Example 05.

22a VLE of Hexane-Butanone-2 Via UNIFAC - Step by Step

Calculate the vapor-liquid equilibrium of the system n-hexane (1) - 2-butanone (2) at 60°C for a mole fraction of
x 1 = 0.5 with the help of the UNIFAC method assuming ideal behavior of the vapor phase.

System: n-hexane (1) - 2-butanon (2) Definitions: kPa  1000Pa

System temperature: T  333.15K ncomp  2

nmgroups  2
Pure component vapor pressures: §75.85 ·
Ps  ¨ ¸ kPa nsgroups  3
©51.90 ¹
i  1  2 j  1  2
§.5 ·
Composition: x ¨ ¸ k  1  3 m  1  3 n  1  3
©.5 ¹

Structural information:

Groups: Subgroup 1 CH3 Maingroup 1 CH3

Subgroup 2 CH2 Maingroup 2 CH2CO
Subgroup 3 CH3CO

Subgroup i belongs to maingroup nord i :

§¨1 ·¸
nord  ¨1 ¸
¨2 ¸
© ¹

Number of subgroups of type i §¨2 1·

¸
in component j (Qi,j): Q ¨4 1¸
¨0 ¸
© 1¹

R- and Q-values for subgroups:

§¨0.9011 ·¸ §¨0.848 ·¸
R ¨0.6744 ¸ Q ¨0.540 ¸
¨1.6724 ¸ ¨1.488 ¸
© ¹ © ¹

Interaction parameters between

§¨ 0 0 476.4 ·
¸ § §¨ 1 1 0.239 ·
n  m· ¸
maingroups: a
a ¨ 0 0 476.4 ¸ K \  exp¨ ¸ \ ¨ 1 1 0.239 ¸
nm © T ¹
¨26.76 ¸ ¨0.923 ¸
© 26.76 0 ¹ © 0.923 1 ¹

Calculation of the combinatorial part (Guggenheim and Stavermann):

§ 4.5 · §3.856 ·
Relative van der Waals volume
and surface of the components:
r 
i ¦ Q k  i ˜Rk r ¨ ¸
©3.248 ¹
q 
i ¦ Q k  i ˜ Qk q ¨ ¸
©2.876 ¹
k k

r
i q
V  §1.162 · i
¦ ¨ ¸ F  §1.146 ·
i r ˜x V

j
j j ©0.838 ¹ i
¦ q ˜x
j j
F ¨ ¸
©0.854 ¹
j

§ V § Vi ·· § 0.0099 ·
lnJC  1  V  ln V  5 ˜ q ˜ ¨1   ln ¨ ¸¸
i
i i i i¨ ¨ Fi ¸¸
lnJC ¨ ¸
©
F
i © ¹¹ © 0.0121 ¹
Calculation of the residual part:

Mixture:

Calculation of group fractions in the mixture: ¦ Q m j ˜xj §¨0.333 ·¸

j
XM  XM ¨0.556 ¸
¦ ¦ Q n  j ˜xj
m
¨0.111 ¸
© ¹
j n

Calculation of group surface fractions Q ˜ XM §¨0.378 ·¸

in the mixture: m m
TM  TM ¨0.401 ¸
¦ Qn˜XMn
m
¨0.221 ¸
© ¹
n

Group activity coefficients in the mixture: § TM ˜ \ ·

m km §¨ 0.08 ¸·
ln*M  Q ˜ ¨1  ln§ ¸
k k¨ ¨ ¦ TM ˜ \ ·
m m  k¸ ¦¦ TM ˜ \
n nm
¸ ln*M ¨0.051 ¸
¨ ©m ¹ m ¸ ¨0.929 ¸
© n ¹ © ¹

Pure Components:

Q §¨0.333 0.333 ·
Calculation of group fractions in the m i ¸
X 
¦
pure components: m i Q X ¨0.667 0.333 ¸
ni ¨ 0
n © 0.333 ¸¹

Calculation of group surface fractions

in the pure components: Q ˜X §¨0.44 0.295 ·
m m i ¸
T 
m i
¦ Q ˜X
n ni
T ¨0.56
¨ 0
0.188 ¸
0.517 ¸¹
n ©
Group activity coefficients in the § T ˜\ ·
m i k m §¨ 0 0.29
¸·
 Q ˜ ¨1  ln§ ¸
pure components: ln*
k i ¦ T
m i
˜\ ·
m  k¸ ¦
¦
k¨ ¨ ¸ ln* ¨ 0 0.185 ¸
T ˜\
¨ ©m ¹ m n  i n  m¸ ¨2.243 ¸
© n ¹ © 0.262 ¹

lnJR 
i ¦ Q k  i ˜ ln*Mk  ln*k  i lnJR
§0.366 ·
¨ ¸ exp( lnJR)
§1.442 ·
¨ ¸
k ©0.323 ¹ ©1.381 ¹

Calculation of the activity coefficients: lnJ  lnJC  lnJR §0.356 · §1.428 ·

i i i lnJ ¨ ¸ J  exp lnJ
i i
J ¨ ¸
©0.311 ¹ ©1.365 ¹

Calculation of the total pressure: P

¦ xi ˜J i ˜Psi P 89.555 kPa
i

Calculation of the vapor composition: x ˜ J ˜ Ps

i i i §0.605 ·
y 
i
y ¨ ¸
P ©0.395 ¹
y
i §1.209 ·
Calculation of the K-factors: K 
i
K ¨ ¸
x
i ©0.791 ¹
K
i § 1 1.529 ·
Calculation of the separation factors: D
ij
 D ¨ ¸
K
j ©0.654 1 ¹