Advanced Thermodynamics

Note 10
Solution Thermodynamics: Theory


Lecturer: 郭修伯
Compositions
• Real system usually contains a mixture of fluid.
• Develop the theoretical foundation for
applications of thermodynamics to gas mixtures
and liquid solutions
• Introducing
– chemical potential
– partial properties
– fugacity
– excess properties
– ideal solution
Fundamental property relation
• The basic relation connecting the Gibbs energy to
the temperature and pressure in any closed system:


– applied to a single-phase fluid in a closed system
wherein no chemical reactions occur.
• Consider a single-phase, open system:
dT nS dP nV dT
T
nG
dP
P
nG
nG d
n P n T
) ( ) (
) ( ) (
) (
, ,
÷ =
(
¸
(

¸

c
c
+
(
¸
(

¸

c
c
=
¿ (
¸
(

¸

c
c
+
(
¸
(

¸

c
c
+
(
¸
(

¸

c
c
=
i
i
n T P
i n P n T
dn
n
nG
dT
T
nG
dP
P
nG
nG d
j
, ,
, ,
) ( ) ( ) (
) (
j
n T P
i
i
n
nG
, ,
) (
(
¸
(

¸

c
c
÷ µ
Define the chemical potential:
¿
+ ÷ =
i
i i
dn dT nS dP nV nG d µ ) ( ) ( ) (
The fundamental property relation for single-phase fluid systems of constant or
variable composition:
When n = 1,
¿
+ ÷ =
i
i i
dx SdT VdP dG µ
,...) ,..., , , , (
2 1 i
x x x T P G G =
x P
T
G
S
,
|
.
|

\
|
c
c
=
x T
P
G
V
,
|
.
|

\
|
c
c
=
The Gibbs energy is expressed as a
function of its canonical variables.
Solution properties, M
Partial properties,
Pure-species properties, M
i

i
M
Chemical potential and phase equilibria
• Consider a closed system consisting of two phases
in equilibrium:

¿
+ ÷ =
i
i i
dn dT nS dP nV nG d
o o o o o
µ ) ( ) ( ) (
¿
+ ÷ =
i
i i
dn dT nS dP nV nG d
| | | | |
µ ) ( ) ( ) (
| o
) ( ) ( nM nM nM + =
¿ ¿
+ + ÷ =
i
i i
i
i i
dn dn dT nS dP nV nG d
| | o o
µ µ ) ( ) ( ) (
| o
µ µ
i i
=
| o
i i
dn dn ÷ =
Mass balance:
Multiple phases at the same T and P are in
equilibrium when chemical potential of
each species is the same in all phases.
Partial properties
• Define the partial molar property of species i:


– the chemical potential and the particle molar Gibbs
energy are identical:
– for thermodynamic property M:

j
n T P
i
i
n
nM
M
, ,
) (
(
¸
(

¸

c
c
÷
i i
G ÷ µ
,...) ,..., , , , (
2 1 i
n n n T P M nM =
¿
+
(
¸
(

¸

c
c
+
(
¸
(

¸

c
c
=
i
i i
n P n T
dn M dT
T
M
n dP
P
M
n nM d
, ,
) (
¿
+
(
¸
(

¸

c
c
+
(
¸
(

¸

c
c
=
i
i i
n P n T
dn M dT
T
M
n dP
P
M
n nM d
, ,
) (
¿
+ +
(
¸
(

¸

c
c
+
(
¸
(

¸

c
c
= +
i
i i i
n P n T
ndx dn x M dT
T
M
n dP
P
M
n Mdn ndM ) (
, ,
0
, ,
=
(
¸
(

¸

÷ +
(
(
¸
(

¸

÷
|
.
|

\
|
c
c
÷
|
.
|

\
|
c
c
÷
¿ ¿
dn M x M n dx M dT
T
M
dP
P
M
dM
i
i i
i
i i
n P n T
0
, ,
= ÷
|
.
|

\
|
c
c
÷
|
.
|

\
|
c
c
÷
¿
i
i i
n P n T
dx M dT
T
M
dP
P
M
dM
and
0 = ÷
¿
i
i i
M x M
Calculation of mixture
properties from partial
properties
0 = ÷
¿
i
i i
M n nM
0
, ,
= ÷
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
¿
i
i i
n P n T
M d x dT
T
M
dP
P
M
¿ ¿
+ =
i
i i
i
i i
dx M M d x dM
The Gibbs/Duhem equation
Partial properties in binary solution
• For binary system
2 2 1 1
M x M x M + =
2 2 2 2 1 1 1 1
dx M M d x dx M M d x dM + + + =
Const. P and T, using Gibbs/Duhem equation
2 2 1 1
dx M dx M dM + =
1
2 1
= + x x
2 1
1
M M
dx
dM
÷ =
1
2 1
dx
dM
x M M + =
1
1 2
dx
dM
x M M ÷ =
The need arises in a laboratory for 2000 cm
3
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 2000 cm
3
of antifreeze at 25°C? The partial and pure molar
volumes are given.
2 2 1 1
V x V x V + = mol cm V / 025 . 24 ) 765 . 17 )( 7 . 0 ( ) 632 . 38 )( 3 . 0 (
3
= + =
mol
V
V
n
t
246 . 83
025 . 24
2000
= = =
mol n 974 . 24 ) 246 . 83 )( 3 . 0 (
1
= =
mol n 272 . 58 ) 246 . 83 )( 7 . 0 (
2
= =
3
1 1 1
1017 ) 727 . 40 )( 974 . 24 ( cm V n V
t
= = =
3
2 2 2
1053 ) 068 . 18 )( 272 . 58 ( cm V n V
t
= = =
Fig 11.2
Fig 11.2
The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is:


Determine expressions for and as functions of x
1
, numerical values for the
pure-species enthalpies H
1
and H
2
, and numerical values for the partial enthalpies at
infinite dilution and
1
H
2
H
·
1
H
·
2
H
) 20 40 ( 600 400
2 1 2 1 2 1
x x x x x x H + + + =
) 20 40 ( 600 400
2 1 2 1 2 1
x x x x x x H + + + =
1
2 1
= + x x
3
1 1
20 180 600 x x H ÷ ÷ =
1
2 1
dx
dH
x H H + =
3
1
2
1 1
40 60 420 x x H + ÷ =
1
2 1
= + x x
3
1 2
40 600 x H + =
0
1
= x
mol
J
H 420
1
=
·
1
1
= x
mol
J
H 640
2
=
·
Relations among partial properties

• Maxwell relation:

¿
+ ÷ =
i
i i
dn G dT nS dP nV nG d ) ( ) ( ) (
n T n P
P
S
T
V
, ,
|
.
|

\
|
c
c
÷ =
|
.
|

\
|
c
c
j
n T P
i
n P
i
n
nS
T
G
, , ,
) (
(
¸
(

¸

c
c
÷ =
|
|
.
|

\
|
c
c
j
n T P
i
n T
i
n
nV
P
G
, , ,
) (
(
¸
(

¸

c
c
=
|
|
.
|

\
|
c
c
i
x P
i
S
T
G
÷ =
|
|
.
|

\
|
c
c
,
i
x T
i
V
P
G
=
|
|
.
|

\
|
c
c
,
PV U H + =
dT S dP V G d
i i i
÷ =
i i i
V P U H + =
Ideal-gas mixture
• Gibbs’s theorem
– 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.
ig
i
ig
i
V M = ) , ( ) , (
i
ig
i
ig
i
p T M P T M =
For those depend on pressure, e.g.,
T const P Rd dS
ig
i
. ln ÷ =
i
i i
i
ig
i
ig
i
y R
P y
P
R
p
P
R p T S P T S ln ln ln ) , ( ) , ( = ÷ = ÷ = ÷
i
ig
i
ig
i
y R P T S P T S ln ) , ( ) , ( = ÷
For those independent of pressure, e.g.,
) , ( ) , ( ) , ( P T H p T H P T H
ig
i i
ig
i
ig
i
= =
¿
=
i
ig
i i
ig
H y H
¿
=
i
ig
i i
ig
U y U
) , ( ) , (
i
ig
i
ig
i
p T M P T M =
¿ ¿
÷ =
i
i i
i
ig
i i
ig
y y R S y S ln
ig
i
ig
i
ig
i
S T H G ÷ =
i
ig
i
ig
i
ig
i
y RT TS H G ln + ÷ =
) , ( ) , ( P T H P T H
ig
i
ig
i
=
i
ig
i
ig
i
y R P T S P T S ln ) , ( ) , ( ÷ = ÷
i
ig
i
ig
i
ig
i
y RT G G ln + = ÷ µ
P y RT T
i i
ig
i
ln ) ( + I = µ
or
P y y RT T y G
i
i i
i
i i
ig
¿ ¿
+ I = ln ) (
P RT T G
i
ig
i
ln ) ( + I =
From integration of P RT dP
P
RT
dP V dG
ig
i
ig
i
ln = = =
Fugacity and fugacity coefficient
• Chemical potential:

– provides fundamental criterion for phase equilibria
– however, the Gibbs energy, hence μ
i
, is defined in
relation to the internal energy and entropy - (absolute
values are unknown).
• Fugacity:
– a quantity that takes the place of μ
i

j
n T P
i
i
n
nG
, ,
) (
(
¸
(

¸

c
c
÷ µ
i i i
f RT T G ln ) ( + I ÷
With units of pressure
i i i
f RT T G ln ) ( + I ÷
P RT T G
i
ig
i
ln ) ( + I =
P
f
RT G G
i
ig
i i
ln = ÷
i
R
i
RT G | ln =
P
f
i
i
= |
Residual Gibbs energy Fugacity coefficient
) . ( ) 1 ( ln
0
T const
P
dP
Z
P
i i
}
÷ = |
VLE for pure species
• Saturated vapor:
• Saturated liquid:
v
i i
v
i
f RT T G ln ) ( + I =
l
i i
l
i
f RT T G ln ) ( + I =
l
i
v
i
l
i
v
i
f
f
RT G G ln = ÷
VLE
0 ln = = ÷
l
i
v
i
l
i
v
i
f
f
RT G G
sat
i
l
i
v
i
f f f = =
sat
i
l
i
v
i
| | | = =
For a pure species coexisting liquid and vapor phases are in equilibrium when they
have the same temperature, pressure, fugacity and fugacity coefficient.
Fugacity of a pure liquid
• The fugacity of pure species i as a compressed
liquid:
sat
i
i
sat
i i
f
f
RT G G ln = ÷
) ( process isothermal dP V G G
P
P
i
sat
i i sat
i
}
= ÷
}
=
P
P
i
sat
i
i
sat
i
dP V
RT f
f 1
ln
Since V
i
is a weak function of P
RT
P P V
f
f
sat
i
l
i
sat
i
i
) (
ln
÷
=
sat
i
sat
i
sat
i
P f | =
RT
P P V
P f
sat
i
l
i
sat
i
sat
i i
) (
exp
÷
=|
For H
2
O at a temperature of 300°C and for pressures up to 10,000 kPa (100 bar)
calculate values of f
i
and φ
i
from data in the steam tables and plot them vs. P.
For a state at P:
i i i
f RT T G ln ) ( + I =
For a low pressure reference state:
* *
ln ) (
i i i
f RT T G + I =
) (
1
ln
*
*
i i
i
i
G G
RT f
f
÷ =
i i i
TS H G ÷ =
(
¸
(

¸

÷ ÷
÷
= ) (
1
ln
*
*
*
i i
i i
i
i
S S
T
H H
R f
f
The low pressure (say 1 kPa) at 300°C:
g
J
H
i
8 . 3076
*
=
gK
J
S
i
3450 . 10
*
=
kPa P f
i
1
* *
= =
For different values of P up to the saturated pressure at 300°C, one obtains the
values of f
i
,and hence φ
i
. Note, values of f
i
and φ
i
at 8592.7 kPa are obtained
Fig 11.3
Values of f
i
andφ
i
at higher pressure:
RT
P P V
P f
sat
i
l
i
sat
i
sat
i i
) (
exp
÷
=|
Fig 11.3
Fugacity and fugacity coefficient:
species in solution
• For species i in a mixture of real gases or in a solution of
liquids:



• Multiple phases at the same T and P are in equilibrium
when the fugacity of each constituent species is the same
in all phases:
i i i
f RT T
ˆ
ln ) ( + I ÷ µ
Fugacity of species i in solution
(replacing the particle pressure)
t | o
i i i
f f f
ˆ
...
ˆ ˆ
= = =
ig R
M M M ÷ =
The residual property:
P y
f
RT
i
i
ig
i i
ˆ
ln = ÷ µ µ
ig
i i
R
i
M M M ÷ =
The partial residual property:
ig
i i
R
i
G G G ÷ =
i
R
i
RT G |
ˆ
ln =
i i i
f RT T
ˆ
ln ) ( + I ÷ µ
P y RT T
i i
ig
i
ln ) ( + I = µ
i
n T P
i
i
G
n
nG
j
=
(
¸
(

¸

c
c
÷
, ,
) (
µ
P y
f
i
i
i
ˆ
ˆ
÷ |
The fugacity coefficient of
species i in solution
For ideal gas,
0 =
R
i
G
1
ˆ
ˆ
= =
P y
f
i
i
i
| P y f
i i
=
ˆ
Fundamental residual-property relation
dT
RT
nG
nG d
RT RT
nG
d
2
) (
1
÷ =
|
.
|

\
|
¿
+ ÷ =
i
i i
dn dT nS dP nV nG d µ ) ( ) ( ) (
TS H G ÷ =
¿
+ ÷ =
|
.
|

\
|
i
i
i
dn
RT
G
dT
RT
nH
dP
RT
nV
RT
nG
d
2
) , , (
i
n T P f
RT
nG
=
G/RT as a function of its canonical variables allows evaluation of all other
thermodynamic properties, and implicitly contains complete property information.
The residual properties:
¿
+ ÷ =
|
|
.
|

\
|
i
i
R
i
R R R
dn
RT
G
dT
RT
nH
dP
RT
nV
RT
nG
d
2
¿
+ ÷ =
|
|
.
|

\
|
i
i i
R R R
dn dT
RT
nH
dP
RT
nV
RT
nG
d |
ˆ
ln
2
or
¿
+ ÷ =
|
|
.
|

\
|
i
i
R
i
R R R
dn
RT
G
dT
RT
nH
dP
RT
nV
RT
nG
d
2
¿
+ ÷ =
|
|
.
|

\
|
i
i i
R R R
dn dT
RT
nH
dP
RT
nV
RT
nG
d |
ˆ
ln
2
Fix T and composition:
x T
R R
P
RT G
RT
V
,
) / (
|
|
.
|

\
|
c
c
=
Fix P and composition:
x P
R R
T
RT G
T
RT
H
,
) / (
|
|
.
|

\
|
c
c
÷ =
Fix T and P:
j
n T P
i
R
i
n
RT nG
, ,
) / (
ˆ
ln
|
|
.
|

\
|
c
c
= |
Develop a general equation for calculation of values form compressibility-
factor data.
i
|
ˆ
ln
j
n T P
i
R
i
n
RT nG
, ,
) / (
ˆ
ln
|
|
.
|

\
|
c
c
= |
}
÷ =
P
R
P
dP
n nZ
RT
nG
0
) (
}
(
¸
(

¸

c
÷ c
=
P
n T P
i
i
P
dP
n
n nZ
j
0
, ,
) (
ˆ
ln|
i
i
Z
n
nZ
=
c
c ) (
1 =
c
c
i
n
n
}
÷ =
P
i i
P
dP
Z
0
) 1 (
ˆ
ln|
Integration at constant temperature and composition
Fugacity coefficient from the virial
E.O.S
• The virial equation:

– the mixture second virial coefficient B:
– for a binary mixture:
• n mol of gas mixture:
RT
BP
Z + =1
¿¿
=
i j
ij j i
B y y B
22 2 2 21 1 2 12 2 1 11 1 1
B y y B y y B y y B y y B + + + =
RT
nBP
n nZ + =
2 2
,
1
, ,
1
1
) (
1
) (
n T n T P
n
nB
RT
P
n
nZ
Z
(
¸
(

¸

c
c
+ =
(
¸
(

¸

c
c
=
2 2
,
1
0
,
1
1
) ( ) ( 1
ˆ
ln
n T
P
n T
n
nB
RT
P
dP
n
nB
RT
(
¸
(

¸

c
c
=
(
¸
(

¸

c
c
=
}
|
2 2
,
1
0
,
1
1
) ( ) ( 1
ˆ
ln
n T
P
n T
n
nB
RT
P
dP
n
nB
RT
(
¸
(

¸

c
c
=
(
¸
(

¸

c
c
=
}
|
22 2 2 21 1 2 12 2 1 11 1 1
B y y B y y B y y B y y B + + + =
22 11 12 12
2 B B B ÷ ÷ ÷ o n n y
i i
/ =
( )
12
2
2 11 1
ˆ
ln o | y B
RT
P
+ =
Similarly:
( )
12
2
1 22 2
ˆ
ln o | y B
RT
P
+ =
For multicomponent gas mixture, the general form:
|
|
.
|

\
|
÷ + =
¿¿
) 2 (
2
1
ˆ
ln
ij ik
i j
j i kk k
y y B
RT
P
o o |
where
kk ii ik ik
B B B ÷ ÷ ÷ 2 o
Determine the fugacity coefficients for nitrogen and methane in N
2
(1)/CH
4
(2) mixture
at 200K and 30 bar if the mixture contains 40 mol-% N
2
.
mol
cm
B B B
3
22 11 12 12
6 . 20 0 . 105 2 . 35 ) 8 . 59 ( 2 2 = + + ÷ = ÷ ÷ ÷ o
( ) | | 0501 . 0 ) 6 . 20 ( ) 6 . 0 ( 2 . 35
) 200 )( 14 . 83 (
30
ˆ
ln
2
12
2
2 11 1
÷ = + ÷ = + = o | y B
RT
P
( ) | | 1835 . 0 ) 6 . 20 ( ) 4 . 0 ( 0 . 105
) 200 )( 14 . 83 (
30
ˆ
ln
2
12
2
1 22 2
÷ = + ÷ = + = o | y B
RT
P
9511 . 0
ˆ
1
= |
8324 . 0
ˆ
2
= |
Generalized correlations for the
fugacity coefficient
}
÷ =
r
P
r
r
r
i i
T const
P
dP
Z
0
) . ( ) 1 ( ln|
1 0
Z Z Z e + =
} }
+ ÷ =
r r
P
r
P
r
r
r
r
T const
P
dP
Z
P
dP
Z
0 0
1 0
) . ( ) 1 ( ln e |
or
1 0
ln ln ln | e | | + =
}
÷ ÷
r
P
r
r
P
dP
Z
0
0 0
) 1 ( ln|
}
÷
r
P
r
r
P
dP
Z
0
1 1
ln|
with
Table E1:E4 or Table E13:E16
) ( 1
1 0
B B
T
P
Z
r
r
e + = ÷
) ( ln
1 0
B B
T
P
r
r
e | + =
) , , ( OMEGA PR TR PHIB = |
For pure gas
For pure gas
Estimate a value for the fugacity of 1-butene vapor at 200°C and 70 bar.
127 . 1 =
r
T
731 . 1 =
r
P
191 . 0 = e
627 . 0
0
= |
and
096 . 1
1
= |
1 0
ln ln ln | e | | + =
Table E15 and E16
638 . 0 = | bar P f 7 . 44 ) 70 )( 638 . 0 ( = = =|
For gas mixture:
|
|
.
|

\
|
÷ + =
¿¿
) 2 (
2
1
ˆ
ln
ij ik
i j
j i kk k
y y B
RT
P
o o |
) (
1 0
B B
P
RT
B
ij
cij
cij
ij
e + =
2
j i
ij
e e
e
+
=
) 1 ( ) (
ij cj ci cij
k T T T ÷ =
Prausnitz et al. 1986
cij
cij cij
cij
V
RT Z
P =
2
cj ci
cij
Z Z
Z
+
=
3
3 / 1 3 / 1
2
|
|
.
|

\
|
+
=
cj ci
cij
V V
V
Empirical interaction parameter
Estimate and for an equimolar mixture of methyl ethyl ketone (1) /
toluene (2) at 50°C and 25 kPa. Set all k
ij
= 0.
1
ˆ
|
2
ˆ
|
2
j i
ij
e e
e
+
=
) 1 ( ) (
ij cj ci cij
k T T T ÷ =
cij
cij cij
cij
V
RT Z
P =
2
cj ci
cij
Z Z
Z
+
=
3
3 / 1 3 / 1
2
|
|
.
|

\
|
+
=
cj ci
cij
V V
V
) (
1 0
B B
P
RT
B
ij
cij
cij
ij
e + =
22 11 12 12
2 B B B ÷ ÷ ÷ o
( ) 0128 . 0
ˆ
ln
12
2
2 11 1
÷ = + = o | y B
RT
P
( ) 0172 . 0
ˆ
ln
12
2
1 22 2
÷ = + = o | y B
RT
P
987 . 0
ˆ
1
= |
983 . 0
ˆ
2
= |
The ideal solution
• Serves as a standard to be compared:



i i
id
i
x RT G G ln + =
cf.
i
ig
i
ig
i
y RT G G ln + =
i
P
i
x P
id
i
id
i
x R
T
G
T
G
S ln
,
÷
|
|
.
|

\
|
c
c
÷ =
|
|
.
|

\
|
c
c
÷ =
i i
id
i
x R S S ln ÷ =
T
i
x T
id
i
id
i
P
G
P
G
V
|
|
.
|

\
|
c
c
÷ =
|
|
.
|

\
|
c
c
÷ =
,
i
id
i
V V =
i i i i
id
i
id
i
id
i
x RT TS x RT G S T G H ln ln ÷ + + = + =
i
id
i
H H =
¿ ¿
+ =
i
i i
i
i i
id
x x RT G x G ln
i
i
i i
i
i
id
x x R S x S ln
¿ ¿
÷ =
i
i
i
id
V x V
¿
=
i
i
i
id
H x H
¿
=
¿
=
i
id
i i
id
M x M
i i
id
i
x RT G G ln + =
i i i
f RT T
ˆ
ln ) ( + I ÷ µ
The Lewis/Randall Rule
• For a special case of species i in an ideal solution:
id
i i
id
i
id
i
f RT T G
ˆ
ln ) ( + I = = µ
i i i
f RT T G ln ) ( + I ÷
i i
id
i
f x f =
ˆ
The Lewis/Randall rule
i
id
i
| | =
ˆ
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.
Excess properties
• The mathematical formalism of excess properties
is analogous to that of the residual properties:

– where M represents the molar (or unit-mass) value of
any extensive thermodynamic property (e.g., V, U, H, S,
G, etc.)
– Similarly, we have:

id E
M M M ÷ ÷
¿
+ ÷ =
|
|
.
|

\
|
i
i
E
i
E E E
dn
RT
G
dT
RT
nH
dP
RT
nV
RT
nG
d
2
The fundamental excess-property relation
Table 11.1
(1) If C
E
P
is a constant, independent of T, find expression for G
E
, S
E
, and H
E
as
functions of T. (2) From the equations developed in part (1), fine values for G
E
, S
E
,
and H
E
for an equilmolar solution of benzene(1) / n-hexane(2) at 323.15K, given the
following excess-property values for equilmolar solution at 298.15K:
C
E
P

=-2.86 J/mol-K, H
E
= 897.9 J/mol, and G
E
= 384.5 J/mol

From Table 11.1:
x P
E
E
P
T
G
T C
,
2
2
|
|
.
|

\
|
c
c
÷ =
. const a C
E
P
= =
T
a
T
G
x P
E
÷ =
|
|
.
|

\
|
c
c
,
2
2
b T a
T
G
x P
E
+ ÷ =
|
|
.
|

\
|
c
c
ln
,
integration
c bT T T T a G
E
+ + ÷ ÷ = ) ln (
integration
From Table 11.1:
x P
E
E
T
G
S
,
|
|
.
|

\
|
c
c
÷ =
b T a S
E
÷ = ln
c aT TS G H
E E E
+ = + =
integration
86 . 2 ÷ = = a C
E
P
c a + = ) 15 . 298 ( 9 . 897
c b a + + ÷ ÷ = ) 15 . 198 ( ) 15 . 298 ( ) 15 . 298 ln( ) 15 . 298 (( 5 . 384
We have values of a, b, c
and hence the excess-
properties at 323.15K
The excess Gibbs energy and the
activity coefficient
• The excess Gibbs energy is of particular interest:
id E
G G G ÷ ÷
i i i
f RT T G
ˆ
ln ) ( + I =
i i i
id
i
f x RT T G ln ) ( + I =
i i
i
E
i
f x
f
RT G
ˆ
ln =
i i
i
i
f x
f
ˆ
÷ ¸
i
E
i
RT G ¸ ln =
The activity coefficient of species i in solution.
A factor introduced into Raoult’s law to
account for liquid-phase non-idealities.
For ideal solution,
c.f.
i
R
i
RT G |
ˆ
ln =
1 , 0 = =
i
E
i
G ¸
¿
+ ÷ =
|
|
.
|

\
|
i
i
E
i
E E E
dn
RT
G
dT
RT
nH
dP
RT
nV
RT
nG
d
2
¿
+ ÷ =
|
|
.
|

\
|
i
i i
E E E
dn dT
RT
nH
dP
RT
nV
RT
nG
d ¸ ln
2
x T
E E
P
RT G
RT
V
,
) / (
|
|
.
|

\
|
c
c
=
x P
E E
T
RT G
T
RT
H
,
) / (
|
|
.
|

\
|
c
c
÷ =
j
n T P
i
E
i
n
RT nG
, ,
) / (
ln
|
|
.
|

\
|
c
c
= ¸
Experimental accessible values:
activity coefficients from VLE data,
V
E
and H
E
values come from mixing experiments.
¿
=
i
i i
E
x
RT
G
¸ ln
) , . ( 0 ln P T const d x
i
i i
=
¿
¸
Important application in phase-equilibrium
thermodynamics.
The nature of excess properties
• G
E
: through reduction of VLE data
• H
E
: from mixing experiment
• S
E
= (H
E
- G
E
) / T

• Fig 11.4

– excess properties become zero as either species ~ 1.
– G
E
is approximately parabolic in shape; H
E
and TS
E
exhibit
individual composition dependence.
– The extreme value of M
E
often occurs near the equilmolar
composition.
Fig 11.4

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