Q NO 2 Solution:

(c) The equilibrium nitrogen adsorption isotherm data obtained at 77 K

for a sample of a carbon adsorbent is shown in Table Q2. Assess the
suitability of at least two types of theoretical isotherm that may be
used to describe these data. To get A12 and A21, GE/(RTx1x2) was
plotted versus x.
Linearizing, A12 would correspond to the intercept and A21 would correspond to the sum of the slope and
A12.

E
Using equation , G /RT was obtained.

γ is calculated using Equation 13.24

The table below shows the computed and given values.
E E
P/kPa x1 y1 x2 y2 γ1 γ2 G /RT G /(RTx1x2)
72.278 0.0287 0.0647 0.9713 0.9353 1.6818 1.0127 0.0272 0.9741
75.279 0.0570 0.1295 0.9430 0.8705 1.7653 1.0111 0.0428 0.7964
77.524 0.0858 0.1848 0.9142 0.8152 1.7234 1.0058 0.0520 0.6632
78.951 0.1046 0.2190 0.8954 0.7810 1.7061 1.0020 0.0576 0.6155
82.528 0.1452 0.2694 0.8548 0.7306 1.5804 1.0263 0.0887 0.7144
86.762 0.2173 0.3633 0.7827 0.6367 1.4972 1.0269 0.1085 0.6379
90.088 0.2787 0.4184 0.7213 0.5816 1.3959 1.0569 0.1329 0.6611
93.206 0.3579 0.4779 0.6421 0.5221 1.2846 1.1027 0.1524 0.6632
95.017 0.4050 0.5135 0.5950 0.4865 1.2435 1.1304 0.1612 0.6689
96.365 0.4480 0.5512 0.5520 0.4488 1.2238 1.1400 0.1628 0.6582
97.646 0.5052 0.5844 0.4948 0.4156 1.1659 1.1933 0.1650 0.6600
98.462 0.5432 0.6174 0.4568 0.3826 1.1551 1.1999 0.1616 0.6512
99.811 0.6332 0.6772 0.3668 0.3228 1.1018 1.2781 0.1514 0.6517
99.950 0.6605 0.6926 0.3395 0.3074 1.0818 1.3168 0.1453 0.6482
100.278 0.6945 0.7124 0.3055 0.2876 1.0617 1.3736 0.1385 0.6530
100.467 0.7327 0.7383 0.2673 0.2617 1.0449 1.4312 0.1280 0.6536
100.999 0.7752 0.7729 0.2248 0.2271 1.0394 1.4846 0.1188 0.6815
101.059 0.7922 0.7876 0.2078 0.2124 1.0370 1.5030 0.1135 0.6893
99.877 0.9080 0.8959 0.092 0.1041 1.0171 1.6444 0.0612 0.7325
99.799 0.9448 0.9336 0.0552 0.0664 1.0179 1.7467 0.0475 0.9111

Plot:
1.0500
y = -0.0182x + 0.7077 R² = 0.0034
GE/(RTx1x2)

0.9500
0.8500
0.7500
0.6500
0.5500
0.4500
0.0000 0.2000 0.4000 x1 0.6000 0.8000 1.0000

The equation of the line is given as y = -0.0182x + 0.7077.

A12 = Intercept = 0.7077 And A21 = Slope + A12 = -0.0182 + 0.7077 = 0.6895

Equations a and b computes for the gamma values given the parameter values of Margules

Using Modified Raoult’s Law, the new final pressure and final composition of the vapor phase
is computed.
 x1 γ1’ γ2’ Pcalc y1 y2
0.0287 1.9478 1.0006 72.2113 0.0750 0.9250
0.0570 1.8729 1.0024 75.3060 0.1373 0.8627
0.0858 1.8019 1.0053 78.1453 0.1917 0.8083
0.1046 1.7583 1.0079 79.8459 0.2232 0.7768
0.1452 1.6707 1.0153 83.1510 0.2827 0.7173
0.2173 1.5353 1.0345 87.9706 0.3674 0.6326
0.2787 1.4375 1.0572 91.2233 0.4255 0.5745
0.3579 1.3316 1.0956 94.5243 0.4885 0.5115
0.4050 1.2780 1.1237 96.1007 0.5218 0.4782
0.4480 1.2345 1.1531 97.3276 0.5505 0.4495
0.5052 1.1838 1.1979 98.6813 0.5872 0.4128
0.5432 1.1544 1.2316 99.4192 0.6111 0.3889
0.6332 1.0965 1.3255 100.6826 0.6681 0.3319
0.6605 1.0820 1.3582 100.9312 0.6860 0.3140
0.6945 1.0658 1.4020 101.1494 0.7090 0.2910
0.7327 1.0499 1.4555 101.2671 0.7359 0.2641
0.7752 1.0349 1.5208 101.2260 0.7679 0.2321
0.7922 1.0297 1.5488 101.1546 0.7813 0.2187
0.9080 1.0057 1.7704 99.6698 0.8877 0.1123
0.9448 1.0021 1.8539 98.7581 0.9288 0.0712

Plot of P(x,y) diagram:

105.0000
100.0000
95.0000
90.0000
P-x Margules
85.0000
r e s s u r eP

P-y Margules
80.0000

75.0000 P-x exp

70.0000 P-y exp
65.0000
60.0000
0.0000 0.5000 1.0000
x1,y1
 (d) For each of your selected theoretical isotherms described in part (c),
determine the values of the key parameters of the isotherm equations for the
carbon adsorbent sample. Explain any physical significance generally attached
to these parameters, and comment on whether this particular interpretation
is appropriate for a microporous carbon adsorbent.

Plot:

1.8
1.6
x1x2/(GE/RT)

1.4
1.2
1
0.8 y = 0.015x + 1.4424
0.6 R² = 0.0008
0.4
0.2
0
0.0000 0.2000 0.4000 x1 0.6000 0.8000 1.0000

Linearizing, the slope is 0 0.015 and the intercept is 1.4424.

Then,
a12 = (1/1.4424)
a12 = 0.6933
a21 = 1/(0.015 + 1.4424)
a21 = 0.6862

Equations a1 and b1 computes for the gamma values given the parameter values of Van Laar

Using Modified Raoult’s Law, the new final pressure and final composition of the vapor phase
is computed.

x1 γ1’ γ2’ Pcalc y1 y2

0.0287 1.9226 1.0006 72.1400 0.0741 0.9259
0.0570 1.8511 1.0023 75.1806 0.1360 0.8640
0.0858 1.7832 1.0052 77.9784 0.1901 0.8099
0.1046 1.7413 1.0077 79.6581 0.2215 0.7785
0.1452 1.6571 1.0148 82.9312 0.2811 0.7189
0.2173 1.5262 1.0335 87.7264 0.3663 0.6337
0.2787 1.4314 1.0556 90.9782 0.4248 0.5752
0.3579 1.3281 1.0932 94.2918 0.4884 0.5116
0.4050 1.2756 1.1207 95.8793 0.5220 0.4780
 0.4480 1.2328 1.1495 97.1174 0.5510 0.4490
0.5052 1.1829 1.1935 98.4866 0.5879 0.4121
0.5432 1.1538 1.2268 99.2353 0.6119 0.3881
0.6332 1.0964 1.3194 100.5254 0.6691 0.3309
0.6605 1.0820 1.3518 100.7827 0.6870 0.3130
0.6945 1.0659 1.3952 101.0124 0.7100 0.2900
0.7327 1.0500 1.4483 101.1438 0.7369 0.2631
0.7752 1.0351 1.5132 101.1194 0.7688 0.2312
0.7922 1.0299 1.5411 101.0550 0.7822 0.2178
0.9080 1.0058 1.7626 99.6244 0.8881 0.1119
0.9448 1.0021 1.8463 98.7313 0.9291 0.0709

Plot of P(x,y) diagram:

105
100
95
Pressure

90 P-x exp
85 P-y exp
80 P-x Van Laar
75
70 P-y Van Laar

65
60
0.0000 0.5000 1.0000
x,y

(f) With the assistance of an appropriately annotated

diagram, explain the phenomenon of hysteresis, as it applies
to adsorption and desorption processes
The values of the parameters Λ12 and Λ21 are obtained by non-linear regression with the use of
equations a11 and b11.
The parameters were solved in MS EXCEL.

γ1 W γ2 W γ1 expt γ2 expt γ1W/γ1expt γ2W/γ2expt (γ1W/γ1expt)*(γ2W/γ2expt)

1.833 1.001 1.6818 1.0127 1.090 0.988 1.077
1.769 1.002 1.7653 1.0111 1.002 0.991 0.993
1.709 1.005 1.7234 1.0058 0.992 0.999 0.991
1.672 1.007 1.7061 1.0020 0.980 1.005 0.985
1.597 1.014 1.5804 1.0263 1.011 0.988 0.998
1.481 1.031 1.4972 1.0269 0.989 1.004 0.993
1.397 1.051 1.3959 1.0569 1.001 0.994 0.995
1.304 1.085 1.2846 1.1027 1.015 0.984 0.999
1.257 1.110 1.2435 1.1304 1.011 0.982 0.993
1.218 1.136 1.2238 1.1400 0.995 0.997 0.992
1.173 1.176 1.1659 1.1933 1.006 0.986 0.992
1.146 1.207 1.1551 1.1999 0.992 1.006 0.998
1.093 1.292 1.1018 1.2781 0.992 1.011 1.002
1.079 1.321 1.0818 1.3168 0.998 1.003 1.001
1.064 1.361 1.0617 1.3736 1.002 0.991 0.993
1.049 1.411 1.0449 1.4312 1.004 0.986 0.989
1.035 1.471 1.0394 1.4846 0.995 0.991 0.987
1.029 1.498 1.0370 1.5030 0.993 0.996 0.989
1.006 1.709 1.0171 1.6444 0.989 1.039 1.028
1.002 1.791 1.0179 1.7467 0.985 1.025 1.009

The parameters obtained are:

Λ12 = 0.7199 Λ21 = 0.6859

Equations a21 and b21 computes for the gamma values given the parameter values of Wilson.

Using Modified Raoult’s Law, the new final pressure and final composition of the vapor phase
is computed.
 x1 γ1’ γ2’ Pcalc y1 y2
0.0287 1.833 1.001 71.8871 0.0709 0.9291
0.0570 1.769 1.002 74.7180 0.1308 0.8692
0.0858 1.709 1.005 77.3388 0.1837 0.8163
0.1046 1.672 1.007 78.9207 0.2147 0.7853
0.1452 1.597 1.014 82.0244 0.2740 0.7260
0.2173 1.481 1.031 86.6338 0.3600 0.6400
0.2787 1.397 1.051 89.8134 0.4199 0.5801
0.3579 1.304 1.085 93.1109 0.4857 0.5143
0.4050 1.257 1.110 94.7162 0.5207 0.4793
0.4480 1.218 1.136 95.9824 0.5509 0.4491
0.5052 1.173 1.176 97.4019 0.5893 0.4107
0.5432 1.146 1.207 98.1902 0.6142 0.3858
0.6332 1.093 1.292 99.5920 0.6731 0.3269
0.6605 1.079 1.321 99.8887 0.6913 0.3087
0.6945 1.064 1.361 100.1719 0.7146 0.2854
0.7327 1.049 1.411 100.3703 0.7418 0.2582
0.7752 1.035 1.471 100.4306 0.7736 0.2264
0.7922 1.029 1.498 100.4037 0.7870 0.2130
0.9080 1.006 1.709 99.2909 0.8912 0.1088
0.9448 1.002 1.791 98.5235 0.9310 0.0690

Plot of P(x,y) diagram:

105
100
95
Pressure

90
P-x exp
85
80 P-y exp
75
70
65
60
0.0000 0.5000 x,y 1.0000 1.5000
(e) If it is required to separate out nitrogen from another two gases at 77 K, using
the IUPAC classification system, suggest which type of isotherm for the other two
gases would lead to the best separation of nitrogen using this carbon sample as
an adsorbent? Sketch the form of this isotherm.
Using excel solver, the following parameters are obtained.

The minimum value for obtained is 4.8254.

A12 = 0.6492 A21 = 0.6599

Residuals of Pressure and Vapor Composition as a function of x1 using Margules:

1.40
00
1.20 00
1.00 00
Residuals

00
0.80 0
00 P exp - P calc
0.600
00
0.40 y exp - y calc
00
0.20 0.0000 0.2000 0.4000 0.6000 0.8000 1.0000 -0.2000
0.00

x1