Sciencemadness Discussion Board - Chloroacetone by Electrolysis

Chloroacetone by Electrolysis

DDTea - 14-9-2003 at 18:08

Alright. I am very new to electrochemistry...new as in, tonight is the first time it has really interested me

.

So, please be gentle with the technobabble for poor Samosa.

I have read that Chloroacetone was first prepared by Electrolysing a mixture of Acetone and Hydrochloric Acid. Now, I have heard of Electrolysing HCl and HF for organic substitutions, such as in Chloroacetic Acid.

But now what I want to know is, how quickly does this reaction take place- has anybody tried it? What power supply what I need? What kind of electrodes should I use? Are the yields very good?

I remember reading on this forum about someone who made Chloroacetone (i don't remember by what method), but I cannot remember which thread it was in...

EDIT: Can Sodium Chloride be used instead of HCl? If so, I imagine it would be gentler on the equipment used. Also, are there any measures that should be taken to avoid overchlorination of the Acetone? If there aren't, it's alright- the reactants are so cheap that I wouldn't care much

[Edited on 9-15-03 by Samosa]

a_bab - 14-9-2003 at 23:32

Well, firstly, the idea is to get chlorine, and with NaCl electrolysis you'll get theoreticaly. But, I'm not sure if it'll stay dissolved when you'll add the acetone, as it might precipitate out (same phenomena involved like in the CIA method for BP production)

I did made several times bromoacetone using pure bromine and pure acetone; it's very simple and effective.

I made NCl3 by electrolising a solution of ammonium chloride, and I used C electrodes and it went OK; since Cl is produced in the reaction aswell, I'd say to use carbon electrodes, as Pt is waaay too expensive.

The speed can be calculated very easy, but my guess is that you'll get a few grams/hour, with a 5 A source.

DDTea - 15-9-2003 at 02:36

Now for the newbie questions... What OTC item can I use as a Carbon Electrode?? And when you say 5 A, do you mean 5 Amp? If so, could you please give some examples of a battery that has a 5 amp current?

Electricity has never been something that I've understood

Mumbles - 15-9-2003 at 14:10

Carbon rods can be found in some batteries, these would be to small however. Pencil lead could potentially be used, but would be very thin I suppose. I am quite sure carbon rods are sold for use in welding. I've seen them laying around my uncle's shop(who happens to be a welder).

The one item that really sticks out in my mind would be none other than golf clubs

. Of course I mean graphite golf club shafts. Perhaps try a golf club store that custom fits clubs for some extra pieces. Buying them from home club production sites could get a bit pricy. I happen to have 10 shafts sitting my garage that I've been trying to make a chlorate cell out of. Its just in theory for now though.

DDTea - 15-9-2003 at 18:23

Hmm. Now that I think about it, Carbon Shafts are made for Archery, and they are quit a good size. The only problem is that they are rather costly

carbon gouging rods

Polverone - 15-9-2003 at 20:50

These are carbon rods used in arc welders for applying heat or (messily) cutting through metal. Go to a place that carries welding supplies. They have a thin copper sheath, but it's easily peeled off. Also, they will disintegrate after a period of use, like other carbon rods.

a_bab - 15-9-2003 at 23:19

Dear Samosa, it's very simple. Electricity is a flux of electrons, right ? Electrons which travels from (-) to (+). The (-) is the emiter of the electrons. That is, the (+) will create a deficit of electrons.

A means Ampers, right. In order to get such an intensity, you will need either a car battery or a transformer.

[Edited on 16-9-2003 by a_bab]

vulture - 16-9-2003 at 00:29

Computer power supplies can deliver up to 10A on 12V IIRC. Perfect for electrolysis.

DDTea - 17-9-2003 at 15:12

Now I need help designing an Electrolysis Cell for this purpose. Here are some things to consider:

-Acetone is flammable.

-Hydrogen and Chlorine can react very violently, perhaps causing an explosion.

-an explosion next to flammable Acetone is dangerous.

-If I understand this properly, Hydrogen will be forming at the Cathode while the actual reaction between Chlorine and Acetone will take place at the Cathode. How should I separate the two parts?

-Most likely, I will be using a computer power supply... Could I use it connected to a wall outlet (AC), since I'm assuming it turns the AC current to DC? Or should I modify it so as to have DC power, as provided by a 12 V battery?

- What kind of wiring should I use? Does it matter? I'm trying to avoid overheating.

Nick F - 18-9-2003 at 01:13

I'd have the anode at the bottom of your cell, so that chlorine has to bubble through a lot of acetone, and hopefully will react, before it escapes, and the cathode at the top. I'd have a gauze or something similar over the top, to keep dust out but allow hydrogen to be vented away effectively.

Unless you're using a huge current, and/or don't have good ventilation of your cell, I wouldn't worry about chlorine and hydrogen reacting.

Use thick wiring, 3mm or something, and select a suitable resisitor to put in series with your cell so that you don't overheat your power supply. This may not be necessary depending on the resisitance of your cell (which can be varied by adjusting the spacing and sizes of the electrodes).

I would do a little test, and see how much, if any, chlorine bubbles to the top and escapes, and I would then select a suitable height for the cell so that no chlorine escapes.

Computer power supplies give out DC, so you'll be alright with one of them.

Haggis - 18-9-2003 at 10:41

I used to work at a golf course, and when a customer wanted a club custom built, around a 6 inch segment of the stock shaft would be cut off and discarded. You could put on a 'nice boy' outfit and give a variation of the science project line, they might save a few scraps for you. A source of the computer power supply can be a standard computer store. I have received many many computer PSU's (in the 20's) from computer stores after they gut problem computers. They save stuff for me instead of throwing it away. You also get a nifty fan in the PSU that is quite versitile.

Platinum electrodes...

Ollie Snowie - 21-9-2003 at 10:03

Actually, platinum wire is not too expensive. I bought about 10cm of it weighing 1g at a jeweler's shop for £11. They said it was 95% platinum but they weren't quite sure what the other 5% was. They said it was probably rhoduim. Anyway, it works fine for electrodes. You can put a huge current through it and it has shown no signs of corroding at all.

Organikum - 20-12-2003 at 10:12

Nick F:
The reaction of the acetone with the chlorine takes place directly at the electrode, The nascent Cl (NOT Cl2!) couples directly to the acetone, the so formed chloroacetone sinking to the bottom as it is much heavier than the acetone/HCl mixture.
If bubbles are visible you use much to much current.
Try 5V to 10V - chlorine bubbles = time to reduce the voltage!
But placing the anode below the cathode seems a good idea to me so no diaphragm is used. Placing the anode at the bottom of the cell is a bad idea as there the chlorinated compound will be after some time and you may get polychlorinated stuff this way.
So - in the middle?
Or use a diaphragm, claypot, plastics...

Samosa:
This is a "cold" reaction. No chlorine should ever be released - if so your current density/voltage whatever is much to high - reduce it!
Roomtemperatur or below - cool the cell in a water/icebath. PE is a perfect material for a cell of this kind.
You nevertheless will need:
A "multimeter" and RTFM.
To understand and to use the "Ohms law".

The finished product is best withdrawn directly at the bottom of the cell and stored in a wellclosed bottle.
Hey! Chilling/freezing the shit makes it much more conveniant to handle.

Anyways:
Happy crying!

Platinum wire!

Hermes_Trismegistus - 20-12-2003 at 23:01

http://www.crscientific.com/platinumwire.html

P.S. please stop talking about carbon fibre products as a viable source of carbon for electrodes. Carbon fibre in products is used like glassfiber in fiberglass boats. The carbon fiber is embedded in epoxy (a resin hardened with hardener)

Okey-Dokey-Smokey?

I think embedding the electrodes in glass might be the trick...it obviously can be done...for a similar setup try looking at the "ketene generator" curently being auctioned on LabX.

[Edited on 21-12-2003 by Hermes_Trismegistus]

hermes

Organikum - 21-12-2003 at 13:37

there is no trick.

axehandle - 19-1-2004 at 08:11

>Platinum electrodes...

>Actually, platinum wire is not too
>expensive. I bought about 10cm of it
>weighing 1g at a jeweler's shop for £11. >They said it was 95% platinum but they
> weren't quite sure what the other 5%
> was. They said it was probably rhoduim.
> Anyway, it works fine for electrodes. You
> can put a huge current through it and it
> has shown no signs of corroding at all.

I did the same thing, and the jeweller thought it was rhodium. But I politely
asked him to call the supplier and find out.
It showed to be palladium. I would hypothesize that "jewellery grade platitum"
is always alloyed with palladium. (Something
about the strength of the alloy or something, can't remember exactly what he said).

akre - 19-1-2004 at 14:09

What is chloroacetone used for?

buhuuuuuu.....!!!!!

Organikum - 19-1-2004 at 17:29

The last two posts actually kill me, shall I flame or shall I cry?

I cry.
Buhuuuuu...!!!

The one insists on using platinium when graphite is perfect usable, with or without diaphragm, doesnt matter as this influences only the ELECTROCHEMICAL yields aka product per Amp/h and not the quality of the product at all, say 20% instead of 90% ELECTROCHEMICAL yield what makes the reaction last a little longer and you waste about 30cents worth of electricity.....
And the second one.....
....Hey if you dont know it you wont need it. No problem.

Best will be I go and tease vulture a lil´ bit, this helps mostly when I feel frustrated.
Highly recommended!

Proud member of the royal vulture teaser society.

akre - 21-1-2004 at 12:17

Organikum, thank you for your in-depth answer!

2.2 Forum behavior
The anonymous and remote nature of the Internet makes rude and stupid behavior even easier and more common than it is in other social settings. Please resist the urge to devolve into a feces-hurling Internet Monkey just because nobody can see your face.

no problem

Organikum - 22-1-2004 at 06:47

ever heard of GOOGLE and ever seen the "search" field here on top?

I am in a hurry but I will gladly flame your lazy ass next time.

lachrymatory

Organikum - 6-2-2004 at 17:02

Chloroacetone is told to be a lachrymator and a teargas - this is more or less true.
Actually it will make your eyes watery quite fast but as a fact HCl (as gas) is far more nasty than chloroacetone.
No police in the world with some attitude will use such a weak compound against the own population - CS/CN are far superior.

I wanted to add this as I have seen horrible things on the devilish properties of chloroacetone posted so often which are to be called chemical myths.

I hate this as it renders serious warnings worthless.

Handling of chloroacetone: Cool it and add water as this covers the haloketone and almost nothing will escape - no crying. Keep DARK as it polymerizes with light really fast. Not UV or strong light, no, just a little light is enough. The water also stabilizes the chloroacetone - some chalk does the same. (stabilisation says it polymerizes not so rapidly under the influence of light)

DDTea - 9-2-2004 at 08:39

To clarify the "tear gas" issue... Chloroacetone was never a true Police/Anti-Riot tear gas, unless I'm mistaken. However, it saw use as a Chemical Warfare agent in WW1 because, as we know, it is a lachrymator. It's lachrymatory properties are similiar to Chloropicrin, if I recall correctly... I believe Chloropicrin had a slightly lower limit of insupportability though. In any case, as a potential expedient lachrymator, it certainly can be used-- but it is far from a "superior" chemical agent. It is also a poison, so prudency is always a good idea.

[Edited on 2-9-04 by Samosa]

meselfs - 13-2-2004 at 16:13

Quote:

Originally posted by Organikum
No police in the world with some attitude will use such a weak compound against the own population - CS/CN are far superior.

FYI, bromoacetone was proposed as a war gas.

dumb & blind ?

Organikum - 13-2-2004 at 18:04

This thread is about CHLOROacetone.
My post referred to CHLOROacetone.

wtf. do you talk about the properties of BROMOacetone here - without any reference given straight
OUT OF YOUR ASS?

And no thats NOT the same just because BROMINE and CHLORINE are both halogens.

have a nice day.
but do so somewhere else please.

TheBear - 22-4-2004 at 10:30

If I were to make this electrolyse, what ratios of Acetone/Water/HCl acid should I use. I thought that the reason for why you would use HCl instead of NaCl is that ionic-compounds like NaCl tend to have low solubility in Acetone/Water mix but the HCl would dissolve much easier, am I right?

Organikum - 22-4-2004 at 10:55

I guess no NaCl is used for the chloroacetone wont like the formed NaOH very much and for electrolysis under basic conditions favors the production of oxygen over the production of chlorine and we want to chlorinate not to oxidise the acetone.

A molar excess of acetone will be a good idea if monochloroacetone is what one is after. Anyways it is favorable to stop the electrolysis long before the reagents are used up completely for to avoid overchlorination.
All reagents have to be distilled - in special the HCl if not labgrade HCl is available. Muriatic acid is highly contaminated with metalsalts which cause polymerisation faster than you can spell the word "tar". Light also causes polymerisation.

After the reaction the monochloroacetone is withdrawn from the bottom - nice to have a faucet there - cooled down and neutralized by chalk, filtered through glasswool and stabilized by some chalk agsin and stored COLD in a DARK glassbottle.
If you skip the coling down before or whilst neutralizing the HCl you will cry a lot. If cooled you will cry too but not so much at all.
Wear swimming googles.

TheBear - 22-4-2004 at 11:25

Quote:

Wear swimming googles.

LOL, imagine a neighbour seeing me..

I would love to see the looks of their faces. Distilling HCl acid: Then I guess this will have to wait until a somewhat proper fumehood is built, or perhaps 2 washing bottles could remove the problem, washing bottle 1 = H2O, 2 = Na2CO3 (aq).

Anyway I will have to improvise the apparatures. What concentration of the reagents should be used? HCl in excess that I understand, but acetone, 20% by weight or is that to much/less?

Organikum - 22-4-2004 at 12:48

A neighbour crying his eyes out because of chloroacetone - this will bring you in serious trouble man, my word on this.

Excess HCl - I didnt tell this - did I?

Distilling HCl is no problem. HCl forms an azeotrope with water at 20% which boils at 108°C. So if you dilute your muriatic shit down to 20% or less you can distill the HCl like water - no problem, no fumes no hassle.
20% acetone w/w is not enough I guess, hey - do the math yourself I dont like to do these calculations either!

TheBear - 23-4-2004 at 10:38

You misinterpretrated my post, I am by no means asking you to do the calculations for me, I only need a approximation on how concentrated the reactants should be in the water, since i have no idea I could think of anything between 1% and 80%. Anyways, if chloroacetone is so unpleasant is there anything else commonly avaible to chlorinate which would give a more easily handled product, etylalcohol?

I'm not really after chloroacetone I'm only interested in trying chlorination through electrolysis..

I feel like I want to appologise if I sounded ignorant which wasn't my intention.

EDIT: Regarding HCl, I don't know why I thought of using it in execss, but it shouldn't hurt? but rather make sure the speed of electrolysation does not stagnate?

[Edited on 23-4-2004 by TheBear]

[Edited on 23-4-2004 by TheBear]

MEXCHEM2006 - 22-9-2006 at 08:23

You can make chloroacetone with SO2Cl2 in metanol/methylene chloride solution in a 85% yield , if you do electrolysis you would get a mixture of chloroacetones.

DDTea - 6-11-2006 at 11:03

Quote:

Originally posted by MEXCHEM2006
You can make chloroacetone with SO2Cl2 in metanol/methylene chloride solution in a 85% yield , if you do electrolysis you would get a mixture of chloroacetones.

You take the fun out of it!

There is always a 'standard' way to prepare such compounds, and Chloroacetone is by no means a challenge to an equipped lab. But this now begs the question: where do we get SO2Cl2? How does one construct such a reaction vessel to handle that?

I'm revisiting this thread because I'm seeing more and more uses for Chloroacetone--it's such a basic (simple, not low pH) compound--that can be used to construct far more interesting compounds. It is therefore of much interest to be able to produce it cheaply from OTC precursors and ghetto reaction cells easily procured by the amateur

Alpha Substitution opens the door to a whole wonderland of compounds! Ah looking back three years ago, I had such tunnel vision to just see Chloroacetone as a lachrymator and tear gas...don't get me wrong: first thing I do to confirm its presence is to sniff it

Then I might run a TLC and all that other more professional rod-up-the-ass white-coat-buttoned-too-tight stuff

Now don't get me wrong, SO2Cl2, SOCl2, POCl3, and other wonderful chlorinating agents are truly invaluable in organic chemistry and unless home chemists can acquire them, they really do face brick walls when they aspire to reach higher goals. No doubt, we'll have to break down those walls eventually.

I've been sitting on my arse entirely too long.

garage chemist - 6-11-2006 at 11:28

SO2Cl2 is different from SOCl2 in that is significantly easier to prepare: react gaseous SO2 with gaseous Cl2 with active charcoal as catalyst (no heating of the catalyst tube required, reaction creates its own heat). NaturesNatrium has done it, but he doesn't seem to be around here much lately.

MEXCHEM2006 - 6-11-2006 at 21:08

I made this reaction before; you fill the bulbs from a bulb condenser with a little fiberglass and then some activated charcoal, leave a little space between the bulbs, pass a DRY gaseous (constant) stream of SO2 and Cl2 from upper part of the condenser thru the condenser, the activated charcoal will start to absorb the gases and half an hour later you will have liquid SO2Cl2 coming out of the condenser.

new-b - 30-7-2007 at 10:00

Could it be possible to obtain 1,3-dichloroacetone with the SO2Cl2 method? Do you have more informations about this method? Thank you.

HOLYMOLYBDENUM - 10-4-2013 at 23:42

Quote: Originally posted by Organikum

A molar excess of acetone will be a good idea if monochloroacetone is what one is after. Anyways it is favorable to stop the electrolysis long before the reagents are used up completely for to avoid overchlorination.

After the reaction the monochloroacetone is withdrawn from the bottom - nice to have a faucet there ...

I can't imagine that there would be separately visible layers between the chloro/acetone layers whilst in this vessel, would there? The chlorinated product is obviously denser, sure, but how could the two compounds be viably separated in that manor if they look identical?

Metacelsus - 11-4-2013 at 05:48

I just did the electrolysis with 1 part acetone to 1 part 37% HCl using graphite electrodes. I got a mixture of mono and dichloroacetone with aldol tar. The dichloroacetone formed as an oily brown layer on the bottom; the color is probably due to aldol products. I estimate my yield of monochloroacetone was about 30%, but I haven't finished purifying the product; I'm having trouble getting all the water out.

[Edited on 11-4-2013 by Cheddite Cheese]

Mildronate - 11-10-2013 at 06:05

can you write it more detailed? Current, electrodes dimensions, how you know that is chloroacetone?

Metacelsus - 11-10-2013 at 08:47

The current was 5A; the current density was about 0.2 A/cm^2. When I purified it by distillation, its boiling point was 118 C, and its final density was 1.1 g/cm^3. The final yield of pure product was quite low: only 9%. I believe this to be because of aldol condensation and the production of polychlorinated acetone, and mechanical losses in purification (damn tar!). When freshly distilled, it was clear, but it has slowly yellowed over time.

Also, I know it to be chloroacteone because of its effects on my eyes -- I had to wear swim goggles to even enter the garage, which is where my electrochemical cell was.

If I do it again, I will use a platinum anode to improve efficiency, and also try to keep the cell temperature down. It rose to about 50 C because of ohmic heating.

[Edited on 11-10-2013 by Cheddite Cheese]