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gE = uE
gE = uE
This is the basic assumption behind van Laars theory
II
T = const
III
Pure liquids P
Liquid Mixture P
(u/v)T = T (P/T)v - P
II
T = const
III
Pure liquids P
Liquid Mixture P
(u/v)T = a/v2
II
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
II
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
II
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
II
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
II
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
II
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
II
T = const
III
Pure liquids P
Liquid Mixture P
II
T = const
III
Pure liquids P
Liquid Mixture P
bmix = x1 b1 + x2 b2
II
T = const
III
Pure liquids P
Liquid Mixture P
II
T = const
III
Pure liquids P
Liquid Mixture P
II
T = const
III
Liquid Mixture P
uE = uI + uII + uIII
Substituting:
uE = a1x1/b1 + a2x2/b2 + 0 - [x12a1 + x22a2 + 2x1x2 sqrt(a1a2) ] / [(x1b1 + x2b2) b1b2 ]
gE = uE
Thus, we obtain
giE = RT ln [ i ] GE = RT i ni ln i
We can calculate the fugacity coefficients of the two components
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
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
T = const
III
Pure liquids P
Liquid Mixture P
T = const
III
Pure liquids P
Liquid Mixture P
The main problem for van Laar was the assumption he used in I
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
uE = ( x1v1 + x2v2 ) 1 2 ( 1 - 2 )2
gE = ( x1v1 + x2v2 ) 1 2 ( 1 - 2 )2
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
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
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
1 - CO 2 - CH4
T = 90.7 K
VLE
1 - C6H6 2 - n-C7H16
T = 70 C
VLE
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