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Hydriodic Acid--Step by Step Write-Up-Argox
Fri Feb 11, 2005 10:38 am |
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Argox
(Hive Bee)
02-22-02 07:05
No 271993
Hydriodic Acid--Step by Step Write-Up
(Rated as: excellent)
Bookmark Reply
STEP-BY-STEP PROCEDURE FOR MAKING HYDRIODIC ACID
PART ONE
TABLE OF CONTENTS
Intro
Background and Terms
General Overview
Step-by-Step Instructions
Obtain ingredients
Test ingredients
Mix ingredients
React ingredients
Redistill product
Hypothetical considerations
Instructions for buying a new Cadillac
Conclusion
INTRO:
This is a really long-winded write-up.
But have faith, your patience will be rewarded. Mixed in with a boring discussion of chemical reactions, Iíve decided to liven things up by including detailed instructions on how to obtain a new luxury car, so bear with me.
Argox has been slandered on this Forum. But none dare say poseur. The following write-up is based on EXPERIENCE, not made-up bullshit that passes for knowledge.
Hydriodic acid is illegal to manufacture or possess in California. It may even be illegal where you live. Find out. In the republic where Argox resides, a person can manufacture hydriodic and not go to jail. The jail time comes from making ---- with it, or selling it to ---- chemists, but avoiding prison is where your native cunning comes into play. Check out the legality of hydriodic in your neck of the woods before you make several hundred liters, just in case.
BACKGROUND AND TERMS:
Hydriodic acid is a fuming corrosive liquid, clear yellow to muddy brown in color. Hydrogen iodide is a transparent fuming corrosive gas. 57% hydriodic acid is a constant boiling (127?C/760 mm) mixture of hydrogen iodide and water.
In this write-up, the notation HI will refer to hydrogen iodide--a gas. The notation HI(aq) will refer to 57% hydriodic acid--a liquid.
HI(aq) is used in the clandestine production of ---- amphetamine. HI(aq) reduces ephedrine to methedrine and can be regenerated by red phosphorus (RP) and water. Instructions for making ---- using this method can be found elsewhere on this Forum. I donít know if the instructions are any good or not. Iíve never made ---- and donít know fuck all about making it. This is absolutely true. However, I am familiar with its market dynamics.
HI and HI(aq) are strictly and successfully controlled by the war-on-drugs agencies, since these compounds are relatively obscure and little used by industry. Any attempt to purchase HI or HI(aq) from a legitimate supplier will draw the attention of the authorities. Guaranteed.
Ephedrine-based ---- laboratories in the 50 to 100 kg/week range will have clandestine sources for ephedrine, RP, and HI(aq). The black market price of HI(aq) varies according to local market conditions. It ranges from $us[deleted] to $us[deleted]per liter in North America, with wide swings in price in the same area depending on its availability and the amount of ---- manufacture taking place at the time. A liter of HI(aq) weighs 1,700 grams and contains 970 grams of HI.
The clandestine ---- chemist without a black market source for HI(aq), or the enterprising chemist who wishes to supply the former, have three choices for making HI(aq):
1. Combine iodine and red phosphorus, carefully add water. This method is widely used by those chemists who supply ---- labs with HI(aq). However, it has the disadvantage of using watched chemicals. Red phosphorus (RP) is controlled. Iodine (I2) is watched. Obtaining OTC RP and I2 is not a serious endevour. OTC RP from match box strikers and OTC iodine from tincture is time consuming and labor intensive. Only tweakers will attempt to make their own RP and I2. Besides, this write-up is all about making HI(aq) from innocuous non-watched ingredients at any scale.
2. Bubble hydrogen sulfide gas through an aqueous slurry of I2, distill HI(aq).
H2S + I2(aq) --> 2HI(aq) + S?
This method is suitable for large-scale production of HI(aq). The disadvantage is that hydrogen sulfide is extremely poisonous. I really want to stress that the novice clandestine chemist should never attempt to generate H2S. H2S is a deadly poison, there is no antidote. With a lethal dose measured in small ppms, death can be expected in 15 minutes from acute cellular asphyxiation.
I was once gassed with hydrogen cyanide, which is similar in toxicity to hydrogen sulfide, luckily there IS an antidote for cyanide poisoning, and my lab was equipped with a Lilly kit and my co-workers were quick to respond, and the chief chemist had the brains to show up at the emergency room in that poor South American town with a bottle of thiosulfate. Had the gas been H2S instead of HCN, Argox would not be here to tell the tale. Having said that, for manufacturing HI(aq) in quantities above 20 liters/day, this would be the most practical method. However, I repeat that H2S is deadly poison, and if anything goes wrong, you and everybody in the immediate area will be at risk of dying. The obnoxious smell of H2S at low concentrations quickly overwhelms the senses at higher concentrations, and it is quite common for the victim to assume that ìthe smell went away, so everythingís OK.î Usually the last wrong assumption they ever make...
3. React potassium iodide with ortho-phosphoric acid, recover HI(aq) and HI. The chemistry of phosphorous is complex. Observation indicates that the following are the major reactions:
1) KI + H3PO4(aq) + delta temp--> HI(aq)+ KH2PO4
2) KH2PO4 + KI + delta temp--> HI + K2HPO4
3) additional HI(aq) and HI is obtained throughout the dehydration of potassium phosphate salts and polymerization of same while reacting with potassium iodide at high temperature--400+?C
This method has the advantage of being safe and controllable and uses non watched ingredients. The process is similar to a simple distillation, and requires only the type of glassware normally owned by the clandestine chemist. For 10 liters/day of HI(aq), this method is ideal, requiring only a 22L RB flask and heating mantle. A 12L-10L RB flask /heating mantle will produce 5 liters/day; a 5L RB flask/heating mantle 2.5 liters/day, etc. The heating mantle is a key element in making HI(aq), oil and sand baths will not take the temperature high enough. The tweaker can use a 1L erlenmeyer with single 24/40 neck on a stirrer/hot plate combo and produce 300-400 cc in a couple of hours. (Percent recovery is a function of scale. At larger scales, more HI(aq) will be recovered mol/mol per KI. 92% recovery mol/mol at the 22L scale and larger, contrasted with only 75% at the 1L scale. Why this is true I can only speculate, but it is true nonetheless.)
Now, for the first time on the Hive, this easy method will be explained step-by-step.
GENERAL OVERVIEW:
Disregard everything that has appeared previously on the Hive regarding the reaction of KI and H3PO4. I used TFSE extensively while initially researching this procedure, and without exception, all previous information is unclear, misleading, and, in several cases, made-up bullshit. The HI FAQ on Rhodiumís page, as regards KI and H3PO4, is erroneous. But you can count on my write-up to tell you exactly how to make HI(aq) safely. No bullshit here.
Here is a general overview of the procedure, specifics to follow:
In general terms, you will be mixing KI powder with H3PO4 liquid in a stirred RB flask on a heating mantle rigged for atmospheric distillation. The RB flask will be equipped with an condenser for downward distillation, a receiver to recover HI(aq), and a second receiver/trap filled with dH2O in which to bubble and recover HI.
KI will be converted first into HI(aq), then into HI(aq) and HI as the reaction proceeds. Hydriodic acid will distill at 105 to 127?C. After the initial run of acid is produced and the contents of the reactor cooled, the dilute hydriodic acid will be redistilled to produce HI(aq). The dilute hydriodic acid from the redistillation that comes over at less than 127?C will be reused in subsequent reactions in the HI trap/receiver. No dilute acid should go to waste. Overall efficiency goes way up by recycling the dilute acid into the next batch.
If this procedure sounds complicated, itís not, and your good buddy Argox will shortly give you all the tips, short cuts, and safety considerations that you will need to successfully make HI(aq) the first time.
Making 10L of HI(aq) in a 22L reactor takes one full 24 hour day from start to finish. This includes setting up the glassware and dismantling and cleaning up for the next batch. You need to stay awake during the reaction. The reaction should not be left unattended for more than 10 minutes, the dynamics are continually changing as the reaction proceeds, suck back can be a concern, you need to stay on top of it. It takes the same amount of time in a [deleted], but if you have the resources and knowledge to set up at that scale, youíre a master, not a student, and need no further instruction from me.
The reaction is simple. However, there are two caveats.
Caveat One--there is a white crystalline precipitate left in the bottom of the flask after the reaction is over and everything has cooled--condensed phosphates. This residue is insoluble in hot water and non polar solvents. It must be physically scraped from the flask. (Not a difficult chore with a 1L or 2 L, but with a 3N 22L RB count on breaking at least one neck. On a larger scale the problem can be solved by investing in a [deleted] with a large center flange opening that will allow you to get your arm inside and scrape.
Caveat Two--the majority of HI(aq) is produced at a temperature above the melting point of Teflon. Teflon paddles will melt and make the phosphate residue even more impervious. Teflon stir bars will melt, revealing the magnet. But really, who cares? Donít sweat the Teflon. (After all, once that first hypothetical batch of HI(aq) goes out the hypothetical door, you can afford to buy a $20 sheet of Teflon and cut a dozen new paddles.) Glass-coated metal rods and blades are the answer for the perfectionist in the audience. Just keep in mind that no exposed metal can be anywhere near HI(aq). Drop one little drop on your heating mantle and watch it burn a hole through the aluminum housing on its way to China. COVER your heating mantle with foil--lots of it! Thatís my way of saying that freshly made HI(aq) is very, very corrosive. So donít even think of entering the lab without eye protection, a lab coat, and good rubber gloves. If two drops of HI(aq) can burn a serious indentation into a cast-iron lab stand base, imagine what a splash of acid will do to your skin, or worse, an eye.
Argox
(Hive Bee)
02-22-02 07:10
No 271994
Hydriodic Acid--Step by Step (Part 2)Write-Up
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PART TWO
STEP-BY-STEP INSTRUCTIONS
1. Obtain ingredients.
Ortho-phosphoric acid, (H3PO4) commonly called phosphoric acid, a thick clear syrupy liquid, can be purchased or ordered from the neighborhood hydroponics store. They sell it as ìpH Down.î Conversely you can order it from the chem supply. Donít respond with posts belly aching about how youíre too paranoid or too smart to buy from the chem supply, and need a write-up that is 100% over-the-counter at Wal-Mart. Argox is not the guy to bitch to about chemicals not being available at the corner Circle K. He recently tried to help in that regard and only received grief for his effort. Finding chems is what separates the men from the boys, the serious from the dilettantes. Back to subject. Buy 75% technical grade phosphoric acid--this works best. Phosphoric acid is non watched and OTC. Itís in everything, even Coca-Cola. Next to sulfuric acid, phosphoric is the most common acid on the planet. You can find it on the shelf at the hydroponics store. DO NOT listen to all those posts about how you can get phosphoric acid at Home Depot or the flooring company. That is bullshit. [A personal aside--I think bees should receive a rating, like on e-bay. Except it would be a bullshit rating. The more bullshit you post, the more negative the rating.] The phosphoric acid sold for cleaning tile is only 15-25% acid, the rest is water, surfactants, soap, and stuff that will fuck up the reaction. Make sure you buy 75% technical grade H3PO4. It is strictly OTC, so no bitching. One gallon on the store shelf retails for $us20--be sure and read the label--some ìpH Downî is nitric acid--you want the label to say ìphosphoric acid.î A 5 gallon pail can be ordered from a hydroponics store for $us65.
Potassium iodide, a heavy white crystalline powder, can be bought at the chem supply. It is non watched and non controlled. You can buy it on-line. Technical grade is OK, but most supply houses only stock the USP grade. The higher price for USP grade in the global scheme of things is insignificant, buy whatever is easiest to obtain. USP KI can be purchased for $us36/kg. There is a boom in KI these days, because of the terrorism scare, take advantage of the general panic and buy a lot if it now, you will absolutely go unnoticed. 1.3 kg of KI will yield one liter of HI(aq) at 94% efficiency (very large scale), so order accordingly, before the WOD reads this post and adds KI to the ìList.î
2. Test ingredients.
Determine the concentration of H3PO4 by boiling it. Below is a chart of boiling points for different concentrations of H3PO4. You want yours to boil at 135?. That will indicate 75% acid. If your sample boils at a lesser temperature, donít despair, boil all your acid until it reaches 135? (and then make sure to get 75% next time). You can boil phosphoric acid in an open beaker on the hot plate. The fumes are non-toxic and non-corrosive--they smell like Sprite (because phosphoric acid is used to give soft drinks that citric flavor). H3PO4 is generally unreactive at room temperature--have no fear about mixing room temperature H3PO4 and KI in the RB flask. Nothing will happen. At room temperature, H3PO4 and KI will not react.
H3PO4
Concentration Boiling point
% by weight ?C
0 100
5 100.1
10 100.2
20 100.8
30 101.8
50 108
75 135
85 158
100 261
105 >300
115 >500
3. Mix ingredients
The mol/mol ratio of KI to H3PO4(100% basis) that works best, according to EXPERIENCE, is about 1:1.2. Here is how that is calculated:
1 mole KI = 166 grams
1 mole H3PO4 (100% basis)= 98 grams = 131 grams of 75% H3PO4
1 X 166 = 166
1.2 X 131 = 157
157/166 = 0.946
Therefore, for every ten grams of KI, add 9.5 grams of 75% H3PO4. Nobody will get mad, if you just add equal parts (weight/weight--w/w) KI and H3PO4. Now you understand how I arrived at this simple formula. Although it sounds almost flippant to say add equal parts by weight KI and 75% H3PO4, truth be told this formula was obtained after lots of trial and error. Adding more acid will not increase yield, but you can try it, nothing bad will happen.
As soon as I post this, three or four of the usual suspects will follow up with posts saying that Iím full of shit and that what you really need to do is add water so that all the HI will have enough water to come over at 57%. See, if you figure 1 mole of KI has 137 grams of iodine and with the one proton donated by the phosphoric acid that makes 138 grams of HI, so 138 grams of HI would need 104 grams of water to make 57% HI(aq). Follow me? These arm-chair chemists will then tell you that the equal w/w 75% H3PO4 to KI only adds about 42 grams of water, therefore they will say to add 62 grams of distilled water in addition to the phosphoric acid for every mole of KI. Donít listen to them. Iím heading them off at the pass right now. The reaction just doesnít work that way. (How do I know? I thought of adding more water from the git-go and tried it. Iíve also experimented with every concentration of phosphoric acid from 50% to 105%.) If you add more water, you will only generate a shit load of dilute acid, which must be distilled off before the real acid is made. See, what the arm-chair chemists donít know because they havenít actually done this, is that most of the HI(aq) comes over AFTER all the water from the 75% H3PO4 has distilled off. The bulk of the HI(aq) is formed from the dehydration of 105% H3PO4 at high temperature, a process typical of the complex chemistry of phosphates. The H3PO4 actually polymerizes into long-chain ìcondensedî phosphates and gives off water and donates a proton in the process. This is the water and hydrogen that make most of the HI(aq). And those long-chain polymers are what stick to the bottom of your flask like stink on a pig. And even if Iím somehow wrong on the theory, in practice I am right on target.
Now that you know how much to add, just dump the two ingredients into an appropriately sized flask. Nothing will happen at room temperature. There is no fizzing or effervescence during the entire reaction, so you can fill the flask fairly full. But no more than 60% for a RB, less for an erlenmeyer. But you already know that, right, because you have at least rudimentary lab skills, right? There will be a period of some massive bumping at a larger scale once the water boils off and the polymerization begins, even with agitation, so if you are faint of heart, fill the flask only 30%. At 1L, 3L and 5L bumping is not a problem. The bumping is nerve-wracking at the 22L scale. At [deleted] scale the bumping will make you jump out of your fucking skin. Agitation helps but doesnít eliminate bumping altogether, so if you get scared easy, add less ingredients. Itís really a function of balls versus greed. If you have the pelotas, then load that sucker up, ícause itís a full 24 hours whether you make a little or a lot. If the doors come down, the charges will be the same, as well, so I say go for it.
4. React ingredients
UNDER A FUME HOOD, heat and stir the ingredients--itís that simple. At 65? an obvious reaction will take place. The clear solution will turn dark brown. This is hydriodic acid being formed. Keep the heat on high, donít let off. The solution will begin to boil at 105?C and a small amount of milky white distillate will come over into the receiver.
READ THIS PART--ITíS IMPORTANT. This initial white distillate and the gas bubbles that are generated at this initial stage of the reaction are poisonous. (OK. OK. Hydriodic acid is hardly something you want to drink for breakfast either, but this white distillate is REALLY poisonous, even compared to HI(aq).) You must remove this white milky distillate once the first drops of yellow or brown acid start to come over. So begin the reaction with a small RB flask as a receiver, say 100 to 250 cc. Collect the initial white distillate and stopper it. DO NOT BREATHE this stuff, Iíll explain what it is in a minute. If you do this reaction on a small scale, the white distillate may only be a few drops, get rid of it anyway. On a large scale, it is enough to kill you. You will have a second receiver filled with dH2O to recover HI. However, at the beginning, substitute it for a small flask filled with dilute NaOH solution or the dilute aqua ammonia (ìclear ammoniaî) that you can buy at the grocery store. Why? Because the first distillate and the initial gas contain H2S (the same hydrogen sulfide that I mentioned being deadly poison at the beginning of this long-winded tome). My guess is that since phosphoric acid is often made from the reaction of sulfuric acid on phosphate rock, trace amounts of sulfur remain in the phosphoric acid. HI is a powerful reducing agent (thatís why the ---- guys need it), so there is a redox between HI and any sulfides. (2HI + MeS + delta temp -->H2S + I2 + Me?. And since H2S is less soluble and more volatile than HI, it comes over first.) This is something else the arm-chair chemists wonít warn you against, but count on Argox to keep you safe, if you pay attention. Like I said, the tweaker with the 1L wonít notice anything, but the bee loading up a 22L could end up very sick, if my advice is not followed. Anyway, add any base, preferably NaOH or ammonia to the white distillate under a fume hood before you toss it out and as long as the initial bubbles are taken up in NaOH solution or ammonia solution, and that solution is also poured down the sink, you will never even know that Argox just saved you from a hospital trip or at least from having to suck on your oxygen bottle for an hour or so. (The arm-chair guys will say that HI smells like H2S and that Iím just confusing one with the other--they are wrong--you can get a good nasal dose of HI fumes and apart from the pain, nothing will happen to you. Get a good dose of H2S and you are going to be unconscious in a few minutes. Initially your teeth will tingle, everything will spin, and as you collapse to your knees, you will realize that this is it, you are going to die. If youíre lucky, like me, youíll wake up in the emergency room puking sodium thiosulfate (oh yeah, thatís cyanide poisoning, for which an antidote exists--if you breath H2S, youíre shit outta luck--thereís no antidote). Anyway I digress: HI smells rotten, but pales in comparison to the deadly stench of H2S.
After getting rid of the initial milky white distillate and taking up the initial bubbles in a dilute base and throwing both away, connect your two regular receivers. This is an atmospheric distillation, so relax. Just keep the heat on high and the overhead or magnetic stirring going. On a smaller scale, stirring is not necessary. For bees with big equipment who lust after the perfect yield, stir.
The reaction is not over when all the brown acid has boiled out of the reactor, it has just begun. Keep the heat on high and watch in amazement as more and more and more acid keeps forming in the condenser. Donít worry about the thermometer at the still head going above 127?C, it is still HI(aq) coming over, just the temp inside the reactor is getting HOT. At 400?C both HI(aq) and HI will come over. Lots of HI at a larger scale, so be prepared for it. About 10% of the total acid production will be in the form of HI that must be collected in the water trap/receiver. HI is exceedingly soluble in water and the dissolution is exothermic, so stirring is not absolutely necessary, but cooling is. More than 10% of the total acid comes over as HI, but most of it is being absorbed by the liquid in the receiver catching the distillate. That is why you keep the dilute acid in the receiver even after the 57% acid comes over. If you remove the initial dilute acid and then collect the 127?C boiling fraction (HI(aq)) as a separate fraction, then to your dismay, you will have loads of HI coming over that must be caught in water. And then you will find that the hydriodic acid in the receiver is incredibly concentrated-- 70% not 57%. The 70% acid gives off so much fumes that handling it is a challenge. So just let ALL the acid collect in the same receiver flask, make sure your receiver is big enough, and you wonít have to deal with much actual HI gas.
{If you donít have a clue about how to set up a for atmospheric distillation with a still head and condenser and water traps and such, and donít know about RBs and heating mantles, and how to control suck-back, and if none of what you are reading makes much sense, and especially if you donít have a good fume cabinet--PLEASE donít try this. There are less dramatic ways to kill yourself than producing a shitload of HI(aq) and spilling it.}
The reaction is over when no more HI(aq) or HI is produced. The reaction is over when no more acid drips into the receiver and/or suck-back begins to be a real problem in the water trap (suck-back with HI is violent--the most violent of any gas Argox has ever worked with, make SURE you have an empty trap to catch suck back). The remaining contents of the reactor will look like white taffy. The dilute acid in the receiver will look dark brown. The dilute acid in the water trap will be a clear brownish yellow. Once no more acid comes over, you can turn off the heat, take off the water trap, and allow the glassware to cool--slowly. Keep in mind that your glassware is at 400+?C, so donít even think about handling it or taking it out of the mantle or off of the hotplate--the thermal shock will crack the flask instantly. Since you know Argox doesnít make this shit up (unlike others, nameless for now), this means that he found out the hard way about thermal shock and cracking glassware, and is saving you a lot of grief with these words of wisdom.
5. Redistill HI(aq)
There are two ways of telling if your acid is 57%:
1) Weigh it in a graduated cylinder--the density of 57% acid is 1.7. 500 cc will weigh 850 grams, exactly. Anything less is not 57%.
2) Boil it. 57% hydriodic acid boils at 125-127?C.
(OK. OK. Get back on your chair. I was just kidding to see if you were awake. A little black humor--of course you donít fucking boil it, it will corrode everything in your lab including your lungs, just weigh it.)
Probably none of the initial acid collected in either of the receivers is going to be 57%. Weigh it to find out. If its density is less than 1.7, then you must redistill. No sweat. There is a short cut that makes this a snap.
The redistillation is a straitforward atmospheric distillation. No gas will be generated. As soon as the acid boils and starts coming over you must watch the thermometer at the still head. As soon as it reaches 125?, change receivers. Everything that comes over from that point forward is 57% HI(aq). The very last drop will distill out of the boiling flask. No residue will be left, it all boils. In fact, after you have done this distillation once, you will quickly figure out the obvious short cut--collect the fraction that comes over at less than 127?, and then turn off the heat and everything left in your boiling flask is 57% HI(aq), no need to distill it--itís already pure. Just allow it to cool before you package it up.
6. Hypothetical considerations
What follows is the only speculative part of this write-up. You might call this Argoxí version of made-up bullshit. However, even my bullshit should be instructive.
How might the public view hypothetical shop-made HI(aq)? (It depends on their intelligence, of course.) See, acid made by the method I have just detailed is dirty brown. This is due to trace amounts of HI being oxidized to I2 as it comes over in the condenser (4HI + O2 = 2I2 + 2H2O) and from impurities in the tech grade KI. The brown color is insignificant, and does not interfere with the potency of shop-made acid. Commercial HI(aq) contains a reducing agent as a stabilizer, usually hypophosphorous acid, and is clear yellow. In the hypothetical case you use this write-up for other than purely theoretical considerations, at some point the topic of off color might arise. But, again, speaking hypothetically, I would recommend that you educate rather than stabilize. Unstabilized shop-made HI(aq) will work just as well as the store-bought variety in a hypothetical userís hypothetical application. The difference is purely cosmetic. The way to convert dirty brown acid into clear yellow acid is to add red phosphorous and heat it. But hey! Wait a minute! Isnít that what a hypothetical user might be doing anyway? Adding RP and heating it? Explain this to whomever, hypothetically. Give whoever a demonstration in a test tube. Convince them. Hypothetically.
Once the hypothetical user overcomes his or her initial reluctance, donít be surprised with the heavy pounding on the door late one night--no, itís not the cops, it might be that hypothetical person begging for more hypothetical acid. The word might hypothetically spread to others, and the all-request line become incessant. Of course, I really wouldnít know anything about any of this...itís all just hypothetical. I am making it up, OK.
As for packaging, hypothetically pour acid into amber glass bottles, or better yet, the red .....oh shit, since this is all hypothetical, I wouldnít want to be hypothetically linked to a certain bottle...hell, if you are intelligent enough to make acid, you can figure out in what to put it. Remember--one liter of HI(aq) weighs exactly 1,700 grams. In the hypothetical case the hypothetical user goes into a production frenzy and needs volume, think black HDPE jerrycans.
HI(aq) must be protected against light and always stored in a cool (temperature and otherwise cool) area AWAY from people. I wouldnít freeze it, but since Iíve never frozen any, I couldnít really say what might happen. The acid will slowly degrade over time, but no big deal. Without a stabilizing agent, HI will slowly revert to I2. But like I said, no problem: the hypothetical userís hypothetical application will solve that hypothetical problem.
With your native intelligence, youíll figure out all sorts of other shortcuts and useful procedures in the off-chance you actually paid attention and hypothetically decide to make a little hypothetical acid.
7. Instructions for buying a new Cadillac.
What? Did I bore you, and you missed that part? You mean you werenít paying attention? Donít recall anything in all this gibberish about chemical reactions and corrosive acid that had anything to do with an expensive car? Oh. Iím sorry. In case you missed it the first time, the highly detailed instructions on how to buy a new Cadillac start at the beginning of this post, right where it says ìINTRO.î
CONCLUSION:
I have three motivations in posting this:
One, to publicly apologize and make up to Rhodium for the ìbadî post from a couple weeks ago (which was deleted so fast few of you even read it).
Two, because Ritter asked about this process in a PM, and if he gets a write-up, then everybody gets a write-up. Sorry to take so long, buddy.
And three, Argox has too much time on his hands while the pots boil. No seriously, itís because I am fucking nuts, besides... once you do the above procedure a few times, you will get tired of staying up all night worrying if your incredibly expensive flask is going to break and shoot a fuming volcano of incredibly corrosive hot acid all over your incredibly expensive heating mantle and burn a hole all the way to the center of the fucking earth, taking most of your lab with it. You will then figure out a better way. But hey! Thatís another write-up.
Regards
Argox
Jetson
(Hive Bee / Eraser)
02-22-02 12:32
No 272101
Re: Hydriodic Acid--Step by Step (Part 2)Write-Up
Bookmark Reply
let me be the first to say, fukin excellent write up bud!
"this could be an illusion but i might as well try..."
codyboy
(Stranger)
02-22-02 17:26
No 272236
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
DUDE........PARTY ON!!!!!!!!!
Thank you,
your time and effort deserves 'el mundo PRAISE.
codyboy
humidbeing
(Can't SWIM)
02-22-02 22:48
No 272362
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
Very comprehensive and astute.
..then when one is cool, one may become groovy. Grooooovy.
SpicyBrown
(Hive Bee)
02-23-02 02:35
No 272432
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
Yes, it's already been said, but .. good writeup! Thanks.
SpicyBrown
Argox
(Hive Bee)
02-23-02 02:56
No 272438
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
Dammit! Upon re-reading my post, I see an error. A very minor error, anyway here's the fix:
The part about how the hydriodic acid distills over brown because of impurities in tech grade KI should have read "tech grade H3PO4."
Anyway, if you like this post then let everybody know publicly, because that's the only payment I will ever receive for sharing this with Hive collective, and any risk I put myself in The bees who only think in terms of mdma and analogs maybe won't understand the significance of this post, but for the ---- guys, this should be a breakthrough. Making HI instead of using I2 will cut down on how much RP they need. In fact it is my understanding that HI alone will reduce ephedrine to ----, without need for any RP, or very little. Of course the part about how I know fuck all about making ---- is true, so don't shoot me down for any mistakes I may make regarding how to make ----.
I get requests, but have so far refrained from heading in that direction. Bad karma. Have you ever seen a ---- addict? Fuck, man. I wouldn't want to be directly responsible for that. They look like death warmed over. What's with that fucking skin disease they all seem to have? Iodide poisoning?
Anyway, let me know what you think of the post.
Regards
Argox
PoohBear4Ever
(Junior Service Representative)
02-23-02 03:08
No 272443
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
A+ information you got there!
PB
ballzofsteel
(Hive Bee)
02-23-02 11:11
No 272537
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
Sounds like a lot of funVery nice,thankyou very much for this info argox.Ballz is going to bed now and will be dreaming of HI all night long.Nice writeup-fun to read.
Cheers dude
ballz.
diogenes
(Hive Bee)
02-23-02 12:18
No 272550
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
Every so often there comes along that certain Bee.
Argox, it's Bees like you that make this place so great!
That was a very nice and informative write-up that's bound for Hive greatness!
Thanks for sharing that with us.
Jetson
(Hive Bee / Eraser)
02-23-02 12:56
No 272562
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
HI will by itself reduce eph. the rp is used to recycle the iodine back into the HI.
breakthrough indeed! swij sees the biggest breakthrough of this though as being the time that argox took to sit down and write this masterpiece. alternative methods of producing HI have been around since the dawn of all things speedy... don't get me wrong, i'm in no way hacking on argox or trying to take anything away from this writeup.
shiftless
(Stranger)
02-25-02 23:08
No 273605
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
Hi, I'm a newbie so if I say anything stupid please correct me.
Is it possible to make HI through the reaction:
HCl + NaI -> NaCl + HI
?? This seems like it would be safer if it works (i.e. not producing the nasty H2S etc). Would that produce the gas or the liquid?
So HI will reduce eph by itself, then? Excellent! What is the ideal ratio of eph to HI in the reaction vessel if no red p is used?
I would just like to comment that this writeup was excellent and will help me a lot. Thanks!!
Rhodium
(Chief Bee)
02-26-02 06:08
No 273747
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
Is it possible to make HI through the reaction: HCl + NaI -> NaCl + HI
No. There are just a few methods available for making HI, and those are covered in this writeup and https://www.rhodium.ws/chemistry/hydriodic.html
Synthia
(Hive Bee)
02-28-02 15:02
No 274898
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
if the teflon on your stirbar is melted off and the magnet is exposed, what will the effect be on the magnet and its stirring/ballance and the effect on the reaction/reactants/user?
also if i may, would the small amount of oxidised HI (to iodine) in the final solution have a buffering or stabilising effect on the acid?
thanks
sYntHIa
guilty of cryptic waffling
psychokitty
(Her Majesty, Stoni's Kitty)
02-28-02 16:02
No 274934
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
My question is like the one above. If the teflon on the stir bar is expected to melt then shouldn't one just place the flat-bottomed flask directly on the hot plate and go from there? What are the advantages and disadvantages to heating in this manner? Any alternatives?
Argox
(Hive Bee)
03-01-02 04:10
No 275240
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
Regarding the above two posts, these thoughts:
The stir bar was melted when experimenting with a 1L FB erlenmeyer with single 24/40 neck placed on a 6"x 6" hot-plate stirrer combo. The part of the stir bar in contact with the bottom of the flask melted and spread out. But this stir bar survived the experience, in fact has seen service since in stirring small flasks. The magnet is ceramic, I believe, and appears to have not suffered any corrosion, although it's a butt-ugly little stir bar now.
But like I said in the write-up, stirring is not essential to success. The ingredients are so cheap (relative to the value of the product) that if you don't have the highest recovery, so what? On a larger scale, then efficiency would be the main goal. At a larger scale the bumping would be too intense without stirring, and the efficiency would probably fall off, but these thoughts are pure speculation, since no non-stirring experiments were attempted at a larger scale. The solution to the problem at your likely scale,and only if you fall in love with your stir bars and can't stand to see them melt, would be a all glass shaft and blade.
Completely off topic (for most)--if you should ever decide to train for the Olympics, faster, stronger (what's that other one?), you will meet a cool old dude named Pflaudler along the way, he's a "righteous" old guy. Once you get to know him, he'll become your new best friend.
Back to topic--Was it clear from the write-up that HI is very corrosive and noxious and that its manufacture should only be considered under proper safety conditions, e.i. not on your kitchen stovetop?
Anyway, good luck.
Regards
Argox
Scottydog
(Hive Bee)
03-14-02 10:24
No 282518
Re: Hydriodic Acid--Step by Step Write-Up
Bookmark Reply
Impressive write-up Argox. I definately learned something new today and although a little late, I still wish to express my gratitude. Excellent detail and very easy to understand. Even for a chemically challenged bee like Swis.
Thanks for providing a viable and cost-effective option.
You can't put a price on enlightenment...
Flinger
(Hive Bee)
03-17-02 00:11
No 283767
Post deleted by LaBTop
Bookmark Reply
Hermetic
(Stranger)
04-02-02 16:16
No 291545
Fantastically detailed, exactly what I need to ...
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Fantastically detailed, exactly what I need to get the info into my head. My question, then, is does anyone think this might work for reduction of that OH group in-situ? If H3PO4 is a by-product of RP/I reduction, then can it be assumed that it is not a large hindrance to the reaction? Would it be beneficial to halogenate the molecule first, and then introduce H3PO4 + KI (or NaI) in excess proportions to drive the equilibrium to the right? My organic skills are weak compared to most, but I'm trainable. I ask this because I2 and H3PO4 are not a problem here, and I can make NaI or KI if necessary.
"Wyatt, I am rolling."
pROcon
(Hive Bee)
04-09-02 06:00
No 294594
Argox
Bookmark Reply
Argox, really...I don't know what to say...
don't call me...I wont answer, or call you back.
myles
(Stranger)
11-02-02 23:25
No 375946
thanks
Bookmark Reply
Works well thank you for your help, from my friend of course.
The BEE game is why im here top score 300 points
mofessto
(Stranger)
11-03-02 19:06
No 376186
You Deserve a Medal!
Bookmark Reply
Thank's alot Argox from a newbee information worth saving.
"For every second passing is yet another missed chance to turn it around"
Ph0enix
(Newbee)
11-05-02 00:20
No 376612
Where the F**K..
Bookmark Reply
has this post been hiding?
Thank you Argox and I'm sorry to see this excellant post go so long before receiving the recognition it should have long ago (since February!?!)
Thanks again.
...though I know no one who employs such methodology it is quite obvious.
~PVnRT_NC8~
Rhodium
(Chief Bee)
11-05-02 02:37
No 376637
History of the thread
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I moved it here from methods discourse recently, as I thought it really should be a sticky thread here instead.
It has also been present on MY PAGE for SEVERAL MONTHS - don't you people search there BEFORE asking things here?
shineon
(Stranger)
11-08-02 21:48
No 377883
could this help the bumping
Bookmark Reply
by putting some broking glass or boilling stones in the reaction,
12345x
(Newbee)
11-21-02 08:03
No 381863
57% stabilized....
Bookmark Reply
in the old days one would buy HI
at the store as 57% stabilized
the fine print would say stabilized with phosphorous acid
now if you heat 46 ml of water
then add some rp "say 20 gms or more"
then add 57 gms of iodine.
and boil for a few min's
and when its a clear color.
you filter out the remaining rp
your liquid is apx 108 gms of 57% HI in water
with apx 8 gms of phosphorous acid."thats what the rp thats used
gets turned into"
now dont you think this is how it was made
when they sold it at chem supply stores?
honeysmoker
(Hive Bee)
01-04-03 04:49
No 395352
IMPRESSIVE
Bookmark Reply
A+++ Quick witted, knowledgeable, Mature. Would read a post from this man again. Good communication. A++++++++++
No bull shit could be detected.
(attempted Hive/E-bay rating)
HS
Rhodium
(Chief Bee)
01-17-03 14:58
No 399133
New ways for making HI
(Rated as: excellent)
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Hydriodic acid from Iodine, Water and Sodium Sulfite
Na2SO3 + H2O + I2 -> 2 HI + Na2SO4
Six parts crystalline sodium sulfite, one part water and three parts iodine (by weight)
is heated together in a flask, gaseous HI is formed together with solid sodium sulfate.
Ref: Philosophical Magazine [3] 35, 345; Jahresbericht ueber die Fortschritte der Chemie 253 (1849)
Hydriodic acid from Iodine, Water, Barium Oxide and Sulfur Dioxide
BaO2 + I2 -> BaI2 + O2
BaI2 + I2 + SO2 + 2 H2O -> BaSO4 + 4 HI
Ref: Comptes Rendus 142, 279; Chemisches Centralblatt I, 732 (1906)
The above preparation methods and many others can be found in
Gmelins Handbuch Der Anorganische Chemie (1909) (https://www.rhodium.ws/djvu/hydriodic.gmelin.djvu)
To view the DejaVu file, you need a browser plugin from http://www.lizardtech.com/download/
ahgreich
(Stranger)
03-17-03 22:26
No 418318
Riddle me this...
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Following Rhodium's last post as a very general guideline, SWIM put around 1/2 cm sodium sulfite in a test tube. Immediately topping it with around 1 gm of dirty pfed fb. a squirt of dh20, and, topped the cake with a slug of I2, approximating the ratios from the previous post.
Taped a punch baloon condensor on the end just in case.
manually placed end of test tube over hot plate on high, jiggling it gently to coax the reagents to mingle.
As soon as the I2 made it through the pfed layer, BANG! instant purple gooness that SWIM assumes is iodopseudo gunked the sides as in a small rp/i type event. Excitement.
Kept heating and gently jiggling the tube, iodo slime was quickly replaced with pale yellow sun goldenness, no I2 visible.
plug of sodium sulfite at the hind end of the tube made a workup attempt seem unfair and not worth SWIM's time. Removal of said condensor and proximal nasal inspection was most unpleasantly harsh, though no visible smoke the duration of the reaction or post reaction.
Does anyone want to venture an explanation?
Could this have been The Stuff?!?
fierceness
(Hive Bee)
03-17-03 22:41
No 418328
Rhodium, could one use this as a RP substitute
Bookmark Reply
Rhodium, could one use this as a RP substitute almost by performing an in situ production of HI?
Sodium Sulfite is very OTC here.. perhaps a suggested experimental for this in situ synth is the following (please correct any errors):
6g freebase pseudo + 8mL H2O + 12g Sodium Sulfite + 6g I2 combined in a small flask and refluxed for 6-12hrs... workup as per usual
Anyone see anything wrong with this before SWIF attempts it?
Rhodium
(Chief Bee)
03-18-03 17:39
No 418814
Old refs
Bookmark Reply
One problem would be that you wouldn't get a solution with so much reagents in so little water, but rather a paste...
Also note that the above references are 100-150 years old, so you might have to research the topic a little bit further before actually using it in a synthesis, unless you have analytic equipment.
fierceness
(Hive Bee)
03-18-03 18:57
No 418846
hmm
Bookmark Reply
ahh, true.. and adding more water would decrease the concentration of HI too low to actually reduce the pseudo.. what about substituting acetic acid for water, or using a 50/50 mix of water and acetic acid, since using acetic acid is supposed to increase the concentration of HI...
is there any way this could work? swif is certainly willing to test this out with his reagents
I think he will just add the ingredients all dry and add enough water to give it the ability to actually reflux
Scottydog
(Hive Addict)
03-18-03 19:41
No 418861
Highly Intriguing
Bookmark Reply
Highly intriguing info Rhodium! The ideas never cease.
Considering that what is being produced here is anhydrous sodium sulfate and HI. According to chemfinder, Na2SO4 has a melting point of an astronomical 884 degrees C. This HI could be essentially driven into a 2nd flask of h20 until a 57% solution is obtained and then this 57% HI solution used in excess (molar ratio of 4HI: 1 pseudo) and refluxed for a day to get golden gear?
Considering that Na2SO4 can withstand the outrageous 884 deg C, high temp does not seem to bee an issue.
So basically this Na2SO3/I2/h20 mixture is heated until all signs of moisture is gone. When the h20 is gone all HI has been formed? This combo can be constantly replenished until the 57% strength is reached?
With sodium sulfite available at approx $60 for 2.5kg and the same amount of KI for under $300, theoretically, HI has never been cheaper?
Thanks much...
___________
Refuse/Resist
fierceness
(Hive Bee)
03-18-03 19:47
No 418864
ahh! thanks scotty.. i was looking for the...
Bookmark Reply
ahh! thanks scotty.. i was looking for the ratio needed for HI to reduce pseudo w/out red phos.. better yet, you could distill out the HI as you say, and reflux with pseudo and some more sodium sulfite.. the sodium sulfite should recycle the iodine as red phos does, right? then you wouldn't need quite as much HI..
swif is still going to attempt it was a straight RP substitute.. he's going to wet it enough to get a reflux going and reflux it for 6 hrs and see if it worked...
I'm still curious about the acetic acid thing.. i wonder if it would improve anything?
fierceness
(Hive Bee)
03-18-03 19:55
No 418871
another idea... crystallization
Bookmark Reply
here's another idea.. i dont fully understand the theory of crystallization, so this idea may be stupid, but I thought i'd throw it out there anyway...
Ratio of 6:2:3 sodium sulfite:water:iodine
I double the amount of water so that we get an approximate 50% of HI in solution.. now, can one drop the temperature of the solution just above freezing to try to crystallize out the sodium sulfate and then filter it leaving HI?
Maybe swif should just try these ideas out instead of asking all the time.. he just doesn't want to inadvertantly create an explosion or some kind of toxic gas (other than HI, of course)
fierceness
(Hive Bee)
03-18-03 21:20
No 418898
TFSE findings
Bookmark Reply
Scotty, there is a chance that your 1:4 ratio is flawed...
Check out Post 386152 (Rhodium: "57% HI", Stimulants) the whole thread.. specifically that one and this one Post 392251 (WizardX: "The problem is the HI dissociation.", Stimulants)
will a 4:1 ratio of HI with no recycling agent (RP) be enough to reduce pseudo to ---- in a 12hr reflux?
fierceness
(Hive Bee)
03-18-03 22:40
No 418924
Little experiment
Bookmark Reply
swif did a little experiment to see what the rxn contents woudl look like at a 6:3:2:2 ratio (Na Sulfite: I2: H20: pseudo)
The reaction contents looked somewhat like the old days of the 'dry' push/pull reactions.. there was a definite liquid portion, and also an insoluble portion (the I2, i assume).. it *Definitely* made HI with little or no heat at all...
swif did not want to continue any furthre, though without some comments here.. there is no way that H2S will be produced by this is there? swif would rather not have hydrogen sulfide poisoning..
Anyway, my point is that even though the 'paste' is not completely a solution, it is possible that this method will work, as he has seen it work in the 'dry' runs.. swif will try this again, as soon as someone convinces me that H2S will not be a problem..
At least HI was definitely made with ease! just double the water and use stirring or swirling if possible... however, scotty's suggestion of piping the HI(g) to a flask of water may not be a bad idea either..
I feel bad for seemingly cluttering this thread -- If you guys feel i should start another one for this, please let me know 
ahgreich
(Stranger)
03-19-03 01:01
No 418954
assumptions about HI concentration...
Bookmark Reply
In Swim's unschooled mind, he was thinking that keeping the dH20 volume very low (just enough to moisten the sodium sulfite), that the HI would a) be a free gas in the tube and 2) as heat was applied, the vapors formed would be very highly concentrated HI aq???
Also, he was thinking that since Pfed FB was used, no HCL to remove, instant iodopseudo, shortening reaction time?
total time for the entire experiment was less than 5 minutes, from raw pfed fb - > iodo - > ?? (pale yellow something on sides of tube). No I2 visible at finish.
fierceness
(Hive Bee)
03-19-03 15:36
No 419163
the pale yellow was probably HI(aq)..
Bookmark Reply
the pale yellow was probably HI(aq).. however, HI as a gas does NOT reduce pseudo.. you need the 57% solution at reflux to efficiently reduce pseudo... see the stimulants FAQ posts by Osmium to confirm this..
The fact that you saw a lot of gas means that you weren't really reducing much.. the little bit of water that you added dissolved as much HI as it could (hence the yellow color)..
amalgum
(Hive Bee)
03-21-03 11:35
No 419851
HI
Bookmark Reply
Well hell yeah! Could this make rp obsolete? SWIM was finishing up a good ol' rp/I2 reaction when SWIM read this, so after hitting a tester of the finished product, SWIM went and searched through an old box of chemicals that was laying around. Low and behold, SWIM came across a big bottle of sodium sulfite.
To test the theory, SWIM placed a little iodine in a beaker. Then some of the anhydrous NaSO3 was thrown on top. The two dry chemicals were mixed, with no apparent rxn. SWIM then went to add the water required to facilitate the rxn, and accidently added what looked like probably too much. SWIM swirled the beaker contents around a little, and it appeared that only about 1/8-1/4 of the total amount of NaSO3 dissolved making the solution yellow. The rest stayed at the bottom, along with the iodine. Nothing was happening. Since SWIM only added a little bit of iodine and a lot of NaSO3, SWIM added more iodine. Swirled the shit around, still nothing. "Fuck it", SWIM thought, "maybe it just needs a little energy, one last try". SO SWIM placed the beaker on the stove burner and turned it on to about 3/4 power. There wasn't much in the beaker, so it only took about a minute to begin to boil. When this happened SWIM took the beaker off the stove (it was soft glass, didn't want to crack it), and swirled it around. This time, as soon as SWIM began to swirl, all of the iodine instantly dissolved, and it looked like about 90% of the NaSO3 dissolved. Then a wonderfull thing happened. Even though there was quite a bit of water, it began to smoke. That white smoke looked awfully good and familiar, and upon a quick wafting of the vapour from the beaker to SWIM's nostril, the umistakable smell of HI was detected. "Hey this smells like the damn rxn SWIM just ran with the rp", SWIM thought.
So, basically, as soon as SWIM's friends uncles dad gets some more pseudo, this rxn will be tested. Let me get some things straight first.
Is the eqaution like this?:
1NaSO3 + 1H2O + 1I2----->2HI + 1NaSO4
If so, this is what SWIM came up with:
Since a double molar amount of HI is needed to reduce e fully to methedrine, SWIM calculated a test reaction ran with four grams e. If the equation of the HI rxn is as above, then that means SWIM would technically need an equalmolar amount of NaSO3 to ephedrine (since double the molar amount of HI is produced). For four grams e HCl, that would mean about 2.5g of NaSO3 is needed (which a slight excess, like 2.7-2.8g is actually used to try to make up for effeceincy losses, and recycle most of left over iodine). As far as iodine goes, again an equalmolar amount is needed. That would mean about 5g of iodine is needed. No excess of iodine is needed, in fact SWIM figures one might get away with using less than an equalmolar amount of iodine, because I2 is reformed when HI reacts with the iodometh (technically, you could get away with adding a little over half an equalmolar amount SWIM guesses, because the half would be enough to turn all e into iodometh, and the slight excess to make enough HI to start reducing the iodometh to I2 and ----, which the I2 is reused, but for a first time SWIM doesn't wanna take that chance). Now the reaction is gonna need some water to start. Since SWIM figures that an equalmolar amount (to the e) of water is produced after it all gets turned into iodometh, only half of the H2O needed to produce the required HI will be added. SWIM doesn't want to add less than that for fear that their might not be enough, because there would be enough to get it started, but not enough is produced to finish the rxn. SWIM doesn't want to add more becuase of the nature of this type of rxn. So basically, a half molar amount of water (again to the e) is used, which is about 400mg, or .4g, or about half a milliliter. First E and I2 will be mixed dry in the rxn vessel, then the H2O will be added. After it's mixed well, the NaSO3 will be added, and the rxn vessel closed up like in a typical rp/I2 rxn (unless of course your using an open vessel and condensor). The four reagents will be mixed well, and then heated enough to start the rxn. Rxn will pretty much be treated like a regular rp/I2 rxn, keeping a close eye on the rxn clues of course (so one could work out proper rxn times, etc). When done, water will be added to the contents, and pour into a pestle and mortar. All the NaSO4 that is present will be crushed under the water as fine as possible. The rxn matrix will then be filtered, and the NaSO4 washed with a little extra water. Then workup will proceed on the rxn matrix as normally done. Washing the solution before basification of course to help get rid of extra iodine if so present.
SWIM knows it is a long post, but what do some of your guys think? It's definitely worth a try!
Rhodium
(Chief Bee)
03-21-03 16:14
No 419934
You need a large excess of HI to reduce ...
Bookmark Reply
You need a large excess of HI to reduce ephedrine, not just two equivalents - that is just the theoretical amount.
amalgum
(Hive Bee)
03-21-03 16:48
No 419947
right
Bookmark Reply
Yeah your right, nothing is ever 100% efficient, esp. this type of rxn. How much exactly of an excess are we talking about? I would try to calculate it using the theoretical amount of HI produced by the rp/I2 method, but there are too many different ratio's for that reaction out there, it's hard to determine which is best.
fierceness
(Hive Bee)
03-23-03 16:14
No 420612
Rhodium: regarding sodium sulfite + I2 + H20
Bookmark Reply
is there any way that the sodium sulfite method of producing HI will produce any extremely poisonous H2S in the process as a side reaction?
We dont want bees killing themselves trying to do this procedure
Rhodium
(Chief Bee)
03-23-03 16:53
No 420616
Redox chemistry of sulfur
Bookmark Reply
As SO32- is itself the reducing agent acting on I2 in this case, that is highly unlikely, as that would mean SO32- could spontaneously disproportionate from S4+ (sulfite) to S2- (sulfide) and S6+ (sulfate), which it doesn't as S2- is oxidized to elemental sulfur by I2 - see https://www.rhodium.ws/chemistry/hydriodic.html
amalgum
(Hive Bee)
03-24-03 10:29
No 420854
more stuff
Bookmark Reply
SWIM has procured new materials today. After SWIM extracts the pseudo he will try a small rxn, and post results.
amalgum
(Hive Bee)
03-28-03 05:22
No 421969
first try
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Alright, SWIM had 4g pseudo to start with. To a 250mL rb flask, SWIM added 4g pseudo, 5g Na2SO3, 10g I2, and about 2mL of water. The flask was stoppered with a glass tube sealed with a balloon. SWIM shook the flask thoroughly to mix the shit. At first it was just wet and clumpy. SWIM added a little heat from a candle (not much, the flask was high above the candle), and the contents got liquidy, and started bubbling a little bit. For the first 15-20, things went along pretty much like an rp rxn. After that, it pretty much died down a lot. SO the flask was lowered closer to the candle. After a few minutes, the shit started getting a lot more liquidy and bubbled more. The balloon also inflated pretty well. It was allowed to go like this for another 20. Then SWIM began to notice that a dark colored smoke appeared, that was kinda purplish, and looked like iodine subliming. SWIM let it stay for about 5 minutes then took it off heat and swirled around really well. SWIM let it cool until the balloon looked like it was gonna be sucked into the flask. Then, it was removed, and about 1.5mL of h2o was added. The balloon was replaced and the flask reheated. The rxn eventually got hot enough to continue like before, so SWIM lowered the flask just a little more, and continued to boil for another 15 minutes or so. Then the candle was blown out.
SWIM is awaiting the contents of the flask cool now, and is still unsure about the outcome of this rxn yet. WIll keep updating.
amalgum
(Hive Bee)
03-28-03 06:29
No 421976
hrmmm
Bookmark Reply
Well, SWIM did a water extract, then acidified with 6 drops of conc HCl and did a couple more extracts. Looks to be a helluva lot of unreacted iodine left folks. All the aqueous extracts had to be washed with xylene about 5 times before becoming devoid of most iodine. SWIM has basified solution with NaOH. A whole lot of freebase of something came out. Although it did not have the look and feel of a completed rxn, nor quite the smell. Looks like probably a bunch of unreacted pseudo. Well, SWIM will go ahead with the a/b, and update. If it didn't work, at least SWIM will have some pseudo back.
amalgum
(Hive Bee)
03-29-03 08:17
No 422265
fucking shit
Bookmark Reply
Well, the rxn was definietly a failure. SWIM doesn't think that a "dry" type reaction will work at all. Even though the theorhetical amount of H2O was present, the mixture still seemed pretty dry, and almost no reaction was evident. SWIM thinks in order for the Na2SO3/I2 reaction to succesfully produce HI, an excess of water is needed. In the "dry" run, the sublimation of iodine inside was noticeable, and at the end it seemed like almost no I2 had reacted. SWIM did another test with the Na2SO3/I2 thing again. SWIM did it like the first little test, added a small amount of Na2SO3 to a beaker, the right amount of I2, and a huge excess of water (enough to submerge everything). Like before, upon a little heating, it seemed almost all the iodine immediately dissolved (the rest like 2 seconds later), and the smell of HI was apparent. After about five minutes, no apparent elemental iodine was detected.
So this leads SWIM to the conclusion that in order for this to work it must be a reflux reduction. SWIM went ahead and used the recovered pseudo (what was left anyway) in a normal rp/I2 for now.
In a little bit, when SWIM gets more funds, a reflux will be tryed. Psuedoephedrine will be dissolved in a minimal amount of dH2O. Reflux apparatus will be setup, and Na2SO3 and I2 will be added. Then SWIM will reflux mixture for about 3-4 hours. By that time, depending on how things are going (this of course would be a small amount for testing, like 2-4g pseudo), SWIM will decide whether or not he should add more Na2SO3/I2 and continue for another few hours, or proceed with workup. Either way, SWIM will probably reflux at minimum 6 hours for starters, keeping HI conc. up of course.
hermanroempp
(Hive Bee)
03-29-03 19:22
No 422369
Wrong pH perhaps?
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I think the reaction needs to be done under acidic conditions. The equation
Na2SO3 + I2 + H2O --> Na2SO4 + 2 HI
looks good on paper, but in the real world another reaction like
Na2SO3 + I2 + H2O --> NaHSO4 + HI + NaI
will also occur. However, the truth is somewhere in between those two reaction paths ....depending on pH, amount of solvent(read: water), temperature etc.
My 2 cents: If the solution of sodium sulfite is acidified prior to reaction (with a non-oxidizing acid, of course) to yield a solution of free H2SO3, and then the iodine is reacted with the acid solution, then a solution of HI will form. But I think the solution of HI will be too diluted to be directly employed in a reduction, it must be concentrated via distillation
Quidquid agis, prudenter agas et respice finem!
ahgreich
(Stranger)
04-08-03 23:54
No 424974
Whoo doggies. Success.
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He's now feeling the product of a successful reduction of Pfed fb with
sodium sulfite,
iodine,
and dh20.
Phan-fucking tastique!!
No RP. Had to happen. It's all in the metaphysics, the incantations, and a few dead chickens.
Swim'll speak in equivalencies instead of empirical weights, as he don't have a scale.
in a 250 ml rbf, he placed the following, in order:
3 teaspoons of very dry, very clean pfeb fb xtals ( slightly over 3gms) pre-sifted with 6 teaspoons of sodium sulfite.
1 1/2 teaspoons of dh20 on the top of the dry pile at bottom |
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