Measurement and Correlation of LiquidâLiquid Equilibria for the

Article pubs.acs.org/jced

Measurement and Correlation of Liquid−Liquid Equilibria for the Ternary Systems of Water + D‑Fructose + 1‑Butanol, Water + D‑Glucose + 1‑Butanol, and Water + D‑Galactose + 1‑Butanol at (288.2, 303.2 and 318.2) K Tiantian Ye, Haibin Qu, and Xingchu Gong* Pharmaceutical Informatics Institute, College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058, P. R. China ABSTRACT: The liquid−liquid equilibrium (LLE) data of ternary systems of water + D-fructose + 1-butanol, water + D-glucose + 1-butanol, and water + D-galactose + 1-butanol were determined at three temperatures (288.2, 303.2, and 318.2 K) and atmospheric condition. The distribution coefficients of the monosaccharides were lower than 0.05. For all the three saccharides, their content in the organic-rich phase increased as their content in the aqueous phase increased. The experimental tie-line data were fitted using the Othmer−Tobias equation. The saccharide universal quasichemical functional-group activity coefficient (S-UNIFAC) model was used to predict the LLE data with all the average absolute deviations (AAD) values higher than 0.013. The modified universal quasichemical model was then used to correlate the LLE data. The correlation results agreed better with experimental data than the prediction results obtained with S-UNIFAC. In the production of traditional Chinese medicines, 1-butanol is a promising extractant used to separate active compounds and saccharides in aqueous herbal extracts.

1. INTRODUCTION Traditional Chinese medicines (TCMs) are attracting more and more attention in the treatment of complex diseases. On most occasions, multiple active compounds in a TCM preparation can act on multiple targets. At present many TCMs are made from medicinal herbs by extraction, concentration, and drying, but without any purification process. Accordingly, these TCM preparations usually contain low contents of active compounds. The patients have to take large amounts of these TCM preparations, which results in poor patient compliance. Therefore, the separation and the purification of active compounds in TCM extracts are required. 1-Butanol is one of the extractants widely used in the pharmaceutical industry.1,2 Many botanical active compounds have large distribution coefficients when 1-butanol is used as the extractant. For example, distribution coefficients of salvianolic acid B, lithospermic acid, rosmarinic acid, and salvianolic acid A can be higher than 100.3 Distribution coefficients of baicalin,4 didymin,5 and clinopodiside A5 can be higher than 5. In a previous work, 1-butanol was found to separate active compounds and saccharides in Salvia miltiorrhiza extracts efficiently.6 When Salvia miltiorrhiza extracts were extracted with 1-butanol, total phenolic compound purity increased from 17.6% to at least 48.3%.6 However, when ethanol precipitation was used to treat Salvia miltiorrhiza extracts, total phenolic compound purity increased from 17.6% to at most 29.8%.6 The water extracts of medicinal herbs usually contain large amounts of saccharides,7 such as D-fructose, D-glucose, and sucrose. These saccharides are not considered as active compounds of TCM preparations. © XXXX American Chemical Society

The separation of active compounds and saccharides can dramatically improve active compound purity in dry matter. However, the equilibrium data of systems containing water, saccharides, and 1-butanol are scarce. In this work, the LLE results of the ternary systems of water + D-fructose + 1-butanol, water + D-glucose + 1-butanol, and water + D-galactose + 1-butanol were measured at T = (288.2, 303.2 and 318.2) K under atmospheric pressure. The obtained tie-line data were fitted using the Othmer−Tobias equation.8−10 The experimental data were predicted using the saccharide universal quasichemical functional-group activity coefficient (S-UNIFAC) model11−13 and correlated using the modified universal quasichemical (UNIQUAC) model.14

2. EXPERIMENTAL SECTION 2.1. Materials. One-component reagent for volumetric Karl Fischer titration (pyridine-free titrating agent, 3−5 mg water/mL) was supplied by Shanghai Macklin Biochemical Co., Ltd. D-Fructose, D-glucose, and D-galactose were dried to constant weight at 60 °C. 1-Butanol and phosphorus pentoxide were used as received. Deionized water was produced by an academic water purification system (Milli-Q, Milford, MA, USA). Information about the chemicals used in this work is given in Table 1. 2.2. Apparatus and Procedure. LLE experiments were carried out in 100 mL jacketed glass cells which were connected Received: March 30, 2017 Accepted: July 17, 2017

A

DOI: 10.1021/acs.jced.7b00302 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

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Table 1. Details of the Chemicals Used in This Study chemical name

CAS

purity (mass fraction)

source

purification method

analysis method

D-fructose

57-48-7 50-99-7 59-23-4 7732-18-5 71-36-3

99.4%a >99.8%a >99%a ultrapure ≥99.5%a

Aladdin Reagent (Shanghai) Co., Ltd. Sangon Biotech (Shanghai) Co., Ltd. Sangon Biotech (Shanghai) Co., Ltd. lab made Chinasun Specialty Products Co., Ltd.

drying drying drying none none

HPLC indirect iodometry HPLC conductivity GC

D-glucose D-galactose

water 1-butanol a

Provided by the supplier.

to a thermostat water bath (THD-1008 W, Ningbo Tianheng Instrument Factory). The mixtures composed of water-monosaccharide (D-fructose, D-glucose, or D-galactose)−1-butanol were added into jacketed glass cells with known weights. After agitating for at least 8 h, the ternary mixtures were allowed to settle for at least 10 h at a controlled temperature of 288.2, 303.2, or 318.2 K. The uncertainty of equilibrium temperature was ±0.5 K. The organic phase and aqueous phase were separated with a separatory funnel. The weight contents of monosaccharides in upper phase and lower phase then were determined by gravimetric method using an electronic balance (AB204-N, Mettler Toledo). Most of the solvents in the samples were evaporated at room temperature and atmospheric pressure. An electric fan (ZJ01−192, Taizhou Jiaojiang Zhongjie Electric Factory) was used to make the evaporation faster. Then, the samples were diluted with water and placed in a vacuum oven (DZF-6050, Shanghai Jing Hong Laboratory Instrument Co., Ltd.) heating at 60 °C until constant mass was reached. Finally, the dried samples were weighed to obtain the monosaccharide weights. To accurately determine the weight contents of monosaccharides in the upper phase, the weights of upper phase samples were no less than 1.56 g. The water contents of the two phases were measured with the Karl Fischer titration method using a titrator (870 KF Titrino plus, Metrohm).15,16 All the experiments were repeated three times. Experimental data of water and monosaccharides were checked by mass balance with eq 1. DOMi % =

|WiwM w + W ioM o − Miadded| Miadded

Table 2. Experimental Tie-Line Values Expressed as Mass Fraction, and Values of the Distribution Coefficients of Monosaccharide (D) for the Ternary System Water + D-Fructose + n-Butanol at Temperature T = (288.2, 303.2 and 318.2) K and Pressure p = 0.1 MPaa organic-rich phase (o) Wowater

100 (1)

where DOM is a relative deviation of mass; W and M are the mass fraction and mass, respectively; subscript i refers to water or a monosaccharide; superscript w, o, and added refer to water phase, organic phase, and the mass added in the equilibrium system, respectively. For the system of water + D-fructose +1butanol, DOMsugar and DOMwater were less than 1.99% and 1.91%, respectively. For the system of water + D-glucose +1butanol, DOMsugar and DOMwater were less than 2.59% and 1.71%, respectively. For the system of water + D-galactose +1butanol, DOMsugar and DOMwater were less than 1.81% and 1.85%, respectively.

Wosugar

0.2033 (0.194418) 0.1797 0.1556 0.1408 0.1288 0.1170 0.1036 0.0899 0.0763

0 0.0034 0.0065 0.0088 0.0114 0.0125 0.0131 0.0141 0.0152

0.2067 (0.206017/ 0.208019) 0.1807 0.1670 0.1408 0.1314 0.1174 0.1046 0.0972 0.0862

0

0.2182 (0.210518/ 0.227720) 0.1841 0.1695 0.1506 0.1382 0.1149 0.1077 0.1024 0.0946

0

0.0051 0.0089 0.0118 0.0126 0.0144 0.0154 0.0166 0.0180

0.0056 0.0100 0.0117 0.0142 0.0157 0.0167 0.0176 0.0187

water-rich phase (w) Wwwater T/K = 288.2 0.9223 (0.923318) 0.8164 0.7265 0.6404 0.5645 0.4998 0.4459 0.3880 0.3341 T/K = 303.2 0.9294 (0.928019) 0.8123 0.7212 0.6440 0.5628 0.5010 0.4344 0.3798 0.3307 T/K = 318.2 0.9334 (0.935118/ 0.939520) 0.8315 0.7304 0.6398 0.5639 0.5028 0.4390 0.3799 0.3286

Wwsugar

D

0 0.125 0.2353 0.3319 0.4145 0.4919 0.5518 0.6103 0.6639

0.027 0.028 0.027 0.027 0.025 0.024 0.023 0.023

0 0.126 0.2366 0.3289 0.4158 0.4896 0.5571 0.6124 0.6677

0.040 0.037 0.036 0.030 0.030 0.028 0.027 0.027

0 0.127 0.2359 0.3343 0.4167 0.4850 0.5538 0.6163 0.6692

0.044 0.042 0.035 0.034 0.032 0.030 0.029 0.028

a

Standard uncertainties are u(T) = 0.5 K, u(p) = 5 kPa, u(Wowater) = 0.0062, u(Wosugar) = 0.0008, u(Wwwater) = 0.0082, u(Wwsugar) = 0.007.

3. RESULTS AND DISCUSSION 3.1. Experimental LLE Data. The experimental LLE data of the ternary systems of water + monosaccharide (D-fructose, D-glucose, or D-galactose) + 1-butanol at 288.2, 303.2, and 318.2 K under atmospheric pressure were listed in Tables 2−4. Wowater and Wwwater are the water mass fractions in organic-rich and water-rich phases, respectively. Wosugar and Wwsugar are the monosaccharide mass fractions in organic-rich and water-rich phases, respectively. Wowater and Wwwater values of binary system water + 1-butanol were close to literature data.17−20 The mass fractions of monosaccharides in the water-rich phase were remarkably higher

than those in the organic-rich phase. Saccharide content in the organic-rich phase increased as its content in the water-rich phase increased. The saccharide content in the organic-rich phase was lower than 0.02 in all the experiments. Distribution coefficients for monosaccharides (D = Wosugar/Wwsugar) were calculated. The experimental distribution coefficients for each system were presented in Tables 2−4. In most cases, the distribution coefficients increased as equilibrium temperature increased. The distribution coefficients also increased when monosaccharide mass fraction in the equilibrium systems decreased at most occasions. Poor extraction ability of 1-butanol was observed B



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good extractant to separate active compounds and saccharides in aqueous herbal extracts if the active compounds can have moderate distribution coefficients. 3.2. Modeling and Prediction of the LLE Data. The Othmer−Tobias8−10 equation was used, expressed as follows:

Table 3. Experimental Tie-Line Values Expressed As Mass Fraction, And Values of the Distribution Coefficients of Monosaccharide (D) for the Ternary System Water + D-Glucose (sugar) + 1-Butanol at Temperature T = (288.2, 303.2 and 318.2) K and Pressure p = 0.1 MPaa organic-rich phase (o) Wowater

Wosugar

0.1823 0.1636 0.1427 0.1271 0.1150

0.0032 0.0052 0.0065 0.0071 0.0080

0.1769 0.1619 0.1429 0.1244 0.1151 0.1099 0.0941

0.0039 0.0058 0.0064 0.0071 0.0077 0.0081 0.0085

0.1830 0.1668 0.1481 0.1281 0.1143 0.1074 0.0937 0.0892

0.0040 0.0060 0.0076 0.0081 0.0086 0.0096 0.0101 0.0106

w o ⎛ 1 − Wwater ⎞ ⎛ 1 − W butanol ⎞ = + ln⎜ ln A B ⎟ ⎜ ⎟ 1 1 w o ⎝ Wwater ⎠ ⎝ W butanol ⎠

water-rich phase (w) Wwwater T/K = 288.2 0.8195 0.7164 0.6482 0.5718 0.4973 T/K = 303.2 0.8112 0.7258 0.6445 0.5745 0.4981 0.4396 0.3822 T/K = 318.2 0.8162 0.7313 0.6483 0.5689 0.5044 0.4387 0.3867 0.3259

Wwsugar

D

0.128 0.2380 0.3262 0.4147 0.4898

0.025 0.022 0.020 0.017 0.016

0.1293 0.2386 0.3325 0.4148 0.4930 0.5540 0.6121

0.030 0.024 0.019 0.017 0.016 0.015 0.014

0.1311 0.2408 0.3346 0.4152 0.4879 0.5550 0.6102 0.6684

0.030 0.025 0.023 0.019 0.018 0.017 0.017 0.016

where represents the mass fraction of 1-butanol in the organic-rich phase; A1 and B1 are the equation parameters calculated by least-squares regression. The fitted parameters and R2 were listed in Table 5. The Othmer−Tobias plot is shown in Figure 1. The R2 values were all higher than 0.95. Table 5. Values of Fitted Parameters and Determination Coefficients Othmer−Tobias equation

288.2 303.2 318.2 288.2 303.2 318.2 288.2 303.2 318.2


a

Table 4. Experimental Tie-Line Values Expressed as Mass Fraction, and Values of the Distribution Coefficients of Monosaccharide (D) for the Ternary System Water + D-Galactose (sugar) + 1-Butanol at Temperature T = (288.2, 303.2 and 318.2) K and Pressure p = 0.1 MPaa Wowater

Wosugar

0.1835 0.1648 0.1465

0.0017 0.0036 0.0045

0.1838 0.1630 0.1476 0.1270

0.0024 0.0035 0.0047 0.0054

0.1868 0.1611 0.1415 0.1301

0.0030 0.0061 0.0070 0.0080

T/K = 288.2 0.8217 0.7162 0.6481 T/K = 303.2 0.8120 0.7206 0.6414 0.5762 T/K = 318.2 0.8322 0.7312 0.6377 0.5740

Wwsugar

D

0.126 0.2341 0.3258

0.014 0.015 0.014

0.128 0.2351 0.3309 0.4129

0.018 0.015 0.014 0.013

0.1285 0.2343 0.3321 0.4134

0.023 0.026 0.021 0.019

B1(SE)

Water + D-Fructose +1-Butanol −5.1843(0.4262) −2.6382(0.2223) −5.7119(0.2743) −6.9349(0.3382) −5.9425(0.4648) −7.3917(0.5866) Water + D-Glucose +1-Butanol −5.6118(0.3999) −6.5982(0.5183) −5.6063(0.3469) −6.5592(0.4225) −5.3172(0.2518) −2.7246(0.1312) Water + D-Galactose +1-Butanol −6.6457(1.2274) −8.0961(1.7496) −5.3505(0.6656) −6.2520(0.8990) −6.4071(0.2253) −7.6975(0.3054)

R2 0.9645 0.9877 0.9676 0.9831 0.9820 0.9883 0.9551 0.9614 0.9972

SE is the standard error of parameter.

The distribution of monosaccharide in liquid−liquid equilibrium systems was calculated through the following equation:

xioγio = xiwγi w

(3)

where x is mole fraction; γ is the activity coefficient; subscript i refers to component i in ternary systems of water−monosaccharide−1-butanol; superscripts o and w stand for organicrich phase and water-rich phase, respectively. The activity coefficients of water, 1-butanol, D-fructose, D-glucose, and 11 D-galactose were calculated using the S-UNIFAC model. In S-UNIFAC model, the activity coefficient γ is composed of a combinatorial term γC and a residual term γR, as shown in eq 4.

water-rich phase (w) Wwwater

A1(SEa)

T/K

a

organic-rich phase (o)

(2)

Wobutanol

ln γi = ln γiC + ln γi R

(4)

The values of γ were calculated using the same equation as the original UNIFAC model.21 The values of γR were calculated using the equation proposed in the original UNIFAC model, but group area parameter q was replaced with modified group area parameter q′. Group division is shown in Table 6.11 Group interaction parameters, group volume parameter r, q, and q′ were taken from the literature.11,22 The calculations were carried out using Matlab (R2016a, Mathworks). The prediction results were shown in Figures 2-4. The average absolute deviation (AAD) values between experimental and calculated results were calculated using eq 5. C

a


because all the distribution coefficients were lower than 0.05. Provided that the distribution coefficient of an active compound is 1, the separation factor of this compound and a monosaccharide can be higher than 20. It indicated that 1-butanol is a

n

AAD = C

2

2

∑K = 1 ∑ J = 1 ∑I = 1 |W exp − W calc| 4n

(5) DOI: 10.1021/acs.jced.7b00302 J. Chem. Eng. Data XXXX, XXX, XXX−XXX


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Figure 1. Othmer−Tobias plot for (a) the system containing water + D-fructose + 1-butanol, (b) the system containing water + D-glucose + 1-butanol and (c) the system containing water + D-galactose + 1-butanol at three temperatures. Solid line, the fitted curve at 288.2 K (○); dashed line, the fitted curve at 303.2 K (□); dotted line, the fitted curve at 318.2 K (△).

where φi is the molecular volume fraction which is calculated as

Table 6. Group Division in S-UNIFAC11 molecular group

a

H2O CH3 CH2 OH CH2OH CHOHax COHax CHOHeq COHeq CH−O−C CH2−O CH−O a

D-glucose

D-fructose

D-galactose

water

1-butanol

0 0 0 0 1 0 0 4 0 0 0 1

0 0 0 0 1.25 1.75 0 1 1 0 0.75 0.25

0 0 0 0 1 1 0 3 0 0 0 1

1 0 0 0 0 0 0 0 0 0 0 0

0 1 3 1 0 0 0 0 0 0 0 0

φi =

∑j xjR j2/3

(7)

where R refers to molecular volume parameter. The values of γR were calculated as follows: ⎡ ln γi R = −Q i⎢ln(∑ θτ j ji) − 1 + ⎢⎣ j

⎞⎤ ⎟⎟⎥ ⎝ ∑k θkτkj ⎠⎥⎦ ⎛

∑ ⎜⎜ j

θτ j ij

(8)

where Q refers to molecular surface area parameter; subscript j and subscript k are component j and component k, respectively. Molecular surface area fraction θ is defined as

θi =

ax = axial; eq = equatorial.

xiQ i ∑j xjQ j

(9)

τ can be calculated with molecular interaction parameters aij: τij = exp(aij /T )

where Wexp and Wcalc are the experimental and calculated mass fractions, respectively; n represents the number of tie-line; I, J and K refer to component, phase, and tie-line, respectively. The AAD values were listed in Table 7. The deviations of the predicted results from the experimental data were still substantial. All the AAD values for the experimental tie-line data were higher than 0.013. The modified UNIQUAC model proposed by Peres and Macedo14 was used to correlate experimental results. In the modified UNIQUAC model, the activity coefficient γ was also calculated using eq 3. The values of γC were calculated according to the work of Larsen et al.:23 ⎛φ ⎞ φ ln γiC = ln⎜ i ⎟ + 1 − i xi ⎝ xi ⎠

xiR i2/3

(10)

Molecular volume parameter and surface area parameter were taken from literature,14,24,25 as seen in Table 8. The interaction parameters between D-glucose and water, D-fructose and water were taken from the literature,14 as seen in Table 9. The interaction parameters between water and 1-butanol were calibrated. In calibration, the following objective function was minimized: Fobj =

∑ |xiwγi w − xioγio|

(11)

25

Winkelman et al. used six parameters to calibrate liquid−liquid equilibrium data between 1-butanol and water, which indicates the difficulties in modeling. In this work, 2 interaction parameters were calibrated according to binary liquid−liquid equilibrium data between 288.2 and 318.2 K,18−20,26−34 as seen in Table 9. Liquid−liquid equilibrium data between 1-butanol and water was

(6) D



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Figure 2. Phase diagrams for the ternary system containing water + D-fructose + 1-butanol at (a) 288.2 K, (b) 303.2 K, (c) 318.2 K. □, Solid lines, experimental tie-line data; ○, dash lines, S-UNIFAC calculated tie-line data; △, dot lines, modified UNIQUAC calculated tie-line data.

Figure 3. Phase diagrams for the ternary system containing water + D-glucose + 1-butanol at (a) 288.2 K, (b) 303.2 K, (c) 318.2 K. □, Solid lines, experimental tie-line data; ○, dash lines, S-UNIFAC calculated tie-line data; Δ, dot lines, modified UNIQUAC calculated tie-line data.

calculated using the calibrated interaction parameters, as seen in Figure 5. Deviations can be observed between experimental results and calibration results. The interaction parameters between water and D-galactose were calibrated using solubility data reported by Jónsdóttir et al.24 and vapor pressure data reported by Apelblat and Korin.35 The solid−liquid equilibrium of D-galactose and water was described using eq 12.11

ln(γgalactosex) = − +

ΔHf ⎛ T ⎞ ΔCp ⎛ Tm − T ⎞ ⎜ ⎟ ⎟+ ⎜1 − RT Tm ⎠ R̅ ⎝ T ⎠ ̅ ⎝ ΔCp ⎛ T ⎞ ln⎜ ⎟ R̅ ⎝ Tm ⎠

(12)

where R̅ is the gas constant; Tm is the melting temperature of D-galactose; ΔHf is the enthalpy of fusion at Tm; ΔCp is the E



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Figure 4. Phase diagrams for the ternary system containing water + D-galactose + 1-butanol at (a) 288.2 K, (b) 303.2 K, (c) 318.2 K. □, Solid lines, experimental tie-line data; ○, dash lines, S-UNIFAC calculated tie-line data; Δ, dot lines, modified UNIQUAC calculated tie-line data.

and 436.15 K, respectively. Vapor−liquid equilibrium is calculated through eq 13.

Table 7. Values of Average Absolute Deviations for the Ternary System at Different Temperatures

Pv = x waterγwaterPwater

AAD value T/K 288.2 303.2 318.2 288.2 303.2 318.2 288.2 303.2 318.2

S-UNIFAC

modified UNIQUAC

Water + D-Fructose + 1-Butanol 0.0147 0.0154 0.0183 Water + D-Glucose + 1-Butanol 0.0138 0.0165 0.0191 Water + D-Galactose + 1-Butanol 0.0140 0.0170 0.0217

where Pv is the vapor pressure of saturated aqueous D-galactose solution; Pwater is the saturated vapor pressure of water. The interaction parameters between water and D-galactose were listed in Table 9. The comparison between experimental results and calculation results can be seen in Figure 6 and Figure 7. The interaction parameters between monosaccharides and 1-butanol then can be calibrated according to eq 10, as seen in Table 9. The correlation results were also shown in Figures 2−4. The AAD values were also listed in Table 7. Some of the AAD values were less than 0.01. The calculation results of the modified UNIQUAC model agreed better with experimental results than those of S-UNIFAC model.

0.0077 0.0108 0.0161 0.0067 0.0116 0.0174 0.0063 0.0095 0.0187

4. CONCLUSIONS The experimental LLE data of ternary systems composed of water + monosaccharide (D-fructose, D-glucose, or D-galactose) + 1-butanol were measured at 288.2, 303.2, and 318.2 K under atmospheric pressure. The mass fractions of monosaccharides in the organic-rich phase were lower than those in the waterrich phase. Saccharide content in the organic-rich phase increased with the rise of its content in the water-rich phase. In all the experiments, saccharide content in the organicrich phase was less than 0.02. The distribution coefficients of monosaccharides were lower than 0.05. The Othmer− Tobias equation fitted well with experimental results. The S-UNIFAC method was used to predict the LLE values, but remarkable deviations between experimental results and

Table 8. Structural Parameters for Different Molecules D-glucose D-fructose D-galactose

water 1-butanol

Ri

Qi

lit.

8.1528 8.1529 5.8028 0.9200 3.9243

7.920 8.004 4.840 1.400 3.668

14 14 24 14 25

(13)

difference between the heat capacities of the pure liquid and the pure solid of D-galactose. The values of ΔHf, ΔCp, and Tm were taken from literature,36 which were 43 778J/mol, 120J/(mol·K), F



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Table 9. Modified UNIQUAC Interaction Parameters j i D-glucose

D-fructose

D-galactose

water 1-butanol a

D-glucose

D-fructose

D-galactose

water

1-butanol

0 0 0a 0a 0a 0a 96.5267b 0.2770b −79.86c 0a

0a 0a 0 0 0a 0a 42.3676b −2.2511b −103.8c 0a

0a 0a 0a 0a 0 0 −14.40c 0.40c 6.563c 0a

−68.6157b −0.0690b −28.2892b 1.7780b −16.80c 0.30c 0 0 134.8c 0a

1381c 0a 1237c 0a 733.0c 0a 277.4c 0a 0 0

Set equal to zero in this work. bTaken from Peres and Macedo.14 cEstimated in this work.

Figure 5. Comparison of calibration results and experimental solubility data of 1-butanol-water system: black □, ref 26; red ○, ref 27; purple △, ref 28; pink ◇, ref 29; gray ◁, ref 30; aqua ▽, ref 31; maroon ▷, ref 32; orange +, ref 19; red ×, ref 33; black ⊕, ref 18; black ∗, ref 34; black ⊙, ref 20; maroon ☆, this work; solid line, modified UNIQUAC correlation; (a) the solubility of 1-butanol in water; (b) the solubility of water in 1-butanol.

Figure 6. Comparison between experimental solubility results with the calculated values using the modified UNIQUAC model for 24 D-galactose. ○, experimental data; solid line, modified UNIQUAC calculated data.

Figure 7. Vapor pressure p of saturated aqueous solution as a function of temperature T. ○, ref 35; solid line, modified UNIQUAC calculated data.

herbs when the distribution coefficients of active compounds are not too small.

calculation results were observed. The modified UNIQUAC model was used to correlate the experiments results with some of the interaction parameters fitted in this work. The correlation results were slightly better than the prediction results. In summary, D-glucose, D-fructose, and D-galactose dissolved in aqueous solution can hardly be extracted using 1-butanol as the extractant. For the production of TCMs, 1-butanol can be a potential extractant to separate active compounds and saccharides in the aqueous extracts of medicinal

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*Tel.: +86 571 88208426. Fax: +86 571 88208426. E-mail: [email protected]. ORCID

Xingchu Gong: 0000-0003-2632-4612 G



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This work was financially supported by National Project for Standardization of Chinese Materia Medica (No. ZYBZH-C-SH-48) Notes

The authors declare no competing financial interest.

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