Fructose Solubility in Mixed (Ethanol + Water) Solvent: Experimental

Fructose (1,3,4,5,6-pentahydroxyhex-2-one) is an important sugar, of great industrial interest, and may be produced by crystallization from its aqueou...
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Fructose Solubility in Mixed (Ethanol + Water) Solvent: Experimental Data and Comparison among Different Thermodynamic Models Carlos E. Crestani, André Bernardo, Caliane B. B. Costa, and Marco Giulietti* Department of Chemical Engineering, Federal University of São Carlos (UFSCar), Rod. Washington Luiz, km 235, São Carlos, SP, Brazil ABSTRACT: Fructose (1,3,4,5,6-pentahydroxyhex-2-one) is an important sugar, of great industrial interest, and may be produced by crystallization from its aqueous solution by adding ethanol as antisolvent. Published data of fructose solubility in mixed (ethanol + water) solvent are scarce in literature, but these data are essential for crystallization studies. In this work, fructose solubility in different ethanol concentrations was determined in temperatures from (283.15 to 333.15) K. A group of activity coefficient models developed in literature to determine phase diagrams of sugars were then selected and evaluated to predict fructose solubility in water and (ethanol + water) solvent. The following models were tested: a modified UNIQUAC, Bio-UNIFAC, A-UNIFAC, and mS-UNIFAC. Bio-UNIFAC was the best model to predict fructose solubility in water and in solutions with ethanol mass fractions in solvent up to 0.4; mS-UNIFAC was the best model for 0.4 to 0.6, and over this ethanol concentration the modified UNIQUAC was the best one. The mean deviation of the best model for pure water as solvent was 0.43 %, and for mixed solvent the mean deviation of the best model of each composition was always lower than 4 %.

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INTRODUCTION Fructose (C6H12O6), IUPAC name 1,3,4,5,6-pentahydroxyhex2-one, is an important sugar, a component of fruit and vegetables, and has great industrial interest. Among the advantages of fructose, when compared to other sugars, is its larger sweetening power and its use in diabetic diets, since no insulin is needed during its metabolism. On the other hand, fructose is highly soluble in water and it has a large metastable zone width (sometimes larger than 30 K), producing highly viscous solutions and affecting the yields of production processes. Fructose crystallization may occur by adding ethanol to an aqueous fructose solution, which decreases fructose solubility making the crystallization process feasible. The study of fructose solid−liquid equilibrium (SLE) in mixed (ethanol + water) solvent is, therefore, of great importance for the crystallization process. The (fructose + water) phase diagram1 is well-known, but solubility data of sugars in alcoholic solvents are limited. Ternary (fructose + ethanol + water) SLE was determined2−4 for only some temperature values and solvent compositions. However, there are published data of fructose crystallization by the addition of ethanol as an antisolvent,5−7 and there are suitable crystallization processes described in patents.8−10 Because of the limited published data of sugar solubility in solvents containing alcohols, some thermodynamic activity coefficient-based methods for sugar systems have been proposed since the 1990s. Thermodynamic models may be used in calculations of bioreactors and separation processes such as crystallization, evaporation, extraction, etc. The thermodynamic modeling of sugar solutions is a complex © 2013 American Chemical Society

work, because of the behavior of the solution, whether by its tautomeric chemical equilibrium6 or by the associative forces generated by hydroxyls in a solution.11 Fructose in solution may be in acyclic or different cyclic forms, but there is only one tautomer in solid form, the β-pyranof ructose. The conformational equilibrium depends on temperature and, for mixed solvents, it depends also on solvent concentration. Table 1 shows equilibrium compositions of fructose in aqueous− ethanolic solutions.6 In these solutions, the most representative tautomer is β-furanof ructose while for aqueous solution, at 303.15 K for example, the mass fraction of β-pyranof ructose in relation with total fructose in solution is higher than 0.70.12 Larsen et al.13 proposed a modification in the combinatorial contribution of the UNIQUAC model. Nonpredictive methods need experimental data in order to estimate the respective parameters. Peres and Macedo14 used experimental data to estimate the interaction parameters of this modified UNIQUAC, hereafter referred as P&M-UNIQUAC. When no experimental data are available, predictive methods can be alternatively used. Specifically for sugar solutions, there are models in literature based on both traditional15,16 and modified11,17−19 UNIFAC, differing each other in the way the sugar molecule is decomposed in functional groups. In general, for sugars, new functional groups are included to represent their complex behavior in solution. Their molecules are not completely dissociated because of the vicinity of functional Received: May 15, 2013 Accepted: September 18, 2013 Published: October 28, 2013 3039

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Table 1. Equilibrium Composition of Fructose in Aqueous− Ethanolic Solutions at Different Ethanol:Water (E:W) Relation in Mass. xTF Is the Mass Fraction of the Tautomer in Relation to Total Fructose6

ln(xsugysug ) = − +

xTF E:W

T/K

β-pyr

β-fur

α-fur

3:1

297.15 303.15 313.15 323.15 297.15 303.15 313.15 323.15 297.15 303.15 313.15 323.15

0.40 0.39 0.40 0.39 0.46 0.39 0.35 0.38 0.38 0.38 0.34 0.39

0.50 0.55 0.53 0.49 0.46 0.55 0.59 0.50 0.57 0.56 0.60 0.48

0.10 0.06 0.07 0.12 0.08 0.06 0.06 0.12 0.05 0.06 0.06 0.13

6:1

9:1

ΔHfus ⎛ T ⎞ ΔCp ⎛ Tm − T ⎞ ⎜ ⎟ ⎟+ ⎜1 − RT ⎝ Tm ⎠ R ⎝ T ⎠ ΔCp ⎛ T ⎞ ln⎜ ⎟ R ⎝ Tm ⎠

(1)

In this equation, xsug is the sugar solubility at the solution temperature (T) expressed in molar fraction; γsug is the activity coefficient of sugar in solution calculated by the thermodynamic model; ΔHfus is the melting enthalpy at the normal melting temperature (Tm) and ΔCp is the difference between the heat capacity of pure solvent and solid sugar and is assumed to be not dependent on temperature. Physical properties at normal pressure are presented in Table 2. Table 2. Physical Properties

groups. Group interaction is important to represent the interaction of the whole molecule in solution, and the inclusion of new functional groups allows for differentiating isomers such as fructose and glucose ((2S,3R,4S,5S)-2,3,4,5,6-pentahydroxyhexanal). Abed et al.,15 Catté et al.,17 Kuramochi et al.19, and Spiliotis and Tassios16 are examples of authors who introduced new decomposition groups to represent sugar molecules. Ferreira et al.11 proposed a method called A-UNIFAC, which uses the interaction groups introduced by Catté et al.,17 adding the associative contribution to the traditional UNIFAC model, a contribution related to the interaction forces of hydroxyl groups in solution. Some of the methods from literature were not tested at the conditions of the present work. For example, some methods used experimental data from only aqueous solutions of sugars in their development.15,17,19 The use of these calculation models in alcoholic solutions should be evaluated because of the interaction of hydroxyls, which may affect the accuracy of predictions. Fructose solubility data from literature are conflicting and, in some temperature ranges and solvent composition, scarce. With the aim to reduce these conflicts, new experimental data of fructose solubility in water and in different compositions of mixed (ethanol + water) solvent in a temperature range from (298.15 to 333.15) K are presented in this work. These data are then compared to previously published experimental data and are used to compare the quality of the predictions of the thermodynamic models. Four models from literature were chosen, the here called P&M-UNIQUAC 14 and three predictive models: the one proposed by Kuramochi et al.19 (Bio-UNIFAC); A-UNIFAC, proposed by Ferreira et al.,11 and the so-called mS-UNIFAC, a modification proposed by Tsavas et al.20 for S-UNIFAC, created by Spiliotis and Tassios.16 Solid−Liquid Equilibrium Calculations. The models used to describe SLE are based on the activity coefficients, and the expression used to calculate the solubility of anhydrous fructose in both water and mixed (ethanol + water) is given by eq 1:21

property

value

ref

ΔHfus,fructose/J·mol−1 ΔTm,fructose/K CSp,fructose/J·mol−1·K−1 Cp,ethanol/J·mol−1·K−1 Cp,water/J·mol−1·K−1

26030 378.15 232 108.56 75.24

22 22 22 23 23

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EXPERIMENTAL SECTION Chemicals. Deionized water produced by a Millipore Elix 10 water purification system, commercial solid fructose (1,3,4,5,6-pentahydroxyhex-2-one) P.A. (Synth), mass fraction purity of 0.9949 and anhydrous ethanol (Quemis) with 0.994 of mass fraction purity were used in experiments without additional purification steps as Table 3 shows. Experimental Procedure. First, the refractive index at 338.15 K was measured for different fructose solution concentrations (both for water and different ratios of (ethanol + water) as solvents), in order to obtain a correlation between this property and the solution composition. Refractive indices obtained for different fructose solution concentrations are presented in Table 4. Second, fructose dissolution time on the solutions was determined. Solutions were prepared with the addition of excess of fructose, and the refractive index was measured periodically in a 72 h period. The objective of these experiments is to determine the time in which fructose concentration does not vary anymore or slightly varies. The method used to determine fructose solubility in water and in mixed (ethanol + water) solvent is based on the one proposed by Myerson.21 A solvent solution was prepared and added to a jacketed glass reactor at the experiment temperature. Based on literature data, a mass of fructose corresponding to 150 % of the one expected to solubilize at the conditions of temperature and solvent concentration for each experiment was added to the reactor. The maximal dissolution period, observed on the second step of this experimental procedure, was about 12 h for the most viscous solutions. Because of this, the solutions were maintained at constant stirring at the experiment temperature for 24 h, to guarantee the complete dissolution of fructose up to the concentration corresponding to it is solubility. After 24 h, a sample was taken out of the reactor and centrifuged. From the supernatant, 2 mL was taken, diluted with a solution with the same solvent composition, and heated to 338.15 K. Refractive index was then measured at this 3040

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Table 3. Sample Table chemical name

source

initial mass fraction purity

purification method

0.999 0.994 0.9949

none none none

a

deionized water ethanol fructose (1,3,4,5,6-pentahydroxyhex-2-one)

Quemis Synth

final mass fraction purity

analysis method

a Deionized water type 2 with TOC < 30 ppb, conductivity < 0.2 μS·cm‑1 and resistivity (5 to 15) MΩcm, produced by Millipore Elix 10 water purification system.

were measured with a thermometer with an uncertainty of 0.1 K.

Table 4. Mean Values of Refractive Index (RI) at 98 kPa and Temperature T of 338.15 K of Fructose Solutions in (Water + Ethanol) Solvent at Different Fructose Mass Fraction xF and Ethanol Mass Fraction in Solvent xES. δ Stands for the Relative Average Deviationa xES

xF

RI

δ/%

0.0

0.0000 0.2189 0.3592 0.4567 0.5286 0.5759 0.5790 0.5836 0.0000 0.1774 0.3013 0.3929 0.4632 0.5190 0.5760 0.0000 0.2448 0.3272 0.3934 0.4476 0.4976 0.0000 0.1151 0.2065 0.2807 0.3422 0.3941 0.4446 0.0000 0.0815 0.1509 0.2105 0.2621 0.3075 0.3477

1.3230 1.3687 1.3945 1.4159 1.4339 1.4393 1.4413 1.4428 1.3363 1.3686 1.3874 1.4045 1.4217 1.4341 1.4427 1.3415 1.3839 1.3957 1.4059 1.4162 1.4262 1.3569 1.3675 1.3792 1.3874 1.3961 1.4035 1.4078 1.3587 1.3667 1.3747 1.3819 1.3892 1.3957 1.4021

0.00 0.01 0.00 0.01 0.27 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.08 0.00 0.00 0.02 0.01 0.01 0.02 0.01 0.00 0.03 0.02 0.00 0.03 0.00 0.01 0.01 0.01 0.02 0.01 0.00 0.01

0.2

0.4

0.6

0.9

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RESULTS AND DISCUSSION Experimental Results. Table 5 shows fructose average experimental solubility in different solvent compositions for temperature values between 298.15 K and 333.15 K and the relative average deviation (δ). In general, deviation is higher in solutions with low ethanol concentration and lower temperatures. High concentrate fructose solutions are extremely viscous, and this type of solution may generate experimental problems in taking samples or in the centrifugation step which could justify the higher deviations. In higher temperatures and ethanol concentrations the viscosity of solution is lower turning this source of error less important. Another source of error that one can cite is in centrifugation. During this operation temperature could decrease which could cause some crystallization in solution before taking out the liquid phase of the sample. This error would be more evident in higher temperatures, but as Table 5 shows errors are not higher at higher temperature values, turning this source of error less important. Finally, the dilution procedure could be cited as an error source together with the higher viscosity of the solution. Fructose average solubility experimental data with its absolute deviation are also presented in Figures 1 to 5 together with published data.1−4,15,24,25 In some charts deviation bars cannot be seen because of its small value. To have a full perspective of the decrease of fructose solubility with the increase of ethanol concentration in solution, Figure 6 was plotted with the mean experimental solubility obtained in this work. Flood et al.2 has already showed that the addition of ethanol significantly reduces the fructose solubility, principally above 0.7. A similar behavior has been observed for sucrose ((2R,3R,4S,5S,6R)-2-[(2S,3S,4S,5R)-3,4-dihydroxy-2,5bis(hydroxymethyl)oxolan-2-yl]oxy-6-(hydroxymethyl)oxane3,4,5-triol),26 glucose ((2S,3R,4S,5S)-2,3,4,5,6-pentahydroxyhexanal),27 xylose ((2R,3S,4R)-2,3,4,5-tetrahydroxypentanal) and mannose ((2S,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal)28 solubility. Thermodynamic Models Comparison. Figures 7 to 11 show experimental solubility data of fructose in different solutions containing (water + ethanol) and calculated data from the models P&M-UNIQUAC, Bio-UNIFAC, A-UNIFAC, and mS-UNIFAC. Figure 7 shows the prediction of fructose solubility in pure water compared with experimental data from (269.3 to 343.15) K. In Figures 8 and 9 the prediction is compared to experimental data obtained by this work from (298.15 to 333.15) K because there are no solubility data out of this range of temperatures in literature. In Figures 10 and 11 experimental data from (273.15 to 333.15) K are used to evaluate the accuracy of the four activity coefficient models predictions. The average absolute deviations (AAD) between experimental solubility data and calculated data from the

a

Uncertainties u are u(xES) = 0.002, u(T) = 0.1 K, u(xF) = 0.002, and u(RI) = 0.0001.

temperature. With the correlation between the refractive index and the solution concentration at 338.15 K obtained beforehand (Table 4), the solution concentration was determined and so the solubility value could be obtained by correcting this value with the dilution made. The procedure was repeated at least three times for each pair of temperature and solvent composition in the following sets: temperatures of 298.15 K, 303.15 K, 313.15 K, 323.15 K and 333.15 K and ethanol mass fractions in solvent of 0, 0.2, 0.4, 0.6, and 0.9. All temperatures 3041

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Table 5. Average of Experimental Fructose Solubility (Fructose Mass Fraction xF) at 98 kPa in Mixed (Ethanol + Water) Solvent at Different Ethanol Mass Fraction in Solvent xES, Temperatures T, and the Relative Average Deviation, δa T = 298.15 K

a

T = 303.15 K

T = 313.15 K

T = 323.15 K

T = 333.15 K

xES

xF

δ/%

xF

δ/%

xF

δ/%

xF

δ/%

xF

δ/%

0.0 0.2 0.4 0.6 0.9

0.799 0.768 0.726 0.612 0.097

2.39 1.54 0.96 0.93 0.42

0.816 0.784 0.744 0.645 0.134

1.52 1.45 0.71 0.01 1.09

0.842 0.821 0.788 0.712 0.209

1.97 1.79 1.11 0.80 1.21

0.866 0.867 0.844 0.812 0.314

0.47 0.16 2.12 1.43 1.42

0.896 0.901 0.899 0.874 0.532

1.55 1.80 0.57 0.98 0.08

Uncertainties u are u(T) = 0.1 K, u(xES) = 0.002, u(xF) = 0.002.

Figure 1. Fructose solubility in pure water expressed as fructose mass fraction xF as a function of temperature T: ◆, this work experimental data; ×, Abed et al.;15 ○, Macedo and Peres;3 □, Silva;24 △, Watanabe;25 +, Young et al.1

Figure 3. Fructose solubility in (ethanol + water) solvent with ethanol mass fraction in solvent xES of 0.4. Solubility expressed as fructose mass fraction xF as a function of temperature T: ◆, this work experimental data; ○, Macedo and Peres;3 □, Silva.24

Figure 2. Fructose solubility in (ethanol + water) solvent with ethanol mass fraction in solvent xES of 0.2. Solubility expressed as fructose mass fraction xF as a function of temperature T: ◆, this work experimental data; ○, Macedo and Peres;3 □, Silva.24

Figure 4. Fructose solubility in (ethanol + water) solvent with ethanol mass fraction in solvent xES of 0.6. Solubility expressed as fructose mass fraction xF as a function of temperature T: ◆, this work experimental data; ▲, Flood et al.;2 ●, Gong et al.;4 ○, Macedo and Peres;3 □, Silva.24

models P&M-UNIQUAC, Bio-UNIFAC, A-UNIFAC, and mSUNIFAC are presented in Table 6. The P&M-UNIQUAC14 model was developed using experimental data between 298.15 K and 333.15 K and is here evaluated in some cases out of this range, as a predictive calculation. Figures 7 to 11 show a comparison of this model with experimental data with average absolute deviations (AAD) lower than 4 % in most of cases, with the exception of the solution with ethanol mass fraction in solvent of 0.6 (Figure

10). In this case, at temperature values lower than 313.15 K the predictions are not reliable. For values lower than 293.15 K the absolute deviation values are higher than 10% resulting in an average of 8.59 % for this ethanol concentration. On the other hand, in Figure 11, at temperatures higher than 323.15 K the P&M-UNIQUAC14 model closely predicted the experimental 3042

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Figure 5. Fructose solubility in (ethanol + water) solvent with ethanol mass fraction in solvent xES of 0.9. Solubility expressed as fructose mass fraction xF as a function of temperature T: ◆, this work experimental data; ▲, Flood et al.;2 ●, Gong et al.;4 ○, Macedo and Peres;3 □, Silva.24

Figure 7. Fructose solubility in pure water expressed as fructose mass fraction xF as a function of temperature T. Comparison among experimental data and different thermodynamic models: ◆, this work experimental data; ×, Abed et al.;15 +, Young et al.;1 -·-·-·, P&MUNIQUAC; ···, Bio-UNIFAC; blue ---, A-UNIFAC; green ---, mSUNIFAC.

Figure 6. Fructose solubility expressed as fructose mass fraction xF at different ethanol mass fraction in solvent xES. Experimental data of this work at ◆, 298.15 K; ■, 303.15 K; ▲, 313.15 K; ×, 323.15 K; and ●, 333.15 K.

Figure 8. Fructose solubility in mixed (ethanol + water) solvent with ethanol mass fraction in solvent xES of 0.2. Solubility is expressed as fructose mass fraction xF as a function of temperature T. Comparison among experimental data and different thermodynamic models: ◆, this work experimental data; -·-·-·, P&M-UNIQUAC; ···, BioUNIFAC; blue ---, A-UNIFAC; green ---, mS-UNIFAC

behavior of solubility data, and was the only model able to do that. The Bio-UNIFAC19 model was developed using experimental data with only pure water as solvent. The model exhibited the best results of fructose solubility in pure water with the lowest AAD among all models. Also for solutions with an ethanol mass fraction in solvent up to 0.4, this model exhibited the lowest AAD, although the more concentrated in ethanol the solvent is, the less reliable the model becomes. The AAD of the A-UNIFAC11 model is higher than 3% only in solutions with ethanol mass fraction in sugar-free basis of 0.9, for which it assumes a high value (21.47%). The fructose molecule in solution is considered by the authors of AUNIFAC to be in the form of β-pyranof ructose, while in aqueous−ethanolic solutions Table 1 shows that the most representative tautomer is the β-f uranof ructose.6 Besides, because of the absent of fructose experimental data, the

number of associating hydroxyls was approximated to that of glucose. As a result, the predictions of the model were not reliable in ethanol highly concentrated solvents. Finally, the mS-UNIFAC20 model exhibited, for almost all solvent compositions and temperature ranges investigated, absolute deviations lower than 6 %, the AAD being lower than 3 % until ethanol mass fraction in solvent of 0.6. The exception is in solutions with ethanol mass fraction in solvent of 0.9 for temperatures higher or equal to 323.15 K in which absolute deviations are 9.90 % at 323.15 K and 27.94 % at 333.15 K, despite the average of 5.55 % for this ethanol concentration. Figure 11 shows this deviation and also that at this ethanol concentration and temperature range only the PM-UNIQUAC model was able to predict experimental behavior of the solubility, as already stressed. 3043

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Figure 9. Fructose solubility in mixed (ethanol + water) solvent with ethanol mass fraction in solvent xES of 0.4. Solubility expressed as fructose mass fraction xF as a function of temperature T. Comparison among experimental data and different thermodynamic models: ◆, this work experimental data; -·-·-·, P&M-UNIQUAC; ···, BioUNIFAC; blue ---, A-UNIFAC; green ---, mS-UNIFAC.

Figure 11. Fructose solubility in mixed (ethanol + water) solvent with ethanol mass fraction in solvent xES of 0.9. Solubility expressed as fructose mass fraction xF as a function of temperature T. Comparison among experimental data and different thermodynamic models: ◆, this work experimental data; ●, Gong et al.;4 -·-·-·, P&M-UNIQUAC; ···, Bio-UNIFAC; blue ---, A-UNIFAC; green ---, mS-UNIFAC.

Table 6. AAD (Average Absolute Deviations) of Thermodynamic Models Compared to Experimental Data at Different Ethanol Mass Fraction in Solvent xESb AAD/%

b

xES

P&M-UNIQUAC

Bio-UNIFAC

A-UNIFAC

mS-UNIFAC

0.0 0.2 0.4 0.6 0.9

2.26 3.44 3.16 8.59 3.31

0.43 0.86 2.41 11.27 46.48

1.74 2.47 2.69 2.90 21.47

1.23 1.08 2.50 2.69 5.55

Uncertainties u are u(xES) = 0.002.

solubility in water and in (ethanol + water), being the best model to describe solutions with ethanol mass fraction in solvent of 0.9. The model was the only one able to predict solubility data at this ethanol concentration in temperature values higher than 323.15 K, closely fitting experimental data behavior. The Bio-UNIFAC model was able to predict fructose solubility in water and in solutions with a small amounts of ethanol with high accuracy. It was the best model until the solution reached 40 % of ethanol in solvent. However, with further addition of ethanol higher deviations are observed. AAD of the A-UNIFAC model presented values lower than 3 % in pure water and in mixed solvent with the exception of the solutions with an ethanol mass fraction in solvent of 0.9. Finally, the mS-UNIFAC model presented good values of AAD in water and in mixed (ethanol + water) with the exception of temperatures higher than 323.15 K in solutions with an ethanol mass fraction in solvent of 0.9, in which only the P&MUNIQUAC model was able to closely predict fructose solubility. The conclusion is that, depending on ethanol concentration in solvent, there is a model which is the best one for the calculations. Bio-UNIFAC was the best one for pure water and ethanol mass fraction in solvent up to 0.4, while the mS-UNIFAC model is the best one for 0.4 to 0.6 mass fractions, and over this value the P&M-UNIQUAC model was the best.

Figure 10. Fructose solubility in mixed (ethanol + water) solvent with ethanol mass fraction in solvent xES of 0.6. Solubility expressed as fructose mass fraction xF as a function of temperature T. Comparison among experimental data and different thermodynamic models: ◆, this work experimental data; ●, Gong et al.;4 -·-·-·, P&M-UNIQUAC; ···, Bio-UNIFAC; blue ---, A-UNIFAC; green ---, mS-UNIFAC.

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CONCLUSIONS Fructose solubility in water and in mixed (ethanol + water) was determined over a temperature range of (298.15 to 333.15) K for different ethanol concentrations, from pure water to ethanol mass fraction in solvent of 0.9. These data are very useful to crystallization studies and are still scarce in literature. Experimental procedure was repeated at least three times for each point, and the mean of these data were compared to that of the scarce literature. Fructose solubility decreases with the increase of ethanol concentration and increases with the increase of temperature over the range of temperatures and concentrations studied. Activity coefficient-based models P&M-UNIQUAC, BioUNIFAC, A-UNIFAC, and mS-UNIFAC were used to predict fructose solubility and the calculations were compared with experimental data both from this work and published in literature. P&M-UNIQUAC was able to describe fructose 3044

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(20) Tsavas, P.; Voutsas, E.; Magoulas, K.; Tassios, D. Phase equilibrium calculations in aqueous and nonaqueous mixtures of sugars and sugar derivatives with a group-contribution model. Ind. Eng. Chem. Res. 2004, 43, 8391−8399. (21) Myerson, A. S. Chapter 1: Solution and solution properties. In Handbook of Industrial Crystallization, 2nd ed.; ButterworthHeinemann: Boston, MA, 2002, pp 12−16. (22) Catté, M.; Dussap, C. G.; Achard, C.; Gros, J. B. Excess properties and solid-liquid equilibria for aqueous-solutions of sugars using a UNIQUAC model. Fluid Phase Equilib. 1994, 96, 33−50. (23) Benson, G. C.; D’arcy, P. J. Excess isobaric heat capacities of water normal-alcohol mixtures. J. Chem. Eng. Data 1982, 27, 439−442. (24) Silva, A. T. C. R. Estudo da cristalização de frutose em diferentes meios. Master thesis, Federal University of São Carlos, São Carlos, SP, Brazil, 2010. (25) Watanabe, T. Studies on the crystallization of fructose. Seito Gigutsu Kenkgu Kaishi 1978, 28, 70 1978. (26) Reber, L. A. The solubility of sucrose in hydroalcoholic solutions. J. Am. Pharm. Assoc. 1953, 42 (No.4), 192−193. (27) Bockstanz, G. L.; Buffa, M.; Lira, C. T. Solubilities of Ranhydrous glucose in ethanol/water mixtures. J. Chem. Eng. Data 1989, 34, 426−429. (28) Gabas, N.; Carillon, T.; Hiquily, N. Solubilities of D-xylose and D-mannose in water−ethanol mixtures at 25 °C. J. Chem. Eng. Data 1988, 33, 128−130.

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Funding

The authors would like to thank PPGEQ-UFSCar, FAPESP and CNPq for the support. Notes

The authors declare no competing financial interest.

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REFERENCES

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dx.doi.org/10.1021/je400471m | J. Chem. Eng. Data 2013, 58, 3039−3045