Nano Cooking... some other ideas about how to go about it...

loki · guinea pig

scrawled on a piece of paper that was floating around as i walked down the street was some information i felt was relevant to this forum:

geezmeister · Busy Bee

Very small "nano" reactions are prone to complete failure if any quantity of precursor is outside the "envelope of success." It is much easier for the clandestine chemist to get the ratios correct when measuring to cook an ounce of precursor than it is to get the ratios correct measuring for a gram. The difference a few degrees on the end of the balance beam makes in a large reaction is negligible. The same variation with a gram sized reaction could well be critical.

Thus the developed preference in small nano reactions to use more precursors than actually needed to assure enough in the reaction to do the job. The infamous "Curbshot nano," as nasty as it often was in execution, did work. Start reducing the ratios and the average pill cook winds up with too little actual red phosphorous or iodine and the whole thing fails.

Phosphorous Acid /I2 is a very surefire nano synth. The "sure" part of the synth derives from doubling the PA, I2, AND water-- doubling the HI in the reaction, then letting it run the full four and a half hours at temperature. Experience suggests the reaction done this way will produce in high yield for such small reactions consistently. Done with molar ratios of precursors, the nano synths frequently fail. Whether this is from the inaccuracies of measurement, or from the small size of the reaction and the fact that the limited size narrows the envelope of success is not known. Both may contribute. As the size goes up, the ratios are scaled back toward molar amounts. At five grams, the ratios of Pseudo:PA:I2:H2O 1:1.4:1.2:0.8 will lead to more complete success than the 1:1.2:1.2:1 ratio for the larger reactions. At one gram, a ratio of 1:1.5:1.5:0.8 seems to work fine; at half a gram, one should probably use a 1:2:2:1 ratio if you want consistent success.

The rP reaction doesn't produce that much pressure (unless you really crank up the heat) and doesn't seem to need pressure at all to complete well. Time, not pressure, guarantees a complete reduction. The reaction will bubble at higher than atmospheric pressure; at pressure there will not be as much bubbling, but there will still be some bubbling. There surely is a pressure at which bubbling ceases, but there is no need for the pressure. After the HI is made and absorbed by the water present the reaction doesn't produce pressure. The balloons so often used for gas containment can be replaced by a cotton plug at the top of the condenser, and the reaction refluxed for hours with no odor problems, and no siginificant escape of HI. The product of an unpressurized reaction is not distinguishable from the product of a pressurized one-- the molecule is the molecule, whether formed under pressure or not.

Pre-reacting the I2, the rP and water to make HI will proceed just fine at room temperature if sufficient water is present to moderate the reaction between the I2 and the rP. Lab grade red phos and good I2 will combine with insufficient moisture in a smoky, wasteful exothermic reaction. The water to mediate the reaction and keep it from being so smoky and so exothermic is the key. The HI made by allowing the precursors to sit at room temp is no better than the HI made by applying gentle heat to them.

That said, the most successful approaches to nano cooks make the HI first, allow the HI to cool, then add the pseudo or ephedrine, then proceed. H3PO2 and H3PO3 nano reactions are preferred to rP reactions in the small sizes, as the precursors will, on average, yield consistently better results than rP reactions will. The H3PO3 reaction at the nano scale will be more likely to fail than the H3PO2 reaction if the pseudo or E is added at the outset, and is much more prone to failure if freebase pseudo is used and added at the start, rather than after the HI is produced and allowed to cool. The temperature at which the H3PO3 reaction makes HI is the likely problem, the the freebase pseudo in particular more susceptible to being damaged by the HI which evolves suddenly at about 87C. Not only is the temperature climbing at the point of rapid HI production, the pseudo is also being converted from the freebase to an HI salt form at this point. Do that all at once at temperature and some of the pseudo seems to get damaged. Yields suffer, and entire nano reactions tend to fail. The failures and yield losses are easily avoided by the expedient of making the HI first, allowing it to cool, then adding the HI again. The H3PO3 reaction seems to complete better if there is containment of the HI in the reaction vessel, which in the nano is usually a test tube. A single balloon will suffice unless the reaction is allowed to exceed about 180C, at which point phosphine gas will be generated and this will seep through the balloon, ignite, and burn small holes in the balloon. The reaction should be done in an oil or sand bath and the temperature kept between 140-170C to avoid this.

H3PO2 nanos are as easy as falling off a log. The HI is evolved at room temperature, except with very dilute H3PO2. Even with dilute acid, the HI is evolved quickly with very little heat applied. At fifty percent concentration the H3PO2 and I2 will make HI at room temp, or with no more heat than from the palm of the hand. A balloon is useful to prevent loss of the gas at this stage since it may evolve very quickly and faster than the water present can absorb it. Chilling the I2 and hypo before adding the pseudo will slow this process, and one can easily control the evolution of the HI by hand warmth and cool water bath. Again, even with this synth, padding the acid and iodine ratios to secure against inadvertent underwieghing will increase the likelihood of successful completion of the reaction.

loki · guinea pig

swim thought that one could get these ratios pretty much well right by starting with known excessive amounts. he figured on 20 matchboxes and a single bottle of 2.5% tincture with 18x 120mg pills. According to swim's calculations, this should result in a 2-4x amount of phosphorus (depending on how pure) and easily 1/3 or better excess of iodine, for a feedstock of a theoretical 2g (18x120mg).

swim threw this mixture together, putting water i2 and phos in first, and it was just let to sit because the e was not ready yet.

the reaction fluid started out reddish but as the reaction progressed it turned yellowish (by 13 hours in).

The sealing of the reaction vessel turned out to be a much easier way to ensure no loss of liquid occurred when running such a small reaction for the full length required.

lemuralia · Wed Jun 15, 2005 3:08 am

Ive done 1 gram nanos with Hypo and got %60 returns many times.

loki · guinea pig

Getting the right amount of water in the reaction is very important, swim used 2ml in the 2g nano but in hindsight thinks that he should have used 1.5ml, as the product was partially unreacted at the end, a lot more than should have taken to get him high was required. Swim had a feeling he put too much water in, and that possibly the phosphorus was not clean enough, on previous occasions he had really went hard on cleaning the phosphorus. the phos swim used seemed to have residual glue in it, which presented a problem at the end when the product wouldn't crystallise, but did crystallise nicely with a dry acetone/ethanol recrystallisation.

I think the key to making nanos work well is to really make the phosphorus clean, it is the limiting factor in the reaction, the cleaner it is, the better it is able to react with the iodine. it really doesn't take as much phosphorus as the 1:3 ratio commonly stated, but most of the time mbrp is too dirty, and mixed up with stuff, and the actual material available to react is probably something like 1/3 of the amount, which means that 3x as much should be used, not 2. for a 2g nano this means 600mg of phosphorus... which does work out to the ratio commonly given. However, because of the density of phosphorus, it still looks a lot less (by a factor of two).

Is there some way to deliberately make phosphorus float on top of a solution? because that would enable the separation of it from the abrasive agents that are added to improve the reaction with potassium chlorate. Phosphorus seems to clump together in acidic solutions, is this because of the residual glue or does the phosphorus resist the surface tension of the water? it doesn't float unfortunately, but maybe a way to make this happen would be to add a bit of bicarb to the acidic solution so that a lot of gas forms in the liquid, which will tend to stick to the phosphorus. Unfortunately this probably happens the same to the abrasive agents.

I am inclined to think that the ideal way to purify mbrp is with a centrifuge. several runs, with a gentle agitation to loosen it up a little would fractionate the substances by their density and particle size, the phosphorus is usually the finest part of the material i believe. A means to build a ghetto centrifuge would be quite useful... being able to centrifuge large quantities in one vessel, like a litre capacity, that would be intensely useful, could be used to force separations too... but i digress.

I think if one applies the appropriate amount of effort to the task it should be possible to get 95% purity reagents and precursors and get a 75-80% yield.

Probably the biggest thing that will provide success is lots of practise, and knowing as much as possible about everything so that the best possible method is applied, it takes time to learn what things are the best, and to know how to avoid mistakes. Nanos are a good way to practise, in part because the process of preparing such a small amount is fairly unobtrusive compared with an ounce batch, and the cost to experience ratio is much higher. Beginners should master nanos to 70% yield of well reacted product before they try anything bigger. When one ends up with a 50% yield and only maybe 80% reacted, it is nowhere near as much of a loss as when the same thing happens to an ounce batch.

zub · Wed Jun 15, 2005 9:14 pm

assuming good ratios at the onset, one can allow the escape of a small amount of gaseous HI, ensuring that the air in the flask has been driven out.
with that air gone, the rxn can be run with no pressure; no bubbling; no signs of activity.
when such a rxn is done (24 hours min), there will be negative pressure as it cools down. an rb flask will prevent implosion.

this approach implies temps of 100c, and not much higher.
one doesn't want to generate steam in a sealed containment.

tina_craig · Thu Jun 16, 2005 2:45 am

The biggest factor in any HI/P reduction is the cleanliness of the pseudoephedrine, get clean E and it is downhill from there.

loki · guinea pig

There is semi-pressure teflon vessels which are designed for microwave reactions, something similar would be suitable for a nano cook too. They are a bit on the expensive side but would be the perfect thing for this.

The question in my mind is, can the reaction be done in a microwave (given the use of measures to reduce the amount of microwaves acting on the reaction fluid), and if yes, how long does the reaction take. Microwaves have, to some degree depending on the particular materials an effect of increasing the amount of electrons in a reaction, although this effect is not great and only really applies to certain types of materials (presumably things like metal powders), but probably the effect which accelerates the reactions the most is that microwaves produce uniform heating through the whole mass of reacting substance and produces temperatures just a little (5%) above the normal boiling point. Hypophosphorous reactions could probably be 100% done in as little as 10 minutes and perhaps the efficiency and selectivity of the solid phosphorous reaction would be improved too. For proof of concept, nano-scale reactions are perfect for this.

regarding the pressurised reaction and steam, at pressure, there is very little steam at all. If one keeps the lid shut from the moment the pseudo is added to the end of the reaction, the pressure in the gas above the reaction is too high for water to even enter it. I think that one could probably reduce the oxidation (some p2p is formed in the rp/i2 reaction) by flooding the semi-pressure reaction vessel with carbon dioxide, which would be perfectly inert to the reaction, acidic when in solution, and generally driven out, and not capable of providing an oxygen atom to do the damage. Butane would also work for this, but probably would not be advised if one is at any risk of having a flask fire.

geezmeister · Busy Bee

Some microwave experimentation with nano rP reactions has been done. These shared a common difficulty with larger rP reactions also attempted in the microwave, and that was the formation of phosphine gas. The experimenter shifted to a lower wattage microwave, he used microwaves in shorter bursts, he used a micro with shorter bursts and a turntable and got the same results. He was containing the HI with balloons of different composition, and tried with condoms.

Balloons failed regularly. Holes would burn through the rubber -- not at the test tube edge, but over the opening of the test tube. Condoms did no better. Thicker latex glove fingers fared better than condoms, but failed during the reaction as well. Small, smoky fires were observed at the points at which the balloons failed. The density of white smoke and the way the fires appeared where holes or leakage in the balloon first appeared-- and I am told the smell of the smoke-- suggested the fires were caused by phosphine gas rather than by overheating the rubber at it most slack and unstretched points.

The person doing the experiments concluded that the energy of the microwaves at the surface of the rP particles in the reaction was generating heat sufficient at that location to generate phosphine; the temp of the reaction fluid was kept below that sufficient to generate the gas, thus the evolution of the gas was considered to be a function of the microwave radiation on the red phosphorous particle itself.

My take was that it is equally likely that the balloons used were degraded by the microwaves and overheated where they were thickest and/or exposed to HI. I did not dismiss the possibility that the microwaves were causing hot spots at the phosphorous particles and generating phosphine, based on the description of the smoke produced (thick, white) and the reported fact that the balloons were not particularly hot to the touch when the fires burned out, and rather than melting or burning themselves, seemed to burn around the edge of holes which themselves did not become larger as the small, bluish-greenish flames persisted.

The same experimenter claimed that he did not have similar problems with phosphorous acid reactions completed at partial power in the microwave. The reported experiences were too few to draw conclusions from, IMHO. He declined my suggestion to drill a test tube size hole in the top of the microwave and drop the tube into the oven leaving the balloon outside of it. His concern was the microwaves, and he was not satisfied by the suggestion that a metal pipe flange above the microwave would be sufficient to prevent leakage.

loki · guinea pig

in microwave chemistry, with a mono-mode (off, on) magnetron, as all domestic ones are, one can get a reduced microwave heating effect by adding containers filled with water onto the turntable.

Regarding the temperatures, it is known that when microwaves boil water it boils at 105`C. Temperature measurements of the reaction conditions have to be done in reaction condions (sans precursor) in order to determine whether one has got sufficient or too much heatsinking. Obviously with this reaction one would start with an excess, test, and if temperatures did not get to working temperature in a minute, take some of the microwave sink water away. It is likely that under microwave conditions this reaction requires very very little energy. Possibly there may be an interaction between phosphorus and microwaves.

Whether this is the case or not could be easily determined by microwaving a pinch of red phosphorus that has been thoroughly dried, not a speck of moisture in it. If it makes the marsh gas or better still, makes a pretty light display, then obviously phosphorus is never going to be usable in a microwave. Bone dry phosphorus, I would say, should not decompose from microwave radiation. According to a bunch of industrial chemistry reference books i read a few months back, phosphorus starts to degrade at 100 degrees and decomposes to phosphine at 130ish and much past that and it goes to diphosphine and autoignites.

I would say that phosphorus was not working for you because it was being microwave water boiled. once some phosphine starts emanating then you have another chemical in there with another set of characteristics with regards to microwaves. Phosphine is not supposed to be made in the reaction, this happens from excessive heat.

I would think that those teflon semi-pressure reaction vessels are exactly the thing needed for doing microwave reactions. The vessel must be able to withstand in excess of 120 plus highly acidic conditions. A jar with a polypropylene lid or some other heat and acid resistant material (melamine? I have an amber glass jar which has a lid like that, used to be a herbal medicine pill bottle) might be ok too. Because the reaction produces vapours, it cannot be done in an open flask like other solvent free reactions done in the microwave. The vapours that emit are needed in the reaction and if they escape at a certain point the reaction fails.

One of the other problems that the experimenter probably encountered has to do with concentrated ionic acids. I have put 37% HCl in the microwave and it makes these unpleasant electric zap sounds. If the iodine was causing any arcing it would have toasted the phosphine too. Possibly this could be remedied with the use of glacial acetic acid, which is inert to microwaves and disperses the hydriodic acid down below the concentrated level without losing the concentrated reactivity. Phosphoric acid may be ok too but I suspect that one is always safer with silica or carbon based substances in the microwave, in general. Phosphoric acid may interact with the microwaves the same way as a concentrated halo-acid, generating arcs...

Now that reminds me! I recall some time ago, with a fairly concentrated potassium/sodium iodide solution which probably also had some iodoform in it, at the surface of the liquid on the edge of the plastic it was arcing (I couldn't see it but i heard it) and after being used on that substance the plastic jug had a pitted texture, especially on the areas the solution was in direct contact with the liquid, as well as from splatters from bubbling.

So, it's possible that it's concentrated hydriodic acid ions that caused the problem. I have seen hydriodide ions cause arcs even in a solution that was nowhere near concentrated (probably about 1/2 or 1/3ish. I do recall, now that i think back, that the arcing did not strart until it got to a certain concentration. I have seen the same effect occur with concentrated sodium hydroxide too. sodium hydroxide at 10% is ok in the oven, but at much higher than that and it too arcs. The reason is obvious really - microwave ovens work their magic by creating a rapidly inverting ionisation in water. In an ionic solution beyond a certain concentration the microwaves generate electric current across the solution, particularly the edges... which then sets phosphorus on fire.

So obviously a 1/4 or better, ratio between hydriodic acid/iodine and the known to be microwave inert solvent acid (I am almost certain that phosphoric acid, too, at conc. will produce arcing problems). Phosphorus will not cause a problem until it's reacted and formed an ionic compound, and then it would add it's own mess to the complications. Spacing it out with non-conductive GAA should solve the problem. Its likely, also, that the reaction can take place at lower concentrations in a microwave due to the reaction vessel passing through a microwave 'hotspot' (a standing wave pattern, most microwaves have areas where they are hotter than others, this is why they have turntables) where the reaction temperature will quickly spike a good 10-20 degrees above the operating temperature (as read by your thermometer).

I think if all of these considerations are borne in mind, the phosphorus/iodine reaction system should be perfectly usable. An alternative would be to use the microwave to iodinate (I know that kaolin clay can do this), extract the iodinated product and cook up in hypophosphorus acid (this too probably will have caveats in a microwave, but again, GAA and microwave sinks should sort that out). It's possible that one could find a way to use sodium hypophosphite directly in a microwave. The iodinations are also done with iodide salts.

p2e3r4f5e6c7t8 · Thu Aug 04, 2005 9:28 am

Well recently swip was day dreaming, Or was it night, HHMMMM, Anyway swip extracted 1grm of pse freebase crystals from 1.800 pse HCI avalible using st8 to bee 3 method.
Swip was using this as a test dream, Extraction, Cook, work up, ECT.
MB RP was used cleaned real good with dilute sulphuric acid witch cleaned it nicly, Then swip made his I2 from tinture and cleaned that real good.
And after all that, This is what swip eventuly dreamed using Acid-melts slacker synth.
1 grm pse freebase crystals.
1.2 gms I2.
1 grm of mbRP.
The E and the RP were combined and sat aside untill he weighed out his I2, Then the I2 was added and nothing happend everything chem wise was real dry in the rxn vessle, After 5 minutes still nothing,So swip put it in the oil bath to see if that would kick it off , Not realy much reacting, So swip added 3ml of dh20 and whooaaaaaa, there was HI smoke, It just kept swerling up & down and around swerling sorta look, So over a 45 minute period swip went from 130~C to 175~C and eventuly the HI smoke disapeared and swip was geting exited beause there was that smell of ,,YEA YOU DREAMERS KNOW THE SMELL, Swip then put a balloon over the flask while it cooled down leting a little air in, Otherwise the baloon would of ended up in the flask from the suction.
Once it was cooled down enough to touch swip filterd it untill he had a nice yellow piss looking color, And that smell, aawww.
But that is as far as swip has goten so far.
What do you other HI nano dreamers think is better when doing the work up, espicly since its a nano reaction, GAS or TITRATE.

OK now fire away with the questions or what ever,
Swip would also give a very big thanks to Video Editor for his efforts with the st8 to bee 3, YOU THE MAN/WOMAN ???

loki · guinea pig

workup is where beginners fuck up more than anywhere else... or so a little gnome told me... the business about making the salt is a bitch however... one of these moons when the gnome visits me again bring back with him a way to explain the 100% foolproof result every time method... cos he has ruined his days work too many times mainly from the workup...

hAzzBEEn · Thu Aug 04, 2005 6:43 pm

SWIh would gas after basing if SWIy know how to do that.

p2e3r4f5e6c7t8 · Fri Aug 05, 2005 9:34 am

Swip will gas he thinks, He has salted out before but the yeilds are always lower than when its been gased.
By the way what is the yeild ratio for the above mentioned pse because swip always see's 70% or some bee saying 50% yeild final weight.
Swip isent realy expecting the whole 1grm back once gased, But seing as he reacted using freebase crystals and thats the first dream swip has ever had using it.
But swip will post results .
One more thing, How come this place is not as busy as the hive, It takes ages for a reply hear and over at WD.
Post your dam results bee's, Swip thinks that even posting fuck ups to get advice should bee more often, (as long as the hard yards have been done).
Anyway latter beee'sssss

p2e3r4f5e6c7t8 · Sun Aug 07, 2005 11:34 am

Well bee's swip went and gassed and there were wisps of white apearing throughout the non polar while gassing and swip even had a few crystals apear on the end of the gassing tube.
And then after 5 or so minuts swip looked at it ready to fillter and it was like the crystals that had formed on the gassing tube and on the inside of the beaker went like a pastey type substance that had no colore, WTF is going on, So in the end swip just added some dH2o and is gone evape that and see wht the fuck he's go or what went wrong, Because as swip mentioned above this was only a test run dream, So before swip moves onto bigger and better dreams he needs to find out were he fucked up and what went wrong and at what stage things started to fuck up.
So is any onther bee using the str8 to bee 3 method ?,
And how come it takes so dam long to get a response anound hear, Why are so many bees leaving the unanswerd questions to the moderators.