# Silver from Litho film fix



## joem (Jul 22, 2010)

hello
does anyone know of a retail chemical to precipitate silver from litho film fix? I tried baking soda, soda ash, aluminum foil, steel wool but it just leaves a lot of rust behind, electroplate but I can't seem to get the current right (SS and carbon, SS and Copper, SS and Aluminum) no effect.
sodium sulfide, sodium borohydride or sodium dithionite are not available to me, so I'm asking about your experience.
thanks
joe


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## Geld Konig (Jul 23, 2010)

Once I used Na2S and silver go to the botton like Ag2S. Let few day to precipitate the silver.Try to heat the solution in becker. After this, I filtrate the solution and take the precipitate -Ag2S - put into a baker and add HNO3 concentrate. You can heat the becker but take care to not overflow the solution. Filtrate the solution and add HCl or NaCl to form AgCl ( a white cloud that will precipitate with the time (let it a overnight to precipitate all AgCl.). Add more NaCl or HCl to know if all AgNO3 (solution) react and in the solution is not any silver.


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## Juan Manuel Arcos Frank (Jul 24, 2010)

Joem:

- "THERE ARE MANY WAYS TO SKIN THE CAT"- (said by The Great Master,GSP)

You can use hypochlorite,NaOH,FeCl3 or oxalic acid processes...just use the search box.

Regards.

Manuel


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## butcher (Jul 24, 2010)

Good place to put in a plug for GSP'S great book on silver, well worth the price for all of that invaluble knowledge he has acummilated, over the years as a proffesional silver refiner, and put into a book. better get one if he still has them.


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## Lino1406 (Jul 25, 2010)

NaOH powder, mix well.
Formalin will augment efficiency somewhat


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## joem (Jul 25, 2010)

All in the name of all that is science
just don't tell my wife about my experiments
I added 1 cup of clorox bleach to two cups of litho silver film fix
here is what happened...

instantly turned brown and an increased in temperature - but a little
I let sit outside for a while and it turned coffee with lots of cream colour
there is about a 1/4 inch of fine brown powder at the bottom.

What's your thoughts on this?
joe


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## Juan Manuel Arcos Frank (Jul 26, 2010)

It could be many things.Since my english is not good enough I understood you wanted to recover silver from litho films...so I was wrong.You can recover silver from litho fix adding sodium sulphide and then refine silver sulphide with a method I have posted here.Also,you can use zinc/sulphuric acid method.You need to know how to measure silver content on your fix and how to refine silver...here are some articles written by me,but,sorry...they are in spanish.I promise to write them in english ASAP.

I hope they help you to recover your silver.

Best regards.

Manuel


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## joem (Oct 28, 2010)

Ok I went back to my original plan of getting silver from Litho film.
Found some Naoh at one location in the city.
Put 1/2 litre of film fix in a jar and added two table spoon size scooped,
stirred until dissolved and it instantly turned black.

Then I found this info on another site, does it have merrit?

"To convert silver chlorides to metallic silver you will need to use dry caustic soda (sodium hydroxide)and dextrose (corn syrup can be used).
Rinse the silver chlorides well with water to remove any residual copper. Place the wet silver chloride sludge in a suitable container 1/3 silver chloride with about 2/3 free board. leave about 4 cm of water on top of the silver chloride. Slowly add the dry sodium hydroxide a scoop at a time, stirring well. The reaction is exothermic as the silver chloride is converted to silver oxide. Some people like to add the dextrose along with the sodium hydroxide as it has a deflocing effect on the silver chloride. The dextrose converts the silver oxide to a metallic form. The dextrose can be added a scoop at a time after the sodium hydroxide has reacted with the silver chlorides. When no more reactions with the sodium hydroxide or dextrose occur the process is complete. The resulting silver is rinsed well, dried and melted. The purity of the silver will be 98% to 99% pure and electrolytic refining should be done for optimum purity. For rough calculations by volume of silver chloride - liters of silver chloride X .30 kilos sodium hydroxide - liters of silver chloride X .15 kilos dextrose"


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## Oz (Oct 28, 2010)

The silver oxide you will get is rather clean using NaOH. I would just wash it with water, dry, and melt. Silver oxide decomposes (turns to silver metal) loosing the oxygen at a bit under 300C. Your molten bars should be as pure as cement silver.


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## rusty (Oct 29, 2010)

Juan Manuel Arcos Frank said:


> It could be many things.Since my english is not good enough I understood you wanted to recover silver from litho films...so I was wrong.You can recover silver from litho fix adding sodium sulphide and then refine silver sulphide with a method I have posted here.Also,you can use zinc/sulphuric acid method.You need to know how to measure silver content on your fix and how to refine silver...here are some articles written by me,but,sorry...they are in spanish.I promise to write them in english ASAP.
> 
> I hope they help you to recover your silver.
> 
> ...



Manuel you may want to touch up on the Bablefish translation then repost the files.


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## goldsilverpro (Oct 29, 2010)

joem said:


> Ok I went back to my original plan of getting silver from Litho film.
> Found some Naoh at one location in the city.
> Put 1/2 litre of film fix in a jar and added two table spoon size scooped,
> stirred until dissolved and it instantly turned black.
> ...



This is fine except you don't have silver chloride to start with. You have a more complicated silver thiosulfate complex and I don't know what the actual reaction products are when the NaOH was added. Chemically, though, I can't see how silver oxide was produced but I could be wrong. Maybe the NaOH broke down the thiosulfate and now you have silver sulfide. Manuel probably knows since he mentioned NaOH in his post above, although I didn't see it in his 3 articles. Whatever, don't add it to any more silver solution until you have proven that you can recover the silver from the 1/2 liter you have already treated. Keep in mind that you don't know if all of the silver is in the black sludge. Some may still be in solution - use Manuel's copper wire technique in his 1st article to check it.


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## goldsilverpro (Oct 29, 2010)

I just searched the internet and got an education.

According to the attachment, sodium hydroxide (NaOH) precipitates silver hydroxide (not silver oxide) sludge from bleach-fix. The guy was able to ppt 96% of the silver by adding NaOH to a pH of 12. I think he says that further additions of NaOH did not improve on the 96% - that seems to be the recovery limit using this method. He also experimented with steel wool and got 99+%. However, separating the silver from the excess steel wool requires a crucible furnace and some know-how. If you don't have these, I would try to do it chemically.

So now you have this voluminous (probably) silver hydroxide sludge. What do you do with it now? No matter what you do, I would think that it would be necessary to first clean the sludge by filtering and rinsing it very well, since the presence of the chemicals in the fixer might (very possibly) cause problems down the line. This may be easier said than done, since most metal hydroxides are notoriously difficult and slow to filter and rinse.

According to this, silver hydroxide will decompose to metal at only 80C (176F), whereas silver oxide decomposes at 200C (392F). After cleaning the sludge, this may be as simple as just heating up a suspension of the sludge in water to a little below boiling. It would surely be worth a try.
http://silversol.net63.net/theory/cstheory.htm

After cleaning the sludge, you could dissolve it in nitric and then either cement the silver with copper or precipitate silver chloride and then reduce it to metal with one of several different methods.

A sugar, such as Karo syrup, would probably reduce the silver hydroxide to silver metal.

Play with it until you get a workable method.


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## joem (Nov 3, 2010)

so now I have about 1/2 an inch of (according to chavalit's paper) silver hydroxide at the bottom of the liquid filled jar. 
How would I go about using corn syrup to reduce to metal (silver oxide)?
And what are the issues with the leftover mix of fix solution and lye?
edit for leftover mix spelling


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## joem (Nov 5, 2010)

so just a bit more information about the fix I'm am trying to recover silver from
two main ingredients
ammonium Thiosulphate
water
lesser equal parts of
Sodium Sulphite
Acetic acid
sodium acetate


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## goldsilverpro (Nov 5, 2010)

joem said:


> so now I have about 1/2 an inch of (according to chavalit's paper) silver hydroxide at the bottom of the liquid filled jar.
> How would I go about using corn syrup to reduce to metal (silver oxide)?
> And what are the issues with the ledtover mix of fix solution and lye?



I was only passing on what I found on the internet. Since I haven't worked with silver hydroxide before, I would assume that Karo syrup would reduce it just as with silver oxide. With silver oxide, it takes about 13.3 ml of Karo syrup to reduce 1 oz of silver. You'll just have to play with it.


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## joem (Nov 5, 2010)

goldsilverpro said:


> joem said:
> 
> 
> > so now I have about 1/2 an inch of (according to chavalit's paper) silver hydroxide at the bottom of the liquid filled jar.
> ...



my question is how do I do that? Do I add an amount of corn syrup to the sludge and stir? Then see what happens.


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## goldsilverpro (Nov 5, 2010)

joem said:


> goldsilverpro said:
> 
> 
> > joem said:
> ...



I would add some water to it and stir it while adding the Karo. Try just a little bit of the sludge and see what happens. When you add the Karo, if it works the same as silver oxide, it will change to a gray, grainy silver, similar in appearance to cemented silver. I don't think it will hurt to have an excess of water or Karo.

To get an idea of how much water to use, when I did silver chloride, besides the NaOH and Karo, I used about 100 ml of water for each ounce of silver.

Like I said, play with it. I'm not sure it will even work.


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## joem (Nov 5, 2010)

thanks gsp
I'll try it this weekend


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## Anonymous (Nov 20, 2010)

joem said:


> hello
> does anyone know of a retail chemical to precipitate silver from litho film fix? I tried baking soda, soda ash, aluminum foil, steel wool but it just leaves a lot of rust behind, electroplate but I can't seem to get the current right (SS and carbon, SS and Copper, SS and Aluminum) no effect.
> sodium sulfide, sodium borohydride or sodium dithionite are not available to me, so I'm asking about your experience.
> thanks
> joe


You can precipitate the silver out with zinc dust; mix it well; let it settle; dry out the mud and fire it. Its easier to get a silver recovery unit from my friend Paul Hess of Rotex Corp. in Ohio. costs a couple of hundred bucks for a small unit and will plate out nice silver. Tell him Shelly from Chgo. referred you.


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## joem (Nov 20, 2010)

thanks precious
does he have a web site?

edit: Is zinc powder the same as zinc oxide powder used for "baby Powders"


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## goldsilverpro (Nov 20, 2010)

joem said:


> thanks precious
> does he have a web site?
> 
> edit: Is zinc powder the same as zinc oxide powder used for "baby Powders"



NO!


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## joem (Nov 20, 2010)

goldsilverpro said:


> joem said:
> 
> 
> > thanks precious
> ...



Alright then. All caps and an exclamation mark. You can't argue with that.
So what is the official name for (I assuming pure zinc) zinc powder so I can test it?


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## joem (Dec 7, 2010)

I now have a metafix silver recovery unit, given to me by a printshop just down the road from me.


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## joem (Dec 12, 2010)

using Naoh I dropped 17 grams of grey powder from 10 liters of litho fix, I just have to melt it to see what happens


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## joem (Apr 2, 2011)

So now I have two metafix silver recovery units. One double unit, which in not working so I will use it for spare parts, and a single working unit. I will run our fix through the system to recover electroplated silver. I'll post pics later.


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## shyknee (Apr 9, 2011)

HI Joem 
Any pictures yet? I am very interested in results good or bad.
And or what in fact is the best recovery method to use, that you have tried with litho fix.


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## joem (Apr 9, 2011)

Not yet I'm still sorting out my boards, clipping fingers, scrapping metals, and gathering people and companies to buy things from. Once my garage is cleared I'll set up the unit with a small pump to circulate the fix through the unit.


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## shyknee (Apr 9, 2011)

thats cool thanks


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## Marcel (Mar 26, 2012)

I have studied this thread but when researching about AgCl and SIlvernitrat I got confused:

1.)


> AgCl quickly darkens on exposure to light by disintegrating *into elemental chlorine and metallic silver*. This reaction is used in photography and film.


source wikipedia on AgCl http://en.wikipedia.org/wiki/Silver_chloride
That would mean, there is nothing but light, that is needed to turn AgCl into elementary Ag!
Adding a chloride "killer" such as Chlorex would help speed up reaction (hopefully not getting to dangerous/explosive!)

2.) The NaOH3 (lye) + corn sirup method to precipitate Ag from AgCl:
This method is described for Silvernitrat (AgNO3), but not for AgCl.
wikipedia on silvernitrat:


> Treatment of silver nitrate with base gives dark grey silver oxide:[5]
> 
> 2 AgNO3 + 2 NaOH → Ag2O + 2 NaNO3 + H2O
> (..)
> ...



Easy destinction - what do I have?
AgNO3 (silvernitrat) is water soluable whereby AgCl(silverchlorid) is mostly not.

Can someone confirm/correct the confusing statements?

Precipation of AgCl vs AGNO3. From my understaning, what is confusing in this thread (also because it remains unclear what material the OP starts with)
- AgCl is not beeing treated with the NaHO3 + corn syrup method to precipitate elemetary silver or silver oxidides.
- Precipitating Ag from AgCl can be enforced by adding temperature and a bleacher, such as Chlorex that is able to remove the chlorides.
- AgNO3 (silvernitrat) can be transformed to Ag by heating and adding copper.


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## lazersteve (Mar 26, 2012)

Marcel said:


> Can someone confirm/correct the confusing statements?
> 
> Precipation of AgCl vs AGNO3. From my understaning, what is confusing in this thread (also because it remains unclear what material the OP starts with)
> - AgCl is not beeing treated with the NaHO3 + corn syrup method to precipitate elemetary silver or silver oxides.


The reaction of silver chloride with lye and corn syrup is not a precipitation reaction, it is a conversion of the silver chloride to silver oxide then a reduction of the silver oxide to silver metal. 


Marcel said:


> - Precipitating Ag from AgCl can be enforced by adding temperature and a bleacher, such as Chlorex that is able to remove the chlorides.


Again not precipitation, but conversion takes place via displacement of the silver from the silver chloride. Typically the silver chloride is covered with a dilute (5-10%) solution of muriatic or sulfuric acid and a base metal higher than copper in the activity series chart is added to the beaker. The base metal dissolves into solution displacing the silver from the silver chloride leaving silver metal and a base metal salt in solution. More reactive base metals (zinc and aluminum) work faster than less reactive base metals (iron). 

I have never heard of using bleach in this reaction. 

Silver chloride can be thermally converted to silver metal in the a two step process (1. silver oxide, 2. silver metal) in the presence of and oxygen soruce in the melt. Both steps occur in the same thermal reaction. It's not uncommon for this reaction to produce toxic silver chloride fumes if careful temperature control is not maintained.


Marcel said:


> - AgNO3 (silvernitrat) can be transformed to Ag by heating and adding copper.


The first reaction is simple decomposition with heat (silver nitrate starts decomposing at 444C according to wiki). The second one is a simple displacement reaction based upon the solubility of silver nitrate and copper nitrates solubility. A little free nitric is required to get the reaction started. The metallic copper dissolves in the solution to copper nitrate and the silver is displaced as a fine gray powder. 

Steve


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## shobhit (Nov 19, 2014)

Hi all,
i want to start silver extraction from Litho films but i don't have much idea about how to do so, what equipment i need etc.
I currently have small amount (in KG's) at my disposal hence want to know a cost effective and basic method for extraction.

I am from India and there are no people to get help from as its a topic lesser known here.

Kindly help me in this.

Thanks & Regards
Shobhit
[email protected]
+91 9953986247


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## Juan Manuel Arcos Frank (Nov 20, 2014)

Shobhit:

INDEED!!!!!!!!!...you have come to the right place.

This topic has been discussed many times.I suggest you to write "Litho films" in the search box and you will have many information about NaOH,ferric chloride,oxalic acid and sodium hypochlorite processes.

Come on,Shobhit,do your homework.We are here to help you.

Kindest regards.

Manuel


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## rickbb (Nov 24, 2014)

shobhit said:


> Hi all,
> i want to start silver extraction from Litho films but i don't have much idea about how to do so, what equipment i need etc.
> I currently have small amount (in KG's) at my disposal hence want to know a cost effective and basic method for extraction.
> 
> ...



See the response to your other post in the other section. 

PS. posting the same question in different places is bad form.

*The other posting has been deleted. Please don't double post. *


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