M ay 16, 2007

12:13

W SPC/Book Trim Size for 9.75in x 6.5in

swp0001

Chapter 3

UNIFAC and Its Related Calculations

Example 3.1 For the binary system diethylamine (1).n-heptane(2) at 308.15 K,
…nd 1 and 2 when x1 = 0:4. The chemical formulas are given as CH3 -CH2 NHCH2 -CH3 (1) and CH3 -(CH2 )5 -CH3 (2). The …gure below illustrates the chemical
structure for diethylamine and n-heptane)

H
H
H

H

H

H

H

H

H
H

H

H

H

H

H
H

H

H

H

H

n-heptane

H

H

H

H

N
H

H
H
diethylamine

Fig. 3.1

Chemical structure for diethylamine (1) and n-heptane (2).

The following table shows the subgroups and their identi…cation numbers k,
values of parameters Rk and Qk , and the number of each subgroup in each molecule:
Obtain the volume contribution for each molecule as:
X (i)
ri =
k Rk ;
k

r1 = (2)(0:9011) + (1)(0:6744) + (1)(1:2070) = 3:6836
r2 = (2)(0:9011) + (5)(0:6744) = 5:1742
15

for this example it is 3 2.6744 1. 2007 12:13 W SPC/Book Trim Size for 9.2070 Qk 0. The size of this matrix is the number of subgroups times the number of components i.75in x 6.540 0. k q1 = (2)(0:848) + (1)(0:540) + (1)(0:936) = 3:1726 q2 = (2)(0:848) + (5)(0:540) = 4:3960 The ri and qi values are molecular properties.3858 0.1 = e2.2 = (i) k Qk qi (1) 1 Q1 q1 (2) 1 Q1 q2 (1) 2 Q2 q1 (2) 2 Q2 q2 (1) 3 Q3 q1 (2) 3 Q3 q2 k 1 2 33 = 2(0:848) = 0:5347 3:1726 = 2(0:848) = 0:3858 4:3960 = 1(0:540) = 0:1702 3:1726 = 5(0:540) = 0:6142 4:3960 = 1(0:936) = 0:2951 3:1726 = 0(0:936) =0 4:396 ek.2 = e2.6142 0.e.0000 . Substitute the known values to obtain the eki which are the surface fractions for each subgroup in each molecule.5347 0.1 = e33.2951 i=2 0. ek. independent of composition.2 = e33..M ay 16.1 = e1.848 0.936 n-heptane (2) (1) k (2) k 2 1 1 2 5 0 In like manner for the surface fractions qi = X (i) k Qk .i i=1 0.1702 0.9011 0.5in swp0001 16 diethylamine (1) Subgroup CH3 CH2 CH2 NH k 1 2 33 Rk 0.i = e1.

2 = 0:4361 2.5in swp0001 17 Determine the overall surface area fraction for each subgroup in the mixture which is a vector of size k.33 = 0:4361 33.k 1 = 2 33 1 a1.k h a i m.1 = 65:33 2 a1.k from .1 2. for this example it is 3 3.i 0:4(3:1762)(0:1702) + 0:6(4:3960)(0:6142) P = 0:4700 = xj qj 0:4(3:1762) + 0:6(4:3960) i j 33 = P i xi qi e33.e.75in x 6. at the given temperature T = 308:15 K.33 m.33 = 255:7 a33.2 = 1 33.1 = 1 33.33 = 0:0 From this matrix. determine the m.1 = 0:8090 = exp = =1 2..M ay 16.33 = 1 1.2 = 0:0 a2.i = 0:0 am. The fraction is de…ned as k = P xi qi ek.33 = 255:7 a2. This is a square matrix whose elements are determined by the number of subgroups i.k T = 1 1.2 = 0:0 a33.1 = 0:0 a33.2 = 0:8090 1.2 = 65:33 33 a1.k m.1 = 0:0 a2.i 0:4(3:1762)(0:2951) + 0:6(4:3960)(0:0000) P = = 0:0958 xj qj 0:4(3:1762) + 0:6(4:3960) j Obtain the interaction parameters matrix for the subgroups from the table.i 0:4(3:1762)(0:5347) + 0:6(4:3960)(0:3858) P = = 0:4342 xj qj 0:4(3:1762) + 0:6(4:3960) i j 2 = P xi qi e2. 2007 12:13 W SPC/Book Trim Size for 9. Notice that ai.i P xj qj i j 1 = P xi qi e1.

The size of this matrix is number of components times the number of subgroups i.0000 33 0.0000 k 2 0.2 = 0:3858(1) + 0:6142(1) + 0(0:8090) = 1:0000 em2 m.33 em2 m.2 = X m 1.9436 1.2 = 0:4342(1) + 0:4700(1) + 0:0958(0:8090) = 0:9817 m s2 = X m s33 = X m m.2 = 0:5347(1) + 0:1702(1) + 0:2951(0:8090) = 0:9436 em1 m.k m s1 = X m m.33 = X = 0:3858(0:4361) + 0:6142(0:4361) + 0(1) = 0:4361 m i.5in 18 Determine the ik .33 = 0:4342(0:4361) + 0:4700(0:4361) + 0:0958(1) = 0:4901 m One last step before you are ready to calculate the combinatorial and residual parts of the activity coe¢ cients is to calculate the volume and surface area contributions swp0001 .1 = 0:4342(1) + 0:4700(1) + 0:0958(0:8090) = 0:9817 m m.1 = X m 1.33 = X = 0:5347(0:4361) + 0:1702(0:4361) + 0:2951(1) = 0:6024 m 2.e.k em1 m.1 = 0:5347(1) + 0:1702(1) + 0:2951(0:8090) = 0:9436 em1 m.33 m 1. ik = X emi m.6024 0..1 = X m 2.75in x 6.2 = X m 2.M ay 16. for this example it is 2 3.4361 Calculate the sk vector (size equal to number of subgroups) from sk = X m m.k i = 1 2 1 0.9436 1.1 = 0:3858(1) + 0:6142(1) + 0(0:8090) = 1:0000 em2 m. 2007 12:13 W SPC/Book Trim Size for 9.

5in swp0001 19 for the molecules i..e. Ji = P ri xj rj j J1 = P r1 3:6836 = = 0:8046 xj rj 0:4(3:6836) + 0:6(5:1742) j J2 = P r2 5:1742 = = 1:1302 xj rj 0:4(3:6836) + 0:6(5:1742) j Li = P qi xj qj j L1 = P q1 3:1720 = = 0:812 xj qj 0:4(3:1720) + 0:6(4:3960) j L2 = P q2 4:3960 = = 1:1253 xj qj 0:4(3:1720) + 0:6(4:3960) j Calculate the combinatorial activity coe¢ cients from ln C i =1 Ji + ln Ji 5qi 1 ln C 1 =1 J1 + ln J1 5q1 (1 =1 0:8046 + ln(0:8046) =1 J2 + ln J2 =1 1:1302 + ln 1:1302 ln C 2 5q2 (1 Ji Ji + ln Li Li J1 J1 + ln ) L1 L1 5(3:1720)(1 0:8046 0:8046 + ln )= 0:812 0:812 2: 134 7 2 10 J2 J2 + ln ) L2 L2 5(4:3960)(1 1:1302 1:1302 + ln )= 1:1253 1:1253 7: 597 6 10 3 .75in x 6. 2007 12:13 W SPC/Book Trim Size for 9.M ay 16.

5in swp0001 20 Determine the residual part of the activity coe¢ cients from " # X i.1 ln k sk sk k = 3:1720(1 (0:4342 0:9436 0:9817 0:6024 +0:0958 0:4901 = 0:14630 " X = q2 1 k R 2 k = 4:396(1 2. 2007 12:13 W SPC/Book Trim Size for 9.k R ln 1 = q1 1 ek.i ln k i = qi 1 sk sk k " # X 1.75in x 6.k 1.k sk 0:3858 ln 1:0000 0:9817 1:0000 0:9817 0:4360 0:0000 ln )) 0:4901 0:6142 ln = 0:14630 + ( 2: 134 7 = 5: 358 3 0:9436 0:9817 0:9436 0:9817 0:6024 0:2951 ln )) 0:4901 # +0:4700 ln 0:5347 ln 0:1702 ln +0:4700 ln 0:9436 0:9817 2 10 2 + ( 7: 597 6 ) = 0:124 95 10 3 ) = 4: 598 5 10 2 .k sk (0:4342 R i R 1 ln 1 = ln 1 = exp(0:124 95) = 1: 133 2 = ln 2 = exp(4: 598 5 ln R 2 + ln C i C 1 = ln + ln + ln C 2 ek.k ln R ek.M ay 16.k i.2 ln 1:0000 0:9817 1:0000 0:9817 0:4360 +0:0958 0:4901 = 5: 358 3 10 2 i 10 2 10 ) = 1: 047 : 2.

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