Some electrochemical properties of the vanadium pentoxide electrode Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/t435gh07j

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  • Vanadium pentoxide single crystals were grown from the melt. These crystals were made the cathode in an electrolytic cell and the polarization and recovery of the electrode were studied under a variety of experimental conditions. A study of the electrode potential versus that of the standard hydrogen electrode as a function of electrolyte pH was carried out on both pure and discharged samples. It was found in both cases that the cell potential decreased an average of 0.059 ± 0.005 v/pH unit, thereby indicating that an equal number of electrons and protons are involved in the discharge reaction. The potential difference between the V₂0₅ and the standard hydrogen electrode was plotted as a function of time during polarization and recovery. The resulting curves were compared with those calculated from a theory based on the diffusion of the discharge product from the surface to the interior of the electrode. This theory successfully predicted the experimental curves between pH 2 and 5.5; outside this range the theory failed due to dissolution at low pH and air oxidation at high pH of the discharge product. Experiments conducted at pH 4.7 utilizing a tritium tracer showed the presence of hydrogen in the electrode following the polarization and recovery of the electrode. A study on the degree of polarization as a function of temperature was conducted; the activation energy for the diffusion of the product from the electrode surface was found to be 6.7 kcal/mole. This value indicates that it is probable protons and electrons diffuse rather than the entire reduced compound.
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