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You are on page 1of 27

VLE IN BINARY

MIXTURE

Vaporization Equilibrium

Ratio

1

VLE FROM K-VALUE CORRELATIONS

given chemical species to partition itself

preferentially between liquid and vapor

phases is the equilibrium ratio Ki, defined as:

y1 x1

12

yi y2 x2

Ki (3.13)

xi K1

12

K2

2

Reference to Eq. (3.1) shows that the K-

value for Raoult's law is:

Pi sat

Ki yiP xiPisat (3.14)

P

modified Raoult's law it is:

i Pi sat

Ki (3.15)

P

3

According to Eq. (3.13) :

y i K i xi

K i xi 1 (3.16a)

i

yi 1

i

yi

xi

Ki yi

1 (3.16b)

i Ki

xi 1

i

4

Bubble point calculation

xi are known,

the problem is to find the set of K-

values that satisfies Eq. (3.16a).

K i xi 1 (3.16a)

i

5

Dew point calculation

yi are known,

the problem is to find the set of K-

values that satisfies Eq. (3.16b):

yi

1 (3.16b)

i Ki

6

Methane

P = 250 Psia

T = 180F

8

EXAMPLE 3.13

mol-% ethane, and 70 mol-% propane at

283.15 K, determine:

a. The dew-point pressure

b. The bubble-point pressure

The K-values are given by Fig. 10.13 (Smith

et al., 2001)

9

SOLUTION 3.13

a. When the system is at its dew point, only an

insignificant amount of liquid is present, and

the given mole fractions are values of yi.

P = 6.9 bar P = 10.34 P = 8.7 bar

i yi bar

Ki yi/Ki Ki yi/Ki Ki yi/Ki

CH4 0.10 20.00 0.005 13.20 0.008 16.00 0.006

C2H6 0.20 3.25 0.062 2.25 0.089 2.65 0.075

C3H8 0.70 0.92 0.761 0.65 1.077 0.762 0.919

yi Ki

i 0.828 1.174 1.000

P = 8.7 bar

10

11

b. When the system is almost condensed, it is

at its bubble-point, and the given mole

fractions are values of xi.

i xi bar

Ki Ki xi Ki K i xi Ki Ki xi

CH4 0.10 5.60 0.560 5.25 0.525 5.49 0.549

C2H6 0.20 1.11 0.222 1.07 0.214 1.10 0.220

C3H8 0.70 0.335 0.235 0.32 0.224 0.33 0.231

Kixi

i 1.017 0.963 1.000

P = 26.54 bar

12

Flash Calculations

(at given T and P)

13

Total Mass Balance:

F L V

Component Mass Balance:

zi F xi L y iV (i = 1, 2, , N)

L V (i = 1, 2, , N)

zi xi y i

F F

z i x i 1 y i (i = 1, 2, , N) (3.14)

V

where

F 14

L V

zi xi y i V

F F

F

F V V F L V

zi xi yi

F F

F V V

zi xi yi

F F F

z i x i 1 y i

z i x i 1 y i

15

yi

According to eq. (3.13): xi , hence

Ki

yi 1

zi 1 y i y i

Ki Ki

z i 1 1 K i 1 K i 1

yi Ki Ki Ki

zi K i

yi (3.15)

1 K i 1

16

Since i yi =1, eq. (3.15) is summed up all

over species:

zi K i

1 (3.16)

i 1 K i 1

17

EXAMPLE 3.14

The system acetone (1)/acetonitrile (2)/

nitromethane (3) at 353.15 K and 110 kPa

has the overall composition, z1 = 0.45, z2 =

0.35, z3 = 0.20. Assuming the Raoults law

is appropriate to this system, determine ,

{xi}, and {yi}. The vapor pressures of the

pure species at 353.15 K are

P1sat = 195.75 kPa

P2sat = 97.84 kPa

P3sat = 50.32 kPa

18

SOLUTION 3.14

to determine Pbubl.

Pbubl xi Pi xP

1 1 x P

2 2 xP

3 3

i

132.40 kPa

19

Second, do DEW P calculation with {zi} =

{yi) to find Pdew.

1 1

Pdew

yi y1 y2 y3

sat

sat sat

i

sat

Pi P1 P2 P3

101.52 kPa

and Pdew, the system is in the two-phase

region, and a flash calculation can be made.

20

sat

Pi

By eq. (3.11): Ki

P

K1 = 1.7795

K2 = 0.8895

K3 = 0.4575

Eq. (2.16):

zi K i

1

i 1 K i 1

21

0.451.7795 0.35 0.8895

1 0.7795 1 0.1105

0.20 0.4575

1

1 0.5425

0.737

zi K i yi

yi xi

1 K i 1 Ki

y1 = 0.5087 x1 = 0.2859

y2 = 0.3389 x2 = 0.3810

y3 = 0.1624 x3 = 0.3331 22

z i x i 1 y i

zi xi xi y i

zi xi y i xi

zi xi y i xi

zi xi

y i xi

z1 x1 0.45 0.2859

0.7365

y1 x1 0.5087 0.2859

23

24

Algoritma:

1. Input: zi, xi, P

2. Hitung i

3. Tebak T

4. Hitung P1sat dan P2sat y i i Pi sat

Ki

5. Hitung Ki xi P

6. Hitung yi

7. Hitung f(y)

8. Jika f(y) 0, kembali ke langkah 3

25

z i x i 1 y i

zi xi xi y i

zi xi y i xi

zi xi

y i xi

26

z1 x1

y1 x1

z1 x1 z2 x2

y1 x1 y2 x2

z2 x2

y2 x2 z1 x1 z2 x2

f y 0

y1 x1 y2 x2

27

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