The Vespiary

The Hive => Stimulants => Topic started by: halfkast on August 28, 2003, 10:00:00 AM

Title: Extracting H3PO3 from phosphite foliar solutions
Post by: halfkast on August 28, 2003, 10:00:00 AM

Disclaimer:
!!!!!!!Educational and informational purposes only!!!!!!!!!!!!!!!

I won't bee held leagally responsible for this cause i don't wanna, but i wanna give it beecause i just wanna. Check your localz laws, if its illegal where you are then its the authors opinion that you should move houses before saving.
Its for educational purposes and i include warnings throughout loud and clear about the dangers.

Objective/Aim:

To isolate H3PO3(s) from an aqeous solution of it's phosphite salt(s), mono/di-potassium phosphonate.


Important numbers & Formulae


H3PO3     = 81.996 g/mol
K                = 39.098 g/mol
KCl            = 74.551 g/mol
H2O          = 18.015 g/mol
KOH         = 56.106 g/mol
HCl           = 36.461 g/mol
KH2PO3 (Mono-potassium phosphonate) = 120.086 g/mol
K2HPO3 (Di-potassium phosphonate) = 158.177 g/mol

This section is simply an analysis of the best and worst case scenarios as far as what the theoretical potential  yields actually are. You can read over this section if you wish or skip to the procedure further down...

HClmin is simply a theoretical quantity I made up to denote the amount of HCl that would be used up during the reaction and required by the procedure if the feedstock contained only the mono-K phosphonate form an unlikely event maybee... but nevertheless I think you'll find the information convenient when weighing your final yield as this quantity represents the upper potential theoretical yield for a given amount of the potion of phosphites.

The HClmax quantity has a more procedural significance...it represents the amount of HCl you'll actually measure out to guarantee a complete reaction whatever the proportion of mono/di-K forms in your foliar solution, specifically it simply assumes that it all contains only the Di-K form – The least phosphorous acid rich form, but this reaction requires more HCl.

Your actual yield will fall between them both, so from 40g, 100ml of 400g/L foliar potion you should get between 20-27g of H3PO3.
If you measure more than 27g, that's great, it just means that you are measuring a little H2O impurity most likely. If you weigh <20g your lab work needs work or your supplier does, because he is a con.

Analysis of HClmin and HClmax reactions and the theoretical outcomes


Quantity analysis of.: HClmin:
 
Formula
KH2PO3(40g, .33 mol) + HCl(12g, .33 mol) ---> KCl(24.83g, .33 mol) + H3PO3(27.3g, .33 mol)

Reactants
KH2PO3  =     40g, 100ml@400g/L
HCl     =     12.145g, 40.48ml@0.3g/ml

Resultants and theoretical quantities of
KCl     =     24.83g
H3PO3   =     27.31g


Quantity analysis of.: HClmax:
 
Formula / Quantities
K2HPO3(40g, 0.25mol) + 2 HCl(18.44g, 0.5mol) ---> 2 KCl(37.5g, 0.5mol) + H3PO3(20.7g, .25mol)

Reactants
K2HPO3  =     40g, 100ml
HCl     =     18.44g, 61.46ml@0.3g/ml

Resultants and theoretical quantities of.:
KCl     =     37.5g
H3PO3   =     20.73g

Materials & Chemicals

Equipment
Electric fry-pan sand/oil-bath or hotplate (no COILS)
Table salt* if you use a hotplate. No oil/sand required
Glass Pyrex boiling jug
Empty wine or champagne bottle
Glass Pyrex tray or suitable casserol dish
Squeezable squirting bottle
Plastic scraper or any plastic object with a flat sharp edge
Fan-forced oven
Kitchen plastic wrap
Pestle – no mortar is needed
Reasonably good ventilation


Chemicals
Methylated spirits a.k.a denatured alcohol (simple, vaguely accurate names for simple, rarely accurate people...Yeah pick on ther yanks when life is going badly for ya, thats fine!)
Foliar spray containing aqueous di-potassium phosphonate and mono-potassium phosphonate salt (phosphites)
300g/litre (8.22M) HCl or muriatic acid
Distilled water; but springwater is fine.



Abstract of procedure
1.Measure 100ml of 400g/litre potassium phosphite solution
2.Measure HClmax solution
3.Add diluted  HClmax solution to diluted potassium phosphonate solution; wait
4.Boil off H2O
5.Refrigerate resultant concentrate
6.Extract [and, decant off] 3-5 times using cold methylated spirits
7.Boil off alcohol and H2O
8.Repeat Steps 6-7
9.Transfer to a large shallow glass pyrex dish
10.Heat until relatively anhydrous using 70-90C temperatures
11.Cover and cool your H3PO3 using a freezer
12.Transfer to a permanently air-tight container to bee buried  8)


Example of procedure


///HUGE WARNING///: PH3 IS PRODUCED UPON DECOMPOSITION OF H3PO3 AT 180C, ENOUGH TO KILL YOU AND PROBABLY ALSO ANYONE WHO ATTENDS TO YOUR LIFELESS BODY.  :)


1.Carefully measure 100ml of a 400g/L potassium phosphonate foliar solution and transfer to a wine or champagne bottle that can accommodate both this solution, aswell as the HCl which will be added. Dilute this with 100-200ml of DH2O.
Leave nothing behind in your measuring instrument, not a trace, cover your tracks using warm water.

2.With good ventilation present, carefully measure 61.50ml of 8.22M(300g/L) HCl solution, carefully dilute this with 200ml of DH2O. Store this in a suitable bottle

3.Using a funnel, add this dilute HCl solution to the wine bottle containing your phosphite salts in 5-10 increments over the course of 1hr, swishing the wine bottle around in a circular motion as you do this to ensure a complete reaction. 
Continue this until all of your dilute HClmax solution has been added to the wine bottle...which now contains H3PO3(aq), KCl(aq) and any excess HCl that wasn't used in the reaction due to the presence of mono-phosphonate salt form.
Shake and settle this reaction mixture for 1-3hrs.

4.Transfer the contents of your wine bottle, a cloudy white H3PO3(aq), KCl(aq) [,and any excess HCl(aq) ] mixture, carefully to your glass pyrex jug.
Cover your tracks from the wine bottle using a generous amount of warm-hot water and add this to your pyrex jug aswell.

5.Pour a generous amount of table salt on your hot plate, (not on coil ones ;D ) to protect the jug against the direct heat. But any type of oilbased sandbath is suitable, even prefered.
Place the pyrex jug on your chosen heating medium and bring to a boil gently and maintain over the course of a few hours or until you begin to see salt (KCl) precipitate. This just indicates that your H3PO3(aq), KCl(aq) mixture has now reached a point where there isn't enough room for them both..and of course the H3PO3 wins that battle allday everyday being strongly hygroscopic and deliquescent-so the KCl(s) is precipitated.
Remove the jug from the heat and allow to cool – Use the refrigerator when you feel it is safe to do so. Make it cool-cold before the next step.
Note: This step has the biggest question mark over it...the more you boil off the better as far as removing the KCl in this step, but it might also reduce your H3PO3 yields. Late brainstorm! It probably won't decompose in the presence of water, but boil the shit out of it at your own risk.

6.Add methylated spirits to this cold solution in tiny increments-you will notice more KCl precipitating out, as the KCl has yet another substance to compete with which it isn't soluble in to any great extent. Continue adding the methylated spirits until no further KCl is being precipitated. Add some more methylated spirits, you can't overdo it.
Note: Keep in mind that this reaction produces a LOT of KCl, so removing it early on is highly preferable or it is likely to trap H3PO3.

7.Carefully pour off this now much purer (though it still contains some KCl(aq)) alcoholic aqueous solution of H3PO3 in to another large jug.
For good measure use your squirt bottle to wash down the inside of the jug. Get a pestel and grind the KCl(s) for the 2nd and 3rd pulls so that it releases any H3PO3 in to the methylated spirits.
Transfer it back in to your (WELL RINSED) boiling jug
Note: Either keep the KCl or throw it away or save it for a nano maybee later. But it probably doesn't contain much phosphorous acid.

8.Repeat Steps 6 and 7. But don't expect to see much if any KCl precipitate out while boiling, your more likely to see it when adding the methylated spirits.

9.Now boil down this aqeous alcoholic H3PO3 once more to a cloudy white (maybee a hint of yellow) concentrate.


10.Pour this carefully in to your pyrex evaporation dish. Place in the oven on the very top shelve, with your fan force on, and the DOOR SLIGHTLY OPEN THROUGHOUT THIS STEP(!!), use a 70-90C heat.
Note: I know it takes a long time but you have to wait. Check it regularly, shine a torch across the liquids surface and tilt it to see how it's going.
When the H3PO3's ready it will STILL BEE A LIQUID, BUT SLIGHTLY VISCUOUS AND SYRUPY, it's melting point is 70C so it'll bee obvious when the ethanol and H2O has gone.
Prepare a big section of plastic kitchen wrap with a sache of drying agent taped to one side. The drying agent isn't necessary, but it will absorb any steam coming off the hot H3PO3...if you don't use it you'll still have the wax.
11.Carefully take your evaporation dish of delicious smelling phosphorous acid out of the oven, and plastic wrap it carefully (no air leaks!).  Place in the freezer. Come back in 30min-1hr and as you can see you are the owner of Excellent-Whoa! PHOSPHOROUS ACID!

12.Use plastic to transfer the goodies...do it in the freezer, the freezer is dry and cold. Weigh the shit. You did good. It's not meth but you can pretend! This shit is reagent grade man, I'd bet my dick on it.

Discussion

The procedure produces a white-yellow pleasant-smelling waxy solid strongly suspected to be made up of predominantly the compund H3PO3 (phosphorous acid) in excellent yields.


Yield
90% yields are quite do-able, of course you'll never know but during testing mine were closer to the HClmin theoretical so I know I probably got close..

If you use the basic lab technique of “covering your tracks” with a solvent that dissolves your desired end product, and carries it from every surface it touches during the procedure to the end-point of the procedure – the freezer.

Don't have any spills. So, think about what your going to bee forced to pour out of. If you have a spill, the work you've put in to covering your tracks seems worthless.

Quality
i.e. H3PO4, Other impurities, Hydration.


There may well bee a small KCl impurity at the end, certain steps repeated will reduce this, with no expense to yield as for example with maybe boiling a concentrated aqeous solution of H3PO3 and KCl.
The use of cold OH really helps with the KCl impurity. Small pulls/extractions also helps because of reasons Rh explained recently in the Solvent Miscibility chart sticky thread in the Newbee forum (where I belong)

HCl impurity will bee near non-existant, the addition of the ethanol may even cause some formation of ethyl chloride with any excess HCl, and bee burnt off during the second boil. Either that, or it is fumed off at the final evaporation in the fan-forced; one of the final steps.
So in one sense, the more excess HCl there is the better, because it means that your solution wasn't entirely made up of the less phosphorous acid rich di-K phosphonate salt.


Worried about H3PO3 impurity? So was I, because at one point I had only seen it as a frozen solid, so to test it I heated the container to about 30C+ in front of the heater. There was only a very small amount of liquid, very insignificant, the vast bulk of it remained a firm solid. I do mean tiny amounts too, not ¼ of it swishing around, I'm talking minute amounts! -1% visually. This is shit that was from a traumatic test procedure I spent days carefully drying.

Keep it in a cold place, as cold as possible, I doubt it will oxidize much at all.

Novel quickies

Okay so the problems associated with this substance as you all probably know are natural oxidation of the substance in the presence of free oxygen(1), drying(2); and the problems this causes for measurment as a reagent(3). So these are what the novel ideas are mainly focused at attempting to solve.

1.Funnel molten h3po3 into PVC tubes or sticks or a large syringe.
2.Add a sache of activated carbon to your container to keep O2 levels down.

Other possible uses
1.Drying agent?
2.A new waterless A/B ingredient?


Conclusion

Using this procedure the waxy solid phosphorous acid (H3PO3(s) can be easily extracted and isolated from an aqeous solution of it's phosphite salt(s), mono/di-potassium phosphonate.
The yields are excellent, the quality although untested in a HI reaction to any extent whatsoever should be quite suitable for the said reaction.
I'd really like a simple way of testing purity, and/or isolating either the phosphoric or the phosphorus acid, but we don't always get what we want...in a reasonable timeframe.

If you need help converting any numbers or concentrations or anything just let me know and we can edit it in to the write-up for future reference. This includes internationalisation of anything.

Best of care,
halfkast

Title: Wow!
Post by: hellman on August 29, 2003, 06:25:00 PM

This is more like it,
Could you possibly pm me and tell us where we find this ambibenevolent foliar spray?,

Great post, fucking great,
Ok, monkeys get to work,

hellman ;)

Title: I've been patiently waiting...
Post by: Lucid_Dreamer on August 30, 2003, 01:25:00 PM

Thank goodness, I was beginning to think I was going to have to post a write-up on this, very nice BTW.

And hellman, if you aren't finding phosphite foliar sprays for disease and fungicide control and prevention then you aren't looking hard enough. They are being used all over the world. The only reason they aren't trademarked and copyrighted is because of some major law suits between two companies who are about to release them here in the U.S. They are however, being sold in some states currently. There are endless posts on the where, when, and how of the foliar phosphite sprays, how could you have missed these unless your search engine finger is broke?

Title: Kudos to you my friend.
Post by: BOS on August 31, 2003, 12:23:00 AM

Kudos to you my friend.
I was beginning to think no-one had the ballz to post a write-up on this magical spray.
I would have,but Ive never tried it-this must change,now I have got meself a recipe. :)

Nice write up cob.

All the best,
Ballzofsteel.

Title: Your all welcome of course
Post by: halfkast on September 03, 2003, 03:52:00 AM

I think it could bee better, it's childishly written but it's functional and pending reaction testing I think that the quality of the product is excellent.

I've been busy for a few days, that's why I haven't returned to hive responsibilities sooner

There's no need to feel anxious about the PH3, I say this because it is safer that you check it regularly and touch the glass, 180C hurts a lot more than 100, faster!
Rotate the glass evap dish if you feel the need too, either because you want to bee ultra safe about the temperature of every part of it or just because it helps distribute the remaining liquid better.

ALSO remember to use your squirt bottle around the inner sides of both your boiling jug as the solution level lowers to wash off any H3PO3, and also do the same with the oven bake evap dish; just so it remains in solution.


In the actual procedure remember to use cold alcohol, it's missing in the write-up procedure, but it is written in the abstract of.

hellman, thanks a lot. I'd love to but I can't, where are you from? I'm sure it's easy to find in google man come on.


BoS hehe well tell me how it goes okay. especially tell me how it goes in a reaction but all feedback is excellent.

Title: shit, what the fuk is this, repost if necessary
Post by: hellman on September 03, 2003, 05:51:00 PM

I just found this, on some chinese site,
i am sorry to post it here:

this was the site:

http://science.2ch.net/test/read.cgi/bake/1000375229/l50 (http://science.2ch.net/test/read.cgi/bake/1000375229/l50)

If this is indeed true, i would be proud, but i have to go,..

15 ml benzene, 15 ml acetone, 25 ml AcOH and 5 mmol(1,01 g) Mn(AcO)3
are boiled under N2 atmosphere until the color of the soln changes from dark brown Mn(AcO)3 to pink Mn(AcO)2 - approx.
1,5 h. The rxn mixtr is diluted w/40 ml ether, washed w/25 ml water and 2x25 ml 5% NaHCO3,
the org layer is dried and evap'd to yield 40% phenylacetone(134 mg)

FOAF

Title: Fester
Post by: abolt on September 03, 2003, 09:27:00 PM

Fester published that synth., years ago.

Title: It might work but that manganese salt is ...
Post by: raffike on September 04, 2003, 08:31:00 AM

It might work but that manganese salt is expensive to say at least.

Title: I can't wait
Post by: halfkast on September 04, 2003, 10:12:00 AM

for your 3 texturous shitstains to bee scraped up, but the unmistakable brown aftermarks will remain unfortunetly...

Title: flashing out impurities note
Post by: halfkast on September 09, 2003, 12:54:00 PM

1. If you are left with a froxen product that is too yellow for your liking, try this... Take the sealed container out of the freezer warm it in front of the heater.
Refreeze it, it should look slightly different, I don't know exactly why, maybe it's just ice.
Anyway now add room temp methylated spirits to the frozen H3PO3 and swish it around and let it settle until the methylated spirits is yellow...the H3PO3 should bee pure white now, and more flakey.
Discard the yellow Metho.
It works just like geezmeister would do an acetone flash, but you can use more metho here, the frozen H3PO3 doesn't dissolve as freely as you (and I) might think, as you can see (when you do it).

That leads on to another small issue.
I wasnt very specific with the temperatures..How much exactly to cool down to, and the temperature of the OH.
That's because it doesn't matter a great deal, I just want to make sure it turns out pure. The KCl really doesn't like dissolving with H3PO3, some water, and a dispropportionatly large amount of OH...whatever the temperature, as long as it is = or < room temp.

Its unfuck-UPable, the flashing note up there works really well if anything does happen to make it through.

Title: Requiem for a phosphonate...
Post by: mickyfinn on September 10, 2003, 12:06:00 AM

I attempted to get help with this a few months ago but to no avail...

Post 440905 (https://www.thevespiary.org/talk/index.php?topic=8364.msg44090500#msg44090500)

(mickyfinn: "phosphonate solution for H3P03 reflux", Stimulants)

A little birdie once told me in a PM that reagarding O-Ethyl Hydrogen Phosphonate:

Phosphorous acid is also called Phosphonic acid.
All salts of Phosphorous acid are called Phosphites and are commonly called Phosphonates. They are all one in the same.

O-Ethyl Hydrogen Phosphonate fungicide:
Mix about 100 grams of the phosphite in 100ml of HCl acid  and VERY SLOWLY heat it, you dont want to ever see it boil or bubble. Heat it as high as you can without boiling. After 1/4 of the solution has evaporated it should be ready for use.

Someone also told me this also works for Sodium and Potassium Phosphite but the ratios are slightly different ( 90 grams, 100 ml )

halfkast, does this make sense to you? I'm going to attempt to read your post again and fully understand it someday but the picture is slowly getting less fuzzy...

Three months ago I attempted to do this and then decided not to try it after combining the 30%HCL and the O-Ethyl Phosphonate powder in a mason jar. It now sits in the dark in the mason jar wrapped in a towel in a tuperware container. At this point, expert advice would be much appreciated as to the viability of this endeavor at this point in time and/or whether this should instead be disposed of properly post haste.

Title: The Na will work just as well, but you'll have
Post by: halfkast on September 10, 2003, 08:22:00 AM

The Na will work just as well, but you'll have an even higher theoretical yield.
But the Na phosphonate brobably won't bee as common, for plants at least, beecause plants don't use it much, so the manufacturers choose the K.


I can't comment on C6H18AlO9P3 (aluminium tris stuff) but I would keep the powder tucked away for the future, in hard times only.
Work with K salts, they're common in aqueous solutions and probably in solid form too, which is excellent...

Okay...what you want to do is mix 1 mole eqivilant of the aqueous solution of phosphites (di actually), with 2 moles of HCl to get a return of 1 mole of H3PO3.

Well, I prefer to call it a solution of phosphites, or if I want to bee specific I would detail that it is a solution of mono-potassium phosphonate and di-potassium phosphonate salts.
I wouldn't say that I have a solution of di-potassium phosphite and mono-potassium phosphite.

You have two choices, actually 3.
1. you can simply multiply divide the amounts that I've used, in ml, or
2. You can calculate the molar ratios; ignoring volumes.

3. Your can give me the relevent numbers (HCl conc. and foliar conc.) and Ill give you the ratios in ml.

I was considering writing a java script so readers could enter they're concentrations of foliar solution and HCl, but a) I thought it was better to get it out there and b) I didn't know if it was suitable for various reasons.

Title: Mn(III) catalyzed acetone/benzene coupling
Post by: Rhodium on September 15, 2003, 11:27:00 AM

Mn(III)-Catalyzed Coupling of Benzene and Acetone (https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.manganese.html)

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.manganese.html)

Title: Highly interesting but..
Post by: halfkast on September 15, 2003, 02:15:00 PM

Why is it here Rh?
Is this a secret post where the gremlins won't look is it?

Title: Oops, off topic.
Post by: Rhodium on September 15, 2003, 02:22:00 PM

I didn't notice at first that it was off topic, as it was discussed above in the three posts listed below. I simply wanted to clarify the procedure when I saw it being discussed.

Post 457094 (https://www.thevespiary.org/talk/index.php?topic=8316.msg45709400#msg45709400)

(hellman: "shit, what the fuk is this, repost if necessary", Stimulants)

Post 457113 (https://www.thevespiary.org/talk/index.php?topic=8316.msg45711300#msg45711300)

(abolt: "Fester", Stimulants)

Post 457173 (https://www.thevespiary.org/talk/index.php?topic=8316.msg45717300#msg45717300)

(raffike: "It might work but that manganese salt is ...", Stimulants)

Title: hmm Forgiven
Post by: halfkast on September 15, 2003, 02:36:00 PM

*screenshot*

That's okay Rhody

Title: This is great!!!!
Post by: awayman on September 15, 2003, 05:15:00 PM

Title: My 2 cents
Post by: abolt on September 16, 2003, 10:28:00 PM

Here are some thoughts I have had about your "fungicide spray" write-up. This should be quicker, higher yielding, and scale up easier

If you have glassware and an aspirator I would add the 30% Hcl (why do you dilute it?), then setup a distillation rig on a water bath and distill off most or all of the water.

Then I would pour in say ~100 ml of MeOH into the solid mass, reflux for 30 mins, and then filter out the left over KCl.

Distill off the Meoh, on a water bath and dry leftover H3PO3.

Why MeOH?............It has less water and unlike Metho (denatured alcohol), it forms no azeotrope with water and can be permanently recycled.

Title: abolt thanks! Wetness of the alcohol doesn't...
Post by: halfkast on September 17, 2003, 12:38:00 AM

awayman, since you put it that way, it's an honour! haha
are you Ozzy?
(PM us if ya want bee)

abolt thanks!

Wetness of the alcohol doesn't matter at all, neither do azeotopes. It might in yours though =)

Bad lab technique

The yield is quantitative for the procedure. I just don't like saying that.

I think DCM can bee used to extract KCl from aqueous solutions. I'm not sure about H3PO3. You?
Ill test it, but Ill have to create another sample and distill some DCM-time. I ONLY tested for the procedure and discarded.  :P


Diluting is probably unecessary, but it's easier to work with when it isn't fuming.

There's quite a few errors in there if you look over it, but it's my first write-up. It functions as stated.

Vacuum drying is highly desired. But the glassware setups looked complicated, but I've seen shorty mention that he vacuum-dried something recently.

Can you think of an easy ghetto vacuum dry?
Is this feasable: A fridge, a large drying tube or dessicator. I want it to bee with anybees household fridge in situ. Disconnect hose for process, reconnect==fridge as normal for anyones grandma. Basic enginuity. Can this bee accomplished?

Add this to the procedure:
During the final evaporation/H3PO3 crystalisation step, construct a means of suspending a piece of mesh loosely covered with large mesh activated carbon over the evaporation dish during this step.

a tightly framed piece of fine mesh for example.
Let there bee no sagging of the mesh in the solution.

Title: another 2 cents
Post by: abolt on September 17, 2003, 01:09:00 AM

Wetness of the alcohol doesn't matter at all

Of course it does, if you can minimise water then you have less chance of KCl piggybacking the H3PO3 in the alcohol pull.

Solubility of KCl = 35 grams/100 ml water
Solubility of H3PO3 = 30 grams/100 ml water

neither do azeotopes

Good Bees recycle their solvents and alcohols. Utilising MeOH is the simplest way to do this, plus it has the added bonus of less water.

I think DCM can bee used to extract KCl from aqueous solutions. I'm not sure about H3PO3. You?
Ill test it, but Ill have to create another sample and distill some DCM-time. I ONLY tested for the procedure and discarded.

I don't think DCM will work. Why would it select the KCl and not the H3PO3 as well? Like attracts like(usually), KCl and H3PO3 are both polar.

Diluting is probably unecessary, but it's easier to work with when it isn't fuming.

There are hardly any fumes with 30% HCl. Diluting it just makes your workup more tedious.

There's quite a few errors in there if you look over it, but it's my first write-up.

It's a good writeup, especially for this forum. It wasn't rated excellent for nothing. ;)

Vacuum drying is highly desired. But the glassware setups looked complicated, but I've seen shorty mention that he vacuum-dried something recently.

If you could do that write up, then you could do a vacuum distill/dry with your eyes shut.

Can you think of an easy ghetto vacuum dry?
Add this to the procedure:
During the final evaporation/H3PO3 crystalisation step, construct a means of suspending a piece of mesh loosely covered with large mesh activated carbon over the evaporation dish during this step.

a framed piece of fine mesh for example.

If this step is for the drying of your H3PO3 crystals then I will give you an easier and more efficient technique.

Place your wet crystal mass, on a dish, in an air tight container (tupperware) and place a glass jar, half filled, with Sulfuric acid (bee careful) next to it then seal the container for a week or so. The sulfuric acid will absorb all the moisture.

Title: Halfkast,
Post by: SHORTY on September 17, 2003, 01:05:00 PM

Any refrigerator compressor will work as a vacuum but it wouldn't bee practical to make one which could be switched back and forth from fridge to vacuum.  Usually the vacuum lines are soldiered to the compressor and evaporator so they have to bee cut which will release all the refrigerant. So to go back to use in the ref. you would have to recharge the system after reconnecting the lines.

However, if you have an old refrigerator or a/c unit it is really easy to use as a vacuum.  Basically you just cut the 2 lines and remove any wiring which goes to the cabinet for lights or whatever and then put a an on/off switch on it.  You should also put some type of drying device in line with the intake cause if you don't it won't last very long.  I found that out the hardway when mine locked up. The whole thing is welded together so i cut it open with a metal cutting disk just to see what it looked like inside.  the piston on mine had become rusted causing it to stick.  I was gonna clean it and weld it back together but havent had time to yet.

Title: Thanks Abolt!
Post by: Scottydog on September 17, 2003, 02:23:00 PM

"If this step is for the drying of your H3PO3 crystals then I will give you an easier and more efficient technique.

Place your wet crystal mass, on a dish, in an air tight container (tupperware) and place a glass jar, half filled, with Sulfuric acid (bee careful) next to it then seal the container for a week or so. The sulfuric acid will absorb all the moisture."

*******

Swim will try this!

He had a jar of LG 97% H3PO3 that after having opened the jar only twice resulted in rxn failure. He was wondering why the rxn failed when the I2 and E reacted perfectly the following day with RP.

He assumed that the acid had oxidized to H3PO4.

He was sadly mistaken.

This salt is extremely hygroscopic and absorbs water from the air yesterday.

The water that is absorbed wreaks havoc when it comes to later additions prior to the rxn so water proportions must bee scaled down.

The jar is 7 mos old and figured it may now bee useless.

He tried only adding "half" the amount of water to the I2/ pseudo FB and H3PO3 as recommended in Rhodiums writeup and it fired off like a charm. Yep, even 7 mos later!

I believe Johndee addressed theoretical shelflife of the H3PO3 somewhere in the past (concerning oxidation)

I assume adding twice the amount of H3PO3 would also work?

Swim is beginning to think that a majority of failures can bee attributed to adding too much water!

Hope this helps others...

Great writeup halfkast. Sounds easy and straight forward.

I'm sure local nurseries would have steady access to this foliar fungicide.

Title: Your right. See, the procedure is really a...
Post by: halfkast on September 17, 2003, 09:19:00 PM

Your right. See, the procedure is really a failsafe softly softly approach, which costs mainly time, but it is fail-safe.
But I agree, all the diluting isn't really necessary and leaving it out would bee optimal.

So in step 1: Don't dilute your 100ml of 400g/L foliar solution.

As for the Hcl  it should bee diluted to a concentration where the individual bee is comfortable working with, with cold water. 50-100ml is fine.

Yeah but the alcohol moves the equilibrium drammatically in the H3PO3's favour
Also I doubt whether those numbers hold true in most cases.
i.e. If you have 100ml of pure water, add 35g of Kcl and 30g of H3PO3. The Kcl will precipitate I think.

Precisely, DCM is non-polar and can extract Kcl from aqueous solutions, see? It's just a matter of whether it also extracts H3PO3, it can bee tested because I'm interested but you'll have to wait!

In any case these types of solutions, extra steps and changes are for a different write-up. That's why it's called the simple extraction of H3PO3 from foliar solutions.

abolt: H3PO3's incompatible with strong oxidizers, so sulfuric is a horrid choice

The charcoal step is for removing oxygen from the atmosphere, not for drying.  ;D  Although that could bee a problem, the carbon getting saturated with OH/H2O vapour.

I thought about the charcoal, I think it would bee an excellent addition to remove O2. But not only for covering the evaporation dish, also add a tray of it on a lower level in the lab oven while pre-heating...as the air in a fan-forced oven is probably mostly circulated for efficiency.
Maybee even better(!) would bee an oven safe carbon filter hanging by some means (wire) at the back of the oven in front of the fan. Or ALL of these additions.

Covering the evaporation tray probably has the most questions hanging over it, doesn't it?
I think if you put a tray of AC on the bottom shelf, and a home-made (any ideas?) carbon filter hung in front of the fan by a wire to each of the side-rails, then placing one over the evaporation dish can bee omitted.



These are the types of changes that can bee made while maintaining simplicity:
1.Changes to dilutions/concentrations of Hcl and the foliar solution.
2.Changes to the rate at which the Hcl is added. i.e you can add it in one addition if you want to
3.Pre-heating the evaporation dish.
4.Any other little shit that you are prepared to change in exchange for no garantees by me that it will work, because I havent tested it.
5.Changes to the heat of both the OH or the temperature of the Kcl/H3PO3 before pulling.
6.Evaporating more water off before the H3PO3 pulls (and OH addition to precipitate out Kcl)
7.Activated carbon relating to the oven already discussed.


Good Bees recycle their solvents and alcohols. Utilising MeOH is the simplest way to do this, plus it has the added bonus of less water.

Very true, good idea. But many bees would rather bee caught with methylated spirits.

Shorty that's just the sort of hands on know-how we needed thanks! Okay so fridges aren't really feasable.
So whats the most basic setup and conditions for this type of vacuum dry do you think?

Hey abolt next time you use that drying technique, add phosphorous pentoxide to the sulfuric. I think it might work even better.  :)

Scottydog, thank you  :)
don't test the sulfuric acid thing! Itll fuck it up hardcore.

Hey thats interesting scotty! So you think it's mainly water causing the problems?
How long and how big were those cooks man?
So you got no visual reaction or no conversion going by bioessay?

For drying your stuff...Pre-heat your oven and evap tray, put your soggy shit on there...heat it 70-90 for 10-15min take it out of the oven cover it with  plastic-wrap with absorbant paper taped to the inner side to absorb moisture and steam. place in the freezer...itll bee dry.

Oh yeah this is what I found.
If you don't use the absorbant paper with a drying agent taped to the plastic-wrap, you'll still get the nice wax, but it'll have some crystaline water upon freezing scattered over its surface.

If you do use the paper/drying agent patch, itll have a smooth surface upon freezing, no crystaline water from frozen steam.

Keep it in a dry place, avoid humidity. freezer is perfect.

Johndee was way too high, too.

Title: Storage Suggestion
Post by: SFOtter on September 18, 2003, 04:54:00 AM

I was just ordered over to this post by HalfKast to help me overcome the horrors of MBRP.

I can't offer much in the way of chemisty, but there's a product available at any good snotty wine merchant that might help prevent oxidation.  They sell small cans of inert gasses (I'm guessing it's nitrogen, but haven't for ingredient's yet).  Says it will prevent wine from oxidizing for up to a year with zero change in flavor.

BTW, thanks HalfKast.  I'm going to finish my first dream as planned out of shear bloodymindedness and then try your way.  That way I'll appreciate it even more.

Title: Another Storage Solution
Post by: awayman on September 18, 2003, 06:01:00 AM

SWIM recently found a device that is used for pressurizing fuel burning laterns. It works with a ordinary co2 cartriage. Instead of using the little pump device that is standard on the latern, you replace it with this thing. Rigging up an adapter for your storage container is easily done by a visit to the hw store, screw it on, insert co2 cartriage, and it's pressurized. Of course larger containers might not work with this device but for a gallon and down it does fine. Maintaining a good seal is crucial so use teflon tape on all connections.

Title: AAAAARRRRGGGHHH!
Post by: abolt on September 18, 2003, 08:36:00 PM

abolt: H3PO3's incompatible with strong oxidizers, so sulfuric is a horrid choice

Hey abolt next time you use that drying technique, add phosphorous pentoxide to the sulfuric. I think it might work even better.


YOU DON'T MIX THEM TOGETHER!

hk, you asked the following question:

Can you think of an easy ghetto vacuum dry?

and I replied:

"Place your wet crystal mass, on a dish, in an air tight container (tupperware) and place a glass jar, half filled, with Sulfuric acid (bee careful) next to it then seal the container for a week or so. The sulfuric acid will absorb all the moisture."

you could place the small glass jar of H2SO4 in another small plastic container, then place it in the tupperware container, as a safety device for spillage.

Precisely, DCM is non-polar and can extract Kcl from aqueous solutions, see? It's just a matter of whether it also extracts H3PO3, it can bee tested because I'm interested but you'll have to wait!

It won't work, that KCl is gonna like water/alcohol a hell of a lot more than it likes DCM...........but try it anyway.

Title: fumes!
Post by: halfkast on September 19, 2003, 06:00:00 AM

abolt there will bee fumes from the sulfuric.
Besides, I'm not even sure it will work to dehydrate the H3PO3. It will halt the hydration of it.

The bottomline is, it's not a good way of drying it. If it was, I'd like the idea; but it ain't.

Let me just check the DCM extracting from saline, I could bee wrong I seemed to have not saved what I was reading. You could bee right.



FOtter: If it is an inert, it's an excellent otc way for inert atmospheres! In the HI reductions too! Thanks  8)

>>I'm going to finish my first dream as planned out of shear bloodymindedness and then try your way.  That way I'll appreciate it even more.

Unwise, by the time you finish plan A, plan B could no longer bee an option.

Title: Concentration
Post by: bigdumbnut on October 09, 2003, 01:40:00 AM

Thanks for this very usefull and detailed info. I've UTFSE with no success though in one last detail. Your proceedure is for 400g/l concentration. SWIB has some foliar fertilizer  0-22-18 derived from phosphorus acid and potassium hydroxide. 100ml weights 127.5 g on a triple beam.Is this the same concentration? If not can you direct me in the right direction? Many thanks

Title: I can't work out very much with those numbers,
Post by: halfkast on October 09, 2003, 01:26:00 PM

I can't work out very much with those numbers, sorry mate. Argox or someone else might bee able to. I don't even know what phosphite densities are, they aren't in the merck.

I find it hard to believe that they didn't put on the label a g/L make-up of the solution. They say nothing at all on the label?

crystalise 100ml of it and weigh it.

Of course you could use the amounts I prescribe, I doubt it is higher than 400g/L. The excess HCl won't do any damage at all.  :)

heh crystalise and weigh it though because I want to know what youv'e got too, plus its more fun, isnt it.  ;D

Title: And the concentration is
Post by: bigdumbnut on October 12, 2003, 12:20:00 AM

100 ml of the foliar solution (forget the name but it was something like Fido-fox)was subjected to the concentration of HCl you used for 400g/l concentration. No additional water was added though.It was heated til slightly cloudy or KCl precipitating, cooled, refrigerated, and then subjected to Freezer stored Denatured OH til no more precipitation. This was repeated all day until no more salt reared it's ugly little head and then popped in the oven at under 200f with the door cracked open and a fan blowing in.The last part was the hardest for this old knuckle head. When is it time to throw it in the freezer with the "sticks everywhere you don't want it to wrap"? 
Well, I came up with 24 grams of h3po3 that surely has some water in it. Also I've saved all the salt in case I need some entertainment some night, I'll grind and wash for a little more.
  Don't know if it'll work but SWIBDN might try using it with less water than suggested to sidestep the overwatered thing. He thinks he can always add as things go on

Title: haha OK thats wonderful, it wasn't a total...
Post by: halfkast on October 12, 2003, 01:43:00 AM

haha
OK thats wonderful, it wasn't a total failure.  ;D

24gm is solid for a first try mate, you must have tried really hard, slick job!  8)

I've made the same mistake on the final evaporation, heh I was expecting to see a solid in the oven (duh me)

OKAY, when it's ready it's slightly viscuous. Not very viscuous but more visuous than alcohol or water.

I think the easiest way to judge its readyness for freezing is by taking a mental note of how it is when there is clearly and obviously some more evaporating to do.

Probably ideally it's best to remove your tray and cover it at the first moment of viscosity man!

But, although it might seem ideal at first thought to have a totally anhydrous wax. For weighting purposes.
With the flawed drying process, that is with some presence of O2 causing oxidisation.

The time that you stopped it could bee right on the mark-I'd take it.

Especially if swibdd one of these eye-balling type cooks, if your confident you can make a concentration of solution that will bee effective then do it.

Title: OK, the idea I did have in mind was to distill
Post by: halfkast on November 02, 2003, 10:07:00 PM

OK, the idea I did have in mind was to distill the water out rather than do it in the open air, but I'm not even certain the Net result will bee the solution and H3PO3 beeing exposed to less oxygen. Plus the time will bee much longer, especially if it isn't transferred to progressively smaller boiling flaskes.

How about a thin layer of cooking oil on top of the aqueous/oh during boiling?

This has been tested- this relates to a certain way to remove KCl in it's entirety...Use HCl to salt it out, perform this in whichever way you like. KCl is practically insoluble in concentrated HCl.
The HCl removes itself.

Maybee even gas the foliar solution from the outset, but that hasn't been tested. Would the concentrated HCl ever salt out the H3PO3?
I've got a strong feeling it wouldn't, but that it might cause more fuming of the HCl, and that if it is filtered in this state it would bee of excellent purity as far as KCl goes. hmm?


Separation and purification of anhydrous mixture of H3PO3 and H3PO4. We simply need to exploit the 30C difference in melting points, H3PO4 m.p at 42.35C, although if it has formed the hemihydrate due to prolonged cooling this portion's m.p will bee 29.32C..this is convenient as both temperatures are well below H3PO3's at 73C.

What needs to bee done, to do this easily, is to have a colomn of the mixture at one side of a sealed square evaporation dish.
To remove this from the freezer and to set this dish up on an angle (?, slight?) on top of a heating pad (?, iron? VCR maybe?) , and to heat it slowly, and evenly...so the H3PO4/phosphIC 'cid makes it's way down the slope.

Title: Proposed easy H3PO4 phosphoric removal
Post by: biotechdude on November 03, 2003, 10:23:00 PM

quote<<
Separation and purification of anhydrous mixture of H3PO3 and H3PO4. We simply need to exploit the 30C difference in melting points, H3PO4 m.p at 42.35C, although if it has formed the hemihydrate due to prolonged cooling this portion's m.p will bee 29.32C..this is convenient as both temperatures are well below H3PO3's at 73C.
>>quote

Just a brain storm re removing SOME of the H3PO4 / phosphorIC'd unwanteds.  Could you turn on the hot and cold taps to get it to the right position that flows out water off as close to 45`C. 

Then get the raw frozen foliar extract in a little jar and raise it up on a little stand (for even heat transfer) inside a small saucepan.  Than let the 45`C tap water flow into and overflow out of the saucepan; slowly heating the contents of the (O2 and H20 sealed) extract jar to as close to 45`C as possible. 

Then could you just decant or suck out the melted liquid (of H3PO4 and phosphorICs); leaving the still solidified H3PO3 inside (as it wont melt until 73`C).  I know this wont remove all of the unwanteds, and you may loose a little H3PO3 (possibly that tightly bound to H20); but the nett effect will bee far purer H3PO3 solids that can be refrozen and used.

Quick, easy....and pointless?? Please advise

Title: the conciencious and astute biotechdude.
Post by: halfkast on November 04, 2003, 01:02:00 AM

the conciencious and astute biotechdude.

Of course, anything you do to apply heat and use gravity to separate will cause some sort of separation one would have to assume.

you know I love that idea of heating. How about we take your saucepanx and place a smaller saucepan upsidedown inside and use that as the heating surface?

Or maybee wrap it in foil? and submerge it in a saucepan containing water of a measured temperature?


this problem isnt going to last long i dont think.  8)

Title: Free water evaporation at room temp.
Post by: halfkast on November 06, 2003, 05:19:00 PM

It's now the authors preference that the free-water is evaporated at room temperature using a regular fan and or an air-conditioner.

It's unknown what rate the H3PO3 oxidates but it will happen much slower at room temperature. It was tested because of reading this that day when you and I were discussing ratios of HI:E when no recylcing agent was used. This is you I'm referring to biotechdude

'As a rule of thumb, reaction rate doubles when T is raised by 10-15°C. Therefore a temperature difference of 100°C means an acceleration of the reaction rate by a factor of 27 - 210, or 130 - 1000 times faster.' Os


Using a fan and and air conditioner or air dehydration unit doesn't take much longer at all.

The end product is pure white, which was surprising. Beecause I put the yellow down to Cl.

The hygroscopic water still hasnt been dealt with but I'm pretty sure the fan + A/C will do it, but the process had to bee shut down and refrigerated for time managment reasons.


I feel crap but I thought it was only right to post the findings so you could work with them.

Title: I might bee completely wrong here but..
Post by: SHORTY on November 06, 2003, 07:43:00 PM

It's now the authors preference that the free-water is evaporated at room temperature using a regular fan and or an air-conditioner.

I havent used this procedure so i may bee way off base here but have you tried using silica gel to remove the water in a sealed container.  It would take longer but in a sealed container the oxidation would bee slowed significantly.

I too have wondered how much oxidation takes place when i make hypo from sodium hypophosphite because i have to evap off alot of water in order to remove the salts from the solution.  I used to bee really worried about it and for a while i evapped under vaccuum until i broke the pump.  Afterwards i just heated it so that it steamed and let it evap slowly without boiling so that only the surface of the solution would bee exposed to air. 

I then figured that if i was oxidizing too much to phosphoric acid then it would not react when iodine was added.  However, I guess this would bee different for phosphorous acid since it has to bee heated before it will react.

Title: And coming up fast in the outside lane
Post by: bigdumbnut on November 07, 2003, 02:09:00 AM

Swib tried something based on several ideas read here. He extracted from 200ml Foliar with no added water. He ended up with 69.2 G which he sucted up in a 100ml syringe. This sat in the freezer for a couple of days of cogitation. He then taped a small water bomb balloon over the discharge end and a large balloon over the plunger to the body of the syringe. The syringe could now be pushed and pulled while sealed from the environment. He then ran hot water into a 16 oz measuring cup for a while, then read 138F on the Tmometer. He put the syringe business end down into the cup with the water running lightly for 15 min. Temp remained constant. The innards of the syringe got semi-liquid. He pulled back the plunger, tapped on the side a little , then pushed in fairly hard. This syringe had no needle but a small opening thru which, now, came some liquid in to the little balloon. This was repeated until no liquid was visible. Then back in the water a couple of min and repeated as above. In the end he had 33.8 G of slightly off white dry flakey/granular acid in the syringe and 35.4 G of smegma in the little balloon. I'm not sure how he'll prove it's purity yet, but I'll repost as soon as he does. Maybe how much I2 a given amount will turn into the correct G/ml acid?

Title: hehe what a liar bigdumbnut, thats pretty...
Post by: halfkast on November 07, 2003, 03:36:00 AM

hehe what a liar bigdumbnut, thats pretty funny, it was crystalline was it?

do ya promise? or did you just add that on for fun?

anyway that part is unimportant.

Excellent experiment. Well done man.

Was it a pretty dry mixture u reckon?

for your next experiment, the balloon covering the plunger isn't required, but it was a great idea. Bee confident that not includeding it will have no detrimental effect as far as water or O2.

I was going to comment on density, hygroscopies of the both and how they would behave in the syringe, but it's not important.


Keep the nozzle on the syringe or whatever the correct name is facing towards the floor.

So was the stuff you expelled from the syringe more yellow or was it just thinner do you think?

Title: Big Flaky, Granular, 50% reagent grade Crystals
Post by: bigdumbnut on November 07, 2003, 04:21:00 AM

Like compacted table salt actually :):). It appears quite dry but is still in the syringe figuring it will keep better there than elsewhere.
The yellowish color left with the liquid expelled and the next day had a greenish tint and had become solid (the expelled liquid that is). The ballon at the discharge contained the splatter that would exist otherwise but when the plunger was pulled back first the little ballon would suck flat and then some leakage would occur at the plunger. Without the big balloon there would have at least been moisture there to suck in. At least I didn't have to wipe water out first.

Title: Question on Extraction of Foliar
Post by: dalewilj on November 13, 2003, 06:52:00 PM

Swims dream did not work. Swim purchased Foliar Fert. from Ogasims Labs :) 0-22-18 : ; from lable. Total N 0%, Aval. Phosphorous Acid (P2O5) 22%, Soluable Potash(K2O) 18%
Derived from Phosphours Acid and Potassium Hydroxide. Name of product is Phy**-**s Foliar Fertilizer. Swim read others dream on how to extract. Follow step by step.Only different was use of iso alc. instead of Meth. Alc. Did not get get any precipitation of KCL xtals. On first step with HCl and foliar. Swim evaporated first step and put in freezer. 0 degrees over night. Did notice two seperater layers bottom more viscous than HCLmax solution.Bottom layer had higher vapor pressure than top layer. Left in fridge over night. In morning dreamt that xtals had precipitated out of solution. Both solutions had not froze. Did iso mix of both solutions no KCl preciptation. Warmed up solutions xtal went back into solution. Now dream is in fridge. Any ideas of what went wrong. Wrong foliar or wrong alc.

Title: I'd bee fairly confident what you have there...
Post by: halfkast on November 13, 2003, 10:19:00 PM

I'd bee fairly confident what you have there has largely gone through this process largely undegraded. So you can still retreive it in good yields.

All that has happened is that the first evaporation you did failed to evaporate enough water to start putting pressure on that KCl to fuck off out of the water - to precipitate.

This is good on one hand, because we know the phosphorous acid has been nice and safe from oxygen because it's in a diluted solution.

1. evaporate off as much of that alcohol and water as you can, using a evaporating dish your comfortable with pouring liquid out of carefully.
(Keeping in mind that the more you evap the better for KCl removal)

2. mix a glass off 50ml of alcohol and 100ml of HCl and add it to the evaporation dish solution, which you've just partially evaporated in order to concentrate it.

3. Mix it gently but thoroughly. Leave it sit there for 10-20min.

4. Pour the solution in to another evaporation dish, leaving the KCl behind.

5. evaporate this final evaporation dish to relative drying using a fan and a/c.

Room temperature fan and air conditioner/de-humidifier is better than the fan forced oven and all that heat.

Title: Evaporation Method ?
Post by: dalewilj on November 14, 2003, 04:48:00 AM

Thank you for your response. Good to know that swim has partial dream. Question, It seems that getting rid of H20 as hypo is very hydroscopic. Would it be unresonalble to make izzy (goldberg) contraption i.e (buckner filter with some dehydrating materal (damp rid, KMNO4,etc) plus small negative air pressure to evaporate. Seeing as swim haas no dehumidifer and it's 20 degrees out side to run a/c.
   One other question. Swim left supernatant in freezer in ice maker with the ice. Now swim has abot 60 grams of a white slurry of xtals in flask. With about 150 ML of fluid. The temp of fluid is about 5 degrees F. Should swim dump the fluid and keep xtals or just dump in  dish and evaporate all xtals and solution.

Title: no worries
Post by: halfkast on November 14, 2003, 10:47:00 PM

The temp of fluid is about 5 degrees F. Should swim dump the fluid and keep xtals or just dump in  dish and evaporate all xtals and solution.

No keep it all, don't throw any liquid away throughout the entire procedure in fact, remembering that every solvent used in the procedure dissolves the desired end product.

much of the crystal formations your seeing are in all likelyhood KCl precipitating out because of the low temperatures, and generally the quantitative and qualitative properties of the constituents (solvent and solutes).

the liquid is the unfrozen methylated spirits.

Evaporate off as much of the liquid you can and then think about how your going to cause the H3PO3 to dissolve leaving the KCl behind. (eg. using alcohol that has been acidified with HCl)

I have no idea about this goldberg apparatus. I mean if you have faith in it use it, but just remember H3PO3 solutions can clog filters pretty quick.
Not potassium permanganate...


Really though, if you find it doesn't really work well for you, know that the a/c and fan work well, and I strongly suspect it's of much higher quality than the origional fan-forced oven variety.  :)

Title: Would there be a reason why 99% ipa wouldn't...
Post by: Un_Chambered on November 15, 2003, 11:36:00 PM

Would there be a reason why 99% ipa wouldn't work as the alchol in this procedure?
Swic is kinda strapped for cash and has lots of the above and none of anything else.My guess would bee yes and thats what swic'll go with barring a more definitive answer.
Thanks and peace,Chambered

Title: ipa is sweet don't worry about the acid either
Post by: halfkast on November 16, 2003, 01:22:00 AM

ipa is sweet
don't worry about the acid either if you don't have it.

Title: Thanks hk Curious as to what you mean when you
Post by: Un_Chambered on November 16, 2003, 01:35:00 AM

Thanks hk
Curious as to what you mean when you say its ok to leave out the acid?
would the procedure then yeild phosphite salts which can be used to reduce as well?
or more likely swic is terribly confused.just curious swic isn't leaving acid out.

Title: I meant Now I'm tellin you that HCl must bee...
Post by: halfkast on November 16, 2003, 02:10:00 AM

I meant

Now I'm tellin you that HCl must bee used in the procedure as is to convert the foliar shit to H3PO... NOTHING has changed here, right?

But I'm also telling you that HCl may bee used as a device to salt out KCl.

But if you don't have it alcohol will work great to salt out the KCl...

And ima also tellin ya that fan/a/c method of drying is a sack of gold nuggets of purity.

Title: As you wish massstaa!
Post by: Un_Chambered on November 16, 2003, 02:34:00 AM

As you wish massstaa!
swic is following your write-up to a t other than ipa as OH,no dillution of foliar solution or HCl(aq),and room temp. evap followed by tupperware dessicator w/NaOH.
Input on drying bee's?

Title: all thats cool. after using de-humidification...
Post by: halfkast on November 16, 2003, 03:48:00 AM

all thats cool.

after using de-humidification
and fan at rT to evaporate off "free moisture".

Throw it in the freezer and think about if its worth trying to dehydrate completely.

I mean, a fan and A/C will get most of the water out inflicting little damage to even the surface of the H3PO3.


No NaOH dessicant, it will effect your H3PO3 by reacting with it to form sodium phosphite salts.

warm it on a hotplate during the fan drying if you want to speed things up and cause more complete dehydration. Then straight to a cool dry place.

The freezer will make it nice and hard for transferring to a permanent container.

Title: tar
Post by: Un_Chambered on November 16, 2003, 10:58:00 PM

Hey all
swic has been messin around with this.
Three attempts have left him with what is obviuosly some phosphorous acid combined with a black viscious fluid that stubbornly refuses to be seperated.
The foliar solution he is using states:
Total nitrogen..........................10%
(urea nitrogen)
available phosphoric acid(P2O5).........10%
soluble potash(K2O)......................5%
sources:Urea,Phosphoric acid,Muriate of potash
Any ideas on what's going wrong here folks?
Swim would like to make this brand work as its available locally.He has tried IPA and MeOH washes with little result.
He has also tried seperation using temp but the liquid is just too thick to seperate.
Any other bee's run into this?

Title: There obviously isn't any H3PO3 in it.
Post by: Osmium on November 17, 2003, 01:36:00 AM

There obviously isn't any H3PO3 in it.

Title: its looking that way. to say the least.
Post by: halfkast on November 17, 2003, 03:21:00 AM

its looking that way. to say the least.

dude finish the procedure and collect the H3PO4. Its not a HI recylcer like H3PO3, but it can be used to create HI.

Title: Iso alk, Scaling up, viscosity & salting out KCl
Post by: spectralshift on January 09, 2004, 10:22:00 AM

When scaling up, greater effort and time should be spent on salting out the KCl it's been discovered.

Another important note is viscosity, when the viscosity of the solution of H3PO3, KCl, H2O and ALky is viscuous, KCl will actually precipitate, a) but much of it will not be able to be filtered out, and b) it won't sink to the bottom as a white layer.


Signs of an overly viscuous solution are a cloudy solution, and perhaps not even any sign at all of a bottom layer (KCl, always KCl, this isn't H3PO3 that has sunk).

The cure if your in this situation is more alcohol, and even a splash of HCl solution if it's on hand. This is followed by a good shake, and generous amount of time to settle at room temp.

As you add more alky to a cloudy one-layer solution (overly viscuous, KCl suspended in H3PO3 solution) you'll gradually see a formation of two layers, KCl on the bottom, and a liquid layer of you-no-what with a slight yellow tinge.

Another thing that works really nicely is sitting the wine bottle in a bath of hot water for a few minutes and then sitting it at room temp to settle...this acheives a formation of layers without addition of further alcohol.

When you've got two layers, this is the time when the solution can bee filtered without clogging.

When it's all cloudy, filtration is primarilly a No-go. two layers good, one layer bad - remember that.


After a filtration session, let it settle and you may see even more KCl precipitate out of the filtrate. So it's not a one-go-show! But don't worry, the H3PO3 is out of harms way so you can take as much time as you like.

If you are desperate for some H3PO3 for a RXN or to put on the garden, just pour a little of the motherload being worked on in to a small bottle and work on it separately OK?
Good.  ;)

You can make it ultra pure really quickly when working with small amounts too...A splash of alkly and a splash of HCl, a dip in a bath of hot water, then time to settle will crash out everything when working with small amounts.



For ghetto drying, I think it's best to use the fan and or an air-con to remove the majority of the free-water, harming the H3PO3 none.
Then use the fan forced for a few minutes..preheat it, because if it isn't pre-heated it will tend to absorb water on the way up to temperature.


OK, finally isopropyl alcohol, TRY it. The story is that during testing, iso was used in one instance and I've got the sneaking suspicion it worked really nicely to salt out KCl. Someone upthread said that he'd been told to use iso, so those people may have had better information there, but I could only be sure on the metho tests, and so this is what I included in the write-up.

I would say that greater molecule sizes would work better,
Ill try to get more information here on alcohol molecule diametres etc.

To some up:

viscosity=bad for filtration & KCl settling out. Cure: more alcohol, a dip in a hot water bath.

10x
halfkast

Title: HIGHLY interesting, possibly useful
Post by: spectralshift on January 23, 2004, 11:06:00 AM

A very small quantity of MgSO4 was used during the KCl precipitation phase, (that was experimental and the idea was to precipitate out a lot of KCl with very little MgSO4, that experiment was inconclusive and not what I came to tell you about.) at the end of the final drying stage a strong rotten egg gas smell, H2S was noted.

HCl was used in excess as a further KCl precipitation technique, (not advised anymore really, for THAT)

By this point I was just thinking that the addition of MgSO4 was a bad idea. The following day the prepared H3PO3 seemed a horrible dark honey colour, believed to be impurities. The smell was still strongly present aswell, and it tended to shit one to tears, and in fact it was returned to the oven in the hopes of driving off the H2S, any remaining HCl and hopefully clarify the colour.

This clarification just didn't occur, the solution became a very dark, much darker, almost black, which was disappointing.

So I checked out the merck entry for H2S in the hopes of shedding some light on how to remove it.

Properties:  Flammable, poisonous gas with characteristic odor of rotten eggs, perceptible in air at concns of 0.02-0.13 ppm, sweetish taste. Burns in air with pale blue flame. Ignition temp 260degrees. Explosive limits when mixed with air: lower limit 4.3% by vol, upper limit 46% by vol. mp minus85.49degrees ; bp minus60.33degrees : Giauque, Blue, J. Am. Chem. Soc. 58, 831 (1936) . Heavier than air; 1.5392 g/l (0degrees; 760 mm). d gas 1.19 (air = 1.00) . Vapor pressure 18.75 times 10 5 Pa. One gram H 2 S dissolves in 187 ml water at 10degrees, in 242 ml water at 20degrees, in 314 ml water at 30degrees; in 94.3 ml abs alcohol at 20degrees; in 48.5 ml ether at 20degrees. Sol in glycerol, gasoline, kerosene, carbon disulfide, crude oil. Water solns of H 2 S are not stable, absorbed oxygen causes the formation of elemental sulfur, and the solns become turbid rapidly. In a 50:50 v/v mixture of glycerol and water the precipitation of sulfur is retar ded considerably. pH of freshly prepd satd water soln 4.5. pKa 1 7.04; pKa 2 11.96. LC 50 in mice, rats ( ppm ): 634 , 712 (1 hr inhalation ) (Vernot) . LC 50 in rats ( ppm ): 444 (4 hr inhalation ) (Tansy) .

What I think is that H2S and H3PO3 stabilise eachother, especially when kept cool, and the H3PO3 stops too much elemental S from precipitating, and maintaining a good amount of H2S dissolved and fused with it. Similar to how glycerol does. That's what I suspect...but I KNOW that it contains H2S.

I KNOW that a small amount of MgSO4 is all that is required to produce this effect.

Someone else knows that, H2S is liberated during a reaction when H3PO3 is prepared like this.

This is so fucken cool, do a search by halfkast, stimulants forum, and in the post content type either rotten or eggs, where I ask geezmeister if he's ever noted that particular scent at the beginning of a phos acid synth.

I had to re-write this, proxy packed up. I was so pissed off, this one lacks the emotion.

*laughs loudly and strongly from the belly*

Title: redox dilema
Post by: spectralshift on January 25, 2004, 03:50:00 AM

After some thought this is what I suppose is happening

the MgSO4 is being reduced by the H3PO3, atleast when the concentration is high and with elevated temperatures to MgSO3 (sulfite).

The MgSO3 is also oxidised easily to the MgSO4, hindering the overall reaction and production of the end-product, H2S.

I'm not sure if the HCl (excess) plays any role to this point, but I'm semi-confident MgCl2 is formed, because flat leaflets have been seen after rapid cooling. but im still confident it's formed irregargless of whether these leaflets are it.

I wouldn't mind the idea of adding some easily oxidizable substancez to the H3PO3 solution throughout the procedure to try stabilise things (as I think H2S would), thing's like ascorbic acid solution perhaps.


unfortunetly, the H3PO3 being oxidised to H3PO4 by the MgSO4 is the problem, and I've got a feeling it takes quite a lot.
But I think it depends on if and when the excess HCl is able to take part.


Well I'm motivated, I opened a book last night. Heh it was meaningful. Sucker.