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View Full Version : Green Chloride from Aqua Regia / Ether Extraction of Magnetite



Vlad
07-20-2009, 08:22 AM
See attachment for the picture.
It's not a good picture but I have no digital camera and was using my built in webcam that is in my laptop in a more or less dark room.

It's really green. The color can be clearly seen on the picture.

I took one teaspoon of fine ground magnetite, added like 40 ml of concentrated aqua regia (a bit more than 3 parts HCl and a little less than 1 part HNO3), let this stand for a day, then decanted the acid into another beaker, added 30-40 ml of diethyl ether, poured all into another beaker and back to mix the ether with the aqua regia (which should be done *carefully* and slowly as this really heats up the mix and if you do it fast and furiously it could explode I think - and it has to be done with concentrated acid, if you dillute the acid with water the extraction doesn't work), then decanted and pipetted off the ether layer colored green yellow floating on top of the acid, and repeated this two more times.

I let the ether evaporate, and when concentrating the acid due to evaporation of the ether the color turned a lot greener.

I had 100 ml of ether right after the extractions. I took 1 milliliter of the ether, dilluted it in distilled water, then precipitated with potassium bicarbonate.

This turned the solution orange-red, which seemed like a colloid or fine suspension or precipitate settling out, and then a LOT of fine white precipitate dropped which gave an energy feeling right in the middle of the forehead typical of monoatomic gold when working with it or eating it.

When settling, the orange-red colored suspension adhered to the white precipitate, coloring it.

I added HCl, which dissolved the precipitate resulting in a clear yellow greenish solution, and reprecipitated with KHCO3, and got the same result.

I added a few drips of 80% phosphoric acid, which dissolved the precipitate resulting in a clear solution like water, with no color at all, and added KHCO3, and got a very fine milky white precipitate looking like the preciptiate gotten from my Dead Sea salt extractions. It looked more like a white suspension in water but it's a precipitate. It's VERY slow to settle.

Adding more KHCO3 turned the solution more beige white and made the precipitate more visible.

Adding KOH dissolved the precipitate and increased the beige white color.
Adding distilled white vinegar resulted in a white precipitate again. Like 30 ml when I checked and it wasn't fully settled yet.

Assuming I would get like 10 ml of initial white preciptiate with the orange adhesion to it from 1 ml of ether taken from the 100 ml ether, that means the 100 ml ether should yield like 1 liter of white precipitate. From one teaspoon of magnetite. That's a LOT. It should amount to 1 liter per teaspoon of magnetite.

I have four kinds of magnetite and tested another one too. This gave very little of the same precipitate and the ether was colored orange-yellow.


The ether extract should be only or mostly goldchloride and probably monoatomic gold since it's green. I suspect there is a little iron extracted along with it giving rise to the orange-red precipitate/suspension and color.

I will see if after drying the red powder can be turned white by dissolving the orange-red dried precipitate or suspension adhering to it in HCl.

Vlad
07-22-2009, 10:01 AM
The red-orange precipitate appears to be an iron salt.
I dried it out.
It deliquisced overnight.
I dried it out again.
I added dillute HCl to the dry red powder.
It dissolved instantly with a lot of fizzing.

The probably white gold can also be taken out by sodium bicarbonate.
Dissolving the red-orange precipitate in phosphoric acid gives the clear solution, and then adding sodium bicarbonate until no more fizzing and saturated of salt, gives about the same volume of white precipitate. It's a bit thicker and creamier in consistency than using potassium or ammonia though, but I've seen that before with white gold precipitates using sodium salts.

Another indication the red-orange is probably iron, is that I took an aqua regia solution which had the magnetite in it, and precipitated it straight, and got a LOT of that orange-red precipitate. Almost all of the solution was it, so it's likely iron.

Now another thing to test is see if the dried white precipitate dissolved in aqua regia or not.

Vlad
07-22-2009, 06:27 PM
Ok so I found out when you have the red precipitate, that when you add phosphoric acid until it dissolves, then add sodium bicarbonate, you get a white precipitate.
I wasn't and still am not satisfied with it. I don't like sodium precipitated gold.

I washed the precipitate three times with like 8 times it's volume in water.
I had like 100 ml left.

This I dissolved with dillute HCl. (Turned slight yellow.)
Titrated with dillute KOH solution.

Color gradually increased to darker yellow to yellow orange to orange with white precipitate dropping along the way but not really the white I thought was 'ok'.

When pH was neutral I added a lot more KOH quickly until I hit very alkaline and on the way the orange became deep blood red again, indicating the red precipitate was still around.

So I added phosphoric acid again, to dissolve everything, and the colors reversed, until I ended up with a solution that is not clear translucents but like it has translucent to white suspension in it. Looking similar to the gelatinous ormus when it precipitates but I'm not sure it's the same. I kept adding phosphoric acid (lots) to get it to dissolve and it sticks around. pH should be pretty damn acid. It's slow to settle too. I'm wondering if it's not iron phosphate or something like that. Should be white as I remember.

This sucks! This red stuff has to go!

The only thing I can come up with now is to try a brand new extraction and add concentrated phosphoric acid to the extract after all the ether has evaporated, and re-extract, and see if the red stuff sticks behind.

Vlad
07-22-2009, 07:34 PM
I had split the three time washed 100 ml preciptiate in two parts.

One part I treated as described above and I have just noticed a white very fluffy fine precipitate is settling in that gives a lot more typical centered energy feeling at the forehead similar to dried white powder gold. I am still not sure it's gold. It could be iron phosphate but it's a bit too fine white fluffy for it. I reckon iron phosphate (which last time I checked was a solid not soluble but I could be wrong) should settle quick and also be in solution since there is also HCl present.

The other part I added Na3PO4 to. Color turned beige to orange. Added KOH solution. Deep orange to red color. Added HCl and H3PO4. Turned to a faint yellow solution that turned almost clear. Added KOH solution again. While adding a little bit (just pouring in), immediatelly the solution turned as the other batch described above and below; with the apparent precipitate. So it seems IF this precipitate is some m-stuff it precipitates in acid pH not near neutral. Now this could be interesting considering the ether extract from this magnetite was quite green, and coincidentally the ether extract from the Dead Sea salt in aqua regia was also quite green (no yellow at all in it), and it also dropped in acid pH. Maybe if the extracted chloride form is green it doesn't drop at neutral pH?
I really think this white stuff is m-gold, as I noticed from the extracts when the white precipitate drops, there is a lot of upward rising bubbles without carbonate or hydrogen peroxide having been added to the mix.
I also recall reading an archived ORMUS_SWG post by August Dunning from 2001 or 2002 when he worked with pure gold and iridium, that he said the noble metal hydroxides precipitate in acid pH.
Either way when I noticed this change with the apparent precipitate in this second batch, I ignored it and kept adding more KOH solution just to see what would happen, and it turned yellow beige, orange, red, and now at pH 14 or so a very deep blood red color, without precipitate. It's a cool color but I think it's iron.

Vlad
07-25-2009, 02:18 PM
The faint fine white precipitate I noticed had settled, and upon closer inspection after decanting the liquid off, I noticed it had a slight pink tinge. I don't know if it was like that or if it got that color from light exposure (unlikely as it's dark at night).

I never saw a light pink-white precipitate yet. I read that gold bhasma is supposed to be pinkish and feel oily to the touch.

I let the light pink precipitate dry overnight at about 50C after two washes with more than 10 times it's volume distilled water.

It felt waxy-wet to the touch. I thought it had deliquisced after I took it off the hotplate to cool this morning, so I put it for like an hour at about 70-75C.
It still felt waxy-wet afterwards, and like a creamy powder, kinda strange.

Tests for dissollution:

Nothing in dillute HCl. Nothing with added 30% H2O2. Left it in for half an hour.
Nothing in cold aqua regia after being left in it for half an hour. I tried precipitating the dilluted aqua regia with NaHCO3 to see if anything dissolved. Nothing.

I then tasted a bit on my tongue. Acid taste. Slight ormus feeling at the chest and forehead middle.
Doesn't feel balanced/good.

I put it in KOH solution since it tasted acid.
It dissolved.

I had about 130 mg (looked like a lot though) from a heavily worked half of a solution of 1 teaspoon magnetite extract.

I added some drips 30% H2O2 to the KOH solution to see if anything would happen like a precipitate drop (since I had noticed with iodine extraction this likes to happen in KOH solution). No reaction.

I then added dillute HCl while stirring lowering the pH

I noticed a cloud of white with a very slight pink tinge precipitate dropping at slightly acid pH, something like the acidity of vinegar when tested with pH paper. This was together with typical m-gold effects at the forehead.

It's probably the same original precipitate that dropped at very low pH yet I have the impression it dropped at a higher pH when going from alkaline to acid instead of from acid to alkalinity.

Vlad
07-26-2009, 12:11 PM
I did a new extraction on a teaspoon of magnetite.

I tested if adding phosphoric acid to one half of the aqua regia before ether extraction would leave the assumed red iron precipitate behind.
This did not work well after adding ether. It formed an emulsion and the ether did not seperate.

To the other half of the aqua regia I added ether and extracted a couple of times, let the ether evaporate, added HCl, distilled water, and got a reddish solution. I added some concentrated phosphoric acid which turned the solution orange then yellow, and I ran out of acid and noticed the color didn't change anymore to clear anyway while adding the remaining phosphoric acid I had.

I then added dillute KOH solution while stirring, and resumed adding it with a slow drip when I noticed a cloud of dark yellow appear upon addition of KOH.

I kept doing this and a precipitate appeared along with typical m-gold feelings at the forehead.
The solution actually turned cloudy yellow from more or less clear yellow. When I noticed this I quit and let the precipitate appear.

It is now settling. From half a teaspoon of magnetite extract, I got like 200 ml of precipitate that in appearance is not gelatinous, but like cloudy-translucent-white, not shining bright, but quite white, not greyish. It looks similar to the m-state precipitate from the 'dry method' on volcanic sands after purifying the silica hydrogel out, like a calcium and magnesium free m-state precipitate. Except these precipitates look more translucent, and this one looks more white.

I could maybe titrate more out of the solution. I will try after I decanted the solution off the settled precipitate. I just quit because I noticed a precipitate and I don't know when it would redissolve and/or the yellow-orange-red precipitate which is assumed iron would drop. It hasn't dropped so adding phosphoric acid seems to work to keep it from precipitating.

Vlad
07-26-2009, 02:38 PM
Well looks like phosphoric acid is not such a good idea either. Most of the precipitate appears to be ferric and/or ferrous phosphate. One is white, the other yellow white and insoluble.
There is just too much precipitate. I was able to titrate nearly a liter out, which can't all be m-state. Nearly all of it comes out in acid pH too which doesn't appear right. There appears to be m-gold in it but it might be tied to the iron somehow or in small amounts. Without phosphoric acid, a red precipitate appears and just before it drops I've seen the white with m-gold feelings so it's apparently there.
Now how to get iron out or keep it in solution... I'm thinking organic acids like citric maybe but these I think turn m-gold back to metal or make it inactive.

Vlad
07-26-2009, 06:47 PM
Well I looked up on the net characteristics of ferric phosphate and that is yellow-white and crystallizes in yelllow crystals. I don't think it's ferric phosphate.
Ferrous phosphate turns blue green on exposure, and also is a slate blue amorphous powder. I doubt it'll turn blue upon drying but it might.
Both are soluble in acids.
I got a light pink powder that is insoluble in aqua regia and seems to be mostly the same thing.
I'll see if this precipitate when dried changes color and dissolves.

Vlad
08-02-2009, 05:14 PM
I looked up something in the archives regarding citric acid and magnetite as I remember I worked some with it years ago.
Turns out citrate is useful for keeping iron in solution up until pH 9, but it appears to turn m-state back to metal at least in the presence of ether and apparently alcohol too.

""As long as the citric concentration remains at least 3 times the
dissolved iron concentration, the iron will not precipitate out as
hydroxide if the solution is further treated to pH 9.5 with extra
addition of ammonia.""

(Webpage mentioned sodium instead of ammonia works just as well.)

I read a post of mine wherein apparently I said it is stated in the booklet the Radiochemistry of Gold that organic acids such as citrate and acetate turn gold ions back to metal. Apparently acetate is dangerous too but I used it frequently to preciptiate m-state without much problem.
It might be a matter of concentration or combination with other hydrocarbons.

I did a new aqua regia/ether extraction on a teaspoon of magnetite I had left, and added a 50% by volume solution of citric acid to the evaporated extract. Like 100 ml. Turned the solution yellow orange.
I took a small a sample and slowly added sodium bicarbonate powder.
The solution gradually turned lemon yellow. Nothing precipitated, not when at or past neutral pH. I did feel energy feelings at the forehead though when still in acid pH right when I added sodium bicarbonate.
I took the rest of the solution and added KOH, and ther solution gradually turned orangish to red. Seems like iron oxide precipitated.

When adding sodium bicarbonate the solution didn't turn any orange or red, this is likely because it never overshoots pH 9 which is what I looked up and stated the pH is up until which citrate keeps iron in solution.

I think there might be digestion needed in low acid pH for possible m-gold to precipitate. I've seen it happen with dead sea salt aqua regia/ether extract. Nothing precipitated when I neutralized to neutral pH. But after 3 days in a sandbath at about 40-50C, a fine white precipitate appeared.

FYI I also tried an aqua regia/ether extraction on LIMA Atlantic sea salt. I got a pale blue-cyan solution. Possibly m-copper color as I read this is what it's supposed to look like (never made it).
Nothing precipitated upon titration with KOH or addition of sodium bicarbonate. It only turned the solution yellow in both cases. Again I think maybe something would precipitate with digestion.

Aleilius
08-02-2009, 08:56 PM
I read a post of mine wherein apparently I said it is stated in the booklet the Radiochemistry of Gold that organic acids such as citrate and acetate turn gold ions back to metal. Apparently acetate is dangerous too but I used it frequently to preciptiate m-state without much problem.
Yeah, I remember recalling this too. I think it hydrolyzes in the presence of water/moisture, but I do think it's somewhat stable in the anhydrous acetate form. This powder, when heated rapidly heated to 80-120C will decompose violently (I think some kind of acetate peroxide is formed FYI). Gold acetate is a deep reddish/brown powder, and smells like vinegar (due to decomposition). This is one way to form gold nanoparticles.

Sunlight/light should also cause decomposition.

I would like to investigate the properties of gold citrate (which also decomposes in the presence of water). This is another way to produce gold nanoparticles, and seems to be particularly effective if using the proper form of citrate.


I think there might be digestion needed in low acid pH for possible m-gold to precipitate.

Your work with magnetite is interesting. I've been watching, but haven't posted much lately. I would like to see where a digestion goes with this.