Tuesday, December 5, 2017

inorganic chemistry - What is the strongest oxidising agent?


I searched for the strongest oxidising agent and I found different results: $\ce{ClF3}$, $\ce{HArF}$, $\ce{F2}$ were among them.


Many said $\ce{ClF3}$ is the most powerful as it oxidises everything, even asbestos, sand, concrete, and can set easily fire to anything which can't be stopped; it can only be stored in Teflon.


And $\ce{HArF}$ could be a very powerful oxidant due to high instability as a compound of argon with fluorine, but was it even used as such?


What compound is actually used as oxidising agent and was proven to be stronger then others, by, for example, standard reduction potential?



Answer




Ivan's answer is indeed thought-provoking. But let's have some fun.


IUPAC defines oxidation as:



The complete, net removal of one or more electrons from a molecular entity.



My humble query is thus - what better way is there to remove an electron than combining it with a literal anti-electron? Yes, my friends, we shall seek to transcend the problem entirely and swat the fly with a thermonuclear bomb. I submit as the most powerful entry, the positron.


Since 1932, we've known that ordinary matter has a mirror image, which we now call antimatter. The antimatter counterpart of the electron ($\ce{e-}$) is the positron ($\ce{e+}$). To the best of our knowledge, they behave exactly alike, except for their opposite electric charges. I stress that the positron has nothing to do with the proton ($\ce{p+}$), another class of particle entirely.


As you may know, when matter and antimatter meet, they release tremendous amounts of energy, thanks to $E=mc^2$. For an electron and positron with no initial energy other than their individual rest masses of $\pu{511 keV c^-2}$ each, the most common annihilation outcome is:


$$ \ce{e- +\ e+ -> 2\gamma}$$


However, this process is fully reversible in quantum electrodynamics; it is time-symmetric. The opposite reaction is pair production:



$$ \ce{2\gamma -> e- +\ e+ }$$


A reversible reaction? Then there is nothing stopping us from imagining the following chemical equilibrium:


\begin{align} \ce{e- +\ e+ &<=> 2\gamma} & \Delta_r G^\circ &= \pu{-1.022 MeV} =\pu{-98 607 810 kJ mol^-1} \end{align}


The distinction between enthalpy and Gibbs free energy in such subatomic reactions is completely negligible, as the entropic factor is laughably small in comparison, in any reasonable conditions. I am just going to brashly consider the above value as the standard Gibbs free energy change of reaction. This enormous $\Delta_r G^\circ$ corresponds to an equilibrium constant $K_\mathrm{eq} = 3 \times 10^{17276234}$, representing a somewhat product-favoured reaction. Plugging the Nernst equation, the standard electrode potential for the "reduction of a positron" is then $\pu{+2 116 413 V}$.


Ivan mentions in his answer using an alpha particle as an oxidiser. Let's take that further. According to NIST, a rough estimate for the electron affinity of a completely bare darmstadtium nucleus ($\ce{Ds^{110+}}$) is $\pu{-204.4 keV}$, so even a stripped superheavy atom can't match the oxidising power of a positron!


... that is, until you get to $\ce{Ust^{173+}}$ ...


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