물 및 디메틸포름아마이드中에서 4-(2-Pyridylazo)-resorcinol의 分光電氣化學的 環元 = Spectroelectrochemical Study for the Reduction of 4-(2-Pyridylazo)-resorcinol in Water and Dimethylformamide

다국어 초록 (Multilingual Abstract)

Spectroelectrochemistry involve the combination of an electrochemical technique with a spectroscopic techinque so that the two measurements may be performed simultaneously in an electrochemical cell. One of the most generally useful spectroelectrochemical technique involves spectral observation of a thin layer of solution. Thin-layer spectroelectrochemistry at the optically transparent thin-layer electrode(OTTLE) takes advantage of the rapid electrolysis (30∼60 sec.) and small volume features of thin-layer electrochemistry.
This study has used controlled potential as the excitation signal. Potential control provides a facile means of presicely adjusting the redox potential of the thin solution layer as determined by the Nernst equation for reversible systems:
E_applied=E^0'+0.059/n log (O)/(R)
In experiment, the slopes of Nernstian plot were 28.3mV in aqeous solution and 53mV in N, N-dimethylformamide(DMF) solution. The results of this study showed that the reduction mechanisms of 4-(2-pyridylazo)-resorcinol(PAR) were one two-electron step in aqueous solution and two one-electrons steps in DMF solution. The formal reduction potentials(E^0') of the PAR were -0.574 volts vs. S.C.E. in aqueous soltion and -0.74 volts vs. Ag/AgClO_4 in DMF solution. These results were generally similar to the reduction mechanism of the other cyclic hydrocarbons in the aprotic solvent.
In aprotic solvent, the product of the first electron transfer is expected to be a relatively stable anion radical. In this experiment tetraethylammonium perchlorate was used as a supporting electrolyte of the DMF solution.