Learning outcomes of the course unit
The course deals primarily with equilibrium properties of macroscopic systems, basic thermodynamics, chemical equilibrium of reactions in gas and solution phases, and rates of chemical reactions.
Mathematics and physics exhaminations.
Course contents summary
The zero law of thermodynamics and the gas properties. Primitive concepts: system, environment. Thermodynamic state functions. The temperature and the zero Law of thermodynamics. The state equation of the ideal gas. Real gases. Van der Waals equation. The principle of corresponding states.
The First law of Thermodynamics. Work, heat and internal energy. The first law of thermodynamics. Expansion work. Heat capacity. The properties of the internal energy. The enthalpy and the transformations at constant pressure. Transformations of the ideal gas. Thermochemistry. Variations of enthalpy in chemical reactions and phases transformations. Standard state of elements and compounds. The standard enthalpies of formation and the reaction enthalpies. The Hess law. The temperature dependence of reaction enthalpies.
The second law of Thermodynamics. The Kelvin and Clausius formulations of the second law. The entropy. The Carnot cycle. The Clausius inequality and the irreversible transformations. Variations of entropy in elementary transformations. The third law of Thermodynamics. The molecular interpretation of the entropy. Criterion for spontaneity for isolated systems. The Helmoltz energy and the spontaneous transformations at constant volume and temperature . The Gibbs free energy and the spontaneous transformations at constant pressure and temperature.
The Gibbs energy and the chemical potentials. The fundamental equation of thermodynamics. The Maxwell relations. The effects of the pressure and temperature on the Gibbs energy. The chemical potential of pure substances. The chemical potential of real gases.
Physical transformations of pure substances. Phases diagrams. The stability of phases. Phases boundaries. The triple point and the critical point. The thermodynamic criterion of the phases equilibrium. The Clapeyron equation and the phase boundaries. The Ehrenfest classification of the phase transitions.
The solutions. Partial molar quantities. Chemical potentials. The Gibbs-Duhem equation. The thermodynamics of mixing. Chemical potentials in ideal solutions. The Raoult law. The Henry law. The properties of solutions. Excess functions. Colligative properties. The thermodynamic activities. The solvent activity. The solute activity. The regular solutions.
Phase diagrams. Phases, components and degrees of freedom. The Gibbs phases rule. Two components systems. Vapor-liquid phases diagrams. Liquid-liquid phases diagrams. Liquid-solid phases diagrams.
Chemical equilibrium. The Gibbs free energy of reaction and the spontaneity of chemical reactions. The standard free energy of reaction, the reaction quotient and the equilibrium constant. Reactions between ideal gases. Reactions in solution. The effect of temperature and pressure on the chemical equilibrium.
Electrochemistry. The thermodynamic properties of ions in solution. The ion activities. The Debye-Hueckel limit law. The electrochemical cells. Half-reactions and electrodes. Standard potentials. Nerst equation. Applications of standard potentials.
Chemical kinetics. The reaction rate: definition and measurements. The kinetic laws and the order of reaction. Integrated forms of the zero, first and second order kinetic laws. The effect of the temperature on the reaction rates.
Atkins,P., and J. de Paula. PhysicalChemistry. New York, NY: W.H. Freemanand Company, 2001. ISBN: 0716735393.