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Lecture 3 - FALL 2024

Thermodynamics Lecture Notes Chapter 10

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11 views

Lecture 3 - FALL 2024

Thermodynamics Lecture Notes Chapter 10

Uploaded by

ally.martin212
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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Summary

Fugacity and fugacity coefficient in solution

Instead of
Fugacity and fugacity coefficient in solution
Virial EOS applied to mixtures
BP
Z 1 
RT simplest model to go
beyond ideal solution model

B  yi y j Bij
i j
How to obtain the cross coefficients Bij

ˆ
Bij B  ij B
0 1

Bij Pcij
Bˆ ij 
Tcij

Mixing rules for Pcij, Tcij, wij, 10-70 to 10.73


Fugacity coefficient ˆ
i

from virial EOS


P
ˆ
ln 1  B11  y2 12 
2

RT
 12 2 B12  B11  B22
For a multicomponent mixture, see eqn. 10.64
When we deal with mixtures of liquids or solids
• We define the ideal solution model

• Compare it to the ideal gas mixture, analyze its similarities and


differences
ig Component i in a mixture
i i (T )  RT ln( yi P) of ideal gases

This eqn. is obtained by combining

ig
Gi i (T )  RT ln P
ig
 Gi (T , P)  RT ln yi
ig
i

Now we define

iid Gi (T , P )  RT ln xi Ideal solution model


how do we evaluate a change of a property M due to mixing

M = M final – M initial

M initial = sum (xi Mi)


Other thermodynamic properties for the ideal solution: partial molar
volume
id
Gi Gi (T , P )  RT ln xi

 Gi id   Gi 
Vi id
    Vi
 P  T , x  P T
V id  xiVi id  xiVi
if an ideal solution
is formed, the final what is DV?
volume is:
i i

https://www.youtube.com/watch?v=wPObK96ui-M
partial molar entropy in the ideal solution
Gi id Gi (T , P )  RT ln xi

 Gi id   Gi 
S i
id
       R ln xi S i  R ln xi
 T  P,x  T P
S  xi S
id
i
id
 xi S i  R  xi ln xi
i i i
partial molar enthalpy in the ideal solution
id
Gi Gi (T , P )  RT ln xi

H iid Gi id  TSiid Gi  RT ln xi  TSi  RT ln xi H i


H id  xi H iid  xi H i
i i
Chemical potential ideal solution

i i (T )  RT ln fˆi Chemical potential component i


in a Real solution

Chemical potential
Gi i (T )  RT ln f i Pure component i
Subtracting:
fˆi
i Gi  RT ln
fi
For the ideal solution
id
ˆf id
i Gi  RT ln i
fi
Lewis-Randall rule
id
i Gi  RT ln xi based on mole fractions

id
ˆf id
i Gi  RT ln i
based on fugacities
fi

to make them
compatible
ˆf id  x f
i i i Lewis-Randall rule

ˆ id
i i (Dividing by Pxi each side of the equation)
Lewis-Randall

ˆf id  x f
i i i

ˆ id
i i
When is the ideal solution valid?
• Mixtures of molecules of similar size and similar chemical nature
• Mixtures of isomers (e.g. n-propane and i-propane)
• Adjacent members of homologous series
Now we want to define a new type of residual properties

• Instead of using the ideal gas as the reference, we use the ideal
solution
Excess properties
E id
M M  M
The most important excess function is
the excess Gibbs free energy GE

Excess entropy can be calculated


from the derivative of GE wrt T

Excess volume can be calculated


from the derivative of GE wrt P

And we also define partial molar excess properties


problem
• For the system methane (1)/ethane (2)/propane (3) as a gas, estimate
fˆ1 , fˆ2 , fˆ3 and ˆ1 , ˆ2 , ˆ3

at T = 100oC, P = 35 bar, y1 =0.21, and y2 =0.43


Assume that the mixture is an ideal solution

Obtain reduced pressures, reduced temperatures, and calculate

id  Prk 0 1 
k exp  ( Bkk  Bkk )
 Trk 
fˆkid k yk P
id
Results: methane (1) ethane (2) propane (3)

ˆ1 1.02; ˆ2 0.88; ˆ3 0.78


Virial model for mixtures
(see slide 10)

fˆ1 7.49; fˆ2 13.25; fˆ3 9.76bar


1 0.98; 2 0.88; 3 0.76 Ideal solution; calculated from
equation in the previous slide

ˆf id 7.18; fˆ id 13.25; fˆ id 9.57bar


1 2 3
https://www.youtube.com/watch?v=OZFB48wVtjw

this video has a discussion of fugacities in multicomponent mixtures

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