Lectures MWF, 9-10am, LRSM Auditorium. Change to 8:30-10am M,W?
Instructor Peter K. Davies (200 LRSM; 898-1013; davies@seas.upenn.edu
)
Office hours: 2:00-3:30pm, Friday.
Webpage: www.seas.upenn.edu/~mse260 (used to post problem sets and solutions;
Text: check regularly.)
Lecture notes/handouts + Introduction to the Thermodynamics of Materials,
D.R. Gaskell, McGraw-Hill, 4th edition.
Course Description
Principles of chemical thermodynamics as applied to macro- and nano-sized materials.
The course covers the fundamentals of classical thermodynamics focusing on the calculation and prediction of phase stability, chemical reactivity and synthesis of materials systems. The size-dependent properties of nano-sized systems are explored through the incorporation of the thermodynamics of surfaces. The prediction of the phase stability of two and three component systems is illustrated through the calculation and interpretation of phase diagrams for a variety of materials systems.
1.
Course Outline
Fundamental Principles and Functions. 1st law of thermodynamics: state
2.
3.
4.
5. functions; path independence, heat and work, internal energy, enthalpy, heat capacity. Types of paths: adiabatic, isothermal, isochoric, isobaric. G2.
2nd law of thermodynamics; reversibility; entropy; equilibrium. Calculation of entropy changes. Entropy and disorder. G3 &4.
Free energy. G5.
Third Law of Thermodynamics. Calculation of enthalpy, entropy, free energy changes. Standard states. Utilizing experimental data. G6.
Phase equilibrium in a one component system. Vapor pressure, co-existence of phases, chemical potential. 1 component phase diagrams. Phase rule. G7
Reaction equilibrium in gaseous systems; standard state for a gas, partial 6.
7. pressure, free energy of mixing, chemical potential. Reaction equilibria; equilibrium constant; meaning of standard free energy change. Why does Le
Chatelier’s principle work ? Balance between chemical stability and entropy of mixing. G11
Heterogeneous equilibria; standard state for solids and liquids, reaction equilibria for metal/metal oxide systems. Ellingham diagrams. Multiple oxidation states in transition metal oxide systems. G12.
8.
Thermodynamics of condensed solutions; Raoult's law; ideal solutions, activity, chemical potential, free energy of mixing in solid solutions, meaning of random mixing. Non-ideal solutions; activity coefficient, excess free energy of mixing, enthalpy of mixing. Mixing models for binary systems; regular solution model, interaction parameter, stability of inorganic solid solutions; relation of mixing energetics to crystal structure. G9
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9.
Phase stability in binary systems. Free-energy - composition relationships; immiscibility in the solid state, common tangents. G 10
10.
Ideal Liquid – ideal solid equilibria; calculation of phase diagrams for ideal solid -liquid coexistence. G 10
11.
Ideal Liquid- non-ideal solid equilibria: eutectic systems, peritectic systems.
Free energy of mixing curves, activity-composition relations. G 13
12.
Binary Phase Diagrams. Cooling curves in binary systems, reading complex diagrams, intermediate compounds, congruent and incongruent melting.
13.
Size dependent properties of nanocrystals: Surface tension, surface free energy,
Kelvin effect. Variation of melting point and solid state phase transformations with particle size and shape in the nano-regime. Changes in phase stability in the nano-regime; nano-sphere and nanowire melting.
14.
Ternary Phase diagrams. (if time permits).
Course Objectives:
1. To provide an understanding of the classical thermodynamic approach to the energetics of complex systems.
2. To provide a foundation for the application of the principles of thermodynamics
3. To provide a consistent picture of thermodynamics concepts when applied to phase equilibria
4. To provide an understanding of the effect of the size dependence on the stability and chemical reactivity of materials systems.
5. To provide the background for other courses in the curriculum
Course Outcomes:
1. Predict chemical reactivity and equilibrium of nano and macro-scale materials at varying temperatures and pressures.
2. Understand key factors affecting the phase diagrams of one, two and three component materials systems.
3. Interpret and read the phase diagrams of materials.
4. Understand thermodynamics for advanced courses: thin film growth, kinetics, materials synthesis, and stability/properties of nano-scale materials.
Assessment Tools:
1. Homework problems, weekly (compulsory). Note: problem sets must be handed in on the due date; 10% of the grade subtracted for each day late.
2. Two mid-semester examinations and one final exam.
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Grades:
Problem sets (10%)
Midterm 1 (25%)
Midterm 2 (25%)
Final (40%)
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