h3po2- stranger things have happened

[bdbro]

swim has been around the hive for around 7 months and has done around 200 synths to date. recently for lack of lg hypo 30% swim has started making the hypo from sodium hypophos, using shorty's method. Recently the rxn's have been completed much quicker than before. who ever said that every synth is different and you learn something new each time is 100% correct. Swim mixes 500g Sodium hypo with 500ml 32% lg hcl and leaves overnight, swirling the contents a few times within this period, after which swim filters with a cloth and ends up with approx 600ml solution. Evapping this solution is a major headache as no matter what swims add eg broken glass etc the solution starts bumping. MAny tries latter swim now constantly stirs the solution till it evaps to the needed volume. Swim evaps a little less than shorty's method, down to 400ml as swim finds after filtering the salts swim ends up with 300ml after which .6ml dh20 is added per ml of h3po2.
if there is anyway to evap without bumbing any input would be a big time saver.
anyway, now to the main point, swims sees the rxn comples much quicker and swim lets rxn continue till there is no activity in the flask. the most recent rxn took approx 3 1/2 hours after which when swim added dh20 to the post rxn mix the whole mix turned milky then clear like dh20. Swim is used to the post rxn fluid turning yellow. When going for the toulene wash, swim noticed that the toulene didnt extract anything dirty so swim figured that the rxn was completely out of iodine and that is why the toulene didnt extract anything unclean as it ususally takes 3-4 toulene washes to remove the yellow and red from the post rxn fluid.
after which base was added(swim add toulene for extracting the freebase MA after basing to ph of 14), after base was added the solution turned red and stayed like that for a while , then it tuned clear and the top layer(which should be the MA) turned whitish and looked a bit like shaving foam. when swim extracted with toulene evrything seemed ok and as normaly would.
if anybody has any idea what happened and why this happened, input would be much appreciated. After doing 200 rxns this is the first time this has happened.
swims ratios are 140/140/220  E/H3po2/I, swim mixes most of the I with the hypo then adds the E then adds the remaining 20g of I added and once it has dissoved the rxn is started.all of swims precusors are LG

swim would like to thank all the bee's that have helped all these days as swim wouldnt have gotten to this stage without everybodies help!

[biotechdude]

"...if there is anyway to evap without bumbing any input would be a big time saver..."

What is your evaporation container? Flask, Pot??  The reason things 'bump' is because there is a concentrated point of heat absorbtion (usually the bottom of a flask).  Logic would see that more even and encompassing heating would lessen the effect Eg; put flask submerged in oil or water bath.  Stirring also lessens bumping as the solution is moving and not getting unevenly heated at one point.  Lastly, a vacuum can lower a bp and induce a solution to boil more evenly as the heat is being pulled away and not pushed from below (and bumping).  These comments are purely observation and Swix thought it would get more confusing if he got all tech and academic.

Re Your H3PO2 Reaction; Swix doesn't use hypo but a old-bee friend does and will answer from a dwindling memory of his activities.

- you were previously using lg 30% hypo; now you make your own from the hypophosphite salts.  The hypo you make is more concentrated so hence its activity (in I recycling to HI) is more vigourous.  This explains the faster cook times and clearness of the solution post reaction. (old-bee's would be clear as well).

"...after which base was added(swim add toulene for extracting the freebase MA after basing to ph of 14), after base was added the solution turned red and stayed like that for a while , then it tuned clear and the top layer(which should be the MA) turned whitish and looked a bit like shaving foam..."

- MMM, not totally sure, will hypothesise.  At post reaction, there was no free iodine and it was just clear HI.  Then when you started adding the base it upset the equalibrium of the HI; causing it to drop I into the solution (goes red).  Then as you continued adding the base, the free I was converted to NaI floaties (and clearing the solution somewhat).  Then as all the base was added (and all meth converted to fb) it migrated into the np.  The whitish appearance of the np could of been from excess Na ions or the like; that will be removed with water washes of the np later on (leaving meth-rich clouded / miraged np)

If all went ok yield and potency wise; i assume these little changes are because of you new source of hypo.  SHORTY will no doubt clear all this up with one post so i'll leave the rest to him...

P.S. Congrats on your quantity and frequency of rxns.  You must appreciate the quickness and ease of the hypo synth.  Your $ources must bee as happy as you

LATE EDIT - 200 rxns in 7 months...thats 1 a day.  Wouldn't u just combine 2 and have a day off??... 0_o

[bdbro]

thanks for the advise
i am using a 1000ml beaker(borosil glass), i add a few broken pieces of glass to it. I will try it in a water bath next time. I have a vacume pump which i use for filtering but no idea how to use it for decreasing the boiling temp and for evapping the solution..

another point for the rxn, it had a very strange smell, nothing like to ususal sweet smell which i am used to from the rp and hypo synths..the smell was really foul.and i wasnt sure what and why this happened.
I havent had the time to do the workup,  i usually  do 5-6 rxns then do all the workups at the same time, of course in different containers though.
also, when i go for cleaning the post rxn fluid with toulene, i get a lot of yellow, even after washing 2,3 and sometimes4 times. and at the bottom of the rxn fluid there is a buildup of red liquid, any idea why this could be?(i figured to much iodine being used)
most of swims hive education was tought to him by Shorty and Geez and for hypo, most of my knowledge is from Shorty, if not for these 2 bees i woulds still be the dumb chemically uneducated bee i wqs 7 months ago.

you are correct my chemical sources are over the moon.
the reason i dont go for an increase in size is due to the safety factor, and i dont think the balloon could handle it as with this ratio the balloon sometimes get huge

thanks again for the input

[biotechdude]

"...which i use for filtering but no idea how to use it for decreasing the boiling temp and for evapping the solution..."

You don't nave to do anything; water naturally boils at a lower temperature under vacuum.  At lower pressure, water boils at a lower temperature...and vice versa.  Get a 'water aspirator'; they're really cheap, and create a vacuum (so it boils away at lower temp and faster).  Just immerse a flask in an oil bath (so u dont have to worry about the water boiling crazily) and put a stopper in the neck and attach the tubing that flows into the water aspirator.  The neatest thing is that the hot steam etc that evaporates goes straight down the drain (so no smell!).  Look it up..., it'll b sweet.


"...another point for the rxn, it had a very strange smell, nothing like to ususal sweet smell which i am used to from the rp and hypo synths..the smell was really foul.and i wasnt sure what and why this happened..."

Foul?  mmm, are you sure you made your hypo cleanly?  I really don't know; perhaps a pill gaak of some sort....although if your pseudo method hasn't changed then the hypo looks to be the culprit.

"...when i go for cleaning the post rxn fluid with toulene, i get a lot of yellow, even after washing 2,3 and sometimes4 times. and at the bottom of the rxn fluid there is a buildup of red liquid, any idea why this could be?(i figured to much iodine being used)..."

This is what is called 'free iodine', either from excess being used, or not enough recycling taking place.  But its definately iodine; possibly with some phosphoric solids (is it gummy, like hard cold honey?)

Swix's advise would be to work up this reaction and have a look at the yields and product.  Because at the moment we are simply discussing the differences caused by a change in your hypo source.  Hopefully the big boys will come to the resuce by then...

P.S - Understandable re balloons - maybe its time to get some bigger equipment?

[bdbro]

will be back with some definate results in a while
i will get the water aspirator as per your advise

[bdbro]

after doing the work up all seems ok, and the yield was not bad either approx 80%. I will test and give a feedback on the potency tommorrow as i want to sleep tonight!
could you give me an idea where i would find a water aspirator. i am in a third world country.
thanks again for your assistance

[SHORTY]

Actually, the proper way to evap the water after filtering off the excess sodium hypophosphite, is to do so under a vaccuum in a oxygen free environment.  However, even with boiling stones and constant agitation the bumping is extremely difficult to control.  I gave up on evapping under vaccuum a long time ago cause its more trouble than its worth.  The only possible way i found is to use a capillary tube to bubble nitrogen into the bottom of the boiling flask to force bubbling.

The problem with stirring in an open container while heating to near boiling point is not only dangerous but as you stir you are exposing more of the hypo to oxygen which will oxidize it to hypophosphoric acid.

The best, easiest and safest way in my opinion is to heat the solution to 90-100C for a couple hours.  I now set mine up on a timer switch which i set and forget.  Don't leave it unattended until you know how long it takes.  If you leave it too long it will ignite and the smoke from this type of fire is unbeleivably thick and can fill a room in seconds.  The fire is also extremly hard to put out.  I threw a wet bath towel over the beaker and carried it outside, removed the towel and whoosh it reignited so i sprayed with hose and it went out.  Seconds after i stopped spraying it again re-ignited.  I ended up filling the beaker with water until it was overflowing before it would stay out.

[MnkyBoy78]

[Hematite]

Once your hypophosphite salt is mixed with hcl and filtered through lab grade filter paper(not just coffee filters)to a clear solution it can be used as is. While the concentration is unknown to me, it is quite funtional for the reduction.
Those who doubt this are advised to use their intelligence and try it before beginning any counter argument.

[SHORTY]

Are you getting any salts precipitating out into the rxn?  My attempts at this all failed and after doing some reading and experimenting i came to this conclusion.

After filtering out the salts the resulting solution is nearly super saturated with the hypophosphite salt.  However, the solution will react with iodine and will make HI.  However, since the solution is nearly super saturated then it can't hold much of the HI.  Then when the pseudo is added it will try to squeeze in there with the hypo salts and HI which will then cause some salts to precipitate out into the refluxing solution.

Don't get me wrong i would love to skip the evaporating step but my previous attempts left me with shitty meth.  Im willing to try it again if it really will work. 

Any ideas on why it wouldn't work for me?

[Hematite]

It is highly probable that your methods and observations are technically less forgiving than mine. While I would not describe the filtered soln as saturated by any means with salts, one could keep coaxing small amounts from solution and remove with filtering for days after it was made if they chose to I think.
The thing is though that unless your hypophosphorus acid is a crystaline solid, then there is ample water in the mix to accommodate solvation of all as is needed. I only mix the hcl and hypophosphite salt for 5 minutes and filter it straight away, perhaps this makes a difference to the production and precipitation of salt? If any is evident as the reflux proceeds a little H20 would do the trick, but that is if it's presence is considered a hinderence to proceedings.......what are your thoughts on that?
The test of this and what will see you proceed confidently from that point on is to witness the ability of the filtered acid to react as is with I2. It does this in a nice gentle manner in comparison to it's concentrated namesake, and the feedstock can be stireed into solution comfortably with a little heat if you like free of the fear of hypomadnessflamefun. Then without the need to chill below room temp (my choice), the entire portion of I2 (within reason of course ) can be added in one go and is contained and within acceptable parrameters of volatility for me, with a condensor and a stopper at top. Sometimes a little pressure is let go by lifting the stopper a little but for the most part in rxns inside an ounce it is not a problem.
I use a flat bottomed flask without stirring at all and extract and process a physical sample as indicator of rxn completion, the times vary and I'd be guessing if I gave any cause I am a shithouse record keeper and have never been one to calculate yeilds because I really dont care, but I know I cant match the claims of clever bees and their high returns round these parts, that's fer sure. You can do the technical bits Shorty, you know about my illness where facts and figures make me dizzy and sick, I've had to avoid them all through life sadly

[SHORTY]

Actually, i don't do it to concentrate it.  What ratios of hypophosphite to hcl do you use?  I use 105ml of 37%hcl and 125g of sodium hypophosphite monohydrate.  I then filter the acid and end up with about 130ml of solution which i then gently heat until about 50ml has evapped off.  That leaves me with about 80ml of solution which is completely full of salt.  I filter this out and then add about 50ml of dh20.  So i then hypo that is no more than 50% concentration.

However, i know you wouldn't say it works if it didn't and having just read a post in another thread then i can another possiblilty.  Rhodium mentioned that hypo should bee strong enough to reduce the pseudo and although i am far from being a chemist or understanding chemical equations, if that is true then it would explain why hypo is so much faster than rp and phosphourus acid synths because they rely on the HI to do all the reducing whereas hypo could be teaming up with the HI to do it.

Since your not heating yours and you don't leave it exposed to air for very long then your hypo is most likely not as oxidized as mine is and therefore it might bee doing a large part of the reducing.

Nevertheless, i will definelty try it your way.  What about those ratios?

[Hematite]

I use 1ml to 1gm and mix equal amounts that are relative to the weight of the feedstock as indicated in this example;
to reduce 30gms feedstock:> 40gm sodium hypophosphite is mixed with 40ml hcl and filtered. Finely ground feedstock is added in portions and stirred to assist solvation.
The solution is transferred to a clean flat bottomed flask on a room temp hotplate with a condensor ready and running with a ground glass stopper loosly fitted at the top.
25gm of I2, again ground finely is added in one portion, and the condensor fitted. Without any heating, shortly therafter the reaction will begin, and during the few minutes it is most volatile I lift the stopper to determine pressure (reassurance for the hypo frightened child within more than anything else)at worst some larger rxns have sent a puff or two of smoke toward the exhauset fan, but that's it.
On my heating control dial, movement of only one increment of the ten  it has is enough to sustain a moderate reflux that is unchanged from beginning to end apart from gradual colour changes that result in the well known pale yellow of the post rxn mix.Mine have remained on the darker side and
I beleive the I2 is still in excess at these ratios but as yet this is unproven.
Thinking over reactions past and your comments Shorty, I do recall some solids being present sometimes and more visible when I used a rb flask, so I geuss some salts drop out along the way with heat and activity, but I can't say if this is of any consequence since I don't concern myself with measurement of yields. I have tried additional H2O dropwise but again havent a guage to determine if this helped or not, sorry I'm a slacker I know but this comes from many years ago when I saw more failure than return and no hive was around to help.....I saw yield calculation as a very depressing thing to burdon myself with and it's stuck.

[SHORTY]

How long are you refluxing it?

[Hematite]

I have to say.....I dont know! (typical or what!) Somewhere around 6 to 8 hours for an ounce sized rxn is typical, but some have taken 12 hours...I no longer question it, when a test indicates that it's done I turn it off, simple as that.

Anyway for no reason at all.....here's some crystal being observed using the infrared spotlight function of my digi cam corder in the dark, resolution suffered in the rapid transfer, but you get the idea, it's truly umm......well.....mostly greenish.