Physical Chemistry Ii with Lab

Chemical Kinetics: Rate expressions and rate constants. First order, second order, zero order reactions. Parallel, consecutive and opposite reactions, the steady state approximation; reaction mechanism, rate determining step.
Temperature effects on reaction rates: the Arrhenius equation, the collisions theory for bimolecular and unimolecular reactions; the transition state theory, potential energy surfaces, the Eyring equation, activation parameters.
Acid-base and enzymatic catalysis. Heterogeneous catalysis: adsorption, the Langmuir-Hishelwood mechanism. Chain reactions, explosive reactions. Kinetic aspects of photoinduced reactions and of photocatalysis.
The thermodynamic description of mixtures. The basis of chemical thermodynamic. Non ideal behaviour, fugacity. Phase transitions: phase stability, phase diagrams. The thermodynamics of mixing; ideal, ideal-dilute and real solutions. The solvent activity, the solute activity. Colligative properties. Phase diagrams of binary systems: temperature-composition diagrams, liquid-liquid phase diagrams, liquid-solid phase diagrams.
Molecular interactions. Electric properties of molecules: electric dipole moments, polarizability, polarization. Interactions between dipoles, repulsive and total interactions.

Goals
Electrochemistry
Introduction to the electrochemistry and the kinetics of electrochemistry, discussing both theoretical and application-oriented aspects. Ability in describing electrolysers and batteries, their working condition and parameters. Capacity in discussing the fundamental aspects of kinetics of electrochemistry.
Laboratory
Introduce students to face and drive chemical and electrochemical kinetics experiments.

acquired skills
Electrochemistry
Figures of merit of electrochemical cells. Comprehension of double layer structure and double layer potential; ability in defining and calculating the potentials of galvanic half-cell and cell: Nernst equation. Comprehension of solvent-ion and ion-ion interactions. Ability in handling the Butler Volmer and Tafel equations and relevant plots.
Laboratory
Capacity to plan experiments for investigating the kinetics of chemical and electrochemical reactions.

Course content
Electrochemistry
Introduction to fundamental electrochemical phenomena. The structure of the double layer: Volta, surface and Galvani potentials. The models describing the double layer: Helmholtz, Gouy-Chapman, Stern. Nernst equation. The electrical capacity of the double layer. Solvent and electrolyte effects. Kinetics in electrochemistry: Butler Volmer equarion, approximation at low and high overpotentials. Tafel equation. Exchange current density and symmetry factor. Diffusion limit current density.
Laboratory
Acidic hydrolysis of esters; bromination of ketones; clock reaction; enzymatic catalysis; exchange current density and symmetry factor determination for oxygen reduction reaction.

Suggested prerequisites
Mathematics, Physics, Laboratory of Physical chemistry I.

Reference material
Slides presented and discussed in the classroom will be provided.
Recommended texts:
· J.O.M. Bockris, A.K.N. Reddy "Modern Electrochemistry - 2A" Kluwer Academic Publishers;
· Allen J. Bard, Larry R. Faulkner; "ELECTROCHEMICAL METHODS: Fundamentals and Applications" - Wiley and Sons INC, New York.
· P. Atkins and J. de Paula. "ATKINS' PHYSICAl CHEMISTRY - 8th edition". W. H. Freeman and Company, New York.

Prerequisites
Laboratory of Physical chemistry I must be already attended.

Assessment method (use at least 2 lines):
Oral. Student must be able to discuss topics presented during the lectures. Student will be asked to face some mathematical exercises and problems, connected with the thermodynamics and the kinetics of electrochemistry. Capacity to comment and discuss graphs, linked with electrochemical parameters, will be tested. Laboratory outcomes will be presented and discussed.

Language of instruction
Italian

Attendance Policy:
Students are warmly asked to attend the lessons
Students must attend the laboratory.

Mode of teaching:
Traditional

Website
https://ariel.unimi.it/