69087 - Thermodynamics and Kinetics

Course Unit Page

Academic Year 2018/2019

Learning outcomes

At the end of the course, the student knows the thermodynamic principles that regulate the energy exchanges between chemical systems, the conversion between different forms of energy, the chemical balance in multi-component and multi-phase systems, and to solve numerical problems. The student will know how to collect scientific data through the use of chemical-physical techniques and methodologies, obtaining molecular properties from calorimetric and electrochemical data. The student also knows classical chemical kinetics, how to describe the gaseous and liquid motions including the diffusive ones, how to investigate classical kinetic patterns and formulate the reaction laws, knows how to face complex kinetic patterns including the homogeneous and heterogeneous catalytic phase, on the surfaces and on the electrodes.

Course contents

Thermodynamics

Thermodynamic systems.

Heat, work and internal energy.

Entropy and its statistical significance. Absolute temperature.

Thermodynamic equilibrium.

Auxiliary state functions: enthalpy, free energy of Gibbs and Helmholtz. Basic equations. Thermal capacities. Termochimica. Chemical potential.

Phase transitions and equilibria (one-component systems). Phase rule. Partial molar quantities, ideal and real solutions, activities.

Phase transitions and equilibria (two-component systems). Phase diagrams. Reactive mixtures: chemical equilibrium and equilibrium constants.

Electrochemical thermodynamics.

Chemical kinetics with elements of statistical thermodynamics

Kinetic theory of gases. Distribution of molecular velocities. Medium free path and collision frequency. Diffusion and effusion.

Distribution of molecular energies. Theorem of equipartition of energies. Boltzmannn distribution law of populations. Need for quantum mechanics in the treatment of molecular energies.

Transport properties of a perfect gas: diffusion, thermal conductivity, viscosity. Conductivity of electrolyte solutions. Infinite dilution conductivity. Law of independent migration. Mobility of the ions.

Introduction to reaction kinetics. Definition of reaction rate, order of reaction, molecularity, elementary processes, unit of measurement of kinetic constants.

Integration of the kinetic equations (first, second order, case A + B-> C, order n) and their applications. half-life times, relationship between kinetics of elementary processes and stoichiometry.

Non-elementary kinetic processes, constructing their differential kinetic equations. Chemical equilibrium as a non-elementary process. Integration of kinetic equation systems.

Approximation of steady state. Consecutive kinetic equations illustrated by means of the analytical solution, of the stationary and numerical state.

Dependency of the reaction rate from the temperature: Arrhenius equation.

Examples of Lindelmann-Hinshelwood reaction mechanisms. Michaelis-Menten; Lineweaver-Burk.

Phase transfer kinetics. Langmuir's equation. Determination of adsorption energy, life time on surfaces. Adsorption in the presence of reactions.

Elements of statistical mechanics. Derivation of the Boltzmann Distribution Law. Probability and entropy. Gibbs set method. Calculation of internal energy. Partition functions and their connection with thermodynamic functions and chemical potential. Calculation of the equilibrium constant from the partition functions. Transition state theory.

Readings/Bibliography

Lecture notes

For all modules: Atkins, J. De Paula Chimica Fisica, Zanichelli

Thermodynamics: S. Bromberg and K:A. Dill, Molecular Driving Forces, Garland Science, New York, 2002. Chapters: 2, 3, 7, 8

Kinetics and elements of statistical thermodynamics: notes from the lecturer distributed online

Teaching methods

The teaching consists of 11 CFUs including 5 CFUs dedicated to thermodynamics and 6 credits to chemical kinetics with elements of statistical thermodynamics. Both parts include 1CFU of laboratory that will be carried out in part in the Educational laboratory of Physical Chemistry and partly in the Computer Laboratory.

The lectures will be aimed at the theoretical understanding and practical use of tools to solve problems of thermodynamics and chemical kinetics. The lessons will be accompanied by numerical exercises and laboratory activities that will provide students with the opportunity to face real problems both individually and in small groups.

Assessment methods

Kinetics: Two written tests that can be sustained in itinere or as partial tests at the end of the course. The proof consists of a theory question on the first part of the course and the resolution of a complex kinetic mechanism. The II test consists of open questions on the theory carried out in the second part of the course. To be admitted to the evaluation of the II test must have passed the I. The validity of the I test is six months, while if it is supported in itinere allows you to support the II trial by the summer session.

Thermodynamics: written and oral examination. The written exam is aimed at the student's achievement of a practical knowledge of how to treat thermodynamic problems. The oral exam is aimed at the student's understanding of the theoretical methodologies of thermodynamics.

The final mark of the integrated course is defined as the weighted average of the marks reported in the two parts of the course.

Teaching tools

Blackboard, projector, educational laboratories (informatic and experimental)

Office hours

See the website of Sonia Melandri

See the website of Francesco Paolucci

See the website of Francesco Scagnolari

See the website of Giovanni Valenti