91207 - Molecular Electrochemistry

Course Unit Page


This teaching activity contributes to the achievement of the Sustainable Development Goals of the UN 2030 Agenda.

Affordable and clean energy Climate Action

Academic Year 2021/2022

Learning outcomes

At the end of the course the student knows the theoretical and experimental bases for the investigation of electron transfer processes, either heterogeneous or homogeneous and intramolecular and for the comprehension of the physical-chemical processes associated to it. The student knows the principles of the main electrochemical techniques for the study of the properties of molecular and supramolecular systems.

Course contents

Lectures (module 1)

  1. Introduction to the course. Measurability of potentials; inner and outer potentials. Volta effect. The electrode potential and Nernst equation.
  2. The structure and properties of the electrified interphases. Differential capacity of the electrode/solution interphase. Models of the electrochemical interphase: Helmholtz model, Gouy-Chapman-Stern model. Adsorption.
  3. The rate of the heterogeneous electron transfer (ET) process. Anodic and cathodic processes. The Butler-Volmer equation: standard rate constant and coefficient of the heterogeneous ET. Overpotential. Tafel diagrams.
  4. Marcus' model of the homogeneous and heterogeneous (outer sphere) ET: the solvent reorganization energy. Non-adiabatic ET: heterogeneneous and intramolecular ET. Photoinduced ET.
  5. Mass transport in solution. Fick's Law and resolution of the diffusion equation in some cases of electroanalytical interest. Methods for mass transport control: forced convection and spherical diffusion (ultramicroelectrodes). Potentiodynamic transient techniques: cyclic voltammetry and electrochemical impedance spectroscopy.
  6. Wrap-up: the (Randles') equivalent circuit

Practical Lab and seminars (module 2)

Simulation of cyclic voltammetric experiments; simple experiments aimed to showing some of the most important electrochemical techniques: cyclic voltammetry and chronoamperometry; ultramicroelectrodes; electrochemiluminescence; electrochemical impedance spectroscopy.


Lecture notes will be distributed by the teacher.

Allen J. Bard, Larry R. Faulkner Electrochemical Methods. Fundamentals and Applications, Wiley, New York, 2001 (second edition)

Teaching methods

Taught classes and seminars. Lab experiences.

Assessment methods

Oral examination, with 3 questions. The candidate presents a subject of his/her own choice and at the end of his/her presentation (normally at the blackboard) another 2 questions are asked about other subjects in the program that are somehow related with the chosen one.

The final grade is the results of the evaluation of the overall performance of the candidate.

Teaching tools

Blackboard, Power Point slides, simple experiments in lab.

Office hours

See the website of Francesco Paolucci

See the website of Giovanni Valenti