InQu 4012

March 7, 2014

Chapter 12

Introduction to
Chemical Engineering
Thermodynamics
Seventh Edition

Smith Van Ness Abbott

Chapter 12 PowerPoint

Solution Thermodynamics: Applications

1.
2.
3.
4.

Liquid-phase properties from VLE data

Models for the excess Gibbs energy
Property changes of mixing
Heat effects of mixing processes

Copyright the McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Chapter 12

The Phase Rule

Solution Thermodynamics: Theory

F N 2

1. Liquid-phase properties from VLE

data

Degrees of freedom (F)

Number of components (N)
Number of phases ()

Fugacity (p. 430)

Activity coefficient (p. 432)
Excess Gibbs energy (p. 435)
Data reduction (p. 437)
Thermodynamic consistency (p. 441)
2. Models for the excess Gibbs energy
3. Property changes of mixing
4. Heat effects of mixing properties

Gibbs variables: P, T, {xi}, {yi}

For VLE in binary systems, F

Fugacity of liquid phase

T
Fugacity is a property of pure components or mixtures in
gas, liquid, or solid phase
Fugacity can be determined in any state regardless of
whether phase equilibrium prevails
Experimental determination is easier when phases are at
equilibrium because of the isofugacity condition

=2

VLE Cell
Experiments:
Isothermal
Isobaric
Gibbs variables measured:
P, T, {xi}, {yi}

Fig. 12.1

Dr. L. Antonio Estvez

InQu 4012

March 7, 2014

Fugacity calculation
Binary systems at low pressure:
f y P
1

f2 y2 P
Ideal-gas behavior

Activity coefficient
From isofugacity condition:
1
Lewis/Randall
rule

y1 P
x1 P1sat

(1 y1 ) P
(1 x1 ) P2sat

All variables in right-hand sides are

available from experimental data

Henrys law
The two lines
are tangent

The two lines

are tangent

df
f
dx
lim lim i
xi 0 x
xi 0 dx
i
i
dxi
df
lim
xi 0 dx
i
Hi

Dr. L. Antonio Estvez

InQu 4012

March 7, 2014

Henrys law
Exercise: Show that if Henrys law applies
to one of the species in a binary system,
then the Lewis/Randall rule will apply to
the other species.
(Hint: Use Gibbs/Duhem equation for
chemical potential.)

Positive and
negative deviations
from the
Lewis/Randall rule

Lewis/Randall
rule

x1d 1 x2 d 2 0
x1d ln f1 x2 d ln f2 0

Excess Gibbs energy

pp 435-437
It can be computed from experimental
data as:

GE
x1 ln 1 x2 ln 2
RT
Read these pages!

Data reduction
pp 437-441
Many models have the form:

GE
x1 x2 ( x1 , x2 )
RT
Therefore, it is convenient to plot:

GE
( x1 , x2 )
x1 x2 RT

Dr. L. Antonio Estvez

InQu 4012

March 7, 2014

If is linear:

( x1 , x2 ) a bx1
A21 x1 A12 x2

For methyl ethyl

ketone + toluene
at 50 [C]

GE
x1 x2 A21 x1 A12 x2
RT
GE
x1 x2 0.198 x1 0.372 x2
RT

System with negative deviations

Data reduction

Data reduction
is linear again:

GE
x1 x2 A21 x1 A12 x2
RT
GE
x1 x2 1.27 x1 0.72 x2
RT

Thermodynamic consistency
Area test:

Residual test:

Area test

0 ln 12 dx1 0
1

d ln 1*
d ln *2
ln 1 x1
x2
2
dx1
dx1

For chloroform +
1,4-dioxane at 50 [C]

ln
ln

dx1 0

1
2

M M model M experim
M M model M *

Dr. L. Antonio Estvez

x1

InQu 4012

March 7, 2014

Residuals test
Example 12.1

Example 12.1

Example 12.1
Data dont follow Gibbs/Duhem
Data reduction based on GE does not work
Use Barkers approach
This works with any model
Here its used with Margules

Example 12.1

Examples of function shapes

Chapter 12

Dr. L. Antonio Estvez

Solution Thermodynamics: Theory

1. Liquid-phase properties from VLE data
2. Models for the excess Gibbs energy

Based on overall composition

Based on local composition

3. Property changes of mixing

4. Heat effects of mixing properties

InQu 4012

March 7, 2014

Models for excess Gibbs energy

Based on rational functions:
Redlich/Kister expansion (general)
Two-suffix Margules
Three-suffix Margules
van Laar

Redlich/Kister expansion
General series expansion:

GE
( x1 , x2 ) a bx1 cx12
x1 x2 RT
Redlich/Kister expansion:

Drawbacks:
No version for multicomponent systems
No explicit temperature dependence

GE
A B( x1 x2 ) C ( x1 x2 ) 2
x1 x2 RT

Margules formulas

Margules formulas
Three-suffix Margules:

Two-suffix Margules:
E

G
( x1 , x2 )
A
x1 x2 RT
Activity coefficients:

GE
A B( x1 x2 ) A B (2 x1 1)
x1 x2 RT

A21 x1 A12 x2
Activity coefficients:

ln 1 Ax22
ln 2 Ax

2
1

ln 1 x22 A12 2 x1 ( A21 A12 )

ln 2 x12 A21 2 x2 ( A12 A21 )

Margules formulas
In many instances, model parameters have to be
calculated from a single data point
In such cases, use the equations:

A12

x2 x1
2
ln 1 ln 2
x22
x1

A21

x1 x2
2
ln 2 ln 1
x12
x2

Dr. L. Antonio Estvez

Margules formulas
Four-suffix Margules (Probs. 12.6 & 12.9):

GE
A21 x1 A12 x2 Cx1 x2
x1 x2 RT

Activity coefficients:

ln 1 x22 A12 2 x1 ( A21 A12 C ) 3Cx12

ln 2 x12 A21 2 x2 ( A12 A21 C ) 3Cx22

InQu 4012

March 7, 2014

van Laar model

van Laar model

1 x1 x2 RT

A B( x1 x2 ) A B(2 x1 1)

GE

x
x
A12 A21
1 2
A12
x2
A21
A12 x1 A21

In many instances, model parameters have to be

calculated from a single data point
In such cases, use the equations:
2

x ln 1
1
x2 ln 2

Activity coefficients:

ln 1

A12

A12 x1
1
A21 x2

A21

ln 2

A21
x2
1
A12 x1

Models for excess Gibbs energy

A12 1 ln 1
2

1

A21
ln 2

Wilson model
GE
x1 ln( x1 x2 12 ) x2 ln( x2 x1 21 )
RT

Based on local composition:

Wilson
NRTL
UNIQUAC (Appendix H)
UNIFAC (Appendix H)

Activity coefficients, eqs. 12.19a & 12.19b:

Features:
Versions for multicomponent systems
Show explicit temperature dependence

12
21

ln 1 ln( x1 x2 12 ) x2

x1 x2 12 x2 x1 21
12
21

ln 2 ln( x2 x1 21 ) x1

x
x
x
x1 21
1 2 12
2

Wilson model
At infinite dilution:

ln 1 ln 12 1 21
ln 2 ln 21 1 12
Model parameters:

V2
a
exp 12
V1
RT
V1
a
21 exp 21
V2
RT
12

Dr. L. Antonio Estvez

Parameters for nine

binary systems in
Table 12.5

InQu 4012

March 7, 2014

NRTL: Nonrandom two-liquid model

NRTL: Nonrandom two-liquid model

G
G2121
G12 12

x1 x2 RT x1 x2G21 x2 x1G12
E

Model parameters b12, b21, :

G12 exp(12 ) G21 exp( 21 )

Activity coefficients, eqs. 12.21a & 12.21b:

2
G

G12 12
21

ln 1 x 21

2
x1 x2G21 ( x2 x1G12 )
2
G

G2121
12

ln 2 x12 21

2
x2 x1G12 ( x1 x2G21 )

i j:
ij 1

N
N x
ln i 1 ln x j ij N k ki
j 1
k 1 x
j 1

b21
RT

Multicomponent NRTL

N
N
i j:
GE
xi ln x j ij
Vj
aij
RT
i 1
j 1
ij V exp RT

Activity coefficients,
eq. 12.23:

21

Parameters for nine binary systems in

Table 12.5

Multicomponent Wilson

b12
RT

12

2
2

G
xi
RT i 1

j 1
N

ji

ji

x G
k

ki

Activity coefficients (not in the book):

ln i

x G
j 1
N

ji

ji

x G
k 1

Chapter 12

x G
k 1

kj

ki

xl Glj lj

x j Gij
ij l N1
N
j 1
xk Gkj
xk Gkj

k 1
k 1

Definition and relationship to excess properties

Solution Thermodynamics: Theory

1.
2.
3.
4.

Liquid-phase properties from VLE data

Models for the excess Gibbs energy
Property changes of mixing
Heat effects of mixing properties

M M xi M i

S S E R xi ln xi

i 1

i 1

V V

H H E
U U E

Dr. L. Antonio Estvez

G G E RT xi ln xi
i 1

A AE RT xi ln xi
i 1

March 7, 2014

Examples of mixing properties

Comparison with excess properties

InQu 4012

Chapter 12

Heat of mixing and heat of solution

Solution Thermodynamics: Theory

1.
2.
3.
4.

Liquid-phase properties from VLE data

Models for the excess Gibbs energy
Property changes of mixing
Heat effects of mixing properties

Heat of solution
Enthalpy/concentration diagrams

Energy balances
Usingheatofformations(Examples12.4and12.5)
Usingenthalpyofsolutions,asinHx diagrams(Examples12.6,
12.7,and12.9)

Dr. L. Antonio Estvez

Sameconceptexpressedonadifferentbasis:
Heatofmixing:permoleofsolution
Heatofsolution:permoleofsolute(1)

Moleratioasconcentrationunit:

H
x1

moles of solvent (2) n2 1 x1

x1
moles of soulte (1) n1

Heats of formation of LiCl

LiCl(s)

408,610 [J]

LiClH2O(s)

712,580 [J]

LiCl2H2O(s)

1,012,650 [J]

LiCl3H2O(s)

1,311,300 [J]

LiCl in 3 mol of H2O

429,366 [J]

LiCl in 5 mol of H2O

436,805 [J]

LiCl in 8 mol of H2O

440,529 [J]

LiCl in 10 mol of H2O

441,579 [J]

LiCl in 12 mol of H2O

442,224 [J]

LiCl in 15 mol of H2O

442,835 [J]

InQu 4012

March 7, 2014

Enthalpy-concentration diagrams
Figure12.17(H2SO4+H2O)andFigure12.19(NaOH+H2O)
Importanttoknowthereferencestatesforeachofthem:
Figure12.17:pureliquidat1[atm]and77[F]forH2SO4 and32[F]
forH2O
Figure12.19:infinitelydilutedsoluteat1[atm]and68[F]for NaOH
andpureliquidat32[F]forH2O
Figure 12.14: Heats
of solution at 25C

Figure 12.17: Hx
diagram for
H2SO4(1)/H2O(2)

Dhring plot
Provides boiling point (b.p.) of
solution as a function of the b.p.
of water
That allows calculation of the
boiling-point elevation (BPE)
also known as boiling-point rise
(BPR)

Dr. L. Antonio Estvez

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