Author Topic: New procedure for hypo rxns!  (Read 17311 times)

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SHORTY

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New procedure for hypo rxns!
« on: March 08, 2004, 05:32:00 PM »
Getting bored with the same procedure I decided to try a different start to my hypo rxns.  I found that I could use about half as much hypo as I had been using. Here’s what I did:

Ingredients

15g Pseudoephedrine HCL
9ml Hypophosphorous Acid (approx 50%)
10ml Dh2O
23g Iodine (recycled from previous rxns)

aterials

250ml Erlenmeyer Flask
2’ Air-Cooled Condenser (Made from fluorescent lightbulb)
Electric Hotplate
Balloon

Procedure

The pseudo was put into the flask along with the dh20.  The solution was swirled until all the pseudo was dissolved and then the iodine was added and swirled. 

The condenser was then attached and hypo was poured into the top in 1ml portions and swirled between each addition.

The balloon was then attached and the flask placed on the hotplate.  The temp was slowly increased until the contents began to react.  The temp was raised just enough to keep the contents reacting until an internal temp of 110-120C was reached and was left refluxing for about 4 hours.

A large amount of square crystals had formed in the condenser and these were washed down using a syringe filled with dh20.  A little over 1ml of dh2o was all that was needed.  About 30 minutes later another slightly smaller amount of crystals had formed and these were treated the same as the first.  Upon checking an hour later there were again a smaller amount of crystals and these were treated the same way.

After a total of about 8 hours the condenser was removed and the solution was diluted with an equal volume of dh20, based and steam distilled.

The results were as good as it gets for me.


Rhodium

  • Guest
Nice!
« Reply #1 on: March 08, 2004, 05:35:00 PM »
The results were as good as it gets for me.

And that corresponds to what kind of yield?


SHORTY

  • Guest
Actually i have made it a point not to weigh...
« Reply #2 on: March 08, 2004, 05:45:00 PM »
My final results due to not being able to achieve the 90% that many bees claim to obtain.  However, since you asked, i just went and weighed the results minus the small amount which was biotested. The yeild was 10.86g.


steam

  • Guest
re: NEW Procedure for hypo rxn_bySHORTY
« Reply #3 on: March 08, 2004, 06:20:00 PM »
Hey,GREAT writeup there SHORTY.

The 9th march 2004 -WILL- be a big part of our incrediBEE HISTORY.

YOU always seem to hit the nail right on the head every time!  8)

The time is right to grab the horse by the reins and go-man-go-man-go-man,GO.HYPO!!!  :)

Thanks SHORTY, there's a collection of literature I have here that YOUR POST is going
on top of.

Hope to see you around the traps, and
ALL-THE-VERY-BEST for sharing your DREAM with the rest of us.


Rhodium

  • Guest
one more clarification
« Reply #4 on: March 08, 2004, 07:16:00 PM »
Shorty: Is that 10.86g of freebase oil directly after the steam distillation, or of hydrochloride salt after gassing?


geezmeister

  • Guest
good notes
« Reply #5 on: March 09, 2004, 08:30:00 AM »
You are running a ratio of pseudo:I2:hypo of 1:1.5:0.6 and the hypo is about 50% concentration, diluted to what I guess is about 25% concentration by the addition of the extra water. You run the reaction near the parameters of the phosphorous acid reaction without the phosphorous acid one would add to recycle the I2 to HI. You need heat at this concentration to generate the HI initially. At this heat the recycling of I2 might be done by phosphorous acid created by the oxidation of the hypo acid during the reaction.

I am curious about the PI3 crystals you describe. You are doing a fairly wet reaction with 9 ml of hypo acid and 10 ml of H20. You are refluxing and I assume you are not losing any moisture. There is plenty of water in this reaction. I am used to seeing PI3 formed in dryer reactions and have not seen it myself with wetter reactions, although this could be that the extra moisture keeps washing the PI3 crytsals back into the flask.

I am not familiar with the dynamics of your condenser and the thought comes to mind that the PI3 crystals might be forming in the condenser where not much moisture condenses. This would allow them to accumulate in the condenser. In a dryer rP type reaction these crystals are seen towared the end of a successful reaction. (At least I have never had them appear in an unsuccessful reaction, and they appear during the I have had them appear the reaction is for the most part complete.) That the PI3 is present in quantity sufficient to crystallize in the condenser in this wet of a reaction is a puzzle to me and I am curious what the formation of these crystals says about the conditions of the reaction. I wonder whether their formation may be a result, even if indirect, of most of the reduction having taken place and there being very little intermediate left to reduce to meth? That is well beyond my ability to reason out, and is just a speculation on my part based on the experience of seeing those crystals late in reactions that are high yielding.

You have obviously shown that the amount of hypo needed to produce the HI and to effect the recycling if I2 is smaller than I thought it would be, and have shown that a longer reflux with less hypo acid in the mix will produce results similar to those achieved in a shorter reaction with an excess of the acid present.  
 
Great work! Thanks for the notes. I think I know someone who will try this out very soon.

Geez


SHORTY

  • Guest
WizardX's writeup gave me the idea to use less...
« Reply #6 on: March 09, 2004, 12:26:00 PM »
Rhodium, that was the weight of the hcl form.

WizardX's writeup gave me the idea to use less hypo.  Actually what i wanted to do was to dissolve all the pseudo in dh20 so that i would know that there was enough water in the rxn to start with.  Even with all that water if i didn't swirl the flask as i added the hypo it would immediately begin to react.  However, since i make my hypo from sodium hypophosphite, i have no definite way of knowing how strong it is.  I estimate it at 50% based on the density which is 1.27g per ml. I also wanted to see what the rxn would bee like if the hypo was added to the iodine and water because i was reading some old chemistry literature which says to add 1 part phosphorous to 10 parts iodine and 4 parts water to make hydriodic acid.  Here is what that same literature says about the square crystals:

A number of complicated changes take place during the preparation of this gas, from the reaction of the different substances mixed together and part of the newly formed products. 
Small cubical crystals may frequently be seen in the neck of the flask or retort employed; they consist of hydriodic acid and Phosphureted hydrogen, and are rapidly decomposed by water with effervescence, this fluid combining with the hydriodic acid.  The hydriodic acid gas is produced by the iodine combining with the hydrogen of a portion of water which is decomposed, the oxygen uniting with the phosphorus.


Heres part of WizardX's writeup about having an excess of hypo:

HYPOPHOSPHOROUS TO HI CALCULATIONS

H3PO2 + H2O + I2 ==>> H3PO3 + 2HI

Hypophosphorous 50% w/w. F.W = 66 g/mol. Density = 1.274 g/ml.

100mls (0.1Lt) of Hypophosphorous 50% w/w contains :

(1.274 / 50)/100 = 0.637 g/ml H3PO2 = 0.00965 mol/ml H3PO2.

0.00965 mol/ml H3PO2 x 100 = 0.965 mol/100ml H3PO2.

OR

(0.637/66) x 1000 = 9.65 moles H3PO2 per 1000 mls. (mol/Lt)

Since we use 100mls (0.1Lt), then 9.65 x 0.1 = 0.965 mol/100ml H3PO2.

Now since the ratio of Ephedrine : HI is 1:3 = (3/1), we require 0.75 moles of HI for every 0.25 moles of ephedrine hydrochloride.

Since we have 0.965 mol of H3PO2 and 0.39 moles of I2 (99/253.8 = 0.39), then the ratio of I2 : HI is 1: 2 = (2/1); so 0.39 moles of I2 reacts with the Hypophosphorous acid to form 0.39 x 2 = 0.78 moles of HI.

Finally, the excess Hypophosphorous acid, H3PO2 is 0.965-0.39 = 0.575 moles of H3PO2 is excess. The ratio for H3PO2 : I2 is 1:1, so only 0.39 moles of H3PO2 is needed to react with 0.39 moles of I2 to form 0.78 moles of HI.

Not only do we have enough HI; 0.78 moles to reduce 0.25 moles of ephedrine hydrochloride, but a large excess of 0.575 moles of H3PO2.




Rhodium

  • Guest
The condenser crystals are PH4I, not PI3!
« Reply #7 on: March 09, 2004, 01:57:00 PM »
they consist of hydriodic acid and Phosphureted hydrogen

Ah, that's very interesting! It means that the crystals aren't PI3 at all, but rather the hydriodic acid salt of phosphine:

HI(g) + PH3(g) -> PH4+I-(s)


geezmeister

  • Guest
What does that tell us?
« Reply #8 on: March 09, 2004, 02:40:00 PM »
And what does that tell us about the reaction? Anything?


Rhodium

  • Guest
What it might tell us
« Reply #9 on: March 10, 2004, 07:35:00 AM »
Well, that the crystals should be scraped back into the reaction container, as it is one of the most strongly reducing species formed in the reaction:

Post 443818 (missing)

(ragnaroekk: "Reference on HI reductions", Stimulants)


Maybe it wouldn't sublime and rather stay in solution if more solvent was used (acetic acid, or perhaps water).

Also, after the reaction one should be careful when basifying, as PH4I turns into phosphine gas under basic conditions.


SHORTY

  • Guest
I add water with a syringe to wash them down..
« Reply #10 on: March 10, 2004, 09:27:00 AM »
I just poke the needle through the balloon and knock them down into the flask by squirting water on them.  When they hit the solution they react immediately.  Sort of like when water is dropped on a hot skillet.  A white smoke fills the flask and condenser for a few minutes and then they start to slowly form again. 

Should i be using even more water?

Does the formation of these crystals indicate that the solution is holding all the HI it possibly can hold and therefore the excess forms on the sides of the condenser?

Or does this mean that the pseudo has all been reduced and the rxn is complete?


Rhodium

  • Guest
Suggestions for improving the reaction
« Reply #11 on: March 10, 2004, 02:13:00 PM »
Does the formation of these crystals indicate that the solution is holding all the HI it possibly can hold and therefore the excess forms on the sides of the condenser? Should i be using even more water?

Could be, it's hard to tell if the formation of these crystals are due to oversaturation of HI in the solution, or if this is something which invariably will happen regardless of solvent volume, without performing some experiments.

I believe it would be very interesting to see if you by increasing the amount of water (or by the addition of some GAA) can minimize the formation of phosphonium iodide crystals, while at the same time keeping yields the same or better. Please do that, and report back the results. Try to keep the workup identical to this reaction, as to minimize interfering variables.

Or does this mean that the pseudo has all been reduced and the rxn is complete?

Nope, not at all.


SHORTY

  • Guest
I think i can already answer that...
« Reply #12 on: March 10, 2004, 08:48:00 PM »
Actually, i have been using the formation of these crystals as an indicator for quite some time.  If they didn't form i would add more iodine until they did and when they did form i would wash them down until they no longer formed.  So yes, more water will prevent them from forming.  As far as GAA is concerned i have never tried it.  I have had a few rxns that never formed the cyrstals and didn't notice any difference in quality nor yeild.  I have also had some unsuccessful rxns when the crystals did form.  In my opinion phosphorous is just a very unpredictable substance as it continues to dissappoint, frustrate, confuse and amaze me.

So do i want to prevent them from forming?


wareami

  • Guest
Very interesting coralations...
« Reply #13 on: March 10, 2004, 09:08:00 PM »
Going on at the Reef...eh SWIMS?
Not too sure about the relevance here but from all observations in the past since doing the LWR, that HI formed and/or created in rxn seemed to do the best reducing when directly in contact with AWE the precursors at the bottom of pool!
This is why Ibee incorpirates the "Checkpoint" walk the plank style knockdowns with the bambouy stick at every hours.
The same white cloud syndrome can be witnessed as everything re-enters the pool as most of the solids collected on the sides are teeming with the h2o that condenses and drips back down! A little prodding by Capt Hooked never hertz... 8)
Shorty's suggestion about the ACCU-puncture technique seems better than a complete opening to prevent gas escaping.
Provided that one can position and aim the squirting to push everything back in the pool!
OHHH YEAH....and provided it doesn't require an excess of h2o to get it AWE back down therebye diluting the reaction to the point of stalling.


geezmeister

  • Guest
water water
« Reply #14 on: March 11, 2004, 08:57:00 AM »
I know Ware refluxes with less water than I use in my rP reactions. I use less red Phos than he uses. I don't see these crystals, but have near complete reduction in my long wet rP refluxes. More water, less phos, no crystals.

Then Shorty describes a wet hypo cook-- wetter than I am accustomed to running hypo cooks-- with the same ratio of I2 in the reaction. He runs at temperatures I have run the reaction, so I doubt temp is the factor. He gets these crystals toward the end of his reaction. They dissolve in additional water. I have never had them in a hypo cook, but its been a long time since I refluxed a hypo cook for six to eight hours.

I recall having my nasty introductions to phosphine fires when I refluxed for longer times at higher temps; I was using more concentrated hypo solutions than Shorty.

Could these crystals be related to the production of phosphine gas in the reaction, and be a sign that we have created the conditions in the flask to produce it? Or is it perhaps the production of these crystals which could lead to the formation of phosphine gas?


Rhodium

  • Guest
The crystals indicate the formation of phosphine
« Reply #15 on: March 11, 2004, 11:13:00 AM »
Could these crystals be related to the production of phosphine gas in the reaction, and be a sign that we have created the conditions in the flask to produce it?

Definitely. They are the result of gaseous phosphine and gaseous hydrogen iodide being present in the flask airspace, and upon contact with the cooler parts they condense into a solid salt.

It's very similar to CTH reductions using ammonium formate as the reducing agent, in which gaseous ammonia and gaseous carbon dioxide is evolved and combine in the condenser to give ammonium carbonate.

Or is it perhaps the production of these crystals which could lead to the formation of phosphine gas?

Chicken or egg?  ;)  In this case the phosphine gas was definitely there first, as only gaseous phosphine can evaporate like that.


geezmeister

  • Guest
Phosphine gas production
« Reply #16 on: March 11, 2004, 02:21:00 PM »
I have understood that phosphine gas production in HI reactions was related to the temperature of the reaction, and that at certain threshold temperatures, phosphine gas could be produced. I seem to recall that temperature as being about 142C, but whether that figure or the source of the information is accurate I do not know. Part of that information was from Law Enforcement information about meth production, which is notoriously misleading and inaccurate.

In my experience, however, phosphine gas was produced in hypo reactions at higher temperatures, during refluxes, and not produced at lower temperatures with the same concentration of hypophosphorous acid. The crystals are seen in dryer, and in hotter, rP reactions than the ones I do. I work at lower temperatures and with more water with rP, and tend to work with higher concentrations of hypo acid but at lower temperatures than Shorty does.


I understand phosphine gas is toxic, and would think that its production should be avoided if possible. It does not appear to be necessary to the reduction process, as both the rP LWR and the lower temp hypo cooks seem to avoid its production. Might this indicate that performing these reactions at lower temperatures than those that seem to produce these crystals is a good idea from a health standpoint, at least for the clandestine chemist?

Does the formation of these crystals in a reaction suggest the temperature of the reaction should be reduced for safety's sake?


Rhodium

  • Guest
Nothing good comes out of condenser xtals
« Reply #17 on: March 11, 2004, 04:46:00 PM »
Might this indicate that performing these reactions at lower temperatures than those that seem to produce these crystals is a good idea from a health standpoint, at least for the clandestine chemist?

Does the formation of these crystals in a reaction suggest the temperature of the reaction should be reduced for safety's sake?


Yes on both accounts, at least in my opinion. Any potential reducing agent crystallizing in the condenser won't do much good for the reaction either.


wareami

  • Guest
Phosphine gas....
« Reply #18 on: March 11, 2004, 04:51:00 PM »
Geez: Ibee's best guesses tell him that phosphine gas is a normal result of marrying I2 and RP or Hypo/h3po3/hp3o4...etc.
In AWE The Kidz Daze since becoming Bees, they have never witnessed the xtal formation phenomenon during rxn...
They felt cheated at first and wondered what they might be doing wrong as everybody elses reports of their presence on the flask neck or inside the condensor coinsided with success reports!
The fact that we reflux with adaquate h2o present throughout the LWR doesn't necessarily mean that phosphine isn't present or wasn't created.
It means we can't see iphosphine in the solid salt form because the dryer conditions don't exist for those of us using ample h2o.
I should have been more explicit too on when Ibee reported seeing the white clouds at checkpoints.
They aren't witnessed at every checkpoint. Just toward the very end of the reaction when knocking down what creeped up on the glass. Little wisps of smoke can be seen and Ibee associated that with condensed h2o trapped in reactants or maybe it's HI trapped and the h2o present at the bottom is what kicks the smoke UP!?#
Isn't that white smoke created by the reaction of h2o and  HI when dh2o comes in contact with HI?
It's almost always present when adding h2o to the end rxn work-up!
Now as to whether or not excess phosphine gas gets created by conditions such as high heat Ibee doesn't know.
It's possible and that may be what translates into excess impurity associated with SpaceCopter Dope!
Most of the bees early references to neckxtals seem to have had a common theme...hot dry/fast P/P types.
If there is a way to reduce the amount of phosphine created, if indeed it is a bad thing and serves no purpose in the reduction whatsoever, I'd hope that an easy solution could be adopted and incorporated into the LWR for health's sake!
Bee it a shift in time, temp, or ratio or the reactants!


wareami

  • Guest
Re: yes on both accounts
« Reply #19 on: March 11, 2004, 05:02:00 PM »
Rhodium: I think that some clarification on specific temp might help some if you could suggest...
Bees that follow the LWR do so under the guidance provided to the best of all our knowledge and experience with the LWR.
It doesn't make allowance for temps exceeding 120°C internal temp. Anything above that temp Ibee doesn't consider a LWR.
Now these are observations basted :)  on health aspects.
So.....if I understand correctly, what is being considered here is a further decrease in temp...
From the 120°C to...............????
Any suggestions as a baseline temp considering AWE tha's been discussed here?