SOLUTION

THERMODYNAMICS:
THEORY

CHE553 CHEMICAL ENGINEERING

THERMODYNAMICS
Part 3
- FUGACITY AND FUGACITY COEFFICIENT: SPECIES IN SOLUTION
- GENERALIZED CORRELATIONS FOR THE FUGACITY COEFFICIENT
- THE IDEAL SOLUTION MODEL
- EXCESS PROPERTIES
 3

FUGACITY AND FUGACITY COEFFICIENT:

SPECIES IN SOLUTION
 The definition of a species in solution is parallel to the definition of the
pure-species fugacity.
 For species i in a mixture of real gases or in a solution of liquids,

i  i (T ) + RT ln fˆi (11.46)
^
where f i is the fugacity of species i in solution, replacing the partial
pressure yiP in eq. (11.29) for ideal gas.
iig  Giig = i (T ) + RT ln ( y i P ) (11.29)
 For species in solution, the phase equilibrium criteria is:
fˆi = fˆi  = ... = fˆi ( i = 1, 2, ...,N )
(11.47)
Multiple phases at the same T and P are in equilibrium when the
fugacity of each constituent species is the same in all phases.
 For the specific case of multicomponent vapor/liquid equilibrium, eq.
(11.47) becomes:
fˆi = fˆi l ( i = 1, 2, ...,N ) (11.48)
 4

 The definition of a residual property is

MR  M − Mig (6.41)
where M is the molar (or unit mass) value of a thermodynamic
property and Mig is the value that the property would have for
an ideal gas of the same composition at the same T and P.
R
 The defining equation for a partial residual property Mi
follows from this equation. Multiplied by n mol of mixture, it
becomes
nMR = nM − nMig
 Differentiation with respect to ni at constant T, P and nj gives
  ( nMR )    ( nM)    ( nMig ) 
  =  − 
  ni  P ,T ,n j   ni  P ,T ,n j  ni  P ,T ,n j
• Reference to eq. (11.7) shows that each term has the form of
a partial molar property. Thus,
MiR = Mi − Mi ig (11.49)
 5

 Written for the residual Gibbs energy, eq. (11.49) becomes

G iR = G i − G iig (11.50)
an equation which defines the partial residual Gibbs energy.
 Subtracting eq. (11.29) from eq. (11.46), both written for the
same T and P, yields    (T ) + RT ln fˆ (11.46)
i i i
fˆi
i − i = RT ln
ig −
  G = i (T ) + RT ln ( y i P )
ig ig (11.29)
yiP i i

 This result combined with eq. (11.50) and the identity i  G i

gives
G iR = RT lnˆi (11.51)

where by definition,
ˆ fˆi
i  (11.52)
yiP
 The dimensionless ratio ˆi is called the fugacity coefficient of
species i in solution.
 6

 Although most commonly applied to gases, the fugacity

coefficient may also be used for liquids, in this case mole
fraction yi is replaced by xi.
 Because eq. (11.29) for an ideal gas is a special case of eq.
(11.46), then
fˆi ig = y i P (11.53)
 Thus the fugacity of species i in an ideal gas mixture is equal
to its partial pressure. Moreover, ˆi = 1 , and for an ideal gas
ig

G iR = 0
fˆi ig y i P
ˆ
i 
ig
= =1 G iR = RT lnˆi ig = RT ln (1) = 0
yiP yiP
 7

Fugacity Coefficients from the Virial Equation

of State
 Values of ˆi for species i in solution are readily found from
equations of state.
 The simplest form of the virial equation provides a useful example.
 Written for a gas mixture it is exactly the same as for a pure
species:
BP
Z = 1+ (3.38)
RT
 The mixture second virial coefficient B is a function of
temperature and composition.
B =  y i y j Bij (11.61)
i j

where y represents mole fractions in a gas mixture, the indices i

and j identify species, and both run over all species present in the
mixture.
 The virial coefficient Bij characterizes a bimolecular interaction
between molecule i and molecule j, and therefore Bij = Bji.
 The summations account for all possible bimolecular interactions.
 8

B =  y i y j Bij (11.61)
i j

 For a binary mixture i = 1, 2 and j = 1, 2; the expansion of eq.

(11.61) then gives
B = y1y1B11 + y1y 2B12 + y 2 y1B21 + y 2 y 2B22
or
B = y12B11 + 2y1y 2B12 + y 2 2B22 (11.62)
 B11 and B22 are pure species virial coefficient and B12 is a
mixture property, known as a cross coefficient. Both are
function of temperature only.
 Expressions such as eqs. (11.61) and (11.62) relate mixture
coefficients to pure species and cross coefficients. They are
called mixing rules.
 9

 Eq. (11.62) allows derivation of expressions for lnˆ1 and lnˆ2 for a
binary gas mixture that obeys eq. (3.38). For n mol of gas mixture,
nBP
nZ = n +
RT
 Differentiation with respect to n1 gives
  ( nZ )   n  P   ( nB ) 
  =   +  
  n1  P ,T ,n2  n
 1  P ,T ,n2 RT   n1  T ,n2

 Because  ( nZ ) ni = Z i and n ni = 1, this reduces to

P   ( nB ) 
Z1 = 1+  
RT  n1 T ,n
2
 From eq. (11.60) yields
ˆ 1 P   ( nB )  P   ( nB ) 
RT 0  n1 T ,n
ln1 =   dP =   lnˆi =  ( Z i −1)
P dP
RT  n1 T ,n (11.60)
2 2
0 P

where the integration is elementary, because B is not function of

pressure. All that remains is evaluation of the derivative.
 10

B = y12B11 + 2y1y 2B12 + y 2 2B22 (11.62)

 Eq. (11.62) for the second virial coefficient may be written:
B = y1 (1− y 2 ) B11 + 2 y1y 2 B12 + y 2 (1− y1 ) B22
= y1B11 − y1y 2 B11 + 2y1y 2 B12 + y 2 B22 − y1y 2B22
or B = y1B11 + y2B22 + y1y 212 with 12  2B12 − B11 − B22
 Multiplying by n and substituting yi = ni/n gives,
n1n2
nB = ny1B11 + ny 2B22 + ny1y 212 or nB = nB1 11 + n B
2 22 + 12
n
 By differentiation,
  ( nB )   1 − n1  n  = B + 1 1− n1  n 
  = B11 +  2  2 12 11   2 12
  n1  T ,n2  n n  n  n 
= B11 + (1− y1 ) y 212 = B11 + y 2212
 Therefore from previous eqn.,
1 P   ( nB )  P   ( nB )  P
lnˆ1 =  
RT 0  n1 T ,n

2
dP = 
RT  n1 T ,n

2
lnˆ1 =
RT
( B11 + y 2212 ) (11.63a)
 Similarly,
P
lnˆ2 =
RT
( B22 + y1212 ) (11.63b)
 11

 Eqs. (11.63) are readily extended for application to

multicomponent gas mixtures; the general equation is

P  1 
lnˆk = B
 kk
RT 
+  i j ( ik ij )
2 i j
y y 2 −  (11.64)


where i and j run over all species, and

 ik  2Bik − Bii − Bkk  ij  2Bij − Bii − Bij
with
 ii = 0,  kk = 0, etc., and  ki =  ik , etc.,
 12

EXAMPLE 11.7
Determine the fugacity coefficients as given by eqs. (11.63)
for nitrogen and methane in a N2(1)/CH4(2) mixture at 200K
and 30 bar if the mixture contains 40 mole % N2. Experimental
virial coefficient data are as follows:
B11 = −35.2 B22 = −105.0 B12 = −59.8 cm3 mol-1
 13

GENERALIZED CORRELATIONS FOR THE

FUGACITY COEFFICIENT
 Eq. (11.35) is put into generalized form by substitution of the
relations,
P = Pc Pr dP = Pc dPr
P dP
lni =  ( Z i −1) ( const T ) (11.35)
0 P
 Hence, Pr dPr
lni =  ( Z i −1) (11.65)
0 Pr
where the integration is at constant Tr. Substitution for Zi by Eq.
(3.57) yields
Z i = Z 0 +  Z1 (3.57)

dPr dP
( Z 0 −1)
Pr Pr
ln =  +   Z1 r
0 Pr 0 Pr
where for simplicity i is omitted.
 14

 This equation may be written in alternative form:

ln = ln 0 +  ln1 (11.66)
where
dPr dPr
( Z 0 −1)
Pr Pr
ln 0   and ln1   Z1
0 Pr 0 Pr
 The integrals in these equations may be evaluated
numerically or graphically for various values of Tr and Pr from
data for Z0 and Z1 given in Table E.1- E.4 (Appendix E).
 Another method, and the one adopted by Lee and Kesler to
extend their correlation to fugacity coefficients, is based on
an equation of state.
 Eq. (11.66) may also be written,
 = ( 0 ) (1 )

(11.67)

 Table E.13 – E.16 present values for these quantities as derived

from the Lee/Kesler correlation as function of Tr and Pr.
 15

EXAMPLE 11.8
Estimate from eq. (11.67) a value for the fugacity of 1-butene
vapor at 200oC (473.15K) and 70 bar.
 16

 A useful generalized correlation for ln  results when the

simplest form of the virial equation is valid.
 Eqs. (3.61) and (3.63) combine to give
BP P (3.61)
Pr 0 1
Z −1 = Z = 1+
( B = 1+ Bˆ r
+ B )
T RT Tr
r
Bˆ = B0 + B1 (3.63)
 Substitution in eq. (11.65) and integration yield
Pr dPr
lni =  ( Z i −1)  Pr 0
Pr 0 1 
0

(11.65)
Pr
ln =
Tr
( B + B1 ) or  = exp 
T
( B +  B ) (11.68)
 r 
where
0.422 0.172
B0 = 0.083 − and B1 = 0.139 −
Tr1.6 Tr4.2
 This equation provides reliable values of  for any nonpolar or
slightly polar gas when applied at conditions where Z is
approximately linear in pressure. E.g. H2, N2, O2, CO2, CH4, C2H4
 Figure 3.14 serves as a guide to its suitability.
17
 18

Extension to Mixtures
 The general expression for calculation of ln ˆk from the second
virial coefficient data is given by eq. (11.64).
P  1 
ˆ
lnk = Bkk +  y i y j ( 2 ik −  ij ) (11.64)
RT  2 i j 
 Values of the pure species virial coefficients Bkk, Bii, etc., are
found from the generalized correlation represented by eqs.
(3.62), (3.63), (3.65), and (3.66).
BP
Bˆ = c (3.62)
RTc
Bˆ = B 0 + B1 (3.63)
0.422
B 0 = 0.083 − (3.65)
Tr1.6
0.172 (3.66)
B1 = 0.139 − 4.2
Tr
 19

 The cross coefficients Bik, Bij, etc., are found from an extension
of the same correlation.
 For this purpose, eq. (3.63) is rewritten in the more general
form
Bˆij = B0 + ij B1 (11.69a)
where
ˆB  Bij Pcij (11.69b)
ij
RTcij
and B0 and B1 are the same functions of Tr as given by eqs.
(3.65) and (3.66).
 Thus,
Bij Pcij
= B 0 + ij B1
RTcij
RTcij
Bij =
Pcij
(B 0
+ ij B1 )
 20

 The combining rules for calculation of ij, Tcij, and Pcij are
i +  j
ij = (11.70 )
2
Tcij = ( TciTcj ) (1− k )
1/ 2
ij (11.71)
Z cij RTcij
Pcij = (11.72 )
Vcij
Z ci + Z cj
Z cij = (11.73)
2
3
 Vci1/ 3 + Vcj1/ 3 
Vcij =   (11.74 )
 2 
 In eq. (11.71), kij is an empirical interaction parameter specific to
an i-j molecular pair.
 When i=j and for chemically similar species, kij = 0. Otherwise, it is
a small positive number evaluated from minimal PVT data or in
the absence of data set equal to zero.
 When i=j, all equations reduce to the appropriate values for a
pure species.
 21

 When ij, these equations define a set of interaction

parameters having no physical significance.
 Reduced temperature is given for each ij pair by Trij ≡ T/Tcij.
 For a mixture, values of Bij from eq. (11.69b) substituted into
eq. (11.61) yield the mixture second virial coefficient B, and
substituted into eq. (11.64) [eq. (11.63) for a binary] yield
values of ln ˆi . Bij Pcij
Bˆ ij  (11.69b)
RT cij

B =  y i y j Bij (11.61)
i j

P  1 
ˆ
lnk = Bkk +  y i y j ( 2 ik −  ij ) (11.64)
RT  2 i j 

P
lnˆ1 =
RT
( B11 + y 2212 ) (11.63a)

P
lnˆ2 =
RT
( B22 + y1212 ) (11.63b)
 22

EXAMPLE 11.9
Estimate ˆ1 and ˆ2 by eqs. (11.63) for an equimolar mixture of
methyl ethyl ketone(1)/toluene(2) at 50oC (323.15 K) and 25
kPa. Set all kij = 0.

Solution:
From Table B.1, the required data are as follows:
ij Tcij/K Pcij/bar Vcij/cm3 mol- Zcij ij
1

11 535.5 41.50 267 0.249 0.323

22 591.8 41.06 316 0.264 0.262
12 562.9 41.30 291 0.257 0.293
Values in the last row have been calculated by eqs. (11.70) –
(11.74).
 23

The values of Trij, B0, B1 and Bij calculated for each ij pair by
eqs. (3.65), (3.66) and (11.69), are as follows:

ij Trij B0 B1 Bij/cm3 mol-1

11 0.603 -0.865 -1.300 -1378.6
22 0.546 -1.028 -2.045 -1873.9
12 0.574 -0.943 -1.632 -1610.4
T Bˆij = B0 + ij B1 (11.69a)
Trij 
Tcij
0.422 Bij Pcij
B = 0.083 − 1.6
0
(3.65 ) Bˆ ij  (11.69b)
Tr RTcij
0.172
B1 = 0.139 − 4.2 (3.66 ) Bij Pcij
Tr = B 0 + ij B1
RTcij
RTcij
R = 83.14 cm3 bar mol-1 K-1 Bij =
Pcij
(B 0
+ ij B1 )
 24

Calculating 12 according to its definition gives:

12 = 2B12 − B11 − B22 = 2 ( −1610.4 ) +1378.6 +1873.9 = 31.7 cm3 mol-1

Eq.(11.63) then yield:

P 25
lnˆ1 =
RT
( B11 + y 2 12 )
2
 =  −1378.6 + ( 0.5 )2 (31.7 )  = −0.0128
( 8314 )(323.15 )  
P 25
lnˆ2 =
RT
( B22 + y1 12 )
2
 =  −1873.9 + ( 0.5 )2 (31.7 )  = −0.0174
( 8314 )(323.15 )  

R = 8314 cm3 kPa mol-1 K-1

Thus,
ˆ1 = 0.987 and ˆ2 = 0.983
 25

THE IDEAL SOLUTION MODEL

 The chemical potential for ideal gas mixture model is given by
eq. (11.24)
−
  G = G iig (T , P ) + RT ln y i
i
ig ig
i
(11.24)

 For an ideal solution,

−
  G = G i (T , P ) + RT ln x i
i
id id
i
(11.75)

 Partial volume,
 G iid   G i 
Vi = 
id
 =  
 P T , x  P T

 By eq. (11.4), ( G i / P )T = Vi ; thus,

(11.76)
Vi id = Vi
 26

 As a result of eq. (11.19),

 G iid   G i  − R ln x
Si = − 
id
 = −   i
 T P , x  T  P

 By eq. (11.5),
Si id = Si − R ln x i (11.77)

 Because Hiid = Giid + TSi id , substitution by eqs. (11.75) and (11.77)

yield
Hiid = G i + RT ln x i + TSi − RT ln x i
or
Hiid = Hi (11.78)

 The summability relation, eq. (11.11), applied to the special

case of an ideal solution, is written:
Mid =  x i Miid
i
 27

 Application to eqs. (11.75) – (11.78) yields

G id =  x i G i + RT  x i ln x i (11.79 )
i i

S id =  x i Si − R  x i ln x i (11.80 )
i i

V id =  x iVi (11.81)
i

H id =  x i Hi (11.82 )
i
 28

The Lewis/Randall Rule

 From eqs. (11.46) and (11.31),
i   i ( T ) + RT ln fˆi (11.46)
G i   i ( T ) + RT ln f i (11.31)
 Subtraction yields the general equation:
( )
i  G i + RT ln fˆi f i

 For the special case of an ideal solution,

(
iid  G iid = G i + RT ln fˆi id f i )
 Comparison with eq. (11.75) gives:
−

fˆi id = x i f i (11.83) iid  G iid = G i (T , P ) + RT ln x i (11.75)

 This equation, known as the Lewis/Randall rule, applies to

each species in an ideal solution at all conditions of
temperature, pressure and composition.
 29

 It shows that the fugacity of each species in an ideal solution

is proportional to its mole fraction.
 Division of both sides of eq. (11.83) by Pxi gives

ˆi  i
fˆ
(11.52 ) fˆi id x i f i
yi P
=
Px i Px i
f
i  i (11.34 ) ˆ id =  (11.84)
P i i

 The fugacity coefficient of species i in an ideal solution is

equal to the fugacity coefficient of pure species i in the same
physical state as the solution and at the same T and P.
 Raoult’s law is based on assumption of ideal solution behavior
for the liquid phase, the same system that obey Raoult’s law
form ideal solution.
 Ideal solutions are liquid phases whose molecules are of
similar size and which are of similar chemical nature.
 30

EXCESS PROPERTIES
 Residual properties are used to measure the deviation of real
fluid properties to ideal gas properties. Although residual
properties can be used for all fluid (both gases and liquids), it
is more convenient to measure the deviation of real solution
(liquid mixtures) to that of ideal solution. This is accomplished
through the use of excess properties.
 Hence, excess properties are analogous to residual properties
(residual for deviation from ideal gas and excess for deviation
from ideal solution).
 Excess properties is defined as:
ME  M − Mid 11.85
 31

The Excess Gibbs Energy and the

Activity Coefficient
 Eq. (11.46) may be written as
G i = i (T ) + RT ln fˆi
 In accord with eq. (11.83) for an ideal solution, this becomes
G iid = i (T ) + RT ln x i f i fˆi id = x i f i (11.83)
 By difference,
fˆi
G i − G = RT ln
id
i
xif i
 The left side of this equation is the partial excess Gibbs energy
G iE ; the dimensionless ratio on the right side is the activity
coefficient of species i in solution, i.
 By definition,
fˆi
i  (11.90)
xifi
 So, G E = RT ln  (11.91)
i i
 32

 These equation establish a thermodynamic foundation for the

activity coefficient, as a factor introduced into Raoult’s law to
account for liquid phase non-idealities.
 Comparison with eq. (11.51) shows that eq. (11.91) relates i to G iE
ˆ
exactly as eq. (11.51) relates i to G iR.
G iR = RT lnˆi (11.51)
For an ideal solution, G i = 0, and therefore i = 1.
E

 A further relation results from combination of eq. (11.91) with eq.

(11.88)
RT ln  i = G i − G iid MiE = Mi − Miid (11.88)

 Elimination of the final term by eq. (11.75) and rearrangement

gives
−
  G = G i (T , P ) + RT ln x i
i
id id
i (11.75)
G i  i = G i + RT ln  i x i (11.92)
 This equation is an alternative definition of the activity coefficient.
 33

 For ideal gas mixture model,

iig = G iig + RT ln y i (11.24)

 For ideal solution model,

iid = G i + RT ln x i (11.75)

 For non-ideal solution,

i = Gi + RT ln  i xi (11.92)
 34

 From summability relation (eq. 11.11),

G E =  x i G iE
i
 Substitution of eq. (11.91),
G iE = RT ln  i (11.91) GE
G = RT  x i ln  i
E
or =  x i ln  i (11.99)
i RT i

 These relation is very important in determining activity

coefficient, i.
 From Gibbs/Duhem eqn. at constant T and P (eq. 11.14):
 x dG
i
i
E
i =0
 Substitution of eq.(11.91),
 x d ( RT ln  ) = 0
i
i i

For constant T and P,


 x d ln 
i
i i =0 (11.100)
 This eqn. is very important to check the thermodynamic
consistency of binary liquid-vapor equilibrium.
 35

REFERENCE
Smith, J.M., Van Ness, H.C., and Abbott, M.M. 2005. Introduction
to Chemical Engineering Thermodynamics. Seventh Edition.
Mc Graw-Hill.
PREPARED BY:
NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
[email protected]
03-55436333/019-2368303