Elementary (Hive Bee)
03-23-02 22:22
No 286988
      Alternative HI preparation  Bookmark   

Patent Number US1380951

Umm, how interesting !!
(Master Searcher)
03-23-02 22:25
No 286989
      [190642]  Bookmark   

Post 190642 (PolytheneSam: "Re: OTC MDMA is now easy and cheap!!", Chemistry Discourse)

ad terra incognita per ars artis gratia
(Hive Bee)
03-23-02 22:27
No 286991
      HI Patent  Bookmark   

(Damn !, you found it before me ! wink)

Here is the ripped patent :


(PDF document)

Umm, how interesting !!
(Hive Bee)
03-24-02 00:21
No 287049
      Rosin  Bookmark   

According to the patent :

A process of making hydriodic acid by bringing pure iodine in contact with rosin oil and subsequently removing the hydriodic acid from the mixture by heating.

Well rosin (Colophane) is freely available as a soldering flux and for use on stringed instruments (violin).

So producing HI this way will avoid the need for H2S gas or phosphoric acid.

I wonder if I dare mention the possibility of rosin being used as a HI recycler in the HI reduction of ephedrine......no, maybe I'm jumping the gun here !

Umm, how interesting !!
(Old P2P Cook)
03-24-02 01:17
No 287084
      yield?  Bookmark   

Does the patent make any claims as to the percentage of iodine converted to HI? When HBr is produced by the action of bromine on tetralin, only half of the bromine is converted to HBr; the rest of the bromine is consumed brominating the teralin.
(Hive Bee)
03-24-02 01:29
No 287091
      yes in a way  Bookmark   

extract :

2C10H16 + 2I2 = 2CH10H16I2
2C10H16I2 = (C10H14)2 + 4HI

In certain cases, the reaction is not so simple as the above and some of the iodine is held combined with the organic substance. In cases where iodine is held as a definite compound, it is necessary to heat the substance in order to liberate the iodine as the acid.

Umm, how interesting !!
04-04-02 17:40
No 292345
      So, are we saying that careful addition of ...  Bookmark   

So, are we saying that careful addition of iodine, either solid or in solution, to turpentine will liberate HI(g) which can then be made into an easily useable aqueous solution?  Also, what about the expolosion hazard that Mr. Frankforter mentions?  He seemed a little vague on that point, maybe he was shell-shocked from his latest blast.  I'm thinking strong tincture (for the iodine challenged) dripped slowly into chilled turpentine with vapors directed into water to collect as HI(aq).  Seems a little less likely to kaboom than solid iodine.  Im going to give it a go.  Probably will attempt the solid addition, though.  Too much solid iodine in the photo-lab to go buy tincture.  Let me know if anyone cares of the results. 

"Wyatt, I am rolling."
(Hive Bee / Eraser)
04-04-02 17:51
No 292348
      results...  Bookmark   

oh yes we cares of the resultswink.  by the by,  how would one test their HI(aq) to ensure that it is indeed HI without doing any illegal manufacturing?  like say,  a drop of HI onto/into this and this will happen...  anyone? 

ps.  what the fuk's up with the subject line lately?  why must poor jetson stress his fingers so much and have to type a new subject line every reply?

the devil is so lonelymad
(Hive Bee)
04-04-02 17:54
No 292349
      no tincture  Bookmark   

if you read the patent, the process involves adding iodine (not an alcoholic solution) to turpentine or rosin.


It was found in working with terpenes such as commercial pinene, usually termed common pinene or with rosin oil, that when iodine is brought in contact with them, even at the ordinary temperature, a vigorous reation takes place between the organic compound and the iodine forming hydriodic acid and an iodo-compound of the organic substance. The latter on standing or on heating breaks off hydriodic acid and a condensed form of the organic substance is formed

Leonard Cohen cheers me up !
(Distinctive Doe)
04-04-02 18:50
No 292364
      testing  Bookmark   

like say,  a drop of HI onto/into this and this will happen...  anyone? 

Titrate it back to pH 7 with a known concentration of NaOH solution.  This will tell you how much HI you get.
Meaning take say 5 mL of you generated acid, start adding say 1M NaOH, add carefully until the pH is exactly 7, then however many moles of NaOH you added is how many moles of HI were generated.


Those who give up essential liberties for temporary safety deserve neither liberty nor safety
(Hive Bee / Eraser)
04-04-02 19:06
No 292369
      damn subject line....  Bookmark   

ok,  so that'll let me know how much HI swij has obtained but how does one test to see for sure if it's indeed HI?  just hypothetically speaking and someone was trying to work out another possible route to HI and just wanted to make sure that the end product is HI.  like a marquis reagent test to test for meth and such...

the devil is so lonelymad
04-04-02 19:12
No 292370
      Why tincture suggested....  Bookmark   

If you read lines 86-7 of the text, it states that, "The iodin [iodine] may be added either as the solid or in solution."  Also in lines 92-100, the patent seeker states that oxy compounds, like alcohols, will also react with iodine in a similar manner.  This leads me, for one, to think that the mixture of iodine dissolved in alcohol (tincture, easier to get for some than iodine crystals) may also be effective.  This may also reduce the explosion hazard he mentioned, but who knows?  At the very least, it shouldn't hinder things, according to Mr. Frankforter.
The proof is in the experimental, not the theoretical, so off to the lab we go, merrily singing the Oscar Meyer weiner song (George B. Frankforter, get it?).
However, I am just now thinking, that depending on the alcohol in the tincture, it may also come over with the HI causing mass hysteria, cats and dogs co-mingling, etc. etc.

"Wyatt, I am rolling."
(Distinctive Doe)
04-04-02 19:24
No 292376
      lol  Bookmark   

If you have acid, then what else could it bee???

Those who give up essential liberties for temporary safety deserve neither liberty nor safety
(Hive Bee)
04-04-02 19:30
No 292379
      why make things more complicated with tincture  Bookmark   

If ethanol is present this may lead to iodoform being produced. If you don't extract the iodine from tincture first then you will waste all that iodine locked up as potassium iodide.

If iodine is added in small amounts, while keeping the reaction cold, I can't see there being any risk of explosion. If you just dump a load of iodine into the turpentine (etc) then you will have fireworks.

Leonard Cohen cheers me up !
(Sector G)
04-04-02 19:32
No 292380
      Ketone Crash  Bookmark   

You can dissolve an equal molarity of acetone and the formed sodium iodide, NaI, into a solvent, and it will precipitate an addition compound, NaI(ketone)3 very much like the bisulfite addition test.

In fact, you can find the details for this procedure on Rhodium's site very easily.

Or you can oxidize it back to iodine from a pure water solution. That should tell you that you had the iodide salt, which you made from HI and NaOH --> NaI and H2O.


Vivent Longtemps La Ruche!
04-05-02 02:10
No 292546
      exciting prelim results  Bookmark   

Elementary, sounds good to me, about the potential ethanol problem and the ice bath I mean.  The use of tincture was not suggested as a complication, it was intended as a way to skip titration of iodine and loss of reagent. The tincture available here has no ethanol or isopropanol, but some type of para-substituted phenol for the solvent which I don't remember the name of, but will try to find (I don't buy it anymore).  The author wasn't very specific about which alcohols, only that unsat and sat may work. 

Pyro, right-on with the test of the contents of my now acidic water layer (see below).

I do have some preliminary results. 

Experiment 1
Into a 125 mL round reaction flask with a flat bottom were placed:
30mL distilled H20
30mL pure gum turpentine (slightly yellow, nauseating odor)
Put on magnetic stirring in ice water bath (created a cloudy solution).
Dropped in all at once 0.5g Iodine crystals.
Corked securely, but not so tight as to prevent popping of the stopper if pressure built up.
Stirred for one hour vigorously. No apparent pressure increase, Fairly exciting reaction at first (I peeked, Iodine crystals just seem to explode into solution when in contact with turpentine).

All Iodine did not react (dissolve).  Solution was pale yellowish-orange while stirring, seperated back into two distinct layers upon removal from stir-plate.  Top layer (turpentine layer) is dark orange to brownish, bottom layer (water layer) is cloudy off-white with oily globules which eventually seem to rise into top layer.  After 10 minutes undisturbed, top layer becomes very light yellow in color almost all at once, in contrast to the dark orange it was. Solution was poured off slowly from unreacted Iodine into a seperatory funnel, and allowed to settle again for 5 minutes (any agitation seems to bring back the orangey-brown color temporarily).  A small amount of water layer was drained, with a pH reading of 0 to 1.  Water layer is cloudy but whitish (like clean frozen water) and uniform, and shows no oily globules remaining.  Ok, there is some species causing acidity, but don't know what yet.

1.  Ice-water bath used as a just-in-case, didn't seem to release much heat, but better safe than sorry.
2.  Turpentine makes me nauseous(sp?).  Not such a strong smell after reaction.
3.  Solution will be allowed to set in sep funnel overnight undisturbed.
4.  My notion is that by putting water directly into the flask with the turps and stirring, that any HI formed will want to go right into solution with the water.  As no pressure increase was noted, and no odd odors prevailed, it may have worked.
5.  Original turpentine layer before addition of Iodine was clear yellow.  Now it appears as an opaque yellow, but of almost the same shade. 
6.  Anybody know what the reaction product from the patent, C10H14, may be? 

Have to stop for the night, girlfriend on the way over.  Will report again tomorrow after testing for the presence of iodine in my water layer.

"Wyatt, I am rolling."
(Hive Bee)
04-05-02 02:35
No 292563
      Nice One !  Bookmark   

Can't wait to here more results ! Looking good ! smile

Leonard Cohen cheers me up !
(Distinctive Doe)
04-05-02 09:05
No 292736
      my thought  Bookmark   

Personally I would prefer to pipe HI gas into water, but that is more dangerous.

Those who give up essential liberties for temporary safety deserve neither liberty nor safety
04-05-02 18:47
No 292869
      Woo-hoo, what's dat?  Bookmark   

Yes, but probably more efficient.  I'm thinking that it would still contain some constituent of the turpentine.  I'll explain why below.  

Here are the rest of my first run results:

Note: Most chemicals used are from the hardware store, photo lab, etc.  This is for the sake of an easily written OTC procedure, should this experiment pan out.

Upon standing overnight in the dark, the water layer completely cleared, except for some odd clear globules stuck to the sides of the glass separatory funnel.  Due to these globules, the water layer was gravity filtered through a Whatman qualitative filter paper into a clean beaker.  The turpentine layer remained in the separatory funnel.

Using the calculated theoretical maximum amount of HI now in solution in the water layer, an equimolar amount of strong base (NaOH) solution was prepared with a volume of 30mL to make the upcoming titration volume a little easier to gauge.

Entire water layer remaining was neutralized with the weak NaOH solution.  It took about one-third of calculated maximum, leading one to believe that only one-third of HI possible had been produced and/or had entered the water layer.  Bear in mind that I'm not using a precision balance chamber here, only a 0.1g accuracy scale.

At a pH of 7.0, mixture had a slight terpene-like odor, but not nauseatingly so like pure turpentine.  Approximately half of the volume was removed and dried to produce a yellowish gummy substance (pine resin perhaps?).  A cold acetone rinse revealed whitish to yellowish crystals, presumably NaI. 

To the remaining aliquot was added 5 mL muriatic acid (31.45%).  As I don't titrate my own Iodine anymore, the exact ratios escape my memory.  Volume was doubled with 3% H2O2, upon addition of which the solution turned immediately brownish orange, with no noticeable heat release.  Since no noticeable Iodine precipitated (pretty dilute solution here, no surprise) my favorite chem-hack method was used to test for iodine.  A small portion was dripped onto a bleached paper towel.  Instant purple success (residual chlorine knocking the iodine out of its comfortable home?).

Of course, one experiment doesn't prove success, and the method will need to be refined.  The water layer apparently had some residual terpene-like product in it.  However, it was postulated above that this might actually recycle iodine during the HI reduction reaction of ephedrine (jump that gun, elementary).

Distillation is the way to try to get a more pure HI(aq), and would eliminate any concentration questions, provided that no terpenes were present in the HI(aq).  Or, as Foxy2 stated, bubbling the produced HI into a massed quantity of H2O until a desired mass was reached would help with this.  As I have a gun-shyness about distilling acids, this is a good method for me, if it proves to pan out.

I never have liked turpentine due to the odor.  I'm starting to fall in love with it, though. 

I just noticed that the patent seeker stated that upon standing, the HI breaks off causing condensation of the terpene (organic not my forte, did the halogen attack the double bond on the alpha- or beta- pinene?  If so, can some organic genius determine the nature and name of the formed condensation product?  The structure of terpene is easily found).  That may explain why the turpentine layer went from orangish-brown to yellow spontaneously and rapidly upon standing.

Preliminary findings (subject to more experimental data):

Yes, one can combine turpentine with iodine crystals and produce an acidic solution containing the I- ion, likely to indicate HI.  The residual terpenes in the HI (if any) may not hinder the reduction of ephedrine, and may actually help to recycle iodine.  Why was my water layer clear, and not brownish like most people think of HI(aq)? Because it didn't get the chance to oxidize any iodine back.  The pure appearance of 57% HI is clear and water-like.  I may expose some of the next test run to UV light to try to get the gradual browning expected.

Coming soon, larger scale experiment, producing about 100mL of HI(aq).  I will try to get a stronger concentration, and titrate precisely to determine HI concentration.  If this run proves out, HI(aq) will be passed on to the man who knows this guy who might have a use for HI(aq) to, uh, clean silver or something, and reduction results will be posted.

Any questions, tips, advice, etc.?  All feedback is appreciated here!  This seems amazing to me, glad for the push-off in this direction Elementary , PolySam, and terbium.

Normally, I’d kill for some redP.  If this works, I may be smoking pole for turps (kidding, just kidding).

"Wyatt, I am rolling."
(Hive Bee)
04-05-02 21:05
No 292919
      Looking Good  Bookmark   

As the patent says the last bit of iodine locked in the organic substance is removed by heating, unfortunately you can't do this (water present).

I would be interested how things would turn out using rosin, as this is a denser substance and may not leave so much smelly contamination of the final HI.

Have you tried just dropping a small amount of iodine into turpentine without a solvent to see just how violent the reaction is (outside with a long pair of tongs !)?

Leonard Cohen cheers me up !
04-06-02 00:35
No 293005
      I first added a single chunk of iodine, ...  Bookmark   

I first added a single chunk of iodine, approximately 5mm square and maybe 2 mm thick to 10ml turpentine.  I wouldn't call this reaction violent on this scale, but semi-spectacular.  The iodine crystals seem to burst into solution over the course of a few minutes.  About four minutes into this, I held a piece of 0-14 range pH paper inside the neck of the 25mL flask, and it turned pink, as if to indicate a low pH.  I would think that heating would serve to condense the remaining halogenated terpene to whatever that will become, and therefore release HI(g) which could be taken up into the water easily as long as vigorous stirring is maintained in an ice-water bath.  I don't really wish to find out what happens upon heating a potentially explosive turpentine/hydriodic acid mixture in a glass vessel.  Not knowing the actual concentration of reactable substances in the turpentine will hinder theoretical calculations a bit, but over time the experimental data can be collected and formulated into a "recipe" if you will.  After my afternoon nap I will continue the experiments.

I assume you to mean gum rosin.  Isn't that what turpentine is produced from?  I don't really know, so I can't say for sure.  It would be nice to know the amount of terpenes, etc. in typical gum turpentine.

If I can get out of the city this weekend, I may try dumping about 0.1 mole iodine crystals into a liter of turps just for kicks.  Maybe I can reach around a big tree and just kind of pour it in all at once.shocked

"Wyatt, I am rolling."
(Hive Bee)
04-06-02 01:03
No 293013
      Thinking about HI gas  Bookmark   

What I'm interesting in is the potential to make HI gas, thats why I'm asking about how lively the reaction is when no water is present. It sounds from what you say that the reaction can be kept relatively tame with lower quantities.

My leaning towards HI gas is its use in replenishing the HI solution in a phosphorus-less HI eph' reduction.

Leonard Cohen cheers me up !
04-06-02 09:33
No 293190
      second run data  Bookmark   

Elementary, the reaction seems very tame, as described below (somewhat).  As for piping HI (g) into a reaction, you’re on your own there.  I have had two nasty incidents with suckback lately (including digging the remnants of a once nice thermometer out of a ceiling.  Those mercury spill cleanup kits are pretty useless for acoustic tiles).  Until I can cure my carelessness, I will be extra cautious.  I am also looking for the no phosphorous route of HI reduction.  Electro has been a bust for me, and more lab-oriented techniques are not possible quite yet.  If I could get quantities of redP, I wouldn’t care so much about the HI.  It does seem that HI (g) was spontaneously coming off of the small sample test of turpentine/iodine, indicated by the pinking of the pH paper in the neck of the flask (above post).

Results of second experiment:

Into a 1000mL Erlenmeyer flask were placed 300mL turpentine with 300mL distilled water.  It was stirred vigorously with magnetic stirring for 5 minutes, and then poured into a separatory funnel.  Upon sitting for 15 minutes, the layers were distinct, with a slightly cloudy water layer (bottom layer).  The water layer was discarded, and the turpentine layer washed 2X with 150mL distilled water.

The now “clean” turpentine was combined into a clean 1000mL Erlenmeyer flask with 100mL distilled water, placed on magnetic stirring, and solid iodine added by the following schedule.

0 minutes 2.0g
12 minutes 3.0g
30 minutes 3.5g
40 minutes 5.1g
66 minutes 4.9g

For a total of 18.5g I2.  Iodine was added without any planned timing, just when it felt right.

Results of each addition were very similar; the solution turned a dark brownish color, nearly black at times.  No gas formation, no pressure increase, and no temperature increase.  Slight fog condensing on walls of flask above the mixture, tested acidic to pH paper.  At 80 minutes, the solution was removed from stirring and poured into a separatory funnel.  Layering was much quicker than with unwashed turpentine (previous post), and very distinct.  Lower water layer was a clear orangish-brown.  Upper turpentine layer remained dark brown to black, even upon standing for one hour.  Both solutions will be allowed to stand overnight in the dark and then inspected further.  The pH of the water layer was 0-1, indicating a strong acidity of some sort.

To the separated turpentine layer was added 50 mL water, it was swirled, and then tested for pH.  Strong acidity was again indicated, leading one to believe that either HI is trapped in the turpentine layer (likely), or that more halogenated terpene was continuing to condense and release HI into the water layer (also distinctly possible, according to the patent text). 

It seems as if the earlier suggestions of using no water in the reaction and directing the formed HI (g) into a receiving vessel containing distilled water may be a better route.  It seems as if the iodine would react quicker, also.  However, I defend my original choice of using water in the experiment as a way to contain formed HI (g).  After all, even failures provide valuable data.  I prefer to start simply, and then gradually move to the goal. 

My next route will be to bite the bullet and distill the acidic water layer, shooting for the azeotrope of HI (aq); then the turpentine layer, bubbling the vapors into a massed quantity of distilled H20.  I found reference to turpentine boiling at 158 C, but do expect some trash to follow the HI since turpentine is a broad mixture of compounds.  Simple distillation may work (30 degrees difference in bp), and will be attempted for the sake of simplicity.  If that fails to produce a clean enough product, follow-up by fractional distillation will be performed.  Copious temperature/volume data will be collected.

-->Since no apparent heat is released, I would expect that larger scale additions of solid iodine into washed turpentine would be relatively safe.  If distillation works out, I will also be trying the tincture addition to turpentine for the solid iodine challenged in the audience.

All in all, I am still pleased with the results.  I would definitely recommend to anyone else experimenting with this process to wash the turpentine first.  Whatever trash was coming out in the water wash of the pre-reaction turpentine could easily carry over into the distillate.

More experimental results will be posted.  Again, please provide feedback if even remotely relevant.

"Wyatt, I am rolling."
(Hive Addict)
04-06-02 21:44
No 293354
      H(x) and Aromatics  Bookmark   

It seems to swim that when any aromatic is halogenated the H(x) is produced.  when 2C-B is brominated you addBr2 and one of the Br attaches and the other Br is converted toHBr which eventually ends up making the HBr salt.  IN the E:I:Rp rxn t he HI is produced as the E first gets iodinated.  so producing the HI doesn't really seem to be a problem here it is the constant regeneration of it.
04-08-02 05:30
No 294000
      1.Couldn’t log in as me, had to register an ...  Bookmark   

1.Couldn’t log in as me, had to register an alias, but this is Hermetic.
2.Pinene is not an aromatic. (But that's not what you meant, right?) http://library.thinkquest.org/3659/orgchem/aromatic.html?tqskip1=1&tqtime=0407
3.HI production is exactly the problem I am having.  If I had redP, I wouldn’t even pretend to care about this subject.

Elementary, I heated the darkly colored turpentine layer from above in a hot-water bath (90C) for 20 minutes.  The solution turned a clear brown, but no significant gas production.  Sorry, I can’t safely go much hotter yet.  However, when I washed it with distilled water, the water came off slightly clear-yellow, and very acidic.  Second wash produced only about a pH of 6, so most of the acidic species went with the first wash.  When I get a new thermometer next week, I will try fractional distillation to get the HI (aq) azeotrope.

Would someone with a familiarity with lab-grade 57% HI (aq) give this a go? 
04-08-02 09:22
No 294127
      Password  Bookmark   

Ask for a new single-use password for your original username at forum@the-hive.ws , then directly change to a new password after first login (when you received at your registered email address your new single-use PW).
You prolly still used the same PW which you got from us, and Lili has made some changes to the database, that's what happened. LT/


04-09-02 01:25
No 294369
      Thanks, LT  Bookmark   

Hey, thanks for noticing my plight.  I tried on Saturday to email my problem in, and it got bounced.  Something about being out of space.  I'll try it again.
07-20-02 14:18
No 335028
      i think this doesn't work  Bookmark   

When I2 is added to turpentine, or the other way round, a highly exothermic reaction occurs which results in the sublimation of I2. Slower addition means that no I2 sublimes.

When no sublimation occurs, there appears to be no gas generated.

The reaction of Iodine with pinene is, I think an example of iodination across a double bond.

Normally this is not so energetically favourable, but because of the ring strain in pinene, the reaction proceeds rapidly and exothermically.

I would be happy to hear of any reason why somebody thinks this will work, but I am skeptical.
(Hive Addict)
07-20-02 21:07
No 335137
      Maybe using turpentine is not the best choice.  Bookmark   

Maybe using turpentine is not the best choice.

But I have seen many references to the production of HI with I2 and rosin.

And I doubt that someone/company would of gone to all the trouble to patent the process if it doesn't work.

I've got nothing to do today but smile !
07-20-02 23:12
No 335183
      agreed  Bookmark   

yes, I also wonder why somebody would patent something that doesn't work.

my observations with turpentine (which contains around 95% pinene, the reaction constituent stated by Mr Frankforter) suggest that HI is not evolved in significant quantities.

Maybe I am doing something wrong.

I also wonder why a method of generating anhydrous HI, which is not an easy thing to do, is so much overlooked by the Hive and Organic textbooks if it in fact works (it's not exactly new, having been patented in 1921)

The following url shows a reaction scheme for the initial reaction to produce the C10h16I2 product.


I'd love this to work, but I'm not sure it does. Rosin Oil also contains pinene.

Maybe I should look up some of those Refs.

Do you have any of those refs. with regard to Rosin that you may be able to share?

Many thanks