Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Determination and Correlation of the Solubility of L‑Fucose in Four Binary Solvent Systems at the Temperature Range from 288.15 to 308.15 K Jingxuan Qiu,† Shuang Song,† Xinglong Chen,† Dengjing Yi,†,§ Mengyao An,‡,§ and Peng Wang*,†,§ School of Chemical Engineering, ‡School of Chemical and Life Science, and §Advanced Institute of Materials Science, Changchun University of Technology, Changchun, Jilin 130012, People’s Republic of China
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†
S Supporting Information *
ABSTRACT: Experimental solubility data of L-fucose in methanol + water, ethanol + water, 2-propanol + water, and acetone + water systems were measured at temperatures ranging from 288.15 to 308.15 K under atmosphere pressure (P = 0.1 MPa), using the gravimetric method. The experimental results indicate that the solubility of L-fucose increases with increasing temperature and water content, as well as decreasing with the composition of organic solvents used in this work. According to the data measured in this experiment, methanol is less effective than ethanol, 2-propanol, and acetone in the antisolvent crystallization process of L-fucose. By means of our research, the solubility of Lfucose in the pure solvents was affected by polarity and hydrogen bond. The modified Apelblat model, CNIBS/R-K model, and Apelblat−Jouyban−Acree model were used to correlate the solubility data, and all three of the thermodynamic models were found to agree well with the measured experimental solubility data.
1. INTRODUCTION −1 L-Fucose (C6H12O5, mole mass 164.16 g·mol , CAS Registry No. 2438-80-4) is a 6-deoxy hexose monosaccharide belonging to the rare series of L-configured sugars. Its chemical structure is shown in Figure 1. L-fucose is a natural monosaccharide
solubility data of L-fucose in the selected four kinds of binary solvent mixtures. In this work, the solubility data of L-fucose in four binary solvent systems were measured with water mole fraction ranging from 0.00 to 1.00 using the gravimetric method, at temperature ranging from 288.15 to 308.15 K under atmospheric pressure. The binary solvent mixtures included methanol + water, ethanol + water, 2-propanol + water, and acetone + water. The obtained solubility data were correlated using the modified Apelblat equation, Redlich−Kister (CNIBS/R-K) model, and the combined form of Jouyban− Acree model (Apel−JA). The correlation results of above models agreed well with the experimental values.
Figure 1. Chemical structure of L-fucose.
2. EXPERIMENTAL SECTION 2.1. Materials. Commercial food grade L-fucose was provided by Guangzhou Shijihuaming Biotech Co., Ltd.; its purity was higher than 0.99 and was used without further purification. The methanol, ethanol, 2-propanol, and acetone used in this work were supplied by Tianjin Fuyu Fine Chemical Co., Ltd., and their mass fraction purity were all higher than 0.997. The electrical resistivity of deionized water which was produced by Merck Millipore Mingche-D 24UV ultrapure water system was 18.2 MΩ·cm at 25 °C. A detailed
present in mammals where it is found predominantly as an Oglycosidically linked component of glycoproteins, glycolipids, and oligosaccharides. It is also present in its free form in human breast milk (human milk monosaccharide). L-fucose plays important roles in the development of the immune and nervous systems and is involved in cognitive function and memory formation.1 Crystallization is a significant means of separation and purification in industry. The solubility data of L-fucose in binary solvent mixtures are essential for the solvent selection of its crystallization process. But the solubility data of L-fucose in solvent mixtures have never been reported. Therefore, the objective of our work was to measure the experimental © XXXX American Chemical Society
Received: May 5, 2018 Accepted: August 28, 2018
A
DOI: 10.1021/acs.jced.8b00361 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 1. Description of L-Fucose, L-Arginine, and Organic Solvents Used in the Experimentsa material L-fucose
methanol ethanol 2-propanol acetone L-arginine
molecular formula
molar mass (g·mol−1)
mass fraction purity
source
analysis method
CAS registry number
C6H12O5 CH4O C2H6O C3H8O C3H6O C6H14N4O2
164.16 32.04 46.07 60.10 58.08 174.20
≥0.990 ≥0.997 ≥0.997 ≥0.997 ≥0.997 ≥0.985
Guangzhou Shijihuaming Biotech Co., Ltd. Tianjin Fuyu Fine Chemical Co., Ltd. Tianjin Fuyu Fine Chemical Co., Ltd. Tianjin Fuyu Fine Chemical Co., Ltd. Tianjin Fuyu Fine Chemical Co., Ltd. Amino Life (Wuxi) Biotech Co., Ltd.
HPLC GC GC GC GC HPLC
2438-80-4 67-56-1 64-17-5 67-63-0 67-64-1 74-79-3
a
Both the analysis method and the mass fraction purity were provided by the suppliers.
h, each of the sediments was filtered and transferred to drying oven to dry for about 72 h and then removed to the PXRD device for testing. The patterns were shown in Figure 2.
description of the materials used in this experiment is listed in Table 1. 2.2. Apparatus and Procedures. The gravimetric method was used to measure the solubility data of L-fucose in the four binary solvents, which has been described previously in other literatures related to the measurement of solubility data.2 The mass of solute and solvents was weighed by an analytical balance (DENVER Instrument SI-224, Sartorius Scientific Instruments (Beijing) Co., Ltd., China), and it has an accuracy of ±0.0001 g. The weighed solute and solvents were added into the jacketed crystallizer kept at a constant temperature by a constant temperature water bath (Shanghai Laboratory Instrument Works Co., Ltd. 501A, China). The mixed solution was continuously stirred by a magnetic stirrer (IKA, RCT B S25, Germany). According to our exploration, the dissolution equilibrium time of L-fucose was about 1 h. After that, the whole solution system was kept still for about 30 min at a constant temperature to ensure that there were no obvious fine particles in the supernatant. Then we took about 2 mL of the supernatant and transferred it into a Petri dish using a syringe. The Petri dish with saturated solution was weighted quickly and then put into a 50 °C vacuum drying oven to dry for about 24 h. In this work, each experimental point was measured at least three times, and then we calculated the mean value as the experimental results. The mole fraction of water (x1) in each mixed solvent system was calculated by eq 1. The saturated mole fraction solubility of Lfucose (xA) in the binary solvents selected was calculated by eq 2. x1 =
xA =
Figure 2. X-ray powder diffraction patterns of the raw material and the residual solids in five pure solvents.
2.4. Verification of the Experimental Method. In order to verify the reliability and accuracy of the experimental method, the solubility data of L-arginine in ethanol + water system were measured in this work. The temperature of this experiment was set at 298.15 K, and the comparisons between the experimental data and the values in the literature3 were tabulated in Table 2. It can be seen in Table 2 that the experimental results are basically consistent with the data in
m1 M1 m1 M1
mA MA
+
+
m2 M2 mA MA m1 M1
(1)
+
m2 M2
Table 2. Comparisons between Experimental Solubility (xAexp) of L-Arginine in Ethanol + Water Solvent System at Temperature T = 298.15 K and Pressure P = 0.1 MPa with the Data Reported in the Literature (xAr)a
(2)
where mA, m1, and m2 represent the mass of L-fucose, water, organic solvents, and MA, M1, and M2 represent the molar mass. 2.3. Characterization. In order to identify the crystallinity of L-fucose used in this experiment, the X-ray powder diffraction (XRPD) spectra of the samples were measured, which used Rigaku SmartLab X-ray Diffractometer in Cu Kα radiation and worked under 200 mA in current and 45 kV for voltage. All the samples were scanned from 5° to 50° in 2θ with the scanning rate of 10° per minute. To verify that the Lfucose remained stable in the solid−liquid equilibrium process, excess solute was added into the monosolvents (methanol, ethanol, 2-propanol, acetone, and water) at a constant temperature to make suspensions. After stirring for about 4
x1
103xAexp
103xAr
RDb
ARDc
0.0000 0.4602 0.7189 0.8847 1.0000
0.1595 1.7714 7.6629 15.6357 21.5044
0.1430 1.2920 6.3030 13.2380 18.6140
0.1152 0.3710 0.2158 0.1811 0.1553
0.2077
a The standard uncertainty of temperature u(T) = 0.05 K, the relative uncertainty of pressure ur(p) = 0.05, and the relative uncertainty of the mole fraction solubility ur(xA) = 0.15. bRD is the relative deviation between the experimental solubility data and the literature data. cARD is the average relative deviation between the experimental solubility data and the literature data.
B
DOI: 10.1021/acs.jced.8b00361 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 3. Experimental (xAexp) and Calculated (xAcal) Mole Fraction Solubility of L-Fucose in Methanol (1 − x1) + Water (x1) at Temperature T (from 288.15 to 308.15 K) and Pressure P = 0.1 MPaa,b x1
103xAexp
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
2.16 2.52 5.93 6.88 9.07 11.94 14.92 20.49 24.67 36.92 51.20
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
2.44 3.27 7.83 9.04 12.23 16.46 21.32 29.35 37.17 53.87 69.86
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80
2.75 3.92 10.00 12.91 17.09 23.56 31.81 44.22 53.94
103xAcal (eq 3)
103xAcal (eq 5)
288.15 K 2.16 2.55 5.91 6.92 9.13 12.02 14.83 20.44 24.65 36.85 51.06 293.15 K 2.44 3.19 7.82 8.92 12.11 16.25 21.53 29.54 36.83 54.08 70.59 298.15 K 2.74 3.94 10.22 12.18 16.99 23.49 32.09 43.90 55.83
103xAcal (eq 6)
x1
103xAexp
2.01 3.20 4.81 6.86 9.31 12.15 15.49 19.69 25.59 35.04 50.81
1.66 2.94 4.89 7.51 10.59 13.82 17.07 20.76 26.19 36.71 45.76
0.90 1.00
77.81 97.86
2.29 4.06 6.38 9.20 12.56 16.63 21.79 28.66 38.16 51.69 69.22
2.10 3.73 6.25 9.69 13.81 18.24 22.83 28.12 35.93 50.89 64.00
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
3.07 4.69 13.56 17.28 24.68 35.50 50.08 66.70 89.05 110.38 128.98
2.57 4.86 8.12 12.37 17.63 24.11 32.19 42.54 56.21
2.62 4.73 8.07 12.74 18.51 24.95 31.90 40.16 52.41
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
3.45 5.80 16.64 26.69 39.37 59.42 75.80 104.35 131.51 152.16 174.22
298.15 K 77.82 96.42 303.15 K 3.08 4.78 13.18 17.53 25.13 36.14 49.00 66.89 85.75 109.90 130.18 308.15 K 3.08 5.73 16.82 26.50 39.07 58.92 76.54 104.33 133.27 152.49 173.84
103xAcal (eq 6)
74.60 96.67
75.70 92.14
2.85 5.99 10.78 17.32 25.78 36.50 50.05 66.95 87.28 109.66 127.35
3.25 6.01 10.51 17.03 25.43 35.27 46.46 60.26 80.97 120.21 136.24
3.20 7.20 14.30 25.36 40.62 59.54 80.97 103.61 126.73 150.28 173.09
4.01 7.64 13.80 23.13 35.77 51.44 72.31 94.67 131.95 202.90 206.48
xAexp is the experimental solubility; xAcal (eq 3), xAcal (eq 5), and xAcal (eq 6) are the calculated solubility according to eqs 3, 5, and 6, respectively. bThe standard uncertainty of temperature is u(T) = 0.05 K, the relative standard uncertainty for mole fraction of water is ur(x1) = 0.001, the relative standard uncertainty of the experimental pressure is ur(P) = 0.05, and the relative standard uncertainty for the mole fraction solubility is ur(xA) = 0.15.
3.2. CNIBS/R-K Model. The nearly ideal binary solvent (CNIBS)/R-K model was proposed by Acree and co-workers,6 and it was given by eq 4
3. THERMODYNAMIC MODELS In this article, the experimental solubility data of L-fucose were correlated by modified Apelblat equation, CNIBS/R-K model, and Apelblat−Jouyban−Acree model. All of them could act as useful tools for a better understanding of solubility behavior of the solute by prediction and correlation. 3.1. Modified Apelblat Equation. The modified Apelblat equation, a simple semiempirical model with three empirical parameters A, B and C, is frequently used to correlate and predict solid−liquid equilibrium data.4 It can be described as follows: B + C ln(T /K ) T /K
103xAcal (eq 5)
a
the literature. Thus, the method in this work could be used to determine the solubility of L-fucose.
ln x1 = A +
103xAcal (eq 3)
N
ln x1 = x 2 ln(x1)2 + x3 ln(x1)3 + x 2x3∑ Si(x 2 − x3)i i=0
(4)
where x1 refers to the mole fraction of the L-fucose in the systems; x2 and x3 are the initial mole fractions of the binary solvents, whereas (x1)2 and (x1)3 represent the solubility values of L-fucose. Si is a model parameter and N stands for the number of “curve fit” parameters. For the binary solvents, eq 5 is shown as follows7 ln x1 = B0 + B1x 2 + B2 x 22 + B3x 23 + B4 x 24
(5)
(3)
where B0, B1, B2, B3, and B4 are parameters of the model obtained by the nonlinear least-squares analysis.8 The x1 is the mole fraction solubility of L-fucose in the mixed solvents selected. 3.3. Apel−JA Model. The Apelblat−Jouyban−Acree model is the combined version of Jouyban−Acree model and Apelblat equation. It is a three-dimensional model used to
where x1 is the mole-fraction solubility of L-fucose at the corresponding absolute temperature T; A, B, and C represent the model parameters gained from the fitting of solubility data. The values of A and B refer to variations in the solution activity coefficient, and the value of C denotes the effect of temperature on enthalpy of fusion.5 C
DOI: 10.1021/acs.jced.8b00361 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 4. Experimental (xAexp) and Calculated (xAcal) Mole Fraction Solubility of L-Fucose in Ethanol (1 − x1) + Water (x1) at Temperature T (from 288.15 to 308.15 K) and Pressure P = 0.1 MPaa,b x1
103xAexp
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.32 0.95 1.04 2.39 3.01 4.55 7.97 11.71 18.80 27.41 51.20
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.38 1.14 1.38 3.50 3.91 6.18 10.89 16.87 27.56 38.84 69.86
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80
0.43 1.42 1.71 3.77 5.17 8.61 15.63 24.14 41.99
103xAcal (eq 3)
103xAcal (eq 5)
288.15 K 0.32 0.92 1.05 2.52 3.88 4.58 7.98 11.76 18.63 27.21 51.06 293.15 K 0.37 1.19 1.76 3.11 3.88 6.10 10.85 16.59 28.05 39.34 70.59 298.15 K 0.44 1.48 1.79 3.94 5.25 8.59 15.60 24.76 42.21
103xAcal (eq 6)
x1
103xAexp
0.35 0.75 1.33 2.12 3.21 4.79 7.29 11.43 19.81 30.31 50.81
0.31 0.73 1.35 2.17 3.32 5.05 7.83 12.46 19.81 30.02 45.16
0.90 1.00
56.73 97.86
0.40 0.94 1.76 2.86 4.35 6.57 10.15 16.24 26.64 43.42 69.22
0.38 0.90 1.68 2.77 4.32 6.69 10.61 17.22 27.96 43.29 64.00
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.57 1.96 2.65 4.79 7.54 12.53 23.47 39.60 65.09 84.45 128.98
0.47 1.11 2.11 3.51 5.56 8.80 14.29 23.88 40.12
0.48 1.14 2.17 3.64 5.78 9.14 14.76 24.38 40.30
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.71 1.97 4.10 7.08 11.02 20.09 37.65 64.01 94.12 118.52 174.22
103xAcal (eq 5)
298.15 K 56.96 96.42 303.15 K 0.55 1.77 2.62 5.11 7.45 12.76 23.62 38.94 63.45 82.56 130.18 308.15 K 0.72 2.06 4.10 6.80 11.06 19.91 37.54 64.28 95.27 119.76 173.84
103xAcal (eq 6)
64.55 96.76
63.59 92.14
0.62 1.56 2.99 4.96 7.90 12.72 21.56 37.44 63.80 98.04 127.35
0.62 1.51 2.92 4.95 7.98 12.82 21.04 35.30 59.24 95.00 136.24
0.73 188 3.91 7.14 12.28 20.76 35.03 58.52 93.69 135.73 173.09
0.85 2.06 4.02 6.92 11.32 18.44 30.67 52.14 88.68 144.19 206.48
a
xAexp is the experimental solubility; xAcal (eq 3), xAcal (eq 5), and xAcal (eq 6) are the calculated solubility according to eqs 3, 5 and 6, respectively. bThe standard uncertainty of temperature is u(T) = 0.05 K, the relative standard uncertainty for mole fraction of water is ur(x1) = 0.001, the relative standard uncertainty of pressure is ur(P) = 0.05, and the relative standard uncertainty for the mole fraction solubility is ur(xA) = 0.15.
proved that there was no crystal transformation in the whole experimental process. 4.2. Solubility Data. In this work, the solubility of L-fucose in four binary solvent mixtures was measured with the different water content (mole fraction from 0.00 to 1.00) at temperatures ranging from 288.15 to 308.15 K using the gravimetric method under atmosphere pressure (P = 0.1 MPa). The scatter plots of L-fucose solubility data in the four binary systems at different solvent compositions and temperatures were graphically plotted in Figures S1−S4 in the Supporting Information, and the experimental solubility data were listed in Tables 3−6. All the figures showed that the solubility of L-fucose (xA) increased with the mole fraction of water (x1) when the experimental temperature is constant in each mixed solvent. Additionally, it increased with the absolute temperature at a fixed composition of solvents (x1), but in the four pure organic solvents the influence of temperature was relatively smaller than other cases. For the five pure solvents (including water, methanol, ethanol, 2-propanol, and acetone), from Figure 3 we could learn that the solubility in water (x1 = 1) is higher than that in the four organic solvents obviously. As for the four organic solvents, it can be observed from Figure 4 that the solubility values of L-fucose in methanol is highest, and about ten times
express the relationship among solubility, solvent composition, and temperature.9 The model can be expressed by eq 6 B i y ln x1 = x 2jjjA1 + 1 + C1 ln T zzz T k { B2 ij y + x3 lnjjA 2 + + C2 ln T zzz T k { Ä É N Å ÅÅ J (x − x )i ÑÑÑ 2 3 Ñ Å ÑÑ + x 2x3∑ ÅÅÅ i ÑÑ ÅÅ T ÑÑÖ i=0 Å Ç
103xAcal (eq 3)
(6)
where x1 is the mole fraction solubility of solute in the binary systems; Ji represent model constants; T is the experimental temperature (K); N refers to 0, 1, 2, and 3; and other symbols stand for the same meanings as in eq 4.
4. RESULTS AND DISCUSSION 4.1. X-ray Powder Diffraction Analysis. From Figure 2, the obtained PXRD patterns showed that the crystallinity of Lfucose used in this work was high. They also revealed that all of the residual solids in the four mixed solvents were as same as the raw material. As we can observe in these patterns, all the PXRD patterns have the same characteristic peaks. Thus, it D
DOI: 10.1021/acs.jced.8b00361 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 5. Experimental (xAexp) and Calculated (xAcal) Mole Fraction Solubility of L-Fucose in 2-Propanol (1 − x1) + Water (x1) at Temperature T (from 288.15 to 308.15 K) and Pressure P = 0.1 MPaa,b x1
103xAexp
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.14 0.58 0.72 1.30 2.41 4.02 6.70 11.16 16.07 28.76 51.20
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.24 0.89 0.92 1.67 3.00 5.29 8.99 15.17 23.64 44.44 69.86
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80
0.32 1.01 1.25 2.08 3.92 6.88 12.42 21.66 35.00
103xAcal (eq 3)
103xAcal (eq 5)
288.15 K 0.14 0.60 0.72 1.31 2.40 4.04 6.71 11.23 15.76 29.24 51.06 293.15 K 0.23 0.82 0.94 1.63 3.01 5.21 8.97 15.04 24.23 42.88 70.59 298.15 K 0.33 1.06 1.23 2.08 3.91 6.94 12.41 21.47 37.75
103xAcal (eq 6)
x1
103xAexp
0.16 0.41 0.85 1.48 2.41 3.84 6.21 10.37 17.72 30.22 50.81
0.19 0.43 0.79 1.32 2.17 3.64 6.31 11.21 19.73 32.27 45.76
0.90 1.00
62.07 97.86
0.27 0.62 1.14 1.88 3.01 4.90 8.32 14.69 26.24 44.89 69.22
0.26 0.58 1.07 1.80 2.97 4.98 8.66 15.44 27.22 44.67 64.00
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.43 1.28 1.59 2.62 5.24 9.49 17.65 31.83 60.34 87.88 128.98
0.35 0.77 1.41 2.37 3.90 6.59 11.55 20.88 37.68
0.35 0.77 1.43 2.43 4.03 6.83 11.97 21.50 38.21
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.56 1.49 2.09 3.54 7.22 13.54 26.12 52.52 78.28 132.22 174.22
103xAcal (eq 3)
103xAcal (eq 5)
298.15 K 62.47 96.42 303.15 K 0.44 1.29 1.60 2.68 5.24 9.54 17.72 32.51 55.02 90.45 130.18 308.15 K 0.55 1.47 2.09 3.50 7.23 13.49 26.07 52.04 81.37 130.14 173.84
103xAcal (eq 6)
64.11 96.76
63.30 92.14
0.47 0.99 1.78 3.00 5.10 9.04 16.83 32.05 59.03 96.27 127.35
0.44 0.99 1.87 3.23 5.45 9.36 16.63 30.27 54.52 91.66 136.24
0.61 1.22 2.24 3.98 7.15 13.25 25.23 47.93 86.16 135.69 173.09
0.55 1.26 2.42 4.25 7.32 12.82 23.21 43.03 78.98 135.41 206.48
a
xAexp is the experimental solubility; xAcal (eq 3), xAcal (eq 5), and xAcal (eq 6) are the calculated solubility according to eqs 3, 5, and 6, respectively. bThe standard uncertainty of temperature is u(T) = 0.05 K, the relative standard uncertainty for mole fraction of water is ur(x1) = 0.001, the relative standard uncertainty of pressure is ur(P) = 0.05, and the relative standard uncertainty for the mole fraction solubility is ur(xA) = 0.15.
dielectric constants of acetone and 2-propanol decrease with the increase of temperature.13 So when the experimental temperature was lower than the intersection point, the dominant factor affecting the solubility behavior was the polarity of solvents, and the solubility tendency was in accordance with the polarity sequence of the five monosolvents. As for the higher temperature region, the solubility curve of L-fucose in 2-propanol was above that in acetone, this may result from the effect of hydrogen-bonding. The −OH groups in 2-propanol solvent could act as the acceptors of the hydrogen bonds comparing with acetone, and there are several −OH groups in the structure of L-fucose molecule, which can act as the hydrogen-bonding donors. Therefore, for the region higher than the intersection point, the hydrogen bonds formed between the solute and solvent molecules may act as a more important role compared with polarity, which could make the solubility values of L-fucose in 2-propanol higher than that in acetone. 4.3. Correlation of Solubility Data. In this study, the experimental solubility data of L-fucose in four binary solvent mixtures were correlated using modified Apelblat model, CNIBS/R-K model and Apelblat−Jouyban−Acree model. To assess the applicability and accuracy of the solubility models used in this article, the average relative deviation (ARD) and
higher than that in ethanol, 2-propanol, and acetone. For the two cases above, the reason may lie in “like dissolves like”;10,11 greater solubility can be achieved when the polarity of solvent is close to that of the solute.12 Dielectric constant is an important factor for affecting polarity of solvents. According to the literature,13 the dielectric constants of the five pure solvents at 298.15 K could be ranked as water (78.54) > methanol (31.50) > ethanol (24.30) > acetone (19.10) > 2-propanol (18.00). Thus, the polarity of water is highest among the monosolvents used in this study, and for the four antisolvents the polarity of methanol is higher than other three organic solvents. It proved that the solubility of L-fucose in water is the highest among the five neat solvents, while it could be more soluble in methanol relative to other organic solvents. From the above, we could conclude that water is appropriate to be the positive solvent in the crystallization process of L-fucose, and for the four organic solvents methanol is less effective to act as an antisolvent compared with ethanol, 2-propanol, and acetone. Additionally, it can be seen in Figure 4 obviously that there is a point of intersection on the scatter plots of the solubility data in 2-propanol and acetone at about 293.15 K, this may attribute to the mutual competition of polarity and hydrogen bond. It can also be obtained from the literature that the E
DOI: 10.1021/acs.jced.8b00361 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 6. Experimental (xAexp) and Calculated (xAexp) Mole Fraction Solubility of L-Fucose in Acetone + Water at Temperature T (from 288.15 to 308.15 K) and Pressure P = 0.1 MPaa,b x1
103xAexp
103xAcal (eq 3)
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.23 0.33 0.44 0.60 1.34 2.38 4.38 7.85 13.92 26.91 51.20
0.23 0.33 0.44 0.59 1.32 2.37 4.41 7.92 13.98 27.27 51.06
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.25 0.36 0.52 0.69 1.60 2.87 5.60 10.63 19.36 37.78 69.86
0.25 0.36 0.52 0.72 1.60 2.91 5.53 10.42 19.21 36.78 70.59
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80
0.28 0.41 0.62 0.91 1.98 3.71 7.42 14.33 27.36
0.28 0.41 0.63 0.91 1.95 3.70 7.42 14.36 27.19
103xAcal (eq 5)
103xAcal (eq 6)
x1
103xAexp
103xAcal (eq 3)
0.24 0.30 0.43 0.71 1.26 2.30 4.26 7.87 14.48 26.77 50.81
0.23 0.29 0.43 0.70 1.24 2.31 4.39 8.32 15.43 27.38 45.76
0.90 1.00
51.77 97.86
51.70 96.42
0.26 0.33 0.50 0.83 1.49 2.82 5.44 10.53 20.15 37.78 69.22
0.26 0.33 0.50 0.83 1.51 2.87 5.59 10.84 20.56 37.36 64.00
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.32 0.47 0.80 1.22 2.38 4.88 10.48 20.30 38.95 73.35 128.98
0.29 0.39 0.60 1.03 1.90 3.67 7.24 14.28 27.74
0.29 0.39 0.60 1.02 1.89 3.68 7.32 14.53 28.20
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
0.38 0.54 0.99 1.47 3.05 6.42 16.17 31.20 59.58 116.26 174.22
288.15 K
103xAcal (eq 5)
103xAcal (eq 6)
298.15 K
293.15 K
298.15 K
303.15 K 0.32 0.46 0.78 1.66 2.42 4.83 10.61 20.65 39.59 75.57 130.18 308.15 K 0.38 0.54 1.00 1.51 3.04 6.46 16.07 30.92 59.15 114.52 173.84
52.58 96.76
52.48 92.14
0.33 0.47 0.74 1.30 2.45 4.87 9.91 20.17 39.91 74.54 127.35
0.33 0.46 0.73 1.28 2.43 4.84 9.85 20.05 39.72 75.70 136.24
0.38 0.55 0.89 1.60 3.15 6.64 14.45 31.18 63.45 114.86 173.09
0.40 0.56 0.91 1.65 3.20 6.52 13.58 28.22 57.35 111.92 206.48
a
xAexp is the experimental solubility; xAcal (eq 3), xAcal (eq 5), and xAcal (eq 6) are the calculated solubility according to eqs 3, 5, and 6, respectively. bThe standard uncertainty of temperature is u(T) = 0.05 K, the relative standard uncertainty for mole fraction of water is ur(x1) = 0.001, the relative standard uncertainty of pressure is ur(P) = 0.05, and the relative standard uncertainty for the mole fraction solubility is ur(xA) = 0.15.
Figure 4. Experimental (xAexp) solubility scatter diagram of L-fucose in the four organic solvents.
Figure 3. Experimental (xAexp) solubility scatter diagram of L-fucose in five monosolvents.
N
ARD =
the root-mean-square deviation (RMSD)14 were calculated using eqs 7 and 8 F
x exp − x cal 1 ∑ i exp i N i=1 xi
(7) DOI: 10.1021/acs.jced.8b00361 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 7. Model Parameters of Apelblat Equation for L-Fucose in the Four Binary Solvent Systemsa x1a
A
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
−33.1153 196.9014 90.1721 −1513.7012 −1523.7295 −1783.5746 −887.8262 −908.1548 −625.5863 181.5040 47.3347
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
−1063.3407 697.5831 −2030.1580 −779.3222 −1395.7851 −1542.1608 −1529.1464 −1564.8188 −281.4322 −302.1645 47.3347
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
1560.4179 1273.6031 −167.0922 −546.3949 −974.6743 −963.2179 −1013.3121 −1698.8514 2.5522 −127.4216 47.3346
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
−722.5058 −523.3535 −759.2208 −577.4780 −546.8820 −861.2581 −1739.1805 −1283.4951 −936.8205 −1194.7642 47.3346
B
C
Methanol + Water −539.9937 5.0947 −12068.8972 −28.4260 −8165.7383 −11.8239 62073.2852 228.3592 62117.3344 230.1518 73175.5774 269.3050 33145.4533 135.7092 34105.5392 138.7670 21327.6447 96.7369 −13553.3451 −24.3259 −6837.8210 −4.6931 Ethanol + water 43949.2278 159.4035 −34354.0988 −103.3551 84909.9651 305.2240 30675.8061 117.7510 56956.9111 210.5275 62845.5537 232.8382 61996.4882 231.1587 63034.5281 236.8896 6214.2278 45.1812 7717.4534 47.9877 −6837.8210 −4.6931 2-Propanol + water −74852.1203 −231.2183 −60378.6612 −189.1924 3090.7977 26.3307 20308.8128 82.8598 38953.3956 147.1637 38076.8746 145.7697 39757.1783 153.6747 69613.9833 256.5158 −6460.9193 2.7756 −95.0281 21.9333 −6837.8186 −4.6931 Acetone + Water 29896.2149 107.7753 21070.0020 78.0814 30325.8995 114.1069 21808.2167 87.2877 20959.3262 82.5515 34271.1616 130.0043 72268.8664 261.8448 51768.5376 194.0501 36069.2635 142.5582 47600.7047 181.1551 −6837.8186 −4.6931
ARD/%
105RMSD
0.15 1.43 1.28 0.82 0.97 0.98 1.12 0.38 1.91 0.25 0.79
0.48 6.48 21.2 14.96 26.28 37.76 60.78 18.90 188.06 27.70 91.87
1.81 5.14 2.30 6.33 0.83 1.00 0.35 1.36 1.40 1.20 0.79
1.02 10.09 4.65 27.65 6.06 13.40 8.93 44.51 93.09 105.34 91.87
2.90 3.54 1.08 1.21 0.25 0.79 0.22 1.08 4.44 2.06 0.79
1.00 3.97 1.52 3.33 0.99 5.07 4.13 38.97 287.45 165.82 91.87
0.17 0.53 1.13 2.84 0.83 0.87 0.74 1.14 0.84 1.73 0.79
0.05 0.23 0.89 3.45 2.31 3.72 7.78 22.43 36.02 134.73 91.87
a
x1a is the initial mass fraction of water in the binary solvent mixtures.
solvents. The fit plots by 3D model are shown in Figures S5− S8.
N
RMSD =
∑i = 1 (xAcal − xAexp)2 N
■
(8)
CONCLUSIONS In this work, the experimental solubility data of L-fucose in the four binary solvent mixtures (methanol + water, ethanol + water, 2-propanol + water, and acetone + water) were measured using the gravimetric method at temperature from 288.15 to 308.15 K. All the solubility data increased with the increasing experimental temperature and the water content.
where N is the number of experimental points; xAcal and xAexp represent the calculated and experiment values, respectively. The parameters obtained by correlating and the ARD and RMSD were listed in Tables 7−9. The fitting results indicated that all the models could give satisfactory correlation of the experimental data at all solvent compositions in the four mixed G
DOI: 10.1021/acs.jced.8b00361 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 8. Model Parameters of CNIBS/R-K Equation for L-Fucose in the Four Binary Solvent Systems T/K
B0
B1
288.15 293.15 298.15 303.15 308.15
−6.2118 −6.0805 −5.9632 −5.8620 −5.7443
4.9292 6.4643 7.1147 8.4134 8.7624
288.15 293.15 298.15 303.15 308.15
−7.9668 −7.8247 −7.6679 −7.3826 −7.2186
8.8547 10.1484 10.2217 11.1011 10.8932
288.15 293.15 298.15 303.15 308.15
−8.7489 −8.2138 −7.9437 −7.6667 −7.4093
11.2496 9.6786 8.9800 8.7000 7.8196
288.15 293.15 298.15 303.15 308.15
−8.3248 −8.2467 −8.1469 −8.0255 −7.8652
0.8703 1.4858 1.9938 2.9084 3.0277
B2
B3
Methanol + Water −2.6213 −1.0798 −8.0437 7.1911 −8.0354 6.4555 −10.6035 9.9206 −6.7286 1.6100 Ethanol + Water −13.5807 15.8251 −17.6287 21.5121 −17.6632 23.1007 −21.9120 31.1341 −16.4786 21.2776 2-Propanol + Water −18.3082 21.4243 −16.8164 23.5006 −14.2398 21.0101 −14.4863 24.3617 −9.4290 17.2872 Acetone + Water 12.4403 −12.7484 10.1166 −8.3277 9.5626 −7.8108 6.5525 −2.7727 5.8834 0.6536
B4
ARD/%
104RMSD
2.0342 −2.1745 −1.8796 −3.9075 0.3679
6.94 6.14 6.46 6.11 6.13
8.80 9.98 15.41 12.38 25.27
−6.1500 −8.9143 −10.3721 −15.0568 −10.2821
9.83 10.62 9.41 8.25 5.82
11.50 17.47 29.93 49.29 63.37
−8.6323 −10.8383 −10.1624 −13.0007 −10.0452
10.23 10.33 8.14 7.98 6.97
9.08 10.30 14.22 30.74 33.23
4.7830 2.3017 2.0658 −0.7235 −3.4535
4.80 4.78 3.28 2.68 4.37
2.19 3.16 4.33 6.99 13.89
Table 9. Model Parameters of Apelblat−Jouyban−Acree Equation for L-Fucose in the Four Binary Solvents Selected solvents
methanol + water
ethanol + water
2-propanol + water
acetone
A1 B1 C1 A2 B2 C2 J0 J1 J2 ARD/% 103RMSD
−2090.1962 86135.2676 315.7937 16.8566 −4334.2286 −1.4504 354.0783 −739.5332 −446.5493 14.64 30.39
−654.1187 22771.3318 100.9770 −1117.4105 45629.4829 167.9163 403.2667 −340.6335 752.4329 10.55 7.02
−919.0112 35142.5135 140.1875 445.0009 −24137.8307 −65.2931 244.0211 −74.9875 783.1539 10.01 4.33
−916.7646 34986.7967 139.8895 −737.3489 30448.1911 110.0600 −404.2789 623.8911 −78.9153 5.39 4.75
■
For the monosolvents used in this study, the solubility values were mainly influenced by polarity and hydrogen bond. To be specific, when the monosolvents were at the lower temperature the main factor was the polarity of solvents, whereas at the higher temperatures, hydrogen-bonding played a more significant role for the solubility of L-fucose in the pure solvents. Three kinds of thermodynamic models (including modified Apelblat equation, CNIBS/R-K equation, and Apelblat-Jouyban-Acree model) were used to correlate the solubility data in the four mixed solvents. In accordance with the fitting results, all the models could give satisfactory correlation for the relationship of solubility, temperature and the composition of solvent. On the basis of the solubility data and correlation, for antisolvent selection, ethanol, 2-propanol, and acetone are better than methanol in the crystallization of Lfucose. Ultimately, it can be concluded that all of the experimental solubility data measured in this study will be useful for designing and optimizing crystallization process of Lfucose in industry.
ASSOCIATED CONTENT
* Supporting Information S
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.8b00361.
■
Experimental solubility scatter diagrams of L-fucose in the four binary solvent systems at the temperature range from 288.15 to 308.15 K and the fitting plots of ln(xA) versus T (from 288.15 to 308.15 K) and x1 (from 0.0 to 1.0) for L-fucose solubility in the four binary solvents by using Apelblat−Jouyban−Acree model (PDF)
AUTHOR INFORMATION
Corresponding Author
*Tel: 86-0431-85968101. Fax: +86-0431-85968101. E-mail:
[email protected]. ORCID
Peng Wang: 0000-0002-1972-6106 H
DOI: 10.1021/acs.jced.8b00361 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Funding
This work was financially supported by the National Natural Science Foundation of China (NNSFC 51603019), the Science and Technology Project of the Education Department of Jilin Province in the 13th Five-Year (No. JJKH20170554KJ), and the Outstanding Young Talents Funding Project of the Science and Technology Development Plan of Jilin Province (No. 20180520164JH). Notes
The authors declare no competing financial interest.
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REFERENCES
(1) Choi, S. S. H.; Lynch, B. S.; Baldwin, N.; Dakoulas, E. W.; Roy, S.; Moore, C.; Thorsrud, B. A.; Röhrig, C. H. Safety evaluation of the human-identical milk monosaccharide, l-fucose. Regul. Toxicol. Pharmacol. 2015, 72, 39−48. (2) Wang, P.; Jiang, J.; Jia, X. a.; Jiang, L.; Li, S. Solubility of trehalose in water + ethanol solvent system from (288.15 to 318.15) K. J. Chem. Eng. Data 2014, 59, 1872−1876. (3) Bowden, N. A.; Sanders, J. P. M.; Bruins, M. E. Solubility of the Proteinogenic α-Amino Acids in Water, Ethanol, and Ethanol−Water Mixtures. J. Chem. Eng. Data 2018, 63, 488−497. (4) Zhou, Y.; Hao, H.; Yang, J.; Zhu, P.; Wang, T.; Hou, B.; Xie, C.; Wang, J. Solid−liquid phase equilibrium and mixing properties of 2Cyano-4’-methylbiphenyl in pure solvents. J. Chem. Thermodyn. 2016, 103, 134−141. (5) Huang, X.; Wang, J.; Hao, H.; Ouyang, J.; Gao, Y.; Bao, Y.; Wang, Y.; Yin, Q. Determination and correlation of solubility and solution thermodynamics of coumarin in different pure solvents. Fluid Phase Equilib. 2015, 394, 148−155. (6) Hu, Y.; Kai, Y.; Cao, Z.; Li, J.; Yang, W. Measurement and correlation solubility and mixing properties of dimethyl succinylsuccinate in pure and mixture organic solvents from (278.15 to 333.15) K. Fluid Phase Equilib. 2013, 354, 259−264. (7) Ali, A.; Ali, M.; Malik, N. A.; Uzair, S.; Khan, A. B. Solvatochromic Absorbance Probe Behavior within Mixtures of the Ionic Liquid 1-Butyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide + Molecular Organic Solvents. J. Chem. Eng. Data 2014, 59, 1755−1765. (8) Barzegar-Jalali, M.; Jouyban-Gharamaleki, A. A general model from theoretical cosolvency models. Int. J. Pharm. 1997, 152, 247− 250. (9) Vahdati, S.; Shayanfar, A.; Hanaee, J.; Martínez, F.; Acree, W. E.; Jouyban, A. Solubility of Carvedilol in Ethanol + Propylene Glycol Mixtures at Various Temperatures. Ind. Eng. Chem. Res. 2013, 52, 16630−16636. (10) Parker, A. J. The effects of solvation on the properties of anions in dipolar aprotic solvents. Q. Rev., Chem. Soc. 1962, 16, 163−187. (11) Zou, F.; Zhuang, W.; Wu, J.; Zhou, J.; Liu, Q.; Chen, Y.; Xie, J.; Zhu, C.; Guo, T.; Ying, H. Experimental measurement and modelling of solubility of inosine-5′-monophosphate disodium in pure and mixed solvents. J. Chem. Thermodyn. 2014, 77, 14−22. (12) Li, M.; Liu, S.; Li, S.; Yang, Y.; Cui, Y.; Gong, J. Determination and Correlation of Dipyridamole p-Toluene Sulfonate Solubility in Seven Alcohol Solvents and Three Binary Solvents. J. Chem. Eng. Data 2018, 63, 208−216. (13) Akerlof, G. Dielectric Constants of Some Organic SolventWater Mixture at Various Temperatures. J. Am. Chem. Soc. 1932, 54, 4125−4139. (14) Leng, Y.; Qi, H. Solubility of Aspartame in Water, Methanol, Ethanol and Different Binary Mixtures in the Temperature Range of (278.15 to 333.15) K. J. Chem. Eng. Data 2014, 59, 1549−1555.
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DOI: 10.1021/acs.jced.8b00361 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
