Chapter 11 - Section A - Mathcad Solutions

11.1 For an ideal gas mole fraction = volume fraction

3
CO2 (1): x1  0.7 V1  0.7m
N2 (2): x2  0.3 V2  0.3m
3

i  1  2 P  1bar T  (25  273.15)K

P˜
¦ Vi
i
n n 40.342 mol
R˜ T
J
'S  n˜ R˜
¦ xi˜ lnxi 'S 204.885
K
Ans.
i
11.2 For a closed, adiabatic, fixed-volume system, 'U =0. Also, for an ideal
gas, 'U = Cv 'T. First calculate the equilibrium T and P.
nN2  4˜ mol TN2  [(75  273.15)K
˜ ] PN2  30˜ bar

nAr  2.5˜ mol TAr  (130  273.15)K

˜ PAr  20˜ bar

TN2 348.15 K TAr 403.15 K

i  1  2
nN2 nAr
ntotal  nN2  nAr x1  x2 
ntotal ntotal

x1 0.615 x2 0.385

3 5
CvAr  ˜R CvN2  ˜R
2 2

CpAr  CvAr  R CpN2  CvN2  R

Find T after mixing by energy balance:
TN2  TAr
T (guess)
2
Given nN2˜ CvN2˜ T  TN2 = nAr˜ CvAr˜ TAr  T T  Find(T)

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 T  273.15˜ K 90 degC

Find P after mixing:

PN2  PAr
P (guess)
2
Given

nN2  nAr ˜ R˜ T = nN2˜ R˜ TN2


nAr˜ R˜ TAr
P PN2 PAr

P  Find ( P) P 24.38 bar

Calculate entropy change by two-step path:
1) Bring individual stream to mixture T and P.
2) Then mix streams at mixture T and P.

'SN2  nN2˜ §¨ CpN2˜ ln §¨

T ·
 R˜ ln §¨
P ·· J
'SN2 11.806
© © TN2 ¹ © PN2 ¹ ¹ K

'SAr  nAr˜ §¨ CpAr˜ ln §¨

T ·
 R˜ ln §¨
P ·· J
'SAr 9.547
© © TAr ¹ © PAr ¹ ¹ K

J
'Smix  ntotal˜ ª R˜
« ¦ xi˜lnxi º
»
'Smix 36.006
K
¬ i ¼
J
'S  'SN2 ''SAr  Smix 'S 38.27 Ans.
K

kg kg
11.3 mdotN2  2˜ mdotH2  0.5˜
sec sec

gm gm
molwtN2  28.014˜ molwtH2  2.016˜ i  1  2
mol mol

mdotN2 mdotH2
molarflowN2  molarflowH2 
molwtN2 molwtH2

mol
molarflowtotal  molarflowN2  molarflowH2 molarflowtotal 319.409
sec

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 molarflowN2 molarflowH2
y1  y1 0.224 y2  y2 0.776
molarflowtotal molarflowtotal

J
'S  R˜ molarflowtotal˜
¦ yi˜ lnyi 'S 1411
˜
secK
Ans.
i

11.4 T1  448.15˜ K T2  308.15˜ K P1  3˜ bar P2  1˜ bar

For methane:


MCPHm  MCPH T1  T2  1.702  9.081˜ 10
3 6
 2.164˜ 10  0.0

MCPS T1  T2  1.702  9.081˜ 10  2.164˜ 10  0.0

3 6
MCPSm 
For ethane:


MCPHe  MCPH T1  T2  1.131  19.225˜ 10
3 6
 5.561˜ 10  0.0

MCPS T1  T2  1.131  19.225˜ 10  5.561˜ 10  0.0

3 6
MCPSe 

MCPHmix  0.5˜ MCPHm  0.5˜ MCPHe MCPHmix 6.21

MCPSmix  0.5˜ MCPSm  0.5˜ MCPSe MCPSmix 6.161

J
'H  R˜ MCPHmix˜ T2  T1 'H 7228
mol
§ T2 · § P2 ·
'S  R˜ MCPSmix˜ ln ¨  R˜ ln ¨  R˜ 2˜ 0.5˜ ln (0.5)
© T1 ¹ © P1 ¹
The last term is the entropy change of UNmixing
J
'S 15.813 TV  300˜ K
mol˜ K
J
Wideal  'H  TV ˜ 'S Wideal 2484 Ans.
mol

11.5 Basis: 1 mole entering air.

y1  0.21 y2  0.79 K t  0.05 TV  300˜ K
Assume ideal gases; then 'H = 0
The entropy change of mixing for ideal gases is given by the equation
following Eq. (11.26). For UNmixing of a binary mixture it becomes:

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 J
'S  R˜ y1˜ ln y1  y2˜ ln y2 'S 4.273
mol˜ K
3 J
By Eq. (5.27): Wideal  '
TV ˜ S Wideal 1.282 u 10
mol
Wideal J
By Eq. (5.28): Work  Work 25638 Ans.
Kt mol

11.16 § 0 · § 1.000 ·
¨ 10 ¨ 0.985
¨ ¸ ¨ ¸
¨ 20 ¸ ¨ 0.970 ¸ lnI1  0 I1  1
¨ 40 ¸ ¨ 0.942 ¸
¨ ¸ ¨ ¸
¨ 60 ¸ ¨ 0.913 ¸
P  ¨ 80 ¸ ˜ bar Z  ¨ 0.885 ¸
¨ ¸ ¨ ¸ end  rows ( P)
¨ 100 ¸ ¨ 0.869 ¸
¨ 200 ¸ ¨ 0.765 ¸ i  2  end
¨ ¸ ¨ ¸
¨ 300 ¸ ¨ 0.762 ¸
Zi  1
¨ 400 ¸ ¨ 0.824 ¸ Fi 
¨ ¨ Pi
© 500 ¹ © 0.910 ¹
Fi is a well behaved function; use the trapezoidal rule to integrate Eq.
(11.35) numerically.

Fi  Fi  1
Ai  ˜ Pi  Pi1 lnIi  lnIi1  Ai
2

I i  exp lnIi fi  I i˜ Pi
Generalized correlation for fugacity coefficient:

For CO2: Tc  304.2˜ K Pc  73.83˜ bar Z  0.224

T
T  ( 150  273.15) ˜ K Tr  Tr 1.391
Tc

ª P º
« Pc »
I G ( P)  exp « ˜ B0 Tr  Z ˜ B1 Tr » fG ( P)  I G ( P) ˜ P
¬ T r ¼
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 Pi fi
bar Ii bar
10 0.993 9.925
Calculate values:
20 0.978 19.555
40 0.949 37.973
60 0.922 55.332
80 0.896 71.676
100 0.872 87.167
200 0.77 153.964
300 0.698 209.299
400 0.656 262.377
500 0.636 317.96

400

fi 300
0.8
Ii bar
200
I G Pi fG Pi
0.6 bar
100

0.4 0
0 200 400 600 0 200 400 600
Pi Pi
bar bar

Agreement looks good up to about 200 bar (Pr=2.7 @ Tr=1.39)

11.17 For SO2: Tc  430.8˜ K Pc  78.84˜ bar Z  0.245

T  600˜ K P  300˜ bar

T P
Tr  Tr 1.393 Pr  Pr 3.805
Tc Pc

For the given conditions, we see from Fig. 3.14 that the Lee/Kesler
correlation is appropriate.

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 Data from Tables E.15 & E.16 and by Eq. (11.67):
Z
I 0  0.672 I 1  1.354 II 0˜ I 1 I 0.724

f  I˜ P GRRT  ln I

f 217.14 bar GRRT 0.323 Ans.

11.18 Isobutylene: Tc  417.9˜ K Pc  40.00˜ bar Z  0.194

a) At 280 degC and 20 bar: T  (280  273.15)K
˜ P  20˜ bar

T P
Tr (T) Tr (T) 1.3236 Pr (P) Pr (P) 0.5
Tc Pc
At these conditions use the generalized virial-coeffieicnt correlation.


f  PHIB Tr (T)P
Zr (P) ˜P f 18.76 bar Ans.

b) At 280 degC and 100 bar: T  (280  273.15)K

˜ P  100˜ bar

Tr (T) 1.3236 Pr (P) 2.5

At these conditions use the Lee/Kesler correlation, Tables E.15 & E.16 and
Eq. (11.67).
Z
I0  0.7025 I1  1.2335 II 0˜ I1 f  I˜ P

I 0.732 f 73.169 bar Ans.

11.19 The following vectors contain data for Parts (a) and (b):
(a) = Cyclopentane; (b) = 1-butene

§ 511.8 · § 45.02 · § 0.196 ·

Tc  ¨ ˜K Pc  ¨ ˜ bar Z ¨
© 420.0 ¹ © 40.43 ¹ © 0.191 ¹
§ 0.273 · § 258 · cm3 § 322.4 ·
Zc  ¨ Vc  ¨ ˜ Tn  ¨ ˜K
© 0.277 ¹ © 239.3 ¹ mol © 266.9 ¹
§ 383.15 · § 275 · § 5.267 ·
T ¨ ˜K P ¨ ˜ bar Psat  ¨ ˜ bar
© 393.15 ¹ © 34 ¹ © 25.83 ¹
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o o
T § 0.7486 · Psat § 0.117 ·
Tr  Tr ¨ Psatr  Psatr ¨
Tc © 0.9361 ¹ Pc © 0.6389 ¹
Calculate the fugacity coefficient at the vapor pressure by Eq. (11.68):

(a) 
PHIB Tr Z
1
Psatr  1
1
0.900
(b) PHIBTr Z
Psatr  2 0.76
2 2
Eq. (3.72), the Rackett equation:

o
T § 0.749 ·
Tr  Tr ¨
Tc © 0.936 ¹
Eq. (11.44):
o
ª 2 º
« »
1Tr 7
§ 107.546 · cm3
Vsat  «¬ Vc˜ Zc »
¼ Vsat ¨
© 133.299 ¹ mol
 o
ª ª ˜  ºº

f  « PHIB Tr Z
Psatr  ˜ Psat˜ exp «
Vsat (
P
R˜ T
Psat )
»»
¬ ¬ ¼¼
§ 11.78 ·
f ¨ bar Ans.
© 20.29 ¹

gm
11.21 Table F.1, 150 degC: Psat  476.00˜ kPa molwt  18˜
mol
3
cm
Vsat  1.091˜ ˜ molwt
gm T  (150  273.15)K
˜ P  150˜ bar

3
cm
Vsat 19.638 T 423.15 K
mol

Equation Eq. (11.44) with IsatPsat = fsat

ª Vsat˜ P  Psat º f
r  exp « » r 1.084 r= = 1.084 Ans.
¬ R˜ T ¼ fsat

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 gm
11.22 The following vectors contain data for Parts (a) and (b): molwt  18˜
mol
Table F.2: (a) 9000 kPa & 400 degC; (b) 1000(psia) & 800 degF:

ª ( 400  273.15) ˜ K º
T1  « »
¬ ( 800  459.67) ˜ rankine ¼
§ 3121.2˜ J · § 6.2915˜ J ·
¨ ¨
gm ¸ gm˜ K
H1  ¨ S1  ¨ ¸
¨ Btu ¸ ¨ Btu ¸
¨ 1389.6 ˜ ¨ 1.5677˜
© lbm ¹ © lbm˜ rankine ¹

Table F.2: (a) 300 kPa & 400 degC; (b) 50(psia) & 800 degF: T2  T1

§ 3275.2˜ J · § 8.0338˜ J ·
¨ ¨
gm ¸ gm˜ K
H2  ¨ S2  ¨ ¸
¨ Btu ¸ ¨ Btu ¸
¨ 1431.7 ˜ ¨ 1.9227 ˜
© lbm ¹ © lbm˜ rankine ¹

Eq. (A) on page 399 may be recast for this problem as:
 o
ª molwt ª 2
H  H ºº § 0.0377 ·
 S2  S1 » »
1
r  exp « ˜« r ¨
¬ R ¬ T1 ¼¼ © 0.0542 ¹
f2 f2
(a) r= = 0.0377 (b) r= = 0.0542 Ans.
f1 f1

11.23 The following vectors contain data for Parts (a), (b), and (c):
(a) = n-pentane (b) = Isobutylene (c) = 1-Butene:

§¨ 469.7 · §¨ 33.70 · §¨ 0.252 ·

Tc  ¨ 417.9 ¸ ˜ K Pc  ¨ 40.0 ¸ ˜ bar Z  ¨ 0.194 ¸
¨ 420.0 ¨ 40.43 ¨ 0.191
© ¹ © ¹ © ¹
§¨ 0.270 · §¨ 313.0 · 3 §¨ 309.2 ·
cm
Zc  ¨ 0.275 ¸ Vc  ¨ 238.9 ¸ ˜ Tn  ¨ 266.3 ¸ ˜ K
¨ 0.277 ¨ 239.3 mol ¨ 266.9
© ¹ © ¹ © ¹
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 §¨ 200 · §¨ 1.01325 ·
P  ¨ 300 ¸ ˜ bar Psat  ¨ 1.01325 ¸ ˜ bar
¨ 150 ¨ 1.01325
© ¹ © ¹

o §¨ 0.6583 · o §¨ 0.0301 ·
Tn Psat
Tr  Tr ¨ 0.6372 ¸ Pr  Pr ¨ 0.0253 ¸
Tc ¨ 0.6355 Pc ¨ 0.0251
© ¹ © ¹
Calculate the fugacity coefficient at the nbp by Eq. (11.68):

(a) 
PHIB Tr Z
1
Pr  1
1
0.9572
(b)  2 2
PHIB Tr Z
Pr  2 0.9618
(c) PHIBTr Z
Pr  3 0.9620
3 3

o
ª 1Tr 0.2857 º
Eq. (3.72): Vsat  «¬ Vc˜ Zc »
¼
 o
ª ª ˜  ºº
Eq. (11.44): f  « PHIB Tr Z 
Pr  ˜ Psat˜ exp «
Vsat (P
R˜ Tn
Psat )
» »
¬ ¬ ¼¼
§¨ 2.445 ·
f ¨ 3.326 ¸ bar Ans.
¨ 1.801
© ¹

11.24 (a) Chloroform: Tc  536.4˜ K Pc  54.72˜ bar Z  0.222

3
cm
Zc  0.293 Vc  239.0˜ Tn  334.3˜ K Psat  22.27˜ bar
mol

T Tn
T  473.15˜ K Tr  Tr 0.882 Trn  Trn 0.623
Tc Tc
2

1Trn 7
cm
3
Eq. (3.72): Vsat  Vc˜ Zc Vsat 94.41
mol

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 Calculate fugacity coefficients by Eqs. (11.68):

P ª Pr ( P ) º
Pr ( P )  I ( P)  exp « 
˜ B0 Tr  Z ˜ B1 Tr »
Pc ¬ Tr ¼
ª
f ( P)  if « P dIPsat I ( P) ˜ P  ( Psat) ˜ Psat˜ exp «
ª Vsat˜ ( P  Psat) º º
»»
¬ ¬ R˜ T ¼¼

ª
I ( P)  if « P dIPsat I ( P)  ( Psat) ˜
Psat ª Vsat˜ ( P  Psat) º º
˜ exp « »»
¬ P ¬ R˜ T ¼¼
P  0˜ bar  0.5˜ bar  40˜ bar

40

Psat Psat
30
f ( P) bar bar
0.8
bar
20 I ( P)
P
bar 0.6
10

0 0.4
0 20 40 0 20 40
P P P

bar bar bar

(b) Isobutane Tc  408.1˜ K Pc  36.48˜ bar Z  0.181

3
cm
Zc  0.282 Vc  262.7˜ Tn  261.4˜ K Psat  5.28˜ bar
mol

T Tn
T  313.15˜ K Tr  Tr 0.767 Trn  Trn 0.641
Tc Tc
2

1Trn 7
cm
3
Eq. (3.72): Vsat  Vc˜ Zc Vsat 102.107
mol

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 Calculate fugacity coefficients by Eq. (11.68):

P ª Pr (P) º
Pr (P) I (P) exp « 
˜ B0 Tr  Z ˜ B1 Tr »
Pc ¬ Tr ¼
ª
( ) if« P dIPsat I (P)P
˜  (Psat)Psat
˜ ˜ exp «
ª Vsat˜ (P  Psat)º º
fP »»
¬ ¬ R˜ T ¼¼

ª
I (P) if« P dIPsat I (P) (Psat)˜
Psat ª Vsat˜ (P  Psat)º º
˜ exp « »»
¬ P ¬ R˜ T ¼¼
P  0˜ bar  0.5˜ bar  10˜ bar

10

Psat Psat
bar bar
fP
() 0.8
bar
5 I (P)
P
bar 0.6

0 0.4
0 5 10 0 5 10
P P P

bar bar bar

11.25 Ethylene = species 1; Propylene = species 2

§ 282.3 · § 50.40 · § 0.087 ·

Tc  ¨ ˜K Pc  ¨ ˜ bar w ¨
© 365.6 ¹ © 46.65 ¹ © 0.140 ¹
§ 0.281 · § 131.0 · cm3
Zc  ¨ Vc  ¨ ˜
© 0.289 ¹ © 188.4 ¹ mol
T  423.15˜ K P  30˜ bar y1  0.35 y2  1  y1
n 2 i  1  n j 1  n k  1  n

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 By Eqs. (11.70) through (11.74)
wi  w j Zci  Zc j
Zi  j  Tc  Tci˜ Tc j Zc 
2 i j i j 2
3
ª 1 1º
« Vc 3
 Vc j
3» Zc ˜ R˜ Tc
i i j i j
Vc  « » Pc 
i j ¬ 2 ¼ i j Vc
i j

T § 1.499 1.317 ·
Tr
i j
 Tr ¨
Tc
i j © 1.317 1.157 ¹
§ 131 157.966 · cm3 § 50.345 48.189 ·
Vc ¨ Pc ¨ bar
© 157.966 188.4 ¹ mol © 48.189 46.627 ¹
§ 0.087 0.114 · § 282.3 321.261 · § 0.281 0.285 ·
Z ¨ Tc ¨ K Zc ¨
© 0.114 0.14 ¹ © 321.261 365.6 ¹ © 0.285 0.289 ¹
By Eqs. (3.65) and (3.66):

B0i  j  B0 Tr  i j
B1i  j  B1 Tr  i j

§ 0.138 0.189 · § 0.108 0.085 ·

B0 ¨ B1 ¨
© 0.189 0.251 ¹ © 0.085 0.046 ¹
R˜ Tc
§ 59.892 99.181 · cm3
˜ B0i  j  Z i  j˜ B1i  j
i j
Bi  j  B ¨
Pc
i j © 99.181 159.43 ¹ mol
By Eq. (11.64):

G i  j  2˜ B i  j  B i  i  B j  j § 0 20.96 · cm3
G ¨
© 20.96 0 ¹ mol

Ihatk  exp ǻ
P ª ºº
¦ ¦ ª¬yi˜y j˜2˜GG i  k 
1
˜ « Bk  k  ˜ i j º¼ » »
« R˜ T « 2 »»
¬ ¬ i j ¼¼

§ 0.957 · § 10.053 ·
fhatk  Ihatk˜ yk˜ P Ihat ¨ fhat ¨ bar Ans.
© 0.875 ¹ © 17.059 ¹
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 For an ideal solution , Iid = I pure species

§ 0.595 · ª Pr k º
Iidk  exp « ˜ B0k  k  Z k  k˜ B1k  k »
P
Pr  Pr ¨
k Pck © 0.643 ¹ « Tr »
¬ kk ¼
§ 0.95 · § 9.978 ·
fhatid  Iidk˜ yk˜ P Iid ¨ fhatid ¨ bar Ans.
k
© 0.873 ¹ © 17.022 ¹
Alternatively,

ª Pr k  k º § 0.95 ·
Iidk  exp « ˜ B0k  k  Z k  k˜ B1k  k »
P
Pr  Iid ¨
i j Pc « Tr » © 0.873 ¹
i j ¬ kk ¼

11.27 Methane = species 1

Ethane = species 2 T  373.15˜ K P  35˜ bar
Propane = species 3

§¨ 0.21 · §¨ 0.012 · §¨ 0.286 ·

y  ¨ 0.43 ¸ w  ¨ 0.100 ¸ Zc  ¨ 0.279 ¸
¨ 0.36 ¨ 0.152 ¨ 0.276
© ¹ © ¹ © ¹
§¨ 190.6 · §¨ 45.99 · §¨ 98.6 · 3
cm
Tc  ¨ 305.3 ¸ ˜ K Pc  ¨ 48.72 ¸ ˜ bar Vc  ¨ 145.5 ¸ ˜
¨ 369.8 ¨ 42.48 ¨ 200.0 mol
© ¹ © ¹ © ¹
n 3 i  1  n j  1  n k  1  n
By Eqs. (11.70) through (11.74)

wi  w j Zci  Zc j
Zi  j  Tc  Tci˜ Tc j Zc 
2 i j i j 2

3
ª 1 1º
« Vc 3
 Vc j
3» Zc ˜ R˜ Tc
i i j i j
Vc  « » Pc 
i j ¬ 2 ¼ i j Vc
i j

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 §¨ 1.958 1.547 1.406 ·
T
Tr
i j
 Tr ¨ 1.547 1.222 1.111 ¸
Tc ¨ 1.406 1.111 1.009
i j
© ¹
§¨ 98.6 120.533 143.378 · 3
cm
Vc ¨ 120.533 145.5 171.308 ¸
¨ 143.378 171.308 200 mol
© ¹
§¨ 45.964 47.005 43.259 · §¨ 0.012 0.056 0.082 ·
Pc ¨ 47.005 48.672 45.253 ¸ bar Z ¨ 0.056 0.1 0.126 ¸
¨ 43.259 45.253 42.428 ¨ 0.082 0.126 0.152
© ¹ © ¹
§¨ 190.6 241.226 265.488 · §¨ 0.286 0.282 0.281 ·
Tc ¨ 241.226 305.3 336.006 ¸ K Zc ¨ 0.282 0.279 0.278 ¸
¨ 265.488 336.006 369.8 ¨ 0.281 0.278 0.276
© ¹ © ¹
By Eqs. (3.65) and (3.66):

B0i  j  B0 Tr  i j
B1i  j  B1 Tr 
i j

R˜ Tc
˜ B0i  j  Z i  j˜ B1i  j
i j
Bi  j 
Pc
i j

By Eq. (11.64):
§¨ 0 30.442 107.809 ·
3
cm
G i  j  2˜ B i  j  B i  i  B j  j G ¨ 30.442 0 23.482 ¸
¨ 107.809 23.482 mol
© 0 ¹

Ihatk  exp ǻ
P ª ºº
¦ ¦ ª¬yi˜y j˜2˜GG i  k 
1
˜ « Bk  k  ˜ i j º¼ » »
« R˜ T « 2 »»
¬ ¬ i j ¼¼
fhatk  Ihatk˜ yk˜ P §¨ 1.019 · §¨ 7.491 ·
Ihat ¨ 0.881 ¸ fhat ¨ 13.254 ¸ bar Ans.
¨ 0.775 ¨ 9.764
© ¹ © ¹

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 For an ideal solution , Iid = I pure species

§¨ 0.761 ·
ª Prk º
˜ B0k  k  Z k  k˜ B1k  k »
P
Prk  Pr ¨ 0.718 ¸ Iidk  exp «
Pck ¨ 0.824 Tr
© ¹ ¬ kk ¼

§¨ 0.977 · §¨ 7.182 ·
fhatid  Iidk˜ yk˜ P Iid
k
¨ 0.88 ¸ fhatid ¨ 13.251 ¸ bar Ans.
¨ 0.759 ¨ 9.569
© ¹ © ¹

GE
11.28 Given: = 2.6˜ x1  1.8˜ x2 ˜ x1˜ x2
RT
(a) Substitute x2 = 1 - x1:

GE
= .8˜ x1  1.8 ˜ x1˜ 1  x1 = 1.8˜ x1  x1  0.8˜ x1
2 3
RT

Apply Eqs. (11.15) & (11.16) for M = GE/RT:

d §¨
GE ·
d §¨
GE ·

 1  x1 ˜ ©
RT ¹
 x1˜ ©
GE GE RT ¹
lnJ1 = lnJ2 =
RT dx1 RT dx1

d¨
§ GE ·
© RT ¹ = 1.8  2˜ x  2.4˜ x 2
1 1
dx1

2 3
lnJ1 = 1.8  2˜ x1  1.4˜ x1  1.6˜ x1
Ans.
2 3
lnJ2 = x1  1.6˜ x1

(b) Apply Eq. (11.100):

GE
 2 3
= x1˜ 1.8  2˜ x1  1.4˜ x1  1.6˜ x1 

RT
 1  x1 ˜ x1  1.6˜ x1
2 3

This reduces to the initial condition:

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 (c) Divide Gibbs/Duhem eqn. (11.100) by dx1:

x1˜

d lnJ1
 x2˜

d lnJ2
= 0
dx1 dx1

Differentiate answers to Part (a):


d lnJ1
= 2  2.8˜ x1  4.8˜ x1
2 
d lnJ2
= 2˜ x1  4.8˜ x1
2
dx1 dx1

x1˜

d lnJ1 2
= 2˜ x1  2.8˜ x1  4.8˜ x1
3
dx1

x2˜

d lnJ1

= 1  x1 ˜ 2˜ x1  4.8˜ x1
2
dx1

These two equations sum to zero in agreement with the

Gibbs/Duhem equation.

(d) When x1 = 1, we see 

d lnJ1
= 0 Q.E.D.
from the 2nd eq. of
Part (c) that dx1

When x1 = 0, we see 
d lnJ2
= 0 Q.E.D.
from the 3rd eq. of
Part (c) that dx1

(e) DEFINE: g = GE/RT

gx1  1.8˜ x1  x1  0.8˜ x1
2 3

lnJ1 x1  1.8  2˜ x1  1.4˜ x1  1.6˜ x1

2 3

lnJ2 x1  x1  1.6˜ x1

2 3

lnJ1 ()
0 1.8 lnJ2 ()
1 2.6 x1  0  0.1  1.0

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 0

gx1 1

lnJ1 x1 lnJ1 (0)

lnJ2 x1
2
lnJ2 (1)

3
0 0.2 0.4 0.6 0.8
x1
H
H1bar
H2bar

§ 0.02715 · § 87.5 ·
¨ ¨
11.32 ¨ 0.09329 ¸ ¨ 265.6 ¸
¨ 0.17490 ¸ ¨ 417.4 ¸
¨ ¸ ¨ 253 ¸
¨ 0.32760 ¸ ¨ 534.5 ¸
¨ 0.40244 ¸ ¨ 531.7 ¸
¨ ¸ ¨ ¸
¨ 0.56689 ¸ ¨ 421.1 ¸
¨ 0.63128 ¸ ¨ 347.1 ¸
¨ ¸ ¨ ¸
¨ 0.66233 ¸ ¨ 321.7 ¸
x1  VE  n  rowsx1 i 1  n
¨ 0.69984 ¸ ¨ 276.4 ¸
¨ ¸ ¨ ¸ x1  0  0.01  1
¨ 0.72792 ¸ ¨ 252.9 ¸
¨ 0.77514 ¸ ¨ 190.7 ¸
¨ ¸ ¨ ¸
0.79243 178.1
¨ ¸ ¨ ¸
¨ 0.82954 ¸ ¨ 138.4 ¸
¨ 0.86835 ¸ ¨ 98.4 ¸
¨ ¸ ¨ ¸
¨ 0.93287 ¸ ¨ 37.6 ¸
¨ 0.98233 ¨ 10.0
© ¹ © ¹
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 (a) Guess: a  3000 b  3000 c  250

ª x1˜ 1  x1 º § 3.448 u 103 ·

« » §¨ a · §¨ a · ¨
F x1  « x1 ˜ 1  x1 »  1  VE  F
2 Ans.
¨ b ¸  linfitx ¨b ¸ ¨ 3.202 u 103 ¸
« » ¨c ¨c ¨
« x13˜ 1  x1 » © ¹ © ¹ © 244.615 ¹
¬ ¼
600

VEi 400

x1˜ ( 1x1) ˜ ª¬ ab˜ x1c˜ ( x1)

2º
¼ 200

0
0 0.2 0.4 0.6 0.8
x1  x1
i

By definition of the excess properties

V = x1˜ x2˜ ª¬ a  b˜ x1  c˜ x1 º¼
E 2

V = 4˜ c˜ x1  3˜ ( c  b) ˜ x1
d E 3 2
 2˜ ( b  a) ˜ x1  a
dx1

Vbar1 E = x2 2˜ ª¬ a  2˜ b˜ x1  3˜ c˜ x1 2 º¼

Vbar2 E = x1 2˜ ª¬ a  b  2˜ (b  c)˜ x1  3˜ c˜ x1 2 º¼
(b) To find the maximum, set dVE/dx1 = 0 and solve for x1. Then use x1 to
find VEmax.

Guess: x1  0.5

Given
3 2
4˜ c˜ ( x1)  3˜ ( c  b) ˜ ( x1)  2˜ ( b  a) ˜ x1  a = 0

x1  Find ( x1) x1 0.353 Ans.

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VEmax  x1˜ (1  x1)˜ a  b˜ x1  c˜ x1
2
VEmax 536.294 Ans.

(c) VEbar1 (x1) (1  x1)2˜ ª¬ a  2˜ b˜ x1  3˜ c˜ (x1)2 º¼

VEbar2 (x1) (x1) ˜ ª¬ a  b  2˜ (b  c)˜ x1  3˜ c˜ (x1) º¼

2 2

x1  0  0.01  1

4000

2000
VEbar 1 (x1)

VEbar 2 (x1)
0

2000
0 0.2 0.4 0.6 0.8
x1  x1

Discussion:
a) Partial property for species i goes to zero WITH ZERO SLOPE as xi -> 1.
b) Interior extrema come in pairs: VEbar min for species 1 occurs at the
same x1 as VEbar max for species 2, and both occur at an inflection point on
the VE vs. x1 plot.
c) At the point where the VEbar lines cross, the VE plot shows a maximum.

11.33 Propane = 1; n-Pentane = 2

T  (75  273.15)K
˜ P  2˜ bar y1  0.5 y2  1  y1

§ 276 466 · cm3

B ¨ ˜ n 2 i  1  n j  1  n
© 466 809 ¹ mol
3
By Eq. (11.61): B
¦ ¦ yi˜y j˜Bi  j B 504.25
cm
mol
i j

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 Use a spline fit of B as a function of T to
find derivatives:
§¨ 331 · 3 §¨ 980 · 3 §¨ 558 · 3
cm cm cm
b11  ¨ 276 ¸ ˜ b22  ¨ 809 ¸ ˜ b12  ¨ 466 ¸ ˜
¨ 235 mol ¨ 684 mol ¨ 399 mol
© ¹ © ¹ © ¹

ª«§¨ 50 · »º §¨ 323.15 ·
t  «¨ 75 ¸  273.15» ˜ K t ¨ 348.15 ¸ K
«¨ 100 » ¨ 373.15
¬© ¹ ¼ © ¹
3
cm
vs11  lspline ( t  b11) B11 ( T)  interp ( vs11  t  b11  T) B11 ( T) 276
mol
3
cm
vs22  lspline ( t  b22) B22 ( T)  interp ( vs22  t  b22  T) B22 ( T) 809
mol
3
cm
vs12  lspline ( t  b12) B12 ( T)  interp ( vs12  t  b12  T) B12 ( T) 466
mol

§d d ·
¨ B11 ( T) B12 ( T)
dT dT § 1.92 3.18 · cm3
dBdT  ¨ ¸ dBdT ¨
¨d d ¸ © 3.18 5.92 ¹ mol˜ K
¨ B12 ( T) B22 ( T)
© dT dT ¹
3
cm
Differentiate Eq. (11.61): dBdT 
¦ ¦ yi˜ yj˜ dBdTi dBdT
j 3.55
mol˜ K
i j
B˜ P Z˜ R˜ T
By Eq. (3.38): Z  1  Z 0.965 V
R˜ T P

P §B ·
By Eq. (6.55): HRRT  ˜ ¨  dBdT HRRT 0.12 HR  HRRT˜ R˜ T
R ©T ¹
P
By Eq. (6.56): SRR   ˜ dBdT SRR 0.085 SR  SRR˜ R
R
3
cm J J
V 13968 HR 348.037 SR 0.71 Ans.
mol mol mol˜ K

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 11.34 Propane = 1; n-Pentane = 2

T  (75  273.15)K
˜ P  2˜ bar y1  0.5 y2  1  y1

§ 276 466 · cm3 n 2 i 1  n

B ¨ ˜
© 466 809 ¹ mol j 1  n

G i j 2˜ Bi j Bii
  B j j

By Eqs. (11.63a) and (11.63b):

Ihat1 (y1) exp ª«

P ª º
˜ ¬ B1  1  (1  y1) ˜ G 1  2 º¼ »
2
¬ R˜ T ¼

Ihat2 (y1) exp « 

ª P ˜ B  y12˜ G
22
º
12 »
¬ R˜ T ¼
y1  0  0.1  1.0
1

0.99

0.98

Ihat1 (y1)
0.97
Ihat2 (y1)

0.96

0.95

0.94
0 0.2 0.4 0.6 0.8
y1

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 § 0.0426 · § 23.3 ·
¨ ¨
11.36 ¨ 0.0817 ¸ ¨ 45.7 ¸
¨ 0.1177 ¸ ¨ 66.5 ¸
¨ ¸ ¨ ¸
¨ 0.1510 ¸ ¨  86.6 ¸
¨ 0.2107 ¸ ¨ 118.2 ¸
¨ ¸ ¨ ¸
¨ 0.2624 ¸ ¨  144.6 ¸
¨ 0.3472 ¸ ¨ 176.6 ¸
¨ ¸ ¨ ¸
¨ 0.4158 ¸ ¨ 195.7 ¸
x1  HE  n  rowsx1 i  1  n
¨ 0.5163 ¸ ¨ 204.2 ¸
¨ ¸ ¨ ¸ x1  0  0.01  1
¨ 0.6156 ¸ ¨ 191.7 ¸
¨ 0.6810 ¸ ¨ 174.1 ¸
¨ ¸ ¨ ¸
0.7621 141.0
¨ ¸ ¨ ¸
¨ 0.8181 ¸ ¨ 116.8 ¸
¨ 0.8650 ¸ ¨ 85.6 ¸
¨ ¸ ¨ ¸
¨ 0.9276 ¸ ¨ 43.5 ¸
¨ 0.9624 ¨ 22.6
© ¹ © ¹
(a) Guess: a  500 b  100 c  0.01

ª x1˜ 1  x1 º § 539.653 ·
« » §¨ a · §¨ a · ¨
F x1  « x1 ˜ 1  x1 » ¨ b ¸  linfit x1  HE  F
2 Ans.
¨b ¸ ¨ 1.011 u 103 ¸
« » ¨c ¨c
« x13˜ 1  x1 » © ¹ © ¹ ¨
¬ ¼ © 913.122 ¹

HEi 100

x1˜ ( 1x1) ˜ ª¬ ab˜ x1c˜ ( x1)

2º
¼ 200

300
0 0.2 0.4 0.6 0.8
x1  x1
i

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 By definition of the excess properties

H = x1˜ x2˜ ª¬ a  b˜ x1  c˜ x1 º¼
E 2

H = 4˜ c˜ x1  3˜ (c  b)˜ x1  2˜ (b  a)˜ x1  a

d E 3 2
dx1

Hbar1 E = x2 2˜ ª¬ a  2˜ b˜ x1  3˜ c˜ x1 2 º¼

Hbar2 E = x1 2˜ ª¬ a  b  2˜ (b  c)˜ x1  3˜ c˜ x1 2 º¼
(b) To find the minimum, set dHE/dx1 = 0 and solve for x1. Then use x1 to
find HEmin.

Guess: x1  0.5 
HE (x1) x1˜ (1  x1)˜ a  b˜ x1  c˜ x1
2

3 2
Given 4˜ c˜ (x1)  3˜ (c  b)˜ (x1)  2˜ (b  a)˜ x1  a = 0

x1  Find (x1) x1 0.512 Ans.


HEmin  x1˜ (1  x1)˜ a  b˜ x1  c˜ x1
2
HEmin 204.401 Ans.

d
(c) HEbar1 (x1) HE (x1) (1  x1)˜ HE (x1)
dx1
§d ·
HEbar2 (x1) HE (x1) x1˜ ¨ HE (x1)
© dx1 ¹
x1  0  0.01  1

500

HEbar 1 (x1) 0

HEbar 2 (x1)
500

1000
0 0.2 0.4 0.6 0.8
x1

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 Discussion:
a) Partial property for species i goes to zero WITH ZERO SLOPE as xi -> 1.
b) Interior extrema come in pairs: HEbar min for species 1 occurs at the same
x1 as HEbar max for species 2, and both occur at an inflection point on the H E
vs. x1 plot.
c) At the point where the HEbar lines cross, the HE plot shows a minimum.

11.37 (a) (1) = Acetone (2) = 1,3-butadiene

y1  0.28 y2  1  y1 T  ( 60  273.15) ˜ K P  170˜ kPa

§ 0.307 · § 508.2 · § 0.233 · § 209 · cm3

w ¨ Tc  ¨ ˜ K Zc  ¨ Vc  ¨ ˜
© 0.190 ¹ © 425.2 ¹ © 0.267 ¹ © 220.4 ¹ mol
n 2 i  1  n j  1  n ki  j  0

§¨ 0.307 0.2485 0.082 ·

wi  w j
Eq. (11.70) Z i  j  Z ¨ 0.2485 0.19 0.126 ¸
2
¨ 0.082 0.126 0.152
© ¹
§¨ 508.2 464.851 ·
Eq. (11.71) Tci  j  Tc ˜ Tc ˜ 1  ki  j Tc ¨ 464.851 425.2 ¸ K
i j
¨ 369.8
© 0 ¹
Zc  Zc §¨ 0.233 0.25 ·
i j
Eq. (11.73) Zci  j  Zc ¨ 0.25 0.267 ¸
2
¨ 0.276 0
© ¹
ª 1 1 º3
« 3»
« Vci  3
 Vc j »
§¨ 209 214.65 · 3
cm
Eq. (11.74) Vci  j  « » Vc ¨ 214.65 220.4 ¸
¬ 2 ¼ ¨ 200 mol
© 0 ¹

§¨ 47.104 45.013 ·
Zci  j˜ R˜ Tci  j
Eq. (11.72) Pci  j  Pc ¨ 45.013 42.826 ¸ bar
Vci  j
¨ 42.48
© 0 ¹
Note: the calculated pure species Pc values in the matrix above do not agree
exactly with the values in Table B.1 due to round-off error in the calculations.
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 T P
Tri  j  Pri  j 
Tci  j Pci  j

§¨ 0.036 0.038 ·
§ 0.656 0.717 ·
Tr ¨ Pr ¨ 0.038 0.04 ¸
© 0.717 0.784 ¹ ¨ 0.824 0
© ¹
Eq. (3.65) B0i  j  B0 Tri  j
§¨ 0.74636 0.6361 0.16178 ·
B0 ¨ 0.6361 0.5405 0.27382 ¸
¨ 0.16178 0.27382 0.33295
© ¹

Eq. (3.66) B1i  j  B1 Tri  j

§¨ 0.874 0.558 0.098 ·

B1 ¨ 0.558 0.34 0.028 ¸
¨ 0.098 0.028 0.027
© ¹

R˜ Tci  j
Eq. (11.69a) + (11.69b) Bi  j  ˜ B0i  j  Z i  j˜ B1i  j
Pci  j

§ 910.278 665.188 · cm3

B ¨
© 665.188 499.527 ¹ mol
n n 3
cm
¦ ¦ yi˜ y j˜ Bi  j
Eq. (11.61)
B B 598.524
mol
i 1 j 1

B˜ P
Eq. (3.38) Z 1 Z 0.963
R˜ T
3
R˜ T˜ Z 4 cm
V V 1.5694 u 10 Ans.
P mol

0.675 0.722
Eq. (6.89) dB0dTri  j  Eq. (6.90) dB1dTri  j 
Tri  j 2.6 Tri  j 5.2
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 Differentiating Eq. (11.61) and using Eq. (11.69a) + (11.69b)
n n
ª y ˜ y ˜ ª R ˜ dB0dTr  Z ˜ dB1dTr º º
dBdT 
¦ ¦ « i j « Pc
¬ ¬ i j
i j i j i j »»
¼¼
i 1 j 1

Eq. (6.55) HR  P˜ T˜ §¨ ·
B J
 dBdT HR 344.051 Ans.
©T ¹ mol
J
Eq. (6.56) SR  P˜ dBdT SR 0.727 Ans.
mol˜ K
J
Eq. (6.54) GR  B˜ P GR 101.7 Ans.
mol
3
cm J
(b) V = 15694˜ HR = 450.322˜
mol mol

J J
SR = 1.006˜ GR = 125.1˜
mol˜ K mol

3 J
cm HR = 175.666˜
(c) V = 24255˜ mol
mol

J
SR = 0.41˜
J GR = 53.3˜
mol˜ K mol

3
cm J
(d) V = 80972˜ HR = 36.48˜
mol mol

J J
SR = 0.097˜ GR = 8.1˜
mol˜ K mol
3
cm J
(e) V = 56991˜ HR = 277.96˜
mol mol

J J
SR = 0.647˜ GR = 85.2˜
mol˜ K mol

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 Data for Problems 11.38 - 11.40

§ 325 · § 15 · § 308.3 · § 61.39 · § .187 ·

¨ ¨ ¨ ¨ ¨
¨ 200 ¸ ¨ 100 ¸ ¨ 150.9 ¸ ¨ 48.98 ¸ ¨ .000 ¸
¨ 575 ¸ ¨ 40 ¸ ¨ 562.2 ¸ ¨ 48.98 ¸ ¨ .210 ¸
¨ ¸ ¨ ¸ ¨ ¸ ¨ ¸ ¨ ¸
350 ¸ 35 ¸ 304.2 73.83 .224
T ¨ P ¨ Tc  ¨ ¸ Pc  ¨ ¸ Z ¨ ¸
¨ 300 ¸ ¨ 50 ¸ ¨ 282.3 ¸ ¨ 50.40 ¸ ¨ .087 ¸
¨ ¸ ¨ ¸ ¨ ¸ ¨ ¸ ¨ ¸
¨ 525 ¸ ¨ 10 ¸ ¨ 507.6
¸ ¨ 30.25
¸ ¨ .301
¸
¨ 225 ¸ ¨ 25 ¸ ¨ 190.6 ¸ ¨ 45.99 ¸ ¨ .012 ¸
¨ ¨ ¨ ¨ ¨
© 200 ¹ © 75 ¹ © 126.2 ¹ © 34.00 ¹ © .038 ¹
§ 1.054 · § 0.244 ·
¨ ¨
¨ 1.325 ¸ ¨ 2.042 ¸
¨ 1.023 ¸ ¨ 0.817 ¸

o ¨ ¸ 
o ¨ ¸
Tr 
T
Tr ¨ 1.151 ¸ Pr 
P
Pr ¨ 0.474 ¸
Tc ¨ 1.063 ¸ Pc ¨ 0.992 ¸
¨ ¸ ¨ ¸
¨ 1.034 ¸ ¨ 0.331 ¸
¨ 1.18 ¸ ¨ 0.544 ¸
¨ ¨
© 1.585 ¹ © 2.206 ¹

11.38 Redlich/Kwong Equation: :  0.08664 <  0.42748

§ 0.02 · § 4.559 ·
¨ ¨
¨ 0.133 ¸ ¨ 3.234 ¸
¨ 0.069 ¸ ¨ 4.77 ¸
 o ¨ ¸ o ¨ ¸
§
E: ¨ ˜
Pr ·
Eq. (3.53) E ¨ 0.036 ¸ q  § < · Eq. (3.54) q ¨ 3.998 ¸
¨ 0.081 ¸ ¨ ¨ 4.504 ¸
© Tr ¹ 1.5
© : ˜ Tr ¹
¨ ¸ ¨ ¸
¨ 0.028 ¸ ¨ 4.691 ¸
¨ 0.04 ¸ ¨ 3.847 ¸
¨ ¨
© 0.121 ¹ © 2.473 ¹
Guess: z 1

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 zE
Given z = 1  E  q˜ E ˜ Eq. (3.52) Z E  q  Find()
z
z˜ z  E

§ Z E i  qi  E i ·
i  1  8 Ii  ln ¨ Eq. (6.65)
© Z E i  qi ¹
I i  expZ E i  qi  1  ln Z E i  qi  E i  qi˜ Ii Eq. (11.37)

fi  I i˜ Pi

Z E i  qi Ii fi
0.925 0.93 13.944
0.722 0.744 74.352
0.668 0.749 29.952
0.887 0.896 31.362
0.639 0.73 36.504
0.891 0.9 8.998
0.881 0.89 22.254
0.859 0.85 63.743

11.39 Soave/Redlich/Kwong Equation :  0.08664 <  0.42748


o o

c 0.480  1.574˜ Z  0.176˜ Z 2 
D  ª¬ 1  c˜ 1  Tr
0.5 º¼
2

§ 0.02 · § 4.49 ·
¨ ¨
¨ 0.133 ¸ ¨ 3.202 ¸
¨ 0.069 ¸ ¨ 4.737 ¸
 o ¨ ¸  o ¨ ¸
E: §¨ ˜
Pr · Eq. (3.53) E ¨ 0.036 ¸ q ¨
§ <D
˜ · Eq. (3.54) q ¨ 3.79 ¸
© Tr ¹ ¨ 0.081 ¸ © : ˜ Tr ¹ ¨ 4.468 ¸
¨ ¸ ¨ ¸
0.028 4.62
¨ ¸ ¨ ¸
¨ 0.04 ¸ ¨ 3.827 ¸
¨ ¨
© 0.121 ¹ © 2.304 ¹
Guess: z 1

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 zE
Given z = 1  E  q˜ E ˜ Eq. (3.52) Z E  q  Find()
z
z˜ z  E

§ Z E i  qi  E i ·
i  1  8 Ii  ln ¨ Eq. (6.65)
© Z E i  qi ¹

I i  expZ E i  qi  1  ln Z E i  qi  E i  qi˜ Ii Eq. (11.37)

fi  I i˜ Pi

Z E i  qi Ii fi
0.927 0.931 13.965
0.729 0.748 74.753
0.673 0.751 30.05
0.896 0.903 31.618
0.646 0.733 36.66
0.893 0.902 9.018
0.882 0.891 22.274
0.881 0.869 65.155

11.40 Peng/Robinson Equation

V  1 2 H  1 2 :  0.07779 <  0.45724


o o

c 0.37464  1.54226˜ Z  0.26992˜ Z 2

D  ª¬ 1  c˜ 1  Tr
0.5 º¼
2

§ 0.018 · § 5.383 ·
¨ ¨
¨ 0.12 ¸ ¨ 3.946 ¸
¨ 0.062 ¸ ¨ 5.658 ¸
 o ¨ ¸  o ¨ ¸
E: §¨ ˜
Pr · Eq.(3.53) E ¨ 0.032 ¸ q ¨
§ <D
˜ · Eq.(3.54) q ¨ 4.598 ¸
© Tr ¹ ¨ 0.073 ¸ © : ˜ Tr ¹ ¨ 5.359 ¸
¨ ¸ ¨ ¸
¨ 0.025 5.527
¸ ¨ ¸
¨ 0.036 ¸ ¨ 4.646 ¸
¨ ¨
© 0.108 ¹ © 2.924 ¹

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 Guess: z 1
zE
Given z = 1  E  q˜ E ˜ Eq. (3.52) Z E  q  Find ( z)
z  HE˜ ˜ z  VE˜

1 § Z E i  qi  VE˜ i ·
i  1  8 Ii  ˜ ln ¨ Eq. (6.65)
2˜ 2 © Z E i  qi  HE˜ i ¹

I i  exp Z E i  qi  1  ln Z E i  qi  E i  qi˜ Ii Eq. (11.37)

fi  I i˜ Pi Z E i  qi Ii fi
0.918 0.923 13.842
0.69 0.711 71.113
0.647 0.73 29.197
0.882 0.89 31.142
0.617 0.709 35.465
0.881 0.891 8.91
0.865 0.876 21.895
0.845 0.832 62.363

I BY GENERALIZED CORRELATIONS

Parts (a), (d), (f), and (g) --- Virial equation:

§ 325 · § 308.3 · § 15 · § 61.39 · § .187 ·

¨ ¨ ¨ ¨ ¨
350 ¸ 304.2 ¸ ¨ 35 ¸ 73.83 ¸ .224 ¸
T ¨ Tc  ¨ P Pc  ¨ Z ¨
¨ 525 ¸ ¨ 507.6 ¸ ¨ 10 ¸ ¨ 30.25 ¸ ¨ .301 ¸
¨ ¨ ¨ ¨ ¨
© 225 ¹ © 190.6 ¹ © 25 ¹ © 45.99 ¹ © .012 ¹

o 
o
T P
Tr  Pr 
Tc Pc
Evaluation of I:

o o
B0  B0 ( Tr) Eq. (3.65) B1  B1 ( Tr) Eq. (3.66)

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  o  o
0.675 0.722
DB0  Eq. (6.89) DB1  Eq. (6.90)
2.6 5.2
Tr Tr

 o § 0.932 ·
ª Pr º ¨
I  exp « ˜ B0  Z ˜ B1 » Eq. (11.60)
(a)
¬ Tr ¼ I ¨ 0.904 ¸ (d)
¨ 0.903 ¸ (f)
¨ (g)
© 0.895 ¹

Parts (b), (c), (e), and (h) --- Lee/Kesler correlation:

Interpolate in Tables E.13 - E.16:

§ .7454 · § 1.1842 · § 0.000 ·

¨ ¨ ¨
.7517 ¸ 0.9634 ¸ 0.210 ¸
I0  ¨ I1  ¨ Z ¨
¨ .7316 ¸ ¨ 0.9883 ¸ ¨ 0.087 ¸
¨ ¨ ¨
© .8554 ¹ © 1.2071 ¹ © 0.038 ¹

o § 0.745 ·
¨
II  0˜ I1Z Eq. (11.67):
I ¨ 0.746 ¸
(b)
(c)
¨ 0.731 ¸ (e)
¨ (h)
© 0.862 ¹

kmol kmol
11.43 ndot1  2 ndot2  4 ndot3  ndot1  ndot2
hr hr
ndot1
x1  x1 0.333 x2  1  x1 x2 0.667
ndot3

a) Assume an ideal solution since n-octane and iso-octane are non-polar and
very similar in chemical structure. For an ideal solution, there is no heat of
mixing therefore the heat transfer rate is zero.

W
b) 'St  R˜ x1˜ ln x1  x2˜ ln x2 ˜ ndot3 'St 8.82 Ans.
K

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 11.44 For air entering the process: xO21  0.21 xN21  0.79
For the enhanced air leaving the process: xO22  0.5 xN22  0.5
mol
ndot2  50
sec
a) Apply mole balances to find rate of air and O2 fed to process
mol mol
Guess: ndotair  40 ndotO2  10
sec sec
Given

xO21˜ ndotair  ndotO2 = xO22˜ ndot2 Mole balance on O 2

xN21˜ ndotair = xN22˜ ndot2 Mole balance on N2

§ ndotair ·
¨  Find ndotair  ndotO2
© ndotO2 ¹
mol mol
ndotair 31.646 Ans. ndotO2 18.354 Ans.
sec sec

b) Assume ideal gas behavior. For an ideal gas there is no heat of mixing,
therefore, the heat transfer rate is zero.

c) To calculate the entropy change, treat the process in two steps:

1. Demix the air to O2 and N2
2. Mix the N2 and combined O2 to produce the enhanced air

Entropy change of demixing 'S12  R˜ xO21˜ ln xO21  xN21˜ ln xN21

Entropy change of mixing 'S23  R˜ xO22˜ ln xO22  xN22˜ ln xN22

Total rate of entropy generation: SdotG  ndotair˜ 'S12  ndot2˜ 'S23

W
SdotG 152.919 Ans.
K

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 §¨ 10 · §¨ 544.0 · §¨ 932.1 ·
J J
11.50 T  ¨ 30 ¸ K  273.15K GE  ¨ 513.0 ¸ HE  ¨ 893.4 ¸
¨ 50 ¨ 494.2 mol ¨ 845.9 mol
© ¹ © ¹ © ¹
Assume Cp is constant. Then HE is of the form: HE = c  a˜ T
Find a and c using the given HE and T values.
J
a  slope (T  HE) a 2.155
mol˜ K
3 J
c  intercept (T  HE) c 1.544 u 10
mol

GE is of the form: GE = a˜ §¨ T˜ ln §¨

T· ·
 T  b˜ T  c
© ©K¹ ¹
Rearrange to find b using estimated a and c values along with GE and T data.
 o
GE  a˜ §¨ T˜ ln §¨
T ·  T·  c §¨ 13.543 ·
B
© © K¹ ¹ B ¨ 13.559 ¸
J
T
¨ 13.545 mol˜ K
Use averaged b value © ¹
3

¦ Bi
i 1 J
b b 13.549
3 mol˜ K
Now calculate HE, GE and T*SE at 25 C using a, b and c values.

HE (T) a˜ T  c J Ans.
HE [(25  273.15)K] 901.242
mol

GE (T) a˜ §¨ T˜ ln §¨
T· · J
 T  b˜ T  c GE [(25  273.15)K] 522.394 Ans.
© © ¹ ¹
K mol

J
TSE (T) HE (T) GE (T) TSE [(25  273.15)K] 378.848 Ans.
mol

373
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