CHEG 211 Chemical Engineering Thermodynamics

Solution to Homework #3

Problem 1)

1.1

Antoine constants of acetonitrile and nitromethane

B
ln
   
TC

For acetonitrile (1): A = 14.8950; B = 3413.10; C = -22.627

P  e . . 




.

For nitromethane (2): A = 14.7513; B = 3331.70; C = -45.550

P  e . .

.


T = 75oC = 348.15 K

P-x diagram:

 . .
P  x P  x P  x e  . .  1 x e
 .    .  
 .  . 
 82.2717x  42.14241 x   42.1424  40.1293x

P-y diagram:

1 1
P 
y 1 y  y 1 y
 .  . 82.2717  42.1424
e .  . . e .  .  . 
1

0.02373 0.01157y
1.2

T-x diagram:
 . .
70  x P  x P  x e . .  1 x e .  . 

at x1 = 0,
 . .
70  0e . .  1 0e .  . 

T = 362.77 K = 89.62oC (boiling point of nitromethane at 70 kPa)

at x1 = 1.0,

 . .
70  1e . .  1 1e .  . 

T = 343.21 K = 70.06oC

Using 70  x e . . 

  1 x e . .


.


.


Determine x1 corresponding to a given temperature in the range 70.06 oC – 89.62oC to

construct the following table, from which the T-x diagram can be drawn.
T, oC 70.06 72.5 75.0 77.5 80.0 82.5 85.0 87.5 89.62
x1 1.000 0.843 0.694 0.555 0.426 0.305 0.192 0.085 0.000

T-y diagram:

Using 70    


. 


.

.  .

 
. 
.

Determine y1 corresponding to a given temperature in the range 70.06 oC – 89.62oC to

construct the following table, from which the T-y diagram can be drawn.

T, oC 70.06 72.5 75.0 77.5 80.0 82.5 85.0 87.5 89.62

y1 1.000 0.914 0.816 0.707 0.587 0.454 0.308 0.148 0.000

1.3

from (1.1),

P=42.1424+40.1293x = 42.1424 + 40.1293 x 0.5 = 62.2 kPa

1
P
0.02373 0.01157y
 1
62.2 
0.02373 0.01157y

y1 = 0.66

y 0.66
K    1.32
x 0.5

1.4

from (1.2),

1
70 
y 1 y 
 .  .
e . . e .  . 

Solve for T with y1=0.5.

T = 354.81 K = 81.66oC
 . .
70  x e .  ..  1 x e .  . . 

x1 = 0.34

0.5
K   1.47
0.34

1.5

L+V=1
xiL + yiV = zi (N equations)
yiP = xiPi* (N equations)
 y  1

From the above,

z K 
 1
1  VK  1



where K   


z1 = 0.5, z2 = 0.5, V = 0.5

  . .
e e
 .    .  
 . .  .  . 
0.5 x 0.5 x
P  P 1
 . .
e e
 .    .  
 . .  .  . 
1  0.5x P 1 1  0.5x P 1

P = 58.88 kPa

1.6

xiL + yiV = zi

yiP = xiPi*

x1 x 0.5 + y1 x 0.5 = 0.5

y1 x 58.88 = x1 x e . 
.. 




.

Solve the two equations simultaneously,

x1 = 0.417, y1 = 0.583

Problem 2)

2.1

P  γ x P  γ x P

γ  e.    e. .   2.357

 

γ  e.    e. .   1.0024

 

P  2.357 x 0.05 x 79.80  1.0024 x 0.95 x 40.5  47.97 kPa

2.2

1
P y y
 
γ P γ P

y1 = 0.5, y2 = 0.95,P  79.80 kPa, P  40.50 kPa

1 1
P 
0.05 0.95 0.05 0.95
79.8γ  40.5γ

79.8e.   40.5e.  
 

0.05P  γ x P  79.8 e.   x


From the above two equations,

. .   

. .
 
.


. .  . . 

Calculated values of NLE variables

Variable Value f(x) Initial Guess
1x 0.0104273 0 0.5 ( 0 < x < 1. )

Nonlinear equations
f(x) = 79.8*x*exp(0.95*(1-x)^2)/0.05 - 1/(0.05/(79.8*exp(0.95*(1-
1
x)^2))+0.95/(40.5*exp(0.95*x^2))) = 0

1
P
0.05 0.95

79.8e. .  40.5e. . 
 

P = 42.2 kPa

2.3

At the azeoptrope,

γ P  γ P

e.   79.8  e.   40.5

 

x1= 0.857 = y1

x2 = 0.143 = y2

P  0.857x 79.8e. .   0.143 x 40.5 e.  .    81.37 kPa

 

Problem 3)

3.1 V  120x  70x  15x  8x x x  120x  701 x   $15x  81
x %x 1 x   70  58x x 7x
  70  58x x 7x  x 58 2x 21x   70  x  14x
!
3.2 V  V x 
substituting x1 = 0.5
V  72
dV
V  V  x  70  58x x 7x   1 x 58 2x 21x 
dx
 128 2x 20x  14x
By substituting x1 = 0.5
V  123.75
3.3
Show that
dV  x dV  x dV  0 is met.
dV   2 40x  42x dx
dV  2x  42x dx
x dV  x dV  x  2 40x  42x dx  1 x 2x  42x dx  0

3.4
By Gibbs-Duhem equation,
x dV  x dV  0
Since x1 and x2 are positive, for a negative dV or a decrease in partial molar volume of
component 1, dV must be positive to meet the Gibbs-Duhem equation or the partial molar
volume of component (2) should increase.

Problem 4)
P, bar 0 10 20 40 60 80 100 200 300 400 500
Z 1.000 0.985 0.970 0.942 0.913 0.885 0.869 0.765 0.762 0.824 0.910
(Z-1)/P, -1.5* -1.5 -1.5 -1.45 -1.45 -1.435 -1.31 -1.175 -0.793 -0.44 -0.18
bar-1x103
*: (Z-1)/P at P=0 is indefinite since (1-1)/0. It was estimated by extrapolation.


Z 1
ln'  ( dP
 P
"
The integration is carried out by obtaining the area between the horizontal axis and 
bounded by two pressures, one at P=0 and the other at the pressure at which fugacity
coefficient is to be determined.

P, bar segmental area 

Z 1 '
ln'  ( dP
 P
0-10 -0.015 -0.015 0.985 at 10 bar
10-20 -0.015 -0.030 0.970 at 20 bar
20-40 -0.0296 -0.0596 0.942 at 40 bar
40-60 -0.029 -0.0886 0.915 at 60 bar
60-80 -0.02885 -0.11745 0.889 at 80 bar
80-100 -0.02745 -0.1449 0.865 at 100 bar
100-200 -0.12425 -0.26915 0.764 at 200 bar
200-300 -0.0984 -0.36755 0.692 at 300 bar
300-400 -0.06165 -0.4292 0.651 at 400 bar
400-500 -0.031 -0.4602 0.631 at 500 bar
Estimation by Eq. (11.68)
P#
Ф  exp + B   ωB 
T#
ω=0.224, Tc= 304.2 K, Pc = 73.83 bar
0.422
B   0.083 .
T#
0.172
B  0.139 .
T#
Tr= (150 + 273.15)/304.2 = 1.391
B0=-0.1659, B1=0.096
P#
Ф  exp +  0.1659  0.224 x0.096
1.391
 "
P, bar Pr Ф by eq. (11.68) Ф by ,  dP
10 0.135 0.986 0.985
20 0.254 0.974 0.970
40 0.507 0.949 0.942
60 0.761 0.924 0.915
80 1.015 0.900 0.889
100 1.269 0.877 0.865
200 2.537 0.768 0.764
300 3.806 0.673 0.692
400 5.074 0.590 0.651
500 6.343 0.517 0.631

Problem 5)
 P
lnФ  +B  y δ /
 RT
 P
lnФ  +B  y δ /
 RT 
δ  2B B B  2x 466— 276— 809  153
 2 bar
lnФ  + 276  0. 5 x153/  0.0164
 cm • bar
83.1 x348.15 K
mol • K

Ф  0.984

 2 bar
lnФ  + 809  0. 5 x153/  0.0533
 cm • bar
83.1 x348.15 K
mol • K

Ф  0.948


Problem 6)

Check if the Gibbs-Duhem equation

x dM  x dM  0 is satisfied.
dM  Adx
dM  Adx
x dM  x dM   Ax  Ax dx  Adx 9 0
Those expressions are not thermodynamically possible.

Problem 7)

7.1
Vapor pressure of methanol = system pressure at mole fraction of methanol = 1 or x1=1.
84.562 kPa
Vapor pressure of water = system pressure at mole fraction of methanol = 0 or x1=0.
19.953 kPa

7.2
P/kPa x1 y1 $ $
γ1(= ) γ2(= )
   
 

19.953 0.0000 0.0000 1.000

39.223 0.1686 0.5714 1.572 1.013
42.984 0.2167 0.6268 1.470 1.026
48.852 0.3039 0.6943 1.320 1.075
52.784 0.3681 0.7345 1.246 1.112
56.652 0.4461 0.7742 1.162 1.157
60.614 0.5282 0.8085 1.097 1.233
63.998 0.6044 0.8383 1.050 1.311
67.924 0.6804 0.8733 1.031 1.350
70.229 0.7255 0.8922 1.021 1.382
72.832 0.7776 0.9141 1.012 1.410
84.562 1.0000 1.0000 1.000

By linear interpolation:
γ1 = 1.162 + (1.097-1.162)/(0.5282-0.4461)x(0.5-0.4461) = 1.119
γ2 = 1.157 + (1.233-1.157)/(0.5282-0.4461)X(0.5-0.4461) = 1.207

7.3
G%
 x lnγ  x lnγ
RT

x1 γ lnγ x2 γ lnγ G%
RT
0.0000 1.0000 1.000 0.0000 0.0000
0.1686 1.572 0.4523 0.8314 1.013 0.0129 0.0870
0.2167 1.470 0.3853 0.7833 1.026 0.0257 0.1036
0.3039 1.320 0.2776 0.6961 1.075 0.0723 0.1347
0.3681 1.246 0.2199 0.6319 1.112 0.1062 0.1481
0.4461 1.162 0.1501 0.5539 1.157 0.1458 0.1477
0.5282 1.097 0.0926 0.4718 1.233 0.2095 0.1478
0.6044 1.050 0.0488 0.3956 1.311 0.2708 0.1366
0.6804 1.031 0.0305 0.3196 1.350 0.3000 0.1166
0.7255 1.021 0.0208 0.2745 1.382 0.3235 0.1039
0.7776 1.012 0.0119 0.2224 1.410 0.3436 0.0857
1.0000 1.000 0.0000 0.0000 0.0000

Problem 8)

Method A:

P  γ x P  γ x P

Determine the constants for the model to best fit measured system pressures

Pressure x1

39.223 0.1686
42.984 0.2167
48.852 0.3039
52.784 0.3681
56.652 0.4461
60.614 0.5282
63.998 0.6044
67.924 0.6804
70.229 0.7255
72.832 0.7776

Model: P = x*84.562*exp(A12*(1+A12*x/(A21*(1-x)))^(-2))+(1-x)*19.953*exp(A21*(1+A21*(1-
x)/(A12*x))^(-2))

By Polymath

A12 = 0.8301

A21 = 0.4677

Method B:
& &
Determine the constants for ln & predicted by the model to best fit ln & determined from
 
experimental data.

γ γ γ
x1 ln
γ
0.1686 1.572 1.013 -0.4394
0.2167 1.470 1.026 -0.3560
0.3039 1.320 1.075 -0.2053
0.3681 1.246 1.112 -0.1138
0.4461 1.162 1.157 -0.00431
0.5282 1.097 1.233 0.1169
0.6044 1.050 1.311 0.2220
0.6804 1.031 1.350 0.2696
0.7255 1.021 1.382 0.3027
0.7776 1.012 1.410 0.3317

Model: y = A21*(1+A21*(1-x)/(A12*x))^(-2)-A12*(1+A12*x/(A21*(1-x)))^(-2)

By polymath

A12 = 0.8283
A21 = 0.5227

Methods A and B give comparable results.

Problem 9)

By Wilson model,
< <
lnγ  ln;  ; <   x  
;  ; < ;  ; <
< <
lnγ  ln;  ; <  ;  
;  ; < ;  ; <
γ ;  ; < < <
ln  ln  
γ ;  ; < ;  ; < ;  ; <
 & &
Determine the constants for ln predicted by the model to best fit ln determined from
& &
experimental data.

γ γ γ
x1 ln
γ
0.1686 1.572 1.013 -0.4394
0.2167 1.470 1.026 -0.3560
0.3039 1.320 1.075 -0.2053
0.3681 1.246 1.112 -0.1138
0.4461 1.162 1.157 -0.00431
0.5282 1.097 1.233 0.1169
0.6044 1.050 1.311 0.2220
0.6804 1.031 1.350 0.2696
0.7255 1.021 1.382 0.3027
0.7776 1.012 1.410 0.3317

Model: y = ln((x+(1-x)*A12)/((1-x)+x*A21))-(A12/(x+(1-x)*A12)-A21/((1-x)+x*A21))

Variable Initial guess Value 95% confidence

A12 0.5 0.3934675 0.0606298
A21 0.5 1.080901 0.0914416

Nonlinear regression settings

Max # iterations = 64

Precision
R^2 0.9970359
R^2adj 0.9966654
Rmsd 0.0045897
Variance 0.0002633

Λ12 = 0.3935, Λ21 = 1.0809

Comparison between experimental and predicted values in activity coefficient and system
pressure.

x1 pressure- pressure- γ -exp γ -cal (γ -exp - γ -exp γ -cal (γ -exp -
exp cal γ -cal)2 γ -cal)2
0.0000 19.953 1.000
0.1686 39.223 40.061 1.572 1.608 0.0013 1.013 1.033 0.0004
0.2167 42.984 44.002 1.470 1.491 0.0004 1.026 1.051 0.0006
0.3039 48.852 49.476 1.320 1.334 0.0002 1.075 1.094 0.0004
0.3681 52.784 53.156 1.246 1.250 0.0000 1.112 1.130 0.0003
0.4461 56.652 57.291 1.162 1.173 0.0001 1.157 1.180 0.0005
0.5282 60.614 61.421 1.097 1.114 0.0003 1.233 1.239 0.0000
0.6044 63.998 65.153 1.050 1.074 0.0006 1.311 1.300 0.0001
0.6804 67.924 68.830 1.031 1.045 0.0002 1.350 1.365 0.0002
0.7255 70.229 71.020 1.021 1.032 0.0001 1.382 1.407 0.0006
0.7776 72.832 73.540 1.012 1.020 0.0001 1.410 1.458 0.0023
1.0000 84.562 1.000
total 0.0033 total 0.0054

Problem 10)

methanol(1)/water(2) x1=0.5282, x2=0.4718, T =333.15 K

Maingroup subgroup k Rk Qk νk
number
species (1) species (2)
1 CH3 1 0.9011 0.848 1 0
5 OH 15 1.0000 1.200 1 0
7 H2O 17 0.9200 1.400 0 1
lnγ  lnγ  lnγ
' (

The subscript C refers to combinatorial term to account for molecular size and shape,
and R is a residual property to account for molecular interaction.
J J
lnγ'  1 J  lnJ 5q  1  ln 
L L
#
where J  ∑
 # 
q
L 
∑* q * x *
r   ν + R +


+
q    ν+ Q +


+
ν+ is the number of subgroups of type k in a molecular species of k. Rk and Qk come from


tabulations in the literature.

β+ β+
lnγ(  q  +1 θ+ e+ ln /
s+ s+
+
ν Q+

e+  +
q

τ,+  exp    where amk come from tabulations in the literature.
β+   e, τ,+
,
∑ x q  e+
θ+ 
∑* x * q *
s+   θ, τ,+
,

(1) Calculation of r1 and r2

 r   ν + R +


+
r1 = 1 x 0.9011 + 1 x 1.000 = 1.9011
r2 = 1 x 0.9200 = 0.9200
(2) Calculation of Ji
#
J  ∑ 
 # 
J1 = 1.9011/(0.5282 x 1.9011 + 0.4718 x 0.9200) = 1.3218
J2 = 0.9200/(0.5282 x 1.9011 + 0.4718 x 0.9200) = 0.6397

(3) Calculation of q1 and q2

q    ν+ Q +


+
q1 = 1 x 0.848 + 1 x 1.200 = 2.048
q2 = 1 x 1.400 = 1.400

(4) Calculation of Li
-
L  ∑  
 - 
L1 = 2.048/(0.5282 x 2.048 + 0.4718 x 1.400) = 1.1755
L2 = 1.400/(0.5282 x 2.048 + 0.4718 x 1.400) = 0.8035
(5) Calculation of lnγ'
J J
lnγ'  1 J  lnJ 5q  1  ln 
L L
1.3218 1.3218
lnγ'  1 1.3218  ln1.3218 5 G 2.048 H 1  ln I
1.1755 1.1755
 0.0305
0.6397 0.6397
lnγ'  1 0.6397  ln0.6397 5 G 1.400 H 1  ln I
0.8035 0.8035
 0.08238

(6) Calculation of eki

ν+ Q +

e+ 
q
e1,1 = 1 x 0.848/2.048 = 0.4141
e15,1 = 1 x 1.200/2.048 = 0.5859
e17,1 = 0
e1,2 = 0
e15,2 = 0
e17,2 = 1 x 1.400/1.400 = 1.000

(7) Calculation of θ+
∑ x q  e+
θ+ 
∑* x * q *
∑* x* q *  0.5282 x 2.048  0.4718 x 1.400  1.7423
0.5282 x 2.048 x 0.4141  0.4718 x 1.400 x 0
θ   0.2570
1.7423
 0.5282 x 2.048 x 0.5859  0.4718 x 1.400 x 0
θ   0.3638
1.7423
0.5282 x 2.048 x 0  0.4718 x 1.400 x 1.000
θ   0.3791
1.7423
(8) Calculation of τ,+
a,+
τ,+  exp  
T
From Table H.2
a1,1 = 0.00, τ,  1
a1,15 = 986.50, τ,  0.05176
a15,1 = 156.4, τ ,  0.6253
a15,15 = 0.00, τ ,  1
a1,17 = 1318, τ,  0.0191
a17,1 = 300.00, τ,  0.4064
a17,15 = -229.10, τ,  1.9891
a15,17 = 353.5, τ ,  0.3461
a17,17 = 0.00, τ,  1

(9) Calculation of s+
s+   θ, τ,+
,
s  θ τ  θ τ ,  θ τ,
 0.2570 x 1  0.3638 x 0.6253  0.3791 x 0.4064  0.6386
s  θ τ,  θ τ ,  θ τ,
 0.2570 x 0.05176  0.3638 x 1  0.3791 x 1.9891  1.1312
s  θ τ,  θ τ ,  θ τ,
 0.2570 x 0.0191  0.3638 x 0.3461  0.3791 x 1  0.5099

(10) Calculation of β+

β+  ∑, e, τ,+

β,  e, τ,  e , τ ,  e, τ,

 0.4141 x 1  0.5859 x 0.6253  0 x 0.4064  0.7805
β,  e, τ,  e , τ ,  e, τ,
 0.4141 x 0.05176  0.5859 x 1  0 x 1.9891  0.6073
β,  e, τ,  e , τ ,  e, τ,
 0.4141 x 0.0191  0.5859 x 0.3461  0 x 1  0.2107
β,  e, τ,  e , τ ,  e, τ,  0 x 1  0 x 0.6253  1 x 0.4064
 0.4064
β,  e, τ,  e , τ ,  e, τ,  0 x 0.05176  0 x 1  1 x 1.9891
 1.9891
β,  e, τ,  e , τ ,  e, τ,  0 x 0.0191  0 x 0.3461  1 x 1
1

(11) Calculation of lnγ(

β+ β+
lnγ(  q  +1 θ+ e+ ln /
s+ s+
+
 β, β, β, β,
lnγ(  q J1 Hθ e, ln I Hθ e , ln I
s s s s
β, β,
Hθ e, ln IK
s s
. . .
 2.048 L1 M0.2570x . 0.4141ln .N M0.3638x .
. . .
0.5859ln N M0.3791x .  01ln . NO  0.1077
.

β, β, β, β,

lnγ(  q  J1 Hθ e, ln I Hθ e , ln I
s s s s
β, β,
Hθ e, ln IK
s s

0.4064 0.4064 1.9891 1.9891

 1.400 J1 H0.2570x 0ln I H0.3638x 0ln I
0.6386 0.6386 1.1312 1.1312
1 1
H0.3791x 1xln IK  0.1755
0.5099 0.5099
(12) Calculation of γ1 and γ2
lnγ  lnγ'  lnγ(
lnγ  lnγ'  lnγ(  0.0305  0.1077  0.1382
γ  1.148
lnγ  lnγ'  lnγ(  0.08238  0.1775  0.2599
γ  1.297
Comparison between experimental and UNIFAC activity coefficients at x1 = 0.5286 and 60oC.

Experimental UNIFAC
γ 1.097 1.148
γ 1.233 1.297