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Author: Subject: Rador Labs Challenge 11-12/2014: High Stakes, High Mass
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[*] posted on 18-11-2014 at 20:48


I think I'll be backing outof this since I am far to underskilled for this I Think. Though I will still be donating shortly on payday.

A) I just dont seem to have the time

B) Well I don't think my skills are grand enough to come up with something above the 500g mark. Though I am looking forward in seeing people results.




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[*] posted on 19-11-2014 at 00:56


First off, I would like to state that this is my own personal opinion, I am merely publishing it as food for thought by the judges and for debate.

I think the question of what is a polymer or not deserves closer attention. IUPAC's gold book defines it as:

Quote:
polymer

A substance composed of macromolecules.(1)


Now that may seem rather unhelpful and broad. Let's dig further, the word macromolecule in this context is hyperlinked to its own definition, so let's see what is IUPAC's says about macromolecules?

Quote:
macromolecule (polymer molecule)

A molecule of high relative molecular mass, the structure of which essentially comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass.
Notes:
1. In many cases, especially for synthetic polymers, a molecule can be regarded as having a high relative molecular mass if the addition or removal of one or a few of the units has a negligible effect on the molecular properties. This statement fails in the case of certain macromolecules for which the properties may be critically dependent on fine details of the molecular structure.
2. If a part or the whole of the molecule has a high relative molecular mass and essentially comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass, it may be described as either macromolecular or polymeric, or by polymer used adjectivally.(2)


Now polymers are disqualified from this contest (and I actually that that was a good idea), but implies that maromolecules are also disqualified.

So there's two parts, it may not be of high relative molecular mass while simultaneously having repeating molecular units. The problem is, what exactly a high relative molecular mass is, is left undefined :mad:

Let's consider an example: heteropolyacids are built-up of repeating molecular units, for example phosphotungstic acid has 24 tungstate units linked up in a regular pattern called a keggin structure. It is definitely potentially a macromolecule, but does its molecular mass of 2880.2g/mol (anhydrous) seal its fate because it is of "high relative molecular mass"?

Also, molecules with some repeating molecules, so long as they are not of "high relative molecular mass" are NOT polymers.

So are oligomers, for example, allowed? Again, at what molecular mass is the cuttoff where repetition puts it into the category of being a polymer/macromolecule.

I urge the judges to make a cuttoff of some sort.

Since we live in a aspiring metric world of base ten, I suggest that 10 repeating units is the cutoff for where something transcends being oligomeric to polymeric.

However, me need to translate this to a molecular mass somehow, because that is what IUPAC states it should be based on. Here I suggest we use tungstate, because it's the heaviest repeating unit that occurs in macromelcules that I know of (as heteropoly acids), that would mean that the cuttoff should be something like 2500amu (WO4 = 247 *10 = 2470~2500)

That would mean that things like cyclodextrins are in, but heteropolyacids are out.

References:

(1) IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. doi:10.1351/goldbook.
Last update: 2014-02-24; version: 2.3.3.
DOI of this term: doi:10.1351/goldbook.P04735.

(2) IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. doi:10.1351/goldbook.
Last update: 2014-02-24; version: 2.3.3.
DOI of this term: doi:10.1351/goldbook.M03667.


[Edited on 19-11-2014 by deltaH]




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[*] posted on 19-11-2014 at 02:50


I thought it was pretty well defined for the purpose of this comp. But maybe it's just my interpretation.

I thought that the synthesis was of a molecule of known molecukar mass. Polymers have indeterminate molecular mass - there is no sense in which all the molecules are identical mass.

I for one would be impressed if someone synthesised a linear alkane C200H402 and could demonstrate that the product was pure. Now, you could call that a polymer if you like but if you could show constant molecular mass then I would expect it to qualify (and be a significant challenge.)

Anyway, that's just how I interpreted the challenge.
Watching with interest.
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[*] posted on 19-11-2014 at 04:40


Quote: Originally posted by bismuthate  
blogfast25, Sb3+ salts are actually quite common, but I'll analyze it.


Not really, and they're not salts in the commonly understood meaning of the term, because they hydrolyse like mad. Certainly SbCl3 can not be seen as a salt, with an MP of 73 C and a BP of 225 C.

In a solution of SbCl3 the concentration of Sb<sup>3+</sup> is almost infinitesimally small. Unless the alleged Sb ferrocyanide is extremely insoluble (very low Ks) it would not precipitate in those conditions.

However, the acids of hexacyanoferrate (II) and hexacyanoferrate (III) exist and are water insoluble. The former is H<sub>4</sub>Fe(CN)<sub>6</sub>, a white insoluble material that precipitates when HCl (e.g.) is added to a solution of K<sub>4</sub>Fe(CN)<sub>6</sub>.

This is the likely cause of the precipitate: H<sub>4</sub>Fe(CN)<sub>6</sub> formed when you added the acidic solution of antimony trichloride to the potassium hexacyanoferrate (II) solution.

You can test this with sodium carbonate, maybe even sodium bicarbonate or strong ammonia, which should dissolve the acid (with CO2 evolution in case of the carbonates).

Quote: Originally posted by deltaH  
Let's consider an example: heteropolyacids are built-up of repeating molecular units, for example phosphotungstic acid has 24 tungstate units linked up in a regular pattern called a keggin structure. It is definitely potentially a macromolecule, but does its molecular mass of 2880.2g/mol (anhydrous) seal its fate because it is of "high relative molecular mass"?



At 2880 it's a 12W kegging, actually. 12 is the modern understanding. 24 was based on P2O5.24WO3, not PO4.12WO3.

[Edited on 19-11-2014 by blogfast25]




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[*] posted on 19-11-2014 at 05:31


My bad, you are correct, a little cluck up on my part. It is indeed 12 units.

Actually my brain is soup today because the repeating unit of tungstate is not WO4 but WO3, so that would make my 10 unit molecular weight cut off a little lower at 10*231.8 = 2318, call it 2300, not 2500.


[Edited on 19-11-2014 by deltaH]




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[*] posted on 19-11-2014 at 11:59


I have a feeling that the currently Wining submission may well be disallowed on the same Purity basis that people have mentioned about others.

In the fervent hope that may be the case, i scanned through Brauer's Handbuch and found a couple of big fat candidates on pages 326 and 623, of which the 326 compound i think i might be able to do...




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[*] posted on 19-11-2014 at 13:31


Quote: Originally posted by aga  
I have a feeling that the currently Wining submission may well be disallowed on the same Purity basis that people have mentioned about others.

In the fervent hope that may be the case, i scanned through Brauer's Handbuch and found a couple of big fat candidates on pages 326 and 623, of which the 326 compound i think i might be able to do...

Interesting! Looking forward to their posting.
Might do some acetone derivative complex, dunno...




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[*] posted on 19-11-2014 at 14:09


Huh ?
No 'dunno', just Do !

If Praxchys's entry gets disallowed, we're in with a chance !

I get the feeling that my first entry could well be disallowed under the rules, so best have a Plan B.




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[*] posted on 21-11-2014 at 06:37


Quote: Originally posted by aga  
Huh ?
No 'dunno', just Do !

If Praxchys's entry gets disallowed, we're in with a chance !

I get the feeling that my first entry could well be disallowed under the rules, so best have a Plan B.

Cool. I've been thinking about some complexig ideas, I'll shoot you some potentially interesting inorganic ligand options.




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[*] posted on 21-11-2014 at 13:08


Still waiting for Bismuthate's response... :cool:



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[*] posted on 21-11-2014 at 15:18


OK.

So are Rador Labs' members allowed to post submissions, despite having Prior Knowledge, and therefore more time, to investigate/research heavy compounds ?

Surely that would be an Unfair advantage.




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[*] posted on 22-11-2014 at 04:03


Quote: Originally posted by aga  
OK.

So are Rador Labs' members allowed to post submissions, despite having Prior Knowledge, and therefore more time, to investigate/research heavy compounds ?



I don't really see a problem with it if said member is excluded from adjudication of the winner and if RL in future announces its competition's subject a fortnight or so before opening the competition. The latter would draw more people in, I think...

[Edited on 22-11-2014 by blogfast25]




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[*] posted on 22-11-2014 at 04:26


Oh yeah I forgot to post that I decided not to analyze it since I managed to make a larger compound which has been taking quite a while to dry already so it would be a waste.

Also I'm not in it for the prize.

I can still analyze it later if you want, but I've had my hands full recently.
[Edited on 22-11-2014 by bismuthate]

[Edited on 22-11-2014 by bismuthate]




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[*] posted on 22-11-2014 at 05:03


Quote: Originally posted by bismuthate  

I can still analyze it later if you want, but I've had my hands full recently.


If by 'it' you're referring to the alleged 'antimony hexacyanoferrate(II)' I think you should at least test it with a carbonate to see what happens.

SM's pages are google indexed: it's not good to have ambiguous information to allow to stand without corroboration if that information is out there on the Interwebs.




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[*] posted on 22-11-2014 at 11:01


Quote: Originally posted by Oscilllator  
Afraid not. That's a polymer with n=10000. Mine is a discrete molecule, 10 points for guessing what it is?

[Edited on 18-11-2014 by Oscilllator]


I now know what it is. But I'm not telling, there's $19 at stake, ferg-dsake! :D

[Edited on 22-11-2014 by blogfast25]




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[*] posted on 22-11-2014 at 11:20


If Rador Labs members win the challenge we're considering rolling the prize over to the next challenge.

Again, this is a test run, so don't be surprised if things get screwy.




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[*] posted on 22-11-2014 at 11:28


I agree with Blogfast25's comment that so long as any Radar personnel entering the competition are not part of the Judging process, then that would be fine.

Even Rador people need money,and it;d be a shame to deny them the prize if they won.




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[*] posted on 22-11-2014 at 19:50


Quote: Originally posted by blogfast25  
Quote: Originally posted by Oscilllator  
Afraid not. That's a polymer with n=10000. Mine is a discrete molecule, 10 points for guessing what it is?

[Edited on 18-11-2014 by Oscilllator]


I now know what it is. But I'm not telling, there's $19 at stake, ferg-dsake! :D

[Edited on 22-11-2014 by blogfast25]

Shhhhhhhhh

The compound I am thinking of is very easy to make, but I'm finding it nearly impossible to isolate :(
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[*] posted on 22-11-2014 at 20:33


Quote: Originally posted by Brain&Force  
If Rador Labs members win the challenge we're considering rolling the prize over to the next challenge.
Not all of us have been considering that...
Sorry people, but if the compound that I've been working on now ends up winning (which is still doubtful), I'm keeping my winnings, because I have no job and I'm broke! I spent all of my money on chemicals. :P




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[*] posted on 23-11-2014 at 06:13


Quote: Originally posted by Oscilllator  
The compound I am thinking of is very easy to make, but I'm finding it nearly impossible to isolate :(


Yup. To be expected. It's a miracle it crystallises at all.




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[*] posted on 23-11-2014 at 09:18


If the compound that you're talking about is what I think you're talking about, well, good luck isolating one pure species of it.



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[*] posted on 23-11-2014 at 19:25
Hmmm, what could it be?




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[*] posted on 23-11-2014 at 20:36


Okay, I get it now. Best of luck with the isolation.
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[*] posted on 23-11-2014 at 22:42


I know at least one other member is trying to synthesise this compound and so in the interests of fair play I will disclose that I have successfully used hydrolysed sucrose and sodium metabisulphite to form the complex, forming visually identical products. I don't actually have any of the reagents that published procedures have used, so at this point I'm just mixing together reagents haphazardly to try and get some results.
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[*] posted on 24-11-2014 at 04:22


Why not just filter that liquid?




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