Author Topic: NaIO3 -> NaI?  (Read 3952 times)

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improv_chem

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NaIO3 -> NaI?
« on: October 14, 2001, 10:34:00 PM »
Swim has a bunch of NaIO3 (don't ask!) and would like a way to easily get rid of the O's and make NaI to be easily converted into solid I2.  Swim can think of two ways of doing this easily but the first would involve a very exothermic rxn with zinc dust or sulfur or something and then to collect the NaI that would be left behind.  SWIM really donesn't want to do that because of flames and large smoke cloud left behind  in the apartment.... The other idea might be to reduce it with an electric cell using carbon electrodes and aqueous solutions with a membrane as a divider.  This seems like a bit too much work for a little NaI.
So is there any easy way of doing this without NaBH4 of some other non-otc chemicals that SWIM doesn't have?  (Don't ask where I got the NaIO3!)
Once the NaI is there it is easily turned into I2 with H2O2 and Hcl.
Any suggestions would be greatly appriciated.
-improv :)

Let's play with nature a little, I'm sure we can make her a little higher....

Osmium

  • Guest
Re: NaIO3 -> NaI?
« Reply #1 on: October 14, 2001, 11:04:00 PM »
The iodate can be reduced by a lot of different compounds. It's a pretty good oxidiser and will react with all kinds of reducing agents.

If I were you I'd use NaI  8)

IO3(-) + 5 I(-) + 6 H(+) --------> 3I2 + 3 H2O

Alternatively:

2 IO3(-) + 5 SO3(2-) + 2 H(+) ----------> I2 + 5 SO4(2-) + H2O
Attention! Too much sulfite will lower your yield!
I2 + SO3(2-) + H2O ------->2I(-) + SO4(2-) + 2 H(+)

improv_chem

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Re: NaIO3 -> NaI?
« Reply #2 on: October 15, 2001, 04:51:00 PM »
Thanks for the help Os!  The only problem with using NaI is that if I had NaI to begin with I wouldn't be playing with the NaIO3!  But it does look like the best route.  Mabe some playing with sulfites might bring me some Iodine!
Making my dreams even sweeter! ;)
-improv :)

Let's play with nature a little, I'm sure we can make her a little higher....

improv_chem

  • Guest
Re: NaIO3 -> NaI?
« Reply #3 on: October 15, 2001, 11:08:00 PM »
Yeah, it worked!  The Iodine color appeared after the bisulfite solution and the NaIO3 were mixed but the Iodine seemed to stay in solution and didn't form globs of solid iodine.  So, what's a bee to do?  One bee just stuck the beaker in the freezer with a watch glass over it to cool it down and then basified with NaOH solution to make NaI until the Iodine color was gone.  Some water was boiled off and the solution cooled and the crystals filtered out(Na2SO4).  The NaI solution was then put in a beaker and a shot of 3% H2O2 and a shot of 35% HCl were added at the same time and nice globs of stinky Iodine crystals were observed.  Vaccum filter the mess and wash the filter with some DW and away you go!
Thanks Os, You saved SWIM a lot of trouble. (SWIM hates those little tincture bottles!)
-improv :)

Let's play with nature a little, I'm sure we can make her a little higher....

PrimoPyro

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Re: NaIO3 -> NaI?
« Reply #4 on: November 11, 2001, 09:10:00 PM »
I have a desire to reduce an alkalai iodate to the iodide salt, without the precipitation of diatomic iodine.

How would a bee go about such a "simple" reaction?

I was thinking of NaIO3(Aq) + 2NH3(Aq) __> NaI(Aq) + 3H2O(L) + N2(G)

The problem is I know that Iodine has a tendency to precipitate out of solutions when it feels like it, and I don't want it to form the triiodide ion, then fall out of solution.

I don't want Iodine as the element, I want the iodide salt of an alkalai from the iodate. I'm currently searching for this simple conversion. I know it's easy, don't tell me that please! But like I said, I think the reaction is a little more tricky than I hope for, so I'm rather slow to dismiss it as one of the methods I'd normally think of.

Thank you for any information you may share.

                                                 PrimoPyro

Vivent Longtemps la Ruche! STRIKE For President!

Osmium

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Re: NaIO3 -> NaI?
« Reply #5 on: November 11, 2001, 09:52:00 PM »
Are you sure that NH3 is a strong enough reducing agent, especially at basic pH? I doubt it.

PrimoPyro

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Re: NaIO3 -> NaI?
« Reply #6 on: November 20, 2001, 12:14:00 PM »
Thats why I was asking. It was just a thought. What would you prefer to use? Dont say sodium borohydride, please.  :P

                                                PrimoPyro

Vivent Longtemps la Ruche! STRIKE For President!

improv_chem

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Re: NaIO3 -> NaI?
« Reply #7 on: November 20, 2001, 05:13:00 PM »
Go to the brewing store and pick up some NaHSO3(Sodium metabisulfite) and use the sulfite reaction that Os stated.  Then when you have your purple solution of Iodine, Do like I did and let it cool and then titrate with NaOH solution.  You can then purify the NaI by crystalizing out the other impurities(Sulfates) by fractional crystalization.  (ie. boil off some water and put it in the fridge.)
SWIM always keeps iodine as the NaI form until it is needed then converts it to the elemental form.  Great way to recycle Iodine from any reaction SWIM's ever used (Nitryle Iodide's,RP/I2, etc.)
It's really great not wasting chemicals all the time!
I really think you should stay away from using NH3 in any reaction using iodine.  That ammonia triiodide is really dangerous stuff and even the possibility of some forming in a reaction and blowing up in your face is enough to make me stay the hell away from it.  That stuff is a very sensitive explosive and shouldn't be taken lightly. 
Hope this has been some help;
-improv

Let's play with nature a little, I'm sure we can make her a little higher....

PrimoPyro

  • Guest
Re: NaIO3 -> NaI?
« Reply #8 on: November 20, 2001, 10:16:00 PM »
Although I truly do appreciate your help, I disagree with several points you have made:

>Go to the brewing store and pick up some NaHSO3(Sodium metabisulfite) and use the sulfite reaction that Os stated.

According to Osmium, this produces diatomic Iodine, which in my post, I stated I do not want.

>hen when you have your purple solution of Iodine, Do like I did and let it cool and then titrate with NaOH solution.  You >can then purify the NaI by crystalizing out the other impurities(Sulfates) by fractional crystalization.  (ie. boil off some >water and put it in the fridge.)[/blue]

Let's think about this. Purple solution of Iodine + NaOH --> NaI + NaOI. Yes the first half is useful, but, opun fractional crystallization, (your boiling part in water) hypoiodite ions degrade into iodide ions and iodate ions. The iodate crystallizes out of a pure hypoiodite solution, leaving aqueous sodium iodide. This is fine and dandy, but the issue is: This is where Im getting the NaIO3 from in the first place! Im just running in circles! I can salvage the NaI from these reactions already, and convert I2 to NaI, but I want the byproduct NaIO3 reduced to NaI, Not I2, or any NaIO3 regenerator.

>I really think you should stay away from using NH3 in any reaction using iodine.  That ammonia triiodide is really dangerous stuff and even the possibility of some forming in a reaction and blowing up in your face is enough to make me stay the hell away from it.  That stuff is a very sensitive explosive and shouldn't be taken lightly.

Let's just say that I humbly disagree. I've worked with the stuff, and these reaction conditions before. I've also made it on purpose, dirty, and with reagent grade materials. It sucks both ways. It's semi-loud, no fire, no light, no spark, just a small purple stain wherever you set it off at, with a noise. Bottom line: Not A Threat, Just A Nuisance; And That's When You Want It To Explode!

As for it's famed sensitivity, I wonder who started that lame ass rumor. The reagent grade shit is fairly sensitive, if you smack it, it will "detonate", and anything made with less than pure ammonia and diatomic iodine will not explode at all, unless its anhydrous and submitted to hella shock trauma.

It will never ever explode in water; this is the recommended storage for it. Even in boiling water, it will never explode, I tried. It can also NOT form in solutions of alkalai iodide, as these combine with iodine to form the triiodide ion. Dont confuse ammonium triiodide with nitrogen triiodide. Nitrogen triiodide NI3 with true ammonium triiodide NH4I3, which Im fairly certain only exists in solution, as I could not isolate it.

Pressure Wave < Black Powder
Shockwave < Less Than Confined Nitrocellulose
Sensitivity < Mercuric Fulminate

Main Charge rating = Piss Poor.
Booster Rating = Pointless.
Primer rating = Not a Chance.

Overall = I can fart with more force.

                                                  PrimoPyro

Vivent Longtemps la Ruche! STRIKE For President!

Rhodium

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Re: NaIO3 -> NaI?
« Reply #9 on: November 21, 2001, 02:04:00 AM »
I have seen nitrogen triiodide detonate under water. It made a very nice brown stain on the whole wall in the school lab.

terbium

  • Guest
Re: NaIO3 -> NaI?
« Reply #10 on: November 21, 2001, 04:08:00 AM »
The reagent grade shit is fairly sensitive, if you smack it, it will "detonate", and anything made with less than pure ammonia and diatomic iodine will not explode at all, unless its anhydrous and submitted to hella shock trauma.
Where do you buy the Reagent Grade NI3? I have never seen it for sale. What are the specifications for this Reagent Grade NI3? Is it an ACS spec?  ;)  Oh, and we are talking about NI3, right (though I have seen some debate about the true composition but, no, I hadn't ever seen it confused with NH4I3). All of the NI3 I have ever made has been extremely sensitive after drying - exploding at even a gentle touch. My father tells the story about how he nearly got kicked out of college when the NI3 he had made in chem lab and set aside to dry, exploded spontaneously during lecture.

PrimoPyro

  • Guest
Re: NaIO3 -> NaI?
« Reply #11 on: November 21, 2001, 04:25:00 AM »
terbium, lol you smartass.

I meant the product obtained by the use of reagent grade reactants, versus reacting cleaning solution ammonia with iodine tincture.

Yes, when it's dry it's very sensitive, and when it'spure it's sensitive. In my reaction above, I hadnt planned on using reagent grade ammonia or iodine, so I hadnt written a response assuming that as the subject.

As for the composition, I was illustrating the point of the triiodide ion, and why it cant be present to form nitrogen triiodide, which I stated IS the explosive, not ammonium triiodide. They may have the same name, but the two Im referring to are completely different.

My point, in a nutshell: diatomic iodine combines in solution with iodide to form the triiodide ion, I3-, which the ammonia will attract, in the form of NH4I3 in solution; which is NOT explosive. Ammonia will react
with diatomic iodine to replace the hydrogen atoms with iodine, forming nitrogen triiodide, which will explode when dry. I still say its a shitty explosive, though.

Since we are operating in an environment with alkalai iodide ions floating around in 5x the molar quantity of IO3, which is being reduced, and therefore could be the only contributor of diatomic iodine upon precipitation; dont you think it has a wonderful chance for uptake as I3-? Im telling you, solutions containing I3 wont form an explosive that will detonate under water!

                                                PrimoPyro

Vivent Longtemps la Ruche! STRIKE For President!

PrimoPyro

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Re: NaIO3 -> NaI?
« Reply #12 on: November 21, 2001, 01:45:00 PM »
Upon rereading this thread from the beginning, and rethinking my plan of attack for the generation of sodium iodide, Ive decided to just crystallize out the iodate and save it for other, pyro needs. It is, afterall, a wonderful oxidizer, and decently unstable around elements like sulfur or Mg. Ive never thrown any into hydrazine before, I wonder what would happen.  :P

Since Id be getting only one fifth (maximum yield) the iodide product from the reduction of the iodate, as Id be getting from the rest of the reactions that produce the iodate, it now seems redundant to do this phase in reality. I'll just find another use for the iodate.

Thanks to everyone who helped me out with my inquiries here. I appreciate your tolerance of my basic chem questions, I really really do. Thank you.

The reason the iodide salt is so important, and NOT diatomic iodine (for those that are curious) is that the plan was to use NaI or KI to form DIM from DCM, a la Rhodium's site, and ALSO for the ketone complex formed with NaI and MD-P2P, used as a substitute for bisulphite purification. If you didnt figure it out before, now you know. OTC all the way, thats my philosophy.

                                                PrimoPyro

Vivent Longtemps la Ruche! STRIKE For President!