thermodynamic activity coefficient
TRANSCRIPT
Advanced Chemical Engineering Thermodynamics
Class 26
Theory of Liquid MixturesChapter 7, Prausnitz
Theoretical Derivation of van Laar’s Equations
Let’s focus on a mixture of 2 liquids
x1 moles of liquid 1x2 moles of liquid 2
The two liquids mix at constant T and P
Let’s focus on a mixture of 2 liquids
x1 moles of liquid 1x2 moles of liquid 2
The two liquids mix at constant T and P
We assume that during mixing
1. There is no volume change
2. The entropy is that of an ideal solution
Theoretical Derivation of van Laar’s Equations
Let’s focus on a mixture of 2 liquids
x1 moles of liquid 1x2 moles of liquid 2
The two liquids mix at constant T and P
We assume that during mixing
1. There is no volume change
2. The entropy is that of an ideal solution
vE = 0
sE = 0
Then
Theoretical Derivation of van Laar’s Equations
Let’s focus on a mixture of 2 liquids
x1 moles of liquid 1x2 moles of liquid 2
The two liquids mix at constant T and P
We remember that
gE = uE + P vE - T sE
Theoretical Derivation of van Laar’s Equations
Let’s focus on a mixture of 2 liquids
x1 moles of liquid 1x2 moles of liquid 2
The two liquids mix at constant T and P
vE = 0
sE = 0If then
We remember that
gE = uE + P vE - T sE
gE = uE
Theoretical Derivation of van Laar’s Equations
Let’s focus on a mixture of 2 liquids
x1 moles of liquid 1x2 moles of liquid 2
The two liquids mix at constant T and P
This is the basic assumption behind van Laar’s theory
gE = uE
Theoretical Derivation of van Laar’s Equations
Theoretical Derivation of van Laar’s Equations
Let’s use it within the thermodynamic cycle
gE = uE
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = const
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step I: The liquids are vaporized isothermally
(∂u/∂v)T = T (∂P/∂T)v - P
Because, we need to find the variation in u
Rigorously,
gE = uE
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step I: The liquids are vaporized isothermally
(∂u/∂v)T = a/v2
Because, we need to find the variation in u
However, van Laar used the VdW EOS, and then
gE = uE
a is the VdW parameter
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step I: The liquids are vaporized isothermally
a1 x1 / v1L
By considering the expansion of both liquids, integrating we get
ai is the VdW parameter for component i
a2 x2 / v2L
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step I: The liquids are vaporized isothermally
ΔuI = a1 x1 / b1 + a2 x2 / b2
If we substitute the molar liquid volumes with the VdW parameter b (not a bad assumption), then we get
ai is the VdW parameter for component i
√
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step II: The two ideal gases are mixed isothermallyWe need to evaluate the variation in internal energy
√
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step II: The two ideal gases are mixed isothermallyWe need to evaluate the variation in internal energy
√
ΔuII = 0
√
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step III: The ideal mixture is compressed to the initial pressureWe need to evaluate the variation in internal energy
√
√
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step III: The ideal mixture is compressed to the initial pressure
√
√
Using, in reverse, the derivation used in step I, and remembering that the total mixture is composed by x1+x2=1 moles, we obtain
ΔuIII = - amix / bmix
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step III: The ideal mixture is compressed to the initial pressure
√
√
To finish, we need to evaluate the a and b parameters for the mixture
ΔuIII = - amix / bmix
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step III: The ideal mixture is compressed to the initial pressure
√
√
Van Laar used:
ΔuIII = - amix / bmix
bmix = x1 b1 + x2 b2
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step III: The ideal mixture is compressed to the initial pressure
√
√
Van Laar used:
ΔuIII = - amix / bmix
amix = x12 a1 + x2
2 a2 + 2 x1 x2 sqrt (a1 a2)
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Step III: The ideal mixture is compressed to the initial pressure
√
√
Van Laar used:
Note that only interactions between 2 molecules are important
ΔuIII = - amix / bmix
amix = x12 a1 + x2
2 a2 + 2 x1 x2 sqrt (a1 a2)
√
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
Now we need to put things together
√
√
ΔuIII = - amix / bmix
√
ΔuII = 0
ΔuI = a1 x1 / b1 + a2 x2 / b2
ΔuIII = - amix / bmix
ΔuII = 0
ΔuI = a1 x1 / b1 + a2 x2 / b2
Theoretical Derivation of van Laar’s Equations
uE = ΔuI + ΔuII + ΔuIII
Substituting:uE = a1x1/b1 + a2x2/b2 + 0 - [x1
2a1 + x22a2 + 2x1x2 sqrt(a1a2) ] / [(x1b1 + x2b2) b1b2 ]
Playing around, we get
uE = x1x2b1b2 / [x1b1 + x2b2] { sqrt(a1)/b1 - sqrt(a2)/b2) }2
Theoretical Derivation of van Laar’s Equations
uE = x1x2b1b2 / [x1b1 + x2b2] { sqrt(a1)/b1 - sqrt(a2)/b2) }2
According to the initial assumption,
gE = uE
Thus, we obtain
gE = x1x2b1b2 / [x1b1 + x2b2] { sqrt(a1)/b1 - sqrt(a2)/b2) }2
This is an expression for the excess Gibbs free energy, which we can use to obtain the activity coefficients
Theoretical Derivation of van Laar’s Equations
gE = x1x2b1b2 / [x1b1 + x2b2] { sqrt(a1)/b1 - sqrt(a2)/b2) }2
Remembering that
giE = RT ln [ γi ]
GE = RT ∑i ni ln γi
We can calculate the fugacity coefficients of the two components
Theoretical Derivation of van Laar’s Equations
gE = x1x2b1b2 / [x1b1 + x2b2] { sqrt(a1)/b1 - sqrt(a2)/b2) }2
ln γ2 = B’ / [ 1 + B’/A’ x2/x1 ]2
ln γ1 = A’ / [ 1 + A’/B’ x1/x2 ]2
But now we have a relationship between molecular parameters and A’ B’:
A’ = b1 / RT [ sqrt(a1)/b1 - sqrt(a2)/b2 ]2
B’ = b2 / RT [ sqrt(a1)/b1 - sqrt(a2)/b2 ]2
Comments• According to the van Laar’s theory, the activity
coefficients are never less than unity
• In other words, the theory predicts always positive deviations from the Raoult’s law
• This is a consequence of the mixing rule,
• which implies
• This means that the force of attraction in the mixture are less than they would be if they were additive on a molar basis
amix = x12 a1 + x2
2 a2 + 2 x1 x2 sqrt (a1 a2)
amix < x1 a1 + x2 a2
Comments
• If we had used mixing rules that result in
• Like, for example,
• Then we would have obtained negative deviations from the Raoult law in all cases
• What if we had used
amix = x1 a1 + x2 a2 + 2 x1 x2 sqrt (a1 a2)
amix > x1 a1 + x2 a2
amix = x1 a1 + x2 a2 ?
Chapter 7The goal of this chapter is to see whether we can use our understanding (theory) of the structure and properties of the liquid mixture to calculate the activity coefficients of the various compounds
The first example was that of the van Laar’s theory
The main problem there was the use of the VdW EOS to calculate ΔuI
However, it was instructive because a simple vision of the solution yield a useful relation often used to fit activity coefficients
The main assumption was that excess entropy and excess volume were 0
The Scatchard-Hildebrand Theory
Stimulated by the results of van Laar’s, Hildebrand introduced the concept of ‘regular solutions’
Regular solutions are those in which the components mix isothermally with no excess entropy provided that there is no volume change upon mixing
Equivalently, the excess entropy is negligiblewhen T=const and V=const
The theory then builds similarly to the procedure van Laar adopted
The Scatchard-Hildebrand Cycle
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
The Scatchard-Hildebrand Cycle
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
The main problem for van Laar was the assumption he used in I
The Scatchard-Hildebrand Cycle
Pure liquidsP
Liquid MixtureP
Pure ideal gasesVery low P
Ideal gas mixtureVery low P
T = constI
II
III
The improvement proposed by both Scatchard and Hildebrand was the introduction of a parameter ‘c’ defined as:
c ≡ Δvap u / vL
Δvap u is the energy of complete vaporization (liquid to ideal gas)vL is the molar volume of the liquidc is the cohesive energy density
The Scatchard-Hildebrand TheoryFollowing the same process as described in the case of van Laar’s equations, Scatchard and Hildebrand obtained:
Defining the volume fractions (vL is replaced by v)
φ1 = x1 v1 / [ x1 v1 + x2 v2 ]
φ2 = x2 v2 / [ x1 v1 + x2 v2 ]
Using the fact that
uEideal gases = 0
uE for the mixture is given by
uE = ( c11 + c22 - 2 c12 ) φ1 φ2 ( x1v1 + x2v2 )
The Scatchard-Hildebrand Theory
uE = ( c11 + c22 - 2 c12 ) φ1 φ2 ( x1v1 + x2v2 )
To use this relation, we need an expression for c12
Here comes the most important assumption:
c12 = sqrt [ c11 c22 ]
The Scatchard-Hildebrand Theory
uE = ( c11 + c22 - 2 c12 ) φ1 φ2 ( x1v1 + x2v2 )
To use this relation, we need an expression for c12
Here comes the most important assumption:
c12 = sqrt [ c11 c22 ]
Which, upon substitution, leads to
uE = ( x1v1 + x2v2 ) φ1 φ2 [ c11 + c22 - 2 sqrt (c11 c22 )]
The Scatchard-Hildebrand Theory
The usefulness of this expression is related to the definition of the solubility parameters:
uE = ( x1v1 + x2v2 ) φ1 φ2 [ c11 + c22 - 2 sqrt (c11 c22 ) ]
uE = ( x1v1 + x2v2 ) φ1 φ2 [ sqrt(c11) - sqrt(c22) ]2
δ1 ≡ sqrt [ c11 ] = sqrt [ Δvap u / v ]1δ2 ≡ sqrt [ c22 ] = sqrt [ Δvap u / v ]2
The Scatchard-Hildebrand Theory
The usefulness of this expression is related to the definition of the solubility parameters:
uE = ( x1v1 + x2v2 ) φ1 φ2 ( δ1 - δ2 )2
δ1 ≡ sqrt [ c11 ] = sqrt [ Δvap u / v ]1δ2 ≡ sqrt [ c22 ] = sqrt [ Δvap u / v ]2
Which allows us to write uE as:
uE = ( x1v1 + x2v2 ) φ1 φ2 [ c11 + c22 - 2 sqrt (c11 c22 ) ]
uE = ( x1v1 + x2v2 ) φ1 φ2 [ sqrt(c11) - sqrt(c22) ]2
The Scatchard-Hildebrand Theory
uE = ( x1v1 + x2v2 ) φ1 φ2 ( δ1 - δ2 )2
The Scatchard-Hildebrand Theory
uE = ( x1v1 + x2v2 ) φ1 φ2 ( δ1 - δ2 )2
If, at constant T and P, sE vanishes (notice that this is an additional assumption, although not too strong because we had assumed already that sE is 0 when the volume is constant), then
gE = uE
Thus we can write:
gE = ( x1v1 + x2v2 ) φ1 φ2 ( δ1 - δ2 )2
The Scatchard-Hildebrand Theory
gE = ( x1v1 + x2v2 ) φ1 φ2 ( δ1 - δ2 )2
From
Remembering that
giE = RT ln [ γi ]
GE = RT ∑i ni ln γi
We can calculate the fugacity coefficients of the two components
The Scatchard-Hildebrand Theory
gE = ( x1v1 + x2v2 ) φ1 φ2 ( δ1 - δ2 )2
From
We obtain the regular-solution equations:
RT ln γ1 = v1 φ22 [ δ1 - δ2 ]2
RT ln γ2 = v2 φ12 [ δ1 - δ2 ]2
Which relate the activity coefficients to the solubility parameters and the molar liquid volumes of the compounds
Comparison: Van Laar’s EquationsgE = x1x2b1b2 / [x1b1 + x2b2] { sqrt(a1)/b1 - sqrt(a2)/b2) }2
ln γ2 = B’ / [ 1 + B’/A’ x2/x1 ]2
ln γ1 = A’ / [ 1 + A’/B’ x1/x2 ]2
Which provide a relationship between molecular parameters a and b and A’ B’:
A’ = b1 / RT [ sqrt(a1)/b1 - sqrt(a2)/b2 ]2
B’ = b2 / RT [ sqrt(a1)/b1 - sqrt(a2)/b2 ]2
The Scatchard-Hildebrand Theory
gE = ( x1v1 + x2v2 ) φ1 φ2 ( δ1 - δ2 )2
From
We obtain the regular-solution equations:
RT ln γ1 = v1 φ22 [ δ1 - δ2 ]2
RT ln γ2 = v2 φ12 [ δ1 - δ2 ]2
Which relate the activity coefficients to the solubility parameters and the molar liquid volumes of the compounds
These expressions are similar to van Laar’sHowever, we accept that they are MUCH IMPROVED
How can we say this?
CommentsThe regular solution equations always predict positive deviations from ideality, as van Laar’s equations do
This is a consequence of the assumptionc12 = sqrt [ c11 c22 ]
CommentsThe regular solution equations always predict positive deviations from ideality, as van Laar’s equations do
This is a consequence of the assumption
The solubility parameters δ1 and δ2 are in general a function of THowever, their difference
δ1 - δ2is almost independent of T
c12 = sqrt [ c11 c22 ]
CommentsThe regular solution equations always predict positive deviations from ideality, as van Laar’s equations do
This is a consequence of the assumption
The solubility parameters δ1 and δ2 are in general a function of THowever, their difference
δ1 - δ2is almost independent of T
The main result is that the difference in solubility parameters between the components in a mixture gives us an idea about the extent of the deviations from ideality
c12 = sqrt [ c11 c22 ]
Table 7.1
Compound vL @ 298K (cm3/mol) δ (J/cm3)1/2
Isopentane 117 13.9
n-pentane 116 14.5
n-octane 164 15.3
Toluene 107 18.2
Benzene 89 18.8
Table 7.1Compound vL @ 298K (cm3/mol) δ (J/cm3)1/2
Isopentane 117 13.9
n-pentane 116 14.5
n-octane 164 15.3
Toluene 107 18.2
Benzene 89 18.8
Regular-solution equations give a good semi-quantitative representation of activity coefficients for many solutions
containing non polar components
Example: Fig. 7.2
1 - CO2 - CH4
T = 90.7 K VLE
Example: Fig. 7.3
1 - C6H62 - n-C7H16
T = 70 C VLE
Example: Fig. 7.4
1 - neo-C5H122 - CCl4
T = 0 C VLE
CommentsRT ln γ1 = v1 φ2
2 [ δ1 - δ2 ]2
RT ln γ2 = v2 φ12 [ δ1 - δ2 ]2
Because of the mathematical formalism of the regular-solution equations, they can behave poorly when they are applied on systems of compounds very similarThe reason is that small errors in the geometric mean used for evaluating c12 have large impact in the calculation for gE when the solubility parameter for two liquids are similar
CommentsRT ln γ1 = v1 φ2
2 [ δ1 - δ2 ]2
RT ln γ2 = v2 φ12 [ δ1 - δ2 ]2
Because of the mathematical formalism of the regular-solution equations, they can behave poorly when they are applied on systems of compounds very similarThe reason is that small errors in the geometric mean used for evaluating c12 have large impact in the calculation for gE when the solubility parameter for two liquids are similarAs a consequence, they are most useful for non-polar mixtureshaving appreciable non idealityEven better, when the compounds have different solubility parameter
Multi-Component MixturesAnother advantage for the Scatchard-Hildebran equations is their simplicityIn fact, they can be easily extended to multi-component mixtures
It can be demonstrated that for a component j in the mixture
RT ln γj = vj [ δj - δ ]2
Whereδ = ∑ φi δi
i = 1
m
The sums are extended to all m compounds in the
mixtureAnd
φj = xj vj / [ ∑ xi vi ]i = 1
m