Chapter 4

FUGACITY
Fundamental equations for closed system consisting of
n moles:

dnU  T dnS   P dnV  (1)

dnH  T dnS   nV  dP (2)

dnA    nS  dT  P dnV  (3)

dnG   nS  dT  nV  dP (4)

 HOMOGENEOUS OPEN SYSTEM
An open system can exchange matter as well as energy
with its surroundings.
For a closed homogeneous system, we consider U to be a
function only of S and V:
U = U(S, V) (5)
In an open system, there are additional independent
variables, i.e., the mole numbers of the various
components present.
nU = nU(S,V, n1, n2, ....., nm) (6)
where m is the number of components.
The total differential of eq. (6) is

  nU   nU   nU

dnU  dS  dV     dni
 S  V ,n  V  S ,n i  ni  S ,V ,n
i i j i

(7)
Where subscript ni refers to all mole numbers and
subscript nj to all mole numbers other than the ith.

Chemical potential is defined as:

  nU
i    (8)
  ni  S ,V ,n j i
We may rewrite eq. (7) as

dnU  T dnS   P dnV     idni (9)

i

For a system comprising of 1 mole, n = 1 and ni = xi

dU  T dS  P dV    idx i (10)
i

Eqs. (9) and (10) are the fundamental equations for an

open system corresponding to eq. (1) for a closed
system.
 Using similar derivations, we can get the following
relations:

dnH  T dnS   nV  dP    idni (11)

i

dnA    nS  dT  P dnV     idni (12)

i

dnG   nS  dT  nV  dP   dni (13)

i

It follows that:
  nU   nH   nA    nG
i         
  ni  S ,V ,n j   n i  S ,P ,n j   ni  T ,V ,n j   n i  T ,P ,n j

(14)
(9)

(15)

(16)

(17)
(18)
(19)

(20)

(21)
Equations (19 – 21) can be written as

dnS 1    dnS 2   dnS 3     dnS    (22)

dnV 1    dnV 2   dnV 3     dnV    (23)

dni1    dni 2   dni3     dni   (24)

Substituting eqs. (22 – 24) into eq. (18) gives:

dnU  T 1   dnS 2   dnS3     dnS    

 P1   dnV 2   dnV 3     dnV    

   i1   dni2   dni3     dni   

i

 T 2 dnS 2   P2 dnV 2     i2 dni2 

i

 T 3 dnS 3   P3 dnV 3     i3 dni3 

i

 T   dnS     P  dnV      i  dni  
i
• All variations d(nS)(2), d(nV)(2), dn1(2), dn2(2), etc., are truly
independent.
• Therefore, at equilibrium in the closed system where
d(nU) = 0, it follows that

 nU
2   0
T  2   T 1 
 nS 

 nU
3   0 T  3   T 1  T 1   T  2     T   
 nS 

 nU
   0 T     T 1 
 nS 
  nU
2   0
P 2   P 1 
 nV 

 nU
3   0 P 3   P 1  P1   P  2     P  
 nV 

 nU
   0 P    P 1 
 nV 
 nU 12   11 
2   0
n1

 nU 13   11 

3   0 11   12     1  
n1

 nU
   0 1    11 
n1
 nU  22    21 
2   0
 n2

 nU  23    21 

3   0 21   22      2 
 n2

 nU
   0  2     21 
n2
 nU m2   m1 
2   0
nm

 nU m3   m1 

3   0 m1   m2     m  
nm

 nU
   0 m    m1 
nm
Thus, at equilibrium

T 1   T  2     T    (25)

P 1   P 2     P   (26)

11   12     1   (27)

21   22     2   (28)



m1   m2     m   (29)

(30)
   nG
Eq. (14): i   
  n i  T ,P ,n j

i  Gi (31)
  nM
Eq. (30): Mi   
  ni  T ,P ,n j

Important relations for partial molar properties are:

M   x i Mi (32)
i

and Gibbs-Duhem equation:

 M  dP   M  dT  x M  0
     i i (33)
 P  T , x  T  P , x i
(34)

(35)
(36)
GIBB’S THEOREM

(37)
(38)

(32):

(39)
Equation (20) of Chapter 3:

dT  V 
dS  CP    dP (3.20)
T  T  P

For ideal gas:

ig
ig ig dT   Vi 
dSi  CPi   dP
T  T  P

ig dT
ig dP
dS  C
i PiR (40)
T P
For a constant T process
dT
ig ig
dS  C i Pi (constant T)
T
Sig
i  T ,P 
dT P


ig
dS  R 
i
(constant T)
i  T ,p i 
Sig pi T

P P
S T , P   S T , pi   R ln  R ln
ig
i
ig
i  R ln y i
pi y iP

Sigi T , pi   Sigi T , P   R ln y i

According to eq. (37):

Siig T , P   Sigi T , pi 
whence

Siig T , P   Sigi T , P   R ln y i

Siig  Sigi  R ln y i (41)

By the summability relation, eq. (32):

Sigi   y i Siig   y i Sigi  R ln y i 

i i

Or:
Sigi   y i Sigi  R  y i ln y i
i i
This equation is rearranged as

Sigi   y i Sigi  R  y i ln y i
i i

1
S   y i S  R  y i ln
ig
i
ig
i (42)
i i yi

the left side is the entropy change of mixing for ideal

gases.
Since 1/yi >1, this quantity is always positive, in agree-
ment with the second law.
The mixing process is inherently irreversible, and for ideal
gases mixing at constant T and P is not accompanied by
heat transfer.
Gibbs energy for an ideal gas mixture:
Gig  Hig  TSig

Partial Gibbs energy :

Giig  Hiig  TSiig

In combination with eqs. (38) and (41) this becomes

Giig  Higi  TSigi  RT ln y i  Gigi  RT ln y i

or:
 igi  Giig  Gigi  RT ln y i (43)
An alternative expression for the chemical potential can
be derived from eq. (2.4):
dGigi   Sigi dT  Viig dP (2.4)

At constant temperature:
dP
ig ig
dGi  Vi dP  RT (constant T)
P
Integration gives:

Gigi  i T   RT ln P (44)

Combining eqs. (43) and (44) results in:

 igi  i T   RT lny iP  (45)
 Fugacity for Pure Species
The origin of the fugacity concept resides in eq. (44), valid
only for pure species i in the ideal-gas state.
For a real fluid, we write an analogous equation:

Gi  i T   RT ln fi (46)

where fi is fugacity of pure species i.

Subtraction of eq. (44) from Eq. (46), both written for
the same T and P, gives:
ig fi
Gi  Gi  RT ln (47)
P
Combining eqs. (3.41) with (47) gives:
fi
R
Gi  RT ln (48)
P
The dimensionless ratio fi/P is another new property, the
fugacity coefficient, given the symbol i:
fi
i 
P (49)
Equation (48) can be written as
GRi  RT ln i (50)
The definition of fugacity is completed by setting the
ideal-gas-state fugacity of pure species i equal to its
pressure:
fiig  P (51)
Equation (3.50):
GRi P dP
  Z i  1 (constant T) (3.50)
RT 0 P

Combining eqs. (50) and (3.50) results in:

P
dP
ln i   Z i  1 (constant T) (51)
0 P

Fugacity coefficients (and therefore fugacities) for pure

gases are evaluated by this equation from PVT data or
from a volume-explicit equation of state.
An example of volume-explicit equation of state is the 2-
term virial equation:

BiP BiP
Zi  1  Zi  1 
RT RT

P
Bi
ln i   dP (constant T)
0 RT

Because the second virial coefficient Bi is a function of

temperature only for a pure species,
BiP
ln i  (constant T) (52)
RT
FUGACITY COEFFICIENT DERIVED FROM
VOLUME-EXPLICIT EQUATION OF STATE

Use equation (3.63):

GRi   Vi  bi   a i  Vi  bi 

 Z i  1  ln Z i    ln 
RT   Vi      biRT  Vi  bi 

Combining eqs. (3.63) and (50) gives:

  Vi  bi   a i  Vi  bi 
ln i  Z i  1  ln Z i    ln 
  Vi      biRT  Vi  bi 

(53)
VAPOR/LIQUID EQULIBRIUM FOR PURE SPECIES

Eq. (46) for species i as a saturated vapor:

GiV  i T   RT ln fiV
(54)

For saturated liquid:

GLi  i T   RT ln fiL (55)

By difference:
V
V L f
Gi  Gi  RT ln i L
fi
Phase transition from vapor to liquid phase occurs at
constant T dan P (Pisat). According to eq. (4):

d(nG) = 0
Since the number of moles n is constant, dG = 0, therefore :
GiV  GLi  0 (56)

Therefore:
fiV  fiL  fisat (57)

For a pure species, coexisting liquid and vapor phases are

in equilibrium when they have the same temperature,
pressure, and fugacity
An alternative formulation is based on the corresponding
fugacity coefficients
sat
sat f
i  i sat (58)
Pi

whence:

iV  Li  isat (59)

FUGACITY OF PURE LIQUID
The fugacity of pure species i as a compressed liquid is
calculated in two steps:
1. The fugacity coefficient of saturated vapor is
determined from Eq. (53), evaluated at P = Pisat and Vi =
Visat. The fugacity is calculated using eq. (49).

  Vi  bi   a i  Vi  bi 
ln i  Z i  1  ln Z i    ln 
  Vi      biRT  Vi  bi 

(53)
fi  iP (49)
2. the calculation of the fugacity change resulting from
the pressure increase, Pisat to P, that changes the state
from saturated liquid to compressed liquid.
An isothermal change of pressure, eq. (3.4) is
integrated to give:
P
Gi  Gisat   VidP (60)
Pisat

According to eq. (46):

Gi  i T   RT ln fi

Gisat  i T   RT ln fisat
(–)
sat fi
Gi  G  RT ln
i (61)
fisat
Eq. (60) = Eq. (61):

fi P
ln sat
  VidP
f
i Pisat

Since Vi, the liquid-phase molar volume, is a very weak

function of P at T << Tc, an excellent approximation is
often obtained when Vi is assumed constant at the value
for saturated liquid, ViL:
fi
ln sat  Vi P  Pisat 
fi
fi  Vi P  Pisat 
sat
 Poynting factor  exp   (62)
fi  RT 
Remembering that:

fisat  isat Pisat

The fugacity of a pure liquid is:

sat sat 
fi  i Pi exp 
Vi P  Pi 
sat

 (63)
 RT 
 Phase Rule
First law of thermodynamics:
dU  Q  W

thermodynamic properties (U, T, P, V) reflect the internal

state or the thermodynamic state of the system.
Heat and work quantities, are not properties; they
account for the energy changes that occur in the
surroundings and appear only when changes occur in a
system.
They depend on the nature of the process causing the
change, and are associated with areas rather than points
on a graph.
 P1 (P1, V1)

P W


(P2, V2)
P2

V1
V V2
• The intensive state of a PVT system containing N
chemical species and  phases in equilibrium is
characterized by the intensive variables, temperature T,
pressure P, and N – 1 mole fractions for each phase.

• These are the phase-rule variables, and their number is

2 + (N – 1)().

• The masses of the phases are not phase-rule variables,

because they have no influence on the intensive state
of the system.
• An independent phase-equilibrium equation may be
written connecting intensive variables for each of the N
species for each pair of phases present.

• Thus, the number of independent phase-equilibrium

equations is ( – 1)(N).

• The difference between the number of phase-rule

variables and the number of independent equations
connecting them is the number of variables that may
be independently fixed.
Called the degrees of freedom of the system F:
F = 2 + (N – 1)() – ( – 1)(N)

F=2–+N (60)

• The intensive state of a system at equilibrium is

established when its temperature, pressure, and the
compositions of all phases are fixed.
• These are therefore phase-rule variables, but they are
not all independent.
• The phase rule gives the number of variables from this
set which must be arbitrarily specified to fix all
remaining phase-rule variables  number of degrees of
freedom (F).
PURE HOMOGENEOUS FLUID

N=1
T, P, V =1
F=2–+N
=2–1+1=2

• The state of a pure homogeneous fluid is fixed

whenever two intensive thermodynamic properties
are set at definite values
VAPOR/LIQUID EQULIBRIUM FOR PURE SPECIES

TV, PV, VV N=1

=2
F=2–+N
TL, PL, VL =2–2+1=1

The state of the system is fixed when only a single

property is specified. For example, a mixture of steam
and liquid water in equilibrium at 101.325 kPa can exist
only at 373.15 K (100°C). It is impossible to change the
temperature without also changing the pressure if vapor
and liquid are to continue to exist in equilibrium
Intensive variables: TV, PV, VV, V, TL, PL, VL, L = 8
Independent equations:
TV = TL = T
PV = P L = P
V = L
VV = f(T, P) ……. biggest root of the eos
V = f(T, P, VV)
VL = f(T, P) ………. smallest root of the eos
L = f(T, P, VL)
Here we have 7 equations with 8 unkowns. It means
that we must define one intensive variable (T or P)
Algorithm:
1. Input: T
2. Assume P
3. Calculate ZV and ZL (cubic equation)
4. Calculate VV and ZL
5. Calculate V (eq. 53 with V = VV)
6. Calculate L (eq. 53 with V = VL)
7. Calculate Ratio = V/ L
8. If Ratio  1, assume new value of P
9. Go to step no. 3