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Sedit
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I have recently been toying around with MnSO4 in the divided cell and getting some success with it. I was truely delighted when the material in the
cell started to turn pink the proceeded to a deep purple and later a dark brown.
Simple alcohols seem to be converted into there aldahyde with ease which is nice because it will be great to have a steady source of formaldahyde and
whatever other use I find for it.
A question that I have it how will this work with double bonds. Will materials such as styrene, or allyl benzene be converted to there
aldahyde/carbonyl... or something else altogether? The reaction that I am really confused with is how substances such as trans-β-butylene will
behave. Will it be converted to an aldahyde or will it place the carbonyl across the double bond?
It appears to be a gental yet effective oxidiser and im just looking at the different uses this may have as far as oxidising various compounds.
Also I wanted to know what it the storage of this oxidiser? If one wanted to extract the solid from the cell and store it how well will it hold up?
[Edited on 13-6-2009 by Sedit]
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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DyD
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Impurities in Pottery-Grade MnO2
I'm planning to attempt to construct an MAA electrochemical oxidation cell to oxidize toluene and methanol. In my attempts at sourcing manganese
compounds, I've constructed the following chart:
--------------------
Source Material PricePerPound Shipping Purity PercentMetal
CC MnCO3 5.80 15usd/15lb 100% 45-47%
CC MnO2 1.50-.8 15usd/15lb 96.8-81% 51-55%
1-5% Fe2O3
1-5% SiO2
1-7% Al2O3
0.2-2% BaO
EBay MnO2 3.99 5.99usd/1lb 99% 63%
--------------------
My question is this: As one can see, the cheapest source of manganese per mol is the manganese dioxide from "Columbus Clay" at 1.50usd for one pound,
and eight dollars for ten pounds. However, the manganese dioxide is, at worst, 81% pure, with Fe2O3 and Al2O3 making up the most relevant impurities.
Would either of these compounds or their respective sulfates negatively impact the performance of a MAA cell?
Thanks!
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not_important
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I wouldn't expect Al2O3 to dissolve in moderately strong H2SO4, certainly not SiO2, so those two should cause problems. Iron wouldn't seem to, but I
have no information one way or another.
You can remove most of the iron by adding an excess of the crude MnO2 to the H2SO4 used to dissolve it, and boil it for awhile. Allow to cool,
decant/filter from remaining solids, and split into two portions of 9/10 and 1/10 of the whole. Treat the 1/10 portion with NaOH to precipitate the
manganese as Mn(OH)2, filter and wash that well, and then stir the Mn(OH)2 into the larger portion and boil for a few minutes. Cool and filter, most
of the iron will be in the precipitate.
Alternatively, MnSO4 can be purified by evaporating to dryness, then heating to red heat. It melts at 700 C and decomposes around 840 C, while almost
all other d block sulfates decompose below 700 C. Cool, dissolve in water, filter to remove the contaminating metals as oxides or basic sulfates.
Only the alkali metals, Mg, and low levels of Ca will remain as contaminates in the MnSO4; it's not likely that those would be in the starting MnO2,
and they except for Mg could be washed out of that before treatment with H2SO4.
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felis
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Is it possible to use tin electrodes instead of lead in this cell? Should be easier to handle since tin salts are not poisonous; in addition, pretty
pure tin can be easily obtained OTC.
/felis
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behemoth
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This thread is a goldmine! In some posts there was mentioned that the mixture oxidizes Alkohols as well. Does anybody have some results for the
oxidation of aliphatic alcohols to aldehydes?
[Edited on 23-8-2009 by behemoth]
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Formula409
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My first go
Ok so I've finally gotten around to making my first cell. I decided to just make a cell the same size as Cycloknight's in order to get a feel for the
reaction conditions, and then do a bucket-size scale up once I am confident. The cell runs at around 3.5A as measured by my digital multimeter.
Naturally I won't be conducting any oxidations in the plastic container. The contents of the cell will be transferred into a glass jar which will
allow it to be heated with toluene. Here are some pictures:
The computer power supply I am using. Capable of 40A at 5V:
The overall setup
The purple colour from the anode
The MMO electrodes from a pool chlorinator. They are rated at 25A over 25 years at an extremely low chloride concentration, would be very exciting to
try out a chlorate cell with them! I do not know their composition, but the grey one is 1m long and flexible and the black one is 50cm long and rigid.
In the cell the black electrode is the anode and the grey one is the cathode.
The lid of the container consists of a rigid outer section and a removable centre.
I turned off the electrolysis as I noticed that after a couple of hours no more purple was being produced. It was also noted that the colour of the
liquid had not shifted to the expected dark purple after a period of time. I put this down to not allowing the MnSO4 time to dissolve, so the cell
will be stirred overnight.
What follows is the overhead stirrer I made from a beater I obtained at a charity shop which sells second hand goods (called Lifeline in Australia), a
pen and a coke bottle. I used a hacksaw to liberate the metal part of the part of the beater that "beats" and used hot glue to attach this to the
casing of a cheap pen which was almost a perfect fit. A coke bottle was then cut up with a Stanley knife and a section of plastic hot glued to the pen
lid to serve as an agitator. I originally planned to use the part of the pen which allows it to be hung from a pocket for this purpose but it was too
streamlined. The only downside to this stirrer is that it obviously cannot be used in the more plastic-unfriendly solvents, so it will not be able to
stir the mixture during the actual oxidation. But manual stirring should be sufficient for this.
The beater itself has three different speeds, but the slowest is usually more than enough. The stand is also very handy as it provides a solid base
and eliminates shaking. I cut a hole in the lid which allows the shaft to pass through but stops any stray acid coming out. Overall pretty successful
for $15.00!
The part that does all the work, quite sophisticated!
It can be seen that the stirrer achieves adequate agitation. All of the off-white precipitate is in suspension when it is running. Unlike magnetic
stirring:
Stirrer
Magnetic
One odd thing I did notice was that upon addition of a couple of drops of 6% hydrogen peroxide solution, the electrolyte turns an odd yellow colour,
which is replaced by the normal "strawberry milkshake" colour after several minutes of electrolysis. I found this by seeing if any purple alum would
be made upon addition of oxidiser, as has been previously posted.
Would someone like to throw a guess at what this material is? I've tried mixing the peroxide with both acidified ammonium and manganese sulfate
solutions by themselves and have not been able to replicate the precipitate. Obviously this leaves the conclusion that it is an oxidation product of
the manganese ammonium sulfate, but wouldn't the oxidation product be the purple compound we are seeking?
Another thing I noticed was that when the 1m long electrode was used as the anode, the reaction would not proceed at all and only 0.04A would be
recorded on the multimeter. I thought this was strange as that electrode would presumably be used as the anode in the chlorinator cell it was designed
for as it is the longest electrode and therefore has more surface area. It doesn't affect the experiment, though as the electrodes have shown no wear
in the past when they were used in similar electrolytes.
If anybody wants some more specific pictures, don't hesitate to ask!
Formula409
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Formula409
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Hmm, I appear to be having an issue. My cell has been running for around 150 amp hours but it is still the dark purple colour. It's meant to be going
for 120 in order for the oxidant to be fully generated! What the hell?
Could this be because I'm using an MMO anode? I thought any anode would work!
Formula409.
[Edited on 6-10-2009 by Formula409]
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Hilski
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Quote: Originally posted by DyD  | I'm planning to attempt to construct an MAA electrochemical oxidation cell to oxidize toluene and methanol. In my attempts at sourcing manganese
compounds, I've constructed the following chart:
--------------------
Source Material PricePerPound Shipping Purity PercentMetal
CC MnCO3 5.80 15usd/15lb 100% 45-47%
CC MnO2 1.50-.8 15usd/15lb 96.8-81% 51-55%
1-5% Fe2O3
1-5% SiO2
1-7% Al2O3
0.2-2% BaO
EBay MnO2 3.99 5.99usd/1lb 99% 63%
--------------------
My question is this: As one can see, the cheapest source of manganese per mol is the manganese dioxide from "Columbus Clay" at 1.50usd for one pound,
and eight dollars for ten pounds. However, the manganese dioxide is, at worst, 81% pure, with Fe2O3 and Al2O3 making up the most relevant impurities.
Would either of these compounds or their respective sulfates negatively impact the performance of a MAA cell?
Thanks! |
Hydroponic grade MnSO4 is the best thing to use in the cell. Its readily available online.
\"They that can give up essential liberty
to obtain a little temporary safety
deserve neither liberty nor safety. \"
- Benjamin Franklin
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sabbath06
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I've been trying to duplicate this cell and my oxidizer is now a dark purple like in the pictures, but when I add the toluene, it doesn't turn back to
the original color. I've left it to react for 12 hours with maximum magnetic stirring and it was the same color as when I first added the toluene,
although I can smell some benzaldehyde, mostly I just smell toluene.
I was thinking maybe it has something to do with a rust inhibitor that may be in my hardware store toluene, should I have distilled it first?
EDIT
Just needed to heat it a little more
[Edited on 6-9-2010 by sabbath06]
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Sedit
International Hazard
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All the information posted on how to use this oxidiser is pretty much wrong. Everyone go back and read the patent more closely and see how to use this
oxidiser. It is not a simple case of just dumping the oxidiser into toluene and waiting. The oxidiser is suppose to be added dropwise into warm
toluene over a period of time.
I found this out after many dissapointing yeilds and decided to reread the patent as closely as possible to see what was amiss. I have not rerun this
because I had since disposed of my oxidiser and did not have the time or money to rerun the reaction at the time. Toluene is also harder for me to get
so I never reran it but it would be great to hear of the results from someone running it the way it should be done.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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sabbath06
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Very interesting. Although I smelled almonds I'm pretty sure I got a crappy yield as well. Will try what you suggested and report back.
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Sedit
International Hazard
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Thats the same results I was getting. A drop left to evaporate would smell like BnO strongly but I was never to isolate a decent amount at all. I feel
this is the reason for it in that it must be done as stated in the patent to get the yeilds given.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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Hexagon
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So, back to the manganese sulfate + ammonium sulfate cell?
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Sedit
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No the so called Mn(IV) patent is the one that spoke of dropwise addition. I can not comment due to no first handexperiance on the MAA.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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Hexagon
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I've got no direct experience with neither of them, but the original manganese alum procedure seems more simple, higher yielding (based on the
substrate) and easier to up-schale...
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roamingnome
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@ sabbath06
"I've been trying to duplicate this cell and my oxidizer is now a dark purple like in the pictures, but when I add the toluene, it doesn't turn back
to the original color. I've left it to react for 12 hours with maximum magnetic stirring and it was the same color as when I first added the toluene,
although I can smell some benzaldehyde, mostly I just smell toluene. "
Are you reacting a 50 degrees Celsius?
I used 2 aquarium type test tube heaters to achieve this temp
Also the ratio of Bz made to toluene left over will be low
What is the best work up?
[Edited on 11-9-2010 by roamingnome]
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Sedit
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BnO not BzO, I was corrected myself sometime ago and I will gladly share the same.
Hex if it does work as patented as per dropwise addition Mn(IV) oxidiser would be better then MAA. Not to mention cheeper startup cost.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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roamingnome
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I had a chance to play around with "royal purple" again this weekend
I tried to drip the purple into the toluene but ultimately the kinetics of the reaction are to slow to for this to be of use Sedit
For kicks I bubbled ozone and later hydrogen into a smaller mix of Tolu and Mn.
The ozone began to form white solids or benzoic acid.
The point is, this reaction needs an activator probably for the toluene because when ozone forms white solids instantaneously that's a reaction
So i have 5 gallons of purple stuff .. any ideas out there
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sabbath06
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Yeah, by heating it more I got all of the purple oxidizer to turn back to it's original color, toluene layer was tinted yellow but does not smell like
benzaldehyde at all. This run was in a 400ml beaker. Will try scaling up to about 1 L and watch the temps more closely
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behemoth
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| Quote: Originally posted by sabbath06 | | Yeah, by heating it more I got all of the purple oxidizer to turn back to it's original color, toluene layer was tinted yellow but does not smell like
benzaldehyde at all. This run was in a 400ml beaker. Will try scaling up to about 1 L and watch the temps more closely |
Are you refering to the manganese alum procedure or to the manganese (IV) in the divided cell setup?
[Edited on 15-9-2010 by behemoth]
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Sedit
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| Quote: Originally posted by sabbath06 | | Yeah, by heating it more I got all of the purple oxidizer to turn back to it's original color, toluene layer was tinted yellow but does not smell like
benzaldehyde at all. This run was in a 400ml beaker. Will try scaling up to about 1 L and watch the temps more closely |
Im pretty keen on the idea of dripping the oxidizer at a rate and Toluene temperature that pretty much converts it as its dripped in and stirred
always allowing an excess of Toluene.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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atomicfire
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I've decided to test out this cell but I have a question.
I dissolved the ammonium sulfate in the 60% sulfuric like stated. I added the amount of manganese sulfate and let it stir for 24 hours. I still have
a 'pink milkshake' of a solution with no visible yellow precipitate. Is this normal?
I don't have the power supply for the electro part yet, so I can't see if this will turn red with electryolsis.
One question I had is that I can obtain manganese sulfate in either anhydrous or monhydrate form. I haven't seen anyone debate this but I wonder if
that extra water does something. I used anhydrous.
Also, whats the stoichiometry of this reaction? If you add toluene and turn that into benzaldehyde you are adding an O atom, where does that come
from?
Thanks
ban DHMO
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DetachablePenis
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A little enlightenment.
Hello,
I constructed and ran such a cell some years ago (about 6 liters total volume of all reagents) and after much the same results as I read now here
regarding low yields, it finally occurred to me that what was occurring was that the toluene was simply evaporating out of the top of the open cell
before it was able to be reacted.
Upon sealing the cell and using a conventional condenser to manage pressure build up I was able to achieve the claimed yields.
If you look at the illustration in the old patent where they used several hundred KG of reagents, you can see that the 'tardis' or I guess even
phallic shaped steel (I assume) reactor they used was a closed unit with a condensing pipe running from the top back down into the main body of the
reactor.
Hope this helps everyone with their frustrations 
P.S. Computer power supplies connected in parallel are a cheap source of lots of amps if you can scrounge old discarded PC's which is very easily done
as you may be aware.
I had about 10 or so CPU power supplies (about 3 plugged into each household circuit) in parallel at up to 35 amps a piece... I did not need any
heating in the cell I did need thick, thick copper braid !
This regenerates fast.
Lead is easily obtained on the cheap from your metal recyclers, melted by a propane flame and poured onto ceramic tiles to create beautiful sheets of
almost pure lead that you can cut up with tin snips or whatever for your anode etc.
Overhead stirring using a medium speed/high torque motor is a must and a bitch to seal. Failing going pro and purchasing a proper lab quality nipple
setup, you can use the brass/s steel combo bearing out of the bottom of a food blender or similar appliance and use silicone or epoxy to jig it up.
Such a setup requires constant replacement of silicone or ptfe based lubricant or the sulfuric will eat the SS. You couple/join the SS center
originally from the blender to a glass stirring shaft and paddle with a plastic "shaft coupler" from a hobby/model shop (looks like a hollow cylinder
standing on its short end with two horizontal plastic hex head screws on the side that grasp the two vertical shafts) as anything else will work loose
in my experience.
I am sure others will think of better ways, this was just what occurred to and worked for me.
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Chemosynthesis
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Excellent insight. Thank you very much for sharing.
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