SOLUTION

THERMODYNAMICS: THEORY
• THEIDEAL GAS MIXTURE MODEL
• FUGACITY AND FUGACITY COEFFICIENT: PURE SPECIES
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
 
ig
V
i  
 ni   ni  T , P ,n j P  ni n P
T , P ,n j j

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
V  Viig  V ig 
i
ig
(11.20)
P 2
 • 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.
yi RT
pi  ig
 yi 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
Miig  Viig by the equation:

Miig T , P   Miig T , pi  (11.21) 3
• The enthalpy of an ideal gas is independent of pressure; therefore

H iig T , P   H iig T , pi   H iig T , P 

• More simply,

H iig  H iig (11.22)

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

• H iig
An analogous equation applies for and other properties that
are independent of pressure. U iig

4
 5
 The entropy of an ideal gas does depend on pressure, and by eq. (6.24),

dT dP
dSiig  C pig R (6.24)
T P
dSiig  Rd ln P  const T 
• Integration from pi to P gives

P P

 dS
ig
i   R  d ln P  const T 
pi pi

P P
Siig  T , P   Siig  T , pi    R ln   R ln  R ln yi
pi yi P

•
S ig
 T , p
Substituting this resulti into eq.   Si T
ig
i (11.21) ,P  R
written
ln y
for thei entropy yields

 

S
i
ig
T , P   S T , P   R ln yi
ig
i
Miig T , P   Miig T , pi  (11.21)
or

(11.23)
S  Siig  R ln yi
i
ig

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

S iig 5
 6
• For the Gibbs energy of an ideal gas mixture, G ig  H ig  TS ig
the parallel relation for partial properties is
  
G  H  TSiig
i
ig ig
i

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


 H iig  H iig (11.22)
G  Hiig  TSiig  RT ln yi
i
ig

(11.23)
S  Siig  R ln yi
i
ig


or (11.24)
iig  G  Giig  RT ln yi
i
ig

• The summability relation, eq. (11.11), with eqs. (11.22), (11.23), and
(11.24) yields
H ig   yi H iig (11.25)
i

S ig   yi Siig  R yi ln yi (11.26)
i i

G ig   yi Giig  RT  yi ln yi (11.27)
i i
6
 7

• When eq. (11.25) is written,

H ig   yi H iig  0
i

the difference on the left is the enthalpy change associated with a

process in which appropriate amounts of the pure species at T and P
are mixed to form one mole of mixture at the same T and P. For ideal
gases, this enthalpy change of mixing is zero.
• When eq. (11.26) is rearranged as
1
S ig   yi Siig  R yi ln
i i yi

the left side is the entropy change of mixing for ideal gases.
• Because 1/yi > 1, this quantity is always positive, in agreement with
the second law.

7
 An alternative expression for the chemical potential  ig
results when
i

in eq. (11.24)
Giig is replaced by an expression giving its T and P
dependence.
 This comes from eq. (6.10) written for an ideal gas:
RT
dGiig  Viig dP  dP  RTd ln P  const T  dG  VdP  SdT
P (6.10)

 Integration gives
Giig  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  i T   RT ln  yi P 
ig
i
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   yi i T   RT  yi ln  yi P  (11.30)
i i 8
 FUGACITY AND FUGACITY
COEFFICIENT: PURE SPECIES
 From eq. (11.6), the chemical potential i provides the fundamental
criterion for phase equilibria as well as for chemical reaction equilibria.

 
However, the Gibbs energy, and hence i iisdefined

i  ...  in  i  1,2,...,
i relation 
toNthe
internal energy and entropy.
  H  TS
Because absolute values of internalGenergy H U 
are unknown, PVsame is true
the
for i.
 Moreover, eq. (11.29) shows that iig approaches negative infinity when
either P or yi approaches zero. This is true not just for ideal gas but for any
gas.


  G  i T   RT ln  yi P 
ig
i
ig
i
(11.29)
 Although these characteristics do not preclude the use of chemical
potentials, the application of equilibrium criteria is facilitated by
introduction of the fugacity, a property that takes the place of i but which
does not exhibit its less desirable characteristics.
9
 The concept of fugacity was introduced so that the ideal gas mixture
equations could be used for real fluids (which deviate from ideal gas
behavior).
 The origin of the fugacity concept resides in eq. (11.28), valid only for
pure species i in the ideal gas state.

Giig  i T   RT ln P (11.28)

 For a real fluid, an analogous equation that defines fi, the fugacity of pure
species i is written:

Gi  i T   RT ln fi (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 fi
Gi  Gi  RT ln
ig

P 10
 By definition of eq. (6.41), M R  M  Mig ; Gi – Giig is the residual
Gibbs energy, GiR; thus
GiR  RT ln i (11.33)
where the dimensionless ratio fi/P has been defined as fugacity
coefficient, given by the symbol i:
fi (11.34)
i 
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):
 Pg 209
GR P dP (6.45)
 J    Z  1  const T 
RT 0 P
 GiR 
lim    lim ln i  J
P 0 RT P 0
  11
 12

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

equal to zero.
SR P  Z  dP P dP
 T     0  Z  1  (6.48)
R 0
 T  P P P

f 
lim ln i  lim ln  i   0
P 0 P 0
P

and f 
limi  lim  i   1
P 0 P
P 0
 
 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
   Z  1  const T  (6.49)
RT 0 P
P dP
ln i    Zi  1  const T  (11.35)
0 P
12
 13

 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
Zi  1 
RT
 Because Bii is a function of temperature only for a pure species,
substitution into eq. (11.35) gives

Bii P
lni   dP  const T 
RT 0

B P (11.36)
ln i  ii
RT
13
 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 R  RT ln 
(11.33)
i i

GR (6.66b)
 Z  1  ln  Z     qI
RT
lni  Z i  1  ln  Z i  i   qi I i (11.37)
where
bP
 (3.50) where:
RT a and b are positive constant
a T   and  are pure numbers, same
q (3.51) for all substances
bRT
1  1   b 
I ln  (6.65b)
    1   b 
14
 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  

15
 16

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 fi (11.38a)

Gil  i T   RT ln fil (11.38b)

 By difference,

f
Gi  Gil  RT ln i l
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.

16
 According to eq. (6.69), Giv - Gil = 0; therefore:

G  G  (6.69)

fi  fil  fi 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.

17
 An alternative formulation is based on the corresponding fugacity
coefficients:
f i sat
i  sat
sat
(11.40)
Pi
whence i  il  isat (11.41)

 This equation, expressing equality of fugacity coefficients, is an

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

18
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:

fi  P  
l 
fi Pisat  f P  f P P
i
l
i
sat
i
l
sat

f P  f P 
 i
Pisat i i
sat
i
l
i
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,
dP
 
Pisat
ln  i
sat
 Z i  1  const T  (11.42)
0 P

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

 Ratio (C) reflects the effect of pressure on the fugacity of pure liquid i.

19
 The basis of its calculation is eq. (6.10), integrated at constant T to
give
P dG  VdP  SdT (6.10)
Gi  Gisat   sat
Vil dP
Pi

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

written for both Gi and Gisat; subtraction then yields
fi Gi  i T   RT ln fi (11.31)
Gi  Gisat  RT ln sat
fi
 The two expressions for Gi – Gisat are set equal:
fi 1 P l
RT Pisat
ln  Vi dP
fisat
 Ratio (C) is then
f il  P  1 P l

fil Pisat 
 exp
RT Pi
sat
Vi dP

 Substituting for the three ratios in the initial equation yields

1 P
fi  isat Pi sat exp 
l
Vi dP (11.43)
RT Pi sat
20
 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,
Vil  P  Pisat 
fi  isat Pi sat exp (11.44)
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.

21
 If Ziv is given by eq. (3.38), the simplest form of the virial equation,
then

 Bii P Bii Pisat

Zi  1  and i
sat
 exp
RT RT

and eq. (11.44) becomes

Bii Pi sat  Vil  P  Pisat 

fi  Pi sat exp (11.45)
RT

22
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.

23
Solution:
Eq. (11.31) is written twice:
First, for a state at pressure P;
Second, for a low pressure reference state, denoted by *,
Both for temperature T:

Gi  i T   RT ln fi and Gi*  i T   RT ln fi *

Subtraction eliminates Гi (T), and yields

fi 1
ln 
fi* RT
 Gi  Gi 
*

By definition Gi = Hi – TSi and Gi* = Hi* - TSi*; substitution gives

fi 1  Hi  Hi* * 
ln *  
fi R T

 Si  Si   (A)

24
The lowest pressure for which data at 300oC (573.15K) are given
in the steam table is 1 kPa. Steam at these conditions is for
practical purposes an ideal gas, for which fi* = P* = 1 kPa. Data for
this state provide the following reference values:

Hi* = 3076.8 J g-1 Si* = 10.3450 J g-1 K-1

Eq. (A) may now be applied to states of superheated steam at

300oC (573.15K) for various values of P from 1 kPa to the
saturation pressure of 8592.7 kPa.

For example, at P = 4000 kPa and 300oC (573.15K):

Hi = 2962.0 J g-1 Si = 6.3642 J g-1 K-1

25
 26

Values of H and S must be multiplied by the molar mass of water

(18.015 g mol-1) to put them on a molar basis for substitution into eq.
(A):

fi 18.015g mol -1   2962.0  3076.8  J g -1 

ln *     6.3642  10.3450  J g K 
-1 -1

fi 8.314 J mol -1K -1  573.15K 

 8.1917
fi
*
 3611.0
fi

 
f i   3611.0  fi*   3611.0  1 kPa   3611.0 kPa

Thus the fugacity coefficient at 4000 kPa is

f i 3611.0
i    0.9028
P 4000
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

fi sat  6738.9 kPa

and
isat  0.7843

27
 28
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:

 
Vil  1.404cm3 g -1 18.015g mol-1 
 25.29 cm3 mol-1

At 10 000 kPa, for example, eq. (11.44) becomes

fi   0.7843  8592.7 kPa  exp

 25.29cm mol  10000  8592.7  kPa
3 -1

 6789.8 kPa
8314cm kPa mol K   573.15K 
3 -1 -1

The fugacity coefficient of liquid water at these condition is

i  fi P  6789.8/10000  0.6790
28
 29
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.
29
REFERENCE
 Smith, J.M.,Van Ness, H.C., and Abbott, M.M. 2005.
Introduction to Chemical Engineering
Thermodynamics. Seventh Edition. Mc Graw-Hill.

30
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303