Advanced Chemical Engineering Thermodynamics

Class 26 Theory of Liquid Mixtures Chapter 7, Prausnitz

Theoretical Derivation of van Laars Equations

Lets focus on a mixture of 2 liquids x1 moles of liquid 1 x2 moles of liquid 2 The two liquids mix at constant T and P

Theoretical Derivation of van Laars Equations

Lets focus on a mixture of 2 liquids x1 moles of liquid 1 x2 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 Laars Equations

Lets focus on a mixture of 2 liquids x1 moles of liquid 1 x2 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 Then vE = 0 sE = 0

Theoretical Derivation of van Laars Equations

Lets focus on a mixture of 2 liquids x1 moles of liquid 1 x2 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 Laars Equations

Lets focus on a mixture of 2 liquids x1 moles of liquid 1 x2 moles of liquid 2 The two liquids mix at constant T and P We remember that gE = uE + P vE - T sE vE = 0 If sE = 0 then

gE = uE

Theoretical Derivation of van Laars Equations

Lets focus on a mixture of 2 liquids x1 moles of liquid 1 x2 moles of liquid 2 The two liquids mix at constant T and P

gE = uE
This is the basic assumption behind van Laars theory

Theoretical Derivation of van Laars Equations

gE = uE
Lets use it within the thermodynamic cycle Pure ideal gases Very low P Ideal gas mixture Very low P

T = const Pure liquids P Liquid Mixture P

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

Step I: The liquids are vaporized isothermally Because, Rigorously,

gE = uE we need to find the variation in u

(u/v)T = T (P/T)v - P

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

Step I: The liquids are vaporized isothermally Because,

gE = uE we need to find the variation in u

However, van Laar used the VdW EOS, and then

(u/v)T = a/v2

a is the VdW parameter

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

Step I: The liquids are vaporized isothermally By considering the expansion of both liquids, integrating we get

a1 x1 / v1L

a2 x2 / v2L

ai is the VdW parameter for component i

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

Step I: The liquids are vaporized isothermally If we substitute the molar liquid volumes with the VdW parameter b (not a bad assumption), then we get

uI = a1 x1 / b1 + a2 x2 / b2
ai is the VdW parameter for component i

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

Step II: The two ideal gases are mixed isothermally We need to evaluate the variation in internal energy

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

Step II: The two ideal gases are mixed isothermally We need to evaluate the variation in internal energy

uII = 0

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

Step III: The ideal mixture is compressed to the initial pressure We need to evaluate the variation in internal energy

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

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

uIII = - amix / bmix

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

Step III: The ideal mixture is compressed to the initial pressure

uIII = - amix / bmix

To finish, we need to evaluate the a and b parameters for the mixture

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

Step III: The ideal mixture is compressed to the initial pressure

uIII = - amix / bmix

Van Laar used:

bmix = x1 b1 + x2 b2

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

Step III: The ideal mixture is compressed to the initial pressure

uIII = - amix / bmix

Van Laar used:

amix = x12 a1 + x22 a2 + 2 x1 x2 sqrt (a1 a2)

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

Step III: The ideal mixture is compressed to the initial pressure

uIII = - amix / bmix

Van Laar used:

amix = x12 a1 + x22 a2 + 2 x1 x2 sqrt (a1 a2)

Note that only interactions between 2 molecules are important

Pure ideal gases Very low P

II

Ideal gas mixture Very low P

T = const

III

Pure liquids P Now we need to put things together

Liquid Mixture P

uI = a1 x1 / b1 + a2 x2 / b2 uII = 0 uIII = - amix / bmix

Theoretical Derivation of van Laars Equations

uI = a1 x1 / b1 + a2 x2 / b2 uII = 0 uIII = - amix / bmix

uE = uI + uII + uIII
Substituting:
uE = a1x1/b1 + a2x2/b2 + 0 - [x12a1 + 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 Laars 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 Laars Equations

gE = x1x2b1b2 / [x1b1 + x2b2] { sqrt(a1)/b1 - sqrt(a2)/b2) }2
Remembering that

giE = RT ln [ i ] GE = RT i ni ln i
We can calculate the fugacity coefficients of the two components

Theoretical Derivation of van Laars Equations

gE = x1x2b1b2 / [x1b1 + x2b2] { sqrt(a1)/b1 - sqrt(a2)/b2) }2

ln 1 = A / [ 1 + A/B x1/x2 ]2 ln 2 = B / [ 1 + B/A x2/x1 ]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 Laars theory, the activity coefficients are never less than unity In other words, the theory predicts always positive deviations from the Raoults law This is a consequence of the mixing rule,
amix = x12 a1 + x22 a2 + 2 x1 x2 sqrt (a1 a2)

which implies

amix < x1 a1 + x2 a2

This means that the force of attraction in the mixture are less than they would be if they were additive on a molar basis

Comments
If we had used mixing rules that result in
amix > x1 a1 + x2 a2

Like, for example,

amix = x1 a1 + x2 a2 + 2 x1 x2 sqrt (a1 a2)

Then we would have obtained negative deviations from the Raoult law in all cases What if we had used
amix = x1 a1 + x2 a2 ?

Chapter 7
The 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 Laars theory The main problem there was the use of the VdW EOS to calculate uI 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 Laars, 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 negligible when T=const and V=const The theory then builds similarly to the procedure van Laar adopted

The Scatchard-Hildebrand Cycle

Pure ideal gases Very low P II Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

The Scatchard-Hildebrand Cycle

Pure ideal gases Very low P II Ideal gas mixture Very low P

T = const

III

Pure liquids P

Liquid Mixture P

The main problem for van Laar was the assumption he used in I

The Scatchard-Hildebrand Cycle

Pure ideal gases Very low P II Ideal gas mixture Very low P

T = const

III

Liquid Mixture Pure liquids P P The improvement proposed by both Scatchard and Hildebrand was the introduction of a parameter c defined as:

c vap u / vL
vap u is the energy of complete vaporization (liquid to ideal gas) vL is the molar volume of the liquid c is the cohesive energy density

The Scatchard-Hildebrand Theory

Following the same process as described in the case of van Laars equations, Scatchard and Hildebrand obtained: Defining the volume fractions (vL is replaced by v) 1 = x1 v1 / [ x1 v1 + x2 v2 ] 2 = x2 v2 / [ x1 v1 + x2 v2 ] Using the fact that uE ideal gases = 0 uE for the mixture is given by

uE = ( c11 + c22 - 2 c12 ) 1 2 ( x1v1 + x2v2 )

The Scatchard-Hildebrand Theory

uE = ( c11 + c22 - 2 c12 ) 1 2 ( 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 ) 1 2 ( 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 ) 1 2 [ c11 + c22 - 2 sqrt (c11 c22 )]

The Scatchard-Hildebrand Theory

uE = ( x1v1 + x2v2 ) 1 2 [ c11 + c22 - 2 sqrt (c11 c22 ) ] uE = ( x1v1 + x2v2 ) 1 2 [ sqrt(c11) - sqrt(c22) ]2
The usefulness of this expression is related to the definition of the solubility parameters: 1 sqrt [ c11 ] = sqrt [ vap u / v ]1 2 sqrt [ c22 ] = sqrt [ vap u / v ]2

The Scatchard-Hildebrand Theory

uE = ( x1v1 + x2v2 ) 1 2 [ c11 + c22 - 2 sqrt (c11 c22 ) ] uE = ( x1v1 + x2v2 ) 1 2 [ sqrt(c11) - sqrt(c22) ]2
The usefulness of this expression is related to the definition of the solubility parameters: 1 sqrt [ c11 ] = sqrt [ vap u / v ]1 2 sqrt [ c22 ] = sqrt [ vap u / v ]2 Which allows us to write uE as:

uE = ( x1v1 + x2v2 ) 1 2 ( 1 - 2 )2

The Scatchard-Hildebrand Theory

uE = ( x1v1 + x2v2 ) 1 2 ( 1 - 2 )2

The Scatchard-Hildebrand Theory

uE = ( x1v1 + x2v2 ) 1 2 ( 1 - 2 )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 ) 1 2 ( 1 - 2 )2

The Scatchard-Hildebrand Theory

From

gE = ( x1v1 + x2v2 ) 1 2 ( 1 - 2 )2
Remembering that

giE = RT ln [ i ] GE = RT i ni ln i
We can calculate the fugacity coefficients of the two components

The Scatchard-Hildebrand Theory

From

gE = ( x1v1 + x2v2 ) 1 2 ( 1 - 2 )2
We obtain the regular-solution equations:

RT ln 1 = v1 22 [ 1 - 2 ]2 RT ln 2 = v2 12 [ 1 - 2 ]2
Which relate the activity coefficients to the solubility parameters and the molar liquid volumes of the compounds

Comparison: Van Laars Equations

gE = x1x2b1b2 / [x1b1 + x2b2] { sqrt(a1)/b1 - sqrt(a2)/b2) }2

ln 1 = A / [ 1 + A/B x1/x2 ]2 ln 2 = B / [ 1 + B/A x2/x1 ]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

From

gE = ( x1v1 + x2v2 ) 1 2 ( 1 - 2 )2
We obtain the regular-solution equations:

RT ln 1 = v1 22 [ 1 - 2 ]2 RT ln 2 = v2 12 [ 1 - 2 ]2
Which relate the activity coefficients to the solubility parameters and the molar liquid volumes of the compounds These expressions are similar to van Laars However, we accept that they are MUCH IMPROVED How can we say this?

Comments
The regular solution equations always predict positive deviations from ideality, as van Laars equations do This is a consequence of the assumption c12 = sqrt [ c11 c22 ]

Comments
The regular solution equations always predict positive deviations from ideality, as van Laars equations do This is a consequence of the assumption c12 = sqrt [ c11 c22 ] The solubility parameters 1 and 2 are in general a function of T However, their difference 1 - 2 is almost independent of T

Comments
The regular solution equations always predict positive deviations from ideality, as van Laars equations do This is a consequence of the assumption c12 = sqrt [ c11 c22 ] The solubility parameters 1 and 2 are in general a function of T However, their difference 1 - 2 is 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

Table 7.1
Compound Isopentane n-pentane n-octane Toluene Benzene vL @ 298K (cm3/mol) 117 116 164 107 89 (J/cm3)1/2 13.9 14.5 15.3 18.2 18.8

Table 7.1
Compound Isopentane n-pentane n-octane Toluene Benzene vL @ 298K (cm3/mol) 117 116 164 107 89 (J/cm3)1/2 13.9 14.5 15.3 18.2 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 - CO 2 - CH4

T = 90.7 K

VLE

Example: Fig. 7.3

1 - C6H6 2 - n-C7H16

T = 70 C

VLE

Example: Fig. 7.4

1 - neo-C5H12 2 - CCl4

T=0C

VLE

Comments
RT ln 1 = v1 22 [ 1 - 2 ]2 RT ln 2 = v2 12 [ 1 - 2 ]2
Because of the mathematical formalism of the regular-solution equations, they can behave poorly when they are applied on systems of compounds very similar The 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

Comments
RT ln 1 = v1 22 [ 1 - 2 ]2 RT ln 2 = v2 12 [ 1 - 2 ]2
Because of the mathematical formalism of the regular-solution equations, they can behave poorly when they are applied on systems of compounds very similar The 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 As a consequence, they are most useful for non-polar mixtures having appreciable non ideality Even better, when the compounds have different solubility parameter

Multi-Component Mixtures
Another advantage for the Scatchard-Hildebran equations is their simplicity In fact, they can be easily extended to multi-component mixtures It can be demonstrated that for a component j in the mixture

RT ln j = vj [ j - ]2
Where

= i i
i=1

And

j = xj vj / [ xi vi ]
i=1

The sums are extended to all m compounds in the mixture