2021

COMPLEX ENGINEERING
PROBLEM
Thermodynamics-II

GROUP MEMBERS
(2018419) SHAHAB UD DIN KHAN NIAZI
(2018158) HUZAIFA AZIZ
(2018394) RIZWAN
(2018113) FARRUKH FAHEEM

SUBMITTED TO:
SIR KHURRAM IMRAN KHAN
Complex Engineering Problem on Applications of
Solution Thermodynamics:
A chemical Industry is separating large batches of acetone and methanol. A process engineer
working in control unit finds unusual differences between output results predicted by the
theoretical model and actual system data. Your job is to use different thermodynamic models to
verify the validity of system data. Following is the set of VLE data for the system acetone
(1)/methanol (2) at 328.15 K (55°C).

a) Basing calculations on ( ), find parameter values

E
for the Margules equation that provide the best fit of G /RT to the data, and prepare a P-
x-y diagram that compares the experimental points with curves determined from the
correlation.
b) Repeat (a) for the Van Laar equation.
c) Repeat (a) for the Wilson equation.
d) Using Barker's method, find parameter values for the Margules equation that provide the
best fit of the P-x1 data. Prepare a diagram showing the residuals δP and δy 1 plotted vs.
x 1.
e) Repeat (d) for the Van Laar equation.
f) Repeat (d) for the Wilson equation.

Page | 1
1. Introduction:
We are given with the experimental data of a chemical industry revolving around the separation
of methanol and acetone. We have observed that the experimental results are slightly different
from the theoretical results. The theoretical results can be obtained from Margules, Van laar and
Wilson model for the excess Gibbs energy. The Margules equations represent a commonly used
empirical model of the solution equation. The Van laar and Margules equation provide great
flexibility in the fitting of VLE data for binary system. However, they have scant theoretical
foundation and therefore fail to admit a rational basis for extension to multicomponent system.
Wilson equation can predict values of activity co-efficient of polar and dissimilar molecules.

2. Purpose of the given problem:

We have to verify the validity of the experimental data by using different thermodynamic models
and how they are different from one another.

3. Models:
 Margules Equation
lnγ1 = x22 [ A12 + 2 ( A21- A12 ) x1 ]
lnγ2 = x12 [ A21 + 2 ( A12- A21 ) x2 ]
 Van Laar Equation

lnγ1 = A12’ [ 1 + (A12’ x1 / A21’ x2)]-2

lnγ2 = A21’ [ 1 + (A21’ x2 / A12’ x1)]-2

 Wilson Equation
lnγ1 = -ln (x1 + x2 ꓥ12) + x2 [(ꓥ12 / x1 + x2 ꓥ12) - (ꓥ21 / x2 + x1 ꓥ21)]
lnγ2 = -ln (x2 + x1 ꓥ21) - x2 [(ꓥ12 / x1 + x2 ꓥ12) - (ꓥ21 / x2 + x1 ꓥ21)]

4. Solution:
For saturation pressures at 55oC we use Antoine equation.

For acetone:

A = 14.3145 B = 2756.22 C = 228.06

By putting these values in above equation, we get, P1sat = 96.885 kpa

Page | 2
For Methanol:

A = 16.5785 B = 3638.27 C = 239.500

By putting these values in above equation, we get, P2sat = 68.728 kpa

We obtain the following table with the help of given equations:

 x2 = 1 – x1 y2 = 1 – y1
 lnγ1 = ln ( y1P / x1P1sat ) lnγ2 = ln ( y2P / x2P2sat )
 GE/RT = x1 lnγ1 + x2 lnγ2

P (kpa) x1 y1 lnγ1 lnγ2 GE/RT GE/ x1x2RT

68.728 0 0 - 0 - -
72.278 0.0287 0.0647 0.519859 0.012595 0.027154 0.974072
75.279 0.057 0.1295 0.568306 0.011046 0.04281 0.796447
77.524 0.0858 0.1848 0.544318 0.005815 0.052019 0.663177
78.951 0.1046 0.219 0.534231 0.001975 0.057649 0.615524
82.528 0.1452 0.2694 0.457698 0.02598 0.088665 0.714367
86.762 0.2173 0.3633 0.403594 0.026561 0.10849 0.637876
90.088 0.2787 0.4184 0.333564 0.055358 0.132894 0.661078
93.206 0.3579 0.4779 0.250435 0.09777 0.152409 0.663204
95.017 0.405 0.5135 0.217894 0.122575 0.161179 0.668862
96.365 0.448 0.5512 0.201923 0.131016 0.162782 0.658248
97.656 0.5052 0.5844 0.153558 0.176864 0.16509 0.66043
98.462 0.5432 0.6174 0.144186 0.182258 0.161577 0.65117
99.811 0.6332 0.6772 0.096934 0.245338 0.151369 0.651727
99.95 0.6605 0.6926 0.078601 0.275189 0.145343 0.648157
100.278 0.6945 0.7124 0.059869 0.31741 0.138548 0.653005
100.467 0.7327 0.7383 0.043919 0.3585 0.128006 0.65359
100.999 0.7752 0.7729 0.038615 0.395133 0.11876 0.681491
101.059 0.7922 0.7876 0.036356 0.407443 0.113468 0.689276
99.877 0.908 0.8959 0.016999 0.497346 0.061191 0.732511
99.799 0.9448 0.9336 0.017708 0.557736 0.047518 0.911123
96.885 1 1 0 - - -
(Table 4.1)

Page | 3
 1

0.9

0.8

0.7

0.6
lny1
0.5
lny2
0.4 GE/RT

0.3 Ge/x1x2RT
Linear (Ge/x1x2RT)
0.2

0.1

x1

(Graph 4.1)

4.1. Part (a):

For Margules Equation, we know that:

At x1=0, GE/ x1x2RT = A12

At x1=1, GE/ x1x2RT = A21

So, from the graph we get,

A12 = 0.708 A21 = 0.685

We obtain the following table with the help of given equations:

 γ1 = exp (x22 [ A12 + 2 ( A21- A12 ) x1 ])

 γ2 = exp (x12 [ A21 + 2 ( A12- A21 ) x2 ])
 Pcalc = x1γ1P1sat + x2γ2P2sat
 y1 = x1γ1P1sat / Pcalc

Page | 4
 x1 γ1 γ2 Pcalc ycalc
0 2.029927 1 68.728 0
0.0287 1.947796 1.000601 72.21168 0.075002
0.057 1.872467 1.002369 75.30465 0.137317
0.0858 1.801142 1.005367 78.14074 0.191608
0.1046 1.757294 1.007977 79.83866 0.223059
0.1452 1.669365 1.015388 83.13685 0.282476
0.2173 1.533589 1.034631 87.94317 0.367133
0.2787 1.435745 1.057369 91.18525 0.425154
0.3579 1.329915 1.095846 94.47496 0.488119
0.405 1.276414 1.123947 96.0462 0.521462
0.448 1.233001 1.153244 97.26936 0.550202
0.5052 1.18252 1.197983 98.61935 0.586903
0.5432 1.153178 1.231608 99.35565 0.61083
0.6332 1.095638 1.324997 100.6172 0.668025
0.6605 1.081233 1.357509 100.8658 0.685969
0.6945 1.065129 1.400983 101.0846 0.709
0.7327 1.049357 1.454035 101.2035 0.736056
0.7752 1.034561 1.5187 101.1649 0.768062
0.7922 1.029423 1.546341 101.0949 0.781548
0.908 1.005655 1.76517 99.63018 0.887974
0.9448 1.002027 1.847309 98.73078 0.929016
1 1 1.983772 96.885 1
(Table 4.1.1.)

105

100

95

90
P (kpa)

85
P given
80
P calc
75

70

65
0

1
0.2787

0.5052

0.9448
0.0287
0.057
0.0858
0.1046
0.1452
0.2173

0.3579
0.405
0.448

0.5432
0.6332
0.6605
0.6945
0.7327
0.7752
0.7922
0.908

x1

Page | 5
 105

100

95

90
P (kpa)

85
P calc
80
P given
75

70

65
0

1
0.4184

0.5844

0.9336
0.0647
0.1295
0.1848
0.219
0.2694
0.3633

0.4779
0.5135
0.5512

0.6174
0.6772
0.6926
0.7124
0.7383
0.7729
0.7876
0.8959
y1

Root mean square deviation in experimental and calculated pressure is,

RMSD = ((Σi (Pi - Pcalc)2)/n)0.5

Pi from table 4.1., Pcalc from table 4.1.1. and n is equal to 22 (no. of values), so,

RMSD = 0.777 kpa

4.2. Part (b):

For Van laar equation, from graph 4.1:

A12’ = 0.693 A21’ = 0.686

We obtain the following table with the help of given equations:


γ1 = exp (A12’ [ 1 + (A12’ x1 / A21’ x2)]-2)

γ2 = exp (A21’ [ 1 + (A21’ x2 / A12’ x1)]-2)
 Pcalc = x1γ1P1sat + x2γ2P2sat
 y1 = x1γ1P1sat / Pcalc

Page | 6
 x1 γ1 γ2 Pcalc ycalc
0 1.999706 - - 0
0.0287 1.922084 1.000576 72.13853 0.074087
0.057 1.850643 1.002274 75.17799 0.135945
0.0858 1.782773 1.005158 77.97493 0.190057
0.1046 1.740935 1.007673 79.65415 0.221494
0.1452 1.656764 1.014825 82.92649 0.281054
0.2173 1.526029 1.033458 87.72089 0.366249
0.2787 1.431192 1.055558 90.97252 0.424797
0.3579 1.327959 1.093105 94.28617 0.488377
0.405 1.275482 1.120624 95.87377 0.522019
0.448 1.232744 1.14939 97.11199 0.550978
0.5052 1.182853 1.193451 98.48151 0.58789
0.5432 1.153748 1.226662 99.23036 0.611903
0.6332 1.096414 1.319293 100.5209 0.669137
0.6605 1.081998 1.351666 100.7784 0.68705
0.6945 1.065848 1.39505 101.0084 0.710014
0.7327 1.049992 1.448133 101.1401 0.736962
0.7752 1.035074 1.513039 101.116 0.768815
0.7922 1.029884 1.540849 101.0519 0.782232
0.908 1.005775 1.762327 99.62276 0.888147
0.9448 1.002074 1.846034 98.73022 0.929065
1 - 1.985757 - 1
(Table 4.2.1)

105

100

95

90
P (kpa)

85
P given
80
P calc
75

70

65
0

1
0.3579

0.448

0.5432

0.6605

0.7327

0.7922

0.9448
0.0287
0.057
0.0858
0.1046
0.1452
0.2173
0.2787

0.405

0.5052

0.6332

0.6945

0.7752

0.908

x1

Page | 7
 105

100

95

90
P (kpa)

85

80 P given
P calc
75

70

65
0

1
0.424797

0.710014
0.074087
0.135945
0.190057
0.221494
0.281054
0.366249

0.488377
0.522019
0.550978
0.58789
0.611903
0.669137
0.68705

0.736962
0.768815
0.782232
0.888147
0.929065
y1

Root mean square deviation in experimental and calculated pressure is,

RMSD = ((Σi (Pi - Pcalc)2)/n)0.5

Pi from table 4.1., Pcalc from table 4.2.1. and n is equal to 22 (no. of values), so,

RMSD = 0.665 kpa

4.3. Part (c):

For Wilson equation, by non-linear least squares minimize the sum of the squared errors using the
Mathcad Minimize function.

Guesses: ꓥ12 = 0.6 ꓥ21 = 0.8

x1i∗ln (x1i + x2i ꓥ12i)
SSE (ꓥ12 , ꓥ21) = Σi [(GE/RT)i + (+ x2i∗ln (x2i + x1i ꓥ21i))]2

ꓥ12
( ) = Minimize (SSE, ꓥ12 , ꓥ21)
ꓥ21
After performing iterations in excel we obtained these results,

ꓥ12 = 0.71 ꓥ21 = 0.681

Page | 8
We obtain the following table with the help of given equations:

 γ1 = exp (-ln (x1 + x2 ꓥ12) + x2 [(ꓥ12 / x1 + x2 ꓥ12) - (ꓥ21 / x2 + x1 ꓥ21)])

 γ2 = exp (-ln (x2 + x1 ꓥ21) - x2 [(ꓥ12 / x1 + x2 ꓥ12) - (ꓥ21 / x2 + x1 ꓥ21)])
 Pcalc = x1γ1P1sat + x2γ2P2sat
 y1 = x1γ1P1sat / Pcalc

x1 γ1 γ2 Pcalc ycalc
0 1.937678 1 68.728 0
0.0287 1.8651 1.000555 71.97868 0.07205
0.057 1.798484 1.002185 74.88418 0.132632
0.0858 1.735338 1.004943 77.56712 0.185973
0.1046 1.696471 1.007341 79.18313 0.217121
0.1452 1.618381 1.014138 82.34618 0.276478
0.2173 1.497248 1.03175 87.02306 0.362223
0.2787 1.409346 1.052541 90.23309 0.421741
0.3579 1.313415 1.087759 93.54594 0.48685
0.405 1.264454 1.113544 95.15152 0.521433
0.448 1.224426 1.140505 96.41388 0.551223
0.5052 1.17746 1.181859 97.8233 0.589147
0.5432 1.149902 1.213102 98.60225 0.613749
0.6332 1.095133 1.300703 99.97376 0.672014
0.6605 1.081228 1.331508 100.2588 0.690119
0.6945 1.065563 1.372966 100.5255 0.713233
0.7327 1.050075 1.423983 100.7023 0.740225
0.7752 1.035381 1.486827 100.7341 0.771959
0.7922 1.030234 1.513919 100.6941 0.785277
0.908 1.005972 1.733487 99.45771 0.889794
0.9448 1.002161 1.818349 98.63317 0.93006
1 1 1.962449 96.885 1
(Table 4.3.1)

Page | 9
 105

100

95

90
P (kpa)

85
P calc
80
P given
75

70

65

x1

105

100

95

90
P (kpa)

85

80 P calc

75 P given

70

65

y1

Root mean square deviation in experimental and calculated pressure is,

RMSD = ((Σi (Pi - Pcalc)2)/n)0.5

Pi from table 4.1., Pcalc from table 4.3.1. and n is equal to 22 (no. of values), so,

RMSD = 0.343 kpa

Page | 10
 4.4. Part (d): (Barker’s method)
For Margules equation, by non-linear least squares minimize the sum of the squared errors using the
Mathcad Minimize function.

Guesses: A12 = 0.6 A21 = 0.8

 γ1 = exp (x22 [ A12 + 2 ( A21- A12 ) x1 ])

 γ2 = exp (x12 [ A21 + 2 ( A12- A21 ) x2 ])

x1γ1P1sat
SSE (A12 , A21) = Σi [Pi - (+ x2γ2P2sat)]2

𝐴12
( ) = Minimize (SSE, A12 , 𝐴21)
𝐴21
After performing iterations in excel we obtained these results,

A12 = 0.644 A21 = 0.672

We obtain the following table with the help of given equations:

 γ1 = exp (x22 [ A12 + 2 ( A21- A12 ) x1 ])

 γ2 = exp (x12 [ A21 + 2 ( A12- A21 ) x2 ])
 Pcalc = x1γ1P1sat + x2γ2P2sat
 y1 = x1γ1P1sat / Pcalc
 δP = Pcalc – P
 δy1 = ycalc – y1

P (kpa) x1 y1 γ1 γ2 Pcalc ycalc δP δy1

68.728 0 0 1.904082 1 68.728 0 0 0
72.278 0.0287 0.0647 1.864005 1.000105 71.9456 0.072041 -0.3324 0.007341
75.279 0.057 0.1295 1.824053 1.000468 74.91405 0.134464 -0.36495 0.004964
77.524 0.0858 0.1848 1.78316 1.001179 77.72814 0.190702 0.204144 0.005902
78.951 0.1046 0.219 1.756431 1.001868 79.45398 0.224029 0.502984 0.005029
82.528 0.1452 0.2694 1.698887 1.004084 82.88805 0.288334 0.360052 0.018934
86.762 0.2173 0.3633 1.598515 1.011096 88.044 0.382238 1.281999 0.018938
90.088 0.2787 0.4184 1.516275 1.02104 91.55877 0.447169 1.470773 0.028769
93.206 0.3579 0.4779 1.416444 1.040831 95.04752 0.516746 1.841519 0.038846
95.017 0.405 0.5135 1.361089 1.057145 96.63697 0.552656 1.619972 0.039156
96.365 0.448 0.5512 1.313471 1.075549 97.81457 0.582843 1.449574 0.031643
97.656 0.5052 0.5844 1.254746 1.106047 99.02808 0.620179 1.372081 0.035779
98.462 0.5432 0.6174 1.218786 1.130663 99.63932 0.643744 1.177321 0.026344
99.811 0.6332 0.6772 1.143796 1.205719 100.5646 0.697752 0.753637 0.020552

Page | 11
 99.95 0.6605 0.6926 1.123962 1.233956 100.7173 0.71413 0.767277 0.02153
100.278 0.6945 0.7124 1.101202 1.273296 100.8308 0.734857 0.55284 0.022457
100.467 0.7327 0.7383 1.07824 1.323663 100.8587 0.7589 0.391698 0.0206
100.999 0.7752 0.7729 1.055994 1.388436 100.7621 0.787108 -0.2369 0.014208
101.059 0.7922 0.7876 1.048085 1.41723 100.6834 0.79897 -0.37564 0.01137
99.877 0.908 0.8959 1.009802 1.667897 99.37998 0.893881 -0.49702 -0.00202
99.799 0.9448 0.9336 1.003581 1.772277 98.58837 0.931801 -1.21063 -0.0018
96.885 1 1 1 1.95815 96.885 1 0 0
(Table 4.4.1.)

105

100

95

90
P (kpa)

85
P calc
80
P given
75

70

65
0

1
0.1046

0.5052
0.0287
0.057
0.0858

0.1452
0.2173
0.2787
0.3579
0.405
0.448

0.5432
0.6332
0.6605
0.6945
0.7327
0.7752
0.7922
0.908
0.9448

x1

Residuals graphs:

1.5

0.5
δP

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

-1

-1.5
x1

Page | 12
 0.045

0.04

0.035

0.03

0.025
δy1

0.02

0.015

0.01

0.005

0 1, 0
0 0.2 0.4 0.6 0.8 1 1.2
-0.005
x1

Root mean square deviation in experimental and calculated pressure is,

RMSD = ((Σi (Pi - Pcalc)2)/n)0.5

Pi and Pcalc from table 4.4.1. and n is equal to 22 (no. of values), so,

RMSD = 0.937 kpa

4.5. Part (e):

For Van laar equation, by non-linear least squares minimize the sum of the squared errors using the
Mathcad Minimize function.

Guesses: A12’ = 0.6 A21’ = 0.8


γ1 = exp (A12’ [ 1 + (A12’ x1 / A21’ x2)]-2)

γ2 = exp (A21’ [ 1 + (A21’ x2 / A12’ x1)]-2)

x1γ1P1sat
SSE (A12’ , A21’) = Σi [Pi - (+ x2γ2P2sat)]2

𝐴12′
( ) = Minimize (SSE, A12′ , 𝐴21′)
𝐴21′

After performing iterations in excel we obtained these results,

A12’ = 0.644 A21’ = 0.672

Page | 13
We obtain the following table with the help of given equations:

γ1 = exp (A12’ [ 1 + (A12’ x1 / A21’ x2)]-2)

γ2 = exp (A21’ [ 1 + (A21’ x2 / A12’ x1)]-2)
 Pcalc = x1γ1P1sat + x2γ2P2sat
 y1 = x1γ1P1sat / Pcalc
 δP = Pcalc – P
 δy1 = ycalc – y1

P (kpa) x1 y1 γ1 γ2 Pcalc ycalc δP δy1

68.728 0 0 1.904082 - - - - -
72.278 0.0287 0.0647 1.83863 1.00051 71.90202 0.071104 -0.37598 0.006404
75.279 0.057 0.1295 1.777853 1.002017 74.75931 0.131329 -0.51969 0.001829
77.524 0.0858 0.1848 1.719614 1.004587 77.414 0.184652 -0.11 -0.00015
78.951 0.1046 0.219 1.683461 1.006835 79.02015 0.2159 0.069148 -0.0031
82.528 0.1452 0.2694 1.610115 1.013258 82.17819 0.275628 -0.34981 0.006228
86.762 0.2173 0.3633 1.494466 1.030122 86.87693 0.362158 0.114933 -0.00114
90.088 0.2787 0.4184 1.409134 1.050295 90.11602 0.422225 0.028019 0.003825
93.206 0.3579 0.4779 1.31471 1.084876 93.46361 0.487759 0.257614 0.009859
95.017 0.405 0.5135 1.26603 1.110417 95.08549 0.522446 0.068493 0.008946
96.365 0.448 0.5512 1.226011 1.137264 96.3597 0.552247 -0.0053 0.001047
97.656 0.5052 0.5844 1.17883 1.178644 97.78104 0.590087 0.125039 0.005687
98.462 0.5432 0.6174 1.151053 1.21002 98.56604 0.614588 0.104045 -0.00281
99.811 0.6332 0.6772 1.095712 1.298281 99.94822 0.672541 0.137216 -0.00466
99.95 0.6605 0.6926 1.081651 1.329363 100.2358 0.690547 0.285815 -0.00205
100.278 0.6945 0.7124 1.065816 1.371197 100.5053 0.713546 0.227343 0.001146
100.467 0.7327 0.7383 1.050175 1.42265 100.6849 0.740423 0.217948 0.002123
100.999 0.7752 0.7729 1.035364 1.485942 100.7192 0.772061 -0.27982 -0.00084
101.059 0.7922 0.7876 1.030186 1.513184 100.6799 0.785351 -0.37906 -0.00225
99.877 0.908 0.8959 1.005905 1.732619 99.44638 0.889837 -0.43062 -0.00606
99.799 0.9448 0.9336 1.002129 1.816642 98.62375 0.930119 -1.17525 -0.00348
96.885 1 1 - 1.95815 - - - -
(Table 4.5.1.)

Page | 14
 105
100
95
90
P (kpa) 85
80 P calc
75 P given
70
65

0.405

0.9448
0.0287
0.057
0.0858
0.1046
0.1452
0.2173
0.2787
0.3579

0.448
0.5052
0.5432
0.6332
0.6605
0.6945
0.7327
0.7752
0.7922
0.908
x1

Residual graphs:
0.4
0.3
0.2
0.1
0
-0.1 0 0.2 0.4 0.6 0.8 1
δP

-0.2
-0.3
-0.4
-0.5
-0.6
x1

0.012
0.01
0.008
0.006
0.004
δy1

0.002
0
0 0.2 0.4 0.6 0.8 1
-0.002
-0.004 0.9448, -0.00348

-0.006
-0.008
x1

Page | 15
 Root mean square deviation in experimental and calculated pressure is,

RMSD = ((Σi (Pi - Pcalc)2)/n)0.5

Pi and Pcalc from table 4.5.1. and n is equal to 20 (no. of values), so,

RMSD = 0.364 kpa

4.6. Part (f):

For Wilson equation, by non-linear least squares minimize the sum of the squared errors using the
Mathcad Minimize function.

Guesses: ꓥ12 = 0.6 ꓥ21 = 0.8

 γ1 = exp (-ln (x1 + x2 ꓥ12) + x2 [(ꓥ12 / x1 + x2 ꓥ12) - (ꓥ21 / x2 + x1 ꓥ21)])

 γ2 = exp (-ln (x2 + x1 ꓥ21) - x2 [(ꓥ12 / x1 + x2 ꓥ12) - (ꓥ21 / x2 + x1 ꓥ21)])

x1γ1P1sat
SSE (ꓥ12 , ꓥ21) = Σi [Pi - (+ x2γ2P2sat)]2

ꓥ12
( ) = Minimize (SSE, ꓥ12 , ꓥ21)
ꓥ21
After performing iterations in excel we obtained these results,

ꓥ12 = 0.732 ꓥ21 = 0.663

We obtain the following table with the help of given equations:

 γ1 = exp (-ln (x1 + x2 ꓥ12) + x2 [(ꓥ12 / x1 + x2 ꓥ12) - (ꓥ21 / x2 + x1 ꓥ21)])

 γ2 = exp (-ln (x2 + x1 ꓥ21) - x2 [(ꓥ12 / x1 + x2 ꓥ12) - (ꓥ21 / x2 + x1 ꓥ21)])
 Pcalc = x1γ1P1sat + x2γ2P2sat
 y1 = x1γ1P1sat / Pcalc
 δP = P – Pcalc
 δy1 = y1 – ycalc

P (kpa) x1 y1 γ1 γ2 Pcalc ycalc δP δy1

68.728 0 0 1.913578 1 68.728 0 0 0
72.278 0.0287 0.0647 1.844966 1.000531 71.9211 0.07133 0.356902534 -0.006629715
75.279 0.057 0.1295 1.781739 1.002094 74.7858 0.13157 0.493199682 -0.00206983
77.524 0.0858 0.1848 1.721575 1.004744 77.44023 0.184801 0.083768596 -5.26653E-07
78.951 0.1046 0.219 1.68443 1.007053 79.04338 0.215961 -0.092382429 0.003038885
82.528 0.1452 0.2694 1.609527 1.013612 82.19071 0.275485 0.337285654 -0.006085428
86.762 0.2173 0.3633 1.492583 1.030679 86.86723 0.361742 -0.105234837 0.001558207

Page | 16
 90.088 0.2787 0.4184 1.407106 1.05092 90.09229 0.421728 -0.004285901 -0.0033284
93.206 0.3579 0.4779 1.31318 1.085376 93.43261 0.487353 -0.226607679 -0.009453452
95.017 0.405 0.5135 1.264961 1.110708 95.05545 0.52217 -0.038453944 -0.008669712
96.365 0.448 0.5512 1.225387 1.137277 96.33314 0.552118 0.031860798 -0.000918193
97.656 0.5052 0.5844 1.178761 1.178174 97.76169 0.59017 -0.105692587 -0.005769676
98.462 0.5432 0.6174 1.151299 1.209175 98.55248 0.614804 -0.090479268 0.002595598
99.811 0.6332 0.6772 1.096459 1.29652 99.94962 0.67299 -0.138622102 0.00421005
99.95 0.6605 0.6926 1.082472 1.327371 100.2419 0.69103 -0.291897751 0.001570129
100.278 0.6945 0.7124 1.06668 1.368994 100.5173 0.71404 -0.239288655 -0.001639712
100.467 0.7327 0.7383 1.051026 1.420372 100.7035 0.740886 -0.236509117 -0.002586375
100.999 0.7752 0.7729 1.036131 1.483889 100.745 0.772434 0.253996246 0.000466223
101.059 0.7922 0.7876 1.030901 1.511345 100.7086 0.785673 0.350435737 0.00192676
99.877 0.908 0.8959 1.00614 1.73543 99.48483 0.889701 0.392167855 0.006199073
99.799 0.9448 0.9336 1.002226 1.822747 98.65584 0.929907 1.143156129 0.003693281
96.885 1 1 1 1.971866 96.885 1 0 0
(Table 4.6.1.)

105

100

95

90
P (kpa)

85
P calc
80
P given

75

70

65

x1

Page | 17
 1.4

1.2

0.8

0.6
δP

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1 1.2
-0.2

-0.4
x1

0.008
0.006
0.004
0.002
0
0 0.2 0.4 0.6 0.8 1
δy1

-0.002
-0.004
-0.006
-0.008
-0.01
-0.012
x1

Root mean square deviation in experimental and calculated pressure is,

RMSD = ((Σi (Pi - Pcalc)2)/n)0.5

Pi and Pcalc from table 4.6.1. and n is equal to 22 (no. of values), so,

RMSD = 0.334 kpa

Page | 18
5. Conclusion:
While solving this complex engineering problem we used different thermodynamic models to
obtain precise theoretical results. We observed through different underlying solutions that there
were slight differences in the theoretical and experimental results of the system of acetone and
methanol at 55oC. The differences between the theoretical and experimental results are
tabulated and shown graphically. After analyzing all the models mentioned above we have
concluded that Wilson model for the excess Gibbs energy is the most effective one.

6. Rubrics for evaluation of CEP:

Page | 19