Alternative HI preparation

[Elementary]

Patent Number US1380951
Umm, how interesting !!

[PolytheneSam]

Post 190642

(PolytheneSam: "Re: OTC MDMA is now easy and cheap!!", Chemistry Discourse)
http://www.geocities.com/dritte123/PSPF.html
ad terra incognita per ars artis gratia

[Elementary]

(Damn !, you found it before me !   )

Here is the ripped patent :

http://geocities.com/c6h5uk/hi.pdf

(PDF document)
Umm, how interesting !!

[Elementary]

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 !!

[terbium]

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.

[Elementary]

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 !!

[Hermetic]

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."

[Jetson]

oh yes we cares of the results .  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 lonely}

[Elementary]

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

Abstract:

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 !

[foxy2]

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.

Foxy

Those who give up essential liberties for temporary safety deserve neither liberty nor safety

[Jetson]

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 lonely}

[Hermetic]

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."

[foxy2]

If you have acid, then what else could it bee???
Those who give up essential liberties for temporary safety deserve neither liberty nor safety

[Elementary]

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 !

[PrimoPyro]

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.

                                                   
                                                  PrimoPyro
Vivent Longtemps La Ruche!

[Hermetic]

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.

Notes:
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."

[Elementary]

Can't wait to here more results ! Looking good !  
Leonard Cohen cheers me up !

[foxy2]

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

[Hermetic]

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."

[Elementary]

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 !