1

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
yi 12
Ki y2 x2 (3.13)
xi K1
12
K2

(K = VER = Vaporization Equilibrium Ratio)

2
Reference to Eq. (3.1) shows that the K-
value for Raoult's law is:

Pi sat
Ki y i P x i Pi sat (3.14)
P

Reference to Eq. (3.9) shows that for

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 temperature calculation
P and 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
Algorithm

1. Input: P, xi
2. Assume T
3. Calculate Pisat
4. Calculate yi
5. If yi 1, return to step 2

6
CONTOH SOAL
Campuran benzena (1), toluena (2), dan etil
benzena (3) berada dalam keseimbangan
uap-cair pada tekanan 110 kPa. Jika
komposisi fase cair adalah x1 = 0,2 dan x2 =
0,3. Tentukan temperatur dan komposisi fase
uap. Sistem tersebut dianggap mengikuti
hukum Raoult.

7
Bubble pressure calculation
T and 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

8
Algorithm

1. Input: T, xi
2. Calculate Pisat
3. Assume P
4. Calculate Ki and yi
5. If yi 1, return to step 3

9
Dew temperature calculation
P and yi are known,
the problem is to find the set of K-
values that satisfies Eq. (3.16b):

yi
1 (3.16b)
i Ki

10
Algorithm

1. Input: P, yi
2. Assume T
3. Calculate Pisat
4. Calculate xi
5. If xi 1, return to step 2

11
Dew pressure calculation
T and yi are known,
the problem is to find the set of K-
values that satisfies Eq. (3.16b):

yi
1 (3.16b)
i Ki

12
Algorithm

1. Input: T, yi
2. Calculate Pisat
3. Assume P
4. Calculate Ki and xi
5. If xi 1, return to step 3

13
Suatu campuran cairan hidrokarbon yang terdiri dari
metana (1), etana (2), propana (3), dan n-butana (4)
berada pada temperatur 30C dengan komposisi x1 =
0,5; x2 = 0,1; x3 = 0,2; x4 = 0,2. Hitung tekanan
bubble dan komposisi fase uap. Sistem ini dianggap
mengikuti hukum Raoult.
Tekanan uap murni masing-masing komponen
dinyatakan dengan persamaan :
ln Psat = A B/(T + C)
Dengan Psat dalam kPa dan T dalam K

A B C
Metana 13.2829 911.23 -6.4690
Etana 13.7097 1528.27 -16.4690
Propana 13.6504 1851.27 -26.1100
Butana 13.6605 2154.70 -34.3610
14
15
Total Mass Balance:

F L V
Component Mass Balance:

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

L V (i = 1, 2, , N)
zi xi y i
F F
zi xi 1 yi (i = 1, 2, , N) (3.17)

V
where
F 16
Component Mass Balance:

Comp. 1: z1F x1L y1V

Comp. 2: z2F x2L y2V

Comp. N: zN F xN L yNV

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

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 L V
zi xi y i V
F F
F
F V V F L V
zi xi yi
F F
L F V
F V V
z i xi y i
F F F

zi xi 1 yi

18
Ki = vaporization equilibrium ratio = yi/xi
yi
According to eq. (3.13): xi , hence
Ki

yi 1
zi 1 yi yi
Ki Ki

zi 1 1 K i 1 K i 1

yi Ki Ki Ki

zi K i
yi (3.18)
1 K i 1
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 z1K1 zi K i
y1 yi
1 K1 1 1 K i 1
z2K2
y2
1 K2 1
z3K3
y3
1 K3 1
(+)
3 zi K i
y1 y2 y3
i 11 K i 1

3 zi K i
yi 1
i i 11 K i 1
20
Since i yi =1, eq. (3.18) is summed up all
over species:

zi K i
1
i 1 K i 1

zi K i
f 1 0
i 1 K i 1
(3.19)

21
Dengan menggunakan metode iteratif
Newton-Raphson, maka nilai dapat
dihitung dengan menggunakan persamaan:

z iKi
1
i 1 j 1 Ki 1
j j 1 0
z i Ki 1

i 1 j 1 Ki 1
2

dengan i : nomor komponen

j : nomor iterasi
22
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
y i P x i Pi sat
P2sat = 97.84 kPa
P3sat = 50.32 kPa
23
SOLUTION 3.14

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

to determine Pbubl.

sat sat sat sat

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

0.45195.75 0.3597.84 0.2050.32

132 .40 kPa

24
Second, do DEW P calculation with {zi} =
{yi) to find Pdew.
1 1
Pdew
yi y1 y2 y3
sat P sat P sat P sat
i Pi 1 2 3

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.
25
 sat
Pi
By eq. (3.11): Ki
P
K1 = 1.7795
K2 = 0.8895
y i P x i Pi sat

K3 = 0.4575 yi Pi sat

xi P
Eq. (2.16):

zi K i
1
i 1 K i 1

26
0.451.7795 0.350.8895
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
27
28
Algoritma:
1. Input: zi, xi, P yi P i xi Pi sat

2. Hitung i
3. Tebak T
4. Hitung P1sat dan P2sat
y i i Pi sat
5. Hitung Ki Ki
xi P
6. Hitung yi
7. Hitung yi
8. Jika yi 1, kembali ke langkah 3

29
yi P i xi Pi sat

i xi Pi sat
yi
P

y i i Pi sat
Ki
xi P

30