00125 - Physical Chemistry I

Learning outcomes

Learning outcomes

Physical Chemistry allows the quantitative and theoretic study of the properties and structure of matter.

Aim of this course is to provide participants with the instruments to understand the basic principles, laws and theories of Physical Chemistry.

The student will develop the ability to solve quantitative problems of chemical type. He will also learn to apply Mathematics and Physics to chemical problems, in such a way to acquire a clear and exhaustive picture of the chemical physics phenomena being studied.

Course contents

Course contents

Thermodynamics. Definitions of temperature and pressure. Gas properties: ideal gases. Equations of state. Gas mixtures. First law of Thermodynamics. PV work. Heat. Enthalpy. Heat capacities. The Joule and Joule-Thompson experiments. State functions and line integrals. The molecular nature of the internal energy. Second law of Thermodynamics. Heat engines. Entropy. Calculation of entropy changes. The thermodynamic temperature scale. Material equilibrium. Entropy and equilibrium. The Gibbs and Helmholtz functions. Thermodynamic relations for a system in equilibrium. Calculations of changes in state functions. Chemical potential and Material equilibrium. Reaction equilibrium. Standard States. Standard enthalpy of reaction. Standard enthalpy of formation. Determinations of the standard enthalpy of formation and reaction. Temperature dependence of reaction heats. Standard Gibbs energy of reaction. Third law of Thermodynamics. Entropies and Third Law. Reaction equilibrium in ideal gas mixtures. Chemical potential in an ideal gas mixture. Ideal-gas reaction equilibrium. Temperature dependence of the equilibrium constant. Ideal-gas equilibrium calculations. Shifts in ideal-gas reaction equilibrium. One component phase equilibrium. The phase rule. The Clapeyron equation.

Real gases. Compression factors. Real-gas equations of state. Condensation. Critical data and equations of state. The critical state. The law of corresponding state. Solutions. Solution composition. Partial molar quantities. Mixing quantities. Determination of partial molar quantities. Ideal solutions. Thermodynamic properties of ideal solutions. Ideally dilute solutions and their thermodynamic properties. Non ideal solutions. Activities, activities coefficients and their determination. Activities coefficients on the molality and molarity concentration scales. Solutions of electrolytes. Determination of electrolyte activity coefficients. The Debye-Huckel theory of electrolyte solutions. Standard-state thermodynamic properties of solution components. Non ideal gas mixtures. Reaction equilibrium in non ideal systems. The equilibrium constant. Reaction equilibrium in non electrolyte solutions, in electrolyte solutions, involving pure solids or pure liquids, in non ideal gas mixtures. Temperature and pressure dependences of the equilibrium constant. Multi component phase equilibrium. Colligative properties. Vapor-pressure lowering. Freezing point depression and boiling point elevation. Osmotic pressure. Two component phase diagrams. Two component liquid-vapor equilibrium. Two component liquid-liquid equilibrium. Two component liquid-solid equilibrium. Structure of phase diagrams. Solubility. Surface chemistry. The inter phase region. Curved interfaces. Thermodynamics of surfaces. Electrochemical systems. Electrostatics. Thermodynamics of electrochemical systems. Galvanic cells. Types of reversible electrodes. Thermodynamics of galvanic cells. Standard electrode potentials. Classification of galvanic cells. Liquid-junction potentials. Applications of EMF measurements. Batteries. Ion-selective Membrane electrodes. Membrane equilibrium. The electrical double layer. Dipole moments and polarization. Intermolecular forces. Hard sphere interaction potential. Lennard-Jones Potential. Hydrogen bond. Kinetic-molecular theory of gases. Pressure of an ideal gas. Temperature. Distribution of molecular speeds in an ideal gas. Applications of the Maxwell distribution. Collision with a wall and effusion. Molecular collision and mean free path.

Introduction to concepts of statistical thermodynamics. Configuration of a system and deduction of Boltzmann distribution. Molecular partition function. Relationship between internal energy of non-interacting molecules and molecular partition function. Heat capacity. Boltzmann formula for entropy. Statistical entropy and molecular partition function. Canonical ensemble, canonical distribution and canonical partition function. Internal energy and entropy in terms of canonical partition function. Fundamental relations. Translational, rotational, vibrational and electronic partition functions.

Readings/Bibliography

P.W. Atkins, J. de Paula - Physical Chemistry - Oxford University Press

D.A. McQuarry, J.D. Simon  Physical Chemistry - Physical Chemistry: A Molecular approach - University science Books

Teaching methods

Teaching methods

Each lesson will consist in the explanation of the theory related to a portion of the course program and in the solution of some numerical exercises. Students will be stimulated to provide the solution of the problems. The aim is to give the students many numerical examples of the physical chemistry theory applications.

Thermodynamics tables will be extensively used. If necessary the students will solve the proposed exercises using graphical methods. Each student should use its own pocket scientific calculator.

Assessment methods

Assessment methods

The student will have one written and one oral exams on the various subjects of the course. The written test will precede the oral exam. In the written test the student must show his/her skills in solving correctly physical chemistry problems. A number of points are attributed to each problem depending on its difficulty, with a maximum of 30. The student can use its pocket scientific calculator. He/she can look for physical chemistry property values in the thermodynamics tables. The time at disposal is 4 hours. It is possible to consult physical chemistry books and lecture notes. The written test is passed if the student gets at least 18/30 marks, being 30/30 the full marks. Once the written exam is passed the student can go on with the oral one. He/she will be requested to answer some questions about the physical chemistry program of the course. The oral exam is passed if the student gets at least 18/30 marks.

The average of the marks of the written and oral examinations will constitute the final mark, with full marks still 30/30.

Teaching tools

Office hours

See the website of Elisabetta Venuti

See the website of Elisabetta Canè