Daffodile
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Chloral from Chloroacetaldehyde
Alright so yesterday I made some Chloroacetaldehyde from Ethanol, and today I hope to Chlorinate it to Chloral, Trichloroacetaldehyde. However, some
water got into it, and I don't know if that will effect the final Chlorination (I've heard different things about it.) Should I distill the
Chloroacetaldehyde to dry it, or is it fine as is?
Photos are only included to show that this is legit.
[Edited on 10-4-2016 by Daffodile]
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blogfast25
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Some information about that part of your process would be welcome.
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Daffodile
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Okay so I took apart some heavy duty batteries, and got two cylinders of Manganese Dioxide, each about 10 centimeters long. I put one in a 500ml
filter flask, added 300ml of 31.45% Hydrochloric Acid, stoppered and heated it to 70 degrees Celcius. The side arm tube led into a 250ml RBF attached
to a leibig condenser circulating icewater. There was 25ml of Ethanol in the RBF that the Chlorine gas was bubbled through. The setup did its stuff
for about two hours, when shut it down and distilled the product. A lot of gas was released as well as some Acetaldehyde at lower temperatures, the
remaining liquid distilling between 83 and 87 degrees. The product was Chloroacetaldehyde.
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Daffodile
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Today I chlorinated the product the same way to try and make Chloral. To test the final product, distilled between 90 and 100 degrees C, I added some
Sodium Hydroxide. It turned brown, boiled (dissolving the rest of the Hydroxide), precipitated and redissolved a white salt, and precipitated a brown
liquid. The brown liquid seemed to be dichloromethane with some chloroform, meaning that the chlorination was not complete. At least I now know how to
make DCM.
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aga
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Whether this is all bullshit or not, i quite like the pipe down the centre of the reflux condenser idea, although for other reactions that do not
produce a solid.
Edit:
Does MnO + HCl produce any Cl2 at all ?
I'd have thought it'd just go MnO + 2 HCl => MnCl2 + H2O
More edit:
Ah. DIOXIDE. ok.
MnO2 + 4 HCl = Cl2 + 2 H2O + MnCl2
Edit some more ...
The reaction for EtOH + Cl2 requires about a 1:3 weight ratio to 'fully' convert to chloroacetaldehyde, giving a max 80% efficiency.
(from J.B. Cohen, Practical Organic Chemistry, 1900 page 99, referencing Liebig, Annalen, 1832 and Dumas, Aim. Chim. Phys. 1834).
Your 25g of EtOH would require a minimum of 75g Chlorine gas to achieve that.
From your figures, a max of 53 grammes of chlorine gas would be produced.
So yes, definitely under-chlorinated.
(especially as the MnO2 reaction produces ~27g of water in the generator reaction).
[Edited on 10-4-2016 by aga]
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gdflp
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Quote: Originally posted by aga  |
Does MnO + HCl produce any Cl2 at all ?
I'd have thought it'd just go MnO + 2 HCl => MnCl2 + H2O
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It's manganese dioxide. MnO<sub>2</sub> + 4HCl --> MnCl<sub>2</sub> + 2H<sub>2</sub>O +
Cl<sub>2</sub>. It only works on some forms of manganese dioxide, some more unreactive forms seem to be unreactive towards HCl.
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battoussai114
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Battery MnO2 does react with HCl, but it's sort of slow and I never actually bothered going forward with it since there are better ways to generate
chlorine and it's inefficient in cleaning MnO2 from glassware.
Batoussai.
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Daffodile
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Yeah I really should use TCCA or Calcium Hypochlorite, but I use all my Hypochlorite to make Hydrazine, and TCCA is expensive.
The most interesting part, for me, was that I can make DCM this way, and I havent been able to find it otherwise.
By the way, the rubber tube was attached to a glass tube, or pipet thing, which bubbled the Chlorine. You can sorta see it in the picture.
[Edited on 10-4-2016 by Daffodile]
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blogfast25
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| Quote: Originally posted by Daffodile |
The most interesting part, for me, was that I can make DCM this way, and I havent been able to find it otherwise.
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How do you know you have DCM? 
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chemrox
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for Cl2 generation see prepchem I like the H2SO4 method to avoid the dehydration step (it's a little messy) The H2SO4 will capture the water.
"When you let the dumbasses vote you end up with populism followed by autocracy and getting back is a bitch." Plato (sort of)
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Daffodile
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Mostly because of smell, also because of boiling point of the Dichloroacetaldehyde. I checked, and it seems that was most of the distilled product.
Also, DCM is insoluble and sinks just like what I separated.
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aga
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Pb behaves similarly 
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Daffodile
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Very funny. I'm pretty sure its DCM, because additional to the evidence I got, I also have a strong feeling about it, the sort you get from being
around the stuff for awhile. After all, if I left you alone in a room with a bottle of Acetone or Ethanol, it certainly wouldn't take you too long to
identify it.
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chemrox
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| Quote: Originally posted by gdflp | | Quote: Originally posted by aga |
Does MnO + HCl produce any Cl2 at all ?
I'd have thought it'd just go MnO + 2 HCl => MnCl2 + H2O
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It's manganese dioxide. MnO<sub>2</sub> + 4HCl --> MnCl<sub>2</sub> + 2H<sub>2</sub>O +
Cl<sub>2</sub>. It only works on some forms of manganese dioxide, some more unreactive forms seem to be unreactive towards HCl.
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See Prepchem for methods of making Cl2. I may have reponded before-lost track of a "quote" anyway H2SO4 picks up the water so no need for inline
desiccators using MgO2/H2SO4 and I tried it and it works
"When you let the dumbasses vote you end up with populism followed by autocracy and getting back is a bitch." Plato (sort of)
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aga
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| Quote: Originally posted by Daffodile | | After all, if I left you alone in a room with a bottle of Acetone or Ethanol, it certainly wouldn't take you too long to identify it.
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If some half-wit had half-chlorinated my Beer i'd know immediately !
The 95% water would have screwed it right up.
Still, never tried that particular random mix, so perhaps worth a Sip to see if it's any good.
I suspect the Hop flavour would be gone altogether.
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Daffodile
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| Quote: Originally posted by aga | | Quote: Originally posted by Daffodile | | After all, if I left you alone in a room with a bottle of Acetone or Ethanol, it certainly wouldn't take you too long to identify it.
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If some half-wit had half-chlorinated my Beer i'd know immediately !
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Hey I'm not that much of a half wit, the U2Us were only slightly serious.
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