Author Topic: Home Made Chloroform and Iodoform  (Read 3970 times)

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wombat

  • Guest
Home Made Chloroform and Iodoform
« on: July 03, 1999, 05:04:00 AM »
Methyl ketones and alcohols react with

halogens in base

to produce trihalomethyl ketones. When OH-

is used haloform forms. Thus acetone +

sodium hypochlorite (CHLOROX!) +

NaOH (red devil lye) will give you

chloroform and acetic acid!!  Replacing

acetone with ethanol will give formic acid

instead of acetic acid!

One can you tincture of iodinde and sodium

hypochlorite to make sodium hypoiodide

and then iodoform.



Android

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #1 on: July 03, 1999, 03:00:00 PM »
Slow down brother!  Your gonna burn up my printer!

CHEM GUY

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #2 on: July 03, 1999, 10:12:00 PM »
I know of the chloroform synthesis of which you speak and I have the blanced equation but the fromic acid synthesis I haven't seen yet.

So,... could you post the blanced equation for the fromic acid synthesis with NaOCl and/or Ca(OCl)2.

Keep it coming!


CHEM GUY

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #3 on: July 03, 1999, 10:18:00 PM »
By the way the chloroform synthesis doesn't need NaOH.   One of the products is NaOH, but NaOH isn't nessesary.  I have done this synthesis with just bleach and pure acetone, no added heat or speacal preparation.  Two layers form, one water and one chloroform. 

As for the alcohol synthesis of organic acids I don't know...

One big word of warning; DON't USE CHLorofrom with amines or NH3.  They combine to create posions, isonitriles (AKA isocyanides, or carbylamines<--sp?)


wombat

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #4 on: July 03, 1999, 10:48:00 PM »
Well ketones add halogens when in basic solution.
The trihalo addition is unique to methyl
ketones and methyl alcohols that are oxidized to methyl ketones. The OH->
hypohalite causes the haloform and a
carboxylic acid to form.

Yes the NaOH is unnecessary since OH- +

halogen -> hypohalite :Cl0- etc.

Thus CH3COCH3 + 3/2Ca(ClO)2 -> COOHCH3 + CHCl3 + 3/2Ca++ +H2O (+O2/2?).

CH3CH2OH + 3/2Ca(ClO)2 -> HCOOH + CHCl3

+ 3/2Ca++ + H2O (+O2/2?).

The ClO- first oxidizes the ethanol

to acetaldehyde CH3CHO.



CHEM GUY

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #5 on: July 06, 1999, 02:00:00 PM »
Sodium acetate (NaOCOCH3) can be prepared by boiling acetone (CH3COCH3)
with sodium hypochlorite (NaClO) the products are chloroform (CHCL3) and sodium
acetate or for calcium acetate (Ca[OCOCH3]2) use calcium hypochlorite (Ca[ClO]2)

    THE EQUATIONS:

2 CH3COCH3  +  3 Ca(ClO)2  -->  2 CHCl3  +  2 Ca(OH)2  +  Ca(OCOCH3)2
  CH3COCH3  +  3 NaClO     -->    CHCl3  +  2 NaOH     +  NaOCOCH3 

   Be careful the stronger bleaching powder and the organic can get
 rather busy.
   This is a proven source of chloroform and acetate salt.

Now I don'y know the equation for the oxidation of the ethanol to acetaldehyde.  It could be this?

CH3CH2OH + NaOCl --> CH3(CO)H + H2O + NaCl

As for the equation for the oxidation of the acetaldehyde to chloroform,...

2 CH3(CO)H  +  3 Ca(ClO)2  -->  2 CHCl3  +  2 Ca(OH)2  +  Ca(O[CO]H)2
  CH3(CO)H  +  3 NaClO     -->    CHCl3  +  2 NaOH     +  NaO(CO)H 

I would prefer the Ca(OCl)2 for the oxidation because it comes  granular, so you don't have to separate water from the CHCl3. 

Also if you are trying to get acetic acid or formic acid from this reaction you should separate the CHCl3 from the base and salt, either by distillation or evaporation.  I would use HCl gas to make the acid and nuetralize the base.  Once that is done if you've used Ca(OCl)2  the CaCl2 will dry the acid of water and you will have 100% anhydrous acid (either acetic acid or formic acid).


ChemHack

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #6 on: July 06, 1999, 08:14:00 PM »
Sodium Hypochlorite (bleach) is made by passing chlorine gas through an aqueous solution of sodium hydroxide.  Some sodium hydroxide will remain in the product.

Or to put it another way:  Your Chlorox already contains some NaOH!


ChemHack

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #7 on: July 06, 1999, 08:23:00 PM »
Oh, and another thing, this is really important so pay the fuck attention!

When you add alcohol or acetone to bleach, not much will happen at first, it takes a little while for the reaction to take off... it is very exothermic!

Now, you may be looking at the half gallon of 5% chlorox thinking to yourself, shesh, if this was more concentrated, I wouldnt be having to use a half gallon of bleach to process a shot glass full of alcohol.

Well, if you can find 10% bleach at the pool shop then you could use it.

RESIST the urge to try pouring alcohol onto a strong solution Calcium Hypochlorite bleaching power or other even strong Soduim Hypochorite.

In higher concentrations the shit gets HOT!

It might not get hot right away, but once the chain rxn gets rolling, watch out!

The temperature will easily surpass the boiling point of the chloroform and it will evaporate away into the air.

Oh well, you tell yourself, I'll just do it in a sealed container... DO NOT DO THIS!  It is a bomb!  It will blow up.  You will get hurt.  You have been warned.

Just play it safe and use the dilute bleach.  The chloroform sinks to the bottom anyway so it will be easy enough to separate.  Please heed my advice.


wombat

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #8 on: July 07, 1999, 03:52:00 AM »
Oh and another thing, chloroform is toxic,

an anesthetic, and a carcinogen as are

alkyl halides in general.


CHEM GUY

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #9 on: July 09, 1999, 04:57:00 PM »
Hey there, I found the equation for the hypochlorite oxidation of ethanol.  Here it is,...

4 C2H5OH + 8 Ca(OCl)2 -->  2 CHCl3 + 3 Ca(O[CO]H)2 + 5 CaCl2 + 8 H2O

2 C2H5OH + 4 Na(OCl) -->   CHCl3 + 3 Na(O[CO]H) +  CaCl + 4 H2O

I only found the Ca(OCl)2 equation.  I then used NaOCl in its place and balenced the equation.  So, I think the NaOCl equation is correct.



CHEM GUY

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #10 on: July 16, 1999, 03:34:00 PM »
In general ethanol is more expensive to get than methanol.  The ethanol usually has impurities in it as well, methanol sometimes.

My question is, What is the oxidation products of hypochloroites with methanol?

Is there a formic acid salt? If so this would be cheaper than using ethanol to make formic acid.


Agent_Smith

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #11 on: May 04, 2001, 12:05:00 PM »
I tired this:  Threw about 150ml of 5% bleach (looked slightly greenish) and 100mls of acetone together, stirred.  In a few seconds, the temp crawled up to 50C but never went higher.  The liquid turned piss yellow, with a small ~10-20 ml clear layer on top.  Wheres the chloroform?  In the 230+ mls of piss yellow stuff?  How do I get it out?


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Chromic

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #12 on: May 04, 2001, 01:13:00 PM »
You're using waaaaaay too much acetone. Use about 90g per 1 gallon 5.75%, you must use a reflux condenser, sometimes even with external cooling.

If you want a big quantity, you're going to have to think big. Get a big glass carboy, the 5 gallon type (SWIC has one for brewing), rig a long 1m leibig style condenser (copper pipe, 1/2" inner diameter, 3/4" outer) with circulating ice water... (SWIC has one for distilling "moon water") load 4 gallon 10% bleach and slowly add about 650g (you should check these #s) of acetone. Do the addition of acetone by a sep funnel, and do it -slowly-. Let it settle. Pour off the top layer, collect your chloroform from the bottom. Wash with sat. bicarbonate, and fractionally distill your acetone in your still.

Chromic

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #13 on: May 04, 2001, 01:18:00 PM »
Btw, what happened is you have a three-component two-phase mixture.

You've got a lot of water, some acetone and a not much chloroform in the bottom layer. You've got a lot of the chloroform, some acetone and not much water in the top layer.

The top layer is floating on water, because you made so little chloroform and the acetone/chloroform mix is less dense than the salt water on the bottom.

Cheapskate

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #14 on: May 04, 2001, 01:23:00 PM »
Go over to Rhodium's page and look for Easy preparation of Chloroform.  It works well and quite easily.  In the case you described you only had about 7 mg of sodium hypochlorite to react.  This just isn't enough to produce a substantial amount of chloroform.  What you can do to test this is take about a liter of bleach and drip acetone into it a drop at a time with stirring and watch the bottom of the jar.  You'll see droplets forming on the bottom as you add the acetone.  The heat will rise so don't get carried away.  What you got was a little chloroform an a lot of acetone water mix that will meet your description.

This reaction works, never tried or saw anyone try the others mentioned above.

Agent_Smith

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #15 on: May 04, 2001, 02:22:00 PM »
Good to know, thanks guys



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Agent_Smith

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #16 on: May 05, 2001, 07:41:00 PM »
One more:  I'm a puss, I don't wanna distill any chloroform, no matter how dangerous it is or is not.

So, in light of that, how bad would it be to simply wash filter and dry it?  (This is a solvent for Os's bromo safrole mehtod, btw)


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goiterjoe

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #17 on: May 06, 2001, 12:53:00 AM »
in reply to the first question, I doubt you could make sodium hypoiodide from sodium hypochloride.  the chlorine should have a stronger attraction to the oxygen than the iodine would.


If pacman influenced us, we'd glide around dark rooms eating pills and listen to repetitive music.

Bwiti

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #18 on: July 10, 2001, 01:40:00 PM »
"Wheres the chloroform?"

  If too much acetone is added, don't dump it out. Just add a shit-load of H2O and the chloroform will crash-out. Peace! :P


  I'm going to help all of you cleanse this diseased planet.

Rhodium

  • Guest
Re: Home Made Chloroform and Iodoform
« Reply #19 on: May 11, 2001, 04:01:00 PM »
Today I found a local chemical supplier selling 99% chloroform in 25L drums for $60 (spring cleaning in their storage room).  25L of anhydrous HPLC quality THF was $120, 2.5L 48% HBr $35 etc... Too bad I have no place to store such drums...


http://rhodium.lycaeum.org