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Offline KarlosTopic starter

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Superman beware..
« on: April 08, 2004, 12:09:58 PM »
For chemists (and anybody else intrested) :-)

Whilst the article isn't exactly new, I was quite surprised to discover that an organic compound (that is carbon based) of Krypton has been prepared.

HKrCCH was prepared by the action of UV radiation on  acetylene in a frozen krypton matrix, breaking off one of the terminal hydrogen atoms. On warming, the remaining carbon bonded to the krypton and the resulting compound comfirmed via IR absorption.

Well, I was impressed anyway :-)
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Offline KarlosTopic starter

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Re: Superman beware..
« Reply #1 on: April 08, 2004, 02:36:11 PM »
Quote

Cymric wrote:
Indeed impressive, although I consider the fact of using a temperature well below minus 200 degrees centigrades a sort-of-a-cheat. Heat the substance to room temperatures and it will most likely dissociate into ethyne and krypton again.


Without doubt. I expect dissociation would occur well below even liquid nitrogen temperatures.

Whilst I was doing my degree, noble gas chemistry was a bit of a side fascination of mine. Before quantum mechanics totally revolutionised the understanding of the chemical bond, comnpounds of any such element were deemed fundamentally impossible, due to the belief that the atom had already had a perfectly stable electronic configuration.

As it goes, the evidence that you could create compounds of the heaver atoms in the series has been around a long time before anybody managed to do so. The notion of an "expanded shell" had been around a long time to explain the electronic configuration for interhalides, oxyanions etc. Nobody ever succeded in attempts to make such compounds directly, however.

It all kicked of in about 1963 IIRC, when a feller called Neil Bartlett discovered a very unusual reaction between molecular oxygen and platinum(VI) fluoride. The compound he got appeared to be PtF6O2, which would indicate a stupidly high oxidation state, even if the oxygen was a superoxide anion.

When he studied it, he actually found he'd created a dioxygen cation compund, (O2)+ (PtF6)-. This is not as unusual as it sounds, since as anybody who has studied molecular orbital bonding theory knows, the highest electrons in the O2 exist unpaired in antibonding orbitals. Removing one actually increases the bonding order from 2 to 2.5.

He then realised that the size and first ionization potential of O2 and Xe were very similar, so he just tried it and managed to repeat the reaction to get what he believed was XePtF6 (in fact it was a mixture of xenon oxidation states).

A flurry of activity followed and it was discovered that direct flouination of Xenon was possible, up to the hexaflouride (high temperature and pressure needed for that one). XeF2 can be made by from exposing a mixture of fluorine and xenon in a sealed glass tube to sunlight.
The flourides can be hydrolysed to oxides and oxyanions. Stabilised perxennate salts are even available for quantitative analysis.

Since then, many compounds of xenon have been prepared and the Xe-C and Xe-N, Xe-H and Xe-D bonds are known.

Krypton, on the other hand is an order of magnitude less reactive, which makes this find even more remarkable.

The stability of these bonds is predicted by advanced molecular orbital calculations (known as "ab initio") and preparing the compound is proof to support the molecular orbital model.

The same team also managed to prepare the only known argon compound, Argon Hydrofluoride (HArF) in a similar manner.

As for a teflon substitute, no chance. Even Xe-C bonds dissociate rapidly at ambient temperatures. You do *not* need that form of carbon radical floating around when there is oxygen and stuff present ;-)
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Offline KarlosTopic starter

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Re: Superman beware..
« Reply #2 on: April 08, 2004, 11:20:01 PM »
Quote

KennyR wrote:
HKrCCH sounds like a Klingon swear word. ;-)


-edit-

:lol: Missed that first time around :-D

-/edit-

Quote

Noble gas chemistry maybe shouldn't be termed chemistry - because the compounds produced are very unstable and often only last for short timeframes, even at a few Kelvin from absolute zero.


Not true for Xenon. Perxennate salts (containing the XeO4 anion) are powerful oxidising agents available for quantitative analysis. Many xenon compounds are stable, but you have to be wary of some. XeO3, in particular is highly explosive and also a powerful oxidising agent. The first preperation left a chemist blind and without arms.

Even the Xe-C bond had a half life of an hour or so at zero celsius - more than long enough for investigation of its chemical properties.

Quote

Its main aim is to expand our understanding of how the physics behind chemistry works. Then we can build new theories. Because, to be honest, many fundamental chemistry theories are a "bit dodgy".

Covalent theory is the one I was brought up with, and describes how atoms combine into molecules. However, chemists quickly found that it doesn't account for many things, one being the chemistry of boron, another being the fact that noble gases can actually form compounds with that stable electron configuration.


I studied molecular orbital bonding theory (basically quantum mechanics as applied to atoms, spread out to molecules) quite a bit. You could'nt possibly do any higher organic chemistry without it since it explains all the oddities that occur rather nicely. Try explaining boron hyrdides such as B2H6 without it and you go mad ;-)

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So research into noble gas chemistry, though seemingly pointless from a practical point of view, stretches the parameters of what we know about quantum physics as it pertains to the atom. And with it we can build new theories.


Well, it's not entirely pointless practically. Xenon forms a range of handy oxidising agents.

Quote

Now I really want to know two things: whether radon is the last of the noble gases or whether there is another one lurking in the transuranics. Secondly, how Blobrana got a stain on her dress. ;-)


There's bound to be a heavier noble gas configuration, but more than likely the nucleus won't adopt any of the so called "islands of stability" predicted for some of the ultra heavy elements (its theorized that an isotope of the element below lead could have a 10 year half life).

The problem for these theorised "metastable" ultra heavy elements is that there's no easy way to get to them (presently). You cant simply take lighter ones and build up fractionally like the later actinides and beyond were. You need to directly fuse heavier nuclei to get there in fewer steps, but fully ionizing eg a Kr for acceleration and bomardment isn't exactly easy.

No idea about the stains.....:-)


-edit-

@blobrana

Ah so they did manage it. I once read in an old radiochemistry book about plans to accelerate a krypton isotope for bombarding another nucleus to get to element 110. That was proposed back in the mid 60's when the book was written, but it was acknowledged that it would have to wait for more powerful accelerators :-)
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Offline KarlosTopic starter

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Re: Superman beware..
« Reply #3 on: April 09, 2004, 02:14:10 AM »
Well, VSEPR is taught on the grounds that it's fundamentally easier to grasp for GCSE/A-level purposes and predicts the shape of most covalent molecules reasonably well.

The fact it relies on the notion of well defined electron pair positions and their electrostatic repulsion is clearly flawed, since the quantum model of the atom (well more specifically the electrons around it) dispenses with this simplistic view of electrons all together.

Back when I did my A levels (1992/3), there was some MO stuff but it was largely qualitative.

I really got into quantum and its applications during my degree, since it, as you point out, explains the observed phenomena so much more accurately and concisely than these other ad-hoc (mostly empirical) methods.

Besides, what other field can you sit and listen to a respected senior lecturer read the imortal words

"..and the reaction intermediate is formed by a backside attack of the HOMO on the LUMO, giving rise to the following excited state..." :lol:

And I, with my accute inuenndo disorder, had to keep a straight face, since the guy lecturing was my supervisor!

Happy days :-D
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Offline KarlosTopic starter

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Re: Superman beware..
« Reply #4 on: April 23, 2004, 03:25:26 PM »
Quote

glockspeel wrote:
Pardon me, but who is this "superman"?


A dude who likes to wear his underpants outside his trousers and is severely allergic to some compound called Kryptonite (which may, possibly, contain krypton) :-D
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