A kinetic study of the electron-transfer reactions Ru(NH3)(5)pz(2+) + Fe(CN)(6)(3-) reversible arrow Ru(NH3)(5)pz(3+) + Fe(CN)(6)(4-) was carried out in several water-organic solvent mixtures at 298.2 K. The free energies of activation for these thermal electron-transfer reactions were calculated from a combination of spectroscopic and thermodynamic data and are compared with those obtained from the kinetic study. Quantitative agreement is found between the two series of data. This shows the possibility of estimating activation free energies for electron-transfer reactions from these (static) measurements.