Fluid Phase Equilibria 217 (2004) 233239

Application of the Perturbed-Chain SAFT equation of state to polar systems

Feelly Tumakaka, Gabriele Sadowski
Universitt Dortmund, Lehrstuhl fr 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 vaporliquid and liquidliquid 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 vaporliquid equilibria at low and at high pressures, as well as liquidliquid equilibria is demonstrated for various systems containing polar components. Solvent systems like acetonealkane 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; Vaporliquid equilibria; Liquidliquid 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 [24]. However, the effect of polar interactions (like dipoledipole forces) was not explicitly taken into account. The modeling of systems where molecules exhibit dipoledipole 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 signicantly to the overall intermolecular forces, are explicitly accounted for in the molecular theory. This is accomplished using a dipolar term proposed by Chapmans 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 dipoledipole interactions in polar systems, we add here a contribution Zdipol as proposed by Chapmans 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.uid.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 centerthe so-called molecularsphere approach (see Fig. 1a, methyl-ethyl-ketone is chosen as a representative alkanone). The new approach proposed by Chapmans Group on the other hand, accounts for the fact

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polar site, this is the experimental value for the dipole moment of the molecule. For multiple polar groups, the dipole moment of each functional group calculated from quantum mechanics can also be used.

3. 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. 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. The modeling results for cloud-point curves in the systems poly(ethylene-co-vinyl acetate) (EVA)/ethylene, poly(ethylene-co-methyl acrylate) (EMA)/propylene and EMA/butane with various polarco-monomer contents of the co-polymers demonstrate the ability to model substances with big differences in molecular size and multiple dipolar functional-groups. 3.1. Phase equilibria in acetone/alkane binary systems Acetone contains a carbonyl group which has a dipole moment perpendicular to the molecular axis. The pure-component parameters of acetone were tted to the saturated-liquid density and vapor-pressure data [7]. The considered alkane solvents are pentane, hexane, decane, and dodecane. Their pure-component parameters are given in ref. [1]. The pure-component parameters of all the solvents are listed in Table 1. The calculations were performed with as well as without including the polar contribution to show the effect of the dipolar term. Fig. 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]. Using kij equal to zero, the original non-polar PC-SAFT model predicts a nearly ideal, non-azeotropic behavior for the

Fig. 1. (a) Molecular model for methyl-ethyl-ketone according to the molecular sphere approach. (b) Molecular model for methyl-ethylketone according to the segment approach.

that the dipoles are located on certain segments in a chain molecule (Fig. 1b) referred to as the segment approach. The advantages of the latter approach are: (a) the effect of the non-spherical shape of the molecule is considered in the polar term, (b) it is possible to account for multiple dipolar functional groups in the molecule, and (c) if a molecule becomes larger in the molecular-sphere approach, the closest distance of dipoles is greater than in the segment approach, which results in an underestimation of the dipolar interactions in the molecular-sphere approach. For a pure polar component i, a total of four parameters needs to be adjusted, namely the segment diameter i , the segment number mi , the segment-energy parameter i /k, and the fraction of dipolar segments on a molecule xP,i . For molecules with a single dipolar site, the last parameter xP,i should be approximately equal to 1/mi . However, for real uids, xP,i is treated as an adjustable parameter. The parameters are determined by simultaneously tting vapor-pressure data and liquid densities. Moreover, the functional-group dipole moment is required. 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) 58.08 86.09 58.08 28.05 42.081 58.123 72.146 86.177 142.285 170.338

m/Mc (mol/g) 0.03766 0.03662 0.04978 0.05679 0.04657 0.04030 0.03728 0.03548 0.03277 0.03115

() 3.6028 3.3879 3.2279 3.4450 3.5356 3.7024 3.7729 3.7983 3.8384 3.8959

/k (K) 245.49 232.33 247.42 176.47 207.19 222.38 231.20 236.77 243.87 249.21

(D) 2.72 1.79 0 0 0 0 0 0 0 0

xP 0.2969 0.2596 0 0 0 0 0 0 0 0

Polar PC-SAFT. Previously published in [1]. The segment number m depends on the molecular mass M of a substance. It is determined from (m/M) by multiplying with the molecular mass M.

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235

20
422.6K

1.2 1

333.15K

15

p / bar

p / bar

0.8 0.6 0.4

10

397.7K

313.15K

0.2
372.7K

0
0 0.0 0.2 0.4 0.6 0.8 1.0

0.2

0.4

0.6

0.8

x Acetone
Fig. 4. Vapor-liquid equilbrium of acetone/decane system. Symbols are experimental data from [11]. Lines are predictions (kij is set to zero) with (non-polar) PC-SAFT (- - -) and polar PC-SAFT ().

xn-Pentane
Fig. 2. Vaporliquid equilbrium of acetone/pentane system. Symbols are experimental data from [8]. Lines are predictions (kij is set to zero) with (non-polar) PC-SAFT (- - -) and polar PC-SAFT ().

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. Considering the system acetone/hexane, the non-polar PC-SAFT model again predicts a nearly ideal, non-azeotropic behavior for this system. In contrast, polar PC-SAFT predicts the azeotropic behavior of the considered system (Fig. 3, solid line) and the modeling result describes the experimental data [9,10] very well even for kij = 0. For the non-polar PC-SAFT, the value of kij parameter was tted (Fig. 3, dashed line) which results in kij = 0.0625. But although using this tted kij value, the non-polar PC-SAFT gives only worse description of the experimental data.

Similar results were also obtained for non-azeotropic acetone/alkane systems like acetone/decane and acetone/dodecane (experimental data from [11]). Fig. 4 shows the predictions (kij is set to zero) of the acetone/decane system. Again, the polar PC-SAFT model gives consistently better predictions of the phase behavior than the original model. By adjusting the binary parameter kij of the (non-polar) PC-SAFT model for acetone/dodecane system (kij = 0.063) (Fig. 5, dashed line), a more accurate t is obtained. However, 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. 5, solid line). 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 , i.e. kij = 0, whereas the non-polar PC-SAFT required in general a tted kij to describe the phase behavior of polar mixtures. Furthermore, the polar PC-SAFT describes the phase behavior more precisely than the non-polar PC-SAFT. Table 2

0.8
313.15K

1.2

333.15K

p / bar

0.6
308.15K

p / bar

0.8 0.6 0.4 0.2

0.4

313.15K

0.2 0.0 0.2 0.4 0.6 0.8 1.0

0.2

0.4

0.6

0.8

xAcetone
Fig. 3. Vaporliquid equilbrium of acetone/hexane system. Symbols are experimental data from [9,10]. Lines are calculations with (non-polar) PC-SAFT (- - -) with kij = 0.0625 and polar PC-SAFT () with kij = 0.

x Acetone
Fig. 5. Vaporliquid equilbrium of acetone/dodecane system. Symbols are experimental data from [11]. Lines are calculations with (non-polar) PC-SAFT (- - -) with kij = 0.063 and polar PC-SAFT () with kij = 0.

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F. Tumakaka, G. Sadowski / Fluid Phase Equilibria 217 (2004) 233239 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 0.063 0.0625 0.063 0.063 Polar PC-SAFT kij 0 0 0 0

m/Mc (mol/g) 0.0263 0.02552 0.02805

() 4.0217 3.5895 3.5354

/k (K) 249.5 214.4 248

(D) 0 1.79 1.77

xP 0 0.2596 0.2597

lists the optimized kij values for all the acetone systems considered here. 3.2. 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, respectively, in the polymer backbone. In the modeling concept of PC-SAFT, the description of a non-polar copolymer (index i) requires the pure-component parameters of the different segment types it constitutes of, namely the segment diameter i , the number of segments mi of type in the chain, and the energy parameter i /k. (The index runs over all constituents of the co-polymer): e.g. for the poly(ethylene-co-vinyl acetate), the pure-component parameters of polyethylene and those of poly(vinyl acetate) are required. In addition, only one additional parameter ki i is needed, which corrects the cross-dispersive energy between different segment types, according to i i = i i (1 ki i ) (2) Further details of the extension of PC-SAFT to co-polymers are given in ref. [4].

Previously published in [2]. Polar PC-SAFT. c The segment number m depends on the molecular mass M of a polymer. It is determined from (m/M) by multiplying with the molecular mass M.

3.3. Poly(ethylene-co-vinyl acetate)/ethylene The segment diameter and the segment number for poly(vinyl acetate) (PVAc) were tted to the liquid polymer density. The dispersion energy parameter of the polymer was obtained by tting the cloud-point data of PVAc with cyclopentane. In addition to these parameters, the experimental values for the dipole moment of vinyl acetate was used as the segment dipole moment, and furthermore the fraction of polar segments xP for pure vinyl acetate (Table 1). The pure-component parameters of the polymers are listed in Table 3. Fig. 6 shows the cloud-point pressures calculated with polar PC-SAFT for the EVA18 /ethylene system for different temperatures (373.15, 403.15, 433.15, and 463.15 K). The subscript indicates the weight percentage of vinyl acetate monomers in the polymer. The parameter kLDPE/ethylene was tted independently (see ref. [2]). The parameters kPVAc/ethylene and kethylene segment/vinyl acetate segment were obtained by tting the copolymer data. Using only constant and temperature-independent binary parameters the effect of

1800 1600 1400

p / bar

1200 1000 800 600 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

EVA weight fraction in ethylene

Fig. 6. Calculated and experimental cloud-point pressures (data are taken from [12]) for the EVA18 /ethylene system at different temperatures (373.15, 403.15, 433.15, and 463.15 K). EVA18 (MW = 126 kg/mol) means that 18 wt.% of vinyl acetate monomers are incorporated in the backbone of the co-polymer.

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1800 1700

Table 5 Binary interaction parameters of the polar PC-SAFT model for EVA co-polymers Co-polymer system Segmentsegment 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

0.04a 0.03 0.0287

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.%) 0 25 58 68

Amount of VA in the backbone / wt-%

Fig. 7. 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 temperature is 433.15 K and the polymer concentration is about 15 wt.%. The molecular weights of the polymers are: EVA0 = LDPE: MW = 103 kg/mol, EVA11 : MW = 161 kg/mol, EVA18 : MW = 138 kg/mol, EVA28 : MW = 126 kg/mol, EVA58 : MW = unknown. The subscripts denote the amount of vinyl acetate monomers incorporated in the backbone of the co-polymers. Circles are experimental data, triangles are calculation results using the experimental MW of the co-polymers. Line is calculated cloud-point pressures with an average MW of 100 kg/mol.

EMA0 = LDPE EMA25 EMA58 EMA68

Using only constant and temperature-independent parameters (see Table 5), the model successfully describes the non-monotonous behavior of the cloud point pressures. 3.4. Poly(ethylene-co-methyl acrylate) The co-polymers considered here are EMA0 = LDPE, EMA25 , EMA58 , and EMA68 . Table 6 lists the characterization of the co-polymers, where the subscript indicates the weight percentage of methyl acrylate monomers in the polymer backbone. Figs. 8 and 9 show the experimental data [14,16] in comparison with polar PC-SAFT calculations for EMA in propylene and butane, respectively. Like EVA/ethylene 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. The calculation was performed monodisperse using the MW of the co-polymer. The effect of incorporated polar co-monomer content on the cloud-point pressures is illustrated in Fig. 7. The amount of vinyl acetate in the polymer backbone varies from 0 to 58 wt.% (EVA0 = LDPE, EVA11 , EVA18 , and EVA58 , see Table 4). The circles are experimental data from [12]. The triangles are the monodisperse calculation results using the experimental MW of the co-polymers (MW of EVA58 is unknown, hence no modeling result is available). The solid line is the calculation with an average polymer molecular weight of 100 kg/mol. Here, 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, whereas a further enhancement of the vinyl acetate amount leads to a signicant elevation of demixing pressures. A similar behavior was also reported in [13] for EVA/cyclopentane system, and in [14,15] for EMA/ethylene and EMA/propylene, respectively.
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.%) 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. 8. 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. The molecular weights of the co-polymers are: EMA0 = LDPE: MW = 106 kg/mol, EMA25 : MW = 75 kg/mol, EMA58 : MW = 109 kg/mol, EMA68 : MW = 110 kg/mol. The subscripts denote the amount of methyl acrylate monomers incorporated in the backbone of the co-polymers. The polymer concentration is about 5 wt.%.

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3000 2500

4. Conclusions
58 % MA 68 % MA

p / bar

2000 1500 1000 500

0 % MA
0 350 400 450 500 550

T/K
Fig. 9. 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. The molecular weights of the co-polymers are the same as in Fig. 8. The polymer concentration is about 5 wt.%.

The PC-SAFT equation of state was extended to account for the dipolar interactions explicitly. A polar term proposed by Chapmans Group was used where the dipoles are assumed to be located on the spherical segments of a chain. The extended model was successfully applied to model phase equilibria of polar low-molecular components, as well as of polar co-polymers. Vaporliquid and liquidliquid equilibria were calculated for mixtures of this type using only one temperature-independent kij parameter. For the acetone/alkane mixtures, 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. Even at a kij value of zero polar PC-SAFT gives good results for these systems, indicating the predictive capability of the extended model. For polar co-polymer systems like poly(ethylene-co-vinyl acetate) EVA/ethylene and poly(ethylene-co-methyl acrylate) EMA/propylene, polar PC-SAFT accurately describes the non-monotonous effect of the polar co-monomer content on the cloud-point behavior. 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,i fraction of polar segments in a molecule i Z compressibility factor Greek letters i /k segment-energy parameter (K) i segment diameter of component i () 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,j component i, j , segment type ,

approach as for EVA/ethylene. All parameters used to calculate EMA/propylene and EMA/butane systems can be taken from Tables 2 and 7. The calculations were performed using the experimental MW of the co-polymers assuming that the polymers are monodisperse. The pure-component parameters of LDPE and kij of LDPE/propylene as well as of LDPE/butane were taken from [2,4]. The pure component parameters of poly(methyl acrylate) (PMA), kij of PMA/propylene, kij of PMA/butane, and kij of ethylene segment and methyl acrylate segment were tted to the EMA/propylene and EMA/butane co-polymer systems, respectively. 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). Using this simple linear function, the co-polymer Perturbed-Chain SAFT model gives good representation of the observed non-linear dependence of solubility on co-monomer content.
Table 7 Binary interaction parameters of the polar PC-SAFT model for EMA co-polymers Co-polymer system Segmentsegment pair EMA/propylene LDPE/propylene PMA/propylene Ethylene segment/methyl acrylate segment LDPE/butane PMA/butane Ethylene segment/methyl acrylate segment ki
j

0.0257a 0.02 0.0619 xMA + 0.0431b 0.011a 0.0331 0.0619 xMA + 0.0431b

in a co-polymer chain

EMA/butane

Acknowledgements The authors thank the German Science Foundation (Deutsche Forschungsgemeinschaft DFG) for the nancial support of this work with grant SAD 700/5. We also thank Prof. Walter G. Chapman for the Fortran codes of the dipolar term.

Previously published in [4]. xMA is the mole fraction of methyl acrylate monomers in the EMA co-polymer. Thus, it is a pure-component property and should not be mixed up with the amount of polymer in solution.
b

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