Fluid Phase Equilibria 194197 (2002) 701715

Modied solvation model for salt effect on vaporliquid equilibria

Hideaki Takamatsu, Shuzo Ohe
Department of Chemical Engineering, Graduated School of Engineering, Science University of Tokyo, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan Received 20 May 2001; accepted 29 October 2001

Abstract The prediction method had been presented for salt effect on vaporliquid equilibria by solvation model. This model assumes that salt effect is caused by solvation and solvated solvent molecular cannot contribute to vaporliquid equilibria. The model took into account the vapor pressure depression in mixed solvent. In this work, the solvation model was modied. The relation between solvation number in pure solvent + salt system and correlation error was conrmed. Solvation number was determined by using a new relation. As a result, the model was satisfactory applied for all binary solvents + salt systems. Furthermore, ternary solvents + salt system was predicted by using solvation number in pure solvent determined from binary solvents + salt system. Good accuracy was shown. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Salt effect; Solvation; Vaporliquid equilibria

1. Introduction It is well known that azeotropic mixture cannot be separated by ordinary distillation method and that some kinds of salt are signicantly effective to diminish the azeotrope. Therefore, investigators of both of academics and industries have studied salt effect on vaporliquid equlibria. The rst method for prediction of salt effect had been proposed by Johnson and Furter [1], which was semi-empirical equation. It is quite important to clarify the mechanism of this effect and to convince the method of correlation and prediction. Although, many investigations have been done for this eld, most of them are modication of conventional thermodynamic model for non-electrolyte component system such as activity coefcients model. These models combined extended non-electrolyte activity coefcients model and DebyeHckel term. The activity coefcients model term was used for describing short-range interaction by van der Waals force. DebyeHckel term was used for describing long-range interaction according to Coulomb force. For example, Tans equation using Wilson equation [2] for describing short-range interaction, electrolyte NRTL model [35] using NRTL equation, extended UNIQUAC [6,7] model and LIQUAC
Corresponding author. Tel.: +81-332604282; fax: +81-332673704. E-mail address: ohe@ms.kagu.sut.ac.jp (S. Ohe). 0378-3812/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 3 7 8 - 3 8 1 2 ( 0 1 ) 0 0 7 8 4 - 1

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model [8,9] using UNIQUAC equation, Kikic et al.s method [10] using UNIFAC equation, Achard et al.s method [11] using modied UNIFAC equation and Yan et al.s method [12] applying LIQUAC model to atomic group contribution method had been presented. However, most of the mixtures of the salt effect system are composed of non-electrolytes and electrolytes component. Thus, a model, which is capable of explaining contributions of these two different kinds of components, should be introduced. A solvation model had been presented. The alteration of vapor phase composition is thought to be caused by a formation of solvates between solvents and salt. The solvates are also thought to take a part for vapor pressure lowering of the system. A rst model in which a salt forms preferential solvate with one of the solvents in a binary solvent system was proposed to predict salt effect on vaporliquid equilibrium [13]. The model was successfully applied to correlate and express the salt effect for 386 binary solvents + 47 single-salt systems [14]. However, this rst model has a drawback that the vapor pressure lowering cannot express sufciently, since the lowering is observed over all the range of liquid composition of solvent. Based on the model, the lowering is zero at the end of composition of the solvent, which is not solvated and increased as the decrease of the component. Then, the modication of the model has been done to overcome this drawback. The model employed a solvation between salt of each of solvent in mixture instead of a preferential solvation. An alteration of vapor phase composition by salt effect thought to be caused by the difference of degree of solvations between solvents. This difference of degree is corresponds to the preferential salvation [15,16]. In this work, relation between solvation number and correlation error is examined. The relation is used to determinate solvation number. And the solvation numbers were used to predict salt effect on vapor liquid equilibria. 2. Lowering of vapor pressure Dissolved salt, which is non-volatile substance, lowers vapor pressure at a given temperature of a solvent. When the behavior of a single solvent and a salt system is assumed to be non-ideal and complete dissociation of salt, the pressure of the system is given by Eq. (1): = Psolvent asolvent . (1) Since the activity is a product of activity coefcient and mole fraction of solvents: asolvent = solvent xsolvent , then the activity coefcient for the pressure is determined from Eq. (1) as follows: solvent = . (2) (Psolvent xsolvent ) The model assumed salt showed complete disassociation. It is assumed that lowering of vapor pressure of pure solvent system is caused by solvated molecule, which does not contribute to vaporization. The activity of the solvent becomes (nsolvent nsalt )S0 asolvent = . (3) (nsolvent nsalt S0 ) + nsalt Dividing both of the denominator and numerator by nsolvent + nsalt will give (xsolvent xsalt )S0 asolvent = , (1 xsalt )S0 where xsolvent = 1 xsalt .

(4)

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Fig. 1. The xy curve for methanol + water + CaCl2 (4 mol%) at 101.3 kPa [17].

3. Effective composition of solvents system containing salt As the concentration of solvent is assumed to be decreased by the number of solvated molecules, the actual solvents composition participating in the vaporliquid equilibrium is changed. Assuming that a salt forms the solvates with each component and that the solvated molecules do not contribute to vaporliquid equilibria, the effective mole fraction xia for the ith solvent is given by Eq. (5) at salt free basis. Since, the sum of solvent mole fraction is equal to 1 xsalt , and the solvation number for the ith solvent is calculated as Si0 xi , and Eq. (5) is obtained. xia = xi (Si0 xi xsalt ) 1 xsalt Si0 xi xsalt (5)

Fig. 2. Solvation numbers for methanol + water + CaCl2 (4 mol%) at 101.3 kPa [17].

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The relation of solvation number Si between that of a singe solvent Si 0 and composition of it xi was recognized experimentally. The example for calculation of solvation number is shown in Figs. 1 and 2. From an experimental data shown in Fig. 1, effective mole fraction xia is able to be calculated from its numerical data. Calculated solvation numbers for each solvent are shown in Fig. 2. It is shown that relation between solvation number Si and the composition of solvent xi has linearity. The relation is caused by a molecular numbers of solvents per salt molecule changing according to stochiometry by changing liquid composition. Therefore, this is one of the strongest pieces of evidence in support of the solvation model. Furthermore, the relation has a physical meaning that solvation number Si depends upon solvent concentration at the condition of capable of making solvates of salt being constant at a given salt concentration in mole fraction, since the number of solvent molecule which can be solvated, increases by the number of itself. 4. Prediction of salt effect from solvation number In the case of mixed solvents system, lowering of vapor pressure may be treated in a similar manner. As total pressure of solvents system, Eq. (6) is given for non-ideal solution, which corresponds to Eq. (1) given for the pure solvent system. Psolvent = Pi i xia (6)

The activity coefcient for vapor pressure lowering is assumed to be average of activity coefcient of each solvent with its mole fraction. Eq. (7) may be derived from the above assumption. mix,solvent = i,solvent xi (7)

Therefore, the basic equation to calculate salt effect on vaporliquid equilibrium corresponds to Eq. (1) is Eq. (8). = Psolvent mix,solvent (1 xsalt ) (8)

Fig. 3. Activity coefcients for methanol + water + CaCl2 (4 mol%) at 101.3 kPa [17].

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Since Psolvent is determined from Eq. (6), substitution of Eq. (6) into Eq. (8) gives the relation = Pi i xia mix,solvent (1 xsalt ) (9)

The relation between activity coefcient of conventionally dened and that given by Eq. (9) is i = i mix,solvent (1 xsalt ) the activity coefcients of each solvent in binary solvents + salt system are shown in Fig. 3. 5. Relation between Sii 0 and correlation error Solvation number in pure solvent is very important factor in this model. The solvation number was used for calculation of liquid effective mole fraction and activity coefcient of vapor pressure depression in mixed solvent. Therefore, the less accurate of solvation number, the less accurate of the prediction. Then, in order to determine the solvation number more accurately, the relation between the solvation number and correlation error was investigated in binary solvents + salt system. The rst, the relation between the solvation number and average of absolute error in vapor phase was investigated. The change of error is shown in Fig. 4. As a result, minimum points of average of absolute error for vapor composition show linear relation between S10 and S20 . The relation is expressed by following equation: S10 = kS20 + S20,preferential (11) (10)

where k is a factor depends on system and S20,preferential is preferential solvation number of component 2.

Fig. 4. Error surface for methanol + water + CaCl2 (4 mol%) at 101.3 kPa [17].

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Fig. 5. Relation between solvation number and average of absolute deviation in boiling point for methanol + water + CaCl2 (4 mol%) at 101.3 kPa [17].

Next, behavior of average of absolute error for boiling point or total pressure was checked on the relation. The result was shown in Fig. 5. Minimum point of average of absolute error for temperature or total pressure shows on Eq. (11). In this work, the solvation numbers are the points that show minimum point of average of absolute error in boiling point or total pressure on Eq. (11). Fig. 6 shows ow chart for determination of solvation number of each solvent in a mixture from observed data.

Fig. 6. Flow sheet for determination of solvation number for each solvent in mixture.

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Fig. 7. Flow sheet for determination of salt effect on vaporliquid equilibria.

6. Procedure of prediction The procedure for predicting the salt effect from the solvation number Si 0 of pure solvent is described as follows. (a) Obtain solvation number Si 0 determined from procedure shown in Fig. 6. (b) The xia is calculated from Eq. (5) by using solvation number Si 0 . (c) Calculate activity coefcients: i for each component of solvent system by activity coefcient equation for example, Wilson equation with effective composition xia . In this work, Wilson equation was used and Wilson coefcients was obtained from Ohes vaporliquid equilibrium Data Book [18] and DECHEMAs vaporliquid equilibrium data collection [19,20]. (d) Estimate activity coefcients: mix,solvent , in Eq. (7), from i ,solvent of each pure solvent for lowering of vapor pressure of solvents system according to salt concentration. The i ,solvent is also determined using Si 0 with the relation of Eq. (4). (e) Predict vapor phase composition and boiling point or total pressure by Eq. (9). Fig. 7 shows ow chart of procedure of prediction.

7. Result and discussion The correlated results for isobaric and isothermal data with determined solvation number are shown in Tables 1 and 2, respectively. The Txy curve and xy curve are shown in Figs. 813. As for isobaric data, 81 data set for binary solvents + salt systems and as for isothermal data, 16 data set were correlated with satisfactory accuracy. As for isobaric system, average error for vapor phase composition calculated was 0.018 mole fraction and average error for boiling point calculated was 0.72 K. As isothermal system, average error for vapor

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Table 1 Correlative error of isobaric binary solvents + salt systems Number System Solvation numbera C1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 Methanol + water + CaCl2 (16.7 wt.%) at 101.3 kPa Methanol + water + CaCl2 (2 mol%) at 101.3 kPa Methanol + water + CaCl2 (4 mol%) at 101.3 kPa Methanol + water + CaCl2 (10 mol%) at 101.3 kPa Methanol + water + KCl (0.5 M) at 101.3 kPa Methanol + water + KCl (1 M) at 101.3 kPa Methanol + water + KCl (2 M) at 101.3 kPa Methanol + water + LiCl (1 M) at 101.3 kPa Methanol + water + LiCl (2 M) at 101.3 kPa Methanol + water + LiCl (4 M) at 101.3 kPa Methanol + water + NaBr (2 M) at 101.3 kPa Methanol + water + NaF (0.25 M) at 101.3 kPa Methanol + water + NaF (0.5 M) at 101.3 kPa Methanol + water + NaF (1 M) at 101.3 kPa Methanol + water + NaNO3 (5 mol%) at 101.3 kPa Methanol + water + NaNO3 (7 mol%) at 101.3 kPa Methanol + water + NaNO3 (8 mol%) at 101.3 kPa Ethanol + water + CaCl2 (16.7 wt.%) at 101.3 kPa Ethanol + water + CaNO3 (1.038 M) at 50.7 kPa Ethanol + water + CaNO3 (2.049 M) at 50.7 kPa Ethanol + water + CH3 COOK (2.5 mol%) at 101.3 kPa Ethanol + water + CH3 COOK (5 mol%) at 101.3 kPa Ethanol + water + CH3 COOK (6.6 mol%) at 101.3 kPa Ethanol + water + CH3 COOK (8.5 mol%) at 101.3 kPa Ethanol + water + NH4 Cl (6 mol%) at 101.3 kPa Ethanol + water + NH4 Cl (8 mol%) at 101.3 kPa 2-Propanol + water + CaCl2 (0.4 M) at 101.3 kPa 2-Propanol + water + CaCl2 (0.8 M) at 101.3 kPa 2-Propanol + water + CaCl2 (1.2 M) at 101.3 kPa 2-Propanol + water + CaCl2 (2.2 wt.%) at 101.3 kPa 2-Propanol + water + CaCl2 (4.3 wt.%) at 101.3 kPa 2-Propanol + water + CaNO3 (1.038 M) at 50.7 kPa 2-Propanol + water + CaNO3 (2.049 M) at 50.7 kPa 2-Propanol + water + NaCl (5 wt.%) at 101.3 kPa Methanol + ethanol + CaCl2 (16.7 wt.%) at 101.3 kPa Methanol + ethanol + CaCl2 (16.7 wt.%) at 101.3 kPa Methanol + ethanol + CaCl2 (23.1 wt.%) at 101.3 kPa 2-Propanol + 1-propanol + CaCl2 (10 wt.%) at 101.3 kPa 2-Propanol + 1-propanol + CaCl2 (13 wt.%) at 101.3 kPa 2-Propanol + 1-propanol + CaCl2 (16.7 wt.%) at 101.3 kPa Acetone + methanol + CaCl2 (5 wt.%) at 101.3 kPa Acetone + methanol + CaCl2 (10 wt.%) at 101.3 kPa Acetone + methanol + CaCl2 (20 wt.% at 101.3 kPa Acetone + methanol + KSCN (1 mol%) at 101.3 kPa Acetone + methanol + KSCN (2 mol%) at 101.3 kPa Acetone + methanol + KSCN (3 mol%) at 101.3 kPa 0.5407 0.5781 0.6284 0.6791 0.3197 0.0000 0.0000 0.0000 0.0000 0.0000 0.0515 0.2551 0.0000 0.0000 0.0000 0.5056 0.5419 0.0304 0.2784 0.1447 0.2991 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.5512 0.5201 0.6310 0.1950 0.0000 0.0000 0.2154 0.0000 0.0000 0.2208 0.1697 0.2419 C2 0.7002 0.6476 0.7703 0.8786 0.4346 0.1853 0.3176 0.0905 0.2611 0.2679 0.2194 0.2801 0.0837 0.1407 0.2936 0.7499 0.8037 0.6615 0.5013 0.5964 0.4937 0.4274 0.5614 0.6433 0.5099 0.6393 0.5162 0.7047 0.8121 0.3474 0.5243 0.5559 0.7583 0.2143 0.2607 0.3123 0.4128 0.2738 0.0751 0.0867 0.3979 0.3085 0.4354 0.2315 0.2169 0.3055 This work | y1 |av 0.009 0.008 0.006 0.015 0.013 0.020 0.026 0.025 0.019 0.029 0.019 0.027 0.016 0.013 0.026 0.010 0.016 0.012 0.024 0.023 0.008 0.018 0.015 0.015 0.014 0.017 0.014 0.013 0.005 0.008 0.009 0.024 0.046 0.015 0.016 0.006 0.010 0.019 0.025 0.016 0.009 0.009 0.018 0.012 0.016 0.019 | T |av (K) 0.46 0.70 0.56 1.35 0.34 0.48 0.89 1.46 0.80 4.49 0.71 0.72 0.59 0.60 0.66 0.29 0.28 0.70 0.31 0.48 0.34 0.44 1.00 1.53 0.31 1.47 0.44 1.11 2.36 0.23 0.44 0.54 2.15 1.08 0.27 0.30 0.31 0.41 1.28 0.40 0.28 0.28 1.37 0.39 0.29 0.22 [23] [17] [17] [17] [24] [24] [24] [25] [25] [25] [25] [25] [25] [25] [26] [26] [26] [23] [27] [27] [28] [28] [28] [28] [29] [29] [30] [30] [30] [31] [31] [27] [27] [32] [31] [33] [33] [23] [23] [23] [34] [34] [34] [35] [35] [35] Reference

H. Takamatsu, S. Ohe / Fluid Phase Equilibria 194197 (2002) 701715 Table 1 (Continued ) Number System Solvation numbera C1 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 Average
a

709

This work | y1 |av 0.023 0.026 0.021 0.021 0.034 0.012 0.012 0.011 0.006 0.009 0.016 0.017 0.020 0.024 0.026 0.034 0.033 0.037 0.041 0.028 0.020 0.029 0.020 0.023 0.005 0.012 0.022 0.014 0.014 0.018 0.021 0.014 0.014 0.018 0.021 0.018 | T |av (K) 0.21 0.23 0.38 0.42 6.49 0.48 0.42 0.36 0.31 0.57 0.23 0.21 0.17 0.17 0.15 0.35 0.51 0.55 0.69 0.21 0.21 0.28 0.69 2.60 0.23 0.65 2.36 0.14 0.21 0.27 0.35 0.14 0.20 0.26 0.35 0.72

Reference

C2 0.3438 0.4002 0.1234 0.2023 0.8148 0.2715 0.1356 0.2069 0.2723 0.3983 0.5721 0.5319 0.5148 0.5669 0.5898 0.5876 0.5828 0.5957 0.6193 0.4187 0.4209 0.4254 0.6496 0.6816 0.2949 0.0000 0.0000 0.7831 0.5758 0.3720 0.1800 0.7831 0.5766 0.3731 0.1800

Acetone + methanol + KSCN (4 mol%) at 101.3 kPa Acetone + methanol + KSCN (5 mol%) at 101.3 kPa Acetonev + methanol + LiCl (0.5 mol%) at 101.3 kPa Acetone + methanol + LiCl (2 mol%) at 101.3 kPa Acetone + methanol + LiCl (12 mol%) at 101.3 kPa Acetone + methanol + LiCl (0.5 mol%) at 101.3 kPa Acetone + methanol + LiCl (0.75 mol%) at 101.3 kPa Acetone + methanol + LiCl (1 mol%) at 101.3 kPa Acetone + methanol + LiCl (3 mol%) at 101.3 kPa Acetone + methanol + LiCl (5 mol%) at 101.3 kPa Acetone + methanol + NaI (1 mol%) at 101.3 kPa Acetone + methanol + NaI (1.5 mol%) at 101.3 kPa Acetone + methanol + NaI (2 mol%) at 101.3 kPa Acetone + methanol + NaI (3 mol%) at 101.3 kPa Acetone + methanol + NaI (4 mol%) at 101.3 kPa Acetone + methanol + NaI (5 mol%) at 101.3 kPa Acetone + methanol + NaI (6 mol%) at 101.3 kPa Acetone + methanol + NaI (7 mol%) at 101.3 kPa Acetone + methanol + NaI (8 mol%) at 101.3 kPa Acetone + methanol + ZnCl2 (1.082 M) at 101.3 kPa Acetone + methanol + ZnCl2 (1.502 M) at 101.3 kPa Acetone + methanol + ZnCl2 (1.751 M) at 101.3 kPa Acetone + water + KCl (1 mol%) at 101.3 kPa Acetone + water + KCl (2.5 mol%) at 101.3 kPa Methanol + ethyl acetate + CaCl2 (5 wt.%) at 101.3 kPa Methanol + ethyl acetate + CaCl2 (10 wt.%) at 101.3 kPa Methanol + ethyl acetate + CaCl2 (20 wt.%) at 101.3 kPa Methanol + THF + CuCl2 (1 mol%) at 101.3 kPa Methanol + THF + CuCl2 (2 mol%) at 101.3 kPa Methanol + THF + CuCl2 (3 mol%) at 101.3 kPa Methanol + THF + CuCl2 (4 mol%) at 101.3 kPa Methanol + THF + LiCl (1 mol%) at 101.3 kPa Methanol + THF + LiCl (2 mol%) at 101.3 kPa Methanol + THF + LiCl (3 mol%) at 101.3 kPa Methanol + THF + LiCl (4 mol%) at 101.3 kPa S10 : C1 (1 x3 )/x3 ; S20 : C2 (1 x3 )/x3 .

0.2684 0.3179 0.0000 0.0000 0.0000 0.2086 0.0171 0.0599 0.0000 0.0000 0.5031 0.4099 0.3571 0.3699 0.3737 0.3610 0.3518 0.3531 0.3806 0.1650 0.1374 0.0307 0.0000 0.0000 0.5224 0.5134 0.6519 0.8111 0.6481 0.5038 0.3914 0.8111 0.6516 0.5110 0.3914

[35] [35] [36] [36] [36] [21] [21] [21] [21] [21] [37] [37] [37] [37] [37] [37] [37] [37] [37] [38] [38] [38] [39] [39] [40] [40] [40] [22] [22] [22] [22] [22] [22] [22] [22]

phase composition calculated was 0.009 mole fraction and average error for total pressure calculated was 0.14 kPa. As shown in Tables 1 and 2, in most of the systems containing non-polar solvent, preferential solvation was observed. For example, acetone + methanol + CaCl2 (Nos. 42, 43) performed preferential solvation. To examine the applicability of modied model for prediction for multi solvents system with a salt, the salt effect of the methanol + ethanol + water + CaCl2 (16.7 wt.%) system at 101.3 kPa with 38

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Table 2 Correlative error of isothermal binary solvents + salt systems Number System Solvation numbera C1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Average
a

This work | y1 |av 0.006 0.006 0.006 0.005 0.028 0.014 0.014 0.007 0.004 0.003 0.012 0.010 0.012 0.003 0.002 0.002 0.009 | TP|av (kPa) 0.03 0.15 0.16 1.10 0.36 0.16 0.11 0.07 0.11 0.29 0.09 0.04 0.11 0.12 0.12 0.11 0.14

Reference

C2 0.6853 0.8542 0.7731 0.8953 0.5629 0.7586 0.8454 0.0000 0.2727 0.0000 0.4994 0.4827 0.5938 0.1213 0.2058 0.2716

Ethanol + water + CaCl2 (5 wt.%) at 298.15 K Ethanol + water + CaCl2 (10 wt.%) at 298.15 K Ethanol + water + CaCl2 (15 wt.%) at 298.15 K Ethanol + water + LiCl (4 M) at 298.15 K 1-Propanol + water + CaCl2 (5 wt.%) at 298.15 K 1-Propanol + water + CaCl2 (7 wt.%) at 298.15 K 1-Propanol + water + CaCl2 (10 wt.%) at 298.15 K Methanol + ethanol + CaCl2 (10 wt.%) at 298.15 K Methanol + ethanol + CaCl2 (15 wt.%) at 298.15 K Methanol + ethanol + CaCl2 (5 wt.%) at 298.15 K Methanol + 1-propanol + CaCl2 (10 wt.%) at 298.15 K Methanol + 1-propanol + CaCl2 (15 wt.%) at 298.15 K Methanol + 1-propanol + CaCl2 (5 wt.%) at 298.15 K 2-Propanol + 1-propanol + CaCl2 (5 wt.%) at 298.15 K 2-Propanol + 1-propanol + CaCl2 (10 wt.%) at 298.15 K 2-Propanol + 1-propanol + CaCl2 (15 wt.%) at 298.15 K S10 : C1 (1 x3 )/x3 ; S20 : C2 (1 x3 )/x3 .

0.4640 0.6168 0.1132 0.6966 0.0000 0.0000 0.0000 0.1817 0.4637 0.1241 0.6364 0.6719 0.6593 0.0000 0.0000 0.0000

[41] [41] [41] [42] [43] [43] [43] [41] [41] [41] [41] [41] [41] [44] [44] [44]

Fig. 8. The xy curve for methanol + water + CaCl2 (10 mol%) at 101.3 kPa [17].

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Fig. 9. The Txy curve for methanol + water + CaCl2 (10 mol%) at 101.3 kPa [17].

data sets was estimated by solvation number in pure solvent + salt system determined from binary solvent + salt system. Systems used for determination of solvation number of each solvent in ternary system are No. 1 of Table 1 for methanol and water, and No. 35 for ethanol, respectively. Values of C for prediction are methanol (0.5407), ethanol (0.2607) and water (0.7002), respectively. The results are shown in Figs. 14 and 15. Fig. 14 shows the predicted result of bubble point of the system with average absolute deviation 0.85 K. Fig. 15 shows the predicted result of vapor composition of the system in mole fraction with average absolute deviation 0.021 for methanol and 0.020 for ethanol, respectively.

Fig. 10. The xy curve for acetone + methanol + LiCl (5 mol%) at 101.3 kPa [21].

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Fig. 11. The Txy curve for acetone + methanol + LiCl (5 mol%) at 101.3 kPa [21].

Fig. 12. The xy curve for methanol + THF + LiCl (1 mol%) at 101.3 kPa [22].

Fig. 13. The Txy curve for methanol + THF + LiCl (1 mol%) at 101.3 kPa [22].

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Fig. 14. Comparison between observed data and predicted data (bubbling point) for methanol + ethanol + water + CaCl2 at 101.3 kPa [45].

Fig. 15. Predicted vapor compositions for methanol + ethanol + water + CaCl2 (16.7 wt.%) at 101.3 kPa [45]; ( ), liquid composition; ( ), predicted vapor composition; ( ), observed vapor composition.

8. Conclusion The modied model of Ohe et al. has been proposed for representing salt effect on vaporliquid equilibria. In this work, a relation between solvation number in pure solvent + salt system and correlation

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error were examined and from this relation, solvation number was determined. It was satisfactory to represent salt effect on vaporliquid equilibria by using the modied model. And ternary solvents + salt system was predicted by using solvation number determined from binary solvents + salt system. Good accuracy was shown in the system. The modied model based on solvation between each solvent and salt to predict and to analyze salt effect on vaporliquid equilibria was proposed and successfully applied to the binary and ternary solvents systems with salt. List of symbols asolvent activity for lowering of vapor pressure of pure solvent system ci constant for solvation number k coefcient in Eq. (11) nsalt mole number of salt nsolvent mole number of solvent P total pressure of system (kPa) Psolvent total pressure of system as solvent system (kPa) Pi vapor pressure of pure component i (kPa) S0 solvation number between solvent and salt Si 0 solvation number of salt with pure component of mixed solvent system xi mole fraction of ith solvent existing salt xi mole fraction of ith solvent at salt free basis xia effective mole fraction of ith solvent at salt free basis xsalt mole fraction of salt xsolvent mole fraction of solvent Greek symbols i activity coefcient of conventionally dened i activity coefcient for effective mole fraction of ith solvent i ,solvent activity coefcient for lowering of vapor pressure of ith solvent mix,solvent activity coefcient for lowering of vapor pressure of mixed solvent system Subscript i References
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