OTC Formic Acid Synth

[hellman]

Hello, and welcome,

Finally,(bet you thought that this little sucker would never materilize) after all this fucking around, on a site that fucks around so much with OTC material, sweet methods, OTC spectactulars and copious amounts of Mdp2p production, you would kind of freaking think BY NOW, that someone would post important stuff like this,.
But no-one, What in the fuck is going on with you people?
-smile

Firstly, there are obviuosly lots of bees who have done this, but for some insane reason, it just hasn't appeared in any legible, followable format,. The only formic acid synth we have, is the one on rhodiums site(god bless) which is a little fucking scarce on the detail, - no offence intended Rhodium,
-I mean the way I see it is that, one more chemical you have to extract from them, is just one more way to spend 5 years, right?,-right!

HOW IN THE FUCK ARE YOU GUYS MAKING YOUR MDP2P'

One of two freaking ways
Wacker or the formic!!!!!!
Can seem a little obvious  but I think - for what ever reasons - that it is time to end this NOW*,.

Welcome everybody, to the uncovering of the Formic Acid Synth, you all use it - But until now you have been purchasing it with a level of paranoia,.

I welcome you all to the complete undoing of the manufacture of this molecule.
By the end of this proceedure we will have formic,
Not just me, or you, but as a community,
God damn it, let's continue with the chemisty,.

Please Enjoy.

Oxalic Acid/ Glycerol synth-*To be continued


I have to go away now for a few days , but i will return,.
With the complete proceedure for you cretons,.

If you think you have a working synth, or valuble experienced insight on the Oxalic Acid/ Glycerol
put it down in this thread, cause that's what's on the menu,.


I leave this synth open ended for you all for two reasons. 
One is so you can stop and think just a bit how important this is and what can be achieved if we work together, and two because .. Well that's none of your buisiness,,,,
IQ is the rate of logic, as Wisdom increases logic, fear & compromise decrease to reveal objectivity

[Chromic]

The peracetic works great on large scale? The oxone method works great on a small scale. I think formic acid is great if you can get it, but why waste time and effort synthing this chemical? Plus it's much nastier to handle than persulfate or acetic acid...

Sure, a good synthesis would be nice, but... not really needed.

If you have access to oxalic acid, why not dream up a peroxalic acid synth? But perhaps it would be too unstable...

Btw, even making acetic acid is easier than making formic acid. Baking soda + vinegar, boil down, sulfuric acid, distill.

[Flip]

>why waste time and effort synthing this chemical?

Well just fer starters you could use zinc/formic acid as a substitute for zinc/ammonium formate in

Post 351892

(foxy2: "Reduction of nitro groups w. Zinc/Ammonium formate", Chemistry Discourse).

I think that this information should be posted somewhere on the Hive for up and coming bees in addition to the one on Rhodium's site as this chemical does indeed have many useful applications. 

Flip
Conclusion /nm./: the place where you got tired of thinking.

[Vibrating_Lights]

Swim would like a otc detailed descriptioon of htis synth.
So much game I could sell a hooker some pussy
Vl_

[raffike]

Is the formic acid the acid that ants contain?My friend whose father,who was beekeeper,had few gallons of that.I don't know for what.
A friend with speed is a friend indeed

[Rhodium]

Yes, formic is the ant-acid  

[raffike]

That's lil off-topic but for what they use it for?That man is has been dead for over 15 years so i can't really ask him about it but i was told that this man keeped bees to get formic acid not honey.Bees give formic acid too?Obviously,yes.Formic acid was valuable then(and is now too,i guess).
A friend with speed is a friend indeed

[Rhodium]

http://www.internode.net/Honeybee/Formic/Default.htm

[hypo]

afaik there is an experiment they show in highshools in my part of the world:

sugar and (a little) formic acid gives honey.
couch terrorist

[lugh]

The only formic acid synth we have, is the one on rhodiums site(god bless) which is a little fucking scarce on the detail, - no offence intended Rhodium

Obviously Rhodium's page wasn't thoroughly read before this thread was posted, his page has a very clear synthesis of formic acid from oxalic acid and glycerol on his page, see

https://www.thevespiary.org/rhodium/Rhodium/chemistry/formic.acid.html

There's also this old account by Coffey and Ward, which goes into much more detail about the chemistry

The well-known process of Tollens for the production of allyl alcohol (Annalen, 1870, 156, 129) is open to very serious objections and is probably based on a false conception of the reaction. À very large excess of glycerol is used and the amount of oxalic acid lost as carbon monoxide is also very large, consequently the yield is very poor. Chattaway (T., 1914, 105, 151; 1915, 107, 407) demonstrated that it was essentially by the decomposition of a dioxalin that allyl alcohol was produced.
The oxalins are initially formed in varying proportions according to the conditions of the experiment. At higher temperatures (110°) the hydrogen oxalins give carbon dioxide and formins. Dioxalin and monoformin dioxalin, at higher temperatures still (220-225°), decompose into carbon dioxide and allyl alcohol and allyl formate respectively, whilst at still higher temperatures (24á°) monoformin gives glycerol and carbon monoxide. Formic acid is produced by the action of an excess of oxalic acid on the formins and distils during the second stage of the reaction. From this it is apparent that a relatively large amount of oxalic acid must be used in the preparation of allyl alcohol.
Chattaway (loc. cit.) drew these conclusions partly from a study of the action of ammonia and aniline on the products of the reaction and partly from the properties of the ethyl oxalates; the results of comparative experiments given below completely confirm the above scheme in every detail.
The experiments also clearly demonstrated the four consecutive reactions, and it was possible to convert nearly the whole of the glycerol in one operation into allyl alcohol and to account for more than 90 per cent of the oxalic acid as free and combined formic acid, carbon dioxide, and water. The net loss, therefore, is negligible.
From the point of view of the student the usual methods of preparing formic acid and allyl alcohol are very uninteresting and unsatisfactory with regard to yield, time, and manipulation. Also the simple equation given in the text-books gives no clue as to where the loss occurs.
The method given below would seem to be far superior to the old method as à laboratory experiment. In the course of one day the student could, in one operation, obtain about 40 grams of formic acid as an approximately 50 per cent solution, and 100 grams of pure allyl alcohol and at the same time follow the whole reaction and account for all his materials.
Allyl chloride is by far the cheapest allyl haloid, but the methods of preparing it leave much to be desired. Eltekow's method (J. Russ. Phys. Chem. Soc., 1882, 14, 394) is long and gives only a 60 per cent yield, whilst the action of phosphorus trichloride on the alcohol gives mainly phosphorous esters and only 10-20 per cent. of allyl chloride. More recently, Bruylant (Rec. Trav. Chim., . 1909, 28, 247) has improved the preparation by heating allyl alcohol and hydrogen chloride under pressure, but he gives no details of yield. Aschan (Finska. Chem. Med., 1918, 3 pp.) finds that allyl chloride is obtained in good yield from allyl formate and hydrogen chloride in the presence of anhydrous zinc chloride. The authors' experiments show that, in the presence of condensing agents, the time of interaction of hydrogen chloride and allyl alcohol may be considerably shortened, but as à rule the yield of allyl chloride is very little better than that, given bó the older methods. The only condensing agent which is of any practical use is zinc chloride.

EXPERIMENTAL.
Preparation of Allyl Alcohol, Allyl Formate, and Formic Acid.
Pure, hydrated, finely divided oxalic acid (500 grams) and anhydrous glycerol (250 grams) are mixed in a litre flask which is connected with a condenser and receiver. The latter is connected with a water-pump and exhausted to about 120-100 mm. The flask is then gently warmed. At about 60° (thermometer in the liquid) the mixture boils vigorously, becomes homogeneous, and water (more than 100 grains) distils. This is the first stage of the reaction, the formation of the oxalins, and usually takes one hour. The pressure then rapidly rises to 480 mm and the thermometer remains stationary at 105-110° for some time. The vigorous ebullition ceases, a rapid effervescence of carbon dioxide sets in, and formic acid distils over with more water. There is no frothing if pure materials are used and the, pressure is maintained below 500 mm. After one to one and a half hours, the pressure in the apparatus slowly falls to about 120 mm; this indicates the end of the second stage, namely, the production of formins from the oxalins by loss of carbon dioxide and their subsequent decomposition into oxalins and formic acid by excess of oxalic acid. The temperature also rises to 190°, when distillation and evolution of gas almost cease. Quite suddenly, at 195-200°, the pressure increases rapidly. The receiver is then changed and the distillation carried on at the ordinary pressure. Carbon dioxide is again rapidly evolved, contaminated with some carbon monoxide and à negligible quantity of allyl formate. Allyl alcohol and allyl formate distil over together and the temperature remains stationary at 226° until distillation ceases, showing the end of the third stage of the reaction. The temperature then rises to 240°, when there is a rapid evolution of almost pure carbon monoxide. The last reaction ceases abruptly after about five minutes, and the colourless residue (80 grains) consists of glycerol. During the last two stages of the reaction the apparratus should be connected with a wash-bottle containing water, and the gases led into; in efficient draught-chamber. If the rate of decomposition is allowed to become too rapid, a large amount of glycerol is liable to distil over. It will be seen from the above description that the changes on the manometer and the thermometer are accurate criteria of the transitions between the various stages of the reaction.
To obtain pure allyl alcohol, the crude allyl alcohol-formate mixture (160 grams) is boiled under reflux with 750 c.c. of 10 per cent sodium hydroxide solution for one hour and fractionated through à long column. All the allyl alcohol passes over below 98° and the distillate is dried with small quantities of anhydrous potassium carbonate. It is then distilled and should give 100 grams of pure allyl alcohol, b. p. 95-97°.
To obtain allyl formate, the crude allyl alcohol formate mixture is washed several times with small quantities (20 c.c.) of water to remove allyl alcohol, and the insoluble ester dried over anhydrous calcium chloride. This on distillation gives à yield of pure ester, b. p. 82-83°, corresponding with 70 per cent of the crude alcohol-formate mixture. The washings may be worked up for allyl alcohol in the usual manner.
Allyl formate may also be obtained by fractionating the crude product several times, but in this case only a 50 per cent yield can be obtained. The formic acid in the first aqueous distillate (stages I and II) may be recovered either as a formate or as formic acid in the usual manner.
Thus, in one operation, 40 grams of formic acid and 100 grams of pure allyl formate, or about 100 grams of allyl alcohol, can be obtained from 250 grams of glycerol and 500 grams of hydrated oxalic acid. The residue of glycerol (80 grams) is quite suitable for further use.
The experiments were performed exactly as described with different initial concentrations of glycerol and oxalic acid. It can be seen that these results are in complete accord with those required by the above reaction scheme, and may be summarised as follows.   
1. The yield of allyl alcohol calculated on the glycerol actually used is always nearly theoretical.
2. As the amount of oxalic acid increases, the yield of allyl formate in comparison with allyl alcohol also increases. This is to be expected, because the larger amounts of oxalic acid are favourable to the production of dioxalin hydrogen oxalate, às is readily shown by à comparison of the amount of the alcohol-formate mixture with the yield of allyl formate. This was actually proved by isolating the allyl formate.
3. With increase of oxalic acid, the amount of free formic acid increases.
4. With increase of oxalic acid, the amount lost as carbon monoxide is diminished. This passes through a minimum in experiment 4, as in experiment 5 the loss increase; again. 1n this experiment the amount of oxalic acid is relatively very large, and no doubt di- and tri-hydrogen oxalins would he produced in appreciable quantities, giving the corresponding formins and ultimately glycerol and carbon monoxide. There is no necessity to use anhydrous oxalic acid in the above preparation (see Chattaway, loc. ca.), as all the water of crystallisation distils over during stages I and II. This effects a saving of several hours in the duration of the experiment.
The amount of carbon monoxide was relatively much larger with smaller amounts of oxalic acid. The quantitative results are not given, but it may be stated that in experiment 3 the ratio CO : CO2, rapidly exceeded unity, whilst in experiment 4 this ratio was not reached until all the allyl alcohol had distilled. In experiment 5 the amount of carbon monoxide was larger for the reason already given.
Preparation of Allyl Chloride.
The best results were obtained as follows
Allyl alcohol (46 grams) and anhydrous zinc chloride (20 grams) were mixed in a distillation flask immersed in a water-bath at 75-82°, and hydrogen chloride was passed into the mixture. The gas was rapidly absorbed and a fluid distilled. The end of the reaction was indicated by hydrogen chloride issuing from the end of the condenser. The crude distillate gave on fractionation: allyl chloride (35 grams) corresponding with à 60 per cent yield, and 10 grams of diallyl ether, b. p. 90-95°. The experiment required only half an hour. With aluminium chloride (anhydrous) alone, allyl alcohol reacts very vigorously, giving very little allyl chloride and a large tar-like residue.
When calcium chloride and allyl alcohol are mixed, an additive compound is obtained, which, when heated at 80-90° in a stream of hydrogen chloride, gives a product boiling at 30-32°. This is probably diallyl ether, and contains only à trace of chloride.
Aschan's method (loc. cit.) for the formation of allyl chloride was tried, but although the yield on the ester actually used is 80 per cent, the reaction is extremely slow, and it is advantageous to prepare the alcohol and then use gíven method given first in this paper. An experiment was made by saturating allyl alcohol in the cold with hydrogen chloride in the presence of zinc chloride. The yield was not improved, however, and the reaction required a long period for completion.

This synthesis was originally published in J Chem Soc 119 1301 (1921)
There's also

Post 228997 (missing)

(cilliersb: "Re: Performic questions (condensor & formic acid)", Chemicals & Equipment)
BTW Cretin is the spelling in my dictionary, not creton      


 

The Real Sooth, and nothing but the Sooth  

[goiterjoe]

oxalic acid isn't always in a very clean form for using to synthesis formic acid.  Methanol and Formaldehyde are, and should be somewhat easy to start from.  Methanol can be oxidized to formaldehyde by potassium dichromate or acidified potassium permanganate.  If an excess of oxidizing agent is used, then the formaldahyde is further reduced to formic acid. 

I once experimented around with using hydrogen peroxide for this, and didn't get very good yeilds.  I wonder if oxone would be strong enough to oxidize methanol all the way to formic acid.  I've often thought that this might be the side reaction going on in an oxone reaction which causes the methanol to heat up.
All paths are the same: they lead nowhere

[hellman]

Excellent post you evil mother fuckin bastard!-smile

Excellent! oncore!!!
I don't want to haggle about details, but I will say it again, But the post's on Rhodiums site ar a little scarce,
Be it subjective, and most probably objectivly, FUCK!
- always wise guys out there, but you loyalty is admirable,.
From the perpective of someone who is actually doing the reaction to someone that just reads it, there is information
that could of been there, as you have just shown in your post,
that i like!, Much more informay-she-on

I found for example the following had no mention of the purity of the formic that was distilled, no reaction formula to asses what byproducts, I would of also like to see some azetrope data, with the water coming over,.Although i assume that there is a neglible amount,

and the aqueous formic acid begins slowly to distill over. When the effervescence tends to subside, remove the Bunsen flame and allow the temperature to fall to 70-80°C: then add a further 40g. of powdered oxalic acid, and continue the heating as before. Ultimately 25-30ml of distillate is obtained, the total period of heating being about 1 hour.

Btw
   -Obviouslly Rhodium's page wasn't thoroughly read before this thread was posted, his page has a very clear synthesis of formic acid from oxalic acid and glycerol on his page, see -
I think Obviously only has one L-smile
-gotta go

- but i think kids needed to know here is that holding the glycerol/oxalic any higer than 110, will produce the formate, the ally, and the alcohols,.-onwards
IQ is the rate of logic, as Wisdom increases logic, fear & compromise decrease to reveal objectivity

[terbium]

I have to go away now for a few days, but i will return,.
With the complete proceedure for you cretons,.
What is a creton?  Certainly you can't mean cretin since someone who is calling someone else a cretin would at least check that his spelling is correct.

[SPISSHAK]

after reading what lugh posted, still can't get a clear understanding of the mechnism of formic acid from oxalic acid and glycerol.
Does it form ester in first stage.
Or does the glycerol reduce the oxalic acid?
Don't know.

[Antoncho]

An amazing post, Lugh - i remember a time when i did a very thorough search on allyl chloride and was forced to conclude that there simply was no practical way to make it at home.

But - lo and beehold!

Thanx a lot,


Antoncho

[placebo]

How safe and scaleable is this if someone wanted say 20L?

[baalchemist]

Creton? speak for yourself jerkoff. Would you understand it better if it was written with a jumbo crayon?
    GODISNOWHERE
Shoot Narcs, Not Drugs

[hellman]

What in fuck is wrong with you cretons,
Obviously your all being a little bit too touchy,

Understandable, with what you associate with,.
Save all this shit for somewhere else, and someone else,
it's not very becoming,
makes you look like a bunch of immature wankers,.
I don't know enough about all of you, to come to some kind of understanding why you are like this,.
But i don't think it's that hard to run up a profile,


- you guys really need to loosen up,
Typos- who gives a fuck, this is chemistry,
not the anal wars-smile
I repeat, i do fear your petty grasping at straws, your bizarre primal playfighting,
your all great guys, doesn't mean you have to put people
down to elevate yourself,
Where's your empathy,
If see anymore bullshit about [people pulling me on small shitty typos, your gonna get, here me, anmd you too baal,
I'll be coming to get ya,.
Don't you all get it?
Your not being judged anymore, you can do typos, within reason, it doesn't matter, it not a badge, or a worth definer, it doesn't mean your bad at english, and if you were what would that matter,.
-I am sure you all don't really care, and your just pulling my chain,.
Maybee it all goes down to what are you relying on to get your happiness,
try to move on from the trivial, you can break free of all this kids,
I can only assunme alot of you that are this anal, are still going through schooling, and bad stuff is rubbing of on you,.



-sorry about the ravings,


I am sorry to offend anybody, really

-I don't think your idiots really at all,
you guys are a crack-up,
I didn't mean for you to take it literally.-Jesus?
- I love you all, specially you Baal,
- you guys make me laugh, who old are you all,
Baalchemest, I suggest you get some sleep,
Terbium- I suggest you stop being so anal


-creton
/"kretn/ noun 1 person with deformity and mental retardation caused by thyroid deficiency. 2 colloquial stupid person. cretinism noun. cretinous adjective.


anal
/"en()l/ adjective of the anus.

Sorry, i have finsihed the prep and will publish it tomorrow,.

sorry everyone, for my harshness,
Your realling pissing me off baal,
I don't think your an idiot, at all, nomore than me,.
just relax everyone,.

IQ is the rate of logic, as Wisdom increases logic, fear & compromise decrease to reveal objectivity

[Rhodium]

Hey! Chill out!

[goiterjoe]

Just cause I'm old and crusty doesn't make me a crouton by any means.  If you didn't like my input, then don't ask me for imperical data to follow up with.


All paths are the same: they lead nowhere