Garage Experiments With Trichloromethane.

Perk -> CHCl3

Cloroform

OK slimz don't sniff it because it obviously killed the brain cells that you use to spell words correctly.

Thats my last week of holidays, so I did some shots for this old project. I would want DCM because is less toxic than chloroform and usually have same dissolving properties. But because not only chloroform but also methylene chloride are watched here (hence I dont know any OTC product here for both susbstances), I think chloroform synthesis would be easier performed on homelab than DCM.


In the backyard some ~120g of (old) poolshock 65% calcium hypochlorite was measured out and added to a large glass container (about 3 L) then 900mL of water (+ 5g NaOH) added to it.

(I was fearing chloroacetone formation, so I added NaOH, but only after experiment and more careful reading I payed attention to the fact that NaOH isnt really necessary since the reaction produces its own base. )

12 ice pieces (each made with about 50mL of water) were then added.
~45mL of acetone ( distilled from a nail polish remover) were mixed with ~150mL of water and this solution was then slowly added to hypo/ice suspension with stirring.

After some minutes from the last addition the smell its totally different. Quite a 'sweet' smell, like all people says.

This mix was left overnight in hope to give better yield.

In the next day the mix was heated in a homemade distiller. In the receiving flask was put some ~30mL water to avoid evaporation of colected chloroform and the flask was put on a ice/water bath for same purpose.

In the start of the step, the tube of distiller started to bubble a unknow gas through the water of the receiving flask. And this gas bubbled through all the distillation. Dont think that would be any chloroacetone though. The white suspension on distilling flask formed a froth and in the end nothing was collected.



I repeated the experiment today, but using less water and also did the modification proposed by polverone: using a greater excess of acetone (all hypo consumed) and neutralizing the calcium hydroxides in the end with HCl.

~120g of hypo was added in a water/ice mix (~300mL water + ~650g ice(13 pieces)) and stirred. Slowly and with vigorous stirring, ~60mL of acetone was added (addition finished in about 5 minutes, without the mix getting warm to touch and ice already floating on it).

This mix was agitated more time and left to stand about 4 hours.
Then, with stirring, it was slowly neutralized by concentrated HCl. Some bubbles were visible and then I put my face backwards and continues mixing. After all was dissolved I could see a large blob of chloroform (~5mL) on the bottom. I extracted the raw chloroform with a dropper and measured: ~6,5mL in a small graduated cilinder.

The solution containg chloroform was then distilled in the backyard with the same setup used before. A slight chocking gas started to evolve but drops of a liquid started to distill and in the end I collected about 8mL of a yellow/green imiscible liquid a the bottom, maybe contaminated chloroform.

I extracted it and breathed (not deep though). In the start it smells like chloroform but after it burns a lot! My eyes started to tear somewhat... argh.... If this is chloroform contaminated with chloroacetone (but probably could be) or other substances I dont know, but I think it wont be easily purified by further distillation, so I added it to the solution from which comes and I soon will destroy all with feonton's reagent before throw all of it away.


The only word I can use here (but thinking in worse words) for that wasted time is PITA!!!!


Now, the natural question would be: how could I get higher yields of calcium hypochlorite method without distilling the calcium suspension?

I was thinking in make conc. bleach from Na2CO3 and Ca(OCl)2, filtering, reacting with acetone, extracting and distilling.. But seems more work..

BTW, was BromicAcid the only person here that tried the electrochemical method?






[Edited on 23-2-2010 by Aqua_Fortis_100%]

After my crude experiments and more detailed experiments from other people, that seems to most promising when working with hypochlorite, although there will be some problems (froth, foaming, some chloroform reacting, etc..)...
The guy from the videos below obtained some very large amounts of chloroform using calcium hypochlorite... I wish to have similair professional distilling setup one day, at least on my dreams

http://www.youtube.com/watch?v=IdfHMz7WeXI&NR=1
http://www.youtube.com/watch?v=Wh_7fjHV_BY

So, by above videos and from reports from other people in this thread, calcium hypochlorite is much more interesting as OCl- source than dilute sodium hypochlorite, but in real life it seems that when not controlling parameters such as water content, temperature, etc and even more when using improvised equipment (like I) will NOT be too easy to reach any good yields.

Arghhh
Water, a necessary evil...

Hey everyone, I did an experiment. So here's what I did. I calculated that for 10 ml of Acetone, I would have 0.135 mol of it.

Now the reaction is Acetone + 3NaOCl --> CHCl3 + 3H2O, so I needed three times as much NaOCl. That's 0.409 mol, which is 30.44 g. The bleach I have is 6%, so i figured that I needed 507 ml of that bleach with 10 ml Acetone to yield 10.94 ml of CHCl3 (theoretical yield).

So I measured out 250 ml of bleach and put it into a 400 ml beaker. The reason I didn't add all of it was because the beaker was only 400 ml capacity, so I would have to get rid of some of the aqueous layer first. Then, in a cooking pot, I added a lot of ice and water and stuck the beaker in with a thermometer. I then added a very small amount of acetone and watched the bleach go from yellow, to cloudy. I stirred gently with the thermometer.

http://img379.imageshack.us/img379/6924/1002256.jpg

After that, I slowly added 100 more ml and a tad more acetone. I stirred and watched the temperature, not letting it go a degree above 30 Celsius.

I measured out the rest of the bleach and added the rest of the acetone, slowly pouring out excess aqueous junk. Then, after about 10 minutes, I took the beaker out, and using a disposable pipette, sucked out all the chloroform I could get. I put this chloroform into a small beaker, and for purposes of showing to all of you, put it in a test tube.

http://img638.imageshack.us/img638/7507/1002271.jpg

I took this and washed the impurities out by adding tap water, then pipetting as much water as possible out. In the process I lost probably 0.1 ml of CHCl3. The final product was measured in a 10 ml graduated cylinder shown below.

http://img62.imageshack.us/img62/4595/1002276u.jpg

My yield was around 5 ml, which is 45.67% of the theoretical yield. I dropped 1 ml on the ground and watched it evaporate quickly like chloroform. Then I transferred to a vial.

http://img709.imageshack.us/img709/5945/1002278a.jpg

I decided to keep this CHCl3, so I added some diluted acetone onto the layer, sealed in a plastic bag and put it in the freezer.

http://img641.imageshack.us/img641/3605/1002285.jpg

The two reagents I used were:

http://img714.imageshack.us/img714/1047/1002259.jpg

and

http://img175.imageshack.us/img175/339/1002257.jpg

Pictures are way too big. Could someone tell me how I can resize them on Imageshack?

[Edited on 14-3-2010 by Rich_Insane]

[Edited on 17-1-2011 by madscientist]

Quote: Originally posted by entropy51

Chloroform 50 gm Ca(OCl)2 and 150 mL H2O was placed in a 1 Liter RBF equipped with magnetic stirring and a reflux condenser and surrounded by a cold (not ice) water bath. 19 mL of acetone was added cautiously, first in 1 mL portions through the condenser until the mixture thickened and foamed. Add remainer of acetone in small portions to maintain a gentle reflux without heating. Finally stir for one hour and arrange condenser for downward distillation. Distill off the CHCl3 using a hot water bath. BP = 60 - 63 C. Yield was about 15 mL. It is important to use an oversize flask as the reaction foams vigorously.

Quote: Originally posted by chemoleo

shadeT - trichloroethylene - sniff it a bit and u know what u *could* use it for

Quote: Originally posted by Haggis

Hello forumites, I bring you some info on my cheap and easy synthesis of trichloromethane.

Quote: Originally posted by trezza

What has gone wrong here and why?

Quote: Originally posted by entropy51

Chloroform 50 gm Ca(OCl)2 and 150 mL H2O was placed in a 1 Liter RBF equipped with magnetic stirring and a reflux condenser and surrounded by a cold (not ice) water bath. 19 mL of acetone was added cautiously, first in 1 mL portions through the condenser until the mixture thickened and foamed. Add remainer of acetone in small portions to maintain a gentle reflux without heating. Finally stir for one hour and arrange condenser for downward distillation. Distill off the CHCl3 using a hot water bath. BP = 60 - 63 C. Yield was about 15 mL. It is important to use an oversize flask as the reaction foams vigorously.

Well, you guys seem to have a lot of fun with this, so I decided to try this interesting experiment, and I devised an apparatus for my synthesis using some of my newly-acquired glassware. I started with 500 ml of 6% Sodium Hypochlorite, and 10 ml of acetone, as suggested in previous posts.

Being weary of this first synthesis of a toxic compound, and knowing that it's exothermic, I took extreme precaution in setting-up my apparatus, even putting a gas scubber on top of the setup to see if the reaction generates any gas. I decided to use a separatory funnel for two distinct uses: 1 To slowly drip the acetone in the bleach, and 2 To separate the final solutions from each other.


This is the synthesis apparatus, I used a round bottom flask set in an ice water bath, and put the separatory funnel on top in order to drip very slowly the acetone in the bleach solution. I dropped a small stubby stir bar in the round bottom flask and set the stirplate to medium. The thermometer was set just to satisfy my curiosity, and see if the ice bath warms up much. The reaction started with both liquids at about 3 deg. celcius.


carefully measured 10 ml of acetone


Pouring the acetone in the separatory funnel, and then I opened the stopcock just barely so that it was dripping about one drop per second.


In this picture, you can see the really cool swirl that started forming as each drop of acetone entered the solution.

With the bath, the slow addition of acetone and the constant swirling action of the stir bar, the reaction was quite rapid, and only slightly exothermic, the flask was barely lukewarm even at its peak.


An then, I saw a very cool reaction... 2 minutes into the acetone addition, (1/3 of the acetone in) WOOSH! the solution turned from transparent to cloudy almost instantly, in less than half a second! I would have missed it if it wasn't the fact that I was staring intensely at the flask!


Another change in the solution, about 6 minutes into the reaction, the solution turned from yellowish beige to a lovely opal color, and you could notice droplets of CHCl₃ forming and swirling around at the bottom. Final temperature of the bath (with all the ice melted) was about 10 deg. celcius. And as for the generated gas? Ziltch! Nada! Nutthin'! There was not even one bubble released in the gas scrubber, and my apparatus was tightly sealed!

The reaction took barely 20 minutes total from the first drop to the coalescing of chloroform at the bottom of the flask. I disassembled the entire apparatus and set-up the separatory funnel with a small 10 ml volumetric flask below.


I pipetted most of the solution on top with... a turkey baster! Hell of a lot faster than a 10 ml pipette! The remaining solution was poured in the separatory funnel to separate the CHCl₃


You can clearly see the clean separation between the chloroform and the remaining solution of sodium acetate, acetone and gunk.


Final yield: about 6 ml of impure chloroform. Yay! You can see the disassembled gear at the back, already cleaned and ready to be put back.

So my first synthesis of that magical product was a success. Just wanted to check if I could do it. As I was looking at the small volumetric flask, I said to myself "Now what?" What do I do with this small amount of chloroform? Since I have no use for it for the moment and it doesn't keep very well, I promply disposed of it.

What helped was that I used the right gear and took my time to set-up everything. Goes to show that there's a tool for every task and when you use the proper tools and good methodology, you get good results. And I want to thank Peach for inspiring me to post this detailed photo-description of my experiment!

Robert



[Edited on 4-3-2011 by Arthur Dent]

Mhh, I have no use for chlorobutanol either, but as for your second suggestion, would a mixture of the two produce methyl chloroacetate? CH₃COOH + CHCl₃ --> C₃H₅ClO₂ ?Sorry, I'm not very well versed in the magic of Ethanoic Acid and acetates...

Robert

Well, since it seems that everybody is performing this reaction, I decided to give it a go.

Here's the setup with the 5.3L jug of 6.15% NaClO in a bucket with snow and water. Chloroform does not attack HDPE.



Acetone was added over the course of an hour in 10mL increments. The temp never exceeded 26C. Total added amount was 125mL.



The vessel was allowed to settle for 30 minutes before the majority of the effluent was decanted from the trichloromethane.



The remainder separated beautifully and was introduced to the bottle using a separatory funnel.



The final raw product is now stored in an amber bottle for further processing. I may end up using it as-is for caffeine extraction or I might distill and dry it to get into chlorobutanol. Final yield was 110mL (±5)



Pretty routine synth. I find myself strangely attracted to the smell of the chloroform. It has a very unique sweet odor which becomes hot at higher concentrations.

[Edited on 8-3-2011 by DougTheMapper]

Quote: Originally posted by Aqua_Fortis_100%

Nice prep. and yields, Arthur Dent and DougTheMapper. Im building an electrochemical chlorine generator (based on this: http://quimicanova.sbq.org.br/qn/qnol/1993/vol16n2/v16_n2_%2... (portuguese) ) in order to make some nice experiments in next hollidays.. I was wondering if direct chlorination of acetone in aqueous NaOH would produce chloroform. I know that reacting chlorine with acetone/H2O/CaCO3 one will make treacherous chloroacetone(s), but Im not sure if high pH of NaOH is sufficient to prevent chloroacetone formation and thus making chloroform.. If this is not possible, then would chlorinating EtOH in aqueous NaOH be an alternative?.. Thanks.

If you guys are trying to get chlorform I recommend the bleach and acetone method. You get a bucket of ice and pour in a gallon of bleach that you can buy from home depot and then add in acetone. I forget the ratio of bleach to acetone. The ice is needed for the right reaction to take place. I think I found that method in the rhodium archive. all you do is stir it like soup until its done and the separate the chloroform layer and distil. I used my chloroform to weld styrofoam.

Low yeilding though.

[Edited on 4-10-2011 by MeSynth]

Been There; Done That

This isn't all that difficult to do. The key to success is to use good hypochlorite. Clorox doesn't work, though a more concentrated form ("Liquid Plumr" -- when it was still basically hypochlorite before they started putting other gunk in it) worked just fine. Keeping the reaction cool, and stirring helps greatly. Add the acetone or MEK (used both) portionwise until the color is discharged. The chloroform drops to the bottom, and is drawn off with a sep funnel. More can be distilled out of the remaining water.

The chloroform can then be distilled, dried over MgSO4, and stored with a little dry ethanol or methanol to clean up whatever phosgene forms (reacts quickly to form ethyl or methyl carbonate). You can boil off the water to recover the sodium acetate or propionate. No sense wasting it (especially the latter) waste not; want not.

Bad Idea #1)

"A bit soaked in paper towel and held to a flame will sizzle slightly and occasionally give off a darker smoke/vapor. I do not know if this is the papertowel burning, or otherwise, but at one point, I sniffed lightly the fumes rising above it and was hit with an odd sensation of burning, pain, shock, suffocation, and general"

Never do that. Burning chloroform (and other methane chlorides) makes phosgene. Not good.

Bad Idea #2)

"As far as the applications of chloroform, how much is needed to "knock out" an hypothetical human subject weighing approximately 120 pounds? How long does it take to "kick in"? And how long until they naturally revive (assuming that they are not in the 1 of 1000 that die from it)?"

Chloroform was once used for anesthesia until it was discovered that 1 out of 4000 people would not survive. Those might seem to be pretty long odds, but if you're wrong, you die. It's a good solvent, but breathing it isn't such a swell idea.

Bad Idea #3)

"He passed out for a few minutes, but came out alive. The good thing about HCN is that it doesn't cause long-term injury- if you recover, it's as if nothing happened . Just make sure to get fresh air".

Actually, HCN does have long term consequences, as it turns into formic acid. It can have the same effect as drinking methanol: ruins your eyesight, and could cause blindness. If working with HCN, a good fume hood is mandatory. If using HCN, it is also inflammable to the N-th degree, and makes explosive mixtures with air. It's also been known to self-detonate as well.

Quote: Originally posted by Steve_hi

I was reading this thread from the begining and someone posted that chloroform doesnt keep that well now i'm wondering about mine which I bought last january I have a litre can of reagent grade is there anything I can do to keep it longer? how long does it take to degrade? it is in a metal can and I have opened it.

Quote: Originally posted by Foss_Jeane

Clorox doesn't work, though a more concentrated form ("Liquid Plumr" -- when it was still basically hypochlorite before they started putting other gunk in it) worked just fine.