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.
Bibliographical noteFunding Information:
The authors gratefully acknowledge support from the German-Israeli Foundation for Scientific Research and Development. RvE also acknowledges financial support from the Deutsche Forschungsgemeinschaft and the Volkswagen-Stiftung. DM wishes to. express his thanks to Mrs Irene Evans for her continued interest and support.
- aqueous phase chemistry
- high-pressure pulse-radiolysis
- reaction kinetics