Sciencemadness Discussion Board - Haloform with IPA 3&4 could really do with some help

Haloform with IPA 3&4 could really do with some help

Little_Ghost_again - 1-10-2014 at 01:39

Hi
I had another try with making Chloroform with IPA, out of curiosity I thought I would go down the same route as last time but with a couple of changes.
Before I get into what I did I really could do with some help trying to work out what products are being made.
The following is the procedure I used, I didnt take pictures but if needed I have a picture of the situation as it is now.

General overview of what I did.
1)
Really very simple. like last time I took approx 2 Ltr (amounts normally seem unimportant with this) of 13% Sodium Hypochlorite solution. For those who dont remember my other posts on this, the following notes may help.
.................................................................................................
The sodium Hypochlorite solution is in a 20Ltr plastic drum, it is labeled 13%, however it has been stored badly and for over 12 months was at a Temperature over 30C.
The solution has lost a lot of its green tint and the smell of bleach is greatly reduced, this time I decanted from its own drum to another empty drum, I found loads of needle like clear crystals in the bottom.
I shook the new drum up which held approx 12 Ltr of this solution, to this I added 1.5 Ltr distilled water. and shook around again. The crystals eventually dissolved.
.................................................................................................................

2) to the Conical flask (2.0Ltr) of solution I added 5g of Sodium Hydroxide prills.
No reaction was seen and no heat generated. This I found odd because I would expect a temp rise due to Sodium Hydroxide and water alone.

3) I then added 600ml IPA solution 99.9% purity (according to label).
The solution goes from a clear slightly green tint to a slightly green cloudy tint, Very slowly over around 15 mins the temperature climbs by 1-2C from room temp (15C).

My thoughts on this are as follows...... I also have an identical set up gong on except this has no Sodium Hydroxide added, this solution stays clear and no temp rise. So I assume the slight rise in temperature is due to the Sodium Hydroxide finding water as a reaction takes place?? Does this sound reasonable?

Both set up just left with temperature taken every couple of hours.After 2hours the solution with Sodium Hydroxide reached 30C (all solutions started at room temp), the other solution without Hydroxide remains unchanged and no reaction at all appears to take place.

After 9 hours I notice the solution that had been reacting still had a cloudy green tint but Also Droplets of what I am sure is Chloroform in the bottom. The temperature had dropped to around 21C, I deviated at this point from my normal practice. What I normally see is the cloudy green colour slowly loose the green and become white and cloudy, if left for 2-3 days this cloudiness clears completely and I have Chloroform on the bottom and normally a small layer of IPA (I assume) in the top.
This time the colour looked slightly more green than normal, so I decided to add another 200ml of IPA. I was thinking maybe it had used up all the IPA, I was expecting the cloudiness to continue and the temp to rise slightly.

However what happened was all the droplets of Chloroform started to rise!!! they formed a layer at the top of the flask! the IPA also seemed to layer out above the chloroform. The colour of the top layers are very clear except at the junction they meet, there is a smokey white thin layer between them less than a mm in thickness.
The temp hasnt risen over night and the solution has now gone to its normal white cloudy stage. However NO Chloroform is present at the bottom. The solution that I believe was Chloroform now smells sweeter than normal Chloroform, its not unpleasant but anything more than a slight wiff makes your head swim a bit.
Any ideas what is going on?

Also can someone explain what reaction should happen and what products should be produced when using IPA and Bleach.
I am currently repeating yet again but with tighter control. This was meant to be a quick knock up of Chloroform to use with some IPA for a TLC experiment. As I have no Ethanol yet I make the Chloroform as I need it to save me having to store it.

Thank you guys.

forgottenpassword - 1-10-2014 at 02:03

Chloroform is soluble in IPA. You could dilute your solution with water to precipitate it again.
As far as I know IPA is oxidised to acetone which reacts to give chloroform and sodium acetate.

Little_Ghost_again - 1-10-2014 at 02:50

Quote: Originally posted by forgottenpassword

Chloroform is soluble in IPA. You could dilute your solution with water to precipitate it again.
As far as I know IPA is oxidised to acetone which reacts to give chloroform and sodium acetate.

Thank you so much..
That really kind of makes sense then, so as the reaction was nearly over I added more IPA and the Chloroform rose to dissolve in the IPA. At the time with the Sodium Hydroxide Prills there would have been little/no water left in solution.
I was advised to add IPA to Chloroform to stabalise it as I didnt have Ethanol. That would now seem to make little sense.

One more question if I may....

As I have added Sodium Hydroxide Prills is it likely I will also have Sodium Hydroxide in there as well? Or will this react with anything in there?

That has really helped me thank you. I can now at least now what I am looking for in there

.

I am still working (hard) on learning how to do reaction equations but not confident enough yet to post my efforts

. I try and do 2 hours a day minimum of reading of the books I got, but its slow going as apart from here I cant really ask anyone.
I could ask my dad some of it but its kind of not fair on him, besides I would like to learn from independent sources.

Very very much appreciated
Logan G

forgottenpassword - 1-10-2014 at 03:11

You only need to stabilise chloroform if you are storing it for long periods of time. You would purify it, dry it, then add a small amount of stabiliser to your bottle. DCM can be used in place of chloroform for TLC, by the way.
The hydroxide reacts with the chlorinated acetone as shown here in pictures 5 through to 10: http://en.m.wikipedia.org/wiki/Haloform_reaction

[Edited on 1-10-2014 by forgottenpassword]

Little_Ghost_again - 1-10-2014 at 03:35

Quote: Originally posted by forgottenpassword

You only need to stabilise chloroform if you are storing it for long periods of time. You would purify it, dry it, then add a small amount of stabiliser to your bottle. DCM can be used in place of chloroform for TLC, by the way.
The hydroxide reacts with the chlorinated acetone as shown here in pictures 5 through to 10: http://en.m.wikipedia.org/wiki/Haloform_reaction

[Edited on 1-10-2014 by forgottenpassword]

Thank you.
I added some water and it did indeed sink to the bottom

, For now I am storing for a couple of weeks in the dark, I might as well leave it in IPA until needed. I am a bit paranoid about phosgene since being given several warnings about how evil it is.
But as its a few weeks at most I will leave in IPA solution in the dark and just make sure there is little air space in the container.

I am going to have a go at trying to get the sodium acetate into crystals. Not too sure thats possible. reading about it tells me it readily dissolves in water and needs drying at 120c, much above this destroys it (Merk 13th).
Maybe best option is to slowly boil it down a bit and see what happens, failing that try salt, failing that use other drying agents.
Hmm lots of avenues to go wondering down

.
The diagrams are helpful, it will take a little while to work it out

But I like that kind of challenge.

The one thing I should do is quantify this properly and get a yield %. apart from being easier for some to get, IPA is not very exothermic with Hypochlorite. I am pretty sure that without adding the Hydroxide prills there would be almost no heat. In my case I still cant get IPA to react with Hypochlorite without adding Sodium Hydroxide. I need to try it with another source of Hypochlorite solution, the way this one has been stored there could be anything in it

.
It dosnt even smell much like bleach until you add Hydroxide.

You have been great with the help, thanks for taking the time

Little_Ghost_again - 1-10-2014 at 03:40

Forgot to add, the Chloroform isnt just for TLC I also use it with my fly experiments (Drosophila). I collect and breed different one's, mostly for eye colour and vestigal wings etc. Pretty much the basic Genetic experiments done with them.

I have a recipe for a TLC plate I have and it uses 2% Chloroform, its for looking for pesticides. I have extracted orange peel etc and wanted to test and see it any pesticides had been used

Amos - 1-10-2014 at 05:51

If you are going to try to get the sodium acetate out of your dead reaction mixture, be aware that there is some chloroform dissolved in there, so do it outside. I wouldn't be too hopeful, because aqueous chloroform tends to turn into all sorts of things in the presence of an acid or base, and if you have leftover acetone you might get some even stranger stuff. Still, it will be interesting to see what you get at the bottom of your beaker. Oh, and I wouldn't worry all that much about destroying your sodium acetate through boiling it; I've intentionally made quite a lot of it, and it's pretty tough to do it wrong.

WGTR - 1-10-2014 at 07:59

For what it's worth, here's an extra pointer that I have used when making small amounts of chloroform from acetone:

When conducting the experiment in glassware, it is easy to see the slight yellow coloration of the bleach solution. After adding close to the stoichiometric amounts of acetone, the acetone is added slowly, drop-wise over several minutes. Once the yellow coloration disappears into a clear white color, a small bit of extra acetone is added just to be sure that all of the bleach is reacted away. This helps ensure that not too much or too little acetone is added.

For IPA, of course, there is an extra oxidation step involved, but the idea is the same.

Little_Ghost_again - 1-10-2014 at 08:12

Thanks guys!!!
This will be interesting becausse now I have no way of knowing whats in there! I also got curious and threw in some salt to a small sample, that has produced cloudy globs on the bottom

.

So pointless doing much with this apart from now trying to separate and distill it

. I will then do it all again without adding anything! I will do it like suggested when done with acetone, but still using IPA.
The hypochlorite I have is a green tint not yellow. Also with IPA I just put it all straight in, and that for me is the bit I dont get. Why so little heat? Unless the extra oxidation step.
But at the moment apart from the soap side of things (I take that very seriously), most of what I am doing is just trying things out and trying to learn techniques, I need more chemicals etc and most of all I need far more knowledge.
This is a tough subject to home learn from scratch, I am only a few weeks in. Great fun but hard work, maybe I should have started with non organic chemistry? I looked at the valence theory books (I shut those pretty quick

), I guess its just a case of sticking with it and asking questions

Little_Ghost_again - 1-10-2014 at 08:15

Quote: Originally posted by No Tears Only Dreams Now

If you are going to try to get the sodium acetate out of your dead reaction mixture, be aware that there is some chloroform dissolved in there, so do it outside. I wouldn't be too hopeful, because aqueous chloroform tends to turn into all sorts of things in the presence of an acid or base, and if you have leftover acetone you might get some even stranger stuff. Still, it will be interesting to see what you get at the bottom of your beaker. Oh, and I wouldn't worry all that much about destroying your sodium acetate through boiling it; I've intentionally made quite a lot of it, and it's pretty tough to do it wrong.

I will get you picks of my beaker

. I will distill this in a large ventilated outbuilding. My plexi Glass should be here soon so then I have a fume cupboard

Amos - 1-10-2014 at 10:31

large ventilated outbuilding... fume cupboard... 20 gallon drums NaClO...

You have me positively salivating

Little_Ghost_again - 1-10-2014 at 11:38

Quote: Originally posted by No Tears Only Dreams Now

large ventilated outbuilding... fume cupboard... 20 gallon drums NaClO...

You have me positively salivating

LOL.
Yes I admit we are blessed living here, there is a farm supply place called Tarff Valley supplies, mostly there town type stores (its a smallish chain) are geared for the horse set, but the rural places are like small where houses and are geared for farming.
They are a ace place to get things pretty cheap, today I went with my mum to get some pig feed, I love having a look around

.
They do the hypochlorite (its diversey lever brand so a good one) at 13% in 25 Ltr drums for around £21.
Also I found out today they do 25Ltr Formaldahyde! its marked 35/10, I am not sure what strength that means but it costs £23.
They also do Ammonia again in 25Ltr drums, I couldnt read the strength as they were out of reach on a shelf, but again cheap! (£30).
And my dads favorite...... REAL CREOSOTE! its not the creocote stuff they flog in DIY shops, it clearly states on the drum that it is creosote only to be sold to manufacturing blah blah blah and then mentions for domestic use it is recommended to use crecote and not this stuff. Again 25 Ltr but around £35. They probably do many things that might be useful, but most you have to ask for as its hidden in the back of the where house. They also do those absolutely HUGE cages with drums in (over 1000 litres but forget what they are called) of hypochlorite, no idea of the price though.
We have a lot of stone and slate out buildings so yes I am lucky. Its a shame no one else from here lives near me, I would gladly share my glassware and lab space for a little tuition

.

Anyway UPDATE.

I got stupid and added salt, plain old table salt with a faded lable, funny kind of whispy smoke like (something) floating around the bottom and a fair amount of very small clear gas bubbels being given off, they seem to form on small beads of Chloroform and on grains of the salt.
Also I can see another layer in the bottom, its not Chloroform. Chloroform (if this is right) forms almost round sparkly blobs that bounce around the bottom of the flask untill they find another then they join. The chloroform looks like a drop of water on a hard surface (that round kind of shape rather than a flat layer. Thi layer above it is completely different, its hard to describe and it dosnt photo well. Best I can come up with is say a highly concentrated solution of sugar is dumped into a weaker solution of sugar or maybe water, you get that funny kind of clear but defined syrupy layer that moves around, it just looks completely different.
it dosnt float so denser than water, it dosnt mix with the chloroform, it seems more like a solvent than say strong salt solution does (it catches the light in a different way, a bit like very clean and new glassware).

So I have decided to stop adding things in a half arsed random manner!

Time to try and separate

Chloroform (I assume anyway it is), this was clear and sparkly and still is in all but 1 of the four flasks I have (I did dfferent things to all four), in one the Chloroform blobs look slightly milky. I will try and suckthose off the bottom of the flask with pipettes. The next layer I will also try and do the same with, but I may have to try and use a sep funnel.

The rest

The salt granules left on the bottom I can filter, then I can split the flasks into two of each of the four, one of each I will distill.
Depending on how that goes I might try and crystallize the other samples by boiling off say 30% to start with then chill them. I can boil a bit more and chill until I get crystals or nothing

.

I know its dreaming but I am kind of hoping the layer above the Chloroform is Acetone or something similar, its def not IPA. Although there is some IPA still in there somewhere!

So gas mask on and away I go, I can get pics of any lab stuff i do but not from the outbuilding (camera issue and privilege rights regarding where I can and cant take it

)

Little_Ghost_again - 2-10-2014 at 08:42

Ok A update.

I did one of these reactions a few weeks ago and posted about it. I added a little citric acid as well.
Well after I had decanted all the Chloroform off I put the 3 litres of cloudyish waste in a large flask and sealed with a lab glove and rubber band,I then placed in a cupboard and promptly forgot all about it.
I found it today and it had gone very clear. Although like this time I had added sodium hydroxide, I had not added any oils or anything like that.
The first thing that hit me when I took the glove off was the smell, not nasty but very very faintly detergent like! so I placed 2ml of the solution in flask and added 250ml of distilled water. This I shook and to my surprise the flask filled with bubbles!
I have no idea what it is but I have been trying it out as a cleaner lol. Cleans glassware superbly. Takes grease and dirt off our wooden shed floor like nothing I have ever seen!
The other strange thing though is I went out today (Hospital) and was away for 4 hours, when I came back none of the bubbles had dispersed in the flask! it was still full of bubbles. is there anyway it could have made something like washing soda?
It really does clean well and my hands are fine (ever so slightly dry but not much).

Opinions appreciated! Apart from a very small amount of citric acid the rest was done as above but left for 2-3 weeks, I could understand it if there had been any oil involved as it would just be a straight soap.
I have taken more of the fluid and evaporated from 200ml to 50ml, it goes cloudy but no crystal yet and the smell gets slightly stronger.

Amos - 2-10-2014 at 18:00

It would help to know what you mean by "detergent-like". And by bubbles that stay around for hours, do you mean it's foamy or soapy on the surface? If I recall correctly, the haloform reaction produces sodium hydroxide as one of many byproducts; this could easily account for the cleaning properties and the washing soda-like tendencies.

Little_Ghost_again - 3-10-2014 at 04:44

Yes it produces a foam like washing up liquid that is shaken with water,the difference being the bubbles dont collapse so easily, The foam in the flask is till there this morning!
Another thing I add sodium chloride and sodium hydroxide, to start with you seem to get a fair size yield of chloroform but as the flask starts to clear this seems to diminish. Once reasonably clear I remove the chloroform and the layer just above, this other layer smells like a solvent, I did a distillation of these layers last night and got strange results, I am going to repeat but with a much more accurate thermometer.
I have a long mercury one that measures in 0.1 degrees C.
Anyway the rest of the liquid at this point has a very high pH my pH probe isnt great so not accurate, but seems around pH 10. After 2-3 weeks the solution in the flask clears totally and refracts light very differently to water, there are very small bubbles slowly evolve still, these (by comparing with small drill bits) seem to be around 0.2 - 0.3mm in diameter.
If you take this solution and smell it, the smell is very faint but very similar to a detergent like SLS.
Shake the flask and it acts like you have added washing up liquid. Take some of the contents and boil 30% off and the detergent smell is greater. The pH is just barely over 7.
However the good bit.............
It cleans grease and dirt like nothing I have seen, I will try and upload some pictures of really bad dirty bits with patches that have been cleaned. Also as soon as you was a sponge out all the dirt flows out the sponge and it looks brand new again. So we have a solution that grabs onto dirt like a tramp grabs a sandwich but loves water and take the dirt with it.
I cant call it soap as there is no oil or fat added, I have no idea what it is but I know a couple of things it isnt.
its not excess hydroxide (too mild on skin and way too low pH), its not a solvent as no solvent like smell and bubbles (foam) dosnt disperse.
put next to flask of RO water thats been charcoal filtered and it refracts the light differently, slightly clearer and almost blue like tinge.
I am making some more but this time everything is going to be weighed and measured, I am also going to take samples from the bottom of the flask as the chloroform is produced. my only guess is somehow chloroform gets turned into a detergent by the large excess of sodium hydroxide I added.
i dont know but honestly both mum and dad were shocked at how mild this 3 week solution was but how easily it cleaned really bad dirt from a unsealed wooden floor,it hasnt bleached it as some solution on a dyed top dosnt bleach, but the cleaned patch of wood looks like its almost been sanded!
The dirt is on a shed floor and been there years, the wood was almost black! 2-3 mins with a sponge and 30ml of this stuff cleaned a small area right back to clean fresh wood.