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Author: Subject: Upsalite ? pure MgCO3
ElectroWin
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[*] posted on 15-8-2013 at 19:54
Upsalite ? pure MgCO3


i was just reading about Upsalite, a recently synthesized zeolite with some surprising properties..

http://banoosh.com/blog/2013/08/15/scientists-make-impossibl...
http://en.wikipedia.org/wiki/Upsalite

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bfesser
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[*] posted on 15-8-2013 at 21:01


I, for one, am very excited. This seems well suited to amateur experimentation.



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Fantasma4500
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[*] posted on 16-8-2013 at 03:33


magnesium oxide (MgO) and carbon dioxide (CO2), dissolved in methanol, a common industrial solvent. The result is pure, dry MgCO3.

this would mean that you would be able to dissolve Al or Al2O3 to form CO2 in solution, as methanol reacts with one of them, not sure at all if it was Al2O3 or actual Al metal
anyhow, then you can get to make CO2 in the solution using methanol and perhaps al foil

i would suggest putting MgO on a piece of cloth
then in a beaker of MeOH you fill the bottom with al foil folded hard together or whatever
then you put the MgO down, so its on top of the aluminium foil, perhaps a sieve of some sort?
the CO2 has to get in contact with the MgO, i suppose

very interesting, sounds like more than just do-able
biggest problem would be to get MgO in decent amounts, magnesium is a waste to burn off to get MgO




~25 drops = 1mL @dH2O viscocity - STP
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[*] posted on 16-8-2013 at 05:37


<strong>Antiswat</strong>, I can't make sense of your reply. Why are you talking about aluminium?

Also, I think it would be interesting to explore the science&mdash;not really concerned with an economical synthesis. However, if you prefer, MgO could be purchased, rather than prepared by burning Mg.

Hooray! They published the paper for free, online:
<strong><a href="http://www.plosone.org/article/fetchObject.action?uri=info%3Adoi%2F10.1371%2Fjournal.pone.0068486&representation=PDF" target="_blank">A Template-Free, Ultra-Adsorbing, High Surface Area Carbonate Nanostructure</a></strong> <img src="../scipics/_pdf.png" />

Quote:
<div align="center"><img src="http://www.plosone.org/article/fetchObject.action?uri=info:doi/10.1371/journal.pone.0068486.g002&representation=PNG_M" /></div>
<strong>Figure 2. Synthesis of Upsalite. i)</strong> In the first step MgO (s) is mixed with methanol under 3 bar CO<sub>2</sub> pressure at 50&deg;C. <strong>ii)</strong> After 2.5 h the HOMgOCH<sub>3</sub> is formed in the solution, the pressure is lowered to 1 bar and the heating is turned off. At the same time the methanol reacts with the CO<sub>2</sub> and forms CH<sub>3</sub>OCOOH (methyl hemicarbonic acid). <strong>iii)</strong> HOMgOCH<sub>3</sub> reacts with CH<sub>3</sub>OCOOH and forms water and H<sub>3</sub>COCOOMgOCH<sub>3</sub> (methyl esther of magnesium methyl carbonate). At this point the solution changes colour from white to light yellow. <strong>iv)</strong> H<sub>3</sub>COCOOMgOCH<sub>3</sub> reacts with the water formed in step iii) and forms HOMgOCOOCH<sub>3</sub> (or MgCO<sub>3</sub>&middot;CH<sub>3</sub>OH) which upon <strong>v)</strong> heating at 70&deg;C releases CH<sub>3</sub>OH and forms MgCO<sub>3</sub>.
doi:<a href="http://dx.doi.org/10.1371/journal.pone.0068486.g002" target="_blank">10.1371/journal.pone.0068486.g002</a> <img src="../scipics/_ext.png" />

. . .

Synthesis
In the current work 4 g magnesium MgO powder was placed in a glass bottle together with 60 ml methanol and a stirring magnet. The solution was put under 3 bar CO<sub>2</sub> pressure and heated to 50&deg;C. After approximately 4 hours the mixture was allowed to cool to RT and the carbon dioxide pressure was lowered to 1 bar, and the reaction continued until a gel had formed. When a gel was obtained, the carbon dioxide pressure was removed and the gel was allowed to solidify and dry at ~70&deg;C during 3 days. A schematic description of the synthesis is found in Fig. 2.

&ndash; Forsgren J, Frykstrand S, Grandfield K, Mihranyan A, Strømme M (2013) <strong>A Template-Free, Ultra-Adsorbing, High Surface Area Carbonate Nanostructure.</strong> PLoS ONE 8(7): e68486. doi:<a href="http://dx.doi.org/10.1371/journal.pone.0068486" target="_blank">10.1371/journal.pone.0068486</a> <img src="../scipics/_ext.png" />


[Edited on 16.8.13 by bfesser]




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[*] posted on 16-8-2013 at 05:45


Quote: Originally posted by bfesser  
<strong>Antiswat</strong>, I can't make sense of your reply. Why are you talking about aluminium?



He's going by analogy. Al carbonate cannot exist in watery medium but could possibly be synthesised by analogy with MgCO3. Remains to be proved, of course...


[Edited on 16-8-2013 by blogfast25]




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[*] posted on 28-8-2013 at 10:15


i was talking about how aluminium could be added to form the CO2, although i recall something about some H2O being formed by CH3OH + Al now, which might ruin the whole thing.. oh well.. perhaps dessicant would be needed if aluminium was used?



~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
http://www.trimen.pl/witek/calculators/stezenia.html
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[*] posted on 28-8-2013 at 11:55


How does aluminum form CO2 from methanol? From Wikipedia, the reaction is:

6 MeOH + 2 Al → 2 Al(MeO)3 + 3 H2

https://en.wikipedia.org/wiki/Methanol

The reaction takes place because MeOH is able to attack the passivization layer around Al, and also because aluminum methoxide is soluble in MeOH.

Neither H2O nor CO2 is formed.




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[*] posted on 28-8-2013 at 12:20


Quote: Originally posted by Cheddite Cheese  

6 MeOH + 2 Al → 2 Al(MeO)3 + 3 H2

https://en.wikipedia.org/wiki/Methanol

The reaction takes place because MeOH is able to attack the passivization layer around Al, and also because aluminum methoxide is soluble in MeOH.



There is nothing in that wikilink to suggest direct reaction between methanol and Al is possible. Do you have any real evidence that it is?

http://en.wikipedia.org/wiki/Alkoxide#By_electrochemical_pro...

... is interesting but doesn't discuss aluminium methoxide...




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[*] posted on 28-8-2013 at 12:20


Quote:
At the same time the methanol reacts with the CO<sub>2</sub> and forms CH<sub>3</sub>OCOOH (methyl hemicarbonic acid). <strong>iii)</strong> HOMgOCH<sub>3</sub> reacts with CH<sub>3</sub>OCOOH and forms water and H<sub>3</sub>COCOOMgOCH<sub>3</sub> (methyl ester of magnesium methyl carbonate). At this point the solution changes colour from white to light yellow.


I find this a dubious mechanism. Direct reaction of the methoxide with carbon dioxide to give the methylcarbonate anion seems a lot more likely than reaction of methanol with carbon dioxide to give the acid, followed by reaction with the base.

I really doubt that a similar method could be used to give aluminum carbonate, since aluminum oxide is such a thermodynamic sink. Slow reaction of aluminum methoxide in anhydrous methanol with carbon dioxide to give nice crystals of alumina sounds intriguing, though...




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[*] posted on 28-8-2013 at 12:30


This is very interesting, it appears that methanol saturated with carbon dioxide (under pressure) can dissolve MgO, since the transient methylcarbonic acid is created. great way to avoid contamination with water, this could be useful for forming other anhydrous magnesium salts

Quote: Originally posted by blogfast25  

There is nothing in that wikilink to suggest direct reaction between methanol and Al is possible. Do you have any real evidence that it is?

It is, I have read about this before. The reaction is very slow, however. Methanol cannot be stored in aluminum fuel tanks for this reason, because it will eventually corrode and burn a hole.

[Edited on 28-8-2013 by AndersHoveland]
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[*] posted on 28-8-2013 at 14:10


Quote:

There is nothing in that wikilink to suggest direct reaction between methanol and Al is possible.


The article discusses the incompatibilities of methanol with aluminum vehicle parts, and specifically cites the reaction.

https://en.wikipedia.org/wiki/Methanol#Fuel_for_vehicles

[Edited on 28-8-2013 by Cheddite Cheese]




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