Peroxide Acid Method 1
Peroxide Acid Method 1
Peroxide Acid Method 1
Here's the strainer I made to keep the scrap (fingers usually) separated from the gold foil/flake:
I typically agitate the bath twice a day by pulling the strainer out, waiting a moment or two, then slowly
letting it back down into the bath. This causes the gold foils to go into the solution thru the bottom of the
strainer and separates them from the finger boards.
Heat helps of course. If I want to hurry it along I'll add a little peroxide every so often to keep the solution
warm (it heats and bubbles when you add more peroxide). Once the copper chloride concentration gets
right (see the copper chloride document on my website) the solution works really good with an occasional
kick start of peroxide. If the solution darkens or precipitates copper chloride ( greenish white crystals ) then
add some more muratic to dissolve the precipitates. The solution will slowly dissolve gold if you get it too
reactive (excessive peroxide). I'm not in any real hurry, so I typically set up a three gallon bucket (lowes)
and let the scrap soak for a few days. I agitate it occasionally to keep the gold foil that has loosened from
blocking the remaining copper plate. You can reuse the stuff forever if you keep it filtered and primed with
HCl and Peroxide occasionally.
Steve
HCl is actually hydrogen chloride (HCl) gas dissolved in water. The vapours are pure HCl. They will rust
any iron or steel they come in contact with. They will also corrode many other metals, such as aluminium.
They are poisonous in a confined area.
The method is safe to use indoors in a non-populated room. The fumes are not produced after the initial
reaction except when evaporation occurs. The active ingredient in this formula is Copper Chloride, not
peroxide or hydrochloric acid. The two ingredients initiate the production of copper chloride which in turn
performs the dissolution of the base metals. You should read the document on my web site about copper
chloride. Copper chloride is not volatile at room temperature and is safe if you wear gloves and don't drink
it. You can not dispose of copper chloride down the drain!!!
I would recommend that you mix up a small batch of the mix and get familiar with the process before
bailing out. Take a 4 cup Pyrex measuring cup and add an ounce of the fingers into the measuring cup. Add
in 1 cup of peroxide and 2 cups of HCl. Let it sit in your bathroom near a window or somewhere else out of
the way of pets, children, and traffic. Twice to three times a day swirl the mix and watch the gold foils
begin to peel away from the finger boards. In four or five days all the foils should be loose enough to be
washed off with a spray bottle of tap water.
You will be able to observe the reaction first hand on a small scale and then make your determination from
there.
Steve
I must admit that, before studying the PDF yesterday, I though that this was a O2/HCl proposition. I now
realize it's an O2/HCL/CuCl/CuCl2 proposition. You still need free HCl and O2 for the system - to convert
the CuCl to CuCl2. Otherwise, when the CuCl concentration reaches only 20 gm/litre, the reaction will
nearly stop. According to a link on the pdf, to dissolve a pound of copper, it takes 1.87 gallons of 3% H2O2
and .32 gallons of HCl. In the quantities you're using, the HCl starts at about 8 Molar. According to the pdf,
the fumes are still pretty strong until this is reduced to about 4 Molar, whereas 2.5 to 3.0 Molar is said to be
best. But, according to the pdf, this takes from 3 to 10 days to stabilize. What happens in the meantime?
Also, in the pdf, it is stated that, at 1 Molar, there are still fumes, even though they are far less.
goldsilverpro
No Urea is needed. Urea is used to neutralize nitric acid in AR. Just add SMB dissolved in water. Let it sit
overnight and don't expect much gold to be in the AP solution if any. You can test the solution with
stannous chloride, but it's sometimes hard to tell if there is gold present. If you plan on reusing the AP don't
bother getting the gold out at all. I drop the gold from the AP when I'm ready to mix up a fresh batch.
lazersteve
After running several batches using HCL/H2O2, I wanted to post the following observations.
Using HCL and 3% peroxide at a ratio of 2:1 didn't seem to be very effective unless it was warmed, still
quite slow at attacking the heavier or more resistant substrates. It works well on fingers and thinner Au
coatings, but if you are processing outside and the temperature is less than 50 F, the reaction is impaired
considerably.
I have just finished two runs of AP using 27.5% hydrogen peroxide- a pool shock product that Lou
recommended. I used a ratio of 1000 ml HCL to 55 ml H2O2 ( 1/9th the volume of a 3% peroxide). The
reaction was immediate and vigorous, the solution heated up moderately with observable vapour rising off
the container. It stripped the parts in a relatively short period of time.
I am in complete agreement with Lou, GSP, Irons and others in regards to minimizing the H2O in this
solution. But use caution, and add the peroxide a little at a time, it is definitely hot stuff!
Yes, be very careful with concentrated hydrogen peroxide. It becomes very dangerous at concentrations of
27% and above. 35% will bleach your skin and clothes instantly, 50% will give horrible boils and burns,
and the 90% material will often explode upon touching organic material (it's also like maple syrup in
consistency). That stuff is used as rocket fuel all by itself!
Also, let me mention that halides decompose peroxide (amongst other things, like fine metal powders,
sunlight, and heat).
So if you do anything with peroxide, keep it away from bromide and iodide, it will rapidly decompose the
peroxide, often explosively (I once had a steam explosion making bromine with peroxide solution).
Lou
I have several gallons of 35% H2O2, but I still use the weaker 3% stuff in my AP. The main reason is for
the extra water. The water allows the Copper II Chloride to become mobile in the solution and keeps the
rejuvenation cycle going. The other main problem with the concentrated stuff is that you end up dissolving
your gold along with the base metals due to the excessive amount of chlorine produced.
If you think about the etching reaction you will realize that the active ingredient is the copper II chloride,
not the peroxide or the muratic acid. With this in mind the water is necessary to allow the exchange of the
copper metal ions in liquid form. If the solution becomes saturated due to lack of solvent (water), the
copper won't convert to from the deactivated (and insoluble form) of copper I chloride back to the soluble
desirable form (copper II chloride). If you find a lot of off white to grey colored sludge in your batches you
are producing copper I chloride. It becomes discoloured by the saturated etching solution which appear
very dark brown in color and very thick.
The Hydrogen Peroxide H202 system of replenishing has been unpopular in the PCB industry, for no
outstanding reason, but not in the closely related Photo-Chemical Milling industry. Perhaps the real reason
why it is not popular, is that a reliable control system, for both components required to replenish the
system, Hydrogen Peroxide, and Hydrochloric Acid, has only recently become available. Previously, it was
probable that those people who took on the challenge of devising their own control system would likely
have chosen the least expensive, and easiest system to control replenishment system, which is the Chlorine
system. The overall etch/replenishment reaction for Hydrogen Peroxide is:
The fact that the replenisher ingredients are supplied in water solutions, as well as the fact that the
replenishment reaction produces water, limits the maximum Cupric Chloride content of the etch, but it is
still possible to get to as high as 40* Be', depending on the concentration of the Peroxide and HCl
replenishers.
..
Just like the Cupric Chloride etchant, the Copper that is already in solution in the etchant, dissolves the
copper metal on the board.
1. The metal is dissolved by being "Oxidized", which means that it loses electrons, which changes it from
the orange metal to a water-soluble blue compound.
2. The electrons are initially removed from the Copper on the panel by the copper that is already in
solution. This seemingly unlikely idea can only happen because copper can exist in 3 forms:
1. Orange Metal - copper with a "correct amount of electrons"
2. Cupric salts, Cu++ (blue) -- copper missing two electrons. This is the blue, water-soluble form we are all
familiar with.
3. Cuprous salts, Cu+ (white) -- copper missing one electron, or half way between form 1. and form 2. This
form is usually insoluble, unless it is chelated, and is not often seen in a board shop in large amounts.
Reaction 1.
Cu* reacts with Cu++ to give 2 Cu+
The cuprous salts are then (supposed to be) immediately oxidized (electrons removed) by the Oxygen in the
air which is being pulled through the etcher. In the process, the spent Oxygen is converted to water. (See
reaction 2.)
Reaction 2.
2 Cu+ + 0(air) + 2 H+ -- 2Cu++ + H20
I find the extra water is to an extent is helping, not harming. I think the optimal amount of water is just
enough to hold the copper II chloride that you need to etch the proper amount of copper off of the scrap.
Steve
AP and HCl-Cl references
GSP wrote: Steve, do you have more data on this - or, your original source for your statement? Seems iffy,
to me, but there could have been some isolated usage, I guess. Have you yet thought of an economical,
efficient, fast way to use either of them on a grand scale? You could very well be on that threshold.
Chris,
I was using AP and HCl-Cl long before I realized it was used in bigger refineries as I have mentioned.
Small Scale Refining of Jewelers Wastes by Roland Loewen pg.175-176 C1995 wrote: Hydrogen Peroxide
and hydrochloric acid will dissolve gold. This is used in several refineries. One refiner reported that the
recovery of PGMs was much improved when hydrogen peroxide rather than nitric acid was the oxidizer.
The known affinity of platinum and palladium for nitrogen compounds make this a believable conclusion.
Unless extended boiling of solutions to remove nitrogen compounds is done it is quite possible that some
forms of nitrogen could combine and hold PGMs.
We have no experience with hydrogen peroxide oxidation. The use of the 50% grade is reported. We
speculate that the metal is in hydrochloric acid solution and is treated by adding the H2O2. Because
hydrogen peroxide is an unstable material considerable care in its use is needed. The stream of peroxide
should not be introduced under the solution because of the chance of draw back to the supply tank. There
the metals present will likely catalyze peroxide decomposition which can be explosive.
Hydrogen peroxide is a very reactive chemical. It also decomposes and a product of decomposition is a gas
(oxygen). In low concentration and with a stabilizer this decomposition is slow. At high concentrations
and/or in the presence of a catalyst (many metals are such catalyst) this decomposition goes at explosive
rates. Damage can be severe.
A through education in the characteristics of hydrogen peroxide must proceed any work with this material.
The manufacturers of hydrogen peroxide can usually give considerable information and advice.
What is odd to me about his mention of the use of peroxide is his lack of references cited on the source of
the material. He has references throughout the book (just about every paragraph) on many subjects, but not
this one. Just above this section he mentions HCl and Chlorine gas without reference also.
I experimentally stumbled across the use of AP for stripping base metals around three years ago. I've own
this book for less than a year. I used AP to dissolve my first batch of monolithic capacitors around two
years ago. The 3% stuff is super slow, but it works very well on Palladium. I really dislike evaporating
nitric acid based PGM solutions. With AP this problem is solved.
As for up scaling the reaction, yes. I have pencilled out a contraption to use AP in a continuous
configuration which works with circulating pumps, filters, and electrolytic reactions. Theoretically you can
electrolytically rejuvenate the AP as it's saturated and recover the copper moss, returning the rejuvenated
solution to the reaction vessel. In essence you can dissolve pounds of copper based pins in a very short time
and retrieve the gold foils when the copper is gone. The copper ends up in a separate bucket in mossy form.
I built a prototype and turned it on, but the spent AP I used was too saturated when I first started the device
. Huge amounts of chlorine gas were evolved in just a few seconds of operation. Ideally you would start
with a fresh solution and turn on the electrolytic cell to maintain the proper CuCl2 concentration to affect
rapid dissolution while plating out the dissolved copper.
Steve
Oxygen from the air can get absorbed into HCl and oxidize gold. The gold ions then form complexes with
the chlorine ions to give auric chloride.
The truth is a very tiny amount of gold will dissolve in HCl until all available oxidizers are used up. This
amount may not be detectable.
Acid peroxide is just a weak form of aqua regia. Aqua regia works by having the nitrate ion oxidize gold as
ions and allowing chloride ions to form complexes. This is why you don't need nitric acid to make a gold
dissolving solution: just use sodium nitrate (which is an oxidizer) for poor man's AR. Those brown fumes
come from the nitrate ions being reduced by the gold as the nitrate ion gives up oxygen to become NO.
Acid peroxide is the same idea. Instead of nitrate as an oxidizer, you're using hydrogen peroxide, which is
also a powerful oxidizer. The hydrogen peroxide oxidizes the gold and the chloride ions form soluble
complexes. Also happening is the dissolution of oxygen into the acid, which helps dissolve gold.
Nitric acid will actually dissolve a tiny undetectable amount of gold into ions, but since gold will not form
soluble compounds with the nitrate ion, the gold does not continue to dissolve.
The reason why nitric acid will dissolve base metals such as copper very fast while hydrochloric acid will
not dissolve it fast is because HCl is a non-oxidizing acid.
HCl cannot oxidize copper metal into an ion so the copper stays intact. It will react with oxides of copper
forming water with the oxygen and hydrogen ion leaving a copper ion to form a compound with the
chloride ion. If there is oxygen in the air that can dissolve into the acid, then that dissolved oxygen can
oxidize the copper which then forms compounds with the acid. In effect, the acid makes the copper corrode
from the air faster because the chlorine is stripping away the protective oxide layer.
Nitric acid is different because it can oxidize copper. The nitrate ion plays a dual role. Free nitrate ions give
up oxygen to oxidize copper. The oxidation of copper simultaneously reduces the nitrate ion into nitrogen
monoxide gas. Free hydrogen ions combine with oxygen to form water and free nitrate ions combine with
the copper ion to form copper nitrate.
The reason why AP is preferred over AR is because it doesn't give off horrible fumes. Gold is least likely to
dissolve in both AR and AP, but each metal does not dissolve precisely sequentially. There is some
overlap. Galvanic action can help make the process more sequential, but not everything is electrically
connected so it doesn't happen effectively.
You can in theory dissolve base metals only with aqua regia by controlling the amount of nitrate ions you
put into the acid. The reason why AR dissolves everything is because we make it such that it will dissolve
everything, but if we limit the amount of nitric acid or NaNO3, then we mimic the effect that acid peroxide
does.
AP will dissolve everything like AR does if and only if you put in wayyyyyyyy too much peroxide without
diluting it too far. It will take a long time but it will happen.
When an AP batch is done, the reason why gold flakes remain is because the oxidizer is all used up, and
gold chloride displaces base metals and gets deposited as a black powdery film. badastro
AP Questions
Astraveller wrote:1. I have been using two strengths of acid (HCl) – 20% and 32% - the 20% seems to
work best – (BTW – both work). Palladium, I know your post answered this question but can I ask it again?
Does 20% work better than 32% for the AP process?
A little extra water won't hurt the AP process, it may even help to keep the gold foils from dissolving if too
much or too strong of a peroxide solution is used.
Astraveller wrote:2. Am I right in assuming that 32% will work better in the Clorox process?
I would use the 32% for sure. The 20% will work, but will retain more chlorine gas due to the extra water.
This dissolved chlorine will help the gold foils dissolve, but any extra after the foils are gone will need to
be removed with heating.
Astraveller wrote:3. When I am filtering, I filter the AP and foils first – keep the AP and return it to the
dish – I clean the fingers in fresh water and discard the stripped ones. Then I clean the un-stripped ones
with a spay bottle and put the fresh water and foils through the same, or different, filter. On this second
pass I have noticed that I sometimes get Gold foils with a grey sludge on top instead of clean gold. What is
this grey/green sludge?
The combined foils from the filters and the bottom of the bucket should remain in the reaction bucket until
they are thoroughly washed free of the gray sludge (copper I chloride). The CuCl is washed out using HCl
followed by water after all the gray sludge is gone. Once the gray sludge is removed and the foil wash
water is 100% clear then transfer the foils to the filter or better yet, directly to the Clorox reaction beaker.
Basically after filtering the AP solution wash the foils that were caught in the filter back into the mash of
foils in the bottom of the bucket. Then wash all the foils together with HCl then water.
Astraveller wrote:4. Can I put these (the foils with a bit of sludge) through the Clorox process as they are?
Or should I put them through the AP again?
No. See above.
Astraveller wrote:5. Can I put the ‘clean’ filter papers into the Clorox solution as they are or scrape out the
gold and keep the filter papers for a separate process?
The filters should be washed down into the reaction bucket with the main foil mash and washed with HCl
and water. After this the clean foils are transferred directly to the clorox reaction beaker. The filters go in
your filter burn box.
Steve
Here are the pics of our first real AP processing and the four tubs system. And btw, thanks to all the Steves
et. al.
Bubbling Air during AP use
Skyline,
Bubbling air thru the AP solution as it etches speeds things up a bit, but it tends to spit and splatter
everywhere, so cover the bucket with a loose fitting lid.
The solution merely grows in volume as it consumes more base metals. The copper chloride formed is the
dissolving agent and is recycled when oxidized. Saturation can occur when the solution has absorbed more
copper than the volume of liquid will hold. Adding a bit of HCl, water, or peroxide will activate it again.
Which one to add and how much is determined by several factors.
The details of what to add when are in a Copper Chloride document on my website,
http://www.goldrecovery.us which anyone interested in the AP reaction should study throughly. It seems
all to often people are asking questions here when the answers have previously been accumulated and
provided here and/or on my website, but they refuse to read the documents provided.
Study your reactions and documentation thoroughly before you begin to use them and it will serve you far
better than any outside assistance. Who knows maybe you can even figure out a something that will make
the reaction work better.
Steve