toothpick93
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Formic Acid from Esy Off Bam
So yesterday i was working and was putting a few things on the shelf in the laundry section and as i do i study the "Active Ingredients" in chemicals
for a quick seconds and noticed one of them said something like 24g/L of Formic Acid and 40g/L of Sulfamic Acid on one of the bottles. It got me
thinking, Is there some sort of way other them distillation to extract the Formic acid? Could you possibly react it with a chemical and then separate
them that way and then later on Remake the Formic Acid?
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Finnnicus
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I'd like you to know that 24g/L is more expensive than reagent grade + shipping. Assuming BAM is ~4$ a bottle. It could be purified by reacting with a
carbonate, then with HCl, but I'm not too sure about the primary extraction.
BTW. Distillation is a no-no, unless you love foam.
EDIT: Just checked, like you should have, and formic acid's BP is 100.8C so its inseparable from water that way.
[Edited on 6-6-2013 by Finnnicus]
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DrSchnufflez
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A great feeling of déjà vu as I have been pondering this exact problem for the past 3 days 
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DrSchnufflez
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Water and Formic acid form an azeotropes that boils at 107.3 and contains 77.5% formic acid by weight
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Finnnicus
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Oh, we'll I guess that solves that problem (unless 77% ident good enough).
Really either buy it or make it, unless there is something otc that is more concentrated.
I saw somewhere about production from oxalic acid, but I forget.
Edit: Oh, here it is, good ol' rhodium.
[Edited on 6-6-2013 by Finnnicus]
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DrSchnufflez
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Nice link... Pity glycerol is so expensive in Australia  otherwise I'd try it and
post the results.
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watson.fawkes
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If you can get lye and fat, you can make glycerol; it's a byproduct from making soap. It's an
easier reaction than making formic acid using the glycerol.
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blogfast25
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Here in the UK, some kettle descalers are formic acid solution. But it's still expensive compared to reagent grade...
Quote: Originally posted by watson.fawkes  | | If you can get lye and fat, you can make glycerol; it's a byproduct from making soap. It's an easier reaction than making formic acid using the
glycerol. |
The problem is isolating it though. Only high vac distillation will work, IIRW...
[Edited on 6-6-2013 by blogfast25]
[Edited on 6-6-2013 by blogfast25]
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Finnnicus
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The internet says this is best and cheapest. I know aussies at least can go to the supermarket and pick up 150ml for 5$, which is cheaper than the 'vaping' kind.
Also, how impure is vegetable glycerin?
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blogfast25
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As pure as you want it to be. As far as I know synthetic glycerine is not big anymore with the advent of biodiesel production.
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watson.fawkes
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You don't need it particularly pure if all you're using it for is the formic acid synthesis, which
esterifies the glycerol with oxalic acid, after all.
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hydride_shift
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I found a great OTC rust removal product today at a hardware store that is 100% oxalic acid via the msds at about $10/kg.
| Quote: Originally posted by watson.fawkes | | You don't need it particularly pure if all you're using it for is the formic acid synthesis, which
esterifies the glycerol with oxalic acid, after all. |
I happen to have lots of waste cooking oil lying around, when one considers formic acid needs to be purified anyway using crude glycerol doesnt seem
problematic.
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violet sin
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oxalic for 10$/Kg not bad, whats the brand? I know you can get 1lb/10$ at ACE as wood bleach. I looked around the other day for glycerol and spent a
few looking online as well. came to the conclusion that its really not that cheap despite it being a byproduct of mass produced goods.
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hydride_shift
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http://www.recochem.com.au/index.php/products/consumer_produ...
not sure if thats any help to you (might be help to someone)
I seen people selling glycerol on ebay for decent prices as low as $15 a gallon
Its a byproduct of producing biodiesel from cooking oil, also soap making is a serious hobby.
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TheChemiKid
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Here is a video I made on synthesizing formic acid using rhodium's synthesis.
When the police come
\( * O * )/ ̿̿ ̿̿ ̿'̿'̵͇̿̿з=༼ ▀̿̿Ĺ̯̿̿▀̿ ̿ ༽
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hydride_shift
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Funny you say that, i just watched this video 
Was wondering, do you intend on attempting to increase the concentration at all? Has anyone attempted any of these to get upto 88%+
http://www.erowid.org/archive/rhodium/chemistry/formic.acid....
-fractional distillation under vac
-use of dehydrating agents such as CuSO4 or boric anhydride
-using an alkali metal salt and dilute sulfuric acid
-Lead formate and hydrogen sulfide
[Edited on 12-1-2014 by hydride_shift]
[Edited on 12-1-2014 by hydride_shift]
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APO
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On the Rhodium synthesis, it states that the glycerin used must be anhydrous, is this just so that it can be measured properly before it soaks up
atmospheric moisture, or does too much water interfere with the reaction?
If it's the fault of the latter, wouldn't anhydrous oxalic acid be needed?
"Damn it George! I told you not to drop me!"
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AJKOER
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As I have previously reported on SM, my Oxalic acid dihydrate appears to have decomposed on its own over the warm summer months. I suspect the
formation of Formic acid, probably from the mild heat in a closed container and possible presence of impurities (gas formation loosening seal allowing
exposure to moisture, which in the presence of metals like Fe may have fuel an electrochemical reduction of the Oxalic acid).
Interestingly, here is a quote (source: an article for bee keepers at http://scientificbeekeeping.com/oxalic-acid-heat-vaporizatio... ):
"In the CRC Handbook of Chemistry and Physics we find that upon heating oxalic acid, the water of hydration boils off first, then at 315°F the oxalic
acid starts to sublime (go directly from solid to vapor), and finally at 372°F any oxalic acid which has not yet sublimed decomposes to formic acid
and carbon monoxide."
OK, so heating Oxalic acid converts H2C2O4.2H2O to crystals of pure H2C2O4 (from sublimation) and leaves some Formic acid along with a problematic
generation of CO. However, carbon monoxide may be addressed employing proprietary solvent containing cuprous aluminum chloride (CuAlCl4) dissolved in
toluene (see http://www.rccostello.com/copure.html ). For another approach, see "The Reaction between Carbon Monoxide and Oxygen on Cuprous Oxide at Room
Temperature" at http://rspa.royalsocietypublishing.org/content/211/1107/472....
This path appears to be confirmed as cited above by Rhodium (see http://www.erowid.org/archive/rhodium/chemistry/formic.acid.... ) as to quote:
"A good yield of formic acid cannot be obtained by merely heating oxalic acid, as a certain portion of the oxalic acid sublimes unchanged."
Unclear on the precise reaction chain or expected yield with mild heating, but here is one possibility ignoring the sublimation of the Oxalic acid
itself (as a fixed portion is sublimed and is recyclable):
2 H2C2O4 ---heat--> 2 HCOOH + 2 CO2
HCOOH ---heat,acid--> CO + H2O
Net:
2 H2C2O4 ---heat--> HCOOH + 2 CO2 + CO + H2O
[Edited on 19-1-2014 by AJKOER]
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