Poor mans Nitric and Silver

[Rreyes097]

This my video of using poor man's nitric acid to process gold fingers. Poor man's AR is HCl and a solid nitrate. PM's nitric acid will work on any material you would use nitric acid on, even silver, just used distilled water instead of tap water.

Is that really all you have to do? Because I was going to be processing gold filled and wanted to recover the silver. But didn't think I could if I use poor man's nitric. I have potassium nitrate lab grade I think. It's pure it says.

 

[Alondro]

Is that really all you have to do? Because I was going to be processing gold filled and wanted to recover the silver. But didn't think I could if I use poor man's nitric. I have potassium nitrate lab grade I think. It's pure it says.

You can't use Poor Man's nitric for silver, because you have chloride in it. That will form silver chloride immediately and mix with whatever junk is left over, making recovery very difficult.

The only relatively cheap option for silver is warm sulfuric acid (at about 80C sulfuric dissolves silver and palladium, and starts to attack platinum weakly) But you must be skilled at handling sulfuric and capturing or venting the SO2 gas released.

I did an interesting small test of little silver-plated electronics parts, adding just enough sulfuric to dissolve the plating and a small amount of the base metal. Once everything that could be dissolved was finished, the mixture turned into 'grey goo' when cooled (all the PMs saturating the solution began to auto-reduce out along with reducing on the remaining copper). I then diluted with water little by little until the mixture ceased heating up (remaining sulfuric reacting with the water additions) and then doubled the volume with water and then stirred it up roughly every few hours to knock loose any silver and other PMs reducing out on the copper bits.

Then I let it sit for a few days to settle. I got a lovely deep blue copper sulfate solution and a fine dark gray powder resting among the copper bits (along with some tiny copper crystals which grew on some pieces that were brass). The copper sulfate could be poured off, and the powder easily washed and separated from the larger base metal pieces.

That powder was mostly silver, confirmed with dissolving a little in nitric acid and dripping a few drops of HCl, for the tell-tale white fluffy blobs of silver chloride.

 

[Rreyes097]

You can't use Poor Man's nitric for silver, because you have chloride in it. That will form silver chloride immediately and mix with whatever junk is left over, making recovery very difficult.

The only relatively cheap option for silver is warm sulfuric acid (at about 80C sulfuric dissolves silver and palladium, and starts to attack platinum weakly) But you must be skilled at handling sulfuric and capturing or venting the SO2 gas released.

I did an interesting small test of little silver-plated electronics parts, adding just enough sulfuric to dissolve the plating and a small amount of the base metal. Once everything that could be dissolved was finished, the mixture turned into 'grey goo' when cooled (all the PMs saturating the solution began to auto-reduce out along with reducing on the remaining copper). I then diluted with water little by little until the mixture ceased heating up (remaining sulfuric reacting with the water additions) and then doubled the volume with water and then stirred it up roughly every few hours to knock loose any silver and other PMs reducing out on the copper bits.

Then I let it sit for a few days to settle. I got a lovely deep blue copper sulfate solution and a fine dark gray powder resting among the copper bits (along with some tiny copper crystals which grew on some pieces that were brass). The copper sulfate could be poured off, and the powder easily washed and separated from the larger base metal pieces.

That powder was mostly silver, confirmed with dissolving a little in nitric acid and dripping a few drops of HCl, for the tell-tale white fluffy blobs of silver chloride.

So no way for me to recover silver when using poor man's nitric? I'm all out of nitric.

 

[Yggdrasil]

So no way for me to recover silver when using poor man's nitric? I'm all out of nitric.

Of course if the Gold content is high enough it can be dissolved directly.
Or one can have mechanic break up of the Chloride layer.
Then the Silver will be left as Chloride “dust” and the Gold dissolved.
Still you will need to deal with the base metals first.

 

[Rreyes097]

If I went with poor man's nitric to dissolve base metals would I be able to get the silver?

 

[Yggdrasil]

The only thing you will be able to with poormans Nitric is to dissolve the base metals.
And that can be done with HCl alone.
Read about Gold filled on the forum.

 

[FrugalRefiner]

You can't use Poor Man's nitric for silver, because you have chloride in it. That will form silver chloride immediately and mix with whatever junk is left over, making recovery very difficult.

Just for the sake of accuracy, there should not be any chloride in poor man's nitric. When properly made, it is a combination of a nitrate salt (sodium nitrate, potassium nitrate, etc.) distilled water, and sulfuric acid. Any chloride content would be minimal and only if the other components were contaminated.

When done properly, the mixture needs to be cooled well below freezing to precipitate the sulfate salt (sodium, potassium, etc.), but a small amount will remain. If you want pure nitric, you'll need to distill the resulting nitric acid. If you don't distill it, some sulfate will remain in the acid, and that can cause a small amount of precipitate of silver sulfate, similar to the problem of silver chloride.

Dave

 

[Shark]

There is a way. Search the forum first. I am short on time right now.

Edit: Dave is close. Look for lazersteve’s recent post on dealing with the sulfate.

 

[Shark]

The remaining sulfate can be easily removed by stirring in a few grams of saturated Ca(NO3)2 solution followed by settling and finally pour off/siphoning. Add the calcium nitrate solution until no more calcium sulfate forms. Gently heating the acid before the siphoning stage promotes formation of the calcium sulfate. Excess saturated Ca(NO3)2 (within reason) should not cause any problems.

Steve

I have not tried this yet. But sounds interesting.

 

[Shark]

Is that really all you have to do? Because I was going to be processing gold filled and wanted to recover the silver. But didn't think I could if I use poor man's nitric. I have potassium nitrate lab grade I think. It's pure it says.

Short answer, yes that is all you have to do so long as you pay close attention to Geo’s video. Now keep in mind what Lazersteve has mentioned in the above quote and go back and read Orvi’s comments on page two.
(changed page number to the correct page)

I have used Geo’s method from his video many times to do gold filled. I treat the silver chloride as being dirty so I use sulfuric and iron to recover the silver and then (depending on how dirty) use a silver cell on it.

Edit:
(The down side is the volume of waste. It is considerably more volume than true nitric)

You now have two potentially new methods that are confusing but offer an opportunity to learn from.

 

[Rreyes097]

Short answer, yes that is all you have to do so long as you pay close attention to Geo’s video. Now keep in mind what Lazersteve has mentioned in the above quote and go back and read Orvi’s comments on page one.

I have used Geo’s method from his video many times to do gold filled. I treat the silver chloride as being dirty so I use sulfuric and iron to recover the silver and then (depending on how dirty) use a silver cell on it.

You now have two potentially new methods that are confusing but offer an opportunity to learn from.

Ok thanks I'll re read those and watch the video again. But I think I already have questions. But I'll save em.

 

[Shark]

But I think I already have questions.

Don’t we all?
It is a never ending search for me, even when I am not working on anything.

 

[Alondro]

Just for the sake of accuracy, there should not be any chloride in poor man's nitric. When properly made, it is a combination of a nitrate salt (sodium nitrate, potassium nitrate, etc.) distilled water, and sulfuric acid. Any chloride content would be minimal and only if the other components were contaminated.

When done properly, the mixture needs to be cooled well below freezing to precipitate the sulfate salt (sodium, potassium, etc.), but a small amount will remain. If you want pure nitric, you'll need to distill the resulting nitric acid. If you don't distill it, some sulfate will remain in the acid, and that can cause a small amount of precipitate of silver sulfate, similar to the problem of silver chloride.

Dave

Ah, the poor man's nitric I've seen used mostly uses sodium/potassium nitrate with HCl, not sulfuric acid.

If the OP is using the form you mention, then it will work just fine.

 

[orvi]

Remember that silver sulfate has low solubility in water, but much better in solutions of H2SO4, heat gratly help to dissolve it. It could indeed be crystallized this way.

 

[FrugalRefiner]

Ah, the poor man's nitric I've seen used mostly uses sodium/potassium nitrate with HCl, not sulfuric acid.

If the OP is using the form you mention, then it will work just fine.

Nitrate plus HCl is poor man's AR.

Dave

 

[butcher]

Poor man nitric should not have many chloride ions involved, as it will have copious amounts of sulfates of potassium or sodium...

To remove chlorides from your homemade nitric you can use silver nitrate, precipitating the chlorides as AgCl

Silver ions and the ions of chloride will form an insoluble precipitant a white cloud or puffballs, it can form a fluffy precipitant that can take time to settle if undisturbed, as it likes to float around in even a slightly moving liquid for some time (sometimes an advantage as when separating silver and lead salts other times sometimes a curse to wait to get silver out...)


Sulfate salts can be removed by using concentration and temperature to your advantage, freezing out the major portion, and then decanting using calcium nitrate to remove the remaining portion as gypsum or calcium sulfate.

The best solution is simple distillation, but you need to understand the safety practices involved to do it safely, so as not to get a face full of acids and exploding hot glass shards.

I do not understand why our new members do not go back in the history of the forum and read the posts there, before asking a question every step of their learning process, or at every roadblock they encounter.

Most of this information has been discussed a million and more times, not in detail as it was in the early days (no one could rehash it all on every question a new member has).

Reading where several of these methods came from will give you an understanding of it, to where you can answer your own questions, solve those problems that pop up in the lab, help ensure your success, and help you develop or expand on the chemistry knowledge to get it done, or done in another way or a better way...

Asking a question will get you out of this mess, but will not ensure you do not just jump into the next mess, or problem which is not just likely but inevitable, it will not insure you will successfully accomplish the next step in a process, with no idea what has gone wrong or what to do next, except to ask another question to proceed to your next problem.
Just getting frustrated doing the same thing and expecting better results...

Educating yourself can be very slow it takes time even to just learn the language much less the chemistry.

To help it is good to read and reread if needed, by reading and doing small experiments (forgetting about dissolving and losing your gold for now) working on educating yourself as to what happens in these many chemical reactions, and the more you do the more you learn not only the language and its meaning but the understanding of the chemistry so you can work successfully.

it is like trying to build a car before you learn how it even works or runs and asking a question at every step or problem you encounter, that is not going to help you get far before frustration takes its toll.

For poor man's Nitric acid or the cupric chloride leach (wrongly named acid peroxide or AP or something like that.), I suggest reading posts at the beginning of the forum using Laser Steve as the Author in your searches.

 

[Rreyes097]

There is a way. Search the forum first. I am short on time right now.

Edit: Dave is close. Look for lazersteve’s recent post on dealing with the sulfate.

I've been reading. I started at the first page, the oldest posts first. And still reading but I haven't found anything yet. I think I need to work on search phrases to get better results. But I'm reading I promise.

Poor man nitric should not have many chloride ions involved, as it will have copious amounts of sulfates of potassium or sodium...

To remove chlorides from your homemade nitric you can use silver nitrate, precipitating the chlorides as AgCl

Silver ions and the ions of chloride will form an insoluble precipitant a white cloud or puffballs, it can form a fluffy precipitant that can take time to settle if undisturbed, as it likes to float around in even a slightly moving liquid for some time (sometimes an advantage as when separating silver and lead salts other times sometimes a curse to wait to get silver out...)


Sulfate salts can be removed by using concentration and temperature to your advantage, freezing out the major portion, and then decanting using calcium nitrate to remove the remaining portion as gypsum or calcium sulfate.

The best solution is simple distillation, but you need to understand the safety practices involved to do it safely, so as not to get a face full of acids and exploding hot glass shards.

I do not understand why our new members do not go back in the history of the forum and read the posts there, before asking a question every step of their learning process, or at every roadblock they encounter.

Most of this information has been discussed a million and more times, not in detail as it was in the early days (no one could rehash it all on every question a new member has).

Reading where several of these methods came from will give you an understanding of it, to where you can answer your own questions, solve those problems that pop up in the lab, help ensure your success, and help you develop or expand on the chemistry knowledge to get it done, or done in another way or a better way...

Asking a question will get you out of this mess, but will not ensure you do not just jump into the next mess, or problem which is not just likely but inevitable, it will not insure you will successfully accomplish the next step in a process, with no idea what has gone wrong or what to do next, except to ask another question to proceed to your next problem.
Just getting frustrated doing the same thing and expecting better results...

Educating yourself can be very slow it takes time even to just learn the language much less the chemistry.

To help it is good to read and reread if needed, by reading and doing small experiments (forgetting about dissolving and losing your gold for now) working on educating yourself as to what happens in these many chemical reactions, and the more you do the more you learn not only the language and its meaning but the understanding of the chemistry so you can work successfully.

it is like trying to build a car before you learn how it even works or runs and asking a question at every step or problem you encounter, that is not going to help you get far before frustration takes its toll.

For poor man's Nitric acid or the cupric chloride leach (wrongly named acid peroxide or AP or something like that.), I suggest reading posts at the beginning of the forum using Laser Steve as the Author in your searches.

Not sure if you meant this for me? But I assure you that I'm in no mess. I know what to do. I just had a question regarding the silver. On wether or not I'd be able to recover it using potassium nitrate and sulphuric acid, or poor man's nitric. The reason I asked is because I'm getting contradictory information. But I'm reading every post from the beginning to the end. Know that.i will do just that, use laseresteve as an author.

 

[butcher]

Relax, it takes a bit for the info to sink in.

Starting out is extremely hard, but as with anything, as you gain, more is given to you.
Seek and find, ask and it will show up.

to become a master Archer you will not start out hitting the bull's eye with every shot, it takes work, in the beginning, you have to overcome the hump of the learning curve, then it's more downhill from there.

I get a question and I almost always find the answers I need, sometimes I can find it relatively quickly sometimes it takes time to sink in, others it may be a lingering question but if I seek I always find it.

I was not referencing anyone in particular if I am addressing a particular member I will by their forum site name.
My focus is to help all (if I am able and they are able).

Basically I never really asked questions on the forum to educate myself, I concentrate my time on educating myself with the principles and the workings...

I do not waste my time asking or focusing on single questions or possibly conflicting answers that will not get me very far in my education.

I would rather know and understand the whole of the principle, rather than just get a simple answer of only one aspect of some minor principle effect that will not really educate me to any degree...

After I understand the whole principle I can many times see the missing details or find gems of information that make the details shine more like gold so that the information comes to life before me.

 

[Shark]

When we make Poormans nitric we get it cold to cause the problematic sulfates to drop out which purifies the nitric to some degree. The problem is it leaves small quantities of the sulfates behind. These can be a potential problem so to get it better we can distill it and remove the remaining sulfates. Distilling acids can be tricky or even dangerous. By using lazersteves ideas we can use calcium nitrate to remove the remaining sulfates instead of distillation. Orvi mentions this in his post as well. While I don’t fully understand this I know that it means there is a way to make the nitric acid usable on silver without the problems generally associated with using poormans nitric. Lazersteve also mentions that the calcium nitrate won’t be a problem if not used in large excess.

How to apply this to the method that Geo uses (nitric acid made in situ) would be the next goal and is where I would be needing to study and question myself. While using it on fingers the excess sulfates aren’t as big a problem as it would be when running silver. These sulfates in quantity can steal varying degrees of silver in the process. Remove those sulfates and eliminate those losses is what the calcium nitrate could do for us. The same thing that distilling it would do if I am understanding it correctly.

 

[Alondro]

When we make Poormans nitric we get it cold to cause the problematic sulfates to drop out which purifies the nitric to some degree. The problem is it leaves small quantities of the sulfates behind. These can be a potential problem so to get it better we can distill it and remove the remaining sulfates. Distilling acids can be tricky or even dangerous. By using lazersteves ideas we can use calcium nitrate to remove the remaining sulfates instead of distillation. Orvi mentions this in his post as well. While I don’t fully understand this I know that it means there is a way to make the nitric acid usable on silver without the problems generally associated with using poormans nitric. Lazersteve also mentions that the calcium nitrate won’t be a problem if not used in large excess.

How to apply this to the method that Geo uses (nitric acid made in situ) would be the next goal and is where I would be needing to study and question myself. While using it on fingers the excess sulfates aren’t as big a problem as it would be when running silver. These sulfates in quantity can steal varying degrees of silver in the process. Remove those sulfates and eliminate those losses is what the calcium nitrate could do for us. The same thing that distilling it would do if I am understanding it correctly.

Calcium nitrate with sulfate ion would yield gypsum (calcium sulfate) which is very insoluble in aqueous solutions.

I'm not sure about its solubility or the ionic equilibrium balance in an acid solution with nitrate. however.

One would have to keep track of the moles of calcium sulfate being used and then calculate the moles of gypsum formed to get a good idea of the amount of sulfate remaining in solution with this process, keeping in mind that unless the gypsum is heated to anhydrous form it will generally exist as a dihydrate (adding an additional 36 g/mol to its molar mass).