# Recycle your used Acid Peroxide.



## Anonymous

Having several gallons of used AP setting around, I experminted several ways to drop the copper out of the used solution.

I tried, as several members said to just put iron in the solution and it will drop. That worked fine but seemed to take forever.

I then had the idea of making a copper cell. I used 2 pieces of iron in an 2000ml flask, connedted 12vdc and the copper just started dropping. (Beware, it takes about 25 amps to runs it). The solution started heating up and I would have to wait until it cooled to start again.

Then idea, filled a tub with cold water and set the cell in the tub. In an hour, all the copper dropped out and I had a nice emerald green acid solution, ready to use again.

Out of 3 1800ml beakers tested, I dropped out 200ml worth of copper in the bottom. That was in each beaker.

The figures show me that 11% of your saturated solution is copper.

I recycled 1 1/2 gallons today and it works good in the bubbler.

Ideas?


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## Shecker

Something to consider would be to use a stainless steel anode and a copper (or stainless steel) cathode and then you have a copper electrowinning cell which can be run at 6 volts DC. This will work in both a hydrochloric acid environment as CuCl and a sulfuric acid environment as CuSO4. This should a layer of metallic copper that is easy to remove and collected.

Randy in Gunnison


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## OMG

Did your iron anode (+) degrade? I would think that your solution changed from a (mostly) copper chloride solution to a (mostly) iron chloride solution...
I guess that would be the same effect as cementing it out with iron, just faster. Did you get much hydrogen coming off the cathode? if so, did it look like it was being absorbed by the copper chloride solution?
When I was messing around with electrolysis similar to that I found if I put in a sprinkling of smb the copper came out very quickly. I believe the SO2 converts the CuCl2 to CuCl and regenerates some of the HCl as well as creating some sulfuric acid. I'm not sure if that would mess up the future AP reaction but you could try it on a small amount to see if it helps.
When I was doing it I was trying to precipitate all the copper without introducing any new metals and regenerate the acid at the same time, but I never found a good way to do it. I even tried a titanium anode, and it just got dissolved. I never got to try a platinum anode, but until I have a proper power supply my electrolysis experiments are on hold - its just too slow for the stuff I want to do.


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## Anonymous

I did not see any de-grading of the anode. It is just as smooth as when I started using it. I don't know about the iron cloride solution, I just know it drops copper and I can re-use the AP.


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## Anonymous

Hey OMG, the anode is starting to deteriate. Just thought I would tell you.


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## lazersteve

Firewalker,

I've had success using a hard graphite anode and cathode.

Steve


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## Anonymous

I tried with stainless, 316 and 408 they both dissolved at the anode.

I would use sulfuric, and distill off the hcl - to reuse - then run the copper sulfate in your cell with a SS cathode and lead anode that will regenerate your sulfuric to convert more CuCL etc, etc,


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## OMG

Thanks fire walker.
I've used all kinds of graphite. The larger and the harder the better, but they all deteriorated on me way too quick (maybe were effective for 6 hours tops).
I would just stick with what you're doing an dissolve the iron in there.
If I were you I'd add a bit of SO2 (from SMB,etc) which would make the CuCl2 into CuCl (and produce some HCl as well, and also use up some water - making it even stronger).
the reaction is 2CuCl2 + SO2 + 2H2O -> 2CuCl + 2 HCl + H2SO4
Then you would deposit out the copper on the cathode and iron would be going into solution.
Then when you go to do your next batch of AP, when you add peroxide to the mix, it will upgrade the iron(2) chloride to iron(3) chloride (FeCl3). 
Conveniently FeCl3 dissolves copper! Quite quickly too.

side note - if you add a lot of so2, you will notice your mix start to fume and heat up. be careful. It is heating up because of the H2SO4 being created, and the fumes coming off are HCl (+water).

try to keep the voltage on your cell low enough that hydrogen doesn't come off the cathode.


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## butcher

Be very carefull using stainless steel as anode in electrolytic cell, chromium produced can be very hazardous, a poision not easily delt with.


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## Barren Realms 007

Can this process be done before any gold or PM's are removed or will it remove them in the process?


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## firewalker

I have never recycled with pgm in solution, I did this to re-use the acid peroxide solution. Usually with the aomunt of copper in solution, it forces the gold out anyway.


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## Barren Realms 007

Wouldn't the gold be plating on the steel while the copper is falling to the bottom. Or vise versa?
Or would they mix?


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## OMG

both gold and copper would fall to the bottom.
every metal that is stable than iron would cement out


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## Barren Realms 007

Then it would be better to drop out the gold and then run the electro..

Once the copper is removed from solution, why is it not discussed to put it in a pile and electro plate it to some stainless steel. That would take it out of the flaky state it is in and make it a solid piec that could be sold.


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## firewalker

I re-read the string of posts and saw I forgot to mention one of the most inportant steps.

I did test the AP with stannus before I droped the copper out and the test's were negative for gold..

I suspect that the solution being saturated with copper had forced the gold out when I went into the recovery stage prior to recycling.

Cheers......Jack


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## Barren Realms 007

Morning Firewalker,

When you dropped the copper out what did you have to do to the mix to make it active again? did you just have to add some peroxide back in the solution again? 

Did you try to replate the copper that had dropped or did you just leave it the way it was for further use or sale?


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## firewalker

Once the solution became clear jade color, I used it in my bubblers. I did not add any chemicals, but will probley have to add peroxide adventually. The copper is in the bottom of 2 5gal buckets and I have not decided what to do with it yet.

Jack


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## Barren Realms 007

Ok excellent info to have.


How many cycles have you processed the liquid?

Or is this still the 2nd go round for it?


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## firewalker

Right now I am using the second recycle group of AP. Figgured it has saved me at least 6 gallons of Muratic. I know that is not much, but its 6 used gallons not sitting around waiting to be spilled.


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## LeftyTheBandit

I was just wondering if anyone is using this process with success?

Is the Iron Chloride as good as Copper Chloride in stripping copper from electronics?

I noticed Steve mention he used graphite rods, and then I noticed someone said they used graphite rods and they only lasted 6hrs. If I used graphite rods would the AP be usable after or is it just steel that gives you re-usable AP.

I have 10 gal's of AP I would like to re-use and sell all that copper in solution.


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## OMG

With AP its the copper chloride that is doing the dissolving, but iron chloride also dissolves copper so why not just try cementing the used AP with iron powder, then add some HCl and H2O2 to oxidize the iron chloride back up so it can dissolve more copper?
FeCl3 + Cu -> CuCl + FeCl2
FeCl3 + CuCl -> CuCl2 + FeCl2

so you end up with CuCl2 and FeCl2 after your done, then just add iron powder and CuCl2 becomes FeCl2 + Cu (precip)
then FeCl2 + H2O2 + HCl -> FeCl3 + H2O
and you are ready to start dissolving again.

Actually, I'll try it on my batch of AP that's been sitting now for a while and then post my results.


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## Barren Realms 007

I tried this on some Nitric Acid I had used and saturated. It was done in a glass jar soaked in water to keep it cool. I had a nice reaction the whole time. I ran from 6V-12V on my battery charger. It took about 7-8 hrs to complete. I ran it till the copper stopped droppig out of the solution. I put about 3/4 of a cup of it in a glass jar and put some brass items that might have been plated with gold and let it set. Then next day no reaction had taken place other than some clear to white crystals have formed. 

Can this be made active again or have I total screwed the pooch on this solution?


I currently have a batch or AP in a fiberglass pan that is long and I am running it on 12V successfully. The electrdes are about 24" apart. Heat should not effect this figerglass and I see no chemical reaction that it should mess up. It was what we use to use when I worked with the stuff.

I will post how things turn out.


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## flexyman

Hi every one,
Electrowinning Copper out of Chloride leach is economical. One has to use an Inert
Anode and a Metal Cathode. The trick is to never leave the Cathode in the Electrolite
without a Negative charge connected. I make my Inert Anodes as follows.
Take a look At Ishor web page to get the idea, because I do not know how to get a sketch
in this reply (help ). Get an unglazed but fired Terra-cotta pot, fill the pot with Dilute
Lye solution place a Mild steel rod into this solution . Now you have an Inert Anode. Posative electrical connection must be made to Steel rod. The Terra-cotta acts as the ionic membrane to stop introducing unwanted metals into the Chloride leach. Now if I could get the sketch attached we will be in business. Oh! the voltage across the Anode and Cathode should not exceed 1.5 volts otherwise the copper will turn black on the Cathode (collector )
AP " Acid Peroxide " Leach can be made two ways 
(1) Muriatc acid + Hydrogen Peroxide 
(2) Sulfuric acid = Hydrogen Peroxide
Precious metals can be disolved into Hydrochloric acid by attaching "PM" to Posative
DC voltage and Negative dc voltage to metal plate and emersing both into the same
container containing Hydrochloride Electrolite. Ofcourse the anode and cathode must
be connected to a low DC voltage. Voltage is the Electrical Pressure and Current is the
quantity of electrical energy
Have Fun

Have fun


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## Barren Realms 007

Are you sure you are adjusting the volts and not the amps in this equation? 1.5 volts is only like a small D cell battery.

in this info from Ishore you are adjusting the current(amps).

http://ishor.com/model.htm#Electroformer

_*Electroforming is a plating process that requires a very special kind of plating machine; an electroformer. All plating machines, electroformers included, work on the same general principle, they use DC current to cause microscopic plates of metal to adhere to, and build up on, the surface of the piece being plated. The low amperage and highly filtered current of electroformers produce small, evenly distributed plates that adhere much better to each other and the underlying substrate than with standard plating rectifiers. With a standard plating process, the thickness of the plating is relatively thin ( a few microns at most) and strong adhesion and even distribution is not critical. With electroforming, however, the plating is hundreds or thousands of times thicker. If a standard rectifier were used to produce such a thick coating, the coating would not only look very uneven, simply rubbing it would cause the plating to peel off the model. A magnetic stirrer is generally used in conjunction with an electroformer to insure a very smooth, even coating. Click hyperlink for electroforming videos. Electroforming is used to do two very different things: to build up models to compensate for shrinkage or to make hollow jewelry from wax models by building up a heavy metal coating on a wax model. When copying models, it is necessary to compensate for the inevitable shrinkage that occurs in the various stages of the casting process. Electroforming is the only known method of doing this. To make hollow jewelry, the wax is painted with a metallic electrically conductive paint (usually silver paint) and the electroformer creates a metal coating on top of the wax. The wax is then heated and drained, leaving a hollow core. For information on water soluble wax, see Shor Water Soluble Waxes. For an article on the electroforming process see Forming a Niche.*_


Is there a sketch on this? The pot idea sounds interesting. Trying to picture what you are talking about tho. Really need a sketch for this one.

Not sure where on Ishor website you are looking at.

I looked in plating on this but didn't find what you are mentioning. Go to the web page and paste it in your message.

http://ishor.com/Plating.htm


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## firewalker

I'm not a chemist, but all I used was pieces of steel to drop the copper out of the AP. After processing with the steel, the AP looked a pretty clear emerald green. That recycled AP I added to my bubbler for re-use. It takes a while when you are only using a 2000ml beaker, but I am going to upscale for the next time.....Jack


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## Barren Realms 007

Afternoon Firewalker, 

Here is a thread on some nitric I did. But still trying to get it active again. 

http://www.goldrefiningforum.com/phpBB3/viewtopic.php?f=37&t=5007


The batch of AP I did seemed to turn out ok and is starting to work again.


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## flexyman

Hello All, 
I appologize for presuming, but then I presumed this thread was how to recyle your
used Acid Peroxide (A.P.)
I use The books " The Hydrometallurgy of Copper" by William greenwalt first edition
1912 and also "The Electroplaters bible"
Using to High a Voltage in Electroplating burns the Cathdode and also excessive Amperage causes Pacification of solution around the Cathode.
I find the most efficient combination of electricity to Electrowin Copper out of Chloride leach (taking Copper out of A.P. leach) is 1.5 Volts, at 0.33 Amps per 100sq.Cm density
at 50mm plate spacing. This way I remove only the Copper in the A.P., Then fresh A.P.
is ready for re-use.
Simply using Iron to drop out the Copper, Changes the Mixture into HCl+FeCl.
Now when I add Peroxide to this, It will disolve Gold as well as Copper. This is not
A.P. that was origionally used. Introduceing Iron into the equation changes all the chemistry Oops! Alchemy. chemistry is an exacting Science
I purchased the "Simplisity refining System' several years ago . This is where I got 
the Inert Anode that I use . I still have not figured out how to add an attachment
have fun


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## flexyman

View attachment 2
View attachment 1


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## Barren Realms 007

So the teracata clay is porus enough to allow the disolved particals to go thru it and leaves the precious metals. 

That is interesting have you tried this yet?


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## flexyman

Barren Realms007,
Did you ever see the Movie called " Forrest Gump" ? If you did then you will
recall the saying that Forrest` s mother had. In the telling of his story Forrest
often mentioned this saying . It ended with "does "
Tell me, barren realms007 ,Where did I mention Precious metals, in prelude to
your recent question ?

Following is an idea on how to regenerate (recycle ) acid to save some Money
hydrogen Sulphide :- 
If hydrogen sulphide is applied to a copper sulphate solution, the copper precipitated as cupric sulphide and an amount of acid regenerated equal to 
that combined with the Copper.

CuSo4 +H2S == CuS + H2SO4
If the solution is a chloride, a similar reaction takes place.
CuCl2 + H2S == CuS + 2HCl
Ain`t Hydrometallurgy Oops! Alchemy grand ?


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## Barren Realms 007

You are right Flex, you didn't say anything about precious metals, and this thread is on recyceling AP. I was making an assumption with out explainin my thought completely. Sorry.

Let me rephrase that statement.

If you put your used AP in the teracata pot. And the solution is charged the copper ions will pass thru the pot wall but the gold and other PM's that are not disolved in the solution will remain in the pot if any exist.

And yea it was a good movie.


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## goldsilverpro

If it reacts the same as a porous cup, and I think it will, the only thing that will pass through is current and water, unless the porosity is so large that it leaks.


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## Barren Realms 007

Ok so it is possible that the pot is not porus enough to let the copper go thru the pot.

But let me ask this. Is there a diffrence in the structure of the copper if it is taken out of solution by reacting with iron to drop the copper versus having a chunk of copper that you try to electroplate to another piece of copper. If there is then is it possible that with the chunk of copper the atomic structure is smaller and will pass thru the pot since it is not reacting with the iron and the iron atomic structure does not come into play?


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## flexyman

OK Barren,
You have peaked my interest. I am going to try a different aproach because,
by your questions, many others will gain knowledge. There is a famous quotation that
that states the following " The first step to Wisdom is to admit ones Ignorance".


One of the fundimantal differences between Electrolytic refining and Electrolytic 
extraction, lies in the The Anode.
In Electrolytic refining of Copper, the Anode is a slab of Copper alloyed with other matels
including Precious metals. This copper slab is incased in an Anode-bag, to prevent un-
disolved particles from fouling the Copper Sulphate Electrolyte. 
The Anode and Cathode Electrodes are placed , a distance apart,in an Electroplating bath
When an apropriate Direct current Electrical supply is applied to the Electrodes then
Electrical current flows. This Copper Anode goes into solution and is diposited on the
Cathode, all the metals that did not disolve are left inside the Anode bag.
Theoretically no acid is consumed and none generated in Electrolyticrefining,since the acid going into combination with the Copper at the Anode is again released as free acid by its deposition at the Cathode.
When Copper already in acid,the conditions are intirely different. The goal then is, to deposit Copper out of the solution by Electrolysis, while no metal is going into solution
This involves the use of an Anode which will conduct the electricity into the copper
solution, while at the same time the Anode itself remains undesolved. Hence to make the The Anode insoluable, the Anode is incased in a Electrolytic Diaphragm. Diaphragm is a partition between the Anode and Cathode,which permits the passage of electric current but prevents the mixing of the Electrolytes in which the electrodes are immeresed
Have Fun


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## Barren Realms 007

flexyman said:


> OK Barren,
> You have peaked my interest. I am going to try a different aproach because,
> by your questions, many others will gain knowledge. There is a famous quotation that
> that states the following " The first step to Wisdom is to admit ones Ignorance".



I will have to be the first to admit my ignorance on the subjects discussed on this forum. 
But like I have always told my emplyees there are no stupid questions. The only stupid question is the one that you don't ask and it causes a HUGE screw up. 



> One of the fundimantal differences between Electrolytic refining and Electrolytic
> extraction, lies in the The Anode.
> In Electrolytic refining of Copper, the Anode is a slab of Copper alloyed with other matels
> including Precious metals. This copper slab is incased in an Anode-bag, to prevent un-
> disolved particles from fouling the Copper Sulphate Electrolyte.
> The Anode and Cathode Electrodes are placed , a distance apart,in an Electroplating bath
> When an apropriate Direct current Electrical supply is applied to the Electrodes then
> Electrical current flows. This Copper Anode goes into solution and is diposited on the
> Cathode, all the metals that did not disolve are left inside the Anode bag.
> Theoretically no acid is consumed and none generated in Electrolyticrefining,since the acid going into combination with the Copper at the Anode is again released as free acid by its deposition at the Cathode.



In this process are we not already dealing with Copper Sulphate which is already an impregnated solution? Therfor can I assume that during this process that the copper anode is disolved but we can not say that 100 % of the copper from that Anode is deposited on the cathode because the flow of voltage throught the solution will charge the exisiting copper in solution and there is an equaling out of the material that gets deposited on the Cathode to keep the solution impregnated. 

And I agree about the impurities being left in the Anode bag. I have herd of pantyhose being used for this in certain applications.

"The flow of current for this process" actually I think it is the flow of Voltage that is creating this process This would be the 6V to 12V application that is applied to the process.Remeber opposites attract that is why we have + and - for the flow of electricity. Current is actually the measure in AMPS, or the load you are putting on the application, the amount of power you are useing to complete the process. individuals think that electricity flows thru wire but it dosen't, it flows on the outside surface area of wire. This is the reasone that a cable with a lot of little wires in it will handle a load more efficently that a cable with just one wire it is because the load is being spread out over the surface area.



> When Copper already in acid,the conditions are intirely different. The goal then is, to deposit Copper out of the solution by Electrolysis, while no metal is going into solution



Both solutions can be impregnated at the start of their processes, in this one we are trying to remove the copper disolved in solution by the reaction of an iron atom that copper reacts with to bring it out of solution or another like metal and in the previous we are not concerned about the soultion staying impregnated with copper?



> This involves the use of an Anode which will conduct the electricity into the copper
> solution, while at the same time the Anode itself remains undesolved. Hence to make the The Anode insoluable, the Anode is incased in a Electrolytic Diaphragm. Diaphragm is a partition between the Anode and Cathode,which permits the passage of electric current but prevents the mixing of the Electrolytes in which the electrodes are immeresed
> Have Fun




In the process that is in discussion now I think that the Anode will have to disolve to a certain extent for the reaction of the iron with the copper to complete the reaction. In the case of the teracata pot if i'm correct most of the ones if not all of them that are not glazed will have soak thru to some extent, therfore there is some transfer of fluid along with the transfer of copper.

Now unless you are totally relying on the transfer of + to - ions to complete the reaction and not a reaction between the Anode and the copper I think that is possible as well in this application but I thiink you will still have some depleation of the Anode, such as useing a solid copper anode that will give off more voltage because of a large surface area and charging more of the copper in solution to attach to the Cathode than is being give up by the Anode. You can also have a depleation of the Cathode under certain conditions with this process. Maybe not with AP but with nitric I had the Cathode disolve as well.

If you use a cell that only the voltage can pass thru and not the copper ions that have reacted with the iron Anode then you are defeating the purpose of this type of cell aren't we? Because in doing this we still have the copper mixed with the PM's.

This type of membrane would work fine in a battery in which it take the 2 types of electrolytes to cause an electrical reaction without the electrolytes mixing. In our objective are we really concerned about the elctrolyte mixing? We are dealing with one electrolyte and we are just trying to clean it up. not all of the reacted copper with adhere to the Cathode some will settle to the bottom of the canister along with PM's that were in solution, we are trying to keep these apart.


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## Platdigger

Flow is current= amperage

Voltage is potential, or as Flex says, pressure.

The "trick here being a low voltage (pressure), and a reletivly high amperage (flow).

Also, Barren, I don't think it would mater that much if the anode in Flexymans cell was
Iron, stainless or even carbon.
The point being it is an "inert anode" that he is going for.
Randy


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## Barren Realms 007

I explained it wrong I guess.

Ohm's Law defines the relationships between (P) power, (E) voltage, (I) current, and (R) resistance. One ohm is the resistance value through which one volt will maintain a current of one ampere. 

( I ) Current is what flows on a wire or conductor like water flowing down a river. Current flows from negative to positive on the surface of a conductor. Current is measured in (A) amperes or amps. 

( E ) Voltage is the difference in electrical potential between two points in a circuit. It's the push or pressure behind current flow through a circuit, and is measured in (V) volts. 

( R ) Resistance determines how much current will flow through a component. Resistors are used to control voltage and current levels. A very high resistance allows a small amount of current to flow. A very low resistance allows a large amount of current to flow. Resistance is measured in ohms. 

( P ) Power is the amount of current times the voltage level at a given point measured in wattage or watts.


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## flexyman

Thank you for those who partisipated in this thread so far, But things seem to be going Bass Ackwards and I an reminded of a quotation my literature teach at high school used to use "Casting Pearls to the swine "
Soon there will be definative answers to the Big Bang Theory, not to mention new
definitions for Watts, Volts, Amps, Resistance, let alone Capacitance, Inductance ,
and Power Factor.
So I bow out to the "wisdom" of majority Voice. 
The Topic of this thread still is " Recycle your used Acid Peroxide" which has not been resolved


Ain`t Hydrometallurgy grand


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## Barren Realms 007

Flex it has not been resolved but this little part of the equation is needed to get the full understanding of the process. There is a point that the reprocessing of the AP can go to far and this has variables in the equation.


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## Platdigger

Flex, have you used this cell to reclaim AP?

To recover copper?


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## glorycloud

Flex, your inference to those who are trying to help you as "swine" is fairly offensive.
Perhaps you could find a different proverb or word of wisdom that might actually
encourage someone to answer your question.

"A kind word turns away wrath."


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## flexyman

Hi Platdigger,
Yes I Extract the copper out of the Acid peroxide with the insolube Anode, replenish
the distilled water,that was lost to evaporation. I then add hydrogen peroxide to
rejuvinate the (A.P. ) leach. I filter the Electrolyte thru a poplyprop bag , to remove
any suspended solids in order to stop the treeing effect. I get very pure Cathode Copper.
I try to have as little acid as possible standing around in containers, I also find I 
am saving money, by not having to continually keep buying HCl.
I have also found that I can use a Carbon Rod ,as an insoluable Anode,only in Chloride Electrolite , to get the same result. I use the recovered cathode Copper to Precipitate
Silver out of Nitrate solutions. I also Electrowin Copper out of the Nitrate Solution but
only with the membragn covered Anode. In all cases careful note is taken of Voltage and
current.
Google COPPER OXYCHLORIDE you will discover the potential ecological dangers of Copper Chloride solutions. So I feel that all should realize the Hazards of willy nilly
mixing of Chemicals.
I am of the Old School, My motto is "Look and Learn"
It is possible to selectively Electrowin different metals out of the same Pregnant Electrolite, If the E.M.F. of each Metal is observed. By using a constant reference point
such as using the same type of Acid in each seperate test one can discover the E.M.F. for each given metal.By building a electrical battery using the different metals.
By placing Copper Electrode and a carbone electrode in HCL at a given distance apart then measuring the voltage ,this will give the voltage generated by the desolving copper.
Now you only have the supply a voltage a little greater to reverse the disolution effect.Each different metal tested this way will produce a specific E.M.F. for itself 

Have fun


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## Barren Realms 007

Flex would you mind sharing your dats on this?

What kind of material are you using for the bag?


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## flexyman

glory,
I am the one that should be offended .
I was trying to contribute factual information,but was confronted by continued stubornly made rash assumption and references. 
I can prove all my statements repeatedly in any accredited Scientific Laboratory, of your choosing and at your expence.Or any University for that matter
Once again A proverb comes to mind " Throwing the baby out with the washwater".
" There are none so blind, as those who wish not to see" Also Do you comprehend
what was discussed on this thread. Or did some one succumb to selective reading,
or was it selective hearing. Oh! another one " If ignorence is bliss, then it would be folly to be wise".
Half baked Chemists are the reason ,responsable Alchemy Hobbyists have to pay
exhaubitant price at the Chemical supply stores, because of Liability Insurance.
One example ;- I was quoted $399.00 for a 5 pound pale of 99% pure Copper Sulphate
in California and I purchased the exact same chemical from a Feed store in Michigan
for $13.99 and S&h $19.00.
Ah! that was a relief now that I have vented, But I am still annoyed


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## Barren Realms 007

Flex I guess that is aimed at me since I have been asking the questions to find out the perticulars as to how this process works. If something has been said to offend you it was not ment to do that, maybe you are not opening your mind to other options of the process. There is a give and take here on the forum to find out information. Maybe there is someone that has more experience in a certain part of this process will you listen to them or act as you are now?


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## flexyman

Hi Barren,
This is my point, I find persons not reading the information that are written. Just skip over the the words, then Make assumptions. please do not take this personaly Barren Realms007 ,even though you say you ask questions, you do not, you make assumptions
and also some times you quote things that you heard from some one else. What I expect from some one that wishes to learn, you should stick to the subject matter. First I make a statement, You read it , then you go into your Laboratory put together the ingredients and test it. Did you not follow the sketch I made? 
In your next post you were sprouting off about Power, amps ,Current ,volts, resistance
Then multistranded wire and copper tubes, which had nothing to do with what I said.
I am annoyed at the assumption Glorycloud aired in his post, regarding the quotation of " casting pearls to the swine " If fact it means " giving Pearls of wisdom to those that do not need it".
Me ,Myself and I, make it a habit to always ask advice from some one that is knowledge able in a particular subject. Ok you do not know if I am knowledgeable in this field, But at least do the effort to prove me wrong. Oh! You did not need to use Electricity to
remove the Copper out of the Nitric Acid . If you just desolve Iron in the acid it goes 
into Acid and the copper will precipitate out of the acid. All the electricity was , was to act as a electric heater,to boil the acid
" For every action there is an opposite equal re-action"
My Mommy says I am so clever, that I am bordering on Genious. Ha! Ha!


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## flexyman

Hi again Barren,
You did ask where to get the Anode Bags. Just Google " Anode Bags"
I get my Polyproperlyne bags from < www.BakerBags.com >


Have fun


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## Barren Realms 007

Hi Flex.

I will admit that I do jump to conclusions sometimes. Sorry if I did that to you it was not ment to happen. I guess that is becausse I work out of my head and keeps 2 steps ahead of wat is happening and try to look at all angles and possabilities. Sorry for that.

If I quoted some one it was not done on purpose, other than the Ishore statement and the Ohm's law I posted( I have to deal with this every day because I am an electrician). If it leads someone in the wrong direction it is not ment to.

I haven't tried your drawing yet but I plan to. I had already finished 12 gals of solution when you had posted the pick. And you did a good job of it too.  In my next reclaim I will try it for sure. I was asking about the pm's in solution because the copper I had dropped had some gold in it, maybe that little bit is not worth getting out but I try for every speck I can.

Thanks for the tip on the Nitric, that tells me I screwed up my batch that I reclaimed the copper out of.

If there are no bad feelings I would like to still pick your brain on this subject!!

I am not sure what type of battery charger you are using, the one I am useing is an old dayton with 6v and 12v charging capabilities it has a slow fast and boost for both voltage settings, which means I have 6 voltage settings. You stated that you were running on a 12v charger. Is the voltage selector adjustable like a reostat? Or is it just a hi and low setting? Also when you are taking your voltage readings are you reading the voltage from touching the Anode and Cathode with you leads on your meter or are you taking the reading from the solution?


More qestions to follow if you don't mind!


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## Barren Realms 007

flexyman said:


> Hi again Barren,
> You did ask where to get the Anode Bags. Just Google " Anode Bags"
> I get my Polyproperlyne bags from < http://www.BakerBags.com >
> 
> 
> Have fun



Polyproperlyne was what was used in some plate filters I have delt with to filter acids. should have used my head on that one but it was 15 yrs ago.

Thanks a bunch for that help.


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## Heaven's Pavement

In wanting to learn this process (recycling Acid Peroxide), the files that flexyman posted have been removed, if this is something that can be shared can we repost or send to me?

Anyone using this process?
what did you do, what are you using?

Trying to expand my brain,
Bill


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## lazersteve

Bill,

This a great chance for you to test out my new search page:

New Forum Search

Enter :

rejuvenate acid peroxide

in the terms box

and 

select 'Post that contain all of the terms" from the drop down list.

Finally click the 'Search' button and enjoy!

If you didn't notice, I'm kind of pushing this feature to forum members so that they can easily find their own answers to questions that have already been asked. :wink: 

Steve


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## Heaven's Pavement

Thank you Steve for the responce.
Do not mind using the search feature at all. 
As a matter of fact going through a search of recycle (as AP is not allowed), several hours of reading, going off some interesting trails ; )
So I am trying... that term did not cross my mind, thank you for the heads up!


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## lazersteve

Bill,

If you are using the forum search you will get those common terms ignored problems. You won't have that problem with the search link I posted. 

You really should check it out, you'll be able to search for any terms no matter how common. 

Click the link above and you will see what I mean.

Steve


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## Heaven's Pavement

Once agian thank you Steve, on it.

Info gather so far some people using Iron to drop copper.... Do not really want to go that path unless there is a way it will not end up in solution.
I want to pull out metals in solution with out adding others for reuse on gold foils type scrap.

Some use some type of graphite (you Steve?). 
If this is the best route, anyone want to volunteer thier source??
Any input welcome.


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## lazersteve

Only add iron when you are preparing the solution for disposal. 

If you want to reuse the solution here's what you need to know:

Reuse AP

and 

AP Reaction

Brown AP

AP Flowchart

Steve


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## Heaven's Pavement

Wow Steve, above and beyond(agian)!
Couple nuggests of info, about adding water, whitish cloud = bad.

Spraying this latest batchwith water got a white cloud momentarly, along with it turns a pretty blue, after agitating it turns emerald green agian.

Where would one get this hard grphite???

thanks once agian.


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## lazersteve

I've got some of the graphite if you need some PM me.

You can also buy it in 10-20 pound lots on ebay.

Steve


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## Heaven's Pavement

Steve, PM sent...


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## lysdexic

This is the closest topic I have found so far on what I've been wondering about. I'll explain the objective the best I can so hopefully it won't be some vague unanswerable question. Long term I plan on taking all of the depopulated circuit boards (solder mask and as much solder as possible removed) and use older CuCl solutions to etch all of the copper from them leaving just the plastic board. Firewalker removed copper from CuCl solution and was able to reuse it (it appears from this thread). What I'm wondering about is when the copper is reduced (? not sure that reduction is the correct term, chemistry class was 39 years ago and mostly forgotten), what happens to the Cl ions? Do they just stay in solution?

If I somewhat grasp this (from Steve's CuCl pdf) (Copper metal) Cu0 + (Cupric ion ?) Cu2+ --> (Produces two Cuprous ions) 2Cu1+

Does this mean that a Copper atom that is missing two electrons is a Cupric ion and one missing one electron is a Cuprous ion? It looks like the equation says that a Cu2+ ion "acquires" an electron from a Cu atom giving us two Cu1+ ions and that is how the Cu metal is "broken down into ions"? ...and that is only looking at what is going on with the Copper. There's more that is required to allow this reaction to take place (sorry I'm not asking to be spoon fed, I'm just not sure if I actually remember any of this or if I'm just getting senile), there needs to be a - ion in the equation and a "medium"(?) for the reaction to take place in, so the - ion...

Cu2+Cl-12 + Cu0 --> 2Cu+1Cl-1 
...the Cu being a solid and the rest being in aquas solution... (cup_ric_ must mean +2 cup_rous_ must mean +1, Chlor_ide_ -1... isn't one called an anion and one called a cation?)...

2HCl + 2CuCl + O --> 2CuCl2 + H2O

I don't understand how the Oxygen converts the CuCl to CuCl2, but I know it does... and the Cl comes from the HCl, the (2)H and the O form H2O ...anyway that is what I suspect all that means inside that little pea sized brain of mine... at some point all of the Cl must be used up and the solution can be revitalized by adding more HCl (yes O is needed and can be provided by bubbling air into solution or adding H2O2. I'm just looking at the Cl part though at the moment. If all the HCl is consumed and I were to remove copper by electrowinning what happens to the solution? The copper has to regain it's electrons from somewhere and that means something loses electrons. Is Cl gas liberated? I don't imagine water gives up it's 2H and reforms HCl liberating O?.

Usually when I think something might be like perpetual motion (CuCl that can be harvested for copper then reused without adding a considerable amount of HCl), the only perpetual motion is me chasing my tail.

(edit - fixed some superscripts)


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## goldsilverpro

> I don't understand how the Oxygen converts the CuCl to CuCl2, but I know it does.



The oxygen, a powerful oxidizer, oxidizes the Cu+1 ion to Cu+2. The Cl ion in both cases is Cl-1. Therefore, to be in balance, they would be CuCl and CuCl2, respectively. 

In other words, it would take one Cl-1 to combine with one Cu+1, but two Cl-1 to combine with one Cu+2. The total electrical charge in each case must equal zero.


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## lysdexic

Thank you GSP, then I am on the right path with the different forms of CuCl (CuCl and CuCl2) and the number of electrons gained or lost. 



goldsilverpro said:


> The oxygen, a powerful oxidizer, oxidizes the Cu+1 ion to Cu+2. The Cl ion in both cases is Cl-1. Therefore, to be in balance, they would be CuCl and CuCl2, respectively.
> 
> In other words, it would take one Cl-1 to combine with one Cu+1, but two Cl-1 to combine with one Cu+2. The total electrical charge in each case must equal zero.



Does that mean that the oxygen that reacts with the CuCl (entering the solution) as it' is bubbled through the solution accepts an electron from a Cu+1 creating a Cu+2 ion and an O-1? or rather it accepts one electron from each of 2 Cu+1 making it O-2... 
2HCl + 2CuCl + O --> 2CuCl2 + H2O
which balances the equation
I think part of what I am missing is 2H+1 + O-2 --> H2O I have H2O stuck in my head as a polar covalent bond and I guess I'm missing a bunch of the "ions and bonding information", so maybe I can focus on looking into that and see if "the light goes on". 

GSP, I do appreciate you taking the time to help me with all of my random questions. I do understand the value of a person's time and I am very grateful you consider my questions worthy of your time.


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## goldsilverpro

https://en.wikipedia.org/wiki/Redox


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## lysdexic

Thank you again GSP. It looks like there is a (again) a lot more reading to do. Each answer brings questions which bring answers which... Right now I have tabs open on a number of things that the wiki page on Redox led to (Redox rang a bell but there wasn't a light that went on until your nudge). The first thing that jumped out at me was:

"Though sufficient for many purposes, these descriptions are not precisely correct. Oxidation and reduction properly refer to a change in oxidation state — the actual transfer of electrons may never occur. Thus, oxidation is better defined as an increase in oxidation state, and reduction as a decrease in oxidation state. In practice, the transfer of electrons will always cause a change in oxidation state, but there are many reactions that are classed as "redox" even though no electron transfer occurs (such as those involving covalent bonds)."

To be honest the thought of H being an ion made me feel a bit queasy. Another area I opened to start learning is electrochemistry. I wouldn't call it a hypothesis, but I'm thinking the the product of using an inert anode and reducing Cu from a CuCl solution is going to yield Cu and Cl (in simplistic theoretical terms). After a bit of study there's plenty here to read. 

Again, thank you!

Doug


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## lysdexic

I am a NOOB! I am NOT a chemist or experienced refiner. What I'm writing is purely speculation in my attempt at understanding this process. There is plenty of factual information on this site... search for it! If you want to follow along and see if someone "grades my homework" fine, maybe we'll learn something. My "homework" however is not to be taken as fact.

Okay... after some further reading I'm thinking Firewalker's Fe electrodes (at least partially) produced a single displacement reaction. 
ClCux + Fe = FeClx + Cu
If the reaction was run to completion it would be a FeCl solution (in the real world nothing is ever as pure as it is on paper) and if the reaction was only partial it would be a contaminated FeCl or CuCl solution (how far the reaction is carried out would determine which one was predominant).

Lazersteve in his experiment with a closed loop CuCl etching/electro rejuvenation tried a saturated CuCl solution and evolved enough Cl gas that he shut the reaction down. I've also read (off site I believe) that Cl gas (edit: removed faulty subscript) is somewhat soluble. I've read that in electrowinng (in this case copper from CuCl solution) the reaction (not sure of the correct term) intensity(?) is determined (in part anyway) by concentration and currant flow through the solution.

My theoretical conclusion is that should I pursue reclaiming of Cu from escrap that using Firewalker's process mentioned here, Cu could be recovered from solution in a more solid state (verses simply dropping as a powder with iron) which would reduce the tendency for the Cu to be oxidized/vaporized when being melted. This could be done with spent solutions as a Cu recovery/waste treatment step but not to rejuvenate CuCl solutions. Electrowinning Cu could possibly rejuvenate CuCl to a degree but fresh HCl would still be required (with oxygen from H2O2 or bubbled air) to keep the CuCl etching solution viable. The electrolyte from electrowinning could be recycled along with "fresher" CuCl leach (solution that was retired from recovering gold) and used to recover Cu from valueless circuit boards.

I'm not looking for a way to get rich. I'm just looking for a complete as possible method of recycling escrap as a hobby. I want the shiny gold and the silver but I want as little waste as possible and as many useful by products as possible. Copper is probably the most plentiful metal component of escrap and therefore the first part of the recovery/waste stream that got my attention (well fumes and hazardous chemicals are actually first along with doing everything safely).

As a useful byproduct of this investigation I have begun to gain an understanding of the chemistry involved in the processes discussed here. It looks like a win no matter where it leads.

Doug


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## butcher

Doug, it is always a win, when we educate ourselves.


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## lysdexic

Thanks butcher... agreed.

Do you mind me asking if you noticed anything amiss with my conclusions?

Doug


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## johnny309

As a matter of fact....I try to get cooper out from AP using electricity and the result were good(minus the fact that the cathode,stainless steel is wearing out ).
The cooper came very pure......but........: you need to dilute your solution of used AP because of ...more concentrated is the solution ,more amps will required .
I have put aside "some" ...gallons....to do some experiments.........because....it is another metal involved......Ni. But...the remaining solution will be combined with H2SO4....and the Sn...is still in the mix(which is an " extra")


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## butcher

Doug, it looks like you are learning and are getting the general Idea, there is some mistakes, but that comes with the learning process. you covered such a wide area, it would be hard for me to comment on all of it.

Electrons of the atoms are transfered, or shared, when elements combined to form compounds, they can form several different types of chemical bonds.

Ionic bonds one atom gives up and electron and the other atom takes this electron the electron is tranfered from one atoms outer shell (of the valence electrons) to the other atoms outer shell in the chemical reaction. 

In covalent bonds the elecron is shared between the two atoms, there is also double covalent bonds, triple covalent bonds, polar and non polar covalent bonding...

The electrons are lost gained or shared, but it is all about the tranfer of these electrons, energy is consumed or released during these chemical reactions, these give us a way to kind of explain what is happening, and also predict what may happen in the chemical reactions.

As far as electrolysis it is in a way, using an external power source, we can separate these bonds, forcing electron movement where it may not naturally occur, separate anions and cations, force oxidation and reduction...

We can also use the electro chemical reaction (movement of electrons) to move electrons through chains of other atoms, like the reaction of two disimilar metals in an acid or base solution (battery), the electro chemical reaction of electrons moving oxidation and reduction, we can force movement of electrons through a chain of copper atoms (wire), producing energy in this wire (heat or light)...

Here I am jumping all over the place, it is simpler for me to stick to one simple point at a time, I can get lost easily if I start thinking about more than one thing at a time. I think my small brain starts running around in circles in my head.


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## lysdexic

Johnny309, It's good to know that electrolysis does work to reclaim Cu. Is the Ni in your solution from the stainless steel anode? I'm just beginning and I already hate Sn. I need it to make testing solution but I'm not going to try and reclaim Tin for that. My plans right now are to use an inert anode (mentioned by flexyman) to reclaim Cu from solutions I plan on reusing and Fe (steel) anode and cathode for solutions that are being retired into the waste stream. I'm not going that route because I think it's the best way, it's just the best way to get the results I'm looking for. Copper simply dropped with Fe is a fine powder that is troublesome to melt. From what I've seen and read copper from electrolysis is in a form better suited for melting. ...thank you.

Butcher, I did chuckle 



butcher said:


> Here I am jumping all over the place, it is simpler for me to stick to one simple point at a time, I can get lost easily if I start thinking about more than one thing at a time. I think my small brain starts running around in circles in my head.



It seems we have something in common, as you mentioned I kind of covered a wide area. I find everything is connected and when I start looking for one answer it leads to more questions and so on. I started here wanting to know if the HCl was recovered as I've read nitric can be in some cases. A simple no would have got me nowhere. I believe that I'm incapable of linear thought. I kind of envy those you can just read Hoke and follow her directions. I need to be able to understand what's happening when I follow those instructions or I get confused.

As for the small brain comment, with all do respect, that's bull...., the only small brains I've seen here were those who made a few scary posts and then were gone. Probably off to hurt themselves, others and or the environment. It seems to me that being smart isn't some simple measurement, everything is a trade off. I've heard people claim they aren't very smart but their common sense and wisdom leaves me in awe. Everyone has strengths and weaknesses, smart people know this and learn to use it to their advantage. Stupid people think they know more than they do and refuse to listen and learn. ...sorry, /end rant

I do remember some about all the things you mentioned (ions, bonding etc). I took High School level Chemistry (Physics, Electronics and 4 years of math), but that was almost 40 years ago and it's very foggy. I do know and understand that anything you (and all members) give is a gift and I'm extremely grateful. I would prefer to be a contributor rather than a consumer, that's not the case at the moment. All of you owe me nothing, I owe all of you everything... maybe if I work hard I can one day give something back. 

Thanks again (to all of you)

Doug


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## butcher

As far as recycling or rejuvenating HCl from a copper chloride solution would be very difficult from a simple electrolytic cell setup.

To setup for this discussion I will use some formulas.

Copper being a fairly un-reactive metal, will not dissolve in a non oxidizing acid like HCl, being placed below hydrogen in the reactivity series of metal.

Cu + HCl --> No Reaction.

Copper metal need to be oxidized (an electron removed) to dissolve in HCl, and to form chloride of copper compound dissolved into solution.

Air, oxygen in water, H2O2 hydrogen peroxide or some other oxidizing agent to oxidize the copper to copper oxide, so the copper oxide can react with the HCl to form copper chlorides dissolved in this water solution.

CuO(s) + 2H+ -->Cu2+(aq) + H2O(l)
CuO + 2HCl --> CuCl2 + H2O
Cu + 2HCl + H2O2 --> CuCl2 + 2H2O

Notice in the reactions above the hydrogen from the acid, the oxygen from the air, H2O2, or from the oxygen of the copper oxide form water in solution.

2H+ + O 2- --> H2O (aq)

HCl, hydrochloric acid, hydrogen and chlorine gas in a chemical redox reaction forms the acid.
H2+ + Cl2- --> 2HCl

Basically the Hydrogen is what makes an acid an acid, and this hydrogen or acid is used up in the reaction, to make the more stable water (although we can have some excess acid in solution depending on our solutions), the hydrogen that forms the chloride acid (hydrochloric acid, HCl) is used, reacting with oxygen or oxides to form water.

When we dissolve the metals in acid or oxidizers we are transferring electrons, like from copper atoms we oxidize (remove an electron from the copper metal atom), The copper is now an ion (Cation), the oxidizer or acid is reduced (gain of electron) to an ion (anion), in this case the Cation Hydrogen (from the acid) and the anion from the oxide or oxygen form the compound of water, the copper forms an Cation with the anion of chloride (reduced acid HCl) to form the compound of copper chloride in this solution of water, the chloric of the acid being reduced to chlorides with the copper as copper chloride salt dissolved in water.

Now when we use electrolysis we can separate the compounds in solution, the compounds of copper chloride can be separated into the anions and Cations in the cell, the Cu+ Cation moves to the cathode compartment, or side of the cell can gain an electron (from our external power source or battery) and plate out as copper metal, this ion being reduced back to metal, as the copper ion gets back the missing electron.
And the chloride anion moves towards the anode where it loses an electron, being oxidized back to elemental chlorine and leaves the solution as gas or can stay in solution (depending on conditions) note it would be harder to keep this solution in the liquid under the conditions most simple cells are run under.

What about the Hydrogen from our original acid that made water? well we can also split this water compound of water in our electrolytic cell , forming hydrogen gas at the anode, and hydroxide at the cathode...
but getting the hydrogen and chlorine gases to form back to HCl acid would not easily work in a simple cell, the conditions these gases form at in the cell may not be under the same conditions of cell operation, capturing of these gases to remake our HCl acid would not be an easy task...

It would take a lot more explanation to give more of an explanation as to why this would not work easily to re-make HCl acid, besides HCl is so common and cheap it would not be worth the trouble, it would be easier to make HCl from sulfuric acid and salt than to try and get it out of copper chloride with electrolysis, at least on a small scale in a homemade electrolytic cell.

Although copper metal is a fairly un-reactive metal, it will oxidize easily with air or oxygen at high heat like when trying to melt it, forming copper oxides which would form a slag of copper oxides, instead of reducing the copper to metal in the melt, for melting copper we need to remove oxygen from the copper and the melting environment, to do this we can use chemistry in our melt, using a reducing flame to heat the environment, use a charcoal fire limiting oxygen in the melt, and or using a carbon source in our flux like flour, charcoal, sugar, sodium carbonate..., to remove oxides or oxygen from the copper and its environment in the chemistry of the melt.

There are other times where we may wish to oxidize the copper in a melt, using an oxygen rich environment or a flux like a nitrate to oxidize the copper into an oxide so it will report into the slag.

Melting metals is a chemical reaction where metals can be oxidized or reduced (again transfer of electrons), (just like other chemical reactions we perform with metals), depending on the metal, and how it reacts with oxygen or other chemicals in the melt, we can change the chemical properties of our melt to get a desired chemical reaction, in the melting environment or with flux or both.

I do not know how well I explained this, or if it will help any with your questions or not.

A few mistake corrected Thanks Dave


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## lysdexic

Butcher, you explained very well. Some I already "kind of" understood some I did not and you connected some dots for me. Thank you. I really didn't expect you to take the time to give me a chemistry lesson but I sure do appreciate it. 

I have no intentions of making heroic efforts to reform HCl. I'll just accept there is no perpetual motion. If I use electrolysis to reduce Cu to metal, then Cl will also be released from solution. I would end up with Cu (solid) Cl (gas) and Water (Plus whatever CuClx that wasn't decomposed). Basically Copper, a dilute CuCl solution and Cl gas is what I'd end up with.



butcher said:


> Although copper metal is a fairly un-reactive metal, it will oxidize easily with air or oxygen at high heat like when trying to melt it, forming copper oxides which would form a slag of copper oxides, instead of reducing the copper to metal in the melt, for melting copper we need to remove oxygen from the copper and the melting environment, to do this we can use chemistry in our melt, using a reducing flame to heat the environment, use a charcoal fire limiting oxygen in the melt, and or using a carbon source in our flux like flour, charcoal, sugar, sodium carbonate..., to remove oxides or oxygen from the copper and its environment in the chemistry of the melt.
> 
> There are other times where we may wish to oxidize the copper in a melt, using an oxygen rich environment or a flux like a nitrate to oxidize the copper into an oxide so it will report into the slag.
> 
> Melting metals is a chemical reaction where metals can be oxidized or reduced (again transfer of electrons), (just like other chemical reactions we perform with metals), depending on the metal, and how it reacts with oxygen or other chemicals in the melt, we can change the chemical properties of our melt to get a desired chemical reaction, in the melting environment or with flux or both.



This caught me totally off guard. I have always seen melting metal as a simple change of state. It should have dawned on me long ago. When iron ore is smelted it is a chemical reaction converting FeO into Fe + O ...wow I can be dense. Fluxing, why, when and what never made sense to me, I just knew it worked, so it should be done. Even here hearing about using nitrates to *oxidize* an undesirable metal it didn't sink in. Anyway... Copper has a tendency to oxidize whether a larger piece or a fine powder? (I've only melted aluminum and zinc alloy ...well a little silver and long ago lead) I've never melted Copper yet ...well once I read that certain Aluminum/Copper alloys were were so brittle they broke like glass, so I melted a couple ounces of aluminum then added close to the same weight of copper and poured it on some sand when it had all melted. After it cooled I picked up the flat "puddle" and dropped it on the concrete... it shattered like glass (sorry for the side track). The scrap yard people told me heavier copper wire is worth more than fine wire because of loss when melting the finer wire. Is there less loss with solid copper than with powder?

There's about 2 acres of charcoal growing in my back yard, and we heat solely with wood, so charcoal would be my fuel of choice for the more heat demanding melts. A covered crucible and a carbon based flux (charcoal) perhaps? 

Still much to learn for me... thanks again

Doug


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## butcher

Fine powder reacts easier, more surface area, kind of similar to when we oxidize a metal with acids to dissolve it, the fine powder is much more reactive in the chemical treatment.


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## johnny309

Ni in AP is the barrier metal between gold plating and the copper circuit...


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## lazersteve

The water soluble starting CuCl2 is dissolved into the fresh solution as it forms. As more copper is dissolved into the solution by the etch the two chlorine atoms are spread across two copper atoms becoming 2CuCl which ultimately saturates the solution as the process repeats and CuCl eventually precipitates as as solid. Adding more HCl dissolves the CuCl as it is soluble in concentrated HCl. If an oxidizer (O2, electrons, etc.) is present, the CuCl2 regenerates and the solution becomes useful again.

The overall reaction is mainly dependent upon the solubility of the active ingredient, CuCl2 and the free HCl in the solution.

1) There should be no sediment forming (insoluble CuCl, tested by adding a few drops of water: Whitish sediment when water added = saturated with CuCl).
2) There should be free HCl in the solution (to keep the CuCl dissolved).
3) There should be a source of oxygen supplied over the course of the reaction (to keep the converting the CuCl back to CuCl2).


Of course, this an overly simplified explanation of the reaction, but it does describe the key points to keeping your solution fresh and ready to consume more copper.

Steve


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## g_axelsson

butcher said:


> Melting metals is a chemical reaction where metals can be oxidized or reduced (again transfer of electrons), (just like other chemical reactions we perform with metals), depending on the metal, and how it reacts with oxygen or other chemicals in the melt, we can change the chemical properties of our melt to get a desired chemical reaction, in the melting environment or with flux or both.


The colored part of the above statement is totally wrong! Melting is a phase transition between a solid and liquid state. The chemical composition is unchanged.

H2O -> H2O

... which side is ice and which is water?

In a melt, just as in a solid or a solution chemical reactions can take place, but melting in it self is NOT a chemical reaction.

Göran, the physicist.


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## butcher

You are correct.
Actually that is true, if we are just talking about the pure metal being melted, and there is nothing for the metal to react chemically with in this melting process.

But in melting many metals this is normally not the case; there is something that will react chemically in the melt.


I understand that simply melting metal is not a chemical reaction.
Melting the metal can cause a chemical reaction with the metal and other components involved in the melt.

Would I be more politically correct if I said something like Melting of metals there is a chemical reaction that can take place, 
where 
Melting metals is a chemical reaction where metals can be oxidized or reduced (again transfer of electrons), (just like other chemical reactions we perform with metals), depending on the metal, and how it reacts with oxygen or other chemicals in the melt, we can change the chemical properties of our melt to get a desired chemical reaction, in the melting environment or with flux or both.

I may not know the best way to say some things.


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## jason_recliner

lysdexic said:


> I find everything is connected and when I start looking for one answer it leads to more questions and so on. I started here wanting to know if the HCl was recovered as I've read nitric can be in some cases. A simple no would have got me nowhere. I believe that I'm incapable of linear thought. I kind of envy those you can just read Hoke and follow her directions. I need to be able to understand what's happening when I follow those instructions or I get confused.


Tell me about it, Doug! What was to be a "basic process" before starting, now has more little branches than a box hedge. So much here to read; it's all interconnected. Fortunately it's also all fascinating when one is in it for love not money. And my edumacation advances just by reading yours...


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## lazersteve

As a simplified acquaintance experiment for learning acid peroxide this is a great post:

Mason Jar AP

Practice the above technique on small batches so that you know what colors and procedure to use before you scale up. Scale up slowly and make note of the changes in your feed stock and how it affects the reaction. A lot of what you will learn from these small reactions carries into the scaled up reactions and helps you to better understand how to deal with pitfalls, when to add more reagents, and how to best harvest your foils. 

Steve


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## johnny309

The AP method is good for fingers....for other types of gold bearing items...try other methods 
The amount of copper to dissolve is ok for fingers in AP...because copper is only 30-40 um thick...but for pins(giving the fact that is a very slow reaction....and ...as I encountered Ag-Pd barrier,instead of the classic Ni...a lot of of work to recover the "extra materials")

P.S: The "GOOD" part of AP....is....for the one's that start now in ....recovering precious gold....is a way to teach them to be patient....(I'll bet that on the first and second try in using AP ....they lose 40% of their gold do to the hurry,filtration....).
After that they learn.


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## lysdexic

butcher said:


> But in melting many metals this is normally not the case; there is something that will react chemically in the melt.



Many many years ago my first experiment in introductory physics we melted moth ball crystals (naphthalene) and then let the liquid cool and solidify. We had to record temperatures and such... as the rest of the class was cleaning up and getting ready to go to their next class my naphthalene was still liquid and well below the supposed "freezing" temperature. When I got my instructor's attention I got a private lesson in super cooling and then he told me to just tap the test tube, which I did and the liquid immediately became solid.

In my first year of electronics our project was to build an AM radio (superheterodyne receiver with 3 intermediate amplifier stages). Once mine was togather and hooked up to an antenna and an audio amplifier I tuned my IF amps (we didn't use any test equipment just trial and error) until I got audio output then tweaked them until I couldn't improve the sound quality any further. When I was about to call the Instructor over I bumped my radio and heard the "bump" from the speaker... so I tapped on the radio and it sounded the same as when you tap on a live microphone. Puzzled I called my Instructor over and showed him. He shook his head and laughed and said it's microphonic he started to explain but it was beyond the scope of the class he realized this so he just said it's a fluke and he's only ever seen it once before.

Both of those experiences gave me a chance to grow but there was I much bigger lesson I gained from those two experiences. Murphy's Law, anything that can go wrong, will go wrong.

In our case here, pure copper in a vacuum raised to the required melting temperature would be a simple state change from solid to liquid. Water or naphthalene change from solid to liquid at more moderate temperatures and water (not sure about naphthalene) is fairly nonreactive with air and whatever contaminants that would likely be present. As you and I both know we don't melt metals in real life in a vacuum or a clean room even. As you mentioned, copper readily oxidizes near it's melting temperature, traces of chlorides, nitrates, etc could be present and cause a reaction (I watched gold powder turn into a purple stain and a yellow stain on a melting dish while a larger portion went to "balloon heaven"). Fluxes are added to cause desirable chemical reactions. (random thought: alloys are just mixtures in the sense that they are not chemically combined).

You may not have said it correctly and I might have responded in like manor but I understood. How about:

When we melt metals chemical reactions will take place to a lessor or greater degree and we need to take steps to minimize or encourage those reactions as suits our needs or goals.


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## lysdexic

lazersteve said:


> The water soluble starting CuCl2 is dissolved into the fresh solution as it forms. As more copper is dissolved into the solution by the etch the two chlorine atoms are spread across two copper atoms becoming 2CuCl which ultimately saturates the solution as the process repeats and CuCl eventually precipitates as as solid. Adding more HCl dissolves the CuCl as it is soluble in concentrated HCl. If an oxidizer (O2, electrons, etc.) is present, the CuCl2 regenerates and the solution becomes useful again.
> 
> The overall reaction is mainly dependent upon the solubility of the active ingredient, CuCl2 and the free HCl in the solution.
> 
> 1) There should be no sediment forming (insoluble CuCl, tested by adding a few drops of water: Whitish sediment when water added = saturated with CuCl).
> 2) There should be free HCl in the solution (to keep the CuCl dissolved).
> 3) There should be a source of oxygen supplied over the course of the reaction (to keep the converting the CuCl back to CuCl2).
> 
> 
> Of course, this an overly simplified explanation of the reaction, but it does describe the key points to keeping your solution fresh and ready to consume more copper.
> 
> Steve



Thank you Steve, I can't really put anything together right at the moment, had a migraine all day. With all the ground work you've done and the willingness of yourself and the other experienced member's to help me (and all the other apprentices and journeymen) I'm (we're) learning. I need to read your pdf again and go over all these posts again before saying any more. I want to be clear with what I do understand and what I'm unsure of so I don't waste the most valuable resource here... all of you guy's time. 

I also read the topic you linked to concerning the mason jar acquaintance experiment and have that tumbling around in my head too right now. Thank you again.

Doug


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## butcher

This kind of reminds me of something, I have done water treatment for boilers for many years, as a boiler man, I never had a chemistry lesson, picked it up in the working environment and leaned it pretty much on my own, most people who done this work didn't really understand chemically what was happening in the tests they performed, but they knew how to do the tests and add chemicals or make adjustments accordingly as needed, we normally had chemical and equipment sales men who were chemist who would also be advisers, one was fairly amazed at my understanding of the chemistry and the process and what was going on chemically with the water, but he would get very mad and argumentative when I called the minerals in water "rock" like calcium magnesium, silicates...

What was funny after working with me for several years he sometimes began calling the minerals in water "rock" also, especially when we would discuss the scale in the boiler. because that is where the minerals came from, and basically what they were, I knew they were minerals and He did too, but the important thing is that we understood each other, with the words we used, and understood the important parts of the communication getting our points across.

Actually I think he learned quite a bit from me (maybe as much as I learned from him) besides using the wrong words to describe the minerals. I have worked as a boiler man for many years, and knew and practiced some of the older chemistry used, some of which the modern chemist may not learn with the more modern chemicals they use today, to do the same thing that we done with things that were not actually considered chemicals, but that when added to the boiler would produce a chemical reaction, understanding these older chemical reactions (which were basically the same chemistry they were using with these modern chemicals), gave me a little advantage on understanding the chemistry going on with these newer chemicals (with names, that were like what shore company uses to keep their chemicals at a high cost,a trade secret, and you can only get it from their company, and the main reactive component of their chemical a trade secret), many of these were common chemicals, or slight modifications to a common chemical like sodium sulfite, basically being sodium sulfite but with names like there company's name followed by BSD 133.

I went to a big lab (a friend there who was a head lab technician for many years) and asked him to help me with some chemistry questions, he was astonished by some of the questions I had, but he said he could not answer them, he said he took many years of college chemistry, but forgot most of it, I asked him how can he still do all of the chemistry he does, and all of these very important tests, He said that they just add the chemicals to the machines,and perform tests, read and record results, they do not have to understand all of the reactions chemically, or what chemicals are used (again many with company trade names), or what the machines are doing or how the chemicals are reacting, they just had to know what to add when, and what buttons to push and know how to read the results and record them.

It is kind of like that with recovery and refining, you wouldn't need to understand all of the goings on chemically, you could just learn to push the right buttons, but I have always wanted to understand more (and believe it is helpful to do so), I want to find out what happens when that button is pushed, and why it happens the way it does.

Try not to get to upset because I call minerals rock.


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## lysdexic

The difference between smart and educated often is knowing a "thingy's" proper nomenclature. Obviously someone who is well educated in a field that demands comprehension of theory, concepts and processes beyond the grasp of most people has to be intelligent. I've found however that being educated doesn't always mean a person is smart and smart people aren't always formally educated.

I have to "translate" everything I say here because of the way I understand things (people wouldn't understand me if I called minerals rocks). I think in pictures and have never got a straight answer from anyone when I ask how their thought process works, so I still don't know if that's how everyone thinks. I often assign personality traits to things so I can remember then expand on that "personality" as I learn more (I see silver as being unpredictable in it's choice of friends and behavior and also somewhat mischievous). Hydrogen "likes" Oxygen more than it "likes" Chlorine and so forth and so on. When I explain electricity to someone that has no understanding whatsoever I compare it to plumbing and water flow, amplification being much like a small pressure switch controlling a much larger water flow valve. Currant is like the volume of water flowing and voltage is the pressure behind it. I always add that a big difference is that a "leak" could very well kill you instead of getting the floor wet.

Something you brought to mind is another interest of mine that is "waiting on parts" (all I need is a couple bags of clay). I want to build Dave Gingerly's machine shop. I would like to learn to learn to "machine" using old fashioned manual controls and methods. A CNC machinists ends up like your friend in the lab and when all the fancy equipment dies everything stops. Old fashioned machines don't have computers and depend on the skill of the operator. I've downloaded (legally) more books on foundry and machine work than I'll ever be able to read (thousands of them from late 1800's - early 1900's), so I have at my fingertips all the knowledge, wisdom and experience of those who made what we have now possible.

My driveway (dooryard) isn't minerals it's smooshed rocks.


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## necromancer

another great post, i do have a further question.....

*how to recycle your used Acid Peroxide (A.P.) after using it to leach MLCC*

i have 2 gallons of used AP, it has been slightly deluded with water & filtered well. (1 part water to 6 parts HCL)

it is purple with some white sediment. the purple comes from the leaching of the MMLC (dye) & *is not a indicator of gold* in this case :!: 
due to the fact that Tin & HCL make Stannous Chloride (SnCl2 or tin (II) chloride) there is no gold in the MLCC i leached.

now with that being said.

how would i regenerate the AP for reuse if it does not have any copper :?: 

do i simply re filter to remove all sediment & add H202 and a bubbler ?

do i need to over saturate with more HCL to remove all tin & then ad H202 & a bubbler ?

or do i ad iron to drop tin, filter ad H202 & a bubbler ?

ok thats 3 questions but you see where i need to go & any suggestions will be welcome

Thanks
Dave C.


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## lysdexic

Dave,
I'm only a beginner learning the chemistry of what has been called the AP (Acid Peroxide) method, so we should wait on some of the experienced members, but from the little I know...



necromancer said:


> how would i regenerate the AP for reuse if it does not have any copper :?:



The process called "AP" is actually the CuCl2 (Copper Chloride) leaching process. If there's no copper then it isn't a CuCl solution/process. HCl isn't an oxidizing acid but it will dissolve copper, which is below Hydrogen on the reactivity series, with the help of an oxidizer (in this case H2O2, Hydrogen Peroxide). Metals above Hydrogen on the reactivity series can displace the Hydrogen in HCl (HCl will dissolve the metal).

CuCl solution can be regenerated with oxygen (there should be free HCl as well), the posts just before your question covers a lot of this... 



necromancer said:


> do i simply re filter to remove all sediment & add H202 and a bubbler ?



I don't know if you have a Ni, Pd or what type of chloride solution, but it's not CuCl so you can't rejuvenate it... better let the others help you with the sediment.



necromancer said:


> do i need to over saturate with more HCL to remove all tin & then ad H202 & a bubbler ?



I wouldn't add any more HCl unless one of the big guys told me to and why... are there values in your solution?



necromancer said:


> or do i ad iron to drop tin, filter ad H202 & a bubbler ?



iron is used on waste CuCl leach to drop the copper after all values have been removed. It forms FeCl (anything above iron on the reactivity series that was dissolved would still be there too I believe) which is a step towards disposal of the waste solution. ...no need to add oxygen I believe.



necromancer said:


> ok thats 3 questions but you see where i need to go & any suggestions will be welcome
> 
> Thanks
> Dave C.



Hope it works out for ya Dave...

Doug


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## g_axelsson

butcher said:


> You are correct.
> Actually that is true, if we are just talking about the pure metal being melted, and there is nothing for the metal to react chemically with in this melting process.
> 
> But in melting many metals this is normally not the case; there is something that will react chemically in the melt.
> 
> 
> I understand that simply melting metal is not a chemical reaction.
> Melting the metal can cause a chemical reaction with the metal and other components involved in the melt.
> 
> Would I be more politically correct if I said something like Melting of metals there is a chemical reaction that can take place,
> where
> Melting metals is a chemical reaction where metals can be oxidized or reduced (again transfer of electrons), (just like other chemical reactions we perform with metals), depending on the metal, and how it reacts with oxygen or other chemicals in the melt, we can change the chemical properties of our melt to get a desired chemical reaction, in the melting environment or with flux or both.
> 
> I may not know the best way to say some things.


I've been thinking of this on and off for a while. Still it is wrong to say that "Melting metals is a chemical reaction". When I see that I cringe just as when I see people talking about melting a metal with acid. :lol: 
Yes, we often have chemical reactions going on in a melt but we also does a lot of melting where no chemical reactions happens, like when we melt our refined gold powder.
The heat and molten metal usually only accelerate the reactions that are going on even when the metal is solid. Just as copper oxidizes by only sitting in the air, heat it up and it oxidizes faster, melt it and it oxidizes even faster. Melts also lets the metal flow so we can expose fresh metal from within the melt, fresh material moves from within to the surface when molten.

I think a more correct way to express it would be something like...


> When melting metals, chemical reactions can occur where metals can be oxidized or reduced depending on the metal, and how it reacts with oxygen or other chemicals in the melting environment (for example the composition of metals, gases, flux and slag). We can change the chemical properties of our melt to get a desired chemical reaction by controlling the reactions via temperature, the environment and the composition of the flux.



Some examples of how the different factors can affect the chemistry of the melt are
- Create an oxidizing or reducing atmosphere, litharge (lead oxide) can be turned into lead (reduced) by adding a carbon source to the flux.
- Lead can be turned into litharge by heating in a oven while letting in oxygen.
- By increasing or lowering the temperature some reactions are favored over others. Mercury oxide is created by heating mercury in oxygen at 350 C, mercury oxide breaks down into mercury and oxygen if heated above 500 C.
- Adding quartz (SiO2) to the flux when smelting chalcopyrite makes the iron react with it and create an iron rich slag. The slag can be easily separated from the raw copper.

By the way, smelting is using chemical reactions in a melt to extract metals from an ore. Maybe that was what you were thinking of.

Göran


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