CHE 411N

Phase and Equilibria of Mixtures

TTh 9:00 – 10:30

D e p a r t m e n t o f Term/Academic Year:
Chemical Engineering First Semester of AY 2018-2019
Talamban, Cebu City, Philippines 6000

Activity Coefficient
Name of Model 𝑮𝒆𝒙 expression Applicability
Expression
The Redlich-Kister expansion is used for the
representation of excess thermodynamic
properties. The number of terms retained in this
Redlich-Kister 𝐺 𝑒𝑥 = 𝑥1 𝑥2 [𝐴 + 𝐵 (𝑥1 − 𝑥2 ) expansion depends on the shape of the Gex
Expansion + 𝐶 (𝑥1 − 𝑥2 )2 + ⋯ ] curve as a function of composition.

The one-constant Margules equation provides a

𝐺 𝑒𝑥
= 𝑥1 𝑥2 [𝐴 + 𝐵 (𝑥1 − 𝑥2 ) satisfactory representation for activity
coefficient behavior only for liquid mixtures
+ 𝐶 (𝑥1 − 𝑥2 )2 + ⋯ ]
containing constituents of similar size, shape,
and chemical nature
One-Constant Where 𝑅𝑇𝑙𝑛𝛾1 = 𝐴𝑥22
Margules A≠0 𝑅𝑇𝑙𝑛𝛾2 = 𝐴𝑥12
B, C, D, … = 0

𝐺 𝑒𝑥 = 𝐴𝑥1 𝑥2
.
 For more complicated systems (mixtures of
dissimilar molecults), the excess Gibbs energy
of a general mixture will not be a symmetric
𝑅𝑇𝑙𝑛𝛾1 = 𝛼1 𝑥22 + 𝛽1 𝑥23 function of the mole fraction, and the activity
𝐺 𝑒𝑥 = 𝑥1 𝑥2 [𝐴 + 𝐵 (𝑥1 − 𝑥2 ) coefficients of the two species in a mixture
+ 𝐶 (𝑥1 − 𝑥2 )2 + ⋯ ] should not be expected to be mirror images.
𝑅𝑇𝑙𝑛𝛾2 = 𝛼2 𝑥12 + 𝛽2 𝑥13
Two-Constant Where
Margules A, B ≠ 0
Where
C, D, … = 0
𝛼𝑖 = 𝐴 + 3(−1)𝑖+1 𝐵
𝐺 𝑒𝑥 = 𝑥1 𝑥2 [𝐴 + 𝐵 (𝑥1 − 𝑥2 )] 𝛽𝑖 = 4(−1)𝑖 𝐵

Similar to the Redlich-Kister expansion, the

Wohl expansion is one that is modeled after the
Virial expansion for gaseous mixtures.
𝐺 𝑒𝑥
𝑅𝑇(𝑥1 𝑞1 + 𝑥2 𝑞2 )
= 2𝑎12 𝑧1 𝑧2
+ 3𝑎112 𝑧12 𝑧2
+ 3𝑎122 𝑧1 𝑧22
+ 4𝑎1112 𝑧13 𝑧2
Wohl Expansion + 4𝑎1222 𝑧1 𝑧23
+ 6𝑎1122 𝑧12 𝑧22 + ⋯

Where
zi = volume fractions of species i
𝑥𝑖 𝑞𝑖
𝑧𝑖 =
𝑥1 𝑞1 + 𝑥2 𝑞2
 𝐺 𝑒𝑥 The liquid-phase activity coefficients for the
𝑅𝑇(𝑥1 𝑞1 + 𝑥2 𝑞2 ) Wohl expansion can be obtained by taking the
= 2𝑎12 𝑧1 𝑧2 𝛼 appropriate derivatives. They are frequently
𝑙𝑛𝛾1 = 𝛼𝑥 used to correlate activity coefficient data.
+ 3𝑎112 𝑧12 𝑧2 [1 + 𝑥1 ]2
+ 3𝑎122 𝑧1 𝑧22 𝛽 2
+ 4𝑎1112 𝑧13 𝑧2
𝛽
+ 4𝑎1222 𝑧1 𝑧23 𝑙𝑛𝛾2 =
Van Laar Equations + 6𝑎1122 𝑧12 𝑧22 + ⋯ 𝛽𝑥
[1 + 𝛼 𝑥2 ]2
1
Where
a12 ≠ 0 Where
a112, a122, … = 0 α = 2q1a12
β = 2q2a12
𝐺 𝑒𝑥
= 2𝑎12 𝑧1 𝑧2 (𝑥1 𝑞1 + 𝑥2 𝑞2 )
𝑅𝑇
Wilson Equation 𝐺 𝑒𝑥 𝑙𝑛𝛾1 The ratio of species 1 to species 2 molecules in
= −𝑥1 ln(𝑥1 + 𝑥2 Λ12 ) − 𝑥2 ln(𝑥2 the vicinity of any molecule is the same as the
𝑅𝑇 = − ln(𝑥1 + 𝑥2 Λ12 )
+ 𝑥1 Λ21 ) Λ12 ratio of their mole fractions. A different class of
+ 𝑥2 [ excess Gibbs energy models can be formulated
𝑥1 + 𝑥2 Λ12
Λ 21 by assuming that the ratio of species 1 to 2
− ] molecules surrounding any molecule also
𝑥1 Λ21 + 𝑥2
depends on the differences in size and
𝑙𝑛𝛾2 energies of interaction of the chosen molecule
= − ln(𝑥2 + 𝑥1 Λ 21 ) with both species. Thus, around each molecule
Λ12 there is a local composition that differs with the
− 𝑥1 [ bulk composition
𝑥1 + 𝑥2 Λ12
Λ 21
− ]
𝑥1 Λ21 + 𝑥2
NRTL (Non- 𝐺 𝑒𝑥 𝜏21 𝐺21 𝜏12 𝐺12 𝑙𝑛𝛾1
Random Two = 𝑥1 𝑥2 ( − ) 2
𝑅𝑇 𝑥1 + 𝑥2 G21 𝑥2 + 𝑥1 G12 𝐺21
Liquid) Model of = 𝑥22 [𝜏21 ( )
𝑥1 + 𝑥2 G21
Renon and 𝜏12 𝐺12
Prausnitz + ]
(𝑥2 + 𝑥1 𝐺12 )2

𝑙𝑛𝛾2
2
𝐺12
= 𝑥12 [𝜏12 ( )
𝑥2 + 𝑥1 G12
𝜏21 𝐺21
+ ]
(𝑥1 + 𝑥2 𝐺21 )2
Flory-Huggins Δ𝑚𝑖𝑥 𝑆 = −𝑅(𝑥1 𝑙𝑛𝜙1 + 𝑥2 𝑙𝑛𝜙2 ) 𝜙1 1 The Flory and Huggins model is meant to apply
Equation 𝑙𝑛𝛾1 = 𝑙𝑛 + (1 − ) 𝜙2 to mixtures of molecules of very different sizes
𝑆 𝑒𝑥 = Δ𝑚𝑖𝑥 𝑆 − Δ𝑚𝑖𝑥 𝑆 𝐼𝑀 𝑥1 𝑚
+ 𝜒𝜙22 (including solutions of polymers).
Δ𝑚𝑖𝑥 𝐻 = 𝐻 𝑒𝑥 = 𝜒𝑅𝑇(𝑥1 + 𝑚𝑥2 )𝜙1 𝜙2
where χ is an adjustable parameter known as 𝜙2
𝑙𝑛𝛾2 = 𝑙𝑛 − (𝑚 − 1)𝜙1
the Flory interaction parameter 𝑥2
+ 𝑚𝜒𝜙12

𝐺 𝑒𝑥 𝐻 𝑒𝑥 − 𝑇𝑆 𝑒𝑥
=
𝑅𝑇 𝑅𝑇

𝐺 𝑒𝑥 𝜙1 𝜙2
= [𝑥1 𝑙𝑛 + 𝑥2 𝑙𝑛 ] + 𝜒(𝑥1
𝑅𝑇 𝑥1 𝑥2
+ 𝑚𝑥2 )𝜙1 𝜙2
UNIQUAC 𝐺 𝑒𝑥 (𝑐𝑜𝑚𝑏𝑖𝑛𝑎𝑡𝑜𝑟𝑖𝑎𝑙) 𝑙𝑛𝛾𝑖 This model is based on the statistical
(Universal Quasi- 𝑅𝑇 = 𝑙𝑛𝛾𝑖 (𝑐𝑜𝑚𝑏𝑖𝑛𝑎𝑡𝑜𝑟𝑖𝑎𝑙) mechanical theory. It allows local compositions
Chemical) Model of 𝜙𝑖 + 𝑙𝑛𝛾𝑖 (𝑟𝑒𝑠𝑖𝑑𝑢𝑎𝑙) to result from both the size and energy
Abrams and = ∑ 𝑥𝑖 𝑙𝑛 differences between the molecules in the
𝑥𝑖
Prausnitz 𝑧
𝑖
𝜃𝑖 mixture.
+ ∑ 𝑥𝑖 𝑞𝑖 𝑙𝑛 𝑙𝑛𝛾𝑖 (𝑐𝑜𝑚𝑏𝑖𝑛𝑎𝑡𝑜𝑟𝑖𝑎𝑙)
2 𝜙𝑖 𝜙𝑖
𝑖
= 𝑙𝑛
𝑥𝑖
𝐺 𝑒𝑥 (𝑟𝑒𝑠𝑖𝑑𝑢𝑎𝑙) 𝑧 𝜃𝑖
𝑅𝑇 − 𝑞𝑖 𝑙𝑛
2 𝜙𝑖
𝜃𝑖
= − ∑ 𝑥𝑖 𝑞𝑖 ln(∑ 𝜃𝑗 𝜏𝑗𝑖 𝑙𝑛 ) + 𝑙𝑖
𝜙𝑗𝑖 𝜙𝑖
𝑖 𝑗 − ∑ 𝑥𝑗 𝑙𝑗
𝑥𝑖
𝑗
Where
ri = volume parameter for species i
qi = surface area parameter for species i 𝑙𝑛𝛾𝑖 (𝑟𝑒𝑠𝑖𝑑𝑢𝑎𝑙) = 𝑞𝑖 [1
θi = area fraction of species i 𝜃𝑗 𝜏𝑖𝑗
𝑥𝑖 𝑞𝑖 = ln(∑ 𝜃𝑗 𝜏𝑗𝑖 ) − ∑ ]
= ∑𝑘 𝜃𝑘 𝜏𝑘𝑗
∑𝑗 𝑥𝑗 𝑞𝑗 𝑗 𝑗
Φi = segment or volume fraction of species i
𝑥𝑖 𝑟𝑖 Where
=
∑𝑗 𝑥𝑗 𝑟𝑗 (𝑟𝑖 − 𝑞𝑖 )𝑧
𝑙𝑖 = − (𝑟𝑖 − 1)
2
𝐺 𝑒𝑥 𝐺 𝑒𝑥 (𝑐𝑜𝑚𝑏𝑖𝑛𝑎𝑡𝑜𝑟𝑖𝑎𝑙)
=
𝑅𝑇 𝑅𝑇 𝑒𝑥
𝐺 (𝑟𝑒𝑠𝑖𝑑𝑢𝑎𝑙)
+
𝑅𝑇
UNIFAC (UNIQUAC 𝑙𝑛𝛾𝑖 (𝑟𝑒𝑠𝑖𝑑𝑢𝑎𝑙) = ∑ 𝑣𝑘 [𝑙𝑛Γ𝑘
(𝑖) The UNIFAC method is used for the prediction
Functional-Group of non-electrolyte activity in non-ideal mixtures.
𝑘
Activity (𝑖) The correlation attempts to describe molecular
− 𝑙𝑛Γ𝑘 ]
Coefficients) Model interactions based on the functional groups
attached to the molecule. This is done as to
reduce the sheer number of binary interactions
that would be needed to be measured for the
prediction of the system’s state.