LiquidâLiquid Equilibrium of Aqueous Two-Phase System Composed

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

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Liquid−Liquid Equilibrium of Aqueous Two-Phase System Composed of Poly(Ethylene Oxide) 1500 and Sodium Nitrate Yulia A. Zakhodyaeva,*,1,2 Danila G. Rudakov,1 Vitaliy O. Solov’ev,2 Andrei A. Voshkin,1,2 and Andrey V. Timoshenko1 MIREA − Russian Technological University, 78 Vernadsky Avenue, Moscow 119454, Russia Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky Prospect 119991, Moscow, Russia

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J. Chem. Eng. Data Downloaded from pubs.acs.org by UNIV OF GLASGOW on 02/19/19. For personal use only.

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ABSTRACT: Liquid−liquid equilibria of an aqueous two-phase system consisting of poly(ethylene oxide) 1500, sodium nitrate, and water at 293.15, 313.15, and 333.15 K were studied. Binodal data and a complete phase diagram with equilibrium liquid-phase compositions were obtained by using conductometry and refractometry techniques. The equilibrium data for aqueous two-phase systems were correlated using the UNIQUAC model, and new binary interaction parameters were calculated.

1. INTRODUCTION Liquid extraction is used in chemical technology to extract and separate a wide range of organic and inorganic compounds.1−5 Creation of extraction systems without organic solvent is a promising direction in the development of extraction methods,6−8 one of which is the aqueous two-phase systems (ATPS).9−14 These systems have exceptional advantages over classical extractants, such as environmental safety, fire safety, and accessibility. Aqueous two-phase systems can be used in biotechnological processes, pharmaceuticals, for the extraction of metal ions, and so on,15−17 which is confirmed by a large number of articles and reviews. Polyethylene oxide (PEO)based systems are some of the most common aqueous twophase systems. The properties and phase equilibrium of systems based on these polymers with different salts (NH4)2SO4, ZnSO4, K2HPO4,18 MgSO4, Na2SO4, Li2SO419 were studied earlier. Modern requirements for technological processes and new tasks of extraction and separation of substances of different origin necessitate the search for new ATPS. For example, the extraction of rare earth and transuranic elements from nitrate solutions20−26 requires ATPS based on them. To date, systems based on sodium nitrate and polyethylene glycols (PEG) with molecular masses of 2000, 4000, 6000, 10000 at 298 K27,28 have been studied. Experimental data were correlated using the Othmer−Tobias equation. ATPS containing NaNO2 and dimethyl ether of polyethylene glycol (PEGDME-2000),29 as well as NaNO3 and PEGDME-200030 and polypropylene glycol (PPG-400)31 were studied. The aqueous two-phase systems based on polyethylene oxide 1500 and sodium nitrate have not been studied in the literature. © XXXX American Chemical Society

PEO-1500 has the most favorable physical and chemical properties for practical use. Data on the liquid−liquid equilibrium (LLE) in a wide temperature range, including binodal data, communication lines, and the presence of a simple mathematical model adequately describing the liquid− liquid equilibrium are essential for the development of extraction processes. In this study, a new two-phase system composed of poly(ethylene oxide) 1500 (PEO-1500), sodium nitrate, and water was prepared, and its binodal data with liquid-phase compositions at 293.15, 313.15, and 333.15 K were determined. In addition, the experimental data were compared with calculated data provided by the UNIQUAC model, and new binary interaction parameters were determined.

2. EXPERIMENTAL SECTION 2.1. Materials. The chemical reactive poly(ethylene oxide) with an average molar mass 1500 was obtained from SigmaAldrich (CAS no. 25322-68-3). The purity of PEO-1500 was 99%. Sodium nitrate (NaNO3) was obtained from SigmaAldrich (ACS reagent, ≥ 99.0%) (CAS no. 7631-99-4). For the preparation of the solutions, double distilled water was used. All chemicals were used as received, without additional purification. 2.2. Procedure. The binodal curve position was determined by the turbidimetric method.18,19 Small amounts Received: November 28, 2018 Accepted: February 5, 2019

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DOI: 10.1021/acs.jced.8b01138 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

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Table 1. Experimental Binodal Values for the PEO-1500−NaNO3−Water System at 293.15, 313.15, and 333.15 K (Compositions in wt%) and Atmospheric Pressure ≈100 kPaa T = 293.15 K

T = 313.15 K

T = 333.15 K

wp

ws

ww

wp

ws

ww

wp

ws

ww

1.08 5.00 12.43 16.62 22.82 25.07 30.20 34.95

45.87 40.63 35.24 33.52 30.52 29.82 27.52 26.03

53.05 54.37 52.33 49.86 46.66 45.12 42.28 39.02

1.10 1.73 3.92 11.43 18.03 21.92 27.49 34.39

49.45 44.22 39.30 33.21 28.37 26.48 24.32 23.35

49.45 54.05 56.78 55.36 53.60 51.59 48.19 42.25

1.47 2.11 4.31 7.04 9.65 16.06 20.70 23.79

48.07 44.05 39.30 34.86 31.68 28.68 27.56 26.66

50.46 53.84 56.39 58.10 58.67 55.26 51.74 49.55

The standard uncertainties σ for components mass fraction, temperature, and pressure are σ(wp) = 0.2 wt%, σ(ws) = 0.5 wt%, σ(T) = 0.2 K and σ(p) = 1 kPa, respectively. a

Table 2. Equilibrium Tie-Line Data for PEO-1500−NaNO3−Water at 293.15, 313.15, and 333.15 K (Compositions in wt%) and Atmospheric Pressure ≈100 kPaa tie-line number

overall wp

ws

top phase ww

wp

ws

1 2 3 4 5

14.29 18.00 18.83 20.04 21.71

36.77 35.00 35.01 35.63 36.21

48.94 47.00 46.16 44.33 42.09

21.15 23.06 24.43 26.42 30.08

1 2 3 4 5

14.98 16.85 16.64 17.00 18.03

33.64 33.07 34.32 36.00 36.20

51.38 50.09 49.04 47.00 45.77

25.95 28.43 29.50 27.13 31.00

1 2 3 4 5

9.98 10.55 11.95 13.66 14.72

33.87 34.65 35.21 35.00 34.74

56.15 54.79 52.84 51.34 50.54

14.20 19.60 22.23 23.50 16.38

T = 293.15 K 31.25 30.84 30.17 29.80 28.54 T = 313.15 K 24.73 24.08 24.00 24.56 23.50 T = 333.15 K 29.79 27.80 26.70 26.30 29.24

bottom phase ww

wp

ws

ww

47.61 46.10 45.41 43.78 41.37

1.73 1.52 1.34 0.82 0.75

46.70 49.06 50.00 53.26 56.03

51.57 49.41 48.66 45.92 43.22

49.32 47.49 46.50 48.31 45.50

2.25 1.46 1.08 1.85 0.22

44.15 47.54 51.29 45.50 53.88

53.60 51.00 47.63 52.65 45.90

56.01 52.60 51.08 50.20 54.38

5.51 3.00 1.90 1.70 4.76

38.20 43.99 46.50 47.50 40.42

56.29 53.01 51.60 50.80 54.82

a The standard uncertainties σ for components mass fraction, temperature, and pressure are σ(wp) = 0.2 wt%, σ(ws) = 0.5 wt%, σ(T) = 0.2 K and σ(p) = 1 kPa, respectively.

of the convenience of the experiment and further determination of the composition of the top and bottom phases. The samples were intensively vortexed for 30 min until the system became turbid and then left at rest for 24 h at the required temperature in order to reach the thermodynamic equilibrium. It was found that 24 h was enough to establish the thermodynamic equilibrium in each of the samples. The equilibrium state was characterized by the absence of turbidity in both top and bottom phases. When the equilibrium was achieved, aliquots of both liquid phases were collected for analysis to determine the salt and polymer concentrations. The amount of sodium nitrate in the equilibrium top and bottom phases was determined by conductometry (OK 102/1, RADELKIS, Hungary). A series of calibration solutions was prepared to calibrate the conductometer, with the sodium nitrate concentration from 0.005 to 0.025 wt%. The electrical conductivity of the prepared solutions was measured at 298.15 K. The cell constant was 0.68. The error in measuring the electrical conductivity is ± 0.0068 mS·cm−1. According to the data obtained, the calibration curve was constructed in the form of the electrical conductivity versus the concentration of

of salt or polymer were dropwise added to the respective aqueous solution. Then, the solution obtained was stirred and allowed to settle after each addition. This procedure was repeated before the appearance of the solution turbidity, indicative of the formation of biphasic system. The experiments were conducted at temperatures of 293.15, 313.15, and 333.15 K and atmospheric pressure ≈100 kPa. The required temperature was maintained by using the temperaturecontrolled shaker with an accuracy of ± 0.2 K (Enviro-Genie SI-1202 (Scientific Industries, Inc., U.S.A.)). The composition of the mixture for each point on the binodal curve was calculated on the basis of the mass of each component in the system. Then, water was added dropwise to the flask to yield a clear one-phase system, and the procedure was repeated. Weighing was performed using the analytical scales (E10640, OHAUS, Switzerland) with an accuracy of ± 0.0001 g. To determine the tie-lines, feed samples were prepared by mixing appropriate amounts of polymer, salt, and water in the centrifugal tube (15 mL). The composition of the system was chosen so that the top and bottom phases ratio was approximately 1:1. This phase ratio was chosen on the basis B



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sodium nitrate. A linear dependence (with equation κ = 14.658ws+0.0016, where κ − electrical conductivity, mS·cm−1, ws − salt mass fraction, correlation coefficient R2 = 1) of the electrical conductivity from the concentration of sodium nitrate was observed. A final salt concentration was determined taking into account the dilution factor (uncertainties of the salt composition is ± 0.5 wt%). The polymer content in both phases was found from the total refractive index value measured using the refractometer (Refracto 30P, Mettler Toledo, Switzerland). The error in measuring the refractive index is ± 0.0001. The relation (1) between refractive indices of binary aqueous solutions of polymer or salt and the ternary aqueous solutions containing all these components make it possible to determine mass fractions of polymer in each phase. The water content in the samples was determined by the difference of mass fractions of each component by eq 2. nD = n w + a pwp + asws (1) ww = 1 − wp − ws

TLL = [(wp T − wp B)2 + (ws T − ws B)2 ]0.5 T

(3)

B

where wp and wp are the polymer concentrations in the top and bottom phases, respectively, and wsT and wsB are those of the salt. On the other hand, the temperature effect was examined by determination of the slopes of the tie-line (STL). The STL can be calculated by eq 4:33 STL = (wp T − wp B)/(ws T − ws B)

(4)

where wpT, wpB, wsT, and wsB are the same concentrations as indicated in eq 3. Table 3 shows the corresponding values. It Table 3. TLL and STL Values for PEO-1500−NaNO3− Water System at 293.15, 313.15, and 333.15 K tie-line number 1 2 3 4 5

(2)

where nD and nw are the refractive indices of ternary solutions and pure water, respectively. wp, ws, and ww represent mass fraction of polymer, salt, and water, respectively. The measured refractive index for pure water is 1.3325 at 298.15 K. The constants ap and as correspond to polymer and salt. Values of ap and as were obtained from linear plots of the corresponding refractive index of binary aqueous solutions. The values obtained are ap = 0.001293 and as= 0.001066, with a correlation coefficient value R2 of 0.9987 and 0.9998 respectively. It should be noted that the equation 1 is valid only for dilute solutions. Therefore, before the refractive index measurements, it was necessary to dilute all samples. Then, the standard curve of refractive index versus polymer composition in the concentration range of 0−10 wt% and the standard curve of refractive index versus salt composition in the range of 0−5 wt% were obtained. The validity of the refractive index additivity principle was also confirmed by verifying that the interval of study concentrations, the refractive index of the aqueous mixture containing wp of the polymer, and ws of the salt was ever equal to the sum of the refractive index values of the polymer wp aqueous solution without the salt and the refractive index of the salt ws solution without the polymer. The uncertainty of the polymer mass fraction wp determined by eq 1 is ± 0.2 wt%.

T = 293.15 K

T = 313.15 K

T = 333.15 K

TLL

STL

TLL

STL

TLL

STL

24.81 28.21 30.43 34.73 40.20

−1.26 −1.18 −1.16 −1.09 −1.07

30.65 35.75 39.40 32.83 43.24

−1.22 −1.15 −1.04 −1.21 −1.01

12.09 23.19 28.38 30.41 16.12

−1.03 −1.03 −1.03 −1.03 −1.04

can be seen that an increase in the TTL value is observed with the total mass concentrations of PEO growth at temperatures of 293.15 and 313.15 K (Tables 2 and 3). The largest absolute value of the STL parameter is observed at a temperature of 293.15 K, and the value of STL decreases with increasing temperature. As shown in Figure 1, the two-phase separation zone is expanding as the temperature rises from 293.15 to 313.15 K.

3. RESULTS AND DISCUSSION Table 1 shows the experimental binodal data for the system formed by PEO-1500, sodium nitrate, and water at 293.15, 313.15, and 333.15 K. Table 2 shows the experimental equilibrium data for this system at 293.15, 313.15, and 333.15 K. All data were collected at atmospheric pressure of ≈100 kPa. The studied liquid−liquid region in this system has the widest possible boundaries at appropriate temperatures. Outside this region precipitation or, conversely, homogeneous liquid phase has been observed. The tie-line lengths (TLL) which represent the final concentration of components in the top and bottom phases are often used to express the effect of system composition on partitioned material. Usually, the TLL are expressed as the difference between the polymer and salt concentrations present in the phases.32 TLL were calculated using eq 3:

Figure 1. Effect of temperature on the liquid−liquid region location at 293.15 (filled diamond, solid line), 313.15 (filled square, dotted line), and 333.15 K (filled triangle, dashed line).

However, if the temperature increases further up to 333.15 K, the two-phase separation zone is reducing. Thus, in the temperature range under study, the system has the widest twophase separation zone at 313.15 K. This behavior of some ATPS was described in the paper34 for the PEG-4000 + ZnSO4 system and in the paper35 for the PEG-1000 + NaH2PO4 system. The approaches to explanation of temperature influence on the behavior of the separation area in ATPS based on the analysis of many studies were summarized in the paper.36 In a thermodynamic view, the entropically unfavorable structuring of water produced by the polymer at low temperatures is overcome by the large decrease in enthalpy. C



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obtained by experimental liquid−liquid composition data regression. It should be noted that aij, bij, cij, and dij are unsymmetrical. Thus, aij may not be equal to aji. Aspen Plus version 9 software was used for experimental data regression and subsequent tie-line modeling. First, the van der Waals volume (R) and the surface (Q) of the polymer and salt molecules by the Bondi method40 were estimated using the Aspen Plus software package. The R and Q values for the water molecule were taken from the Aspen Properties database. Table 5 shows the R and Q parameters for

It is due to the energetically favorable and highly directional interactions, such as hydrogen bonding between the unlike entities, water, and the polymer. Provided that the structure of water in the polymer hydration shell does not break down too rapidly with increasing temperature, the unfavorable entropy contribution becomes prominent and the polymer phase separates itself. At very high temperatures the structure disappears, and a homogeneous phase can be formed. The regularity of the obtained experimental data can be checked by applying the Othmer−Tobias correlation37 given by eq 5: ln[(1 − ws B)/ws B] = A + Bln[[(1 − wp T)/wp T]

Table 5. Volume and Surface Parameters of the Investigated Compounds

(5)

where wsB and wpT are the salt mass fraction in the bottom phase and the PEO-1500 mass fraction in the top phase, respectively. The values of A and B parameters depend on the individual system properties. Equation 5 is given by an empirical correlation that ensures the consistency of the experimental data through the linearity of the graph. To determine the A and B coefficients as well as the correlation factor R2 for each system, the Othmer−Tobias correlation was plotted in coordinates ln[(1 − wsB)/wsB] versus ln[(1 − wpT)/ wpT]. Table 4 shows the results. The correlation factor (R2) is approximately identical, and the linearity of the plots indicates the degree of the consistency of the measured LLE data.

A

B

R2

293.15 313.15 333.15

1.1533 0.8901 1.024

1.2195 0.5883 1.5936

0.9868 0.9678 0.9991

R

Q

PEO-1500 NaNO3 water

54.9651 1.63744 0.92

45.808 1.604 1.4

the components of the system under study. The maximum likelihood estimation was used to select the binary parameters of the model. The quality of the described experimental data was the criterion for selecting the required number of parameters. The best description of the experimental data was achieved with the use of four adjustable binary parameters. Since the parameter eij has small effect on the final result, it was not evaluated. Moreover, when using five parameters, there were difficulties with convergence. Table 6 shows the binary parameters of the UNIQUAC equation.

Table 4. Othmer−Tobias Correlation Parameters and Regression Coefficients temperature, K

component

Table 6. Estimated binary UNIQUAC parameters component i

units

component j aij aji bij bji cij cji dij dji

Liquid−Liquid Equilibria Modeling. There exist two basic approaches for the mathematical modeling of two-phase water systems. The first approach is based on a “detailed” description of the interaction between the real particles present in the solution: cations and anions (the dissociation reaction is taken into account) with water and polymer molecules. The main flaw of this model is the large number of used parameters and, as a consequence, the high dimensionality of the task which leads to the convergence of the calculation problems. The second approach uses a simplified scheme for considering the interaction between components involved in the phase equilibriumthe “gross compositions” of each of the components are considered, without taking into account the particles actually present in the solution. The UNIQUAC activity coefficient model was used in this work.38 It is generally recommended for highly nonideal chemical systems, and can be successfully used for liquid− liquid equilibria modeling. The UNIQUAC model was not originally intended for systems that involve electrolytes in its classical form. Nevertheless, it has been used in liquid−liquid equilibria modeling in systems with electrolytes. For example, work39 shows that UNIQUAC provided potentially useful results along with the special electrolyte-oriented models, such as eNRTL. The UNIQUAC model has adjustable parameters for each binary pair aij, bij, cij, dij, and eij, individual components molecule volume and surface parameters. aij, bij, cij, dij, and eij are empirical parameters that describe the intermolecular behavior between components. In this work, its values are

− − K K K K K K

PEO-1500

PEO-1500

NaNO3

NaNO3

water

water

−2.9486 10.3866 103.90 −9991.36 −0.60108 6.27703 −0.01770 −0.06393

−25.7914 −29.1765 7140.00 9989.30 −4.38720 −7.18476 0.09842 0.10805

−37.6193 −1.3967 9997.10 544.39 −6.24199 −0.24990 0.13152 0.00338

The equilibrium compositions of the liquid phases in the PEO-1500−NaNO3−water system were calculated at three different temperatures (293.15, 313.15, and 333.15 K) using estimated parameters of the UNIQUAC equation. The rootmean-square deviation (RMSD) for predicted equilibrium compositions of the liquid phases is 1.96. Figures 2−4 clearly illustrate good agreement between the calculated and experimental liquid−liquid tie-lines. However, there is a slight deterioration in the description of the phase equilibrium at a temperature of 293.15 K. This can be explained by the fact that sometimes the regression problem has multiple solutions especially when it comes to solving for the parameters of especially for highly nonideal systems.

4. CONCLUSIONS Experimental liquid−liquid equilibria data for the new aqueous two-phase system consisting of poly(ethylene oxide) 1500, sodium nitrate, and water at 293.15, 313.15, and 333.15 K using conductometry and refractometry methods were obtained. This system produces a two-phase region, adequate D



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ORCID

Yulia A. Zakhodyaeva: 0000-0002-5719-2061 Danila G. Rudakov: 0000-0002-9892-7909 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The study was supported by the Russian Science Foundation (RSF project no. 17-73-10486). ABBREVIATIONS A, B Othmer−Tobias equation constants a, b, c, d, e UNIQUAC binary parameters PEO-1500 poly(ethylene oxide) 1500 p pressure, kPa Q surface parameter R volume parameter R2 correlation coefficient T temperature, K w concentration, wt% κ electrical conductivity, mS·cm−1

Figure 2. Experimental (filled diamond, solid line) and correlated (filled square, dashed line) tie-lines at T = 293.15 K.

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SUPER/SUBSCRIPTS i, j components p polymer s salt w water

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to be applied in extraction processes. The widest immiscibility region is observed at a temperature of 313.15 K. When the temperature increases to 333.15 K, the two-phase separation zone is slightly shifted toward the lower concentrations of polymer and salt. Then experimental data were correlated with the UNIQUAC activity coefficient model. The modeling results for this model seem to be satisfactory; however, there is a slight deterioration in the description of the phase equilibrium at a temperature of 293.15 K.

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REFERENCES

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