Sciencemadness Discussion Board - Rador Labs Challenge 11-12/2014: High Stakes, High Mass

In the mean time I'll submit my one mole block of iron.

Iron isn't a compound.

blogfast25 - 7-12-2014 at 05:34

Quote: Originally posted by unionised

You may not have noticed, but the rules of pretty much any game make it harder and more interesting.

Also, since they force you into thinking of unconventional solutions to the problem, they improve the intellectual content of the work done.

No, they don't.

Quote: Originally posted by unionised

for example,, while I'm in 2 minds about whether the Mo blue is a polymer or not, at least including it for discussion led me to some interesting stuff about big Mo clusters.
If it was just a matter of "search the web for the heaviest protein you can find" it's not interesting at all.

Just searching the web for the heaviest protein isn't synthesis.

The compounds that have been entered so far, including 'Mo Blues', have also been looked up on the Internet. So far the leader is a compound that's a standard in the detection of phosphates, just how mind-bogglingly 'interesting' is that?

You keep making my case for me. Much obliged!

[Edited on 7-12-2014 by blogfast25]

unionised - 7-12-2014 at 07:27

So, you think that, for example, they banned the use of performance enhancing drugs in sport because they made people run slower?
They stop you using your hands in soccer because it's more difficult to pick up something and take it somewhere than to kick it and get it to land in the same place?
(That must make mealtimes at your house interesting).

The idea is absurd- if there is a rule it is there because, otherwise, people would do what the rule forbids. You don't need a rule that bans hitching a lift on the back of a tortoise in a running race. But there is a rule that stops you using a bicycle.
The rules stop you doing things the easy way (or,as it's referred to in that context, "cheating".

The fact that Mo blue has been in use for ages isn't very interesting. So, there wan't much point in you mentioning it- most of us will have already known.
The structure of the stuff is interesting
Did you somehow come to the conclusion that they knew the structure when they used it for checking phosphates in plants and such?

Synthesising the biggest protein you can find isn't very interesting either.

Incidentally, perhaps you can explain how, if I buy or make - for example UHMW polythene you can guarantee that there are no short chains in it.
what you end up with is a probability distribution and, while it tends to zero for very hi and lo MW, it never quite gets there.
Anyway, if you have got your pants all twisted up by the idea of someone winning by making MO blue, do something a bit more clever, and win. How about this?
http://www.chem.gla.ac.uk/cronin/publications/papers/2009/15...

[Edited on 7-12-14 by unionised]

bismuthate - 7-12-2014 at 08:13

How would I go about making a polymer with an exact formula. You need to give an exact formula with a submission.

Should we let football (or soccer) be played with hands because only using feet limits the game?

Chemosynthesis - 7-12-2014 at 09:32

Quote: Originally posted by unionised

So, you think that, for example, they banned the use of performance enhancing drugs in sport because they made people run slower?

Minor point, but the relative ease of competition is not why performance enhancing drugs are banned. Performance enhancing drugs are banned due to perceived issues of artifice versus natural ability/training, or the concern of purchasing an advantage through pharmacological means rather than dedication and genetic lot, in my opinion. You see technological advances such as use of triggers or new bow materials for archery allowed in many competitions. Golf club material or weight isn't really regulated either, though where men and women start from is standardized as a rule, which doesn't necessarily impact course difficulty.

blogfast25 - 7-12-2014 at 10:33

Unionised:

Keep making ever more far fetched analogies and getting nowhere.

The truth is far more simple: creating an actual polymer doesn't give you an advantage in terms of easiness, it's by no means cheating. Comparing this competition to a game or a sport is absurd. Let the best guy win, ferchrissake, not the one who manages to comply to your petty rules!

Polymers are interesting things to make, high MW and far more interesting than e.g. ammonium P molybdate. Or Mo Blue, but at least that one has the redeeming feature of being truly high MW.

"Incidentally, perhaps you can explain how, if I buy or make - for example UHMW polythene you can guarantee that there are no short chains in it."

That just shows how little you know about commercial polymers.

'Pants twisted'? Dear G-d. How about YOU do something interesting, huh?

[Edited on 7-12-2014 by blogfast25]

bismuthate - 7-12-2014 at 10:59

Yet... you still don't actually explain how to make a polymer with a specific formula.

[Edited on 7-12-2014 by bismuthate]

blogfast25 - 7-12-2014 at 11:04

Yet... you still don't actually explain how to make a polymer with a specific formula.

[Edited on 7-12-2014 by bismuthate]

And you still have a compound in the competition that doesn't even exist!

Polymers HAVE a specific formula, unlike your non-existent antimony thingy.

[Edited on 7-12-2014 by blogfast25]

bismuthate - 7-12-2014 at 11:06

No, I acknowledged that the references to this compound's existence weren't strong enough so I replaced my entry.
You seem to be taking this very personally.
And haven't answered my question.

[Edited on 7-12-2014 by bismuthate]

blogfast25 - 7-12-2014 at 11:34

No, I acknowledged that the references to this compound's existence weren't strong enough so I replaced my entry.
You seem to be taking this very personally.
And haven't answered my question.

[Edited on 7-12-2014 by bismuthate]

Where?

Stop mind reading. You're not good at it.

I was arguing my case. Nothing more. I'm done with it now.

Good luck with the competition.

bismuthate - 7-12-2014 at 11:36

Ok. Can a mod cut the debate part out?

aga - 7-12-2014 at 11:55

It really would be better to have competitions OFF of the 'Chemistry in General' topic.

My apologies for posting mine here.

Could a Mod please move mine to a new Competitions topic, or Beginnings, in order to prevent the relentless 'top of list' syndrome.

Edit:

Perhaps the general populace could chime in and say what they would prefer, en-masse, rather than just the few.

[Edited on 7-12-2014 by aga]

unionised - 7-12-2014 at 12:06

Quote: Originally posted by blogfast25

Unionised:

Keep making ever more far fetched analogies and getting nowhere.

The truth is far more simple: creating an actual polymer doesn't give you an advantage in terms of easiness, it's by no means cheating. Comparing this competition to a game or a sport is absurd. Let the best guy win, ferchrissake, not the one who manages to comply to your petty rules!

Polymers are interesting things to make, high MW and far more interesting than e.g. ammonium P molybdate. Or Mo Blue, but at least that one has the redeeming feature of being truly high MW.

"Incidentally, perhaps you can explain how, if I buy or make - for example UHMW polythene you can guarantee that there are no short chains in it."

That just shows how little you know about commercial polymers.

'Pants twisted'? Dear G-d. How about YOU do something interesting, huh?

[Edited on 7-12-2014 by blogfast25]

OK, so it seems you are happy that the guy on a motorbike wins (we are disregarding the "petty rule" that it's a running race.
My analogy may be strained but others seem to understand it.
Anyway, back somewhere near the topic, (and since a few of us have asked) how do you make a polymer with a defined formula?
For example, how do you make polystyrene that is exactly (C7H8)1000 and doesn't contain the 999mer or the 1001mer?
Can you?
If not, how could you enter the product into the competition? It doesn't have a single defined MW (it has at least two depending on the definition)

And you may be surprised how much I know about commercial polymers. Did it occur to you that I'm not asking because I want to find out; I'm asking how you think it's possible so I can correct you?

Chemosynthesis - 7-12-2014 at 12:27

I am curious about the polymer lengths from either perspective. It's definitely not my field, but I have spent time in a polymer lab watching people work, and I remember making a graduate student very uncomfortable by accidentally betraying that his photovoltaic polymers weren't as long in chain length as the PI intended. This was in infancy, obviously, and I would love to know conceptual stats on radical termination and quality control, or however you guys are envisioning it.

j_sum1 - 7-12-2014 at 14:50

Well, here's my two cents.
I didn't know that moly blues were such a large complex. To me their structure definitely is interesting.
I thought the omission of polymers for this comp was clear and sensible from the start. If you object to that ruling for some kind of philosophical reason then tough. You aren't the one making the rules.
Blogfast, in my considered opinion you are taking this all a bit personally. Rador is giving a smattering of cash to someone of their choosing and I am learning some chemistry. (The comp may or may not be fair and might come down to rule interpretation. But I think it is the challenge and the ideas that are the draw card not the money or the robust nature of the rules.)
I support a new topic for comps.

aga - 7-12-2014 at 15:02

Quick mind bender:

Perhaps Molly Blue is not quite so stable as one may imagine.

Perhaps the components swap places continuously, and the Measurements made are merely averages.

Same holds true for all highly Complex systems.

The Volatile Chemist - 7-12-2014 at 17:38

Despite all the debate, has anyone made a polymer they want to submit?
If not, forget it.

amazing

quantumcorespacealchemyst - 13-12-2014 at 04:24

Quick mind bender:

Perhaps Molly Blue is not quite so stable as one may imagine.

Perhaps the components swap places continuously, and the Measurements made are merely averages.

Same holds true for all highly Complex systems.

that is the kind of stuff i like. i wonder too.

blogfast25 - 14-12-2014 at 08:55

Not really, no. There's no reason to suspect any swapping. The structure is now well understood.

aga - 14-12-2014 at 09:26

Probably so.

Personally i prefer to imagine things as dynamic equilibria rather than static.
Fits better with nature to my eye.

E.g. the notion that the entirety of observed matter is just 1 sufficiently energetic particle moving impossibly fast in all dimensions, seems fairly reasonable.

gdflp - 14-12-2014 at 10:06

Here's my submission, it just crystallized today.

Donated : Yes
Compound : Borotungstic Acid
Molecular Formula : H₅BW₁₂O₄₀*30H₂O
Molecular Mass : 3402.49

Synthesis : Tunsten disulfide obtained as dry lube was heated to decomposition at 1250°C. The yellow powder obtained, WO₃ was dissolved in a stoichometric amount of NaOH and the solution was stirred overnight. The solution was then gravity filtered and a portion of the extraction was taken. To this portion, a 10% excess of HCl and H3BO3 were added and the solution was filtered. Next the solution was put into a sealed bag with sodium hydroxide and evaporated to dryness. Final Yield : 0.85g Borotungstic acid, Confirmed by crystal appearance and low melting point.
Note : The crystals are actually light grey. The camera didn't pick up the color well.

Brain&Force - 14-12-2014 at 10:52

The challenge ends at 0000 UTC! Submit your write-ups before then.

The current winner is gdflp with borotungstic acid (above).

bismuthate - 14-12-2014 at 18:21

I anticipated this would happen so I came prepared.

Barium phosphomolybdate
Ba3(PMo12O40)2
4056.9205 g/mol
Materials:
ammonium phosphomolybdate (made the way I posted earlier)
Ba(OH)2(Made from decomposing BaCO3 and adding the BaO to water)
Water
Vinegar

1 Make a solution by dissolving 1g of Ba(OH)2 in 50mL of hot water
2 Add .61g of ammonium phosphomolybdate to the solution and heat to about 60 degrees Centigrade for 5 minutes.
3 Ammonium gas is released and after all the yellow solid dissolves let the solution evaporate.
4 After it is evaporated add 50mL of cold vinegar to the solid and let it sit in an ice bath for 2 minutes.
5 Fliter, wash, and dry the slightly more orange solid.

2(NH4)3PMo12O40+3Ba(OH)2==>Ba3(PMo12O40)2+6NH3+6H2O

https://www.dropbox.com/sc/y1b471p9cwp2os3/AADDFBCm5cQMwUnYs...

[Edited on 15-12-2014 by bismuthate]

[Edited on 15-12-2014 by bismuthate]

gdflp - 14-12-2014 at 19:31

You missed the submission deadline though.

bismuthate - 14-12-2014 at 19:46

Oh crap I forgot It's UTC!

gdflp - 14-12-2014 at 20:02

I also made the barium salt of borotungstic acid by adding the acid to BaCO₃. Ba₅[BW₁₂O₄₀]₂ weighing in at 6399.3g/mol, I just never left time for it to crystallize. I suspected someone might have a higher compound waiting so I waited. :cool:

[Edited on 12-15-2014 by gdflp]

Molybdenum what?

Oscilllator - 14-12-2014 at 20:13

Compound name: Molybdenum blue
Molecular weight: No idea! Lots though.

Materials:
-Sodium molybdate
-Concentrated Glucose/Fructose solution, prepared by dissolving 200g of -sucrose in 350ml of water, adding a few drops of 30% HCl, then heating.
-30% HCl

Synthesis: ~5g of sodium molybdate was dissolved in ~15ml of the concentrated glucose/fructose solution. This took about 10 minutes, with swirling. ~10ml of 30% HCl solution was then added and the mixture was left to stand for several weeks, suring which time a very dark precipitate formed of the unknown molybdenum complex.
This mixture was then filtered:

and dried:

to obtain a yield of 1.41g (I don't trust the last decimal place on that scale.).

Discussion:
Although this is clearly some kind of molybdenum blue complex, its precise nature is unclear. Glucose and Fructose are reducing agents because they have an equilibrium with an open ring structure, at one end of which is an aldehyde and so I surmised that they might be able to Create a molybdenum blue complex, since many other reducing agents can including:
Hydrazine sulfate
Sodium dithionite
Sodium metabisulphite
Sodium thiosulphate
Sodium hypophosphite
And a whole bunch of others (see attached paper)

However it is unclear which compound I have formed, since all of the characterised compounds in the attached paper have some kind of cation (either sodium or ammonium) and so I think that the actual molybdate complex is probably present as an anion. However I don't see how this can be the case with my compound, since I can't see anything that could form a cation. I think perhaps I may have synthesised a complex that is not composed of cations and anions, which would explain its low solubility in water.

Finally I'd just like to say that I don't expect this to be accepted as a valid entry, but I hope that some other members could shed some light on the possible nature of this compound.

gdflp - 14-12-2014 at 20:20

Didn't you use sodium molybdate? If so, couldn't the sodium be the cation? My guess is that it is some sort of compound with a sodium cation, and an organomolybdenum complexed anion. In any event it's a rather interesting synthesis and that's a very neat color.

bismuthate - 15-12-2014 at 04:12

I found that my borax was able to reduce molybdate to molybdenum blue when i was trying to make boromolybdates.
Mailinmypocket, now you need to write the balanced equation

Just kidding

[Edited on 15-12-2014 by bismuthate]

Praxichys - 15-12-2014 at 06:07

Congratulations gdflp for winning the challenge!

You win $27 USD.

Please U2U me to verify that sending the money to your PayPal account is the collection method of choice.

Thank you to everyone who participated in the challenge, especially if you donated. There are a lot of great synthesis reports in this thread, and I look forward to seeing more in upcoming challenges.

Great work, everybody!

aga - 15-12-2014 at 09:07

so i didn't win then ?

damn.

blogfast25 - 15-12-2014 at 13:08

so i didn't win then ?

damn.

Come away, son, Dad will buy you an ice cream...

The Volatile Chemist - 17-12-2014 at 12:50

Quote: Originally posted by blogfast25

so i didn't win then ?

damn.

Come away, son, Dad will buy you an ice cream...

Lol,
Nice job everyone. There was a lot of activity in the end, too bad Blogfast missed the entry-time.

Mailinmypocket - 17-12-2014 at 13:11

I found that my borax was able to reduce molybdate to molybdenum blue when i was trying to make boromolybdates.
Mailinmypocket, now you need to write the balanced equation

Just kidding

[Edited on 15-12-2014 by bismuthate]

This time of year I can't even balance my diet

deltaH - 18-12-2014 at 08:42

Congratz to everyone who submitted an entry and gdflp for winning!

I'm disappointed nobody found this gem... the crystalline 77888 amu H₂₄₉₆Mo₃₆₈Na₄₈O₂₄₆₄S₄₈ molyblue (structure confirmed by single crystal x-ray diff.). I'm posting it below for anyone who wants to synthesise a wopper

Full text with impressive crystal structure available for free here:

http://www.researchgate.net/publication/10983409_Inorganic_c...

This paper was "Dedicated to Professor Dieter Fenske
on the occasion of his 60th birthday". :cool:

Structure of the beast from [1]:

Synthesis [1]:

Quote:

Na2S2O4 (0.15 g, 0.86 mmol) as reducing agent was added to a stirred solution of Na2MoO4.2H2O (3 g, 12.4 mmol) in water (10 mL) which was acidified with 0.5 H2SO4 (35 mL; immediate color change to blue). The solution was stored in a closed flask and after 2 weeks the precipitated deep-blue crystals of 1 were collected by filtration, yield: 80 mg (two crystal types: major part showing from top view a characteristic form like an elongated benzene molecule, while a much smaller fraction of the crystals is grown together).

Characteristic IR bands (KBr pellet): 1616 (m,(H2O)), 1191 (w), 1122 (w), 1060 (all as(SO4)), 975/954 (s) ((MoO)), 761 (s), 700 (sh), 627 (w), 555 (m), 464 (w) cm1; approximate wavenumbers of the very broad Raman bands (KBr dilution; e 1064nm): 810 (m), 680 (w), 460 (m) cm1; Vis (in H2O): 740 (very broad) nm.

Reference:

[1] Achim Müller et al. Inorganic Chemistry Goes Protein Size: A Mo₃₆₈ Nano-Hedgehog Initiating Nanochemistry by Symmetry Breaking. Angewandte Chemie International Edition. 2002, 114, Nr. 7, 1210-1215.

[Edited on 18-12-2014 by deltaH]

aga - 18-12-2014 at 09:24

77888 amu

!!!

Is each molecule the size of a small car ?

deltaH - 18-12-2014 at 09:40

I heard a polio virus tried to hump it

The Volatile Chemist - 18-12-2014 at 10:27

I heard a polio virus tried to hump it

You know, there's just been nothing worth responding to on SM today...

blogfast25 - 18-12-2014 at 10:43

Quote: Originally posted by The Volatile Chemist

Nice job everyone. There was a lot of activity in the end, too bad Blogfast missed the entry-time.

No, I didn't enter it, in a spirit of protest. Think of that what you will.

But it sure was entertaining enough...

Maybe next time...

[Edited on 18-12-2014 by blogfast25]

MrHomeScientist - 18-12-2014 at 10:50

Quote:

That's a really interesting synthesis! Not having sodium dithionite, I found (Wikipedia) it can be made from the reaction between sodium bisulfite and zinc: 2 NaHSO3 + Zn → Na2S2O4 + Zn(OH)2

I don't suppose sodium metabisulfite would work as a replacement? That's what I have on hand at the moment.

blogfast25 - 18-12-2014 at 10:55

Quote: Originally posted by MrHomeScientist

Yes, most sulphites (OS of S < 6) should work. I got that blue with ordinary sodium sulphite. There's also a recipe with a hypophosphite. Just adjust for t'electrons.

The reduction really doesn't seem very dependent on the type of reducing agent. I'm guessing even plain zinc might work.

[Edited on 18-12-2014 by blogfast25]

deltaH - 18-12-2014 at 11:18

I was also thinking of metabisulfite as it's easily available, but I'm guessing there's a good reason to use the dithionite... though exactly why eludes me. I suppose one could always email the authors about it. This is an incredibly impressive example of synthetic inorganic chemistry, so I doubt the authors overlooked the use of less exotic reagents.

This molyblue has sulfate units as part of its structure, so the neat thing about the reducing agent is that it is oxidised to sulfate... so no contaminant is introduced. Perhaps it's important to have only the reduced moly salts and sulfate in solution for the crystals to form.

Anyhow, if you get crystals after two weeks with a "characteristic form like an elongated benzene molecule"... I'd say you can safely assume success.

[Edited on 18-12-2014 by deltaH]

MrHomeScientist - 18-12-2014 at 12:40

To be clear, I meant using metabisulfite as a substitute for bisulfite in the equation I posted. I still planned on using dithionite for the actual moly blue reaction. The plan would be as follows:

1) Make a very cold solution of sodium metabisulfite and stir in zinc powder.
2) Filter off unreacted zinc and the zinc hydroxide precipitate. The solution now contains dithionite (Soln. A)
3) Make a solution of sodium molybdate (or ammonium molydbate, can't remember which I have) acidified with sulfuric acid (Soln. B).
4) Combine solutions A and B with stirring. After mixing, cap and set aside for several weeks.
5) Profit.

deltaH - 18-12-2014 at 12:46

Ah ok, I misunderstood you. Best to follow a literature recipe for the dithionite... since it's for profit

blogfast25 - 18-12-2014 at 14:29

Ah ok, I misunderstood you. Best to follow a literature recipe for the dithionite.

On what grounds though? A reduction is a reduction, in most cases.

deltaH - 18-12-2014 at 14:44

Experience tells that even the simplest chemistry sometimes doesn't work or performs poorly when not done under specific conditions... it doesn't hurt to check the literature when it's available.

Perhaps there is a competing reaction that can be minimised, for example, just looking at that equation above, the reaction

Zn + HSO3(-) => Zn(+) + SO3(2-) + 1/2H2

springs to mind as a possible problem, haven't checked reduction potentials though.

Anyhow, whatever the case be... a cursory check of the literature would not hurt when it's probably available.

Oscilllator - 18-12-2014 at 17:28