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| Author(s): |
Claudia Giovedi
Total Authors: 1
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| Document type: | Doctoral Thesis |
| Press: | São Paulo. |
| Institution: | Universidade de São Paulo (USP). Conjunto das Químicas (IQ e FCF) (CQ/DBDCQ) |
| Defense date: | 1998-09-18 |
| Examining board members: |
Roberto Tokoro;
Luis Alberto Avaca;
Julien Françoise Coleta Boodts;
Nelson Ramos Stradiotto;
Henrique Eisi Toma
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| Advisor: | Roberto Tokoro |
| Abstract | |
The electrochemical behaviour of cobalt(II), nickel(II), manganese(II), iron(II) and zinc(II) was studied in the presence of azide in two conditions: varying the ligand concentrations in solution from 0.0 to 2.0 mol/L and just pre-adsorbing it onto the mercury electrode surface, in order to evaluate the determining aspects on the extent of the action of the ligand as a mediator in facilitating electron transfer. The results obtained in the two sets of experiments showed to what extent the action of the ligand as a mediator is dependent on the metal studied. In the first case, the addition of azide to solutions of these metaIs causes the following: a progressive anticipation in the reduction waves of Co(lI) and Ni(II); the shift towards more negative potentials for Mn(II) and Fe(II); and for Zn(TT) a small shift towards more positive potentials at low azide concentrations followed by a shift towards more negative potentials. The experiments carried out with the pre-adsorption ofthe azide onto the mercury surface showed the shift of the reduction waves of Co(lI) and Ni(II) towards more positive potentials, a small shift towards more negative potentials for Zn(II) and the complete elimination of the electrode reaction for Mn(II). The differences observed in the two experiments proved the importance of the complexation phenomenon onto the electrode surface in order to occur the action of the ligand as a mediator. However, inspite of the need of the interaction between metal and ligand to facilitate the electron transfer, the complex formed onto the electrode surface cannot be thermodynamically more stable than its metal aquo-ion, as in this case it will be observed the shift of the reduction potential towards more negative potentials. (AU) | |