1. Multi-component Homogeneous System: Solution Thermodynamics
Byeong-Joo Lee
POSTECH - MSE

2. Thermodynamic Properties of Gases - mixture of ideal gases
1 mole of ideal constant T:
Mixture of Ideal Gases
Definition of Mole fraction: xi
Definition of partial pressure: pi
Partial molar quantities:

3. Thermodynamic Properties of Gases - mixture of ideal gases
Heat of Mixing of Ideal Gases
Gibbs Free Energy of Mixing of Ideal Gases
Entropy of Mixing of Ideal Gases

4. Thermodynamic Properties of Gases - Treatment of nonideal gases
Introduction of fugacity, f as
For Equation of state
※ actual pressure of the gas is the geometric mean of the fugacity and the ideal P
※ The percentage error involved in assuming the fugacity to be equal to the
pressure is the same as the percentage departure from the ideal gas law

5. Thermodynamic Properties of Gases - Treatment of nonideal gases
Alternatively,
Example) Difference between the Gibbs energy at P=150 atm and P=1 atm
for 1 mole of nitrogen at 0 oC

6. + → Solution Thermodynamics - Mixture of Condensed Phases Vaper A: oPA
Condensed Phase A
Vaper B: oPB
Condensed Phase B
Vaper A+ B: PA + PB
Condensed Phase A + B + →
for gas

7. Solution Thermodynamics - ideal vs. non-ideal solution

8. Draw a composition-activity curve for an ideal and non-ideal solution
Solution Thermodynamics - Thermodynamic Activity
Thermodynamic Activity of a Component in Solution →
for ideal solution
Draw a composition-activity curve for an ideal and non-ideal solution
Henrian vs. Raoultian

9. Solution Thermodynamics - Partial Molar Property
▷ Partial Molar Quantity
▷ Molar Properties of Mixture
Gibbs-Duhem Equation

10. Solution Thermodynamics - Partial Molar Quantity of Mixing
definition of solution and mechanical mixing
where
is a pure state value per mole
왜 partial molar quantity를 사용해야 하는가?

11. Solution Thermodynamics - Partial Molar Quantities

12. Solution Thermodynamics - Partial Molar Quantities
Evaluation of Partial Molar Properties in 1-2 Binary System
Partial Molar Properties from Total Properties
example)
Partial molar & Molar Gibbs energy
Gibbs energy of mixing vs. Gibbs energy of formation
Graphical Determination of Partial Molar Properties: Tangential Intercepts
Evaluation of a PMP of one component from measured values of a PMP
of the other
example)

13. Solution Thermodynamics - Chemical Potential as a Partial Molar Quantity
※ Relationships among Partial Molar Quantities:
Chapter 5에서 언급한 Thermodynamic Relationship 들이 모두 적용됨

14. Solution Thermodynamics - Non-Ideal Solution
▷ Activity Coefficient
▷ Behavior of Dilute Solutions

15. Example
Gibbs energy of formation과 Gibbs energy of mixing의
차이는 무엇인가?
2. Solution에서 한 성분이 Henrian 또는 Raoultian 거동을
한다는 것을 무엇을 의미하는가?
Molar Gibbs energy가 다음과 같이 표현되는 A-B 2원
Solution phase에서 각 성분은 dilute 영역에서는 Henrian
거동을, rich 영역에서는 Raoultian 거동을 보인다는 것을
증명하시오.

16. Solution Thermodynamics - Use of Gibbs-Duhem Relation - I

17. Solution Thermodynamics - Use of Gibbs-Duhem Relation - II

18. Solution Thermodynamics - Introduction of α-function

19. Solution Thermodynamics - Composition Dependence of α-function
Fe-Ni Fe-Cu

20. Hildebrand, 1929. (using van Laar Equation)
Solution Thermodynamics - Regular Solution Model
Margules, 1895.
Hildebrand, (using van Laar Equation)

21. Solution Thermodynamics - Quasi-Chemical Model, Guggenheim, 1935.

22. Solution Thermodynamics - Regular Solution Model
Sn-In Sn-Bi

23. Solution Thermodynamics - Sub-Regular Solution Model
Sn-Zn Fe-Ni

24. Composition and temperature dependence of Ω
Solution Thermodynamics - Regular Solution Model
Composition and temperature dependence of Ω
Extension into ternary and multi-component system
Sublattice Model
Inherent Inconsistency