Academic Year 2016/2017 - 2° Year
Teaching Staff: Carmelo LA ROSA
Credit Value: 8
Scientific field: CHIM/02 - Physical chemistry
Taught classes: 40 hours
Term / Semester:

Learning Objectives

The student must learn the quantitative notions and problem solving of: weak forces and interactions, conservation and energy transfers in the form of heat, entropy and thermal machines, chemical equilibrium, phase diagrams, electrochemistry of reversible processes.

Detailed Course Content

Matter aggregation states. /2/

Macroscopic world, microscopic world and correlations properties - structure. Solid, liquid, gaseous and plasma state. Guiding forces in the assembly of condensed phases. Morse curve, interaction potentials and Madelung's problem.

Properties of the gases./4/

Perfect gas state equation; molar mass; perfect gas mixtures, ideality deviations and real gas state equations. The compressibility factor; actual gas mixtures.

First principle of Thermodynamics./3/

Heat, work and energy conservation. Expansion and compression work. Concept of reversibility and spontaneous phenomena. Route functions. Status and differential functions.


Specific heat and heat capacity. Internal energy and temperature; enthalpy and temperature: relations between specific heat. Isothermal and adiabatic processes - reversible or irreversible. The zero law of thermodynamics.


Reaction enthalpy and Hess law; Standard enthalpy, relations between ΔH and ΔU; ΔH depending on temperature. Ion enthalpy in solution. Born-Haber cycle.

The second principle./10/

The second principle. Efficiency of thermal machines and Carnot cycle. The refrigerant of Carnot. Definition of entropy. Entropy and cyclic integral. General test for the cyclic integral of entropy. The inequality of Clausius. Exact differential properties. Entropy in operation of T,V and T,P. Changes in state and entropy.

The third law./3/

Entropy variations for the ideal gas. The standard status for the ideal gas. The third law and standard entropy. Entropy changes for a chemical reaction and temperature dependence.

Entropy and probability./5/

Entropy, probability and spontaneity. Probability, thermodynamic probability and entropy. General form for thermodynamic probability. Energy distribution. Third principle, entropy of mixing and point defects. Apparent exceptions - and not - to the third law.

Spontaneity and equilibrium./7/

Entropy of the system, environmental entropy and conditions of spontaneity and equilibrium. The Helmotz function and the Gibbs function. The fundamental equation of thermodynamics. Gibbs function and variations of T, P and composition. The chemical potential. Chemical potential of ideal gas and real gases. The concept of formal uniqueness and fugacity.

Phase changes ./4/

Chemical potential and principle of phase stability. First order phase transitions. Second order phase transitions. Water status diagram. Surface, surface tension and capillarity.

Mixtures and activity./4/

Molar volume in the mixtures. The law of Gibbs-Duhem. Mixing and spontaneity processes. Solutions of non-volatile solutions; colligative properties: ebullioscopy, cryoscopy and osmosis. Mixtures of volatile liquids: the concept of activity. The limit laws of Raoult and Henry. The limit equations of Chemistry.

Chemical equilibrium./4/

The criterion of spontaneity and equilibrium for a chemical reaction. Equilibrium, the equilibrium constant and the influence of catalysts, inert substances, temperature and pressure.


Ion activity in Debye-Huckel's solution and law. The concept of ionic strength and the influence on solubility. Form of the limit laws of dilute solution chemistry. Electrochemical potential. Most common electrodes and electrochemical cells. Standard electrochemical potentials and electrochemical series. The equation of Nernst.

Phase equilibrium./10/

Free mixing energy and phase diagrams. Phase rule, lever rule and phase diagrams. One component systems. Two component systems. Two-component systems with one or more products. Three-component systems. Influence of ionic force.

Textbook Information

Suggested books:

- P. Atkins, J. De Paula : Chimica Fisica (Zanichelli). English and Italian version

- G.W. Castellan : Physical Chemistry (Addison-Wesley Pu. Co.).

- S. Capasso : La Chimica Fisica attraverso esercizi (Loghia)

- G.K. Vemulapalli : Chimica Fisica (EDISES).