CHE553 (CHEMICAL ENGINEERING

THERMODYNAMICS)

CHAPTER 2 - SOLUTION
THERMODYNAMICS:
THEORY AND APPLICATION

EDITED BY: MEOR MUHAMMAD HAFIZ SHAH BUDDIN

CONTENT – PART 2
THE IDEAL GAS MIXTURE MODEL

FUGACITY AND FUGACITY COEFFICIENT:

PURE SPECIES
Course Learning Outcome
■ Understand the fundamental properties relation, fugacity of pure
species and species in solution.
■ Apply the concept of solution thermodynamics and various models for
the excess Gibbs Energy

2
 3

THE IDEAL GAS MIXTURE MODEL

■ The molar volume of an ideal gas is V = RT/P. All ideal gases, whether
pure or mixed, have the same molar volume at the same T and P.
■ The partial molar volume of species i in an ideal gas mixture is found
from eq. (11.7) applied to the volume; superscript ig denotes the ideal
gas state:
−   ( nV ig )    ( nRT / P )  RT  n  RT
V =
i
ig
 =  =   =
  ni  T ,P ,n j  ni  T ,P ,n j
P  ni  nj
P

where the final equality depends on the equation n = ni +  j n j

■ This means that for ideal gases at given T and P the partial molar
volume, the pure species molar volume, and the mixture molar volume
are identical:
−
RT
Vi ig = Vi ig = V ig = (11.20)
P
 4

■ Partial pressure of species i in an ideal gas mixture is define as the

pressure that species i would exert if it alone occupied the molar
volume of the mixture.
y RT
pi = i ig = y i P ( i = 1, 2, ..., N )
V

where yi is the mole fraction of species i. The partial pressures

obviously sum to the total pressure.
■ Gibbs’s theorem statement:
A partial molar property (other than volume) of a constituent species in an
ideal gas mixture is equal to the corresponding molar property of the
species as a pure ideal gas at the mixture temperature but at a pressure
equal to its partial pressure in the mixture.

− −
■ This is expressed mathematically for generic partial property M V
ig
i i
ig

by the equation: −
(11.21)
Miig ( T , P ) = Miig (T , pi )
 5

■ The enthalpy of an ideal gas is independent of pressure; therefore

−
H ( T , P ) = Hiig (T , pi ) = Hiig ( T , P )
ig
i

■ More simply,
−
H = Hiig
ig
i (11.22)

where Hiig is the pure species value at the mixture T and P.

ig
■ An analogous equation applies for Ui other properties that are
and
independent of pressure.
 6
■ The entropy of an ideal gas does depend on pressure, and by eq. (6.24),
dT dP
dSiig = C pig −R
T P
(6.24)
dSiig = −Rd ln P ( const T )
■ Integration from pi to P gives
P P

 dS = −R  d ln P ( const T )
ig
i
pi pi

P P
Siig ( T , P ) − Siig (T , pi ) = −R ln = −R ln = R ln y i
pi yiP

Siig ( T , pi ) = Siig ( T , P ) − R ln y i

■ Substituting this result into eq. (11.21) written for the entropy yields

− −

S ( T , P ) = S ( T , P ) − R ln y i
ig
i
ig
i
Miig ( T , P ) = Miig (T , pi ) (11.21)

or −
S = Siig − R ln y i
ig
i (11.23)
where Siig is the pure-species value at the mixture T and P.
 7
■ For the Gibbs energy of an ideal gas mixture, G = H − TS ig ig ig

the parallel relation for partial properties is

− − −
G = H − TSiig
ig
i
ig
i

■ In combination with eqs. (11.22) and (11.23) this becomes

− −
H = Hiig
ig (11.22)
G = H − TS + RT ln y i
ig
i
ig
i
ig
i
i

−
(11.23)
S = Siig − R ln y i
ig
i

−
or   G = G iig + RT ln y i
ig ig
(11.24)
i i

■ The summability relation, eq. (11.11), with eqs. (11.22), (11.23), and
(11.24) yields
H ig =  y i Hiig (11.25)
i

S ig =  y i Siig − R  y i ln y i (11.26)
i i

G ig =  y i G iig + RT  y i ln y i (11.27)
i i
 8

■ Property change of mixing for ideal gas is defined as:

Mig −  y i Miig = 0
i

■ From eq. (11.25), enthalpy change of mixing for ideal gas is zero.
H ig −  y i Hiig = 0
i

■ From eq. (11.26), entropy change of mixing for ideal gas is:
1
S ig −  y i Siig = R  y i ln
i i yi
Because 1/yi > 1, this quantity is always positive, in agreement with
the second law.
■ From eq. (11.27), Gibbs free energy change of mixing for ideal gas is:

G ig −  y i G iig = RT  y i ln y i
i i
■ An alternative expression for the chemical potential iig
results when 9

G iigin eq. (11.24) is replaced by an expression giving its T and P

dependence.
■ This comes from eq. (6.10) written for an ideal gas:
RT dG = VdP − SdT (6.10)
dG iig = Vi ig dP = dP = RTd ln P ( const T )
P
■ Integration gives
G iig =  i ( T ) + RT ln P (11.28)

where  i ( T ) , the integration constant at constant T, is a species-dependent

function of temperature only.
■ Eq. (11.24) is now written as

− −
  G = G + RT ln y i (11.24)
i
ig ig
i
ig
i   G =  i ( T ) + RT ln ( y i P )
i
ig ig
i
(11.29)

where the argument of the logarithm is the partial pressure.

■ Application of the summability relation, eq. (11.11), produces an expression for the
Gibbs energy of an ideal gas mixture:

G ig =  y i  i ( T ) + RT  y i ln ( y i P ) (11.30)
i i
 10

FUGACITY AND ITS IMPORTANCE

■ Ideal gases and ideal gas mixtures have analytical and well defined
equations but their applications are limited. They cannot be used to
describe the behavior of real fluids (which deviate significantly from ideal
gas behavior).
■ The concept of fugacity was introduced so that the ideal gas mixture
equations could be used for real fluids.
■ Fugacity is a property related to chemical potential. Chemical potential
cannot directly measured. Thus fugacity takes the place of chemical
potential.
■ Fugacity measure the tendency of a substance to prefer one phase
(liquid, solid, gas) over another. The phase with the lowest fugacity will be
the most favorable. Therefore, fugacity is useful for predicting the phase
state of multi-component mixtures at various temperatures and
pressures.
■ This chapter will concentrate on the definitions and formula of fugacities.
The next chapter will discuss on the applications of fugacities in vapor
liquid equilibrium.
 11

■ The origin of the fugacity concept resides in eq. (11.28), valid only for
FUGACITY AND FUGACITY
pure species i in the ideal gas state.

COEFFICIENT: PURE SPECIES

G iig =  i ( T ) + RT ln P (11.28)
■ The concept of fugacity was introduced in order for eq. (11.28) to be
valid for pure species, real fluid at constant temperature.
■ Thus, for a real fluid, an analogous equation that defines fi, the
fugacity of pure species i is written:
G i =  i ( T ) + RT ln f i
(11.31)
■ This new property fi, with units of pressure, replaces P in eq. (11.28).
If eq. (11.28) is a special case of eq. (11.31), then:
f i ig = P (11.32)
and the fugacity of pure species i as an ideal gas is necessarily equal
to its pressure.
■ Subtraction of eq. (11.28) from eq. (11.31), both written for the same
T and P, gives
f
G i − G iig = RT ln i
P
■ A residual property is simply the difference of a system property to the12
property
if the system behaves as an ideal gas (or ideal gas mixture)
MR  M − Mig (6.41)
■ In previous eqn., Gi – Giig is the residual Gibbs energy, GiR; thus
G iR = RT lni (11.33)
where the dimensionless ratio fi/P has been defined as fugacity coefficient,
given by the symbol i:
fi
i  (11.34)
P

■ Eq. (11.34) apply to pure species i in any phase at any condition.

■ As a special case they must be valid for ideal gases, for which GiR = 0, i = 1,
and eq. (11.28) is recovered from eq. (11.31).
■ Eq. (11.33) may be written for P = 0, and combine with eq. (6.45):
GR P dP
= J +  ( Z −1) ( const T ) (6.45)
RT 0 P
 G iR 
lim   = lim lni = J
P → 0 RT
  P →0
 13

■ In connection with eq. (6.48), the value of J is immaterial, and is set

equal to zero.
HR GR
RT RT

SR HR G R SR P Z  dP dP
= −T  
P
= −
R RT RT
(6.47)
R

0  T  P
P
− 0 ( Z − 1)
P
(6.48)

f
limlni = limln  i  = 0
P →0 P →0 P

and f
lim i = lim  i  = 1
P →0 P →0  P 

■ The identification of ln i with GiR/RT by eq. (11.33) permits its

evaluation by the integral of eq. (6.49)

GR P dP (6.49)
=  ( Z −1) ( const T )
RT 0 P
P dP
lni =  ( Z i −1) ( const T ) (11.35)
0 P
 14

■ Fugacity coefficients (and therefore fugacities) for pure gases are

evaluated by eq. (11.35) from PVT data or from a volume explicit
equation of state.
■ For example, when the compressibility factor is given by eq (3.38),

PV BP
Z= = 1+ (3.38)
RT RT
Bii P
Z i −1 =
RT

■ Because the second virial coefficient, Bii is a function of temperature

only for a pure species, substitution into eq. (11.35) gives
B P
lni = ii  dP ( const T )
RT 0

Bii P
lni =
RT (11.36)
 15

DETERMINATION OF FUGACITY
COEFFICIENT
■ There are a few methods for the determination of fugacity coefficient
of pure species:
– Compressibility factor method, useful for academic purpose
– Generalized correlations (e.g. Lee-Kesler), easy and practical
– Derived from Equation of States (e.g. Virial, etc.), useful especially in
computer simulation
 16

FUGACITY COEFFICIENTS FROM THE GENERIC

CUBIC EQUATION OF STATE
■ Evaluation of fugacity coefficients through cubic equations of state (e.g. the
Van der Waals, Redlich/Kwong, and Peng Robinson eqs) follows directly from
combination of eqs. (11.33) and (6.66b):
G iR = RT lni (11.33)

GR
= Z −1− ln ( Z −  ) − qI (6.66b)
RT
lni = Z i −1− ln ( Z i −  i ) − qi Ii
(11.37)
bP
 (3.50) where:
RT
a and b are positive constant
where a (T )  and  are pure numbers,
q (3.51)
bRT same for all substances

1 1+  b 
I= ln 
 −   1+  b  (6.65b)
 17

■ This eqn. written for pure species i (for the van der Waals equation, Ii
= βi/Zi).
■ Application of eq. (11.37) at a given T and P requires prior solution of
an equation of state for Zi by eq. (3.52) for a vapor phase or eq. (3.56)
for a liquid phase.
Z −
Z = 1 +  − q (3.52)
( Z +  )( Z +  )
1+  − Z 
Z =  + ( Z +  )( Z +  )   (3.56)
 q  
 18

VAPOR/LIQUID EQUILIBRIUM FOR PURE

SPECIES
■ Eq. (11.31) may be written for species i as saturated vapor and as a
saturated liquid at the same temperature:

Gi =  i ( T ) + RT ln f i (11.38a)

G il =  i ( T ) + RT ln f i l (11.38b)

■ By difference,
 f i
G i − G = RT ln l
l
i
fi

■ This eqn applies to the change of state from saturated liquid to

saturated vapor, both at temperature T and at the vapor pressure
Pisat.
 19

■ According to eq. (6.69), Giv - Gil = 0; therefore:

G = G  (6.69)

f i = f i l = f i sat (11.39)

where fisat indicates the value for either saturated liquid or saturated
vapor.
■ Coexisting phases of saturated liquid and saturated vapor are in
equilibrium; eq. (11.39) therefore expresses a fundamental principle:

For a pure species coexisting liquid and vapor phases are in

equilibrium when they have the same temperature, pressure
and fugacity.
 20

■ An alternative formulation is based on the corresponding fugacity

coefficients:
f i sat
i = sat
sat

Pi (11.40)

whence (11.41)
i = il = isat

■ This equation, expressing equality of fugacity coefficients, is an equally

valid criterion of vapor/liquid equilibrium for pure species.
 21

FUGACITY OF A PURE LIQUID

■ The fugacity of pure species i as a compressed liquid may be
calculated from the product of easily evaluated ratios:

fil (P ) =
f i

( P i
sat
) f i
l
( Pi
sat
) f i (P )
l
Pi sat
Pi sat
f i ( Pi ) f i ( Pi )
 sat l sat

( A) (B) (C )

■ Ratio (A) is the vapor phase fugacity coefficient of pure vapor i at its
vapor/liquid saturation pressure, designated isat. It is given by eq.
(11.35), written,
Pisat dP
lni sat
=
0
( Zi −1) P
( const T ) (11.42)

■ In accord with eq. (11.39) ratio (B) is unity.

■ Ratio (C) reflects the effect of pressure on the fugacity of pure liquid i.
 22
■ The basis of its calculation is eq. (6.10), integrated at constant T to
give
P
G i − G isat = 
l
sat
Vi dP dG = VdP − SdT (6.10)
Pi

■ Another expression for this difference results when eq. (11.31) is

written for both Gi and Gisat; subtraction then yields
f G i =  i ( T ) + RT ln f i
G i − G isat = RT ln sati (11.31)
fi
■ The two expressions for Gi – Gisat are set equal:
fi 1 P l
ln
f i sat
=
RT Pi
sat
Vi dP

■ Ratio (C) is then fil (P ) 1 P

f i l ( Pi sat )
= exp
RT  Pi sat
Vi l dP

■ Substituting for the three ratios in the initial equation yields

1 P l (11.43)
f i = isat Pi sat exp
RT Pi
sat
Vi dP
 23

■ Because Vil, the liquid phase molar volume, is a very weak function of P
at temperatures well below Tc, an excellent approximation is often
obtained when Vil is assumed constant at the value for saturated liquid.
In this case,

Vi l ( P − Pi sat ) (11.44)
f i = isat Pi sat exp
RT

■ The exponential is known as Poynting factor. Data required for

application of this equation:
– Values of Ziv for calculation of isat by eq. (11.42). These may come
from an equation of state, from experiment, or from a generalized
correlation.
– The liquid phase molar volume Vil, usually the value for saturated
liquid.
– A value for Pisat.
 24

■ If Ziv is given by eq. (3.38), the simplest form of the virial equation, then

BP Bii Pi sat

Z i −1 = ii and  i
sat
= exp
RT RT

and eq. (11.44) becomes

Bii Pi sat + Vi l ( P − Pi sat )

f i = Pi sat exp (11.45)
RT
 25

EXAMPLE 11.5
For H2O at a temperature of 300oC (573.15K) and for pressures up to
10 000 kPa (100 bar) calculate values of fi and i from data in the
steam tables and plot them vs. P.
 26

Similar calculations at other

pressures lead to the values
plotted in Fig. 11.3 at pressures
up to the saturation pressure
Pisat = 8592.7 kPa. At this
pressure,
Hi = 1345.1 J g-1
Si = 3.2552 J g-1 K-1
Substitution in eq. (A) yields
f i sat = 6738.9 kPa
and
isat = 0.7843
 27

According to eqs. (11.39) and

(11.41), the saturation values are
unchanged by condensation.
Although the plots are therefore
continuous, they do show
discontinuities in slope.
Values of fi and i for liquid water at
higher pressures are found by
application of eq. (11.44), with Vil
equal to molar volume of saturated
liquid water at 300oC:
Vi l = (1.404 cm3 g -1 ) (18.015 g mol-1 )
= 25.29 cm3 mol-1
At 10 000 kPa, for example, eq. (11.44) becomes

f i = ( 0.7843) ( 8592.7 kPa ) exp

( 25.29 cm3mol-1 ) (10000 − 8592.7 ) kPa
= 6789.8 kPa
( 8314 cm kPa mol K ) (573.15K )
3 -1 -1

The fugacity coefficient of liquid water at these condition is

i = f i P = 6789.8 /10000 = 0.6790
 28

Such calculations allow completion of Fig.

11.3, where the solid lines show how fi and i
vary with pressure.
The curve for fi starts at the origin, and
deviates increasingly from the dashed line
for an ideal gas (fi = P) as the pressure rises.
At Pisat there is discontinuity in slope, and the
curve then rises very slowly with increasing
pressure, indicating that the fugacity of liquid
water at 300oC (573.15K) is a weak function
of pressure.
This behavior is characteristic of liquids at
temperatures well below the critical
temperature.
The fugacity coefficient i decreases steadily
from its zero pressure value of unity as the
pressure rises. Its rapid decrease in the
liquid region is a consequence of the near-
constancy of the fugacity itself.