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12.

19 It is impractical to provide solutions for all of the systems listed in thetable on page 474; we present
as an example only the solution for thesystem 1-propanol(1)/water(2). Solutions for the other
systems can beobtained by rerunning the following Mathcad program with theappropriate
parameter values substituted for those given. The fileNRTL.mcd reproduces the table of NRTL
parameters on Page 474 andincludes the necessary Antoine coefficients.

1-Propanol: A1 :=16.1154 B1 :=3483.67K C1 :=205.807K

Water: A2 :=16.3872 B2 :=3885.70K C2 :=230.170K


B1
Psat1(T ) := [1 ].kPa
(T273.15.K)+C1

B2
Psat2(T) := [A2 (T273.15.K)+C2].kPa

Parameters for the NRTL equation:

cal 2 4
b12 := 500.40 b21 := = = 0.5081
mol 2

b12 b21
12() = 21() =
RT RT

12(): = exp() 12(T) 21() = exp() 21(T)

21() 2 21()21()
[ [
1(1, 2, ) = x22 21() ( 1+221() ) +
(1+221())2
]]
12() 2 21()21()
[ [
2(1, 2, ) = x12 12() ( 2+112() ) +
(1+221())2
]]

(a) BUBL T: = 101.33 1 = 0.3 2 = 1 1

Guess: = (60 + 273.15) 1 = 0.3 2 = 1 1

Given 1 = 1 1(1, 2, ) 1 ()

1 + 2 = 1

2 = 2 2(1, 2, ) 2 ()

{ 1 } : = (, 1, 2)
2

= 360.84K 1 = 0.415 2 = 0.585 Ans.


(b) DEW T: = 101.33 1 = 0.3 2 = 1 1

Guess: = (90 + 273.15) 1 = 0.05 2 = 1 1

Given 1 = 1 1(1, 2, ) 1 ()

1 + 2 = 1

2 = 2 2(1, 2, ) 2 ()

{ 1 } : = (, 1, 2)
2

= 364.27 1 = 0.042 2 = 0.958 Ans.

(c) P,T-flash Calculation


+
= = 101.33 1 = 0.3
2

1=0.1 2=11
Guess: = 0.5
1=0.1 2=11

11(1,2,)1 ()
Given 1 = 1 + 2 = 1

22(1,2,)2 ()
2 = 1 + 2 = 1

1 (1 ) + 1 = 1 Eq. (10.15)
1
2
1 : = (1, 2, 1, 2, )
2
()
1 = 0.069 2 = 0.931 1 = 0.352 2 = 0.648 = 0.816

(d) Azeotrope Calculation

Test for azeotrope at: = 101.33


1 = [( 1
1ln(


)
)
1 +273.15 ] 1 = 370.349

2 = [( 2
2ln(


)
)
2 +273.15 ] 2 = 373.149

1(0,1, 2) = 14.699 2(1,0, 1) = 4.05

1(0,1,T)Psat1 (Tb2)
120 = 120 = 17.578
P
P
121 = 121 = 0.27
2(1,0,T)Psat2 (Tb1)

Since one of these values is >1 and the other is <1, an azeotrope exists.
See Ex. 10.3(e).
Guesses:

= (90 + 273.15) 1 = 0.4 2 = 1 1 1 = 0.4 2 =


1 1
Given 1 = 1 1(1, 2, ) 1 () 1 + 2 = 1

2 = 2 2(1, 2, ) 2 () 1 + 2 = 1

1 = 1
1
2
1 : = (1, 2, 1, 2, )
2
( )
= 360.676 1 = 0.4461 1 = 0.4461

12.20 Molar volumes & Antoine coefficients:

74.05 14.3145 2756.22


= (40.73) = (16.5785) = (3638.27)
18.07 16.3872 3885.70

228.060
= (239.500)
230.170

(,) : = [ = ] = (65 + 273.15)
( 273.15)+

0 161.88 291.27

Wilson parameters: = { 583.11 0 107.38 }
1448.01 469.55 0

(, , ) =


exp (,
.
) = 1. .3 = 1. .3 = 1. .3

(a) BUBL P calculation: No iteration required.

1 = 0.3 2 = 0.4 3 = 1 1 2

(, , ): = [[ 1- = ln[j(xj A)(i, j, T) ]+ = ((,,)




)(,,)

]]
xi,(i,x,T)Psat(i,T)
= ( ) (, , ) (,) =
Pbubl

0.527
= (0.367) = 117.1 Ans.
0.106

(b) DEW P calculation:


1 = 0.3 2 = 0.4 3 = 1 1 2

Guess: 1 = 0.05 2 = 0.2 3 = 1 1 2 =


Given

.1 = 1 (1, , ) (1,) .2 = 2 (2, , ) (2,)

.3 = 3 (3, , ) (3,) = 1
1
2
( ) : = (1, 2, 3, )
3

0.035
= ( 0.19 ) = 69.14 Ans.
0.775

(c) P,T-flash calculation:

+
P= = 338.15
2
1 = 0.3 2 = 0.4 3 = 1 1 2

Guess: = 0.5 Use x from DEW P and y from BUBL P as initial guess.
Given . 1 = 1 (1, , ) (1,) . 2 = 2 (2, , ) (2,)

. 3 = 3 (2, , ) (2,)

1 (1 ) + 1 = 1 2 (1 ) + 2 = 2

3 (1 ) + 3 = 3

= 1 = 1

1
2
3
1 : = (1, 2, 3, 1, 2, 3, )
2
3
()

0.109 0.109
x= (0.345) y= (0.345) = 0.677 Ans.
0.546 0.546

12.22 Molar volumes & Antoine coefficients:

74.05 14.3145 2756.22 228.060


V= (40.73) A= (16.5785) B= (3638.27) C= (239.500)
18.07 16.3872 3885.70 230.170
(,) : = [

(273.15)+
] = 101.33

0 161.88 291.27

Wilson parameters: = { 583.11 0 107.38 }
1448.01 469.55 0

(, , ) =


(.,)

i := 1..3 j := 1..3 p := 1..3

(a) BUBL T calculation:

1 = 0.3 2 = 0.4 3 = 1 1 2

(, , ): = [[ 1- = ln[j(xj A)(i, j, T) ]+ = ((,,)




)(,,)

]]
Guess: = 300 1 = 0.3 2 = 0.3 3 = 1 1 2
Given

. 1 = 1 (1, , ) (1,) . 2 = 2 (2, , ) (2,)

. 3 = 3 (3, , ) (3,) P= ( )(, , ) (, )

1
2
( ) : = (1, 2, 3, )
3

0,536
y= (0.361) = 334.08 Ans.
0.102

(b)DEW T calculation:
1 = 0.3 2 = 0.4 3 = 1 1 2
Guess: 1 = 0.05 2 = 0.2 3 = 1 1 2 =
Given

. 1 = 1 (1, , ) (1,) . 2 = 2 (2, , ) (2,)

. 3 = 3 (3, , ) (3,) = 1
1
2
( ) : = (1, 2, 3, )
3

0.043
= (0.204) = 347.4
0.753
Tdew +Tbubl
(c)P,T-flash calculation: T = T = 340.75K
2
1 = 0.3 2 = 0.2 3 = 1 1 2
Guess: = 0.5 Use x from DEW P and y from BUBL P as initial guess.
Given

. 1 = 1 (1, , ) (1,) 1 (1 ) + 1 = 1

. 2 = 2 (2, , ) (2,) 2 (1 ) + 2 = 2

. 3 = 3 (3, , ) (3,) 3 (1 ) + 3 = 3

= 1 = 1
1
2
3
1 : = (1, 2, 3, 1, 2, 3, )
2
3
()
0.125 0.125
= ( 0.17 ) = ( 0.17 ) V = 0.426 Ans.
0.705 0.705

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