Class 25 Group Contribution Methods Chapters 6-7 and Appendix F, Prausnitz

GE and Activity Coefficients
• We demonstrated that

giE = RT ln [ γi ]
• Now we need to remember that
GE = ∑i ni giE

• Thus

GE = RT ∑i ni ln γi

• These are the most important relations for the chapter

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 γ1 = A/RT x22 ln γ2 = A/RT x12 The activity coefficients at infinite dilution are: ln γ1∞ = A/RT ln γ2∞ = A/RT .

Wohl’s 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’ .

at infinite dilution. we obtain A’ = 2 q1 a12 B’ = 2 q2 a12 ln γ1∞ = A’ ln γ2∞ = B’ .Van Laar Equation gE / RT = 2 a12 x1 x2 q1 q2 / [ x1 q1 + x2 q2 ] We can calculate the fugacity coefficients of the two components ln γ1 = A’ / [ 1 + A’/B’ x1/x2 ]2 ln γ2 = B’ / [ 1 + B’/A’ x2/x1 ]2 And.

B’ x13 At infinite dilution ln γ1∞ = A’ + B’ ln γ2∞ = A’ + 1/2 B’ .Three-Suffix Margules Equations gE / [RT (x1q1 + x2q2)] = 2 a12 z1z2 + 3 a112 z12z2 + 3 a122 z1z22 + 4 a1112 z12z2 + 4 a1222 z1z23 z1 = x1 q1 / [ x1 q1 + x2 q2 ] z2 = x2 q2 / [ x1 q1 + x2 q2 ] ln γ1 = A’ x22 + B’ x23 ln γ2 = (A’ + 3/2 B’) x12 .

x1 q1’ ln [ θ1’ + θ2’ τ21 ] .x2 q2’ ln [ θ2’ + θ1’ τ12 ] φ* is the segment fraction θ.UNIQUAC gE / RT = [ gE / RT ]combinatorial + [ gE / RT ]residual For a binary mixture UNIQUAC states that: [gE/RT]combinatorial = x1 ln [φ1*/x1] + x2 ln [φ2*/x2] + z/2 { x1q1 ln [θ1/φ1*] + x2q2 ln [θ2/φ2*]} [gE/RT]residual = . and θ’ are area fractions z is the coordination number In UNIQUAC z=10 .

UNIQUAC Segment fractions φ1* = x1 r1 / [ x1 r1 + x2 r2 ] φ2* = x2 r2 / [ x1 r1 + x2 r2 ] The parameters ‘r’ are pure-component molecular structure constants Area fractions θ1 = x1 q1 / [ x1 q1 + x2 q2 ] θ1’ = x1 q1’ / [ x1 q1’ + x2 q2’ ] θ2 = x2 q2 / [ x1 q1 + x2 q2 ] θ2’ = x2 q2’ / [ x1 q1’ + x2 q2’ ] For fluids other than water and lower alcohols q = q’ Energy parameters τ12 = exp ( -Δu12 / RT ) ≡ exp ( -a12 / RT ) τ21 = exp ( -Δu21 / RT ) ≡ exp ( -a21 / RT ) These parameters are given in terms of characteristic energies .

from Table 6.33 1.97 3.92 3.82 1.96 0.43 1.Parameters.82 0.92 1.11 0.97 1.00 2.50 q 2.86 q’ 2.43 2.86 * * * .9 Compound CCl4 CH3OH C2H5OH H2O Toluene N-Hexane r 3.92 4.97 3.40 2.

93 -100.31 -123.Binary Parameters.99 379.71 -108. from Table 6.30 242.20 -525.01 230.42 1354.53 947.64 a21/K 93.23 -75.90 924.13 -138.10 System Acetone/Chloroform Acetone/Water Acetone/Methanol Ethanol/n-octane Ethanol/n-heptane Ethanol/Benzene Ethanol/CCl4 Formic acid/Water N-Hexane/Nitromethane T/K 323 331-368 323 348 323 350-369 340-351 374-380 318 a12/K -171.86 .71 530.85 -5.92 1380.57 -105.

1) .1) l2 = z/2 (r2 .l1 r2/r1 ) .UNQUAC Activity Coefficients gE / RT = [ gE / RT ]combinatorial + [ gE / RT ]residual ln γ1 = ln (φ1*/x1) + z/2 q1 ln (θ1/φ1*) + φ2* (l1 .q2) .τ12 / (θ2’+θ1’τ12)] ln γ2 = ln (φ2*/x2) + z/2 q2 ln (θ2/φ2*) + φ1* (l2 .q2’ ln ( θ2’ + θ1’ τ12 ) + θ1’q2’ [ τ12 / (θ2’ + θ1’ τ12) .q1) .(r2 .l2 r1/r2 ) .q1’ ln ( θ1’ + θ2’ τ21 ) + θ2’q1’ [ τ21 / (θ1’ + θ2’ τ21) .τ21 / (θ1’+θ2’τ12)] l1 = z/2 (r1 .(r1 .

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 .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.

Example Let’s suppose we have one mixture of acetone and toluene .

Example Let’s 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 .

that we think are responsible for molecule-molecule interactions: Acetone CH3 C=O CH3 CH CH CH Toluene CH CH C CH3 .Example Let’s 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 Let’s 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 . within these molecules.Example Let’s suppose we have one mixture of acetone and toluene Then we identify a number of groups.

that we think are responsible for molecule-molecule interactions: Acetone CH3 C=O CH3 CH CH CH Toluene CH CH C CH3 .Example Let’s 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 Let’s suppose we have one mixture of acetone and toluene Then we identify a number of groups. within these molecules.

Example Let’s 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 .

and we ‘predict’ the behavior of untested mixtures .Example Let’s 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.

but is often poor in LLE predictions . Jones. at best. that when no experimental data are used to ‘improve’ the estimation of the interaction parameters. however.UNIFAC The Universal Functional Activity Coefficient theory is the best known theory that uses this approach First introduced by Fredenslund. UNIFAC works. as a good first approximation in VLE. 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.

UNIFAC: The Method ln γi = ln γiC + ln γiR .

calculated as in the case of UNIQUAC This is the ‘residual’ contribution.UNIFAC: The Method ln γi = ln γiC + ln γiR This is the ‘combinatorial’ part. which depends on group-group interactions .

calculated as in the case of UNIQUAC ln γiC = FC (x. θ) ln γiR = FR (X. φ.UNIFAC: The Method ln γi = ln γiC + ln γiR This is the ‘combinatorial’ part. T. 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 . Q. amn) This is the ‘residual’ contribution.

Example: Fig. F4 methanol + water @ 50C Such good theory-experiment agreement is not common .

Example: Fig. F5 n-hexane + methyl ethyl ketone @ 65 C This is more typical .

are in general not very accurate n-hexane + methyl ethyl ketone P/bar UNIFAC Experiments Fig. many other systems have not been reported UNIFAC. F-5 L V x/n-hexane .Appendix F Many binary systems have been studied and the corresponding data have been published DIPPR-AIChE provides a continuously-improving compilation Unfortunately. or other group-contribution methods.

Appendix F Let’s suppose we can obtain only 2 experimental data point Which ones shall we get? P/bar L V x/n-hexane .

binary parameters can be calculated from activity coefficients at infinite dilution These often provide the most valuable experimental information . regardless of whether or not they form an azeotrope.Appendix F Let’s 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.

Appendix F: Example Let’s suppose we decide to use any functional form for gE of the mixture of interest we like: gE = F (x. A.B the two parameters that depend on the specific F we like . B) x = composition A.

A. B) RT ln γ2 = F2 (x.Appendix F: Example Let’s suppose we decide to use any functional form for gE of the mixture of interest we like: gE = F (x. A. depending on F. A. B) x = composition A. B) The specific F1 and F2 will depend on our choice for F .B the two parameters that depend on the specific F we like We saw that. we can express the activity coefficient for both compounds as RT ln γ1 = F1 (x.

A. B) A. A. A. we can express the activity coefficient for both compounds as RT ln γ1 = F1 (x. A. B) RT ln γ2 = F2 (x. depending on F.B are the two parameters we need to implement F If we measure γ1∞ and γ2∞. B) / RT] = ln γ2∞ Which is a system of 2 equations in 2 unknowns x2→0 .Appendix F: Example We saw that. then x1→0 lim [F1 (x. B) / RT] = ln γ1∞ lim [F2 (x.

Appendix F: Example Van Laar’s equations ln γ1∞ = A’ ln γ2∞ = B’ .

Appendix F: Example Van Laar’s equations ln γ1∞ = A’ ln γ2∞ = B’ And we can predict the activity coefficients of both components at any composition: ln γ1 = A’ / [ 1 + A’/B’ x1/x2 ]2 ln γ2 = B’ / [ 1 + B’/A’ x2/x1 ]2 .

Appendix F: Example Three-SuffixMargules equations ln γ1∞ = A’ + B’ ln γ2∞ = A’ + 1/2 B’ .

B’ x13 .Appendix F: Example Three-SuffixMargules equations ln γ1∞ = A’ + B’ ln γ2∞ = A’ + 1/2 B’ And we can predict the activity coefficients of both components at any composition: ln γ1 = A’ x22 + B’ x23 ln γ2 = (A’ + 3/2 B’) x12 .