91207 - MOLECULAR ELECTROCHEMISTRY

Conoscenze e abilità da conseguire

At the end of the course the student has acquired the theoretical and experimental basis for the comprehension and investigation of the physical-chemical processes associated to electron transfer processes, either heterogeneous or homogeneous and intramolecular.

Contenuti

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. The kinetic overpotential. Inner sphere processes: the HER and OER. Volcano plots, Tafel plots and the Potential Determining Step concept (thermodynamic overpotential).
   
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)

Digital 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.

Testi/Bibliografia

Lecture notes distributed by the teacher are available on Virtuale.

Allen J. Bard, Larry R. Faulkner, Henry S White Electrochemical Methods. Fundamentals and Applications, Wiley, New York, 2022 (third edition)

Metodi didattici

Taught classes and seminars. Lab experiences.

As concerns the teaching methods of this course unit, all students must attend Module 1, 2 [https://www.unibo.it/en/services-and-opportunities/health-and-assistance/health-and-safety/online-course-on-health-and-safety-in-study-and-internship-areas] on Health and Safety, online.

Modalità di verifica e valutazione dell'apprendimento

The evaluation is based on 2 alternative types of exam (at choice of the student):

1) a written exam in which the candidate prepares a written elaborate (1-2 pages) about one of the topics of the course (chosen out of a list of 4-5 topics) plus answers 5-6 questions to verify the general knowledge of the program

or

2) oral exam where the candidate presents (normally at the blackboard) a subject of his/her own choice which will then be briefly discussed with the examiners. Additional questions concerning other parts of the program will be asked

The final grade is the results of the evaluation of the overall performance of the candidate in either type of exam.

Students with learning disabilities (LD) or temporary or permanent disabilities: please contact the relevant University Office ([https://site.unibo.it/studenti-con-disabilita-e-dsa/it]) promptly. This office will advise the affected students of any accommodations. These accommodations must be approved by the instructor at least 15 days in advance, who will evaluate their suitability, also taking into account the course's learning objectives.

Strumenti a supporto della didattica

Blackboard, Power Point slides, simple experiments in lab.

Orario di ricevimento

Consulta il sito web di Francesco Paolucci

Consulta il sito web di Giovanni Valenti