Nama : M.

Asyraf Hazzamy
NIM : 1410245243
Termodinamika Lanjut

Example 8-13
Using UNIFAC for liquid-phase activity coefcients, calculate vapor liquid
equilibria Pxy for the binary methanol (1)water (2) at 50 and 100 oC

Jawaban:
a. At Temperature 50 oC
yiiP = xiisiPvpi(PC)i (i = 1,2)
Pvpi = Vapor pressure component i (methanol, water)
yi,xi = vapor-phase and liquid phase mole fractions of component i
P = Equilibrium Total Pressure
s
i i = fugacity coefficient in the mixture and pure component
coeficcient at saturation
i = Activity Coefficient
(PC)i = Poynting factor

( PC )i=exp
[ 1
R ( t+273.15 )
v Li (PP vpi)
] (i =1,2)

R = Gas Universal t = 50 oC
v iL = Molar volume of pure liquid i at t 50 oC
Pvpi = 417.4 mmHg (Methanol)
= 92.5 mmHg (water)

Vapor pressure Methanol, water < 760 mmHg, vapor phase assumed to be
ideal.
yiP = xiPvpii (i = 1,2)

i is calculated from UNIFAC di 50 oC.

Step 1. Assign phase liquid fraksi mol methanol (x1) dari 0 ke 1, dengan
interval 0.1. masing masing fraksi x1, terdapat dua equation yang tidak
di ketahui, P dan y1; x2 dan y2 variabel tidak independen karena
mengikuti persamaan x1 + x2 = 1 dan y1 + y2 =1

Step 2. Masing masing x1, gunakan UNIFAC untuk menghitung koefisien

aktivitas untuk kedua komponen mengikuti langkah seperti 8-12.

Group Rk Qk
CH3OH 1.4311 1.432
H2O 0.9200 1.400
Group-group parameter interaksi di gunakan dalam kalkulasi koefisien aktivitas
residu (K)

Group CH3OH H2O

CH3OH 0 -181.0
H2O 289.6 0

Step 3. Calculate the total pressure

P = (y1 + y2)P = x11Pvp1 + x22Pvp2
Step 4. Evaluate vapor phase mole fraction y1
x P
y 1= 1 1 vp 1
P

Step 5. Return to step 2 with the next value of x1

Result after calculate at temperature 50 0C:

Mai Secon
n d amn V R Q r q
1,431 1,4 1,431 1,43
(1) Methanol 6 7 -181 1 1 3 1 2
289,
(2) Water 7 6 6 1 0,92 1,4 0,92 1,4

li 6,7 7,6
0,60869 0,50565 -0,4356 1,75132 1
0,39131 0,49435 -2,32 0,40796 1

ln ln C C R

- 0,30669 0,1104 1,1167 1,1
(1) Methanol 1,181913 1 5 8 0 2
1,604783 4,97678 1,2092 1,2
(2) Water 3 1 0,19 5 0 1

From App D, Vapor Pressure Correlations Parameter

Methanol Water
A= 5,20277 A= 5,11564
B= 1580,88 B= 1687,537
C= 238,5 C= 230,17
So, We can get data:

pv (1) 0,5286 1 1,11678

pv (2) 0,1237 2 1,2092
 Calculated 5
x1 P (mmHg) y1
0 113,68644 0
0,1 147,18181 0,30482 Pxy0 and yx diagrams for methanol (1)-water (2) at
0,2 180,67718 0,496621 50 C
0,3 214,17255 0,628428
0,4 247,66792 0,724583
Experiment
0,5 281,1633 0,797828
0,6 314,65867
x1 P0,85548 y1
(mmHg)
0,7 348,15404 0,902038
0 92,5 0
0,8 381,64941 0,940424
0,0453 122,73 0,086
0,9 415,14478 0,972615
0,0863 146,74 0,191
1 448,64015 1
0,1387 174,21 0,245
0,1854 194,62 0,434
0,3137 239,97 0,619
0,4177 266,99 0,662
0,5411 298,44 0,75
0,6166 316,58 0,824
0,7598 352,21 0,911
0,8525 376,44 0,969
0,9514 403,33 0,9817
1 417,4 1

x,y vs P
500

400

300
P (mmhg) 200

100

0
0 0.2 0.4 0.6 0.8 1

x1,y1
 x vs y
1.2
1
0.8
Calculated
0.6
y Experiment
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1

b. At Temperature 100 0C

Using the same steps at temperature 50 0C, we get data and diagrams pyx and xy
at 100 0C

Mai Secon
n d a V R Q r q
(1) 1,43
Methanol 6 7 -181 1 1,4311 2 1,4311 1,432
289,
(2) Water 7 6 6 1 0,92 1,4 0,92 1,4

li 6,7 7,6
0,608694 0,50565 -0,436 1,62459 1
0,391306 0,49435 -2,32 0,46006 1

ln ln C C R
(1) -
Methanol 0,7753159 0,460558 0,11045 1,11678 0 1,117
(2) Water 1,5438159 4,682424 0,19 1,20925 0 1,209

From App D, Vapor Pressure Correlations Parameter

Methanol Water
A= 5,20277 A= 5,11564
B= 1580,88 B= 1687,537
C= 238,5 C= 230,17
We can get data:

pv (1) 3,4082 1 1,11678

pv (2) 1,0105 2 1,20925

Pxy and yx diagrams for methanol (1)-water (2) at 100 0C

Calculated Experiment
x1 P (mmHg) y1 x1 P (mmHg) y1
0 928,6543 0 0 760 0
0,1 1125,057 0,25711 0,011 827,6 0,086
0,2 1321,459 0,4378 0,035 931 0,191
0,3 1517,862 0,57173 0,053 1003,2 0,245
0,4 1714,265 0,67497 0,121 1235,8 0,434
0,5 1910,667 0,75698 0,281 1536 0,619
0,6 2107,07 0,82371 0,352 1624,1 0,662
0,7 2303,472 0,87905 0,522 1882,5 0,75
0,8 2499,875 0,9257 0,667 2115,1 0,824
0,9 2696,278 0,96556 0,826 2337,8 0,911
1 2892,68 1 0,932 2508 0,969
1 2650,9 1

x,y vs P
500

400

300
P (mmhg) 200

100

0
0 0.2 0.4 0.6 0.8 1

x,y
 x vs y
1.2
1
0.8
Calculated
0.6
y Experiment
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1