# Silver Mud



## MrCrusher (Dec 25, 2016)

Hi all

I just encountered a new issue let me explain.

I have been doing silver for a little while now and know what to expect from each operation.
I just got some material that someone else melted it was a good price for what it was suppose to be so I got it. I have now processed some of it in nitric and it had a little darker color then sterling but I expected that.

Where the issue is, now that I have reduced it back to silver with salt, sugar and Lye it is like the finest mud you ever saw. When I do this process I normally get nice clumps that are very easy to filter. needless to say this stuff does not filter well. I may be wrong but I think the material had some steel in it and that contamination caused the issue? If I am correct can I just rinse it back to neutral PH and then run it through some hydrochloric acid to remove the steel?

If it may be some other issue I am open for suggestions.
Merry Christmas
Thanx
Mr_Crusher


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## Palladium (Dec 25, 2016)

It may be a contaminate, but i'm guessing it has more to do with the nucleation of the silver crystals.
1. Was the solution you were working with diluted? What i mean is was the silver content low in the materials you were processing.
2. Did you add the naoh first or the sugar?


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## Palladium (Dec 25, 2016)

Per GSP instructions:

For each troy ounce of silver (41.3g of AgCl), it takes 20g of NaOH and 13.3ml of Light Karo syrup along with 135ml of water. Use a 10% excess to ensure conversion!

Here is Juan Manuel's method:

For 500g of scrap silver:

600g of salt (without iodine)
1000g sodium hydroxide (Lye)
600g of sugar
200 ml. of HCl (for rinsing)


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## MrCrusher (Dec 25, 2016)

Palladium,

Thanx for the reply.

You may be on to something there. In an effort to minimize waste waters it was not diluted as much as I normally have it, when I add the salt. I then rinse until clear of any color. I use my Buchner funnel and rinse about 5 times. Each rinse I let draw down until it is just moist and only drips about once per 5 sec.
sometimes I need 6 or 7 rinses. but it is always clear before I move on.

Then I add the lye, until thee is no more white color and it is all black. This may be where I started the issue. I just barely had the nitrate covered with water when I started adding the lye. Then I add the sugar
Most times I dilute the sugar in water first this time I did not. ( again trying to minimize waste waters)

While I may have less waste waters now, I have a product that is very difficult to work with. Do you think this could have been the problem?

If it is, I guess I need to chalk it up to experience  . . not a good one but experience just the same.

Thanx again
Mr_Crusher


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## Palladium (Dec 25, 2016)

Nucleation is basically the initial phase in the progress of either another structure via self-gathering or self-association. Nucleation is commonly considered to be the technique that decides to what extent an observer needs to wait before the new stage or self-sorted out structure shows up. Nucleation in two identical systems can even occur at different times, thus this is a stochastic process. The impurities present in the system might affect the nucleation process; thus making it necessary to differentiate between the homogeneous and heterogeneous nucleation. 

Homogeneous nucleation occurs arbitrarily and impulsively without any special nucleation sites within the interior of uniform substance, whereas heterogeneous nucleation occurs at specific nucleation sites like container surfaces, dislodgments, imperfections, and impurities.

When we are talking about the neculation of crystals or metals from solution many factors can determine the fineness or the coarseness of the formations. Not only do you have the neculation of crystals from solution, but you have a secondary step of the crystals coming together under different forces that form complex structures. The combinations are affected by multiple variables in the equation. Temperature, saturation, and choice of precipitation method just to name a few. The formations are like snow flakes in the fact no two formations are alike in nature. It's an amazing field of study and will explain a lot if you can follow it. Start here with the part titled: Neculation Kinetics and read down. https://books.google.com/books?id=gJ7KNvbMtREC&lpg=PA143&ots=oQ-ZReutIF&dq=van%20der%20waals%20effect%20nucleation&pg=PA143#v=onepage&q=van%20der%20waals%20effect%20nucleation&f=false

It an amazing world to have a view into. It's like looking at the randomness of quantum mechanics but yet knowing it's not really random! Refining is much the same way. You can work it all out on paper and with books, but at the end of the day you are really pretty much flying by the seat of your pants. Experience, education, and the power of observation are your best tools in refining, at least for me! Only you will figure out the answer to your question. Water may or may not be your problem, but water acts as an intermediate in many processes. I've grown nano silver using capping agents before that was fine as black ink and you basically couldn't filter it no matter what. I had to use the wash and decant method instead of the buchner funnel. I add my sugar before the naoh. Seems to give a better reaction to me. Sugar itself is not the reducing agent if your using plain sugar. The sugar is broken down by an excess of naoh in the solution to form glucose and fructuose, glucose is a reducing sugar so the reaction with silver oxide will reduce it to metallic silver. I add my sugar first. Water is your friend!


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## MrCrusher (Dec 26, 2016)

Palladium,

Wow I am such a noob. While you are explaining things I never dreamed of, I find this all so totally amazing I cannot put it down. I will make my best effort to try and understand this Nucleation aspect. As by your explanation I do realize to grasp a basic understanding of this process would be very helpful for many of these processes in refining.

You said you add the sugar first. I thought in your video you did the lye first. ( I will watch that again to be sure I did not miss something ) I know Streetips did the lye first. If you say it works better for you I will try that on my next batch. Since I am lacking much experience in these processes and can only remember seeing it done with the lye first, I thought the order was important.

Also you posted measurement calculation's for the process. I understand those numbers would need adjustment depending on the size of each batch and that they are "basic" guidelines do you measure out the ingredients for each batch? When you add the sugar first do you dilute the sugar in water first or add it raw granulated? What happens to the nitrate when the sugar is added first? Then when you add the naoh do you need to add it slowly like when adding the sugar due to the exothermic reaction. I have had one boil over from adding the sugar too fast. ( I don't do that anymore )

I can not thank you enough for all your words of wisdom. This forum is such a valuable asset to all the beginners in this science. I really appreciate everyone here that has taken the time to respond to my questions. Without everyone's guidance I would hate to think how little I would have progressed so far.

On a side note:
I got my silver cell back up and running and my starting concentration was around 150 grams per liter. The last run it was 100 grams per liter. I have also filled the bowl a little higher to get the anode basket a little deeper into the solution. It has been an amazing difference. It was running at 3.5 volts and 1.8 amps. This time it is 3.5 volts and between 2.9 amps and as high as 3.5 amps. The crystal growth is much much faster. So far in only 3 days I have added over 25 toz to the basket. It took me at least a week to add that much last time. Also my crystal growth is much more dense.

Thanx
Mr_Crusher


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## Palladium (Dec 26, 2016)

Are you doing the conversion in beakers or 2 1/2 gallon or 5 gallon buckets?
How much silver are you converting at one time?

I'm sorry i don't know what video about silver chloride conversion you are referring to. I haven't done any on my youtube channel. I add an excess of water in a 5 gallon bucket and add my sugar to that. I then use a paint stirrer to agitate the solution while i add the naoh. 

When you add naoh first you have a chemical reaction that can get ornery. Then when that chemical reaction is done you add the sugar which means a 2nd reaction takes place to convert the silver oxide to silver metal. You have two reactions that gets ornery. By adding the sugar first with the silver chlorides and water no reaction takes place. Then when you add the naoh and it kicks of the whole process in one step.

Doing silver does generate a lot of waste water that has to be dealt with. I use an atmospheric evaporator to concentrate my solutions back down before waste treatment and disposal. They are cheap and easy to build from common trade day or scrap yard items. Mine cost less than $100 to build.

Are you using shot or bars in your anode basket? I take it your using the bowl design for your silver cell?


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## MrCrusher (Dec 26, 2016)

Palladium,

I am sorry I did get confused about the video. I have watched so many of yours and Sreetips and some others. After looking for it again I realized I had made a mistake.

As far as the volume I do at a time. I use a 2000ml beaker to digest my silver. I then filter and transfer into a 5000ml beaker to convert back to silver. I normally do about 10 toz at a time.

Yes it is a bowl type silver cell. I use shot or cornflake in the anode basket. I just melt my silver and pour slowly into water to make it. I will be looking into the atmospheric evaporator.

If I use the sugar first I would think I need to measure the proper amount so once the naoh is added the reaction can occur properly. I would also think I need to add the naoh slowly to avoid a boil over.

Thanx
Mr_Crusher


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## Slochteren (Dec 31, 2016)

> Doing silver does generate a lot of waste water that has to be dealt with. I use an atmospheric evaporator to concentrate my solutions back down before waste treatment and disposal. They are cheap and easy to build from common trade day or scrap yard items. Mine cost less than $100 to build.



Would be nice to see a video or pictures off this setup, or waste treatment in general.


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## MrCrusher (Dec 31, 2016)

Palladium, Or anyone that wants to chime in  

After your response of doing both reactions at the same time I looked at the numbers you listed. While I have no idea what the sugar content is in 1.3ml of Karo light syrup unless my math is bad these 2 sets of numbers are not even close on the amount of NaOH. Someone want to check my math?

1 statement says:

For each troy ounce of silver (41.3g of AgCl), it takes 20g of NaOH and 13.3ml of Light Karo syrup along with 135ml of water. Use a 10% excess to ensure conversion!

the 2nd formula says:

For 500g of scrap silver:
600g of salt (without iodine)
1000g sodium hydroxide (Lye)
600g of sugar
200 ml. of HCl (for rinsing)

well to make the measurements equal I did this

500 grams of scrap silver = 16.1 ozt (I could not calculate the sugar)

So then per the first statement 20g of NaOH per ounce would be 321.5 grams for 500 grams of silver
the 2nd one would be 1000g of NaOH that is almost 3 times the amount of the first formula.

Nevertheless I took out about 5 ozt of AgCl and tried this process. I will admit I used what I thought was about right ( yes I know not the best method ) either way I did not get a complete reaction. Also I noticed I had no heat produced. 
At this point what I am curious of is you said how you do it but you did not mention the volumes of each ingredient you use.

And yea I would also like to see your evap set-up I have some thoughts for building one using a box with an inlet and a fan for exhausting and some trays to make lots of surface area for the water to evaporate from.

Someone also mentions Lou recommending the sulfuric and nails in a tumbler. I have been searching for days ( I am not good at searching) And have found some things about the process but not much detail. If anyone can point me in the direction to it I would be grateful. As I have a 5ozt mess to fix  

Thanx
Mr_Crusher


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## Topher_osAUrus (Dec 31, 2016)

There are literally hundreds of ways to convert agcl back to metal silver.

Dilute sulfuric and iron (agcl must contact the iron, displacement reaction) [I used about 10-15% H2SO4 and it worked well]

Also, dilute HCl and Zn will work too

Dilute HCl and aluminum will work too (harold used this method, but did not recommend it really, as the aluminum makes it hard to filter)

GSP mentioned in a thread that there was a book or resource he had that listed over 100+ ways to convert AgCl.

I usually do either sulfuric and iron or HCl and zinc. Just because both of the acids are already available in my workspace.


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## FrugalRefiner (Dec 31, 2016)

MrCrusher said:


> Someone also mentions Lou recommending the sulfuric and nails in a tumbler. I have been searching for days ( I am not good at searching) And have found some things about the process but not much detail. If anyone can point me in the direction to it I would be grateful.


I'll try to help you learn to search while finding your answer.

First, go to the advanced search by clicking on the gear shaped icon at the right of the Search box. Not the Google search, but the one above it. 

Look at the second portion named SEARCH QUERY. In the Search for keywords: box type "sulfuric nails" without the quotes. In the Search for author: box type Lou. Hit the enter key and you'll get two results.

You could also search for "sulfuric iron", again with Lou as the author, and you'll get another 30 results.

There are other options in the advanced search, but just using a keyword or two and an author can often provide good results.

Hope that helps you to find the posts as well as improving your search skills.

Dave


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## MrCrusher (Dec 31, 2016)

Dave,

I do those things I just don't use the right "key words" I guess, I never thought of sulfuric nails hehe it does sound funny.

Thanx
Mr_Crusher


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## MrCrusher (Jan 2, 2017)

Ok after all my searches I get the idea on AgCl conversion with the nails and sulfuric acid. however I have a few questions.

When you tumble it won't there be iron in the silver? What would be the preferred method to remove the iron. What is the sulfuric acid doing? When it is done should I rinse like normal? Do I need to rinse my converted AgCl to remove the copper first? ( I would think so ) After all my searches I can not find the answers to these questions. I may have more but I do admit it sounds like a good process.

Thanx
Mr_Crusher


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## Topher_osAUrus (Jan 2, 2017)

MrCrusher said:


> Ok after all my searches I get the idea on AgCl conversion with the nails and sulfuric acid. however I have a few questions.
> 
> When you tumble it won't there be iron in the silver? What would be the preferred method to remove the iron. What is the sulfuric acid doing? When it is done should I rinse like normal? Do I need to rinse my converted AgCl to remove the copper first? ( I would think so ) After all my searches I can not find the answers to these questions. I may have more but I do admit it sounds like a good process.
> 
> ...



Yes, the nails will still be in the silver. You can remove them with a magnet. 
Sulfuric acid is creating a displacement reaction i believe, where the iron is going into solution and the silver is converting back to its metal state. Yes you should rinse the copper first, or it too will be reduced.


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## anachronism (Jan 2, 2017)

Topher

If you use HCl/zinc and use zinc powder would an excess of HCl at the end get rid of any additional zinc powder ?


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## Topher_osAUrus (Jan 2, 2017)

Jon, I have only done it with HCl/zinc once, (dirty AgCl that was caught in filters, containing gold as well from goldfilled dissolutions that ended up stopping the reaction from agcl crust) and had a couple pieces of zinc that werent quite powder and did indeed need a bit more HCl to dissolve.(should've used my mortar and pestle!)

I was worried that it would end up converting the silver back to agcl. In the end, it wound up being a good conversion and the zinc was gobbled up by minimal additions of hcl.

After that, i chose to incinerate to remove the filters and possible HCl residue that i couldn't rinse out, proceeding on to a nitric dissolution, and then ar.

Ended up recovering 2.5 grams of gold and about 37 of silver(that i cemented on copper and melted for my cell.)
This material was strictly from the goldfilled I have processed in the past 6 months or so.

I went this route instead of sulfuric and iron, as i didnt want the sulfuric to make a mess of the filters.

Edit to add:I'm not sure if powder or something with a large surface area would be better, since it's a contact conversion.
I liked the idea of powder, since i needed it to slurry and mix with the filters and what not. (i stirred constantly for quite some time) But, should it be clean agcl, I think a sheet of metal may be more beneficial.

Regards
Toph


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## anachronism (Jan 2, 2017)

Thanks Toph

It's not something I had thought of hence the question. 

Jon


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## aga (Jan 2, 2017)

MrCrusher said:


> Someone want to check my math?


I can try, but i also do not know how much of whichever suger is in Karo syrup.
Isn't that all fructose ?

Here's the spreadsheet i use for working out the 'stoichimetry' which is basically how much of each thing you _theoretically_ need in a reaction to get what you want.

Sometimes you need a large excess of one reagent, sometimes not.
This tool just calculates the minimums required.

View attachment Molecular Weight Calculator.xlsx

The first page is where you stick in the elements and numbers to get the molecular weight of a compound in the Green boxes.

It should be set up for :-
Ag 1
Cl 1
to mean AgCl

The second page is where you put in the molecular weights you looked up or calculated using page 1 and the reaction co-efficients, then calculates how much of each thing you need to make another.

It should say : 2 Ag + 1 Cl2 => 2 AgCl after you download it, with the molecular/atomic weights already set.

The 'determinant' box is where you put the weight of the One thing you either want or have.

E.g. if you want 100g of AgCl, put 100 in the green 'determinant' box under AgCl and it calculates the amounts of the starting materials you need. 

Same if you only have 10g of Silver. Put that in the 'determinant' box under Ag and it will tell you the max AgCl you can end up with. Can only have 1 number in 1 'determinant' box.

The W% box is how concentrated your reagent is, so if you got 20% HCl, put 20 in the W% box under where you put HCl. The box under that tells you the total you will need to have enough.

Ignore the TCA (trichloroacetic acid) and Congo Red pages as they're just works in progress for some organic chemistry things that are still on my TODO list as they are still probably beyond my skill.

Words like 'stoichimetry' tend to put people off Chemistry.

All it means is that if you chuck 1g each of two things in a pot, the results Must weigh 2g (including any gas given off).

E.g. 
Ag + Cl2 => AgCl doesn't work. A Cl atom popped out of existence. 

Chlorine tends to come as Cl2, so 
2 Ag + Cl2 => 2 AgCl does work : no missing or extra bits.

This doesn't mean the reaction will happen at all, but it does tell you if there is enough of each thing to end up with you what you want.

Here's a couple of things i typed up a few years back. 
The 'Balancing Equations' one shows how to work out the 'co-efficients'.

View attachment Balancing Equations.pdf

This one shows what 'moles' and 'molarity' mean, and how/why to use them.

View attachment Moles and Molarity.pdf

Hopefully these will be of help to someone.

Edit: just noticed that that Avogadro's number in the 'Moles and Molarity' document is wrong,
Should be 6.023 x 1023, not 6.022, not that it makes much odds.


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## Topher_osAUrus (Jan 2, 2017)

anachronism said:


> Thanks Toph
> 
> It's not something I had thought of hence the question.
> 
> Jon



Dont mention it, I actually got the idea from one of nicks post, so i am going to extend that gratitude to him.
-thank you nickvc

I wondered if it would have been a better move to finish off the excess zinc with NaOH instead, which would also convert the remaining AgCl to AgO. -that was actually plan B if the excess HCl backfired and turned some of the fresh ag+ back to agcl. But, it worked out swimmingly.


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