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guy
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[*] posted on 1-8-2006 at 12:25
MnO2 from batteries


I have a 6 volt lantern battery, and I tried to get the MnO2 out. It seems that the MnO2 is also mixed with a carbon paste because when I reacted it with acid/H2O2 it still was black, even after heating. Do these batteries have a carbon paste?



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not_important
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[*] posted on 1-8-2006 at 16:55


Most likely :

http://www.energizer.com/learning/howbatterieswork.asp
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Mr. Wizard
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[*] posted on 1-8-2006 at 19:37


I've thought about scavenging the MnO2 from batteries, and I have a 5 gallon bucket full of dead alkaline batteries. I plan to split them down the side with a wood chisel and drop the whole mess into a 5 gallon bucket full of warm water. I plan to stir and rinse a few times, allowing the black solids a day or two to settle in between stirs and to discard the liquid, and any dissolved material. The solids I plan to rinse through a plastic window screen to remove paper, metal, and anode rod chunks. After another good rinsing and a few days to allow the solids to settle I will use a siphon to remove as much water as possible, without stirring up the sludge on the bottom. I then plan to warm the material in a cast iron or steel pot until it is red hot. I'm hoping this will oxidize any carbon black or charcoal mixed in the solids and leave the MnO2. Any suggestions or comments?
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[*] posted on 1-8-2006 at 22:51


I've had some success in rendering batteries for manganese. I look for carbon-zinc - (not alkalines) in D or 6V lantern size at places like Big Lots. Often you can buy a whole big package of cheap cells for a few bucks. First I remove the outer metal jacket. Then by grasping the cathode with pliers, I attempt to extract the carbon rod by twisting and pulling. If I'm lucky, the little disk of black asphaltum pulls free as well. The carbon rod is put aside for other use. I try to separate the inner cardboard cup along with its contents cleanly from the zinc cup but it is difficult. You can pierce the base of the cup and introduce compressed air to blow the contents out, but be careful as it may fly out as a projectile. What you want is the little cardboard cup and contents intact and cleanly parted from the zinc anode, which is also saved as good Zn. The carbon/MnO paste is incredibly messy to work with and gets all over everything. So I simply toss the whole thing into a crucible (tin can) and heat it to cherry-red incadescence in the furnace or other hot fire. This burns away some of the carbon and vaporizes the NH4Cl electrolyte, leaviing you with dry material in lumps instead of sticky paste. The product at this stage can be used as is for making chlorine, gives a nice steady stream of Cl2 from HCL that lasts for quite a while. The spent liquor can then be boiled down and suction filtered if it's the Mn you're after. I've always been fascinated with Mn and have played... oops I mean experimented with it extensively, using cheap batteries as my primary source. I love the colors and have grown crystals of its compounds, trying unsuccessfully to achieve the beautiful rose red hue of rhodochrosite from the crystalline hydrates of various Mn 2+ salts. It is all great fun for me.

:D




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MadHatter
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[*] posted on 1-8-2006 at 22:52
Manganese Dioxide


If there's a pottery store close to you, don't even bother with batteries. MnO2 is one of the
cheapest compounds I've ever purshased.

An example of the prices where I live:

www.clayworkssupplies.com

Click "ENTER HERE", "CHEMICALS", "Oxides" in that order and you'll see what
I mean.


[Edited on 2006/8/2 by MadHatter]




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[*] posted on 1-8-2006 at 23:06


How about reducing the C/MnO2 mix with H2O2/H+ then filter out the Mn2+ and precipitating with NaOH and H2O2?

Elawr:

Does the burning or the carbon support itself without additional heat? And will it reduce MnO2 to Mn?




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[*] posted on 2-8-2006 at 00:45


Depending on how it was made, MnO2 starts to lose O2 at 200 C up to 530 C (that when made by heating the nitrate). All of the manganese oxides, when heated in air, will give Mn3O4 when heated to above 950 - 1050 C, which is cherry-red to red-orange. This is in effect MnO . Mn2O3, containg Mn(III) which will give chlorine when heated with HCl.

Back in the days when I had to use batteries as sources of raw materials, I'd start off as Mr. Wizard and Elawr have said. I'd let the water extract of the contents settle, the filter it off. I'd then rinse with a smaller amount of water, filtering that as well. The aqueous extract would be allowed to evaporate to get mostly NH4Cl with sone ZnCl2.whatever H2O I'd the sublime off the NH4Cl.

The paste would get stirred with water again, and allowed to settle for a short time, then poured off through a filter. Repeat several times, this seemed to remove much of the carbon into the filter while leaving most of the MnO2 behind. I'd treat the filter contents per Elawr to get oxide for making Mn salts, while the washed oxide was for first making chlorine and the a source of MnCl2 (filter to remove carbon and other trash).



[Edited on 2-8-2006 by not_important]
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[*] posted on 2-8-2006 at 12:10


Converting the Hydrous form

Is it possible to convert the MnO2 from batteries to the Hydrous form where it is more reactive for aqueous chemistry. Would boiling in water work?




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[*] posted on 2-8-2006 at 12:18


No*, you have to get the Mn into solution and generate the MnO2 from scratch.


* It might be possible under hydrothermal conditions, high pressure and >100 C. But not something you're going to pull off easy.
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[*] posted on 4-8-2006 at 14:40


I put some of the battery stuff in a pan an heated it up till most of the carbon went away and left with a brown powder. I put this in HOAc + H2O2 and leached out the Mn2+. The solution was slightly blue (is there copper in there?). Also there is also a lot of unreacted particles left that is not MnO2 (didn't reacti with H2O2).



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[*] posted on 4-8-2006 at 15:32


If you have it, try a few drops of strong HCl and a bit of the leftover powder in a test tube. Could be uncooperative manganese oxides, could be carbon.

Other test is (Na or K)(carbonate or hydroxide) + (nitrate or chlorate) mixed with some of the powder. In the old days I'd say "use a bottle cap as a container" but it can't be aluminum. Fuse the mix for 10 minutes or so, cool, knock it out of the cap and dissolve in bit of water. Managese will give green solution, CO2 will give ppt of MnO2 and purple-pink solution of permanganate.

Or do a bead test, the old standby. With a borax or microcosmic salt bead Mn is violet when hot or cold if melted in the oxidizing part of the flame; generally colouless, but sometimes grey or brown, in the reducing. Picking up a crystal of KNO3 and remeltsing the bead for the oxidising tezt, or a bit of sugar and remelt for the reducing, can be used for forcing the reactions. Sugar is a very good source of carbon when you need metal and sulfur free carbon.


As for the blue, there might be a bit of other metals. Try concentrating it to the point of getting crystals, see if the colour intensifies and stays in solution or with the crystals. Either way, take bit of crystals and a few drops of the solution, add the strongest NH3 solution you have, look for the blue getting stronger and deeper; as you add NH3 you may get a pale blue ppt of copper hydroxide but it redissolves. Nickle can also give a blue-green colour, and acts a bit like copper with NH3. If the pan was stainless steel you might have picked up a trace of nickle.

If the pan is stainless, and the blue colour fades, likely to be some Cr from the pan.

http://www.sas.org/E-Bulletin/2002-08-23/chem/body.html



You can make stronger ammonia from household by heating some to drive the NH3 off and capturing it in some more of the NH3(aq) kept cool. If all you have is sudsy cleaning ammonia, use distilled water to catch the ammonia; some people do that anyway. Remember about suck-back. If you've no trouble getting lye and ammonium sulfate, mix those instead (oversimplification - gets hot, needs some water,...)
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