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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 3
V2 := 0.3m

i := 1 .. 2 P := 1bar T := ( 25 + 273.15)K

P⋅
∑ Vi
i
n := n = 40.342 mol
R⋅ T

∑ ( xi⋅ ln( xi) )


J
∆S := −n⋅ R⋅ ∆S = 204.885 Ans.
K
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)

341
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 ⎠ ⎝ PN2 ⎠ ⎠ K

∆SAr := nAr⋅ ⎛⎜ CpAr⋅ ln ⎛⎜


T ⎞
− R⋅ ln ⎛⎜
P ⎞⎞ J
∆SAr = −9.547
⎝ ⎝ TAr ⎠ ⎝ PAr ⎠ ⎠ K

∑ ( xi⋅ln( xi) ) ⎤⎥
J
∆Smix := ntotal⋅ ⎡ −R⋅ ∆Smix = 36.006
⎢ K
⎣ i ⎦
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⋅
mol mol i := 1 .. 2

mdotN2 mdotH2
molarflowN2 := molarflowH2 :=
molwtN2 molwtH2

mol
molarflowtotal := molarflowN2 + molarflowH2 molarflowtotal = 319.409
sec

342
molarflowN2 molarflowH2
y1 := y1 = 0.224 y2 := y2 = 0.776
molarflowtotal molarflowtotal

∑ ( yi⋅ ln( yi) )


J
∆S := −R⋅ molarflowtotal⋅ ∆S = 1411 Ans.
sec⋅ K
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
, −2.164⋅ 10 , 0.0)
−6

MCPSm := MCPS ( T1 , T2 , 1.702 , 9.081⋅ 10 , −2.164⋅ 10 , 0.0)


−3 −6

For ethane:

(
MCPHe := MCPH T1 , T2 , 1.131 , 19.225⋅ 10
−3
, −5.561⋅ 10 , 0.0)
−6

MCPSe := MCPS ( T1 , T2 , 1.131 , 19.225⋅ 10 , −5.561⋅ 10 , 0.0)


−3 −6

MCPHmix := 0.5⋅ MCPHm + 0.5⋅ MCPHe MCPHmix = 6.21

MCPSmix := 0.5⋅ MCPSm + 0.5⋅ MCPSe MCPSmix = 6.161

∆H := R⋅ MCPHmix⋅ ( T2 − T1)
J
∆H = −7228
mol

⎛ T2 ⎞ ⎛ P2 ⎞
∆S := R⋅ MCPSmix⋅ ln ⎜ − R⋅ ln ⎜ + R⋅ 2⋅ 0.5⋅ ln ( 0.5)
⎝ T1 ⎠ ⎝ P1 ⎠
The last term is the entropy change of UNmixing
J
∆S = −15.813 Tσ := 300⋅ K
mol⋅ K
J
Wideal := ∆H − Tσ ⋅ ∆S Wideal = −2484 Ans.
mol

11.5 Basis: 1 mole entering air.


y1 := 0.21 y2 := 0.79 η t := 0.05 Tσ := 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:

343
∆S := R⋅ ( y1⋅ ln ( y1) + y2⋅ ln ( y2) )
J
∆S = −4.273
mol⋅ K
3 J
By Eq. (5.27): Wideal := −Tσ ⋅ ∆S Wideal = 1.282 × 10
mol
Wideal J
By Eq. (5.28): Work := Work = 25638 Ans.
ηt mol

11.16 ⎛ 0 ⎞ ⎛ 1.000 ⎞
⎜ 10 ⎜ 0.985
⎜ ⎟ ⎜ ⎟
⎜ 20 ⎟ ⎜ 0.970 ⎟ lnφ1 := 0 φ 1 := 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 ⎟
⎜ 400 ⎟ ⎜ 0.824 ⎟ Zi − 1
Fi :=
⎜ ⎜ Pi
⎝ 500 ⎠ ⎝ 0.910 ⎠
Fi is a well behaved function; use the trapezoidal rule to integrate Eq.
(11.35) numerically.

Fi + Fi − 1
Ai := ⋅ ( P i − P i − 1) lnφi := lnφi−1 + Ai
2

φ i := exp ( lnφi) fi := φ i⋅ Pi
Generalized correlation for fugacity coefficient:

For CO2: Tc := 304.2⋅ K Pc := 73.83⋅ bar ω := 0.224


T
T := ( 150 + 273.15) ⋅ K Tr := Tr = 1.391
Tc

⎡ P ⎤
⎢ Pc ⎥
φ G ( P) := exp ⎢ ⋅ ( B 0 ( T r ) + ω ⋅ B 1 ( T r ) )⎥ fG ( P) := φ G ( P) ⋅ P
⎣ Tr ⎦
344
Pi fi
= =
bar φi = 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
φi bar
f G ( Pi )
200
φ G ( 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 ω := 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.

345
Data from Tables E.15 & E.16 and by Eq. (11.67):
ω
φ 0 := 0.672 φ 1 := 1.354 φ := φ 0⋅ φ 1 φ = 0.724

f := φ ⋅ P GRRT := ln ( φ )

f = 217.14 bar GRRT = −0.323 Ans.

11.18 Isobutylene: Tc := 417.9⋅ K Pc := 40.00⋅ bar ω := 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) , Pr ( P) , ω ⋅ 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).
ω
φ0 := 0.7025 φ1 := 1.2335 φ := φ0⋅ φ1 f := φ ⋅ P

φ = 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 ω := ⎜
⎝ 420.0 ⎠ ⎝ 40.43 ⎠ ⎝ 0.191 ⎠
⎛ 0.273 ⎞ ⎛ 258 ⎞ cm3 ⎛ 322.4 ⎞
Zc := ⎜ Vc := ⎜ ⋅ Tn := ⎜ ⋅K
⎝ 0.277 ⎠ ⎝ 239.3 ⎠ mol ⎝ 266.9 ⎠
⎛ 383.15 ⎞ ⎛ 275 ⎞ ⎛ 5.267 ⎞
T := ⎜ ⋅K P := ⎜ ⋅ bar Psat := ⎜ ⋅ bar
⎝ 393.15 ⎠ ⎝ 34 ⎠ ⎝ 25.83 ⎠
346

→ ⎯⎯→
T ⎛ 0.7486 ⎞ Psat ⎛ 0.117 ⎞
Tr := Tr = ⎜ Psatr := Psatr = ⎜
Tc ⎝ 0.9361 ⎠ Pc ⎝ 0.6389 ⎠
Calculate the fugacity coefficient at the vapor pressure by Eq. (11.68):

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


T ⎛ 0.749 ⎞
Tr := Tr = ⎜
Tc ⎝ 0.936 ⎠
Eq. (11.44):
⎯⎯⎯⎯⎯⎯→
⎡ 2⎤
⎢ ⎥
⎢ (1−Tr) 7 ⎥ ⎛ 107.546 ⎞ cm3
Vsat := ⎣ Vc⋅ Zc ⎦ Vsat = ⎜
⎝ 133.299 ⎠ mol
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →
f := ⎡⎢ PHIB Tr , Psatr , ω ⋅ Psat⋅ exp ⎡⎢
⋅ − ⎤⎤
( ) Vsat ( P Psat )
⎥⎥
⎣ ⎣ R⋅ T ⎦⎦
⎛ 11.78 ⎞
f=⎜ bar Ans.
⎝ 20.29 ⎠

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 φsatPsat = fsat

⎡ Vsat⋅ ( P − Psat) ⎤ f
r := exp ⎢ ⎥ r = 1.084 r= = 1.084 Ans.
⎣ R⋅ T ⎦ fsat

347
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:

⎡ ( 400 + 273.15) ⋅ K ⎤
T1 := ⎢ ⎥
⎣ ( 800 + 459.67) ⋅ rankine ⎦
⎛ 3121.2⋅ J ⎞ ⎛ 6.2915⋅ J ⎞
⎜ ⎜
gm⋅ K
H1 := ⎜
gm ⎟
S1 := ⎜ ⎟
⎜ Btu ⎟ ⎜ Btu ⎟
⎜ 1389.6 ⋅ ⎜ 1.5677 ⋅
⎝ lbm ⎠ ⎝ lbm⋅ rankine ⎠

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

⎛ 3275.2⋅ J ⎞ ⎛ 8.0338⋅ J ⎞
⎜ ⎜
gm⋅ K
H2 := ⎜
gm ⎟
S2 := ⎜ ⎟
⎜ Btu ⎟ ⎜ Btu ⎟
⎜ 1431.7 ⋅ ⎜ 1.9227 ⋅
⎝ lbm ⎠ ⎝ lbm⋅ rankine ⎠

Eq. (A) on page 399 may be recast for this problem as:
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →
⎡ molwt ⎡ 2
H − H ⎤⎤ ⎛ 0.0377 ⎞
− ( S 2 − S 1) ⎥ ⎥
1
r := exp ⎢ ⋅⎢ r=⎜
⎣ R ⎣ T1 ⎦⎦ ⎝ 0.0542 ⎠
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 ω := ⎜ 0.194 ⎟
⎜ 420.0 ⎜ 40.43 ⎜ 0.191
⎝ ⎠ ⎝ ⎠ ⎝ ⎠
⎛⎜ 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
⎝ ⎠ ⎝ ⎠ ⎝ ⎠
348
⎛⎜ 200 ⎞ ⎛⎜ 1.01325 ⎞
P := ⎜ 300 ⎟ ⋅ bar Psat := ⎜ 1.01325 ⎟ ⋅ bar
⎜ 150 ⎜ 1.01325
⎝ ⎠ ⎝ ⎠

→ ⎛⎜ 0.6583 ⎞ ⎯⎯→ ⎛⎜ 0.0301 ⎞
Tn Psat
Tr := Tr = ⎜ 0.6372 ⎟ Pr := Pr = ⎜ 0.0253 ⎟
Tc ⎜ 0.6355 Pc ⎜ 0.0251
⎝ ⎠ ⎝ ⎠
Calculate the fugacity coefficient at the nbp by Eq. (11.68):

(a) ( 1 1 )
PHIB Tr , Pr , ω 1 = 0.9572
(b) ( 2 2 )
PHIB Tr , Pr , ω 2 = 0.9618
(c) PHIB ( Tr , Pr , ω 3) = 0.9620
3 3
⎯⎯⎯⎯⎯⎯⎯⎯

⎡ (1−Tr) 0.2857 ⎤
Eq. (3.72): Vsat := ⎢⎣ Vc⋅ Zc ⎥

⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →
f := ⎡⎢ PHIB Tr , Pr , ω ⋅ Psat⋅ exp ⎡⎢
⋅ − ⎤⎤
Eq. (11.44): ( ) Vsat ( P
R⋅ Tn
Psat )
⎥⎥
⎣ ⎣ ⎦⎦
⎛⎜ 2.445 ⎞
f = ⎜ 3.326 ⎟ bar Ans.
⎜ 1.801
⎝ ⎠

11.24 (a) Chloroform: Tc := 536.4⋅ K Pc := 54.72⋅ bar ω := 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

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

349
Calculate fugacity coefficients by Eqs. (11.68):

⎡ Pr ( P )
Pr ( P) :=
P
φ ( P) := exp ⎢ (
⋅ B0 ( Tr ) + ω ⋅ B1 ( Tr ) ⎥ )⎤
Pc ⎣ Tr ⎦

f ( P) := if ⎡⎢ P ≤ Psat , φ ( P) ⋅ P , φ ( Psat) ⋅ Psat⋅ exp ⎡⎢


Vsat⋅ ( P − Psat) ⎤ ⎤
⎥⎥
⎣ ⎣ R⋅ T ⎦⎦

φ ( P) := if ⎡⎢ P ≤ Psat , φ ( P) , φ ( Psat) ⋅ ⋅ exp ⎡⎢


Psat Vsat⋅ ( P − Psat) ⎤ ⎤
⎥⎥
⎣ P ⎣ R⋅ T ⎦⎦
P := 0⋅ bar , 0.5⋅ bar .. 40⋅ bar

40

Psat Psat
30
f ( P) bar bar
0.8
bar
20 φ ( 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 ω := 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

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

350
Calculate fugacity coefficients by Eq. (11.68):

⎡ Pr ( P )
Pr ( P) :=
P
φ ( P) := exp ⎢ ( )⎤
⋅ B0 ( Tr ) + ω ⋅ B1 ( Tr ) ⎥
Pc ⎣ Tr ⎦

f ( P) := if ⎡⎢ P ≤ Psat , φ ( P) ⋅ P , φ ( Psat) ⋅ Psat⋅ exp ⎡⎢


Vsat⋅ ( P − Psat) ⎤ ⎤
⎥⎥
⎣ ⎣ R⋅ T ⎦⎦

φ ( P) := if ⎡⎢ P ≤ Psat , φ ( P) , φ ( Psat) ⋅ ⋅ exp ⎡⎢


Psat Vsat⋅ ( P − Psat) ⎤ ⎤
⎥⎥
⎣ P ⎣ R⋅ T ⎦⎦
P := 0⋅ bar , 0.5⋅ bar .. 10⋅ bar

10

Psat Psat
bar bar
f ( P) 0.8
bar
5 φ ( 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 ⎠ ⎝ 46.65 ⎠ ⎝ 0.140 ⎠
⎛ 0.281 ⎞ ⎛ 131.0 ⎞ cm3
Zc := ⎜ Vc := ⎜ ⋅
⎝ 0.289 ⎠ ⎝ 188.4 ⎠ 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

351
By Eqs. (11.70) through (11.74)
wi + w j Zci + Zc j
ω i , j := Tc := Tci⋅ Tc j Zc :=
2 i, j i, j 2
3
⎡ 1 1⎤
⎢ ( Vc ) 3 + ( Vc ) 3 ⎥ Zc ⋅ R⋅ Tc
i, j i, j
Vc := ⎢ ⎥
i j
Pc :=
i, j ⎣ 2 ⎦ i, j Vc
i, j

T ⎛ 1.499 1.317 ⎞
Tr := Tr = ⎜
i, j Tc
i, j ⎝ 1.317 1.157 ⎠
⎛ 131 157.966 ⎞ cm3 ⎛ 50.345 48.189 ⎞
Vc = ⎜ Pc = ⎜ bar
⎝ 157.966 188.4 ⎠ mol ⎝ 48.189 46.627 ⎠
⎛ 0.087 0.114 ⎞ ⎛ 282.3 321.261 ⎞ ⎛ 0.281 0.285 ⎞
ω =⎜ Tc = ⎜ K Zc = ⎜
⎝ 0.114 0.14 ⎠ ⎝ 321.261 365.6 ⎠ ⎝ 0.285 0.289 ⎠
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 ⎠ ⎝ 0.085 0.046 ⎠
R⋅ Tc
⎛ −59.892 −99.181 ⎞ cm3
⋅ ( B0i , j + ω i , j⋅ B1i , j)
i, j
Bi , j := B=⎜
Pc
i, j ⎝ −99.181 −159.43 ⎠ mol
By Eq. (11.64):

δ i , j := 2⋅ Bi , j − Bi , i − B j , j ⎛ 0 20.96 ⎞ cm3
δ =⎜
⎝ 20.96 0 ⎠ mol

φhatk := exp ⎡⎢
P ⎡ ⎤⎤
∑ ∑ ⎡⎣yi⋅y j⋅( 2⋅δ i , k − δ i , j)⎤⎦ ⎥⎥ ⎥⎥
1
⋅ ⎢ Bk , k + ⋅
⎢ R⋅ T ⎢ 2
⎣ ⎣ i j ⎦⎦

⎛ 0.957 ⎞ ⎛ 10.053 ⎞
fhatk := φhatk⋅ yk⋅ P φhat = ⎜ fhat = ⎜ bar Ans.
⎝ 0.875 ⎠ ⎝ 17.059 ⎠
352
For an ideal solution , φid = φ pure species

⎛ 0.595 ⎞ ⎡ Pr k ⎤
φidk := exp ⎢ ⋅ ( B0k , k + ω k , k⋅ B1k , k)⎥
P
Pr := Pr = ⎜
k Pck ⎝ 0.643 ⎠ ⎢ Tr ⎥
⎣ k,k ⎦
⎛ 0.95 ⎞ ⎛ 9.978 ⎞
fhatid := φidk⋅ yk⋅ P φid = ⎜ fhatid = ⎜ bar Ans.
k
⎝ 0.873 ⎠ ⎝ 17.022 ⎠
Alternatively,

⎡ Pr k , k ⎤ ⎛ 0.95 ⎞
φidk := exp ⎢ ⋅ ( B0k , k + ω k , k⋅ B1k , k)⎥
P
Pr := φid = ⎜
i, j Pc ⎢ Tr ⎥ ⎝ 0.873 ⎠
i, j ⎣ k,k ⎦

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
⎝ ⎠ ⎝ ⎠ ⎝ ⎠
⎛⎜ 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
⎝ ⎠ ⎝ ⎠ ⎝ ⎠
n := 3 i := 1 .. n j := 1 .. n k := 1 .. n
By Eqs. (11.70) through (11.74)

wi + w j Zci + Zc j
ω i , j := Tc := Tci⋅ Tc j Zc :=
2 i, j i, j 2

3
⎡ 1 1⎤
⎢ ( Vc ) 3 + ( Vc ) 3 ⎥ Zc ⋅ R⋅ Tc
i, j i, j
Vc := ⎢ ⎥
i j
Pc :=
i, j ⎣ 2 ⎦ i, j Vc
i, j

353
⎛⎜ 1.958 1.547 1.406 ⎞
T
Tr := Tr = ⎜ 1.547 1.222 1.111 ⎟
i, j Tc
i, j ⎜ 1.406 1.111 1.009
⎝ ⎠
⎛⎜ 98.6 120.533 143.378 ⎞ 3
cm
Vc = ⎜ 120.533 145.5 171.308 ⎟
⎜ 143.378 171.308 200 mol
⎝ ⎠
⎛⎜ 45.964 47.005 43.259 ⎞ ⎛⎜ 0.012 0.056 0.082 ⎞
Pc = ⎜ 47.005 48.672 45.253 ⎟ bar ω = ⎜ 0.056 0.1 0.126 ⎟
⎜ 43.259 45.253 42.428 ⎜ 0.082 0.126 0.152
⎝ ⎠ ⎝ ⎠
⎛⎜ 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
⎝ ⎠ ⎝ ⎠
By Eqs. (3.65) and (3.66):

B0i , j := B0 Tr ( i , j)
(
B1i , j := B1 Tr
i, j )
R⋅ Tc
⋅ ( B0i , j + ω i , j⋅ B1i , j)
i, j
Bi , j :=
Pc
i, j

By Eq. (11.64):
⎛⎜ 0 30.442 107.809 ⎞ 3
cm
δ i , j := 2⋅ Bi , j − Bi , i − B j , j δ = ⎜ 30.442 0 23.482 ⎟
⎜ 107.809 23.482 mol
⎝ 0 ⎠

φhatk := exp ⎡⎢
P ⎡ ⎤⎤
∑ ∑ ⎡⎣yi⋅y j⋅( 2⋅δ i , k − δ i , j)⎤⎦ ⎥⎥ ⎥⎥
1
⋅ ⎢ Bk , k + ⋅
⎢ R⋅ T ⎢ 2
⎣ ⎣ i j ⎦⎦
fhatk := φhatk⋅ yk⋅ P ⎛⎜ 1.019 ⎞ ⎛⎜ 7.491 ⎞
φhat = ⎜ 0.881 ⎟ fhat = ⎜ 13.254 ⎟ bar Ans.
⎜ 0.775 ⎜ 9.764
⎝ ⎠ ⎝ ⎠

354
For an ideal solution , φid = φ pure species

⎛⎜ 0.761 ⎞
⎡ Prk ⎤
⋅ ( B0k , k + ω k , k⋅ B1k , k)⎥
P
Prk := Pr = ⎜ 0.718 ⎟ φidk := exp ⎢
Pck ⎜ 0.824 Tr
⎣ k,k ⎦
⎝ ⎠
⎛⎜ 0.977 ⎞ ⎛⎜ 7.182 ⎞
fhatid := φidk⋅ yk⋅ P φid = ⎜ 0.88 ⎟ fhatid = ⎜ 13.251 ⎟ bar Ans.
k
⎜ 0.759 ⎜ 9.569
⎝ ⎠ ⎝ ⎠

= ( −2.6⋅ x1 − 1.8⋅ x2) ⋅ x1⋅ x2


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

= ( −.8⋅ x1 − 1.8) ⋅ x1⋅ ( 1 − x1) = −1.8⋅ x1 + x1 + 0.8⋅ x1


GE 2 3
RT

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

d ⎛⎜
GE ⎞
d ⎛⎜
GE ⎞

lnγ1 =
GE
+ ( 1 − x1) ⋅ ⎝ RT ⎠ lnγ2 =
GE
− x1⋅ ⎝ RT ⎠
RT dx1 RT dx1

d ⎛⎜
GE ⎞
⎝ RT ⎠ = −1.8 + 2⋅ x + 2.4⋅ x 2
1 1
dx1

2 3
lnγ1 = −1.8 + 2⋅ x1 + 1.4⋅ x1 − 1.6⋅ x1
Ans.
2 3
lnγ2 = −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:

355
(c) Divide Gibbs/Duhem eqn. (11.100) by dx1:

x1⋅
(
d lnγ1
+ x2⋅
)d lnγ2
= 0
( )
dx1 dx1

Differentiate answers to Part (a):

(
d lnγ1 )
= 2 + 2.8⋅ x1 − 4.8⋅ x1
2 (
d lnγ2 )
= −2⋅ x1 − 4.8⋅ x1
2
dx1 dx1

x1⋅
(
d lnγ1 ) 2
= 2⋅ x1 + 2.8⋅ x1 − 4.8⋅ x1
3
dx1

x2⋅
(
d lnγ1 ) (
= ( 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 lnγ1
= 0
) Q.E.D.
from the 2nd eq. of
Part (c) that dx1

When x1 = 0, we see (
d lnγ2
= 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

lnγ1 ( x1) := −1.8 + 2⋅ x1 + 1.4⋅ x1 − 1.6⋅ x1


2 3

lnγ2 ( x1) := −x1 − 1.6⋅ x1


2 3

lnγ1 ( 0) = −1.8 lnγ2 ( 1) = −2.6 x1 := 0 , 0.1 .. 1.0

356
0

g ( x1 ) 1

lnγ1 ( x1 ) lnγ1 ( 0)

lnγ2 ( x1 )
2
lnγ2 ( 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 ⎟
⎜ ⎟ ⎜ ⎟
x1 := ⎜ 0.66233 ⎟
VE := ⎜ 321.7 ⎟
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
⎝ ⎠ ⎝ ⎠
357
(a) Guess: a := −3000 b := −3000 c := 250

⎡ x1⋅ ( 1 − x1) ⎤
⎛⎜ a ⎞ ⎛⎜ 3.448 × 10 ⎞
3
⎢ ⎥ ⎛⎜ a ⎞
F ( x1 ) := ⎢ x1 ⋅ ( 1 − x1) ⎥ ⎜ b ⎟ := linfit ( x1 , VE , F) ⎜ b ⎟ = ⎜ −3.202 × 103 ⎟
2 Ans.
⎢ ⎥ ⎜c ⎜c ⎜
⎢ x13⋅ ( 1 − x1) ⎥ ⎝ ⎠ ⎝ ⎠ ⎝ 244.615 ⎠
⎣ ⎦
600

VEi 400

x1⋅ ( 1−x1) ⋅ ⎡⎣ a+b⋅ x1+c⋅ ( x1)


2⎤
⎦ 200

0
0 0.2 0.4 0.6 0.8
x1 , x1
i

By definition of the excess properties

V = x1⋅ x2⋅ ⎡⎣ a + b⋅ x1 + c⋅ ( x1) ⎤⎦


E 2

V = −4⋅ c⋅ ( x1) + 3⋅ ( c − b) ⋅ ( x1) + 2⋅ ( b − a) ⋅ x1 + a


d E 3 2
dx1

( Vbar1) E = ( x2) 2⋅ ⎡⎣ a + 2⋅ b⋅ x1 + 3⋅ c⋅ ( x1) 2 ⎤⎦

( Vbar2) E = ( x1) 2⋅ ⎡⎣ a − b + 2⋅ (b − c)⋅ x1 + 3⋅ c⋅ ( x1) 2 ⎤⎦


(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.

358
(
VEmax := x1⋅ ( 1 − x1) ⋅ a + b⋅ x1 + c⋅ x1
2 ) VEmax = 536.294 Ans.

(c) VEbar1 ( x1) := ( 1 − x1) 2⋅ ⎡⎣ a + 2⋅ b⋅ x1 + 3⋅ c⋅ ( x1) 2 ⎤⎦

VEbar2 ( x1) := ( x1) ⋅ ⎡⎣ a − b + 2⋅ ( b − c) ⋅ x1 + 3⋅ c⋅ ( x1) ⎤⎦


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 ⎠ mol

∑ ∑ ( yi⋅y j⋅Bi , j)
3
By Eq. (11.61): B := cm
B = −504.25
i j mol

359
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
⎝ ⎠ ⎝ ⎠ ⎝ ⎠

⎡⎢⎛⎜ 50 ⎞ ⎥⎤ ⎛⎜ 323.15 ⎞
t := ⎢⎜ 75 ⎟ + 273.15⎥ ⋅ K t = ⎜ 348.15 ⎟ K
⎢⎜ 100 ⎥ ⎜ 373.15
⎣⎝ ⎠ ⎦ ⎝ ⎠
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)
⎛ 1.92 3.18 ⎞ cm3
dBdT := ⎜ ⎟
dT dT
dBdT = ⎜
⎜d d ⎟ ⎝ 3.18 5.92 ⎠ mol⋅ K
⎜ B12 ( T) B22 ( T)
⎝ dT dT ⎠
3

∑∑ ( yi⋅ y j⋅ dBdTi ,dBdT


j)
cm
Differentiate Eq. (11.61): dBdT := = 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 ⎠
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

360
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 ⎠ mol j := 1 .. n

δ i , j := 2⋅ Bi , j − Bi , i − B j , j

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

φhat1 ( y1) := exp ⎡⎢


P ⎡ ⎤
⋅ ⎣ B1 , 1 + ( 1 − y1) ⋅ δ 1 , 2 ⎤⎦ ⎥
2
⎣ R⋅ T ⎦

φhat2 ( y1) := exp ⎡⎢


P
( 2 ⎤
⋅ B2 , 2 + y1 ⋅ δ 1 , 2 ⎥)
⎣ R⋅ T ⎦
y1 := 0 , 0.1 .. 1.0
1

0.99

0.98

φhat1 ( y1)
0.97
φhat2 ( y1)

0.96

0.95

0.94
0 0.2 0.4 0.6 0.8
y1

361
⎛ 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
⎝ ⎠ ⎝ ⎠
(a) Guess: a := −500 b := −100 c := 0.01

⎡ x1⋅ ( 1 − x1) ⎤
⎢ ⎥ ⎛⎜ a ⎞ ⎛⎜ a ⎞ ⎛⎜ −539.653 ⎞
F ( x1 ) := ⎢ x1 ⋅ ( 1 − x1) ⎥ ⎜ b ⎟ := linfit ( x1 , HE , F) ⎜ b ⎟ = ⎜ −1.011 × 103 ⎟
2 Ans.
⎢ ⎥ ⎜c ⎜c
⎢ x13⋅ ( 1 − x1) ⎥ ⎝ ⎠ ⎝ ⎠ ⎜⎝ 913.122 ⎠
⎣ ⎦
0

HEi 100

x1⋅ ( 1−x1) ⋅ ⎡⎣ a+b⋅ x1+c⋅ ( x1)


2⎤
⎦ 200

300
0 0.2 0.4 0.6 0.8
x1 , x1
i

362
By definition of the excess properties

H = x1⋅ x2⋅ ⎡⎣ a + b⋅ x1 + c⋅ ( x1) ⎤⎦


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 + 2⋅ b⋅ x1 + 3⋅ c⋅ ( x1) 2 ⎤⎦

( Hbar2) E = ( x1) 2⋅ ⎡⎣ a − b + 2⋅ (b − c)⋅ x1 + 3⋅ c⋅ ( x1) 2 ⎤⎦


(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 ⎠
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

363
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 ⎠ ⎝ 425.2 ⎠ ⎝ 0.267 ⎠ ⎝ 220.4 ⎠ mol
n := 2 i := 1 .. n j := 1 .. n ki , j := 0

⎛⎜ 0.307 0.2485 0.082 ⎞


wi + w j
Eq. (11.70) ω i , j := ω = ⎜ 0.2485 0.19 0.126 ⎟
2 ⎜ 0.082 0.126 0.152
⎝ ⎠
⎛⎜ 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 ⎠
Zc + Zc ⎛⎜ 0.233 0.25 ⎞
i j
Eq. (11.73) Zci , j := Zc = ⎜ 0.25 0.267 ⎟
2 ⎜ 0.276 0
⎝ ⎠
⎡ 1 1 ⎤3
⎢ ⎥
Eq. (11.74) Vci , j := ⎢
( ) 3 + ( Vc j) 3 ⎥
⎢ Vci
⎛⎜ 209 214.65 ⎞ 3
Vc = ⎜ 214.65 220.4 ⎟
cm

⎣ 2 ⎦ ⎜ 200 mol
⎝ 0 ⎠

⎛⎜ 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 ⎠
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.
364
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 ⎠ ⎜ 0.824 0
⎝ ⎠
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
⎝ ⎠

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
⎝ ⎠

R⋅ Tci , j
Eq. (11.69a) + (11.69b) Bi , j := ⋅ ( B0i , j + ω i , j⋅ B1i , j)
Pci , j

⎛ −910.278 −665.188 ⎞ cm3


B=⎜
⎝ −665.188 −499.527 ⎠ mol
n n 3

∑ ∑ ( yi⋅ y j⋅ Bi , j)
Eq. (11.61) cm
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 × 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
365
Differentiating Eq. (11.61) and using Eq. (11.69a) + (11.69b)
n n
⎡ y ⋅ y ⋅ ⎡ R ⋅ ( dB0dTr + ω ⋅ dB1dTr )⎤ ⎤
dBdT :=
∑ ∑ ⎢ i j ⎢ Pc
⎣ ⎣ i, j
i, j i, j i, j ⎥⎥
⎦⎦
i=1 j=1

Eq. (6.55) HR := P⋅ T⋅ ⎛⎜ ⎞
B J
− dBdT HR = −344.051 Ans.
⎝T ⎠ 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
J GR = −53.3⋅
SR = −0.41⋅ mol
mol⋅ K
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

366
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 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟
T := ⎜
350 ⎟
P := ⎜
35 ⎟
Tc := ⎜ ⎟ Pc := ⎜ ⎟ ω := ⎜ ⎟
304.2 73.83 .224
⎜ 300 ⎟ ⎜ 50 ⎟ ⎜ 282.3 ⎟ ⎜ 50.40 ⎟ ⎜ .087 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟
⎜ 525 ⎟ ⎜ 10 ⎟ ⎜ 507.6
⎟ ⎜ 30.25
⎟ ⎜ .301

⎜ 225 ⎟ ⎜ 25 ⎟ ⎜ 190.6 ⎟ ⎜ 45.99 ⎟ ⎜ .012 ⎟
⎜ ⎜ ⎜ ⎜ ⎜
⎝ 200 ⎠ ⎝ 75 ⎠ ⎝ 126.2 ⎠ ⎝ 34.00 ⎠ ⎝ .038 ⎠
⎛ 1.054 ⎞ ⎛ 0.244 ⎞
⎜ ⎜
⎜ 1.325 ⎟ ⎜ 2.042 ⎟
⎜ 1.023 ⎟ ⎜ 0.817 ⎟

→ ⎜ ⎟ ⎯
→ ⎜ ⎟
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 ⎠ ⎝ 2.206 ⎠

11.38 Redlich/Kwong Equation: Ω := 0.08664 Ψ := 0.42748

⎛ 0.02 ⎞ ⎛ 4.559 ⎞
⎜ ⎜
⎜ 0.133 ⎟ ⎜ 3.234 ⎟
⎜ 0.069 ⎟ ⎜ 4.77 ⎟
⎯⎯⎯ → ⎜ ⎟ ⎯⎯⎯⎯ → ⎜ ⎟

β := ⎜ Ω ⋅
Pr ⎞
Eq. (3.53) β = ⎜ 0.036 ⎟
q :=
⎛ Ψ ⎞ Eq. (3.54) q = ⎜ 3.998 ⎟
⎜ 0.081 ⎟ ⎜ ⎜ 4.504 ⎟
⎝ Tr ⎠ 1.5
⎝ Ω ⋅ Tr ⎠
⎜ ⎟ ⎜ ⎟
⎜ 0.028 ⎟ ⎜ 4.691 ⎟
⎜ 0.04 ⎟ ⎜ 3.847 ⎟
⎜ ⎜
⎝ 0.121 ⎠ ⎝ 2.473 ⎠
Guess: z := 1

367
z−β
Given z = 1 + β − q⋅ β ⋅ Eq. (3.52) Z ( β , q) := Find ( z)
z⋅ ( z + β )

⎛ Z ( β i , qi) + β i ⎞
i := 1 .. 8 Ii := ln ⎜ Eq. (6.65)
⎝ Z ( β i , qi) ⎠
φ i := exp ( Z ( β i , qi) − 1 − ln ( Z ( β i , qi) − β i) − qi⋅ Ii) Eq. (11.37)

fi := φ i⋅ Pi

Z ( β i , qi) = φi = 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 Ω := 0.08664 Ψ := 0.42748


⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
→ ⎯⎯⎯⎯⎯⎯⎯⎯

(
c := 0.480 + 1.574⋅ ω − 0.176⋅ ω
2
) (
α := ⎡⎣ 1 + c⋅ 1 − Tr
0.5 ) ⎤⎦ 2
⎛ 0.02 ⎞ ⎛ 4.49 ⎞
⎜ ⎜
⎜ 0.133 ⎟ ⎜ 3.202 ⎟
⎜ 0.069 ⎟ ⎜ 4.737 ⎟
⎯⎯⎯ → ⎜ ⎟ ⎯⎯⎯ → ⎜ ⎟
β := ⎛⎜ Ω ⋅
Pr ⎞ Eq. (3.53) β = ⎜
0.036 ⎟ ⎛
q := ⎜
Ψ ⋅ α ⎞ Eq. (3.54) q = ⎜ 3.79 ⎟
⎝ Tr ⎠ ⎜ 0.081 ⎟ ⎝ Ω ⋅ Tr ⎠ ⎜ 4.468 ⎟
⎜ ⎟ ⎜ ⎟
⎜ 0.028
⎟ ⎜ 4.62

⎜ 0.04 ⎟ ⎜ 3.827 ⎟
⎜ ⎜
⎝ 0.121 ⎠ ⎝ 2.304 ⎠
Guess: z := 1

368
z−β
Given z = 1 + β − q⋅ β ⋅ Eq. (3.52) Z ( β , q) := Find ( z)
z⋅ ( z + β )

⎛ Z ( β i , qi) + β i ⎞
i := 1 .. 8 Ii := ln ⎜ Eq. (6.65)
⎝ Z ( β i , qi) ⎠

φ i := exp ( Z ( β i , qi) − 1 − ln ( Z ( β i , qi) − β i) − qi⋅ Ii)Eq. (11.37)

fi := φ i⋅ Pi

Z ( β i , qi) = φ i = 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

σ := 1 + 2 ε := 1 − 2 Ω := 0.07779 Ψ := 0.45724
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
→ ⎯⎯⎯⎯⎯⎯⎯⎯

(
c := 0.37464 + 1.54226⋅ ω − 0.26992⋅ ω )
2
(
α := ⎡⎣ 1 + c⋅ 1 − Tr
0.5 ) ⎤⎦ 2
⎛ 0.018 ⎞ ⎛ 5.383 ⎞
⎜ ⎜
⎜ 0.12 ⎟ ⎜ 3.946 ⎟
⎜ 0.062 ⎟ ⎜ 5.658 ⎟
⎯⎯⎯ → ⎜ ⎟ ⎯⎯⎯ → ⎜ ⎟
β := ⎛⎜ Ω ⋅
Pr ⎞ Eq.(3.53) β = ⎜ 0.032 ⎟ ⎛
q := ⎜
Ψ ⋅ α ⎞ Eq.(3.54) q = ⎜ 4.598 ⎟
⎝ Tr ⎠ ⎜ 0.073 ⎟ ⎝ Ω ⋅ Tr ⎠ ⎜ 5.359 ⎟
⎜ ⎟ ⎜ ⎟
⎜ 0.025
⎟ ⎜ 5.527

⎜ 0.036 ⎟ ⎜ 4.646 ⎟
⎜ ⎜
⎝ 0.108 ⎠ ⎝ 2.924 ⎠

369
Guess: z := 1
z−β
Given z = 1 + β − q⋅ β ⋅ Eq. (3.52) Z ( β , q) := Find ( z)
( z + ε⋅β ) ⋅( z + σ ⋅β)

1 ⎛ Z ( β i , qi) + σ ⋅ β i ⎞
i := 1 .. 8 Ii := ⋅ ln ⎜ Eq. (6.65)
2⋅ 2 ⎝ Z ( β i , qi) + ε ⋅ β i ⎠

φ i := exp ( Z ( β i , qi) − 1 − ln ( Z ( β i , qi) − β i) − qi⋅ Ii) Eq. (11.37)

fi := φ i⋅ Pi Z ( β i , qi) = φi = 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

φ BY GENERALIZED CORRELATIONS

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

⎛ 325 ⎞ ⎛ 308.3 ⎞ ⎛ 15 ⎞ ⎛ 61.39 ⎞ ⎛ .187 ⎞


⎜ ⎜ ⎜ ⎜ ⎜
T := ⎜
350 ⎟
Tc := ⎜
304.2 ⎟ ⎜ 35 ⎟ ⎜ 73.83 ⎟
ω := ⎜
.224 ⎟
P := Pc :=
⎜ 525 ⎟ ⎜ 507.6 ⎟ ⎜ 10 ⎟ ⎜ 30.25 ⎟ ⎜ .301 ⎟
⎜ ⎜ ⎜ ⎜ ⎜
⎝ 225 ⎠ ⎝ 190.6 ⎠ ⎝ 25 ⎠ ⎝ 45.99 ⎠ ⎝ .012 ⎠

→ ⎯

T P
Tr := Pr :=
Tc Pc
Evaluation of φ:

⎯⎯→ ⎯⎯→
B0 := B0 ( Tr) Eq. (3.65) B1 := B1 ( Tr) Eq. (3.66)

370
⎯⎯ → ⎯⎯ →
0.675 0.722
DB0 := Eq. (6.89) DB1 := Eq. (6.90)
2.6 5.2
Tr Tr

⎯⎯⎯⎯⎯⎯⎯⎯⎯ → ⎛ 0.932 ⎞

φ := exp ⎡⎢ ⋅ ( B0 + ω ⋅ B1)⎥ Eq. (11.60)
Pr ⎤ (a)
⎣ Tr ⎦ φ = ⎜ 0.904 ⎟ (d)
⎜ 0.903 ⎟ (f)
⎜ (g)
⎝ 0.895 ⎠

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

Interpolate in Tables E.13 - E.16:

⎛ .7454 ⎞ ⎛ 1.1842 ⎞ ⎛ 0.000 ⎞


⎜ ⎜ ⎜
φ0 := ⎜
.7517 ⎟
φ1 := ⎜
0.9634 ⎟
ω := ⎜
0.210 ⎟
⎜ .7316 ⎟ ⎜ 0.9883 ⎟ ⎜ 0.087 ⎟
⎜ ⎜ ⎜
⎝ .8554 ⎠ ⎝ 1.2071 ⎠ ⎝ 0.038 ⎠

⎯⎯⎯→ ⎛ 0.745 ⎞

(
φ := φ0⋅ φ1
ω ) Eq. (11.67):
φ =⎜
0.746 ⎟
(b)
(c)
⎜ 0.731 ⎟ (e)
⎜ (h)
⎝ 0.862 ⎠

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.

b) ∆St := −R⋅ ( x1⋅ ln ( x1) + x2⋅ ln ( x2) ) ⋅ ndot3


W
∆St = 8.82 Ans.
K

371
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 ⎠
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

372
⎛⎜ 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
⎝ ⎠ ⎝ ⎠ ⎝ ⎠
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 × 10
mol

GE is of the form: GE = −a⋅ ⎛⎜ T⋅ ln ⎛⎜


T⎞ ⎞
− T + b⋅ T + c
⎝ ⎝K⎠ ⎠
Rearrange to find b using estimated a and c values along with GE and T data.
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →
GE + a⋅ ⎛⎜ T⋅ ln ⎛⎜
T ⎞ − T⎞ − c ⎛⎜ −13.543 ⎞
B := ⎝ ⎝ K⎠ ⎠ B = ⎜ −13.559 ⎟
J
T
⎜ −13.545 mol⋅ K
Use averaged b value ⎝ ⎠
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.
⎝ ⎝ ⎠ ⎠
K mol

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

373