Chapter 11

Solution Thermodynamics: Theory

Chapter 6 treats the thermodynamic
properties of pure species or constant-
composition fluids. However, the preceding
chapter demonstrates that applications of
chemical engineering thermodynamics are
often to systems wherein composition is a
primary variable.

1
Chapter 11
Solution Thermodynamics: Theory
In the chemical, petroleum, and
pharmaceutical industries multicomponent
gases or liquids commonly undergo
composition changes as the result of
mixing and separation processes, the
transfer of species from one phase to
another, or chemical reaction.

2
Chapter 11
Solution Thermodynamics: Theory
Because the property of such systems
depend strongly on composition as well as
on temperature and pressure, our purpose
in this chapter is to develop the theoretical
foundation for application of
thermodynamics to gas mixture and liquid
solution.

3
Chapter 11
Solution Thermodynamics: Theory
The theory is introduced through
derivation of a fundamental property
relation for homogeneous solution of
variable composition. Convenience here
suggests the definition of a fundamental
new property called the chemical potential,
upon which the principles of phase and
chemical reaction equilibrium depend.
4
Chapter 11
Solution Thermodynamics: Theory
This leads to the introduction of a new
class of thermodynamic properties known
as partial properties. The mathematical
definition of these quantities allows them
to be interpreted as properties of the
individual species as they exist in solution.
For example, in a liquid solution of ethanol and water the two species have partial
molar properties whose values are somewhat different from the molar properties of
pure ethanol and pure water at the same temperature and pressure.

5
Chapter 11
Solution Thermodynamics: Theory
Property relations for mixtures of ideal
gases are important as references in the
treatment of real-gas mixtures, and they
form the basis for introduction of yet
another important property, the fugacity.
Related to the chemical potential, it is vital
in the formulation of both phase and
chemical reaction equilibrium relations.
6
Chapter 11
Solution Thermodynamics: Theory
Finally, a new class of solution properties
is introduced. Known as excess properties,
they are based on an idealization of
solution behavior called the ideal solution.
Its role is like that of the ideal gas in that
it serves as a reference for real-solution
behavior. Of particular interest is the
excess Gibbs energy, a property which
underlies the activity coefficient.
7
 Chapter 11
Solution Thermodynamics: Theory
Properties depend strongly on composition,
T and P.
Gas mixtures and liquid solutions
New terms: chemical potential, partial properties,
fugacity, and excess property (e.g. excess Gibbs
energy).
Why we have to study Solution Thermodynamics?......
The prediction of the equilibrium existing between
phases, and to understand the process and to calculate
phase and chemical reaction equilibria.
8
Chapter 11
Solution Thermodynamics: Theory
What is the most important property ?
G.
For pure component;
G = G (T, P)
For a homogeneous mixture e.g.
containing i components mixture;
G = G (T, P, n1, n2, , ni)

9
 11.1 Fundamental Property Relation
Equation (6.6) expresses the basic relation
connecting the total Gibbs energy to the
temperature and pressure in any closed
system:

where n is the total number of moles of

the system.

10
 11.1 Fundamental Property Relation
An appropriate application is to a single
phase fluid in a closed system wherein no
chemical reactions occur. For such a
system the composition is necessarily
constant, and therefore:

The subscript n indicates that the numbers

of moles of all chemical species are held
constant. 11
 11.1 Fundamental Property Relation
For the more general case of a single phase,
open system, material may pass into and
out of the system, and nG becomes a
function of the numbers of moles of the
chemical species present. Presumably, it is
still a function of T and P, and we
rationalize the functional relation:

where ni is the number of moles of species i.

12
 11.1 Fundamental Property Relation

The total differential of nG is then:

The summation is over all species present,

and subscript nj indicates that all mole
numbers except the i th are held constant.

13
 11.1 Fundamental Property Relation

The derivative in the final term is given its

own symbol and name. Thus, by definition
the chemical potential of species i in the
mixture is:

14
 11.1 Fundamental Property Relation
With this definition and with the first two
partial derivatives replaced by (nV) and
(nS), the preceding equation becomes:

Equation (11.2) is the fundamental

property relation for single phase fluid
systems of variable mass and composition.
15
 11.1 Fundamental Property Relation
It is the foundation upon which the
structure of solution thermodynamics is
built. For the special case of one mole of
solution, n=1 and ni=xi :

Implicit in this equation is the functional

relationship of the molar Gibbs energy to
its canonical variable, here: T, P, and {xi}:

16
 11.1 Fundamental Property Relation
Although the mole number ni of Eq. (11.2)
are independent variables, the mole
fraction xi in Eq. (11.3) are not, because
i xi = 1. This precludes certain
mathematical operations which depend
upon independence of the variables.
Nevertheless, Eq. (11.3) does imply:

17
 11.1 Fundamental Property Relation
Other solution properties come from
definitions.
When the Gibbs energy is expressed as a
function of its canonical variables, it plays
a role of a generating function, providing
the means of calculation of other
thermodynamics properties by simple
mathematical calculations and implicitly
represents complete property information.
18
 11.2 The Chemical Potential
Consider a closed system containing of two
phases in equilibrium. Within this closed system,
each individual phase is an open system, free to
transfer mass to the other. Equation (11.2) may
be written for each phase:

d(nG) (nV) dP (nS) dT i dni
d(nG) (nV) dP (nS) dT i dni
Total system property nM (nM) (nM)
d(nG) (nV)dP (nS)dT i dni i dni
19
 11.2 The Chemical Potential

Phases and .
Free mass transfer between
phases and

20
 11.2 The Chemical Potential

Two phases are closed, and

at equilibrium.

i dni i dni 0

dni dni

(i - i )dni 0

i i

21
 11.2 The Chemical Potential
Chemical Potential ()
is an extensive property,
provides a measure of the work of a
system is capable when a change in
mole numbers occurs e.g. chemical
reaction or a transfer of mass.

22
 11.2 The Chemical Potential
For phases at equilibrium, and N is the
number of species.

......
i i i (i 1,2,...N ) (11.6)

Thus, multiple phases at the same T and P

are in equilibrium when the chemical
potential of each species is the same in all
phases.

If i i
What will be happened?
23
 11.3 Partial Properties Mi
The partial molar property: any extensive
property of a solution changes with respect
to the number of moles of any component
i in the solution at constant T, P and
composition of the others.
Partial property and molar property
(except for ideal solution).

24
 11.3 Partial Properties
M = solution properties
For example: V, U, H, S, G

Mi = partial properties
For example: Vi , Ui , Hi , Si , Gi

Mi = pure species properties

For example: Vi , Ui , Hi , Si , Gi

25
 11.3 Partial Properties
Partial molar property Mi of species i in
solution is defined as

It is a response function, i.e., a measure of

the response of total property nM to the
addition at constant T and P of a
differential amount of species I to a finite
amount of solution.
26
 11.3 Partial Properties
Comparison of Eq. (11.1) with Eq. (11.7)
written for the Gibbs energy shows that
the chemical potential and the partial
molar Gibbs energy are identical; i.e.,

Thus, the partial molar Gibbs energy is the

chemical potential.

27
 11.3 Partial Properties
The definition of a partial molar property,
Eq. (11.7), provides the means for
calculation of partial properties from
solution property data. Implicit in this
definition is another, equally important,
equation that allows the reverse, i.e.,
calculation of solution properties from
knowledge of the partial properties.
nM M(T,P,x1,x 2 ,....xi )
28
 11.3 Partial Properties
The total differential of nM is:

(nM) (nM)
d(nM) dP dT M i dni
P T,n T P,n

29
 11.3 Partial Properties
Because the first two partial derivatives on
the right are evaluated at constant n and
because the partial derivative of the last
term is given by Eq. (11.7), this equation
has the simpler form:
(M) (M)
d(nM) n dP n dT M i dni (11.9)
P T,x T P,x

30
 11.3 Partial Properties
Since ni = xin:
dni xi dn ndxi
And
d(nM) ndM Mdn
Substitute these terms to Eq. (11.9), and
then rearrange:
M M
dM- dP- dT- M i dxi n M xi M i dn 0
P T,x T P,x i i
31
 11.3 Partial Properties

M M
dM- dP- dT- M i dxi 0
P T,x T P,x i

M M
dM dP dT M i dxi (11.10)
P T,x T P,x i

M xi M i 0
i

M xi M i (11.11)
i

nM ni M i (11.12)
i
Summability relations 32
 11.3 Partial Properties
Differentiate Eq. (11.11),
dM xi d M i M i dxi
i i

Comparison of this equation with Eq.

(11.10) yields Gibbs / Duhem equation:

M M
dP dT- xi d M i 0 (11.13)
P T,x T P,x i

33
 11.3 Partial Properties
This equation must be satisfied for all
changes in P, T, and the Mi caused by
changes of state in a homogeneous phase.
For the important special case of changes
at constant T and P, it simplifies to:

x dM
i
i i 0 at const T and P (11.14)

34
 11.3 Partial Properties
Gibbs/Duhem equation
M M
dP- dT xi d M i
P T,x T P,x i

If T and P constant:
x dM
i
i i 0

35
 11.3 Partial Properties
Solution property : M
(nM)
Partial property : M i
ni P ,T ,n j
Pure-species property : Mi

36
 11.3 Partial Properties
Binary system
dM
M 1 M x2 (11.5)
dx1
dM
M 2 M x1 (11.6)
dx1
d M1 dM2
x1 x2 0 (E)
dx1 dx1
d M1 x2 d M 2
0 (F)
dx1 x1 dx1
37
 11.3 Partial Properties
For two components
dH TdS VdP (1 )S,P dn1 (2 )S,P dn2
dU TdS PdV (1 )V,S dn1 (2 )V,S dn2
dG VdP -SdT (1 )T,P dn1 (2 )T,P dn2
dA PdV -SdT (1 )T,V dn1 (2 )T,V dn2
H U G A
1
n1 S , P ,n2 n1 V , S ,n2 n1 T , P ,n2 n1 T ,V ,n2

38
 Example 11.3
The need arise in a laboratory for 2000 cm3 of an
antifreeze solution consisting of 30 mol % methanol in
water. What volumes of pure methanol and of pure
water at 25 C must be mixed to form the of antifreeze,
also at 25 C ? Partial molar volumes for methanol and
water in a 30 mol % methanol solution and their pure-
species molar volume, both at 25 C , are:
Methanol (1) and water (2):

V1 38.632 cm3mol 1 V1 40.727 cm3mol 1

V2 17.765 cm3mol 1 V2 18.068 cm3mol 1

39
 Example 11.3
Solution

V x1V1 x2V2 (0.3)(38 .632 ) (0.7)(17 .765 )

1
V 24 .025 cm mol3

t 3
V 2000 cm
n 3 1
83 .246 cm 3
V 24 .025 cm mol
n1 x1n (0.3)(83 .246 ) 24 .974 mol
n2 x2 n (0.7)(83 .246 ) 58 .272 mol

40
 Example 11.3
Solution

41
 Example 11.3
Solution
The line drawn tangent to the V-x1 curve at
x1=0.30, illustrates the values of V1=40.272
cm3 mol-1 and V2=18.068 cm3 mol-1.
1
V1t
(24 .497 mol )( 40 .727 cm mol )
3

V1t
1017 cm 3

1
V2t
(58 .272 mol )(18 .068 cm mol )
3

V2t
1053 cm 3
V1 V2 42
 Relations among Partial Properties
We show now how partial properties are
related to one another. By Eq. (11.8), i
Gi, and Eq. (11.20 may be written:
d(nG) (nV)dP (nS)dT Gi dni ( 11.17 )
Application of the criterion of exactness, Eq.
(6.12) , yields the Maxwell relation,
V S
- ( 6.16 )
T P,n P T,n
43
 Relations among Partial Properties
We have two additional equations:
Gi (nS) Gi (nV)
- and
T P
P,n i P,T,n j
n T,n ni P,T,n j
One can write the RHS in the form of
partial molar, and change the composition
from n to x. Gi i
T Si
P,x T P,x
Gi i
Vi
P P T,x
T,x
44
 Relations among Partial Properties
Every equation that provides a linear
relation among thermodynamic properties
of a constant-composition solution has as
its counterpart an equation connecting
the corresponding partial properties of
each species in the solution.

45
 Relations among Partial Properties
H U PV
For n moles, nH nU P(nV)

( nH ) ( nU ) ( nV )
P
ni P,T,n j ni P,T,n j ni P,T,n j
H i U i P Vi
Gi Gi
d Gi dP
T
dT

P T , x P,x
d Gi Vi dP S i dT
46
 Relations among Partial Properties
This may be compared with Eq. (6.10).
These examples illustrate the parallelism
that exists between equations for a
constant composition solution and the
corresponding equations for the partial
properties of the species in solution. We
can therefore write simply by analogy
many equations that related partial
properties.
47
 11.4 The Ideal-Gas Mixture Model
Dalton Law
Every gas has the same V and T.

ni
Pi yi Pt where yi
nt
Pt Pi
i

48
 11.4 The Ideal-Gas Mixture Model

Amagat Law
Every gas has the same P and T.

Vi yiV t

V Vi
t

49
11.4 The Ideal-Gas Mixture Model

(nV ig
i )
(nRT)/P RT n
Vi
ig

ni P,T,n j ni P,T,n j P ni n
j

n ni n j
j

Vi ig Vi ig

50
 11.4 The Ideal-Gas Mixture Model
Properties of each component species are
independent of the presence of other
species.
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.
51
 11.4 The Ideal-Gas Mixture Model
M iig(T,P) M iig(T,pi ) (11.21)
H ig yi H iig (11.23)
i

U ig yiU iig (11.23)

i

H ig yi H iig 0
i

S ig yi S iig -R yi ln yi (where yi pi /P ) (11.25)

i i

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

The entropy change of an ideal gas mixing is
1
S yi S i R yi ln
ig ig

i i yi 52
11.4 The Ideal-Gas Mixture Model

G G
ig
i i
ig
i
ig
RT ln yi ( 11.26 )
RT
From dG Vi dP
i
ig
dP RTd ln P
ig

P
Gi i(T) RT ln P
ig
( 11.27 )
i(T) is the integratio n constant
iig i(T) RT ln yi P ( 11.28 )
G yi i(T) RT
ig
y i ln yi P ( 11.29 )
i i

53
 11.4 The Ideal-Gas Mixture Model
Problem 11.1
What is the change in entropy when 0.7
m3 of CO2 and 0.3 m3 of N2 each at 1 bar
and 25 C blend to form a gas mixture at
the same condition? Assume ideal gases.

54
 11.4 The Ideal-Gas Mixture Model
Solution

The entropy change of an ideal gas mixing is

1
S mixing S y S
ig
i i
ig
R yi ln
i i yi
1 1
8.314 J (g mol) K (0.3 ln
-1 -1
0.7 ln )
0.3 0.7
5.079 J (g mol) K
-1 -1

55
11.5 Fugacity & Fugacity Coefficient: Pure Species

As evident from Eq. (11.6), the chemical

potential i provides the fundamental
criterion for phase equilibria. This is true as
well for chemical reaction equilibria.
However, it exhibits characteristics which
discourage its use. The Gibbs energy, and
hence i , is defined in relation to the
internal energy and entropy. Because
absolute values of internal energy are
unknown, the same is true for i .
56
11.5 Fugacity & Fugacity Coefficient: Pure Species

Moreover, Eq. (11.20) shows that iig

approaches negative infinity when either P
or yi approaches zero. This is true not just
for an ideal gas but for any gas. 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.
57
11.5 Fugacity & Fugacity Coefficient: Pure Species

The origin of the fugacity concept resides

in Eq. (11.28), valid only for pure species i
in the ideal gas state. For a real fluid, we
write an analogous equation that defines fi,
the fugacity of pure species i:

58
11.5 Fugacity & Fugacity Coefficient: Pure Species

The origin of the fugacity concept resides

in Eq. (11.28), valid only for pure species i
in the ideal gas state. For a real fluid, we
write an analogous equation that defines fi,
the fugacity of pure species i:
G (T ) RT ln f (11.31)
i i i

This new property fi , with units of pressure,

replaces P in Eq.(11.28). Clearly, if (11.28)
is a special case of Eq. (11.31), then:
59
11.5 Fugacity & Fugacity Coefficient: Pure Species

fi 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 G RT ln
i
ig

P
By the definition of Eq. (6.41), Gi Giig is
the residual Gibbs Energy, GiRthus
60
11.5 Fugacity & Fugacity Coefficient: Pure Species

G RT ln i
i
R
(11.33)
where the dimensionless ratio fi /P has
been defined as another new property, the
fugacity coefficient, given by symboli :
fi
i (11.34)
P
These equations apply to pure species i in any phase
at any condition. However, 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). 61
11.5 Fugacity & Fugacity Coefficient: Pure Species

Moreover, we may write Eq. (11.33) for

P = 0, and combine it with Eq. (6.45):

R
G
lim ( ) lim ln
i
J
P 0 RT P 0 i

As explained in connection with Eq. (6.48),

the value of J is immaterial, and is set
equal to zero. Whence,
lim ln
P 0
i
lim ln(
P 0
fi
P
) 0

62
11.5 Fugacity & Fugacity Coefficient: Pure Species

And
lim
P 0
i
lim
fi
P 0 P
1

The identification of lni with GiR / RT by

Eq. (11.33) permits its evaluation by the
integral of Eq. (6.49):
P
dP
ln i (Z1 1 ) (const T) (11.35)
0
P

63
11.5 Fugacity & Fugacity Coefficient: Pure Species

Fugacity coefficients (and therefore

fugacities) for pure gases are evaluated by
this equation from P V T data or from a
volume-explicit equation of state.
For example, when the compressibility
factor is given by Eq. (3.38),
Bii P
Z i 1
RT
64
11.5 Fugacity & Fugacity Coefficient: Pure Species

Because the second virial coefficient Bii is a

function of temperature only for a pure
speciues, substitution into Eq. (11.35)
gives:
P
Bii
ln i
RT 0 dP (const T)

Bii P
Whence, ln i (11.36)
RT

65
11.5 Fugacity & Fugacity Coefficient: Pure Species
Fugacity Coefficients from the Generic
Cubic Equation of State

66
11.5 Fugacity & Fugacity Coefficient: Pure Species
Vapor/Liquid Equilibrium for Pure Species

G (T ) RT ln f i
i
v v
(11.38a)
G (T ) RT ln f i
i
l l
(11.38b)
v
fi
G G RT ln l
i
v
i
l

fi
At equilibriu m : f i f i f i
v l sat
(11.39)

67
11.5 Fugacity & Fugacity Coefficient: Pure Species
Vapor/Liquid Equilibrium for Pure Species
For a pure species coexisting liquid and
vapor phases are in equilibrium when they
have the same temperature, pressure, and
fugacity.
sat
fi
i
sat
sat (11.40)
Pi
i
f
i
v
i
sat
(11.41)
68
11.5 Fugacity & Fugacity Coefficient: Pure Species
Fugacity of a Pure Liquid

69
11.6 Fugacity & Fugacity Coefficient: Species in
Solution
The definition of the fugacity 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, the equilibrium analogous to Eq.
(11.20), the ideal-gas expression, is:

i i (T ) RT ln fi (11.46)
70
11.6 Fugacity & Fugacity Coefficient: Species in
Solution
where fi is the fugacity of species i in
solution, replacing the partial pressure yiP.
This definition of f does not make it a
partial molar property, and it is therefore
i

identified by a circumflex rather than by

an overbar.
A direct application of this definition
indicates its potential utility. Equation
(11.6) is the fundamental criterion for
phase equilibrium.
71
11.6 Fugacity & Fugacity Coefficient: Species in
Solution
At equilibrium

fi

f i ..... f i

(11.47)
Thus, multiple phases at the same T and P
are in equilibrium when the fugacity of
each constituent species is the same in all
phases.
This criterion of equilibrium is the one
usually applied by chemical engineers in
the solution of phase-equilibrium problems.
72
11.6 Fugacity & Fugacity Coefficient: Species in
Solution
For the specific case of multicomponent
vapor/liquid equilibrium, Eq. (11.47)
becomes:
f v f l (i 1, 2, ..., N) (11.48)
i i
Equation (11.39) results as a special case
when this relation is applied to the
vapor/liquid equilibrium of pure species i.

73
11.6 Fugacity & Fugacity Coefficient: Species in
Solution
The definition of a residual property is
given in Sec. 6.2:
M M M
R ig
(6.41)
Where M is the molar (or unit mass) value of a thermodynamic
property and M ig is the value that the property would have for
an ideal gas of the same composition at same T and P. The
defining equation for a partial residual property

R
M
74
11.6 Fugacity & Fugacity Coefficient: Species in
Solution

75
11.6 Fugacity & Fugacity Coefficient: Species in
Solution

76
11.6 Fugacity & Fugacity Coefficient: Species in
Solution

77
11.6 Fugacity & Fugacity Coefficient: Species in
Solution

78
11.6 Fugacity & Fugacity Coefficient: Species in
Solution

79
11.6 Fugacity & Fugacity Coefficient: Species in
Solution

80
11.6 Fugacity & Fugacity Coefficient: Species in
Solution
Fugacity Coefficients from the Virial
Equation of State

81
11.7 Generalized Correlations for the Fugacity
Coefficient

82
11.8 The Ideal Solution Model

83
 11.8 The Ideal Solution Model
The Lewis/Randall Rule

84
11.9 Excess Properties

85
 11.9 Excess Properties
The Excess Gibbs Energy and the Activity
Coefficient

86
 11.9 Excess Properties
Excess Property Relations

87
 11.9 Excess Properties
The Nature of Excess Properties

88
11.5 Fugacity & Fugacity Coefficient: Pure Species

dG VdP-SdT
dG VdP (con st T)
G P

dG VdP
G* P*
Consider the change in G to G* at very low pressure
P
G-G* VdP
P*
P
G* G
P*
VdP
lim G* G
G 0 89
Fugacity & Fugacity Coefficient: Pure Species

From dG VdP-SdT
RT
dG ig V dP
ig
dP ( const T)
P
dG ig RTd ln P (const T) ideal gas
dG RTd ln f (const T) real gas

90
Fugacity & Fugacity Coefficient: Pure Species

Gi i(T) RT ln f i (11.30)
where f i fugacity
fi
Gi G RT ln
i
ig

P
GiR RT ln i (11.31)
where i fugacity coefficient
fi
i (11.32)
P
f i ig P (11.33)
P
dP
ln i (Z1 1 ) (const T) (11.34)
0
P
91
Fugacity & Fugacity Coefficient: Pure Species
P
dP
ln i (Z1 1 ) (const T) (11.34)
0
P
nd
Using 2 virial coeeficient to calculate Z.
P
Bii dP
ln i
RT 0 P (const T)

Bii P
ln i (11.35)
RT
Using cubic EOS to calculate Z.
ln i Z i -1- ln (Z i -i )-qi I i (11.36)

92
Generalized Correlations for the Fugacity Coefficient
P Pc Pr
dP Pc dPr
Pr
dPr
ln i ( Z i 1) (11.62)
0
Pr
Pr r P
dPr 1 dPr
ln ( Z 1)
0
Z
0
Pr 0
Pr
ln ln 0 ln 1 (11.63)
Pr
dPr
where ln ( Z 1)
0 0

0
Pr
Pr
dPr
ln Z
1 1

0
Pr
93
Generalized Correlations for the Fugacity Coefficient

Z 1
Pr 0
Tr

B B1
ln
Pr 0
Tr
B B1
Pr 0 1

exp B B (11.65)
Tr

The average properties at the critical point and the 2nd

Virial coefficient can be determined from Equation 11.66-
11.71

94
 Fugacity of a Pure Liquid
fi of a compressed liquid is calculated in 2 steps:

fi of saturated liquid and vapor f i f isat Pi sat

Compress liquid from Psat to P

V l
( P P sat
)
fi f i Pi exp
sat sat i i
(11.40)
RT

95
 Fugacity and Fugacity Coefficient: Species in
solution
fi of a solution is parallel to the pure solution
The ideal solution (analogous to the ideal gas)

i i (T ) RT ln fi (11.42)

At equilibrium:

Thus, multiple phases at the same T and P are in equilibrium

when the fugacity of each constituent species is the same in
all phases.

96
 Fugacity and Fugacity Coefficient:
Species in solution

A partial residual property, M iR

G iR G i G ig
i (11.46)

G iR RT ln i (11.47)

f
i i (11.48)
yi P

97
The Fundamental Residual-Property
Relation

nG R nV R R

nH
d dP dT ln i dni (11.52)
RT RT 2
RT i

nV R (G R / RT )
(11.53)
RT P
T , x
HR (G R / RT )
T (11.54)
RT T
P, x

( nG R
/ RT )
ln i (11.55)
ni
P ,T , x

98
 Fugacity Coefficient from the Virial EOS
For mixture
B y y B
i j
i j ij (11.57)

e.g. binary mixture

B = y1y1B11 + y1y2B12 + y2y1B21+ y2y2B22
B = y12B11 + 2y1y2B12 + y22B22 (11.58)
12 2 B12 B11 B22

ln 1
P
RT
B11 y 2212 (11.59)

ln 2
P
RT
B22 y1212 (11.60)

yi y j (2 ik ij )
P 1
ln k Bkk (11.61)
RT 2 i
j
99
 The Ideal Solution
Serves as a standard to which real-solution behavior
can be compared.
Giid Gi RT ln xi (11.72)
S iid S i R ln xi (11.73)
Viid Vi (11.74)
H iid H i (11.75)
Giid x G RT x ln x
i
i i
i
i i (11.76)

S iid x S R x ln x
i i i i (11.77)
i i

Viid xV i i (11.78)
i

H iid x H i i (11.79)
i 100
 The Ideal Solution: The Lewis/Randall Rule

Fugacity calculation of i in ideal solution.

iid Giid i (T ) RT ln fiid

fiid xi f i (11.80)

iid i (11.81)

101
 Excess Properties

M E M M id (11.82)
G E H E -TS E (11.83)
M E M R ( M ig M id )

Fundamental of excess property relation

nG E nV E E
GiE

nH
d dP dT dni (11.86)
RT RT 2
RT
RT i

102
The Excess Gibbs Energy and the Activity
Coefficient

Gi i (T ) RT ln fi
G iid i (T ) RT ln xi f i
fi
Gi G iid RT ln
xi f i
G iE Gi G iid RT ln i

103
 The Excess Gibbs Energy and the Activity
Coefficient

nG E nV E E

ln dn
nH
d dP dT (11.89)
RT RT 2 i i
RT i

V E (G E / RT )
(11.90)
RT P T , x

HE (G E / RT )
T (11.91)
RT T P, x

(G E / RT )
ln i (11.92)
n i P ,T , n
j

104
The Excess Gibbs Energy and the
Activity Coefficient

ln i Vi E
(11.93)
P T , x RT

ln i H iE
(11.94)
T P , x RT 2
nG E
RT
x ln
i
i i (11.95)

x d ln
i
i i 0 (const T, P) (11.96)

105
 Gibbs-Duhem Equation

x d ln 0
i
i i (const T, P) (11.96)

n d 0
i
i i (const T, P)

n d ln f
i
i i 0 (const T, P)

i
xi d ln fi 0 (const T, P)

106
 The Nature of the Excess Properties
All MEs become 0 as either species approaches purity.
Plot between GE vs. x1 is approximately parabolic in shape,
Both HE and TSE exhibit individualistic composition
dependencies
When an excess property has a single sign (as does GE in
all six cases, the extreme value of ME (maximum or minimum)
Often occurs near the equimolar composition.

107
 Review
Mixtures
What is the definition of partial molar property? Try saying
it in words rather than equation.
Why is the partial molar property not the same as the pure
property? What can happen when we mix different species?
How is excess property defined?
Do ideal gases always form ideal mixtures when allowed to
mixed?
Pick a property, say V,. Review the ways we can calculate
the partial molar volume. What about straight differentiation?
What is the alternative way that only works for binary
mixture? What about graphically?
108
 Review
Mixtures
What is Gibbs-Duhem equation? In what ways is it useful?
For ideal solution, what is the molar volume?
For ideal solution, what is the molar enthalpy?
For ideal solution, what is the molar entropy?
For ideal solution, what is the molar Gibbs free energy?
What is the definition of infinite dilution property?

109