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Chapter 3

VLE IN BINARY
MIXTURE
Vaporization Equilibrium
Ratio

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VLE FROM K-VALUE CORRELATIONS

A convenient measure of the tendency of a


given chemical species to partition itself
preferentially between liquid and vapor
phases is the equilibrium ratio Ki, defined as:
y1 x1
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yi y2 x2
Ki (3.13)
xi K1
12
K2

(K = VER = Vaporization Equilibrium Ratio)


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Reference to Eq. (3.1) shows that the K-
value for Raoult's law is:

Pi sat
Ki yiP xiPisat (3.14)
P

Reference to Eq. (3.9) shows that for


modified Raoult's law it is:

i Pi sat
Ki (3.15)
P

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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

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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

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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

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Methane
P = 250 Psia
T = 180F

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EXAMPLE 3.13

For a mixture of 10 mol-% methane, 20


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)

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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
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b. When the system is almost condensed, it is
at its bubble-point, and the given mole
fractions are values of xi.

P = 26.2 bar P = 27.6 bar P = 26.54


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
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Flash Calculations
(at given T and P)

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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

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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

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

zi K i
1 (3.16)
i 1 K i 1

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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
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SOLUTION 3.14

First, do BUBL P calculation with {zi} = {xi)


to determine Pbubl.

sat sat sat sat


Pbubl xi Pi xP
1 1 x P
2 2 xP
3 3
i

0.45 195.75 0.35 97.84 0.20 50.32

132.40 kPa
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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

Since the given pressure lies between Pbubl


and Pdew, the system is in the two-phase
region, and a flash calculation can be made.
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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

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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
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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
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z i x i 1 y i

zi xi xi y i

zi xi y i xi
zi xi

y i xi

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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

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