Lecture 28 - CHE303

kfupm.edu.
sa
Chemical Engineering Thermodynamics (CHE 303)

Lecture 28: Partial properties II
Dr. Wael A. Fouad
Assistant Professor
Chemical Engineering Department
King Fahd University of Petroleum and Minerals
Chapter 10:
The Framework of Solution

Thermodynamics
2
Partial properties (previous lecture)
• For a thermodynamic property M (e.g., V, U, H, S, G, A), we

can define the partial molar property of species i in a
mixture as:
  (nM ) 
Mi =  
 ni  P ,T ,nˆi
• Thus, by definition the chemical potential is identical to

the partial molar Gibbs free energy:
 (nG )
i    = Gi
 ni  P ,T ,n j
3
Equations for partial properties
• Summability relation: M =  xi M i
i
dM dM
in binary mixtures: M 1 = M + x2 M 2 = M − x1
dx1 dx1
• Limit (for pure species): M i (xi = 1) = M i
 M   M 
• Gibbs/Duhem:   dT +   dp −  xi dM i = 0
 T  p , x  p  T , x i
(thermodynamic consistency test at constant p,T)

4
Partial properties in binary solutions
• Summability for a binary solution: M = x1M 1 + x2 M 2
• Total differential of M: dM = x1dM1 + M1dx1 + x2 dM 2 + M 2 dx2
• From Gibbs/Duhem equation at constant p and T:

 M   M 
 T  dT +  p  dp −  xi dM i = 0 x1dM1 + x2 dM 2 = 0
  p,x  T ,x i
• Since: x1 + x2 =1 dx1 = −dx2

dM
• Total differential: dM = M 1dx1 − M 2 dx1 = M1 − M 2
dx1
Slope of tangent = difference
between two partial properties
5
Graphical representation
6
Partial properties in binary solutions
• Summability: M = x1M 1 + x2 M 2
M = (1 − x2 )M 1 + x2 M 2 M = M 1 − x2 (M 1 − M 2 )
dM
M 1 = M + x2
dx1
M = x1M 1 + (1 − x1 )M 2 M = M 2 + x1 (M 1 − M 2 )
dM
M 2 = M − x1
dx1
• From Gibbs/Duhem at constant T,p:  x dM

i
i i =0
dM 1 dM 2 dM 1 x 2 dM 2
x1dM 1 + x2 dM 2 = 0 x1 + x2 =0 =−
dx1 dx1 dx1 x1 dx1
7
Example 1 – Chapter 11
Methanol (1) and water (2) are mixed at constant T and p to

form a 2000 cm3 solution of 30% methanol
• Given:
V1 = 40.727 ml/mol V1 ( x1 = 0.3) = 38.632 ml/mol
V2 = 18.068 ml/mol V2 ( x1 = 0.3) = 17.765 ml/mol
• Determine the amounts of pure methanol (n1V1) and pure
water (n2V2) that should be mixed to form this solution
8
• Solution:
V = x1V1 + x2V2
V = 0.3  38.632 + 0.7 17.765 = 24.025 ml/mol
( nV ) 2000
n= = = 83.246 mol
V 24.025
n1V1 = (0.3  83.246)  40.727 = 1017 ml
(x1 n) V1
n2V2 = (0.7  83.246)  18.068 = 1053 ml

(x2 n) V2
9
Molar volume for methanol(1)/water(2) at 25ºC and 1atm
V1
V1
V2
V2
x1=0.3 10
Two components are mixed at constant p, T
• Given: V1 = 100 − 20 x22 (ml/mol)
V2 = 110 ml/mol
• Determine: V2 ( x2 = 0.5) V ( x2 = 0.5)
Solution:
• At constant p, T:  x dM
i
i i = 0 (Gibbs/Duhem)
x1dV1 + x2 dV2 = 0 Deriving with respect to x2

dV1
with: V1 = 100 − 20 x 2
2
= −40x2
dx2
x1 (− 40 x2 )dx2 + x2 dV2 = 0 11
dV2 = 40 x1dx2 = 40(1 − x2 )dx2 integrating

( )
V2 = −20 1 − x2 + C
2
Constant of integration
V2 ( x2 = 1) = V2 = 110 C = 110
V2 = −20(1 − x2 ) + 110
2
V2 ( x2 = 0.5) = −20  (1 − 0.5) 2 + 110 = 105 ml/mol
V1 ( x2 = 0.5) = 100 − 20  0.52 = 95 ml/mol
V ( x2 = 0.5) = 0.5  V1 ( x2 = 0.5) + 0.5  V2 ( x2 = 0.5)

= 0.5  95 + 0.5 105 = 100 ml/mol 12
The volume of a binary liquid system of species 1 and 2 at fixed

T and p is given by:
V = 100 x1 + 80 x2 + 2.5 x1 x2 (ml/mol)
• Determine expressions for the partial volumes of species 1
and 2 as functions of x1
• What is the volume of both pure species (V1 and V2) and
what are the partial volumes at infinite dilution?
Solution:
13
• Volume: V = 100 x1 + 80 x2 + 2.5 x1 x2

• Partial volume of species 1 (by definition):
  (nV ) 
V1 =  
 n1  p ,T ,n2
d   100n1 n2 
(n1 + n2 )
80n2 n1
= + + 2 .5 
dn1   n1 + n2 n1 + n2 n1 + n2 n1 + n2 
d  n1n2 
= 100n1 + 80n2 + 2.5 
dn1  n1 + n2 
 n2 (n1 + n2 ) − 1  n1n 2 

= 100 + 0 + 2.5    = 100 + 2.5  x 2
(n1 + n2 ) 2  2
  14
Example 3
• Partial volume of species 2:
  (nV )  d  n n 

V2 =  
 = 100n1 + 80n2 + 2.5 1 2

  n2  p ,T , n1 dn2  n1 + n2 
 n1 (n1 + n2 ) − 1  n1n 2 

= 0 + 80 + 2.5    = 80 + 2.5  x 2
(n1 + n2 ) 2  1
 
• Alternatively: V = 100 x1 + 80 x2 + 2.5 x1 x2 and x2 = 1 − x1
V = −2.5 x12 + 22.5 x1 + 80
dV
= −5 x1 + 22.5
dx1
15
= −2.5 x12 + 22.5 x1 + 80 + (1 − x1 )(− 5 x1 + 22.5)

dV
V1 = V + x2
dx1
= 2.5 x12 − 5 x1 + 102.5
= 100 + 2.5 x22

dV
V2 = V − x1 = −2.5 x12 + 22.5 x1 + 80 − x1 (− 5 x1 + 22.5)
dx1
= 2.5 x12 + 80
16
• Volume: V = 100 x1 + 80 x2 + 2.5 x1 x2
• Partial volumes: V1 = 100 + 2.5 x22 V2 = 2.5 x12 + 80
• Pure volumes: V1 = V1 ( x1 = 1) = 100 ml/mol
V2 = V2 ( x2 = 1) = 80 ml/mol
• Partial volumes at infinite dilution:

x2=1
V1  = V1 ( x1 = 0 ) = 102.5 ml/mol
V2 = V2 ( x2 = 0 ) = 82.5 ml/mol

x1=1
17
A student thinks that the chemical potential of both species in
a binary mixture can be described by the following equation:
i = Gi + RT ln xi + A(1 − xi ) + B(1 − xi )2
but it appears that not all values for A and B are allowed.
• Show which values of A and B lead to thermodynamic
consistency
Solution:
18
• Thermodynamic consistency at constant p, T:  x dG

i
i i =0
 xi di = 0
i
x1d1 + x2 d 2 = 0 (Gibbs/Duhem)
d1 d 2
(1 − x2 ) + x2 =0
dx2 dx2
with:
1 = G1 + RT ln(1 − x2 ) + Ax2 + Bx22 (given in the question for i components)
d1 RT
=− + A + 2 Bx2
dx2 1 − x2
 2 = G2 + RT ln x2 + A(1 − x2 ) + B(1 − x2 )2
d 2 RT
= − A − 2 B (1 − x2 ) 19
dx2 x2
d1 d 2
• Consistency when: (1 − x2 ) + x2 =0
dx2 dx2
d1 RT
• Fill in: =− + A + 2 Bx2
dx2 1 − x2
d 2 RT
= − A − 2 B(1 − x2 )
dx2 x2
− RT + A(1 − x2 ) + 2 Bx2 (1 − x2 ) + RT − Ax2 − 2 B(1 − x2 )x2 = 0
A=0
A(1 − x2 ) − Ax2 = A − 2 Ax2 = 0
B can be any number
20

Lecture 28 - CHE303

Uploaded by

Copyright:

Available Formats

Lecture 28 - CHE303

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Lecture 28 - CHE303

Uploaded by

Copyright:

Available Formats

kfupm.edu.

Chemical Engineering Thermodynamics (CHE 303)

The Framework of Solution

• For a thermodynamic property M (e.g., V, U, H, S, G, A), we

• Thus, by definition the chemical potential is identical to

• Limit (for pure species): M i (xi = 1) = M i

(thermodynamic consistency test at constant p,T)

• Summability for a binary solution: M = x1M 1 + x2 M 2

• Total differential of M: dM = x1dM1 + M1dx1 + x2 dM 2 + M 2 dx2

• From Gibbs/Duhem equation at constant p and T:

• Since: x1 + x2 =1 dx1 = −dx2

• From Gibbs/Duhem at constant T,p:  x dM

Methanol (1) and water (2) are mixed at constant T and p to

n2V2 = (0.7  83.246)  18.068 = 1053 ml

x1dV1 + x2 dV2 = 0 Deriving with respect to x2

dV2 = 40 x1dx2 = 40(1 − x2 )dx2 integrating

V2 ( x2 = 0.5) = −20  (1 − 0.5) 2 + 110 = 105 ml/mol

V1 ( x2 = 0.5) = 100 − 20  0.52 = 95 ml/mol

V ( x2 = 0.5) = 0.5  V1 ( x2 = 0.5) + 0.5  V2 ( x2 = 0.5)

The volume of a binary liquid system of species 1 and 2 at fixed

• Volume: V = 100 x1 + 80 x2 + 2.5 x1 x2

• Alternatively: V = 100 x1 + 80 x2 + 2.5 x1 x2 and x2 = 1 − x1

V = −2.5 x12 + 22.5 x1 + 80

= −2.5 x12 + 22.5 x1 + 80 + (1 − x1 )(− 5 x1 + 22.5)

= 100 + 2.5 x22

• Partial volume of species 2:

• Volume: V = 100 x1 + 80 x2 + 2.5 x1 x2

• Partial volumes: V1 = 100 + 2.5 x22 V2 = 2.5 x12 + 80

• Pure volumes: V1 = V1 ( x1 = 1) = 100 ml/mol

• Partial volumes at infinite dilution:

V2 = V2 ( x2 = 0 ) = 82.5 ml/mol

• Thermodynamic consistency at constant p, T:  x dG

− RT + A(1 − x2 ) + 2 Bx2 (1 − x2 ) + RT − Ax2 − 2 B(1 − x2 )x2 = 0

You might also like

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.