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Additional recommended knowledge
The Grotthuss Mechanism is the mechanism by which an 'excess' proton or protonic defect diffuses through the hydrogen bond network of water molecules or other hydrogen-bonded liquids through the formation/cleavage of covalent bonds.
In his seminal 1806 publication “Theory of decomposition of liquids by electrical currents”, Theodor Grotthuss proposed a unique theory of water conductivity. Grotthuss envisioned the electrolytic reaction as a sort of ‘bucket line’ where each oxygen atom simultaneously passes and receives a single hydrogen atom. It was an astonishing theory to propose at the time, since the water molecule was thought to be OH not H2O and the existence of ions was not fully understood. On its 200th anniversary his article was reviewed by Cukierman.
Although Grotthuss was using an incorrect empirical formula of water his description of the passing of protons through the cooperation of neighboring water molecules proved to be remarkably fortuitous.
Proton Transport Mechanism / Proton Hopping mechanism
The Grotthuss Mechanism is now a general name for the proton-hopping-mechanism. In liquid water the solvation of the excess proton is idealized by two forms; the H9O4+ (Eigen cation) or H5O2+ (Zundel cation). While the transport mechanism is believed to involve the inter-conversion between these two solvation structures, the details of the hopping/transport mechanism is still debated.
Currently there are two plausible mechanisms:
In 2007, Omer Markovitch and Noam Agmon reported for the first time the energetics of the hydronium solvation shells and suggested that the activation energies of the two proposed mechanisms do not agree with their calculated hydrogen bond strengths, but mechanism (I) might be the better candidate of the two.
The anomalous diffusion of protons
The Grotthuss mechanism explains the unusually high diffusion of the proton relative to other the typical ionic diffusion of other cations (Table 1) which is due simply to random thermal motion i.e. Brownian motion.
|This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Grotthuss_mechanism". A list of authors is available in Wikipedia.|