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Fluid Phase Equilibria 217 (2004) 233–239

Application of the Perturbed-Chain SAFT equation of state to polar systems
Feelly Tumakaka, Gabriele Sadowski∗
Universität Dortmund, Lehrstuhl für Thermodynamik, Emil-Figge-Str. 70, 44227 Dortmund, Germany Received 9 August 2002; accepted 10 December 2002

Abstract The Perturbed-Chain SAFT (PC-SAFT) equation of state is applied to pure polar substances as well as to vapor–liquid and liquid–liquid equilibria of binary mixtures containing polar low-molecular substances and polar co-polymers. For these components, the polar version of the PC-SAFT model requires four pure-component parameters as well as the functional-group dipole moment. For each binary system, only one temperature-independent binary interaction kij is needed. Simple mixing and combining rules are adopted for mixtures with more than one polar component without using an additional binary interaction parameter. The ability of the model to accurately describe azeotropic and non-azeotropic vapor–liquid equilibria at low and at high pressures, as well as liquid–liquid equilibria is demonstrated for various systems containing polar components. Solvent systems like acetone–alkane mixtures and co-polymer systems like poly(ethylene-co-vinyl acetate)/solvent are discussed. The results for the low-molecular systems also show the predictive capabilities of the extended PC-SAFT model. © 2003 Elsevier B.V. All rights reserved.
Keywords: PC-SAFT; Equation of state; Vapor–liquid equilibria; Liquid–liquid equilibria; Dipolar interactions; Co-polymer

1. Introduction The PC-SAFT model [1] is a theoretical-based equation of state, which was proposed for the thermodynamic modeling of systems containing long-chain molecules like polymers. In contrast to many other models, PC-SAFT explicitly accounts for the non-spherical shape of a molecule, particularly of a polymer. Therefore, PC-SAFT reveals strong predictive capabilities and allows save correlations as well as extrapolations for polymer systems. The equation of state was already successfully applied to a huge number of systems containing gases, solvents, polymers, and co-polymers, as well as to associating systems [2–4]. However, the effect of polar interactions (like dipole–dipole forces) was not explicitly taken into account. The modeling of systems where molecules exhibit dipole–dipole interactions still remains a challenging problem. In this study, the

PC-SAFT equation of state is extended to polar systems. The dipolar interactions, which contribute significantly to the overall intermolecular forces, are explicitly accounted for in the molecular theory. This is accomplished using a dipolar term proposed by Chapman’s Group [5,6].

2. Theory In terms of the compressibility factor Z, the equation of state is given as the sum of the ideal gas contribution (Zid = 1), the hard-chain term (hc), the dispersive part (disp) (details are given elsewhere [1]). To account for the dipole–dipole interactions in polar systems, we add here a contribution Zdipol as proposed by Chapman’s Group (details given in references [5,6]) due to: Z = 1 + Zhc + Zdisp + Zdipol (1)

Abbreviations: EMA, poly(ethylene-co-methyl acrylate); EVA, poly(ethylene-co-vinyl acetate); LDPE, low density polyethylene; PMA, poly(methyl acrylate); PVAc, poly(vinyl acetate) ∗ Corresponding author. Tel.: +49-231-755-2635; fax: +49-231-755-2572. E-mail address: G.Sadowski@bci.uni-dortmund.de (G. Sadowski). 0378-3812/$ – see front matter © 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.fluid.2002.12.002

Most of the previous approaches to account for the dipolar interactions consider the dipolar molecule as a sphere with a dipole at the molecular center—the so-called “molecularsphere approach” (see Fig. 1a, methyl-ethyl-ketone is chosen as a representative alkanone). The new approach proposed by Chapman’s Group on the other hand, accounts for the fact

i should be approximately equal to 1/mi .7024 3. The modeling results for cloud-point curves in the systems poly(ethylene-co-vinyl acetate) (EVA)/ethylene. that the dipoles are located on certain segments in a chain molecule (Fig. for real fluids.6028 3. the last parameter xP.05 42.04030 0.05679 0.79 0 0 0 0 0 0 0 0 xP 0. xP.19 222.2279 3.09 58. which results in an underestimation of the dipolar interactions in the molecular-sphere approach. (b) Molecular model for methyl-ethylketone according to the “segment” approach. Their pure-component parameters are given in ref. the segment number mi . the segment-energy parameter εi /k. For molecules with a single dipolar site. For molecules with a single Table 1 Pure-component parameters of the Perturbed-Chain SAFT equation of state for the considered low-molecular weight substances Component Acetonea Vinyl acetatea Acetone Ethyleneb Propyleneb Butaneb Pentaneb Hexaneb Decaneb Dodecaneb a b c M (g/mol) 58. the closest distance of dipoles is greater than in the segment approach.234 F.123 72. The advantages of the latter approach are: (a) the effect of the non-spherical shape of the molecule is considered in the polar term.03115 σ (Å) 3. hexane. the dipole moment of each functional group calculated from quantum mechanics can also be used.49 232.47 207. and dodecane.i is treated as an adjustable parameter. 3. Phase equilibria in acetone/alkane binary systems Acetone contains a carbonyl group which has a dipole moment perpendicular to the molecular axis. The calculations were performed with as well as without including the polar contribution to show the effect of the dipolar term. 2 gives a comparison of experimental vapor-liquidequilibrium data and calculation results for the polar PC-SAFT and the non-polar PC-SAFT model for acetone/pentane mixtures at different temperatures [8]. The segment number m depends on the molecular mass M of a substance.338 m/Mc (mol/g) 0. this is the experimental value for the dipole moment of the molecule.7983 3. It is determined from (m/M) by multiplying with the molecular mass M.03766 0.21 µ (D) 2. the functional-group dipole moment µ is required. 3. and the fraction of dipolar segments on a molecule xP.8384 3. and (c) if a molecule becomes larger in the molecular-sphere approach.20 236.081 58. To demonstrate the ability of the theory to model mixtures containing polar as well as non-polar molecules the modeling of the phase behavior in acetone/alkane systems is considered.08 86.04657 0.08 28. For multiple polar groups.38 231.5356 3. (a) Molecular model for methyl-ethyl-ketone according to the “molecular sphere” approach.87 249. However.72 1.77 243.03662 0. Sadowski / Fluid Phase Equilibria 217 (2004) 233–239 polar site.177 142. .2969 0. The parameters are determined by simultaneously fitting vapor-pressure data and liquid densities.3879 3.146 86.03548 0. the original non-polar PC-SAFT model predicts a nearly ideal.i . poly(ethylene-co-methyl acrylate) (EMA)/propylene and EMA/butane with various polar–co-monomer contents of the co-polymers demonstrate the ability to model substances with big differences in molecular size and multiple dipolar functional-groups.03728 0. Fig.285 170.03277 0.33 247. G. (b) it is possible to account for multiple dipolar functional groups in the molecule. [1]. a total of four parameters needs to be adjusted. decane. The pure-component parameters of acetone were fitted to the saturated-liquid density and vapor-pressure data [7].04978 0. Results and discussion The extended PC-SAFT model (hereafter referred to as polar PC-SAFT) is applied to molecules containing single or multiple dipolar segments. Moreover. Tumakaka.2596 0 0 0 0 0 0 0 0 Polar PC-SAFT.7729 3. non-azeotropic behavior for the Fig.4450 3. Previously published in [1]. The pure-component parameters of all the solvents are listed in Table 1. For a pure polar component i. namely the segment diameter i . 1b) referred to as the “segment approach”. Using kij equal to zero. 1. The considered alkane solvents are pentane.42 176.8959 ε/k (K) 245.1.

F.2 0. Table 2 0. Again. 5..4 0.. solid line) and the modeling result describes the experimental data [9.0 0 0 0.7K 313.15K 5 0. Similar results were also obtained for non-azeotropic acetone/alkane systems like acetone/decane and acetone/dodecane (experimental data from [11]). Tumakaka. solid line). xn-Pentane Fig. the polar PC-SAFT describes the phase behavior more precisely than the non-polar PC-SAFT. the polar PC-SAFT model gives consistently better predictions of the phase behavior than the original model. Symbols are experimental data from [11].-) with kij = 0. acetone/pentane system whereas polar PC-SAFT predicts the azeotropic behavior of the considered system and the modeling result is in good agreement with the experimental data even for kij = 0. 4 shows the predictions (kij is set to zero) of the acetone/decane system. x Acetone Fig.2 1 333.-) with kij = 0.4 0.4 0. Lines are calculations with (non-polar) PC-SAFT (. dashed line) which results in kij = 0.4 0. 3. But although using this fitted kij value.2 333. Lines are calculations with (non-polar) PC-SAFT (. i. the non-polar PC-SAFT gives only worse description of the experimental data.0 0 0.-) and polar PC-SAFT (—).4 10 397. Vapor–liquid equilbrium of acetone/pentane system. Sadowski / Fluid Phase Equilibria 217 (2004) 233–239 235 20 422. non-azeotropic behavior for this system.8 1 xAcetone Fig. However.10] very well even for kij = 0. Vapor-liquid equilbrium of acetone/decane system.7K 0 0 0.4 313. non-polar PC-SAFT is unable to capture accurately the shape of the bubble-point curves compared to the polar PC-SAFT result for kij = 0 (Fig.6 0.063) (Fig.15K p / bar 0. Symbols are experimental data from [8].6 0.15K 15 p / bar p / bar 0.063 and polar PC-SAFT (—) with kij = 0. Furthermore.2 372. 4. whereas the non-polar PC-SAFT required in general a fitted kij to describe the phase behavior of polar mixtures.2 0. Lines are predictions (kij is set to zero) with (non-polar) PC-SAFT (. Considering the system acetone/hexane.2 0. For the non-polar PC-SAFT. a more accurate fit is obtained.. In contrast.0 0. 3. 5. Fig.0625.10].15K 0.6 308.6 0. Vapor–liquid equilbrium of acetone/hexane system.0 0.6K 1.6 0. dashed line). Symbols are experimental data from [9. the non-polar PC-SAFT model again predicts a nearly ideal.8 0. By adjusting the binary parameter kij of the (non-polar) PC-SAFT model for acetone/dodecane system (kij = 0.4 0.8 1. G. . 2.6 0. polar PC-SAFT predicts the azeotropic behavior of the considered system (Fig.8 1.2 0. the value of kij parameter was fitted (Fig. Vapor–liquid equilbrium of acetone/dodecane system. kij = 0.8 0.2 0.. All the calculation results with the polar term show a significant improvement compared to non-polar PC-SAFT: polar PC-SAFT does not need a binary parameter kij .8 313.0625 and polar PC-SAFT (—) with kij = 0. 3.e. 5. Lines are predictions (kij is set to zero) with (non-polar) PC-SAFT (.8 1 x Acetone Fig.6 0.-) and polar PC-SAFT (—).15K 1. Symbols are experimental data from [11].2 0.15K 1 p / bar 0.

063 0. In the modeling concept of PC-SAFT. for the poly(ethylene-co-vinyl acetate).2 0. The parameters kPVAc/ethylene and kethylene segment/vinyl acetate segment were obtained by fitting the copolymer data. It is determined from (m/M) by multiplying with the molecular mass M.15.% of vinyl acetate monomers are incorporated in the backbone of the co-polymer.15.2597 lists the optimized kij values for all the acetone systems considered here. the description of a non-polar copolymer (index i) requires the pure-component parameters of the different segment types it constitutes of. EVA18 (MW = 126 kg/mol) means that 18 wt. [4]. 3. according to √ εi i = εi εi (1 − ki i ) (2) Further details of the extension of PC-SAFT to co-polymers are given in ref. namely the segment diameter σ i .02805 σ (Å) 4.063 Polar PC-SAFT kij 0 0 0 0 m/Mc (mol/g) 0.5354 ε/k (K) 249.3.15.g. and 463.5 0.0263 0.5895 3. The pure-component parameters of the polymers are listed in Table 3. 6 shows the cloud-point pressures calculated with polar PC-SAFT for the EVA18 /ethylene system for different temperatures (373. G. 403. in the polymer backbone.02552 0.3 0.15.4 0.0217 3. .15 K). Tumakaka. Sadowski / Fluid Phase Equilibria 217 (2004) 233–239 Table 3 Pure-component parameters of the Perturbed-Chain SAFT equation of state for the considered polymers Polymer Polyethylene (LDPE)a Poly(vinyl acetate)b Poly(methyl acrylate)b a b Table 2 Binary interaction parameters of the PC-SAFT model for the calculated acetone systems System Acetone/pentane Acetone/hexane Acetone/decane Acetone/dodecane Non-polar PC-SAFT kij 0.0625 0.79 1.063 0.2. and the energy parameter εiα /k.1 0. the number of segments mi of type in the chain. In addition.15.7 T EVA weight fraction in ethylene Fig. Using only constant and temperature-independent binary parameters the effect of 1800 1600 1400 p / bar 1200 1000 800 600 0 0. only one additional parameter ki i is needed.5 214.6 0. The parameter kLDPE/ethylene was fitted independently (see ref. respectively. 433.15. Polar PC-SAFT. and furthermore the fraction of polar segments xP for pure vinyl acetate (Table 1). 6. Previously published in [2]. the pure-component parameters of polyethylene and those of poly(vinyl acetate) are required. and 463. 433. The dispersion energy parameter of the polymer was obtained by fitting the cloud-point data of PVAc with cyclopentane. c The segment number m depends on the molecular mass M of a polymer. Fig. The subscript indicates the weight percentage of vinyl acetate monomers in the polymer. In addition to these parameters. Poly(ethylene-co-vinyl acetate)/ethylene The segment diameter and the segment number for poly(vinyl acetate) (PVAc) were fitted to the liquid polymer density. [2]). 3.4 248 µ (D) 0 1. Phase equilibria in polar co-polymer/solvent system The co-polymers considered here are poly(ethylene-covinyl acetate) (EVA) and poly(ethylene-co-methyl acrylate) (EMA) with different contents of vinyl acetate and methyl acrylate. 403. which corrects the cross-dispersive energy between different segment types.2596 0. Calculated and experimental cloud-point pressures (data are taken from [12]) for the EVA18 /ethylene system at different temperatures (373.236 F. (The index runs over all constituents of the co-polymer): e. the experimental values for the dipole moment of vinyl acetate was used as the segment dipole moment.77 xP 0 0.15 K).

8 and 9 show the experimental data [14. Here. The molecular weights of the polymers are: EVA0 = LDPE: MW = 103 kg/mol. and EMA68 .15] for EMA/ethylene and EMA/propylene. EMA0 = LDPE EMA25 EMA58 EMA68 Using only constant and temperature-independent parameters (see Table 5). Like EVA/ethylene system. Circles are experimental data. respectively. 8. EMA68 : MW = 110 kg/mol. EMA58 : MW = 109 kg/mol. .0287 a Previously published in [2]. Table 6 Molecular characterization of EMA co-polymers Polymer MW (kg/mol) 106 75 109 110 MA (mol%) 0 10 31 41 MA (wt. Figs. EMA25 : MW = 75 kg/mol.%.16] in comparison with polar PC-SAFT calculations for EMA in propylene and butane.% (EVA0 = LDPE. the model successfully describes the non-monotonous behavior of the cloud point pressures. G. Sadowski / Fluid Phase Equilibria 217 (2004) 233–239 237 1800 1700 Table 5 Binary interaction parameters of the polar PC-SAFT model for EVA co-polymers Co-polymer system Segment–segment pair LDPE/ethylene PVAc/ethylene Ethylene segment/vinyl acetate segment ki j p / bar 1600 1500 1400 1300 1200 0 10 20 30 40 50 60 EVA/ethylene 0. EMA25 . EMA58 .4. EVA28 : MW = 126 kg/mol. 3. Line is calculated cloud-point pressures with an average MW of 100 kg/mol.15 K and the polymer concentration is about 15 wt. 7. A similar behavior was also reported in [13] for EVA/cyclopentane system. EMA/propylene also shows a non-monotonous phase behavior which is well described by the polar PC-SAFT model using the same modeling temperature on the cloud-point pressures is well described by the model.03 0. see Table 4). Poly(ethylene-co-methyl acrylate) The co-polymers considered here are EMA0 = LDPE. EVA58 : MW = unknown. Calculated and experimental cloud-point pressures (data are taken from [12]) for the EVA/ethylene system as a function of the amount of vinyl acetate monomers incorporated in the backbone of the co-polymer. The effect of incorporated polar co-monomer content on the cloud-point pressures is illustrated in Fig.%. Calculated and experimental cloud-point pressures (data are taken from [14]) for the EMA/propylene system as a function of the amount of methyl acrylate monomers incorporated in the backbone of the co-polymer. and in [14. EVA18 . the cloud-point pressure exhibit a non-monotonous behavior where an initial increase of the polar co-monomer results in a better solubility of the co-polymer in the solvent. The temperature is 433. The subscripts denote the amount of vinyl acetate monomers incorporated in the backbone of the co-polymers. EVA11 : MW = 161 kg/mol. triangles are calculation results using the experimental MW of the co-polymers. The solid line is the calculation with an average polymer molecular weight of 100 kg/mol. Tumakaka. The subscripts denote the amount of methyl acrylate monomers incorporated in the backbone of the co-polymers. The triangles are the monodisperse calculation results using the experimental MW of the co-polymers (MW of EVA58 is unknown. Table 6 lists the characterization of the co-polymers. EVA11 .%) 0 11 18 28 58 1500 p / bar 1000 68 % MA 58 % MA 0 % MA 25 % MA 500 0 380 390 400 410 420 430 440 T/K Fig.%) 0 25 58 68 Amount of VA in the backbone / wt-% Fig. The circles are experimental data from [12]. EVA18 : MW = 138 kg/mol. The polymer concentration is about 5 wt.04a 0. and EVA58 .F. hence no modeling result is available). The amount of vinyl acetate in the polymer backbone varies from 0 to 58 wt. The calculation was performed monodisperse using the MW of the co-polymer. where the subscript indicates the weight percentage of methyl acrylate monomers in the polymer backbone. 7. The molecular weights of the co-polymers are: EMA0 = LDPE: MW = 106 kg/mol. whereas a further enhancement of the vinyl acetate amount leads to a significant elevation of demixing pressures. Table 4 Molecular characterization of EVA co-polymers Polymer EVA0 = LDPE EVA11 EVA18 EVA28 EVA58 MW (kg/mol) 103 161 138 126 Unknown VA (wt. respectively.

it is a pure-component property and should not be mixed up with the amount of polymer in solution. 9.011a 0. b a . The molecular weights of the co-polymers are the same as in Fig. Thus. approach as for EVA/ethylene. The pure component parameters of poly(methyl acrylate) (PMA). Even at a kij value of zero polar PC-SAFT gives good results for these systems. Previously published in [4]. Table 7 Binary interaction parameters of the polar PC-SAFT model for EMA co-polymers Co-polymer system Segment–segment pair EMA/propylene LDPE/propylene PMA/propylene Ethylene segment/methyl acrylate segment LDPE/butane PMA/butane Ethylene segment/methyl acrylate segment ki j 0.i fraction of polar segments in a molecule i Z compressibility factor Greek letters εi /k segment-energy parameter (K) σi segment diameter of component i (Å) µ dipole moment (D) Superscripts dipol contribution due to dipolar interactions disp contribution due to dispersive attraction hc residual contribution of hard-chain system Subscripts i. We also thank Prof.0257a 0. kij of PMA/propylene. The last one (kij for the interaction of ethylene segment and methyl acrylate segment) is a linear function of the mole fraction of methyl acrylate monomer units in the co-polymer EMA (Table 7).%. Tumakaka. Calculated and experimental cloud-point pressures (data are taken from [16]) for the EMA/butane system as a function of the amount of methyl acrylate monomers incorporated in the backbone of the co-polymer. Walter G.j component i. Sadowski / Fluid Phase Equilibria 217 (2004) 233–239 3000 2500 4. G.0431b 0. The PC-SAFT equation of state was extended to account for the dipolar interactions explicitly. j . the polar PC-SAFT results are in much better agreement with the experimental data than those where the polar contribution is not explicitly accounted for.02 0. The calculations were performed using the experimental MW of the co-polymers assuming that the polymers are monodisperse.238 F. The polymer concentration is about 5 wt. as well as of polar co-polymers. kij of PMA/butane. the co-polymer Perturbed-Chain SAFT model gives good representation of the observed non-linear dependence of solubility on co-monomer content. List of symbols kij binary interaction parameter ki i binary interaction parameter between different segment types and of component i mi number of segments per chain of component i MW weight-average molar mass (kg/mol) p pressure (bar) T temperature (K) xi mole fraction of component i xP. xMA is the mole fraction of methyl acrylate monomers in the EMA co-polymer.0619 xMA + 0. polar PC-SAFT accurately describes the non-monotonous effect of the polar co-monomer content on the cloud-point behavior. A polar term proposed by Chapman’s Group was used where the dipoles are assumed to be located on the spherical segments of a chain. Chapman for the Fortran codes of the dipolar term. segment type . respectively.0431b in a co-polymer chain EMA/butane Acknowledgements The authors thank the German Science Foundation (Deutsche Forschungsgemeinschaft DFG) for the financial support of this work with grant SAD 700/5.0619 xMA + 0. indicating the predictive capability of the extended model. The extended model was successfully applied to model phase equilibria of polar low-molecular components. 8. Using this simple linear function. The pure-component parameters of LDPE and kij of LDPE/propylene as well as of LDPE/butane were taken from [2.0331 0.4]. For the acetone/alkane mixtures. and kij of ethylene segment and methyl acrylate segment were fitted to the EMA/propylene and EMA/butane co-polymer systems. For polar co-polymer systems like poly(ethylene-co-vinyl acetate) EVA/ethylene and poly(ethylene-co-methyl acrylate) EMA/propylene. Vapor–liquid and liquid–liquid equilibria were calculated for mixtures of this type using only one temperature-independent kij parameter. All parameters used to calculate EMA/propylene and EMA/butane systems can be taken from Tables 2 and 7. Conclusions 58 % MA 68 % MA p / bar 2000 1500 1000 500 0 % MA 0 350 400 450 500 550 T/K Fig.

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