Chemical Engineering and Processing 40 (2001) 531 535 www.elsevier.

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Predicting diffusivities in liquids by the group contribution method

W.Y. Fei a, H.-J. Bart b,*
b

Department of Chemical Engineering, Tsinghua Uni6ersity, Beijing 100084, Peoples Republic of China Thermische Verfahrenstechnik, Uni6ersity of Kaiserslautern, Postfach 3049, 67653 Kaiserslautern, Germany
a

Received 30 March 2000; received in revised form 21 October 2000; accepted 22 October 2000

Abstract The group contribution method to predict diffusivities in binary liquid systems is compared with other well-known semi-empirical correlations, such as WilkeChang, HaydukMinhas and Tyn Calus, by means of literature data including also systems of commercial interest, e.g. sulfolanearomatics systems. This comparison indicates that the group contribution method is superior to the other correlations investigated. Furthermore, the prediction of diffusivities with the group contribution method is explained step-by-step by means of several examples. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Diffusivity; Liquid; Group contribution method

1. Introduction The diffusion coefcient in liquids is an important parameter for the understanding of complex mass transfer processes and for the design of mass transfer equipment such as distillation, absorption and extraction columns. Diffusivities in liquids [1,2] are essential for the advanced non-equilibrium stage model, which is applied nowadays to separation column calculations in nearly all cases [3,4]. However, the prediction of diffusivities in liquids is still not satisfying for many commercial systems. In our extensive review paper on the theory and prediction of diffusion coefcients [5], a new practical approach to predict diffusivities in liquids has been introduced in detail [6]. The basis of this model is the principle of group contributions, a principle that has been successfully applied to predict thermodynamic equilibria with the UNIFAC model. Therefore, a similar approach for diffusivities seems very attractive since in this way the vast number of compounds and mixtures can be reduced to a limited number of functional groups. Once the functional group parameters are de* Corresponding author. Tel.: + 49-631-2052414; fax: + 49-6312052119. E -mail addresses: fwy-dce@mail.tsinghua.edu.cn (W.Y. Fei), bart@mv.uni-kl.de (H.-J. Bart).

termined from existing data the estimation of diffusivities of new compounds is a simple task. However, two questions still remain. First, is this new approach really much better than other semi-empirical equations? As we know, these equations give good results within the experimental conditions from which they have been derived. Second, how can one obtain diffusivities from this new approach? Prior to answering these questions a brief description of the model derivation is given, followed by a systematic comparison of this new method with other semi-empirical equations. Afterwards it is shown step-by-step how to compute diffusivities from the group contribution method proposed by Ye [7] by means of several examples.

2. Derivation of the functional group contribution approach The proposed model [7] assumes that the diffusivity is governed by the diffusion area and the activation energy of the molecules A and B. The diffusion area and the activation energy are both functions of the single contributions of each group of the composing molecules. The equations have been derived from the Eyring equation and the model parameters from experimental

0255-2701/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 2 5 5 - 2 7 0 1 ( 0 0 ) 0 0 1 5 1 - 3

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W.Y. Fei, H.-J. Bart / Chemical Engineering and Processing 40 (2001) 531 535

data. The models to predict diffusivities in dilute solutions are summarized in Table 1. Examples of the calculation of the molecular diffusion areas of solutes and solvents are listed in Appendix B. The group diffusion activation energies of a few groups are summarized in Appendix C. For ideal solutions the diffusion area of a pseudo-solute and a solvent is calculated with: SA = % AKQk;
k=1 m

cluding Wilke Chang, Tyn Calus and Hayduk Minhas, [8], are listed in Table 1. Diffusivities in concentrated binary solutions can be predicted from these equations by applying an interpolation scheme, such as the Vignes equation (Eq. (8)) [8] whereas Y accounts for the non-idealities of the mixture.
xA xB DAB = Y (D 0 D0 BA AB )

(8)

SB = % BKQk;
k=1

(1)

where Qk is the group diffusion area and AK, BK are the numbers of the Qk considered in molecule A and B, respectively. The correlation to predict diffusivities at innite dilution is given by:
5 D0 AB = 2.0 10

For the comparison of the semi-empirical equations and the group contribution method Eq. (8) is used once the diffusivities at innite dilution have been determined from these correlations. The volume at boiling temperature necessary for some calculations can be obtained from the Tyn Calus equation. Vb = 0.285V 1.048 C (9)

S 0.95 E A T 0.5 exp 0.15 RT SB

(2)

(association factor = 8 for H2O, = 2 for alcohols except methanol, otherwise = 1). In the case of an ideal solution the diffusion areas of the pseudo-solute and the solvent are calculated as follows: S1 = xBSA + xASB; S2 = xASA + xBSB (3)

Combining Eqs. (2) and (3) results in: D id AB = K (xBSA + xASB)0.95 1/2 E T exp 0.15 (xASA + xBSB) RT

The data that are used for the comparison have been obtained from the literature, among these data are also sulfolane aromatics mixtures [7] since these systems are extremely non-ideal and of commercial interest. The results are given in Table 2. It is apparent from the comparison that the group contribution method is superior to the other methods for all systems investigated. This becomes obvious especially in the case of the technical important sulfolane aromatics systems. In such systems the maximum relative deviation of the group contribution method is 13.779% while the predicted diffusivities from the semi-empirical correlations show larger deviations, in some cases the relative error exceeds 100%.
Table 1 Methods to estimate binary diffusivities at innite dilution [8] Method WilkeChang [9] TynCalus [10] HaydukMinhas [11] Relation D0 AB = 7.4108(bMB)1/2T pBV 0.6 A

(4)

where K is dened as K = 2.0 10 5 . Eq. (4) can be extended to be applicable also for non-ideal solutions by introducing a thermodynamic correction factor. Y=1+ d ln kA d ln xA
id AB

(5)

8 D0 AB = 8.9310

Thus, the diffusivity is given by. DAB = D Y (6) Here, kA is the activity coefcient which is calculated with the UNIFAC model. The diffusion activation energy necessary for the calculation of the diffusivities is dened as: EAB = % % AiBj Eij
i=1 j=1 n n

V 0.267 T |B B V 0.433 pB |A A

 

0.15

8 D0 AB = 1.5510

V 0.27 T 1.29 | 0.125 B B 0.42 V A p 0.92 | 0.105 B A 3VB VA

2/3

Scheibel [12]

D0 AB = 8.2

108 1+ Reddy [13] D0 AB =

  

T /3 p BV 1 A

/2 KM 1 B T K pB(VAVB)1/3

(7)

3. Comparison between this new method and other semi-empirical approaches Several well known semi-empirical correlations to estimate diffusion coefcients at innite dilution, in-

8 1010 = 8.5108 Lusis [14] D0 AB =

(8.52108)T VB 1.40 /3 pBV 1 VA B + VB VA

  

VB 51.5 VA VB ]1.5 VA

1/3

W.Y. Fei, H.-J. Bart / Chemical Engineering and Processing 40 (2001) 531 535 Table 2 Comparison of calculated results using various models [15]; % error System n-Heptanebenzene n-Hexanebenzene cyclo-Hexanebenzene Toluenebenzene Toluenecyclo-hexane Sulfolanebenzene Sulfolanetoluene Sulfolaneethylbenzene Sulfolanen-propylbenzene This model 10.854 6.833 3.147 1.352 2.548 13.779 10.363 5.808 13.695 WilkeChang 58.354 16.217 3.243 1.785 82.830 28.723 39.337 83.129 80.883 TynCalus 41.115 12.419 12.362 3.050 86.459 29.060 36.626 68.286 67.520 HaydukMinhas 38.943 14.845 11.324 3.177 90.107 25.295 34.033 72.975 72.143 Scheibel 106.607 23.640 10.222 29.002 134.507 37.225 51.839 126.102 123.688 Reddy 40.888 20.570 15.375 4.646 79.084 31.766 38.824 72.020 65.785 Lusis 62.915 13.899 13.243 4.505 90.016 32.322 42.050 83.931 81.047 References [16,17] [16,17] [7,17] [17] [17] [7] [7] [7] [7]

533

Even in the systems cyclohexane benzene and toluene benzene for which the most commonly used correlation, the Wilke Chang equation, gives accurate results the estimated diffusivities of the group contribution method deviate less from the measured values.

wB1 = 5, E11 = 58.0; wA1 = 6, wB2 = 2 and E12 = 667.4 the diffusion activation energy is EAB = 9748.8 (J/mol). Combining the calculated parameter values and Eq. (2) one yields DAB = 3.468 10 9 (m2/s).

4.2. Example 2
4. Case studies The new approach seems straightforward. However, since it is difcult for non-experienced users to obtain diffusivities from this method, in the following the prediction of diffusion coefcients in liquids is explained step-by-step by means of several examples. Calculate the diffusivity at innite dilution of n-heptane in benzene.

4.1. Example 1
Calculate the diffusivity at innite dilution of benzene in n-heptane. The molecular diffusion areas of the solute and solvent are calculated with Eq. (1). According to Appendix B for the solute benzene wA1 = 6 and QA1 = 1.179 is valid, therefore, SA = 7.074; for the solvent n-heptane one obtains with wB1 = 5, QB1 = 0.54; wB2 = 2, QB2 = 0.848 the following value for the diffusion area, SB = 4.396. Thus, the diffusivity at innite dilution is calculated according to Eq. (2), where T = 298 K, R = 8.314 J/(mol K) once the diffusion activation energy E is calculated with Eq. (7). The necessary diffusion activation energies between the functional groups are listed in Appendix C. By applying wA1 = 6,

The molecular diffusion areas and the diffusion activation energies of the functional groups are identical with those determined in Section 4.1. However, the SA and SB in Eq. (2) should change position. Hence, one obtains for the diffusivity DAB = 2.055 10 9 (m2/s).

4.3. Example 3
Calculate the innite dilution diffusivity of toluene in benzene. The molecular diffusion areas of the solute and the solvent are calculated with Eq. (1). According to Appendix B the parameters of the solute toluene are wA1 = 1, QA1 = 5.168 and hence SA = 5.168; the parameters of the solvent benzene are given by wB1 = 6, QB1 = 1.179 and, therefore, SB = 7.074. The diffusion activation energy is calculated according to Eq. (7). The necessary diffusion activation energies between the functional groups are listed in Appendix C. Here the parameters are wA1 = 6, wB1 = 1, E11 = 1746.8. Thus fol-

Table 3 Comparison of experimental and calculated diffusivities at innite dilution System Benzene in n-heptane n-Heptane in benzene Toluene in benzene D experimental (109 [m2/s]) 3.4 2.1 1.85 D calculated (109 [m2/s]) 3.468 2.055 1.783 (%) 2.0 2.1 3.6

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lows EAB = 1 6 E11 = 10480.8 (J/mol). Together with Eq. (2) the diffusivity can be estimated as DAB = 1.783 10 9 (m2/s).

5. Discussion and conclusions The experimental and calculated diffusivities at innite dilution of the three systems mentioned above are listed in Table 3. It is clear from the comparison that the experimental and the calculated values show high resemblance. The relative error of the estimated values is less than 4% for the case studies. The prediction of diffusion coefcients in liquids based on the principle of group contribution is simple and accurate enough for engineering purposes once the functional group parameters are known. However, due to the lack of functional group parameters it is still difcult to predict diffusivities of many commercial systems. Therefore more diffusivity measurements are indispensable, espe-cially for systems of commercial interest. In this way additional model parameters can be obtained and hence the data basis of the functional group parameters can be extended. From this improvement it can be expected that the prediction of diffusion coefcients in liquids based on the principle of group contribution will become a powerful, universal approach after profound research work on this area. The group contribution method for the prediction of binary diffusion coefcients has been compared with other semi-empirical relations. It is apparent that the group contribution approach is superior to all other correlations tested, especially for the technical important systems like sulfolane aromatics. It has been shown in the case studies that this new method is simple and accurate enough for engineering purposes if the functional group parameters are known. More research is indispensable in order to extend the data basis of the functional group parameters.

M n Q R S T V Vb Vc V xi Greek k p | Y

number of components in the liquid mixture number of groups in the liquid mixture group diffusion area gas constant (8.314 J/(molK)) molecular diffusion areas temperature (K) volume (cm3/mol) volume at the normal boiling point volume at critical temperature number of group in molecule mole fraction of i activity coefcient viscosity (cP) surface tension (N/m2) association parameter for the solvent thermodynamic correction factor

Superscripts 0 innite dilution id ideal mixture Subscripts A, B components A and B m mixture i, j components i and j

Appendix B. Examples of group molecular diffusion areas Group CH3 CH2 [CH2] ACH C6H5CH3 C6H5CH2 Q 0.848 0.540 1.292 1.179 5.168 4.457 Examples n-heptane n-dodecane cyclo-hexane benzene toluene n-butyl-benzene S = 6 j Qj 4.396 7.096 7.75 7.06 5.168 6.385

Acknowledgements The authors wish to thank the DAAD for nancial support. Appendix C. Examples of group diffusion activation energies
CH3 CH2 851.4 312.00

Appendix A. Notation DAB E K MA binary diffusion coefcient of A diffusing into B (m2/s) group diffusion activation energies (J/mol) constant parameter molecular weight of A (g/mol)

27.67 [CH2] 461.79 101.06 333.58 ACH 667.40 58.00 306.58 294.44 C6H5CH3 3395.1 423.18 1799.7 1746.8 10038.0 C6H5CH2 3395.1 423.18 1676.75 1746.8 10038.0 10038.0 Group CH3 CH2 [CH2] ACH C6H5CH3 C6H5CH2

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References
[1] E.L. Cussler, Multicomponent Diffusion, Elsevier, Amsterdam, 1976. [2] H.J.V. Tyrell, R.Q. Harris, Diffusion in Liquids, Butterworths, London, 1948. [3] R. Krishnamurthy, R. Taylor, Am. Inst. Chem. Eng. J. 31 (1985) 513. [4] R. Taylor, R. Krishna, Multicomponent Mass Transfer, Wiley, New York, 1993. [5] W.Y. Fei, X.M. Wen, R.X. Xie, Solvent Extraction in the Process Industries, vol. 2, Elsevier, London, 1993, p. 1253. [6] W.Y. Fei, H.-J. Bart, Chem. Eng. Tech. 21 (1998) 659.

[7] M.H. Ye, Ph.D. dissertation, Tsinghua University, Beijing, 1988. [8] R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Gases and Liquids, fourth ed., McGraw-Hill, New York, 1987. [9] C.R. Wilke, P.C. Chang, Am. Inst. Chem. Eng. J. 1 (1955) 264. [10] M.T. Tyn, W.F. Calus, J. Chem. Eng. Data 20 (1975) 106. [11] W. Hayduk, B.S. Minhas, Can. J. Chem. Eng. 60 (1982) 295. [12] E.G. Scheibel, Ind. Eng. Chem. 46 (1954) 2007. [13] K.A. Reddy, L.K. Doraiswamy, Ind. Eng. Chem. Fundam. 6 (1967) 966. [14] M.A. Lusis, G.A. Ratcliff, Can. J. Chem. Eng. 46 (1968) 385. [15] Y.D. Lin, M.Sc. dissertation, Tsinghua University, Beijing, 1999. [16] K.R. Harris, C.K.N. Pua, P.J. Dunlop, J. Phys. Chem. 74 (1970) 3518. [17] S.A. Sanni, P. Hutchison, J. Chem. Eng. Data 18 (1973) 317.