# silver fixer



## jjohio (Aug 11, 2011)

Does anyone heat this stuff to evaporate the liquid down to silver mud?..Iheard it works good,just cant boil or Uwill lose some silver...curious to see if anone has done this


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## jjohio (Aug 12, 2011)

anyone???


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## goldsilverpro (Aug 12, 2011)

Doesn't sound very feasible to me. I would think you would just end up with a sludge of silver thiosulfate, sodium thiosulfate, and everything else that was originally in the fixer. You *might* be able to flux melt this in a crucible furnace, however, but I would bet it would involve using something like rebar to slag out the sulfur. There are better ways of doing this. Search the forum.

Did wherever you heard this explain how to get the silver out of the sludge? If so, what was it?


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## jjohio (Aug 12, 2011)

couldnt you put the "sludge" in some nitric, than drop it back out as pure silver


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## jjohio (Aug 12, 2011)

Sounds like the eastiest method would be to add lye right to the fixer to drop the silver...sound right?


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## Juan Manuel Arcos Frank (Aug 15, 2011)

No way...follow GSP´s directives.

Manuel


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## jjohio (Aug 15, 2011)

I tried the crock pot method...put some fixer in crock pot...ran it on low to evaporate...did 3 fill ups...silver sludge was left...i than added distilled water to the sludge and am now evaporating it..waitin to see what happens....


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## jjohio (Aug 15, 2011)

my thinking is...the silver is already there...dont have to precipitate it...why not evaporate off liquids???


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## goldsilverpro (Aug 15, 2011)

jjohio said:


> my thinking is...the silver is already there...dont have to precipitate it...why not evaporate off liquids???



Then what?


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## 4metals (Aug 15, 2011)

Buy some sodium thiosulfate powder, add water, evaporate water, what's left? Hint: it's a salt.

Just adding water and evaporating water does nothing to reduce the salt, in your case silver thiosulfate. You need to reduce the salt to metal, then separate the two. 

time for more reading.


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## jeneje (Aug 15, 2011)

I just done three gallons of fixer, so learn from my mistakes.... add lye to the fixer ONLY and let set, it will take a day or two but the silver will drop out, filter, wash and then melt. Do not expect a quick drop it does not happen that way, at least not for me.

Kenneth


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## jjohio (Aug 16, 2011)

goldsilverpro said:


> jjohio said:
> 
> 
> > my thinking is...the silver is already there...dont have to precipitate it...why not evaporate off liquids???
> ...


then melt, I dont believe in adding any salts or anything else...why mess with the purity if u dont have to...I know a guy that melts this silver sludge in his melting oven without it being dry...it works, try some


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## 4metals (Aug 16, 2011)

There are reasons why you are being told not to melt the sludge, but apparently you are not interested. So melt it, just use a hood.


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## jeneje (Aug 16, 2011)

4metals said:


> There are reasons why you are being told not to melt the sludge, but apparently you are not interested. So melt it, just use a hood.



4metals, I should'nt but I will. Don't get mad at me... :lol: The first thing is the sludge is not pure silver, second...if you breath the fumes from your one and only melting experince...it might be your last. Silver fumes are toxic follow 4metal advice use a fume hood and stay clear, or better yet follow the advice given here by the experts, they really do know what they are doing.

Good luck with your silver :roll: 
Kenneth


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## jjohio (Aug 16, 2011)

so what should i do with the sludge than?


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## jeneje (Aug 16, 2011)

jjohio said:


> so what should i do with the sludge than?



Ok...I am going to try to help you here. First take the sludge and wash it with tap water a couple of time and filter. Next rinse the sludge into a beaker or glass container, use a spray bottle to rinse it off the filter into the container. Next add an equal amount of HNO3 ( nitric). Place container in a fume hood or outside away from people and anminals. The solution will digest the silver. Let it set overnight or 24 hr's. 

When you have done this take photos and repost here on this thread.

jjohio I strongly suggest you get a copy of hokes book on refining and read the section about silver. The members here only ask that one reads and understand what they are trying to do. Then if you get stuck they are more than happy to help you.

What I have discribed is the way I would handle the sludge. They may be a better way and if I am misleading in anyway the senior members will correct me. 

If they chime in - it is in your best interest to listen to what they have to say. They are experts and have done this many years ... most all their adult life.

Repost after you have digested the sludge.
Kenneth


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## goldsilverpro (Aug 16, 2011)

jeneje said:


> jjohio said:
> 
> 
> > so what should i do with the sludge than?
> ...



Confusing thread. Is the sludge from the addition of NaOH or is it from evaporation? In the following, I assume it was evaporated.

The silver thiosulfate in the evaporated sludge is soluble in a sodium thiosulfate solution and the sodium thiosulfate in the sludge is soluble in water. Therefore, rinsing will dissolve some silver thiosulfate.

I think the addition of nitric will create a black stinking mess.

If you have already evaporated this solution, were it me, I think I would attempt to get everything re-dissolved and back to where you started. Maybe, just some warm water would do it, especially if it isn't totally dry. If that didn't work, you might add a little fresh sodium thiosulfate to the water. I would first experiment with this in small quantities. If you can get everything re-dissolved, start from scratch - several methods for reducing the silver from the hypo solution have been given on the forum. Ask Manuel about all this - he has more experience working with these solutions than anybody. The evaporation is really a bad idea, in my humble opinion.


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## Palladium (Aug 17, 2011)

I was just reading and had some questions myself. Silver is not my thing. Does the NaOh method work by just adding NaOh and melting? Number two, where can you buy bulk sodium sulfide and how much does it generally take to drop silver from a solution of sodium thiosulfate? I also heard someone mention copper recovery. If so is that like a cementation process we do with gold? Does it drop metallic silver in metal form?

I know sounds like a newbie. Lol


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## goldsilverpro (Aug 17, 2011)

Palladium said:


> I was just reading and had some questions myself. Silver is not my thing. Does the NaOh method work by just adding NaOh and melting? Number two, where can you buy bulk sodium sulfide and how much does it generally take to drop silver from a solution of sodium thiosulfate? I also heard someone mention copper recovery. If so is that like a cementation process we do with gold? Does it drop metallic silver in metal form?
> 
> I know sounds like a newbie. Lol



As far as adding NaOH is concerned, it seems to be assumed that silver oxide or silver hydroxide is formed. So far, though, there has been a lot of talk and little action. Has anyone been totally successful doing this - by totally, I mean 100% recovery? If so, how do you know you got it all? Has anyone even been partially successful? I have grave doubts about this process. Prove me wrong, guys.


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## Juan Manuel Arcos Frank (Aug 17, 2011)

GSP´s directives are right and wise.

Adding NaOH to spent fixer is a process used by many people,in my own experience it did not work,I have added NaOH,cold,warm,with sugar,boiling the solution for a while and I have never got any mud or silver,for all these reasons I gave up using this process.

About Palladium´s questions,first one answer is "YES",but I can not be able to get the mud(GSP is right,that mud should be silver oxide or silver hydroxide),second one answer is:sodium sulphide(Na2S) is wide used in food´s industry,it bleaches some grains,like corn,wheat,barley or oats so you can get sodium sulphide pretty easy,here in Mexico I buy 25 Kg. for $ 24 USD.
Reaction between Na2S and silver thiosulfate complex is an instantaneous one,it forms silver sulphide(Ag2S) which takes some time to settle down,spent fixer is regenerated.
The process for making metallic silver from silver sulphide has been posted in this wonderful Forum.
Cementation techniques(copper or iron wool) for spent fixers work well.
_________________________________________________________________________________________________

Jjohio:

Man,you are in trouble but you have come to this Forum to find answers,so let us try to solve your problem:
First of all,we have to know if you have silver dissolved in your fixer,so dip a piece of clean copper wire for 5 seconds into your fixer and tell us what happens.If there is any silver dissolved we will use zinc/sulphuric acid or sodium sulphide process to recover that silver.
If you have any mud then filter it and dry it,this mud could be many things(silver oxide/silver hydroxide/silver sulphide/insoluble metal sulphides/insoluble metal hydroxides),we need to melt it with potassium nitrate(salpeter) with 1:3 ratio(1 part mud+3 parts of saltpeter) this action will lead us to metallic silver.

Keep us posted.

Kindest regards.

Manuel


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## jeneje (Aug 17, 2011)

Well, it seems that I have mislead on this matter. So I now have a question? The process that i typed above is the same method i used on my fixer after missing up. Here are some photos of the process, now to my question what do I have?

Thanks
Kenneth

The pics are backwards sorry.


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## 4metals (Aug 17, 2011)

If you add caustic (lye) to your silver nitrate you will form silver oxide. Silver oxide can be melted directly as the oxide decomposes before the melting point of silver. What it gives off is O2, a bit tamer than chlorides or sulfides.


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## Palladium (Aug 17, 2011)

Juan Manuel Arcos Frank said:


> First of all,we have to know if you have silver dissolved in your fixer,so dip a piece of clean copper wire for 5 seconds into your fixer and tell us what happens.If there is any silver dissolved we will use zinc/sulphuric acid or sodium sulphide process to recover that silver.
> 
> Manuel



http://goldrefiningforum.com/phpBB3/viewtopic.php?f=50&t=3558&p=30524&hilit=photo+fixers#p30524


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## Palladium (Aug 17, 2011)

Meow !


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## jjohio (Aug 18, 2011)

i found some stuff called photographers sodium sulfide...comes in 100 gram bottle, is this what i want to drop silver?..anybody no more places to purchase this stuff


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## NoIdea (Aug 18, 2011)

Palladium said:


> .......... Number two, where can you buy bulk sodium sulfide and how much does it generally take to drop silver from a solution of sodium thiosulfate? I also heard someone mention copper recovery. If so is that like a cementation process we do with gold? Does it drop metallic silver in metal form?
> 
> I know sounds like a newbie. Lol




Hi All – Funny this should pop up now, I’ve bin doing a few experiments using hydrogen sulphide to strip copper from AP and HCl/Cl solutions. 

If anyone is interested ill throw together some pictures of the colour change and what was filtered from solution.

I keep reading about waste waste waste, sorry I spend more time finding solutions to waste problems than I do extracting gold. 

I prefer the AP (aquarium bubbler) approach due to the ease at which copper can be stripped from solution and at the same time reducing the pH of the solution for reuse. Nickel on the other hand …. :roll: 

Has anyone tried this approach?

Cheers

Deano


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## qst42know (Aug 18, 2011)

How are you getting the copper out?


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## jeneje (Aug 18, 2011)

qst42know said:


> How are you getting the copper out?



Out of solution, or out of the solids?

Kennth


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## NoIdea (Aug 18, 2011)

Hi - Sorry, i re-read my post, it's missing a bit, ill try again.  

I use the AP method, using an aquarium bubbler instead of H2O2 thus keeping the solution volume down. Recovery of copper is a performed after ALL PM’s are removed from said solution. Bubbling H2S gas through a bubbler with intense agitation and copper will precipitate out as the sulphide leaving behind the H+, thus lowering the pH. The copper sulphide is removed by filtration.

Before reintroducing the solution back into the AP process, it’s advantageous to purge the solution with air to get rid of any H2S still lurking around.

The nickel is another problem Im working on, looked at a patient that used an ethanol soluble dyglime (is that the correct spelling) was used to impregnate polyurethane foam, letting it dry, then run your nickel solution through it and it will capture the nickel, wash with water, dry, and then wash out with ethanol, the rest I forget, though this may be my next approach.


Cheers

Deano


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## jjohio (Aug 18, 2011)

jjohio said:


> i found some stuff called photographers sodium sulfide...comes in 100 gram bottle, is this what i want to drop silver?..anybody no more places to purchase this stuff


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## Juan Manuel Arcos Frank (Aug 18, 2011)

Palladium:

It seems like silver sulphide mud,try to make a test using my process to convert silver sulphide to metallic silver.

Do not buy anything without assying.If it is silver then you have found an urban silver mine.

Good Luck.

Manuel


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## qst42know (Aug 18, 2011)

> The nickel is another problem Im working on, looked at a patient that used an ethanol soluble dyglime



Dimethylglyoxime? The same as for testing for palladium?

http://en.wikipedia.org/wiki/Dimethylglyoxime

This could be used in a basic solution for a pink precipitate, but kind of expensive for nickel.


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## jjohio (Aug 19, 2011)

jjohio said:


> i found some stuff called photographers sodium sulfide...comes in 100 gram bottle, is this what i want to drop silver?..anybody no more places to purchase this stuff


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## Palladium (Aug 19, 2011)

Meow !!!


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## Barren Realms 007 (Aug 19, 2011)

Sounds like you might have found your solution when you melted the first button. I would take a couple of ounces out of the same barrel and melt them up and then run them in nitric and see what happens. I would do this after a good wash with water to remove any residues of the old chemical. I feel that washing the old chemical out will be your biggest problem. If it turns out that is all you need to do and then melt it I would build a large vacume filter or build a series of them to put the residues in and wash the old chemicals out. Here is the $64,000 question, how will you dispose of the old chemicals?

Congrats on the possible great find.

You know what you are doing, don't second guess your decisions.

How about some pictures? Especialy if it turns out to be all silver a picture with all of the bars melted would be awsome.


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## Juan Manuel Arcos Frank (Aug 21, 2011)

Palladium:

BINGO!!!!!!...all sludge stuff is a mixure of sulphides,among them,silver sulphide so test the liquid wiht a copper wire,if it does not turn grey/silver in 5 seconds it means that there is no silver in solution,so all silver is in the mud(as silver sulphide).

To process the mud let it dry and melt it with potassium nitrate(ratio 3:1 of potassium nitrate:silver sulphide).Take 100 gr of dry silver sulphide,300 gr of saltpetre,mix them well and follow my process for converting silver sulphide to metallic silver,you will get a nice button of silver,weight it and you will know how much silver you have in your black mud.

Palladium,be ready for cooling many bottles of champagne.

Kindest regards.

Manuel


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## Palladium (Aug 21, 2011)

Thanks again friend. I will still have that drink though. After all it is my Birthday. :twisted:


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## qst42know (Aug 21, 2011)

Well, Happy birthday then. 8)


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## Juan Manuel Arcos Frank (Aug 21, 2011)

Happy Birthday,Palladium!!!! 

I am sure you will find another silver urban mine pretty soon.

Congratulations!!!!!

Manuel


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## Juan Manuel Arcos Frank (Aug 21, 2011)

If a process does not work for me it does not mean that the process is unuseful,probably I did something wrong,besides,I am an old dog that has no willingness to learn new tricks so I am posting all the information I have about NaOH process for fixers.

Please,keep us posted about your progress.

Kindest regards.

Manuel


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## markbooth (Aug 26, 2011)

Hello,
I am new to recovery/refining of metals. I have another member here helping me with a fixer solution problem I have encountered. Basically I have 700 gallons of spent solution that has set untouched since 1972. I have separated the sludge from the brown liquid. I have the sludge and have safely stored the barrels and liquid.There was a considerable amount of sludge in each barrel. Most barrels contained sludge that was extremely silvery, it looked basically like silver fingernail polish. Some barrels contained a mostly black sludge. All the barrels have the reddish brown solution in them and have formed crystals on the walls(some more than others). I am currently debating a fire assay or a spectral analysis. While I decide, I have done a few experiments on small samples. I tried drying the silver sludge and using the karo syrup method. It produced silver, but was only in minute amounts. I add sodium sulfide to to the brown liquid and it turned black like ink but had no precipitant. I added sodium sulphide to the silvery sludge and it turned greenish brown and gave off chlorine smell. All this was done outside and in extremely small batches. I have tried adding copper to brown solution, it had no effect. I put a clean copper wire in the brown solution and the silvery sludge, it did not plate either, but I just read that ph level affects this and I will determine it and adjust accordingly. What others that are helping, and I think, is the metals in the solution precipitated themselves due to the fact they were sitting so long exposed to the elements.(almost 40 years) If that is the case, then I cannot find any research dealing with this particular problem. I know that the fire assay will(should) tell me how much silver is there, but I am wondering if a complete analysis would be more prudent and possibly help in determining what method is best economically and efficiently. There is a member that mentioned sodium sulphide turning the liquid black and I have messaged him on the subject.
Again, I am on a fact finding mission and if I do anything wrong or dangerous I hope someone (and I know they will) will step up and say STOP! The quest for knowledge and the journey getting there is what I enjoy. To be successful in recovering the silver the safest best way possible is my goal. The money from the silver, if there is any, is just a wonderful bonus that allows me to devote more time and energy to learning. I will post pics of the various solutions and sludges, so others may give their advice. Thanks in advance for all your help.and to the ones that have been helping already. 

P.S. there have been previous posts on this exact material. For reasons I'd rather not go into and have no bearing on the outcome, some of these posts have been removed, by their author, with good reason. Suffice it to say that all previous and future help from him or any other member of the forum is appreciated. I have read Hoke's book, and have copies of Lazersteve's videos and GSP's also. It's a lot of info and I am still sorting through it and trying to understand it all. In regards to previous posts on this subject, I am the one that encountered the lady who had it originally, it took about a month of talks and getting to know her before she would tell me all the story and the location of the barrels. She was generous in her price for the product ,and I believe, genuine in here belief of the value of the product. Whether that belief is true or false has no bearing on her good intentions or on the value of the knowledge and friends I have gained on this quest. As I said, I will post pics and what knowledge I have about the subject hopefully in the next few days. Until then, Thanks
Sincerely,
Mark Booth


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## Juan Manuel Arcos Frank (Aug 26, 2011)

Mark:

Iron reduces silver compounds...if an iron slab is dipped on the spent fixer then a silver mud is formed,besides,if barrel is iron maden then the same reaction takes place on the barrel´s walls.

The silver should be somewhere...

1.-If it is in the liquid then the copper wire gets silvered.
2.-If it is in the mud then melting it with saltpeter or nitric acid process will lead you to metallic silver.
3.-If silver is in the barrel´s walls then treat the crust with saltpeter or nitric acid process
4.-None of above,finally we have found the silver: silver has taken away by the seller,the silver is in her/his pockets and sold you a worthless material,try to find a refund.

Please,write me to my e mail because my pm box is not working: [email protected]

Regards.

Manuel


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## markbooth (Aug 27, 2011)

Here are the pics I said I would post. I don't know if this helps or not, but I figure a visual couldn't hurt. Thanks


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## Harold_V (Aug 28, 2011)

While I processed a generous amount of silver, it was, primarily, from inquartation, so it was of a known quality. I have no experience with silver from film aside from one large lot that had been harvested from an electrical recovery unit. 

Ok, having said that, I do have a little experience in working with sulfides, and I can't help but wonder if that's what you have. If so, it's possible you could effect a good recovery from the material you showed by melting in a furnace with a borax and soda ash flux, along with some scrap steel, so any sulfides that may be present will yield the silver. It's worth a try. Once everything is molten, allow the material to soak, and monitor the piece of inserted scrap. As silver gives up the sulfur, steel is dissolved. When you see no further dissolution of the added steel, you can expect the conversion to be complete. Remove the piece of steel (I used to use lengths of rebar), and pour the material to a cone mold. If you have silver, it will be at the bottom, with a layer of iron sulfide in the middle, then a layer of slag on top of the sulfide. This is one of the rare cases where you can separate by stratification.

If you have any doubts about the full recovery of silver, try running the sulfide layer once again, using steel. If you find no more silver, you can rely on a given period of time in the furnace to recover the silver. 

Be advised that the flux in question is rather aggressive towards crucibles, so experiment with a small sample before committing to a large lot. 



Harold


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## markbooth (Aug 28, 2011)

Thanks Harold and Manuel. I'll try the re-bar method with a small sample and see. I'm waiting on nitric to do other tests and drying out samples for Harold's suggestion, as we speak. (at least I think they need to be mostly dry) I do not have a cone crucible, but may be able to borrow or make a temporary one for a small sample. If it works at all, I will invest in a proper one. There seems to be many options and possibilities. Before I commit the whole lot of several hundred pounds to one method, I am gonna create a homogenous blend of all sludge's and scrapings from the original barrel walls and send for fire assay. The cost associated with recovering silver from an amount this large can vary widely from process to process. I think it will be prudent to determine possible silver content first. Again, that's my thinking, and I've been wrong enough that I welcome anyone to play the devil's advocate. It'll make me research harder to prove to myself I'm right or wrong. Thanks


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## Harold_V (Aug 29, 2011)

You will never be sorry for having an assay, so you'll understand what you face. The only possible reason I can think of to not combine all the lots is that one or more may be barren. Not suggesting that be the case----but if you have a valueless lot (or more), discarding would be preferred over paying to process the additional weight, all for no gain. You most likely could conduct the minor tests I proposed on each lot to determine the presence of values, or not. 

If you are concerned about making a determination of content, dry and weigh representative samples of each lot before processing by furnace. You can process a small sample (a few ounces) in assay crucibles and a simple furnace made of fire brick, if necessary. You can even use a propane torch, assuming you can retain the heat. A Turbo torch (fed by a large bottle, such as used on a BBQ), should provide enough heat, although only with the aid of a furnace of sorts. All depends on how much effort you care to expend. In any case, be certain to use scrap steel, to liberate any silver that may be bound as a sulfate. 

Note that the cone I spoke of is not a crucible, but a mold. It serves to make separation of the values from the slag very easy. If one is not at your disposal, consider pouring to a piece of angle iron with an end plate welded. Tip the angle so you end up with a three sided button, taking advantage of the corner of the mold. 

Harold


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## clint s (Sep 14, 2011)

hi all I have a similar thing going on, i have hypo solution that was ran through 5 gallon buckets of steel wool it had sat for 15 years or so it is dry and looks like dirt some of it is black and some has red color to it, i dissolved it in 50/50 nitric then turn it to silver cloride then used iron and sulfuric to change it to metallic silver , but what i am finding is that the nitric did not dissolve all the silver .i used heat as well , how i know is i have took the left over sludge i have filtered off, and took my torch and melted it and am get silver out of it still , any ideas way the first time it did not dissolve all the silver ? i have even added more nitric to make sure i got it all on the first time it just wont dissolve it all ,not sure way ? i am going to melt all the left over sludge to see, but shouldn't it dissolve the first time around with nitric and h2o?


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## butcher (Sep 15, 2011)

You have made it harder to get your silver, you may have silver chloride mixed with silver sulfide, nitric will not dissolve these.

If I have silver nitrate and mixed with a sulfide the silver would become a sulfide, the nitric would not dissolve this silver sulfide.

If I had silver nitrate and added a chloride the silver would become a chloride.

There is an order of which acids will take the metal from another acid (I do not know what they call this in chemistry but I have seen this order, it is similar to the reaction series for metals, but I have never seen a reaction series for acids in print)


I believe the only silver you were able to dissolve with your nitric was elemental silver that was converted to metal silver by Iron wool, the method Harold posted above will convert silver sulfide, I would neutralize the nitric and was it first with caustic soda (sodium hydroxide) this may help to convert some of silver chloride if it is in this mix, if you try and melt the silver chloride it will most likely be lost.

Manuel and GSP have made many posts dealing with what you are facing, including on others who have made the same mistake you have made reading them would help better than my advice, they have much, much more experience with this than I do.


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## clint s (Sep 15, 2011)

i think you are right ,there must be sulfides in the mix or chloride i would guess sulfides i am gonna try Harold's advice to heat with furnace first with soda ash borax and iron i had it assayed when i started the assayer said it was 40 % by weight but i am only getting less than 1.5 percent with the nitric and h2o method, i have kept all the sludge i have filtered so i hope i have not lost any silver in the nitrate solution,that i have filtered and drop with hci to silver cloride i kept most of the left over solution but there shouldn't be any values in the solution i hope, i added more hci just to check and no more silver clorides are droping the left over sludge from the one bucket is kinda green the other bucket is tan colored like mustard powder ok lets say we have sulfides is the furnace the best way to convert ? like Harold said .


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## butcher (Sep 15, 2011)

The silver sulfide would need Iron in melt as Harold suggested, but if you had silver chloride in the mix it would be difficult to melt the chloride portion.

Juan Manuel Arcos Frank, just gave some very good advise recently to another member that done something very similar, I believe he was working with xray film.


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