Solid–Liquid Equilibrium of Isomaltulose in Five Pure Solvents and

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Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Solid−Liquid Equilibrium of Isomaltulose in Five Pure Solvents and Four Binary Solvents from (283.15 to 323.15) K Shuang Song,† Jun Guo,† Jingxuan Qiu,† Jinyu Liu,† Mengyao An,‡,§ Dengjing Yi,†,§ Peng Wang,*,†,§ and Huixuan Zhang*,†,§ †

School of Chemical Engineering, ‡School of Chemistry 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: The solubility of isomaltulose in five monosolvents (water, methanol, ethanol, isopropanol, and acetone) and four different binary solvents (water + methanol, water + ethanol, water + isopropanol, and water + acetone) was measured by a gravimetric method at temperatures ranging from (283.15 to 323.15) K. Results showed that the solubility of isomaltulose increased with increasing temperature. The order of isomaltulose solubility in these selected pure solvents at a given temperature was water > methanol > ethanol > isopropanol > acetone. In water + acetone solvent system, the solubility of solute just increased with increasing water mole fraction. In water + alcohol solvent systems, the minimum solubility values were achieved at a certain solvent composition because of the influence of polarity and hydrogen bond. The Apelblat model, the CNIBS/R-K model, and the modified version of the Jouyban−Acree model (the Apel-JA model) were used to correlate the experimental data, and the results indicated that those models were all suitable to correlate the solubility results.

1. INTRODUCTION Isomaltulose (also named palatinose, a-D-glucopyranosyl-1,6-dfructofuranose; CAS. No. 13718-94-0), a reducing disaccharide composed of a glucose and a fructose joined by an a-1,6glycosidic bond, is a natural component of honey and sugar cane and is considered suitable for the formulation of foods for athletes and diabetics. As an isomer of sucrose (a-Dglucopyranosyl-1,2-d-fructofuranose), isomaltulose is hardly fermented by environmental or oral microbes and can inhibit the formation of insoluble glucans; therefore, it shows a reduced cariogenic potential compared to sucrose.1,2 In addition, isomaltulose is completely metabolized in the intestine much more slowly than sucrose and other sugars.3,4 As a result, it causes a very low glycemic and insulinemic response, a property that is favorable for both diabetics and nondiabetics because it provides the same amount of energy as common sugar but for a significantly longer period.5 In industrial manufacturing, isomaltulose goes through several separation processes to purify it. In those processes, solution crystallization and further recrystallization are the key steps. Given this situation, it is necessary to determine the solubility of isomaltulose in potential solvents systematically. The solubility data of isomaltulose in pure water was reported in the literature.6 However, the solubility data in binary solvent mixtures of isomaltulose have never been studied to date. Thus, it is necessary to measure the solid−liquid phase equilibrium data of isomaltulose in commonly used binary solvent mixtures. In the present work, experimental solubility data for isomaltulose in five different pure solvents (water, methanol, © XXXX American Chemical Society

ethanol, isopropanol, and acetone) and four binary solvent mixtures (water + methanol, water + ethanol, water + isopropanol, and water + acetone) were determined at temperatures ranging from (283.15 to 323.15) K using a gravimetric method at atmospheric pressure. Additionally, the obtained solubility data of isomaltulose was correlated by the Apelblat model, the CNIBS/R-K model, and the combined version of the Jouyban− Acree model (Apel-JA model). It was found that all of the models showed satisfactory correlation results with the experimental values, which could be applied for the industrial purification process of isomaltulose.

2. EXPERIMENT 2.1. Materials. Isomaltulose (C12H22O11, Figure 1, Mw = 360.32) with a mass fraction purity higher than 99.0% was

Figure 1. Chemical structure of isomaltulose. Received: September 17, 2018 Accepted: February 6, 2019

A

DOI: 10.1021/acs.jced.8b00823 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 1. Description of Chemicals and Solvents Used in the Experiments material

molecular formula

CAS

isomaltulose methanol ethanol isopropanol acetone maltitol xylose

C12H22O11 CH4O C2H6O C3H8O C3H6O C12H24O11 C5H10O5

13718-94-0 67-56-1 64-17-5 67-63-0 67-64-1 585-88-6 41247-05-6

molar mass (g·mol−1) mass fraction purity ≥0.990 ≥0.995 ≥0.997 ≥0.997 ≥0.995 ≥0.990 ≥0.995

342.30 32.04 46.07 60.10 58.08 344.31 150.13

source

analysis method

Guilin Welpont Biotelchnology Co., Ltd. Beijing Chemical Works Tianjin Fuyu Fine Chemical Co., Ltd. Beijing Chemical Works Beijing Chemical Works Shandong Futaste Pharmaceutical Co. Ltd.. Shandong Futaste Pharmaceutical Co. Ltd..

HPLCa GCb GCb GCb GCb HPLCa HPLCa

a High-performance liquid chromatography. bGas−liquid chromatography. Both the analysis method and the mass fraction purity were provided by the suppliers.

Table 2. Model Parameters of the Apelblat Equation for Isomaltulose in Five Monosolvents solvent

A

B

C

ARD/%

104RMSD

methanol ethanol isopropanol acetone water

−398.0174 −23.3804 −120.8864 −249.5763 −309.6195

14808.0812 −3375.5256 797.2801 6940.1728 11530.4227

60.1616 4.8568 19.3263 38.0040 46.9154

3.06 5.46 3.48 1.97 1.00

1.62 0.65 0.18 0.01 4.63

Table 3. Model Parameters of the Apelblat Equation for Isomaltulose in Four Binary Solvents x2a

A

0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

−662.1728 −422.2485 −668.8257 −985.5321 −584.8244 −488.4891 −216.6720 −569.4236 −238.8019 −227.8636

0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

−1039.2507 −331.8829 −589.2046 −780.1330 −560.2471 −691.9188 −714.0205 −339.8579 −478.8010 −479.6850

0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

−480.4605 −195.1053 −194.8119 422.2598 −629.5315 −223.4490 −682.5972 −643.1809 −152.0444 −540.9079

0.10 0.20 0.30 0.40 0.50

−518.7774 −23.3934 −380.0741 −402.6174 −265.3570

B Water + Methanol 26091.9766 14921.8862 25799.4037 39936.0895 21848.4682 17678.1907 5242.4439 21701.0083 6863.9946 7143.9629 Water + Ethanol 43821.0799 11967.0668 21543.9017 31219.3745 21255.1722 27377.5055 28372.6223 11285.3863 17894.8695 18364.9591 Water + Isopropanol 17839.4048 5152.1921 5191.2934 −22700.8448 24663.0902 6231.1381 27104.6456 25269.1702 2940.3112 20702.7294 Water + Acetone 19331.7637 −2820.8491 13493.7088 15037.5200 8158.2905 B

C

ARD/%

104RMSD

99.7033 64.1132 100.9854 148.3016 88.6923 74.3390 34.0295 86.3269 37.1108 35.0868

4.68 5.69 6.70 3.32 3.53 4.89 3.35 2.80 5.91 0.89

0.84 0.75 0.92 0.64 1.07 2.37 2.50 3.57 9.86 2.02

155.0501 49.6210 89.1263 117.1329 84.5151 104.1596 107.5742 52.0719 72.6794 72.6508

2.22 1.34 4.86 0.74 0.95 3.06 1.89 0.62 3.84 0.57

0.07 0.03 0.12 0.03 0.11 0.85 1.10 0.45 5.36 1.86

72.2192 29.5878 29.5646 −62.2285 94.5918 34.3221 102.7746 97.0521 24.1090 82.0034

3.91 1.46 1.72 3.79 4.08 4.18 1.70 5.95 4.82 1.97

0.09 0.02 0.04 0.10 0.20 0.52 0.54 3.70 5.87 3.70

78.0115 4.1727 57.2030 60.3374 40.4405

2.91 3.79 1.37 1.29 4.33

0.05 0.06 0.02 0.04 0.29 DOI: 10.1021/acs.jced.8b00823 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 3. continued x2a

A

0.60 0.70 0.80 0.90

−440.7905 −414.9835 −514.1488 −208.5238

B

C

Water + Acetone 15996.1972 14480.1453 19199.6631 5886.2706

66.7775 63.2839 78.0515 32.3842

ARD/%

104RMSD

3.67 4.04 5.13 2.55

0.81 1.56 5.46 4.47

a

x2 is the initial mass fraction of water in the binary solvents.

Table 4. Model Parameters of the CNIBS/R-K Equation for Isomaltulose in Four Binary Solvents T/K

B0

B1

283.15 293.15 303.15 313.15 323.15

−6.2428 −5.9087 −5.5862 −5.1364 −4.7286

−16.2191 −18.1282 −13.8238 −13.7878 −12.0715

283.15 293.15 303.15 313.15 323.15

−7.9944 −7.6862 −7.1631 −6.7067 −6.3061

−23.1980 −23.6556 −24.9027 −24.1487 −23.2042

283.15 293.15 303.15 313.15 323.15

−9.0702 −8.5025 −8.1096 −7.5398 −6.9736

−12.9003 −13.9960 −14.1412 −14.7985 −17.4745

283.15 293.15 303.15 313.15 323.15

−10.4380 −10.0079 −9.4703 −8.9720 −8.4557

2.9703 2.8144 2.0355 3.0575 1.7160

B2

ARD/%

104RMSD

29.7928 34.9930 24.2538 25.4588 24.2224

10.41 10.61 7.45 8.55 8.50

4.32 7.83 7.26 11.18 14.98

53.6407 54.2687 56.6251 54.3726 53.4937

15.47 17.44 23.45 24.87 27.51

8.23 11.31 17.56 24.99 43.61

29.7732 29.5243 29.3491 26.0268 30.7623

7.91 9.88 12.23 11.05 12.55

1.37 1.93 6.03 9.58 27.57

−7.7427 −9.6438 −12.9277 −21.0918 −19.6254

5.05 5.95 8.15 7.77 9.37

3.11 3.17 5.16 11.14 20.94

B3

Water + Methanol 60.7287 −72.0253 69.3421 −83.9957 53.5042 −61.8026 54.8885 −64.5921 50.5635 −60.7960 Water + Ethanol 99.4418 −125.7982 101.3032 −127.8812 106.2411 −134.1548 103.6513 −130.2452 101.5083 −128.1848 Water + Isopropanol 61.1883 −73.0107 62.3521 −73.1265 64.0873 −74.6258 63.4720 −70.3195 73.2306 −82.3105 Water + Acetone −0.8570 12.0063 −2.1713 15.2037 −1.4709 18.3048 −9.3766 33.1169 −4.7112 28.1596

supplied by Guilin Welpont Biotelchnology Co., Ltd. The organic solvents, including methanol, ethanol, isopropanol, and acetone, were analytical reagent grade and used without additional purification. Deionizated water was produced by a Merck Millipore Mingche-D 24UV ultrapure water system at 298.15 K with the electrical resistivity of 18.2 MΩ·cm. More detailed information about materials in this work are listed in Table 1. 2.2. Characterization. The Rigaku Smartlab X-ray Diffractometer (PXRD) was used for the crystallinity test of the isomaltulose, which used Cu Kβ radiation and worked under 200 mA in current and 45 kV for voltage. The samples were scanned from 10° to 50° in 2θ with a scanning rate of 10° per minute. To prove that isomaltulose remained stable during the experimental process, excess isomaltulose was added into the five pure solvents and the four binary solvents (x2 = 0.50) respectively to make suspensions. After the suspensions were stirred for 12 h, the sediments were filtered, dried, and characterized by PXRD. 2.3. Apparatus and Procedures. The solubility of isomaltulose was measured in various solvents by the gravimetric method.7−9 To begin, some excess isomaltulose was added into a crystallizer which contains a known amount of solvent. The mass of solute and solvents was weighed with an analytical balance (Denver Instrument SI-224, Sartorius Scientific Instruments Co., Ltd., China) with an accuracy of ±0.0001 g.

B4

Table 5. Model Parameters of the Apel-JA Equation for Isomaltulose in Four Binary Solvents solvents

water + methanol

water + ethanol

water + isopropanol

water + acetone

A1 B1 C1 A2 B2 C2 J0 J1 J2 ARD/% 103RMSD

−312.0244 10703.5109 47.8249 −658.0563 25810.0251 99.2832 −1025.8901 1986.0789 −2161.4321 12.57 2.96

−472.3332 18090.9710 71.6236 −576.2096 22395.5850 86.6423 −1183.1964 3054.8312 −4110.8987 21.88 3.83

−464.1598 17736.3543 70.3823 −182.0539 4510.9030 27.8475 −1134.3074 2472.1163 −2195.7018 12.69 2.64

−367.9629 13352.7148 56.0659 −309.8301 10033.8110 46.7672 −1046.4279 1044.4790 1054.3886 10.36 1.73

The temperature was controlled by a thermostatic water bath (Shanghai Laboratory Instrument Works Co., Ltd., 501A, China). Then the mixed solution was stirred at constant temperature for 60 min (determination of the dissolution equilibrium time is shown in the Supporting Information) with a magnetic stirring apparatus (IKA, RCTBS25, Germany). The suspensions were settled for about 30 min at a constant temperature to make sure that there were no visible particles in the supernatant. Finally, about 3 mL of the upper clear solution C

DOI: 10.1021/acs.jced.8b00823 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Figure 2. Comparison of X-ray powder diffraction patterns of the raw material and residual solids in five monosolvents and four mixed solvents at the water content x2 = 0.50.

filtered by organic membranes (0.45 μm, Φ13 mm) was transferred into a Petri dish and dried at 323.15 K for about 24 h. In our work, every experimental point was measured more than three times and expressed by the average value. The saturated mole fraction solubility of isomaltulose (x1) in solvent was calculated by eq 1, and the mole fraction of water (x2) in the mixed solvent was calculated by eq 2. m1/M1 x1 = m1/M1 + m2 /M 2 + m3 /M3 x2 =

m2 /M 2 m2 /M 2 + m3 /M3

N

ARD =

∑i = 1 (xical − xiexp)2 N

(5) exp

where N is the number of experimental points and x1 and x1cal represent the experimental and calculated values, respectively. The values of the three parameters A, B, and C together with the ARD and RMSD are listed in Tables 2 and 3. 3.2. CNIBS/R-K Model. The combined nearly ideal binary solvent/Redlich−Kister (CNIBS/R-K) model describes the relationship between experimental solubility data and initial mole fraction compositions in a binary system under isothermal conditions.9 It could be described by eq 6 as follows:

(1)

(2)

N

ln x1 = x 2 ln(x1)2 + x3 ln(x1)3 + x 2x3∑ Si(x 2 − x3)i i=0

(6)

where x1 is the saturated mole fraction solubility of isomaltulose and x2 and x3 refer to the initial mole fraction of water and organic solvents in the absence of isomaltulose, respectively (x2 = 1 − x3, for binary solvent systems). Meanwhile (x1)2 and (x1)3 are the solubility of isomaltulose in pure water and organic solvents. Si are model parameters, and N determines the number of “curve-fit” parameters. For binary solvent systems, N equals 2; thus, eq 6 can be rewritten as eq 7.

3. THERMODYNAMIC MODELS 3.1. Apelblat Model. The Apelblat model was used to correlate and predict the solid−liquid equilibrium solubility data of isomaltulose and evaluate the relationship between the mole fraction solubility of isomaltulose and temperature.12,13 It can be described as follows: B + C ln T T

(4)

N

RMSD =

where m1, m2, and m3 represent the mass (g) of isomaltulose, water, and organic solvent, respectively; M1, M2, and M3 represent the molar mass (g·mol−1) of isomaltulose, water, and organic solvent, respectively. Verification of the experimental method is shown in the Supporting Information by comparing the experimental or calculated data with the values in the literature.6,10,11

ln x1 = A +

x exp − x cal 1 ∑ i exp i N i=1 xi

ln x1 = ln(x1)3 + x 2(ln(x1)2 − ln(x1)3 + S0 − S1 + S2)

(3)

+ x 22( −S0 + 3S1 − 5S2) + x 23( −2S1 + 8S2)

where T refers to the absolute temperature (K); x1 is the mole fraction solubility of isomaltulose at T; A, B, and C are model parameters. Values of A and B correspond to the variation in the solution activity coefficient. Constant C denotes the effect of temperature on the fusion enthalpy.13 The average relative deviation (ARD) and the root-mean-square deviation (RMSD) are used to calculate the deviation between experimental and calculated data and are defined as follows:

+ x 24( −4S2)

(7)

This equation could be simplified into the general single equation as eq 8, which is called the variant of CNIBS/R-K model. ln x1 = B0 + B1x 2 + B2 (x 2)2 + B3(x 2)3 + B4 (x 2)4 D

(8)

DOI: 10.1021/acs.jced.8b00823 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 6. Experimental (x1exp) and Calculated (x1cal) Mole Fraction Solubilities of Isomaltulose in Water + Methanol at Temperature T and Pressure P = 0.1 MPaa,b x2

104x1exp

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

23.278 8.542 5.402 5.546 7.798 10.276 18.342 24.757 46.971 68.179 108.092 179.778

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

33.580 10.260 7.035 6.835 9.910 14.573 25.063 38.893 63.873 91.522 150.595 230.793

0.00 0.05 0.10 0.20 0.30 0.40

42.924 18.219 13.840 13.905 18.102 27.251

104x1cal (eq 3)

104x1cal (eq 8)

283.15 K 23.610 8.238 5.170 5.268 7.599 10.001 17.662 24.121 45.971 65.147 107.348 180.579 293.15 K 32.001 11.312 7.927 7.833 10.633 15.624 27.709 41.787 67.344 103.310 153.422 229.378 303.15 K 45.490 17.017 12.702 12.714 17.196 26.188

104x1cal (eq 12)

x2

104x1exp

19.444 9.970 6.579 5.075 6.450 10.481 18.157 30.027 45.595 65.679 99.601 189.536

17.423 9.021 6.061 4.927 6.657 11.445 20.616 34.485 51.078 68.737 92.794 149.298

0.50 0.60 0.70 0.80 0.90 1.00

49.056 76.557 108.697 179.727 225.703 305.341

27.157 12.914 8.180 6.257 8.327 14.371 26.067 43.813 65.423 90.507 131.564 247.884

24.392 12.985 8.891 7.357 9.946 16.966 30.278 50.301 74.304 100.053 135.135 216.229

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

69.296 28.021 21.364 22.794 31.702 47.600 80.886 126.410 181.706 273.339 328.539 403.100

37.493 21.310 15.142 12.730 16.780 27.683

37.346 20.346 14.138 11.826 15.902 26.775

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

102.900 47.409 35.522 40.386 63.690 85.902 140.557 216.248 308.563 426.259 485.833 580.443

104x1cal (eq 3)

104x1cal (eq 8)

303.15 K 45.882 72.539 106.015 165.700 222.792 302.354 313.15 K 67.365 27.702 21.130 22.252 31.529 46.631 79.560 126.003 177.561 268.149 327.806 411.419 323.15 K 103.331 48.289 36.288 41.569 64.469 87.460 143.503 218.753 313.706 436.941 487.547 575.324

104x1cal (eq 12)

48.368 80.263 120.252 163.896 217.017 316.015

47.094 77.293 113.234 151.676 203.769 322.506

58.787 33.577 24.094 20.820 28.213 47.409 83.038 135.457 195.463 251.906 311.195 420.423

61.782 34.301 24.102 20.256 26.954 44.591 76.952 124.191 179.556 238.044 316.485 493.124

88.388 54.441 41.341 38.182 52.758 87.570 148.599 232.519 320.717 395.085 466.768 601.912

109.287 61.603 43.629 36.643 48.039 77.774 131.173 207.328 294.568 384.794 504.048 769.996

a

x1exp is the experimental solubility; x1cal (eq 3), x1cal (eq 8), and x1cal (eq 12) are the calculated solubilities according to eqs 3, 8, and 12, respectively. bThe standard uncertainty of T is u(T) = 0.05 K. The relative uncertainty of the solubility is ur(x1) = 0.15. The relative uncertainty of pressure is ur(P) = 0.05. The relative uncertainty of the initial mass fraction of water in the binary solvents is ur(x2) = 0.001.

B B y i y i ln x1 = x 2jjjA1 + 1 + C1 ln T zzz + x3 lnjjjA 2 + 2 + C 2 ln T zzz T T { k { k

where B0, B1, B2, B3, and B4 are constants of this model.13−15 These parameters together with the ARD and RMSD are listed in Table 4. 3.3. Apel-JA Model. The Jouyban−Acree model is especially well-known because of its ability to investigate the dependence of both initial mole fraction composition of binary solvent mixtures and temperature on the solubility of isomaltulose.6,16 The model can be expressed by eq 9.

N

+ x 2x3∑ [Ji (x 2 − x3)i /T ] i=0

The values of the nine parameters A1, B1, C1, A2, B2, C2, J0, J1, and J2 together with the ARD and RMSD are listed in Table 5.

N

4. RESULTS AND DISCUSSION 4.1. X-ray Powder Diffraction Analysis. The X-ray powder diffraction (PXRD) patterns verified the identity and the crystallinity of isomaltulose used in this work. The obtained patterns also revealed that all the suspension solids were the same as the raw material. As shown in Figure 2, the PXRD patterns of all the samples had the same characteristic peaks. Whereas some great changes in peak height were found, most were clearly explained as preferred orientation effects due to the morphology and insufficient grinding of the crystals.17 Therefore, the results demonstrated that there was no degradation or crystal form transformation during the experimental process.

ln x1 = x 2 ln(x1)2 + x3 ln(x1)3 + x 2x3∑ [Ji (x 2 − x3)i /T ] i=0

(9)

where Ji represents the model constants; the other symbols are the same as in eq 6. The (x1)2 and (x1)3 were replaced by the corresponding values of the Apelblat model as follows: ln(x1)2 = A1 +

B1 + C1 ln T T

(10)

ln(x1)3 = A 2 +

B2 + C2 ln T T

(11)

(12)

Then, eqs 10 and 11were substituted into eq 9 as follows: E

DOI: 10.1021/acs.jced.8b00823 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 7. Experimental (x1exp) and Calculated (x1cal) Mole Fraction Solubilities of Isomaltulose in Water + Ethanol at Temperature T and Pressure P = 0.1 MPaa,b x2

104x1exp

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

3.943 1.147 0.782 0.514 1.952 3.346 8.059 15.949 24.602 53.753 96.224 179.778

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

6.031 1.266 1.030 0.748 2.599 4.743 10.280 20.904 38.997 70.156 132.130 230.793

0.00 0.05 0.10 0.20 0.30 0.40

12.336 1.596 1.388 1.469 4.050 7.538

104x1cal (eq 3)

104x1cal (eq 8)

283.15 K 3.781 1.141 0.779 0.495 1.943 3.322 7.873 15.722 24.675 52.196 96.513 180.579 293.15 K 6.721 1.264 1.031 0.815 2.635 4.822 10.809 21.553 38.609 75.314 131.462 229.378 303.15 K 11.565 1.655 1.417 1.434 3.994 7.510

104x1cal (eq 12)

x2

104x1exp

3.374 1.335 0.795 0.693 1.277 3.221 8.209 17.737 31.007 47.604 79.238 200.808

3.581 1.286 0.722 0.613 1.182 3.212 8.760 19.654 34.174 49.863 75.999 173.147

0.50 0.60 0.70 0.80 0.90 1.00

16.409 32.706 61.463 118.549 191.191 305.341

4.591 1.784 1.050 0.913 1.702 4.372 11.345 24.799 43.398 65.822 106.692 259.613

4.877 1.825 1.052 0.910 1.739 4.625 12.348 27.304 47.196 68.869 104.819 235.223

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

19.877 2.636 2.072 2.840 6.638 12.591 28.187 55.720 103.230 191.754 287.502 403.100

7.747 2.862 1.634 1.396 2.650 7.018

7.176 2.789 1.646 1.446 2.735 7.119

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

30.596 4.239 2.898 5.058 12.115 21.522 46.182 94.616 172.830 302.339 467.072 580.443

104x1cal (eq 3)

104x1cal (eq 8)

303.15 K 16.338 32.663 62.193 115.117 190.401 302.354 313.15 K 19.321 2.509 2.011 2.675 6.670 12.430 26.844 53.989 102.660 184.878 290.742 411.419 323.15 K 31.420 4.321 2.932 5.241 12.116 21.680 47.408 96.209 172.958 309.809 464.678 575.324

104x1cal (eq 12)

18.652 41.003 70.396 102.089 154.944 349.338

18.602 40.507 69.515 101.273 153.676 339.449

12.227 4.662 2.720 2.375 4.533 11.996 31.809 69.589 117.854 165.173 233.338 461.121

11.286 4.541 2.738 2.437 4.556 11.606 29.674 63.594 108.230 157.187 237.474 516.022

18.252 7.258 4.376 3.990 7.776 20.688 54.573 117.880 195.767 266.860 362.432 676.837

18.802 7.809 4.800 4.319 7.975 19.879 49.727 104.834 176.764 255.597 383.989 820.442

a

x1exp is the experimental solubility; x1cal (eq 3), x1cal (eq 8), and x1cal (eq 12) are the calculated solubilities according to eqs 3, 8, and 12, respectively. bThe standard uncertainty of T is u(T) = 0.05 K. The relative uncertainty of the solubility is ur(x1) = 0.15. The relative uncertainty of pressure is ur(P) = 0.05. The relative uncertainty of the initial mass fraction of water in the binary solvents is ur(x 2) = 0.001.

4.2. Solubility Data. The measured solubility of isomaltulose in the monosolvents and the binary solvents was measured from (283.15 to 323.15) K by a gravimetric method at atmosphere pressure (P = 0.1 MPa). The mole fraction solubilities of isomaltulose in the five monosolvents are listed in Tables 6−9. As can be seen from Figures S2 and S3 (in the Supporting Information), the solubility of isomaltulose in all the solvents was positively related to temperature, which confirmed that the dissolution process was endothermic. The isomaltulose solubility in water was relatively high, followed by methanol, ethanol, isopropanol, and acetone. Polarity is a critical factor influencing the solubility of isomaltulose in the selected pure solvents, and the dielectric constant of the five monosolvents increases according to the following order: isopropanol (18.00) < acetone (19.10) < ethanol (24.30) < methanol (31.50) < water (78.54) at 298.15 K.18 For water, methanol, and ethanol, the order of isomaltulose solubility from low to high was consistent with the sequence of dielectric constant mentioned above. As for the other two solvents, although the polarity of the acetone molecule was greater than that of isopropanol, it was more soluble in isopropanol for isomaltulose. This may be caused by the formation of hydrogen bonds between the free electron of

the hydroxyls of isopropanol and isomaltulose, which may contribute to the higher solubility. Isomaltulose has large dipole moments and may offer strong nonspecific dipole−dipole interactions with the solvent,19 so it may form hydrogen bonds with a solvent that has electron donor sites. The solute−solvent interactions by hydrogen bonds could have an important influence on the solubility behavior. From the above analysis, water could be the positive solvent apparently, while acetone with the lowest dissolving capacity was considered to be the most suitable antisolvent in the purification and separation process of isomaltulose. The solubility results of isomaltulose in the binary solvent mixtures are shown in Tables 6−9 and graphically presented in Figures S4−S7, which indicate that the solubility of isomaltulose increased with increasing temperature at constant solvent compositions. In the water + acetone solvent system, as shown in Figure S7, it was observed that the solubility of isomaltulose increased with the rising of mole fraction of water without inflection point. However, from Figures S4−S6, there was a critical water content at about 0.05−0.20 corresponding to the minimum point of each curve. Below the critical point, the solubility of isomaltulose declined with mole fraction of water, which may be attributed to the influence of hydrogen bonding. F

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Table 8. Experimental (x1exp) and Calculated (x1cal) Mole Fraction Solubilities of Isomaltulose in Water + Isopropanol at Temperature T and Pressure P = 0.1 MPaa,b x2

104x1exp

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

1.257 0.607 0.520 0.706 0.986 2.401 4.864 13.596 26.355 40.686 83.342 179.778

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

2.448 0.891 0.805 1.071 1.577 2.922 6.756 17.730 31.142 58.168 111.899 230.793

0.00 0.05 0.10 0.20 0.30 0.40

3.901 1.224 1.155 1.538 2.850 4.998

104x1cal (eq 3)

104x1cal (eq 8)

283.15 K 1.291 0.607 0.524 0.707 0.958 2.326 4.711 13.483 25.183 39.217 82.073 180.579 293.15 K 2.294 0.868 0.786 1.056 1.702 3.177 7.319 18.230 34.825 63.539 116.700 229.378 303.15 K 4.009 1.315 1.187 1.587 2.716 4.729

104x1cal (eq 12)

x2

104x1exp

1.151 0.697 0.544 0.589 1.048 2.363 5.594 12.380 24.486 44.438 81.601 179.594

1.369 0.733 0.524 0.516 0.909 2.138 5.412 12.790 26.372 47.778 82.495 158.636

0.50 0.60 0.70 0.80 0.90 1.00

11.950 28.018 55.402 106.143 183.433 305.341

2.030 1.168 0.871 0.874 1.470 3.195 7.406 16.249 32.123 58.486 107.590 235.509

2.089 1.146 0.830 0.822 1.426 3.273 8.064 18.588 37.563 66.988 114.041 215.432

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

6.677 2.249 1.826 2.468 4.004 7.691 18.714 43.212 89.990 172.335 288.241 403.100

3.007 1.724 1.292 1.331 2.338 5.331

3.200 1.799 1.323 1.322 2.274 5.125

0.00 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

11.976 3.391 2.742 3.603 5.158 12.734 28.150 76.308 143.849 254.275 485.989 580.443

104x1cal (eq 3)

104x1cal (eq 8)

303.15 K 11.479 27.125 52.581 102.461 177.804 302.354 313.15 K 6.902 2.092 1.803 2.398 3.938 7.581 18.139 43.851 85.653 164.383 287.510 411.419 323.15 K 11.712 3.475 2.746 3.637 5.249 12.960 28.823 76.170 149.004 262.300 489.380 575.324

104x1cal (eq 12)

12.911 29.135 57.672 101.155 170.393 320.576

12.367 27.989 55.771 98.475 166.243 310.349

5.315 2.947 2.133 2.073 3.510 7.945 19.610 45.853 93.909 165.805 264.399 424.665

4.913 2.831 2.117 2.145 3.673 8.174 19.437 43.432 85.794 150.758 253.646 470.404

9.362 4.646 3.134 2.892 5.012 11.983 31.217 75.396 154.636 265.587 405.535 629.270

7.550 4.463 3.396 3.499 5.995 13.241 31.183 69.139 136.038 238.973 402.479 744.944

a

x1exp is the experimental solubility; x1cal (eq 3), x1cal (eq 8), and x1cal (eq 12) are the calculated solubilities according to eqs 3, 8, and 12, respectively. bThe standard uncertainty of T is u(T) = 0.05 K. The relative uncertainty of the solubility is ur(x1) = 0.15. The relative uncertainty of pressure is ur(P) = 0.05. The relative uncertainty of the initial mass fraction of water in the binary solvents is ur(x 2) = 0.001.

satisfactory correlation results. For Apelblat, CNIBS/R-K, and Apel-JA models, the maximum ARD values were 6.70%, 27.51%, and 21.88%, respectively, and the maximum RMSD values were 9.86 × 10−4, 4.36 × 10−3, and 3.83 × 10−3, respectively.

To be specific, except for polarity, the solubility was also affected by the mutual competition of hydrogen bonding interactions between the solute−solvent and solvent−solvent. Pure alcohol solvents had better dissolving ability compared with the binary solvent at inflection point because of the formation of hydrogen bonds between pure alcohols and isomaltulose. As for water content below the critical point, the introduction of water with both hydrogen bonding donors and acceptors would preferably interact with hydrogen bonding solvent molecules such as the alcohols, which could weaken the hydrogen bonding interactions between isomaltulose and alcohols. This was the reason why the solubility decreased with water content below the critical point. Above the critical point, the polarity of water played the dominant role in determining the solubility of isomaltulose in mixed solvents. As a result, a continuous rising trend for the solubility could be observed in this region. 4.3. Data Correlation. The solubility data of isomaltulose were correlated with the Apelblat equation, CNIBS/R-K equation, and the combined version of the Jouyban−Acree equation (Apel-JA equation). Tables 2−5 present the parameter, ARD, and RMSD values. The experimental and calculated data are shown in Tables 6−9. From the tables, all the models could give

5. CONCLUSIONS In this work, the solubility data of isomaltulose was measured in five monosolvents and four binary solvent systems at temperature from (283.15 to 323.15) K at atmospheric pressure. It turned out that the solubility of isomaltulose was a function of temperature and solvent composition for all solvent systems. The solubilities all increased with increasing temperature in the solvent system measured. In the binary water + alcohol solvent mixtures, there was a minimum solubility corresponding to a critical x2 value at about 0.05−0.20 due to the mutual competition of hydrogen bonding interactions between the solute−solvent and solvent−solvent. However, an inflection point was not found in binary solvent mixtures of water + acetone because acetone without hydrogen bonding donors or acceptors could not interact with isomaltulose. The Apelblat model, CNIBS/R-K model, and the Apel-JA model were used to correlate the solubility data. The corresponding results showed G

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Table 9. Experimental (x1exp) and Calculated (x1cal) Mole Fraction Solubilities of Isomaltulose in Water + Acetone at Temperature T and Pressure P = 0.1 MPaa,b x2

104x1exp

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

0.281 0.429 0.573 0.794 1.434 2.786 7.014 14.835 36.046 76.344 179.778

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

0.430 0.645 0.841 1.096 1.941 3.748 9.818 20.791 46.922 107.611 230.793

0.00 0.10 0.20 0.30 0.40 0.50

0.755 0.927 1.476 1.708 2.598 6.868

104x1cal (eq 3)

104x1cal (eq 8)

283.15 K 0.277 0.431 0.556 0.786 1.440 2.697 6.941 14.379 34.661 74.849 180.579 293.15 K 0.448 0.629 0.903 1.126 1.910 4.108 10.258 22.594 51.498 113.330 229.378 303.15 K 0.734 0.734 0.978 1.427 1.681 2.661

104x1cal (eq 12)

x2

104x1exp

0.293 0.395 0.558 0.859 1.482 2.887 6.271 14.744 35.730 83.440 172.316

0.321 0.402 0.522 0.762 1.310 2.674 6.309 16.183 40.906 89.151 141.421

0.60 0.70 0.80 0.90 1.00

17.061 39.124 84.256 178.911 305.341

0.450 0.592 0.806 1.202 2.028 3.914 8.530 20.246 49.330 113.620 222.621

0.485 0.611 0.797 1.165 1.991 4.018 9.329 23.476 58.249 125.244 198.146

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

1.221 1.684 2.269 2.616 3.933 9.974 24.587 63.616 143.047 269.427 403.100

0.771 0.947 1.239 1.836 3.188 6.490

0.753 0.955 1.251 1.830 3.116 6.228

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

2.003 2.718 3.240 4.105 5.810 15.773 43.863 107.866 228.585 407.391 580.443

104x1cal (eq 3)

104x1cal (eq 8)

303.15 K 6.369 15.926 37.005 81.385 173.160 313.15 K 1.214 1.605 2.199 2.597 3.869 10.020 25.795 62.776 135.618 266.448 411.419 323.15 K 2.019 2.760 3.314 4.133 5.834 15.952 43.317 109.721 236.519 412.185 575.324

104x1cal (eq 12)

15.033 37.292 90.376 189.229 293.483

14.258 35.284 86.131 183.063 289.198

1.269 1.618 2.026 2.815 4.667 9.434 22.578 59.086 148.404 298.539 381.572

1.195 1.524 2.008 2.944 4.997 9.910 22.412 54.652 131.517 276.785 437.090

2.127 2.473 3.014 4.250 7.294 15.306 37.611 98.900 242.623 461.826 541.179

1.928 2.476 3.284 4.828 8.182 16.121 36.076 86.844 206.394 430.766 680.631

a exp x1 is the experimental solubility; x1cal (eq 3), x1cal (eq 8), and x1cal (eq 12) are the calculated solubilities according to eqs 3, 8, and 12, respectively. bThe standard uncertainty of T is u(T) = 0.05 K. The relative uncertainty of the solubility is ur(x1) = 0.15. The relative uncertainty of pressure is ur(P) = 0.05. The relative uncertainty of the initial mass fraction of water in the binary solvents is ur(x 2) = 0.001.

*Tel: +86-431-85716465. Fax: +86-431-85716465. E-mail: [email protected].

that those models could give satisfactory correlation results. The experimental results along with model parameters could be utilized to optimize the purification process for isomaltulose in industry.

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ORCID

Peng Wang: 0000-0002-1972-6106 Huixuan Zhang: 0000-0001-7914-192X

ASSOCIATED CONTENT

S Supporting Information *

Funding

The authors are grateful for the financial support of the National Natural Science Foundation of China (NNSFC 51603019), the Outstanding Young Talents Fund Project of the Science and Technology Development Plan of Jilin Province (20180520164JH), and the Science and Technology Project of the Education Department of Jilin Province in the 13th Five-Year (JJKH20170554KJ).

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.8b00823. (1) Determination of the suitable dissolution equilibrium time for the experiments; (2) verifications of the gravimetrical method for solubility measurement in this work; (3) experimental solubility scatter diagrams of isomaltulose in the four binary solvent systems at the temperature range from 283.15 to 323.15 K; (4) fitting plots of ln(x1) versus T (from 283.15 to 323.15 K) and x2 (from 0.0 to 1.0) for isomaltulose solubility in the four binary solvents by using the Apelblat−Jouyban−Acree model (PDF)

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Notes

The authors declare no competing financial interest.

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REFERENCES

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AUTHOR INFORMATION

Corresponding Authors

*Tel: +86-431-85968101. Fax: +86-431-85968101. E-mail: [email protected]. H

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