Sciencemadness Discussion Board - Drunken Aga Challenge #1 - Finished

Am I missing something or does
"distil it through a half decent fractionating column"
not count for some reason?
The product you are after (6M HCl 21.9%) is pretty close to the azeotrope (about 20.2%).

Aga, the point he's making is that your task poses not much of a challenge, therefore isn't worthy of prizes or even of much praise when executed successfully.

A worthy competition needs a decent challenge, not something you just made up to get something going.

Let members put forward some ideas and commenters decide which of the proposals meets decent criteria.

[Edited on 11-11-2014 by blogfast25]

blogfast25 - 11-11-2014 at 14:21

My proposal:

Synthesis of a 'pure' solid salt of the Fe(NO)2+ complex cation. This dark complex forms when cold nitric acid is added to a ferrous salt solution. I've never heard of any solid salts of it being isolated though.

[Edited on 11-11-2014 by blogfast25]

aga - 11-11-2014 at 14:23

So HCl purification is too difficult then ?

bismuthate - 11-11-2014 at 14:24

Step 1: https://www.dropbox.com/s/uaotferzs2guekn/Photo%20Nov%2011%2...
Take .1mL of the 250mL of impure HCl and add it to 1 liter of reagent grade 6M HCl. Dump the rest of the impure HCl into a container if you want to use it for something else.

Step 2: Drink the unsafe beer that you tried to use in a salting out experiment.
https://www.dropbox.com/s/eq42pcj0w9puyls/Photo%20Nov%2011%2...
I agree this was too easy.
Although the process was a pain with the super small measurement.

[Edited on 11-11-2014 by bismuthate]

aga - 11-11-2014 at 14:40

*IF* this task is soooo easy to all the Experts, why are there Zero photos, Zero formulae, zero Prize payouts.

Perhaps this trivially simple task is rather too tasking ?

aga - 11-11-2014 at 14:44

Read the Rules.

Follow said rules, collect cash.

Edit

Did you not read rule 11 ?

[Edited on 11-11-2014 by aga]

bismuthate - 11-11-2014 at 14:49

Ok. The temp was ambient and the leftover HCl must me mixed with the beer to see if anything happens.

aga - 11-11-2014 at 14:53

A worthy competition needs a decent challenge, not something you just made up to get something going.

Let members put forward some ideas and commenters decide which of the proposals meets decent criteria.

An Excellent suggestion.

Aga Challenge #2 will certainly be along those lines.

Aga Challenge #1 remains unsolved.

aga - 11-11-2014 at 14:56

@bismuthate : Rules 1 ,3 and 5 remain unstated. Photos were nice.

[Edited on 11-11-2014 by aga]

bismuthate - 11-11-2014 at 15:06

The impure HCl was 11% by weight. There where no chemical reactions for rule 1.
Unfortunately without access to my full lab rule 5 remains unfulfilled.
Oh well I couldn't have claimed the money anyway.

aga - 11-11-2014 at 15:16

Dissolution of an acid in water *is* a chemical reaction.

An equilibrium even.

Metacelsus - 11-11-2014 at 15:20

I will attempt this this weekend. The can of beer might prove problematic, but I think I can find one.

Praxichys - 11-11-2014 at 15:23

Well, here we go.

1. Measure out exactly 250ml of your dirty HCl. Close-up here to show dirty color.

2. Set up for simple distillation.

3. Distill. HCl has a negative azeotrope, so water comes over first. Measure and throw away the distillate until you have thrown away 130ml (this gives some leeway). Beer is good at this point because there will be a lot of waiting. Proceed to dryness, collecting everything at 110C. You should collect theoretically 120mL of 6M HCl. (Note that the azeotrope is slightly LESS than 6M, but there was no significant digit specified, and it's well above 5.5M.) :cool:

A sample of the product:

Absolutely no dissolved ions, of course, and well within the concentration specification. You can titrate that if you don't believe me.

A pic of the test method for demonstrating the concentration:

And finally, the test for iron. A sample of the original solution and a sample of the distillate were basified with excess sodium hydroxide, causing heating and boiling. Iron content is shown in the original by flocs of iron hydroxides, which are not present in the distillate, indicating that the iron has been substantially removed.

[Edited on 11-11-2014 by Praxichys]

[Edited on 12-11-2014 by Praxichys]

aga - 11-11-2014 at 15:30

Close, but no banana.

Rules 4 and 5 apply.

WGTR - 11-11-2014 at 15:44

The time limit on the procedure: does that include setup time, or just the time required for the purification, once the setup is completed?

aga - 11-11-2014 at 15:50

The time limit is the Time it would take from getting the Starting Material to delivering the required product(s).

If you happen to be already set up for that process, you have an advantage.

aga - 11-11-2014 at 15:53

@praxichays : all that is lacking is the Fe2+ tests, and explanation of How : Rule #5

Etaoin Shrdlu - 11-11-2014 at 15:59

I'm cracking up so hard.

Does a bottle of anhydrous ethanol count as really high purity beer?

Chemosynthesis - 11-11-2014 at 16:02

Aga, is it possible to post a procedure in advance to follow over the weekend?

MrBlank1 - 11-11-2014 at 16:04

Reagent = IC ?

Theoretical solution, titrate then flocculate with CaOH, filter, gas with dry HCl to the desired concentration

j_sum1 - 11-11-2014 at 16:14

Quote: Originally posted by MrBlank1

Reagent = IC ?

Iodine Carbide? That's a new one on me!

http://www.abbreviations.com/serp.php?st=IC&p=99999

Praxichys - 11-11-2014 at 16:25

Edited again with the Fe2+ test. (Test for ANY Fe for that matter) C'mon banana! Praxi needs beer money. Wooo

WGTR - 11-11-2014 at 17:04

I have what is possibly the world's dumbest observation.

Fe2+ can be eliminated simply by adding a bit of hydrogen peroxide, and converting it all to Fe3+.

Somehow, I don't think this is what Aga has in mind...

bismuthate - 11-11-2014 at 17:20

@aga HCl is a strong acid so all of the HCl in solution would already have been disassociated. Therefor there would be no reaction

bismuthate - 11-11-2014 at 17:43

https://www.dropbox.com/s/qjat2zfx298tlwj/Photo%20Nov%2011%2...
Here: the addition of potassium ferricyanide gives no blue color.

Brain&Force - 11-11-2014 at 22:56

Rador Labs will have its own challenge starting November 15 and running until December 15. Protip - find some heavy metals.

aga - 11-11-2014 at 23:12

Bannana Time.

Praxichys Wins 1st Prize.

bismuthate wins 2nd, mostly due to creative rule bending.

U2U pp details please.

aga - 12-11-2014 at 05:13

Having sobered up and re-read Praxichys' post, there stands a great example of what i'm personally after.

In one post there is theory, procedure and photos concisely showing how to achieve the objective.

Suggestions for DAC #2 ?

Suggestion #1

aga - 12-11-2014 at 05:14

My proposal:
Synthesis of a 'pure' solid salt of the Fe(NO)2+ complex cation. This dark complex forms when cold nitric acid is added to a ferrous salt solution. I've never heard of any solid salts of it being isolated though.

j_sum1 - 12-11-2014 at 05:21

Is this even possible? I haven't ever come across complex ions except in solution. (At least not that I can recall.)

I am not equipped to play at the moment but I will watch with interest.
(The last one was simultaneously hilarious and informative.)

blogfast25 - 12-11-2014 at 05:58

Quote: Originally posted by j_sum1

Is this even possible? I haven't ever come across complex ions except in solution. (At least not that I can recall.)

I am not equipped to play at the moment but I will watch with interest.
(The last one was simultaneously hilarious and informative.)

It's possible to prepare solid, pure salts of MANY cation complexes, no problem. Maybe not this one (but we don't know that yet), in which case prize should go to the experimenter or team who proves it basically cannot be done.

Another 5 proposals to follow later.

"The last one was simultaneously hilarious and informative."

Hardly a challenge, though...

[Edited on 12-11-2014 by blogfast25]

bbartlog - 12-11-2014 at 06:12

Would http://en.wikipedia.org/wiki/Roussin%27s_black_salt qualify as a pure solid salt of Fe(NO)2+? Or am I confused about the oxidation state here?

WGTR - 12-11-2014 at 07:30

For what it's worth, allow me to make some suggestions:

Next time, structure the project by phases. The first one would be a short period of time for interested parties to submit their proposals. A general description of the materials and methods need to be included in the proposal. The proposals would have to be approved by the client (in this case Aga) before experimentation begins. Certainly, someone could start experimenting early before receiving approval, but they will run the risk of misunderstanding the task; or using unapproved methods, materials, or documentation methods.

The second phase would begin at a specific time (GMT), and end at a specific time. Pick some reasonable amount of time, perhaps a few days. This would be the time to conduct the actual experiment and documentation.

The last part of the project would be ranking the participants according to how well they accomplished the task. Cost, documentation quality, product purity, practicality, etc., could be used as guides, but these should be stated up front during the proposal phase.

This may make things more of a challenge, and provide more interesting results. Does anyone have anything to add?

aga - 12-11-2014 at 07:43

That sounds like a much better Plan WGTR.

I suppose people should suggest the experiments, then there's a vote on which one to do.

After results are in, they should be judged by peers to choose the winner(s).

Sounds like they will end up being Bigger (much more difficult) tasks, so may i also suggest that there can be more than 1 simultaneous 'challenge' - the Biggies, and an occasion trivial that i throw in when extreemly drunk.

DAC and dAC respectively.

Praxichys - 12-11-2014 at 07:45

I second what WGTR said, but it could be simpler than that even.

Leave it open for about a week, then pick the best method/writeup. Otherwise it's just a race. If you want to get crazy about it, open a poll thread when the week is up and we can all vote on which method was the best.

EDIT: Aga beat me to posing this!

[Edited on 12-11-2014 by Praxichys]

plante1999 - 12-11-2014 at 07:56

I have an idea. Turning proteins into usable ammonia. Not only is it a reasonable goal, but many ways to acheive it. One would have to find a protein source, hair, horn etc, and find the process.

The purer and more concentrated ammonia, the better.

blogfast25 - 12-11-2014 at 09:55

Quote: Originally posted by bbartlog

Would http://en.wikipedia.org/wiki/Roussin%27s_black_salt qualify as a pure solid salt of Fe(NO)2+? Or am I confused about the oxidation state here?

The Fe seems to have a mixed (II,III) state. But it's an interesting find, thanks!

My other proposals:

1) KAlCl4:

With that precise composition (KCl.AlCl3

it has a very low MP (245 C) and is a candidate as a solvent for the non-aqueous electrodeposition of electropositive metals like REEs. Has already been discussed here but no one has put their money where their mouth is. A 'how to' reference was posted on SM a few months ago.

2) Rb or Cs alum of Mn(III) sulphate:

Quite a challenge because of Mn(III) instability. Should be pretty coloured.

3) Ceric ammonium nitrate:

Attempted by me once but then abandoned, this not as easy as it may seem.

4) Isolating the hydrates of H2SnCl6 and HSbCl6:

Both are strong acids and acc. Holleman ('Inorganic Chemistry') solid hydrates of both can be isolated.

===========

Someone mentioned 'a few days' but that seems far too short to me. As amateurs we have many obligations and can only work very part-time on our projects.

DrMario - 12-11-2014 at 10:10

Quote: Originally posted by j_sum1

Is this even possible? I haven't ever come across complex ions except in solution. (At least not that I can recall.)

Absolutely yes. In fact, most of those complex ions you've seen in solution, can be crystalized. Also, there's a whole huge lot of insoluble complexes.

DrMario - 12-11-2014 at 10:15

3) Ceric ammonium nitrate:

Attempted by me once but then abandoned, this not as easy as it may seem.

I'm a bit fuzzy on the rules here, but I'll point out, not meaning to offend anyone, that ceric ammonium nitrate can be easily purchased. I'm looking right now at an eBay seller (from the US no less) that's selling it fairly cheaply.

aga - 12-11-2014 at 11:29

If the Target product can be bought, that really does not matter.

The next challenge will require a write-up of how the product was made, in precise and photographic detail.

Simply posting a screenshot of the ebay listing, then an opened box won't win the prize money !

phlogiston - 12-11-2014 at 11:33

I suppose people should suggest the experiments, then there's a vote on which one to do.

Be aware that people can suggest a challenge that they have an (perhaps unfair) advantage in, or even something that they already accomplished.

Also, consider to use the opportunity to buy solutions/good writeups for practical problems many members have been struggling with in the past but that are not necessarily the most difficult (rather than very difficult but 'academic' problems that are a of particular interest to only very few or even just one person).

aga - 12-11-2014 at 11:41

Quote: Originally posted by phlogiston

Be aware that people can suggest a challenge that they have an (perhaps unfair) advantage in, or even something that they already accomplished.

Doesn't mean their already accomplished method will be the Best method, or be voted for above other methods.

Quote: Originally posted by phlogiston

solutions/good writeups for practical problems many members have been struggling with in the past

Such as ....

DrMario - 12-11-2014 at 12:32

If the Target product can be bought, that really does not matter.

The next challenge will require a write-up of how the product was made, in precise and photographic detail.

Simply posting a screenshot of the ebay listing, then an opened box won't win the prize money !

Believe me, part of me could see this coming. And yet, another part of me thought/hoped that the challenges of the type "Synthesize compound X" would have X be a substance either hard to come by, or prohibitively expensive - e.g. Luminol.

(Yes, I know there's a well known method for synthesizing Luminol; this was just an example of an expensive compound.)

aga - 12-11-2014 at 12:45

So a Luminol synthesis is a suggested Challenge.

Nice one. The photos would look great too.

Edit :

Any synthesis that has interesting chemistry attached will be good, whether the resulting product(s) are useful or not.

[Edited on 12-11-2014 by aga]

unionised - 12-11-2014 at 12:58

Quote: Originally posted by plante1999

I have an idea. Turning proteins into usable ammonia. Not only is it a reasonable goal, but many ways to acheive it. One would have to find a protein source, hair, horn etc, and find the process.

The purer and more concentrated ammonia, the better.

Are you taking the piss?

DrMario - 12-11-2014 at 13:00

Quote: Originally posted by plante1999

Are you taking the piss?

Hahah, good one!

aga - 12-11-2014 at 13:23

Removing Urine from alcohol :

Step 1. Find a suitable reaction vessel.

barney.png - 43kB

blogfast25 - 12-11-2014 at 13:51

Quote: Originally posted by phlogiston

Avoiding cheating will never be 100 % possible but detecting cheating is not that hard, in most cases.

blogfast25 - 12-11-2014 at 14:01

Are you taking the piss?

What makes you think that he is?

Recovering ammonia from glycine (recovered from hair e.g.) could be interesting and certainly not easy to do without enzymatic activity to 'snip off' that amine function as NH3.

The Volatile Chemist - 12-11-2014 at 14:25

You should add a competitions page to the sciencemadness wiki, I think that'd be cool, to have a central place for competitions.

aga - 12-11-2014 at 14:45

Personally i don't understand the Rador thing.

It appears (to me) to be a schism in the SM thing, driven by Age differences, which is totally understandable.

For me, SM is the dog's bollocks, so the DAC will stay here for now (if permitted).

Edit:

I'm amazed i was allowed out of Beginnings without being mugged !

[Edited on 12-11-2014 by aga]

DrMario - 12-11-2014 at 14:50

Are you taking the piss?

Looks like someone missed the joke entirely...

Brain&Force - 12-11-2014 at 14:55

It's actually supposed to be a collaborative outreach project to put together videos and make chemistry "cool" for outsiders. I'm happy to organize competitions and things - I don't have a lab thus I have no unfair advantage, as I can't participate. It's not a schism as we're still going to be doing stuff on the forums anyway and have no plans to separate - in fact, we hope to draw more people to the forum and keep them interested.

I also do outreach at university, I just want to bring it to SM.

aga, stick to running small challenges, just like the one you just posted, and we at Rador can handle the big ones. Again, there will be a Rador Labs challenge by November 15, and it lasts for a month.

[Edited on 12.11.2014 by Brain&Force]

aga - 12-11-2014 at 15:14

Thanks for the clarification.

At the very least there should be no further challenge here before the 16th then.
(I'll drink a bit less to try to make that so)

Big and Little demarcation ?

I feel sure that the SM community can handle Difficult as well as Easy.

Edit:

It just occurred to me: appologies if my random post has stolen some thunder from a plan i was unaware of.

[Edited on 12-11-2014 by aga]

Brain&Force - 12-11-2014 at 16:40

Our challenge is going to last about a month. But you can run whatever smaller challenges you want throughout that time.

Actually, I may cut it to 15 days...

aga - 12-11-2014 at 16:47

Perhaps some collaboration would be in order to prevent any difficulties.
Best move to U2U, so as not to reveal anything pre-facto.

zenosx - 12-11-2014 at 19:37

Loved this post.. I don't have time to hit the lab when I want to or I would love to participate!
Maybe I'll have time since there is no winner yet!

Texium - 12-11-2014 at 19:48

Quote: Originally posted by Brain&Force

Our challenge is going to last about a month. But you can run whatever smaller challenges you want throughout that time.

Actually, I may cut it to 15 days...

YOU may cut it to 15 days?
Now now, you're not the only one who gets to decide that.

Also, I see no problem with aga's challenges. Nobody has any real authority here over who can and can't organize little events like these, and it doesn't seem like it will effect our thing in any negative way.

[Edited on 11-13-2014 by zts16]

DistractionGrating - 12-11-2014 at 20:32

Quote:

1. Concept/process must be accompanied by stoichiometric chemical formulae.

I submit that this requirement was never met.

Etaoin Shrdlu - 12-11-2014 at 20:48

I submit that

Quote: Originally posted by Praxichys

HCl

technically counts.

blogfast25 - 13-11-2014 at 05:57

So a Luminol synthesis is a suggested Challenge.

He didn't mean it that way. There are probably numerous 'How To' and Utoobs on Luminol. Not really a challenge if ready to use instructables are readily available.

Brain&Force - 13-11-2014 at 10:40

One of the ideas I had was fastest synthesis of a random compound - first one to synthesize a compound (kept secret until the start of the challenge) wins.

Amos - 13-11-2014 at 10:43

@Brandon: photos of the synthesis with some sort of physical verification(like the date on paper)? That could work.

DrMario - 13-11-2014 at 11:12

So a Luminol synthesis is a suggested Challenge.

He didn't mean it that way. There are probably numerous 'How To' and Utoobs on Luminol. Not really a challenge if ready to use instructables are readily available.

Indeed. It was just an example of a compound that, while buyable, is extremely expensive. But I know of at least two processes for synthesis of Luminol.

WGTR - 13-11-2014 at 12:27

I second the idea of limiting the competition to substances that are either expensive or hard to get, and either useful to a variety of people or chemical reactions. "Hard to get" doesn't necessarily mean "unavailable on eBay". It could also mean "not available locally over-the-counter".

The previous competition to purify HCl was a good idea. Not everyone can buy reagent grade HCl, and purifying the OTC stuff is a useful skill to have. The idea potentially could have generated more interesting responses than it did, which is why I suggested some extra structure to the competition next time.

The topic of acids is an interesting one. Nitric acid is a very useful substance that is only going to become more difficult and expensive for people to obtain in the future. Nitrate salts are in the same category of increasing unavailability and expense. This is a shame, because nitric acid is a generically useful chemical that has many important uses in a lab.

As one possible idea, I would propose a competition to make nitric acid from non-nitrate salts. If ammonia oxidation is performed, then less than 1g of platinum is allowed (about $50 on eBay). A better design would incorporate a non-precious metal catalyst, if it gives useful lab-scale results. A Birkeland Eyde process could be used. Starting materials other than air and ammonia can be used, as long as they are not nitrate salts, and are cheaply and readily available.

Entries could be judged according to ($) input vs. nitric acid output for various quantities. A Birkeland Eyde process uses air as a starting material, but the process is inefficient. Electricity cost becomes significant. Ammonia oxidation requires more expensive starting materials, but is more efficient. Industrially, it is a cheaper process. One drawback is that it normally uses expensive catalysts. Also, safety is an important consideration. A design that has high voltages tucked away from inquisitive fingers, or designs that minimize the risk from fuel-air explosions, would take priority. A winning project needs to be documented well enough for someone else to duplicate it, using components that other people can order.

I've thought of doing the Birkeland Eyde process myself, and I do have a personal advantage on the electronics side of the equation. I haven't gotten around to doing this, though. I'm not proposing that a reward be offered, other than the ego trip from knowing that one's design is better than everyone else's. The real reward would be to the forum, which would benefit from the knowledge that would be shared.

aga - 13-11-2014 at 13:03

I like that one. Cheers.
Alternate non-bases-of-nitric-acid methods for making HNO3 would be very useful, and hopefully challenging !

plante1999 - 13-11-2014 at 13:05

By experience, making an Ostwald reactor CANT be a reasonable goal unless the prize is like 1000$, and that barely cover the costs of making a reactor that is productive.

That's why I think that making experiments that is in the reach of almost everyone in the term of budget is better, such as extracting ammonia from proteins.

WGTR - 13-11-2014 at 14:21

plante1999, for the love of the dog, what have you done?!?! You have just said that it is impossible for me to do something!!! Now I have no choice but to stay in the lab for the next 72 hours, proving that it can be done!!! Argghhh!!!

Seriously, though, I'm motivated differently. If I was interested in the money, I wouldn't try it unless the reward was something like 50-100k. However, if the results were useful to a wide variety of people, then it makes my donation of time a willing one. If other people get involved with their own designs, it makes the competition fun. I have a lot of stuff laying around my lab, and I could probably make something functional for around $100-$200. The idea is for a lab scale process, making perhaps 1L of 20-30% nitric acid per week.

I think that extracting ammonia from proteins would be an interesting project, and anyone doing it would learn useful skills. Personally, though, it's just not complicated enough for me. I already have a 20lb bag of ammonium sulfate in my lab, and it was dirt cheap. It's fertilizer. One thing I don't have, however, is an easy way of making glyoxal without using nitric acid. And without glyoxal, I can't make expensive imidazole-based ionic liquids. Without the ionic liquids, I don't have a room temperature wide electrochemical window electrolyte, and so on. Without all of that, I don't have this cool synthesis of BMIM-HFP to post on here.

aga - 13-11-2014 at 17:13

Personally, i think as a Species we are approaching that point where we think we have enough accumulated knowledge to make the assumption that we (collectively) know it All.

The Reality is that We don't know very much at all.

@WGTR: go for it.

j_sum1 - 13-11-2014 at 18:02

You know, I would love a comp on how to make HNO3 from otc chemicals. There are a variety of routes and otc means very different things in different parts of the world. The product may vary from dilute to 30% to azeotropic to fuming to 100% with different techniques arriving at each one. Winner and prize would be incidental although I am sure that the rule of aga's decision is mostly final (or something of that ilk) would apply. We would end up with a highly useful documented resource to produce a reagent of fundamental importance to people in a variety of situations.

Anyway, huge number of different ideas here. Let me add my support for a competition subforum. Perhaps the standard format could be to have two separate threads for each competition -- one for instructions and discussion and the other for submissions. And links to the second could of course be made in the first.

arkoma - 14-11-2014 at 04:04

aga's challenge, aga's rules...................and trust me his m***** is G**D

[Edited on 11-14-2014 by arkoma]

Chemosynthesis - 14-11-2014 at 04:16

I'm somewhat surprised no one gassed dry-ish HCl into a known volume or saturated solution. Anyone consider and reject this?

Edit- and yes, by gassing, I do mean NaCl or CaCl2 in sulfuric acid, or a similar generator.

[Edited on 14-11-2014 by Chemosynthesis]

arkoma - 14-11-2014 at 04:19

Edit- and yes, by gassing, I do mean NaCl or CaCl2 in sulfuric acid, or a similar generator.

[Edited on 14-11-2014 by Chemosynthesis]

LMFAO

The Volatile Chemist - 14-11-2014 at 05:19

Quote: Originally posted by arkoma

aga's challenge, aga's rules...................and trust me his m***** is G**D

[Edited on 11-14-2014 by arkoma]

his m***** ? I know G**D is G^D. But is m***** m /\ 4 /\ m where /\ 4 /\ is arrow notation?

Sorry, just messing around as I have no clue as to what you were saying.

blogfast25 - 14-11-2014 at 05:55

Quote: Originally posted by WGTR

plante1999, for the love of the dog, what have you done?!?! You have just said that it is impossible for me to do something!!! Now I have no choice but to stay in the lab for the next 72 hours, proving that it can be done!!! Argghhh!!!

In 72 hours... good luck with that!

blogfast25 - 14-11-2014 at 05:56

I'm somewhat surprised no one gassed dry-ish HCl into a known volume or saturated solution. Anyone consider and reject this?

Edit- and yes, by gassing, I do mean NaCl or CaCl2 in sulfuric acid, or a similar generator.

It has been done, also on SM. By me among others. Hardly a challenge though...

Etaoin Shrdlu - 14-11-2014 at 07:23

It has been done, also on SM. By me among others. Hardly a challenge though...

Look, some people enjoy thinking of multiple clever solutions to an easy problem. Some people have never tried to purify HCl and would find it a challenge. Some people think this is all ridiculously simple and therefore abstain, or push themselves to complete the requirements as quickly as possible in order to beat everyone else who found it ridiculously simple. Some people joke about booze. Who cares? It was fun.

Here's one for you, then:

Proposal: First synthesis of TEMPO starting from OTC reagents.

Prize: Can only offer $300 at the moment. The girlfriend is already watching me side-eyed after my last chemical order.

Deadline: 5/1/2014

1. Definition of OTC is "something available to the general public for purposes other than synthesis." For example, sure, you could use a bar of silver or handfuls of lawn grass, even if you had to order them online/collect them yourself because no one around you actually sold them over a counter.

2. You can skip steps to non-OTC intermediates if you can link to a confirmed synthesis already performed and written up on ScienceMadness. Patent/research paper writeups must be confirmed by yourself or someone on ScienceMadness no matter how awesome they are.

3. All equipment reasonably well-available to the hobbyist is allowed.

4. Procedures must be clear, easy to follow, and accompanied by images where the synthesis was performed by yourself.

5. Teams are allowed. Name a head researcher, I'll send the prize to them, you split it up yourselves.

Thoughts?

[Edited on 11-14-2014 by Etaoin Shrdlu]

gdflp - 14-11-2014 at 07:53

There might be some issues with completing it in -6 months.

blogfast25 - 14-11-2014 at 08:21

Quote: Originally posted by Etaoin Shrdlu

Proposal: First synthesis of TEMPO starting from OTC reagents.

Prize: Can only offer $300 at the moment. The girlfriend is already watching me side-eyed after my last chemical order.

One serious problem is characterisation of such compounds, that usually requires techniques hobbyists don't have access to.

But it would appear that the project can be 'reduced' to converting 2,2,6,6-tetramethylpiperidin-4-one to TEMPO, assuming that is at all possible, of course.

Synthesis of 2,2,6,6-tetramethylpiperidin-4-one is very simple and OTC (ammonia and acetone, essentially):

http://www.sciencemadness.org/talk/viewthread.php?tid=3960

Getting rid of the carbonyl in 2,2,6,6-tetramethylpiperidin-4-one and subsequent oxidation of the 2,2,6,6-tetramethylpiperidine to TEMPO will be a lot harder.

There appear to be several ways of synthesising 2,2,6,6-tetramethylpiperidine, though...

[Edited on 14-11-2014 by blogfast25]

Chemosynthesis - 14-11-2014 at 09:17

It has been done, also on SM. By me among others. Hardly a challenge though...

Yeah, but what I mean is simple distillation has to have been done before, and arguably isn't much of a challenge either, though the negative azeotrope is a bit quirky. Gassing could be more variable on time, which could be a pro despite being less friendly to those with poor ventilation.

Metacelsus - 14-11-2014 at 09:25

Wolff-Kishner reduction of the oxo compound should work, and hydrazine is possible to make from OTC materials. (I in fact have some hydrazine sulfate prepared already). Oxidation to TEMPO shouldn't be that hard.

I am going to attempt this when I get the time. The $300 prize is definitely worth it.

[Edited on 14-11-2014 by Cheddite Cheese]

blogfast25 - 14-11-2014 at 09:46

I’m game if it’s worth £50 to anyone. HCl generator to produce at least sup-azeotropic HCl (call it > 25 w%).

Quote: Originally posted by Cheddite Cheese

Wolff-Kishner reduction of the oxo compound should work, and hydrazine is possible to make from OTC materials. (I in fact have some hydrazine sulfate prepared already). Oxidation to TEMPO shouldn't be that hard.

I am going to attempt this when I get the time. The $300 prize is definitely worth it.

There’s plenty of info on TEMPO synths and it’s all doable. But I really don’t like the ‘OTC only’ restriction. It’s silly because those who only have access to OTC chems are unlikely to want to synth TEMPO, while those capable of synthing it will have access to non-OTC chemicals, and why should they NOT use these? Was progress in chemistry made by constantly harking back to the simplest precursors? That’s a Luddite approach, as far as I’m concerned. With or w/o OTC, it's still a nice challenge and a first for SM.

Having said that, so far hydrazine seems to be the only non-OTC required for one route to 2,2,6,6 tetramethylpiperidine that I found.

So, good luck!

[Edited on 14-11-2014 by blogfast25]

Metacelsus - 14-11-2014 at 09:51

I'm basically just doing it for the money (if I wanted TEMPO I'd buy it). I might also try reduction with zinc, which is easier to get than hydrazine.

Etaoin Shrdlu - 14-11-2014 at 09:56

One serious problem is characterisation of such compounds, that usually requires techniques hobbyists don't have access to.

That's not a serious problem. Not even a problem in my mind. The compound in question is very distinctive. If you follow a reasonable-looking synthesis and get a red-orange solid that behaves as TEMPO does, I'll believe you.

???

I want an OTC synth because non-OTC ones already exist. You're just ticked off I didn't allow free reign in precursors so you could point to papers and remark how "easy" it was, eh? (That was meant to be more lighthearted than it came out, sorry.)

You're all thinking along the same lines as I would. But it's not a challenge for me. (EDIT: I mean, it's not directed at me, it probably would be a challenge due to time and space constraints alone.) Glad to see someone's willing to go for it.

[Edited on 11-14-2014 by Etaoin Shrdlu]

[Edited on 11-14-2014 by Etaoin Shrdlu]

blogfast25 - 14-11-2014 at 09:59

Quote: Originally posted by Cheddite Cheese

I'm basically just doing it for the money (if I wanted TEMPO I'd buy it). I might also try reduction with zinc, which is easier to get than hydrazine.

Not good enough for ketones, I think. Maybe that new method of acid + Al powder + Cu(II) salt?

blogfast25 - 14-11-2014 at 10:04

Quote: Originally posted by Etaoin Shrdlu

I want an OTC synth because non-OTC ones already exist. You're just ticked off I didn't allow free reign in precursors so you could point to papers and remark how "easy" it was, eh?

Glad to see someone's willing to go for it.

You should mind your language, Sir. I didn't say or think it was easy. It isn't. Doable but not easy.

But whoever does it will do it along classic lines, probably dodging the OTC restriction somehow. No one is going to reinvent a complex wheel for the sake of 'OTC'.

Etaoin Shrdlu - 14-11-2014 at 10:40