Estimation of electron transfer rate constants by static (optical and electrochemical) measurements |
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| Authors: | Manuel Lpez-Lpez Pilar Prez-Tejeda Pilar Lpez-Cornejo Francisco Snchez |
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| Institution: | Departamento de Química Física, Facultad de Química, Universidad de Sevilla, C/Profesor García González s/n, 41012 Sevilla, Spain |
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| Abstract: | A kinetic study of the reduction of Co(NH3)5(DMSO)3+ (DMSO=dimethylsulfoxide) by Fe(CN)64− has been carried out in several water–cosolvent mixtures at 298.2 K. The cosolvents used were ethylene glycol, acetonitrile, methanol and glucose. The free energies of activation for this thermal electron-transfer reaction have been calculated from a combination of spectroscopic and electrochemical data and compared with those obtained from the kinetic study. Quantitative agreement is found between both series of data. This shows the possibility of estimating activation free energies for electron transfer reactions from these (static) measurements. |
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| Keywords: | Optical and thermal electron transfer reactions MMCT band Reorganization free energy Free energy change and activation free energy |
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