Lec 4-Phase Equilibria II - Fugacity-Part 1

Chemical Engineering Thermodynamics II
Lec 3: Phase Equilibria: Fugacity-part 1
Dr.-Eng. Zayed Al-Hamamre
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Tel. +962 6 535 5000 | 22888
Content
 Learning Objectives
 Fugacity Definitions
 Criteria for Chemical Equilibria in Terms of Fugacity
 Fugacity & Fugacity Coefficient of Pure Species
 Fugacity Coefficient of species in solution

Tel. +962 6 535 5000 | 22888
Learning Objectives
 State the criteria for chemical equilibrium in terms of fugacity.

 Define fugacity, fugacity coefficient
 Find the fugacity and fugacity coefficient of gaseous species i as a pure species and
in a mixture using charts, tables, equations of state, and general correlations.
 Identify the appropriate reference state.

Tel. +962 6 535 5000 | 22888
Introduction
 Τhe chemical potential provides the criteria for chemical equilibrium of species i
between phases α and β in a multicomponent system
 It is a derived thermodynamic property, it provides a simple criterion for chemical equilibria of

each species i.
 The chemical potential does not have an immediate equivalent in the physical world and it is
therefore desirable to express the chemical potential in terms of some auxiliary function that
might be more easily identified with physical reality.
 A useful auxiliary function is obtained by the concept fugacity..
 Fugacity is new derived thermodynamic property that is mathematically better behaved but
provides just as simple a criterion for equilibrium.

Tel. +962 6 535 5000 | 22888
Definitions

Tel. +962 6 535 5000 | 22888
Definitions
 Integrating between a reference state and the state of the
system,
 Or
I

Tel. +962 6 535 5000 | 22888
Definitions
II
II I

Tel. +962 6 535 5000 | 22888
Criteria for Chemical Equilibria in Terms of Fugacity

 For phases α and β at equilibrium at the same T, P
Gi  i T   RT ln f i Gi  i T   RT ln f i 
They are in equilibrium

Gi  Gi or i  i
f i
Gi  Gi  RT ln 0
fi 
f i  f i  (11.39)
 For vapor-liquid equilibrium

fi v  fi l  fi sat (11.39)
Coexisting vapor and liquid phases have the same fugacity 8

Tel. +962 6 535 5000 | 22888
 Also,
f i sat
 i
sat
 sat (11.40) Where Φi is the fugacity
Pi coefficient
iv P sat  il P sat
 And hence i f  iv  isat (11.41)
the same fugacity coefficient

9

Tel. +962 6 535 5000 | 22888

 In similar manner we defined the fugacity coefficient of species in a mixture fî
 For species i in a mixture of real gases or in a solution of liquids, the chemical

potential of species i is expressed as:
i  i T   RT ln fî
fî fugacity of species in solution (mixture)
 For phases α and β at equilibrium at the same T, P
i  i
i T   RT ln fî  i T   RT ln fî 
fî  fî  Criteria for multicomponent equilibrium
10

Tel. +962 6 535 5000 | 22888
 For multiple phases and the same T and P in equilibrium
i  i    i i  1, 2,, N 

fî  fî     fî  i  1, 2,, N 
 The fugacity of each species is the same in all phases

 The equality of the fugacity can be used for the criteria of phase equilibrium instead of the equ
ality of chemical potential.
11

Tel. +962 6 535 5000 | 22888
Fugacity of Pure Species

 The chemical potential μi provides the fundamental criterion for phase as well as
chemical reaction equilibria.
i  i    i i  1, 2,, N 

 The Gibbs energy, and hence μi , is defined in relation to the internal energy and
entropy. Because absolute values of internal energy are unknown, the same is true for
μi .
 For ideal gas  ig  i T   RT ln yi P 
i
G iig  i T   RT lnP 
 The concept of fugacity is introduced when considering real fluid (gas or liquid)
Gi  i (T )  RT ln fi
12

Tel. +962 6 535 5000 | 22888
Fugacity of Pure Species
f i ig  P
and the fugacity of pure species i as an ideal gas is necessarily equal to its pressure
13

Tel. +962 6 535 5000 | 22888
Residual Gibbs energy &Fugacity of Pure Species

Gi  Giig  (i (T )  RT ln fi )  (i (T )  RT ln P)
G iR  RT ln  i
fi
 i 
P system
 These equations apply to pure species i in any phase at any condition
 At low pressures ( < 1 bar ), the fugacity of real species approaches the pressure
 For ideal gas f

lim
P  0
 i
 lim
P  0 P
i
 1 G iR  0 .0
14

Tel. +962 6 535 5000 | 22888
Fugacity and Fugacity Coefficient of Pure Gases
 To use fugacity in practice, the first step is to identify an appropriate reference state.
 There is an obvious choice of reference state for gases: a low enough pressure that
the gas behaves as an ideal gas.
 With this choice,
 The reference state must be at the same temperature as the system of interest
 The expression for fugacity of pure species i using the ideal gas reference state
becomes:
15

Tel. +962 6 535 5000 | 22888
Fugacity and Fugacity Coefficient of Pure Gases
 Also
 The fugacity of a real gas can be calculated using three possible sources of data for
pure gases or vapors:
16

Tel. +962 6 535 5000 | 22888
Expression for the Fugacity Coefficient of a Pure Gas Using Tables
 Tables of thermodynamic properties typically have h, s, T, and P.
 Using the h, s, T, properties, g can be calculated.
Since
Example
Determine the fugacity and the fugacity coefficient for saturated steam at 1 atm.
The steam tables provide the appropriate data to solve this problem
17

Tel. +962 6 535 5000 | 22888
Example Cont.
for saturated steam at 1 atm
 To find the fugacity, we must now choose a reference state.

 We want as a low a pressure as possible at the same temperature as the system of
interest (100° C).
 We can find this state in the superheated steam tables (Appendix B.4). The lowest
pressure available in the steam tables is 10 kPa.
 So for the reference state, we choose 10 kPa, 100° C:
18

Tel. +962 6 535 5000 | 22888
Example Cont.
At
Since
19

Tel. +962 6 535 5000 | 22888
Example Cont.
 Solving for the fugacity coefficient, we must use the system pressure
 Even with its strong dipole moment (and associated forces of attraction), the
fugacity coefficient of water deviates from ideality by less than 2% at 1 atm.
20

Tel. +962 6 535 5000 | 22888
Expression for the Fugacity Coefficient of a Pure Gas Using Equations of State
 Also, when the EOS is explicit in pressure,
Equation of state to is then used to relate
Example
Determine an expression for the fugacity of a pure gas from the van der Waals equation
of state.
21

Tel. +962 6 535 5000 | 22888
Example Cont.
At constant temperature, we can differentiate Equation
Using partial fractions
22

Tel. +962 6 535 5000 | 22888
Example Cont.
23

Tel. +962 6 535 5000 | 22888
Example Cont.
24

Tel. +962 6 535 5000 | 22888
Example Cont.
 If the virial form of the van der Waals equation truncated to the second term is used.
The van der Waals equation written in virial form becomes
Solving for
25

Tel. +962 6 535 5000 | 22888
Expression for the Fugacity Coefficient of a Pure Gas Using

Generalized Correlations
 Use general correlations to solve for the fugacity coefficient in terms of reduced
temperature and reduced pressure by developing a relationship between the
compressibility factor,, and the fugacity coefficient,, for the pure species i.
 Using the ideal gas reference state, the definition for fugacity of a pure species is:
26

Tel. +962 6 535 5000 | 22888
 Combining the integrals on the left-hand side and integrating and rewriting the
logarithmic terms on the right-hand side gives:
GiR

RT
const T  Where
or, in terms of reduced variables P  Pc Pr
27

Tel. +962 6 535 5000 | 22888

 we can analytically integrate the equation with the appropriate equation of state , or
 We can use charts available for the compressibility factor as a function of the
reduced variables, Tr and Pr by graphically integrate the right-hand side of the
Equation and come up with a chart for the fugacity coefficient in reduced
coordinates.
28

Tel. +962 6 535 5000 | 22888
Excursion: Correspondence principle
 Correspondence principles and generalized charts exist for

fugacity and other thermodynamic properties.
 For fugacity, both two- and three-parameter generalized
charts have been developed.
 Again, these are to be used only in the absence of reliable
experimental data.
29

Tel. +962 6 535 5000 | 22888
Reduced variables of a gas are defined as:

Pr = P/Pc Tr = T/Tc Vr = V/Vc
Principle of corresponding states - real gases in the
same state of reduced volume and temperature exert
approximately the same pressure. Another way to
say this is, real gases in the same reduced state of
temperature and pressure have the same reduced
compressibility factor.
This fact can be used to calculate PVT properties of
gases for which no EOS is available.
30

Tel. +962 6 535 5000 | 22888
I. We can use this equation together with the generalized Z

charts.
1) Look up Pc and Tc of gas
2) Calculate Pr and Tr values for desired T’s and P’s
3) Make a Table of Z from the generalized charts at various values of Tr
and Pr. Of course, we must have Pr values from 0 to the pressure of
interest at each temperature.
4) Graph (Z-1)/Pr vs. Pr for each Tr.
5) Determine the area under the the graph from Pr = 0 to Pr = Pr to get ln
.
II. Used generalized fugacity charts.
31

Tel. +962 6 535 5000 | 22888
32

Tel. +962 6 535 5000 | 22888
33

Tel. +962 6 535 5000 | 22888
34

Tel. +962 6 535 5000 | 22888
Example
Calculate the fugacity of CO2 at 600°C (873 K)

and 1200 atm.
Tc = 304.2 K; Pc = 72.8 atm
Tr = 2.87; Pr = 16.48
From the chart   1.12
so
fi
 i  f = (1.12)(1200) = 1344 bars
P
35

Tel. +962 6 535 5000 | 22888

Virial equation of state
Bii P
Z i 1 
RT
 Where the second virial coefficient Bii is a function of temperature only for a pure
species
ln i   Z i  1 const T 
P dP
0 P
Bii P dP
P
ln i 0 RT P (const T )
BP
ln i  ii
RT 36

Tel. +962 6 535 5000 | 22888
37

Tel. +962 6 535 5000 | 22888

Lee-Kesler correlation
fugacity coefficients charts
38

Tel. +962 6 535 5000 | 22888
Fugacity coefficient based on the Lee–Kesler equation of state 39

Tel. +962 6 535 5000 | 22888

Fugacity coefficient based on the Lee–Kesler equation of state 40

Tel. +962 6 535 5000 | 22888
 If the EOS is explicit in pressure, we can use the relation
Using the original Redlich-Kwong equation:

RT a
P  12
(V  b) T V (V  b)
41

Tel. +962 6 535 5000 | 22888

V 1
P
Using the equation ln       P
0
RT P 
 V  b 2a V  b 
ln   ln    ln  
 
3
 V b  V b RT 2
b  V 
a  V  b  b  PV
  ln      ln
RT 2 b   V  V  b 
3
RT
42

Tel. +962 6 535 5000 | 22888
V 1
P
 For the equation ln       P

0
RT P 
Change the integrating variable from P to v using the product rule
then
43

Tel. +962 6 535 5000 | 22888

44

Tel. +962 6 535 5000 | 22888
Using the van der Waals equation:
RT a
P  2
V  b V
OR
But
45

Tel. +962 6 535 5000 | 22888

 V  b 2a PV
ln   ln     ln
 V  b  V  b V RT RT
Generic Cubic EOS
46

Tel. +962 6 535 5000 | 22888
Example
47

Tel. +962 6 535 5000 | 22888
Example
Determine the fugacity, in bars, for R134a for a Redlich-Kwong gas at 90 oC and 10
bar. Compare against Van der Waals EOS.
48

Tel. +962 6 535 5000 | 22888
Fugacity and fugacity coefficient of a Vapor Mixture
 In addition to temperature and pressure, the fugacity of species i depends on what
other species are present in the mixture.
 In a mixture, the chemical nature of the interactions between species i and all the
other species in the mixture must be taken into account.
 For an ideal gas mixture, the chemical potential is
 ig  i T   RT ln yi P 
i
 For real fluid (gas or liquid)
Gi  i (T )  RT ln fi
 For species I in a mixture of real gases or in a solution of liquids, the equilibrium

analogous to Eq. (11.20), the ideal-gas expression, is:
49

Tel. +962 6 535 5000 | 22888
i  i T   RT ln fî
fi fugacity of species pure species
fî fugacity of species in solution (mixture)
 The definition of a residual property is given in Sec. 6.2:
The defining equation for a

M R  M  M ig (6.41) partial residual property
 Where M is the molar (or unit mass) value of a thermodynamic property and M ig is
the value that the property would have for an ideal gas of the same composition at
same T and P. 50

Tel. +962 6 535 5000 | 22888
 The residual Gibbs energy is nG R  nG  nG ig
the partial residual Gibbs energy is Gi R  Gi  Giig
fî
Gi  i    RT ln
R ig
i
yi P
 The fugacity coefficient of species i î in mixture is defined as
51

Tel. +962 6 535 5000 | 22888
fî
Gi R  RT lnî î 
yi P
 In an ideal gas mixture, the fugacity of species i is equal to its partial pressure
fî ig  yi P îig  1
 In an ideal gas of pure species, the fugacity is equal to (total) pressure
52

Tel. +962 6 535 5000 | 22888
The Fundamental Residual-Property Relation
Determination of fugacity G  1 G
d    dG  dT
coefficient in solution  RT  RT RT 2
dG  V dP  S dT   Gi dni G  H  TS
i
G  V H G
Substituting d    dP  2
dT   i dni
 RT  RT RT i RT
 For an ideal gas  G ig  V ig H ig Gi ig

d    dP  dT   dni
 RT  RT RT 2 i RT
Subtraction gives
 GR  VR HR Gi R
d    dP  2
dT  i RT dni
 RT  RT RT
53

Tel. +962 6 535 5000 | 22888

 nG R  nV R nH R Gi R
d    dP  2
dT  i RT dni
 RT  RT RT
 nG R  nV R nH R
d
 RT



 RT
dP 
RT 2
dT   ln ˆ dn
i
i i (11.52)
nV   (G / RT ) 
R R
  (11.53)
RT  P 
 T , x
HR   (G R / RT ) 
 T   (11.54)
RT   T 
  P, x
  ( nG R / RT ) 
ln î    (11.55)
  n 
 i  P ,T , x
  ln î  R
  ln î  R
   Vi     Hi 2
 P   T 
 T , x RT   P,x RT
54

Tel. +962 6 535 5000 | 22888
ˆ   (nG R / RT ) 
ln i   
 n i  P ,T , x
GR
  dP
P
And combine with eq. (6.49)
RT
 0 Z  1
P
(const T )
55

Tel. +962 6 535 5000 | 22888
56

Tel. +962 6 535 5000 | 22888
 Volume-explicit virial equation of state
BP
Z 1 
RT
 The mixture second virial coefficient B is a function of T and composition.
For mixture
B  y y B
i j
i j ij (11.57) [volume/mol]
e.g. binary mixture

B = y1y1B11 + y1y2B12 + y2y1B21+ y2y2B22
B = y12B11 + 2y1y2B12 + y22B22 (11.58)
57

Tel. +962 6 535 5000 | 22888
with Bij = Bji

B11, B22 pure species virial coefficients
B12 cross virial coefficient (mixture property)
Bij is a function only of temperature
Re-arrange
58

Tel. +962 6 535 5000 | 22888
59

Tel. +962 6 535 5000 | 22888
60

Tel. +962 6 535 5000 | 22888
lnˆ1 
P
RT

B11  y2212  (11.59)
lnˆ2 
P
RT

B22  y1212  (11.60)
61

Tel. +962 6 535 5000 | 22888
62

Tel. +962 6 535 5000 | 22888 62
Example
N2 / CH4 y1 = 0.4, T = 200K, P = 30 bar
B11 = –35.2 B22 = –105.0 B12 = –59.8 cm3/mol

12 = 20.6 cm3/mol
lnˆ1 
P
RT
 
B11  y2212 (11.59)
lnˆ2 
P
RT

B22  y1212  (11.60)
ˆ1 = 0.9511 ˆ2 = 0.8324

63

Tel. +962 6 535 5000 | 22888
64

Tel. +962 6 535 5000 | 22888
65

Tel. +962 6 535 5000 | 22888
Excursion: Residual properties
GR
  dP
P
RT
 0 Z  1
P
(integration at const. T )
GR f
and  ln  ln 
RT P
HR
T

  G R / RT   HR P  Z  dP
 T    (const T )
T  RT 0
 T  P P
RT  P
SR from GR and HR
G R  H R  TS R
66

Tel. +962 6 535 5000 | 22888
SR P  Z  dP
  dP
P
T     0 Z  1 (const T )
R 0
 T  P P P
or, in terms of reduced variables P  Pc Pr T  TcTr
67

Tel. +962 6 535 5000 | 22888
Volume-explicit virial equation for nonideal gas :V(T,P) or Z(T,P)
B
Z  1 P
RT
GR
  dP BP dP BP
P P
RT
 0 Z  1
P

0 RT P

RT
HR
 T 

  G R / RT    BP / RT  
 T 
P  1 dB B  P  B dB 
 T      
T  T  R  T dT T 2  R  T dT 
RT  P  P
68

Tel. +962 6 535 5000 | 22888
SR H R GR P dB
  
R RT RT R dT
Pressure-explicit forms of equation of states Z(T,V)
Change of variables is useful
PV P
Z 
RT RT  = 1/V molar density
P  ZRT
dP  RT  Zd   dZ  const T 
69

Tel. +962 6 535 5000 | 22888
RT d dZ
dP RTZ
 d  dZ    const T 
P P P  Z
GR  d
  dP
    dZ
P Z
RT
 0 Z  1
P
 0 Z  1
 1
 Z  1
Z
(const T )
GR  d
  Z  1  Z  1  ln Z (const T )
RT 0 
HR   Z  d
T     Z 1 (const T )
RT   
0 T
SR   Z  d  d
R
 ln Z  T   
  
0 T
  Z  1 
0
(const T )
70

Tel. +962 6 535 5000 | 22888
 The approach based on the use of the compressibility factors can be applied to the
present instance to evolve generalized correlations for computing enthalpy and
entropy changes for gases.
 We start with the Pitzer-type expression for the compressibility factor:
71

Tel. +962 6 535 5000 | 22888
 Both the above equations may be rewritten individually as follows:
72

Tel. +962 6 535 5000 | 22888
73

Tel. +962 6 535 5000 | 22888
74

Tel. +962 6 535 5000 | 22888
75

Tel. +962 6 535 5000 | 22888
76

Tel. +962 6 535 5000 | 22888
77

Tel. +962 6 535 5000 | 22888

Lec 4-Phase Equilibria II - Fugacity-Part 1

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

Lec 4-Phase Equilibria II - Fugacity-Part 1

Uploaded by

Copyright:

Available Formats

Chemical Engineering Thermodynamics II

Lec 3: Phase Equilibria: Fugacity-part 1

Dr.-Eng. Zayed Al-Hamamre

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

 State the criteria for chemical equilibrium in terms of fugacity.

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

 It is a derived thermodynamic property, it provides a simple criterion for chemical equilibria of

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Criteria for Chemical Equilibria in Terms of Fugacity

They are in equilibrium

 For vapor-liquid equilibrium

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

iv P sat  il P sat

 And hence i f  iv  isat (11.41)

the same fugacity coefficient

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Criteria for Chemical Equilibria in Terms of Fugacity

 For species i in a mixture of real gases or in a solution of liquids, the chemical

fˆi fugacity of species in solution (mixture)

 For phases α and β at equilibrium at the same T, P

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

i  i    i i  1, 2,, N 

 The fugacity of each species is the same in all phases

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Fugacity of Pure Species

i  i    i i  1, 2,, N 

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Residual Gibbs energy &Fugacity of Pure Species

 For ideal gas f

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Fugacity and Fugacity Coefficient of Pure Gases

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

for saturated steam at 1 atm

 To find the fugacity, we must now choose a reference state.

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

 Also, when the EOS is explicit in pressure,

Equation of state to is then used to relate

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

At constant temperature, we can differentiate Equation

Using partial fractions

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

The van der Waals equation written in virial form becomes

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Expression for the Fugacity Coefficient of a Pure Gas Using

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

or, in terms of reduced variables P  Pc Pr

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Expression for the Fugacity Coefficient of a Pure Gas Using

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

 Correspondence principles and generalized charts exist for

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Excursion: Correspondence principle