Back to Chapter 6

 In chapter 6, thermodynamic properties (such as U, S, H, A, G..) have been related

to T, P and V.

Chemical Engineering Thermodynamics II

CHE-303

INSTRUCTOR: Dr. NAYEF M. ALSAIFI

Chapter 11 & 12: Chemical potential & fugacity

Back to Chapter 6 What if we have an open system

 The change of the thermodynamic properties (dU, dS, dH, dA and dG) have also
been derived in four fundamental equations called Gibbs equations.  Recall:

 Mass flow determines the type of the system whether it is a closed or open.

Vapor Vapor Vapor

Liquid Liquid Liquid

Vapor and liquid form Liquid alone is an Vapor alone is an

a closed system open system open system

 The above equations represent the change of properties in a closed system.

3 4

What if we have an open system Let’s derive dG for an open system

 For simplicity, let’s take a system composed of the substances A and B

 For an open system:
 = (, ,  ,  ) 12.1
 Besides, T, P and V, the thermodynamic properties depend on the number of
moles:  The total differential dG is given by:
 If amount of moles of i component is added or withdrawn from the system,
the thermodynamic properties change:        
  =  +  +  +  12.2
 , ,
 , ,
 ,,
 ,,
 Change in U with the addition of small amount of moles of
 the ith component keeping all the other variables constant
,,

.  Recall
. Change of G with the addition
.  or removal of small amount of 
− =
.  while the other variables constant

. 
V= Change of G with the addition
 
or removal of small amount of 
 while the other variables constant
Change in G with the addition of small amount of moles of
 ,,
the ith component keeping all the other variables constant

   
  = −   +   +  +  12.3
 ,,
 ,,

5 6
 Let’s derive dG for an open system dG for a multicomponent system

     For an open system, the total differentials of   is given by:

  = −   +   +  +  12.3
 ,,
 ,,

 
  = −   +   +   12.5
    
 What are and ?  ,,
 ,,  ,,

 or
()
 Recall  =
 (Partial property)
 ,,
  = −   +   +    12.6


 Therefore ()
= 
 ,, Let’s give the partial  ≡   For the special case of n=1 and  = 
Gibbs free energy a
()
new symbol: 
 ≡ 
= 
 ,,
  = − +  +    12.7

 The partial Gibbs free energy is normally given a special symbol  and called
chemical potential.

 Therefore   = −   +   +   +   12.4

7 8

Chemical potential Chemical potential as a criteria for equilibrium

 The role of the chemical potential is similar to temperature and pressure:

 Let’s assume we have two phases  and :
 In heat transfer course, you have learned that heat transfers as a result of
temperature gradient:
temperature difference is a potential for heat transfer.
Phase 
∆ = potential for heat flow 


 In Fluid mechanics course, you have learned that fluid flows as a

result of pressure gradient: 
pressure difference is a potential for fluid flow.
Phase 
∆ = potential for fluid flow

 In this course, you should learn that chemical work is a result of

gradient or difference in chemical potential.  3 criteria for equilibrium

∆ = potential for chemical work

Note that chemical work is performed either by chemical reaction

or by diffusion.

9 10

Chemical potential as a criteria for equilibrium Chemical potential as a criteria for equilibrium

 Let’s assume we have two phases  and :  Let’s assume we have two phases  and :

Phase  Phase 
open system open system
  
= −    +    +      
= −    +    +   
 
   

Open system    

= −    +   
 +   

Open system    
= −    +   
 +   


 
Phase  Phase 


 The change in the total Gibbs energy (  ) of the two-phase system is the sum of  
and    :
Closed system
 
  =   +  
Phase   
 Similarly for total entropy and total volume:   = −   +   +    +   
  
 
Closed system 
  =   +   For a closed system:   = −   +  

 
  =   
+   
    +    = 
 
11 Phase  12
 Chemical potential as a criteria for equilibrium A special case of the chemical potential

 
   +    =  12.8
  ()
 =  =
 ,,

Phase 
 Mass conservation requires that


 12.9
 =-   What if we have a pure component?


Phase 
()
= =
 ,

 
   +    =     −    = 
 
  −   = 
   To summarize:
  

 For a component in a mixture, the chemical potential is the partial Gibbs free energy

 =  12.10
 For a pure component, the chemical potential is the Gibbs free energy

13 14

Ideal gas mixtures Ideal gas mixtures

 Thermodynamic properties of ideal gas mixture are given by:

Pure component 1

Ideal gas 
Ideal gas   =   
12.11
+ Mixture 

Pure component 2   =   

12.12

Ideal gas
What are the  =   


. thermodynamic 12.13

+ properties and the
partial properties of 
.   =    −    ln( )
ideal gas mixtures? 12.14
.  


Pure component i   =    +    ln( )
12.15
 
Ideal gas

15 16

Ideal gas mixtures Ideal gas mixtures

 The change of the Gibbs free energy is given by:

 Partial properties of ideal gas mixture are given by:
 = −  +   12.21

 
 =   At constant temperature, the change of the Gibbs free energy is given by:
12.16

 =   12.22
  (, ) =   (, )
 
12.17
 For pure-species of an ideal gas, the above equation is given by:

 
  (, ) =  (, )
  =   12.23
 
12.18

 For an ideal gas  is given by:
  
 ,  =  ,  −  
12.19  =

 Therefore,
 
 ,  =  ,  +  12.20     
12.24
 =    =   = 

 Integrate the last equation:

 = Γi  + () 12.25

17
where Γi  is an integration constant at Constant T. 18
 Let’s get back to Chemical potential Let’s examine equation 12.27 carefully

 Remember: chemical potential is the partial Gibbs free energy: 

 = Γi  + ( ) 12.27

 ≡ 
 For ideal gas:
 What if  → ? 
 ≡  
 ≡ 
  → ∞
 What if P → ?
 Let’s get back to equation 12.20:
 What is Γi  ? How to get an absolute value for Γi  ?
 
 ,  =  ,  +  12.20

 
 =  ,  +  12.26 Gilbert Newton Lewis
To overcome these difficulties, G. N. Lewis developed a property
called fugacity as an alternative to the (1875-1946)
  chemical potential.
  is defined by equation 12.25:  = Γi  + ()

 Therefore, substitute equation 12.25 into 12.26, we get:

 
 = Γi  +   +   = Γi  + ( ) 12.27  The advantage of fugacity is only computational; particularly for mixtures.

19 20

How was fugacity defined? How was fugacity defined?

 Let’s start from equation 12.24:


 =  12.24

 Equation 12.24 is limited to ideal gas, for a real fluid, the above equation becomes:

 =  12.28 To make things more obvious, let’s see how fugacity was defined starting from
a pure component.

 For real fluid, pressure was replaced with  which is called fugacity.

 What is the unit of fugacity? (It is clear that it is pressure unit).

 Therefore, we could think of fugacity as “ corrected pressure”.

 It is clear that for ideal gas:

 12.29
 =

21 22

How was fugacity defined? Let’s explore more advantages of fugacity

 As previously mentioned, at constant temperature, the change of Gibbs of free energy is given by:
 − ∗ =   12.30
 =   12.22


 =    =   =    =  
 or  −  ∗ =  

 As previously mentioned, for a pure component, the chemical potential is the Gibbs free energy:
 (note that  ∗ was defined as Γi  in the pervious slides)

 =    =  

 As pervsiouy mentioned  ∗ (  ∗ , Γ  ) has no absolute value but now because

   
of fugacity we could replace the difference term on the left hand side with a ratio measure
  =      =    in the right hand side.
∗ ∗ ∗ ∗


 − ∗ =    ∗ is called “standard state” and
∗ taken either 1 atm or 1bar.

 Therefore,  − ∗ =   12.30

23 24
 Fugacity nomenclatures Fugacity as a criteria of equilibrium

 Consider a mixture system :

 Fugacity and fugacity coefficients could be calculated for pure species and
 at constant T and P
mixtures.
 has two phases ( and )
 The system is considered at equilibrium if THREE criteria are satisfied:

Fugacity and fugacity Fugacity and fugacity

coefficient of pure species coefficient of pure
species in a mixture
1. thermal equilibrium   =  
2. mechanical equilibrium   = 
 
3. chemical equilibrium  = 


 
 =
  = Due to the encountered computational difficulty of
 
chemical potential, the chemical criteria is replaced by the
equality of fugacity


 = 
25 26

At equilibrium, fugacity equality is equivalent to chemical potential equality A new criteria of equilibrium

 Let’s see how chemical potential equality is equivalent to fugacity equality

 Let’s start from equation 12.25 which is for ideal gas and pure species : At equilibrium

 = Γi  + () We replaced chemical potential
Vapor with fugacity but how to
 For real fluid, equation 12.25 is given by: determine fugacity

 = Γi  + ( )  = Γi  + ( )

 Let’s apply the last equation for vapor and liquid phases Liquid

 = Γi  + ( ) (a)

 = Γi  + ( ) (b) Vapor (V)  =  ≡  = 

 Subtract b from a:

 −  = ( )

Liquid (L)
 At equilibrium, we know that  =   −  = 

 
 Therefore,  −  = (

)  = (

)  = 
27 28

Fugacity and residual Gibbs free energy Fugacity is related to residual properties

 We have shown that one of the main advantages of fugacity is that it is a new criteria  There is a connection between fugacity and residual properties. Therefore, it is possible to
of equilibrium. estimate fugacity if we know how estimate residual properties.

 In chapter 6, we learn how to estimate residual properties. Now, we will explore more  Let’s see what the connection between fugacity and residual properties is:
advantage of residual properties.

 As shown previously, the Gibbs free energy  12.25

of an ideal gas of a pure species  = Γi  + ()

 For a real fluid, the fugacity (f ) replaces P  = Γi  + ( ) 12.30


 Subtract 12.25 from 12.30:  −  = Γi  − Γi  + ( )-()

 
 −  = ()-()  = ( ) 12.31


 It is clear that the residual Gibbs free energy of a pure species is a function of fugacity of
a pure species.

 In equation 12.31, the dimensionless ratio is defined as fugacity coefficient (  ):


 
 = ( )  = ( ) or = ( ) 12.32
29
  30
 Back to chapter 6: how to get residual properties! Let’s explore equation 12.33 more



  =   −  12.33
0 

 It is clear that to calculate the fugacity (or fugacity coefficient), we need

compressibility factor

 In chapter 6, different methods have been shown to estimate Z


   

 From chapter 6, we knew that: = − or =   − 
 0   0  *
 In the pervious slide, equation 12.32 is given by: 
= ( ) 12.32



 Combine the last two equations:   =   −  12.33
0  31 32

Methods to compute fugacity coefficient

 Fugacity coefficient could be obtained for gas and liquid.

 There are different methods to compute fugacity coefficients.

 Because some methods are limited to gases; others are limited to liquids, each case (i.e gas 1
or liquid) should be studied separately:

Fugacity
Coefficient for
gases
1 2

Fugacity Fugacity
Coefficient for Coefficient for
gases liquid

 Fugacity coefficients of species in mixtures are more complicated from those of pure components.

33 34

Methods to compute fugacity coefficient for gases

 For gases, the following methods are usually used to compute fugacity coefficient:

Tables Virial EOS

Virial EOS
(pure species)
Fugacity
coefficient Equation of state (EOS)
For gases
Cubic EOS
Generalized correlations

35 36
 Fugacity coefficient from virial equation of state

 In chapter 6, the virial equation of state for a pure species was given by:

  
−= or  −  = 12.34
 

 If equation12.33 is used, the fugacity coefficient of the virial EOS is obtained:

Virial EOS
  
     (mixtures)
  =   −    =    =  
0  0   0 

 
  = 12.35


37 38

Fugacity coefficient from virial equation of state Fugacity coefficient from virial equation of state

 For a binary system, equation 12.36 is expanded as follows:

  ) in the mixture is given by:
 For multicomponent mixture, the fugacity coefficient of a species i (     
= ln 1 = ( +   11 − 11 + 1 2 11 − 12 + 2 1 21 − 21 + 2 2 21 − 22 )
 
 11  1 1   
 
ln  =  +      −  12.36  = ,  =   = ,  =   = ,  =   = ,  = 
  
 
 Apply equation 12.40:

    
ln 1 = ( +   11 − 11 + 1 2 11 − 12 + 2 1 21 − 21 + 2 2 21 − 22 )
 =  −  −  12.37  =  12.38  11  1 1   
0 0 0 0
 =  −  −  12.39  =  =  =  12.40    
ln 1 = ( +   −12 + 2 1 21 − 21 + 2 2 21 )
 11  1 2  
 Apply equation 12.38:
   
ln 1 = ( +   −12 + 2 1 21 + 2 2 21 )
 11  1 2  


ln 1 = ( + 2 2 21 ) 12.41
 11

 For k=2, equation 12.36 becomes:


ln 2 = ( + 1 1 21 ) 12.42
 22
39 40

Fugacity coefficient from virial equation of state Fugacity coefficient from virial equation of state

 The cross second virial coefficient could be estimated by:

 To summarize equation 12.36 to a binary system:
 0
  =  +  1
ln 1 = ( + 2 2 21 ) 12.41  12.43
 11


ln 2 = ( + 1 1 21 ) 12.42  +  0.5
12.45
 22  = 12.44  =   ( −  )


 Note that 21 is determined from equation 12.37 or the equation 12.39
   + 
 = 12.46  = 12.47
 =  −  −  12 = 12 − 11 − 22  

1/3 1/3 3
 Therefore, to determine 1 and 2 , 11 , 12 and 22 are required.  + 
 = 12.48

 11 is the second virial coefficient of pure component 1
 22 is the second virial coefficient of pure component 2
. .7
 12 is the cross second virial coefficient 0 = .8 − 1.6 12.49 1 = .9 − 12.50
 4.2
 If 11 and 22 are not available, they could be estimated from the methods presented
in Chapter 3 (see lecture 4 slide 18)
 kij is called binary interaction parameter, if it is not available , set it to zero.
 To estimate 12 , see next slide
41 42
 Fugacity coefficient from Equation of state (EOS)

 Fugacity coefficient could be obtained from equations of state by starting from

equation 12.33.

 For pure species, fugacity coefficient from van der Waals EOS is given by:

 − 
 =  −  −  − 12.51
Cubic EOS  
(pure species)
 For pure species, fugacity coefficient from Redlich-Kwong (RK) EOS is given by:

 +
 =  −  −   −  −  12.52
 

 For pure species, fugacity coefficient from Soave-Redlich-Kwong (SRK) EOS is given by:

 +
 =  −  −   −  −  12.53
 

 For pure species, fugacity coefficient from Peng-Robinson (PR) EOS is given by:
 + + 
 =  −  −   −  − 
  + −  12.54

43 Where i  = 44


Fugacity coefficient from Cubic equation of state (EOS)

 Example
Estimate the fugacity of ammonia vapor at 19.5 bar and 321.55 K assuming it obeys the
RK equation of state.
Solution
 The fugacity coefficient from Redlich-Kwong (RK) EOS is given by:
 +
 =  −  −   −  −  12.52
 

Generalized correlations
 Find the critical constants of ammonia from Table B1

 Calculate a, b and B

 At the specified T and P, find molar volume.

(note iteration is required to find V)

 In equation 12.52, Z=PV/RT

 = −.89  = .888


= .888  = .  bar Ans.


45 46

Generalized Correlations The generalized second virial coefficient correlation

 In chapter 3, the virial equation of state in terms of reduced temperature and pressure
 In chapter 3, the generalized correlations were used to obtain compressibility factor from was given by:
two different methods: 
 =  +  12.40

 Lee-Kesler method
 The generalized second virial coefficient correlation  = 0 + 1

. .7
 In chapter 6, the above two generalized correlations were used to estimate the residual 1 = .9 − 12.41
0 = .8 − 4.2
properties. 1.6

 Insert equation 12.40 into equation 12.36 and integrate to get:

 In this chapter, the generalized correlations will also be utilized to estimate fugacity
coefficients using:  0
 =  + 1  0
 Lee-Kesler method   =   + 1 12.42

 The generalized second virial coefficient correlation

 Therefore, to estimate the fugacity coefficient from the generalized second virial
coefficient, equation 12.42 could be used where the  0 and 1 are defined by
equations12.41 and 12.42.

47 48
 Lee-Kesler method

 To apply Lee-Kesler method to estimate the fugacity coefficient, we start with

equation 12.33:


  =   − 
0 

 Then, we write equation 12.33 in terms of reduced pressures:

  = 

 − 

12.36
2
0 

 As shown in Chapter 3, the compressibility factor was estimated by: Fugacity

Coefficient for
 =  0 + 1 12.37
liquid

 Insert equation 12.37 into 12.36:

 
 
  =  0 −  + ω  1
0  0  12.38

 0 1
 Therefore,

 =  0 + 1  =  0 1  12.39

0 1
  and  are tabulated in Appendix E (Tables E13-E16).
49 50

Fugacity coefficient for liquids Fugacity at saturation line

 Recall: PT diagram of pure species

 Since the saturation line is actually the equilibrium line, the fugacities of
vapor and liquid must be equal:

C Saturation line
 = 
Solid B
Pressure

liquid
 We could also say that:

A liquid C
 =  =
vapor  Saturation
Pressure
B line

Temperature
vapor A
 Let’s demonstrate how to calculate fugacity at A, B and C.
Temperature
 In other words, determine the fugacity at:
 the gas region (A) (it has been explained in the previous slides)
 the saturated line (B)
 the compressed liquid region(C) 51 52

Fugacity in the compressed liquid region Fugacity in the compressed liquid region

 How to determine fugacity in the compressed liquid region? 


 Let’s take the path from B to C (constant T).  =    12.59
 
  
 = −  +    =     =    −  =     12.55
    The molar volume of liquid is a weak function of pressure. Therefore,   could be taken
outside the integral:
 We know the Gibbs free energy of a real fluid is given by: 
 
 =      =    − 
 = Γi  + ( )   
12.56


 At saturation line, we could write: C 
 =  exp  −  12.60

 = Γi  + ( ) 12.57  liquid
Saturation
Pressure

B line
 Subtract 12.57 from 12.56:  Equation 12.60 is used to determine the fugacity of liquid for pure species


 −  = (

) 12.58 vapor A
 How to determine  ?
 From 12.58 and 12.55: Temperature   
 At the saturation line, we know that  =  = .
Therefore, we could use the methods used for determining the fugacity of vapor @  .


 =     12.59
 
53 54
 Example Example
Compute the fugacity and fugacity coefficient for hexane at 140 oC, for the pressure range Compute the fugacity and fugacity coefficient for hexane at 140 oC, for the pressure range
from 0 to 9 bar. The vapor pressure of hexane @ 140 oC is 6.128 bar while the saturated molar from 0 to 9 bar. The vapor pressure of hexane @ 140 C is 6.128 bar while the saturated molar
volume is 161.28 cm3/mol? volume is 161.28 cm3/mol?
Solution  Therefore, from 0 to 6.128 bar, the generalized Solution
second virial coefficient correlation could be used to
9 compute fugacity and fugacity coefficients
 0
 =   + 1 P (atm)  

6.128
Pressure (bar)

9 0 0 1
 0
 =   + 1
 1 0.97653 0.97653
Fugacity at saturation condition is 6.128 3 2.7937 0.93123

Pressure (bar)
 4 3.6375 0.90938
 =   0 + 1


20 100 140 5 4.4402 0.88803

 From 6.128 bar and up to 9 bar, the fugacity and
Temperature (°C) fugacity coefficient of the liquid could be calculated 6.128 5.298 0.86456
from:
 It is clear that the pressure range is from gas 7 5.3197 0.75996
phase region to the compressed liquid region.  ( −  ) 20 100 140
 =  exp 8 5.3448 0.66810
 Temperature (°C)
 ( −  ) 9 5.3699 0.59666
 =   exp

55 56

Back to ideal solution: Ideal solution in terms of fugacity

Lewis-Randall rule

 Show that at the vapor-liquid equilibrium line, the fugacity of the liquid equals the fugacity
of the vapor.
 The ideal solution has previously been studied. Review Chapters 10 & 11.

At the saturation line,  =6.128 bar,  =161.28 cm3/mol  The ideal solution could be given in terms of fugacity as:

 0
 =   + 1 = 5.298 bar
  =   12.61

Note that the above equation could be used up to the saturation line. Therefore, the  The above equation is called Lewis-Randall rule. Note that  could be determined from 12.60.
Calculated fugacity at P=  =6.128 will give you the saturated fugacity.

 Lewis-Randall rule says that the fugacity of a component in a mixture could be

 =5.298 bar determined from fugacity of pure species only.

 ( −  )
 =  exp = 5.298 bar


57 58

Fugacity and activity coefficient Fugacity and activity coefficient

 If vapor and liquid are at equilibrium, we know that:

 Recall Raoult’s law:   =  
 =  12.63
 Raoult’s law has been modified by introduction the activity coefficient to account for non ideality:

 From the definition of fugacity coefficient of a component in a mixture given in slide 25:
  =   

 Similarly, we could introduce  to the Lewis-Randall rule to account for non-ideality:  =
 
 =    12.62
 For the vapor, the above equation can be given by:

 The above equation gives the fugacity of a component in a liquid mixture.  =   12.64

 Now, substitute 12.62 & 12.64 into 16.63

  =   12.65

59 60
 Fugacity and activity coefficient Fugacity coefficient of the overall mixture

  =   12.65  For a pure species, the fugacity coefficient is related to the residual Gibbs free energy by:


 Note that  represents the fugacity of pure species that is given by 12.60: : = ( ) 12.32


 =  exp  −  12.60  For mixture, similar relation could be derived for the partial Gibbs free energy:


= ( )
 Insert 12.60 into 12.65: 

  From the definition of the partial molar property (chapter 11),

  =   exp  −  12.66



 =    11.8

 The exponential term (i.e exp  −  ) is called Poynting factor 


 

=  
 At low and moderate pressures, the Poynting factor equals to 1:  



  =   12.67 =   ( )



 Note if  =1 and  =  , Equation 12.67 reduces to modified Raoult’s law
   =   ( )


61   is the fugacity coefficient of the overall mixture. 62

Gibbs-Duhem equation and fugacity

Example:  At constant temperature and pressure, the Gibbs/Duhem equation is given by:

 A binary gas mixture contains 60 mol % A and 40 mol % B. At a pressure of 20 bar

and temperature of 340 K. The fugacity coefficient of components A and B in the  = 
  
Mixture are 0.8 and 0.9; respectively. What is the fugacity of the overall mixture?
(const T, P) 11.9


Solution:
We know that:

   =   ( ) = ( )



   = .(.8) +.(.9)

Therefore, for a binary system

  = .889 bar 1 1 + 2 2 = 

1 1 + 2 2 = 

63 64