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Solution Thermodynamics : Theory - KOCw

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Dankook University

Dept. of Chemical Engineering Key concepts

- Theoretical foundation for thermodynamics (gas mixture, liquid solution)

- Fundamental property relation

- Chemical potential( )/Fugacity( )

- Partial property : : the meaning of partial property

- Excess property( ) Why need to obtain the excess property?

- ideal liquid solution : , no mixing property except &

Then, what phenomena does happen for & in mixing process of more than two components?

*Question : is larger than ?

Check point :What is the mixing effect for entropy and Gibbs free energy?

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󰋫 for any closed system For a single phase and no chemical reaction system

󰋫 Extending to a single phase, open system

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Dankook University

Dept. of Chemical Engineering

chemical potential of component i :

(one mole basis)

:

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*Chemical Potential Index of chemical state as an intensive property

The Chemical Potential and Phase Equilibrium When two phase is in equilibrium,

To identify for each phase(α & β) ;

Since when T and P are constant for overall system

in Equilibrium.

since

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Dankook University

Dept. of Chemical Engineering For π-phases

(i=1, 2, ···, N) Criteria for Chemical equilibrium of π-phases

󰋫 Partial Properties

Response function- "A measure of the response of total property nM

to the addition of a differential amount of species i "

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EXAMPLE 11.1

What's the physical interpretation ?

total volume change :

: effective molar volume

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Dankook University

Dept. of Chemical Engineering

When T, P and are constant,

in equi-molar solution

󰋫 Equation Relating Molar and Partial Molar Properties.

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and

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Dankook University

Dept. of Chemical Engineering

Calculation of mixture properties from partial properties :

Calculation of partial properties from Mixture properties Check point : What's the meaning of partial molar property?

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Gibbs/Duhem

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Dankook University

Dept. of Chemical Engineering Since ,

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Dankook University

Dept. of Chemical Engineering

* Differential of Gibbs/Duhem equation

(provided is infinite)

(provided is infinite)

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Dankook University

Dept. of Chemical Engineering

■ Stanley I. Sandler, Chemical, Biochemical, and Engineering Thermodynamics, Wiley, 2006

■ Davis R. Gaskell, 재료열역학, 홍릉과학출판사, 2009

Referensi

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