Sciencemadness Discussion Board

Tricky Ferrate

Rhodanide - 27-9-2017 at 09:14

Yesterday, I thought I'd have a hand at trying to isolate Barium Ferrate from a solution of Na2FeO4. I planned on making the Na salt by the addition of FeCl3 to a basic solution of Bleach at room temperature. I got a precipitate of Fe Hydroxide as expected, and proceeded to stir the mixture gently and let it warm up on the hotplate. I got some Chlorine gas bubbles as expected, but only a few. I left it to settle and came back the next morning to find a weakly pink solution with excess Iron Hydroxide on the bottom. I put this in a glass bottle, and left it to react for two more days. I came back two days later, and the pink color had intensified a bit, but the Hydroxide was annoying. I opened the bottle, and was met with a surprisingly large amount of a pressurized, colorless, odorless gas from the container. However, the pink color had disappeared as soon as I opened the bottle. I filtered the mix, and kept the clear liquid. What's a reliable way of making Ferrates? I don't have easy access to nitrates (Besides Ammonium, which won't work), so that can't work right now. All wet chemical processes that I've tried have failed. Regardless, wouldn't it be near impossible to obtain even slightly pure Barium Ferrate from a basic solution of K or Na Ferrate? Wouldn't the product be massively contaminated with Ba(OH)2?
I'm waiting on Iron powder in the post, and will try to source some Nitrate salts, though it's a tough search so far. Any help would be greatly appreciated.

Thanks,
T/Rhodanide

clearly_not_atara - 27-9-2017 at 13:11

A precipitate of KNO3 can be prepared by adding KCl to saturated aqueous NH4NO3 at 0 C. The solubility of KNO3 at 0 C is 13% w/w; of KCl is about 20% w/w, and of NH4NO3 is 116% w/w. If KCl is not available, potassium carbonate can be used, but the rxn mixture will release ammonia, so be prepared for the smell.

However for this purpose I think it is wise to keep in mind that ferrate is highly unstable in any aqueous solution. Long rxn times are probably not a good idea. Rather the barium should be added immediately. However, it appears to be practically impossible to prepare solutions of ferrate ion from barium ferrate, as the latter salt is very insoluble and decomposes whenever you try to dissolve it.

Fusion with potassium nitrate appears to be the best way to produce soluble ferrates in the solid state. I am not aware of any methods to successfully "dry" a ferrate solution without decomposing FeO4(2-).

[Edited on 27-9-2017 by clearly_not_atara]

Sir M - 28-9-2017 at 01:51

I agree, ferrate solutions are too unstable - you have to use it quickly after preparation. When I prepared it with iron/nitrate method, the slag from reaction was washed with water and the ferrate dissolved. But in ten minutes, Fe2O3 percipitated and all ferrate has decomposed.
Are you planning to use the barium ferrate, or do you just want to prepare it as experiment?
Also, I think, that BaFeO4 is even less soluble than the hydroxide, so it should not be too contaminated.

Rhodanide - 28-9-2017 at 06:53

Quote: Originally posted by Sir M  
I agree, ferrate solutions are too unstable - you have to use it quickly after preparation. When I prepared it with iron/nitrate method, the slag from reaction was washed with water and the ferrate dissolved. But in ten minutes, Fe2O3 percipitated and all ferrate has decomposed.
Are you planning to use the barium ferrate, or do you just want to prepare it as experiment?
Also, I think, that BaFeO4 is even less soluble than the hydroxide, so it should not be too contaminated.


I would like to do some tests with it, yes. As for the unstable aspect, I had that pink solution in the bottle for HOURS... DAYS even! No change until I opened the bottle... No pink after that. So strange.

ave369 - 28-9-2017 at 07:04

Leaving it to sit for a night, I think, was the reason why it decomposed. When you work with ferrates, you gotta get them solid ASAP. There's no simple way of making solid sodium ferrate from its solution, so you better stick to potassium ferrate.

If you want barium ferrate only, use the "ferrate volcano" slag reaction, dissolve the results in concentrated alkali, quicky (!) run the solution through a sintered glass filter and start adding Ba(NO3)2. You should get your barium ferrate pretty fast.

Rhodanide - 28-9-2017 at 07:10

Quote: Originally posted by ave369  
Leaving it to sit for a night, I think, was the reason why it decomposed. When you work with ferrates, you gotta get them solid ASAP. There's no simple way of making solid sodium ferrate from its solution, so you better stick to potassium ferrate.

If you want barium ferrate only, use the "ferrate volcano" slag reaction, dissolve the results in concentrated alkali, quicky (!) run the solution through a sintered glass filter and start adding Ba(NO3)2. You should get your barium ferrate pretty fast.



Don't have fritted glass :(
Too poor :(
Anything else?

ave369 - 28-9-2017 at 10:55

Quote: Originally posted by Tetra  

Don't have fritted glass :(
Too poor :(
Anything else?


Try a Buchner funnel with a polyethylene circle in which you poke, like, bajillions of little holes with a pin. Works as a poor man's substitute for fritted glass if the particles are coarse enough. Mineral wool also works, but this you must calcine before using to destroy any organic additives. Remember: absolutely no paper. Ferrate reacts with that.

By the way, I can give you a prep of potassium ferrate from the simplest stuff. You need:

* car battery acid;
* ammonium nitrate;
* iron nails;
* bleach;
* table salt;
* potassium hydroxide (sold in soap making shops);
* car starter fluid (ether + hydrocarbons);
* Everclear (ethanol).


First, you need to make strong potassium bleach. Make a concentrated solution of potassium hydroxide. In another flask, mix car battery acid and table salt, and start to drip bleach into it. You'll get a lot of chlorine, which you need to bubble through potassium hydroxide until it gets greenish. This is your super strong potassium bleach.

Afterwards, you need iron nitrate. First, let's make some nitric acid. It can be made in two steps:

* Boil down car battery acid until it fumes. You'll have 75% sulfuric acid.
* Add this sulfuric acid to ammonium nitrate and carefully distill. The liquid that comes over is very concentrated nitric acid. If it fumes, dilute it with water until it stops fuming.
* Add iron nails into a beaker with the nitric acid. Carefull, NOx will emerge, do it outside. The acid may overheat, boil, foam and spit. When the reaction stops, you'll have a concentrated solution of iron (III) nitrate.

Carefully add this solution to our super strong potassium bleach. Add concentrated potassium hydroxide. If everything was done right, you will see crystals of crude potassium ferrate forming. Filter them away.

This crude ferrate is not very stable, so you need to recrystallize it. Dissolve the crystals in a weak solution of KOH. When they are dissolved, filter the solution and pour it into a saturated solution of KOH. You'll see more potassium ferrate crystals forming. Filter them away, wash with ice-cold Everclear and dry quickly. To dry, use the car starter fluid: wash the filter with it. It will evaporate quickly and the resulting product will be dry.

For best results, you should carefully distill the car starter fluid beforehand. Remember, no fire: use hot water to heat the boiling flask. You'll get ether of reasonable purity. Use this to dry your ferrate.

[Edited on 28-9-2017 by ave369]

Rhodanide - 2-10-2017 at 04:47

Quote: Originally posted by ave369  
Quote: Originally posted by Tetra  

Don't have fritted glass :(
Too poor :(
Anything else?


Try a Buchner funnel with a polyethylene circle in which you poke, like, bajillions of little holes with a pin. Works as a poor man's substitute for fritted glass if the particles are coarse enough. Mineral wool also works, but this you must calcine before using to destroy any organic additives. Remember: absolutely no paper. Ferrate reacts with that.

By the way, I can give you a prep of potassium ferrate from the simplest stuff. You need:

* car battery acid;
* ammonium nitrate;
* iron nails;
* bleach;
* table salt;
* potassium hydroxide (sold in soap making shops);
* car starter fluid (ether + hydrocarbons);
* Everclear (ethanol).


First, you need to make strong potassium bleach. Make a concentrated solution of potassium hydroxide. In another flask, mix car battery acid and table salt, and start to drip bleach into it. You'll get a lot of chlorine, which you need to bubble through potassium hydroxide until it gets greenish. This is your super strong potassium bleach.

Afterwards, you need iron nitrate. First, let's make some nitric acid. It can be made in two steps:

* Boil down car battery acid until it fumes. You'll have 75% sulfuric acid.
* Add this sulfuric acid to ammonium nitrate and carefully distill. The liquid that comes over is very concentrated nitric acid. If it fumes, dilute it with water until it stops fuming.
* Add iron nails into a beaker with the nitric acid. Carefull, NOx will emerge, do it outside. The acid may overheat, boil, foam and spit. When the reaction stops, you'll have a concentrated solution of iron (III) nitrate.

Carefully add this solution to our super strong potassium bleach. Add concentrated potassium hydroxide. If everything was done right, you will see crystals of crude potassium ferrate forming. Filter them away.

This crude ferrate is not very stable, so you need to recrystallize it. Dissolve the crystals in a weak solution of KOH. When they are dissolved, filter the solution and pour it into a saturated solution of KOH. You'll see more potassium ferrate crystals forming. Filter them away, wash with ice-cold Everclear and dry quickly. To dry, use the car starter fluid: wash the filter with it. It will evaporate quickly and the resulting product will be dry.

For best results, you should carefully distill the car starter fluid beforehand. Remember, no fire: use hot water to heat the boiling flask. You'll get ether of reasonable purity. Use this to dry your ferrate.

[Edited on 28-9-2017 by ave369]



You are a saint, thank you.

ave369 - 3-10-2017 at 02:05

Could you please post the results of your experiments if you try my procedure?

Deathunter88 - 3-10-2017 at 04:54

Quote: Originally posted by Tetra  
Quote: Originally posted by ave369  
Quote: Originally posted by Tetra  

Don't have fritted glass :(
Too poor :(
Anything else?


Try a Buchner funnel with a polyethylene circle in which you poke, like, bajillions of little holes with a pin. Works as a poor man's substitute for fritted glass if the particles are coarse enough. Mineral wool also works, but this you must calcine before using to destroy any organic additives. Remember: absolutely no paper. Ferrate reacts with that.

By the way, I can give you a prep of potassium ferrate from the simplest stuff. You need:

* car battery acid;
* ammonium nitrate;
* iron nails;
* bleach;
* table salt;
* potassium hydroxide (sold in soap making shops);
* car starter fluid (ether + hydrocarbons);
* Everclear (ethanol).


First, you need to make strong potassium bleach. Make a concentrated solution of potassium hydroxide. In another flask, mix car battery acid and table salt, and start to drip bleach into it. You'll get a lot of chlorine, which you need to bubble through potassium hydroxide until it gets greenish. This is your super strong potassium bleach.

Afterwards, you need iron nitrate. First, let's make some nitric acid. It can be made in two steps:

* Boil down car battery acid until it fumes. You'll have 75% sulfuric acid.
* Add this sulfuric acid to ammonium nitrate and carefully distill. The liquid that comes over is very concentrated nitric acid. If it fumes, dilute it with water until it stops fuming.
* Add iron nails into a beaker with the nitric acid. Carefull, NOx will emerge, do it outside. The acid may overheat, boil, foam and spit. When the reaction stops, you'll have a concentrated solution of iron (III) nitrate.

Carefully add this solution to our super strong potassium bleach. Add concentrated potassium hydroxide. If everything was done right, you will see crystals of crude potassium ferrate forming. Filter them away.

This crude ferrate is not very stable, so you need to recrystallize it. Dissolve the crystals in a weak solution of KOH. When they are dissolved, filter the solution and pour it into a saturated solution of KOH. You'll see more potassium ferrate crystals forming. Filter them away, wash with ice-cold Everclear and dry quickly. To dry, use the car starter fluid: wash the filter with it. It will evaporate quickly and the resulting product will be dry.

For best results, you should carefully distill the car starter fluid beforehand. Remember, no fire: use hot water to heat the boiling flask. You'll get ether of reasonable purity. Use this to dry your ferrate.

[Edited on 28-9-2017 by ave369]



You are a saint, thank you.


Before you spray starter fluid on your product, try spraying some on a clean piece of glass. Some starter fluids contain lubricating oils that will mess you up.

Rhodanide - 3-10-2017 at 05:25

Quote: Originally posted by Deathunter88  
Quote: Originally posted by Tetra  
Quote: Originally posted by ave369  
Quote: Originally posted by Tetra  

Don't have fritted glass :(
Too poor :(
Anything else?


Try a Buchner funnel with a polyethylene circle in which you poke, like, bajillions of little holes with a pin. Works as a poor man's substitute for fritted glass if the particles are coarse enough. Mineral wool also works, but this you must calcine before using to destroy any organic additives. Remember: absolutely no paper. Ferrate reacts with that.

By the way, I can give you a prep of potassium ferrate from the simplest stuff. You need:

* car battery acid;
* ammonium nitrate;
* iron nails;
* bleach;
* table salt;
* potassium hydroxide (sold in soap making shops);
* car starter fluid (ether + hydrocarbons);
* Everclear (ethanol).


First, you need to make strong potassium bleach. Make a concentrated solution of potassium hydroxide. In another flask, mix car battery acid and table salt, and start to drip bleach into it. You'll get a lot of chlorine, which you need to bubble through potassium hydroxide until it gets greenish. This is your super strong potassium bleach.

Afterwards, you need iron nitrate. First, let's make some nitric acid. It can be made in two steps:

* Boil down car battery acid until it fumes. You'll have 75% sulfuric acid.
* Add this sulfuric acid to ammonium nitrate and carefully distill. The liquid that comes over is very concentrated nitric acid. If it fumes, dilute it with water until it stops fuming.
* Add iron nails into a beaker with the nitric acid. Carefull, NOx will emerge, do it outside. The acid may overheat, boil, foam and spit. When the reaction stops, you'll have a concentrated solution of iron (III) nitrate.

Carefully add this solution to our super strong potassium bleach. Add concentrated potassium hydroxide. If everything was done right, you will see crystals of crude potassium ferrate forming. Filter them away.

This crude ferrate is not very stable, so you need to recrystallize it. Dissolve the crystals in a weak solution of KOH. When they are dissolved, filter the solution and pour it into a saturated solution of KOH. You'll see more potassium ferrate crystals forming. Filter them away, wash with ice-cold Everclear and dry quickly. To dry, use the car starter fluid: wash the filter with it. It will evaporate quickly and the resulting product will be dry.

For best results, you should carefully distill the car starter fluid beforehand. Remember, no fire: use hot water to heat the boiling flask. You'll get ether of reasonable purity. Use this to dry your ferrate.

[Edited on 28-9-2017 by ave369]



You are a saint, thank you.


Before you spray starter fluid on your product, try spraying some on a clean piece of glass. Some starter fluids contain lubricating oils that will mess you up.


Yes, that's a good idea. Mine's just DEE and Heptane so it should be fine, but I do also have some Tetrachloroethylene on hand as well.

ave369 - 3-10-2017 at 12:37

Quote: Originally posted by Deathunter88  

Before you spray starter fluid on your product, try spraying some on a clean piece of glass. Some starter fluids contain lubricating oils that will mess you up.


That's why I advise to distill the fluid beforehand.