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Journal of Supercritical Fluids 15 (1999) 109–116

Partition coefficients of aromatic organic substances in two-phase mixtures of water and carbon dioxide at pressures from 8 to 30 MPa and at temperatures of 313 to 333 K. Part II
Klaus-D. Wagner, Karlheinz Brudi, Nicolaus Dahmen *, Helmut Schmieder
Forschungszentrum Karlsruhe, Institut fur Technische Chemie, CPV, PO Box 3640, D-76021 Karlsruhe, Germany ¨ Received 10 August 1998; received in revised form 24 December 1998; accepted 28 December 1998

Abstract In the two phase system of water and supercritical carbon dioxide, the partitioning behavior of two single solutes, aniline and benzaldehyde, was measured at temperatures of 313, 323 and 333 K and pressures up to 30 MPa using a recirculation view cell apparatus. Samples were taken from both phases and analyzed either by UV-spectroscopy or gas chromatography. The partition coefficient in this case is defined as the ratio of molar fractions of a substance in the carbon dioxide-rich phase and the aqueous phase in equilibrium. Partition coefficients between 0.21 and 3.03 were found for aniline and 2.5 up to 62.9 for benzaldehyde. In addition to the single solute measurements, the distribution behavior of an aqueous solution of phenol, benzyl alcohol, cyclohexanol and 2-hexanone was examined at 323 K. While the alcohols were entrained in the fluid phase, the other compounds were retained in the aqueous phase. Analogous to high pressure binary solid fluid phase equilibria, an enhancement factor is introduced to describe partitioning equilibria. Differences in the distribution behavior of single solutes are discussed in terms of the enthalpy of hydration. © 1999 Elsevier Science B.V. All rights reserved.
Keywords: Enhancement factor; Enthalpy of hydration; Partition coefficient; Phase equilibria; Supercritical carbon dioxide

Nomenclature
a,b,A∞ c i E,E∞ h i Daq H l Dg H aq Dg H s Dg H l constants at constant temperature concentration of component i enhancement factor Henry constant of solute i molar enthalpy of mixing enthalpy of hydration enthalpy of sublimation enthalpy of vaporization

Daq H s K K c K x p p ref p* v p i R T xj i r r ref

* Corresponding author. Tel.: +49-7247-82-2596; fax: +49-7247-82-2244. E-mail address: nicolaus.dahmen@itc-cpv.fzk.de (N. Dahmen)

enthalpy of solubilization partition coefficient partition coefficient based on concentrations partition coefficient based on molar fractions pressure reference pressure (1 Pa) vapor pressure of the pure substance partial vapor pressure of solute i above an aqueous solution gas constant temperature molar fraction of component i in phase j density of pure carbon dioxide reference density (700 kg m−3)

0896-8446/99/$ – see front matter © 1999 Elsevier Science B.V. All rights reserved. PII: S0 8 9 6 -8 4 4 6 ( 9 9 ) 0 0 00 4 - 2

ous phase causes no problems.110 K. Due to the compressibility of the fluid carbon dioxide phase. To check the agreement of both methods. In addition. The high pressure cell is filled by half with an aqueous solution of the organic substances. In contrast. K. Results and discussion The partition coefficient is defined as the ratio of concentrations.1 K. we now report on two further substances. and the samples are analyzed afterwards. 3. Samples were taken from both phases by means of six-way valves with sampling volumes of 250 ml for the aqueous and 100 ml for the CO -phase. SPME (solid phase micro extraction) and gas chromatography (GC ) were used to determine the composition of the mixture components. c .% 2-hexanone at 323 K was examined. the sampling process in the fluid phase causes the organic material to precipitate as the carbon dioxide expands. In addition to single solute measurements. K is strongly dependent on temperature and pressure.1. which is placed in a liquid bath whose temperature is kept constant within ±0. the partitioning behavior of an aqueous solution containing four organic compounds was investigated. aniline and benzaldehyde. Introduction For the proper design of a separation process. x . while pressure is measured in the autoclave by a pressure transducer equipped with a front membrane. Salts are especially likely to increase K [2]. 3. 1 wt.% benzyl alcohol. Eq. 0. as the components to be determined remain in solution. the partitioning of a substance is affected by the presence of other solutes. Wagner et al.% phenol. i. describing the distribution of solutes between the two immiscible phases. Partitioning of single solutes Distribution behavior is mainly determined by the solubility of the solute in the CO phase. K c x was calculated using the density data of pure water and carbon dioxide at the distinct temperatures and pressures [1] from reference equations. / Journal of Supercritical Fluids 15 (1999) 109–116 1. the mutual miscibility of water and carbon dioxide is very limited. in both i phases: cCO K= i 2 c cH O 2 i xCO K = i 2 x xH O 2 i (1a) 2. the distribution behavior of an aqueous solution of 1 wt.5 wt. often a type III phase diagram according to the classification of . In continuation of previous measurements of the partitioning behavior of monofunctional aromatic compounds [1]. This material is completely washed into a sampling vial by water. Sampling the aque2 (1b) While K is the direct result of the analysis. The carbon dioxide phase is recirculated by a gear pump until equilibrium is attained. but other organics present in the solution can also influence partition coefficients. The analysis was conducted by UV-spectroscopy in the case of aniline. The temperature is measured by a Pt-100 resistance thermometer in the wall of the cell. At the required temperature. benzaldehyde was measured independently in both ways ( Table 1). In the experimental range studied here. the relevant phase equilibria have to be known accurately. in which organic substances are to be removed from an aqueous solution by supercritical carbon dioxide. Eq.% cyclohexanol and 3 wt. 2 Regarding the binary solute–carbon dioxide systems with liquids of low volatility. SPME as a pretreatment method allows the analysis of aqueous samples directly by GC.-D. Phase equilibrium in context with countercurrent extraction is often characterized by partition coefficients. In this context. (1b) of the substance. (1a) or the ratio of molar i fractions. CO is compressed in the cell by a 2 pneumatic pump until the final pressure is reached. Experimental The measurement of the partition coefficients in two-phase mixtures was performed using an analytical method with a recirculation view cell apparatus [1].

17 10.45 0.7 12.05 12.2 43. Wagner et al.9 20. leading to a higher vapor pressure of the solute.5 12.9 8.00 3.03 2.29 29.16 3.03 0.6 12.91 30.13 1. as well as in the partition coefficient.6 45.04 1.12 36.26 0.84 62.73 3.74 29.6 10.3 11.32 2.22 25. Near the critical end points.85 0. which determines the dissolving power of the solvent. In Fig.38 1.47 9.23 0.9 8.18 15. 8.4 25.95 3.43 0. The nearer the temper2 ature approaches to the critical end points.31 19.9 33.0 47.3 17.23 10.02 12.0 13.45 1.39 2.2 40.2 13.07 2.4 15. With increasing temperature.5 15.42 15.65 30. 323 and 333 K [4].93 15.7 10. Intersection of the isotherms.08 30.02 K 111 x 0.15 20.14 20.71 25.43 0.56 30.56 15.29 1.65 15.71 25.21 and 3.83 8. The partitioning obeys a phase behavior as discussed above.93 0.7 33.2 10. usually is not far from the critical point of pure solvent (CP1).5 5. the solubility and the parti- tion coefficient increases at higher pressures. As the critical end point (CE) and the lower critical end point (LCEP).7 23.98 29.23 2.53 12.2 14.41 20.7 Benzaldehyde.50 1.57 2.79 3.06 3.01 1. / Journal of Supercritical Fluids 15 (1999) 109–116 Table 1 Fluid phase concentrations and partition coefficients of aniline and benzaldehyde 313 K p (MPa) Aniline 8.95 0. respectively.09 1.4 11.0 a Molar fractions of benzaldehyde vary between both detection methods because of different initial concentrations.00 2.09 2.81 25. x. as observed commonly in other systems.43 5.39 12.01 2.26 Benzaldehyde.8 46. the isotherms of benzaldehyde at the three temperatures are plotted versus pressure [4].92 56.8 25.5 49.11 1.50 2. the increase becomes smaller with rising pressure.7 33. 2 shows the experimental results of the distribution measurements with aniline at 313.15 20.4 40.30 1.1 55.70 2.6 40.88 2.K. was not determined in the experimental pressure range. the strongest increase in the solubility.41 24.96 51. If the solutes are solid.5 7.82 25.99 1.5 10.13 0. The partitioning coefficient reaches values up to 62.09 24. Fig.38 2. The determination of the solute concentration by the two analytical methods show reasonably good agreement of GC with SPME and UV-spectroscopy.84 333 K p (MPa) xCO2 (10−3) i 0.95 3.04 24.1 25.09 K x 0.09 10.6 62.8 40.10 19.9 12.36 1.41 0.03.07 1.37 30.3 10.6 14.90 2.72 K x 323 K p (MPa) xCO2 (10−3) i 0.97 10.6 46. K.36 10. 1).05 3.13 1.98 0.-D. the more steep is the change in x and K.22 10.5 23. the most pronounced changes in solubility occur [3]. is observed near the critical point of CO in most cases.2 9. Similar to the density behavior of pure carbon dioxide.9.73 1.03 GC-SPME detectiona 6.14 xCO2 (10−3) i 1. van Konynenburg and Scott is found. the critical line in many cases is interrupted by a solid phase equilibrium ( Fig.80 2.46 2.30 2.5 27.31 15.27 1.08 15.94 2. The contrary effect of rising temperature on vapor pressure and density often leads to the intersection of isotherms.21 1.26 0.4 30. The partition coefficients obtained ranged from 0. .82 2.1 43. 3.21 20.8 11.50 15.55 20.1 35.42 7.05 45.34 10. UV-Vis detectiona 8.72 1.

Partition coefficients of benzaldehyde at temperatures of 313. Additionally. 3. 3. 1. 3. the curvature of the isotherms is changed in a way that the partition coefficients of the mixtures show a slight maximum. The entrainment of the alcohols can be explained qualitatively by cosolubility phenomena. 4. Fig. Data for phenol.2. possessing higher Kvalues. 323 and 333 K and pressures from 8 to 30 MPa. and 2-hexanone. In the context of high pressure. Interpretation analogous to solid–fluid phase equilibria In the following.-D. These effects are presented in Table 2. solid–fluid phase equilibria. Partition coefficients of aniline at temperatures of 313. remains unchanged or is even retained in the aqueous solution. 2 Fig. Typical p. 2. a correlation is developed to describe the partitioning behavior in terms of enthalpy of hydration. Partitioning of mixtures In comparison with single solute measurements. 2-hexanone and benzaldehyde in a logarithmic scale are displayed in Fig. determination of the solute concentration by GC with SPME and UV/Vis-spectroscopy.112 K. 323 and 333 K and pressures from 8 to 30 MPa.3.T-projections of binary solute–CO systems containing liquids or solids of low volatility. Wagner et al. as discussed by Knopf [5] on the basis of binary solute–solute interactions and the relative volatilities of the single solutes. / Journal of Supercritical Fluids 15 (1999) 109–116 Fig. the enhance- . it was found that the alcoholic components with their lower single-solute partition coefficients are enhanced.

39 0.0 Cyclohexanol 8.20 4.2 15.5 25.S is the saturation molar fraction of i solute at pressure p.68 89.1 xCO2 (10−3) i 13.75 0.44 1. / Journal of Supercritical Fluids 15 (1999) 109–116 Table 2 Fluid phase concentrations and partition coefficients of a mixture containing phenol.4 20. the enhancement factor in the case of partitioning E∞.55 1. it is necessary to introduce a reference density r =700 kg m−3 [7].82 2.4 20.59 2.21 1.5 25.72 2.0 Phenol 8.82 0.49 17. benzyl alcohol.1 10.55 103.84 0.6 25. binary solid–fluid phase equilibria. the logarithm of E∞ can be related to a linear function of density r of the pure carbon dioxide [7]: ln(E∞)=a+br (4) 0. for which 1 Pa is used in the following ref calculations.6 25.85 3. Wagner et al.0 10. Just as in x high pressure.37 23.06 2. (3).5 30.13 4. cyclohexanol and 2-hexanone at 323 K p (MPa) 2-Hexanone 8.0 10.49 4.18 2.06 4.1 Benzyl alcohol 8.19 above an aqueous solution p at the same temperi ature: xCO p xCO p p E∞= i 2 = i 2 =K (3) xh p xH2Oh i i i i On the assumption of a dilute solution.18 2.83 2.16 3.27 101. 4. 2-hexanone and benzaldehyde in a multicomponent mixture (solid symbols) in comparison with single solute measurements (open symbols) at 323 K. xH2O is the molar i fraction of the solute in the aqueous phase and h i the Henry constant.95 0.5 30.69 15.49 1.3 20.86 3. Analogous to binary phase equilibria. ref This leads to the following equation: ln(K p/p )=[a+ln(h /p )+br ] x ref i ref ref +b(r−r )=A∞+b(r−r ) ref ref (5) .75 0.3 15.3 15.-D.45 3. 2.27 Fig.14 1. Partitioning of phenol.76 K x 113 94.3 20. is defined as the ratio of the partial vapor pressure of the solute in the supercritical phase to the partial vapor pressure of the solute with temperature dependent constants a and b. h is substituted in a first step by a reference n i pressure p . is the ratio of the partial vapor pressure of the solute in the supercritical phase to the vapor pressure of the pure solute p* at the n same temperature [6 ]: xCO .08 66. In a second step. With Eq.81 19.15 0. p can i be expressed by Henry’s law.15 3. As h of low volatile solutes is as seldom known as i p* .6 30.40 98.75 2.1 10. E.49 3.26 1.73 ment factor.6 30.83 0.67 19. (1b).S p (2) E= i 2 p* v where xCO2. the partition coefficient K is inserted into Eq.K.43 1.2 15.29 2.

51 kJ mol−1 [32].30±0.80 [9] [11] [13] [16 ] [19] 50±4 [15] 35±5 [17.42 49. c Calculated as the difference Dg H=Dg H−Daq H. b From solubility in carbon dioxide. / Journal of Supercritical Fluids 15 (1999) 109–116 Fig.10 ±0.21 [20] Dg H at 298 K aq Daq H l 1. Plot of ln(K p/p ) of phenol versus density ( p−p ) at x ref ref temperatures of 308. DH . The enthalpies of hydration.42c Daq H at 298 K l −10.13 [12] 0.50 [23] Dg H at 298 K s 89.94±0. The data points correlate adequately with this linear function down to values of (r−r )= ref −100 kg m−3.18] Dg Hb s 71±7 [21. DH .3±0. 6. Fig. of mixing and of phase transition for phenol and the Table 3 Enthalpy of hydration. The interpolation lines in Figs.22±0.4] is shown.5 [10] 1. respectively. Analogous to the enthalpy of sublimation or vaporization.70 kJ mol−1 [33] was extrapolated to 298.13c 53. 5.46d Daq H s Dg H at 298 K s 68.114 K. aq l l dCalculated as the difference Daq H=Daq H−Dl H=12.70 [30] Benzoic acid Vanillin Caffeine a From partition coefficients between water and carbon dioxide. the x ref values of A∞ are plotted versus 1/T. In Fig. From the slope of the resulting linear correlation. from hydr 2 2 sub/vap solubility in CO in comparison with literature data 2 Substance 2-Hexanone Cyclohexanone Aniline Benzyl alcohol Benzaldehyde Dg Ha aq 23±6 24±4 38±2 45±6 24±2 Dg Ha aq 35±2 Dg Ha aq 22±3 31±1 36±7 Dg H at 298 K aq 55. from partitioning between CO and H O and enthalpy of sublimation/vaporization.90 [27] 90. an enthalpy of hydration of 35±2 kJ mol−1 is obtained in the case of phenol.08 44. Wagner et al. 323 and 333 K. l s s eThe observed value Dg H=88. In Fig. 6.22] Dg Hb s 75±4 [24–26 ] 73 [28] 74±2 [29] Phenol Dg H at 298 K aq 56.-D. 5.16c 59.15 K using the ‘Sidgwick correction’ [34].89±0.88±0.03 60.54 [14] Dg Hb l Dg H at 298 K l 42.95±0. 2 and 3 were calculated using the corresponding linear correlations of ln(K p/p ).83±0.19±1.66± 0. a plot of A∞ versus 1/T should result in a linear function with a slope of −Dg H/R. s . Plot of A∞-values of phenol versus temperature.97 [31]-11. 313. with Dg H being the enthalpy of hydraaq aq tion [8].29±0.80±0.2e 105.63 55. 1/T. a plot of ln(K p/p ) versus (r−r ) x ref ref for the experimental data of phenol [1.75±0.

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