On completion of the module, students will be able to:
A. Statistical thermodynamics
1) Derive the Boltzmann distribution and use it to predict the populations of states in systems at thermal equilibrium. 2) Define what is meant by the molecular partition function, interpret it, and, in certain simple cases, calculate it. 3) Develop closed approximations to the partition function, where exact analytical functions cannot be obtained, for certain simple cases. 4) Describe how thermodynamic information, such as the internal energy or the statistical entropy of a system, may be extracted from the partition function. 5) Generalize the statistical thermodynamic approach to describe systems that are composed of assemblies of interacting particles. 6) Employ the partition function to obtain any thermodynamic function, for example, the Helmholtz energy, the pressure, the enthalpy, the Gibbs energy, for a system. 7) Factorize the molecular partition function into a product of translational, rotational, vibrational and electronic contributions. 8) Use spectroscopic data to calculate the molecular partition function and, from this, to calculate thermodynamic properties in order to gain insight into a variety of physical, chemical and biological processes (mean energies/heat capacities, equations of state/molecular interactions in liquids, residual entropies, and equilibrium constants).
B.Advanced Kinetics
1) Describe molecular motion in gases using the kinetic model of gases. 2) Provide a quantitative explanation for rates of bimolecular elementary reactions using the collision theory. 3) Understand how the RRK model predicts the steric factor and rate constant of unimolecular reactions. 4) Describe the factors that affect the rates of diffusion-controlled reactions in solution and understand how the material balance equation takes account of diffusion, convection, reaction. 5) Understand how the concepts of statistical thermodynamics can be applied to the calculation of rate constants using the Eyring equation of the transition state theory. 6) Describe advanced experimental techniques used to monitor the dynamics of molecular collisions. 7) Describe the progress of selected reactions in terms of the motion of molecules along and through potential energy surfaces.

This module is an introduction to advanced thermodynamic and kinetic analysis of chemical processes. In the first part, statistical thermodynamics is introduced. The Boltzmann distribution is derived and used to predict the populations of states in systems at thermal equilibrium. To this end, the partition function is defined, interpreted, and, in some cases, calculated. It is shown how thermodynamic information may be extracted from the partition function. Also, a generalized approach to describing systems that are composed of assemblies of interacting particles is demonstrated. To calculate chemically significant quantities, partition functions are related to thermodynamic functions. Formulas that permit partition functions to be factorized into each mode of motion are developed. On this basis, partition functions are applied to gain insight into a variety of physical, chemical and biological processes. In the second part, the dynamics of molecular collisions are described in detail in terms of the motion of molecules along and through potential energy surfaces. The factors that affect the rates of chemical reactions are reviewed. Both the collision theory and the transition state theory are introduced in order to provide a quantitative explanation for reaction rates in gases and in liquids.

CHEM30320 Chemical Thermodynamics and Physical Transformations and CHEM30060 Quantum Mechanics and Molecular Spectroscopy

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