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Off-Topic Discussion => General Discussion => Topic started by: jr2 on December 20, 2007, 02:41:09 am

Title: Heat until frozen
Post by: jr2 on December 20, 2007, 02:41:09 am
Quote from: http://physicsworld.com/cws/article/news/20325
Sep 24, 2004
Law-breaking liquid defies the rules

Physicists in France have discovered a liquid that "freezes" when it is heated. Marie Plazanet and colleagues at the Université Joseph Fourier and the Institut Laue-Langevin, both in Grenoble, found that a simple solution composed of two organic compounds becomes a solid when it is heated to temperatures between 45 and 75°C, and becomes a liquid when cooled again. The team says that hydrogen bonds are responsible for this novel behaviour (M Plazanet et al. 2004 J. Chem. Phys 121 5031).

Solids usually melt when they are heated, and liquids turn into gas, although exceptions do exist when heating leads to chemical changes that cannot be reversed, such as polymerisation. However, a reversible transition in which a liquid becomes a solid when heated has never been observed until now.

Plazanet and colleagues prepared a liquid solution containing α-cyclodextrine (αCD), water and 4-methylpyridine (4MP). Cyclodextrines are cyclic structures containing hydroxyl end groups that can form hydrogen bonds with either the 4MP or water molecules.

At room temperature, up to 300 grams of αCD can be dissolved in a litre of 4MP. The resulting solution is homogenous and transparent, but it becomes a milky-white solid when heated. The temperature at which it becomes a solid falls as the concentration of αCD increases.

Neutron-scattering studies revealed that the solid phase is a "sol-gel" system in which the formation of hydrogen bonds between the αCD and the 4MP leads to an ordered, rigid structure. At lower temperatures, however, the hydrogen bonds tend to break and reform within the αCD, which results in the solution becoming a liquid again.

Molecular dynamics simulations by Plazanet and co-workers confirmed that the cyclodextrine ring becomes distorted as it is heated up to close to the solidification temperature. The hydrogen bonds within the αCD break and the hydroxyl groups rotate towards the outside, which allows a network of bonds to form between the different molecules. The team has found a number of cyclodextrine/pyridine systems that also become solid when heated, and is now looking more closely at the structure of the sol-gel system to understand the solidification mechanism in more detail.
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Title: Re: Heat until frozen
Post by: Hellstryker on December 20, 2007, 03:15:48 am
:jaw: what the hell will come next, a replacement for water? O_o
Title: Re: Heat until frozen
Post by: jr2 on December 20, 2007, 03:35:38 am
jr2, Bobboau and 0 Guests are viewing this topic.

*waits for wisdom from above*  :lol:
Title: Re: Heat until frozen
Post by: karajorma on December 20, 2007, 04:55:00 am
As soon as I read the line about hydrogen bonding I had a pretty good handle on what was going on there. It's one of those things that had you asked me if it could happen I'd have said probably but obviously I wouldn't be able to name any examples. To be honest I'm kinda surprised that this is the first time it has been seen.

The mechanism surprised me a bit though. I'd have expected it to work by ring-opening rather than distortion of the ring. Then again I only ever worked with monosaccharides and that was years ago. :)
Title: Re: Heat until frozen
Post by: Nuke on December 20, 2007, 07:28:42 am
what would happen if you kept pushing up the temperature? would it become harder/melt/catch on fire/explode? i only ask because of potential applications for high temperature materials, you know things such as rocket engines and fusion reactors :D
Title: Re: Heat until frozen
Post by: karajorma on December 20, 2007, 10:09:45 am
I'd imagine that it would caramelise if you pushed the temperatures too much higher.

We're basically talking about something not too dissimilar to starch in terms of chemical properties. By the way, in case that sounds tasty I should warn you that the other chemical  4-methylpyridine probably has a putrid fishy smell. :D


Hydrogen bonding isn't that strong in the scheme of things. It's strong enough to stop water being a gas at room temperature but it's nowhere near as strong as metalic bonds (let alone ionic or covalent bonds like you find in rubies or diamonds).
Title: Re: Heat until frozen
Post by: Mika on December 20, 2007, 07:24:06 pm
I don't have access to that journal, but the thing I was wondering is actually the circumstances when the discovery was made. Was it accidental or something which was simulated beforehand?

Mika
Title: Re: Heat until frozen
Post by: G0atmaster on December 20, 2007, 10:28:06 pm
another cool chemistry oddity is the so-called "Water Bridge," formed by subjecting pure, deionized water to extremely high voltage:

http://www.physorg.com/news110191847.html

Title: Re: Heat until frozen
Post by: Hellstryker on December 20, 2007, 11:05:41 pm
Interesting.. depending on how fast you could get the water to flow and stay within such a confined space you could have quite an interesting weapon there..
Title: Re: Heat until frozen
Post by: FUBAR-BDHR on December 20, 2007, 11:19:42 pm
Hmm I was thinking more in the line of shields.   Some kind of array of these bridges that could be instantly frozen when a projectile is detected heading toward an area.
Title: Re: Heat until frozen
Post by: Hellstryker on December 20, 2007, 11:50:07 pm
I was thinking somthing more along the lines of a defense grid for military buildings
Title: Re: Heat until frozen
Post by: FUBAR-BDHR on December 20, 2007, 11:53:38 pm
Defense grid, shield array what's the diff?  Still does the same thing.
Title: Re: Heat until frozen
Post by: jr2 on December 21, 2007, 12:47:46 am
another cool chemistry oddity is the so-called "Water Bridge," formed by subjecting pure, deionized water to extremely high voltage:

http://www.physorg.com/news110191847.html



:jaw:
Title: Re: Heat until frozen
Post by: G0atmaster on December 21, 2007, 01:43:31 am
God makes truly amazing toys  :D
Title: Re: Heat until frozen
Post by: karajorma on December 21, 2007, 02:33:24 am
Don't troll. :p

I don't have access to that journal, but the thing I was wondering is actually the circumstances when the discovery was made. Was it accidental or something which was simulated beforehand?

My bet is that it was an accident. I've not used it but 4-methylpyridine seems like a reasonable choice of solvent for an experiment. I can easily imagine a PhD student or post doc wanting to warm the solution up before the experiment and finding it turned solid when he tried.
Title: Re: Heat until frozen
Post by: G0atmaster on December 21, 2007, 02:49:44 am
Were you referring to me, kara?  I didn't know that was considered trolling, sorry sir.
Title: Re: Heat until frozen
Post by: Mefustae on December 21, 2007, 02:51:56 am
Were you referring to me, kara?  I didn't know that was considered trolling, sorry sir.
Oh, don't be coy. :p
Title: Re: Heat until frozen
Post by: G0atmaster on December 21, 2007, 02:57:29 am
more vocabulary!! what the heck is a coy?!
Title: Re: Heat until frozen
Post by: redsniper on December 21, 2007, 02:59:25 am
www.dictionary.com !!!
DO YOU USE IT!!!
Title: Re: Heat until frozen
Post by: G0atmaster on December 21, 2007, 03:03:19 am
Thank you for that.  No I don't regularly.

So now you WANT me to troll?

Kara says don't troll, Mefustae says not to be coy, whose synonym is shy.  You're sending me mixed signals!
Title: Re: Heat until frozen
Post by: Hazaanko on December 21, 2007, 03:09:45 am
Careful man.  Someone mentions God, trolls come out of the woodwork, someone gets offended, and before you know it - people start getting their eyes poked out and kittens start dying.  KITTENS START DYING.  Total chaos and madness ensue.
Title: Re: Heat until frozen
Post by: karajorma on December 21, 2007, 03:14:04 am
Alright, back on topic.
Title: Re: Heat until frozen
Post by: Mika on December 21, 2007, 07:46:58 am
Quote
another cool chemistry oddity is the so-called "Water Bridge," formed by subjecting pure, deionized water to extremely high voltage:

http://www.physorg.com/news110191847.html

Ah, something everyday related from the basic research. Nice to see things like these researched and published for a chance. It is an interesting phenomenom, I would like to know about the voltages they are putting on it.

Coming next: how much similarities are there between this effect and the liquid nitrogen property of climbing up from a container?

Mika
Title: Re: Heat until frozen
Post by: karajorma on December 21, 2007, 09:14:06 am
I've not heard of nitrogen doing it. Do you mean helium?
Title: Re: Heat until frozen
Post by: Bob-san on December 21, 2007, 10:12:19 am
Quote
another cool chemistry oddity is the so-called "Water Bridge," formed by subjecting pure, deionized water to extremely high voltage:

http://www.physorg.com/news110191847.html

Ah, something everyday related from the basic research. Nice to see things like these researched and published for a chance. It is an interesting phenomenom, I would like to know about the voltages they are putting on it.

Coming next: how much similarities are there between this effect and the liquid nitrogen property of climbing up from a container?

Mikaz
If you mean surface-tension, I'm not even sure of the properties of Liquid N2. If it did that on any scale such as this--that N would evaporate when exposed to room temperatures, not to mention when heated by DC. Besides--why would computer enthusists use litres of N2 without it climbing out and freezing their hands?
Title: Re: Heat until frozen
Post by: Mika on December 21, 2007, 10:17:34 am
Sorry, that should have read "Helium" rather than "Nitrogen". 5 years of Industrial Optics makes one a dull boy in Quantum Mechanics.

I meant that the phenomena have similar qualities, not that they are caused by the same reason. It will be interesting to hear if they find any parallels between them.

Mika
Title: Re: Heat until frozen
Post by: G0atmaster on December 21, 2007, 12:25:34 pm
I heard of a guy trying to cool his highly overclocked computer with LHe2.  He was scared about bringing electronics that close to Absolute Zero.  But everyone told him it'd be ok, so I think he went through with it.
Title: Re: Heat until frozen
Post by: Tyrian on December 21, 2007, 09:30:09 pm
I heard of a guy trying to cool his highly overclocked computer with LHe2.  He was scared about bringing electronics that close to Absolute Zero.  But everyone told him it'd be ok, so I think he went through with it.

I remember seeing the video of that.  He pushed the system past 5.5Ghz, I *think.*  I'll see if I can find it.

EDIT:  Here it is. (http://www.youtube.com/watch?v=u3RjkURB6To)
Title: Re: Heat until frozen
Post by: G0atmaster on December 22, 2007, 02:35:30 am
No, that one's Liquid Nitrogen.  LHe2 is Liquid Helium.  FAR colder.  Like, the coldest we've ever gotten in cryogenics cold.
Title: Re: Heat until frozen
Post by: Nuke on December 22, 2007, 09:37:02 am
is liquid nitrogen conductive? meaning would a full system immersion be possible?
Title: Re: Heat until frozen
Post by: karajorma on December 22, 2007, 11:35:52 am
Liquid nitrogen is no doubt a very good insulator. The problem is that unless you do a good job sealing your container it slowly condenses oxygen out of the air since the boiling point of nitrogen is lower than that of oxygen.

Once the concentration of oxygen gets high enough you have a serious fire/explosion hazard on your hands.


And that's before we consider water condensing out of the air. :) But I prefer to mention the danger that gives you a nice big bang first. :)
Title: Re: Heat until frozen
Post by: G0atmaster on December 22, 2007, 05:37:54 pm
Plus, all that cold would turn your PCBs and ICs to glass.  Not literally, but they'd be very ready to shatter.  The plastic and such.

One modding group tried to run Fluorinert (http://en.wikipedia.org/wiki/Fluorinert) through pipes dipped in LN2, and then into a tank containing their computer, but the Fluorinert wound up turning to gel.