SKF 2213 Chemical Engineering

Thermodynamics
Chapter 14: Topics in Phase Equilibria

The Gamma/Phi Formulation of VLE

Revision

Revision

Margules Equations for i

x1 1 P1sat
x1 1 P1sat
y1

P
x1 1 P1sat x 2 2 P2sat

Revision

See equations
12.20, 12.21a,
12.21b etc for
more details.

Revision

The Wilson equation

GE
xi ln x j ij
RT

j
i

(12.22)

xk ki
ln i 1 ln x j ij -
j
k x j kj

(12.23)

where
ij

Vj
Vi

exp

aij
RT

(i j)

(12.24)

aij is binary parameters and

Vi is molar volume of pure liquid i at T

Revision

Wilson equation for binary system,

GE
x1 ln(x1 x2 12 ) x2 ln(x2 x1 21 )
RT
that gives,

12
21
ln 1 ln(x1 x2 12 )+x 2

1
2 12
2
1 21

12
21

ln 2 ln(x2 x1 21 )-x1

x1 x2 12 x2 x1 21
where
ln 1 ln 12 1 21

ln 2 ln 21 1 12
6

VLE Criteria for

Multicomponent System
l
v

fi fi
l

So,

i xi f i i yi P

We know that,
fi fi l isat Pi sat exp

Vi l (P Pi sat )
RT

(11.44)
8

Substitute,

Vi (P Pi )
exp
i yi P
RT
l

i xi P

sat sat
i
i

sat

Rearrange,

i xi Pi

sat

i yi P
l
sat
(P

P
)
V
sat
i
i
i exp
RT

l
sat
i
Vi (P Pi )
yi sat exp
P
RT
i

Define,
i
Vi l (P Pi sat )
i sat exp

RT
i

At low to moderate pressure,

Vi (P Pi )
1
exp
RT
l

So,

sat

i
i sat
i

(14.2)
10

Then, we get
the Gamma/Phi formulation,

i xi Pi

sat

yi i P

(14.1)

11

For low to moderate pressure, we

can use two-term Virial EOS,
P
i exp
RT

Bii

y j y k (2 ji jk )
j
k

1
2

where
ji 2B ji B jj Bii

ii jj 0 and
Bij
Pcij

RTcij
Pcij

Zcij RTcij
Vcij

and jk 2B jk B jj Bkk

ij ji

B ij B
0

(11.64 & 14.4)

Zcij

ij

i j

Zci Zcj
2

Tcij (TciTcj )1/ 2 (1 k ij )

V
Vcij

1/ 3
ci

1/ 3
cj

12

Also,
isat

Bii Pi sat
i exp

RT

(11.36 & 14.5)

Note : Bii B
Where, eqn 3.62 and 3.63 give,
BPc
B0 B1
RTc
0.422
B 0.083 1.6
Tr
0

3.63
0.172
and B 0.139 4.2
Tr
1

13

Therefore,
P
exp
Bii

i
RT
i sat

y j yk (2 ji jk )
j
k

Bii Pi sat
exp

RT

P
= exp
Bii

RT

1
2

sat

B
P
1
ii i

y
y
(2

j k
ji
jk
2
RT

j
k

Bii (P Pi sat ) 12 P y j yk (2 ji jk )

j
k
= exp

RT

(14.6)

14

Apply to binary system,

B11 (P P1sat ) Py2212
1 = exp

RT

(14.7a)

B22 (P P2sat ) Py1212

2 = exp

RT

(14.7b)

15

Note: We could use the following eqn that is

based on generic cubic EOS to calculate i,

bi

ln i
Z 1 ln(Z ) qi I
b

(14.50)

16

 i xi Pi

sat

yi i P

For ideal gas mixture, in equilibrium with

non-ideal liquid solution i 1

i xi Pi sat yi P

Modified Raoult's Law

For ideal gas mixture in equilibrium with

i i =1
ideal liquid solution

xi Pi

sat

yi P

Raoult's Law
17

 i xi Pi

sat

yi i P

For VLE calculation, we need

i (T , P, y1 , y2 ,....y N 1 )

such eqn 14.6

i (T , x1 , x2 ,....x N 1 )

see chapter 12 for correlations

Pi sat f (T )

such as Antoine Eqn

18

Bubblepoint Calculations

xi K i xi

i Pi sat

i P

yi

i xi Pi sat
i P

(14.8)

Bubble pressure calculation,

P xi
i

i Pi sat

(14.10)

Bubble temperature calculation,

sat
j

P
xi i Pi
Psat
i
i
j

sat

Since {yi} is not known,

we cant evaluate i .
Calculation needs
iteration (single loop).
For algorithm,
see Figure 14.1 and 14.3

(14.13)

19

P xi
i

i Pi sat
i

(14.10)

yi

i xi Pi sat
i P

(14.8)

Note : is tolerance or acceptable error

20

* T sat
i
T

Bi
- Ci
Ai ln P

Bj
Aj ln Pjsat

(14.12)

- Cj

(14.15)

Pjsat

P
xi i Pi
P sat
i
i
j

yi

sat

i xi Pi sat
i P

(14.13)

(14.8)

21

Example: BULB T Calculation

See page 550 for input data:
Antoines constant and Virial Cross-Coefficients.
UNIFAC correlation is used for gamma (its
parameters have to be provided)

22
LOOK AT THE ACCURACY

Dewpoint Calculation
yi
yi
K Psat 1
i
i
i i

xi

yi i P

i Pi

sat

(14.9)

i P

Dew pressure calculation,

1
(14.11)
P
yi i

sat
P
i i

Dew temperature calculation,

Pjsat P

sat
yi i Pj

i Pi sat

Since {xi} and P are not known,

we cant evaluate i and i .
Calculation needs iteration
(double loop).
For algorithm, see Figure 14.2

Since {xi} and T are not known,

we cant evaluate i and i .
(14.14) Calculation needs iteration
(double loop).
23
For algorithm, see Figure 14.4

1
yi i

sat

(14.11)

xi

yi i P

i Pi

sat

(14.9)

i i

Normalize,

x j,norm =

xj

xi

24

Ti

sat

Bi

- Ci
Ai ln P

Pjsat P

(14.12)
T

Bj
Aj ln Pjsat

- Cj

(14.15)

xi

sat
yi i Pj

i Pi sat

yi i P

i Pi

sat

(14.14)
(14.9)

25

Flash Calculations
zi K i
yi
1 V ( K i 1)

(10.16)

zi K i
Fy yi 1
1 0
1 V ( K i 1)
zi
xi
1 V ( K i 1)

(10.17) or (14.17)

(14.16)

zi
Fx xi 1
1 0
1 V ( K i 1)

(10.17) or (14.17)
26

F Fx - Fy 0
zi ( K i 1)
F
0
1 V ( K i 1)
zi ( K i 1)2
dF

2
dV
1 V ( K i 1)

(14.19)

(14.20)

dF/dV is always negative, hence the F vs. V is monotonic.

This will give rapid convergence for iteration with Newtons
method.

dF
dF
F
V F
(Vn1 Vn ) 0

dV
dV

(14.21)
27

Ki

i Pi sat

(14.22)
i P
z (K 1)
F i i
0
(14.19)
1 V (K i 1)
zi ( K i 1)2
dF

2
dV
1 V (K i 1)
xi

zi
1 V ( K i 1)

(14.20)

(14.16)

*
*

For initial value of V , i and i ,

At dew point
V 1, Pdew , i,dew , i,dew
At bubble point
V 0, Pbubl , i,bubl , i,bubl
Interpolation

i i,dew
P Pdew
V 1

Pbubl Pdew 0 1 i,bubl i,dew

i i,dew 28
P Pdew

Pbubl Pdew i,bubl i,dew

Example: Flash Calculation,

29

Assignment

Problems:
-12.16 (a,b) for Acetone (1)/Water (2) binary
system
-14.1
(due 13/4, Wednesday)

30