Sciencemadness Discussion Board - and i Thought i just bought some Toluene ...

and i Thought i just bought some Toluene ...

aga - 16-9-2014 at 10:22

At a big hardware store in Malaga i bought a 1L tin of 'Super Disolvente' which stated on the can :-

Toluene, Methanol, Methyl Acetate and Acetone (Propanone, Pah!) as ingredients.

I read that Toluene isn't soluble/miscible with water, so i dumped 500ml into some water and then into a separatory funnel.
Within a minute two distinct layers formed, so based on density, i assumed the top layer to be mostly Toluene.

Distilling the Bottom layer, i have seen 11 distinct B.P.s held for at least 2 minutes each, distillates of which which were separately collected and stored, and have been trying to identify them by their BPs.

7 of them appear to be :-

56 - 59 C Methyl Acetate + Acetone
62 - 63 C Chloroform (!)
64 - 68 C Methanol
69 - 72 C Hexane
76 - 77 C Carbon tetrachloride
78 - 79 C Ethanol
80 - 83 C Benzene

I would appreciate some suggestion what the other 4 might be, as i can find no data for probable candidates :-

74-75 C
83 C
84-85 C
86 C

11 substances so far, before even starting on the larger Toluene layer !

All distillates ignite easily, and some smell very different to the others.

EDIOT : (an idiot editing)

80 - 85 C Benzene
changed to what the notes *actually* say : 80 - 83 C Benzene

[Edited on 16-9-2014 by aga]

forgottenpassword - 16-9-2014 at 10:29

If chloroform, carbon tetrachloride and benzene were present, they would surely be soluble in the toluene layer rather than the water layer.

unionised - 16-9-2014 at 10:31

God knows what you have got there but you need to be aware of this
http://en.wikipedia.org/wiki/Azeotrope

aga - 16-9-2014 at 10:32

Where the Toluene is will remain a mystery until i heat it up to 110 C

I just assumed it'd be in the top layer, but i could easily be 100% wrong.

aga - 16-9-2014 at 10:34

Azeotropes are probably in there in abundance !

Would you happen to have any link to a table of the BPs of some azeotropes?

Amos - 16-9-2014 at 10:35

Neither chloroform nor carbon tetrachloride can burn or be ignited. I also have to agree that those two and benzene would certainly dissolve in the toluene rather than the aqueous layer(although you neglected to mention how much water you added, so that could complicate things. But if you still want my input the 83 C distillate could be ispropanol. And there could also be a million different azeotropes happening here. Not to say that that these separations can't be done with time and effort, but it's not nearly as simple as you're making it out to be.

Amos - 16-9-2014 at 10:36

And rather than try to identify them by their boiling points, start to examine the properties of each of your distillates (try salting some of them out, for example, and see what happens)

careysub - 16-9-2014 at 10:51

One strategy to try with processing this 'witches brew' of solvents is to let CaCl2 soak up everything it can first, this should remove all alcohols and acetone and simplify the distillations I would think.

I suppose with sufficient heating the alcohols+acetone would be distilled off the CaCl2?

Amos - 16-9-2014 at 11:06

How does CaCl2 get rid of the alcohols and acetone? Doesn't it only take in water?

[Edited on 9-16-2014 by No Tears Only Dreams Now]

aga - 16-9-2014 at 12:19

A quick google says that Chloroform does not burn per-se, but decomposes rapidly releasing, amongst other things, Hydrogen, which does.

Carbon tet seems not to burn at all.

I thought i'd start with BPs as i like distilling stuff, and can do that.

aga - 16-9-2014 at 12:23

Quote: Originally posted by No Tears Only Dreams Now

it's not nearly as simple as you're making it out to be.

I am sure it isn't, however i'm just telling what i did, and asking for advice.

There is no radical new theory being put forward here, it's just a noob with a disty rig and a bottle of Dissolve-it-All, wondering what is in it.

[Edited on 16-9-2014 by aga]

careysub - 16-9-2014 at 12:29

Quote: Originally posted by No Tears Only Dreams Now

How does CaCl2 get rid of the alcohols and acetone? Doesn't it only take in water?

[Edited on 9-16-2014 by No Tears Only Dreams Now]

It is well know for taking up alcohols, forming complexes, but it does this to acetone also, though apparently not as strongly:
http://pubs.rsc.org/en/Content/ArticleLanding/1917/CT/ct9171...

Dr.Bob - 16-9-2014 at 12:50

I would guess that the 76-77 range material might be ethyl acetate, it is common in paint thinners and such, and might be somewhat water soluble.

I agree that 2-propanol would be around 82-83, that would be somewhat water soluble as well.

aga - 16-9-2014 at 13:12

The Assumption is that the Lower layer, which was distilled, is the non-toluene layer.

I don't know anything at all about it really, just that it was the Lower layer when about 15~20% by volume water was added.

The Upper layer was visibly more viscous, reacting in a 'lazy' way when the flask was tapped.

The Upper layer also burns easily, with an orange flame, and lots and lots of soot. Almost like a burning rubber tyre.

The Lower layer distillates all burn with a blue, or barely visible flame, and no soot at all.
Some have an orange flame, but still no soot.

All are easily ignited.

forgottenpassword - 16-9-2014 at 13:21

It doesn't contain ethyl acetate. The 'fractions' comprise a continous range from 53 to 86 Celsius -- supposedly WATER-SOLUBLE hexane, benzene, chloroform and tetrachloromethane! It is a nonsense.
I would say that it is a fair bet that the stated ingredients are far more accurate than this attempted fractionation. The flammable distillates are obviously various ratios of methanol, methyl acetate, water and acetone.

[Edited on 16-9-2014 by forgottenpassword]

kmno4 - 16-9-2014 at 13:26

Quote: Originally posted by aga

(...)
7 of them appear to be :-

56 - 59 C Methyl Acetate + Acetone
62 - 63 C Chloroform (!)
64 - 68 C Methanol
69 - 72 C Hexane
76 - 77 C Carbon tetrachloride
78 - 79 C Ethanol
80 - 83 C Benzene

I would appreciate some suggestion what the other 4 might be, as i can find no data for probable candidates :-

74-75 C
83 C
84-85 C
86 C

11 substances so far, before even starting on the larger Toluene layer !
(...)

Another spammer's crappy post......
With your total lack of chemical knowlede, you will harm yourself, sooner or later.
Better start collecting stamps, not impossible to get fractions.
Grow up and post no more.

aga - 16-9-2014 at 13:31

As i have said at least twice, i could easily have the Water solubility entirely wrong, both in Identification and most likely in Concept.

Varying ratios of 4 ingredients leading to 11 multi-minute Stable distillate vapour temperatures ?
Fascinating.

Not having much understanding (or any stock) of Phase diagrams, i would be very appreciative of an explanation of how that can happen, if your suggestion is that they form multiple azeotropes, and also somehow break azeotropic state to yield distillate, hence breaking the azeotropes they take part in.

aga - 16-9-2014 at 13:41

Quote: Originally posted by kmno4

Thanks sooo much for the Honest feedback.

I wish my chemistry knowledge were as Comprehensive and Utterly Complete as yours, so that i could also Stamp on noobs with impunity, with the full force of my thereby Fully Justified self-righteous pomposity.

Oh ! Crap. Appologies.
I posted this in the wrong forum - it should have been 'Beginnings'.

Thanks for pointing that out Clearly, and Succinctly.

(mod please move it to the right place. Detritus or Beginnings, you chose)

forgottenpassword - 16-9-2014 at 13:51

Quote: Originally posted by aga

Varying ratios of 4 ingredients leading to 11 multi-minute Stable distillate vapour temperatures ?

Yes, that seems most likely. The boiling points of your supposed fractions cover such a large and continuous temperature range that the idea of these being discrete azetotropic mixtures seems unlikely.

[Edited on 16-9-2014 by forgottenpassword]

Bert - 16-9-2014 at 13:53

Moved as requested-

aga - 16-9-2014 at 13:55

thank you Bert

aga - 16-9-2014 at 13:57

Quote: Originally posted by forgottenpassword

The thing is, each temperature range held for several minutes, some 5 mins+, which led me to think they were distinct compounds or mixtures.

Can complex azeotropes do that ?

forgottenpassword - 16-9-2014 at 14:06

Maybe they are azeotropes then. If you are certain that they are fractions then looking up data for all of the different possible azeotropes and pure components will help you to identify the fractions, if that's what you want to do.
I see no reason to assume contamination from unlisted components -- especially those which would be poorly soluble in an aqueous layer, as previously mentioned.

[Edited on 16-9-2014 by forgottenpassword]

aga - 16-9-2014 at 14:07

Would you happen to have any links to azeotrope BP tables handy ?

Not Certain at all, just saw the thermometer in the still head Hold at the stated temperatures for many minutes before rising, at which point i switched receiver vessels.

[Edited on 16-9-2014 by aga]

forgottenpassword - 16-9-2014 at 14:11

Some are listed on the Wikipedia azetrope (data) page. I don't think that the relevant ternary azeotropes are included, though.

[Edited on 16-9-2014 by forgottenpassword]

aga - 16-9-2014 at 14:18

Cheers!
Any data is good for this exercise.

forgottenpassword - 16-9-2014 at 14:26

Methanol 64.7
Methyl acetate 57.0
Acetone 56.5
Methyl acetate / water 56.1
Methanol / acetone 55.7
Methanol / methyl acetate 53.8

Etc.

[Edited on 16-9-2014 by forgottenpassword]

aga - 16-9-2014 at 14:32

Many thanks forgottenpassword.

It would be great to bring all the BP data for everything into one place, so anyone could look up the possibilities

I'll try to get the 'toluene' (i.e. Upper) layer distilled tomorrow and see what that brings.

Probably Benzene, and Dragon Bile.

Amos - 16-9-2014 at 18:07

By any chance, do you have the name of the product you are distilling? I'd like to look into this a bit for myself.

kt5000 - 16-9-2014 at 19:52

Thanks for posting this aga. I've looked at the paint thinner aisle also, and all I find are complex mixtures like you have there. I wouldn't know where to start such a complex separation. I may give it a shot!

I was looking at a product called Strip-X, if memory serves.

[Edited on 17-9-2014 by kt5000]

aga - 17-9-2014 at 01:00

Quote: Originally posted by kt5000

I wouldn't know where to start such a complex separation.

Me neither, hence the simple distillation.

> I may give it a shot!
That's the Spirit (pun intended)

This tin says UN 1A1/Y1.8/100/14/E/B-1026/IMV which i need to look up.

aga - 17-9-2014 at 01:29

Seems that the UN 1A1/Y1.8/100/14/E/B-1026/IMV marking is more about the Tin than it's contents.

UN = United.Nations.
1A1 = Tighthead.Steel.Drum.
Y = Packing.Group.II.6.Moderate.Hazard.
1.8 = Specific.Gravity.
100 = Kilopascal.Pressure.Rating.

source: www.myerscontainer.com/docs/POP-MCC-Section.pdf

The B-1026 seems to refer to 'Heptanes'

source: http://en.wikipedia.org/wiki/List_of_UN_numbers_1201_to_1300

Little_Ghost_again - 17-9-2014 at 01:30

I found and posted a table from wikipedia, but my account was deleted! I cant find it now. But will search some more.
Basicaly I think it said you could add some Hydroxide and get the methyl acetate to gice acetone and acetic acid it also gave all the azeotropes likely

http://en.wikipedia.org/wiki/Azeotrope_%28data%29
there you go that should help

[Edited on 17-9-2014 by Little_Ghost_again]

aga - 17-9-2014 at 02:17

Perfect LG2.
Thanks.
Sorry to unionised for not spotting the link at the bottom of the page in his earlier suggestion.

MrHomeScientist - 17-9-2014 at 06:11

Quote: Originally posted by Little_Ghost_again

I found and posted a table from wikipedia, but my account was deleted! I cant find it now.

That's very strange. Even all the threads you started have been completely removed, which is a damn shame because there was lots of good information in those. U2U Polverone or woelen and find out what happened.

Little_Ghost_again - 17-9-2014 at 06:50

Quote: Originally posted by MrHomeScientist

Quote: Originally posted by Little_Ghost_again

I found and posted a table from wikipedia, but my account was deleted! I cant find it now.

It appears the quality of my writing was deemed spam by the protection software lol.
So I was DELETED!!!
No ones fault except maybe mine, I have asked for details via U2U of how to avoid this in the future. Yes a shame so much good information is gone but..........
Fresh start and hopefully I can avoid spamming

. The irony of it is I posted the wikipedia link above and it was just after that I was zapped lol.
Having seen the vast quantity of spam that has apered today after the protection was disabled, it is far better I understand how to avoid the protection than it is to keep it switched off.
It is not fair on the Moderator and Admin team to have to waste so much time dealing with the huge amount of nonsense spam. So much time energy and money is spent chasing people for downloading films etc, and yet spamming is allowed to clog the internet and ruin peoples enjoyment and experience of a truly great resource such as the internet. I strongly believe that there should be severe penalties imposed on those that operate and use these bot's (intentionally).
Maybe another option is for the software to place all spam (as it see's it) into another forum, and rather than delete accounts it places a ban upon the names etc. At least then there is a chance for resurrection when the odd inevitable mistake is made.
LG

aga - 17-9-2014 at 06:59

Quote: Originally posted by Little_Ghost_again

It appears the quality of my writing was deemed spam by the protection software l

Really ?!?

I'm doomed

Today i started distilling the Upper layer, and stopped after 20 minutes because the VT stuck at 63 C all the way through.

Stuffing all the Wiki azeotrope BP data into a spreadsheet, the candidates for a BP of 63 +/- 1 C are :-

chloroform
n-propyl bromide + ethanol
ethyl acetate + methanol
toluene + methanol
n-octane + methanol
tetrachloroethylene + methanol
acetonitrile + methanol
isopropanol + methanol
n-hexane + isopropanol
n-hexane + tetrahydrofuran
cyclohexane + ethanol
cyclohexane + methyl ethyl ketone

As it is stated on the Tin that it is a mixture, forgottenpassword's suggestion that it is most likely an azeotrope, or complex mix of azeotropes fits very well.

NTODN is also right, in that the 63 C fraction cannot be cholorform, as it ignites very easily.

The layer that floated on water appears to be a mix of toluene + methanol, seeing as they fit the BP, and are already stated to be in there.

Next is splitting the Toluene & Methanol ...

Surprisingly this mix might be split using water as an entrainer :
www.ijcps.org/issue7/p2.pdf

There is also is a 'polydimethylsiloxane' membrane which seems to separate out the methanol.

Haven't got one of those.

Making some CaCl₂ instead.

[Edited on 17-9-2014 by aga]

[Edited on 17-9-2014 by aga]

Praxichys - 17-9-2014 at 10:57

Wash repeatedly in water.

Methanol is miscible with water in all proportions. Only half a gram of toluene will dissolve in a liter of water at 20C.

Shake your mixture vigorously with about the same volume of water, discard the water, and repeat 4 or 5 times. This will remove essentially all of the methanol from the toluene. Shake the toluene over anhydrous CaCl2 to remove the last traces of methanol and water. Filter out the CaCl2 and distill. You will then have reasonably dry and pure toluene.

You can obtain your toluene by using this same process on the 'Super Disolvente' directly, without distilling first, since AcOH, MeOAc, and acetone are all very soluble in water, although you may have to perform the wash a few more times - perhaps 6 or 7.

[Edited on 17-9-2014 by Praxichys]

aga - 17-9-2014 at 11:05

Fantastic ! Thanks very much for that.

As the saying goes, Praxichys makes Perfect !

Edit:

Just HAD to go give that a try straight away.
Interesting result.

100ml 'Disolvente' in a 250ml sep funnel with 100ml DDIW.
Immediately two layers appeared.

On shaking vigorously, a milky white liquid occurs.
Left to stand for a few seconds, a slightly milky top layer formed fast, with the bottom layer less milky.

Draw off the bottom layer, add 100ml DDIW, shake, wait, draw off bottom layer.
Repeat 4 times.

At iteration 5, the Top layer became Clear, and the lower layer milky with tiny, but visible droplets.

Subsequent iterations yield the same, with the Top layer perfectly clear, which i took to be the point at which i could stop adding, shaking etc, as the toluene is now as 'clean' as it can be with this water process.

Lesson learned : wait for advice from someone who actually has done this before and knows what to do !

[Edited on 17-9-2014 by aga]