Author Topic: Hydriodic Acid--Step by Step Write-Up  (Read 15597 times)

0 Members and 1 Guest are viewing this topic.

Argox

  • Guest
Hydriodic Acid--Step by Step Write-Up
« on: February 22, 2002, 05:05:00 AM »
STEP-BY-STEP PROCEDURE FOR MAKING HYDRIODIC ACID FROM NON-WATCHED INGREDIENTS


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, I’ve 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 meth with it, or selling it to meth 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 (127ºC/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 meth amphetamine.  HI(aq) reduces ephedrine to methamphetamine and can be regenerated by red phosphorus (RP) and water.  Instructions for making meth using this method can be found elsewhere on this Forum.  I don’t know if the instructions are any good or not.  I’ve never made meth and don’t 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 meth 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 meth manufacture taking place at the time.     A liter of HI(aq) weighs 1,700 grams and contains 970 grams of HI.

   The clandestine meth 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 meth 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) + Sº

   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 “the smell went away, so everything’s OK.”  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+ºC

    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 Rhodium’s 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 127ºC.  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 127ºC 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, it’s 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, you’re 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?  Don’t 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!  That’s my way of saying that freshly made HI(aq) is very, very corrosive.  So don’t 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

  • Guest
Hydriodic Acid--Step by Step (Part 2)Write-Up
« Reply #1 on: February 22, 2002, 05:10:00 AM »

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 “pH Down.”  Conversely you can order it from the chem supply.  Don’t respond with posts belly aching about how you’re 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.  It’s 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 “pH Down” is nitric acid--you want the label to say “phosphoric acid.”  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 “List.”

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 135º.  That will indicate 75% acid.  If your sample boils at a lesser temperature, don’t despair, boil all your acid until it reaches 135º (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                    ºC

   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 I’m 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.  Don’t listen to them.  I’m heading them off at the pass right now.  The reaction just doesn’t work that way.  (How do I know?  I thought of adding more water from the git-go and tried it.  I’ve 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 don’t know because they haven’t 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 “condensed” 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 I’m 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 doesn’t eliminate bumping altogether, so if you get scared easy, add less ingredients.  It’s really a function of balls versus greed.  If you have the pelotas, then load that sucker up, ’cause it’s 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--it’s that simple.   At 65º an obvious reaction will take place.  The clear solution will turn dark brown.  This is hydriodic acid being formed.  Keep the heat on high, don’t let off.  The solution will begin to boil at 105ºC  and a small amount of milky white distillate will come over into the receiver. 

READ THIS PART--IT’S 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, I’ll 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 (“clear ammonia”) 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 (that’s why the meth guys need it), so there is a redox between HI and any sulfides.  (2HI + MeS + delta temp -->H2S + I2 + Meº.  And since H2S is less soluble and more volatile than HI, it comes over first.)  This is something else the arm-chair chemists won’t warn you against, but count on Argox to keep you safe, if you pay attention.  Like I said, the tweaker with the 1L won’t 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 I’m 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 you’re lucky, like me, you’ll wake up in the emergency room puking sodium thiosulfate (oh yeah, that’s cyanide poisoning, for which an antidote exists--if you breath H2S, you’re shit outta luck--there’s 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.  Don’t worry about the thermometer at the still head going above 127ºC, it is still HI(aq) coming over, just the temp inside the reactor is getting HOT.  At 400ºC 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 127ºC 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 won’t have to deal with much actual HI gas.


   {If you don’t have a clue about how to set up a for atmospheric distillation with a still head and condenser and water traps and such, and don’t 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 don’t have a good fume cabinet--PLEASE don’t 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+ºC, so don’t 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 doesn’t 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 125-127ºC.
   (OK. OK.  Get back on your chair.  I was just kidding to see if you were awake.  A little black humor--of course you don’t 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 125º, 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 127º, and then turn off the heat and everything left in your boiling flask is 57% HI(aq), no need to distill it--it’s 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 Argox’ 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 user’s 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!  Isn’t 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, don’t be surprised with the heavy pounding on the door late one night--no, it’s 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 wouldn’t know anything about any of this...it’s 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 wouldn’t 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 wouldn’t freeze it, but since I’ve never frozen any, I couldn’t 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 user’s hypothetical application will solve that hypothetical problem. 

With your native intelligence, you’ll 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 weren’t paying attention?  Don’t recall anything in all this gibberish about chemical reactions and corrosive acid that had anything to do with an expensive car?  Oh.  I’m 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 “INTRO.”   



CONCLUSION:

   I have three motivations in posting this: 

One, to publicly apologize and make up to Rhodium for the “bad” 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, it’s 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!  That’s another write-up. 

Regards
Argox

Jetson

  • Guest
Re: Hydriodic Acid--Step by Step (Part 2)Write-Up
« Reply #2 on: February 22, 2002, 10:32:00 AM »
let me be the first to say,  fukin excellent write up bud!

"this could be an illusion but i might as well try..."

codyboy

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #3 on: February 22, 2002, 03:26:00 PM »
DUDE........PARTY ON!!!!!!!!!
Thank you,
your time and effort deserves 'el mundo PRAISE.
codyboy

humidbeing

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #4 on: February 22, 2002, 08:48:00 PM »
Very comprehensive and astute.

..then when one is cool, one may become groovy. Grooooovy.

SpicyBrown

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #5 on: February 23, 2002, 12:35:00 AM »
Yes, it's already been said, but .. good writeup! Thanks.

SpicyBrown

Argox

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #6 on: February 23, 2002, 12:56:00 AM »
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 meth 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 meth, without need for any RP, or very little.  Of course the part about how I know fuck all about making meth is true, so don't shoot me down for any mistakes I may make regarding how to make meth. 

I get requests, but have so far refrained from heading in that direction.  Bad karma.  Have you ever seen a meth 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

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #7 on: February 23, 2002, 01:08:00 AM »
A+ information you got there!

PB

ballzofsteel

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #8 on: February 23, 2002, 09:11:00 AM »
Sounds like a lot of fun :) Very 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

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #9 on: February 23, 2002, 10:18:00 AM »
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. 8)

Jetson

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #10 on: February 23, 2002, 10:56:00 AM »
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

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #11 on: February 25, 2002, 09:08:00 PM »
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

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #12 on: February 26, 2002, 04:08:00 AM »
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.thevespiary.org/rhodium/Rhodium/chemistry/hydriodic.html


Synthia

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #13 on: February 28, 2002, 01:02:00 PM »
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

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #14 on: February 28, 2002, 02:02:00 PM »
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

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #15 on: March 01, 2002, 02:10:00 AM »
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

  • Guest
Re: Hydriodic Acid--Step by Step Write-Up
« Reply #16 on: March 14, 2002, 08:24:00 AM »
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

  • Guest
Post deleted by LaBTop
« Reply #17 on: March 16, 2002, 10:11:00 PM »

Hermetic

  • Guest
Fantastically detailed, exactly what I need to ...
« Reply #18 on: April 02, 2002, 02:16:00 PM »
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

  • Guest
Argox
« Reply #19 on: April 09, 2002, 04:00:00 AM »
Argox, really...I don't know what to say...



don't call me...I wont answer, or call you back.

myles

  • Guest
thanks
« Reply #20 on: November 02, 2002, 09:25:00 PM »
Works well thank you for your help, from my friend of course.

The BEE game is why im here top score 300 points

mofessto

  • Guest
You Deserve a Medal!
« Reply #21 on: November 03, 2002, 05:06:00 PM »
Thank's alot Argox from a newbee information worth saving.

"For every second passing is yet another missed chance to turn it around"

Ph0enix

  • Guest
Where the F**K..
« Reply #22 on: November 04, 2002, 10:20:00 PM »
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

  • Guest
History of the thread
« Reply #23 on: November 05, 2002, 12:37:00 AM »
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

  • Guest
could this help the bumping
« Reply #24 on: November 08, 2002, 07:48:00 PM »
by putting some broking glass or boilling stones in the reaction,

12345x

  • Guest
57% stabilized....
« Reply #25 on: November 21, 2002, 06:03:00 AM »
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

  • Guest
IMPRESSIVE
« Reply #26 on: January 04, 2003, 02:49:00 AM »
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

  • Guest
New ways for making HI
« Reply #27 on: January 17, 2003, 12:58:00 PM »
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.thevespiary.org/rhodium/Rhodium/djvu/hydriodic.gmelin.djvu)
To view the DejaVu file, you need a browser plugin from

http://www.lizardtech.com/download/


ahgreich

  • Guest
Riddle me this...
« Reply #28 on: March 17, 2003, 08:26:00 PM »
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

  • Guest
Rhodium, could one use this as a RP substitute
« Reply #29 on: March 17, 2003, 08:41:00 PM »
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

  • Guest
Old refs
« Reply #30 on: March 18, 2003, 03:39:00 PM »
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

  • Guest
hmm
« Reply #31 on: March 18, 2003, 04:57:00 PM »
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

  • Guest
Highly Intriguing
« Reply #32 on: March 18, 2003, 05:41:00 PM »
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

  • Guest
ahh! thanks scotty.. i was looking for the...
« Reply #33 on: March 18, 2003, 05:47:00 PM »
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

  • Guest
another idea... crystallization
« Reply #34 on: March 18, 2003, 05:55:00 PM »
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

  • Guest
TFSE findings
« Reply #35 on: March 18, 2003, 07:20:00 PM »
Scotty, there is a chance that your 1:4 ratio is flawed...
Check out

Post 386152 (missing)

(Rhodium: "57% HI", Stimulants)
  the whole thread.. specifically that one and this one

Post 392251 (missing)

(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 meth in a 12hr reflux?

fierceness

  • Guest
Little experiment
« Reply #36 on: March 18, 2003, 08:40:00 PM »
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

  • Guest
assumptions about HI concentration...
« Reply #37 on: March 18, 2003, 11:01:00 PM »
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

  • Guest
the pale yellow was probably HI(aq)..
« Reply #38 on: March 19, 2003, 01:36:00 PM »
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

  • Guest
HI
« Reply #39 on: March 21, 2003, 09:35:00 AM »
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 methamphetamine, 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 meth, 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

  • Guest
You need a large excess of HI to reduce ...
« Reply #40 on: March 21, 2003, 02:14:00 PM »
You need a large excess of HI to reduce ephedrine, not just two equivalents - that is just the theoretical amount.

amalgum

  • Guest
right
« Reply #41 on: March 21, 2003, 02:48:00 PM »
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

  • Guest
Rhodium: regarding sodium sulfite + I2 + H20
« Reply #42 on: March 23, 2003, 02:14:00 PM »
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

  • Guest
Redox chemistry of sulfur
« Reply #43 on: March 23, 2003, 02:53:00 PM »
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.thevespiary.org/rhodium/Rhodium/chemistry/hydriodic.html


amalgum

  • Guest
more stuff
« Reply #44 on: March 24, 2003, 08:29:00 AM »
SWIM has procured new materials today.  After SWIM extracts the pseudo he will try a small rxn, and post results.

amalgum

  • Guest
first try
« Reply #45 on: March 28, 2003, 03:22:00 AM »
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

  • Guest
hrmmm
« Reply #46 on: March 28, 2003, 04:29:00 AM »
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

  • Guest
fucking shit
« Reply #47 on: March 29, 2003, 06:17:00 AM »
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

  • Guest
Wrong pH perhaps?
« Reply #48 on: March 29, 2003, 05:22:00 PM »
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  ::)


ahgreich

  • Guest
Whoo doggies. Success.
« Reply #49 on: April 08, 2003, 09:54:00 PM »
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 of flask (enough that the whole pile was wet enough to sling about, yet not thin - consistency of black-strap molasses.

He then 'staged' around 11g I in a small beaker, readied  his punch baloon: dumped in the I, snaped the balloon on top, taped the hell out of it, and waited.

20 sec or so, exotherm began without addition of ANY external heat source.

pile got nasty purple, bubbling. NO SMOKE. He watched it for about 10 minutes until the I had been reacted (no longer a purple nasty mass, but light pale beige-ish. No smoke yet, no balloon movement inflation. bubbling subsided.

On to the stove he went, appling liberal heat such that the punch balloon was the size of a large grapefruit. The flask contents evolved a brilliant yellow. Removed from heat, watched some clear liquid run down flask neck, waited for flask to cool (15 minutes or so) - the pasty flask contents became white as it cooled. At room temp, was nearly as white as sodium sulfite. All the while, he was fondling the flask, rolling it, jiggling it, keeping the liquid moving.

Back to the stove, heat until boil and balloon inflated, contents turned back yellow! Removal from heat and close observation revealed that the contents where getting shiny-like.

Did this routine 3 times, each time yellow when hot, white when cool.

last time cool, removed balloon, no smoke, didn't stick his nose in for a smell - strange really, no strong smells to speak of during the whole party. The strong-ass punchy was secured on the flask before any reaction started, retaining all gas.

workup - 2 tolly washes of post rxn b4 basing into 3rd shot of tolly with
Ass-load of NaOH (he reckons to polarity-crawl back through the aq NaSO4 (from the sodium sulfate rxn product).

Should have washed the tolly with base a few more times, however, as he is sailing through the bioassay:
HCL/dH20 xtylzation - exceptional. Da real medicine, all nice like.
long legs, slight whitish residue (see prior sentence about washing NP better prior to HCL/H20).


RP/I smells not noticable during the endeavor.

Why did it succeed? He thinks:
1. JUST enough dH20 to have high enough concentration of aqHI as HI was generated yet not so much that ALL of the HI would have a place to go as soon as it was made.
3. application of heat meant that the HI concentration in dH20 was affected causing the yellowing. However, the heat facilitated the mobility of the flask contents, at times becoming a true reflux.


Whooeeee. How bout them apples?

ballzofsteel

  • Guest
Well done dude, Not to be a knocker,as I think
« Reply #50 on: April 09, 2003, 12:18:00 AM »
Well done dude,

 Not to be a knocker,as I think it is brilliant that you have explored un-trodden ground and reported a successful reaction,which,If true holds many possibilities for all of us,
Butt...I feel you owe it to yourself to bring some credibility to your experimental results by composing a complete write-up,with accurate measurements etc.
This will help other, less forgiving bees believe and share in your enjoyment.
Please replicate and document this for me.

Good work dude.

Organikum

  • Guest
thats true new
« Reply #51 on: April 09, 2003, 07:47:00 AM »
and beats the shit out of every phosphor(o)us reaction in availability of needed chems.
Ballz, ahgreich has no scale and for me are accurate teaspoon measurements as good as mikrograms.

so thanks ahgreich!  ;D
Please report further success as misfortune on this - I am eager to hear more!

ORG


RepVip

  • Guest
ahgreich - more info please
« Reply #52 on: April 12, 2003, 06:26:00 PM »
In reference to

Post 399133

(Rhodium: "New ways for making HI", Stimulants)

and

Post 424974

(ahgreich: "Whoo doggies. Success.", Stimulants)


ahgreich can you please provide more info on your "successful" experiment? I'm surprised you didn't use a scale. Unless you are intimately aquainted with iodine and sodium sulfite, 'staging' accurate amounts is really, really difficult. A pinch of this and a dash of that just isn't going to cut it.

It's hard not to be a critic - it sounds too good to be true! And you know what they say... Please prove me wrong!! This method seems one of the best yet - if it works.

Anybees with more information please post! I'd experiment myself, but I'm lacking a few chems. However, I'll be forced to if nobee does  :)

ropoctl

  • Guest
Acidified SO 3 2- is SO2(g).
« Reply #53 on: July 28, 2003, 08:23:00 PM »
Acidified SO32- is SO2(g).  The species H2SO3 does not exist, just as H2CO3 or NH4OH cannot be isolated.

bloosh

  • Guest
can you please help me ?
« Reply #54 on: February 10, 2004, 06:22:00 PM »

NMR

  • Guest
There is a much easier, faster, and cheaper way
« Reply #55 on: October 31, 2004, 08:09:00 AM »
The phosphoric/iodide reaction is good in that it uses non watched ingredients, but it requires extensive glassware, a heating mantel and considerable time to complete.
   The second method that you outline is the preferred method, that is, the hydrogen sulfide method; it is fast, it is cheaper than the above method, and it requires no special equipment or facilities.
   I will quickly outline it as follows:

   This method requires three ingredients: hydrogen sulfide gas, elemental iodine, and water.

1.   Iodine is procured as usual or may be obtained from the potassium iodide used in the other author's reaction by treating an aqueous solution of potassium iodide with a small amount of concentrated sulfuric acid to first convert the iodide and then by adding slowly with much stirring sodium hypochlorite solution to form chlorine gas insitu to force the crystalline iodine out of solution.  The iodine thus formed may be filtered for further use.

2.   Hydrogen sulfide gas is formed and bubbled into a flask containing crystalline iodine from above and water with constant stirring and or swirling.  When the reaction is complete one will have a clear liquid, also known as aqueous HI with a spongy yellow wad of sulfur in the bottom of the flask.  Simply pick out the spongy sulfur wad and throw it away and you are done; you now have fresh, crystal clear, concentrated HI, for use in doing whatever.

3.   Hydrogen sulfide gas is formed by dropping a chunk of ferrous sulfide into a weak solution of any acid that you might have available and piping the gas to the bottom of the container containing the iodine and water, just like any other gassing operation that you are familiar with.

4.   Ferrous sulfide is very easily and cheaply made in unlimited quantities, here is an example synthesis:
   1. Weigh out 1 mole (32.1 grams) of Sulfur, purchased in any garden supply store or hardware store.
   2. Weigh out 1 mole (55.85 grams) of Iron filings or Super Fine Steel Wool Pads if you can't find the iron filings purchased at a hardware store.
   3. Combine the two above ingredients in a large stainless steel cooking pot with a good fitting lid.
   4. Add one half gallon of water, less if filings are used because they are more compact than the puffy steel wool pads.  Make sure that the pads are covered completely, add more water if necessary to cover the pads.
   5. Bring to a boil and boil until dry.  The reaction begins rather quickly, you will notice that the pads become quite black and the water becomes black.  Since a faint odor of sulfide is given off during boiling and conversion, a good stove top exhaust fan is a must.  After half an hour or so, if convenient, finish off the boiling to dry outside, say, on a barbeque grill.
   6.  When boiled dry, you will have enough ferrous sulfide to make enough hydrogen sulfide to make a half gallon of acid.

STORE ANY UNUSED FERROUS SULFIDE IN AN AIR TIGHT CONTAINER, AS IT SLOWLY REACTS WITH AIR AND MOISTURE TO GIVE OFF SMALL QUANTITIES OF HYDROGEN SULFIDE GAS.  BEST TO STORE IT OUTSIDE IN A TOOL SHED OR IN SOME OTHER WELL VENTILATED PLACE UNLESS STORED IN A VERY AIRTIGHT CONTAINER.
HYDROGEN SULFIDE IS A POISONOUS GAS, MAKE THE GAS AND USE IT OUTSIDE AND STAY UP WIND, DO NOT BREATH IT, IT SMELLS LIKE ROTTEN EGGS, SO YOU CAN'T MISS IT, BE CAREFUL.

ONCE THE PRECURSOR IS MADE, THE TIME TO MAKE THE ACID IS LESS THAN AN HOUR, NO HEAT REQUIRED, IT IS DONE AT ROOM TEMPERATURE, NO MUSS, NO FUSS.

Zen

  • Guest
A+ Write Up (HI the right way.)
« Reply #56 on: October 31, 2004, 09:47:00 PM »
Nice procedure and no high explosives.

Easy does it, make sure you have tight seals, poisonous gases can make you unhappy.

Awesome write up NMR. 8)

Lestat

  • Guest
I like it, nice and simple HI, I just want to...
« Reply #57 on: November 01, 2004, 01:23:00 AM »
I like it, nice and simple HI, I just want to add a couple of things, about H2S, it is HIGHLY toxic, problem is, if you inhale sublethal amounts, it quickly knocks out your sense of smell, causing the would-bee chemist to beelieve the H2S has dissipated and causing said chemist's removal from the gene pool :o

And dropping ferrous sulfide into an acid works, but dripping the acid SLOWLY onto the sulfide is a much safer way of going about things so as to avoid a runaway reaction and generation of overlarge amounts of H2S from beeing possible :)

Another way, SWIM uses occasionally to generate H2S, is to mix candle wax and sulfur powder and heat, this generates quite considerable amounts of H2S, although likely there is a fair amount of volatilised S vapor, and a little SO2 assuming the heating/gassing setup hasn't firsthand been purged of oxygen.

When working with H2S I advise a scrubbing setup to bee put in place, with a tank full of something for surplus H2S to reduce, preferably one that would produce a possibly useful reagent, or ammonia solution.

If you used NH3 solution, then perhaps you could get into selling stinkbombs as a little side-earner, as ammonium sulfides smell rather foul. Stinkbombs made with it are quite certainly effective ;)


Scottydog

  • Guest
Water Ratio?
« Reply #58 on: November 01, 2004, 02:03:00 AM »
The method seems fairly self explanatory but lacking in one minor detail.

"2. Hydrogen sulfide gas is formed and bubbled into a flask containing crystalline iodine from above and water with constant stirring and or swirling.  When the reaction is complete one will have a clear liquid, also known as aqueous HI with a spongy yellow wad of sulfur in the bottom of the flask.  Simply pick out the spongy sulfur wad and throw it away and you are done; you now have fresh, crystal clear, concentrated HI, for use in doing whatever."

What is the proper water ratio in relation to weight of iodine to bee gassed?

I suppose a push/pull with a NaOH solution might work to eliminate excess H2S gas?

Might make for a good "theoretical" camping project. SWIM likes the idea of dropping the FeS into the dilute acid to produce the H2S gas. Could actually bee self-supervising! Drop in the precursor, affix the stopper and then leave for a few hrs, returning later to the HI solution that only requires a filtering of the sulfur.

Great followUP!


Zen

  • Guest
scrubbing setup
« Reply #59 on: November 01, 2004, 02:51:00 AM »
A scrubber is good idea # 2.

H2S isn't very soluble in water.

psst.. you can also bubble hydrogen through
 iodine solution and "mysterious catalyst" to yield HI
 most effectively, but this works too.



Zen

  • Guest
ref.
« Reply #60 on: November 01, 2004, 06:01:00 AM »
Correction H2S is pretty explosive.  ;)

"Hydriodic acid, HI, is formed by the direct union of its components in the presence of a catalytic agent; for this purpose platinum black is used, and the hydrogen and iodine vapour are passed over the heated substance. On shaking up iodine with a solution of sulphuretted hydrogen irf water, a solution of hydriodic acid is obtained, sulphur being at the same time predpitated. The acid cannot be prepared by the action of concentrated sulphuric acid on an iodide on account of secondary reactions taking place, which result in the formation of free iodine and sulphur dioxide. The usual method is to make a mixture of amorphous phosphorus and a large excess of iodine and then to allow water to drop slowly upon it; the reaction starts readily, and the gas obtained can be freed from any admixed iodine vapour by passing it through a tube containing some amorphous phosphorus. It is a colorless sharp-smelling gas which fumes strongly on exposure to air. It readily liquefies at 0 C. under a pressure of four atmospheres, the liquefied acid boiling at 34-14 C. (730-4 mm-); it can also be obtained as a solid melting at 50-8 C. It is readily soluble in water, one volume of water at io C. dissolving 425 volumes of the acid. The saturated aqueous solution is colorless and fumes strongly on exposure to air; after a time it darkens iii color owing to liberation of iodine. The gas is readily decomposed by heat into its constituent elements. It is a powerful reducing agent, and is frequently employed for this purpose in organic chemistry; thus hydroxy acids are readily reduced on heating with the concentrated acid, and nitro compounds are reduced to amino compounds, &c. It is preferable to use the acid in the presence of amorphous phosphorus, for the iodine liberated during the reduction is then utilized in forming more hydriodic acid, and consequently the original amount of acid goes much further. It forms addition compounds with unsaturated compounds."

"IODINE." LoveToKnow 1911 Online Encyclopedia. © 2003, 2004 LoveToKnow.

http://33.1911encyclopedia.org/I/IO/IODINE.htm


Lestat

  • Guest
Please don't consider leaving anything ...
« Reply #61 on: November 01, 2004, 09:16:00 AM »
Please don't consider leaving anything generating something as deadly as H2S for all to find, even if it is off the beaten track, a small child could open that, or for that matter the parents, and you would have been responsible for the death quite possible, of an innocent man, and child >:(


NMR

  • Guest
Yes, you are quite correct regarding the ...
« Reply #62 on: November 01, 2004, 09:50:00 AM »
Yes, you are quite correct regarding the preferred method of gas generation, that is, dropping acid upon sulfide rather than dropping chunked sulfide into weak acid.
   My purpose, however, was to tailor a procedure that required no special glassware.  Unfortunately, most do not have dropping funnels, Erlenmeyers, burets and separatory funnels with stopcocks, etc. for such fine control.
   An additional consideration that factored into my choice of gas generation technique was the fact that the crude ferrous sulfide thus generated was in the form of hard chunks semi-coated with un-reacted sulfur.  The experimenter will find that these chunks decompose in weak acid a very constant rate giving quite nice control of the rate of evolution of gas.  Should faster gas evolution be desired, this may be effectuated by simply adding more concentrated acid to the gas generator.  Once the desired rate is achieved, by  adjusting the concentration of the acid in the gas generator, gas will be evolved at a constant and controlled rate for many hours with no further adjustments being necessary until very near the end of the HI production, if at all.  It is almost automatic once it is going.
   However, since you are one of the lucky ones with all of the equipment, let me share a little secret with you.  I would guess that you are one of the ones who generates HCl gas for final conversion, instead of using pool acid like most everyone else does.  You probably drop H2SO4 on NaCl to generate your HCl gas.  The problem with that is that you generate wet HCl gas that must be dried first before introduction into your amine solvent solution.  Instead of using NaCl, use instead CaCL2.  Sulfuric on calcium chloride will generate very, very dry HCl gas, therefore no drying needed, greatly simplifies apparatus needed, cuts much time, and produces better product.

WizardX

  • Guest
Precautions !
« Reply #63 on: November 01, 2004, 10:13:00 AM »
I think I've covered the HI synthesis via H2S + I2 well enough in my X File, so if you take ALL the precautions as indicated, and use some common sense, you SHOULD be OK!

NMR

  • Guest
Reply to Scotty dog about water ratio
« Reply #64 on: November 01, 2004, 10:18:00 AM »
57% is the usual HI concentration made.  Percentage solutions usually are expressed in grams, not moles.  So, in this case, for example, a 57% aqueous solution of something would mean that if I had 100 grams of the solution, 57 grams would be the something and 43 grams would be water.  Here the "something" is HI.  Well, the weight of hydrogen is negligible, so we can just ignore it, therefore we need 57 grams of iodine.  Now, the weight of water is one gram /ml, so 43 grams of water is 43 mls.

   So, for every 57 grams of iodine in your flask add 43 mls of water to get 100 grams of a 57% solution.  Now remember, I said to get 100 grams of solution, not 100 mls.  Since iodine is very dense, HI will also be very dense, much more dense than water.  You will be shocked to see all of that iodine disappear into that little bit of water, but it will in an hour or so of slow bubbling with constant stirring or swirling.

   Also, be careful not to let the sulfur wad that forms on the end of your bubbling tube block the tube, which will easily happen if you stop stirring.  If it does become blocked, mechanically and quickly unblock it or your gas tube outlet will become completely blocked and can cause you gas generator rubber stopper to blow off.

Organikum

  • Guest
H2S produces not 57% HI
« Reply #65 on: November 01, 2004, 03:26:00 PM »
The reaction of H2S with iodine produces not constant boiling HI of 57% whats no "concentrated" HI anyways as HI comes as high as about 70% in concentration so called "fuming HI".
HI made by the reaction of H2S and iodine has to be redistilled to get the wanted 57%.

The reaction setup as published by WizardX in his X-file is inherently hazardous - dont do it this way. If you want how this is done right download the Vogel´s 3rd from Rhodiums page and look it up there.

Wiz, no offense, but I PM´d you about this times ago and I am astonished to see you recommend your dangerous setup here again. Whats up?

The best procedure for HI from H3PO4 was posted by SHORTY - search for it.
This ARGOX stuff is mostly boasting.
The production of HI from H3PO4 makes it possible to get HI stronger than 57% and thats preferred, the stronger the better as stronger HI allows the reaction to be run at lower temperatures and that supresses the formation of byproducts (azides).


Rhodium

  • Guest
azides & aziridines
« Reply #66 on: November 01, 2004, 07:42:00 PM »
stronger HI allows the reaction to be run at lower temperatures and that supresses the formation of byproducts (azides).

Azides are never formed as byproducts in the HI reduction, and I fail to see how the formation of aziridines could be suppressed by a lowered reaction temperature... Could you elaborate?

In my opinion aziridines are formed due to incomplete reduction, while excessive temperatures favor higher condensation products such as the several dozens of known dimers.


Organikum

  • Guest
uups
« Reply #67 on: November 01, 2004, 09:16:00 PM »
aziridines of course.

Wasnt it you Rhodium who posted that high temperatures and high HI concentration favor the formation of aziridines? I think yes. Will do a search when time is by hand.


Rhodium

  • Guest
aziridines are forged by impatience
« Reply #68 on: November 02, 2004, 01:13:00 AM »
Wasnt it you Rhodium who posted that high temperatures and high HI concentration favor the formation of aziridines? I think yes.

Now I catch your drift - the study you are referring to reviewed the infamous "short dry hot cook", in which insufficient water is used and the reaction is not allowed to go to completion. It is the ephemeral and arid aspects of that technique which is to blame, rather than its blazing fury, which merely result in a rather non-specific destruction of precursors and product through condensations, dimerizations and cyclizations.

The article you are referring to might be either the following one, or the one above it in the same thread:

Post 362724 (missing)

(Rhodium: "Methamphetamine impurity identity profiling", Stimulants)



WizardX

  • Guest
What?
« Reply #69 on: November 02, 2004, 11:36:00 AM »
Organikum: states...


The reaction setup as published by WizardX in his X-file is inherently hazardous - dont do it this way. If you want how this is done right download the Vogel´s 3rd from Rhodiums page and look it up there.




The X-file procedure is a merge of references from (1) Vogel´s 3rd Ed, (2) Vogel´s 5th Ed, (3) Journal of Inorganic Chemistry, and two other sites that I can't be bothed right now to look up.


Wiz, no offense, but I PM´d you about this times ago and I am astonished to see you recommend your dangerous setup here again. Whats up?




Post me AGAIN ABOUT YOUR CONCERNS? PLEASE!


Organikum

  • Guest
I will see if I have the PM exchange on disk...
« Reply #70 on: November 02, 2004, 06:27:00 PM »
I will see if I have the PM exchange on disk somewhere Wiz, where I uttered my critics and YOU advised me to use the method as described in Vogel´s 3rd instead.


WizardX

  • Guest
Compare Procedures.
« Reply #71 on: November 03, 2004, 01:33:00 AM »
Organikum: Lets for argument sake I responded, "where I uttered my critics and YOU advised me to use the method as described in Vogel´s 3rd instead."

This is to give you a reference to read and compare both procedures.

Organikum

  • Guest
Two points: - H2S + I will not produce 57% HI...
« Reply #72 on: November 03, 2004, 03:12:00 PM »
Two points:
- H2S + I will not produce 57% HI without redistillation
- magnetic stirring the vessel where the HI is formed and sulfur precipitates is impossible, the stirrbar WILL clog. Thats why Vogel advises a STRONG OVERHEAD stirrer.

My advises:
- use pitch to seal the vessels and connections
- do this under a fumehood, outsides or at a window with a fan blowing out
- dissolve the iodine in a solution of KI or NaI and dont stirr at all
- redistill (preferred), or alternativly use the KI/NaI-HI solution produced together with anhydrous H3PO4 directly for reduction.
- go slowly

The setup is:
H2S generator - into - KI/NaI-iodine in water solution - over - water - into - soda crystals.
Avoid any more schickmick in the setup it WILL cause trouble and will NOT provide more safety.


WizardX

  • Guest
HI
« Reply #73 on: November 04, 2004, 03:18:00 AM »


From X-File 9

57% HI SOLUTION (HYDRIODIC ACID) : B.p 125.5-126.5 deg C/760mm Hg ;
Density 1.70 gr/ml ;  55-57%  w/w HI is 0.936 to 0.99  grams of HI per ml.

H2S + I2 ===>> 2HI + S

In a fume cupboard a 1.5 three neck flask is added a mixture of 480 grams of
iodine and 600 mls of distilled water. The centre neck is added a sealed stirring unit which leads almost to the bottom of the flask. The left neck is fitted and sealed with a glass tube which extends almost to the bottom of the flask but does not touch the stirrer. This is connected to the hydrogen sulphide (H2S) generator.  The right neck is fitted and sealed with a short glass tube connected with a plastic tube to the bottom of an inverted   funnel in a 5% sodium hydroxide solution.

The mixture is vigorously stirred and a stream of hydrogen sulphide (H2S) gas is passed rapidly in the iodine/water mixture as rapidly as it reacts with the iodine. After several hours, 2-3 hours, the iodine disappears and the liquid assumes a yellow colour (sometimes almost colourless) and most of the precipitated sulphur sticks together in the form of a hard lump.[NOTE 1]
This liquid contains a mixture of HI, H2S and S. The liquid is now filtered through a large funnel plugged with glass wool to  remove the sulphur S. No need removing the dissolved H2S as this enhances the reductive power. Add a few crystals of iodine to this HI/H2S solution and store at 0-5 deg C.

[NOTE 1] The sulphur lump in the flask can be removed by refluxing with concentrated nitric acid.


From X-File 11

FLASK C: H2S GAS ABSORBION TRAP and HYDRIODIC ACID SYNTHESIS

57% HI SOLUTION (HYDRIODIC ACID) : B.p 125.5-126.5 deg C/760mm Hg ;
Density 1.70 gr/ml ;  55-57%  w/w HI is 0.936 to 0.99  grams of HI per ml.

H2S + I2 ===>> 2HI + S

In a fume cupboard a 1.5 three neck flask is added a mixture of 480 grams of
iodine and 600 mls of distilled water. The centre neck is added a sealed stirring unit which leads almost to the bottom of the flask. The left neck is fitted and sealed with a glass tube which extends almost to the bottom of the flask but does not touch the stirrer. This is connected to the hydrogen sulphide (H2S) generator.  The right neck is fitted and sealed with a short glass tube connected with a plastic tube to the bottom of an inverted   funnel in a 5% sodium hydroxide solution.

The mixture is vigorously stirred and a stream of hydrogen sulphide (H2S) gas is passed rapidly in the iodine/water mixture as rapidly as it reacts with the iodine. After several hours, 2-3 hours, the iodine disappears and the liquid assumes a yellow colour (sometimes almost colourless) and most of the precipitated sulphur sticks together in the form of a hard lump.[NOTE 1]
This liquid contains a mixture of HI, H2S and S. The liquid is now filtered through a large funnel plugged with glass wool to  remove the sulphur S. No need removing the dissolved H2S as this enhances the reductive power. Add a few crystals of iodine to this HI/H2S solution and store at 0-5 deg C.

[NOTE 1] The sulphur lump in the flask can be removed by refluxing with concentrated nitric acid.



I suggested the magnetic stirring if you want to contain the entire reaction in the glass fish tank. There are magnetic stirring units that have good torque with a large stirring magnet.

Azeotropic distillation (57% HI SOLUTION (HYDRIODIC ACID) : B.p 125.5-126.5 deg C/760mm Hg) will ONLY give 57% HI at 760mmHg. Increase pressure, increase HI concentration.

A 57% HI SOLUTION (HYDRIODIC ACID) cooled to 0-5 deg C, will increase in HI concentration IF you bubble HI gas into it. Approx 60-61% HI SOLUTION (HYDRIODIC ACID) at 0-5 deg C.


NMR

  • Guest
Reply to WizardX regarding your numbers
« Reply #74 on: November 04, 2004, 07:25:00 AM »
Dear WizardX:

     I have had a chance to read some of your Xfiles; they are very well done and you have quite a flare for making clear write-ups.
     But, it appears that you may have accidently mis-transcribed some numbers from your notebooks in your posting above:
     Your figures above do not appear to be correct.  You call for 480 g Iodine and 600 mililiters of water; these amounts do not make a 57% solution:

     480 g Iodine/(480 g Iodine + 600 ml's of Water)X100=(480/1080)X100=44.44% solution

For 480 g Iodine, the calculation is as follows:

     Let y=grams of solvent=grams H2O:
                                                  
                                                    480 g Iodine/(480 g Iodine + y) X 100 = 57
                                                    480 X 100                                      = 57(480 + y)
                                                                                             48,000 = 27,360 + 57y
                                                                                                  57y= 20,640
                                                                                                     y= 362.11 ml's

So, for 480 grams Iodine, you add only 362.11 ml's of water and gas with hydrogen sulfide to get a 57% solution.

WizardX

  • Guest
HI
« Reply #75 on: November 04, 2004, 12:59:00 PM »
I2     +   H2S  ==>  2HI     +  S

253.8  +  34.1  ==>  2x127.9 + 32.1

287.9           ==>  287.9

Reaction is balanced.

Now, 1 mol of I = 126.9 grams/mol.   So, 480/126.9 = 3.78 moles of I.

OR

Now, 1 mol of I2 = 253.8 grams/mol.   So, 480/253.8 = 1.89 moles of I2, equivalent to 3.78 moles of I.

Ratio of I2:HI is 1:2  Therefore, 2 x 1.89 moles of I2 = 3.78 moles of HI.

Concentration = moles/volume (Lt)

Concentration of HI = 3.78/(600/1000) = 3.78/0.6

Concentration of HI = 6.3 mol/Lt

OR

6.3 x 127.9 = 805.77 grams of HI per Lt. This is a 47% w/w HI.

Since, 55-57%  w/w HI is 0.936 to 0.97 grams of HI per ml. Therefore, 0.99 x 1000mls  = 990 grams of HI per 1Lt (1Lt = 1000mls)

When you azeotropic distill at B.P 125.5-126.5 deg C/760mm Hg you get 57% HI with is 0.97 grams of HI per ml, (7.58 mol HI/Lt) = (7.58 x 127.9 = 969.5 grams of HI per Lt)

NOTE The Vogel reference states a 57% w/w HI as 0.99 grams of HI per ml.

NMR

  • Guest
Reply to WizardX re: HI route
« Reply #76 on: November 05, 2004, 02:35:00 AM »
Ok, so you agree with my figures for the most part, the difference between my 44.5% and your 47% being the result of the simplification I used in the calculation, that is, disregarding the hydrogen in HI and just calculating from the weight of the iodine only.

   So, what you are saying, then, is that the Vogel method uses the strategy of first getting a good rough acid strength approximation first, as in your example, say 47%, and then relies upon a distillation to get the final concentration.

   In other words, the initial H2S preparation is intentionally less that the desired end product, relying upon a separate process, azeotropic distillation in this case, to arrive at the final concentration.  OK, I see that.

   Now, the question naturally arises, is this two step process, as opposed to the single step process, with its attendant added difficulties and glassware requirement, of any demonstrable benefit if the HI is not being used for analytical purposes?

    That is, yes, of course, the two step process will give a purer product, a result necessary if the HI is to be used in quantitative analysis, but is that extra purity and precise control of concentration of any demonstrable benefit when the acid is to be used in a reduction reaction, especially when the recycling phosphorus is coming from matchbooks?

   My point is this: HI by the sulfide reaction affords the average user a quick, cheap, and unlimited access to strong HI and reduces the phosphorus requirement by 75%
    But that advantage to the average user vanishes if he is constrained to do a complex distillation with equipment that he likely does not have.  In other words, it appears to be an unnecessary and artificial roadblock to what should be seen, otherwise, as a holy grail route to the acid.
   In other words, it seems much like the pointlessness that I am guilty of above, that is, using a calculation simplification that introduces a 2% error and then reporting my result to two decimal places, silliness that is a result of pure habit.

   An additional minor point, if distillation is performed, any remaining H2 S is lost, dissolved H2S in the acid will actually reduce further the phosphorus need in the main reductive reaction, a minor point though.

Can anyone tell me how to work all of those buttons and choices on the posting page, any instructions around?

NMR

Organikum

  • Guest
Dear NMR, you dont get 57% HI from H2S and...
« Reply #77 on: November 07, 2004, 03:53:00 PM »
Dear NMR, you dont get 57% HI from H2S and iodine at all without redistillation. Thats the point. No matter how much iodine you throw into the mixture, there is something called "equilibrium".
Look it up.


Zen

  • Guest
H2S / I / E via Reflux
« Reply #78 on: November 08, 2004, 02:53:00 AM »
Reaction Mechanism:

1.  Fe(II) + S => FeS

2.  FeS + 2HCl => H2S + FeCl2
 
3.  H2S + I2 => 2HI + S

4.  2HI + E-OH => E-I + HI + H2O

5.  HI + E-I => M-H + I2

Summary:

1.  5.58 g Iron (II) plus 3.21 g Sulphur hydrated with 100 ml d:H2O then evaporated to dryness at 100 C to yield 8.79 g Grey Ferrous Sulphide.

2.  Iron Sulphide plus 7.29 g Hydrogen Chloride in acid solution is treated in a Kipp's Apparatus to produces 3.40 g (2.2 L) Sulphuretted Hydrogen Gas.  

3.  25.38 g Elemental Iodine reacts with Hydrogen Sulphide to yield 25.58 g Hydrogen Iodide in solution plus 3.20 g Sulphur precipitate.

4.  16.52 g Ephedrine Freebase in the presence of 12.79 g HI reduces to 1.80 g H2O.

5.  Remaining 12.79 g HI reduces Iodated Ephedrine to 14.92 g Methamphetamine and 25.38 g Iodine is returned.

Notes:

1.   Straight forward enough, glass vessel recommended because product sticks to stainless steel. Do not over evaporate.

2.   Kipp's apparatus is implemented for the production of a gas by interaction of a liquid and a solid.  It consists of three receptacles.  The top is a reservoir for the liquid and is connected to the bottom.  The middle contains the solid and a tap for the gas.  When gas is released the liquid rises and reacts with the solid. When the tap is closed the back pressure returns the liquid to the lower reservoir and the reaction ceases.

3.   A 2 L reaction vessel can contain most of the evolved gas when connected to a push pull gas trap/scrubber.  A low temperature dry ice condenser fabricated from 1/4" SS tubing could also be implemented.  A 3 L pressurized vessel (aka bomb) would also be capable of containing the fumes from this reaction and allow for easier agitation of solution.  A small portion of THF may be added as dilute providing an excellent solvent for increasing reaction rates and yields by improving gas permeability.

4.   The hydroxy group is reduced to an Iodate under high acidity (45-50%) where by the reaction is hydrated and acidity slightly diluted.

5.   The second half of the reduction will succeed with a lower acid concentration (35-40%) under light reflux (70 C). In a theoretical molar perfect reaction resulting mixture should be easily quenched with distilled water to yield a low volatile solution.  A second volume of gassing would accelerate the reaction but result in a more volatile end solution.  If reaction is preformed in situ FeCl2 acts as drying agent and yields 1,2,4,6 hydrates, furthermore, initial H2O is introduced via muriatic acid solution.


lsd

  • Guest
Re - 115% concentration?
« Reply #79 on: November 12, 2004, 04:07:00 AM »
How do you get a concentration of 115%?
100% is a whole portion isn't it or is it like your yanky over proof alcohol?

WizardX

  • Guest
Expression
« Reply #80 on: November 12, 2004, 05:37:00 AM »
Most commercial/industrial solution concentrations are expressed either as...

%v/v  volume/volume

%w/w  weight/weight

%w/v  weight/volume

to convert %w/w  weight/weight to grams per ml (g/ml) use this formula.

(density of solution x %w/w)/100 = g/ml

Download my calcpack at

http://www.angelfire.com/scifi/WizardX/calculation/calcpack.zip