Learning outcomes of the course unit
The student will be provided the fundamental knowledge of the chemical thermodynamics and kinetics. Particular attention will be devoted to the evaluation of the energy balances and to the discussion concerning the equilibrium conditions in chemical and biological processes and in some selected cases of phase transitions in simple systems. In the ambit of the chemical kinetics some mechanisms of biological interest will be dealt with.
General and inorganic chemistry.
Course contents summary
System and surroundings. State of the system, intensive and extensive variables. Thermodynamic equilibrium, reversibile and ed irreversible changes. The temperature concept. The zeroth law of Thermodynamics.
The gaseous state.
The laws of Boyle, Charles, Gay-Lussac, Avogadro. The ideal gas. The equation of state of the ideal gas. Mixtures of gases and Dalton’s law. Real gases. The compression factor. The van der Waals equation. The P-V diagram for the real gas. Liquefaction.
The laws of Thermodynamics.
Work and heat. Exothermic and endothermic processes. Work of expansion. The first law of Thermodynamics Internal energy and enthalpy. Heat capacity at constant pressure and at constant volume. The calorimeter. The latent heat in the phase transitions. Thermodynamics of the ideal gas: isothermal, isobaric, adiabatic, isochoric changes. Thermochemistry: the heat of reaction. Standard enthalpy of reaction. Enthalpy of the physical changes. The Hess’s law. The Kirchoff’s law. The second law of Thermodynamics. The concepts of spontaneity and irreversibility. Entropy: statistical and thermodynamic definition. System and surroundings: the Clausius inequality. Entropy changes: isothermal expansion of an ideal gas, mixing of ideal gases, phase transitions, heating processes. The third law of Thermodynamics. Absolute entropies. Entropy changes in chemical reactions. Gibbs and Helmholtz functions. dG of a process. The meaning of dA, dG in terms of maximum work. Standard dG of reaction. The Gibbs-Helmholtz equation. Phase equilibria: the Clapeyron and Clausius-Clapeyron equations. Phase diagrams.
Concentration units. Partial molar quantities. Chemical potential. Thermodynamics of mixing. The Raoult’s law. Ideal solutions. The Henry’s law. Ideal diluted solutions. The activity. Colligative properties: lowering of the vapor pressure, elevation of the boiling point, depression of the freezing point, osmosis. Electrolyte solutions. Electrical conductivity in solution. The Kohlrausch’s law. The Ostwald’s dilution law. Ionic mobility. Thermodynamics of the ions in solution: formation energies. Mean ionic activity and chemical potential of electrolyte solutions. Salting-in and salting-out effect. Colligative properties of electrolyte solutions. Donnan effect.
Chemical reaction in a system of ideal gases. Extent of reacion. Reaction quotient and equilibrium constant. Real gases: fugacity. Chemical equilibrium in solution. Heterogeneous equilibria. van’t Hoff’s equation. Le Chatelier’s principle
The reaction rate. Reaction order and rate constant. Rate laws and integrated rate laws. Zero, first and second order reactions. The determination of the rate law. The Arrhenius eqution. Energy of activation and transition state. Opposite reactions. Consecutive reactions. Kinetically determinant state apporximation. Steady state approximation. Pre-equilibrium. Catalysis: general outline. Enzymes. The Michaelis-Menten mechanism.
R. Chang, Chimica Fisica, vol. 1, Ed. Zanichelli 2003.
P. Atkins, J. De Paula, Elementi di Chimica Fisica, Ed. Zanichelli 2007.
P. Atkins, J. De Paula, Chimica Fisica, Ed. Zanichelli 2004.
Any other offical chemical Physics textbook can be conveniently used.