Materials 2D03: Solution Thermod namics Sol tion Thermodynamics

Calendar Description: Thermodynamic activity in solid and liquid systems: Gibbs energy of solutions; binary phase diagrams, equilibrium constant; reaction equilibria in gases; Ellingham diagrams. Three lectures, one tutorial; second term Prerequisite: CHEM 1A03 or 1E03; and MATLS 2B03 Antirequisite: MATLS 2B06 Lecture Hours: Tuesday, Thursday and Friday at 11:30-12:20 T13/125; Tutorial Hours: Thursday 9:30-10:20 in BSB-106

Course Co rse Description

Instructors: Dr G Xu (JHE 357/S) Ext: 27341 xugu@mcmaster ca Dr. G. (JHE-357/S) 27341,xugu@mcmaster.ca TAs: Xinxin Zhao (JHE-356), Ext: 23316, zhaox8@mcmaster.ca Morteza Ghasri Khouzani (JHE-A204), Ext. 27326, ghasrim@mcmaster.ca ghasrim@mcmaster ca Text Book: D.R. Gaskell, "Introduction to the Thermodynamics of M t i l " 5th ed., D R G k ll "I t d ti t th Th d i f Materials" d Taylor & Francis, 2008 (The 4th edition is not very different). Assessment: 5 assignments 2 hour midterm test 3 hour final examination

20 % 30 % (at a date to be determined) 50 %

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Course Communication Co rse Comm nication

The Instructor and TA will be communicating with you by email regarding course content and deadlines for work. It is your responsibility to maintain an email address that is valid and to ensure that the mailbox is not full. There is a password-protected website for this course that will have course notes and other information posted on it: https://mselabs.mcmaster.ca/ Username: mselabs password: gryh386

University Policy Uni ersit Polic - Discrimination

The Faculty of Engineering is concerned with ensuring an environment that is free of all discrimination. If there is a problem, individuals are reminded that they should contact the Department Chair, the Sexual Harassment Officer or the Human Rights Consultant, as the problem occurs.

University Policy Uni ersit Polic Academic Honest Honesty

"Academic dishonesty consists of misrepresentation by deception or by other fraudulent means and can result in serious consequences, e.g. the grade of zero on an assignment, loss of credit with a notation on the transcript (notation reads: "Grade of F assigned for academic dishonesty"), and/or suspension or expulsion from the university. It is your responsibility to understand what constitutes academic dishonesty. For information on the various dishonesty kinds of academic dishonesty please refer to the Academic Integrity Policy, specifically Appendix 3, located at http://www.mcmaster.ca/senate/academic/ac_integrity.htm http://www mcmaster ca/senate/academic/ac integrity htm

University Policy Uni ersit Polic Academic Honest Honesty

The following illustrates only three forms of academic dishonesty: 1. Plagiarism, e.g. the submission of work that is not one's own or for which other credit has been obtained. This includes submission of assignments that one did not produce. 2. Improper collaboration in group work. There is no group work in this course; all assignments, tests and examinations are individual work. 3. Copying or using unauthorized aids in tests and examinations. Further information will be provided before tests and examinations.

Course Lect re Co rse Lecture Content

1.Introduction (2 hours) 1.1 Overview of the Course 1.2 Review of Building Blocks from Materials 2B03 (Gaskell Ch. Ch 5 & 7) 2. The behavior of solutions and activity (9 hours) 2.1 Chemical 2 1 Ch i l potential (Gaskell 5.7) and fugacity (Gaskell t ti l (G k ll 5 7) d f it (G k ll 8.7) 2.2 Raoult's law and Henry's law (Gaskell 9.2) 2.3 2 3 Activity (Gaskell 9 3) 9.3) 2.4 Gibbs-Duhem equation (Gaskell 9.4 & 9.5) 2.5 Ideal solution (Gaskell 9.6) 2.6 2 6 Examples
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Course Lect re Co rse Lecture Content

3. The behavior of nonideal solutions (6 hours) 3.1 Activity coefficient (Gaskell 9.7) 3.2 Determination of activity (Gaskell 9.8) 3.3 Regular solution (G k ll 9.9) 33R l l ti (Gaskell 9 9) 3.4 Subregular solution (Gaskell 9.11) 3.5 Examples

Course Lect re Co rse Lecture Content

4. Reactions involving gases (6 hours) 4.1 Gas mixture (Gaskell 11.2) 4.2 Temperature effect (Gaskell 11.3) 4.2 Pressure effect (G k ll 11 4) 42P ff t (Gaskell 11.4) 4.3 Reaction equilibrium - H versus S (Gaskell 11.5) 4.4 SO2-SO3-O2 System 4.5 O-H 4 5 H2O H2 and CO2-CO Systems CO 4.6 Examples

Course Lect re Co rse Lecture Content

5. Reactions involving pure condensed and gaseous phases (6 hours) 5.1 Standard free energy (Gaskell 12.3) 5.2 Ellingham di 5 2 Elli h diagrams (G k ll 12 4) (Gaskell 12.4) 5.3 Effect of phase transformation (Gaskell 12.5) 5.4 Carbon oxides (Gaskell 12.6) 5.5 Metal-carbon-oxygen 5 5 Metal carbon oxygen (Gaskell 12.7) 12 7) 5.6 Examples

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Course Lect re Co rse Lecture Content

6. Phase diagrams (6 hours) 6.1 Regular solutions (Gaskell 10.3) 6.2 Phase stability (Gaskell 10.4) 6.3 Liquid d S lid t d d t t (Gaskell 10.5) 6 3 Li id and Solid standard states (G k ll 10 5) 6.4 Phase diagrams (Gaskell 10.6) 6.5 Binary systems (Gaskell 10.7) 4.6 4 6 Examples Plus 2 hours Mid-Term Test and 2 hour Final Review Total of 39 hours

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Core Co rses in MSE Courses

Thermodynamics, Kinetics, Materials Processing Th d i Ki ti M t i l P i What is Thermodynamics? Thermodynamics = thermo + dynamics (heat and force) Is it possible? How far can it go? As a total, not individuals For example Reaction: A+BC+D Possible? How far? P ibl ? H f ? thermodynamics th d i How fast? kinetics How to do it? processing Separation: (A+B) A + B p ( ) Possible? How far? thermodynamics How fast? kinetics How to do it? processing

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Thermodynamics is the Key Sustainability Ke to S stainabilit

Almost every human activity involves the use of energy The production and use of energy is central problem to sustainability (CO2 emissions, radioactive waste, land use for renewable energy sources) Materials Engineering has an important role in this area:
Materials Processing uses large amounts of energy (e.g. the g g gy ( g steel industry emits about 5% of global CO2) Improved materials for power generation and efficient use

In this course you will learn why:

It takes 20 MJ to make a kg of steel It takes 220 MJ to make a kg of aluminum

Understanding energy use is the key to a sustainable future g gy y

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What can thermodynamics do? thermod namics

Predicts heat effects due to mixing, reactions etc. based on a minimum amount of data. Predicts maximum yield for thermodynamically controlled reactions Predicts phase equilibrium and thus separations based on a minimum amount of data Efficiency of p y processes:
Calculate maximum possible Can characterize real processes Formulate models for comparison with real processes

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What Thermodynamics cannot do Thermod namics

It cannot tell us anything about the fundamental chemistry of materials, such as why does aluminum melt at a lower temperature than iron Cannot predict reaction rates Cannot predict mass transport properties or rates

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Relation between Kinetics and Thermod namics Thermodynamics

Show the forward reaction activation energy Reverse reaction activation energy Show free energy change for forward reaction

Energy
0

Eaf A B

Ear

Sign f Si of G? Reverse reaction?

Reaction Coordinate

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Relating Thermod namics to Kinetics Thermodynamics

Chemical Kinetics the Arrhenius EQn Thermodynamics

k=A Ae

Ea RT

Grx = GPr od Greact

How is reaction rate constant, k, related to the free energy of reaction, Grx?

Grx = Ea forward Eareverse

k forward Grx = RT ln(K ) = RT ln k reverse
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Chemical Kinetics versus Diff sion ers s Diffusion

When chemists speak of kinetics, they mean the rates at which atoms or molecules react with one another To investigate these rates, they need specially designed experiments to ensure that the reactants are present at the reaction site, and that products are removed at a rate faster than the reaction itself In most real world chemical reactions and industrial processes the rate is governed by diffusion and convection (mass transport)
Gases fastest Liquids next Solids slowest

This topic is covered in Mass Transfer (Materials 3E04)

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Review of Building Blocks from Materials 2B03 (Chap 5 4 & 5 5) 5.4 5.5)
Gibbs Free Energy, G, is the most important function for examining change of state in a reaction:
Applies at constant pressure (isobaric) Many processes operate at atmospheric pressure Others are controlled to operate at a constant pressure

G = H TS G = H TS
The later equation applies for a reaction at constant T Criterion for equilibrium for isobaric isothermal reaction is:

dG = 0 G = 0
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Review of Building Blocks from Materials 2B03 (Chap 7 2) 7.2)

Example in one-component system (H2O)

H 2O( solid ) H 2O( liquid ) at 1 atm & 273 K G = G H 2O ( l ) G H 2O ( s )

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