Graduate Thesis Or Dissertation
 

Studies of electrode processes with voltage scanning coulometry

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  • Voltage scanning coulometry was used to study the effects of electrode surfaces and metals on the electrochemistry of the ferric-ferrous couple and the silver ion-silver metal couple. The analytical technique called voltage scanning coulometry is very similar to controlled potential coulometry. The main difference is that in voltage scanning coulometry the potential of the working electrode is scanned through a voltage range rather than remaining at a constant potential. The equations for voltage scanning coulometry were verified for the ferric-ferrous couple and silver deposition on a gold electrode. Indirect evidence is presented relating the activity of the silver deposit to the fraction of the electrode surface covered by the deposit. Evidence is presented showing the presence of both gold and platinum oxides on the surface of the electrodes. Electrode treatments and their effects on the use of electrodes is thoroughly evaluated in terms of the electrochemical systems studied here. Evidence is presented showing that the ferric-ferrous couple is catalyzed by a ceric treated electrode surface. The activity of a silver deposit on a ceric treated surface is found to be much greater than its activity on a crystalline surface. Qualitative evidence verifying the potential energy calculations for silver deposition at various surfaces is presented, also. The effective to geometric surface area ratio for a crystalline gold electrode is found to be 2.3 for silver deposition. The deposition of the first monolayer of silver on a crystalline gold surface is found to occur at lattice sites with three different adsorption energies.
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