SOLUTION

THERMODYNAMICS:

ERT 206: Thermodynamics

Miss Anis Atikah Ahmad
Tel: 04-9763245
Email: anis atikah@unimap.edu.my
 OUTLINE
1. Fundamental Property Relation
2. Chemical Potential & Phase Equilibra
3. Partial Properties
4. The Ideal-Gas Mixture Model
5. Fugacity & Fugacity Coefficient: Pure Species
6. Fugacity & Fugacity Coefficient: Species in
Solution
7. Generalized Correlations for Fugacity Coefficient
1. Fundamental Property Relation
• Total Gibbs energy change of any CLOSED system:
d nG   nV dP  nS dT
*applied to a single phase fluid in a closed system wherein no
chemical reactions occurs & the composition is constant.

Therefore;

  nG    nG 
 P   nV  T   nS
  T ,n   P ,n
No of moles of all chemical species are held constant.
 1. Fundamental Property Relation
• For single phase, OPEN system (material pass into
& out of the system),
  nG    nG    nG 
d nG     dP    dT     dni
 P  T ,n  T  P ,n i  ni  P ,T , n
j

*where ni is the no of moles of species i.

* nj indicates that all mole no except the ith are held constant.

ntial , μi
  nG  hemic
al p ote
i    Defi n e d as c
 ni  P ,T ,n j
 1. Fundamental Property Relation
 nG   nG    nG 
• Since  P   nV ,  T   nS , i   
T ,n P ,n  ni  P ,T ,n j

total change of Gibbs energy for OPEN system

becomes:
d nG  nV dP  nSdT  i dni
i

This equation is a fundamental property relation for

SINGLE-PHASE FLUID SYSTEM of variable mass &
composition
 1. Fundamental Property Relation
• For special case of one mol of solution, n=1 & ni = xi ,
d nG  nVdP nSdT  i dni
i
becomes
dnG  VdP SdT  i dxi
i G as a function of T, P
G  GT, P, x1, x2 ,....xi ,.. and xi

At constant T & x: At constant P & x: At constant P & x:

 G 
 G   G  H  G T 
V   S     T  P , x
 P  T , x  T  P , x from H  G  TS
 2. The Chemical Potential &
Phase Equilibra
• For a CLOSED system consisting of TWO
phases in equilibrium, each individual phase
is OPEN to other (mass transfer between phases
may occur).
d nG  nV  dP  nS  dT   i dni
    
phase
i

d nG  nV  dP  nS  dT   i dni

    

i
Presumption: At equilibrium, T & P are the
same in all phases.
 2. The Chemical Potential &
Phase Equilibra
• The change in total Gibbs energy of the two-
phase system is the sum of these equations:
d nG  nV  dP  nS  dT   i dni
    

i
+

d nG  nV  dP  nS  dT   i dni

    

d nG  nV dP  nS dT   i dni   i dni

   

i i
Reduced to this form:
nM  nM  nM
 
 2. The Chemical Potential &
Phase Equilibra
d nG  nV dP  nS dT   i dni   i dni
   

i i
• At equilibrium,  
The changes of dni & dni

 dni   i dni  0
    result from mass transfer
i btween the phases.
i i
 
dni  dni
Therefore,  i

dni   i  dni  0
 
 

i i

 
  
i  i dni  0
i
 2. The Chemical Potential &
Phase Equilibra
 
• Since  i  i  dni  0
i

   
Therefore, i  i  0 or i  i

 
i  i  ...  i

i  1,2..., N 
Multiple phases at the same T & P are in
equilibrium when the chemical potential of
each species is the SAME in all phases.
 3. Partial Properties
Partial molar property, M i of species i in solution,
 nM 
Mi   
 ni  P ,T ,n j

is a measure of the response of total property nM

to the addition at constant T & P of differential
amount of species i to a finite amount of
solution.
 3. Partial Properties
Properties example
Solution properties M V ,U , H , S , G

Partial properties Mi Vi ,U i , H i , Si , Gi

Pure-species properties Mi Vi ,U i , H i , Si , Gi
 3. Partial Properties

  nM 
Since Mi   
 ni  P ,T ,n j

Therefore,
  nG 
Gi   
 ni  P ,T , n j
or Gi  i
Because:
  nG 
i   
 ni  P ,T ,n j
 3.1 Molar Properties & Partial
Molar Properties
The total thermodynamic properties of a homogeneous
phase are functions of T, P, and the no of moles of
individual species.
nM  ΜT , P, n1 , n2 ,..., ni ,...

The total differential of nM is:

 nM   nM   nM 
d nM     dP    dT     dni
 P  T ,n  T  P ,n i  ni  P ,T ,n j
 3.1.1 Molar Properties from
Partial Molar Properties
The total differential of nM is:
 nM   nM    nM 
d nM     dP    dT     dni
 P  T ,n  T  P ,n i  ni  P ,T ,n j

At constant n,
 M   M 
d nM   n  dP  n  dT   M i dni
 P T , x  T  P , x i

*x denotes differentiation at constant composition  nM 

Mi   
 ni  P ,T ,n j
 3.1.1 Molar Properties from
Partial Molar Properties
 M   M 
d nM   n  dP  n  dT   M i dni
 P T , x  T  P , x i

Because ni  xi n,
dni  d xi n 

According to product rule,

d xi n   xi dn  ndxi
d nM   ndM  Mdn

 M   M 
ndM  Mdn  n  dP  n  dT   M i xi dn  ndxi 
 P T , x  T  P , x i
 3.1.1 Molar Properties from
Partial Molar Properties
 M   M 
ndM  Mdn  n  dP  n  dT   M i xi dn  ndxi 
 P T , x  T  P , x i

Factorizing n and dn terms,

  M   M    
dM    dP    dT   M i dxi n  M   xi M i dn  0
  P T , x  T  P, x i   i 

Mathematically,
 M   M  M   xi M i  0
dM    dP    dT   M i dxi  0 i
 P T , x  T  P, x i
M   xi M i
 M   M  i
x n
dM    dP    dT   M i dxi nM   ni M i
 P T , x  T  P, x i i
 3.1.1 Molar Properties from
Partial Molar Properties
  M   M    
dM    dP    dT   M i dxi n  M   xi M i dn  0
  P T , x  T  P, x i   i 

 M   M  M   xi M i summability

 dT   M i dxi
equation
dM    dP   i
 P T , x  T  P , x i  
Co
mp
dM  d   xi M i 
ari  i 
ng
dM   xi dM i   M i dxi
i i

 M   M 
  dP    dT   M i dxi   xi dM i   M i dxi
 P T , x  T  P , x i i i

 M   M 
  dP    dT   xi dM i  0 Gibbs/Duhem  x dMi i 0
 P  T , x  T  P , x i equation i
(at constant T & P)
 3.2 Partial Properties in Binary
Solutions
For binary solution, the summability relation, M   xi Mbecomes:
i
i
M  x1M1  x2 M 2 (A)

dM  x1dM1  M1dx1  x2dM 2  M 2dx2 (B)

At constant T & P, Gibbs/Duhem eq,

 M   M 
  dP    dT   xi dM i  0
becomes
 x dM
i i 0
 P  T , x  T  P , x i i

Thus, for binary solution, Gibbs/Duhem eq. can be written as,

x1dM 1  x2 dM 2  0 (C)
 3.2 Partial Properties in Binary
Solutions
Substituting x1dM 1  x2 dM 2  0 into differential of summability
relation:
dM  x1dM1  M1dx1  x2dM 2  M 2dx2 (B)

dM  M1dx1  M 2dx2
Because x1+x2=1, x1=1-x2 and dx1=-dx2,
dM  M 1dx1  M 2 dx1

dM  M 1  M 2 dx1
dM
 M1  M 2  (D)
dx1
 3.2 Partial Properties in Binary
Solutions
The summability relation, M  x1M1  x2 M 2 can also be written
as:
M  1  x2 M1  x2 M 2 M  x1M1  1  x1 M 2
 M1  x2 M1  x2 M 2  x1M1  M 2  x1M 2
M  M1  x2 M1  M 2  M  x1 M1  M 2  M 2

M1  M  x2 M1  M 2  M 2  M  x1 M1  M 2 
dM dM
M1  M  x2 M 2  M  x1
dx1 dM dx1
 M1  M 2 
dx1
 3.2 Partial Properties in Binary
Solutions
Gibbs/Duhem equations, x1dM 1  x2 dM 2  0 may be written in
derivative forms:

dM 1 dM 2
x1  x2 0
dx1 dx1

dM 1 x2 dM 2

dx1 x1 dx1
 3.3 Relations among Partial
Properties
The change of Gibbs energy,
d nG   nV dP  nS dT    i dn i
i

d nG   nV dP  nS dT  G i dn i

i

Application of the criterion of exactness yields:

 V   S  Recall:
    
 T  P , n  P  T , n  nM 
Mi   
 n  P ,T ,n j
 Gi    nV   Gi  i

        Vi
 P T ,n   n i  P ,T , n j  P T ,n

 Gi    nS    Gi


   S i
     
 T  P ,n   n i  P ,T , n j  T  P ,n
 4. The Ideal-Gas Mixture
Gibbs 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 pressure equal to its partial
pressure in the mixture

Thus, for general partial property;

M i
ig
T , P   M T , pi 
i
ig

The enthalpy of an ideal gas is independent of pressure;

H i
ig
T , P   H T , pi   H T , P 
i
ig
i
ig

Also applies to other property that are

H iig  H iig [1]
independent of pressure
 4. The Ideal-Gas Mixture
The entropy of an ideal gas does depend on pressure;

dS iig   Rd ln P (const T)
P P

 i   R  ln P
ig
S
pi pi
P
S T , P   S T , pi    R ln
i
ig
i
ig

pi
P
  R ln  R ln yi
yi P
S i
ig
T , pi   S T , P   R ln yi
i
ig
 4. The Ideal-Gas Mixture
S i
ig
T , pi   S T , P   R ln yi
i
ig
A partial molar
property ideal gas
mixture is equal to the
Since M i
ig
T , P   M i T , p i 
ig
molar property of the
species as a pure ideal
gas at the mixture
S iig T , pi   S iig T , P  temperature but at
pressure equal to its
partial pressure in the
Thus, mixture

S iig T , P   S iig T , P   R ln yi
or
ig ig
S i  S  R ln yi
i [2]
 4. The Ideal-Gas Mixture
For Gibbs energy of an ideal-gas mixture, G ig  H ig  TS ig
the partial properties is:
Gi ig  H iig  T S iig Recall:
H iig  H iig
Thus,
ig
Gi  H i
ig
 ig
 T S  R ln yi
i  S iig  S iig  R ln yi

ig ig
H i  TS  RT ln yi
i

or
 iig  Gi ig  Giig  RT ln yi [3]

Recall:
Gi  i
 4. The Ideal-Gas Mixture
So far, we have derive:
H iig  H iig [1]

S iig  S iig  R ln yi [2]

Gi ig  Giig  RT ln yi [3]

Substituting [1], [2] & [3] into the summability relation, M   yi M i

i

H ig   yi H ig H ig   yi H iig [4]
i i

S ig   yi S ig S ig   yi S iig  R  yi ln yi [5]
i i i
Gig   yiG ig G ig   yi Giig  RT  yi ln yi [6]
i i i
 4. The Ideal-Gas Mixture
The properties of mixture for enthalpy, entropy and Gibbs energy:
H ig   yi H iig [4]
i

S ig   yi S iig  R  yi ln yi [5]
i i

G ig   yi Giig  RT  yi ln yi [6]
i i

Rearranging [4] & [5] give enthalpy & entropy change of mixing;
For ideal gas, mixing at constant T & P is
H ig
  yi H i
ig
0 not accompanied by heat transfer
i

1
S   yi S
ig
i
ig
 R  yi ln
i i yi
 4. The Ideal-Gas Mixture
Alternatively, Giig in eq [3] ( Gi ig  Giig  RT ln yi ) can be
expressed by giving its T and P dependence:
dG ig  Vi ig dP (const T)

ig RT
dG  dP
P Integration constant
Integration gives; at constant T

G ig   i T   RT ln P [7]

Thus eq [3] becomes:

Gi ig  i T   RT ln P  RT ln yi
 i T   RT ln  yi P  [8]
 4. The Ideal-Gas Mixture
Gi ig  i T   RT ln  yi P  [8]

Substituting eq [8] into summability relation, G ig

 i
i
y G ig

ig
Thus, Gibbs energy of an ideal-gas mixture,G becomes:

Gig   yi i T   RT ln yi P

i

G ig   yi i T   RT  yi ln yi P 
i i
 5. Fugacity & Fugacity Coefficient:
Pure Species
Fugacity of pure
• For real fluid; species i, with units
of pressure
Gi  i T   RT ln f i [8]

• Substracting eq [7] , G ig  i T   RT ln P from eq [8] ;

ig  fi 
Gi  Gi  RT ln  
P
fi
GiR  RT ln i i  Fugacity: pressure
P of an ideal
Residual Fugacity gas which has the
Gibbs coefficient same chemical
energy potential as the real
gas.
5. Fugacity & Fugacity Coefficient:
Pure Species
GiR  RT ln i

GiR
 ln i
RT
P
GiR dP
From previous chapter,   Z i  1
RT 0 P
Thus,
P
dP
ln i   Z i  1 (const T)
0
P
 5. Fugacity & Fugacity Coefficient: Pure
Species
PV BP
From previous chapter, Z   1
RT RT
OR
BP
Z 1 
RT
Bii P
Z i 1 
RT
P
dP
Thus, ln i   Z i  1 becomes:
0
P
P
Bii Bii P
ln i 
RT  dP
0
(const T) ln i 
RT
 5. Fugacity & Fugacity Coefficient: Pure
Species
• For vapor/liquid equilibrium;
G  i T   RT ln f i
i
v v
For saturated vapor

Gil  i T   RT ln f i l For saturated liquid

• By difference:  f v

Gi  Gi  RT ln  l 
v l i

 fi 
v l
• At equilibrium, G i  G i
v l
• Thus, G i  G i  0
 5. Fugacity & Fugacity Coefficient: Pure
Species
• Therefore,
 fiv 
RT ln  l   0
 fi 
 fiv  For a pure species coexisting
ln  l   0
 fi  liquid & vapor phases, they are
in equilibrium when they have
fiv the same temperature, pressure
l
1
fi & fugacity.

f i v  f i l  f i sat

sat f i sat
 i  sat iv  il  isat
Pi
 5.Fugacity & Fugacity Coefficient: Pure
Species
• For pure liquid,

f i P  
l f i
v
P i
sat
f   
i
l
Pi
sat
f i P 
l
P sat

Pi sat v
   
f i Pi sat l
f i Pi sat i

A B C

Pi sat
dP Bii P
ln  i
sat
  Z  1 i
v
i
v
Z 1 
0
P RT
Pi sat
 Bii P  dP  exp Bii P

sat
  exp  
i
0  RT  P RT
 5. Fugacity & Fugacity Coefficient: Pure
Species
• For pure liquid,

f i P  
l f i
v
   
P i
sat
f i
l
Pi
sat
f i P 
l
P sat

Pi    
sat v
f i Pi sat l
f i Pi sat i

A B C

 
f i l Pi sat
1
 
v
f i Pi sat
 5. Fugacity & Fugacity Coefficient: Pure
Species
• For pure liquid,

f i P  
l f i
v
P   
i
sat
f i
l
Pi
sat
f i P 
l
P sat

Pi sat
   v
f i Pi sat l
f i Pi sat i

A B C

From
sat fi Gi  i T   RT ln f i
Gi  G i  RT ln
f i sat Gisat  i T   RT ln f i sat
P
From dG  VdP  SdT
Gi  Gisat   i dP
l
V
Pi sat
(at constant T)
 5. Fugacity & Fugacity Coefficient: Pure
Species
• Ratio C becomes,
f i l P 
P
1
 i dP
l
 exp V
f i Pi 
l sat
RT Pi sat

 exp

Vi l P  Pi sat 
RT
• Substituting A, B, and C terms;
Bii P
sat sat
f i   Pi exp
l

Vi P  Pi sat
  exp
RT
i
RT
V
f i  isat Pi sat exp i

l
P  Pi
sat

RT
6. Fugacity & Fugacity Coefficient: Species in
Solution
• For a species i in a mixture of real gas or in a
solution of liquids;
Fugacity of species i in
 i  i T   RT ln fˆi solution

• At equilibrium;
Multiple phases at the same
fˆi  fˆi  ...  fˆi
   T & P are in equilibrium
when the fugacity of each
constituent species is the
same in all species
6. Fugacity & Fugacity Coefficient: Species in
Solution
• For a species i in a mixture of real gas or in a
solution of liquids;
Gi R  Gi  Gi ig Partial residual Gibbs energy

Gi R  RT ln ˆi
Fugacity coefficient of species
i in solution
ˆ
f
ˆi  i
yi P
 6. 1 Fugacity Coefficient from the Virial
Equation of State
• Fugacity coefficient;
P
dP
ln i   Z i  1
ˆ
0
P
• Virial equation of state:
BP
Z  1
RT
• For n mol of gas mixture:
the bimolecular
nBP B    yi y j Bij
nZ  n  interaction
RT B B
i j between
ij ji molecule i and j
 6. 1 Fugacity Coefficient from the Virial
Equation of State
nBP
nZ  n 
RT
• Differentiation with respect to n1:
  nZ  P   nB 
Z1     1  
  n1  RT   n1  T , n2

P
• Thus ln ˆi   Z i  1 dP becomes;
0
P
P   nB 
P
ˆ
ln 1  
dP P   nB 
    
0
RT   n1  T , n2 P RT   n1  T , n2
6. 1 Fugacity Coefficient from the Virial Equation of State

• For binary mixture:

B  y1 y1 B11  y1 y 2 B12  y 2 y1 B21  y 2 y 2 B22
 y12 B11  2 y1 y 2 B12  y 22 B22
OR can be written as:

B  y1 1  y 2 B11  2 y1 y 2 B12  y 2 1  y1 B22

 y1 B11  y1 y 2 B11  2 y1 y 2 B12  y 2 B22  y1 y 2 B22

OR

B  y1 B11  y 2 B22  y1 y 2 12 with  12  2 B12  B11  B22

 6. 1 Fugacity Coefficient from the Virial
Equation of State
Multiplying by n;
nB  ny1 B11  ny 2 B22  ny1 y 2 12

Substituting yi  ni n ;
n1n2
nB  n1 B11  n2 B22   12
n
By differentiation;

  nB   1 n1 
   B11     n2 12
 n1  T , n2  n n2 
 B11  1  y1 y 2 12  B11  y 22 12
 6. 1 Fugacity Coefficient from the Virial
Equation of State

nB ˆ P   nB 
into ln 1 
2
Substituting    B11  y212   ;
n
 1 T ,n2 RT  n1  T , n
2

P
ˆ
ln 1 
RT

B11  y 22 12 
Similarly;
P
ˆ
ln  2 
RT

B22  y 22 12 
 6. 1 Fugacity Coefficient from the Virial
Equation of State

For multicomponent gas mixtures;

P  1 
ˆ
ln  k   Bkk    yi y j 2 ik   ij 
RT  2 i j 
where
 ik  2 Bik  Bii  Bkk  ij  2 Bij  Bii  B jj
and
with  ki   ik
 ii  0,
 kk  0,
 7. Generalized Correlation for Fugacity
Coefficient
• For pure gases;
P  Pc Pr
dP  Pc dPr
P
dP
ln i   Z i  1
• Hence,at P=Pr , 0
P becomes;
Pr
dPr
ln i  
 i
Z  1 At constant Tr
0
Pr

• From Pitzer
0
correlation;
1
Z  Z  Z
 7. Generalized Correlation for Fugacity
Coefficient
• Substitution of Z i , ln  becomes;
Pr Pr
dPr 1 dPr
ln    Z  1 0
  Z
0
Pr 0
Pr

OR
0 1
ln   ln    ln 
Where;
Pr Pr
dPr dPr
  ln    Z
0 0 1 1
ln   Z 1
0
Pr 0
Pr
7. Generalized Correlation for Fugacity
Coefficient

0 1
ln   ln    ln  can also be written as:

   0
 
1 
 7. Generalized Correlation for Fugacity
Coefficient
Pr
dPr
ln i  
 i
Z  1 can also be simplified by substituting:
0
Pr

Pr 
Z 1 
Tr

B  B1 
Thus,
Pr
Pr  1 dPr
ln i  
T
B  B Pr

0 r

 Pr  1 
ln i 
Pr 

B  B1  OR 
i  exp B  B  
Tr  Tr 
 7. Generalized Correlation for Fugacity
Coefficient
• For gas mixtures;
P  1 
ˆ
ln  k   Bkk    yi y j 2 ik   ij 
RT  2 i j 
Where;
0.422 0.172
Bˆij  B 0  ij B1 0
B  0.083  1.6 1
B  0.139  4.2
Tr Tr
and

ˆ Bij Pcij
Bij 
RTcij
 7. Generalized Correlation for Fugacity
Coefficient
• The calculation for ij , Tcij , Pcij (proposed by Prausnitz et al. );

ci  cj
Tcij  TciTcj  1  kij 
1/ 2
cij  Interaction
2 parameter
(specific to
Zci  Zcj Zcij RTcij i-j molecule
Zcij  Pcij  pair)
2 Vcij
3
V 1/ 3
V 1/ 3

Vcij   
ci cj
 2 
 
 7. Generalized Correlation for Fugacity
Coefficient
EXAMPLE: Estimate ˆ1 & ˆ2 for an equimolar mixture of
methyl ethyl ketone (1)/toluene(2) at 50°C and 25kPa. Set all kij=0

ij Tcij /K Pcij/bar Vcij/cm3mol-1 Zcij ωij

11 535.5 41.5 267 0.249 0.323

22 591.8 41.1 316 0.264 0.262

 7. Generalized Correlation for Fugacity
Coefficient
EXAMPLE – Step 1: Calc Tcij, Vcij, Zcij &ωcij for ij=12

ij Tcij /K Pcij/bar Vcij/cm3mol-1 Zcij ωij

11 535.5 41.5 267 0.249 0.323

22 591.8 41.1 316 0.264 0.262

12 563.0 41.3 291 0.256 0.293

3 ci  cj
 Vci1/ 3  Vcj1/ 3  cij 
Tcij  TciTcj  1  kij 
1/ 2 Zcij RTcij Vcij   
Pcij    Z Z 2
Vcij  2  Zcij  ci cj
2
 7. Generalized Correlation for Fugacity
Coefficient
EXAMPLE- Step 2: Calc Trij, B0, B1 & Bij for all ij

ij Trij /K B0 B1 Bij/cm3mol-1

11 0.603 -0.865 -1.300 -1,387

22 0.546 -1.028 -2.045 -1,860

12 0.574 -0.943 -1.632 -1,611

T Bˆij  B 0  ij B1
Trij  0.422 Bˆ ij RT cij
B 0  0.083  1 0.172
B  0.139  4.2
Tcij Tr1ij .6 Bij 
Trij Pcij
 7. Generalized Correlation for Fugacity
Coefficient
EXAMPLE: Step 3:Estimate ˆ1 & ˆ2

 12  2 B12  B11  B22

 2 1611   1387  1860  25cm 3 mol 1

ˆ
ln 1 
P
RT
 2

B11  y 2  12 
25
8314 323 .15 
 2

 1387  0.5  25 

  0 .0128
ˆ
ln  2 
P
RT
 2
B22  y1  12   25
8314 323 .15 

 1860  0.5 25 
 2

  0 .0172
ˆ1  0.987 ˆ2  0.983