Thermodynamic Properties of the β-Diketone–ZnSO4–(NH4) 2SO4

Article pubs.acs.org/jced

Thermodynamic Properties of the β‑Diketone−ZnSO4−(NH4)2SO4− NH3(aq)−H2O System Qinxiang Li,†,‡,§ Mark Zhu,†,‡ Huiping Hu,§ Zhiying Ding,*,§ and Zhoulan Yin*,§ †

China National Rare Metals Engineering Research Centre, Qingyuan 511517, Guangdong Province, China Vital Advanced Materials Research and Development Centre, Vital Materials Company, Limited, Qingyuan 511517, Guangdong Province, China § College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China ‡

ABSTRACT: Solubility of β-diketone (4-ethyl-1-phenyl-1, 3-octadione, abbreviated as HA, C16H22O2, molecular weight, 246.34)−ZnSO4−(NH4)2SO4− NH3(aq)−H2O system at T = (298.15, 308.15) K is elaborately measured by isothermal method. The results show that the solubility of ZnA2(o), NH4A(o), H2O(o), Zn2+(w), NH4+(w), SO42−(w), and HA(w) increases with the increase of the concentration of zinc sulfate. In contrast, the solubility of HA(o), H2O(w), and NH3(w) decreases with the increase of the concentration of zinc sulfate. The distribution ratio and extraction equilibrium isotherm of zinc in extraction system are obtained at T = (298.15, 308.15) K. The consequence indicates that extraction equilibrium isotherm is connected with temperature, and at the same condition, the distribution ratio of Zn(II) at 298.15 K is greater than 308.15 K. The activity coefficient of the components in mixture electrolyte solutions is calculated by Pitzer model, and the activity coefficient in organic phase is gained by correlating the extraction thermodynamic equilibrium constant with Gibbs− Duhem formula.

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INTRODUCTION Ammoniacal solution has been widely used for dissolving zinc from the refractory zinc oxide ores and industrial wastes.1−4 Hence, it is a matter of instant importance for recovering and separating zinc from ammoniacal solution. Liquid−liquid extraction is much more efficient than other separating processes for the recovery and separation of metallic species in hydrometallurgical, especially when it is used to deal with the dilute solutions arising from the treatment of leaching lowgrade materials. A lot of literature reported the recovery of copper, nickel and cobalt from leach liquors using solvent extraction processes.5−10 In fact, the copper recovery by solvent extraction is already a well-implemented process in several industrial plants.11−13 Hence, a large amount of investigations describing the zinc extraction from various aqueous solutions by different extractants have been reported.14−19 The extractants β-diketones are particularly useful in the extraction of zinc from ammoniacal media. LIX 54 is a β-diketone that has been widely used in the treatment of ammoniacal solutions.11 In 1999, Alguacil and Alonso performed some studies on zinc extraction from ammonium sulfate solutions with LIX 54.20 The experimental data showed that the concentration of zinccomplex decreased with increasing ammonium sulfate concentration of the aqueous phase. The decrease was attributed to the formation of metal ammine complexes in the aqueous phase thereby decreases the free zinc ion concentration. Unexpectedly, it has been discovered at the Escondida plant that LIX 54 reacts with ammonia which results in the increase of the © XXXX American Chemical Society

entrainment of aqueous in the loaded organic and the decrease of the stripping rate of metal ions.21 Therefore, a series of sterically hindered extractants were synthesized and applied to solve these problems. In particular, it was reported that a sterically hindered β-diketone, 4-ethyl-1-phenyl-1,3-octadione can extract zinc from ammoniacal/ammnoium chloride solution and some thermodynamic parameters including ΔH, ΔS, and ΔG were offered.22 Jiugang Hu et al.23 and Qiyuan Chen et al.24 have also studied the extraction behavior of zinc by 1-(4′dodecyl)-phenyl-3-tertiary butyl-1,3-octadione from ammoniacal solutions in different organic solvent. The results indicate that sterically hindered β-diketones are appropriate for extracting zinc from ammoniacal solutions because of their high stability, good extraction, and strip performance. Then, Qinxiang Li et al.25 investigated the solubility and activity coefficient of β-diketone in ammoniacal solutions. However, the thermodynamic properties of β-diketone in the extraction process are still poorly characterized. Hence, the solubility of HA−ZnSO 4−(NH 4)2SO4 −NH3(aq)−H2O system at T = (298.15, 308.15) K was elaborately measured by the isothermal method in this work. The Pitzer model was used to calculate the activity coefficient and the water activity in aqueous phase. Although the activity coefficient of organic phase was calculated Received: November 17, 2015 Accepted: March 7, 2016

A

DOI: 10.1021/acs.jced.5b00969 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 1. Solubility of Organic Phase in HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O System at T = (298.15, 308.15) Ka

by connecting the extraction thermodynamic equilibrium constant express with Gibbs−Duhem formula.

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EXPERIMENTAL SECTION Extraction equilibrium experiments were carried out in a thermostat (Techne 18/TE-10D, England) with temperature stability of ±0.05 K. The temperature was measured by a calibrated glass thermometer (Miller & Weber, Inc., U.S.A) with accuracy of ±0.01 K. An analytical balance (Shimadzu AUY 220, Japan) was used for weighing with an error of ±0.1 mg. An automatic Karl Fisher moisture meter (V30, Mettler Toledo, Inc., Switzerland) was used for measuring water in organic phase with the content from 1 ppm to 100%. An autokjeldahl’s device (K9840, Hanon Inc., U.S.A) was applied to determine the content of nitrogen. HA was synthesized by Claisen condensation of acetophenone and methyl 2-ethylhexanoate in the presence of sodium hydride.26 The crude product was acidified with sulfuric acid and washed with water and brine. After drying by anhydrous sodium sulfate, the final product with a purity of 98% was obtained by vacuum distillation.23 All the experimental solutions were prepared with distilled water and reagents of analytical grade. In the extraction equilibrium system, HA, ZnSO4 and ammoniacal solutions were stirred fully by a magnetic stirrer for certain period of time until the extraction equilibrium was reached. The equilibrium time and the setting time were found to be within 48 and 36 h, respectively. The solubility of Zn (II) in aqueous phase and organic phase was measured by titration with EDTA. The content of sulfate ion was determined by gravimetric method. All samples were measured in triplicate. The mean deviation between triplicate analysis was ±0.5%.

composition of organic phase (mass percent/%)

T/K 298.15

308.15

ZnSO4(w1) (mass percent /%)

ZnA2(O)(w2)

NH4A(O)(w3)

H2O(O)(w4)

HA(O)(w5)

5.687 9.018 14.922 17.242 21.057 24.061 5.687 9.018 14.922 17.242 21.057 24.061

8.915 18.431 26.578 30.640 37.525 41.878 8.245 17.309 25.817 29.660 36.467 41.468

6.687 10.551 15.359 16.868 19.477 20.749 5.308 8.454 12.751 14.074 16.954 19.002

0.362 0.382 0.958 0.860 1.035 1.083 0.377 0.519 0.544 0.741 0.605 0.747

84.035 70.637 57.105 51.633 41.963 36.290 86.069 73.717 60.888 55.525 45.974 38.782

a

o represents organic phase. w is mass fraction. The standard uncertainty of T is u(T) = 0.05K. The relative standard uncertainty of solubility measurement is u(w1) = 0.005, u(w2) = 0.005, u(w3) = 0.008, u(w4) = 0.02, u(w5) = 0.008.

(II) concentration in aqueous phase, and the extraction equilibrium isotherm at 298.15 K is higher than that at 308.15 K. The phenomenon indicates that extraction equilibrium isotherm is connected with temperature, and on the same condition, the distribution ratio of Zn (II) at 298.15 K is greater than 308.15 K. Mixture Electrolyte Solutions: Activity Coefficients and Water Activity. In 1974, Pitzer developed an equation with the guidance of statistical theories of electrolytes that was designed for convenient and accurate representation and prediction of the thermodynamic properties of aqueous electrolytes including mixtures with any number of components. The equation can be applied to a wide variety of mixed aqueous electrolytes at room temperature and at ionic strengths up to 6 mol/L in many cases and occasionally even higher.27−30 The Pitzer equations can be found in literature.28 In the past several decades, by means of collecting osmotic coefficient values of more than two hundreds kinds of singe electrolyte solutions, the integrated binary Pitzer parameters have been obtained. On the assumption that the triple ion−ion or ionneutral mixing parameters were zero, the binary Pitzer parameters of the system of ZnSO4−H2O (β(0) = 0.1949, β(1) = 2.883, β(2) = −32.81, C(0) = 0.0290) and the system of (NH4)2SO4−H2O (β(0) = 0.040875, β(1) = 0.6585, C(0) = −0.001161) are used to calculate the single ion activity coefficient values and the water activity values in mixture electrolyte solutions. The results are displayed in Table 4. It is seen that the activity coefficient data and the water activity decrease with the increase of the ions concentration at T = (298.15, 308.15) K. Organic Phase: Activity Coefficient. In organic extraction phase, there is dissolved water, HA, zinc-extractant complex and ammonia-extractant complex. The formula of zincextractant complex is recognized as ZnA2.22 However, the extraction mechanism and the formula of the ammoniaextractant have not been researched clearly. For simplicity, the ammonia-extractant complex is assumed to be NH4A.

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RESULTS AND DISCUSSION Solubility Data. The solubility data in this work is expressed in terms of mass fraction. To observe the influence of temperature on the extraction system, the liquid−liquid extraction equilibrium data of HA−ZnSO4−(NH4)2SO4− NH3(aq)−H2O system at T = (298.15, 308.15) K are reported in Tables 1 and 2 and plotted in Figures 1 to 10 with corresponding zinc sulfate concentrations. From Figures 1 and 2, it is found that the solubility of ZnA2 and NH4A in organic phase increases linearly with the increase of zinc sulfate concentration at T = (298.15, 308.15) K. Nevertheless, the concentration of ZnA2 and NH4A at 298.15 K is higher than that at 308.15 K, which means that rising temperature is disadvantageous to zinc extraction. Figure 3 displays that the solubility of H2O in organic phase also increases with the increase of zinc sulfate concentration at T = (298.15, 308.15) K. However, it is obviously seen that the solubility of HA in organic phase decreases sharply with the increase of zinc sulfate concentration in Figure 4. From Figures 5 to 10, it is exhibited that the solubility of Zn2+, NH4+, SO42−, and HA in aqueous phase increases with the increase of zinc sulfate concentration at T = (298.15, 308.15) K. Although the solubility of H2O and NH3(aq) decreases with the increase of zinc sulfate concentration. By the knowledge of the solubility of zinc in organic phase and aqueous phase, it is straightforward to obtain the distribution ratio of zinc. The data are reported in Table 3 and plotted in Figure 11. As it can be viewed that the solubility of Zn (II) in organic phase increases with the increase of Zn B

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Table 2. Solubility of Aqueous Phase in HA−ZnSO4−(NH4)2SO4−NH3(aq)−H2O System at T = (298.15, 308.15) Ka composition of water phase (mass percent/%) T/K

ZnSO4(w1) (mass percent /%)

Zn2+(w)(w6)

NH4+(w)(w7)

H2O(w)(w8)

HA(w)(w9)

SO42−(w)(w10)

NH3(w)(w11)

298.15

5.687 9.018 14.922 17.242 21.057 24.061 5.687 9.018 14.922 17.242 21.057 24.061

0.450 0.828 1.203 1.430 1.826 2.145 0.460 0.880 1.282 1.485 1.862 2.190

1.409 1.466 1.571 1.594 1.637 1.694 1.386 1.413 1.459 1.510 1.601 1.619

86.075 85.141 82.412 80.987 78.991 77.474 85.425 85.048 81.387 80.770 79.373 77.642

2.511 2.998 3.792 4.637 5.566 6.154 3.255 3.884 5.155 5.069 5.225 6.142

4.419 4.458 5.955 6.349 7.045 7.633 4.371 4.278 5.773 6.206 7.001 7.532

5.136 5.109 5.067 5.003 4.936 4.900 5.103 4.997 4.944 4.960 4.938 4.876

308.15

a w represents aqueous phase. w is mass fraction. The standard uncertainty of T is u(T) = 0.05K. The relative standard uncertainty of solubility measurement is u(w6) = 0.005, u(w7) = 0.008, u(w8) = 0.02, u(w9) = 0.008, u(w10) = 0.0005, u(w11) = 0.008.

Figure 3. Solubility of [H2O](o) in organic phase of HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K.

Figure 1. Solubility of [ZnA2](o) in organic phase of HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K.

Figure 4. Solubility of [HA](o) in organic phase of HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K. Figure 2. Solubility of [NH4A](o) in organic phase of HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K.

potentials of water in the organic phase and aqueous phase are equal when metal solvent extraction reaches equilibrium. Hence, there is μH O(o) = μH O(aq) (1)

When the system of HA−ZnSO4−(NH4)2SO4−NH3(aq)− H2O reaches equilibrium, the content of water must be saturation. In the hypothesis that the chemical state of water in organic phase is identical with the aqueous phase, the chemical

2

C

2

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Figure 5. Solubility of [Zn2+](w) in aqueous phase of HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K.

Figure 8. Solubility of [HA](w) in aqueous phase of HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K.

Figure 6. Solubility of [NH4+](w) in aqueous phase of HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K.

Figure 9. Solubility of [SO42−](w) in aqueous phase of HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K.

Figure 7. Solubility of [H2O](w) in aqueous phase of HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K.

Figure 10. Solubility of [NH3](w) in aqueous phase of HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K.

where μH2O(o) is the chemical potential of water in organic phase; and μH2O(aq) is the chemical potential of water in aqueous phase.

Supposing the standard chemical state of water in both phase is pure water, there is a H2O(o) = a H2O(aq) (2) D

DOI: 10.1021/acs.jced.5b00969 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 3. Distribution Ratio of Zinc in HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O System at T = (298.15, 308.15) Ka T/K

ZnSO4(w1) (mass percent/%)

Zn2+(w)(w6) (mass percent/%)

ZnA2(O)(w2) (mass percent/%)

distribution ratio, D

5.687 9.018 14.922 17.242 21.057 24.061 5.687 9.018 14.922 17.242 21.057 24.061

0.450 0.828 1.203 1.430 1.826 2.145 0.460 0.880 1.282 1.485 1.862 2.190

8.915 18.431 26.578 30.640 37.525 41.878 8.245 17.309 25.817 29.660 36.467 41.468

19.81 22.26 22.09 21.43 20.55 19.52 17.92 19.67 20.14 19.97 19.58 18.94

308.15

The conventional standard state for aqueous solution is taken at infinite dilution where all activity coefficient became unity. The activity of water is related to the osmotic coefficient ln a H2O(aq) = −18.02ϕ ∑ mivi /1000

(3)

i

According to eq 2 and 3, the activity coefficient of water in organic phase is described as α H 2O fH O = 2 x H 2O (4) Here, aH2O(o), xH2O(o), and f H2O(o) are the water activity, mole fraction, and the activity coefficient of water in organic phase, respectively. aH2O(aq), ϕ, mi, vi, and i represent the water activity, osmotic coefficient, molality, valence, and ion species in aqueous phase, separately. The zinc-extractant and ammonia-extractant reaction can be expressed as follows

a

o and w mean organic phase and aqueous phase, respectively. w represents mass fraction. D is distribution ratio calculated by w2/w6. The standard uncertainty of T is u(T) = 0.05 K. The relative standard uncertainty of solubility measurement is u(w6) = 0.005, u(w2) = 0.005.

Zn 2 + + HA ⇌ ZnA 2 + H+ K a1

(5)

NH3(aq) + HA ⇌ NH4A K a2

(6)

The extraction thermodynamic equilibrium constant (Ka1) of reaction 5 can be represented as K α1 =

x H2fH2 x ZnA 2fZnA

2

2 2 x Zn 2+fZn 2+ x HA fHA

(7)

Differentiating eq 7, there is ln K a1 = ln

x H2fH2 x ZnA 2 2 x Zn 2+fZn 2+ x HA

2 + ln fZnA − ln fHA 2

(8)

The extraction thermodynamic equilibrium constant (Ka2) of reaction 6 can be described as Ka2 =

Figure 11. Extraction equilibrium isotherm of HA−ZnSO4− (NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K.

x NH4AfNH A 4

x NH3fNH x HAfHA

(9)

3

Differentiating eq 9, there is Table 4. Activity Coefficient of Aqueous Phase and Water Activity in HA−ZnSO4−(NH4)2SO4−NH3(aq)−H2O System at T = (298.15, 308.15) Ka T/K

m1 mol·kg−1

γZn2+

m2 mol·kg−1

γNH4+

m3 mol·kg−1

γSO42+

aw

298.15

0.08 0.149 0.223 0.270 0.354 0.423 0.082 0.158 0.241 0.281 0.359 0.431

0.072 0.067 0.061 0.059 0.055 0.052 0.068 0.063 0.057 0.055 0.051 0.048

0.909 0.957 1.059 1.093 1.151 1.215 0.901 0.923 0.996 1.039 1.121 1.158

0.517 0.493 0.469 0.458 0.440 0.427 0.509 0.484 0.459 0.449 0.431 0.418

0.535 0.545 0.753 0.817 0.929 1.026 0.533 0.524 0.739 0.800 0.919 1.011

0.056 0.051 0.045 0.043 0.039 0.037 0.053 0.048 0.043 0.041 0.037 0.035

0.971 0.967 0.958 0.954 0.953 0.948 0.971 0.968 0.962 0.959 0.954 0.949

308.15

m1, m2, and m3 are molality of [Zn2+], [NH4+], and [SO42−] in aqueous phase, respectively. γZn2+, γNH4+and γSO42+ are the calculated activity coefficient according to solubility data in Table 2. aw represents the activity of water.

a

E

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Table 5. Activity Coefficient of Organic Phase in HA−ZnSO4−(NH4)2SO4−NH3(aq)−H2O System at T = (298.15, 308.15) Ka T/K

xH2O

f H2O

xZnA2

f ZnA2

xNH4A

f NH4A

xHA

f HA

298.15

0.050 0.056 0.136 0.127 0.156 0.166 0.052 0.074 0.081 0.110 0.096 0.120

19.446 17.372 7.043 7.511 6.121 5.697 18.798 13.135 11.853 8.701 9.937 7.907

0.040 0.0870 0.122 0.146 0.183 0.208 0.037 0.080 0.125 0.143 0.187 0.216

1.000 1.295 1.520 1.685 1.920 2.087 1.000 1.258 1.590 1.719 2.055 2.250

0.063 0.105 0.149 0.170 0.200 0.218 0.050 0.082 0.130 0.143 0.184 0.209

1.000 0.246 0.089 0.056 0.030 0.022 1.000 0.256 0.052 0.037 0.012 0.006

0.847 0.752 0.593 0.557 0.461 0.407 0.862 0.765 0.664 0.604 0.533 0.455

1.000 0.767 0.518 0.485 0.409 0.377 1.000 0.767 0.588 0.512 0.449 0.392

308.15

a

xH2O, xZnA2, xNH4A, and xHA are the mole fraction of H2O, ZnA2, NH4A, and HA in organic phase, respectively. f H2O, f ZnA2, f NH4A, and f HA are the calculated activity coefficient according to solubility data in Table 1.

x NH4A

ln Ka2 = ln

x NH3fNH x HA

+ ln fNH A − ln fHA 4

2

(10)

3

where xH, xZn, xHA, xNH3, xZnA2, and xNH4A denote the mole fraction of H+, Zn2+, HA, NH3, ZnA2, and NH4A, severally. f H, f Zn, f HA, f NH3, f ZnA2, and f NH4A indicate the activity coefficient of H+, Zn2+, HA, NH3, ZnA2, and NH4A, separately.The appropriate derivatives yield the Gibbs−Duhem equation

−

−

∫x ∫x

∑ xidμi = ∑ xidln xi + ∑ xidln fi i

i

HA

HA

−

i

i

(11)

* ln f NH = A 4

−

∑ dxi = 0

(12)

i

Hence,

− (13)

2

x H2fH2 x ZnA 2 2 x Zn 2+fZn 2+ x HA

+ x NH4A + 2x ZnA 2

d ln fH O 2

ln fNH A = 0

(14)

4

By introducing eqs 8 and 10, eliminating parameters, and integrating, eq 14 can be rewritten as follows

∫x

x ZnA 2 HA

+ 2x ZnA 2 + x NH4A x NH4A

+ 2x ZnA 2 + x NH4A

dln

x H 2O HA

+ 2x ZnA 2 + x NH4A

dln

+ 2x ZnA 2 + x NH4A )

2 x Zn 2+fZn 2+ x HA

x NH4A x HA dln x NH3fNH x HA + 2x ZnA 2 + x NH4A ) 3

2x ZnA 2 HA

x H2fH2 x ZnA 2

+ 2x ZnA 2 + x NH4A )

∫ (x

dln

x H 2O HA

+ 2x ZnA 2 + x NH4A )

x NH4A x NH3fNH x HA 3

d ln fH O 2

CONCLUSION The Solubility, distribution ratio and extraction equilibrium isotherm of HA−ZnSO4−(NH4)2SO4−NH3(aq)−H2O system at T = (298.15, 308.15) K have been obtained by means of the isothermal solution method. The results indicated that rising temperature is disadvantageous to zinc extraction. The Pitzer model was used to calculate the activity coefficients and water activity of mixture electrolyte solutions, whereas the activity

2 x ZnfZn x HA

x NH4A x NH3fNH x HA 3

2

HA

d ln

■

x H2fH2 x ZnA 2

dln fH O

HA

x ZnA 2

where the point of the minimum or maximum value of xHA, xZnA2, or xNH4A can be regarded as the reference state. In order to simplify these equations as much as possible, the values of xH and f H are set to be 1. The calculated activity coefficient value of organic phase in HA−ZnSO 4 − (NH4)2SO4−NH3(aq)−H2O system at T = (298.15 and 308.15 K) is displayed in Table 5.

2

∫x

HA

3

(17)

x H2Odln fH O + x HA dln fHA + x ZnA 2 dln fZnA + x NH4A d

−

dln

x NH3fNH x HA

x H2fH2 x ZnA 2 2 x Zn 2+fZn 2+ x HA

2x H2O

∫ (x

∫ (x −

The eq 13 is applied to the organic components, there is

HA

+ x NH4A + 2x ZnA 2

∫x

∫ (x

=0

i

∫x

x HA dln + x NH4A + 2x ZnA 2

x NH4A

(16)

because

* = ln f HA

+ x NH4A + 2x ZnA 2

HA

dln

i

=0

∑ xid ln fi

2x NH4A

x NH4A

∑ dxi + ∑ xidln fi

=

+

∫x

* = ln f ZnA

(15) F

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coefficients of organic phase were calculated by correlating extraction thermodynamic equilibrium constant expression with the Gibbs−Duhem formula.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. Tel.: +86-731-88879616. Fax: +86731-88879616. Notes

The authors declare no competing financial interest.

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REFERENCES

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DOI: 10.1021/acs.jced.5b00969 J. Chem. Eng. Data XXXX, XXX, XXX−XXX