Thermodynamics Asst. Professor A. N.

Al-Mosawi
6
2nd Course /Lecture 22 3rd Year/Chem. Eng.

Fugacity and Fugacity Coefficient

Fugacity
Fugacity is a state function property so as chemical potential (μi) and it is used to
describe phase and reaction equilibrium. The fugacity is rather more conventional to
be used than the chemical potential because:
1) The fugacity of a perfect gas can be calculated from PVT data.
2) The fugacity of component in a perfect gas mixture varies linearly with the
concentration of that component.
3) At the low pressure, the fugacity reduces to the partial pressure for species i in
solution.
Starting with equation:

Assume ideal gas, where: Vi=RT/P

For ideal gas only:

By analog for real fluid (gas or liquid) that defines a new property f.
For real gas:
Where: f is fugacity with pressure units.
For solutions, there are three set of eqs.
Pure species i
Mixture (‫)مزيج‬
Species i in solution
Where: (−) is overbar for partial propery, (ˆ) is circumflex for fugacity property.
Note that the subtraction and integration of the two last eqs. give:
… …………..eq. (*)
Thermodynamics Asst. Professor A. N. Al-Mosawi
6
2nd Course /Lecture 22 3rd Year/Chem. Eng.

Fugacity coefficient
The dimensionless ratio f/P is a mixture property called the fugacity coefficient and
given the symbol  .
For pure species i
For gas mixture or solution

For species i in solution

Note:
For ideal gas Z =1 i    1 fi = f = P
 
For mixture ideal gas mix & ideal sol f i  yi P f i  xi f i

A- Fugacity of Gases From PVT Data

These include deducing the compressibility factor. There are two methods, the
generalized correlation and the second virial coefficient.
1. Generalized Correlations Method

……………eq. (1)

……………eq. (2)
Subtraction eq. (1) from (2):

……………eq. (3)
as:
so, ……………eq. (4)
Substitution eq. (4) into eq. (3) gives:
f
(V  V ig ) dP  R T d ln ……………eq. (5)
P
Integrating eq. (5):
f 1 P
 d ln P  RT  0
(V  V ig ) dp

f 1 P
ln 
P RT 
0
(V  V ig ) dP ……………eq. (6)
Thermodynamics Asst. Professor A. N. Al-Mosawi
6
2nd Course /Lecture 22 3rd Year/Chem. Eng.

ZRT RT
as: V  and V ig 
P P
f 1 P ……………eq. (7)
then: ln
P
 ln  
RT 
0
( Z  1) dP
P
The generalized methods (Lee Kesler) developed for the compressibility factor Z of
pure gases may apply here to the fugacity coefficient. Equation (7) is put into
generalized form by substitution of the relationships P=Pc Pr and dP=Pc dPr

........................eq. (8)
Where integration is at constant T. Substitution for Z=Z°+ωZ1 yields:

Alternatively, we may write

Where:

Thus ……………eq. (9)

Eq. (9) is called Lee Kesler equation can be used by finding values of
From charts 11.2 & 11.4 for Pr ˂ 1 ‫ﺗﺳﺗﺧدم اﻟطرﯾﻘﺔ اﻟﻌﻣوﻣﯾﺔ اذا ﻛﺎﻧت‬
P. 336-339 ‫اﻟﻧﻘﺎط ﺗﺣﻘق اﻟﻣﻧﺣﻧﻰ أو أن‬
From charts 11.3 & 11.5 for Pr ˃ 1 Vr < 2

Note These charts can be used if Tr and Pr intersection points are located inside
curves or whenever Vr ˂ 2. Otherwise the virial method must be used:
Example 11.5, P.335 Text
Estimate a value for the fugacity of 1-butene vapor at 200°C and 70 bar.
Solution
Tr=1.13 Pr=1.74 ω=0.187
From Figs. 11.3 and 11.5 at these conditions (points located inside curves)
Thermodynamics Asst. Professor A. N. Al-Mosawi
6
2nd Course /Lecture 22 3rd Year/Chem. Eng.
‫ﺗﺳﺗﺧدم طرﯾﻘﺔ اﻷرﺗﺑﺎط اﻟﻌﻣوﻣﻲ اذا‬
‫ﻛﺎﻧت اﻟﻧﻘﺎط ﻻﺗﺣﻘق اﻟﻣﻧﺣﻧﻰ أو أن‬
2. Second Virial Coefficient Method Vr > 2

A particularly simple generalized correlation for ln  , results when simplest form of

the Virial equation is valid.
According to eq. (8):
PV B BP BP BPC Pr
as: Z  1  1  Z 1   ……………eq. (10)
RT V RT RT RTC Tr

and the second virial coefficient: B 

PC

RTC 
B   B1  ……………eq. (11)

Substitution eq. (11) into (10), and then eq. (10) becomes:

Z 1 
Tr

Pr 
B   B1  ……………eq. (12)

Substitution eq. (12) into (8) gives:

ln   
Pr

0
Pr 
Tr

B   B1
dPr
Pr

……………eq. (13)
Where:

Equation (13) , used in conjunction witb B° and B1 eq to provide values of  for

s.

different pure gases. For binary gas mixture the interaction second virial coefficients
B11, B12, B22 have to calculated to find B and then apply the following eq. for  :
BP
ln   ……………eq. (14)
RT
B- Fugacity of Gases From Residual Property
Useful Relations
By analog to eq. (4), the residual Gibbs energy is written:

Note that MR = M - Mig

so, VR = V - Vig = (z-1) RT/P
Thermodynamics Asst. Professor A. N. Al-Mosawi
6
2nd Course /Lecture 22 3rd Year/Chem. Eng.

Previously we take the following equations:

……………eq. (1)
……………eq. (2)
and by subtraction of eq. (1) from (2):
……………eq. (3)
f
d (G  G ig )  RT d ln
p

As (G-Gig) is the residual Gibbs energy GR; the dimensionless ratio f/P is  thus:

........................eq. (15)
Integration of eq. (15) yields the relation

Thus for the special case of an ideal gas, GR = 0,  = 1, and the integration constant
therefore C(T) = 0, and equation may be written
........................eq. (16)
The identification of ln  with (GR/RT) allows eq. (**) to be rewritten as:
........................eq. (17)

Fugacity coefficients (and therefore fugacities) are evaluated by equation (17) from
PVT data or from an equation of state.
Thermodynamics Asst. Professor A. N. Al-Mosawi
6
2nd Course /Lecture 22 3rd Year/Chem. Eng.

Example 2
Calculate the fugacity of isopropanol at 200°C and 20 bar, given that:
Z=1− 9.86×10-3P −11.41×10-5P2
Also calculate the fugacity using the generalized correlation charts and compare the
two results.
Solution
Using eq. (17):

P dP
ln    (1  9.86 10 3 P  11.4110 5 P 2  1)
0 P
P dP
ln    (9.86 10 3 P  11.4110 5 P 2 )
0 P
P
ln    (9.86 10 3  11.4110 5 P) dP
0

ln   9.86 10 3 P  5.705 10 5 P 2 ]020

ln   0.22

f
 0.8025
P
f  0.8025  20  16.05 bar

Repeat calculation using charts:

For isopropanol: Tc=512.6 Pc=81 ω=0.559
So: Tr=0.922, Pr=0.246
From chart 11.2    0.88
From chart 11.4  1  0.97
Using Lee Kesler equation:
  (  )( 1 ) 
  0.88 (0.97) 0.559
  0.865
f  0.865  20 17.3 bar
Thermodynamics Asst. Professor A. N. Al-Mosawi
6
2nd Course /Lecture 22 3rd Year/Chem. Eng.

Vapor/liquid equilibrium for pure species

For the change of state from saturated liquid to saturated vapor, both at temperature T
satsat
and at the vapor pressure fP
i i dGi = RT d ln fi

........................eq. (18)
Since coexisting phases of saturated liquid and saturated vapor are in equilibrium,
dGilv =0 (i.e Giv - Gil = 0); therefore
........................eq. (19)
Where: fisat indicates the value for either saturated liquid or saturated vapor. The
corresponding fugacity coefficient is
........................eq. (20)
Whence
........................eq. (21)
The equality of fugacities as expressed by eqs. (19) and (21) criterion of vapor/liquid
equilibrium for pure species.
Fugacity of pure liquid
The evaluation of the change in fugacity of pure liquid with increase in pressure
above Psat, the required equation follows directly from eq. (2) written for pure
species:
........................eq. (22)
together with eq. (4) written for pure species i,
........................eq. (23)
Whence
........................eq. (24)
Integration from the state of saturated liquid to that of compressed liquid gives:

........................eq. (25)
Since Vi the liquid-phase molar volume assumed constant for saturated liquid and
equal Vil:
........................eq. (26)
Thermodynamics Asst. Professor A. N. Al-Mosawi
6
2nd Course /Lecture 22 3rd Year/Chem. Eng.

Substituting fisat from eq.(20) and solving for fi gives:

........................eq. (27)
The exponential is known as the Poynting factor.

How to solve problems of liquids:

1. calculation of fisat at (required T, and psat for this T) using the previous method of
gases, because (fisat)vap= (fisat)liq
2. if the vapor pressure pisat <5 bar, then assume fisat = pisat
3. apply eq. (26) to find fi and i

Example- 11.3, p.329 Text

For H2O at a temperature of 300°C and for pressures up to 10000 kPa (100 bar),
calculate values of fi and i .
Solution
From steam table at 300°C, pisat =8592.7 kPa so fisat not equal Pisat

573 8592.7
Tr   0.885 Pr   0.385
647.3 (101.3) 220.5 Note: Lee Kesler equation
0.422
B   0.08  1.6  0.433 (9) also can be used
Tr
0.172
B1  0.139   0.148
Tr4.2

Using eq. (13) to find i sat

Pr  0.385
ln isat  ( B   B1 )  (0.433  0.344  0.148)  0.2105
Tr 0.885

i sat  0.8102

f i sat  i P sat  0.8102  8592.7  6961.6 kPa

sat

Taking Vil equal to the molar volume of sat. liquid of water at 300°C (steam table-1)
Vil = 1.404 cm3/gm = 1.404×18=25.27 cm3/gmol
pisat =8592.7 kPa
fisat =6961.6 kPa
Thermodynamics Asst. Professor A. N. Al-Mosawi
6
2nd Course /Lecture 22 3rd Year/Chem. Eng.

fi 25.27 (100  85.927)

ln 
6961.6 83.14  (300  273)

fi = 7013.76 kPa fugacity of liquid water

i = fi /P = 7013.76/10000= 0.7014 fugacity coefficient of liquid water

Example 4
Estimate the fugacity of liquid acetone at 110°C and 275 bar. the vapor pressure of
acetone at 110°C is 4.360 bar and the molar volume of saturated liquid acetone is 73
cm3 mol-1.
Solution
Note: At T= 110°C the vapor pressure pisat =4.36 bar (low value < 5 bar) and in this
case we take fisat = pisat = 4.36 bar
Using eq. (26)

fi 73 (275  4.36)
ln   0.620
4.36 83.14  (110  273)

fi
 i  1.859
4.36

fi = 8.1 bar