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The well-known linear relationship (TΔS# =αΔH# +β, where 1 >α > 0,β > 0) between the entropy (ΔS#) and the enthalpy (ΔH#) of activation for reactions in polar liquids is investigated by using a molecular theory. An explicit derivation of this linear relation from first principles is presented for an outersphere charge transfer reaction. The derivation offers microscopic interpretation for the quantitiesα andβ. It has also been possible to make connection with and justify the arguments of Bell put forward many years ago

Molecular interpretation of the linear relationship between the entropy and the enthalpy of activation of charge transfer reactions in polar liquids