Svnas 8e Ism Chapter 10

SVNAS 8th Edition Annotated Solutions Chapter 10
Siig T , P   Siig T , pi   Siig T , P   R ln yi
N N N
1
Smix
ig
 S ig   yi Siig   R yi ln yi  R yi ln
i 1 i 1 i 1 yi
Updated 4/5/2017 p. 1 of 53
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 


 


Siig T , P   Siig T , pi   Siig T , P   R ln yi
N N N
1
Smix
ig
i 1 i 1 i 1 yi
Updated 4/5/2017 p. 2 of 53
Wideal  H  T S
  

 

N
1
Smix
ig
 R yi ln
i 1 yi


 
Updated 4/5/2017 p. 3 of 53
T1 (K) T2 (K) A B (1/K) C (1/K2) D (K2) ICPH (K) H (J/mol)

448.15 308.15 1.702 9.08E-03 -2.16E-06 0.00E+00 -6.75E+02 -5614
T2
 1 1
R    
Cp B 2 C 3
ICPH  dT  A  T2  T1   T2  T12  T2  T13  D   
2 3  T2 T1 
T1
T1 (K) T2 (K) A B (1/K) C (1/K2) D (K2) ICPS S (J/(mol K))

448.15 308.15 1.702 9.08E-03 -2.16E-06 0.00E+00 -1.794 -14.92
T2
 T2 
 RT dT  A ln  T   B T  T   2 T   
Cp C D 2
ICPS  2 1 2
2
 T12  T2  T1 2
1 2
T1
T1 (K) T2 (K) A B (1/K) C (1/K2) D (K2) ICPH (K) H (J/mol)

448.15 308.15 1.131 1.92E-02 -5.56E-06 0.00E+00 -1.06E+03 -8843
T2
 1 1
 R dT  AT  T   2 T   
Cp B C 3
ICPH  2 1 2
2
 T12  T2  T13  D   
3  T2 T1 
T1
T1 (K) T2 (K) A B (1/K) C (1/K2) D (K2) ICPS S (J/(mol K))

448.15 308.15 1.131 1.92E-02 -5.56E-06 0.00E+00 -2.821 -23.45
T2
T 
    
Cp C 2 D 2
ICPS  dT  A ln  2   B T2  T1   T2  T1  T2  T1 2
2
RT  T1  2 2
T1
 
 
Updated 4/5/2017 p. 4 of 53
 
Wideal  H  T S
Wideal
t  work required    0.05
Ws
Ws  20Wideal  20  H  T S 
N N N
1
Smix
ig
i 1 i 1 i 1 yi
Updated 4/5/2017 p. 5 of 53
Ϻ Ϻ Ϻ
Ϻ
Ϻ
Ϻ Ϻ
Ϻ
Ϻ Ϻ Ϻ
Ϻ
Ϻ
Ϻ
Updated 4/5/2017 p. 6 of 53
dM dM
M1  M  x2  M  1  x1 
dx1 dx1
dM
M 2  M  x1
dx1
1 1
V 
 a0  a1 x1  a2 x12
dV a1  2a2 x1

 a0  a1 x1  a2 x12 
2
dx1
V1  V  1  x1 
dV

1

1  x1  a1  2a2 x1 
dx1 a0  a1 x1  a2 x1  a  a x  a x 2 2
2
0 1 1 2 1
a0  a1 x1  a2 x12  a1  2a2 x1  a1 x1  2a2 x12

V1 
a  a1 x1  a2 x12 
2
0
a0  a1  2a1 x1  2a2 x1  3a2 x12

V1 
a  a1 x1  a2 x12 
2
0
dV 1 x1  a1  2a2 x1 
V2  V  x1  
dx1 a0  a1 x1  a2 x1  a  a x  a x 2 2
2
0 1 1 2 1
a0  2a1 x2  3a2 x12

V2 
a  a1 x1  a2 x12 
2
0
Updated 4/5/2017 p. 7 of 53
   nM  
Mi   
 ni  T , P ,n ji
   nM  
M1   
 n1  T , P ,n2 ,n3
M2
M3
M1
M2
M3
x1M1  x2 M 2  x3M 3
lim x1 0 M1
lim x2 0 M 2
lim x3 0 M 3
Updated 4/5/2017 p. 8 of 53
Updated 4/5/2017 p. 9 of 53
and
   nV  
Vi   
 ni  T , P ,n j  i
Updated 4/5/2017 p. 10 of 53
V1 
V1 
V1 
V1 
V1 
V2 
V2 
V2 
V2 
V2 
x1V1  x2V2
Updated 4/5/2017 p. 11 of 53
 x dV
i 1
i i 0
x1dV1  x2 dV2  0
V1 
V1 
V1 
V2 
V2 
V2 
dV1 
dV2 
x1dV1  x2 dV2  0
x1dV1  x2 dV2
x1dV1  x2 dV2
dV1 
dV2 
dV1
 2  40 1  42 1  0
dx1 x1 1
dV2
 2  0   42  0   0
dx1 x1  0
Updated 4/5/2017 p. 12 of 53
SVA problem 11.13(e)
140
Total or Partial Molar Volume (cm 3/mol)
V1,  128
130 V1 V1  120
120
110
100
V
90 V2,  85
V2  70
80 V2
70
60
0 0.2 0.4 0.6 0.8 1
x1
   nH  
Hi   
 ni  T , P ,n ji
 n1   n2 
nH  n1  a1  b1   n2  a2  b2 
 n1  n2   n1  n2 
   nH    n1  n1n2 n22
H1     
 1 1
a b 
 1 b  b
 n1  T , P ,n2  n1  n2   n1  n2   n1  n2 
2 2 2
H1   a1  b1 x1   b1 x1 x2  b2 x22
H 2   a2  b2 x2   b2 x1 x2  b1 x12
Updated 4/5/2017 p. 13 of 53
x1 H1  x2 H 2  x1  a1  b1 x1   b1 x12 x2  b2 x1 x22  x2  a2  b2 x2   b2 x1 x22  b1 x12 x2

x1 H1  x2 H 2  x1  a1  b1 x1   x2  a2  b2 x2 
dH
H1  H  x2
dx1
dH
H 2  H  x1
dx1
Ϻ Ϻ
Updated 4/5/2017 p. 14 of 53
P
Zi  1
ln i 

0
P
dP


P (Z-1)/P f
(bar) Z (1/bar) ln(Phi) Phi (bar) 0.000000
10 0.9850 -0.001500 -0.0150 0.9851 9.85 0 100 200 300 400 500 600
-0.000200
20 0.9700 -0.001500 -0.0300 0.9704 19.41
-0.000400
40 0.9420 -0.001450 -0.0595 0.9422 37.69
(Z - 1)/P (1/bar)
60 0.9130 -0.001450 -0.0885 0.9153 54.92 -0.000600
80 0.8850 -0.001438 -0.1174 0.8893 71.14
-0.000800
100 0.8690 -0.001310 -0.1449 0.8652 86.52
200 0.7650 -0.001175 -0.2691 0.7641 152.81 -0.001000
300 0.7620 -0.000793 -0.3675 0.6925 207.74 -0.001200
400 0.8240 -0.000440 -0.4292 0.6510 260.42
-0.001400
500 0.9100 -0.000180 -0.4602 0.6312 315.58
-0.001600
Pressure (bar)
 
Updated 4/5/2017 p. 15 of 53
T (K) P (bar) Tc (K) Pc (bar) 

423.15 10 304.2 73.83 0.224
Tr Pr B0 B1 
1.3910 0.1354 -0.1659 0.0960 0.9860
0.422
B0  0.083   
Tr1.6


  exp  B 0   B 1  TP
r
r


0.172
B1  0.139 
Tr4.2
Pale blue boxes are input fields, pink box is the final output.
T (K) P (bar) Tc (K) Pc (bar)  Tr Pr

423.15 200 304.2 73.83 0.224 1.391026 2.708926
Table Points

Tr Pr 
0

Tr (1) Pr(1) 1.30 2.00 0.7345 1.1776
Tr (1) Pr(2) 1.30 3.00 0.6383 1.2853
Tr (2) Pr(1) 1.40 2.00 0.7925 1.1858
Tr (2) Pr(2) 1.40 3.00 0.7145 1.2942
Interpolated for Pr=2 0.7873 1.1851

Interpolated to Tr, Pr 0.7308 1.2619
Final Value of  0.7699
Updated 4/5/2017 p. 16 of 53
Using appropriate Using 2nd virial

method coefficient for all
P f Percent f Percent
(bar) Phi (bar) difference Phi (bar) difference
10 0.9860 9.86 0.09% 0.9860 9.86 0.09%
20 0.9723 19.45 0.19% 0.9723 19.45 0.19%
40 0.9453 37.81 0.33% 0.9453 37.81 0.33%
60 0.9191 55.15 0.41% 0.9191 55.15 0.41%
80 0.8936 71.49 0.49% 0.8936 71.49 0.49%
100 0.8689 86.89 0.43% 0.8689 86.89 0.43%
200 0.7699 153.98 0.76% 0.7549 150.98 -1.20%
300 0.7074 212.22 2.16% 0.6559 196.77 -5.28%
400 0.6626 265.04 1.78% 0.5699 227.96 -12.46%
500 0.6422 321.10 1.75% 0.4952 247.60 -21.54%

600 300 430.8 78.84 0.245 1.3928 3.8052
Table Points
 
0 1 R 0 R 1 R 0 R 1 0 1
Tr Pr Z Z (H ) /(RT c) (H ) /(RT c) (S ) /R (S ) /R
Tr (1) Pr(1) 1.30 3.00 0.6344 0.2079 -2.274 -0.3 -1.299 -0.481 0.6383 1.2853
Tr(1) Pr(2) 1.30 5.00 0.7358 0.0875 -2.825 -1.066 -1.554 -1.147 0.5383 1.3868
Tr(2) Pr(1) 1.40 3.00 0.7202 0.2397 -1.857 -0.044 -0.99 -0.29 0.7145 1.2942
Tr(2) Pr(2) 1.40 5.00 0.7761 0.1737 -2.486 -0.504 -1.303 -0.73 0.6237 1.4488
Interpolated Values 0.7378 0.2092 -2.1382 -0.2567 -1.1367 -0.4876 0.6722 1.3542
Final Values
R

R
Z 0.7891 H /(RT c) -2.20103 S /R -1.25615 0.723998
3 R R
V (cm /mol) 131.2 H (J/mol) -7883.38 S (J/(mol K)) -10.4436 f (bar) 217.1995
R
G /(RT) -0.32419
 0.723111
f (bar) 216.9334
 
GiR H R  TS R
ln i  
RT RT
 
Updated 4/5/2017 p. 17 of 53



553.15 20 417.9 40 0.194
0 1
Tr Pr B B 
1.3236 0.5000 -0.1865 0.0860 0.9379
0.422
B 0  0.083 
 
Tr1.6
0.172 

  exp  B 0   B 1  TP
r
r


B1  0.139 
Tr4.2
Pale blue boxes are input fields, pink boxes are the final output.
Updated 4/5/2017 p. 18 of 53

553.15 100 417.9 40 0.194 1.323642 2.5
Table Points

 
0
Tr Pr
Tr (1) Pr(1) 1.30 2.00 0.7345 1.1776
Tr (1) Pr(2) 1.30 3.00 0.6383 1.2853
Tr (2) Pr(1) 1.40 2.00 0.7925 1.1858
Tr (2) Pr(2) 1.40 3.00 0.7145 1.2942

Interpolated to Tr, Pr 0.7023 1.2335
Final Value of  0.7314
     
Updated 4/5/2017 p. 19 of 53
fi  isat Pi sat exp 

i 
 V sat P  P sat
i  
 RT 
 

383.15 5.267 511.8 45.02 0.196
0 1
Tr Pr B B 
0.7486 0.1170 -0.5876 -0.4412 0.9000
0.422
B 0  0.083 
 
Tr1.6
0.172 

  exp  B 0   B 1  TP
r
r


B1  0.139 
Tr4.2
 107.5 cm3 mol-1  275  5.267  bar 

fi  0.9000 *5.267 bar*exp  
 83.145 cm3 bar mol-1 K -1 *383.15 K 
 
fi  11.78 bar
Updated 4/5/2017 p. 20 of 53
fi

fi i 
 exp 
i  
fi sat isat Pi sat  RT 
 

fi  19.65 cm3 mol-1 150  4.76  bar 

 exp    1.085
fi sat  83.145 cm3 bar mol-1 K -1 * 423.15 K 
 
Gi  i T   RT ln fi
G final  Ginitial  i T   RT ln f final  i T   RT ln f initial

 f final 
G final  Ginitial  RT ln  
 finitial 
f final  G final  Ginitial   G   H S 

 exp    exp    exp  
finitial  RT   RT   RT R 

 
Updated 4/5/2017 p. 21 of 53

 
f final  H S   2775.08 31.396 
 exp     exp   
finitial  RT R   8.3145* 673.15 8.3145 
f final
 exp  0.4958  3.7761  0.0376
finitial
Gi  i T   RT ln fi
G final  Ginitial  i T   RT ln f final  i T   RT ln f initial

 f final 
G final  Ginitial  RT ln  
 finitial 
f final  G final  Ginitial   G   H S 

 exp    exp    exp  
finitial  RT   RT   RT R 
 
  
 
  
f final  H S   758.6 6.397 
 exp     exp   
finitial  RT R   1.986 *1259.7 1.986 
f final
 exp  0.30323  3.2210   0.0541
finitial

i 
i  
 RT 
 
Updated 4/5/2017 p. 22 of 53



309.2 1.013 469.7 33.7 0.252
0 1
Tr Pr B B 
0.6583 0.0301 -0.7408 -0.8568 0.9573
0.422
B 0  0.083 
 
Tr1.6
0.172 

  exp  B 0   B 1  TP
r
r


B1  0.139 
Tr4.2
 119.4 cm3 mol-1  200  1.01 bar 

fi  0.9573*1.013 bar*exp  
 83.145 cm3 bar mol-1 K -1 *309.2 K 
 
fi  2.4 bar

i 
i  
 RT 
 
Updated 4/5/2017 p. 23 of 53

266.3 1 417.9 40 0.194
Tr Pr B0 B1 
0.6372 0.0250 -0.7848 -1.0025 0.9623
0.422
B 0 0.083

Tr1.6
0.172 

  exp  B0   B1  TP 
r
r
B1 0.139
Tr4.2

i 
i  
 RT 
 
 82.0 cm3 mol-1  200  1.01 bar 
fi  0.9623 *1.013 bar*exp  
 83.145 cm3 bar mol-1 K -1 * 266.3 K 
 
fi  2.04 bar

i 
i  
 RT 
 
Updated 4/5/2017 p. 24 of 53

266.9 1.01325 420 40.43 0.191
Tr Pr B0 B1 
0.6355 0.0251 -0.7887 -1.0158 0.9620
0.422
B 0 0.083

Tr1.6
0.172 

  exp  B0   B1  TP 
r
r
B1 0.139
Tr4.2

i 
i  
 RT 
 
 91.43 cm3 mol-1  200  1.01 bar 
fi  0.9620 *1.013 bar*exp  
 83.145 cm3 bar mol-1 K -1 * 266.9 K 
 
fi  2.21 bar
Updated 4/5/2017 p. 25 of 53
T (K) Psat (bar) Tc (K) Pc (bar)  Vc (cm3/mol) Zc

473.15 22.27 536.4 54.72 0.222 239.0 0.293
Tr B0 B1 Vsat (cm3 /mol) P (bar)  f (bar)

0.8821 -0.4328 -0.1523 122.7 0.0 1.000 0.00
0.5 0.995 0.50
Below P sat 1.0 0.990 0.99
1.5 0.986 1.48
0.422
B 0 0.083 2.0 0.981 1.96
 P 
0.172 
Tr1.6
  exp  B0   B1 r 
Tr 
  2.5
3.0
0.976
0.971
2.44
2.91
B1 0.139 4.2 3.5 0.967 3.38
Tr
4.0 0.962 3.85
4.5 0.957 4.31
Above P sat 5.0 0.953 4.76
5.5 0.948 5.22

i 
i   6.0 0.944 5.66
 
6.5 0.939 6.10
RT
  7.0 0.935 6.54
7.5 0.930 6.98
8.0 0.926 7.40
8.5 0.921 7.83
9.0 0.917 8.25
9.5 0.912 8.67
Fugacity and Fugacity Coefficient of Chloroform at 200 °C

20 1.0
18 0.9
16 0.8
Fugacity Coefficient
14 0.7
Fugacity (bar)
12 0.6
10 0.5
8 0.4
6 0.3
4 0.2
2 0.1
0 0.0
0 5 10 15 20 25 30 35 40
Pressure (bar)
Updated 4/5/2017 p. 26 of 53
Spreadsheet for computing fugacity coefficients in a binary mixture (Applied to Problem 11.25)
T (K) P (bar)
423.15 30
Mole Vc
3
Name Fraction Tc (K) Pc (bar) (cm /mol) Zc  Tr Pr B0 B1
Species 1 Ethylene 0.35 282.3 50.4 131 0.281 0.087 1.4989 0.5952 -0.1378 0.1076
Species 2 Propylene 0.65 365.6 46.65 188.4 0.289 0.14 1.1574 0.6431 -0.2510 0.0459
Vc
Cross-Parameters kij Tc (K) Pc (bar) (cm3/mol) Zc  Tr Pr B0 B1
0 321.26139 48.19 158.0 0.2850 0.1135 1.3172 0.6225 -0.1886 0.0849
i   j
Tcij  TciTcj 1 kij 
2nd Virial Coefficients (cm3/mol) 0.422
ij  B 0  0.083 
B11 -60 2 Tr1.6
B22 -159
Zcij RTcij Zci  Zcj B1  0.139 
0.172
B12 -99 Pcij  Zcij  Tr4.2
Vcij 2
12 (cm /mol)
3
20.83 3
 V 1/3  Vcj1/3 
ln ˆ Vcij   ci 

B  ij B1 
-0.04351 RTcij
Bij 
1 0
 2 
ln ˆ2 -0.13371 Pcij
 ˆ1 0.957 ln ˆ1 
P
 B11  y22 12   RT
P
 B11  y22  2 B12  B11  B22  
ˆ 2 0.875 RT
ln ˆ2 
P
RT
 B22  y12 12   RT
P
 B22  y12  2 B12  B11  B22  
fêthylene  êthylene yethylene P  0.957*0.35*30 bar  10.05 bar

fˆpropylene  ˆpropylene y propylene P  0.875*0.65*30 bar  17.06 bar
fîid  yi fi  yii P
Updated 4/5/2017 p. 27 of 53

423.15 30 282.3 50.4 0.087
0 1
Tr Pr B B 
1.4989 0.5952 -0.1378 0.1076 0.9503
0.422
B 0  0.083 
 
Tr1.6
0.172 

  exp  B 0   B 1  TP
r
r


B  0.139 
1
Tr4.2

423.15 30 365.6 46.65 0.14
0 1
Tr Pr B B 
1.1574 0.6431 -0.2510 0.0459 0.8729
0.422
B 0  0.083 
 
Tr1.6
0.172 

  exp  B 0   B 1  TP
r
r


B1  0.139 
Tr4.2
fêthylene
id
 yethyleneethylene P  0.35* 0.9503*30 bar  9.98 bar
fˆpropylene
id
 y propylene propylene P  0.65* 0.8729 *30 bar  17.02 bar
Updated 4/5/2017 p. 28 of 53
P  
yi y j  2 ik   ij  
1 N N
ln ˆk   kk
RT 
B  
2 i 1 j 1 
 ik   ki  2 Bik  Bii  Bkk

 ij   ji  2 Bij  Bii  B jj
 ii   jj   kk  0
ln ˆ1 
P
RT
 B11  y2212  y3213  y2 y3 12  13   23  
ln ˆ2 
P
RT
 B22  y32 23  y1212  y3 y1  23  12  13  
ln ˆ3 
P
RT
 B33  y1213  y22 23  y1 y2 13   23  12  
Updated 4/5/2017 p. 29 of 53
Spreadsheet for computing fugacity coefficients in a binary mixture (problem 11.27 in SVA)
T (K) P (bar)
373.15 35
Mole Vc
3 0 1
Name Fraction Tc (K) Pc (bar) (cm /mol) Zc  Tr Pr B B
Species 1 Methane 0.21 190.6 45.99 98.6 0.286 0.012 1.9578 0.7610 -0.0610 0.1288
Species 2 Ethane 0.43 305.3 48.72 145.5 0.279 0.1 1.2222 0.7184 -0.2231 0.0650
Species 3 Propane 0.36 369.8 42.48 200 0.276 0.152 1.0091 0.8239 -0.3330 -0.0266
Vc
0 1
Cross-Parameters kij Tc (K) Pc (bar) (cm3/mol) Zc  Tr Pr B B
1,2 0 241.22641 47.01 120.5 0.2825 0.0560 1.5469 0.7446 -0.1270 0.1115
1,3 0 265.488 43.26 143.4 0.2810 0.0820 1.4055 0.8090 -0.1618 0.0978
2,3 0 336.00586 45.26 171.3 0.2775 0.1260 1.1105 0.7734 -0.2738 0.0283
3
2nd Virial Coefficients (cm /mol) i   j
Tcij  TciTcj 1  kij 
0.422
B11 -21  ij  B 0  0.083 
B22 -113 2 Tr1.6
B33 -244 Z cij RTcij Z ci  Z cj 0.172
Pcij  Z cij  B1  0.139 
B12 -52 Vcij 2 Tr4.2
B13 -78 3
 V 1/ 3  Vcj1/ 3 
B   ij B 1 
B23 -167 RTcij
Vcij   ci  Bij  0
 2
12 (cm /mol)
3
30.33
  Pcij
13 (cm /mol)

3
107.52
23 (cm /mol)
3
23.10
ln ˆ1 0.01895
ln ˆ1 
P
RT
 B11  y2212  y3213  y2 y3 12  13   23  
ln ˆ2
 B22  y32 23  y1212  y3 y1  23  12  13  
-0.12320 P
ln ˆ3
ln ˆ2 
-0.25478 RT
ˆ1 1.019 f1 (bar) 7.49 ln ˆ3 
P
 B33  y1213  y22 23  y1 y2 13   23  12  
ˆ2 0.884 f2 (bar) 13.31 RT
ˆ3 0.775 f3 (bar) 9.77
fîid  yi fi  yii P

373.15 35 190.6 45.99 0.012
0 1
Tr Pr B B 
1.9578 0.7610 -0.0610 0.1288 0.9771
0.422
B 0  0.083 
 
Tr1.6
0.172 

  exp  B 0   B1  TP
r
r


B1  0.139 
Tr4.2
Updated 4/5/2017 p. 30 of 53

373.15 35 305.3 48.72 0.1
0 1
Tr Pr B B 
1.2222 0.7184 -0.2231 0.0650 0.8805
0.422
B 0  0.083 
 
Tr1.6
0.172 

  exp  B 0   B1  TP
r
r


B1  0.139 
Tr4.2

373.15 35 369.8 42.48 0.152
0 1
Tr Pr B B 
1.0091 0.8239 -0.3330 -0.0266 0.7594
0.422
B 0  0.083 
 
Tr1.6
0.172 

  exp  B 0   B1  TP r
r


B1  0.139 
Tr4.2
f1 (bar) 7.18
f2 (bar) 13.25
f3 (bar) 9.57
Updated 4/5/2017 p. 31 of 53
, and
I II
Part G1E H1E S1E CPE S2E H2E G2E S2E H2E G2E
a -622.0 -1920.0 -4.354 4.2 -3.951 -1794 -497.4 -4.354 -1920.0 -491.4
b 1095.0 1595.0 1.677 3.3 1.993 1694 1039.9 1.677 1595.0 1044.7
c 407.0 984.0 1.935 -2.7 1.677 903 352.8 1.935 984.0 348.9
d 632.0 -208.0 -2.817 23.0 -0.614 482 683.5 -2.817 -208.0 716.5
e 1445.0 605.0 -2.817 11.0 -1.764 935 1513.7 -2.817 605.0 1529.5
f 734.0 -416.0 -3.857 11.0 -2.803 -86 833.9 -3.857 -416.0 849.7
g 759.0 1465.0 2.368 -8.0 1.602 1225 699.5 2.368 1465.0 688.0
x1 VE
0.02715 87.5
0.09329 265.6
0.1749 417.4
0.3276 534.5
0.40244 531.7
0.56689 421.1
0.63128 347.1
0.66233 321.7
0.69984 276.4
0.72792 252.9
0.77514 190.7
Updated 4/5/2017 p. 32 of 53
0.79243 178.1
0.82954 138.4
0.86835 98.4
0.93287 37.6
0.98233 10
600
500
400 VE actual
VE
300
200
100
0
0 0.2 0.4 0.6 0.8 1
x1
Updated 4/5/2017 p. 33 of 53
3500
3000
2500
VE1
2000 VE2
VE
1500
1000
500
0
-500 0 0.2 0.4 0.6 0.8 1
x1
B  y12 B11  2 y1 y2 B12  y22 B22
BP 504.25* 2
Z 1 1  0.965
RT 83.14*348.15
H R BP P dB 504.25* 2 2
    *3.55  0.1202
RT RT R dT 83.14*348.15 83.14
SR P dB 2
  *3.55  0.08540
R R dT 83.14
Updated 4/5/2017 p. 34 of 53
1
0.95
0.9
0.85
ɸhat1 ɸhat2
0.8
0.75
ɸhat1
0.7
ɸhat2
0.65
0.6
0.55
0.5
0 0.2 0.4 0.6 0.8 1
y1
Updated 4/5/2017 p. 35 of 53
isa function of T only:

, ; substitution yields:
x1 HE
0.0426 -23.3
0.0817 -45.7
0.1177 -66.5
0.151 -86.6
0.2107 -118.2
0.2624 -144.6
0.3472 -176.6
0.4158 -195.7
0.5163 -204.2
0.6156 -191.7
0.681 -174.1
0.7621 -141
0.8181 -116.8
0.865 -85.6
0.9276 -43.5
0.9624 -22.6
Updated 4/5/2017 p. 36 of 53
0
0 0.2 0.4 0.6 0.8 1
-50
-100
HE
-150
-200 HE actual
equation
-250
x1
Updated 4/5/2017 p. 37 of 53
100
0
0 0.2 0.4 0.6 0.8 1
-100
HEbar1
-200
HEbar2
HEbar
-300
-400
-500
-600
-700
x1
N N
B   yi y j Bij B  y12 B11  2 y1 y2 B12  y22 B22
i 1 j 1
B
Pc

RTc 0
 0.422 0.172
B   B1 , with B0  0.083  1.6 and B1  0.139  4.2
Tr Tr
Updated 4/5/2017 p. 38 of 53
i   j
ij 
2
Z cij RTcij
Pcij 
Vcij
Z ci  Z cj
Z cij 
2
3
V 1/ 3
 Vcj1/ 3 
Vcij   ci

 2
 
dB dB dB dB
 y12 11  2 y1 y2 12  y22 22
dT dT dT dT
dBij RTc  dBij0 dBij1  R  dBij0 dBij1  dBij0 0.675 dBij1 0.722
       , with  2.6 and 
dT Pc  dT dT  Pc  dTr dTr  dT Tr dT Tr5.2
   
RT dB dB
V B, G R  BP , H R  BP  TP , and S R   P
P dT dT
Updated 4/5/2017 p. 39 of 53
Spreadsheet for computing residual properties of a binary mixture, for SVA problem 11.37(a)
T (K) P (bar)
333.15 1.7
Vc 0 1
Mole dB dB
3 0 1
Name Fraction Tc (K) Pc (bar) (cm /mol) Zc  Tr Pr B B dT dT
Species 1 Acetone 0.28 508.2 47.01 209 0.233 0.307 0.6555 0.0362 -0.7464 -0.8744 2.0236 6.4892
Species 2 1,3-butadiene 0.72 425.2 42.77 220.4 0.267 0.190 0.7835 0.0397 -0.5405 -0.3402 1.2729 2.5674
0 1
Vc dB dB
0 1
Cross-Parameters kij Tc (K) Pc (bar) (cm3/mol) Zc  Tr Pr B B dT dT
0 464.8512 45.02 214.6 0.2500 0.2485 0.7167 0.0378 -0.6361 -0.5579 1.6049 4.0817
3
0.422
B11 -912 ij  B 0  0.083 
2 Tr1 .6
B22 -500 Zcij RTcij Zci  Zcj 0.172
B12 -665 Pcij  Zcij  B  0.139 
1
Vcij 2 Tr4 .2
3 3
Derivatives of 2nd Virial Coefficients (cm /((mol K))  Vci1/ 3  Vcj1/ 3  RTcij
dB11/dT 7.10 Vcij  

 2 

Bij 
Pcij
B 0
  ij B 1 
dB22/dT 3.42
dB12/dT 4.84
dBij RTc  dBij0 dBij1  dBij0 0.675 dBij1 0.722
3     , with  2.6 and  5.2
Mixture 2nd Virial Coefficient (cm /mol) dT Pc  dT dT  dT T dT Tr
B -599   r
3
Derivative of Mixture 2nd Virial Coefficient (cm /((mol K)) B  y1 B11  2 y1 y2 B12  y2 B22
2 2
dB/dT 4.28
dB dB dB dB
Mixture Properties:  y12 11  2 y1 y2 12  y22 22
V (cm3/mol) 15695 dT dT dT dT
Z 0.9632
R RT dB dB
G (J/mol) -101.8 V B, GR  BP , H R  BP  TP , and S R  P
R
H (J/mol) -344.3 P dT dT
R
S (J/(mol K)) -0.728
N N
i 1 j 1
B
RTc 0
Pc
  0.422 0.172
B   B1 , with B0  0.083  1.6 and B1  0.139  4.2
Tr Tr
Updated 4/5/2017 p. 40 of 53
i   j
ij 
2
Z cij RTcij
Pcij 
Vcij
Z ci  Z cj
Z cij 
2
3
V 1/ 3
 Vcj1/ 3 
Vcij   ci

 2
 
dB dB dB dB
 y12 11  2 y1 y2 12  y22 22
dT dT dT dT
dBij RTc  dBij0 dBij1  R  dBij0 dBij1  dBij0 0.675 dBij1 0.722
       , with  2.6 and 
dT Pc  dT dT  Pc  dTr dTr  dT Tr dT Tr5.2
   
RT dB dB
P dT dT
N N
i 1 j 1
B
RTc 0
Pc
  0.422 0.172
B   B1 , with B0  0.083  1.6 and B1  0.139  4.2
Tr Tr
Updated 4/5/2017 p. 41 of 53
i   j
ij 
2
Z cij RTcij
Pcij 
Vcij
Z ci  Z cj
Z cij 
2
3
V 1/ 3
 Vcj1/ 3 
Vcij   ci

 2
 
dB dB dB dB
 y12 11  2 y1 y2 12  y22 22
dT dT dT dT

    , with  2.6 and 
dT Pc  dT dT  dT Tr dT Tr5.2
 
RT dB dB
P dT dT
Updated 4/5/2017 p. 42 of 53
Spreadsheet for computing residual properties of a binary mixture, for SVA problem 11.37(c)
T (K) P (bar)
298.15 1
Mole Vc dB0 dB1
3
Name Fraction Tc (K) Pc (bar) (cm /mol) Zc  Tr Pr B0 B1 dT dT
Species 1 Methyl chloride 0.45 416.3 66.8 143 0.276 0.153 0.7162 0.0150 -0.6369 -0.5599 1.6078 4.0963
Species 2 Ethyl chloride 0.55 460.4 52.7 200 0.275 0.190 0.6476 0.0190 -0.7627 -0.9278 2.0889 6.9148
Vc dB0 dB1
Cross-Parameters kij Tc (K) Pc (bar) (cm3/mol) Zc  Tr Pr B0 B1 dT dT
0 437.7951 59.02 169.9 0.2755 0.1715 0.6810 0.0169 -0.6973 -0.7245 1.8326 5.3221
3
0.422
B11 -374 ij  B 0 0.083
2 Tr1.6
B12 -507 Pcij  Z cij  B1 0.139
Vcij 2 Tr4.2
3
Derivatives of 2nd Virial Coefficients (cm3/((mol K))  V 1/ 3  Vcj1/ 3  RTcij
dB11/dT 2.78 Vcij   ci

 2 

Bij 
Pcij
B 0
 ij B1 
dB22/dT 5.37
dB12/dT 3.87
    , with  2.6 and 
Mixture 2nd Virial Coefficient (cm3/mol) dT Pc  dT dT  dT Tr dT Tr5.2
B -533  
3
2 2
dB/dT 4.10
dB dB dB dB
Mixture Properties:  y12 11  2 y1 y2 12  y22 22
Z 0.9785
GR (J/mol)
RT dB dB
-53.3 V B, G R  BP , H R  BP  TP , and S R   P
HR (J/mol) -175.6 P dT dT
SR (J/(mol K)) -0.410
N N
i 1 j 1
B
RTc 0
Pc
 0.422 0.172
B   B1 , with B0  0.083  1.6 and B1  0.139  4.2
Tr Tr
i   j
ij 
2
Z cij RTcij
Pcij 
Vcij
Z ci  Z cj
Z cij 
2
3
 V 1/ 3  Vcj1/ 3 
Vcij   ci 
 2
 
Updated 4/5/2017 p. 43 of 53
dB dB dB dB
 y12 11  2 y1 y2 12  y22 22
dT dT dT dT
RTc  dBij 
0
dBij dBij1 dBij0 0.675 dBij1 0.722
    , with  2.6 and 
 
RT dB dB
P dT dT
Spreadsheet for computing residual properties of a binary mixture, for SVA problem 11.37(d)
T (K) P (bar)
293.15 3
Mole Vc dB0 dB1
3
Name Fraction Tc (K) Pc (bar) (cm /mol) Zc  Tr Pr B0 B1 dT dT
Species 1 Nitrogen 0.83 126.2 34 89.2 0.289 0.038 2.3229 0.0882 -0.0266 0.1340 0.0754 0.0090
Species 2 Ammonia 0.17 405.7 112.8 72.5 0.242 0.253 0.7226 0.0266 -0.6267 -0.5343 1.5711 3.9114
Vc dB0 dB1
Cross-Parameters kij Tc (K) Pc (bar) (cm3/mol) Zc  Tr Pr B0 B1 dT dT
0 226.2727 62.00 80.6 0.2655 0.1455 1.2956 0.0484 -0.1959 0.0810 0.3443 0.1878
2nd Virial Coefficients (cm 3/mol) i   j

0.422
B11 -7 ij  B 0 0.083
2 Tr1.6
B22 -228 Z RT Z ci  Z cj 0.172
B12 -56 Pcij  cij cij Z cij  B 0.139
1
Vcij 2 Tr4.2
3
V V 
3 1/ 3 1/ 3
Derivatives of 2nd Virial Coefficients (cm /((mol K))
RTcij
Vcij   B  ij B1 
ci cj
dB11/dT 0.19   Bij  0
 2  Pcij
dB22/dT 1.89
dB12/dT 0.50
dBij RTc  dBij0 dBij1  dB0 0.675 dBij1 0.722
    , with ij  and  5.2
Mixture 2nd Virial Coefficient (cm 3/mol) dT Pc  dT dT  dT T 2.6 dT Tr
  r
B -27
3
dB/dT 0.32
dB 2 dB11 dB dB
Mixture Properties:  y1  2 y1 y2 12  y22 22
Z 0.9967
RT dB dB
GR (J/mol) -8.1 V B, G R  BP , H R  BP  TP , and S R   P
SR (J/(mol K)) -0.097
Updated 4/5/2017 p. 44 of 53
N N
i 1 j 1
B
RTc 0
Pc
  0.422 0.172
B   B1 , with B0  0.083  1.6 and B1  0.139  4.2
Tr Tr
i   j
ij 
2
Z cij RTcij
Pcij 
Vcij
Z ci  Z cj
Z cij 
2
3
 V 1/ 3  Vcj1/ 3 
Vcij   ci 
 2
 
dB dB dB dB
 y12 11  2 y1 y2 12  y22 22
dT dT dT dT
RTc  dBij 
0
dBij dBij1 dBij0 0.675 dBij1 0.722
    , with  2.6 and 
 
RT dB dB
P dT dT
Updated 4/5/2017 p. 45 of 53
Spreadsheet for computing residual properties of a binary mixture, for SVA problem 11.37(e)
T (K) P (bar)
293.15 4.2
Mole Vc dB0 dB1
3
Name Fraction Tc (K) Pc (bar) (cm /mol) Zc  Tr Pr B0 B1 dTr dTr
Species 1 sulfur dioxide 0.32 430.8 78.84 122 0.269 0.245 0.6805 0.0533 -0.6983 -0.7274 1.8365 5.3445
Species 2 ethylene 0.68 282.3 50.4 131 0.281 0.087 1.0384 0.0833 -0.3143 -0.0078 0.6120 0.5934
Vc dB0 dB1
Cross-Parameters kij Tc (K) Pc (bar) (cm3/mol) Zc  Tr Pr B0 B1 dTr dTr
0 348.7332 63.06 126.4 0.2750 0.1660 0.8406 0.0666 -0.4741 -0.2176 1.0601 1.7809
i   j
3
2nd Virial Coefficients (cm /mol)
0.422
B11 -398 ij  B 0 0.083
2 Tr1.6
B12 -235 Pcij  Z cij  B1 0.139
Vcij 2 Tr4.2
3
Derivatives of 2nd Virial Coefficients (cm 3/((mol K))  V 1/ 3  Vcj1/ 3  RTcij
dB11/dT 3.32 Vcij   ci

 2


Bij 
Pcij
B 0
 ij B1 
dB22/dT 1.09
dB12/dT 1.79
R  dBij 
0 1
dBij dBij dB0 0.675 dBij1 0.722
    , with ij  and  5.2
Mixture 2nd Virial Coefficient (cm 3/mol) dT Pc  dTr dTr  dTr Tr2.6 dTr Tr
 
B -211
3
dB/dT 1.62
dB 2 dB11 dB dB
Mixture Properties:  y1  2 y1 y2 12  y22 22
Z 0.9637
RT dB dB
GR (J/mol) -88.5 V B, G R  BP , H R  BP  TP , and S R   P
SR (J/(mol K)) -0.682
and then and
Updated 4/5/2017 p. 46 of 53
Updated 4/5/2017 p. 47 of 53
has the same sign over the whole composition range, both and
Updated 4/5/2017 p. 48 of 53
2
ME
MEbar1
1.5
MEbar2
ME values
0.5
-0.5
0 0.2 0.4 0.6 0.8 1
xi
35
30
25
ME
ME values
20
MEbar1
15 MEbar2
10
0
0 0.2 0.4 0.6 0.8 1
xi
Updated 4/5/2017 p. 49 of 53
Updated 4/5/2017 p. 50 of 53
Updated 4/5/2017 p. 51 of 53
. Therefore the sign of is the same as the sign of . Similarly, at
, and by the same argument the sign of is of opposite sign as the
T (K) GE (J/mol) HE (J/mol)

283.15 544 932.1
303.15 513 893.4
323.15 494.2 845.9
Updated 4/5/2017 p. 52 of 53
Updated 4/5/2017 p. 53 of 53

Svnas 8e Ism Chapter 10

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Svnas 8e Ism Chapter 10

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SVNAS 8th Edition Annotated Solutions Chapter 10

Siig T , P   Siig T , pi   Siig T , P   R ln yi

Siig T , P   Siig T , pi   Siig T , P   R ln yi

T1 (K) T2 (K) A B (1/K) C (1/K2) D (K2) ICPH (K) H (J/mol)

T1 (K) T2 (K) A B (1/K) C (1/K2) D (K2) ICPS S (J/(mol K))

T1 (K) T2 (K) A B (1/K) C (1/K2) D (K2) ICPH (K) H (J/mol)

T1 (K) T2 (K) A B (1/K) C (1/K2) D (K2) ICPS S (J/(mol K))

a0  a1 x1  a2 x12  a1  2a2 x1  a1 x1  2a2 x12

a0  a1  2a1 x1  2a2 x1  3a2 x12

a0  2a1 x2  3a2 x12

SVA problem 11.13(e)

x1 H1  x2 H 2  x1  a1  b1 x1   b1 x12 x2  b2 x1 x22  x2  a2  b2 x2   b2 x1 x22  b1 x12 x2

T (K) P (bar) Tc (K) Pc (bar) 

T (K) P (bar) Tc (K) Pc (bar)  Tr Pr

Interpolated for Pr=2 0.7873 1.1851

Using appropriate Using 2nd virial

T (K) P (bar) Tc (K) Pc (bar)  Tr Pr

T (K) P (bar) Tc (K) Pc (bar) 

T (K) P (bar) Tc (K) Pc (bar)  Tr Pr

Interpolated for Pr=2 0.7482 1.1795

fi  isat Pi sat exp 

T (K) P (bar) Tc (K) Pc (bar) 

 107.5 cm3 mol-1  275  5.267  bar 

fi  19.65 cm3 mol-1 150  4.76  bar 

G final  Ginitial  i T   RT ln f final  i T   RT ln f initial

f final  G final  Ginitial   G   H S 

G final  Ginitial  i T   RT ln f final  i T   RT ln f initial

f final  G final  Ginitial   G   H S 

fi  isat Pi sat exp 

T (K) P (bar) Tc (K) Pc (bar) 

 119.4 cm3 mol-1  200  1.01 bar 

fi  isat Pi sat exp 

T (K) P (bar) Tc (K) Pc (bar) 

fi  isat Pi sat exp 

fi  isat Pi sat exp 

T (K) P (bar) Tc (K) Pc (bar) 

fi  isat Pi sat exp 

T (K) Psat (bar) Tc (K) Pc (bar)  Vc (cm3/mol) Zc

Tr B0 B1 Vsat (cm3 /mol) P (bar)  f (bar)

fi  isat Pi sat exp 

Fugacity and Fugacity Coefficient of Chloroform at 200 °C

fˆethylene  ˆethylene yethylene P  0.957*0.35*30 bar  10.05 bar

T (K) P (bar) Tc (K) Pc (bar) 

T (K) P (bar) Tc (K) Pc (bar) 

 ik   ki  2 Bik  Bii  Bkk

13 (cm /mol)

T (K) P (bar) Tc (K) Pc (bar) 

T (K) P (bar) Tc (K) Pc (bar) 

T (K) P (bar) Tc (K) Pc (bar) 

B  y12 B11  2 y1 y2 B12  y22 B22

isa function of T only:

dBij RTc  dBij0 dBij1  dBij0 0.675 dBij1 0.722

2nd Virial Coefficients (cm 3/mol) i   j

and then and

. Therefore the sign of is the same as the sign of . Similarly, at

, and by the same argument the sign of is of opposite sign as the

T (K) GE (J/mol) HE (J/mol)

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fˆethylene  ˆethylene yethylene P  0.9570.3530 bar  10.05 bar