Monday, September 30, 2019

reaction mechanism - What did actually happen when Staudinger tried to synthesise diamond?


It is a famous reaction that used to be a teaching lab experiment, but is now banned in Germany, because it is too dangerous. To quote-translate quite liberally from the German www.seilnacht.com:



In a stone quarry near Zurich, Hermann Staudinger attempted to artificially produce a diamond by reacting the potassium-sodium melt with tetrachlorocarbon in a bomb tube. The attempt failed as the mixture tore the bomb tube apart.
In einem Steinbruch bei Zürich versuchte Hermann Staudinger einen Diamanten künstlich herzustellen, indem er die Kalium-Natrium-Schmelze mit Tetrachlorkohlenstoff in einem Bombenrohr reagieren ließ. Der Versuch misslang, da die Mischung das Bombenrohr zerfetzte.



I was probably one of the last students who were still able to see this experiment, and while considerably down scaling the actual set-up, it was still one of the most powerful explosions I ever witnessed.


To me it was actually surprising that I found pages, while researching this reaction, that asked whether $\ce{CCl4}$ can act as a solvent in the Wurtz Reaction, or that in the Wurtz reaction of carbon tetrachloride and sodium no product would be formed, because $\ce{CCl4}$ is too stable to react.


However, due to this I found the following passage in Inorganic Chemistry:




Tetrahaloalmethanes can be reduced by strong reducing agents, such as alkali metals. For example, the reaction of carbon tetrachloride with sodium is highly exoergic: \begin{align} \ce{CCl4 (l) + 4 Na (s) &-> 4 NaCl (s) + C (s)}& \Delta_\mathrm{r}G^\circ &=\pu{-249 kJ mol^-1} \end{align} This reaction can occur with explosive violence with $\ce{CCl4}$ and other polyhalocarbons, so alkali metals such as sodium should never be used to dry them.



Unfortunately I reached a dead end with finding more literature about the reaction. I am especially interested in the mechanism, and the final products. I would assume that the above equation only represents a theoretical model, and the products will likely be carbon dioxide and other combustion related products. I'd be interested to know if there are any practical and/ or theoretical studies to the kinetics and thermodynamics of the reaction.


If the source does not cover tetra-, but tri-, or bihalogenated methane, I assume it is fine, too, but it should go beyond the Wurtz reaction ($\ce{2 R-Cl + 2 Na -> R-R + 2 NaCl}$).




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