开始时间: 01/19/2015 持续时间: 11 weeks
授课老师： Christopher J. Cramer
Statistical Molecular Thermodynamics is a course in physical chemistry
that relates the microscopic properties of molecules to the macroscopic behavior
of chemical systems. Quantized molecular energy levels and their use in the
construction of molecular and ensemble partition functions is described.
Thermodynamic state functions, their dependence on the partition function, and
their relationships with one another (as dictated by the three Laws of
Thermodynamics) are all examined in detail. Analysis and demonstration takes
place primarily in the context of ideal and real gases. This eight-week course
covers slightly more than half of a typical semester-long course in chemical
thermodynamics. Typical topics to be addressed subsequently would be phase
equilibria, liquids, solutions of non-electrolytes and electrolytes, and
chemical reaction equilibria.
who successfully complete the course will be able to predict how
changes in molecular properties will influence the macroscopic behavior
of those substances; they will understand the relationships between
energy, heat, and work, and be able to predict how much work can be
extracted from a given chemical process under various sets of
conditions; they will understand the role of entropy in physical and
chemical processes; and they will be able to engineer conditions to make
chemical reactions spontaneously favorable (or not). Students will also
become adept with differential calculus as a tool to derive and
manipulate relationships between connected thermodynamic variables and
Overview of thermodynamics and its importance and utility.Week 2:
Molecular energy levels from quantum mechanics.
Ideal gases; Equations of state; PV diagrams.Week 3:
Gases and liquids; Corresponding states.
Dispersion; Intermolecular interactions; Real gases.
Boltzmann probability and connection to energy; Ensemble properties.Week 4:
Heat capacity; Partition functions.
Atomic and molecular partition functions; Connections to quantum mechanics (statistical thermodynamics).
Electronic and translational partition function for gases; Rovibrational partition functions.Week 5:
First law of Thermodynamics; Energy; PV Work; State functions.Week 6:
Adiabaticity; Reversibility; Heat and work.
Enthalpy; Heat capacity redux; Heat of transition.
Enthalpy of chemical reaction; Heat of formation; Standard-state enthalpy.
Second law; Order/disorder; Entropy.Week 7:
Spontaneity and entropy; Statistical thermodynamics and entropy; Reversibility.
Entropy and the interconversion of heat and work; Entropy and the partition function.
Third law; Temperature limits; Perfect crystals; Phase transitions.Week 8:
Experimental determination of third-law entropies; Standard-state entropy.
Helmholtz and Gibbs free energies; Ensemble conditions.
Maxwell relations; Ideal gas state functions; Independent variables.
Gaseous standard state; Gibbs-Helmholtz equation; Fugacity.
This introductory physical chemistry course examines the connections between molecular properties and the behavior of macroscopic chemical systems.