CHE 553 – CHEMICAL

ENGINEERING
THERMODYNAMICS
ASSIGNMENT 2

NAME MATRIC ID
MUHAMMAD SHAMMIL ASHMAN BIN MOHD SAUPI 2018441592
 CHE553 – CHEMICAL ENGINEERING THERMODYNAMICS
ASSIGNMENT 2
SUBMISSION DATE: WEEK 14

QUESTION 1

Vapor liquid equilibrium (VLE) data for acetone(1) and methanol (2) system was obtained at
fixed temperature of 60oC. Data collected is shown below:

Table 1: VLE data for acetone(1)/methanol (2) at 60oC

P x1 y1
68.728 0.0000 0.0000
72.278 0.0287 0.0647
75.279 0.0570 0.1295
77.254 0.0858 0.1848
78.951 0.1046 0.2190
82.528 0.1452 0.2694
86.762 0.2173 0.3633
90.088 0.2787 0.4184
93.206 0.3579 0.4779
95.017 0.4050 0.5135
96.365 0.4480 0.5512
98.462 0.5432 0.6174
99.811 0.6332 0.6772
99.950 0.6605 0.6926
100.278 0.6945 0.7124
100.467 0.7327 0.7383
100.999 0.7752 0.7729
101.059 0.7922 0.7876
99.877 0.9080 0.8959
96.885 1.0000 1.0000
By using the data in Table 1,
a) Determine the vapor pressure for both components and the composition of azeotrope.

P-XY DIAGRAM
120

100

80
Pressure

60

40

20

0 0.77
0 0.2 0.4 0.6 0.8 1 1.2

x1 and y1

x1 y1

Vapor Pressure: 101

Composition of Azeotrope: 0.77
 b) Evaluate the parameters for Van Laar and NRTL model.

Van Laar Model:

Pressure x1 y1 x2 y2 ln γ1 ln γ2 Ge/RT x1x2RT/Ge

68.728 0 0 1.0000 1.0000 #DIV/0! 0.0000 #DIV/0! #DIV/0!
72.278 0.0287 0.0647 0.9713 0.9353 0.5199 0.0126 0.0272 1.0266
75.279 0.057 0.1295 0.9430 0.8705 0.5683 0.0110 0.0428 1.2556
77.254 0.0858 0.1848 0.9142 0.8152 0.5408 0.0023 0.0485 1.6163
78.951 0.1046 0.219 0.8954 0.7810 0.5342 0.0020 0.0576 1.6246
82.528 0.1452 0.2694 0.8548 0.7306 0.4577 0.0260 0.0887 1.3998
86.762 0.2173 0.3633 0.7827 0.6367 0.4036 0.0266 0.1085 1.5677
90.088 0.2787 0.4184 0.7213 0.5816 0.3336 0.0554 0.1329 1.5127
93.206 0.3579 0.4779 0.6421 0.5221 0.2504 0.0978 0.1524 1.5078
95.017 0.405 0.5135 0.5950 0.4865 0.2179 0.1226 0.1612 1.4951
96.365 0.448 0.5512 0.5520 0.4488 0.2019 0.1310 0.1628 1.5192
98.462 0.5432 0.6174 0.4568 0.3826 0.1442 0.1823 0.1616 1.5357
99.811 0.6332 0.6772 0.3668 0.3228 0.0969 0.2453 0.1514 1.5344
99.95 0.6605 0.6926 0.3395 0.3074 0.0786 0.2752 0.1453 1.5428
100.278 0.6945 0.7124 0.3055 0.2876 0.0599 0.3174 0.1385 1.5314
100.47 0.7327 0.7383 0.2673 0.2617 0.0439 0.3585 0.1280 1.5297
100.999 0.7752 0.7729 0.2248 0.2271 0.0386 0.3951 0.1188 1.4674
101.059 0.7922 0.7876 0.2078 0.2124 0.0364 0.4074 0.1135 1.4508
99.877 0.908 0.8959 0.0920 0.1041 0.0170 0.4973 0.0612 1.3652
96.885 1 1 0.0000 0.0000 0.0000 #DIV/0! #DIV/0! #DIV/0!

P1 sat 96.885
P2 sat 68.728
 x1x2RT/Ge
1.8000

1.6000

f(x) = 0.11 x + 1.42

1.4000 R² = 0.05

1.2000

1.0000

0.8000

0.6000

0.4000

0.2000

0.0000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

x1x2RT/Ge Linear (x1x2RT/Ge)

1 1
Value for ' and ' obtained by substituting value x = 0 and x = 1 into equation y =
A 12 A 21
0.1128x + 1.4219.
Using eq. y = 0.1147x + 1.4269, calculate at x = 0, x = 1
X=0 X=1
Y = 1.4269 Y = 1.5416

1 1
'
=1.4269 ' =1.5416
A 12 A 21
1 1
A' 12= =0.7008 A ' 21= =0.6487
1.4269 1.5416
NRTL Model:

From Table 12.5

b12 184.70 cal/mol
b21 222.64 cal/mol
α 0.3084
R 1.987 cal/mol.K
T 333 K

184.70 222.64
τ 12= =0.279 τ 21= =0.336
1.987 ×333 1.987 × 333

G12=exp (−0.3084 × 0.279 ) G21=exp ⁡(−0.3084 ×0.336)

G12=0.9176 G 21=0.9016
 GE GE
c) Generate the data of ln γ 1,ln γ 2 , and for each model as well as the
RT x1 x 2 RT
experimental data and plot these data versus x1.

Van Laar Model:

Pressure x1 x2 ln γ1 ln γ2 γ1 γ2 Ge/RT Ge/x1x2RT
68.728 0 1.0000 0.7008   2.0154 1.0000 0.0000 0.7008
72.278 0.0287 0.9713 0.6581 0.0006 1.9311 1.0006 0.0195 0.6992
75.279 0.057 0.9430 0.6175 0.0024 1.8543 1.0024 0.0375 0.6976
77.254 0.0858 0.9142 0.5777 0.0055 1.7820 1.0055 0.0546 0.6960
78.951 0.1046 0.8954 0.5525 0.0081 1.7377 1.0082 0.0651 0.6950
82.528 0.1452 0.8548 0.5003 0.0156 1.6493 1.0157 0.0860 0.6927
86.762 0.2173 0.7827 0.4147 0.0345 1.5139 1.0351 0.1171 0.6888
90.088 0.2787 0.7213 0.3488 0.0563 1.4174 1.0579 0.1378 0.6855
93.206 0.3579 0.6421 0.2730 0.0916 1.3139 1.0960 0.1565 0.6812
95.017 0.405 0.5950 0.2327 0.1165 1.2620 1.1235 0.1636 0.6787
96.365 0.448 0.5520 0.1990 0.1416 1.2201 1.1521 0.1673 0.6765
98.462 0.5432 0.4568 0.1343 0.2051 1.1437 1.2277 0.1666 0.6715
99.811 0.6332 0.3668 0.0854 0.2749 1.0891 1.3164 0.1549 0.6669
99.95 0.6605 0.3395 0.0728 0.2978 1.0756 1.3470 0.1492 0.6655
100.278 0.6945 0.3055 0.0587 0.3276 1.0604 1.3876 0.1408 0.6638
100.47 0.7327 0.2673 0.0447 0.3625 1.0457 1.4369 0.1296 0.6619
100.999 0.7752 0.2248 0.0314 0.4032 1.0319 1.4966 0.1150 0.6597
101.059 0.7922 0.2078 0.0267 0.4200 1.0271 1.5219 0.1085 0.6589
99.877 0.908 0.0920 0.0052 0.5422 1.0052 1.7198 0.0546 0.6532
96.885 1 0.0000 #DIV/0! 0.6487   1.9131 0.0000 0.6487

P1 sat 96.885 A’12 = 0.7008 A’21 = 0.6487

P2 sat 68.728
 Van Laar Model
0.8000

0.7000

0.6000

0.5000 Ge/RT
Ge/x1x2RT
ln γ1
0.4000
ln γ2

0.3000

0.2000

0.1000

0.0000
0 0.2 0.4 0.6 0.8 1 1.2
NRTL Model:
Pressure x1 x2 ln γ1 ln γ2 γ1 γ2 Ge/RT Ge/x1x2RT
68.728 0 1.0000 0.5920 0.0000 1.8076 1.0000 0.0000 0.5920
72.278 0.0287 0.9713 0.5577 0.0005 1.7466 1.0005 0.0165 0.5916
75.279 0.057 0.9430 0.5249 0.0020 1.6903 1.0020 0.0318 0.5911
77.254 0.0858 0.9142 0.4927 0.0044 1.6366 1.0045 0.0463 0.5907
78.951 0.1046 0.8954 0.4722 0.0066 1.6035 1.0066 0.0553 0.5904
82.528 0.1452 0.8548 0.4295 0.0127 1.5365 1.0128 0.0732 0.5899
86.762 0.2173 0.7827 0.3590 0.0283 1.4319 1.0287 0.1002 0.5889
90.088 0.2787 0.7213 0.3042 0.0464 1.3555 1.0475 0.1182 0.5881
93.206 0.3579 0.6421 0.2404 0.0762 1.2717 1.0791 0.1349 0.5872
95.017 0.405 0.5950 0.2061 0.0973 1.2289 1.1022 0.1414 0.5866
96.365 0.448 0.5520 0.1772 0.1188 1.1938 1.1262 0.1450 0.5862
98.462 0.5432 0.4568 0.1210 0.1740 1.1287 1.1900 0.1452 0.5852
99.811 0.6332 0.3668 0.0779 0.2356 1.0810 1.2656 0.1357 0.5844
99.95 0.6605 0.3395 0.0667 0.2561 1.0690 1.2918 0.1310 0.5842
100.278 0.6945 0.3055 0.0540 0.2828 1.0555 1.3268 0.1239 0.5839
100.47 0.7327 0.2673 0.0413 0.3144 1.0422 1.3694 0.1143 0.5836
100.999 0.7752 0.2248 0.0292 0.3515 1.0296 1.4211 0.1016 0.5833
101.059 0.7922 0.2078 0.0249 0.3669 1.0253 1.4432 0.0960 0.5832
99.877 0.908 0.0920 0.0049 0.4806 1.0049 1.6171 0.0487 0.5824
96.885 1 0.0000 0.0000 0.5819 1.0000 1.7895 0.0000 0.5819

G12 0.9176
G21 0.9016
τ 12 0.279
τ 21 0.336
 NRTL Model
0.7000

0.6000

0.5000

Ge/RT
0.4000 ln γ1
ln γ2
Ge/x1x2RT
0.3000

0.2000

0.1000

0.0000
0 0.2 0.4 0.6 0.8 1 1.2
d) Compare the composition of azeotrope of the mixture obtained by using the models and
experimental data found in (a).

Azeotrope using experimental data in (a):

Vapor Pressure: 101
Composition of Azeotrope: 0.77

Azeotrope using Van Laar Model:

Pressure x1 x2 ln γ1 ln γ2 γ1 γ2 P new y1 new
68.728 0 1.0000 0.7008 0.0000 2.0154 1.0000 68.728 0
72.278 0.0287 0.9713 0.6581 0.0006 1.9311 1.0006 72.167 0.0744
75.279 0.057 0.9430 0.6175 0.0024 1.8543 1.0024 75.209 0.1362
77.254 0.0858 0.9142 0.5777 0.0055 1.7820 1.0055 77.990 0.1899
78.951 0.1046 0.8954 0.5525 0.0081 1.7377 1.0082 79.652 0.2211
82.528 0.1452 0.8548 0.5003 0.0156 1.6493 1.0157 82.873 0.2800
86.762 0.2173 0.7827 0.4147 0.0345 1.5139 1.0351 87.557 0.3640
90.088 0.2787 0.7213 0.3488 0.0563 1.4174 1.0579 90.715 0.4219
93.206 0.3579 0.6421 0.2730 0.0916 1.3139 1.0960 93.925 0.4851
95.017 0.405 0.5950 0.2327 0.1165 1.2620 1.1235 95.465 0.5187
96.365 0.448 0.5520 0.1990 0.1416 1.2201 1.1521 96.667 0.5479
98.462 0.5432 0.4568 0.1343 0.2051 1.1437 1.2277 98.732 0.6096
99.811 0.6332 0.3668 0.0854 0.2749 1.0891 1.3164 100.001 0.6682
99.95 0.6605 0.3395 0.0728 0.2978 1.0756 1.3470 100.257 0.6865
100.278 0.6945 0.3055 0.0587 0.3276 1.0604 1.3876 100.488 0.7101
100.47 0.7327 0.2673 0.0447 0.3625 1.0457 1.4369 100.628 0.7377
100.999 0.7752 0.2248 0.0314 0.4032 1.0319 1.4966 100.622 0.7702
101.059 0.7922 0.2078 0.0267 0.4200 1.0271 1.5219 100.569 0.7839
99.877 0.908 0.0920 0.0052 0.5422 1.0052 1.7198 99.300 0.8905
96.885 1 0.0000 #DIV/0! 0.6487   1.9131 96.885 1

P1 sat 96.885
P2 sat 68.728

Pnew =∑ X i γ i Psat i

x i γ i Psat i
y i=
Pnew
 P-xy Diagram Van Laar Model
120.000

100.6
100.000

80.000

60.000

40.000

20.000

0.73
0.000
0 0.2 0.4 0.6 0.8 1 1.2

y1 x1

Vapor Pressure: 100.6

Composition of Azeotrope: 0.73
Azeotrope using NRTL Model:

Pressur
e x1 x2 ln γ1 ln γ2 γ1 γ2 P new y1 new
68.728 0 1.0000 0.5920 0.0000 1.8076 1.0000 68.728 0.0000
72.278 0.0287 0.9713 0.5577 0.0005 1.7466 1.0005 71.646 0.0678
75.279 0.057 0.9430 0.5249 0.0020 1.6903 1.0020 74.273 0.1257
77.254 0.0858 0.9142 0.4927 0.0044 1.6366 1.0045 76.716 0.1773
78.951 0.1046 0.8954 0.4722 0.0066 1.6035 1.0066 78.197 0.2078
82.528 0.1452 0.8548 0.4295 0.0127 1.5365 1.0128 81.114 0.2665
86.762 0.2173 0.7827 0.3590 0.0283 1.4319 1.0287 85.484 0.3527
90.088 0.2787 0.7213 0.3042 0.0464 1.3555 1.0475 88.528 0.4134
93.206 0.3579 0.6421 0.2404 0.0762 1.2717 1.0791 91.720 0.4808
95.017 0.405 0.5950 0.2061 0.0973 1.2289 1.1022 93.291 0.5169
96.365 0.448 0.5520 0.1772 0.1188 1.1938 1.1262 94.542 0.5481
98.462 0.5432 0.4568 0.1210 0.1740 1.1287 1.1900 96.759 0.6139
99.811 0.6332 0.3668 0.0779 0.2356 1.0810 1.2656 98.223 0.6752
99.95 0.6605 0.3395 0.0667 0.2561 1.0690 1.2918 98.549 0.6941
100.278 0.6945 0.3055 0.0540 0.2828 1.0555 1.3268 98.877 0.7182
100.47 0.7327 0.2673 0.0413 0.3144 1.0422 1.3694 99.138 0.7462
100.999 0.7752 0.2248 0.0292 0.3515 1.0296 1.4211 99.287 0.7789
101.059 0.7922 0.2078 0.0249 0.3669 1.0253 1.4432 99.302 0.7924
99.877 0.908 0.0920 0.0049 0.4806 1.0049 1.6171 98.627 0.8963
96.885 1 0.0000 0.0000 0.5819 1.0000 1.7895 96.885 1.0000

P1 sat 96.885
P2 sat 68.728

Pnew =∑ X i γ i Psat i

x i γ i Psat i
y i=
Pnew
 P-xy Diagram NRTL Model
120.000

100.000

80.000

60.000

40.000

20.000

0.000
0.0000 0.2000 0.4000 0.6000 0.8000 1.0000 1.2000

y1 x1

Vapor Pressure: 99.3

Composition of Azeotrope: 0.77

e) Supply a diagram to show the consistency of data (δP) for each model. Given that:
 δP=¿ Pcalc −Pexp ∨¿

(60 marks)
Van Laar Model:
P exp x1 x2 ln γ1 ln γ2 γ1 γ2 P cal δP
68.728 0 1.0000 0.7008 0.0000 2.0154 1.0000 68.728 0.0000
72.278 0.0287 0.9713 0.6581 0.0006 1.9311 1.0006 72.167 0.1113
75.279 0.057 0.9430 0.6175 0.0024 1.8543 1.0024 75.209 0.0699
77.254 0.0858 0.9142 0.5777 0.0055 1.7820 1.0055 77.990 0.7364
78.951 0.1046 0.8954 0.5525 0.0081 1.7377 1.0082 79.652 0.7011
82.528 0.1452 0.8548 0.5003 0.0156 1.6493 1.0157 82.873 0.3454
86.762 0.2173 0.7827 0.4147 0.0345 1.5139 1.0351 87.557 0.7948
90.088 0.2787 0.7213 0.3488 0.0563 1.4174 1.0579 90.715 0.6266
93.206 0.3579 0.6421 0.2730 0.0916 1.3139 1.0960 93.925 0.7194
95.017 0.405 0.5950 0.2327 0.1165 1.2620 1.1235 95.465 0.4477
96.365 0.448 0.5520 0.1990 0.1416 1.2201 1.1521 96.667 0.3022
98.462 0.5432 0.4568 0.1343 0.2051 1.1437 1.2277 98.732 0.2703
99.811 0.6332 0.3668 0.0854 0.2749 1.0891 1.3164 100.001 0.1896
99.95 0.6605 0.3395 0.0728 0.2978 1.0756 1.3470 100.257 0.3065
100.278 0.6945 0.3055 0.0587 0.3276 1.0604 1.3876 100.488 0.2103
100.47 0.7327 0.2673 0.0447 0.3625 1.0457 1.4369 100.628 0.1580
100.999 0.7752 0.2248 0.0314 0.4032 1.0319 1.4966 100.622 0.3767
101.059 0.7922 0.2078 0.0267 0.4200 1.0271 1.5219 100.569 0.4900
99.877 0.908 0.0920 0.0052 0.5422 1.0052 1.7198 99.300 0.5766
96.885 1 0.0000 #DIV/0! 0.6487   1.9131 96.885 0.0000

NRTL Model:
Pressure x1 x2 ln γ1 ln γ2 γ1 γ2 P new δP
68.728 0 1.0000 0.5920 0.0000 1.8076 1.0000 68.728 0.0000
72.278 0.0287 0.9713 0.5577 0.0005 1.7466 1.0005 71.646 0.6325
75.279 0.057 0.9430 0.5249 0.0020 1.6903 1.0020 74.273 1.0063
77.254 0.0858 0.9142 0.4927 0.0044 1.6366 1.0045 76.716 0.5378
78.951 0.1046 0.8954 0.4722 0.0066 1.6035 1.0066 78.197 0.7544
82.528 0.1452 0.8548 0.4295 0.0127 1.5365 1.0128 81.114 1.4137
86.762 0.2173 0.7827 0.3590 0.0283 1.4319 1.0287 85.484 1.2784
90.088 0.2787 0.7213 0.3042 0.0464 1.3555 1.0475 88.528 1.5601
93.206 0.3579 0.6421 0.2404 0.0762 1.2717 1.0791 91.720 1.4862
95.017 0.405 0.5950 0.2061 0.0973 1.2289 1.1022 93.291 1.7260
96.365 0.448 0.5520 0.1772 0.1188 1.1938 1.1262 94.542 1.8235
98.462 0.5432 0.4568 0.1210 0.1740 1.1287 1.1900 96.759 1.7028
99.811 0.6332 0.3668 0.0779 0.2356 1.0810 1.2656 98.223 1.5881
99.95 0.6605 0.3395 0.0667 0.2561 1.0690 1.2918 98.549 1.4009
100.278 0.6945 0.3055 0.0540 0.2828 1.0555 1.3268 98.877 1.4009
100.47 0.7327 0.2673 0.0413 0.3144 1.0422 1.3694 99.138 1.3317
100.999 0.7752 0.2248 0.0292 0.3515 1.0296 1.4211 99.287 1.7117
101.059 0.7922 0.2078 0.0249 0.3669 1.0253 1.4432 99.302 1.7565
99.877 0.908 0.0920 0.0049 0.4806 1.0049 1.6171 98.627 1.2499
96.885 1 0.0000 0.0000 0.5819 1.0000 1.7895 96.885 0.0000
 𝛿𝑃 For Van Laar & NRTL Model
2.0000

1.8000

1.6000

1.4000

1.2000
δP Van Laar
δP NRTL
1.0000

0.8000

0.6000

0.4000

0.2000

0.0000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
QUESTION 2
Ammonia gas (NH3) is produced from a catalytic reaction between hydrogen (H2) and
nitrogen (N2) as follows:
N2 + 3 H2 ↔ 2 NH 3

Your group was assigned by your superior to assess the practicality of the current condition
of a fixed bed reactor that operates at temperature and pressure of 250 oC and 100 bar,
respectively. The pressure can vary between 50 to 400 bar.
a) Evaluate the equilibrium constants and conversion at varying pressure. Provide a plot of
ε as a function of pressure and conversion of H2 as a function of pressure.
b) Determine the composition of the reactant and product at the optimum pressure.
c) State the assumption made.

(40 marks)