THERMODYNAMICS II

Fugacity And Fugacity

Coefficient of Pure Species
Recap
RT
dg  v dP 
ig
i
ig
i dp  RTd ln P(const T ) [36]
P

g  i (T )  RT ln P
ig
i
[37]

  i (T )  RT ln yi P
ig
i
[38]

g   yi i (T )  RT  yi ln yi P
ig [39]
 The Chemical Potential
 The chemical potential µi, provides a criterion for phase
equilibria

 Absolute values for chemical potential do not exist

although they are important for phase & chemical
equilibria.

Where problem solving is concerned μ is deficient for

the following reasons:
 Chemical Potential
i) it is related to primitive quantities, u & s
through g

ii) from eq. (38): μi -∞ as P or y 0 (40)

iii)as P or species i concentration approaches 0

μ goes to -∞
. Fugacity

 Need for a more robust parameter that

accommodates values of P & y down to zero
which is the domain of ideal gases

 A quantity that behaves like μ without its

deficiencies

 G. N. Lewis suggested defining a new

thermodynamic property: fugacity, f
 Fugacity
 Tendency to flee (escape) and an exact measure of
a component’s volatility

 Fugacity has units of pressure and plays the same

role in real gases that partial pressures play in
ideal gases.

Starting with the equation:   i 

   vi
 P  T ,n j (41)

d i  vi dP At constant T (42)
 Fugacity
 using the ideal gas relation for this low
pressure situation:
 v  RT
d i    dP  dP (43)
 ni  T , P ,n j 1 P

 Choosing a reference state denoted by “o”

P
 i   i  RT ln o
o

P (44)

pi
 i   i  RT ln o
o
(45)
pi
fˆ
Fugacity is defined as:  i   io  RT ln io (46)
fˆi
 Fugacity
 Fugacity has units of pressure and is to real gases as
partial pressure is to ideal gases

 Fugacity applies to liquid as well as solids

 Since as pressure tends to zero gases approach ideality

we may complete the fugacity definition, thus:
 fˆi 
lim 0    1 (ideal gas ) (47)
p p 
 i
 Which together with eq. (46) forms the definition for
Fugacity
Fugacity coefficient
fˆi fˆi
 ˆ i 
pi , sys y i Psys (48)

ˆ i  1 Attractive & repulsive forces balance

ˆ i  1 Tendency to escape is less than for an ideal gas

ˆ i  1 Stronger repulsive forces

Other forms of Fugacity
ˆf   nf  
 i  n  or f   x i
ˆ
f i
 i T .P,n j  i i (49)

 Total solution fugacity f

g  g  RT ln
o

fo (50)
f 
lim 0   1
p P  (51)
 
f
 (52)
Psys
Pure species fugacity fˆi
g i  g  RT ln o
o

fˆi
i
(53)
 fi  fi
lim 0    1 & i  (54)
P
p
Psys
Fugacity for chemical equilibrium
mia =mib (55)

é fˆ a ù b ,o é fˆ b ù
mi +RTlnê ai ,o ú=mi +RTlnê ib ,o ú
a ,o (56)
ë fi û ë fi û

é ˆ
f a ,o ù é ˆ
f bù
mia ,o-mib ,o=RTlnê i b ,o ú+RTlnê ia ú
ë fi û ë fi û (57)

Definition from(46)
é fˆ b ù
0=RTlnê ia ú
ë fi û (58)

(59)
or fˆia = fˆi b
Pure gas fugacity
 Vapour-liquid equilibria
ˆf v  fˆ l (60)
i i
 For gases the reference state must be low enough
pressure to approximate ideal gas behaviour at the
system temperature
 f iv 
g i  g  RT ln 
o
i 
 low 
P (61)

v
f
 iv  i (62)
Psys
Pure gases
 Data for fugacity calculation may be obtained
from

 1. tables
 2. E.O.S
 3. Generalized correlations
 Eg.
 (a)Determine the fugacity and fugacity coefficient
of saturated steam at 1.0 atm.
 Derive an expression for the fugacity of a
pure gas from the van der Waals E.O.S
 Using the viral form of the van der Waals EOS
truncated to the 2nd term:
  a  
PV  n  RT   b   P  tenms in P 2
, P 3
,......
  RT  

P  RT a   fiv 
 Plow  P  b  RT  dP  RT ln  Plow 

 a   f iv 
b   P  RT ln    RT ln  i
 RT   P 

f v
 a  P  For an ideal gas a=b=0 so φ=1 as
for pure i :  iv  i  exp  b   
P  RT  RT  expected
Fugacity from generalized correlations
P
 f iv 
g i  g   vi dP  RT ln 
o

i
Plow
Dividing
 Plow  by RT and subtracting ᶴ (1/P)dP (63)
from each side gives:
P
vi P
1  f iv  P 1
 RT
dP   dP  ln 
P
   dP
 Plow  Plow P
Plow Plow Combining integrals on the (64)
LHS and simplifying the RHS:
P
 v 1  f iv 
  RT P 
    v
dP ln   ln i
Plow  P In terms of compressibility factor (65)

P
dP
ln    z  1
v
i i
P
Pideal
In terms of reduced variables (66)

Pr
dPr
ln  iv    z  1
Pr , ideal
Pr
(67)
 Residual Property
 No experimental method to directly measure g or g/RT

 Residual properties have readily numerical values

 Residual Gibbs energy : gR=g – gig (same T & P)

 Similarly : vR = v- vig = v – RT/P but v = zRT/P

v R

RT
 z  1
P

m R  m  m ig
Fundamental property relations for
residual properties
 Recall:  g  v h
d  dp  dT
 RT  RT
2
RT


 For an ideal gas : d 
g ig
 v ig h ig

 RT   dP  2
dT
  RT RT

 Subtracting:
 gR  vR h R
d    dP  2
dT
  RT  RT RT
Other forms
v R  g R / RT 
 
RT  P  T

h R
 g / RT 
R
 T  
RT  T  P

g R  h R  TS R
 R R R
s h g
 
R RT RT

g  v
R R
d    dP (const P )
 RT  RT
int egrating
R R
g v P
 dP (const T )
RT 0 RP
 R R
g v
 z  1
dP
P
 (const T )
RT 0 RT P
R
differentiating and substituting for h
P  z  dP
R
h
 T    (const T )
0 T
RT  P P

P  z  dP
R
  z  1
s P dP
 T    (const T )
0 T
R  P P 0 P
 Residual Property Relation
 Recall: mR=m-mig multiplying by n & differentiating w.r.t ni:


  nm R     nm 

  
  nm ig 

 Each term has the form
   
 n i  T , P ,n j  n i  T , P ,n j  n i  T , P ,n j of a partial property (68)

ig
m i  mi  m i
R
Rewriting for residual
Gibbs energy (68)

ig Defines partial residual

g i  gi  g i
R
Gibbs energy (68)

fˆi
i   ig
i  RT ln̂ From μi=gi
(68)
yi P

g i  RT ln  i
R
(68)
Residual Property Relation
 The fundamental residual property relation can also
be written for fugacity coefficient as:


  ng R / RT 
ln ˆ i  

 (69)
  ni  P,T ,n j

 Which demonstrates that lnφi is a partial property

w.r.t gR/RT

 Eg.
 Develop a general equation for calculating lnφi
values from compressibility-factor data
 Lee-Kesler EOS
 Lee-Kessler correlations may be used to solve for φ
 Log φi =log φ(o) + ωlog φ(1)

 Eg.
 Determine the fugacity and fugacity coefficient of
ethane at a pressure of 50.0 bar and a temperature
of 25.0 oC using generalized correlations.

 Pc=48.7 bar, Tc=305.5 K, ω=0.099