# deleted



## zzz (Dec 6, 2012)

deleted

It is against board policy to delete posts. If you don't want information put before the readers, don't post. 

I am banning you from the forum for violating our rules of operation. 

Harold


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## goldenchild (Dec 6, 2012)

zzz said:


> *Recovery the nitrate salt for make distillation*: obviusly the nitric used to make aqua regia is irrecoverable...



Could you not recover nitric if a reaction is performed in a distillation setup? This process seems a bit involved. Would you ever consider making a video?


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## zzz (Dec 6, 2012)

goldenchild said:


> zzz said:
> 
> 
> > *Recovery the nitrate salt for make distillation*: obviusly the nitric used to make aqua regia is irrecoverable...
> ...



You can setup an apparatus for bubbling no2 in water or h2o2, but I find it uncomfortable. If you keep copper nitrate and sulfate salt, you will make one large quantitative procedure, that increase yield. You need to do that for a large scale of recovery not for 100ml.

(i'd like to make a video, but right now i have not the time for make one...maybe a will make a photo tutorial so everyone will can see the result)


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## goldenchild (Dec 6, 2012)

I was actually thinking of fractional distillation with the feed stock placed into the reaction vessel to react. No bubbling.


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## zzz (Dec 6, 2012)

goldenchild said:


> I was actually thinking of fractional distillation with the feed stock placed into the reaction vessel to react. No bubbling.


goldenchild,
there are not distillation of nitric from aqua regia because with heat you will form nitrosyl chloride (and not nitric) that decompose in NO2 and Cl.


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## butcher (Dec 6, 2012)

This sounds a lot like a process I use to make nitric acid when I remove gold from pins, and also make copper sulfate.

http://www.google.com/search?hl=en&as_q=kill+two+birds+one+stone+&num=1000&ft=i&as_sitesearch=goldrefiningforum.com&as_qdr=all&as_occt=any


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## goldenchild (Dec 6, 2012)

zzz said:


> goldenchild said:
> 
> 
> > I was actually thinking of fractional distillation with the feed stock placed into the reaction vessel to react. No bubbling.
> ...



So the red fumes coming off a reaction are not nitric and can't be condensed? I'm talking about dissolving metals with both AR or just nitric.


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## zzz (Dec 7, 2012)

goldenchild said:


> zzz said:
> 
> 
> > goldenchild said:
> ...



Pure nitric acid is trasparent, like water.

I tried also to add directly sulfuric acid into reaction vessel of gold pins with nitric to restore nitric strengt, it work, but is a little wasteful and you need to work with an excess of water because sulfate salt created can crystallize, or can form foam, and could give you a lot of trouble (like metastannic).


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## butcher (Dec 7, 2012)

> "I tried also to add directly sulfuric acid into reaction vessel of gold pins with nitric to restore nitric strengt, it work, but is a little wasteful and you need to work with an excess of water because sulfate salt created can crystallize, or can form foam, and could give you a lot of trouble (like metastannic)."



zzz,
Did you read how I do the reaction in to kill two birds with one stone? 

The pins need to be clean of tin and solder for best results, also cutting the pins help to get all of the copper to react easier.

I have no foaming other than when concentrated HNO3 in solution azeotropes, this reaction of vigorous bubbling that I am talking about at the point of azeotrope of the acid would happen even if the only thing I had in the reaction vessel was NaNO3 and sulfuric acid, I am not sure if the reaction I have is the same thing as you are describing when your mentioning you noticed foam or not, but when I see the tiny bubbles of this reaction begin the heat is lowered till the reaction of vigorous bubble are slowed from HNO3 wanting to react too fast and boil out almost all at once later the heat is raised again.

A little extra water I use in the reaction is not a problem for me because I can concentrate the nitric made to 68% by evaporation, or use the more dilute nitric as is, or dilute it further if needed.

The blue copper sulfate that forms if you do not let them cool or form hard salts (keeping them hot and adding boiling water before they harden to salt, to dissolve them before they harden so your gold foils precipitates to the bottom of the dilute blue copper sulfate solution.


The brown fumes of NO2 if bubbled into water will form nitric acid, a little peroxide in solution can help and if some clear fumes of NO the H2O2 can help to make nitric out of these also, there is some lose of the gases also because the bubble are usually large and some of them will not covert the first time they go through water (not enough reaction time in the jar going through water if you were concerned with the little bit of lost gas you could rig up a series of jars to bubble the gases through.

As far as recovering nitric from aqua regia, capturing the NOx gas bubbling it into water to make nitric acid, yes some chloride gases will be carried over and as the NOx forms. Chlorides could be removed with silver nitrate, but that would take a lot of silver nitrate and you then be making silver chloride to deal with, I would not mess with that.

What I do every once in a while is use the evaporated gases from the aqua regia process bubbling it into a water diluted HCl solution with additions of 3% peroxide to make a very dilute aqua regia that can be used with the heat of evaporation on another batch, but aqua regia cannot be stored, and does not last long so this is not done if you cannot use it soon on another batch, (can also be used help clean some of the heavy sludge bubbled into in a stock pot), (this can help to tame some of those rougher fumes from around your aqua regia solution and do a little work with them).


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## zzz (Dec 8, 2012)

butcher said:


> > "I tried also to add directly sulfuric acid into reaction vessel of gold pins with nitric to restore nitric strengt, it work, but is a little wasteful and you need to work with an excess of water because sulfate salt created can crystallize, or can form foam, and could give you a lot of trouble (like metastannic)."
> 
> 
> 
> ...



I saw your post, but too long to read I stopped after 20% of his introduction. Personally i find not convenient to recover nitric bubbling NO2, too uncomfortable, contaminating, and low yield.


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## butcher (Dec 8, 2012)

If you have not read or done a process, how would you know if it would work or not?

This process was not to just make nitric acid that can be done by just using a nitrate salt and sulfuric acid and distilling.

This process is to recover gold from copper plated pins; make nitric acid in the process, and to make a useful byproduct copper sulfate in one operation, with practically no waste to deal with.

The home made pickle jar distilling rig is a bit unconventional but works well if care is taken, precautions must be taken and principles understood of thermal shock, suck back of cold fluids into a hot vessel, and the other safety concerns of the process, basically the same concerns if you will have if you are using a conventional lab glass distilling rig

The nitric acid I produce from the reaction is not contaminated, and can be used in recovering or refining of metals, it can even be used to dissolve silver, where nitric made with the cold method cannot be used because of the sulfate salts involved, the gold foils come out ready to process, the copper sulfate is re-crystallized to pure crystals of copper sulfate.

The nitric produced is a bit dilute, not a problem for me in most process, many times I use dilute HNO3 in my processes, the dilute HNO3 can be evaporated to 68% if needed.



To kill two birds with one stone
Recover gold; make nitric acid, leaving copper sulfate as a usable byproduct.

Process for pins, nitric acid and copper sulfate

Kill two birds one stone

A few principles:
You need sulfuric with nitrates to create nitric acid,
Gold will not dissolve in nitric acid alone,
Copper will dissolve in nitric acid evolving NO2 gas. 
NO2 gas bubbled into water can form nitric acid.
NO2 + H2O --> HNO3
Gold will not dissolve in copper nitrate or copper sulfate.
Nitric acid will evaporate from a solution at a much lower temperature than a sulfate will.
2 NaNO3 + H2SO4 --> Na2SO4 + 2HNO3 
Nitrate fertilizer + sulfuric acid = sodium sulfate + nitric acid.
In our case we are using copper to help.
Copper dissolving in nitric acid evolves NO2 fumes.
Cu + 2 HNO3 --> CuNO3 + 2NO2(g) + 2 H2O
When we distill this copper nitrate we remove the Nitrate and leave the copper sulfate behind, diluting this to retrieve our un-dissolved gold.
Copper sulfate is water-soluble.

This is my method for pins (which can be adapted to distill copper nitrate), 

(This process can be adapted to other recovery or refining methods to kill two birds with one stone, like recovering nitric or aqua regia while dissolving karate gold)

A distilling unit rig (I have a nice lab distilling unit), but I like my homemade kit, and use it for this process, my unit has survived many distillations, but as with any distilling glass precautions must be observed,

Some supplies I use: 
(My Pickle jar distilling kit) 
Large pot with handles
Sand
Canning gallon pickle jar
A lid for gallon jar --made from 1/2" thick Teflon, turned on a lath beveled edge to tightly fit jar, small lip on top edge, a hole in center for tight fit of 1/4" hose.
8' 1/4" Teflon hose
Long neck bottle
(For this bottle either loose fitting Teflon cork with hole or just use tape)
Gallon bucket of ice water
Double burner electric hot plate 
(Ground fault protected electrical outlet)
Fiberglass catch tray for burner to sit on to catch any spill
Pyrex coffee pot
Some wire, plumbers Teflon tape, cloth tape, electricians black tape
New battery sulfuric acid 10 cups, (we will boil down to 6 cups)
Cup of sodium or Potassium nitrate fertilizer
One pound of (copper) gold plated pins no solder (cut to expose copper to acid)
(Teflon will withstand temperature and fumes of these acids)
(A nearby box of baking soda and water for safety)

Required:
Understand the dangers of these acids, and precautions to take, understand the danger of the nitrous gases formed, and precautions to take, understand the principles of distilling and precautions needed, understand glass cannot withstand thermal shock (rapid temperature change), never cool or lower temperature to boiling reaction vessel without removing line to condenser, work outdoor using breeze or with fume hood, take safety precautions.

Double hotplate sits on fiberglass catch tray; ground fault electrical source is used outdoors

10 cups of sulfuric battery acid boiled down to 6 cups in the Pyrex coffee pot on one burner boil down to 6 cups and cool. To boil off some water in the acid, it will still contain some water (We will use this cool sulfuric acid later)
The large pot, pour an couple of inches of sand in bottom of it spread flat, the gallon canning pickle jar is sit on this sand centered in pot and sand poured in between pots metal and outside jar, to make a boiling reactor with a sand bath. This will help to protect our glass from thermal shock, allowing heat to change slowly, and can act as catch basin if we make a mistake. The 1/4" Teflon hose fits tightly into Teflon lid for our gallon boiling reaction vessel, we will be collecting NOx gas from this vessel, so hose just in through the lid just a little ways.
(Later we will tape on this lid, and tie it down)
(Get tape and wire ready and handy within reach, we will need it as soon as acid is added later)
Get ice water in gallon bucket (plastic ok), 
Put small amount of water in the long neck bottle for NOx gas to bubble through ( I add a little H2O2 peroxide to help conversion, it is not necessary), put one end of the Teflon 1/4" hose into this bottle all the way down into bottom of bottle, (through a loose fitting Teflon cork or else just tape hose to top of bottle, air, and some gas will need to escape from this bottle, and we do not want to prevent this with a tight fitting lid), this long neck bottle needs to sit down in iced water of bucket above to condense gas to liquid, and we need to hold it down in ice water (it wants to float till it fills), so we tie in down into ice water, this is our condenser receiver for the NOx fume's which will bubble into water in this longneck bottle and convert to nitric acid, a few loops of this hose is under ice water to help condense fumes also.

Set large pot sand bath with our fancy pickle jar boiler reaction vessel on cold electric hotplate, put one pound solder free (copper) gold plated pins, (cut to expose copper to acid I cut mine small for more exposure), in reaction vessel, add one cup of sodium nitrate fertilizer, (with lid and tape handy ready we will need to put on lid to contain brown NOx fumes in next step), pour in cooled 6 cups sulfuric acid on these, quickly put on Teflon fitting on lid and taping on the with Teflon plumbers tape first, then bandage cloth tape, then black electrical tape sealing this lid well, the insulated solid copper tie wire is tied to one handle of the pot over top of lid on jar and tied to other pot handle, this will hold down the lid when pressure builds, 
As soon as you pour the sulfuric acid on the nitrate fertilizer and copper, red brown nitrous gas NOx begins to form, so getting lid on quickly and taping to seal is needed, we will need no heat yet, as it creates its own heat from chemical reaction, turning burner on warm will start to heat pot and sand, with time, the heat will saturate sand and starts to warm the jar. When reaction slows (bubbling in receiver slows) and pot is warm raise heat a little, (little bit at a time) giving time for heat to reach and react chemicals as red fume slow, or gas bubble slow in receiver, we want a steady few bubbles, not too fast we only want the gas to go to the condenser and receiver. (There is a point to where nitric will concentrate to azeotrope in the boiling flask and reaction begins to get more vigorous with red fume’s of NOx gas), keeping a steady stream of bubble into our receiver is our goal, not liquid the blue liquids from our boiling flask).

Caution we do not want to change temperature on glass fast, this thermally shocks glass and will crack or break it, always keep this in mind.
Do not lower the temperature of the boiling vessel, with the hose in the condenser receiver, always remove this hose from the receiver first allowing it to suck air, (this higher temperature in the boiling vessel creates a pressure, and if we lower the temperature on this boiling vessel, it will go into a vacuum, this will suck the cooler condensed liquid back into this hot boiling flask, thus causing thermal shock and cracking our jar, by removing this hose first it just suck’s back air, and not liquid, as the pressure lowers in this boiler reaction vessel.

(I preheat a coffee pot of water, just below boil for procedure below, starting the water heating before hand)

We do not want to evaporate this now forming copper sulfate to a dry salt, we just want to drive out the formed nitric acid, so we evaporate to thick syrup, (I have noticed a color change from blue-green to blue-blue as the nitrates are driven out of the copper sulfate),
After we have evaporated down to syrup, 
We want to remove hose from the condenser receiver, before lowering temperature.
(See caution on suck-back of these cooler liquids when lowering temperature of reaction vessel, thermal shock),
We can let cool before diluting this copper sulfate syrup, but this will form salts and it takes more water to dilute, (that may be best for you as this step if not done properly can thermally shock your boiling vessel), I use the water we heated above getting this water to about the same temperature of this syrup, and very slowly adding this water to the syrup to dilute it, starting with just drops at a time, not pouring in all at once, this dissolves the blue copper sulfate and leaves gold shells and powder from pins.
Allow this dilute copper sulfate liquid to settle the gold, and then decant and filter.

These gold foils will need further treatment to refine to pure gold.

This copper sulfate can be evaporated to nice blue crystals of copper sulfate for other chemical reactions, or for an electro cell or other uses, wall mart sells them at a high price to keep roots from growing in sewer lines.

This nitric acid tested for strength, and evaporated to 68% concentration azeotrope if necessary, cool, store the nitric in amber nitric bottle with proper lid, store the nitric acid out of light (light breaks down nitric). Store in safe place for later use in recovery or refining

Distilling copper nitrate, (adding copper or gold plated copper can assist creating NOx fumes in boil, which also is a way I get gold plating from Pins. killing two birds one stone) would get nitric back from copper chloride solutions, bubble NOx gas into water, for dilute nitric, which can then evaporate water from dilute nitric until 68%HNO3 azeotrope, (many acids form azeotropes), so if just evaporating a dilute nitric solution, below the boiling point of the acid (for the concentration that the acid is at the time in solution), would boil off water (or other volatile components if in solution), making the acid more concentrated in solution, up to the azeotrope of the acid, which for nitric is about 68%, further boiling would only boil off the 68% solution till dry, meaning it cannot be further concentrated by this method, by using the boiling point information a person can have a good idea if they are boiling off acid or just water, the concentration can be tested with specific gravity, or judged by how it attacks metals.

(100% H2O) boils @100 degC density 1.00.
20% HNO3 density 1.115- boiling point 103 degC.
30% HNO3 density1.180 boiling point 107 degC. 
50% HNO3 density 1.310 boiling point 116 degC.
70% HNO3 density 1.413 boiling point 121.5 degC.

As you can see the boiling points change with how concentrated the acid is. Keeping below the boiling point most all of your acid stays in solution, and mostly water vapors off, above the boiling point acid leaves solution in vapors with the water. 
Other acids and have reaction similar to this. For more information you can study the azeotrope of acid, boiling points, acid concentrating.


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## zzz (Dec 8, 2012)

butcher said:


> If you have not read or done a process, how would you know if it would work or not?


With intuition, because large scale is ever better than small scale...
i talked about how to recover a large amount of nitric and how to recover sulfuric from any sulfate salt.


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## Palladium (Dec 8, 2012)

For some of the long informative post Butcher writes i almost feel i should be paying him. Great job brother!


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## butcher (Dec 8, 2012)

you are correct the process I posted would not be good for making nitric acid on a large scale.

I guess what you determine to be a large scale could also make a difference in what approach would be best to make the HNO3,
Industrially using nitrate and sulfuric acid methods are not used as much as us little guys use to make the acid in our back yard.

Recovering sulfuric acid from a salt why?

I would find a use for the salt or find a market for the salt,change the form of the salt to another useful salt,on a small scale, or if doing this on large scale.
the salts can be worth more than the sulfuric acid made from them.

Sulfide ore or Rock is cheap, and can be made into sulfuric acid, it is the fuel ($) and the equipment needed that makes making sulfuric acid hard or expensive, especially if not done industrially, it would be just as easy to roast sulfide ore and make oleum then dilute to make sulfuric acid, but why? sulfuric is a byproduct of company's having to comply with emissions and air quality standards in their processing, these company's need to get rid of this byproduct, and sell it cheap and also look for markets to get rid of all of the sulfuric acid they generate.


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## zzz (Dec 9, 2012)

I posted some useful tricks...good luck with yours...


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## butcher (Dec 9, 2012)

I do have good luck when I make nitric acid, I make it with many different methods and different strengths, I also like use my byproducts in several reaction's or other processes.

If I am just making nitric acid, one of the things I like using my sulfate salts for is a batch of pretty green crystals of ferrous sulfate, (this works best when using bisulfate salts from when you make the stronger nitric) , I use the ferrous sulfate (copperas) crystals to test for gold in solution or to precipitate gold from solution.

ZZZ, I like how you are also working (and thinking) to use your byproducts when you work, that is a good idea, and a smart thing to do. I noted some things below from what I understood in your the post above, that I believe would not work well, if I am understanding what you were saying in that post.



zzz said:


> *Hi everyone, some weeks ago i wrote a post where i said that i'm able to make 5 liters of high concentrated nitric acid with 2 $ of spending.
> Well the yield is better because you will only need the first spending for sulfuric and nitric salt than you can recovery all you have used.
> We need to have an initial point where to make our first nitric acid distillation. I personally prefer potassium nitrate and sulfuric used for clean.*
> 
> ...


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## zzz (Dec 9, 2012)

butcher said:


> I do have good luck when I make nitric acid, I make it with many different methods and different strengths, I also like use my byproducts in several reaction's or other processes.
> 
> If I am just making nitric acid, one of the things I like using my sulfate salts for is a batch of pretty green crystals of ferrous sulfate, (this works best when using bisulfate salts from when you make the stronger nitric) , I use the ferrous sulfate (copperas) crystals to test for gold in solution or to precipitate gold from solution.
> 
> ...



In the first example the subject was nitric acid.
In the second = maybe it will form also a little bit of uranium in addition to what you said.


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## FrugalRefiner (Dec 9, 2012)

:shock: :shock: :shock:


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## Palladium (Dec 9, 2012)

zzz said:


> butcher said:
> 
> 
> > I do have good luck when I make nitric acid, I make it with many different methods and different strengths, I also like use my byproducts in several reaction's or other processes.
> ...




Is that suppose to be funny after that man went out of his way to try and help you?


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## butcher (Dec 9, 2012)

ZZZ, 
How can we discuss this subject to where we both get a better understanding, so we will both come up with good processes?
I have to admit I had a hard time understanding what you were describing in that post, and I may have misunderstood the intent, or the chemistry you were trying to describe.
Lets see if we can work together to help each other learn more.


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## zzz (Dec 10, 2012)

I have problem with language, because english in not my first, but i think is explained fair enough.


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## butcher (Dec 10, 2012)

ZZZ, 
You have done very good considering this forum is not in your language, I do not think I would do as well trying to explain myself in another language as you have done here.

Lets begin again new with our discussion and try to help each other:

Lets look at what we would have if we tried to recover our aqua regia through distilling, while we were dissolving some gold.

When we mix aqua regia the two acids react and form volatile gases in solutions, these gases also help us to dissolve gold as they react, they will not stay in the solution long, and will leave the solution in time, they can also be driven off with heat or from the heat of the reaction (faster than they would if the conditions were different), this is why it is not recommended to make your Aqua regia before you need to use it, on standing these volatile gases would leave the solution, if you stored it for a while, these gases could also build pressure in a closed vessel breaking the vessel if the gasses had no escape, once these gases leave the solution it is no longer aqua regia, yes it will still be a very strong acid, but it will not be able to dissolve much gold without these volatile gases reacting with the gold.

When we distill the aqua regia solution as it reacts with the gold, we do get these volatile gases coming over in our distillation with the first water that is distilling off (these gases are still volatile some may react with the water and reform some acid, and much of it would just vapor of even if we tried to capture them)
So what would our product be from capturing the aqua regia with distillation evaporating the solution and condensing it back to an acidic solution free of metals left behind in our boiling flask of gold metal, the condensed acid would still be very strong, but it would no longer be Aqua regia (just as storing aqua regia the volatile gases either reacted and left our solution, but we would still have a very acidic solution containing ions of hydrogen, chlorides, and nitrates, in our receiving vessel.
What were these volatile gases we are talking about nitrosyl chloride and chlorine, as well as other gases in the reaction with gold like nitric oxides.

Can we reuse this very strong acid we captured to dissolve other metals? Yes we can.
Can we use this in other chemical reactions to make salts of other metals? Yes we can.

Why do I say we cannot use this to dissolve silver? The solution would contain Chlorides.

But what about the fact that the gases evaporate off of our solution at different times during the process with water first, then nitric, then HCl, why can't we separate these and condense them separately, this way we could distill back nitric from our aqua regia, well first these gases will not evaporate off as pure substances, and they will also be mixed with these other volatile gases we discussed above reacting in the solution or with the gold.

So this is why I replied to this statement: 
Recovery the nitrate salt for make distillation: obviusly the nitric used to make aqua regia is irrecoverable, but if you used that for dissolve silver for inquartation
By saying:
(Silver will passivate in the chloride solution)

You can use this strong acid you distilled off, for many things, but using it to try to dissolve silver would be a bad idea, because of the chlorides involved and the problem of silver passivation of silver chlorides.


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## zzz (Dec 10, 2012)

You have tried to spot errors where there are none, now you are off topic.


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## butcher (Dec 10, 2012)

ZZZ, 
Sorry you feel that way, I will no longer attempt to discuss this subject with you, you apparently want to see this your way, and do not wish to see where your thoughts on how the chemistry may work differently than you think it does.

Or you seem to feel what I say about what I see wrong (or what I understand of the chemistry) that we discuss has something to do with you or what you have written, or you personally,.
ZZZ, that is not my reason for looking for or spotting errors. 


Personally I want to learn how things work even if it does not work the way I think it does, this way I can adjust my thinking on the subject and see how things really do work.

Chemistry is very complex, to learn it we need to be able to see things differently, or see when things are not the way we think they are.

Yes I do try to spot errors, I guess that is how I work, when I know the error, I can then fix the problem, or understand the chemistry better.

You seem to feel I am spotting errors has something to do with you personally:
That is not the case here.


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## Dr_Code (Dec 10, 2012)

I found this thread by searching for butcher's thread about 'killing two birds with one stone', related to processing pins from PCI slots and the like. I will get to reading my intended thread soon. This method reminds me of a video I saw on how to make nitric acid using a condenser.

Being a new thread, I wanted to add something about the saftey aspect of pure, or 'fuming' Nitric Acid - It is DANGEROUS STUFF.

Pure Nitric Acid will form a protective coating arround copper (called passivation) (I'm not sure about what other metals this happens with...I've seen it done with copper), making it dissolve very slowly, untill the acid is diluted a little. Then the reaction is VERY violent!

Yet another reason to add acid to water. AAA. Always Add Acid. (At least that is how I remember it)


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## Dr_Code (Dec 10, 2012)

Perhaps the inital process was misunderstood. There are many ways to make Nitric Acid. Taking three ways to make Nitric Acid, and turning them in to one way. Two processes use Cu (copper) (which I did not see in the inital example). If used, the Cu could be recovered using Al (Aluminum). (I also did not see Al in the first reaction. I did see CuSO4...which made me think of this method).

It may have all been a mixup from a Nurdrage video (MOD's, please edit this if necessary).


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## cableman (Feb 28, 2013)

I realize that I am adding to an older post but I am researching ways to make my own nitric acid. Right now I really need the simplest method to begin with but I read your distillation method closely where your use your gold plated copper pins to recover the gold off of the pins while using the underlying copper to help make your reaction all the while producing the nitric acid I need. I am very interested in this method but I am not experienced in distillation processes. I have most of the equipment I need except for a few inexpensive pieces and I would love to see a detailed picture of your setup if you could take one the next time you have it properly set up for the process you explain using the gold plated copper pins and distilling using sulphuric acid. I only need to find an inexpensive place for the copperas you use since all I have used so far is SMB.

If you ever see my addition to this post and have the time I would greatly appreciate any pictures you might have of your setup. I would also like to know the simplest method to make the strongest nitric acid I can preferably using sodium nitrate. I don't mind using a little extra materials so long as they are not expensive. My only goal is to get some usable nitric acid to precipitate and refine several grams to an ounce of gold so I can use this funding to purchase the rest of my preferred equipment and chemicals. I only need to make a pint (give or take an ounce or so) of nitric to achieve my goals.


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## butcher (Feb 28, 2013)

cableman,

Sorry for not answering sooner, had trouble with my internet connection, the company that services my area was having antenna troubles, (some competitor company put up an 2.4giga hertz antenna on the tower right below his antenna and drowned out his signal, well I contacted them this morning as I was wanting to be able to use the internet, and asking why it has taken them 3 weeks to get this thing working right, he said he has the antennas ordered from Europe he said his tower man was hurt, and could not do it now, so I volunteered to climb his tower to replace the antennas for him, 7 hours in the cold, 3 hour trip up and down eight dollar mountain well now I got my internet working again, and the owner Rob said he would pay me for the tower-work with free internet connection. 

If you have a lab glass distilling rig you can use it, the glass is better than the gallon pickle jar, but as I explained in the post killing two birds with one stone, precautions are need to be taken to keep from breaking glass, read the thread paying attention to how to treat your glass so as not to thermal shock the glass, or create hot spots, and on preventing suck backs, of cold liquids into the hot boiling vessel, do some study on distilling before using your glass ware distilling rig.

A lab beaker and home made Teflon lid would work also, I have a coffee pot shaped like a flask I made a Teflon cork for with a hole drilled in it that is also used to distill with. I have bought a lab glass distilling rig and never used it as my homemade stuff works just fine, I have started buying some pieces of lab glass, and working towards getting a larger distilling rig setup a piece at a time, I got a nice condenser that should work better than a plastic hose coiled in a bucket of iced water, I still need some joints and other parts before I will have it working though.

If I get a chance I will take a picture, nothing impressive, I explained what it was, the only important part is the lid for the pickle jar is made out of Teflon turned on a lath, to fit the jar tight and with a lip to seal at jar top lip with a hole for the hose for the gases to pass out of the gallon pickle jar which is sitting in the pot (sand bath) to evenly heat the pickle jar.

If you just want to make nitric acid the best way is to use Laser Steve's recipe for cold poor mans nitric acid, freeze out the sulfate salts as much as possible, this makes about 50% HNO3, His recipe make about 150ml:

100ml distilled boiling water 
170g NaNO3 (or 202g KNO3) dissolve
Cool below boiling
Very slowly add 56ml of 98% sulfuric acid, reaction creates heat and can boil over from reaction if acid added too fast.
We want the salts to dissolve and convert, stir solution well,
Cool solution down slowly to room temperature (potassium sulfate crystals can lock up some HNO3 if cooled too fast 
Chill solution in freezer, or in salt ice bath (do not seal vessel to allow for expansion and contraction, Steve recommends -5 deg C.
Decant HNO3 liquid from sulfate salts while solution is cold.
Makes ~150ml of ~ 50% HNO3
To get 68% azeotropic nitric acid evaporate water, heat till water vapors escape, but do not bring to a boil 50% HNO3 has a boiling point of 114 deg C so we want to keep temperature below this, as acid concentrates the boiling point rises a little, but water will vapor off below the boiling point of the acid at that concentration of the acid, 68% HNO3 has a boiling point of 120.5 degrees C, after the acid reaches azeotrope the boiling point of the acid begins to lower, we cannot concentrate the acid past the azeotrope as further heating would just vapor off 68% acid, (68% nitric acid the strongest you can make it with this method), I know how to make nitric stronger but there is no reason for it in recovery or refining, So there is no need to post a process that someone could use for the wrong reasons such as making explosives.

You can use the recipe above, for larger batches
Times X 6 formula to fit in a Mr. coffee pot sitting in a casserole dish on a solid burner hot plate with a watch glass lid to make about a quart of HNO3:
600ml of distilled boiling water
1020g NaNO3
Or
1212g KNO3
Cool solution
15ml 30% H2O2 (helps to keep NOx fumes down and convert them to acid) 
Slowly add
336ml of 98% H2SO4 (add it very slowly, taking pre-caution of boil overs).
Stir well when salts dissolve cool down pour into two Quart canning jars, with loose fitting plastic lids
Cool to room temp, freeze to form sulfate salts, decant while still cold,
This will make about a quart of 50% HNO3, evaporate off water to 68% HNO3 (you can use the specific gravity test for percentage if you are concerned about how strong it is)
The HNO3 can just be distilled for higher purity to use on silver.
The 50% nitric will need diluted for use on base metal or silver so no reason to concentrate if wish not to, also the 50% nitric acid can be used in aqua regia just fine where you are heating solutions any way which will concentrate the acid then (this also helps to lower NOx fumes during the process)…

Store HNO3 in dark glass, light destroys HNO3; lids should be able to handle acid.

You can then distill the homemade 68% nitric acid to distill a clean nitric acid (leaving the remainder of the sodium or potassium sulfate salt behind in your boiling vessel, giving you a more pure nitric acid that can be used on silver.
(Sulfate salts left in home made nitric will form unwanted silver sulfate with silver)

Killing two birds with one rock is also a nice process if you have pins to remove the gold from, and want to make nitric acid and copper sulfate in one reaction, it is actually a little harder to master, than just distilling HNO3 but once you do it properly you will love the process.

Ferrous sulfate (copperas) also called Iron II sulfate, is also easy to make, I have made several posts on how to make it using cleaned Iron from scrap transformer laminates and 10% H2SO4, heated, (sodium bisulfate NaHSO4 can be substituted for sulfuric acid in the reaction), the bisulfate will act like sulfuric in many chemical reactions.


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## JesseSShaw (Apr 1, 2013)

After reading this thread for awhile, I figured I would share information on how I produce nitric acid for my PM recovery. Thanks to our government (tongue in cheek) it is very expensive for me to acquire nitric acid. I can not find it anywhere near close enough to my location and it is ridiculously expensive to order it and have it shipped. Yet I can buy sulfuric acid comparatively cheap online, go figure. I make semi-small amounts of nitric acid so I do not need to store much for when I need it. My batches are concentrated above 86%. As you may or may not know, nitric acid is considered highly concentrated when it fumes and it starts to fume at 86% concentration. My homemade nitric acid is contaminated with nitrogen dioxide but the contamination seems to be non-reactive when I am using it for PM recovery.

I use sulfuric acid and sodium nitrate in a basic distillation apparatus to produce my nitric acid. Sodium nitrate is more readily available to me than other pure nitrate salts but you should be able to use any pure nitrate such as potassium nitrate, calcium nitrate, or ammonium nitrate. It is a simple process but can be dangerous if the proper safety precautions are not met so make sure you do this outside or under a proper fume hood. You don't want to experience nitric dioxide or nitric monoxide poisoning. First you must have a distillation apparatus that will handle the extremely corrosive substances involved in the process. I used a distillation apparatus with rubber stoppers for the first few times and the rubber reacted by breaking down. It didn't seem to effect the reaction but still, not easy to clean up afterwards. Best to use an all-glass setup if possible to avoid unwanted reactions. I combine 100g sodium nitrate with about 60ml to 70ml of sulfuric acid. Then I distill the solution until there is no more distillate to collect. The collected distillate will be nearly pure nitric acid. It will have a somewhat yellow tint because of the decomposition of nitric dioxide contamination but it isn't much. You will still have very pure nitric acid (I would say somewhere between 90% to 95% pure). The stoichiometric quantities for this reaction do not seem to work as expected, unless my calculations are just incorrect. I played with the amounts and found the quantities that I mentioned to work best.

I took a lot of information for granted in this post. Don't use this procedure unless you have at least a basic idea of what the process involves. DO NOT underestimate the dangers of nitric acid especially in a pure state. I just wanted to share information on what I do for acquiring the ridiculously expensive nitric acid.


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## lazersteve (Apr 5, 2013)

Jesse,

Your rig looks like it would make a lot of NOx vapors in the area where the reaction is run. The reason I say this is because your collection flask and condenser do not have a good seal with one another. When I distill nitric acid using the chemicals you suggest, I get a clear to yellow liquid, with red vapors in the condenser, especially near the end point of the reaction. I use a laboratory grade rig with blown glass Pyrex and ground glass joints to prevent this gas from escaping. I use a one liter flask for my reaction vessel and a 500 mL collection flask. If my joints on the rig are not tight (I use Teflon tape to seal them), I get red vapors emitting from the collection end of the rig towards the end of the reaction. 

How do you contain the red vapors exiting the condenser? I would recommend that anyone who wants to distill their own nitric acid to use a closed connection to the collection flask with a salt water and ice cube bath on the outside of the collection flask. I use a vacuum flask for my collection vessel. Additionally, if you run the reaction under a vacuum, your acid will distill over at a lower temperature. By cooling the collection flask, you ensure the acid vapors are properly condensed and collected in the collection flask.

I'll see if I can dig up some photos of my rig in action. Distilling nitric acid is fine for lab scale quantities as long as you do it safely. For larger scale work, purchasing nitric acid is the best way to go. 

Your numbers may be off on you calculations due to the concentration of your sulfuric acid and/or your nitrate purity/water content. 

Steve


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## JesseSShaw (Apr 5, 2013)

lazersteve said:


> Your rig looks like it would make a lot of NOx vapors in the area where the reaction is run. The reason I say this is because your collection flask and condenser do not have a good seal with one another. When I distill nitric acid using the chemicals you suggest, I get a clear to yellow liquid, with red vapors in the condenser, especially near the end point of the reaction.


That's right. Nitrogen oxides are an unavoidable byproduct of the process. That is why I indicated that the process must be done either outside or under a proper fume hood (or good forced air ventilation of some kind). I will add that if you are doing it outside then make sure to stay upwind lol.


lazersteve said:


> I use a laboratory grade rig with blown glass Pyrex and ground glass joints to prevent this gas from escaping. I use a one liter flask for my reaction vessel and a 500 mL collection flask. If my joints on the rig are not tight (I use Teflon tape to seal them), I get red vapors emitting from the collection end of the rig towards the end of the reaction.


It is best to use an all glass setup as I indicated. The reason is for preventing unwanted reactions. Also, I prefer to use lab quality or cooking quality borosilicate glassware which has very low thermal expansion so there is less chance of the glass breaking due to thermal shock.


lazersteve said:


> How do you contain the red vapors exiting the condenser? I would recommend that anyone who wants to distill their own nitric acid to use a closed connection to the collection flask with a salt water and ice cube bath on the outside of the collection flask. I use a vacuum flask for my collection vessel. Additionally, if you run the reaction under a vacuum, your acid will distill over at a lower temperature. By cooling the collection flask, you ensure the acid vapors are properly condensed and collected in the collection flask.


That is certainly one way to go. Turn the collector into a second condenser. However, I am not worried about the oxide gases escaping. Actually, I prefer not to further contaminate the distillate with the decomposing nitrogen oxides. However, I understand that there may be a process to further purify the nitric acid by exposing the end product to a bubbling vacuum of some kind but I have not looked into it. Your vacuum collection vessel may indeed provide that additional purification step. The HNO3 that escapes as vapor is very little so I am not inclined to complicate the distillation setup. Maybe I will try an enclosed collection system sometime and see what I get but the process I outlined works extremely satisfactory for me.


lazersteve said:


> Your numbers may be off on you calculations due to the concentration of your sulfuric acid and/or your nitrate purity/water content.
> 
> Steve


I considered that but It doesn't seem like it would throw off the calculations that much with the sulfuric acid being 98% concentration and the sodium nitrate being 99.2+% concentration. I will have to go over my calculations a few more times and see if I can spot errors that I might have made, which is very possible.

I want to add that I am not a chemist. I am in fact a computer and electronics technician and have been one for about 30 years. That is where my true vocation is but I also have a love for the sciences in general. I just make the effort to learn all I can about whatever it is I feel I need/want to learn for any given circumstance or situation I find myself in. I try to make sure I have a comprehension of whatever it is that I am working on. Since science is everything and everything is science then that encompasses just about everything.


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## au-artifax (Jun 11, 2013)

The reason a lot of readers are having a hard time understanding is that there are so many mistakes and errors. For example, will someone please tell me how, if you use ammonium nitrate fertilizer and sulfuric acid you end up with sodium sulfate? 
And so many places some writings are totally oblivious to the laws concerning conservation of matter and energy. Ex:so we take all this wonderful NOX and just pump it through water, or condense it, and "pooof", it's HNO3 again. First, if we are talking about the waste gasses from AR, they are of a nitrosyl chloride complex. If we are just talking about dissolving silver, copper, and base metals then we are loosing most of the nitrogen molecules making silver or copper nitrate. So we are supposed to forget that the hydrogen ever existed? The NOx gasses coming from the reaction with HNO3 making salts with metals is the decomposition of the nitric acid and NOT all the waste is NO2.... Some just NO.... Some free H.... Some fre
You're not gonna have your cake and eat it too when using nitric because you never know what state of decomposition it is in. Ultimately it will be just break down to its elemental state...with some water too.

I will be posting in the future how I make my 1.51 WFNA without a retort, without a vacuum, without water, without electric arcs, just three chemicals and three stores. Cost runs between $30-45/lt after making the rig.


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## butcher (Jun 11, 2013)

au-artifax,
I know how and can make nitric acid that strong, I am not sure what method your talking about right now but I believe it is besides the point, there is no reason for nitric acid stronger than 70% in recovery and refining, nitric of higher concentration has no place in refining, and we really discourage instruction for the fuming nitric, there are places where anyone making it can learn without being here on the forum, nitric of this concentrations is usually made to make other things that we also do not wish to have discussed here on the forum, this forum and its members are already flagged as characters for the governments to watch, we do not need more prying eyes, also not only dangerous and useless in recovery or refining, teaching others here how to make fuming nitric could get people hurt.

Lower the concentration of your nitric to around 70% and make your tutorial of that concentration, we will all then be very interested in reading your methods.


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## au-artifax (Jun 12, 2013)

Thank you for your help. You are right. I should be discussing something more to the point. Given that, I usually start from the 1.51 with no free NOx and then dilute it. It is actually easier for me with less steps to do it that way, and I do end up with 70% at my second to last stage/vessel, and altogether the reaction shows no leftover fumes in mylast vessel which de-acidifies anything that sneaks past. I guess you could say my method involves counteracting/not allowing decomposition to occur. There is a designed failsafe in my rig, and a fee must do's, so the chance IS someone would take a short cut and get hurt. 

Seeing as the initial thread had to do with "efficiency", I thought this was the right place. I do agree with you though, and will skim around the complete picture of the rig.

Anyways, the question I have is how do you do an accurate dilution of full strength HNO3 to 68-70%? Is it just a simple ratio of volume, or weights? I don't know for sure.


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## butcher (Jun 12, 2013)

Nitric acid Has an azeotrope of 68% to 70%, nitric acid if made with some water involved in the acid or reaction will make nitric acid of a strength of the acid/water involved, so if you were making nitric with sulfuric acid, diluting your sulfuric acid to about 70% will make close to 70% HNO3 (for safety we always add water to concentrated sulfuric acid),depending on which nitrate source you use, sodium or potassium can also have an effect on how much water you would wish to add, when distilling it is best to have a little more acid and water, so at the end of distilling you are not cooking salts in your distilling rig.

Extra water is no problem, because we can distill a weaker nitric acid, and then concentrate it up to its azetrope 68% by simple evaporation.

It is possible to make nitric acid with ammonium nitrate, but this can be dangerous and so we try not to discuss it here on the forum, ammonium nitrate can be too dangerous if the reaction is not run properly.

It is also possible to make nitric acid out of other metal salts besides sodium nitrate or potassium nitrate, we can also use copper nitrate salts or other metals salts.

It is also possible to make nitric acid in a reaction while you are dissolving the copper from gold plated pins, to recover the gold foils, distilling off the gases to make a useable and clean nitric acid leaving you with gold foils in a solution of copper sulfate (the copper sulfate can be used in electrolysis or for other uses in the lab, I have posted a method I use to do this called killing two with one rock.

making nitric acid is fairly easy, distilling nitric acid is easy, a good product can be made that will serve well in recovery and refining, dilute nitric about 35% HNO3, can be made and used to dissolve base metals and can then be distilled to dissolve and recover a purer silver, or the nitric acid can be made 68 % and distilled at its azeotrope, and then diluted for silver or use on base metal, the 68% can be used with aqua regia, also you can make aqua regia with a more dilute nitric acid and use heat in the reaction while dissolving metals, many times this can actually be benificial in many reactions like with the PGM's or with gold that has more silver than is desired, it can also help on fumes and help to make the acids go a bit further.

Distilling is easy but it has to be done properly, before trying it a person need to study how it is done and study the safety precautions, they need to understand simple principles, like a pressure vessel builds pressure on a boiling flask but when the heat is removed and solution cools it can create a vacuum, this vacuum can suck back cold liquids into the hot boiling reaction flask, then this cold liquids hitting the hot acids and hot glass can shatter the boiling vessel splashing hot acids all over you or your lab, an understanding and simple precautions can prevent this, and of course simple common knowledge in the lab to prevent thermal shock on glass ware, or fume control and its dangers and other safety concerns...

Here is a link to killing two birds with one rock, in this I use a pickle jar as a distilling rig, a lab-glass distilling rig would be better and can be used, but it is not totally necessary if precautions are followed, I also discuss some of the safety aspects when distilling or using a distilling rig.

http://www.google.com/search?hl=en&as_q=kill+two+birds+one+stone+&num=1000&ft=i&as_sitesearch=goldrefiningforum.com&as_qdr=all&as_occt=any

I have also made many posts on making nitric acid, and have given information in posts on nitric acids properties including boiling points, density, specific gravity, and azeotrope, and formulas, Nitric acid is one topic that I have studied in great depth to learn everything I could find out about it, so I do have considerable knowledge in its subject.

The density of nitric acid is a measure of weight (compared to water).
The content or percentage of nitric acid in water ( or fumes) is also by weight.
Nitric acid has specific boiling points, for a specific density or concentration.
Density or percentage of nitric can be measured with specific gravity or by titration, but can also be determined by its boiling point.


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## au-artifax (Jun 13, 2013)

There is a little known realm of science that deals with multiple atmospheres. Example, atmospheric pressure has a given effect on fluids (including gases), but not every substance is affected the same. Water is affected to a different degree than say nitric acid. So what if two substances vapor pressures can changed? One might have its boiling point rise ten degrees at two atmospheres, while another might see it's boiling point increase fifty degrees at the same two atmospheres.

This is where the noise starts.... I study pressures..... And I do my procedures using multiple amospheres, including distillation. I push the product through, not suck it trough, and I can control vapor pressures and purity better.
Now you can start talking about safety, but it's easy to make fail-safes part of an apparatus.


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## au-artifax (Jun 13, 2013)

I forgot to mention, pressure affects crystal formation too. Everything has a crystalline structure. Certain precipitated can form... Or not form.... Given a specific pressure. Think about it....that diamond your significant other wears is really just a limp of coal.


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## butcher (Jun 14, 2013)

As a boiler-man I am well aware of the effects of pressure or vacuum and boiling points of water, but I have not done as much study concerning many of the different fluids or acids, although I have done some study on the subject of using vacuum or pressure to distill nitric acid and other ideal and non ideal liquids, Raoults laws,and fractional distillation of liquids,and phase diagrams, and so on, enough to understand the principles, I also understand much of the safety concerns with working with liquids at high pressures and vacuums.

I am always willing to learn more.


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## solar_plasma (Jun 14, 2013)

@Butcher

Thank you for your great tutorials, your patience and the time you spend for writing those!


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## butcher (Jun 14, 2013)

Solar,
I just do the same as you and others share what I learn, I just share what I learn form the rest of you great forum members.


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## lazersteve (Jun 14, 2013)

au-artifax said:


> ...I will be posting in the future how I make my 1.51 WFNA without a retort, without a vacuum, without water, without electric arcs, just three chemicals and three stores. Cost runs between $30-45/lt after making the rig.



You can easily buy high purity 68-70% nitric acid for less than $10 a gallon (~$2.60 per liter) in bulk quantities. Unless you are in a region where the laws prohibit such purchases, I see no reason for anyone to have to manufacturer nitric acid themselves unless it is for educational purposes or for use in small scale experiments.

For purely academic reasons, I for one would like to see your post on making nitric acid, but from a practical stand point, you are better off just buying high grade nitric acid from a company that manufactures nitric acid.

Steve


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## g_axelsson (Jun 15, 2013)

butcher said:


> Nitric acid Has an azeotrope of 68% to 70%, nitric acid if made with some water involved in the acid or reaction will make nitric acid of a strength of the acid/water involved, so if you were making nitric with sulfuric acid, diluting your sulfuric acid to about 70% will make close to 70% HNO3 (for safety we always add water to concentrated sulfuric acid),depending on which nitrate source you use, sodium or potassium can also have an effect on how much water you would wish to add, when distilling it is best to have a little more acid and water, so at the end of distilling you are not cooking salts in your distilling rig.


I know what you mean but the way you have written it could be mistaken by someone not knowing better. Just want to add that...
You should always pour concentrated sulfuric acid into water, not the other way around.

And butcher... that's one long sentence! :lol: 

Göran


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## butcher (Jun 16, 2013)

Thank you Göran,
I was thinking of pouring the acid into water to dilute it, but somehow I did write that wrong, or backwards, I am glad you caught it.

I will also try not to make long sentences. :lol:


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## au-artifax (Jan 11, 2014)

lazersteve said:


> au-artifax said:
> 
> 
> > ...I will be posting in the future how I make my 1.51 WFNA without a retort, without a vacuum, without water, without electric arcs, just three chemicals and three stores. Cost runs between $30-45/lt after making the rig.
> ...




Thank you Steve... so true, and frankly I use your cold recipe for on demand uses for refining. Because of my other hobby which is upscale model rocketry, I have need of the more pure hno3, which IF I were to have a permit and licensing, (meet all the federal storage, safety, inventory, security etc regulations set forth by EPA, ATFE, DHS etc..), and were to purchase the same product, one liter would cost upwards of $1500.00 per liter.

I do not have the means, like so many like me, to go buy a regulated chemical in bulk, and of course this is why home recipe methods are so popular. But even at my best, doing small batches still cost more than how you buy it jn bulk; productiin cost for me to make 68% would be $18-20 per liter.

It depends on what, when, why, and how much you need to establish if something is of value, and the most important thing we alllll know, value is a product of supply and demand.

I have started to work with some fabricators to make interchangable parts for my process. The whole rig should be able to be assembled for somewhere between $85-110, with readily available parts. The only exception is that I am trying to fabricate the quick join connectors that will increase the service span of the rig tenfold.

The connections are the key, as this is a pressurized rig, not relying on vaccuum. In any case, tack another $7 on the cost of the pure wfna for the rig.

And after all my blathering, I am above all greatfull for you be generous with you vast knowledge. My focus is so limited, that without this forum, I would be makin so many huge mistakes, even after my studying.
As always, I am open to suggestions.

Thank you all for your guidance in the past.


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