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2002, 41, 899-913

899

**A Priori Phase Equilibrium Prediction from a Segment Contribution Solvation Model
**

Shiang-Tai Lin and Stanley I. Sandler*

Center for Molecular and Engineering Thermodynamics, Department of Chemical Engineering, University of Delaware, Newark, Delaware 19716

An activity coefficient model using molecular solvation based on the COSMO-RS method is proposed. In this model, quantum mechanical COSMO calculations are performed to obtain the screening charges for molecules in a perfect conductor. A statistical mechanical model that considers molecules to be a collection of surface segments is developed for the calculation of segment activity coefficients using these screening charges. Activity coefficients for molecules are then obtained by summing the contributions of the segments. This model requires only a single radius for each atom in the COSMO solvation calculations, one universal parameter to discern hydrogen-bond acceptors and donors, and two universal parameters to determine segment interactions. This is a significantly fewer number of parameters for phase equilibrium calculations than group contribution methods such as the UNIFAC (168 parameters) and modified UNIFAC (612 parameters) models. The resulting completely a priori prediction method results in absolute average deviations of 0.03 in vapor-phase mole fractions and 9% in total pressure for vaporliquid equilibrium predictions of 243 binary mixtures and root-mean-square deviations of the octanol/water partition coefficient log KOW, infinite dilution activity coefficients ln γ∞ in water, and in hexane for 64 compounds of 0.48, 1.65, and 0.50, respectively. This model is general and applicable for the a priori prediction of the phase behavior of most compounds, though admittedly it is less accurate than group contribution and other methods with many more parameters whose values have been obtained by regressing large amounts of data.

Introduction In classical thermodynamics, the Lewis-Randall activity coefficient is frequently used to describe liquidphase mixture nonidealities using activity coefficients. A variety of models have been proposed to describe the dependence of the activity coefficient on mixture composition, molecular structure, and intermolecular interactions. All of these models focus on the excess Gibbs free energy (Gex), from which the activity coefficient is derived. At low and moderate pressures, the vapor phase can usually be assumed to be ideal so that only the Gex model and pure component properties are needed to describe vapor-liquid-phase behavior, including the formation of azeotropes. In addition, Gex models can be used to correlate or predict the mutual solubility of partially miscible binary mixtures, as well as the partitioning of a solute between two partially miscible solvents. The most successful predictive Gex models are UNIFAC1 and modified UNIFAC2 in which a molecule is described as a collection of independent functional groups and a mixture is formed from these functional groups. The activity coefficient of a molecule in a mixture is obtained from the sum of the activity coefficients of the constituent groups in the mixture. Such group contribution methods greatly reduce the number of parameters needed for predicting the phase behavior for a large variety of mixtures. However, as is true for all group contribution methods, UNIFAC and modified

* To whom correspondence should be addressed. E-mail: sandler@udel.edu. Phone: 302-831-2945. Fax: 302-831-4466.

UNIFAC suffer from the inability to distinguish between isomers and inaccuracies when compounds with several strong nonalkyl functional groups are considered.3 The functional group activity coefficients, which are dependent on the interactions between functional groups, cannot be measured; only the activity coefficient for the whole molecule can be obtained by fitting experimental phase equilibrium data. As a consequence, the quality of UNIFAC predictions depends on the similarity of the new system to the database used in its parametrization. There is no obvious way to improve these models other than empirical approaches, such as adding additional functional groups, introducing secondand higher-order functional groups (to account for the intramolecular interactions between functional groups), and increasing the database used to fit parameters. Recently Klamt4 proposed a completely new perspective in liquid-phase thermodynamics. In contrast to the Gex models, Klamt started from the solvation of molecules in a conductor and developed a “conductor-like screening model for real solvent” (COSMO-RS) that, in principle, can be used to determine the chemical potential of any species in any mixture from quantum mechanical calculations. An interesting and unique feature of the COSMO-RS method is that it does not presuppose a specific concentration dependence of the Gex function as is the case with UNIFAC, for example, which is based on the UNIQUAC equation. This provides greater flexibility in treating systems of very different chemical functionality but also suggests that care must be taking in formulating the model to ensure that all thermodynamic boundary conditions are met.

10.1021/ie001047w CCC: $22.00 © 2002 American Chemical Society Published on Web 12/22/2001

∆G*i/S. based on surface segment contributions. the dielectric properties of the solvent are increased to that of a perfect conductor. This new model. and the restoring free energy was. 5. Vol. and the summation is over all of the species in the mixture.6 Schafer et al. Then. li ) (z/2)[(ri qi) . Chem. Restoring Free Energy. the charges on the solute are turned off. the charges are turned on. Eng.(ri . The solvation free energy is usually calculated through a two step process.. Because the ideal solvation free energy is the same for dissolution of the solute in solvent S and in pure liquid i. especially when traditional group contribution methods such as UNIFAC fail because of missing group parameters or the presence of more than one strong nonalkyl functional group on the same molecule.∆G*i/i + ln γi/SSG ln γi/S ) RT (2) where the Staverman-Guggenheim combinatorial term is ln γi/SSG ) ln φi θi φi z + qi ln + li xi 2 φi xi ∑xjlj j (3) with θi ) (xiqi)/(Σjxjqj). molecules are treated as a collection of surface segments. First. Then. ∆G*is. First. The corresponding free-energy change in these two processes are referred to as the cavity formation free energy. and the charging free energy. ∆G*cav. molecules are dissolved in a perfect conductor in which they are completely screened.5 The chemical potential of each molecule is then obtained by summing the contributions of the segments.10. Ideal solvation in the conductor is obtained from an ab initio COSMO calculation.1)]. a new expression is derived for this quantity in order to remove the inconsistencies in the original model.7 and Klamt and Eckert8 showed that COSMO-RS can also be used to make phase equilibrium predictions. only one atomic radius is needed for each atom in the ideal solvation calculation. Furthermore. z is the coordination number. during which each molecule gains an electrostatic energy of EiCOSMO . Here. An exact expression for the segment chemical potential that satisfies all boundary conditions is derived. Res. Recently.900 Ind. is useful for making completely a priori phase equilibrium predictions. In the next section. where xi is the mole fraction of component i. and only two universal parameters are used for calculating segment interactions. is defined as the free energy change when a solute molecule i is transferred from a fixed position in an ideal gas to a fixed position in a solution S at constant temperature and pressure. and the free energy required to remove the screening charges on the solute in the restoring process. ∆G*chg. and the resulting equation for the activity coefficient is thermodynamically consistent. On the basis of this view. This process is equivalent to further decomposing the charging process used by Lin and Sandler into two steps: first. An expression for the chemical potential of segments in the condensed phase was derived in which needed interaction energies between segments were determined from COSMO calculations. we present a derivation leading to an activity coefficient model in the COSMO-RS framework that resolves the difficulties that appear in the COSMO-RS model. Although the COSMO-RS method has provided promising results.. Theory Activity Coefficient from Solvation Free Energy. with an average accuracy of within a factor of 2. which are required in traditional continuum solvation models and generally not available especially for mixed solvents. The molecules are first dissolved in a perfect conductor (and consequently are perfectly screened). the screening charges are removed to restore the real fluid state. determined from consideration of segment interactions.15 improved the calculation of cavity formation free energy from that used previously. the charging free energy is the sum of the ideal solvation free energy. and the remaining hard particle is inserted into the solvent. the dissolution of the solute into a perfect conductor and second. An advantage of using ideal solvation from the COSMO model is that the dielectric properties of solvent.∆G*i/i + ln γi/SSG RT (4) ln γi/S ) sol sol ∆G*i/S . 41. and then the solvent properties are restored to their normal values (removal of the screening charges). sol The solvation free energy. ri and qi are the normalized volume and surface area parameters for i.13 have shown that using the Staverman-Guggenheim combinatorial term14. usually taken to be 10. respectively. The starting point is our previously developed group contribution solvation (GCS) model. No. this free energy is calculated in a two-step process: first. the GCS model reduces to ln γi/S ) res res ∆G*i/S . the equation for the segment chemical potential used in COSMO-RS does not correctly converge to certain boundary conditions. Originally the solvation free energy was obtained from ab initio solvation calculations. with this new description. the restoration of the conductor to the actual solvent. Lin and Sandler9. the need of scientists and engineers for predictive methods is so great that this model is being incorporated into process simulators. are no longer necessary.9 in which the activity coefficient is calculated from the solvation free energy of molecules in a solution.11 In this work.. and the charges on the solute are turned on (ideal solvation). and the final expression for the activity coefficient fails to satisfy thermodynamic consistency relations. similar to COSMO-RS. 2002 In COSMO-RS. Recently Klamt4 proposed a new path for computing solvation energies. and the electronic configuration of the solute is restored. The activity coefficient γi/S for the solute is then determined from12 where cj is the molar concentration of fluid j (which can be pure fluid i or solution S) and the superscript * is used to emphasize that the solute is at a fixed position. Tanpipat et ¨ al. φi ) (xiri)/(Σjxjrj). Regardless of these problems. ∆G*res. and they proposed the following GCS model9 for the activity coefficient chg chg ∆G*i/S .∆G*i/i cS + ln RT ci (1) The restoring free energy ∆G*res can be obtained from the so-called “chemical potential of segment” in the COSMO-RS model. Consider the formation of a liquid mixture from molecules in an ideal gas to occur using the thermodynamic cycle shown in Figure 1.EiIG . This model was originally applied to the prediction of vapor pressures and partition coefficients.

The probability of finding a segment with charge density σ in a mixture is the weighted sum of the σ profiles of all of the components pS(σ) ) ∑xinipi(σ) ∑xiAipi(σ) i i ) Φtot ) Φi + Φ(q) ) 0 (5) ∑xini i ∑ xi A i i (7) where Φi and Φ(q) are the electrostatic potentials resulting from molecule i and the ideal screening charge q. No. The induced screening charges appearing on the cavity surface of the conductor are determined from the requirement of zero total potential Φtot at the cavity boundary. Chem. molecules are allowed to polarize to lower the total free energy of the system (R′ ) 0. 2002 901 Figure 1. quantifies the electronic properties of a fluid and is the most important characteristic of each species in the COSMORS model. which is the same for all molecules and is one adjustable parameter in this method. each segment is assumed to pair with another segment. the average screening charge qavg characterizes the segment identity. 5. In a condensed phase. By defining a standard segment surface area aeff. The probability of finding a segment with a surface charge density σ ) qavg/aeff in pure liquid i is pi(σ) ) ni(σ)/ni ) Ai(σ)/Ai (6) The σ profile. Molecules in this ideally screened state are described by the Poisson equation. Schematic representation of condensation of dipolar molecules through an ideal solvation process. This quantity is obtained from quantumchemical COSMO calculations. where ni(σ) is the number of segments with charge density σ in a single molecule i and Ai(σ) ) aeffni(σ) is the total surface area from all of these segments. N/2 pairs will form. Because ideal screening charges do not exist in real solvents.Ind. Res. Therefore. For a system containing a total of N segments. molecules are in close contact with each other.. Because the molecules are ideally screened in the conductor. That is. In the final step. that is pi(σ) as a function of σ. Vol. and the activity coefficient is determined solely on the basis of this information. and a dispersion energy of ζAi. where Ai is the surface area of molecule i and ζ is the dispersion constant. Eng. these hypothetical charges must be removed . each molecule contributes ni ) Ai/aeff surface segments to the mixture. 41.64R). they can move freely without changing the total energy of the system.

1. the ideal screening charges on the molecular surface are determined from a solvation calculation for each molecule in the conductor (the COSMO calculation) at the same VWN-BP/DNP level with default atomic radii (Å) (H.nEpair(σm. and 16 is followed. 2002 to return to the real fluid. The former contribution is obtained from on the results from a quantum mechanical COSMO calculation. σn) kT (10) ]} where ∆W(σm. the exchange energy becomes µS(σm) ) -kT ln { [ ∑ exp σ n -Epair(σm. The screening charge densities σ* from the COSMO output are averaged to give the “apparent” charge density σ on a ln ΓS(σm) ) -ln {∑ σn pS(σn) ΓS(σn) exp [ -∆W(σm. Therefore. max and min indicate that the larger and smaller values of their arguments are used. σdon + σhb] + cne (13) where R′ is a constant for the misfit energy that is calculated from the surface area of a standard segment as (0. The procedure for the calculations is outlined as follows.ln Γi(σm)] + ln γi/SSG σ m (12) . 0) being the chemical potential of a segment in a fluid consisting of neutral segments. chb is a constant for the hydrogen-bonding interaction. and these paired segments are assumed to have no interaction with each other. RT ln Γ(σm) ) res res res ∆G*σm/S . 1. each independent of the other.0. mostly dispersion.4. 2. σacc σhb] min[0. C. and nonelectrostatic. respectively. called the exchange energy. N. is the energy required to obtain one (σm.e. σn) + Ene(σm.83. and the nonelectrostatic contribution Ene is assumed to be a constant cne. σn) ) (R′/2)(σm + σn)2 + chb max[0. each of opposite charge to that in the ideally screened state. The total energy of the system is increased by the self-energies.00. σacc and σdon are the larger and smaller values of σm and σn.. Cl. σn) + Ehb(σm. σdon + σhb] (14) It should be noted that nonelectrostatic interactions cancel out in ∆W(σm. 8. (1) When the procedure established for COSMO-RS as used in refs 4.0. the segments of the molecules are decoupled. σn) ) (R′/2)(σm + σn)2 + chb max[0. σacc . σn) + µS(σn) + kT kT ln pS(σm) (9) ]} where µS(σm) is the chemical potential of a surface segment with charge density σm in a solution S. RT ln ΓS(σm) is the free energy required to add a segment with charge density σm at a fixed position in the solution (i. the physical picture of the liquid becomes that of an ensemble of paired surface segments.8. of the compensating paired surface segments Etot ) ∑(EiCOSMO + ζAi) + m.72.Epair(0.395 × 10-4 (e2 mol)/(kcal Å) being the permittivity of free space. O. which they refer to as the misfit energy Emf. with µ0(0) )1/2Epair(0. Default values are used for all other parameters except that the numerical integration grid is set to fine. we have ∆W(σm.16 This energy contains contributions from the electrostatic interactions. 0). the hydrogen-bonding interactions Ehb. where the Staverman-Guggenheim combinatorial contribution is zero because the segments are equal in size.30 . while the latter is determined from only the size and shape of the molecules. the result is Epair(σm. The self-energy of a segment pair Epair necessary for the calculation of the segment activity coefficient in eq 10 has been extensively discussed by the developers of COSMO-RS in their excellent papers. σn) . 41. To simplify the problem. and the second summation is over all segment pairs. Therefore.µ0(0))/kT.05) used to define the cavity. therefore. ∆G*res. The restoring free energy.. No. Next.17-19 The equilibrium geometry of the molecules in the ideal gas phase is first obtained from molecular energy minimization using the densityfunctional theory with nonlocal VWN-BP functional at the DNP (double numeric with polarization functions. interactions Ene. This is done by adding additional paired segments to all surfaces. the first summation is over all molecules. σn) ) Epair(σm. the first step is to establish the σ profile for each species in a mixture using the quantum chemistry package DMol3 implemented in Cerius2.e. 1.. the restoring free energy of the segment). Res. the activity coefficient of a molecule is determined from two separate contributions: the restoring free energy of the solute from the segment activity coefficient (eq 10) and the cavity formation free energy from the Staverman-Guggenheim model (eq 3). σn) pair from a neutral pair. version 4.∆G*σ)0/σ)0 ) ∆G*σm/S). σn) ) Emf(σm.902 Ind. Vol. An exact expression for the chemical potential of these segments based on a rigorous statistical mechanical argument is presented in Appendix 1. σn) because of the assumption of constant Ene.3 × aeff3/2)/ 0. with 0 ) 2. σn) ∑ i (8) We will refer to this equation as the COSMO segment activity coefficient (COSMO-SAC) model.64 × 0. The restoring free energy of the solute can be obtained by summing the contributions from the segments res ∆G*i/S ) RT ∑ ni(σm) σ m [ res ∆G*σm/S RT ] ) ni ∑pi(σm) ln ΓS(σm) σ m (11) so that the final equation for the activity coefficient is ln γi/S ) ni ∑pi(σm)[ln ΓS(σm) . Eng. The physical meaning of the segment activity coefficient can be understood by relating this quantity to eq 2 (i.50 Å) basis set level. Computational Details. σhb is a cutoff value for hydrogen-bonding interactions. In the COSMO-SAC model (eq 12). so that where σm and σn are charge densities of the paired segments m and n. 5. with a real space cutoff set to 5. Chem. is equivalent to the work required to add the additional segments on the surface of the solute to remove the screening charges. 2.σhb] min[0. Defining the segment activity coefficient Γ(σ) through the expression ln pS(σm) ΓS(σm) ) (µS(σm) . Epair.

jex . The standard segment was found to be 7.) For most compounds. one cutoff surface charge density σhb for distinguishing hydrogen-bond donors and acceptors. Res. and this single-molecule ideal solvation calculation needs to be done only once for each molecule. hexane. methyl tert-butyl ether. The two remaining adjustable parameters were sequentially determined by minimizing the root-mean-square (rms) deviation of the calculated excess Gibbs free energy from that obtained from VLE data rms ) [ ∑( 1 M j Gcalc.025 to 0. The rms deviation in Gex/RT for hydrogen-bonding mixtures was 0. Note that it is only to obtain the σ profiles of the molecules (step 1) that a quantum mechanics calculation must be done. Only aeff and chb are considered as adjustable parameters in this work. 2-methylpentane. acetone. Gex is the molar excess Gibbs free energy.2-dimethylbutane. here. As the use of a different reff for the averaging process appears arbitrary and was not justified.15 K) were used to obtain the hydrogen-bonding coefficient chb ) 85 580 (kcal/mol Å4/e2). only simple algebraic calculations are required for the computation of the activity coefficient as a function of solvent and composition for any mixture. the restoring free energies and the Staverman-Guggenheim contribution from the previous two steps are used in the COSMO-SAC model (eq 12) to obtain the activity coefficient. therefore. and dmn is the distance between segments m and n.15 K. propoinitrile. C.025 e/Å2. the COSMO-SAC model is currently limited to compounds containing atoms H.02 in mole fractions and 5%. this model is.08. These systems (1526 data points from 273. (3) Next. pS(σ)and pi(σ). diethyl ether. and the vapor pressures Pivap of the pure compounds were calculated from the Antoine equation. not the revised model we have developed here and. respectively. Eng.yjcalc|) and absolute average percentage deviation in total pressure (AAD% ) (1/M)ΣjM(|Pjexp Pjcalc|)/Pjexp) for these systems are 0. the surface area of a standard segment aeff ) 7. 1-hexene. Parameter Optimization.0084 e/Å2.. Those parameters were optimized using a large data set with COSMO-RS. the ideal screening charge density falls within the range of -0. The cutoff value σhb for hydrogen-bonding interactions is set to 0. The segment activity coefficient in the mixture and in the neat liquid. may not be optimal for this new model. 5. 1-butene. the activity coefficient of a species in a mixture is obtained as a function of composition without specifying a priori the form of this composition dependence using a model.03 and 9%. as stated earlier.15 to 373. The other parameters are taken from previous work of Klamt. 41. methyl acetate. octane. O. ethyl acetate. propanal.07. However. 2-butanone. Interestingly. Here. The absolute average deviations in the vapor-phase composition (AAD ) (1/ M)ΣjM|yjexp .69 Å3) and surface area (79. 1-hexanol. are then determined from eq 10 by iteration using the σ profiles.jex RT M )] 2 1/2 (16) with Gcalcex/RT ) Σxi ln γi/S and Gexptex/RT ) Σxi ln((yiexptPexpt)/(xiPivap)). which are then substituted into the Staverman-Guggenheim expression in eq 3. the σ profile for a mixture is calculated using eq 7. 1-pentanol. This interval is partitioned to 50 parts. butyronitrile. Chem.Ind. Once the σ profile is obtained for the pure compounds.Gexpt.50 Å2. pentane. 102 associating binary mixtures that consisted of two of the six hydrogen-bonding species (ethanol. nitromethane. and nitroethane). in principle. the same as that in the COSMO-RS model. No. covering a temperature range from 238. we use the natural value of reff based on the standard segment. The AAD in vapor-phase composition and AAD% in total pressures were 0. butyraldehyde. (It should be noted that Klamt used a smaller value of reff to achieve better results. The COSMO-SAC model currently uses a total of eight parameters.50 Å2) is the radius of the standard surface segment. or Cl. respectively. 1-heptene.21 The aeff parameter was first optimized using VLE data for 70 nonassociating binary mixtures (918 data points collected from the Dortmund Data Bank (DDB)21) formed from the 23 simple monofunctional compounds (butane. 2002 903 standard surface segment using the following expression:16 ∑ σ n* n σm ) rn2reff2 rn2 + reff2 exp - ∑ n rn2reff2 rn2 + reff2 exp - ( ( dmn2 rn2 + reff2 dmn2 rn2 + reff2 ) ) (15) where reff ) aeff/π (aeff ) 7.15 to 383. 3-pentanone. Next. These include the radii for the five atoms mentioned earlier for use in the COSMO calculation. with aeff fixed at 7. (4) Finally.8 For the calculation of the exchange energy ∆W. regardless of the mixture in which the molecule appears. Vol. 1-butanol. heptane. The values of these universal parameters were determined from fitting experimental vapor-liquid equilibrium (VLE) data (details are given later). and two segment interaction-related variables (the surface area of a standard segment aeff and the hydrogen-bonding coefficient chb). slightly higher than for the nonassociating systems.53 Å2) of a functional group to yield the r and q parameters. (2) The second step is to determine the restoring free res energy of the solute in the mixture ∆G*i/S and in its res neat liquid phase ∆G*i/i .001 e/Å2 increment.50 Å2 with the rms deviation in Gex/RT being 0. It is worth mentioning that because other atomic radii have not been determined. These normalization constants are different from the values originally used in the UNIQUAC model20 because slightly larger atomic radii had been used to define the molecules in ref 8. Once these are known.50 Å2 and the hydrogenbonding coefficient chb ) 85 580 (kcal/mol Å4/e2) are used. 1-propanol. M is the total number of data points. rn ) an/π is the radius of segment n. the molecular volume and surface area obtained from the COSMO calculation of each compound are normalized to a standard volume (66. and water) or one of the 24 compounds (previous 23 compounds and methylpropionate) and one of the six hydrogen-bonding species were retrieved from DDB. ln ΓS(σ) and ln Γi(σ). N. . respectively. The physical constraint that the segment restoring free energy RT ln Γ(σm) from misfit energy be positive was imposed in the optimization. 2. The restoring free energies can then be obtained from eq 11. and the histogram (weighted by the area of each segment) of the averaged charge density is computed at each 0.

the peak in the σ profile at 0. Chem. and 1-octanol from COSMO calculations. This peak leads to negative values of ln Γ(σ) in Figure 3 for σ < -0.15 K. it is impossible to distinguish between the hydrogen-bond donor from chloroform and from the alcohol molecule in the segment mixture. applicable to all substances once all of the elementspecific radii (F. for example. chb ) 0) for chloroform with other species.03 in the deviation of vapor-phase mole fractions and 9% in total pressure. 5. which means that work is required to remove the screening charges in the restoring process. Figure 2 shows the σ profiles for four common solvents. 0. Because n-methylformamide cannot be defined using current parameter sets in the UNIFAC and modified UNIFAC models. new functionalities (cyclohexane. Another advantage of the COSMOSAC model is its consistent accuracy when extrapolated . hexane. it should be noted that the COSMO-SAC model uses only two adjustable parameters. 1-Octanol has a long alkane chain and a hydroxyl group that can hydrogen bond.2-dichloroethane. If a strong hydrogen bond is formed after the removal of the screening charges. hexane.e..01 e/Å2 because extra free energy is gained from forming hydrogen bonds when adding a hydrogen-bond donor segment to acetone.) are parametrized. The two vertical dashed lines in Figure 2 are the locations of the cutoff values for the hydrogen-bond donor (σ < -0. its σ profile extends outside both H-bond cutoff values. This indicates that the COSMO-SAC model is capable of making a priori predictions for new molecular species without any experimental data.. The three electronegative chlorine atoms produce a significant positive charge on the hydrogen that exceeds the cutoff value for hydrogen-bond donor. The accuracy of the predictions for these new compounds remains at the same level as that for those mixtures used in the parametrization. The Γ(σ) profile of water is negative at large positive and negative σ values because of the stabilizing effect of forming hydrogen bonds.0084 e/Å2) and acceptor (σ > 0. No. benzene. chloroform. it is necessary to refine the COSMO calculation to provide a better σ profile for chloroform. for chloroform/ alcohol mixtures. The compounds chosen here include extensions of homologous series (1-octene and acetonitrile). ketones and alcohols are incorrectly over predicted. and 1-octanol at 298. isomers (2-butanol. 2002 Figure 2. The DDB was used to search for consistent binary mixture data that contain one of the 30 compounds mentioned earlier and one of the new compounds listed in Table 1.904 Ind. the interactions between chloroform and. Si. The resulting Γ(σ) profile in Figure 3 for hexane is parabolic and positive. and tetrachloromethane). tert-butyl alcohol. The σ profile for hexane lies within the hydrogen-bonding cutoff values. and isobutanol). etc. therefore. therefore. Surface area weighted σ profiles for water. which is beyond the scope of our study here. however. VLE Calculations. and one new atom (chlorine in chlorobenzene. It is worth mentioning that there is a competing effect between the free energy of removing the screening charges (positive) and that of forming hydrogen bonds (negative). Although COSMO-SAC predictions are not as accurate as those from group contribution models such as UNIFAC and modified UNIFAC (Table 1). Br. Segment activity coefficient ln Γ(σ) as determined from eq 10 for water. 41. aeff and chb. pyridine. The area under each curve corresponds to the molecular surface area of the compound.4-dioxane. acetone. Figure 3. Eng. Figure 4 shows the VLE prediction of benzene/nmethylformamide binary mixture. the COSMO-SAC model is useful when no interaction parameter information is available for use in these group contribution methods. The utility of the proposed model is demonstrated by considering the VLE predictions for compounds not included in its parametrization. the net restoring free energy would be negative.8 This solution is useful for chloroform/ketone systems. phenol. The poor results for mixtures of chloroform are due to the overpolarization of the hydrogen atom in the COSMO calculation. and the corresponding segment activity coefficients Γ(σ) at 298. 1. This results in a large negative deviation in the calculated activity coefficient.15 K are shown in Figure 3. Results and Discussion σ Profile and Restoring Free Energy.011 e/Å2 is a result of the oxygen atom in the carbonyl group and indicates that acetone is a hydrogen-bond acceptor.0084 e/Å2). tetrahydrofuran. More importantly. acetone. 1. Water is both a hydrogen-bond donor and acceptor. Vol. butylamine. For acetone. the COSMO-SAC model provides a valuable a priori prediction in such a case. Res. indicating its inability to form hydrogen bonds with other species. This is to be compared to the 168 and 612 parameters used in the UNIFAC and modified UNIFAC models for similar calculations. One possible solution suggested in COSMO-RS is to turn off the hydrogenbonding correction interactions (i. its Γ(σ) profile is similar to that of hexane at small σ values and to that of water at large σ values. and trimethylamine). Therefore. Therefore.

15 343.15 313.41 6.43.15 358. 5. to new systems.97 1.26 1.15 343.50 6.27 3.15 max Tf 348.15 368.91 3. Calculated results for octanol/water partition coefficients and infinite dilution activity coefficients in water and hexane for 64 compounds are listed in Table 2 and shown in Figure 6.26 1.47 0.15 358.31 1.02 2.16 The lone pair electrons tend to be hindered in the large cavity defined for the alkyl groups.47 2.52 1.4-dioxane benzene pyridine phenol chlorobenzene 1.23 2. Therefore.76 0. c Average absolute error in vapor-phase composition. corresponding to average errors of 422%.2-dichloroethane chloroform tetrachloromethane butylamine trimethylamine overall no.90 1. as shown in Figure 5. b Total number of data points. 41.70 2. The rms deviations of the natural log of the infinite dilution activity coefficient in water from the three models are 1.15 298.35 343. Amines.93 2.15 383.15 0. Chem.72 0.15 333.93 4.43 5. preliminary results show that COSMO-RS leads to better predictions than COSMO-SAC for some systems and poorer predictions for others. The worst prediction of the COSMOSAC model is for triethylamine.15 373.85 1.15 308.35 1.75 6.13 modified UNIFAC 1.69 3. and modified UNIFAC are 0.24 1.94 1.15 353.69 4.15 313.15 308.64 1.44 2.07 1.20 12.43 modified UNIFAC 1.72 1.15 a Number of binary systems.4-dioxane binary mixtures.35 0.48 1.15 348.15 298.55 1. are known to be difficult to model using UNIFAC with one set of parameters for the ether group because of the strong hydrogen-bonding interactions between the two components22 so that a new cyclic ether group was defined in the modified UNIFAC model.86 9. There is a trend that the quality of the predictions from COSMO-SAC decreases for highly hydrophobic solutes.06 0.54 3.e.15 368.83. respectively.65.67 0.73 0. Predictions of VLE for Compounds Not Included in Parametrization 100 × AAD in yc compound name 1-octene 2-butanol tert-butyl alcohol isobutanol acetonitrile cyclohexane tetrahydrofuran 1.55 0. Vol. No. and 1034% in γ∞.15 and 328.22 0.19 0.13 For hydrophobic compounds.07 1.98 0.31 1. especially trialkylamines.15 298.08 1.22 354.15 7.24 5. and 575% in KOW.36 0. corresponding to an average error of 203%.04 UNIFAC 2.11 7.83 1.76 1. are known to be difficult to model using classical methods.15 283. 2.15 351.65.75 383.84 4.93 2. ptsb 23 129 46 152 171 584 157 126 865 107 12 11 207 557 274 14 52 3487 COSMO-SAC 0.77 0.15 1.01 0.. Eng.15 298.81 1.18 0. and 0. and modified UNIFAC models for water (1)/1. VLE prediction from COSMO-SAC for benzene (1)/nmethylformamide (2) at temperatures of 318. UNIFAC.80 5. Comparison of VLE prediction from COSMO-SAC.17 2.77 0.15 1. e Minimum temperatures in the systems.62 1. f Maximum temperatures in the systems.21 2.11 3.15 K. Water/1. Figure 5.48 UNIFAC 1.56 1. Res.02 6.57 1. d Average absolute percentage error in total pressure. 0. The predictions are satisfactory compared to the results from UNIFAC and modified UNIFAC model.92.15 333.60 0.15 369.15 9.28 6.77 0.78 0.15 and 323. 1.30 2. stma 1 8 2 12 13 38 10 12 62 8 1 1 13 39 17 2 4 243 no. Figure 4. an accurate ln Γ(σ) profile of water at small charge densities (i. This is also reflected in the lower accuracy of KOW predictions for large values of this parameter because the octanol/water partition coefficient is proportional to the infinite dilution activity coefficient in water.15 333.98 1. 348%. Two examples of VLE prediction from the two models are provided in Appendix 2.15 K. 585%.15 353.58 0.75 AAD% in Pd COSMO-SAC 2.20 3.21 1.68 5. A comparison between the COSMO-SAC model proposed here and COSMO-RS cannot be made here because we have not yet found an easy way to control the DMol3 program to calculate the activity coefficient for a specific solution composition for which experimental data are available.94 0.23 1.4-dioxane (2) at temperatures of 308.15 333. Octanol/Water Partition Coefficients and Infinite Dilution Activity Coefficients.17 0. However.62 0.50 5.93 1. 2002 905 Table 1. the screening charges may not be evaluated appropriately. the COSMO-SAC model is capable of describing these systems without introducing additional parameters. In contrast.75 2.54 1. The rms deviation in log KOW from COSMO-SAC.04 6.48 1.05 24.96 1.15 288..15 283.73 0.Ind.15 323.15 293.57 3.15 1.43 2.60 1.15 383. -σhb < σ < σhb) is .89 5.64 min Te 348.81 2. UNIFAC.63 6.48.

31 0.95 4.91 1.36 3.59 3.47 1.72 3.49 4.22 8.i.90 1.10 0.24 3.09 2.04 1.49 0.30 0.42 7.02 0.27 2.10 10.40 3.21 1.92 3.56 2.91 2.38 14.87 1.25 2.67 6.55 0.79 2.14 1.96 2.07 1.08 0.47 0.77 -1.69 5.80 10.39 3.24 2.22 4.22 2.83 7.72 3.70 4.18 -0.03 0.58 3.12 4.81 1.07 1.98 1.53 1.00 1.56 1.09 -1.21 7.46 8.08 -0.48 0.45 -1.32 2.76 1.15 2.90 2.22 0.09 10.48 0.52 3.34 2.38 0.59 0.69 3.47 1.24 2.65 15.63 0.20 3.75 0.80 6.43 7.99 4.69 2.86 1.01 6.40 1.60 0.43 3.88 -0.00 0.44 1.74 0.12 -1.98 4.04 -0.70 0.10 6.47 3.90 0.17 3.85 5.14 3.72 2.73 6.83 1.46 1.00 0.90 0.17 6.51 5.23 0.15 1.88 1.47 3.41 3.86 0.66 2.81 1.49 2.18 0.24 6.67 2.18 -0.17 2.03 3.47 0.30 5.08 9.76 3.04 3.02 0.91 1.72 -1.19 3. Infinite Dilution Activity Coefficient in Water ln γi/W∞.02 4.22 0.41 3.41 3.12 9.32 0.13 1.89 3.55 2.86 0.60 12.42 1.38 1.04 1.00 6.68 2.53 -1.02 0. 5.74 3.88 2.65 -0.22 1. No.49 2.43 7.70 0.18 13.11 8.34 9.82 2.81 1.90 1.39 5.24 0.47 1.18 0.55 3.41 1.60 0.96 4.75 2.99 3.74 1.49 5.58 4.01 3.26 1.74 4.99 2.75 1.91 1.46 0.53 2.94 5.90 0.12 0.44 9.68 0.48 6.37 4.15 0.41 3.50 0.66 0.28 3.07 0.49 4.00 0.82 6.43 4.25 11.08 10.25 1.73 6.47 1.54 1.43 -0.58 4.96 2.86 4.08 1.99 -0.80 3.85 8.66 5.01 4.15 0.74 3.35 1.39 -1.53 4.50 -0.39 1.92 0.97 3.73 2.77 9.63 4.95 2.81 1.25 0.97 3.03 0.58 2.06 0.67 9.46 9.20 7.68 -0.95 4.25 3.44 2.4-dioxane ethylamine butylamine triethylamine acetone 2-butanone 2-pentanone 3-pentanone propanal butyraldehyde n-methylformamide methylformate methyl acetate ethyl acetate aceticanhydride dimethyl carbonate methylpropionate nitromethane nitroethane nitropropane acetonitrile propoinitrile butyronitrile cyanogen malonic acid dinitrile 1.90 1.89 0.80 4.00 8.56 1.44 2.21 2.24 2.47 2.03 0.51 1.08 0.25 0.28 2.15 .31 4.31 8.43 2.17 0.23 1.04 6.81 9.82 -0.07 1.92 0.10 2. Calculations for Octanol/Water Partition Coefficient log KOW.15 2.34 3.92 -1.65 -0.85 4.26 0.80 1.64 1.44 1.27 10.03 0.87 1.02 2.00 0.09 0.63 4.97 -0. 2002 Table 2.48 1.01 -0.12 1.10 8.26 1.34 0.00 -0.26 0.78 0.05 1.58 0.60 1.03 0.71 2.13 0.99 1.38 0.39 3.21 0.64 1.08 0.29 6.16 0.93 1.29 0.54 4.86 2.25 0.78 8.90 2.35 7.91 2.24 0.13 0.97 7.16 3.08 0.94 0.00 3.89 0.40 4.08 12.01 0.94 0.16 0.50 -0.60 10.65 3. Eng.86 6.00 0.89 1.17 0.30 3.28 0.83 7.91 0.86 2.41 0.10 1.25 3.18 4.82 0.31 0.42 0.79 4.06 3.27 8.31 1.67 1.43 3.88 1.32 2.34 1.47 12.81 0.93 5.36 5.48 1.i compound name butane pentane hexane heptane octane 2.91 0.13 1.79 1.00 -0.48 0.99 5.93 1.63 1.03 0.90 8.93 1.31 5.43 0.62 3.64 12.33 7.11 0.28 7.20 0.00 7.44 -1.63 0.27 5.99 4.89 2.99 6.89 5.13 1.71 1.28 2.92 5.26 11.57 3.60 3.77 0.36 0.37 3.59 1.66 9.97 0.87 -0.41 3.93 3.16 3.11 0.94 -0.57 2.55 13.65 6.77 2.47 0.92 0.73 -0.16 0.38 1.67 7.91 -0.75 2.37 0.90 3.47 11.50 7.98 1.95 3.65 3.12 2.73 2.36 4.28 1.81 0.19 3.68 3.68 2.53 0.48 3.56 4.38 4.13 2.68 3.76 15.33 11.96 10.00 0.32 4.66 -0.75 -0.51 -0.25 0.51 4.36 1.96 1.97 2.52 1.43 5.53 4.15 K log KOW.01 0.20 1.35 0.83 2.01 8.50 4.13 3.08 1.33 7.50 0.08 3.87 2.16 1.00 7.67 5.25 3.45 0.72 1.99 -0.20 0.51 1.90 1.50 4.12 3.11 0.85 4.47 0.45 3.44 2.04 1.69 0.77 2.08 0.82 0.89 0.48 0.72 0.16 1.36 0.22 5.59 -0.35 0.13 14.34 0.72 4.59 3.50 1.80 3.73 4.28 8.19 1.18 0.00 0.91 2.73 1.48 1.00 1.35 2.02 0.15 0.00 0.50 5.53 1.34 0.69 3.35 12.27 2.74 2.27 -0.86 2.18 1.88 0.86 1.85 2.09 7.84 2.09 0.21 1.03 0.47 -0.46 4.82 1. and Hexane ln γi/H∞ at 298.25 0.32 3.56 3.08 6.2-dicyanoethane glutaronitrile water ethanol 1-propanol 1-butanol 2butanol tert-butyl alcohol isobutanol 1-pentanol 1-hexanol 1-octanol acetic acid butyric acid benzene pyridine aniline phenol chlorobenzene chloroform tetrachloromethane 1.77 -0.76 9.03 3.40 0.15 1.91 3.45 2.38 2.80 6.2-dimethylbutane 2-methylpentane cyclohexane 1-butene 1-hexene 1-heptene 1-octene 1-hexyne 1-heptyne diethyl ether methyl tertbutyl ether tetrahydrofuran 1.99 0.11 2.52 0.00 3.00 -1.45 4. Vol.20 4.06 0.45 9.22 4.91 1.58 0.17 0.26 -0.24 -0.12 1.33 0.29 -1.40 0.53 2.83 4.28 3.24 4.29 4.62 5.78 0.87 0.65 6.05 2. 41.17 1.84 3.09 -0.33 2.15 0.23 -0.80 -0.00 -0.77 -0.45 1.61 3.81 5.14 2.09 5.39 0.20 0.39 4.76 9.00 1.72 2.44 0.05 1.56 8.87 -0.06 4.25 6.43 0.14 0.94 0.13 2.58 1.57 2.62 2.92 2.33 0.18 0.81 -0.96 0.86 -0.77 -0.32 3.48 3.10 2.80 4.00 0.23 3.49 3.92 3.41 3.37 1.64 0.00 2.55 0.19 5.71 4.26 13.01 0.88 7.59 3.53 1.54 1.00 0.15 3.30 4.64 3.63 3.82 8.48 0.07 0.16 4.00 -0.90 0.61 0.84 10.07 0.74 11.70 1.44 3.93 4.49 5.72 3.99 3.53 10.48 0.66 -0.61 9.906 Ind.48 1.07 -0.78 3.64 1.83 1.55 3.89 6.47 4.16 2.06 0.70 2. Res.56 2.74 2.32 1.34 6.32 0.55 6.06 3.77 2.11 6.91 3.. Chem.29 1.00 0.46 4.78 2.93 4.05 -0.03 -0.93 13.04 11.81 1.00 0.48 5.88 2.15 1.17 5.44 1.45 11.26 1.40 0.68 1.39 1.08 0.30 2.16 0.13 1.47 2.93 9.01 -0.77 3.03 1.65 3.15 -0.98 4.82 9.16 1.84 1.90 1.42 6.01 0.40 6.58 2.00 0.40 -0.57 0.57 3.47 0.97 0.66 10.85 4.03 0.65 4.05 -0.40 -0.04 0.51 2.24 0.07 0.28 0.31 0.46 16.91 -0.46 3.98 3.17 0.31 1.89 1.98 3.29 0.93 0.12 2.82 2.65 9.90 4.72 2.04 -1.79 8.01 -0.77 0.13 0.42 6.01 0.67 2.03 0.67 1.18 1.37 1.43 1.47 3.95 0.84 1.24 7.41 2.29 1.53 0.01 3.40 3.36 0.33 3.22 0.25 0.22 0.00 2.41 0.06 1.08 0.72 0.64 -0.03 0.01 3.99 11.44 4.25 3.68 2.14 3.19 0.10 0.59 0.98 0.76 11.05 3.2-dichloroethane max abs dev rms ln γi/W∞ ln γi/H∞ COSMOmodified COSMOCOSMOmodified COSMOCOSMOmodified COSMOSAC UNIFAC UNIFAC RS expt SAC UNIFAC UNIFAC RS expt SAC UNIFAC UNIFAC RS expt 2.71 1.77 4.69 -0.02 0.65 0.81 3.03 0.21 9.71 1.15 3.00 -0.45 10.13 0.82 2.18 11.16 1.01 10.18 1.10 2.45 2.44 -0.33 2.90 -0.31 9.54 2.49 1.28 9.14 4.55 1.89 3.17 1.25 6.65 2.05 3.00 0.65 6.90 4.

50. and an empirical λ parameter) in the COSMO-RS model but not in COSMO-SAC. Therefore. The COSMO-RS results are obtained with the DMol3 program in Cerius2. µCOSMO-RS(σ) diverges to negative infinity as the number of molecules increases so that the total number of segments in the system goes to infinity. the accuracy of the COSMO-SAC model would be improved in a consistent manner.Ind. First. modified UNIFAC. necessary. UNIFAC. all segments are labeled and. in the remainder of this paper. This may be a weak indication that COSMO-SAC is a more reliable model for new compounds as compared to the COSMO-RS model and that with all parameters optimized (including atomic radii). Chem. consequently. The superiority of COSMO-RS over the COSMO-SAC model in these cases may be because (1) the COSMO-RS model parameters were optimized using data for partition coefficients. With the utility of the COSMO-SAC model established. and other models. rms deviations of where N is the total number of segments in the mixture. Comparison of calculated and experimental values for (a) octanol/water partition coefficient and infinite dilution activity coefficients in (b) water and (c) hexane from COSMO-SAC.33. corresponding to 65%. 41. However. COSMO-RS. The consistent results from COSMO-SAC for γ∞ in water and in hexane suggest that this model may also be applicable for predictions of mutual solubility.17 (Interested readers are referred to ref 16 and the users’ manual of DMol3 for the exact procedure and parameters used in the COSMORS calculations. A comparison of the COSMO-SAC and COSMO-RS models for the octanol/water partition coefficients and the infinite dilution activity coefficient in water and hexane is also shown in Figure 6 and summarized in Table 2. eq 17 is exact only in the limit when each segment in the mixture has a different charge density. and chb) by including phase equilibrium data of water/alkane mixtures in the regression of these parameters or by a better description for the segment dispersion interactions. The central equation in COSMO-RS is. This equation provides a completely new prospective by treating molecules in condensed phases as paired surface segments and allows determination of the segment interactions from fast quantum mechanical COSMO calculations. 5. it is also interesting to point out that the maximum absolute deviations from COSMO-SAC are smaller than those from COSMO-RS. Res. UNIFAC. in the derivation of eq 17.4 µCOSMO-RS(σm) ) -kT ln N { 2 ∑p(σ ) exp n σn [ -Epair(σm. 0. However. This may require further refinement of model parameters (the atomic radii. the predictions from the COSMO-SAC and COSMO-RS models are comparable. in the general case. and (3) we used several COSMO-RS default parameters that were not optimized for COSMO-SAC calculations. a correlation factor fcorr. with COSMO-RS being exceptionally good for alkanes in water. Vol. for the chemical potential of charged surface segments.. Because segments with the same charge density are indistinguishable.15 K. However. 40%. whereas VLE data were used for the COSMO-SAC model. 2002 907 ln γ∞ are 0.) In general. and COSMO-RS models at 298. we compare the theoretical bases of the COSMO-SAC. 0. (2) there are additional parameters (such as an averaging radius rav. and modified UNIFAC. σn) + µCOSMO-RS(σn) kT (17) ]} Figure 6. respectively. taken to be distinguishable in solution. No. and 34% errors in γ∞ for COSMO-SAC.29. aeff. Eng. Comparison of the Segment Chemical Potential in the COSMO-SAC and COSMO-RS Models. eq 17 overcounts the degeneracy of the ensemble of segments and leads to the following problems. the chemical potential is an intensive property . The predictions from COSMO-SAC for γ∞ in hexane compares reasonably well with the other two models.

Figure 7 shows the activity coefficient profiles for water and hexane calculated from eqs 21 and 23. respectively. Vol. as “p(σ) f 0”) is finite while this chemical potential should diverge to negative infinity in this limit. Res. either a small value of λ (0. the surface area parameter q also equals 1 for all segments.Epair(σn.∑ σ σ ∑p(σk) τkn σ n n k p(σn) τmn ] (21) with τmn ) exp - [ Epair(σm.. whereas the derivation we present here is rigorous and coherent.Epair(σm.16 this term has been replaced with λkT ln AS. To compare eq 21 to the model we have developed here. It is interesting to note that the activity coefficient of a surface segment can also be determined from lattice theory-based models.ln [ ∑p(σn) τnm .24 we obtain the following expression for the activity coefficient of surface segments in solution: ln ΓUNIQUAC(σm) ) 1 . 0) .. σn) . The contribution from molecular size and shape effects should appear from the insertion of molecule into the solution in the ideal solvation process not from the restoring process. In contrast.e. this term gives λkT ln A2/A1 for one infinite dilution limit and -λkT ln A2/A1 for the other.e. σ). the chemical potential for segments derived here (eq 9) satisfies all these necessary boundary conditions. V. σn) + Epair(σn. In the latest version of COSMO-RS. However. µCOSMO-RS(σ) for a segment in the infinite dilution limit (i. Eng.23 or it has been diluted with the arbitrary addition of an engineering combinatorial term.8 the activity coefficient is calculated as follows: COSMO-RS becomes identical to that from COSMOSAC. The interaction energy U(σm. 2002 and should not depend on the size of the system. Because all surface segments are of the same size. and the results are similar: the UNIQUAC expression tends to . T) ) e-β(N/2)Epair(σ. σm) 2kT ln γi/SCOSMO-RS ) ni (24) ] ∑pi(σm) exp σ m [ µS′COSMO-RS(σm) . Therefore. the chemical potential µ0(σ) of a segment in such pure fluid is µ0(σ) ) -kT ∂ ln Q(N.) Therefore. Each surface segment with its charge density can be treated as a functional group. T) ∂N | T. where AS is the mole fraction weighted surface area of all of the species in the mixture and λ is an adjustable parameter.Epair(σm. Chem. this normalization leads to an unrealistically large nikT ln N dependence of the chemical potential of molecules. σn) ) Epair(σm.ln with τ′mn ) ∑p(σn) Γ′(σn)τ′mn σ n (23) exp - [ Epair(σm.V ) 1/2Epair(σ. In recent modifications of COSMO-RS.Epair(σn. These problems in the COSMO-RS model has been masked by the ad hoc introduction of a normalization µ′COSMO-RS(σ) ) µCOSMO-RS(σ) + kT ln N. σ) (18) whereas it is (N/2)Epair(σ.e. No. Furthermore. with β ) 1/kT.µ0(σ))/ kT. σn) between two segments can then be calculated as follows: U(σm. the activity profiles from the two models have a striking similarity.16 this term has been neglected completely. 0) 2kT (22) ] It should be noted that the reference state used in eq 21 is a pure segment fluid consisting of identical charge densities.e. eq 10 becomes ln Γ′(σm) ) . there is no net combinatorial contribution for the equally sized surface segments. 5.14) has been used. Comparison of Segment Activity Coefficient from COSMO-SAC and Lattice Theory-Based Models. V. does not satisfy the Gibbs-Duhem relation.Epair(σn. it is necessary to change the reference state used in eq 10 from a fluid of neutral segments to that in eq 21. and the incorrect system number dependence has been attributed to the decoupling of the segments. Moreover. The formation of paired segments is equivalent to setting the coordination number z to 1.. p(σm) ) 1/N). σ). However.µi′COSMO-RS(σm) kT ] - λ ln(AS/Ai) + ln γi/SSG (19) Interestingly. ln p(σm) Γ′(σm) ) (µ(σm) . In addition. σn) .8 As has been explained previously.. while for water the UNIQUAC model deviates from the exact solution at large charge densities. 0) . (For binary mixtures. with µ0(σ) ) 1/2Epair(σ. λkT ln AS/Ai. µCOSMO-RS(σ) does not satisfy the proper boundary condition in the “pure” segment limit (i.908 Ind. The partition function of a system composed of N identical segments with charge density σ in this case is Q(N. 0) (20) Substituting these relations into the formulas of the UNIQUAC or Wilson models. 41. all identical segments with charge density σ). that is. eq 9 does not depend on the total number of segments in the system and diverges to negative infinity at the infinite dilution limit p(σm) f 0. The two profiles are almost identical for hexane. σ) from eq 17. when COSMO-RS has been used for phase equilibrium predictions. the molecular activity coefficient from Although the UNIQUAC model was derived from a very different basis (local composition assumption). σn) . p(σm) ) 1) and becomes the same as COSMO-RS (eq 17) in the limit when all segments are distinct (i. σn) + Epair(σm. σn) . the activity coefficient derived from this term. This coincidence results from the expedient and ad hoc introduction of a Staverman-Guggenheim term to COSMO-RS.8. This term has been misinterpreted as the combinatorial contribution. Therefore.Epair(σm. We have examined such profiles for other solvents. as demonstrated with examples in Appendix 2.. with the definition for segment activity coefficient ln ΓCOSMO-RS(σ) ) µ′COSMO-RS(σ)/RT and setting λ to zero. Equation 9 converges to eq 18 in the limit when all segments are identical (i.

15 K. the Figure 8. for mixtures containing dissimilar species. Res. Eng. It is useful to compare and summarize the calculation methods used in UNIFAC. exaggerate hydrogen-bonding effects. No.Ind. 5. such differences accumulate when summing over contributions from the segments. The sum of these profiles. each weighted by the mole fraction for each component. COSMO-RS. and COSMO-SAC. produces the profile of a mixture. The UNIFAC model breaks an isolated molecule into functional groups and uses group frequencies (i. and COSMO-SAC. Chem.. is less successful for modeling mutual solubility and simultaneous VLE-LLE phase equilibrium predictions. Interestingly. 41. COSMO-RS. based on the UNIQUAC equation.. which are computed from partitioning an ideally screened molecule into surface segments. Comparison of segment chemical potential from eq 21 and the exact model from eq 23 at 298. In the UNIFAC model. This group frequency distribution is in some ways analogous to the σ profiles in COSMO-RS and COSMOSAC.e. and COSMO-SAC. The group frequency distribution and the σ profile are the unique characteristics of each molecule. 2002 909 Figure 7. However. COSMO-RS. while very successful in correlating VLE data. Comparison of Methodology in UNIFAC. Methodology comparison between UNIFAC. there is a similarity between the three approaches as shown in Figure 8. errors may cancel when the compounds in a mixture are similar. . Vol. Because such exaggeration is consistent. This may explain why the UNIQUAC model. the number of each type of functional group contained in a molecule) for each pure compound.

In this picture.26 the Boublık-Mansoori-Carnahan-Starling-Leland model ´ (BMCSL). One advantage of COSMO-SAC and COSMO-RS is the use of a more detailed group partition method (i. .T. which is most sensitive to the atomic radii and the level of quantum mechanical calculations. and so on to nf segments with charge density σf (or equivalently. the COSMO-SAC model uses an exact statistical mechanical model for the segment activity coefficient (eq 10)..e. these models are able to distinguish between isomers and resolve problems of intramolecular proximity effects. In this model.3 More importantly. The molecular activity coefficient is then obtained by summing the contributions from the segment activity coefficients. That is. it is likely that the accuracy of COSMO-SAC would be improved by optimizing these parameters using a very large data bank.30 experimental vapor pressures can be used to directly check the calculated ideal solvation free energy. No. Finally. unlike the UNIQUAC.. NRTL. cancels out of such phase equilibrium calculations. the probability p(σ) of finding a segment with charge density σ is equivalent to the mole fraction of that type of molecule in the solution. nf molecules of species f). . ¨ Appendix I.24 no composition dependence of Gex is presupposed. n1 molecules of species 1.28 or information theory (IT). and of similar accuracy.. Acknowledgment The authors would like to thank the National Science Foundation (Grants CTS-9521406 and CTS-0083709) and the Department of Energy (Grant DE-FG0285ER13436) for financial support of this research. This suggests that the COSMO-RS and COSMO-SAC are of a new class of models that is universally applicable. the VLE or partition coefficient data may not be the best to use for such parameter estimations. molecules are considered to consist of a collection of equally sized surface segments. One possible way to directly examine ∆G*is is to consider the vapor pressure determined from the free energy Conclusion A modification to the COSMO-based activity coefficient model has been developed here that has a welldefined theoretical basis. The composition dependence arises naturally here and depends on the species involved and. nmn pairs formed by segments with charge densities ln Pivap ) sol ∆G*i/i + ln ciRT ) RT is res cav ∆G*i/i + ∆G*i/i + ∆G*i/i + ln ciRT (25) RT When combined with a cavity formation model for pure fluid. S. all three models sum the contributions from groups or segments to give molecular activity coefficients and generate the phase diagram. Although the results are satisfactory. 5.e. Derivation of the Chemical Potential of Charged Surface Segments [Note: To assist in understanding the following derivation. In contrast. n2 molecules of species 2. To compute segment interactions. Res.L. with their interactions determined from the screening charges they acquire on ideal solvation.] Consider a mixture consisting of n1 segments with charge density σ1. considerably fewer parameters are necessary.. the COSMO-SAC (eq 10) and COSMO-RS (eq 17) models determine the segment activity coefficient or chemical potential from the mixture σ profile with segment interactions calculated from the charge density on each segment. Vol. Chem. and infinite dilution activity coefficients in water and hexane. This is because the ideal solvation free energy ∆G*is. the mixture contains (1 + f)(f/2) types of pairs (n11 pairs formed by segments with charge densities σ1 and σ1.910 Ind. Because the segments are assumed to form pairs in the liquid phase. Eng. In this work. therefore. the exact statistical mechanical expression for the activity coefficient of segments in a mixture of segment pairs developed here provides a necessary boundary condition for other lattice theory-based models and can be valuable for the future development of more complicated models that take into account different segment/group sizes and varying coordination numbers. Gmehling for his generous offer and kind help on the usage of the Dortmund Data Bank during his stay at the Universitat Oldenburg. and other activity coefficient models. 2002 group activity coefficient is computed using the mixture group frequencies and a predetermined set of energy parameters. the level of theory and the atomic radii in the quantum mechanical calculation). There is one important feature of both COSMO-RS and COSMO-SAC that should be emphasized. n2 segments with charge density σ2. Although similar to COSMO-RS. the σ profile).27. octanol/water partition coefficients. UNIFAC. Once the parameters have been optimized in this manner. there is no interaction among segments of different pairs). and segment interactions are confined within each pair (i. Also. changes from mixture to mixture. In addition. is grateful to Professor J. as well as considering other methods for computing the σ profile. Consequently. while the segment chemical potential (eq 17) used in COSMO-RS is exact only in the limit when all segments are distinguishable. 41.e. the segment interactions can be determined from the charge densities of the segments. This model provides a valuable a priori estimate of the thermophysical properties of new or previously unmeasured species and of the phase equilibria for new mixtures. for all mixtures. such as the scaled particle theory (SPT). this model requires only atomic radii for calculating the screening charges that we have taken from previous publications and two universal parameters for computing the segment interactions that we have fit to VLE data. one can imagine that segments with the same charge density σ are one type of molecule and that the ensemble is a mixture that contains many different types of molecules. we have used values for most parameters in the COSMO calculation from the previous work for the COSMO-RS model (i. Wilson. it may be possible to predict accurate vapor pressures from this method. in which case it may not be necessary for a scientist or engineer to use different models for different types of mixtures... The consistent accuracy of the predictions for new compounds from this model has been demonstrated by calculations for VLE.. therefore.29.25. A statistical mechanical model has been derived for the segment activity coefficients based on the assumptions that the segments are paired in the solution. n12 pairs formed by segments with charge densities σ1 and σ2.

+ nmf nm ) n1 + n2 + .7) ]} (A1. Thermodynamic Consistency of the COSMO-SAC and COSMO-RS Models In this appendix. σn) Q(N .. The experimental data are taken from the Dortmund Data Bank. To obtain the chemical potential of segments.6 are combined and the terms are rearranged.µ(σm) . Because the total number of each type of segment must be conserved. + nf ) p(σm) (A1. σn) + µ(σn) + kT kT ln p(σm) (A1. A(N .. nf)/2 nmn (A1. and nff pairs formed by segments with charge densities σf and σf).1) which is applicable because the points are calculated along an isotherm and the product of the pressure and the excess volume term is negligible. The Helmholtz free energy A(N) of the system is then A(N) ) -kT ln Q(N)... Tables 3 and 4 contain the activity coefficients predicted from the two models.4). + nf)/2 pairs formed in the mixture and the probability p(σm. we test consistency using The partition function is the sum of the Boltzmann factors for all possible states of the system so that the probability p(σm... σn) ) Q(N) -Epair(σm. .3) which is eq 9 in the text. σn) + µ(σm) + µ(σn) kT ] (A1. small fluctuations about zero are acceptable.. + nmf /2 Np ) There are a total of Np ) (n1 + n2 + .. we consider COSMO-SAC and COSMO-RS calculations for two arbitrarily chosen systems to compare the differences in predictions and consider the question of thermodynamic consistency. σn) + µ(σm) + µ(σn) (A1.5) From eq A1. σn) ) This probability can be calculated exactly based on statistical mechanics. 41. this term in the tables should be zero at each point. σn) pair in an N-segment system is calculated from the summation of the probabilities of finding a (σm. From these tables... there will be an increase of degeneracy by a factor of 2 because interchanging the positions of the segments results in different states.21 The difference in the predictions emphasizes the fact that the COSMO-RS and COSMO-SAC. of removing one (σm.2) ) A(N) . The product of the Boltzmann factor for the (σm. No.. together with the results of a Gibbs-Duhem point-to-point consistency test for the two models. Res.. σn) pair. There.. The COSMO-RS predictions were made using the program DMol3 in Cerius2. Because the segment pairs are assumed to be independent from each other. we see that the COSMO-SAC model satisfies the thermodynamic consistency test.. while based on the same physical picture.. we have nmn ) p(σm. + n2f ) n2 l nf 1 + nf 2 + .. Eng.. + 2nff ) nf (A1.1) n)1 2 ∑ f 1 t p(σm. in the limit of large N. When the two segments are distinct (m * n).4.e.2) kT ) p(σm.. σn) pair in states that contain (σm. 5. When the two segments are the same. however...µ(σn).4) 2t exp kT 2t exp - [ ] [ ] with t ) 0 when m ) n and t ) 1 when m * n.. we have f independent conservation equations paired with any other segment. + nmm + .1 and (1 + f)(f/2) relations by combining eqs A1. + 2nmm + .. p(σm)) 2n11 + n12 + .e. Suppose that the partition function Q(N) for the N segments is known.2) ) exp kT Q(N) [ ] { [ ∑ exp n)1 f -Epair(σm. because the value is calculated by numerical differentiation rather than analytically. For thermodynamic consistency. we obtain the following expression for chemical potential of the charged surface segments: µ(σm) ) -kT ln µ(σm) + µ(σn) Q(N . + nf n1 + n2 + . using the conservation equations.. There are a total of (3 + f)(f/2) unknowns [(1 + f)(f/2) from the pairings nmn and f from the chemical potentials µ(σm)). Appendix II. and the COSMO-SAC predictions were made as described here. σn) pairs Epair(σm.2 and A1. are different models. + n1f ) n1 n21 + 2n22 + .5 and A1.. σn) ) nm1/2 + nm2/2 + .2) ) -kT ln Q(N . This is equivalent to finding a segment with charge density σm in the mixture (i. σn) pair and Q(N . σn) of finding a (σm.. σn) pair is equivalent to a decrease due to the chemical potentials of the two segments (i. while COSMO-RS does . they are indistinguishable and do not result in an increase of degeneracy when interchanging positions.6) When eqs A1..Ind. we consider the probability of finding a segment with charge density σm x1 ∂ ln γ1 ∂ ln γ2 + x2 )0 ∂x1 ∂x1 (A2. Figures 9 and 10 show the predictions of both methods for these systems. Therefore ∑ exp n)1 f [ -Epair(σm.. and we have (3 + f)(f/2) relations to solve for all of the unknowns (f conservation equations in eq A1. σn) of finding a pair formed by segments with charge densities σm and σn is nm1 + nm2 + . the reduction of the Helmholtz free energy. Chem. σn) ) Np (n1 + n1 + .2) includes all the possible states that contain at least one (σm.. 2002 911 σm and σn.2) ∑ n)1 f 1 2t p(σm. Vol.

166 -0.2) -0.000 -0.5550 1.001 -0.0653 0.05 K COSMO-RS x1 2.1160 0.001 -0.1230 1. Table 4. A1 ) 43.002 -0.099 -0.8786 1.177 0.0000 -0.80 × 10-1 9.20 × 10-1 6.000 0.003 -0.0197 0. No.4530 2.083 1.2140 0.0901 0.013 0.001 0.001 0.5250 0.002 -0.0000 ln γ2 GDa GDb (eq A2.122 0.3030 0.000 -0.40 × 10-6 2. 2002 Table 3.109 0.9090 1.0000 0. with λ ) -0.195 -0.0009 0.002 0.0076 0.3294 0.00 × 10-1 8.89 × 10-1 9.90 × 10-3 1.6300 1.6200 0. a GD ) x (∂ ln γ /∂x ) + x (∂ ln γ /∂x ) is calculated from 1 1 1 2 2 1 numerical differentiation.6981 0.217 0.4244 1.5850 1.51 × 10-1 9.3770 1.207 0. and A2 ) 120.002 0.0220 1.79 × 10-1 6.002 GDb (eq A2.4510 0.5620 0.7330 3.65 × 10-1 8.2) 0. with λ ) -0.2620 0.7640 1.40 × 10-2 1.7440 1.05 × 10-1 3.1718 1.0000 ln γ2 0.1010 2.0000 0.03 Å.003 0.22 × 10-1 9.152 0.002 Figure 10.0317 0.138 -0.4850 2. Vol.60 × 10-1 9.2136 0.0894 3.209 -0.001 Figure 9.001 -0.52 × 10-1 4.202 -0.0575 0.6662 1.087 COSMO-SAC ln γ1 3.7229 1.0000 ln γ2 0.1690 0.0289 0.153 -0.178 -0.202 -0.155 0.092 2.0000 0.107 3.088 0.026 0. 41.0800 0.1956 2.158 0.2690 0.000 0.112 0.103 0.001 0.001 0.0100 0.113 0. a GD ) x (∂ ln γ /∂x ) + x (∂ ln γ /∂x ) is calculated from 1 1 1 2 2 1 numerical differentiation.3780 0.0040 0.A2))/(x1A1 + x2A2).5745 1.018 0.170 0.223 0.0463 0.0004 0.6100 0. A1 ) 114.05 K.3130 2.0490 2.076 2.40 × 10-1 1.0316 0.1129 0.001 0.125 -0.27 Å.0200 0.86 × 10-1 8.0340 0.144 -0.2631 0.30 × 10-2 2.1360 1..095 0.25 × 10-1 7.249 -0.001 -0.8150 0.50 × 10-1 6.072 -0.36 × 10-1 9.000 0.163 -0.5240 0.2000 2.3919 0.135 0.22 × 10-1 4.0135 2.5701 0.1060 0. and A2 ) 43.140 0. VLE prediction from COSMO-SAC and COSMORS for water (1)/1.090 -0.5050 2.221 -0.8953 2.3613 3. Eng.2884 1.141 0.091 -0.2247 2.10 × 10-2 2.14.0000 0.6560 0.66 × 10-1 1.5844 0.113 0.139 0. VLE prediction from COSMO-SAC and COSMORS for methyl acetate (1)/water (2) binary mixture at 330.0090 0.056 3.062 0.2953 0.189 0. Comparison of Activity Coefficient and Gibbs-Duhem Term from COSMO-RS and COSMO-SAC Models for Water (1)/1.180 -0.0137 0.9170 0.3674 0.4-dioxane (2) binary mixture at 308.8441 0.0090 0.63 × 10-1 5.912 Ind.96 × 10-1 2.4575 1.154 0.8240 0.0010 0.6695 0.2570 2. b GD ) (-λ(A1 .0893 3.168 -0.0882 0.5345 1.0710 0.012 0.4051 0.23 × 10-1 9.1428 0.0000 0.00 × 10+0 10-9 ln γ1 3.0000 ln γ2 0.250 COSMO-SAC ln γ1 2.1310 0.001 0.46 Å.163 0.1947 0.3380 0.0047 0.0094 1.00 × 10+0 ln γ1 2.0504 3.002 0.183 0.122 -0.002 0.8780 0.246 -0.096 -0.19 × 10-1 9.0738 0.9223 1.11 × 10-1 3.006 0.131 0.7380 3.4-Dioxane (2) Mixture at 308.008 -0.2115 0.2376 GDa 0.133 -0.002 -0.0000 0.5200 3.113 0.0280 0.238 -0.8990 2.222 0.000 0.90 × 10-3 4.148 0.2580 2.001 0.149 0.0032 0.0341 2.0010 0.145 0.451 0.A2))/(x1A1 + x2A2).001 -0. .0935 0.40 × 2.002 -0.60 × 10-2 4.9920 0.2347 0. Comparison of Activity Coefficient and GibbsDuhem Term from COSMO-RS and COSMO-SAC Models for Methyl Acetate (1)/Water (2) Mixture at 330.7000 2.5140 GDa -0.5521 0.228 0.6940 3.70 × 10-2 9.024 0.3250 0.117 -0.0000 0.77 × 10-1 7.001 0.6500 3.212 0.40 × 10-4 2.0080 0.0830 0.037 -0.109 -0.228 0.085 0.0110 0.9340 1.172 -0.090 -0.4614 0.5409 2.001 -0.9563 2.3670 1.115 -0.5010 1.1290 0.4856 0.96 × 10-1 9.70 × 10-2 7.002 0.195 0.1940 1.226 0.136 -0. Res.7960 0.4730 0.001 -0.094 0.0001 0.0000 0.0000 0.180 -0.1742 0.0002 0.15 K COSMO-RS x1 4.1680 0.62 × 10-1 4.27 Å.0030 0.0492 3. b GD ) (-λ(A1 .50 × 10-2 9.347 0.90 × 10-5 4.4055 1.4584 2.0330 0.0000 0.1350 0.002 -0.2000 0.0328 1.087 0.215 -0.001 -0.9894 0.128 -0.5660 0.001 0.93 × 10-1 5.29 × 10-1 2.8582 0.094 -0.0970 0.0000 0.2020 0.10 × 10-2 5.0856 3.121 -0. Chem.0216 0.2513 GDa -0.001 -0.2938 0.229 0.009 -0.201 0.7541 1.3080 3.6820 0.3560 2.002 0.003 0.65 × 10-1 9.5771 0.090 0.0510 0.0137 2.099 -0.0003 0.2000 2.004 0.213 -0.001 0.0347 0.002 0.0013 0.0432 0.8454 0.1630 0.4210 0.30 × 10-1 8.4380 0.2460 0.1480 0.7616 0.1050 0.111 -0.002 0.032 -0.3760 0.96 × 10-1 1.67 × 10-1 3.0000 0.16 × 10-1 1.9573 1.001 0.002 -0.001 -0.0136 0.0500 0.98 × 10-1 1.090 1.2571 0.114 -0.229 0.227 -0.018 -0.001 0.0470 0.0410 1.232 -0.182 0.110 1.78 × 10-1 9.019 -0.0001 0.8260 1.0000 0.243 -0.8072 1.7209 2.4460 0.4235 0.0978 2.0140 0.3702 2.248 -0.2800 1.1800 0.0230 0. 5.15 K.0000 -0.0230 0.7380 3.082 -0.14.1149 0.0639 1.0109 0.90 × 10-8 4.164 -0.001 -0.2540 1.50 × 10-3 4.001 -0.9030 2.01 × 10-1 9.188 -0.1869 0.128 -0.8060 0.57 × 10-1 8.0630 0.

J. Present Parameter Matrix and Results for Different Thermodynamic Properties. (21) Gmehling. M. S. J. J. Paulaitis. Mennucci..2) where Ai is the surface area of component i in the binary mixture. 799. Chem. 889.. R. Prentice Hall: New York. 69. 369. Chem.. Prediction of Octanol-Water Partition Coefficients Using a Group Contribution Solvation Model. J. I. C. H. Soc.. R. A.. Res. L. A. K. S.-Tech.. 4664. D.0.Ind. Refinement and Parametrization of Cosmo-Rs.. A Priori Calculation of Phase Equilibria for Thermal Process Engineering with the Aid of CosmoRs. 21. Garcia. J.. I. J. Chem. 1986. T. 30. T. S.. J. 99. 2000. 8951. G. (6) Tanpipat. (2) Gmehling. Chem. 54. Pays-Bas 1950. H.A2) + x2 ) ∂x1 ∂x1 x1A1 + x2A2 (A2. Garde. 1987. Fluid Phase Equilib. 1999. Trav.. J... J. (16) Klamt. Acad. Pratt. Chem. 92. 7099. Cosmo Implementation in Turbomole: Extension of an Efficient Quantum Chemical Code Towards Liquid Systems. Rev. Received for review December 1. B 1998. L. Ind. Self-Consistent-Field Calculation of Pauli Repulsion and Dispersion Contributions to the Solvation Free Energy in the Polarizable Continuum Model. L. 97. Eckert. 1959. Fischer. J. Phys. A. 163. Molecular-Interactions in Solutions an Overview of Methods Based on Continuous Distributions of the Solvent. ¨ F. G. Carnahan. A. 2. S. L. 93. 104. Lebowitz. Klamt. Phys. B. Furthermore. It should be noted that the inconsistency of the COSMO-RS model is a result of x1 ∂ ln γ1COSMO-RS ∂ ln γ2COSMO-RS -λ(A1 . 94. E. J. Literature Cited (1) Fredenslund. 10469.. 1523. Eades. Ind. ´ 1970. 2002 913 not. 2000.. 2000. U. E. Plenum Press: New York.. D. Res. T. A. A. Lohrenz. Hydrophobic Effects on a Molecular Scale. Eckert. U671. 1999.. Pohorille. Solvation Thermodynamics. J. Schuurmann. I. G. (23) Clausen. Chem. Chem. J. L. The Dortmund Data Bank and the Integrated Software Package. (11) Amovilli. J. W. S. 1993. An Information Theory Model of Hydrophobic Interactions. (27) Boublık. 1971. A. J. Chem. T. Phys.. Mixtures.. Dmol3. J. H.. E.. 1995. Res. 38. Chem. 5. AIChE J.. 1966. K... Soc. 32. A. 1994. 2606. G. J.. E. 1051. 5074. 2000. Jonas. (28) Mansoori. Statistical Thermodynamics of Liquid-MixturessNew Expression for Excess Gibbs Energy of Partly or Completely Miscible Systems. Phys. Infinite Dilution Activity Coefficients from Ab Initio Solvation Calculations. Phys. 2187.. (25) Reiss. D.A. N. J. Natl. 72. Menke. H.2 is not zero unless the surface areas (A1 and A2) are identical. 2001 Accepted November 2. N. M. Phys... 1999.-Ing. 217. (19) Andzelm. J. Chem. Chem. 43. Lohrenz. (9) Lin. R. Sandler. Garde. Pratt. Ind. (24) Prausnitz. M. A. Chem. 45.. S. Ausnitz. E. 4081. Recl. (26) Reiss. Test of New Groups in Unifac. C.. Vol.. A. AIChE J. 1996. (20) Abrams. A. 1975. J.. I. Chim. Multipole Corrections to Account for Structure and Proximity Effects in Group Contribution Methods: Octanol-Water Partition Coefficients. 1990.. (17) Cerius2. F. 101.. Pap. Eng. AIChE J. 1952. (13) Lin. 116.. Jones. 2000. Chem. J. M. Equation A2. Lichtenthaler. Sci. 1991. R. (22) Wu. Chem. Andzelm. 2 1993. Prausnitz. Li.sAm. Fish. Chem. S.. Cosmo-Rs: A Novel and Efficient Method for the a Priori Prediction of Thermophysical Data of Liquids. M. (8) Klamt. CA. W. No. 2. 2224. Garcia. J. Phys.K. (14) Staverman. R.. Hard-Sphere Equation of State. the inconsistency problem becomes more severe for systems containing components that are very different in size. (4) Klamt. version 4. Phys. A. Clarendon Press: Oxford.. M.. J.. Perkin Trans. 2. I. 727. V. GroupContribution Estimation of Activity-Coefficients in Nonideal LiquidMixtures. C. Burger.. J. 172. (10) Tomasi. (3) Lin.. Eng. Chem.. (29) Hummer. I. A. Statistical Mechanics of Rigid Spheres. Phys. Arlt. N. Chem. The Entropy of High Polymer Solutions. Azevedo. 102. Chem. B. Phys. An All-Electron Numerical-Method for Solving the Local Density Functional for Polyatomic-Molecules. Abstr. Molecular Thermodynamics of Fluid-Phase Equilibria. (15) Guggenheim. Phys. U. S. 2nd ed. 53. Eng. T. B 1997. J. Equilibrium Thermodynamic Properties of the Mixture of Hard Spheres. d. (12) Ben-Naim. S. Conductor-Like Screening Model for Real Solventssa New Approach to the Quantitative Calculation of Solvation Phenomena. Phys. Sandler. S. Use of Ab Inito Quantum Mechanics Calculations in Group Contribution Methods. Sandler. 102. A. (18) Delley. Adv. C. W. Cosmosa New Approach to Dielectric Screening in Solvents with Explicit Expressions for the Screening Energy and Its Gradient. Theoretical-Study of Chemical-Reactions Using Density-Functional Methods with Nonlocal Corrections. Res. 21. Starling. Klamt. G. Phys. Chem. 1993. 9. Clausen. In preparation. 2027. W. Sosa. Persico. Schiller. A Modified Unifac Model. Sandler.S. 508. 2001 IE001047W .. 1086. E. A. Fluid Phase Equilib. T. (30) Hummer. S. (5) Klamt.. 1999. Molecular Simulations Inc. Sattel. 471.. Chem. 2000 Revised manuscript received July 10. 178.: San Diego.. J. Proc. 41... Chem. A. Rarey. Eng. A 1998. 1. F. (7) Schafer. Leland. Dmol/ Cosmo-Rs: A Bridge between Chemistry and Chemical Engineering. J. 1975. 31.

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