Journal of Supercritical Fluids 15 (1999) 109116

Partition coecients 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 coecient in this case is dened as the ratio of molar fractions of a substance in the carbon dioxide-rich phase and the aqueous phase in equilibrium. Partition coecients 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 uid phase, the other compounds were retained in the aqueous phase. Analogous to high pressure binary solid uid phase equilibria, an enhancement factor is introduced to describe partitioning equilibria. Dierences 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 coecient; 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 coecient partition coecient based on concentrations partition coecient 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 m3)

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

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1. Introduction For the proper design of a separation process, in which organic substances are to be removed from an aqueous solution by supercritical carbon dioxide, the relevant phase equilibria have to be known accurately. Phase equilibrium in context with countercurrent extraction is often characterized by partition coecients, K, describing the distribution of solutes between the two immiscible phases. In continuation of previous measurements of the partitioning behavior of monofunctional aromatic compounds [1], we now report on two further substances, aniline and benzaldehyde. In the experimental range studied here, the mutual miscibility of water and carbon dioxide is very limited. Due to the compressibility of the uid carbon dioxide phase, K is strongly dependent on temperature and pressure. In addition, the partitioning of a substance is aected by the presence of other solutes. Salts are especially likely to increase K [2], but other organics present in the solution can also inuence partition coecients. In this context, the partitioning behavior of an aqueous solution containing four organic compounds was investigated.

ous phase causes no problems, as the components to be determined remain in solution. In contrast, the sampling process in the uid phase causes the organic material to precipitate as the carbon dioxide expands. This material is completely washed into a sampling vial by water, and the samples are analyzed afterwards. In addition to single solute measurements, the distribution behavior of an aqueous solution of 1 wt.% phenol, 1 wt.% benzyl alcohol, 0.5 wt.% cyclohexanol and 3 wt.% 2-hexanone at 323 K was examined. The analysis was conducted by UV-spectroscopy in the case of aniline. SPME (solid phase micro extraction) and gas chromatography (GC ) were used to determine the composition of the mixture components. SPME as a pretreatment method allows the analysis of aqueous samples directly by GC. To check the agreement of both methods, benzaldehyde was measured independently in both ways ( Table 1).

3. Results and discussion The partition coecient is dened as the ratio of concentrations, c , Eq. (1a) or the ratio of molar i fractions, x , Eq. (1b) of the substance, i, in both i phases: cCO K= i 2 c cH O 2 i xCO K = i 2 x xH O 2 i (1a)

2. Experimental The measurement of the partition coecients in two-phase mixtures was performed using an analytical method with a recirculation view cell apparatus [1], which is placed in a liquid bath whose temperature is kept constant within 0.1 K. The high pressure cell is lled by half with an aqueous solution of the organic substances. At the required temperature, CO is compressed in the cell by a 2 pneumatic pump until the nal pressure is reached. The temperature is measured by a Pt-100 resistance thermometer in the wall of the cell, while pressure is measured in the autoclave by a pressure transducer equipped with a front membrane. The carbon dioxide phase is recirculated by a gear pump until equilibrium is attained. 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. Sampling the aque2

(1b)

While K is the direct result of the analysis, 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. 3.1. Partitioning of single solutes Distribution behavior is mainly determined by the solubility of the solute in the CO phase. 2 Regarding the binary solutecarbon dioxide systems with liquids of low volatility, often a type III phase diagram according to the classication of

K.-D. Wagner et al. / Journal of Supercritical Fluids 15 (1999) 109116 Table 1 Fluid phase concentrations and partition coecients of aniline and benzaldehyde 313 K p (MPa) Aniline 8.23 10.05 12.08 15.21 20.09 24.91 30.26 Benzaldehyde, 8.47 9.93 15.15 20.82 25.08 30.14 xCO2 (103) i 1.09 2.32 2.80 2.79 3.16 3.01 2.72 K x 323 K p (MPa) xCO2 (103) i 0.45 0.94 2.07 2.57 2.95 3.09 K x 0.21 1.29 1.90 2.03 2.46 2.84 333 K p (MPa) xCO2 (103) i 0.73 1.30 2.50 2.95 3.00 3.05 3.02 K

111

0.36 1.13 1.82 2.00 2.23 2.38 2.42

7.97 10.31 15.10 19.41 24.98 29.83

8.22 10.39 12.42 15.15 20.22 25.56 30.26

0.23 0.45 1.09 1.70 2.39 2.73 3.03

GC-SPME detectiona 6.5 7.5 15.5 27.6 14.1 43.6 12.0 47.0 13.1 55.3 11.6 62.2

10.50 15.31 19.81 25.37 30.36

10.4 11.7 10.8 11.5 12.3

17.7 33.4 40.5 49.6 46.5

10.65 15.55 20.71 25.09

10.3 10.7 12.7 23.2

9.8 25.1 35.6 40.7

Benzaldehyde, UV-Vis detectiona 8.07 1.43 5.6 10.13 1.29 29.9 12.11 1.12 36.4 15.72 1.05 45.9 20.13 0.96 51.4 25.41 0.92 56.4 30.26 0.84 62.9

8.34 10.53 12.56 15.41 20.71 25.65 30.43

0.43 0.85 0.98 0.99 1.01 1.04 1.06

3.2 13.5 23.9 33.2 40.2 43.8 46.9

8.17 10.02 12.18 15.14 20.04 24.74 29.93

0.38 1.30 1.50 1.27 1.03 0.95 0.88

2.5 5.2 14.1 25.7 33.8 40.6 45.0

a Molar fractions of benzaldehyde vary between both detection methods because of dierent initial concentrations.

van Konynenburg and Scott is found. If the solutes are solid, the critical line in many cases is interrupted by a solid phase equilibrium ( Fig. 1). Near the critical end points, the most pronounced changes in solubility occur [3]. As the critical end point (CE) and the lower critical end point (LCEP), respectively, usually is not far from the critical point of pure solvent (CP1), the strongest increase in the solubility, x, as well as in the partition coecient, K, is observed near the critical point of CO in most cases. The nearer the temper2 ature approaches to the critical end points, the more steep is the change in x and K. Similar to the density behavior of pure carbon dioxide, which determines the dissolving power of the solvent, the increase becomes smaller with rising pressure. With increasing temperature, leading to a higher vapor pressure of the solute, the solubility and the parti-

tion coecient increases at higher pressures. The contrary eect of rising temperature on vapor pressure and density often leads to the intersection of isotherms. Fig. 2 shows the experimental results of the distribution measurements with aniline at 313, 323 and 333 K [4]. The partition coecients obtained ranged from 0.21 and 3.03. The partitioning obeys a phase behavior as discussed above. In Fig. 3, the isotherms of benzaldehyde at the three temperatures are plotted versus pressure [4]. The partitioning coecient reaches values up to 62.9. Intersection of the isotherms, as observed commonly in other systems, was not determined in the experimental pressure range. The determination of the solute concentration by the two analytical methods show reasonably good agreement of GC with SPME and UV-spectroscopy.

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Fig. 1. Typical p,T-projections of binary soluteCO systems containing liquids or solids of low volatility. 2

Fig. 2. Partition coecients of aniline at temperatures of 313, 323 and 333 K and pressures from 8 to 30 MPa. Fig. 3. Partition coecients of benzaldehyde at temperatures of 313, 323 and 333 K and pressures from 8 to 30 MPa; determination of the solute concentration by GC with SPME and UV/Vis-spectroscopy.

3.2. Partitioning of mixtures In comparison with single solute measurements, it was found that the alcoholic components with their lower single-solute partition coecients are enhanced, and 2-hexanone, possessing higher Kvalues, remains unchanged or is even retained in the aqueous solution. Additionally, the curvature of the isotherms is changed in a way that the partition coecients of the mixtures show a slight maximum. These eects are presented in Table 2. Data for phenol, 2-hexanone and benzaldehyde in a logarithmic scale are displayed in Fig. 4. The entrainment of the alcohols can be explained qualitatively by cosolubility phenomena, as discussed

by Knopf [5] on the basis of binary solutesolute interactions and the relative volatilities of the single solutes. 3.3. Interpretation analogous to soliduid phase equilibria In the following, a correlation is developed to describe the partitioning behavior in terms of enthalpy of hydration. In the context of high pressure, soliduid phase equilibria, the enhance-

K.-D. Wagner et al. / Journal of Supercritical Fluids 15 (1999) 109116 Table 2 Fluid phase concentrations and partition coecients of a mixture containing phenol, benzyl alcohol, cyclohexanol and 2-hexanone at 323 K p (MPa) 2-Hexanone 8.0 10.2 15.3 20.5 25.5 30.0 Cyclohexanol 8.0 10.2 15.3 20.5 25.5 30.0 Phenol 8.1 10.3 15.4 20.6 25.6 30.1 Benzyl alcohol 8.1 10.3 15.4 20.6 25.6 30.1 xCO2 (103) i 13.67 19.37 23.81 19.69 15.49 17.76 K x

113

94.68 89.55 103.27 101.40 98.08 66.84

0.15 0.75 0.95 0.83 0.75 0.82

0.85 3.49 4.06 4.13 4.16 3.27

Fig. 4. Partitioning of phenol, 2-hexanone and benzaldehyde in a multicomponent mixture (solid symbols) in comparison with single solute measurements (open symbols) at 323 K.

2.45 3.20 4.15 3.86 3.49 3.59

2.06 2.18 2.83 2.82 2.75 2.19

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, p can i be expressed by Henrys law. xH2O is the molar i fraction of the solute in the aqueous phase and h i the Henry constant. With Eq. (1b), the partition coecient K is inserted into Eq. (3). Just as in x high pressure, binary soliduid 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)

0.14 1.21 1.55 1.49 1.43 1.39

0.26 1.72 2.18 2.29 2.44 1.73

ment factor, E, 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 ,S p (2) E= i 2 p* v where xCO2,S is the saturation molar fraction of i solute at pressure p. Analogous to binary phase equilibria, the enhancement factor in the case of partitioning E, is dened 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. As h of low volatile solutes is as seldom known as i p* , h is substituted in a rst step by a reference n i pressure p , for which 1 Pa is used in the following ref calculations. In a second step, it is necessary to introduce a reference density r =700 kg m3 [7]. ref This leads to the following equation: ln(K p/p )=[a+ln(h /p )+br ] x ref i ref ref +b(rr )=A+b(rr ) ref ref

(5)

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Fig. 6. Plot of A-values of phenol versus temperature, 1/T. Fig. 5. Plot of ln(K p/p ) of phenol versus density ( pp ) at x ref ref temperatures of 308, 313, 323 and 333 K.

Analogous to the enthalpy of sublimation or vaporization, respectively, a plot of A versus 1/T should result in a linear function with a slope of Dg H/R, with Dg H being the enthalpy of hydraaq aq tion [8]. In Fig. 5, a plot of ln(K p/p ) versus (rr ) x ref ref for the experimental data of phenol [1,4] is shown. The data points correlate adequately with this

linear function down to values of (rr )= ref 100 kg m3. The interpolation lines in Figs. 2 and 3 were calculated using the corresponding linear correlations of ln(K p/p ). In Fig. 6, the x ref values of A are plotted versus 1/T. From the slope of the resulting linear correlation, an enthalpy of hydration of 352 kJ mol1 is obtained in the case of phenol. The enthalpies of hydration, of mixing and of phase transition for phenol and the

Table 3 Enthalpy of hydration, DH , from partitioning between CO and H O and enthalpy of sublimation/vaporization, DH , 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 236 244 382 456 242 Dg Ha aq 352 Dg Ha aq 223 311 367 Dg H at 298 K aq 55.191.13c 53.950.16c 59.750.42c Daq H at 298 K l 10.30.5 [10] 1.880.13 [12] 0.54 [14] Dg Hb l Dg H at 298 K l 42.220.08 44.890.63 55.830.03 60.290.42 49.800.80 [9] [11] [13] [16 ] [19]

504 [15] 355 [17,18] Dg Hb s 717 [21,22] Dg Hb s 754 [2426 ] 73 [28] 742 [29]

Phenol

Dg H at 298 K aq 56.940.21 [20] Dg H at 298 K aq

Daq H l 1.46d Daq H s

Dg H at 298 K s 68.66 0.50 [23] Dg H at 298 K s 89.300.90 [27] 90.2e 105.10 0.70 [30]

Benzoic acid Vanillin Caeine

a From partition coecients between water and carbon dioxide. b From solubility in carbon dioxide. c Calculated as the difference Dg H=Dg HDaq H. aq l l dCalculated as the dierence Daq H=Daq HDl H=12.97 [31]-11.51 kJ mol1 [32]. l s s eThe observed value Dg H=88.70 kJ mol1 [33] was extrapolated to 298.15 K using the Sidgwick correction [34]. s

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115

other organic substances examined in Ref. [1] and this paper are shown in Table 3. The values of Dg H obtained from partitioning coecients in aq this way are compared with values from the literature. These values are calculated from the enthalpy of sublimation or vaporization minus the enthalpy of solution or mixing for each compound, respectively. The same comparison was done for the solubility data of the substances in carbon dioxide. For 2-hexanone, cyclohexanone, aniline, benzyl alcohol, benzaldehyde and phenol, the values of Dg H or Dg H, respectively, as well as of Dg H from s l aq the literature and from the experiments show the same relative order within the errors. For the investigated substances, the values for Dg H deters,l mined from solubility data lie signicantly below the values from the literature. This is obviously transferred to the values of Dg H from partition aq experiments, which lie below the literature data too. For substances of lower volatility, the determined Dg H-values show larger deviations from aq the literature or expected data. In the above discussion, eects of composition, association and temperature are not taken into account. While literature enthalpy data was measured at 298 K, the solubility data covers a dierent temperature range for each substance. As partition data, except for phenol, was measured at 313333 K, the resulting enthalpy of hydration refers to 323 K. Nevertheless, it is possible to obtain the same relative order of enthalpies from the partition experiments compared with the literature data. In addition, the introduced correlation of the partition coecients provides a simple method for interpolations in pressure and temperature.

correlated and discussed in terms of the enthalpy of hydration, resulting in an adequate agreement with data reported in the literature regarding the simplicity of the estimate.

References
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4. Conclusion In completion of previous results on single solute measurements, the partition coecients of aniline and benzaldehyde were determined. Regarding the multicomponent mixture of phenol, benzyl alcohol, cyclohexanol and 2-hexanone, it was found that K of the alcohols is increased possibly by x co-solubility of the 2-hexanone. The experimental results of the single solute measurements were

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