Copperas storage

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MarcoP

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I've read many time about the making and storage of copperas, this time I've bought some and I wanted to store it properly in a PTFE container with double lid under 96% sulfuric acid but I don't know if this is what it's supposed to look like.
From a nice green it changed to a pale gray with shades of dark gray. I'm a bit confused now...
 

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Take some and dissolve in water to see if it makes a green solution.
I believe that the sulfuric acid pulled all the water from the hydrated copperas and turned it into anhydrous copperas.

The temperature rise is the hint.

I have no experience of copperas but I believe that you shouldn't use concentrated sulfuric acid.

Göran
 
Thank you Göran, I've saturated 25ml, the temperature raised to 45C and the colour is a very very pale green.

In each and every post I've read 10% sulfuric acid was used to make copperas but not percentage was given for storage so I understood it had to be concentrated. If this turns out to be a mistake how do I properly dispose of it or how do I fix the error?
I still have plenty of copperas but fixing the mistake could get me some knowledge.
 
It's been a long time since I used copperas to drop gold. I don't remember exactly how I did it but I probably followed the instructions in the Hoke book (p. 46). She says that 1 pound will drop about 2.5 oz of gold. Dissolve fresh green copperas in water - about 1 pound per quart of water. Add a little HCl to make the solution a clear green.

I see nothing in there about using sulfuric.
 
goldsilverpro said:
It's been a long time since I used copperas to drop gold. I don't remember exactly how I did it but I probably followed the instructions in the Hoke book (p. 46). She says that 1 pound will drop about 2.5 oz of gold. Dissolve fresh green copperas in water - about 1 pound per quart of water. Add a little HCl to make the solution a clear green.

I see nothing in there about using sulfuric.
GSP thank you for your reply, I'm not trying to drop gold with it, I only need to store it without let it oxidizing. Butcher used to make his own copperas and store it under sulfuric acid but something I've just noticed is the he didn't fully covered the copperas with sulfuric but only added a little.
 
Looks like you are using copperas made by Hi-Yield. You are supposed to use water to dissolve it with an addition of HCL. Look like you put too much powder in your container. Get you a larger container and add 2x the water, stir it very well and let it sit for a day and settle out. Then siphon off the solution leaving the white sediment. Filter the solution. You can store in a used HCL plastic bottle with a top on it. Don't know what the sulphuric will do to it though.
 
From wiki : All iron sulfates dissolve in water to give the same aquo complex [Fe(H2O)6]2+, which has octahedral molecular geometry and is paramagnetic.
Iron(II) sulfate anhydrous
Síran_železnatý.PNG

Iron(II) sulfate heptahydrate
799px-Iron(II)-sulfate-heptahydrate-sample.jpg

I agree that the concentrated sulfuric acid would have created the anhydrous form.
 
Those nice green crystals are what is desirable. If one starts with the already prepared crystals, storing them with acid is not required. Simply keep them in a jar with a sealed lid, keeping them dry. They should last for a long time. Even stored in paper bags, it doesn't degrade all that rapidly.

In regards to the amount needed--it was my experience that an ounce of crystal would precipitate an ounce of gold. A slight excess guarantees a full recovery, although one can test with stannous chloride to determine if there is still any gold left in solution. Do remember, the stannous chloride test is extremely sensitive to even traces of gold. If a solution tests barren, you can rest assured it has no value, assuming your stannous chloride is not oxidized. Test with a standard gold solution to make that determination.

I used copperas exclusively for some time, but eventually switched to SO2 in a cylinder when I came to prefer to work with smaller volumes of solutions.

Harold
 
But it is so, so cheap. Both to buy the chemical itself and to buy the things that are needed to make it from scratch. Why worry about it? Store it like Harold says. If $5 worth goes bad in a year or two, get some more. To me, I wouldn't like to handle it after concentrated sulfuric had been added. Why make a very simple problem dangerous?
 
Thank you for all your replies and your help, but sorry for the late reply as I couldn't get to my "lab" even if in the same building.

@Barren Realms 007, I've done as suggested but I diluted the original 300ml of concentrated sulfuric acid with about 2 liters of water, the day after it was settled already but 3 days later the solution cleared more and the crystals started getting back the original color.
Click for hi-def image:

It looks like it needs a good mix and ready to be stored, the diluted acid could be evaporated to collect any more crystals it forms. At least that's what I believe, am I that far from fixing this mistake? I need a way to fix it, please.

@Geo, yes that is what it did look like, but I never got it to dry and always left under solution so I cannot certain about it.

@Harold_V, that's exactly what I did now. I've followed your advice and got some more out the bag, filled up the PTFE container and simply stored.

@GSP, yes it is cheap! This is an agricultural area and I could only found a 25Kg bag but for only €8, go figure. But even if cheap I didn't want to waste any so I wanted to be sure to store it properly and give the remaining away before it oxides.
 
The difference I see here is that I make my copperas from scratch, and crystalize the fresh crystals, and store them, before they oxidize, storing the fresh crystals with just a little of their own solution, adding just a little sulfuric acid (a few drops to keep the solution and the crystals acidic) for storage, the fresh crystals sitting in the slightly acidic liquid helps to keep oxygen away from the crystals keeping them fresh and green, just like the copperas crystals shown above from the Wikipedia article.

If you buy good copperas there is no reason to dissolve it, and recrystallize before storage.

If you buy agricultural ferrous sulfate, normally dry crystals, most of them that I have seen are oxidized to white or brownish crystals, and not the bright green crystals we need to precipitate or test for gold with.

The white or brown ferrous sulfate for agricultural use powders or crystals have sit dry and have had fair exposure to oxygen from sitting in the bag, sometimes for long periods of time, and may or may not contain much copperas left in their crystal structure.

I could not find true copperas crystals in my area, every bag sold for agriculture use, I would buy was mainly oxidized iron compounds, not the bright green copperas we need. This is one reason I decided to make my own copperas, and found it an easy process giving me a good product of copperas I could not find locally.

most of the ferrous sulfate I have seen for agriculture use are basically oxidized iron compounds with very little ferrous sulfate left in them, trying to re-dissolve them or adding dilute H2SO4 would give only the ferrous sulfate solution of those crystals that were not oxidized (yet) to some other form of oxidized iron compounds, the oxidized iron would not go into solution easily, I suspect from the pictures you show above much of the copperas you started with was oxidized.

Marcop,
From your first picture of the milky looking solution it looks like much of the iron was oxidized, but from your last picture it looks like you have some good ferrous sulfate in solution (the green solution), and some ferrous sulfate crystals (the bright green crystals), but it also looks like you also have some oxidized iron compound that is not wanted in your solution, (the whitish powder).
This whitish powder is possibly from oxidization of the original ferrous crystal you started with.

You can separate the liquid copperas carefully decanting it from the crystals (green crystals and white powders of un-dissolved oxidized iron compounds), this good green copperas solution can be stored as a liquid in a plastic jug, or recrystallized to bright green copperas crystal if you prefer crystals.

To separate the ferrous sulfate (green crystals) and the oxidized iron compounds (white powders), left after decanting the solution above, you can put the copperas crystals back into solution, on a hot plate in a corning-ware pyro Ceram dish and adding heat, you need to add a little water and a few drops of H2SO4, to dissolve the crystals, the white powder most likely will not dissolve (giving you the milky looking solution), after getting the copperas back into solution, you can filter the solution letting the copperas go through the filter, filtering out the oxidized iron compound, leaving it as white powders or iron powders that may change color on exposure to air, in the filter paper.

You can then store the copperas solution as is, or return the filtered copperas solution to the dish, add heat to evaporate water and recrystallize it into the bright green crystals, storing them as I have described before, you do not use concentrated sulfuric acid, just keeping them a bit acidic is all that is needed, 10% H2SO4 is all that is needed.
 
Thank you butcher, will also do as you suggest. I'm sorry I made you all guess the original material I started with, next time I'll have to give you all as much information I think relative. Anyhow I'm attaching a picture of the original copperas I bought and I was lucky to find a good grade copperas, at least that's what it looks like, and really cheap too.



Thank you all for your inputs, really appreciated.
 
Those crystal should be kept as is in a sealed container. A good oxygen barrier is what you want. The crystals will dissolve in water giving the hydrated form of ferrous sulfate. You could seal in a ziplok storage bag with some oxygen absorbing material, iron filings perhaps.
 
I have recently started using copperas to precipitate gold for the first refining.

I use the hardware store plant food variety.

In a 600ml beaker I fill it about 1/3 full of copperas, then add distilled water to about 2/3 full.

I place it on the hot plate on low and stir with a magnetic stir bar.

The solution looks kind of brownish yellow so I add about 3 or 4 ml HCl and it turns nice and pale green.

After it dissolves I gravity filter the hot solution - this take a while but the solution comes out just a touch cloudy and green.

I found that there are bits of iron metal that cling to the magnetic stirrer. If the copperas is added right out of the bag and not filtered then these bits of iron would get in with the gold powder.

The gold solution turns black when enough filtered copperas solution has been added to precipitate all the gold.

I then filter out the gold and hen rinse the gold powder with HCl while it is still in the filter.

The HCl rinses out any copperas that is still in the gold powder as it sits in the filter, then rinse with distilled water.

The filter paper with the rinsed gold powder is then transferred to a clean beaker, filter paper and all, where it is dissolved a second time with fresh AR.

The gold dissolves and the filter paper disintegrates. The disintegrated filter paper make a nice filter medium and gets all the cloudiness out when I filter the gold solution.

After filtering I use SMB for the second precipitation and again filter out the gold.

Using two different precipitants makes some nice clean gold powder that is real light tan in color and the gold alway assays via XRF at three nines.

Any left over filtered copperas solution is saved for the next batch. Upon cooling in grows some very nice looking green crystals.

Using copperas takes a little extra time but the results are always very impressive.

kadriver
 

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