Sciencemadness Discussion Board
Not logged in [Login ]
Go To Bottom

Printable Version  
 Pages:  1    3
Author: Subject: chemiluminescence!!
Alexein
Harmless
*




Posts: 35
Registered: 14-7-2007
Member Is Offline

Mood: Metastable

[*] posted on 27-10-2008 at 12:49
chemiluminescence!!


Hey all, after many failed attempts i was able to make chemluminescence with bis(trichlorophenyl) oxalate, some 9,10-bis(diphenylethynyl)anthracene dye and H2O2 and diethyl phthalate solvent. Sprinkle a bit of sodium acetate on top... :)

Synthesizing TCPO was a bitch....

Here it is with the lights on.

[img]http://www.xtremesystems.org/forums/attachment.php?attachmentid=87795&stc=1&d=1225084323[/img]

Lights off
[img]http://www.xtremesystems.org/forums/attachment.php?attachmentid=87796&stc=1&d=1225084323[/img]


The crystals in the bottom are *pure* TCPO. Hard to see, but you can tell that the the crystals themselves aren't glowing, but the surface is as the TCPO dissolves into the solvent and reacts.

there is enough in there to last a month (really, i've measured).
View user's profile View All Posts By User
Picric-A
International Hazard
*****




Posts: 796
Registered: 1-5-2008
Location: England
Member Is Offline

Mood: Fuming

[*] posted on 27-10-2008 at 13:04


Nice work!! looks awsome!
Can you explain how you made your TCPO? seems interesting! i wana try! :D
View user's profile View All Posts By User This user has MSN Messenger
Jor
International Hazard
*****




Posts: 950
Registered: 21-11-2007
Member Is Offline

Mood: No Mood

[*] posted on 27-10-2008 at 13:13


React oxalyl chloride with trichlorophenol.

Oxalyl chloride is very expensive. You need PCl5 or TCT to make it. PCl5 hard to get and with low yields. TCT cheap, hard to get, but also very toxic.
View user's profile View All Posts By User
Alexein
Harmless
*




Posts: 35
Registered: 14-7-2007
Member Is Offline

Mood: Metastable

[*] posted on 27-10-2008 at 13:35


Start with 2,4,6-trichlorophenol and dissolve it in dry toluene or dry dichloromethane. "wet" solvents are ok but the yield will be reduced. Add one molar equivalent of a suitable organic base. I used triethylamine. stir until everything is dissolved.

chill the solution with ice and add in SLOWLY 0.5 mol equivalents of oxalyl chloride. Its going to heat up.... ALOT... so keep it stirring and chilled.

Once its all added remove the ice and let it warm to room temperature with continous stirring. I find purity increases if you let it stir overnight.

The TCPO is a fine white powder mixed with triethylamine hydrohloride at this point. Suction filter the mixture and keep the suction on to dry out the powder. Discard the filtrate.

pour water directly onto the white powder and wash out the triethylamine hydrochloride. Dry the powder again.

The powder is TCPO, its still pretty impure but usable. If you want nice big pure crystals (like the ones in the picture) you can dissolve TCPO in tetrahydrofuran, filter, and recrystalize.
View user's profile View All Posts By User
Silverado7
Harmless
*




Posts: 14
Registered: 24-10-2008
Member Is Offline

Mood: No Mood

[*] posted on 27-10-2008 at 13:36


It's so beautiful... Great work!
Fascinating...
View user's profile View All Posts By User
Picric-A
International Hazard
*****




Posts: 796
Registered: 1-5-2008
Location: England
Member Is Offline

Mood: Fuming

[*] posted on 27-10-2008 at 13:43


Thanks, will give that a try!
I will probably buy a small amount of Oxalyl chloride. It isnt THAT expencive... but its gonna be worth it :D
The only real chemiluminescence i have done is oxidation of luminol, TCCA + H2O2 and NaOH/H2O2 + Cl2... and they are boring :D
View user's profile View All Posts By User This user has MSN Messenger
Alexein
Harmless
*




Posts: 35
Registered: 14-7-2007
Member Is Offline

Mood: Metastable

[*] posted on 27-10-2008 at 14:57


I should also mention a couple of things:

I *STRONGLY* reccomend the solvent that you do your chemiluminescent reaction in be diethyl phthalate. The reaction is MUCH brighter and lasts MUCH longer than if you do it in tetrahydrofuran or acetonitrile. Other solvents don't even work.

DEP is also relatively non-toxic and fairly inexpensive.

Trichlorophenol is a known carcinogen. While this doesn't stop most of us here on science madness do please take precautions.

A list of good dyes to make all kinds of funky colors can be found in http://en.wikipedia.org/wiki/Lightstick I've personally tested BPEA (which is seen in the pictures) and DPA.
View user's profile View All Posts By User
Ozone
International Hazard
*****




Posts: 1269
Registered: 28-7-2005
Location: Good Olde USA
Member Is Offline

Mood: Integrated

[*] posted on 27-10-2008 at 16:00


I really like this one, it's a classic.

I have made this reaction work fine in EtOAc (although the yield and duration of light is minimal) using DNPO, bis-dinitrophenyloxalate. I used either perylene (expensive, turquoise) or rhodamine 6G (cheap, red-orange) for the dyes.

If you want your TCPO reaction to be its best, add some sodium salicylate (this is not required with DNPO because the higly EW DNP rings are good leaving groups).

Both dioctylphthalate (DOP) and the bis-2-ethylhexyl (frequently confused with DOP) analogue also work.

The reaction is carried out in toluene; you can add excess toluene and azeotrope out the water with a short forerun. This is essential when making DNPO with DNP, which is sold containing considerable water to reduce the risk of explosion (it is both toxic and potentially explosive; it goes right through nitrile gloves). Cool, then add the oxalyl chloride (mine says it can contain <0.5% phosgene). After a short induction period, the mixture outgasses. Close and stir overnight.

Take off the solvent and bring up the residue in chloroform. Filter this and retain the solid. Mine worked fine (as a chemiluminescent probe) as-is. Make sure all of the chloroform is removed b/c it will quench your phosphorescence.

Also, oxalyl chloride in EtOAc with dye and added H2O2 will also work. The esterification only serves to make the oxalyl moiety easier to handle.

Cheers,

O3




-Anyone who never made a mistake never tried anything new.
--Albert Einstein
View user's profile View All Posts By User
Alexein
Harmless
*




Posts: 35
Registered: 14-7-2007
Member Is Offline

Mood: Metastable

[*] posted on 27-10-2008 at 16:22


Yeah, Sodium Salicylate works too.

I used sodium acetate because it was onhand. It works just as well IMHO.
View user's profile View All Posts By User
Alexein
Harmless
*




Posts: 35
Registered: 14-7-2007
Member Is Offline

Mood: Metastable

[*] posted on 29-10-2008 at 16:49
Now comes in blue


Same chemiluminescent reaction but with 9,10-diphenylanthracene to give a blue color.


Lights on.
[img]http://www.xtremesystems.org/forums/attachment.php?attachmentid=88027&stc=1&d=1225323034[/img]

Lights off.
[img]http://www.xtremesystems.org/forums/attachment.php?attachmentid=88028&stc=1&d=1225323034[/img]

I like this one better cause you can see the crystals and the "glow layer" as they dissolve.
View user's profile View All Posts By User
bfesser
Resident Wikipedian
*****




Posts: 2114
Registered: 29-1-2008
Member Is Offline

Mood: No Mood

[*] posted on 29-10-2008 at 19:07


Why 2 vials?
View user's profile View All Posts By User
Alexein
Harmless
*




Posts: 35
Registered: 14-7-2007
Member Is Offline

Mood: Metastable

[*] posted on 29-10-2008 at 20:15


Old saying: "why not?"

The dyes stain BADLY and the trichlorophenol waste is a known carcinogen. Also, as the reaction progresses, carbon dioxide is produced and tiny droplets that were stuck on the rim of the cap push out around the vial and get on the outside.

i left some vials around (singles) for a month and when i picked them up some of the contents had leaked out to the outside and onto my hand. I was not too happy that a carcinogenic substance that's proven to go through skin was on me.

So I double vial. haven't had a single accident since. One of my older samples had leaked out but the spill was entirely contained within the outer vial.

[Edited on 10-30-2008 by Alexein]
View user's profile View All Posts By User
Klute
International Hazard
*****




Posts: 1378
Registered: 18-10-2006
Location: France
Member Is Offline

Mood: No Mood

[*] posted on 30-10-2008 at 09:09


Very beautifull! Pretty impressive, the pictures are really well taken.

I agree with you for the douible-vial. Never too precautious.
It's a pity oxalyl chloride cna't be reaplace dby soemthing more easily obtained.




\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"

-Alice Parr
View user's profile View All Posts By User
JohnWW
International Hazard
*****




Posts: 2849
Registered: 27-7-2004
Location: New Zealand
Member Is Offline

Mood: No Mood

[*] posted on 30-10-2008 at 09:46


A very good do-it-yourself means of emergency lighting without electricity or fuel. And just in time for Halloween, too.
View user's profile View All Posts By User
Alexein
Harmless
*




Posts: 35
Registered: 14-7-2007
Member Is Offline

Mood: Metastable

[*] posted on 30-10-2008 at 10:07


Yeah, I got enough stuff here to fill a 20 gallon plastic bucket.

I'm going to load it up with the green stuff, put a radioactive label on it, cart it around my school and scare the crap outta my buddies and my teachers :D

Sure its freaking expensive.... but its going to be so worth it..... ;)
View user's profile View All Posts By User
UnintentionalChaos
International Hazard
*****




Posts: 1454
Registered: 9-12-2006
Location: Mars
Member Is Offline

Mood: Nucleophilic

[*] posted on 30-10-2008 at 21:24


Any reason for the use of dinitrophenol and not say, picryl groups? I imagine the picryl would be a much better leaving group, no? Would the reaction proceed too quickly because of this? Is the picric acid strongly colored enough to interfere? Or would the threat of explosion make it not even close to worth it?

What about home-brew tribromophenyl oxalate? IIRC tribromophenol is astoundingly easy to make. The oxalyl chloride not so much.




Department of Redundancy Department - Now with paperwork!

'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
View user's profile View All Posts By User
Alexein
Harmless
*




Posts: 35
Registered: 14-7-2007
Member Is Offline

Mood: Metastable

[*] posted on 31-10-2008 at 07:29


I think explosion danger is an issue. In theory the picryl groups would work very well.

I made the trichlorophenol derivative cause i knew i would bung up my first few attempts and i didn't want to have any possibility of explosions from my screw ups.

I suppose tribromophenol would also work. The reaction works with just straight phenol so anything better than that would have to work.

Getting the oxalyl chloride was the expensive part. But easier for me than making/handling PCl5 or cyanuric chloride precursors.
View user's profile View All Posts By User
Alexein
Harmless
*




Posts: 35
Registered: 14-7-2007
Member Is Offline

Mood: Metastable

[*] posted on 5-11-2008 at 13:09


This awesome paper details instructions on how to make a great deal of chemiluminescent reactions, not just peroxylates.

Chances are, if you can't obtain materials for one type you might be able to get materials for another type.

equally awesome is that it details mechanisms for how each one works. (or at least what the best proposed mechanisms are.)

Its a must have for anyone interested in chemiluminescence.

[Edited on 11-5-2008 by Alexein]

Attachment: Demonstrations of Chemiluminescence.pdf (1.4MB)
This file has been downloaded 6969 times

View user's profile View All Posts By User
Klute
International Hazard
*****




Posts: 1378
Registered: 18-10-2006
Location: France
Member Is Offline

Mood: No Mood

[*] posted on 5-11-2008 at 14:48


Thank you very much! Indeed a very complete and informative paper!



\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"

-Alice Parr
View user's profile View All Posts By User
Alexein
Harmless
*




Posts: 35
Registered: 14-7-2007
Member Is Offline

Mood: Metastable

[*] posted on 25-11-2008 at 21:27


I know i'm kicking a dead horse by reviving this thread but i wanted to post a video of TCPO crystals i made.

<object width="425" height="344"><param name="movie" value="http://www.youtube.com/v/cVQ9jjdU0l8&hl=en&fs=1"></param><param name="allowFullScreen" value="true"></param><param name="allowscriptaccess" value="always"></param><embed src="http://www.youtube.com/v/cVQ9jjdU0l8&hl=en&fs=1" type="application/x-shockwave-flash" allowscriptaccess="always" allowfullscreen="true" width="425" height="344"></embed></object>
Plenty of chemiluminescence videos out there. But i don't think any of them have crystals *that* big.

Sorry for the picture quality.

[Edited on 11-26-2008 by Alexein]
View user's profile View All Posts By User
Klute
International Hazard
*****




Posts: 1378
Registered: 18-10-2006
Location: France
Member Is Offline

Mood: No Mood

[*] posted on 26-11-2008 at 02:13


Very nice!



\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"

-Alice Parr
View user's profile View All Posts By User
Ozone
International Hazard
*****




Posts: 1269
Registered: 28-7-2005
Location: Good Olde USA
Member Is Offline

Mood: Integrated

[*] posted on 26-11-2008 at 22:51


The picryl moiety (TNPO) may be too good of a leaving group. The DNPO works without the salicylate (or acetate) promoter because it is a better leaving group than TCP. DNPO is also much less stable on storage (stored dry, under N2 or made as needed).

I imagine that TNPO would be even more unstable leading back to picric and oxalic acids (the explosive hazard should not exceed that of picric acid*, unless metals are present).

*dry picric acid can be a bit "hairy".

Cheers,

O3




-Anyone who never made a mistake never tried anything new.
--Albert Einstein
View user's profile View All Posts By User
raiden
Harmless
*




Posts: 38
Registered: 4-2-2008
Member Is Offline

Mood: Curious

[*] posted on 27-11-2008 at 22:47


That stuff is BEAUTIFUL! I will have to give it a go if I can procure the supplies.
View user's profile View All Posts By User
Alexein
Harmless
*




Posts: 35
Registered: 14-7-2007
Member Is Offline

Mood: Metastable

[*] posted on 28-11-2008 at 07:22


Quote:
Originally posted by raiden
That stuff is BEAUTIFUL! I will have to give it a go if I can procure the supplies.


Post pictures if you can.

You planning to make your own oxalyl chloride or buying it?

I'm currently scrapping together enough cash to get more chemicals and make more of the TCPO. I'll post a full video of how to do it eventually.

[Edited on 11-28-2008 by Alexein]
View user's profile View All Posts By User
Formatik
International Hazard
*****




Posts: 927
Registered: 25-3-2008
Member Is Offline

Mood: equilibrium

thumbup.gif posted on 13-2-2009 at 20:58


I've found two videos, both are quite interesting. The first is description of the method also using TCPO, NaOAC, BPEA dye, and 30% H2O2, but using EtOAC as a solvent. Then the second is a scale-up done in a 2 L pop bottle:

http://www.youtube.com/watch?v=kH19EIf5GtE

http://www.youtube.com/watch?v=mUCdGMeTveM
View user's profile View All Posts By User
 Pages:  1    3

  Go To Top