# kill two birds one rock, making HNO3, CuSO4, Gold from pins



## butcher (Dec 16, 2009)

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 ot 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, stored in amber nitric bottle with proper lid put 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 Nitrate 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.
and 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 vapor's 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.

My hope is this is readable and understandable, and someone will gain information or it will spark ideas in others.


Richard

Edit I hade wrote chloride when meant to write nitrate.


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## dick b (Dec 17, 2009)

Hello butcher:

Nice post and sorry that you lost it the first time.

I printed a copy and plan to try it out.

Really like that it produces no waste.

Not sure that I like the idea of dumping the copper sulfate down the drain though, it is very hard on sewer treatment plant bacteria.
Most sewer and water treatment plants monitor for heavy metal concentrations in their inflow and outflow. Heavy metals such as copper kill the bacteria that are beneficial in treating waste.

Thanks for your time putting this together.

dickb


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## butcher (Dec 17, 2009)

Dick, there are many uses for copper sulfate, I was just trying to give an example, the EPA allows copper sulfate in sewer lines to kill roots for this application, as well as for putting it on grapes, and used in mining and metal recovery, many other application's,
most mine is used in electrolysis and recovery methods.
if we have a chemical there are usually many uses for them with a little study, we can recycle our waste products as much as possible.

I tried to post a link to Wikipedia on copper sulfate, but could not get the link to work


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## PreciousMexpert (Dec 17, 2009)

Hi Butcher
Thanks for that post 
The only thing is I love birds and nature and I dont like that saying.
Anyway you always try to help people in this forum thanks.


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## patnor1011 (Dec 17, 2009)

PreciousMexpert said:


> Hi Butcher
> Thanks for that post
> The only thing is I love birds and nature and I dont like that saying.
> Anyway you always try to help people in this forum thanks.



I am sure butcher meant birds which are cariers of avian bird flu. :lol:


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## Anonymous (Dec 17, 2009)

Hey Butcher,
If you get some glassware that can take the temp you can distill sulfuric from the copper sulfate which also works with the copper nitrate.

If you use lead for the anode you can directly electrolyse the sulfuric back out of the copper sulfate and make copper at the same time.

Jim


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## golddie (Dec 18, 2009)

Hi Richard
Thanks for all that work you did.
I was wondering if it was possible to see pictures of some of these things, it would make it more understandable.
Thanks again


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## butcher (Dec 18, 2009)

I am a computer bozo, I could get my wife to get the picture in our computer but I dont know how to get it into the forum post.

there is really not much to a homade distilling rig, if you are afraid of the canning jar a chemistry beaker or flask can also be used with this sand bath, you can buy distilling rig for around $100 and up, I have one (but its too perty to use). made for this.
I have a pyrex coffee pot that looks like a elmer flask(?spelling) with a handle have distilled HCL with it, the cork with this one mase from that new deck fake wood, i think is made from recycled milk jugs, it holds up to HCl and temperature but not sure about it with nitric, I know teflon can take the nitric.

nitric eats rubber, thats why the teflon is important.

james from my understanding we need close to 300 degrees to distill the SO2 gas from sulfuric, or copper sulfate, but when mixed with oxygen from air changes to SO3, and if we bubbled this into sulfuric acid would make oleum, which if we diluted would make sulfuric acid,
you are right, there are so many choices we have and options we can take for useing our waste materials. 

speaking of electrolyzing the copper sulfate, I have a question, with lead, if it was used at the anode so it did not dissolve, (lead sulfate passivation), then my Hydrogen should not gas off at the cathode, is this assumption of mine correct?
and if I used Iron as the anode which would desolve with SO4, replacing copper in solution with ferrous sulfate (copperas), then I can get Hydrogen gas at the cathode and oxygen at anode?
I am slightly unclear as to the gassing at the anode in diferent circumstances, maybe someone can help here.

I too love wild life, and protect it, but I also eat meat, and growing up on wild meat, I prefer it over meat raised eating out of its own bathroom, (bred to genetically alter the animal and how fast it grows) (fed hormones and doped up with antibiotic because of its enviroment)I love plants too and think we need to protect them and not be cruel to them, but I also am a vegitable and fruit eater, so when I harvest my garden I try to be as humane as possible when I pick the vegitables from the vine, so as to not let them suffer, the same as when I take an animal for the meat of my table, I take the animals life so he does not suffer. that is natural, but if you like to get your food from the store and think you dont take life great, just be humane about it. :lol:


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## Oz (Dec 19, 2009)

butcher said:


> I too love wild life, and protect it, but I also eat meat, and growing up on wild meat, I prefer it over meat raised eating out of its own bathroom, (bred to genetically alter the animal and how fast it grows) (fed hormones and doped up with antibiotic because of its enviroment)I love plants too and think we need to protect them and not be cruel to them, but I also am a vegitable and fruit eater, so when I harvest my garden I try to be as humane as possible when I pick the vegitables from the vine, so as to not let them suffer, the same as when I take an animal for the meat of my table, I take the animals life so he does not suffer. that is natural, but if you like to get your food from the store and think you dont take life great, just be humane about it. :lol:




I have always found it amusing when I am criticized for hunting by someone that eats meat. If however I am held to task for hunting by a vegetarian and they refuse to use animal products like leather or cosmetics, I then have respect for their opinions as they are at least not being hypocritical. Somehow people seem to think that those cellophane packages containing meat are picked off of trees. They pay someone else to do the killing thinking their hands are clean.

I think every meat eater should at least once in their life have to look their dinner in the eye as they take their life. It is the natural order of things that life takes life to live, but people have lost the ability to comprehend the sacrifices that are made for their continued existence. There would be a lot more vegetarians out there if for once in their life they had to face the reality and consequences of what they ask others to do for them in order to enjoy their typical dinner.

Odder still to me are those that will lament and cry for the deer, squirrel, or rabbit that has been hit by a car with what is surely a fatal wound yet just watch it slowly die wreathing in pain instead of ending its life and suffering. Then of all things once it is dead just leave it on the side of the road to rot. That is what makes it an empty death of no use. Those same people will tell me how insensitive I am when I dispatch the wounded animal and put it in my truck for dinner that evening.


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## Harold_V (Dec 19, 2009)

Oz said:


> I think every meat eater should at least once in their life have to look their dinner in the eye as they take their life.



I agree. I am not a hunter, although I own guns and have hunted in the past. The one and only deer I shot was a head shot, and instant death. I didn't take pleasure in watching the beautiful animal die, so I no longer hunt. I am not against the harvest, and I enjoy the meat, gladly accepting what little I am offered by friends. It's just not in me to do the killing. 

Harold


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## golddie (Dec 19, 2009)

Hi Richard 
Thanks for your help
If you are able to get your picture on your computer then place it on this web site 
http://img12.imageshack.us/

click browse
then click upload
tthats it

Then give us the link so we can see it.
Thanks


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## golddie (Dec 19, 2009)

Everyone loves nature but in this world that we live in we cant hold on to it.
Everything we do is against nature.


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## Anonymous (Dec 19, 2009)

golddie said:


> Everyone loves nature but in this world that we live in we cant hold on to it.
> Everything we do is against nature.




No, everything we do is not against nature. We are a product of nature and do what nature has intended us to do, just like everything else in this world. We follow natures process of distruction and rebirth, the earth has changed several times and will always change, even long after we are gone.

Jim


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## butcher (Dec 19, 2009)

Here is a labware type.


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## PreciousMexpert (Dec 19, 2009)

Hi Butcher 
Thanks for that picture


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## butcher (Dec 19, 2009)

thanks Oz you explain things well, and we see many things the same, I do not like putting the life out of a suffering animal, but it is to me better to put the animal down, much more kind than to turn my back and pretend not to see it suffer, and as far as leather or fur, I feel the leather should be used for more than just to fertilize the grass, which eventually it will any way,
to me life is like chemistry, the life is not destroyed just replaced just as iron will displace copper in solution, so life is displaced,the bird eating a live grass seed or a live worm, the life from the grass seed is transferred to the bird, it is not destroyed, the shell my be but not the life.
I think in modern society especially in city's people have lost touch with reality, kinda reminds me on tv I seen a show of that hulk hogan family gonna save the planet, gonna go green, here they were not going to flush there toilet, and to drink bottled water from plastic store bought recyclable bottles, turning the thermostat down on there mansion, getting into the Humvee to drive across the city to recycle the bottle, 
that's what this world needs city environmentalist saving us from the planet. and from our food.
a living thing does not live long by eating death a living thing needs to eat life to live, and all humans eat life,even if they just eat grass, and I don't know anything that lives forever, but everything including us give our life to some other living thing to eat of our flesh, as humans we prefer to feed ours to worms disease or fire, 
life move from the living grass, to the buffalo, then moved from the buffalo to the small Indian boy eating the jerky, then moved from the old dead Indian to the worms, then moved to the bird, and back to the grass, these cycles are nature and are in everthing everything. 

sorry for the rant, I do love nature, and animals, and have nursed many wild wounded animals back to live a good long life, but I have also ate from the woods and from animals I have raised for meat, and had to put down many animals we have loved for years as part of our family, my daughters are grown now, you will not find many who love and care for animals more than they have, and still do, they worked for petting zoo's and often would make pets out of the animals that were in too bad of shape for the petting zoo,(which would have put the animal down) we had our own zoo, and they raised all kinds of animals, wild and domestic, my daughter's at 12 years old would put those animals to death by gun that they loved so much instead of watch them suffer a lingering slow painful death, yes it is hard and unsightly, but I believe my daughter had more love and care for that animal than the city person who dumps there dog out on the country road because they are tired of taking care of him, so then I end with their starving dogs and cats, on my property and end up having to put this dog down, because I cannot afford to feed all these sickly starving dogs, these environmentalist's dump thinking this dog will find a good home, and not wanting to do there own dirty work, lying to themselves saying they love animals, Yes I kill animals, and eat animals, but have never abandoned one, or let it suffer, yes I cut down trees, and dig in the ground, I feel I am the real animal lover, and the real environmentalist, I have lived with the forest, not in some concrete city, watching tv, and being hypnotized by it, devouring all the products provided by nature and our environment, lying to myself and others, preaching how others are destroying my planet, and should not be able to live. 
what a crock of bull.

how do we get from distilling, and metal recovery to this?


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## goldnugget77 (Dec 19, 2009)

Hi Butcher
Can you explain that picture a bit
Thanks


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## butcher (Dec 19, 2009)

it is a lab glass distillation unit, distillation is nothing more than boiling something, making some part of it boil to gas, condensing the gas back to liquid,thus separating it.
Ole time stills in the mountains of Kentucky used this principle with corn mash or sugar to make some good strong spirits, by the light of the moon.

the boiling flask is on the left, it has joints made to fit tight to each other, the liquid we want to distill would be added to this flask, there is also a thermometer, small long thing on top, because certain volatiles or acids have differing boiling points knowing the temperature can be very helpful and especially if separation of two components you are boiling have very close boiling points,
heat is put under this flask on the left, the boiling flask or reaction vessel, the gasses evaporate from this flask and go to the condenser the glass pipe in between the two flasks, this condenser is actually a glass tube inside a glass tube, the gas from your boiling flask goes through the one tube and is cooled of to condensate (liquid) by water flow through the outer tube, cool water is usually flowed through this outer tube from a faucet or pump, the condensate of these condensed gases are captured in the receiver, the flask on the right. the stand is just holding the lab glass in position.

I have no formal chemistry education and can only explain this from what I have learned on my own, and I ain't good at talk'in or explaining thing's so I may call something different than a chemist would, distilling though is easy, any hillbilly can do it. and many a hillbilly, had some very creative stills.


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## goldnugget77 (Dec 19, 2009)

Hi Butcher
Maybe you dont have formal chemistry education but your explanations are very good 
Thanks


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## golddie (Jan 4, 2010)

Hi Richard
Thanks for posting this interesting topic
From what I understand you have the REACTOR VESSEL and the container that acts like a SCRUBBER 

This is how I picture your experiment
1) REACTOR VESSEL
A pot with sand and in that pot with sand a pickling jar with with a lid and a 1/4" Teflon attached to the top

2) the container that acts like a SCRUBBER
gallon bucket (plastic ok) with ice water 
in this bucket a bottle with hydrogen peroxide(optional)

You have the hose from the reactor going to the scrubber 

In the reactor you have
6 cups of sulfuric acid
copper
1 cup sodium nitrate

Maybe I have to read it a few more times 
can you tell me if this is correct and also the bottle in the scrubber side how do you save it and keep it for future use


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## butcher (Jan 5, 2010)

you pretty much have the picture,
what you are calling a scrubber, is not really a scrubber,
but a collection bottle (to collect and condense the gas (cool back to liquid) gas bubbling these gases in water(H2O2 can help to NO2 gas in solution, and assist to make a nitric acid) this reciever collection bottle is sitting in Ice water bucket, to keep it cold so gas change's to liquid,
after the acid is made in this reciever bottle, the acid is moved to a storage bottle, or used as needed.

I can see where you see it as a scrubber, as a reciver bottle can be used to scrub or destroy the acidic gasses ( called scrubbing the gas), but the chemistry is different in that use of the collector bottle.

a lab beaker, boiling flask, erlenmeyer flask, or a chemistry distilling lab glass rig ( best), can be used instead of old pickle jar, the sand bath is to protect the glass from heat and sudden chenges in temperature, (glass does not like that), I just like the wide mouth of the jar.

the good fitting teflon lid is important if making nitric acid, as nitric will eat rubber and can react with some materials. and hose type is also important, a lab distilling unit would be the best it's joints are ground glass tight fitting,

read it good before trying it and ask questions if you are not sure about something, it is really simple just hard to explain.


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## golddie (Jan 5, 2010)

Hi Richard 
Thanks for your help.
I have been reading reading this thread carefully and I find it very helpful
Here are some questions and observations 

1) 
2NO2(g)
what does the g stand for 

2)
you didnt use hcl to drive off the nitric

3) 
how much is the amount of water you add to dilute the syrup.

4)


> nitric bottle with proper lid put of light in safe place for later use in recovery or refining


what do you mean by put of light

Thanks again


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## Barren Realms 007 (Jan 5, 2010)

golddie said:


> 4)
> 
> 
> > nitric bottle with proper lid put of light in safe place for later use in recovery or refining
> ...



I think he ment to say _*out*_ of the light


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## butcher (Jan 5, 2010)

Yes keep your nitric acid from light, it breaks down in light, that is why they use amber bottles (brown bottles) to store it in. even then I keep it in a dark place. (I edited typo in original post thanks for catching that).

(g) in the formula stands for gas.
(aq) is a solution in water

In this we do not use HCl to drive off nitric, that is a different process.
Here we are driving the gas from nitric, with its boiling point, this NO2 and NOx gas is bubbled into the reciever with water forming nitric acid.

Sulfuric acid acts a a dehydrating agent, beside making nitric from fertilizer by giving the hydrogen to the nitrates, and giving the sulfate to the copper.

Copper can help to form the NO2 gas we are using to make nitric acid with, copper also heps to drive these gases out of the boiling flask.

We add just enough water to dissolve the copper sulfate salts when cool, so we can get the gold flake's seperated from the soluble salts of copper sulfate. If we did not have the gold in with the copper we would not need to dissolve them.


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## golddie (Jan 5, 2010)

> Here we are driving the gas from nitric, with its boiling point, this NO2 and NOx gas is bubbled into the reciever with water forming nitric acid.


Hi Richarcd
Are you driving the gas off with sulfiuric acid or jus water


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## butcher (Jan 5, 2010)

Goldie, it is only heat that drive's off gas from our boiling solution.

In the boiling vessel we are making a poor mans nitric acid, using the nitrate fertilizer, for this we are adding a sulfuric acid (which will have some water in it), the more concentrated the sulfuric the more concentrated the nitric we will produce, the reason for not using pure sulfuric is we dont need too strong of nitric, about 68% or less.(this is about as strong as we could get it unless we done thing's differently like changing pressure), now this boiling vessel we are also dissolving copper (to get gold off of pins).

there is something call azeotrope and acids and water(concentration) in solutions have certain azeotrope's they will determine the boiling point of the NO2 gas in the solution, and the concentration of the solution will determine which will boil out of boiling flask as gases first,the acid cation, or water
nitric acid and water has an azeotrope of 68% this is why it is sold at that concentration. when boiling a solution with a lower than 68% concentration of nitric acid, mostly water comes out as vapor, and solution concentrates untill it gets to 68% concentration then the ntiric will boil off as NOx gas untill dry. or if we started with a very concentrated nitric say 98% and 2% water, and boiled this the water does not boil out first, if we boil, we boil off NO2 untill solution reaches azeotrope 68% and then if we further boil we still just boil off NO2 till dry. so you can see from this we can not concentrate it to a higher concentration by boiling,(we would need reduced pressure and minimum water in the mix).

Also different concentrations of acid (water) have different boiling points, when we work with these acids and heat, knowing this can help us to know what temperature we need to keep our NOx (cation) in solution or to boil it out of solution which ever we are trying to do. 

Sulfuric acid acts as a dehydrator, this means it helps to absorb the water, here sulfuric in solution can help keep water in the boiling flask and our nitric we are making will be somewhat stronger.

To answer your question we are using neither sulfuric or water to drive the gas from solution.
We are using heat, and the boiling point to drive these vapors out of the boiling vessel, (now copper in this solution helps this also, as copper dissolves it releases the NO2 gas from the nitric).
what boils out depends on concentration, temperature, pressure, and the acids azeotrope.


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## golddie (Jan 6, 2010)

Hi Richard
Thanks for taking the time to explain


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## maynman1751 (Mar 16, 2012)

One more question Richard. How much H2O, H2O2 do you put in the receiving vessel? What's enough but not too much that it would require less evaporating(not boiling  ) to concentrate the resulting Nitric? Would a longer, thinner column of water (vessel) have a tendency to collect more from the bubbling gases? Thanks as always.


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## publius (Mar 16, 2012)

butcher said:


> Here is a labware type.



I really find this picture somewhat disturbing. I recall s a story of an assayer who kept the out put end if his mercury retort, under water to collect any Hg vapors that might not have been condensed within the water jacket. One day the gas when out. The retort began to cool and sucked water into the hot end of the retort. Long story-short: BOOM! :shock: 

No one hurt. But there could have been.

As long as there is some kind of vacuum breaker on your system there should not be a problem.

Now someone asked about the long(er) column being more efficient. The answer is yes and no. The colder the liquid is the more efficiently it will absorb a gas. The more pressure that liquid is under the more gas can be absorbed. so if you column is 1 meter tall the pressure is greater at 1 meter than it is at 500 cm. If the fluid is chilled to near freezing the greater the absorption is. If you reduce the size of the bubbles the faster they will diffuse into the fluid. Each of these factors has an optimum pressure/temperature/and diameter.

That being said, Because you are relying on pressure developed from a boiling a fluid and then cooling it to condense some component, you may not have enough pressure to push past the pressure developed by the column of fluid (H2O and H2O2 in this case) to even be able to develop a bubble.

Then re-read the first part of my post, for what I expect to happen is something goes awry with the system...


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## Geo (Mar 16, 2012)

my redneck condenser.


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## kuma (Mar 16, 2012)

Hello Butcher , how are tricks?
I hope your well chief!


butcher said:


> this reciever collection bottle is sitting in Ice water bucket, to keep it cold so gas change's to liquid,


This is another case of it's so simple , it's genius!
I probably wouldn't have thought of that off of my own back , it's 'lil tid-bits like that that seem to make all the difference , especialy to noobs like myself , so once again thank you chief! 
All the best for now , and kind regards ,
Chris :mrgreen:


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## butcher (Mar 16, 2012)

Kuma, thanks I am doing good, we learn tricks from each other.

Geo, very nice condenser, and it is long enough to condense the fume to liquid.

maynman, I use the least water to start I can, as it will develop more liquid in the receiver as it distills.


publius,
yes you are correct distilling this hot liquid and bubbling it into a receiver is very dangerous if not done properly, the boiling flask if heat is removed becomes a vacuum source, and if it is cooled without removing the condenser tube to the cooler liquid this liquid will suck back and hit the hot glass full of boiling liquids and will break the glass.

I am glad you brought up the caution, as the details of the warnings and dangers involved should not be taken lightly, If a person wanted to distill and did not wish to bubble into a condenser, they could, as long as condenser was capable of cooling the gases to liquid, they can then leave the tube open to atmospheric air and drip condensed liquid into the receiver, there would be some gases that may escape, and some NOx gas loss, and it would be safer if you did not pay much attention to details of the process, there are several details of the process that can be dangerous if you do not pay attention to warnings, or how you perform the task, but if you do pay attention to details it can be done safely.


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## maynman1751 (Mar 16, 2012)

Geo, what did you use for the center tube on your condenser?


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## maynman1751 (Mar 16, 2012)

Butcher, instead of concentrating battery acid could you use 98% sulfuric? If so, how much to balance the recipe?


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## Geo (Mar 16, 2012)

maynman1751 said:


> Geo, what did you use for the center tube on your condenser?



i bought some glass tubing from a local neon sign company.its pyrex and melts with a small propane or mapp gas torch. that particular piece is 3/8" and 4' without the bend. i buy it at $2.00 a stick. i got 5 each of 1/4",3/8" and 1/2".


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## butcher (Mar 16, 2012)

I found that some water in the reaction worked better, so diluting the 98% sulfuric would work well.

Again, this is dangerous and requires attention to details:
Always dilute the acid by pouring it into water.

(Never pour water into concentrated sulfuric acid):!: 

copper is major player in making nitric acid in this process helping to generate NOx gases, the nitrous oxides need oxygen to convert to nitrogen dioxide gas or the will just bypass the condense and escape the system, the nitrogen dioxide gases need water to convert to nitric acid.

You want to try and get about 60% to 70% nitric acid, other members are much better at the math

Here is how I look at it you will have 40% water in the 60% nitric acid, 

0.40 X 6cups = 2.4 cups water

6cups total – 2.4 cups water = 3.6 cups of 98% sulfuric acid

2.4 cups water divided by 3.6 cups sulfuric 98% = 0.6 (60% acid and 40% water)

We could calculate by density and milliliters, but I would try this and see how it worked, my math skills need work, you can test the density of the nitric made to see if you need to adjust recipe.


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## Topher_osAUrus (Apr 1, 2016)

Just had to bump this old thread.

Butcher, you are a brilliant man, and very detail oriented.

I used a combination of this and a couple other threads to set up a type of still/scrubber unit to recycle the HNO3 ive wasted on dissolving copper, but only doing it part way (impatience as a noobile, not letting the reaction finish before adding another bit of acid.. 

Only problem with this thread, is the title... You, good sir, are getting 3 birds with 1 stone... The nitric...the copper sulfate...and the gold. Three very beneficial things in one fell swoop..

Recycle, recycle, recycle.


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## butcher (Apr 3, 2016)

If you wish to recycle as much nitric acid as possible, remember, the more NO2 gas that leaves the reaction the less nitric you will be able to recover from nitrates.
Diluting a reaction will help, also add a little H2O2 can help, this has been discussed many times on the forum.

I am glad you like recycling or making some of your own reagents.

I have made several post on that topic, many other forum members have very good topics on it.


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## Topher_osAUrus (Apr 4, 2016)

butcher said:


> If you wish to recycle as much nitric acid as possible, remember, the more NO2 gas that leaves the reaction the less nitric you will be able to recover from nitrates.
> Diluting a reaction will help, also add a little H2O2 can help, his has been discussed many times on the forum.
> 
> I am glad you like recycling or making some of your own reagents.
> ...



(i couldnt choose color on my phone, but for some reason could make it ridiculously large)

I usually run my acid diluted to cut back on loss of NO2, but i havent tried h2o2 in mt AR or when I run silver in nitric. I believe i read(when i first started my scholastic journey a year ago) of someone adding h202 in the middle of their process (AR-unknown material[at least i dont remember it]) and it caused him some problems.

Was this because he used too much h202 and did not replenish the nitric? 

I only use h2o2 to help capture and convert the NO2 gas to HNO3 when i have the still set up...

Although, admittedly, i bought 4 gallons when i was going to the schoom of youtube, thinking i would need it in my AP just as much as HCL....such a fool.. But, you dont know what you dont know until its right in front of you sometimes... If only i would have found this forum before those videos..

Thank you butcher, you are a brilliant man and an absolute blessing to this forum. Your contributions to my learning have no bounds.


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## butcher (Apr 5, 2016)

The only thing that comes to mind is too strong of hydrogen peroxide with silver. 

Strong H2O2 can reduce silver, we can use the H2O2 aspect when converting silver chloride using H2O2 and NaOH, to reduce silver chloride to powders of metal silver.

Also using too strong Hydrogen peroxide with silver can be dangerous in some instances, or under some conditions silver can act as a catalyst, giving a violent reaction, (makes me think of a think Jet engine in your beaker of acid.

What I was referring to was a little dilute hydrogen peroxide, 3% for example that is mostly water, and a solution dilute with water. We only need a little peroxide to provide some oxygen to convert the NO gas to NO2 gas, then the water converts the NO2 gas to HNO3. 

This is a small example where I will study well before I try something I read, This is basically chemistry we are working with. Some things can get dangerous, if we do them wrong, or we do not know, or understand enough of what we are doing.

I want to be able to understand the reaction or what could happen, or how to use the information I read. Many times we may read a little about something, but do not get the whole picture, or understand all of the possible reactions. in our educated mind we may think we know enough (we read a few pages of info and watched several you tube videos, and we could try something. which may turn out to become a mess, or even worse a dangerous lab accident, a foam over if we are lucky, a possible explosion if we are not, being blinded, or worse, from the glass beaker we had in our hands.

Like reading HCl and nitric acid dissolves gold,We can do that sounds really easy, so we pour some HCl in a beaker, add a gold ring and dump in some nitric, well we could have many problems from here, some of our gold may dissolve as we cough and choke on the red clouds of deadly gas. then we may have other problems not getting much of it to dissolve, or trouble getting it back out of solution... All because we got in a hurry and did not research enough, thinking we done research...

Study everything, and study it more, and keep studying. You can never learn enough in this field of chemistry, and the other arts associated with precious metal recovery and refining.


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## Topher_osAUrus (Apr 5, 2016)

I agree completely butcher.

You can truly never know enough, can you? 
(unless you are my wife, who is infallible and knows everything)

You answered my question spot on though (i believe, but I want to clarify just in case)

When adding dilute H2O2 to an AR solution, you in reality, are probably cutting the HNO3 down to around a 10-20% concentration level, assuming its already 50-70%, then cut to 35 with water, then remainder of the dilution from H202 and water thats in the HCl, correct? 

I want to give it a go, but don't want to cause any unwanted issues down the line... 

Thanks again, for the thread, the wisdom, and many things i have yet to learn from you and GRF.


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## butcher (Apr 6, 2016)

I normally do not add H2O2 to aqua regia, although you could. Diluting the solution usually works well for me.

In aqua regia we are normally just using it to dissolve gold or other noble metals, very nonreactive metals like the platinum group metals, ideally with very little base metals or silver, in aqua regia the nitric acid is the oxidizer. Alone the nitric acid will not react with gold, and HCl will not react with gold. When these acids are mixed to make aqua regia they react with each other to make volatile gases in solution which forms nitrosyl chloride NOCl, and chlorine Cl2 gas.
HNO3 + 3HCl --> NOCl (g) + Cl2(g) + 2H2O

The nitric acid in aqua regia will help to oxidize the gold, to slightly attack it, taking electrons from the gold. But it is probably not the nitric as much being the primary oxidizer in solution, as it is the nitrosyl chloride and the chlorine gas being the primary oxidizing agent attacking the gold.

The NOCl and Cl2 gas are volatile in solution, and begin to gas out of the aqua regia as soon as we make aqua regia by mixing the two acids, a concentrated solution, a hot solution or a solution with metals involved, can make the gases leave the solution faster. Dilution of the solution, lower temperature, (less base metals in the metals especially the more reactive metals we are dissolving), the longer these gases can remain in solution to react with our gold. Dilution and lower temperatures can insure the gas stays in solution to react with gold, raising the temperature can make it react faster but will also cause more of our gas to leave the reaction, giving us less gas in solution, or what we need in solution to dissolve our gold.

So starting out with lower temperatures, and diluting the solution can help to insure we get more metal dissolved into our acid with a certain volume of acids used, or more bang for our buck with less acid used to dissolve the gold. This also makes less loss of the valuable volatile gases leaving our solution or polluting our air.

Adding H2O2 to aqua regia may help somewhat, but in aqua regia, unlike where we dissolve silver, or copper in nitric acid, Nitric oxide NO and nitrogen dioxide NO2 are not our primary gases formed which act as the oxidizing agent for the metals. 

Although we do get the several different nitrogen oxide (NOx) gases forming from these reactions in aqua regia, and leaving our solution from decomposition of the nitrosyl chloride, NOCl decomposes to form nitric oxide (NO) and chlorine (Cl2) gas.

2NOCl(g) --> 2NO(g) + Cl2 (g)

Because the nitric oxide (NO) reacts with oxygen in the atmospheric air above the beaker, we can see the gases as brown fumes, nitrogen dioxide reacting with the air, the brown fumes of NO2 which form from the reaction of nitric oxide and oxygen, producing nitrogen dioxide gas.
2NO + O2 --> 2NO2

Dilution is very useful with aqua regia, H2O2 may not help that much in my view.


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## Topher_osAUrus (Apr 6, 2016)

Thank you for that information butcher.

I greatly appreciate it.

After i read Mrs. Hokes book, i quickly grabbed my old chemistry book and began reading it cover to cover to brush back up on my fundamental chemistry knowledge (its been a long time since my freshman year of highschool).

It is very apparent to me that you are a thorough and meticulous man. Just like a great many of other members of this forum... As dave has said, we are men cut from the same cloth.

Thanks for taking time to give me valuable insight. Hope the weather is fair for you up northwest. I got my first truly nice day in awhile here, so now its time to build some stuff.

Have a good one. And thank you again.


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## butcher (Apr 7, 2016)

The weather here is just beautiful, but it is a shame, I have been too busy to be able to enjoy it.

I feel I need to make a few more points to add my last post, dilution of aqua regia helps keep gases in solution, but it can also slow down the reactions. A double edge sword, you need to determine when to use.

Heat along with dilution can be helpful in many reactions.
Heat can speed up many reactions, or drive off gases, (wanted or unwanted), sometimes make salts more soluble...
Each of these can have polar opposite effects.
Cooling can help keep gases in solution, or it can slow down many reactions, it can also be used to make many different salts more insoluble...

When to heat, dilute, cool or concentrate, with many reactions, we do, these can be on dependent on many different factors or circumstances, like how the acids react with metals, if we wish to conserve gases in solution, what metals we are reacting acids with,which acids we are using, and many more reasons this list can go on and on, basically when we learn the reactions and what happens in them, or gain experience, we can decide, or know, when dilution heat or the combination of, can give us an advantage for a desired outcome....

I never had any chemistry in school, (maybe some in high school where I did not learn a darn thing) I learned most of the chemistry from the forum, my research, work in my trades and from my little lab under the shade of an oak tree, recovering and refining what little gold I can get my hands on, Oh, and also from a few times from my mistakes (well maybe more than a few) :lol: ...

Topher_osAUrus, 
You are the kind of member that makes this forum such a great place, you are interested, and will take time time to find answers, and do the needed research, in doing so you will be teaching us.
Welcome to the forum.

Education is as good as gold in our pockets, actually it is better, it will help us to put gold in our pocket, as well as the understanding in our minds.


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## Topher_osAUrus (Apr 7, 2016)

Butcher, that is flattering, to say the least... But, i am simply here to learn and pass that on to whomever cares to hear me ramble... As Mrs Hoke said (a quote from another book that i coild not find to download...although i tried for many a hour to find it)
"No matter how a text is written, one reader will yearn for more
details while another will be bored by the tedious explicitness."

The greatness of this forum comes from the compilation of minds who are the former of that quote... We all have an insatiable thirst for knowledge, and only those with great hubris can say they know it all..

I love science....chemistry is wonderful and amazing....captivating. When i was young i wanted to make my own fireworks... Now im old(er...ish..) and i do just that... And that hobby lead me to another... And that one, this one, i like so much more... To see noble metals evade corosion from our natural atmospheric oxidation but yet bend to my will..(unless you have MASSIVE amounts of acid rain...I live on the outskirts of a big city...JUST far enough out of the limits to excercise my second ammendment rights without local law enforcement pestering me) 

I make my nitric depending on how i feel that day....sometimes i recycle my stupid mistakes... Sometimes i make some mickey mouse acid (as gsp originally called it lol)..but, for that one. I do it slightly different... I (of course) keep the molar ratios intact (for the most part) but... I do this

1. Bring 100 mL Distilled H2O to boil, remove from high heat
2. Add 250 g of NaNO3 (i will elaborate shortly)
3. Stir until nitrate no longer dissolves
4.filter hot solution to remove impurities
5. Allow solution to slowly (VERY slowly) cool to precipitate pure nitrate crystals.
6.decant the remaining nitrate liquid 
7. Dry and weigh crystals (sometimes i skip this)
8. Bring fresh 100ml h20 to boil(then lower heat)
9.add 170 g of pure NaNO3 crystals
10. Then i continue to do the traditional cold method until i distill the nitric off... The only other step in it i add, is snother filtration of the NaSO4 crystals before i put my solution in my salt/ice bath to sit overnight

I add a surplus of the initial nitrate prills because i am unsure of the purity (it says its a certain percent, but is that per prill, are nitarte prills mixed with bunk prills...etc... So, my logic was to mske as pure of a nitric as possible to put into my still)

Id appreciate any comments or concerns with this modified procedure.

Forgive my mis-punctuated paragraphs and typo's, writing this reply on my phone is a pain.

Again, thank you, i eagerly await your reply


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## Anonymous (Apr 7, 2016)

Praise from Butcher indeed Topher. You've been here a couple of months and had those kind words from Butcher. Some of us have been here years and hardly even been acknowledged 8) 8) 

(Butcher my tongue is firmly in cheek here - don't think I'm upset in any way :lol: )


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## FrugalRefiner (Apr 7, 2016)

While dissolution, filtering, and crystalization can all be used for purification, it depends on what you start with whether it will accomplish your goal.

If you dissolve common rock salt and filter the solution you will remove insoluble material and end up with a purer salt solution.

Likewise, you can separate lead chloride from silver chloride by dissolving the lead chloride with hot water, leaving the insoluble silver chloride behind, then cooling/evaporating the solution for relatively clean lead chloride.

But if you have a mixture of sugar and salt, dissolving it, filtering it, and evaporating it will still leave you with a mixture of sugar and salt.

Whether your process will yield a purer NaNO3 depends on what it might be combined with.

Dave


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## Topher_osAUrus (Apr 7, 2016)

FrugalRefiner said:


> Likewise, you can separate lead chloride from silver chloride by dissolving the lead chloride with hot water, leaving the insoluble silver chloride behind, then cooling/evaporating the solution for relatively clean lead chloride.
> 
> 
> Whether your process will yield a purer NaNO3 depends on what it might be combined with.
> ...



Yes, there is another step that the original guide for making nitric (besides the cold nitric one) i use sometimes, depending on if im refining with the product acid or if im doing extracurricular activities with it... And that step is, if the ppt salt of the NaNO3 is not in good crystal form, indicating impurities, it can be washed with isopropyl alcohol (there was another solvent that could also help remove impurities, but im not by my desk at the moment and dont want to give misleading information by my forgetfulness)

I also want to thank you dave, you've beeb very helpful in accommodating in my short lived forum career so far. I appreciate the warm welcome to a noobie.

You are all great


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## butcher (Apr 7, 2016)

I Have praise, admiration, amazement, thankfulness, and, many other feelings and thoughts of the great members we have here on the forum.
But if I patted everyone on the back, thanked them for the great information they provided, told them how amazed I was at their insight, or knowledge insight or wisdom, how great of a job they were doing... 
I could easily double, or more, my post count, and most likely fill the forums data base with praises...
Many times I am at loss of words, have a hard time saying things, or could not come close to expressing my admiration, or appreciation.

Do not feel, or think, I do not recognize,or am amazed at your skills, your wisdom or knowledge, that I do not have appreciation for... 
The forum, and its great members mean to a lot to me, many here are a special breed of humanity.

I may not say it out loud, or recognize members in words,or individually. but that does mean I do not have a special appreciation, gratitude, or that special place in my heart, for you, and your contribution.
If I do not mention your name it is not because I do not recognize you.

All I can say is the forum members are great, and I thank you all.


Topher_osAUrus,
Distilling in itself is can be a major improvement in purification, or separation.
When distilling anything that is not volatile will stay in the boiling flask if the distillation process is run properly.
Some things like NaCl salts (which also can form volatile HCl gas), can be mostly removed from your feed stock using solubility rules, re-crystallization, filtration, and other methods...
As well as discarding of the first gases of a distillation run, which can help to remove the more volatile gases like HCl from your final product... 
Much like the refining of metals. The more trash in, the more trash out which could add to contamination to our final products...
Again the more we understand and have knowledge of, the better we get in our chemistry of these metals, acids and salts...
Education is as good as gold in our pockets.


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## Topher_osAUrus (Apr 7, 2016)

Butcher, i agree COMPLETELY...with everything i have read of yours.. 

I still feel flattered that i was one of the ones to get positive affirmation from you. It truly means alot and is another source of inspiration... But, yes... If i were to thank everyone that has helped me learn here...id have over 2,000 posts already and wouldnt ever have any time to refine my skills as a refiner!

Every. Single. Member...that is an active member ...well...you nailed it... They are a special breed. And i am glad to be apart of this community...and will continue to be until the day i die...or the internet does.. 

Hopefully by then i have read all 200k posts and have 60 notebooks full instead of just 6.

I wish the best to all of you.

Hopefully you can get some time to refine butcher... I had to steal some time today, but its beautiful outside. So i am glad to be out from behind my desk inside and outdoors, doing what i love


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