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giE = RT ln [ i ]
Now we need to remember that
GE = i ni giE
Thus
GE = RT i ni ln i
Expressions for GE
gE = 0 gE = 0 when when x1 = 0 x2 = 0
The two-suffix Margules equations were derived from: gE = A x1 x2 A more complex form for gE as a function of composition can be: gE = x1 x2 [ A + B (x1 - x2) + C (x1 - x2)2 + D (x1 - x2)3 + ] This is the Redlich-Kister expansion
Two-Suffix Margules
The two-suffix Margules equations were derived from: gE = A x1 x2
ln 1 = A/RT ln 2 = A/RT
Wohls Expansion
gE / [RT (x1q1 + x2q2)] = 2 a12 z1z2 + 3 a112 z12z2 + 3 a122 z1z22 + 4 a1112 z12z2 + 4 a1222 z1z23 + 6 a1122 z12z22 + z1 = x1 q1 / [ x1 q1 + x2 q2 ] z2 = x2 q2 / [ x1 q1 + x2 q2 ]
The parameters q are effective volumes or cross sections of the molecules The parameters a are interaction parameters The contribution to gE of the interaction parameters a is weighted by the products that contain the factors z
A = 2 q1 a12 B = 2 q2 a12
ln 1 = A ln 2 = B
UNIQUAC
gE / RT = [ gE / RT ]combinatorial + [ gE / RT ]residual For a binary mixture UNIQUAC states that: [gE/RT]combinatorial = x1 ln [1*/x1] + x2 ln [2*/x2] + z/2 { x1q1 ln [1/1*] + x2q2 ln [2/2*]} [gE/RT]residual = - x1 q1 ln [ 1 + 2 21 ] - x2 q2 ln [ 2 + 1 12 ] * is the segment fraction , and are area fractions
UNIQUAC
Segment fractions 1* = x1 r1 / [ x1 r1 + x2 r2 ] 2* = x2 r2 / [ x1 r1 + x2 r2 ]
Area fractions 1 = x1 q1 / [ x1 q1 + x2 q2 ] 1 = x1 q1 / [ x1 q1 + x2 q2 ] 2 = x2 q2 / [ x1 q1 + x2 q2 ] 2 = x2 q2 / [ x1 q1 + x2 q2 ]
Energy parameters 12 = exp ( -u12 / RT ) exp ( -a12 / RT ) 21 = exp ( -u21 / RT ) exp ( -a21 / RT )
These parameters are given in terms of characteristic energies
Comments
In all the methods we discussed, it is necessary to have some experimental data to obtain the fitting parameters for any binary mixture of interest
When experimental data are not available, an alternative approach is to look at the molecular structure of the compounds and to try obtaining the fitting parameters from the molecular structure of the interacting molecules
Example
Lets suppose we have one mixture of acetone and toluene
Example
Lets suppose we have one mixture of acetone and toluene To obtain the interaction parameters, we first look at the chemical structure of both compounds: Acetone CH3 C=O CH3 CH CH CH Toluene CH CH C CH3
Example
Lets suppose we have one mixture of acetone and toluene Then we identify a number of groups, within these molecules, that we think are responsible for molecule-molecule interactions: Acetone CH3 C=O CH3 CH CH CH Toluene CH CH C CH3
Example
Lets suppose we have one mixture of acetone and toluene Then we identify a number of groups, within these molecules, that we think are responsible for molecule-molecule interactions: Acetone CH3 C=O CH3 CH CH CH Toluene CH CH C CH3
Example
Lets suppose we have one mixture of acetone and toluene Then we identify a number of groups, within these molecules, that we think are responsible for molecule-molecule interactions: Acetone CH3 C=O CH3 CH CH CH Toluene CH CH C CH3
Example
Lets suppose we have one mixture of acetone and toluene Then we identify a number of groups, within these molecules, that we think are responsible for molecule-molecule interactions: Acetone CH3 C=O CH3 CH CH CH Toluene CH CH C CH3
Example
Lets suppose we have one mixture of acetone and toluene Then we identify a number of groups, within these molecules, that we think are responsible for molecule-molecule interactions: Acetone CH3 C=O CH3 CH CH CH Toluene CH CH C CH3
Example
Lets suppose we have one mixture of acetone and toluene Acetone CH3 C=O CH3 CH CH CH Toluene CH CH C CH3
The basic assumption is that each group will behave in any mixture independently on the molecule it is part of
Example
Lets suppose we have one mixture of acetone and toluene Acetone CH3 C=O CH3 CH CH CH Toluene CH CH C CH3
The basic assumption is that each group will behave in any mixture independently on the molecule it is part of We obtain this contribution from available experimental data, and we predict the behavior of untested mixtures
UNIFAC
The Universal Functional Activity Coefficient theory is the best known theory that uses this approach First introduced by Fredenslund, Jones, and Prausnitz in 1975 The main advantage of the procedure is that in typical mixtures of non electrolytes the number of group-group interactions is much less than the possible number of molecule-molecule pairs Another advantage is that correlations are always easier than the experiments they try to substitute Remember, however, that when no experimental data are used to improve the estimation of the interaction parameters, UNIFAC works, at best, as a good first approximation in VLE, but is often poor in LLE predictions
This is the combinatorial part, calculated as in the case of UNIQUAC ln iC = FC (x, , ) ln iR = FR (X, Q, T, amn)
This is the residual contribution, which depends on group-group interactions As defined for UNIQUAC
X = group mole fraction Q = group external surface area amn = interaction energy between groups n and m
Example: Fig. F4
Example: Fig. F5
Appendix F
Many binary systems have been studied and the corresponding data have been published DIPPR-AIChE provides a continuously-improving compilation Unfortunately, many other systems have not been reported UNIFAC, or other group-contribution methods, are in general not very accurate n-hexane + methyl ethyl ketone P/bar UNIFAC Experiments Fig. F-5 L
V x/n-hexane
Appendix F
Lets suppose we can obtain only 2 experimental data point Which ones shall we get? P/bar L
V x/n-hexane
Appendix F
Lets suppose we can obtain only 2 experimental data point Which ones shall we get? P/bar L
V x/n-hexane For all binary mixtures, regardless of whether or not they form an azeotrope, binary parameters can be calculated from activity coefficients at infinite dilution These often provide the most valuable experimental information
Appendix F: Example
Lets suppose we decide to use any functional form for gE of the mixture of interest we like: gE = F (x, A, B) x = composition A,B the two parameters that depend on the specific F we like
Appendix F: Example
Lets suppose we decide to use any functional form for gE of the mixture of interest we like: gE = F (x, A, B) x = composition A,B the two parameters that depend on the specific F we like We saw that, depending on F, we can express the activity coefficient for both compounds as RT ln 1 = F1 (x, A, B) RT ln 2 = F2 (x, A, B) The specific F1 and F2 will depend on our choice for F
Appendix F: Example
We saw that, depending on F, we can express the activity coefficient for both compounds as RT ln 1 = F1 (x, A, B) RT ln 2 = F2 (x, A, B) A,B are the two parameters we need to implement F If we measure 1 and 2, then
x10
lim [F1 (x, A, B) / RT] = ln 1 lim [F2 (x, A, B) / RT] = ln 2 Which is a system of 2 equations in 2 unknowns
x20
Appendix F: Example
Van Laars equations
ln 1 = A ln 2 = B
Appendix F: Example
Van Laars equations
ln 1 = A ln 2 = B
And we can predict the activity coefficients of both components at any composition:
Appendix F: Example
Three-SuffixMargules equations ln 1 = A + B ln 2 = A + 1/2 B
Appendix F: Example
Three-SuffixMargules equations ln 1 = A + B ln 2 = A + 1/2 B And we can predict the activity coefficients of both components at any composition: ln 1 = A x22 + B x23 ln 2 = (A + 3/2 B) x12 - B x13