your if your drying area is damp, In my case it dryed out in about 24 hours as I had it in actone,

The extra water that you havent used is a good thing it means that your reaction didnt start to get away from you, if your mixture starts boiling pour water into the jar faster then ASAP I mean NOW, never think about it when it comes to safety first ... as the nike commercial says ... JUST DO IT

Always wear acid resistant gloves and a chemical cartridge respirator when working with acids/volitile chemicals
------------------------------------------

I typed that up just before going to bed so there may be slight errors, please inform me if you find any

Now for the picture
... AH cant seem to post pics atm sorry, but i will give a quick note on the picture now so once i am able to post it you will see


The AP on the right is the newer mix using this formula posted above, it a very fine powder the pile on the left is my first batch, you will see a few table spoons on the left nothing to get excited about the crystals are very big.

As you can see the yields using this method are much better in the order of 2000%, As i do not have a scale to weight them and the drying time is 14 days for the oldr 2 days for the new

Time to place it all in water storage

[Cobalt.45]

I fail to see the point in all this.

You've taken a relatively safe (less exothermic) process that takes several hours, and turned it into a week-long process with the added deficit of increased risk from an uncontrolled exothermic reaction.

Please explain what I'm missing.

[knowledgehungry]

Rayman is using the "DPPP Procedure" to make AP. There really is no benefit of doing it that way since DPPP is not created by that procedure.

Rayman if I were you I would mix the Acetone and H2O2 first, chill, then slowly add acid. It lowers the chance of runaway exotherm and as a rule you add acid to water, not water to acid, or else you will get hotspots and spotboiling like you said you got.

[rayman]

I may have made error's, If I knew every thing already I would not be here :-)

But thank you for pointing them out, Yes I turn it into a longer process and it can be done in a day, But my wife would kill me if I messed up the stove in anyway shape or form

I use the DPPP ( I Learned the the recipe in a thread called 'DPPP the holy grail proxide 'or some such so the name has stuck) (HCI - ACTONE - H2O2) method as thats the one i know and it works very well for me

I have not read the other methods in depth to even try to figure out the diffrence in the methods, NOt saying that any/eather are better then the other

Anyway, heres the picture as taken, You look you decide, Thats using 100 ml of hci-actone 200 ml h2o2@35%
'http://img81.imageshack.us/img81/5010/picture002qy9.jpg'

Thank you

[c.Tech]

Anyway, heres the picture as taken, You look you decide, Thats using 100 ml of hci-actone 200 ml h2o2@35%

:eek: How much do you make at a time? To dry huge piles of AP is extremely dangerous, if some of it goes off the whole thing will detonate but if you dried it bits at a time even if there is a pile which detonates it wouldn’t lead to catastrophe.

Why did you need that much AP in the first place?

[knowledgehungry]

I would be far more worried about AP killing you than your wife killing you Rayman. I never make more than 10 grams of AP at a time(not that I make any AP nowadays), my advice is that you separate that pile into many smaller amounts and store separately in water.

AP is extraordinarily unpredictable and has killed people who did not take our warnings seriously.

[Cobalt.45]

If you just went with the first "recipe" that you happened upon, you need to reassess your methods. Especially a method that has been shown to not produce the peroxide compound that it was originally touted to produce.

DPPP procedure? I wouldn't dignify it as a procedure for anything. Unless you were after the dimer form, as a primary result.

Elsewhere, an exhaustive study was done to disprove the synthesis of DPPP by the method mentioned.

Research is at the root of any synthesis, be it AP or ?.

But my wife would kill me if I messed up the stove in anyway shape or form
You make AP on a lit stove, you won't have to worry about the wife killing you...:rolleyes:

[c.Tech]

and store separately in water.

Also a good idea to keep it in the fridge, if its not kept cold the crystals get bigger (being more hazardous) and changes from TATP to the more sensitive DADP.

[mike16]

Blimey, thats a lot of highly sensitive dry AP you have there.

When I make AP I use 50ml H2O2 (35%) and 40ml of acetone and usually end up with about 15-20 grams.

I would suggest you VERY carefully put it all in a bucket full of water and dry small 3-4 gram amounts at a time, I presume you will use it for blasting caps?

A couple of weeks ago I tested a very small piece of my AP by hitting it with a hammer, I was suprised it only needed about 3-4 centimetre drop from a small hammer.

Be careful.

[rayman]

I did not know what amount would be made from the reaction, The pile has been in the fridge in water/actone storage for several days now, I will break down the amount into several containers as that sounds like good advice

Thank you

[Controlled Chaos]

I keep hearing it can be at pool supply shops. I've been looking online and can't seem to find any. What's the name for it or what is it for/what does it do in pools/spas?

Hydrogen Peroxide is used as an alternative to chlorine for pools. It keeps the water clean for people who are sensitive to chlorine. I was asked if I wanted it for a science project, so I just replied "yes, it's a science experiment" :rolleyes: . I don't know what it is about me that make people think I am not using it for its intended purposes. :D

I would suggest looking locally for your H2O2. I bought mine from one of many local pool shops for about 18$ a gallon. It was Baquacil 27% H2O2. It says right on the back of the jug the ingredients and its sealed in a plastic bag.

It works Great and should last you a while unless you are making kilos of peroxide explosive at a time :eek: .

[c.Tech]

'http://www.geocities.com/thugsta785/Experiments.html'
Take a look at this, it seems that AP yield is greatly minimised when there is unreacted or excess acetone, letting some of the acetone evaporate would greatly increase the yield.

[Controlled Chaos]

Nice c.Tech, something everyone has been looking for.

How does H2SO4 compare to HCL when making AP. For example yields and reaction times?

[c.Tech]

As I have never been able to get H2SO4 I don’t know but I’ve heard somewhere that sulfuric gives better yields than hydrochloric. Don’t know how accurate it is. I assume it’s correct.

[Cobalt.45]

In that the acid is a catalyst, and not "used up" in the synthesis, it shouldn't matter, IMHO.

H2SO4 is more exothermic than HCl when used to make acetone peroxide. This leads to the belief that the dimer form might be produced "locally" due to heating of the solution at the point where the sulfuric acid is added.

Slowly adding the H2SO4 will negate this effect, mostly.

As previously noted, the H2O2 concentration is what makes the big difference in yields.

[SafetyLast]

Back when I was reckless (before I lost a couple fingertips from the stuff) I used to use 100ml of Baquacil Chlorine Free Shock and Oxidizer (27% H2O2) with 75ml of Acetone. This would generally produce between 45 and 50 grams of AP. This is about 60-70% of the theoretical yield. There is hardly any liquid left when you go to filter.
I don't reccomend making that much in one batch, so scale down accordingly.
If you don't want to buy a 4 gallon lot for $60 then just go to a pool store that carries it, I paid about $15 for a gallon and it lasted me a couple years.

I've never had any real luck with the 3% stuff, maybe because the HCl becomes volatile and doesn't allow the catalysis of the reaction.
You should be more patient wayman, calculate your ratios carefully.
Too much acetone will dissolve any AP and cause a very low yield.

Clairol makes a product called Clairoxide 40, this is 40 volume (12%) H2O2
It should be available from beauty supply/salons. Price is about $5/qt.
The proper ratio when using 12% H2O2 is 20ml of peroxide to 7ml of acetone.
H2O2 is volatile below the boiling point of water so just because you boiled it to 1/4 volume doesn't mean that it is 12%. AP, when still wet will cause a small "poof" when dry it will burn in more of a quick "woomph" with a fireball.

[stupid939]

I did an experiment with HCL vs. H2SO4 awhile back (before I could get 27% H2O2), and these are the results that I got. (These amounts are not exactly Stoichiometric, but they worked fine)

I used:

500ml of 3% Hydrogen Peroxide
165ml of Acetone
50ml of 95% H2SO4 and 185ml 31.45% HCl

I let them react for 45 hours (fairly optimal for 3%) and I got a yield of 14.3g with the sulfuric acid, and a yield of 7.6g with the Hydrochloric acid. That is 1.88 times as much. I'm sure the results would vary with different reaction times and percentage of H2O2, but I think that this was long enough to wait.

I would use H2SO4 if you are using a low percentage H2O2, but once you start using something like 30%, you would either need to use HCl, add the H2SO4 very slowly, or water the H2SO4 down.

[no_fear]

OK, so what would be the best, safest ratio of the chemicals be to get the highest % yield of AP?

[stupid939]

For the greatest yield, take a look at the link that c.Tech posted on the end of page 1. As the experiment shows, an excess of H2O2 was best, and I would probably do a half batch to get 5g. It is a lot more than you would think, and is plenty for a few caps.

The safest way to do it would be to maybe use HCl instead, and keep it as cool as you can (close to 0°C).

[c.Tech]

OK, so what would be the best, safest ratio of the chemicals be to get the highest % yield of AP?

UTFSE, its in numerous threads around the forum as is in documents on other websites that can be found through google and on Mega’s site.

[no_fear]

alright thanks guys. I got it figured out now.

[al3x]

I recently made a batch of AP for a detonator.

Using 150ml of 3% H. peroxide with 50ml HCl and 50ml acetone. I washed it with a sodium hydroxide solution and the final TATP yield was 4.7g.

It's not much but its all I needed at the time.

[SafetyLast]

I've never used a hydroxide solution for the wash, I've always stuck to bicarb,
works fine for me and is cheap and plentiful.
I'd reccomend a few more rinses with water alone if you were using NaOH as you wouldn't want your AP to be left basic and react with metal.
HMTD is notorious for being corrosive to metal, there was once a forum member that lost a large chunk of his leg from a CO2 cylinder filled with HMTD which went off in his pocket. (not sure if that was from friction or from reactivity or both) AP is only slightly corrosive compared to HMTD.
I always use an excess of H2O2, not acetone as dissolved AP is not something to be fooled around with. It can form large needly crystals when the solvent evaporates.

I don't know if anybody listed this yet, but the stoichiometry for the trimer is:
3H2O2+3C3H6O-(*catalyst)->(C3H6O2)3+3H2O

I write AP like that all the time, I don't know why.

In grams that's 102g H2O2, 174g Acetone
and products 222g C9H18O6/TATP with 54g H2O

When using 27% "Baquacil" that throws in 276g (~15mol) of H2O with your 3 mols of H2O2. H2O cannot be written into the reaction since it is merely a carrier.

The catalyst is any mineral acid, I've even had success from Sulfamic.
Usually catalysts are written above the arrow, but I have no idea how to write superscripts or subscripts.