# Siver cell leftover electrolyte



## Gwar (Apr 8, 2022)

I restarted my silver cell and ran about 10ozt of shot through the basket, I am going to have a few jars of electrolyte after I shut it down, is it possible to recover any Ag from the liquid that may have not been processed? What would be the best method to cement it out if possible and do I have to add anything or perform a special procedure to do so ?


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## FrugalRefiner (Apr 8, 2022)

See When In Doubt, Cement It Out.

Dave


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## Gwar (Apr 8, 2022)

Thanks for the informative reply FrugalRefiner, I see that I have some construction to do !


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## Gwar (Apr 8, 2022)

I have a few more ozt to run through, the electrolyte is a few weeks old, I did have a jar with un-contaminated solution that I used to replenish the stock, the crystals are dense and thick but not a lot of growth, my setting are 1.10v, 3.5amp, 4.0watts, the biggest area of success is the middle bottom of the cell..


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## Gwar (Apr 8, 2022)

OMG, FrugalRefiner, that works wonders !!


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## Gwar (Apr 8, 2022)

This is definitely the way to go !


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## FrugalRefiner (Apr 8, 2022)

It's 4metals' design. He deserves the credit.

Dave


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## Gwar (Apr 8, 2022)

Thanks 4metals !


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## kurtak (Apr 9, 2022)

Gwar said:


> , I am going to have a few jars of electrolyte after I shut it down,


First - I have not really been following your process &/or what you have been posting - however I see that orvi & AMS-pro have been helping you so you are getting VERY good advice

However - looking at the picture of your electrolyte (recovered after running your cell) in this post I am seeing "a bit" of a problem (though not a big problem)

Why is the electrolyte so cloudy ? --- it should not be cloudy like that - it "appears" that somewhere in your process a very small amount chloride is getting into your silver nitrate creating a very small amount of silver chloride

As I say - it's not a big problem - *but it should not be happening at all *so we need to figure out when &/or this is happening

So - at what point in your process are you seeing this "cloudy" appear in your other wise "clear" silver nitrate

Kurt


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## Gwar (Apr 9, 2022)

Hello kurtak, thanks for the response, in regard to the cloudy appearance in the electrolyte, the attached picture of the jar was taken when I had to stop the cell and travel for a week, I suctioned off all of the liquid into the jar for future use, usually the electrolyte is clear with a visual rippling inside as it cools, after a few conversations with AmsPro and orvi, I started to use smaller amounts of HNO3 and if it seemed the nitric wasn't all used I added more Ag until a small amount of the bar was left over, however, I am still confused as to the amount of distilled water to add after the process. I will explain my last try, I started with



Pure Silver oztPure Silver GramsNHO3 ml NeededDistilled Water ml385.0585.0585.051.546.65100100131.1100100131.150100131.100
I then added 300ml of distilled water and let cool. I have read that many set up cells by the litre, and that would be fine by me if I did the proper math, I ran out of the shot that I had made from a batch of coins yesterday and based on the advise of FrugalRefiner I used a method by 4metals to extract the remaining Ag from the electrolyte, I was surprised at the amount of cemented mixture that I recovered and was quite frankly confused as to why there is so much (attached photo), I did harvest approx 12ozt of crystals, I have been reading as many threads as I can pertaining to Ag and the procedures used and heed the recommendations by more seasoned members in order to have a better understanding of where I am going wrong and how to address it in future situations, again, many thanks for taking the time to add to the thread, Mike


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## 4metals (Apr 9, 2022)

What is the total volume of your silver cell? From that we can determine how much metal to digest to create a new solution and how much Distilled Water to add to dilute to make an operating solution.


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## orvi (Apr 9, 2022)

Gwar said:


> OMG, FrugalRefiner, that works wonders !!


Stirring of the liquid, in means of aerating or magnetic stirrer, or drill-stirr bit is necessary for achieving quick and complete precipitation. It also hepls to remove the precipitated metal from the surface of copper quickly, helping to form cleaner precipitate with less passivation CuO drop-off (if the redox potential is high = strong AgNO3 solution). I experienced darker precipitates of silver (obviously contamined with Cu+Cu2O+CuO) when the precipitating metal cannot easily fall off the copper surface - I used twisted copper wire. Some precipitate get stuck in between the turns of the coiled wire and when carefully peeled off, dark deposit was found underneath.

With proper stirring of precipitate, and thus whole volume of liquid, it is easy to achieve full precipitation (negative NaCl test) in matter of one hour and even less.


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## Gwar (Apr 9, 2022)

Hello 4metals, The best answer I can offer is that it varies, I have two cell configurations, one is a 64oz jar using a graphite cathode and Ag as a anode, the other is a SS bowl using the Ag cathode, the SS is roughly 7" in diameter and 5" deep, or perhaps I misunderstand the question..


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## Gwar (Apr 9, 2022)

orvi, yes, I have noticed the same type of incident, I usually have to shake or brush the metal off of the Cu.


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## Gwar (Apr 9, 2022)

I also must admit, I have never been a slow-moving individual, I rush everything I do, I think I need to SLOW down and observe, operate and complete one step at a time, in the correct order and precise.


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## orvi (Apr 9, 2022)

Gwar said:


> I also must admit, I have never been a slow-moving individual, I rush everything I do, I think I need to SLOW down and observe, operate and complete one step at a time, in the correct order and precise.


I have similar problem myself, but I learned how to "manage myself" over the years to the acceptable level of "rush" 

Sometimes slight discrepancies that happen in the course of refining push you to the deeper understanding of the subject. I do not mean making some dumb mistakes, but some conceptionally OK things, which happen to proceed bit funky or not as planned. You just need to be dilligent, moderate your "rush" a bit and always want the answer "why ?".

As an example, blackening of the Ag precipitate when cementing on copper. I also didn´t known what is going on. Firstly, I just thought that it is just more finely divided silver, but when the powder fell from the copper surface, I clearly saw blackish colour on the surface. I put the copper out, washed it with water, and wiped the surface with bit of paper towel to obtain that mysterious black powder.
Putting the towel into HCl revealed extremely faint green i doubt my eye only see it because i expect it  but one pour of ammonia into the test sample developed nice blue colour = black stuff contained copper.

So then I learn that stronger Ag solution can passivate copper and thus contamine the Ag cement.

Similarly, cloudy solution of electrolyte is clearly a sign of something which shouldn´t happen. Then comes the hard part - finding what is going on and how to prevent it. From my experience, cloudiness could arise when pH of solution is too high. If this isn´t the case, there is probably some impurity in the solution. Or just anode mud leaking from the basket 

Learning comes in so many different ways, you just cannot consider all at any moment. But you can focus, study, self-test the hypothesis, and this will help you to tune up your procedures and raise the quality of your refined products  and it also apply to anything in the life, not just refining.


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## 4metals (Apr 9, 2022)

orvi said:


> Stirring of the liquid, in means of aerating or magnetic stirrer, or drill-stirr bit is necessary for achieving quick and complete precipitation. It also hepls to remove the precipitated metal from the surface of copper quickly, helping to form cleaner precipitate with less passivation CuO drop-off (if the redox potential is high = strong AgNO3 solution). I experienced darker precipitates of silver (obviously contamined with Cu+Cu2O+CuO) when the precipitating metal cannot easily fall off the copper surface - I used twisted copper wire. Some precipitate get stuck in between the turns of the coiled wire and when carefully peeled off, dark deposit was found underneath.


I always preferred air agitation through a plastic pipe containing the copper. The air dislodges a lot of the Silver and helps keep the Copper clean and exposed for more Silver to drop. Lots of guys use copper pipe which works fine but it can be difficult to clean the copper from the pipe ID. Flattening the copper pipe helps but nothing is as effective as a Copper slab with good circulation past the slab. Generally pieces of the copper used for cementing break off when it gets thin and this results in a lower assay of the Silver cement. Never an issue if you are just collecting Silver from old electrolyte to make new anodes.


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## Gwar (Apr 9, 2022)

Many thanks 4metals !


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## 4metals (Apr 9, 2022)

Gwar said:


> The best answer I can offer is that it varies, I have two cell configurations, one is a 64oz jar using a graphite cathode and Ag as a anode, the other is a SS bowl using the Ag cathode, the SS is roughly 7" in diameter and 5" deep, or perhaps I misunderstand the question..


I like to operate a cell at 60 grams of Silver per liter. To make up your 64 ounce cell assume 64oz x 28 ml/oz = 1792 ml. Let's call it 1.75 liters. 1.75 x 60 = 105 grams of Silver needed in the cell. weigh out the Silver keeping in mind sterling is 7.5% Copper so you will need more sterling to get the Silver content to 60g/l. Add a mix of nitric and distilled water slowly to digest all of the metal but do not add any excess. Then dilute this concentrate with distilled water to 1.75 liters and you will have a good working electrolyte to start with. 

If you were running higher purity Silver the cell would run great with no additional nitric additions as the solution will deposit one silver atom at the cathode and dissolve one at the anode and stay in equilibrium. Unfortunately the copper content of sterling consumes that nitric as the copper requires more nitric to dissolve than silver so the copper levels in solution climb and the silver levels drop. In larger production cells this is overcome by nitric acid additions based on daily titrations to determine the quantity of nitric needed to keep up the Silver concentration as the Copper levels climb. 

To avoid titrations on a simple small cell you can calculate the Copper that dissolves in the cell and add 4.15ml of 70% Nitric Acid to make up for the nitric that was consumed to dissolve every gram of copper. 

The copper can build up to levels equal to the Silver concentration if you keep the acid balanced by constant slow additions and don't exceed 600A/m2 current density without copper contamination of the cathode.


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## Gwar (Apr 9, 2022)

Sounds like a plan, I have the materials to complete this and will start right away in the a.m., many thanks for the detailed instructions, I will make a record of all my movements and share soon, again, Many Thanks !! Mike


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## Gwar (Apr 10, 2022)

I will use these 162 grams recovered from the electrolyte in the new test in the a.m.


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## Gwar (Apr 10, 2022)

4metals, should I use 1ml of HNO3 per gram with an equal amount of distilled for the electrolyte, I will be using the recommended amount of 110 grams to round off, or, should I add very small increments of HNO3 / distilled until there is just a small trace of Ag left ?


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## snoman701 (Apr 10, 2022)

To dissolve your silver yes, then dilute that to around 60 grams of silver per liter of water. Silver cells are pretty forgiving though.


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## kurtak (Apr 10, 2022)

Gwar said:


> 4metals, *should I use 1ml of HNO3 per gram with an equal amount of distilled for the electrolyte*, I will be using the recommended amount of 110 grams to round off, or, should I add very small increments of HNO3 / distilled until there is just a small trace of Ag left ?


Per the bold print - how much acid you use to dissolve a given amount of metal will depend* A LOT* on the conditions involved in dissolving the metal

I have posted about this many times here on the forum because there have been so many times when the question of -"how much acid does it take to dissolve X amount of metal" --- & then someone will answer with - "*it TAKES* X ml of acid to dissolve X grams of metal - or - *You NEED* X ml acid to dissolve X grams metal"

There is no such thing as - it takes - or - you need --- X amount acid to dissolve X amount metal because in fact the amount of metal that can/will dissolve with the acid you are using *will very GREATLY* depending on the conditions you employ when dissolving metal with acid

Though this is a long post - after reading it - you should have a very clear understanding of the role conditions play in dissolving metal with acid & how you can use those conditions to your advantage - the advantage being - using *less acid* to dissolve *more metal*









Dissolving the Copper in Sterling (nitric Qty?)


I'm trying to determine how much nitric I need. I've read that about 2ml will dissolve 1gr of silver. But how much more to account for the copper? For example, if I had enough sterling to yield 10ozt silver, I'd also have about 1ozt copper. According to my calculations I'd need about 660ml to...




goldrefiningforum.com





Kurt


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## Gwar (Apr 10, 2022)

Thanks snoman701, I am making some shot as I type..


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## Gwar (Apr 10, 2022)

Thanks kurtak, I am using technical grade 70% HNO3 and am going to use my harvested crystals, I will back off a bit and see what transpires.


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## kurtak (Apr 10, 2022)

Gwar said:


> Thanks kurtak, I am using technical grade 70% HNO3 and am going to use my harvested crystals, I will back off a bit and see what transpires.


Gwar - I see the link I post to goes to "the short answer"

The "long answer" (in that link) is posted after that short answer - you want to read that "long answer" so scroll down to my next post after the answer the link takes you to

Kurt


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## justinhcase (Apr 10, 2022)

When I have a heavily laded electrolyte I tend to run a refinement by crystallization.
As long as most of the solution Is silver nitrate it will crystallise out of a reduced solution quite easily.
This can then be returned to work in your cell.
The remainder of the liqueur which is high in impurities can be processed for P.G.M and silver.
Saves a little acid.


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## orvi (Apr 10, 2022)

justinhcase said:


> When I have a heavily laded electrolyte I tend to run a refinement by crystallization.
> As long as most of the solution Is silver nitrate it will crystallise out of a reduced solution quite easily.
> This can then be returned to work in your cell.
> The remainder of the liqueur which is high in impurities can be processed for P.G.M and silver.
> Saves a little acid.


Nice lifehack.


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## Gwar (Apr 11, 2022)

UPDATE: I started with 106gms of Ag crystals, I added 50ml each of HNO3 and distilled, after a bit I added another 50ml HNO3 / Distilled my HNO3 wasn't reacting to well at dissolving, so I added 25ml of HNO3/ distilled and had to add exactly 2gms of AG and all action ceased, I was confident that the nitric was used up completely, I filtered the substance through the Buchner funnel after it was cool and added the mixture to a 2 liter bottle with distilled water to about 2/3's full, after setting up the cell and running it for 8-10 hours the liquid is still clear and I have had to add a bit of the cell solution to take into account for evaporation and usage, it seems to be running smooth enough, I was using the following settings on the power source, it seems to work best at crystal growth at the low end of voltage, the basket eventually had a small hole in the holding bag, which I had to replace. I am wondering if I set up the next cell with everything a bit bigger, (Bowl, Electrolyte, etc if my crystal growth will increase in size, on a side question, has anyone ever used a small air tube device on a timer switch to circulate the electrolyte a few times an hour ?


TimeVoltsAmpsWatts3:30 p.m.23.737.34:00 p.m.3.26.1519.54:15 p.m.1.12.282.57:00 p.m.1.111.8829:15 p.m.23.637.2


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