Effect Of Pressure On An Intramolecular Electron-Transfer Reaction Induced By Pulse-R Adioly Sis

The pressure dependence of an intramolecular electron-transfer reaction between p-nitrobenzoate and the pentaamminecobalt (III) species was studied with the aid of a combined high-pressure pulse-radiolysis technique. The resulting volume of activation of +7.50.3 cm3mor-1 is ascribed to an intrinsic volume increase due to the reduction of Co(III) to Co(II) and some desolvation of the coordinated ligand during the electron-transfer process. The results are compared with related data obtained using conventional kinetic techniques.