Chapter 14 - Section A - Mathcad Solutions

14.1 A12 := 0.59 A21 := 1.42 T := ( 55 + 273.15) ⋅ K

Margules equations:

γ 1 ( x1) := exp ⎡⎣ ( 1 − x1) ⋅ ⎣⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

2

γ 2 ( x1) := exp ⎡⎣ x1 ⋅ ⎡⎣ A21 + 2⋅ ( A12 − A21) ⋅ ( 1 − x1) ⎤⎦ ⎤⎦

2

Psat1 := 82.37⋅ kPa Psat2 := 37.31⋅ kPa

(a) BUBL P calculations based on Eq. (10.5):

Pbubl ( x1) := x1⋅ γ 1 ( x1) ⋅ Psat1 + ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2

x1⋅ γ 1 ( x1) ⋅ Psat1

y1 ( x1) :=
Pbubl ( x1)

x1 := 0.25 Pbubl ( x1) = 64.533 kPa y1 ( x1) = 0.562

x1 := 0.50 Pbubl ( x1) = 80.357 kPa y1 ( x1) = 0.731

x1 := 0.75 Pbubl ( x1) = 85.701 kPa y1 ( x1) = 0.808

(b) BUBL P calculations with virial coefficients:

3 3 3
cm cm cm
B11 := −963⋅ B22 := −1523⋅ B12 := 52⋅
mol mol mol

δ 12 := 2⋅ B12 − B11 − B22

⎡ B11⋅ ( P − Psat1) + P⋅ y22⋅ δ 12 ⎤

Φ 1 ( P , T , y1 , y2) := exp ⎢ ⎥
⎣ R⋅ T ⎦
⎡ B22⋅ ( P − Psat2) + P⋅ y12⋅ δ 12 ⎤
Φ 2 ( P , T , y1 , y2) := exp ⎢ ⎥
⎣ R ⋅ T ⎦

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 Psat1 + Psat2
Guess: P := y1 := 0.5 y2 := 1 − y1
2
x1 := 0.25 Given

y1⋅ Φ 1 ( P , T , y1 , y2) ⋅ P = x1⋅ γ 1 ( x1) ⋅ Psat1

y2⋅ Φ 2 ( P , T , y1 , y2) ⋅ P = ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2

y2 = 1 − y1
⎛ y1 ⎞
⎛ y1 ⎞ ⎜ ⎛⎜ 0.558 ⎞
⎜
⎜ y2 ⎟ := Find ( y1 , y2 , P) ⎜ 2 ⎟ = ⎜ 0.442 ⎟
y

⎜ ⎜ P ⎟ ⎜
⎝P⎠ ⎜ ⎝ 63.757 ⎠
⎝ kPa ⎠

x1 := 0.50 Given

y1⋅ Φ 1 ( P , T , y1 , y2) ⋅ P = x1⋅ γ 1 ( x1) ⋅ Psat1

y2⋅ Φ 2 ( P , T , y1 , y2) ⋅ P = ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2

y2 = 1 − y1

⎛ y1 ⎞
⎛ y1 ⎞ ⎜ ⎛⎜ 0.733 ⎞
⎜
⎜ y2 ⎟ := Find ( y1 , y2 , P) ⎜ y2 ⎟ = ⎜ 0.267 ⎟
⎜ ⎜ P ⎟ ⎜
⎝P⎠ ⎜ ⎝ 79.621 ⎠
⎝ kPa ⎠
x1 := 0.75 Given

y1⋅ Φ 1 ( P , T , y1 , y2) ⋅ P = x1⋅ γ 1 ( x1) ⋅ Psat1

y2⋅ Φ 2 ( P , T , y1 , y2) ⋅ P = ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2

y2 = 1 − y1
⎛ y1 ⎞
⎛ y1 ⎞ ⎜ ⎛⎜ 0.812 ⎞
⎜
⎜ y2 ⎟ := Find ( y1 , y2 , P) ⎜ y2 ⎟ = ⎜ 0.188 ⎟
⎜ ⎜ P ⎟ ⎜
⎝P⎠ ⎜ ⎝ 85.14 ⎠
⎝ kPa ⎠

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 14.3 T := 200⋅ K P := 30⋅ bar y1 := 0.95
3
cm
H1 := 200⋅ bar B := −105⋅
mol

Assume Henry's law applies to methane(1) in the liquid phase, and that the
Lewis/Randall rule applies to the methane in the vapor:
l v
fhat1 = H1⋅ x1 fhat1 = y1⋅ φ 1⋅ P

φ 1 := exp ⎛⎜
B⋅ P ⎞
By Eq. (11.36): φ 1 = 0.827
⎝ R⋅ T ⎠
Equate the liquid- and vapor-phase fugacities and solve for x1:

y1⋅ φ 1⋅ P
x1 := x1 = 0.118 Ans.
H1

14.4 Pressures in kPa

⎛ 0.000 ⎞ ⎛ 12.30 ⎞ ⎛ 0.000 ⎞

Data: ⎜ ⎜ ⎜
⎜ 0.0895 ⎟ ⎜ 15.51 ⎟ ⎜ 0.2716 ⎟
⎜ 0.1981 ⎟ ⎜ 18.61 ⎟ ⎜ 0.4565 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟
x1 := ⎜ 0.3193 ⎟
P := ⎜ 21.63 ⎟
y1 := ⎜ 0.5934 ⎟
⎜ 0.4232 ⎟ ⎜ 24.01 ⎟ ⎜ 0.6815 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟
⎜ 0.5119 ⎟ ⎜ 25.92 ⎟ ⎜ 0.7440 ⎟
⎜ 0.6096 ⎟ ⎜ 27.96 ⎟ ⎜ 0.8050 ⎟
⎜ ⎜ ⎜
⎝ 0.7135 ⎠ ⎝ 30.12 ⎠ ⎝ 0.8639 ⎠
i := 2 .. rows ( P) x2 := 1 − x1 Psat2 := P1
(a) It follows immediately from Eq. (12.10a) that:

ln ⎛⎝ γ 1 ⎞⎠ = A12
∞

Combining this with Eq. (12.10a) yields the required expression

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 (b) Henry's constant will be found as part of the solution to Part (c)

(c) BARKER'S METHOD by non-linear least squares.

Margules equation.
The most satisfactory procedure for reduction of this set of data is to find
the value of Henry's constant by regression along with the Margules
parameters.

γ 1 ( x1 , x2 , A12 , A21) := exp ⎡⎣ ( x2) ⋅ ⎣⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

2

γ 2 ( x1 , x2 , A12 , A21) := exp ⎡⎣ ( x1) ⋅ ⎡⎣ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

Guesses: H1 := 50 A21 := 0.2 A12 := 0.4

Mininize the sums of the squared errors by
setting sums of derivatives equal to zero.

Given ⎡d ⎡ ⎛ ⎞⎤ ⎥⎤
2

( )
H1
0=
∑ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 , x2 , A12 , A21 ⋅
⎢ dA12 ⎢ ⎜ i i i exp ( A 12)
... ⎥
⎟⎥ ⎥
i ⎢
⎣
⎢
⎣ ( )
⎜ + x2i⋅ γ 2 x1i , x2i , A12 , A21 ⋅ Psat2
⎝
⎥ ⎥
⎠⎦ ⎦

⎡d ⎡ ⎛ ⎞⎤ ⎥⎤
2

( )
H1
0=
∑ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 , x2 , A12 , A21 ⋅
⎢ dA21 ⎢ ⎜ i i i exp ( A 12)
... ⎥
⎟⎥ ⎥
i ⎢
⎣
⎢
⎣ ( )
⎜ + x2i⋅ γ 2 x1i , x2i , A12 , A21 ⋅ Psat2
⎝
⎥ ⎥
⎠⎦ ⎦

⎡d ⎡ ⎛ ⎞⎤ ⎥⎤
2

( )
H1
0=
∑ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 , x2 , A12 , A21 ⋅
⎢ dH1 ⎢ ⎜ i i i exp ( A 12)
... ⎥
⎟⎥ ⎥
i ⎢
⎣
⎢
⎣ ( )
⎜ + x2i⋅ γ 2 x1i , x2i , A12 , A21 ⋅ Psat2
⎝
⎥ ⎥
⎠⎦ ⎦
⎛ A12 ⎞ ⎛ A12 ⎞ ⎛ 0.348 ⎞
⎜ ⎜ ⎜
⎜ A21 ⎟ := Find ( A12 , A21 , H1) ⎜ 21 ⎟ ⎜ 0.178 ⎟
A = Ans.
⎜H ⎜H ⎜
⎝ 1⎠ ⎝ 1 ⎠ ⎝ 51.337 ⎠

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 (d) γ1 ( x1 , x2) := exp ⎡⎣ x22⋅ ⎡⎣ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

γ2 ( x1 , x2) := exp ⎡⎣ x1 ⋅ ⎡⎣ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

( ) exp( A12) + x2i⋅ γ2 ( x1i , x2i) ⋅ Psat2

H1
Pcalc := x1 ⋅ γ1 x1 , x2 ⋅
i i i i

( )
H1
x1 ⋅ γ1 x1 , x2 ⋅
i i i exp ( A 12)
y1calc :=
i Pcalc
i

0.2

0
Pi−Pcalc
i

(y1i−y1calci)⋅ 100
0.2

0.4

0.6
0 0.2 0.4 0.6 0.8
x1
i
Pressure residuals
y1 residuals

Fit GE/RT data to Margules eqn. by least squares:

i := 2 .. rows ( P) y2 := 1 − y1

Given 2
⎡⎛ ⎛ y1 ⋅ Pi ⎞ ⎞ ⎤
∑ ⎢ ⎜ x1 ⋅ ln⎜ ... − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
d i
0=
dA12 ⎢ ⎜ i ⎜ H1 ⎟ ⎟ ⎜ i i i⎥
⎢⎜ ⎜ x1 ⋅ ⎟ ⎜⎝ + A12⋅ x2i ⎠ ⎥
⎝ i exp ( A12) ⎠
i
⎢⎜ y ⋅P
⎟ ⎥
⎢ ⎜ + x ⋅ ln⎛⎜ 2i i ⎞ ⎟ ⎥
⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎥
⎣⎝ ⎝ i ⎠ ⎠ ⎦
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 2
⎡⎛ ⎛ y1 ⋅ Pi ⎞ ⎞ ⎤
∑ ⎢ ⎜ x1 ⋅ ln⎜ ... − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
d i
0=
dA21 ⎢ ⎜ i ⎜ H1 ⎟ ⎟ ⎜ i i i⎥
⎢⎜ ⎜ x1 ⋅ ⎟ ⎜⎝ + A12⋅ x2i ⎠ ⎥
⎝ i exp ( A12) ⎠
i
⎢⎜ y ⋅P
⎟ ⎥
⎢ ⎜ + x ⋅ ln⎛⎜ 2i i ⎞ ⎟ ⎥
⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎥
⎣⎝ ⎝ i ⎠ ⎠ ⎦
2
y1 ⋅ Pi
d ⎡⎢ ⎛⎜ ⎛ ⎞ ⎞ ⎤
∑ ⎜ ... − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
i
0= x1 ⋅ ln
dH1 ⎢ ⎜ i ⎜ H1 ⎟ ⎟ ⎜ i i i⎥
i
⎢⎜ x 1 ⋅
⎜ i exp ( A ) ⎜ +
⎟ ⎝ 12 2i ⎠
A ⋅ x ⎥
⎢⎜ ⎝ 12 ⎠
⎟ ⎥
⋅
⎢ ⎜ + x ⋅ ln ⎛⎜ 2i i ⎞
y P
⎟ ⎥
⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎥
⎣⎝ ⎝ i ⎠ ⎠ ⎦

⎛ A12 ⎞ ⎛ A12 ⎞ ⎛ 0.375 ⎞

⎜ ⎜ ⎜
⎜ A21 ⎟ := Find ( A12 , A21 , H1) ⎜ A21 ⎟ = ⎜ 0.148 ⎟ Ans.
⎜H ⎜H ⎜
⎝ 1⎠ ⎝ 1 ⎠ ⎝ 53.078 ⎠

γ1 ( x1 , x2) := exp ⎡⎣ x2 ⋅ ⎡⎣ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

2

γ2 ( x1 , x2) := exp ⎡⎣ x1 ⋅ ⎣⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

( ) ( )
H1
Pcalc := x1 ⋅ γ1 x1 , x2 ⋅ + x2 ⋅ γ2 x1 , x2 ⋅ Psat2
i i i i exp ( A 12) i i i

( )
H1
x1 ⋅ γ1 x1 , x2 ⋅
i i i exp ( A 12)
y1calc :=
i Pcalc
i

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 0

0.2
Pi−Pcalc
i

(y1i−y1calci)⋅ 100
0.4

0.6

0.8
0 0.2 0.4 0.6 0.8
x1
i
Pressure residuals
y1 residuals

14.5 Pressures in kPa

⎛ 0.3193 ⎞ ⎛ 21.63 ⎞ ⎛ 0.5934 ⎞

⎜ ⎜ ⎜
Data:
⎜ 0.4232 ⎟ ⎜ 24.01 ⎟ ⎜ 0.6815 ⎟
⎜ 0.5119 ⎟ ⎜ 25.92 ⎟ ⎜ 0.7440 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟
x1 := ⎜ ⎟ P := ⎜ ⎟ y1 := ⎜ ⎟
0.6096 27.96 0.8050
⎜ 0.7135 ⎟ ⎜ 30.12 ⎟ ⎜ 0.8639 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟
⎜ 0.7934
⎟ ⎜ 31.75
⎟ ⎜ 0.9048
⎟
⎜ 0.9102 ⎟ ⎜ 34.15 ⎟ ⎜ 0.9590 ⎟
⎜ ⎜ ⎜
⎝ 1.000 ⎠ ⎝ 36.09 ⎠ ⎝ 1.000 ⎠
i := 1 .. 7 x2 := 1 − x1 Psat1 := P8
(a) It follows immediately from Eq. (12.10a) that:

ln ⎛⎝ γ 2 ⎞⎠ = A21
∞

Combining this with Eq. (12.10a) yields the required expression.

(b) Henry's constant will be found as part of the solution to Part (c).

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 (c) BARKER'S METHOD by non-linear least squares.
Margules equation.
The most satisfactory procedure for reduction of this set of data is to find
the value of Henry's constant by regression along with the Margules
parameters.

γ 1 ( x1 , x2 , A12 , A21) := exp ⎡⎣ ( x2) ⋅ ⎡⎣ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

2

γ 2 ( x1 , x2 , A12 , A21) := exp ⎡⎣ ( x1) ⋅ ⎣⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

Guesses: H2 := 14 A21 := 0.148 A12 := 0.375

Mininize the sums of the squared errors by
setting sums of derivatives equal to zero.

⎡d 2⎤
Given 0 =
∑ ( )
⎢ dA ⎡⎢Pi − ⎛⎜ x1i⋅ γ 1 x1i , x2i , A12 , A21 ⋅ Psat1 ... ⎞⎤ ⎥
⎥
⎢ 12 ⎢ ⎜ ⎟⎥ ⎥
( )
i H2
⎢ ⎢ ⎜ + x2i⋅ γ 2 x1i , x2i , A12 , A21 ⋅ exp ( A21) ⎥ ⎥
⎣ ⎣ ⎝ ⎠⎦ ⎦
⎡d 2⎤
0=
∑ ⎢⎢ dA21 ⎡⎢Pi − ⎛⎜x1 ⋅γ 1 ( x1 , x2 , A12 , A21) ⋅ Psat1 ...
i i i
⎞⎤
⎥ ⎥
⎥
⎢ ⎜ ⎟⎥
( )
i H2
⎢ ⎢ +
⎜ i x ⋅ γ x , x , A , A ⋅ ⎥ ⎥
exp ( A21)
2 2 1 2 12 21
⎣ ⎣ ⎝ i i
⎠⎦ ⎦
⎡d 2⎤
0=
∑ ( )
⎢ dH ⎡⎢Pi − ⎛⎜ x1i⋅ γ 1 x1i , x2i , A12 , A21 ⋅ Psat1 ... ⎞⎤ ⎥
⎥
⎢ 2⎢ ⎜ ⎟⎥ ⎥
( )
i H 2
⎢ ⎢ ⎜ 2i 2 1i 2i 12 21 exp ( A21) ⎥ ⎥
+ x ⋅ γ x , x , A , A ⋅
⎣ ⎣ ⎝ ⎠⎦ ⎦

⎛ A12 ⎞ ⎛ A12 ⎞ ⎛ 0.469 ⎞

⎜ ⎜ ⎜
⎜ A21 ⎟ := Find ( A12 , A21 , H2) ⎜ 21 ⎟ ⎜ 0.279 ⎟
A = Ans.
⎜H ⎜H ⎜
⎝ 2⎠ ⎝ 2 ⎠ ⎝ 14.87 ⎠

(d) γ1 ( x1 , x2) := exp ⎡⎣ x22⋅ ⎡⎣ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

γ2 ( x1 , x2) := exp ⎡⎣ x1 ⋅ ⎣⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

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 ( ) ( )
H2
Pcalc := x1 ⋅ γ1 x1 , x2 ⋅ Psat1 + x2 ⋅ γ2 x1 , x2 ⋅
i i i i i i i exp ( A 21)

y1calc :=
i i (
x1 ⋅ γ1 x1 , x2 ⋅ Psat1
i )
i Pcalc
i

The plot of residuals below shows that the procedure used (Barker's
method with regression for H2) is not in this case very satisfactory, no
doubt because the data do not extend close enough to x1 = 0.

Pi−Pcalc 1
i

(y1i−y1calci)⋅ 100 2

4
0.2 0.4 0.6 0.8
x1
i
Pressure residuals
y1 residuals

Fit GE/RT data to Margules eqn. by least squares:

i := 1 .. 7 y2 := 1 − y1

Given 2
⎡⎛ ⎛ y1 ⋅ Pi ⎞ ⎞ ⎤
⎢ ⎜ x1 ⋅ ln⎜ i
∑ − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
d
0= ...
dA12 ⎢ ⎜ i ⎜ x1i⋅ Psat1
⎝ ⎠ ⎟ ⎜ i i i⎥
i
⎢⎜ ⎛ y ⋅
2 Pi ⎞ ⎟ ⎜⎝ + A12⋅ x2i ⎠ ⎥
⎢ ⎜ + x ⋅ ln⎜ i ⎟ ⎥
⎢ ⎜ 2i ⎜ H2 ⎟ ⎟ ⎥
⎢⎜ ⋅
⎜ i exp ( A )
x 2 ⎥
⎣⎝ ⎝ 21 ⎠ ⎠ ⎦

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 2
⎡⎛ ⎛ y1 ⋅ Pi ⎞ ⎞ ⎤
⎢ ⎜ x1 ⋅ ln⎜ i
∑ − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
d
0= ...
dA21 ⎢ ⎜ i ⎜ x1i⋅ Psat1
⎝ ⎠ ⎟ ⎜ i i i⎥
i
⎢⎜ ⎜ +
⎟ ⎝ 12 2i ⎠
A ⋅ x ⎥
⎛ y ⋅
2 Pi ⎞
⎢ ⎜ + x ⋅ ln⎜ i ⎟ ⎥
⎢ ⎜ 2i ⎜ H2 ⎟ ⎟ ⎥
⎢⎜ ⎜ x2i⋅ exp ( A ) ⎥
⎣⎝ ⎝ 21 ⎠ ⎠ ⎦
2
d ⎡⎢ ⎛⎜ ⎛ y1i⋅ Pi ⎞ ⎞ ⎤
x1 ⋅ ln ⎜
0=
∑ dH2 ⎢ ⎜ i ⎜ x1i⋅ Psat1
⎝ ⎠
... − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
⎟ ⎜ i i i⎥
i
⎢⎜ ⎛ y ⋅
2 Pi ⎞ ⎟ ⎜⎝ + A12⋅ x2i ⎠ ⎥
⎢ ⎜ + x ⋅ ln ⎜ i ⎟ ⎥
⎢ ⎜ 2i ⎜ H2 ⎟ ⎟ ⎥
⎢⎜ ⋅
⎜ i exp ( A )
x 2 ⎥
⎣⎝ ⎝ 21 ⎠ ⎠ ⎦

⎛ A12 ⎞ ⎛ A12 ⎞ ⎛ 0.37 ⎞

⎜ ⎜ ⎜
⎜ A21 ⎟ := Find ( A12 , A21 , H2) ⎜ 21 ⎟ ⎜ 0.204 ⎟
A = Ans.
⎜H ⎜H ⎜
⎝ 2⎠ ⎝ 2 ⎠ ⎝ 15.065 ⎠

γ1 ( x1 , x2) := exp ⎡⎣ x2 ⋅ ⎣⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

2

γ2 ( x1 , x2) := exp ⎡⎣ x1 ⋅ ⎡⎣ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

( ) ( )
H2
Pcalc := x1 ⋅ γ1 x1 , x2 ⋅ Psat1 + x2 ⋅ γ2 x1 , x2 ⋅
i i i i i i i exp ( A 21)

y1calc :=
i (
x1 ⋅ γ1 x1 , x2 ⋅ Psat1
i i )
i Pcalc
i

548
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 0

Pi−Pcalc 0.2
i

(y1i−y1calci)⋅ 100
0.4

0.6
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x1
i
Pressure residuals
y1 residuals

This result is considerably improved over that obtained with Barker's method.

14.6 Pressures in kPa

Data: ⎛ 15.79 ⎞ ⎛ 0.0 ⎞ ⎛ 0.0 ⎞

⎜ ⎜ ⎜
⎜ 17.51 ⎟ ⎜ 0.0932 ⎟ ⎜ 0.1794 ⎟
⎜ 18.15 ⎟ ⎜ 0.1248 ⎟ ⎜ 0.2383 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟
⎜ 19.30 ⎟ ⎜ 0.1757 ⎟ ⎜ 0.3302 ⎟
⎜ 19.89 ⎟ ⎜ 0.2000 ⎟ ⎜ 0.3691 ⎟
P := ⎜ ⎟ x1 := ⎜ ⎟ y1 := ⎜ ⎟
⎜ 21.37 ⎟ ⎜ 0.2626 ⎟ ⎜ 0.4628 ⎟
⎜ 24.95 ⎟ ⎜ 0.3615 ⎟ ⎜ 0.6184 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟
⎜ 29.82 ⎟ ⎜ 0.4750 ⎟ ⎜ 0.7552 ⎟
⎜ 34.80 ⎟ ⎜ 0.5555 ⎟ ⎜ 0.8378 ⎟
⎜ ⎜ ⎜
⎝ 42.10 ⎠ ⎝ 0.6718 ⎠ ⎝ 0.9137 ⎠
i := 2 .. rows ( P) x2 := 1 − x1 Psat2 := P1

(a) It follows immediately from Eq. (12.10a) that:

ln ⎛⎝ γ 1 ⎞⎠ = A12
∞

Combining this with Eq. (12.10a) yields the required expression

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 (b) Henry's constant will be found as part of the solution to Part (c)

(c) BARKER'S METHOD by non-linear least squares.

Margules equation.

The most satisfactory procedure for reduction of this set of data is to

find the value of Henry's constant by regression along with the
Margules parameters.

γ 1 ( x1 , x2 , A12 , A21) := exp ⎡⎣ ( x2) ⋅ ⎡⎣ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

2

γ 2 ( x1 , x2 , A12 , A21) := exp ⎡⎣ ( x1) ⋅ ⎣⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

Guesses: H1 := 35 A21 := −1.27 A12 := −0.70

Mininize the sums of the squared errors by

setting sums of derivatives equal to zero.

Given ⎡d ⎡ ⎛ ⎞⎤ ⎥⎤
2

( )
H1
0=
∑ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 , x2 , A12 , A21 ⋅
⎢ dA12 ⎢ ⎜ i i i exp ( A 12)
... ⎥
⎟⎥ ⎥
i ⎢
⎣
⎢
⎣ ( )
⎜ + x2i⋅ γ 2 x1i , x2i , A12 , A21 ⋅ Psat2
⎝
⎥ ⎥
⎠⎦ ⎦

⎡d ⎡ ⎛ ⎞⎤
2⎤
( )
H1
0=
∑ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 , x2 , A12 , A21 ⋅
⎢ dA21 ⎢ ⎜ i i i exp A
... ⎥ ⎥
( 12) ⎟⎥ ⎥
i ⎢
⎣
⎢
⎣ ( )
⎜ + x2i⋅ γ 2 x1i , x2i , A12 , A21 ⋅ Psat2
⎝
⎥ ⎥
⎠⎦ ⎦

⎡d ⎡ ⎛ ⎞⎤ ⎥⎤
2

( )
H1
0=
∑ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 , x2 , A12 , A21 ⋅
⎢ dH1 ⎢ ⎜ i i i exp ( A 12)
... ⎥
⎟⎥ ⎥
i ⎢
⎣
⎢
⎣ ( )
⎜ + x2i⋅ γ 2 x1i , x2i , A12 , A21 ⋅ Psat2
⎝
⎥ ⎥
⎠⎦ ⎦
⎛ A12 ⎞ ⎛ A12 ⎞ ⎛ −0.731 ⎞
⎜ ⎜ ⎜
⎜ A21 ⎟ := Find ( A12 , A21 , H1) ⎜ 21 ⎟ ⎜ −1.187 ⎟
A = Ans.
⎜H ⎜H ⎜
⎝ 1⎠ ⎝ 1 ⎠ ⎝ 32.065 ⎠

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 γ1 ( x1 , x2) := exp ⎡⎣ x2 ⋅ ⎡⎣ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦
2
(d)

γ2 ( x1 , x2) := exp ⎡⎣ x1 ⋅ ⎡⎣ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

( ) exp( A12) + x2i⋅ γ2 ( x1i , x2i) ⋅ Psat2

H1
Pcalc := x1 ⋅ γ1 x1 , x2 ⋅
i i i i

( )
H1
x1 ⋅ γ1 x1 , x2 ⋅
i i i exp ( A 12)
y1calc :=
i Pcalc
i

0.5

Pi−Pcalc 0.5
i

(y1i−y1calci)⋅ 100 1

1.5

2
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
x1
i
Pressure residuals
y1 residuals

Fit GE/RT data to Margules eqn. by least squares:

i := 2 .. rows ( P) y2 := 1 − y1

Given 2
⎡⎛ ⎛ y1 ⋅ Pi ⎞ ⎞ ⎤
∑ ⎢ ⎜ x1 ⋅ ln⎜ ... − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
d i
0=
dA12 ⎢ ⎜ i ⎜ H1 ⎟ ⎟ ⎜ i i i⎥
i
⎢⎜ x 1 ⋅
⎜ i exp ( A ) ⎜ +
⎟ ⎝ 12 2i ⎠
A ⋅ x ⎥
⎢⎜ ⎝ 12 ⎠
⎟ ⎥
⋅
⎢ ⎜ + x ⋅ ln⎛⎜ 2i i ⎞
y P
⎟ ⎥
⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎥
⎣⎝ ⎝ i ⎠ ⎠ ⎦

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 2
⎡⎛ ⎛ y1 ⋅ Pi ⎞ ⎞ ⎤
∑ ⎢ ⎜ x1 ⋅ ln⎜ ... − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
d i
0=
dA21 ⎢ ⎜ i ⎜ H1 ⎟ ⎟ ⎜ i i i⎥
i
⎢⎜ x 1 ⋅
⎜ i exp ( A ) ⎜ +
⎟ ⎝ 12 2i ⎠
A ⋅ x ⎥
⎢⎜ ⎝ 12 ⎠
⎟ ⎥
⋅
⎢ ⎜ + x ⋅ ln⎛⎜ 2i i ⎞
y P
⎟ ⎥
⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎥
⎣⎝ ⎝ i ⎠ ⎠ ⎦
2
y1 ⋅ Pi
d ⎡⎢ ⎛⎜ ⎛ ⎞ ⎞ ⎤
∑ x1 ⋅ ln ⎜ ... − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
i
0=
dH1 ⎢ ⎜ i ⎜ H1 ⎟ ⎟ ⎜ i i i⎥
⎢⎜ ⎜ x1 ⋅ ⎟ ⎜⎝ + A12⋅ x2i ⎠ ⎥
⎝ i exp ( A12) ⎠
i
⎢⎜ y ⋅P
⎟ ⎥
⎢ ⎜ + x ⋅ ln ⎛⎜ 2i i ⎞ ⎟ ⎥
⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎥
⎣⎝ ⎝ i ⎠ ⎠ ⎦

⎛ A12 ⎞ ⎛ A12 ⎞ ⎛ −0.707 ⎞

⎜ ⎜ ⎜
⎜ A21 ⎟ := Find ( A12 , A21 , H1) ⎜ 21 ⎟ ⎜ −1.192 ⎟
A = Ans.
⎜H ⎜H ⎜
⎝ 1⎠ ⎝ 1 ⎠ ⎝ 33.356 ⎠

γ1 ( x1 , x2) := exp ⎡⎣ x2 ⋅ ⎣⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

2

γ2 ( x1 , x2) := exp ⎡⎣ x1 ⋅ ⎡⎣ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

( ) ( )
H1
Pcalc := x1 ⋅ γ1 x1 , x2 ⋅ + x2 ⋅ γ2 x1 , x2 ⋅ Psat2
i i i i exp ( A 12) i i i

( ) exp( A12)
H1
x1 ⋅ γ1 x1 , x2 ⋅
i i i
y1calc :=
i Pcalc
i

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 0

0.5

Pi−Pcalc 1
i

(y1i−y1calci)⋅ 100 1.5

2.5
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
x1
i
Pressure residuals
y1 residuals

14.7 Pressures in kPa

⎛ 0.1757 ⎞ ⎛ 19.30 ⎞ ⎛ 0.3302 ⎞

⎜ ⎜ ⎜
Data: ⎜ 0.2000 ⎟ ⎜ 19.89 ⎟ ⎜ 0.3691 ⎟
⎜ 0.2626 ⎟ ⎜ 21.37 ⎟ ⎜ 0.4628 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟
⎜ 0.3615 ⎟ ⎜ 24.95 ⎟ ⎜ 0.6184 ⎟
⎜ 0.4750 ⎟ ⎜ 29.82 ⎟ ⎜ 0.7552 ⎟
x1 := ⎜ ⎟ P := ⎜ ⎟ y1 := ⎜ ⎟
⎜ 0.5555 ⎟ ⎜ 34.80 ⎟ ⎜ 0.8378 ⎟
⎜ 0.6718 ⎟ ⎜ 42.10 ⎟ ⎜ 0.9137 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟
⎜ 0.8780 ⎟ ⎜ 60.38 ⎟ ⎜ 0.9860 ⎟
⎜ 0.9398 ⎟ ⎜ 65.39 ⎟ ⎜ 0.9945 ⎟
⎜ ⎜ ⎜
⎝ 1.0000 ⎠ ⎝ 69.36 ⎠ ⎝ 1.0000 ⎠
i := 1 .. 9 x2 := 1 − x1 Psat1 := P10
(a) It follows immediately from Eq. (12.10a) that:

ln ⎛⎝ γ 2 ⎞⎠ = A21
∞

Combining this with Eq. (12.10a) yields the required expression.

(b) Henry's constant will be found as part of the solution to Part (c).

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 (c) BARKER'S METHOD by non-linear least squares.
Margules equation.
The most satisfactory procedure for reduction of this set of data is to
find the value of Henry's constant by regression along with the
Margules parameters.

γ 1 ( x1 , x2 , A12 , A21) := exp ⎡⎣ ( x2) ⋅ ⎣⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

2

γ 2 ( x1 , x2 , A12 , A21) := exp ⎡⎣ ( x1) ⋅ ⎡⎣ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

Guesses: H2 := 4 A21 := −1.37 A12 := −0.68

Mininize the sums of the squared errors by
setting sums of derivatives equal to zero.

Given
⎡d 2⎤
0=
∑ ⎢⎢ dA12 ⎡⎢Pi − ⎛⎜x1 ⋅γ 1 ( x1 , x2 , A12 , A21) ⋅ Psat1 ...
i i i
⎞⎤
⎥ ⎥
⎥
⎢ ⎜ ⎟⎥
( )
i H2
⎢ ⎢ +
⎜ i x ⋅ γ x , x , A , A ⋅ ⎥ ⎥
exp ( A21)
2 2 1 2 12 21
⎣ ⎣ ⎝ i i
⎠⎦ ⎦

⎡d 2⎤
0=
∑ (
⎢ dA ⎡⎢Pi − ⎛⎜ x1i⋅ γ 1 x1i , x2i , A12 , A21 ⋅ Psat1 ...) ⎞⎤ ⎥
⎥
⎢ 21 ⎢ ⎜ ⎟⎥ ⎥
( )
i H2
⎢ ⎢ ⎜ + x2i⋅ γ 2 x1i , x2i , A12 , A21 ⋅ exp ( A21) ⎥ ⎥
⎣ ⎣ ⎝ ⎠⎦ ⎦

⎡d 2⎤
0=
∑ ⎢⎢ dH2 ⎡⎢Pi − ⎛⎜x1 ⋅ γ 1 ( x1 , x2 , A12 , A21) ⋅Psat1 ...
i i i
⎞⎤
⎥ ⎥
⎥
⎢ ⎜ ⎟⎥
( )
i H2
⎢ ⎢ +
⎜ i x ⋅ γ x , x , A , A ⋅ ⎥ ⎥
exp ( A21)
2 2 1 2 12 21
⎣ ⎣ ⎝ i i
⎠⎦ ⎦

⎛ A12 ⎞ ⎛ A12 ⎞ ⎛ −0.679 ⎞

⎜ ⎜ ⎜
⎜ A21 ⎟ := Find ( A12 , A21 , H2) ⎜ 21 ⎟ ⎜ −1.367 ⎟
A = Ans.
⎜H ⎜H ⎜
⎝ 2⎠ ⎝ 2 ⎠ ⎝ 3.969 ⎠

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 (d) γ1 ( x1 , x2) := exp ⎡⎣ x22⋅ ⎡⎣ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

γ2 ( x1 , x2) := exp ⎡⎣ x1 ⋅ ⎡⎣ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

( ) ( )
H2
Pcalc := x1 ⋅ γ1 x1 , x2 ⋅ Psat1 + x2 ⋅ γ2 x1 , x2 ⋅
i i i i i i i exp ( A 21)

y1calc :=
i (
x1 ⋅ γ1 x1 , x2 ⋅ Psat1
i i )
i Pcalc
i

Pi−Pcalc 0
i

(y1i−y1calci)⋅ 100
1

2
0 0.2 0.4 0.6 0.8
x1
i
Pressure residuals
y1 residuals

Fit GE/RT data to Margules eqn. by least squares:

i := 1 .. 9 y2 := 1 − y1

2
Given ⎡⎛ ⎛ y1 ⋅ Pi ⎞ ⎞ ⎤
⎢ ⎜ x1 ⋅ ln⎜ i
∑ − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
d
0= ...
dA12 ⎢ ⎜ i ⎜ x1i⋅ Psat1
⎝ ⎠ ⎟ ⎜ i i i⎥
i
⎢⎜ ⎛ y ⋅
2 Pi ⎞ ⎟ ⎜⎝ + A12⋅ x2i ⎠ ⎥
⎢ ⎜ + x ⋅ ln⎜ i ⎟ ⎥
⎢ ⎜ 2i ⎜ H2 ⎟ ⎟ ⎥
⎢⎜ ⋅
⎜ i exp ( A )
x 2 ⎥
⎣⎝ ⎝ 21 ⎠ ⎠ ⎦

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 2
⎡⎛ ⎛ y1 ⋅ Pi ⎞ ⎞ ⎤
⎢ ⎜ x1 ⋅ ln⎜ i
∑ − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
d
0= ...
dA21 ⎢ ⎜ i ⎜ x1i⋅ Psat1
⎝ ⎠ ⎟ ⎜ i i i⎥
i
⎢⎜ ⎛ y ⋅
2 Pi ⎞ ⎟ ⎜⎝ + A12⋅ x2i ⎠ ⎥
⎢ ⎜ + x ⋅ ln⎜ i ⎟ ⎥
⎢ ⎜ 2i ⎜ H2 ⎟ ⎟ ⎥
⎢⎜ ⋅
⎜ i exp ( A )
x 2 ⎥
⎣⎝ ⎝ 21 ⎠ ⎠ ⎦
2
d ⎡⎢ ⎛⎜ ⎛ y1i⋅ Pi ⎞ ⎞ ⎤
x1 ⋅ ln ⎜
0=
∑ dH2 ⎢ ⎜ i ⎜ x1i⋅ Psat1
⎝ ⎠
... − ⎛ A21⋅ x1 ... ⎞ ⋅ x1 ⋅ x2 ⎥
⎟ ⎜ i i i⎥
i
⎢⎜ ⎜ +
⎟ ⎝ 12 2i ⎠
A ⋅ x ⎥
⎛ y ⋅
2 Pi ⎞
⎢ ⎜ + x ⋅ ln ⎜ i ⎟ ⎥
⎢ ⎜ 2i ⎜ H2 ⎟ ⎟ ⎥
⎢⎜ ⎜ x2i⋅ exp ( A ) ⎥
⎣⎝ ⎝ 21 ⎠ ⎠ ⎦

⎛ A12 ⎞ ⎛ A12 ⎞ ⎛ −0.845 ⎞

⎜ ⎜ ⎜
⎜ A21 ⎟ := Find ( A12 , A21 , H2) ⎜ A21 ⎟ = ⎜ −1.229 ⎟ Ans.
⎜H ⎜H ⎜
⎝ 2⎠ ⎝ 2 ⎠ ⎝ 4.703 ⎠

γ1 ( x1 , x2) := exp ⎡⎣ x2 ⋅ ⎡⎣ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤⎦ ⎤⎦

2

γ2 ( x1 , x2) := exp ⎡⎣ x1 ⋅ ⎣⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤⎦ ⎤⎦

2

( ) ( )
H2
Pcalc := x1 ⋅ γ1 x1 , x2 ⋅ Psat1 + x2 ⋅ γ2 x1 , x2 ⋅
i i i i i i i exp ( A 21)

y1calc :=
i (
x1 ⋅ γ1 x1 , x2 ⋅ Psat1
i i )
i Pcalc
i

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 1

Pi−Pcalc 0
i

(y1i−y1calci)⋅ 100
1

2
0 0.2 0.4 0.6 0.8
x1
i
Pressure residuals
y1 residuals

14.8 (a) Data from Table 12.1

⎛ 15.51 ⎞ ⎛ 0.0895 ⎞ ⎛ 0.2716 ⎞ ⎛ 1.304 ⎞ ⎛ 1.009 ⎞

⎜ 18.61 ⎜ 0.1981 ⎜ 0.4565 ⎜ 1.188 ⎜ 1.026
⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟
⎜ 21.63 ⎟ ⎜ 0.3193 ⎟ ⎜ 0.5934 ⎟ ⎜ 1.114 ⎟ ⎜ 1.050 ⎟
⎜ 24.01 ⎟ ⎜ 0.4232 ⎟ ⎜ 0.6815 ⎟ ⎜ 1.071 ⎟ ⎜ 1.078 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟
P := ⎜ 25.92 ⎟ kPa x1 := ⎜ 0.5119 ⎟ y1 := ⎜ 0.7440 ⎟ γ 1 := ⎜ 1.044 ⎟ γ 2 := ⎜ 1.105 ⎟
⎜ 27.96 ⎟ ⎜ 0.6096 ⎟ ⎜ 0.8050 ⎟ ⎜ 1.023 ⎟ ⎜ 1.135 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟
⎜ 30.12 ⎟ ⎜ 0.7135 ⎟ ⎜ 0.8639 ⎟ ⎜ 1.010 ⎟ ⎜ 1.163 ⎟
⎜ 31.75 ⎟ ⎜ 0.7934 ⎟ ⎜ 0.9048 ⎟ ⎜ 1.003 ⎟ ⎜ 1.189 ⎟
⎜ ⎜ ⎜ ⎜ ⎜
⎝ 34.15 ⎠ ⎝ 0.9102 ⎠ ⎝ 0.9590 ⎠ ⎝ 0.997 ⎠ ⎝ 1.268 ⎠

n := rows ( P) n=9 i := 1 .. n x2 := 1 − x1 y2 := 1 − y1
i i i i
Psat1 := 36.09kPa Psat2 := 12.30kPa T := ( 50 + 273.15)K

Data reduction with the Margules equation and Eq. (10.5):

y1 ⋅ Pi y2 ⋅ Pi
i i
γ 1 := γ 2 :=
i x1 ⋅ Psat1 i x2 ⋅ Psat2
i i

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 i := 1 .. n
i i ( )
GERTi := x1 ⋅ ln γ 1 + x2 ⋅ ln γ 2
i i ( )
Guess: A12 := 0.1 A21 := 0.3
n
f ( A12 , A21) :=
∑ ( )
⎡⎣ GERTi − A21⋅ x1i + A12⋅ x2i ⋅ x1i⋅ x2i ⎤⎦
2

i=1
⎛ A12 ⎞
⎜ := Minimize ( f , A12 , A21) A12 = 0.374 A21 = 0.197 Ans.
⎝ A 21 ⎠
n

∑ ( )
⎡⎣ GERTi − A21⋅ x1i + A12⋅ x2i ⋅ x1i⋅ x2i ⎤⎦
2

i=1
RMS Error: RMS :=
n

−3
RMS = 1.033 × 10 x1 := 0 , 0.01 .. 1

0.1

GERT i
0.05
⎡⎣ A21⋅ x1+A12⋅ ( 1−x1) ⎤⎦ ⋅ x1⋅ ( 1−x1)

0
0 0.2 0.4 0.6 0.8
x1 , x1
i

Data reduction with the Margules equation and Eq. (14.1):

3 3 3
cm cm cm
B11 := −1840 B22 := −1800 B12 := −1150
mol mol mol

δ 12 := 2⋅ B12 − B11 − B22

⎡ ⎡ B11⋅ ( Pi − Psat1) + Pi⋅ y2 2⋅ δ 12 ⎤ ⎤

⎢
Φ 1 := exp ⎢ ⎣
i ⎦⎥ ( ) γ 1 :=
y1 ⋅ Φ 1 ⋅ Pi
i i
⎥
i ⎣ R⋅ T ⎦ i x1 ⋅ Psat1
i

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 ⎢
Φ 2 := exp ⎢ ⎣
i ( )
⎡ ⎡ B22⋅ ( Pi − Psat2) + Pi⋅ y1 2⋅ δ 12 ⎤ ⎤
⎦⎥ γ 2 :=
y2 ⋅ Φ 2 ⋅ Pi
i i
⎥
i ⎣ R⋅ T ⎦ i x2 ⋅ Psat2
i
i := 1 .. n
i i ( )
GERTi := x1 ⋅ ln γ 1 + x2 ⋅ ln γ 2
i i ( )
Guess: A12 := 0.1 A21 := 0.3
n
f ( A12 , A21) :=
∑ ( )
⎡⎣ GERTi − A21⋅ x1i + A12⋅ x2i ⋅ x1i⋅ x2i ⎤⎦
2

i=1
⎛ A12 ⎞
⎜ := Minimize ( f , A12 , A21) A12 = 0.379 A21 = 0.216 Ans.
⎝ A 21 ⎠

n
( )
⎡⎣ GERTi − A21⋅ x1i + A12⋅ x2i ⋅ x1i⋅ x2i ⎤⎦
2
RMS Error: RMS :=
∑ n
i=1

−4
RMS = 9.187 × 10 x1 := 0 , 0.01 .. 1

0.1

GERT i
0.05
⎡⎣ A21⋅ x1+A12⋅ ( 1−x1) ⎤⎦ ⋅ x1⋅ ( 1−x1)

0
0 0.5 1
x1 , x1
i

The RMS error with Eqn. (14.1) is about 11% lower than the RMS error
with Eqn. (10.5).

Note: The following problem was solved with the temperature (T) set at
the normal boiling point. To solve for another temperature, simply change
T to the approriate value.

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 14.9 (a) Acetylene: Tc := 308.3K Pc := 61.39bar Tn := 189.4K
T
T := Tn Tr := Tr = 0.614
Tc

For Redlich/Kwong EOS:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

−1
α ( Tr ) ⋅ R ⋅ Tc
2 2
a ( Tr) := Ψ ⋅
2 Eq. (3.45)
α ( Tr) := Tr Table 3.1
Pc

Ψ ⋅ α ( Tr ) Ω ⋅ Pr
q ( Tr) := Eq. (3.54) β ( Tr , Pr) := Eq. (3.53)
Ω ⋅ Tr Tr

Define Z for the vapor (Zv) Guess: zv := 0.9

Given Eq. (3.52)

zv − β ( Tr , Pr)
zv = 1 + β ( Tr , Pr) − q ( Tr) ⋅ β ( Tr , Pr) ⋅
( zv + ε ⋅ β ( Tr , Pr) ) ⋅ ( zv + σ ⋅ β ( Tr , Pr) )
Zv ( Tr , Pr) := Find ( zv)

Define Z for the liquid (Zl) Guess: zl := 0.01

Given Eq. (3.56)

⎛ 1 + β ( Tr , Pr) − zl ⎞
( )(
zl = β ( Tr , Pr) + zl + ε ⋅ β ( Tr , Pr) ⋅ zl + σ ⋅ β ( Tr , Pr) ⋅ ⎜ )
⎝ q ( T r ) ⋅ β ( T r , Pr ) ⎠
To find liquid root, restrict search for zl to values less than 0.2, zl < 0.2

Zl ( Tr , Pr) := Find ( zl)

Define I for liquid (Il) and vapor (Iv)

⎛ Zl ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞
Il ( Tr , Pr) :=
1
⋅ ln ⎜
σ−ε ⎝ Zl ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠

⎛ Zv ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞
Iv ( Tr , Pr) :=
1
⋅ ln ⎜ Eq. (6.65b)
σ−ε ⎝ Zv ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠
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 ( )
lnφl ( Tr , Pr) := Zl ( Tr , Pr) − 1 − ln Zl ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Il ( Tr , Pr)
Eq. (11.37)

( )
lnφv ( Tr , Pr) := Zv ( Tr , Pr) − 1 − ln Zv ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Iv ( Tr , Pr)

1bar
Guess Psat: Psatr :=
Pc
Given lnφl ( Tr , Psatr) = lnφv ( Tr , Psatr) Psatr := Find ( Psatr)

Zl ( Tr , Psatr) = 4.742 × 10 Zv ( Tr , Psatr) = 0.965

−3
Psatr = 0.026

Psat := Psatr⋅ Pc Psat = 1.6 bar Ans.

The following table lists answers for all parts. Literature values are interpolated
from tables in Perry's Chemical Engineers' Handbook, 6th ed. The last column
shows the percent difference between calculated and literature values at 0.85Tc.
These range from 0.1 to 27%. For the normal boiling point (Tn), Psat should be
1.013 bar. Tabulated results for Psat do not agree well with this value.
Differences range from 3 to > 100%.
Tn (K) Psat (bar) 0.85 Tc (K) Psat (bar) Psat (bar) % Difference
@ Tn @ 0.85 Tc Lit. Values
Acetylene 189.4 1.60 262.1 20.27 19.78 2.5%
Argon 87.3 0.68 128.3 20.23 18.70 8.2%
Benzene 353.2 1.60 477.9 16.028 15.52 3.2%
n-Butane 272.7 1.52 361.3 14.35 12.07 18.9%
Carbon Monoxide 81.7 0.92 113.0 15.2 12.91 17.7%
n-Decane 447.3 2.44 525.0 6.633 5.21 27.3%
Ethylene 169.4 1.03 240.0 17.71 17.69 0.1%
n-Heptane 371.6 2.06 459.2 7.691 7.59 1.3%
Methane 111.4 0.71 162.0 19.39 17.33 11.9%
Nitrogen 77.3 0.86 107.3 14.67 12.57 16.7%

14.10 (a) Acetylene: ω := 0.187 Tc := 308.3K Pc := 61.39bar Tn := 189.4K

T
T := Tn Note: For solution at 0.85T c, set T := 0.85Tc. Tr :=
Tc
For SRK EOS: Tr = 0.614

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

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 2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + ( 0.480 + 1.574ω − 0.176ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ 2 ⎜ 2 ⎥
Table 3.1

a ( Tr) := Ψ ⋅
(
α Tr , ω ⋅ R ⋅ Tc ) 2 2
Eq. (3.45)
Pc

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54) β ( Tr , Pr) :=
Ω ⋅ Pr
Eq. (3.53)
Ω ⋅ Tr Tr

Define Z for the vapor (Zv) Guess: zv := 0.9

Given Eq. (3.52)

zv − β ( Tr , Pr)
zv = 1 + β ( Tr , Pr) − q ( Tr) ⋅ β ( Tr , Pr) ⋅
( zv + ε ⋅ β ( Tr , Pr) ) ⋅ ( zv + σ ⋅ β ( Tr , Pr) )
Zv ( Tr , Pr) := Find ( zv)

Define Z for the liquid (Zl) Guess: zl := 0.01

Given Eq. (3.56)

⎛ 1 + β ( Tr , Pr) − zl ⎞
( )(
zl = β ( Tr , Pr) + zl + ε ⋅ β ( Tr , Pr) ⋅ zl + σ ⋅ β ( Tr , Pr) ⋅ ⎜ )
⎝ q ( T r ) ⋅ β ( T r , Pr ) ⎠
To find liquid root, restrict search for zl to values less than 0.2, zl < 0.2

Zl ( Tr , Pr) := Find ( zl)

Define I for liquid (Il) and vapor (Iv)

⎛ Zl ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞
Il ( Tr , Pr) :=
1
⋅ ln ⎜
σ−ε ⎝ Zl ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠
Eq. (6.65b)
⎛ Zv ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞
Iv ( Tr , Pr) :=
1
⋅ ln ⎜
σ−ε ⎝ Zv ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠

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 ( )
lnφl ( Tr , Pr) := Zl ( Tr , Pr) − 1 − ln Zl ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Il ( Tr , Pr)
Eq. (11.37)

( )
lnφv ( Tr , Pr) := Zv ( Tr , Pr) − 1 − ln Zv ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Iv ( Tr , Pr)

2bar
Guess Psat: Psatr :=
Pc
Given lnφl ( Tr , Psatr) = lnφv ( Tr , Psatr) Psatr := Find ( Psatr)

Zl ( Tr , Psatr) = 3.108 × 10 Zv ( Tr , Psatr) = 0.975

−3
Psatr = 0.017

Psat := Psatr⋅ Pc Psat = 1.073 bar Ans.

The following table lists answers for all parts. Literature values are interpolated
from tables in Perry's Chemical Engineers' Handbook, 6th ed. The last column
shows the percent difference between calculated and literature values at 0.85Tc.
These range from less than 0.1 to 2.5%. For the normal boiling point (Tn), Psat
should be 1.013 bar. Tabulated results for Psat agree well with this value.
Differences range from near 0 to 6%.

Tn (K) Psat (bar) 0.85 Tc (K) Psat (bar) Psat (bar) % Difference
@ Tn @ 0.85 Tc Lit. Values
Acetylene 189.4 1.073 262.1 20.016 19.78 1.2%
Argon 87.3 0.976 128.3 18.79 18.70 0.5%
Benzene 353.2 1.007 477.9 15.658 15.52 0.9%
n-Butane 272.7 1.008 361.3 12.239 12.07 1.4%
Carbon Monoxide 81.7 1.019 113.0 12.871 12.91 -0.3%
n-Decane 447.3 1.014 525.0 5.324 5.21 2.1%
Ethylene 169.4 1.004 240.0 17.918 17.69 1.3%
n-Heptane 371.6 1.011 459.2 7.779 7.59 2.5%
Methane 111.4 0.959 162.0 17.46 17.33 0.8%
Nitrogen 77.3 0.992 107.3 12.617 12.57 0.3%

14.10 (b) Acetylene: ω := 0.187 Tc := 308.3K Pc := 61.39bar Tn := 189.4K

T
T := Tn Note: For solution at 0.85T c, set T := 0.85Tc. Tr :=
Tc
For PR EOS:
Tr = 0.614

σ := 1 + 2 ε := 1 − 2 Ω := 0.07779 Ψ := 0.45724 Table 3.1

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 2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + ( 0.37464 + 1.54226ω − 0.26992ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ 2 ⎜ 2 ⎥ Table 3.1

a ( Tr) := Ψ ⋅
( )
α Tr , ω ⋅ R ⋅ Tc
2 2
Eq. (3.45)
Pc

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54) β ( Tr , Pr) :=
Ω ⋅ Pr
Eq. (3.53)
Ω ⋅ Tr Tr

Define Z for the vapor (Zv) Guess: zv := 0.9

Given Eq. (3.52)

zv − β ( Tr , Pr)
zv = 1 + β ( Tr , Pr) − q ( Tr) ⋅ β ( Tr , Pr) ⋅
( zv + ε ⋅ β ( Tr , Pr) ) ⋅ ( zv + σ ⋅ β ( Tr , Pr) )
Zv ( Tr , Pr) := Find ( zv)

Define Z for the liquid (Zl) Guess: zl := 0.01

Given Eq. (3.56)

⎛ 1 + β ( Tr , Pr) − zl ⎞
( )(
zl = β ( Tr , Pr) + zl + ε ⋅ β ( Tr , Pr) ⋅ zl + σ ⋅ β ( Tr , Pr) ⋅ ⎜ )
⎝ q ( T r ) ⋅ β ( T r , Pr ) ⎠
To find liquid root, restrict search for zl to values less than 0.2,zl < 0.2

Zl ( Tr , Pr) := Find ( zl)

Define I for liquid (Il) and vapor (Iv)

⎛ Zl ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞
Il ( Tr , Pr) :=
1
⋅ ln ⎜
σ−ε ⎝ Zl ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠
Eq. (6.65b)
⎛ Zv ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞
Iv ( Tr , Pr) :=
1
⋅ ln ⎜
σ−ε ⎝ Zv ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠

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 ( )
lnφl ( Tr , Pr) := Zl ( Tr , Pr) − 1 − ln Zl ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Il ( Tr , Pr)
Eq. (11.37)

( )
lnφv ( Tr , Pr) := Zv ( Tr , Pr) − 1 − ln Zv ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Iv ( Tr , Pr)

2bar
Guess Psat: Psatr :=
Pc
Given lnφl ( Tr , Psatr) = lnφv ( Tr , Psatr) Psatr := Find ( Psatr)

Zl ( Tr , Psatr) = 2.795 × 10 Zv ( Tr , Psatr) = 0.974

−3
Psatr = 0.018

Psat := Psatr⋅ Pc Psat = 1.09 bar Ans.

The following table lists answers for all parts. Literature values are interpolated
from tables in Perry's Chemical Engineers' Handbook, 6th ed. The last column
shows the percent difference between calculated and literature values at 0.85Tc.
These range from less than 0.1 to 1.2%. For the normal boiling point (Tn), Psat
should be 1.013 bar. Tabulated results for Psat agree well with this value.
Differences range from near 0 to 7.6%.
Tn (K) Psat (bar) 0.85 Tc (K) Psat (bar) Psat (bar) % Difference
@ Tn @ 0.85 Tc Lit. Values
Acetylene 189.4 1.090 262.1 19.768 19.78 -0.1%
Argon 87.3 1.015 128.3 18.676 18.70 -0.1%
Benzene 353.2 1.019 477.9 15.457 15.52 -0.4%
n-Butane 272.7 1.016 361.3 12.084 12.07 0.1%
Carbon Monoxide 81.7 1.041 113.0 12.764 12.91 -1.2%
n-Decane 447.3 1.016 525.0 5.259 5.21 0.9%
Ethylene 169.4 1.028 240.0 17.744 17.69 0.3%
n-Heptane 371.6 1.012 459.2 7.671 7.59 1.1%
Methane 111.4 0.994 162.0 17.342 17.33 0.1%
Nitrogen 77.3 1.016 107.3 12.517 12.57 -0.4%

14.12 (a) van der Waals Eqn. Tr := 0.7

σ := 0 ε := 0 1 27 α ( Tr) := 1
Ω := Ψ :=
8 64
Ψ ⋅ α ( Tr) Ω ⋅ Pr
q ( Tr) := β ( Tr , Pr) := zv := 0.9 (guess)
Ω ⋅ Tr Tr
zv − β ( Tr , Pr)
Given zv = 1 + β ( Tr , Pr) − q ( Tr) ⋅ β ( Tr , Pr) ⋅ Eq. (3.52)
2
( zv)

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 Zv ( Tr , Pr) := Find ( zv)

zl := .01 (guess)

2 1 + β ( Tr , Pr) − zl
Given zl = β ( Tr , Pr) + ( zl) ⋅ Eq. (3.56) zl < 0.2
q ( Tr) ⋅ β ( Tr , Pr)

Zl ( Tr , Pr) := Find ( zl)

β ( Tr , Pr) β ( Tr , Pr)
Iv ( Tr , Pr) := Il ( Tr , Pr) := Case II, pg. 218.
Zv ( Tr , Pr) Zl ( Tr , Pr)
By Eq. (11.39):

lnφv ( Tr , Pr) := Zv ( Tr , Pr) − 1 − ln ( Zv ( Tr , Pr) − β ( Tr , Pr) ) − q ( Tr) ⋅ Iv ( Tr , Pr)

lnφl ( Tr , Pr) := Zl ( Tr , Pr) − 1 − ln ( Zl ( Tr , Pr) − β ( Tr , Pr) ) − q ( Tr) ⋅ Il ( Tr , Pr)

Psatr := .1

Given lnφl ( Tr , Psatr) − lnφv ( Tr , Psatr) = 0 Psatr := Find ( Psatr)

Zv ( Tr , Psatr) = 0.839 Zl ( Tr , Psatr) = 0.05 Psatr = 0.2

lnφl ( Tr , Psatr) = −0.148 lnφv ( Tr , Psatr) = −0.148 β ( Tr , Psatr) = 0.036

ω := −1 − log ( Psatr) ω = −0.302 Ans.

(b) Redlich/Kwong Eqn.Tr := 0.7

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748
− .5
α ( Tr) := Tr

Ψ ⋅ α ( Tr) Ω ⋅ Pr
q ( Tr) := β ( Tr , Pr) := Guess: zv := 0.9
Ω ⋅ Tr Tr

zv − β ( Tr , Pr)
Given zv = 1 + β ( Tr , Pr) − q ( Tr) ⋅ β ( Tr , Pr) ⋅ Eq. (3.52)
zv⋅ ( zv + β ( Tr , Pr) )
Zv ( Tr , Pr) := Find ( zv)
Guess: zl := .01

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 1 + β ( Tr , Pr) − zl
Given zl = β ( Tr , Pr) + zl⋅ ( zl + β ( Tr , Pr) ) ⋅ Eq. (3.55)
q ( Tr) ⋅ β ( Tr , Pr)

zl < 0.2 Zl ( Tr , Pr) := Find ( zl)

⎛ Zv ( Tr , Pr) + β ( Tr , Pr) ⎞ Il ( Tr , Pr) := ln⎛ Zl ( Tr , Pr) + β ( Tr , Pr) ⎞

Iv ( Tr , Pr) := ln ⎜ ⎜
⎝ Zv ( Tr , Pr) ⎠ ⎝ Zl ( Tr , Pr) ⎠
By Eq. (11.39):

lnφv ( Tr , Pr) := Zv ( Tr , Pr) − 1 − ln ( Zv ( Tr , Pr) − β ( Tr , Pr) ) − q ( Tr) ⋅ Iv ( Tr , Pr)

lnφl ( Tr , Pr) := Zl ( Tr , Pr) − 1 − ln ( Zl ( Tr , Pr) − β ( Tr , Pr) ) − q ( Tr) ⋅ Il ( Tr , Pr)

Psatr := .1

Given lnφl ( Tr , Psatr) = lnφv ( Tr , Psatr) Psatr := Find ( Psatr)

Zv ( Tr , Psatr) = 0.913 Zl ( Tr , Psatr) = 0.015 Psatr = 0.087

lnφv ( Tr , Psatr) = −0.083 lnφl ( Tr , Psatr) = −0.083 β ( Tr , Psatr) = 0.011

ω := −1 − log ( Psatr) ω = 0.058 Ans.

14.15 (a) x1α := 0.1 x2α := 1 − x1α x1β := 0.9 x2β := 1 − x1β

Guess: A12 := 2 A21 := 2

γ1α ( A21 , A12) := exp ⎡⎣ x2α ⋅ ⎣⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1α ⎤⎦ ⎤⎦

2

γ1β( A21 , A12) := exp ⎡⎣ x2β ⋅ ⎣⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1β ⎤⎦ ⎤⎦

2

γ2α ( A21 , A12) := exp ⎡⎣ x1α ⋅ ⎣⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2α ⎤⎦ ⎤⎦

2

γ2β( A21 , A12) := exp ⎡⎣ x1β ⋅ ⎣⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2β ⎤⎦ ⎤⎦

2

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 Given x1α⋅ γ1α ( A21 , A12) = x1β⋅ γ1β( A21 , A12)

x2α⋅ γ2α ( A21 , A12) = x2β⋅ γ2β( A21 , A12)

⎛ A12 ⎞
⎜ := Find ( A12 , A21) A21 = 2.747 A12 = 2.747 Ans.
⎝ A 21 ⎠

(b) x1α := 0.2 x2α := 1 − x1α x1β := 0.9 x2β := 1 − x1β

Guess: A12 := 2 A21 := 2

γ1α ( A21 , A12) := exp ⎡⎣ x2α ⋅ ⎡⎣ A12 + 2⋅ ( A21 − A12) ⋅ x1α ⎤⎦ ⎤⎦

2

γ1β( A21 , A12) := exp ⎡⎣ x2β ⋅ ⎡⎣ A12 + 2⋅ ( A21 − A12) ⋅ x1β ⎤⎦ ⎤⎦

2

γ2α ( A21 , A12) := exp ⎡⎣ x1α ⋅ ⎡⎣ A21 + 2⋅ ( A12 − A21) ⋅ x2α ⎤⎦ ⎤⎦

2

γ2β( A21 , A12) := exp ⎡⎣ x1β ⋅ ⎡⎣ A21 + 2⋅ ( A12 − A21) ⋅ x2β ⎤⎦ ⎤⎦

2

Given x1α⋅ γ1α ( A21 , A12) = x1β⋅ γ1β( A21 , A12)

x2α⋅ γ2α ( A21 , A12) = x2β⋅ γ2β( A21 , A12)

⎛ A12 ⎞
⎜ := Find ( A12 , A21) A12 = 2.148 A21 = 2.781 Ans.
⎝ A 21 ⎠
(c) x1α := 0.1 x2α := 1 − x1α x1β := 0.8 x2β := 1 − x1β
Guess: A12 := 2 A21 := 2

γ1α ( A21 , A12) := exp ⎡⎣ x2α ⋅ ⎣⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1α ⎤⎦ ⎤⎦

2

γ1β( A21 , A12) := exp ⎡⎣ x2β ⋅ ⎣⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1β ⎤⎦ ⎤⎦

2

γ2α ( A21 , A12) := exp ⎡⎣ x1α ⋅ ⎣⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2α ⎤⎦ ⎤⎦

2

γ2β( A21 , A12) := exp ⎡⎣ x1β ⋅ ⎣⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2β ⎤⎦ ⎤⎦

2

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 Given x1α⋅ γ1α ( A21 , A12) = x1β⋅ γ1β( A21 , A12)

x2α⋅ γ2α ( A21 , A12) = x2β⋅ γ2β( A21 , A12)

⎛ A12 ⎞
⎜ := Find ( A12 , A21) A12 = 2.781 A21 = 2.148 Ans.
⎝ A 21 ⎠

14.16 (a) x1α := 0.1 x2α := 1 − x1α x1β := 0.9 x2β := 1 − x1β
Guess: a12 := 2 a21 := 2

Given
⎡⎢ −2 −2
⎛ a12⋅ x1α ⎞ ⎥⎤ ⎡⎢ ⎛ a12⋅ x1β ⎞ ⎥⎤
exp a12⋅ ⎜ 1 +
⎢ ⋅ ⎥ ⋅ x1α = exp ⎢ a12⋅ ⎜ 1 + a21⋅ x2β ⎥ ⋅ x1β
⎣ ⎝ a21 x2α ⎠ ⎦ ⎣ ⎝ ⎠ ⎦

⎡⎢ −2 −2
⎛ a21⋅ x2α ⎞ ⎥⎤ ⎡⎢ ⎛ a21⋅ x2β ⎞ ⎥⎤
exp a21⋅ ⎜ 1 +
⎢ ⋅ ⎥ ⋅ x2α = exp ⎢ a21⋅ ⎜ 1 + a12⋅ x1β ⎥ ⋅ x2β
⎣ ⎝ a12 x1α ⎠ ⎦ ⎣ ⎝ ⎠ ⎦

⎛ a12 ⎞
⎜ := Find ( a12 , a21) a12 = 2.747 a21 = 2.747 Ans.
⎝ ⎠
a21

(b) x1α := 0.2 x2α := 1 − x1α x1β := 0.9 x2β := 1 − x1β

Guess: a12 := 2 a21 := 2

⎡⎢ −2 −2
⎛ a12⋅ x1α ⎞ ⎥⎤ ⎡⎢ ⎛ a12⋅ x1β ⎞ ⎥⎤
Given
exp a12⋅ ⎜ 1 +
⎢ ⋅ ⎥ ⋅ x1α = exp ⎢ a12⋅ ⎜ 1 + a21⋅ x2β ⎥ ⋅ x1β
⎣ ⎝ a21 x2α ⎠ ⎦ ⎣ ⎝ ⎠ ⎦

⎡⎢ −2 −2
⎛ a21⋅ x2α ⎞ ⎥⎤ ⎡⎢ ⎛ a21⋅ x2β ⎞ ⎥⎤
exp a21⋅ ⎜ 1 +
⎢ ⋅ ⎥ ⋅ x2α = exp ⎢ a21⋅ ⎜ 1 + a12⋅ x1β ⎥ ⋅ x2β
⎣ ⎝ a12 x1α ⎠ ⎦ ⎣ ⎝ ⎠ ⎦

⎛ a12 ⎞
⎜ := Find ( a12 , a21) a12 = 2.199 a21 = 2.81 Ans.
⎝ ⎠
a21

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 (c) x1α := 0.1 x2α := 1 − x1α x1β := 0.8 x2β := 1 − x1β
Guess: a12 := 2 a21 := 2

⎡⎢ −2 −2
⎛ a12⋅ x1α ⎞ ⎥⎤ ⎡⎢ ⎛ a12⋅ x1β ⎞ ⎥⎤
Given
exp a12⋅ ⎜ 1 +
⎢ ⋅ ⎥ ⋅ x1α = exp ⎢ a12⋅ ⎜ 1 + a21⋅ x2β ⎥ ⋅ x1β
⎣ ⎝ a21 x2α ⎠ ⎦ ⎣ ⎝ ⎠ ⎦

⎡⎢ −2 −2
⎛ a21⋅ x2α ⎞ ⎥⎤ ⎡⎢ ⎛ a21⋅ x2β ⎞ ⎥⎤
exp a21⋅ ⎜ 1 +
⎢ ⋅ ⎥ ⋅ x2α = exp ⎢ a21⋅ ⎜ 1 + a12⋅ x1β ⎥ ⋅ x2β
⎣ ⎝ a12 x1α ⎠ ⎦ ⎣ ⎝ ⎠ ⎦

⎛ a12 ⎞
⎜ := Find ( a12 , a21) a12 = 2.81 a21 = 2.199 Ans.
⎝ ⎠
a21

14.18 (a) a := 975 b := −18.4 c := −3

a
T := 250 .. 450 A ( T) := + b − c⋅ ln ( T)
T

2.1

A ( T) 2

1.9
250 300 350 400 450
T

Parameter A = 2 at two temperatures. The lower one is an UCST,

because A decreases to 2 as T increases. The higher one is a LCST,
because A decreases to 2 as T decreases.

Guess: x := 0.25

A ( T) ⋅ ( 1 − 2⋅ x) = ln ⎛⎜
1 − x⎞
Given Eq. (E), Ex. 14.5
⎝ x ⎠
x≥0 x ≤ 0.5 x1 ( T) := Find ( x) x2 ( T) := 1 − x1 ( T)

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 UCST := 300 (guess)

Given A ( UCST) = 2 UCST := Find ( UCST) UCST = 272.93

LCST := 400 (guess)

Given A ( LCST) = 2 LCST := Find ( LCST) LCST = 391.21

Plot phase diagram as a function of T

T1 := 225 , 225.1 .. UCST T2 := LCST .. 450

500

T1
400
T1
T2
T2 300

200
0.2 0.3 0.4 0.5 0.6 0.7 0.8
x1 ( T1 ) , x2 ( T1 ) , x1 ( T2 ) , x2 ( T2 )

(b) a := 540 b := −17.1 c := −3

a
T := 250 .. 450 A ( T) := + b − c⋅ ln ( T)
T
2.5

A ( T) 2

1.5
250 300 350 400 450
T
Parameter A = 2 at a single temperature. It is
a LCST, because A decreases to 2 as T decreases.
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 Guess: x := 0.25

A ( T) ⋅ ( 1 − 2⋅ x) = ln ⎛⎜
1 − x⎞
Given Eq. (E), Ex. 14.5
⎝ x ⎠

x≥0 x ≤ 0.5 x1 ( T) := Find ( x)

LCST := 350 (guess)

Given A ( LCST) = 2 LCST := Find ( LCST) LCST = 346

Plot phase diagram as a function of T T := LCST .. 450

450

400
T
T
350

300
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
x1 ( T ) , 1−x1 ( T)

(c) a := 1500 b := −19.9 c := −3

a
T := 250 .. 450 A ( T) := + b − c⋅ ln ( T)
T

2.5
A ( T)
2

1.5
250 300 350 400 450
T

Parameter A = 2 at a single temperature. It is

an UCST, because A decreases to 2 as T increases.

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 Guess: x := 0.25

A ( T) ⋅ ( 1 − 2⋅ x) = ln ⎛⎜
1 − x⎞
Given Eq. (E), Ex. 14.5
⎝ x ⎠
x≥0 x ≤ 0.5 x1 ( T) := Find ( x)

UCST := 350 (guess)

Given A ( UCST) = 2 UCST := Find ( UCST) UCST = 339.66

Plot phase diagram as a function of T T := UCST .. 250

350

T
300
T

250
0 0.2 0.4 0.6 0.8
x1 ( T ) , 1−x1 ( T)

14.20 Guess: x1α := 0.5 x1β := 0.5

Given Write Eq. (14.74) for species 1:

x1α⋅ exp ⎡⎣ 0.4⋅ ( 1 − x1α) ⎤⎦ = x1β⋅ exp ⎡⎣ 0.8⋅ ( 1 − x1β) ⎤⎦

2 2

x1α x1β
+ = 1 (Material balance)
1 − x1α 1 − x1β

⎛ x1α ⎞
⎜ := Find ( x1α , x1β) x1α = 0.371 x1β = 0.291 Ans.
⎝ x1β ⎠

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 14.22 Temperatures in kelvins; pressures in kPa.

P1sat ( T) := exp ⎛⎜ 19.1478 −

5363.7 ⎞
water
⎝ T ⎠
P := 1600

P2sat ( T) := exp ⎛⎜ 14.6511 −

2048.97 ⎞
SF6
⎝ T ⎠

Find 3-phase equilibrium temperature and vapor-phase composition (pp.

594-5 of text):
Guess: T := 300
Given P = P1sat ( T) + P2sat ( T) Tstar := Find ( T) Tstar = 281.68
P1sat ( Tstar) 6
y1star := y1star⋅ 10 = 695
P
Find saturation temperatures of pure species 2:

Guess: T := 300
Given P2sat ( T) = P T2 := Find ( T) T2 = 281.71

P2sat ( T)
TII := Tstar , Tstar + 0.0001 .. T2 y1II ( T) := 1 −
P
P1sat ( T)
TI := Tstar , Tstar + 0.01 .. Tstar + 6 y1I ( T) :=
P
Because of the very large difference in scales appropriate to regions I and
II [Fig. 14.21(a)], the txy diagram is presented on the following page in two
parts, showing regions I and II separately.

281.7
TII
Tstar
281.69

281.68
0 100 200 300 400 500 600 700
6 6
y1II ( TII) ⋅ 10 , y1II ( TII) ⋅ 10

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 288

286

TI
284
Tstar

282

280
650 700 750 800 850 900 950 1000 1050
6 6
y1I ( TI) ⋅ 10 , y1I ( TI) ⋅ 10

14.24 Temperatures in deg. C; pressures in kPa

P1sat ( T) := exp ⎛⎜ 13.9320 −

3056.96 ⎞
Toluene
⎝ T + 217.625 ⎠
P := 101.33
P2sat ( T) := exp ⎛⎜ 16.3872 −
3885.70 ⎞
Water
⎝ T + 230.170 ⎠

Find the three-phase equilibrium T and y:

Guess: T := 25

Given P = P1sat ( T) + P2sat ( T) Tstar := Find ( T) Tstar = 84.3

P1sat ( Tstar)
y1star := y1star = 0.444
P
For z1 < y1*, first liquid is pure species 2.

y1 := 0.2 Guess: Tdew := Tstar

P2sat ( Tdew)
Given y1 = 1 − Tdew := Find ( Tdew)
P
Tdew = 93.855 Ans.

For z1 > y1*, first liquid is pure species 1.

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 y1 := 0.7 Guess: Tdew := Tstar

P1sat ( Tdew)
Given y1 = Tdew := Find ( Tdew)
P
Tdew = 98.494 Ans.

In both cases the bubblepoint temperature is T*, and the mole fraction of
the last vapor is y1*.

14.25 Temperatures in deg. C; pressures in kPa.

P1sat ( T) := exp ⎛⎜ 13.8622 −

2910.26 ⎞
n-heptane
⎝ T + 216.432 ⎠
P := 101.33

P2sat ( T) := exp ⎛⎜ 16.3872 −

3885.70 ⎞
water
⎝ T + 230.170 ⎠

Find the three-phase equilibrium T and y:

Guess: T := 50

Given P = P1sat ( T) + P2sat ( T) Tstar := Find ( T) Tstar = 79.15

P1sat ( Tstar)
y1star := y1star = 0.548
P

Since 0.35<y1*, first liquid is pure species 2.

P2sat ( T)
y1 ( T) := 1 −
P
Find temperature of initial condensation at y1=0.35:

y10 := 0.35 Guess: Tdew := Tstar

Given y1 ( Tdew) = y10 Tdew := Find ( Tdew) Tdew = 88.34

Define the path of vapor mole fraction above and below the dew point.

y1path ( T) := if ( T > Tdew , y10 , y1 ( T) ) T := 100 , 99.9 .. Tstar

Path of mole fraction heptane in residual vapor as temperature is

decreased. No vapor exists below Tstar.
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 100

95

90 Tdew
T
85

Tstar
80

75
0.3 0.35 0.4 0.45 0.5 0.55
y1path ( T )

14.26 Pressures in kPa. P1sat := 75 P2sat := 110 A := 2.25

γ1 ( x1) := exp ⎡⎣ A⋅ ( 1 − x1) ⎤⎦

2 (
γ2 ( x1) := exp A⋅ x1
2 )
Find the solubility limits:

Guess: x1α := 0.1

Given A⋅ ( 1 − 2⋅ x1α) = ln ⎜
⎛ 1 − x1α ⎞ x1α := Find ( x1α)
⎝ x1α ⎠
x1α = 0.224 x1β := 1 − x1α x1β = 0.776
Find the conditions for VLLE:

Guess: Pstar := P1sat y1star := 0.5

Given Pstar = x1β⋅ γ1 ( x1β) ⋅ P1sat + ( 1 − x1α) ⋅ γ2 ( x1α) ⋅ P2sat

y1star⋅ Pstar = x1α⋅ γ1 ( x1α) ⋅ P1sat

⎛ Pstar ⎞
⎜ := Find ( Pstar , y1star) Pstar = 160.699 y1star = 0.405
⎝ y1star ⎠
Calculate VLE in two-phase region.

Modified Raoult's law; vapor an ideal gas.

Guess: x1 := 0.1 P := 50

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 Given P = x1⋅ γ1 ( x1) ⋅ P1sat + ( 1 − x1) ⋅ γ2 ( x1) ⋅ P2sat

x1⋅ γ1 ( x1) ⋅ P1sat

P ( x1) := Find ( P) y1 ( x1) :=
P ( x1)
Plot the phase diagram.

Define liquid equilibrium line:

PL ( x1) := if ( P ( x1) < Pstar , P ( x1) , Pstar)

Define vapor equilibrium line:

PV ( x1) := if ( P ( x1) < Pstar , P ( x1) , Pstar)

Define pressures for liquid phases above Pstar:

Pliq := Pstar .. Pstar + 10

x1 := 0 , 0.01 .. 1

200

175 Pstar

PL ( x1) 150
PV ( x1)
125
Pliq
Pliq 100

75

50
0 0.2 0.4 0.6 0.8 1
x1 , y1 ( x1) , x1α , x1β

x1 := 0 , 0.05 .. 0.2

x1 = PL ( x1) = y1 ( x1) =
0 110 0
0.05 133.66 0.214
0.1 147.658 0.314
0.15 155.523 0.368
0.2 159.598 0.397

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 x1 := 1 , 0.95 .. 0.8

x1 = PL ( x1) = y1 ( x1) =
1 75 1
0.95 113.556 0.631
0.9 137.096 0.504
0.85 150.907 0.444
0.8 158.506 0.414

x1α = 0.224 x1β = 0.776 y1star = 0.405

14.27 Temperatures in deg. C; pressures in kPa.

P1sat ( T) := exp ⎛⎜ 16.3872 −

3885.70 ⎞
Water:
⎝ T + 230.170 ⎠

P2sat ( T) := exp ⎛⎜ 13.7667 −

2451.88 ⎞
n-Pentane:
⎝ T + 232.014 ⎠

P3sat ( T) := exp ⎛⎜ 13.8622 −

2910.26 ⎞
n-Heptane:
⎝ T + 216.432 ⎠

P := 101.33 z1 := 0.45 z2 := 0.30 z3 := 1 − z1 − z2

(a) Calculate dew point T and liquid composition
assuming the hydrocarbon layer forms first:

Guess: Tdew1 := 100 x2α := z2 x3α := 1 − x2α

Given P = x2α⋅ P2sat ( Tdew1) + x3α⋅ P3sat ( Tdew1)

z3⋅ P = x3α⋅ P3sat ( Tdew1)

x2α + x3α = 1
⎛⎜ x2α ⎞
⎜ x3α ⎟ := Find ( x2α , x3α , Tdew1)
⎜ Tdew1
⎝ ⎠
Tdew1 = 66.602 x3α = 0.706 x2α = 0.294

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 Calculate dew point temperature assuming the water layer forms first:

x1β := 1 Guess: Tdew2 := 100

Given x1β⋅ P1sat ( Tdew2) = z1⋅ P Tdew2 := Find ( Tdew2)

Tdew2 = 79.021
Since Tdew2 > Tdew1, the water layer forms first

(b) Calculate the temperature at which the second layer forms:

Guess: Tdew3 := 100 x2α := z2 x3α := 1 − x2α

y1 := z1 y2 := z2 y3 := z3

Given P = P1sat ( Tdew3) + x2α⋅ P2sat ( Tdew3) + x3α⋅ P3sat ( Tdew3)

y1⋅ P = P1sat ( Tdew3)

y2 z2
= y1 + y2 + y3 = 1
y3 z3
y2⋅ P = x2α⋅ P2sat ( Tdew3) x2α + x3α = 1

⎛ y1 ⎞
⎜
⎜ y2 ⎟
⎜ y3 ⎟
⎜ ⎟ := Find ( y1 , y2 , y3 , Tdew3 , x2α , x3α)
⎜ Tdew3 ⎟
⎜ x2α ⎟
⎜
⎝ x3α ⎠

y1 = 0.288 y2 = 0.388 y3 = 0.324

Tdew3 = 68.437 x2α = 0.1446 x3α = 0.8554

(c) Calculate the bubble point given the total molar composition of the
two phases

z2 z3
Tbubble := Tdew3 x2α := x3α :=
z2 + z3 z2 + z3
x2α = 0.545 x3α = 0.455

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 Given

P = P1sat ( Tbubble) + x2α⋅ P2sat ( Tbubble) + x3α⋅ P3sat ( Tbubble)

Tbubble := Find ( Tbubble) Tbubble = 48.113

P1sat ( Tbubble)
y1 := y1 = 0.111
P
x2α⋅ P2sat ( Tbubble)
y2 := y2 = 0.81
P
x3α⋅ P3sat ( Tbubble)
y3 := y3 = 0.078
P

14.28 Temperatures in deg. C; pressures in kPa.

P1sat ( T) := exp ⎛⎜ 16.3872 −

3885.70 ⎞
Water:
⎝ T + 230.170 ⎠

P2sat ( T) := exp ⎛⎜ 13.7667 −

2451.88 ⎞
n-Pentane:
⎝ T + 232.014 ⎠

P3sat ( T) := exp ⎛⎜ 13.8622 −

2910.26 ⎞
n-Heptane:
⎝ T + 216.432 ⎠

P := 101.33 z1 := 0.32 z2 := 0.45 z3 := 1 − z1 − z2

(a) Calculate dew point T and liquid composition

assuming the hydrocarbon layer forms first:
Guess: Tdew1 := 70 x2α := z2 x3α := 1 − x2α

Given P = x2α⋅ P2sat ( Tdew1) + x3α⋅ P3sat ( Tdew1)

z3⋅ P = x3α⋅ P3sat ( Tdew1) x2α + x3α = 1

⎛⎜ x2α ⎞
⎜ x3α ⎟ := Find ( x2α , x3α , Tdew1)
⎜ Tdew1
⎝ ⎠

Tdew1 = 65.122 x3α = 0.686 x2α = 0.314

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 Calculate dew point temperature assuming the water layer forms first:

x1β := 1 Guess: Tdew2 := 70

Given x1β⋅ P1sat ( Tdew2) = z1⋅ P Tdew2 := Find ( Tdew2)

Tdew2 = 70.854
Since Tdew1>Tdew2, a hydrocarbon layer forms first

(b) Calculate the temperature at which the second layer forms:

Guess: Tdew3 := 100 x2α := z2 x3α := 1 − x2α

y1 := z1 y2 := z2 y3 := z3

Given P = P1sat ( Tdew3) + x2α⋅ P2sat ( Tdew3) + x3α⋅ P3sat ( Tdew3)

y2 z2
y1⋅ P = P1sat ( Tdew3) = y1 + y2 + y3 = 1
y3 z3

y2⋅ P = x2α⋅ P2sat ( Tdew3) x2α + x3α = 1

⎛ y1 ⎞
⎜
⎜ y2 ⎟
⎜ y3 ⎟
⎜ ⎟ := Find ( y1 , y2 , y3 , Tdew3 , x2α , x3α)
⎜ Tdew3 ⎟
⎜ x2α ⎟
⎜
⎝ x3α ⎠

y1 = 0.24 y2 = 0.503 y3 = 0.257

Tdew3 = 64.298 x2α = 0.2099 x3α = 0.7901

(c) Calculate the bubble point given the total

molar composition of the two phases
z2 z3
Tbubble := Tdew3 x2α := x3α :=
z2 + z3 z2 + z3

x2α = 0.662 x3α = 0.338

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 Given P = P1sat ( Tbubble) + x2α⋅ P2sat ( Tbubble) + x3α⋅ P3sat ( Tbubble)

Tbubble := Find ( Tbubble) Tbubble = 43.939

P1sat ( Tbubble)
y1 := y1 = 0.09
P
x2α⋅ P2sat ( Tbubble)
y2 := y2 = 0.861
P
x3α⋅ P3sat ( Tbubble)
y3 := y3 = 0.049
P

⎛ 0.302 ⎞ ⎛ 748.4 ⎞ ⎛ 40.51 ⎞

14.32 ω := ⎜ Tc := ⎜ K Pc := ⎜ bar
⎝ 0.224 ⎠ ⎝ 304.2 ⎠ ⎝ 73.83 ⎠
P := 10bar , 20bar .. 300bar
⎯
→
T
T := 353.15K Tr :=
Tc
Use SRK EOS

From Table 3.1, p. 98 of text:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748

⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
→
(
α := ⎡⎣ 1 + 0.480 + 1.574⋅ ω − 0.176⋅ ω ⋅ 1 − Tr
2
)( 0.5 ) ⎤⎦ 2
⎯⎯⎯⎯⎯ → ⎯⎯⎯ →
2 2
Ψ ⋅ α ⋅ R ⋅ Tc Ω ⋅ R⋅ Tc
a := Eq. (14.31) b := Eq. (14.32)
Pc Pc

⎛ 6.842 ⎞ kg m5 ⎛ 1.331 × 10− 4 ⎞ m3

a=⎜ b=⎜
⎝ 0.325 ⎠ s2 mol2 ⎜ 2.968 × 10− 5 mol
⎝ ⎠
b2⋅ P a2
β 2 ( P) := Eq. (14.33) q2 := Eq. (14.34)
R⋅ T b2⋅ R⋅ T

z2 := 1 (guess)

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 Given

z2 − β 2 ( P)
z2 = 1 + β 2 ( P) − q2⋅ β 2 ( P) ⋅ Eq. (14.36)
( )(
z2 + ε ⋅ β 2 ( P) ⋅ z2 + σ ⋅ β 2 ( P) )
Z2 ( P) := Find ( z2)

⎛ Z 2 ( P) + β 2 ( P) ⎞
I2 ( P) := ln ⎜ Eq. (6.65b)
⎝ Z 2 ( P) ⎠
For simplicity, let φ1 represent the infinite-dilution value of the fugacity
coefficient of species 1 in solution.
Eq. (14.103): l12 := 0.088

⎡ ⎡ ⎡ b1 ⎤ ⎤⎤
φ 1 ( P) := exp ⎢ ⎢ ⎢ ⋅ ( Z2 ( P) − 1) − ln ( Z2 ( P) − β 2 ( P) )⎥ ... ⎥ ⎥
⎢ ⎢ ⎣ b2 ⎦ ⎥⎥
⎢⎢ ⎡ ⎛ a1 ⎞
0.5
b1 ⎤ ⎥⎥
⎢⎢ + − q 2 ⋅ ⎢2 ⋅ ( 1 − l12) ⋅ ⎜ − ⎥ ⋅ I2 ( P ) ⎥⎥
⎣⎣ ⎣ ⎝ a2 ⎠ b2 ⎦ ⎦⎦
3
cm
Psat1 := 0.0102bar V1 := 124.5
mol
Eqs. (14.98) and (14.99), with φsat1 = 1 and (P - Psat1) = P, combine to give:

Psat1 ⎛ P⋅ V 1 ⎞
y1 ( P) := ⋅ exp ⎜
P ⋅ φ 1 ( P) ⎝ R⋅ T ⎠

0.1

0.01
y1 ( P)

1 .10
3

1 .10
4
0 50 100 150 200 250 300
P
bar

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 ⎛ 0.302 ⎞ ⎛ 748.4 ⎞ ⎛ 40.51 ⎞
14.33 ω := ⎜ Tc := ⎜ K Pc := ⎜ bar
⎝ 0.038 ⎠ ⎝ 126.2 ⎠ ⎝ 34.00 ⎠
P := 10bar , 20bar .. 300bar
⎯
→
T
T := 308.15K (K) Tr :=
Tc
Use SRK EOS

From Table 3.1, p. 98 of text:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748

⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
→
(
α := ⎡⎣ 1 + 0.480 + 1.574⋅ ω − 0.176⋅ ω ⋅ 1 − Tr
2 0.5 ⎤
⎦ )( ) 2

⎯⎯⎯⎯⎯ → ⎯⎯⎯ →
2 2
Ψ ⋅ α ⋅ R ⋅ Tc Ω ⋅ R⋅ Tc
a := Eq. (14.31) b := Eq. (14.32)
Pc Pc

⎛ 7.298 ⎞ kg m5 ⎛ 1.331 × 10− 4 ⎞ m3

a=⎜ b=⎜
⎝ 0.067 ⎠ s2 mol2 ⎜ 2.674 × 10− 5 mol
⎝ ⎠
b2⋅ P a2
β 2 ( P) := Eq. (14.33) q2 := Eq. (14.34)
R⋅ T b2⋅ R⋅ T
z2 := 1 (guess)

Given

z2 − β 2 ( P)
z2 = 1 + β 2 ( P) − q2⋅ β 2 ( P) ⋅ Eq. (14.36)
( )(
z2 + ε ⋅ β 2 ( P) ⋅ z2 + σ ⋅ β 2 ( P) )
Z2 ( P) := Find ( z2)

⎛ Z 2 ( P) + β 2 ( P) ⎞
I2 ( P) := ln ⎜ Eq. (6.65b)
⎝ Z 2 ( P) ⎠
For simplicity, let φ1 represent the infinite-dilution value of the fugacity
coefficient of species 1 in solution.

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 l12 := 0.0 Eq. (14.103):

⎡ ⎡ ⎡ b1 ⎤ ⎤⎤
φ 1 ( P) := exp ⎢ ⎢ ⎢ ⋅ ( Z2 ( P) − 1) − ln ( Z2 ( P) − β 2 ( P) )⎥ ... ⎥ ⎥
⎢ ⎢ ⎣ b2 ⎦ ⎥⎥
⎢⎢ ⎡ ⎛ a1 ⎞
0.5
b1 ⎤ ⎥⎥
⎢⎢ + − q 2 ⋅ ⎢2 ⋅ ( 1 − l12) ⋅ ⎜ − ⎥ ⋅ I2 ( P ) ⎥⎥
⎣⎣ ⎣ ⎝ a2 ⎠ b2 ⎦ ⎦⎦
3
−4 cm
Psat1 := 2.9⋅ 10 bar V1 := 125
mol
Eqs. (14.98) and (14.99), with φsat1 = 1 and (P - Psat1) = P, combine to
give:

Psat1 ⎛ P⋅ V 1 ⎞
y1 ( P) := ⋅ exp ⎜
P ⋅ φ 1 ( P) ⎝ R⋅ T ⎠

10

5
y1 ( P) ⋅ 10

1
0 50 100 150 200 250 300
P
bar

Note: y axis is log scale.

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 14.45 A labeled diagram of the process is given below. The feed stream is taken as
the α phase and the solvent stream is taken as the β phase.

F R
nF Feed nR
xF1 = 0.99 xα1
xF2 = 0.01 xα2 = 0.001
Mixer/
Settler
S E
nS Solvent nE
xS3 = 1.0 xβ2
xβ3
Define the values given in the problem statement. Assume as a basis a feed
rate nF = 1 mol/s.
mol
nF := 1 xF1 := 0.99 xF2 := 0.01 xS3 := 1
s
xα2 := 0.001 xα1 := 1 − xα2

Apply mole balances around the process as well as an equilibrium relationship

From p. 585 A12 := 1.5 A23 := −0.8

γα 2 ( x2) := exp ⎡⎣ A12⋅ ( 1 − x2) ⎤⎦ γβ 2 ( x2) := exp ⎡⎣ A23⋅ ( 1 − x2) ⎤⎦

2 2

Material Balances

nS + nF = nE + nR (Total)

nS = xβ3⋅ nE (Species 3)

xF1⋅ nF = xα1⋅ nR (Species 1)

Substituting the species balances into the total balance yields

1 xF1
nS + nF = ⋅ nS + ⋅ nF
xβ3 xα1

Solving for the ratio of solvent to feed (nS/nF) gives

nS ⎛ xα1 − xF1 ⎞ ⎛ xβ3 ⎞

= ⎜ ⋅⎜
nF
⎝ 1 − xβ 3 ⎠ ⎝ xα1 ⎠

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 We need xβ3. Assume exiting streams are at equilibrium. Here, the only
distributing species is 2. Then

xα2⋅ γα 2 = xβ2⋅ γβ 2

Substituting for γα2 and γβ2

( ) (
xα2⋅ exp ⎡⎣ A12⋅ 1 − xα2 ⎤⎦ = xβ2⋅ exp ⎡⎣ A23⋅ 1 − xβ2 ⎤⎦
2 2
)
Solve for xβ2 using Mathcad Solve Block

Guess: xβ2 := 0.5

Given

( ) (
xα2⋅ exp ⎡⎣ A12⋅ 1 − xα2 ⎤⎦ = xβ2⋅ exp ⎡⎣ A23⋅ 1 − xβ2 ⎤⎦
2 2
)
xβ2 := Find xβ2 ( ) xβ2 = 0.00979 xβ3 := 1 − xβ2 xβ3 = 0.9902

From above, the equation for the ratio nS/nF is:

⎛ xα1 − xF1 ⎞ ⎛ xβ3 ⎞

nSnF := ⎜ ⋅⎜
⎝ 1 − xβ 3 ⎠ ⎝ xα1 ⎠

a) nSnF = 0.9112 Ans.

b) xβ2 = 0.00979 Ans.

c) "Good chemistry" here means that species 2 and 3 "like" each other, as
evidenced by the negative GE23. "Bad chemistry" would be reflected in a
positive GE23, with values less than (essential) but perhaps near to GE12.

14.46 1 - n-hexane
2 - water
Since this is a dilute system in both phases, Eqns. (C) and (D) from Example
14.4 on p. 584 can be used to find γ1α and γ2β.
520 2
xα1 := xα2 := 1 − xα1 xβ2 := xβ1 := 1 − xβ2
6 6
10 10

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 xβ1 3
γα 1 := γα 1 = 1.923 × 10 Ans.
xα1
1 − xα1 5
γβ 2 := γβ 2 = 4.997 × 10 Ans.
1 − xβ1

3
cm
14.50 1 - butanenitrile Psat1 := 0.07287bar V1 := 90
mol
3
cm
2- benzene Psat2 := 0.29871bar V2 := 92
mol
3 3 3
cm cm cm
B1 , 1 := −7993 B2 , 2 := −1247 B1 , 2 := −2089 B2 , 1 := B1 , 2
mol mol mol

T := 318.15K P := 0.20941bar x1 := 0.4819 y1 := 0.1813

i := 1 .. 2 j := 1 .. 2 k := 1 .. 2 x2 := 1 − x1 y2 := 1 − y1
Term A is calculated using the given data.
yi⋅ P
term_Ai :=
xi⋅ Psati
Term B is calculated using Eqns. (14.4) and (14.5)

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

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

⎛ Bi , i⋅ Psati ⎞ φhati
φsati := exp ⎜ term_Bi :=
⎝ R⋅ T ⎠ φsati

Term C is calculated using Eqn. (11.44)

⎡ ⎡Vi⋅ ( P − Psati)⎤⎦ ⎤
fi := φsati⋅ Psati⋅ exp ⎢ ⎣
fsati
fsati := φsati⋅ Psati ⎥ term_Ci :=
⎣ R⋅ T ⎦ fi
⎛ 1.081 ⎞ ⎛ 0.986 ⎞ ⎛1 ⎞
term_A = ⎜ term_B = ⎜ term_C = ⎜ Ans.
⎝ 1.108 ⎠ ⎝ 1.006 ⎠ ⎝1 ⎠
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 14.51 a) Equivalent to d2(∆G/RT)/dx12 = 0, use d2(GE/RT)/dx12 = -1/x1x2

For GE/RT = Ax1x2 = A(x1-x12)

d(GE/RT)/dx1 = A(1-2x1)

d2(GE/RT)/dx12 = -2A

Thus, -2A = -1/x1x2 or 2Ax1x2 = 1.

Substituting for x2: x1-x12 = 1/(2A) or x12-x1+1/(2A) = 0.
2
1+ 1−
A
The solution to this equation yields two roots: x1 =
2

2
1− 1−
A
and x1 =
2
The two roots are symmetrical around x1 = 1/2
Note that for:

A<2: No real roots

A = 2: One root, x1 = 1/3 (consolute point)
A>2: Two real roots, x1 > 0 and x1 <1
b) Plot the spinodal curve along with the solubility curve

+ 21.1 − 3 ln ⎛⎜
−540K T⎞
From Fig. 14.15: A ( T) :=
T ⎝K⎠
Both curves are symmetrical around x1 = 1/2. Create functions to
represent the left and right halves of the curves.
From above, the equations for the spinodal curves are:

1 1 A ( T) − 2
xspr1 ( T) := + ⋅ 1 1 A ( T) − 2
2 2 A ( T) xspl1 ( T) := − ⋅
2 2 A ( T)

xr := 0.7 xl := 0.3
From Eq. (E) in Example 14.5, the solubility curves are solved using
a Solve Block:
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 A ( T) ⋅ ( 1 − 2xr) = ln ⎛⎜
1 − xr ⎞
Given xr > 0.5 xr1 ( T) := Find ( xr)
⎝ xr ⎠

A ( T) ⋅ ( 1 − 2xl) = ln ⎛⎜
1 − xl ⎞
Given xl < 0.5 xl1 ( T) := Find ( xl)
⎝ xl ⎠
Find the temperature of the upper consolute point.

T := 300K Given A ( T) = 2 Tu := Find ( T) Tu = 345.998 K

T := 250K .. 346K

360

340

320

300

280

260

240
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
xl1
xr1
xspl1
xpr1

14.54 The solution is presented for one of the systems given. The solutions for the
other systems follow in the same manner.
f) 1- Carbon tetrachloride

ω 1 := 0.193 Tc1 := 556.4K Pc1 := 45.60bar

A1 := 14.0572 B1 := 2914.23 C1 := 232.148

⎡ B1 ⎤
Psat1 ( T) := exp ⎢ A1 − ⎥ kPa
⎢ ⎛ T − 273.15⎞ + C ⎥
⎜ 1
⎣ ⎝K ⎠ ⎦
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 2 - n-heptane

ω 2 := 0.350 Tc2 := 540.2K Pc2 := 27.40bar

A2 := 13.8622 B2 := 2910.26 C2 := 216.432

⎡ B2 ⎤
Psat2 ( T) := exp ⎢ A2 − ⎥ kPa
⎢ ⎛ T − 273.15⎞ + C ⎥
⎜ 2
⎣ ⎝K ⎠ ⎦

T := ( 100 + 273.15)K

T Psat1 ( T)
Tr1 := Tr1 = 0.671 Psat1r := Psat1r = 0.043
Tc1 Pc1

T Psat2 ( T)
Tr2 := Tr2 = 0.691 Psat2r := Psat2r = 0.039
Tc2 Pc2

Using Wilson's equation Λ 12 := 1.5410 Λ 21 := 0.5197

γ 1 ( x1) := exp ⎡ −ln ⎡⎣ x1 + ( 1 − x1) ⋅ Λ 12 ⎤⎦ ...

⎢ ⎥⎤
⎢ + 1 − x ⋅⎡ Λ 12 Λ 21 ⎤ ⎥
( 1) ⎢ − ⎥
⎢
⎣ ⎣ x 1 + ( 1 − x 1) ⋅ Λ 12 ( 1 − x 1) + x 1 ⋅ Λ 21 ⎦
⎥
⎦
γ 2 ( x1) := exp ⎡ −ln ⎡⎣( 1 − x1) + x1⋅ Λ 21⎤⎦ ...
⎢ ⎥⎤
⎢ + −x ⋅ ⎡ Λ 12 Λ 21 ⎤ ⎥
( 1) ⎢ − ⎥
⎣ x1 + ( 1 − x1) ⋅ Λ 12 ( 1 − x1) + x1⋅ Λ 21 ⎦
⎢ ⎥
⎣ ⎦
For part i, use the modified Raoult's Law. Define the pressure and vapor
mole fraction y1 as functions of the liquid mole fraction, x 1.
Pi ( x1) := x1⋅ γ 1 ( x1) ⋅ Psat1 ( T) + ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2 ( T)

x1⋅ γ 1 ( x1) ⋅ Psat1 ( T)

yi1 ( x1) := Modified Raoult's Law: Eqn. (10.5)
Pi ( x1)

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 For part ii, assume the vapor phase is an ideal solution. Use Eqn. (11.68)
and the PHIB function to calculate φhat and φsat.

(
φsat1 := PHIB Tr1 , Psat1r , ω 1 ) φsat1 = 0.946

φhat1 ( P)
φhat1 ( P) := PHIB ⎛⎜ Tr1 ,
P
, ω1
⎞ φ 1 ( P) :=
⎝ P c1 ⎠ φsat1

(
φsat2 := PHIB Tr2 , Psat2r , ω 2 ) φsat2 = 0.95

φhat2 ( P)
φhat2 ( P) := PHIB ⎛⎜ Tr2 ,
P
, ω2
⎞ φ 2 ( P) :=
⎝ P c2 ⎠ φsat2

Solve Eqn. (14.1) for y1 and P given x1.

Guess: y1 := 0.5 P := 1bar

Given

y1⋅ φ 1 ( P) ⋅ P = x1⋅ γ 1 ( x1) ⋅ Psat1 ( T)

Eqn. (14.1)
( 1 − y1) ⋅ φ2 (P)⋅ P = ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2 (T)
fii ( x1) := Find ( P , y1)
fii is a vector containing the values of P and y 1. Extract the pressure, P and
vapor mole fraction, y1 as functions of the liquid mole fraction.

Pii ( x1) := fii ( x1) 0 yii1 ( x1) := fii ( x1) 1

Plot the results in Mathcad x1 := 0 , 0.1 .. 1.0

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 2

1.9

1.8

Pi ( x1 ) 1.7
bar
Pi ( x1 ) 1.6
bar
1.5
Pii ( x1 )
bar
1.4
Pii ( x1 )
bar 1.3

1.2

1.1

1
0 0.2 0.4 0.6 0.8
x1 , yi1 ( x1 ) , x1 , yii1 ( x1 )
P-x Raoult's
P-y Raoult's
P-x Gamma/Phi
P-y Gamma/Phi

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