1 Basic of thermodynamic by Dr. Srimala room 2.07 Albert Einstein

2 School Of Materials And Mineral Resources Engineering Engineering Campus Course Structure Form Course Code:EBB 236 Course Title : Material Thermodynamic Course Unit : 3 Type of Course : Core OBE

3 Contribution of Assessment :  Final Examination 70%  Coursework : 30% Assessment Methods for Coursework:  Test 1 (Dr.Projjal Basu) =10marks  Test 2 (Dr. Srimala)= 7 marks  Quiz/ Tutorial – 5marks  Assignment and Report Writing (PBL)-8 marks

4 Course Outcomes (CO) : At the end of the course, the students should be able to:  interpret the fundamental aspects of thermodynamics which are related to general principles of matter such as structure and properties  predict behaviors of matters based on thermodynamic principles as it undergoes various changes in condition  design new process and improve the existing process using thermodynamic principles  create materials with desired properties.  derive relationship among the properties of matter based from few general and pervasive principles (the law of thermodynamics)  solve problems of practical interest using thermodynamic equation

5 Teaching Plans / Syllabus Equilibrium (week 8) Phase Equilibrium Liquid-Vapor Phase Equilibrium Gibbs Phase Rule P-T Phase Diagrams & Clausius Clapeyron Equation The Clausius-Clapeyron Equation Liquid-Vapour (Vaporization) Equlibrium Triple Point Calculation solid-liquid-gas triple point

6 Teaching Plans / Syllabus Thermodynamic of Phase Diagram (week 9 and 10) Thermodynamically stable phase Unary Heterogeneous Systems P - T Diagram -Unary, Single Component Phase Diagram logP – 1/T Diagram -Unary, Single Component Phase Diagram Conclusion-Unary P - T Diagrams G-T Phase Diagrams G - T Diagram - Unary, Single Component Phase Diagram – V G-T Diagram - Unary, Single Component Phase Diagram - L,V G-T Diagram - Unary, Single Component Phase Diagram- ,L,V G- T Diagram - Single Component Phase Diagram - , , L, V 3.5 Metastability

7 Teaching Plans / Syllabus Thermodynamic of Phase Diagram Chemical Potential and Gibbs Free Energy of Single Component Phases Enthalpy & Entropy of Transformation Compute Phase Equilibria from Free Energy Relations Binary System Binary liquid system Binary solutions with total solid solubility Binary systems without solid solution Free Energy-Composition (G-X) Diagram Free energy diagrams of total solubility systems Free energy diagram for binary solutions with a miscibility gap Free energy diagram of binary systems without solid solution (eutectic system) Phase boundary Calculations

8 Teaching Plans / Syllabus Crystal Defects (week 11) Perfect Crystal Processing, Microstructure and Properties Crystal defect Vacancies and Interstitials Impurity Atoms Point Defects in Ionic Crystals Defect Complexes Vacancies formation Divacancy Defects in the ionic compounds Kroger-Vink notation Frenkel Defect Schottky defects

9 Teaching Plans / Syllabus Phase Transformation (week 12) Homogeneous Nucleation Gibbs Free Energy Energies involved in homogeneous nucleation Critical radius & Critical free energy Nucleation rate Heterogeneous Nucleation Energies Involved in heterogeneous nucleation

10 Teaching Plans / Syllabus Energy of Interfaces (week 13) Surface tension  Surface free energy Surface stress Equilibrium shape of surfaces Presence of secondary phase Bulk Face Edge and Corner Applications

11 References Robert T. DeHoff, Thermodynamic in materials science, Mc Graw Hill,1993 Mac Geon Lee, Chemical thermodynamic for Metals and Materials, Imperial College Press, David V.Ragone, Thermodynamics of Materials, Volume I, John Wiley & Sons, Inc. David V.Ragone, Thermodynamics of Materials, Volume II, John Wiley & Sons, Inc. John D. Verhoeven, Fundermentals of Physical Metallurgy,, John Wiley & Sons, Inc,1975

12 Basic of thermodynamic Content 1.0What is Thermodynamics 2.0Thermodynamic Systems – Definitions 3.0Thermodynamic State Properties 4.0Idealized Thermodynamic Processes 5.0Spontaneous Reaction Direction

13 1.0What is Thermodynamics Thermodynamics: A set of of mathematical models and concepts that allow us to describe the way changes in the system state (temperature, pressure, and composition) affect equilibrium.

14 Why are we interested in studying thermodynamics? Thermodynamics allows us to predict the direction of natural change (reactions) and the final state (equilibrium composition) of a system.

15 Examples If we know the composition of a soil solution or a groundwater in contact with soil or aquifer solids, thermodynamics allows us to predict: If solids will dissolve If solids will precipitate If the system is at equilibrium When several minerals are present and in contact with the same aqueous phase, we can predict the direction of mineral evolution. E.g., we may predict that a granites mineral composed of quartz, feldspar, and mica will eventually weather into smectite clay

16 In discussing thermodynamics, we’ll refer frequently to systems Mixture of stuff that may react (t=0) System (contained in some fashion) 2.0Thermodynamic Systems - Definitions

17 Isolated System: No matter or energy cross system boundaries. No work can be done on the system. Open System: Free exchange across system boundaries. Closed System: Energy can be exchanged but matter cannot. Adiabatic System: Special case where no heat can be exchanged but work can be done on the system (e.g. PV work).

18 What information can thermodynamics give us about a system? X X X X X Thermodynamics deals with macroscopic phenomena – measurable at the laboratory scale. X X Provided by Thermodynamics? Yes No Whether change will occur Direction of change Rate of change Reaction mechanisms Microscopic processes Final composition of system

19 3.0Thermodynamic State Properties Extensive: These variables or properties depend on the amount of material present (e.g. mass or volume). Intensive: These variables or properties DO NOT depend on the amount of material (e.g. pressure, and temperature).

20 4.0Idealized Thermodynamic Processes Irreversible: Initial system state is unstable or metastable and spontaneous change in the system yields a system with a lower-energy final state. Reversible: Both initial and final states are stable equilibrium states and the path between them is a continuous sequence of equilibrium states. NOT ACTUALLY REALIZED IN NATURE.

21 5.0Spontaneous Reaction Direction