A Sodium Chloride–Zinc Chloride–Water System: Solubility of Solids

Chemistry Department, Lomonosov MSU, Moscow, 119991, Russian Federation. J. Chem. Eng. Data , 2016, 61 (7), pp 2426–2432. DOI: 10.1021/acs.jced.6b00...
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A Sodium Chloride−Zinc Chloride−Water System: Solubility of Solids and Density of Liquid in Wide Range of Temperatures Ekaterina V. Belova, Mikhail N. Mamontov, and Irina A. Uspenskaya* Chemistry Department, Lomonosov MSU, Moscow, 119991, Russian Federation ABSTRACT: The equilibrium phase diagrams of NaCl−ZnCl2− H2O system at 260.35 and 250.15 K were studied by method of isothermal solution saturation, wet residues, and thermogravimetric analysis. Water content in precipitate at these temperatures for hydrate 2NaCl·ZnCl2·nH2O was determined, n = 3. Densities of ternary NaCl−ZnCl2−H2O solutions were measured at 288.15−321.35 K and compared with values predicting by the Laliberte model. It was shown that the model provides mainly underestimated density values.

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INTRODUCTION Phase diagrams are useful tools for the design of various processes. 1 To optimize the conditions of substances’ separation and purification, the solubility of components at various temperatures is necessary as well as information about the density and viscosity of solutions. One of the zinc salts’ solution features is a relatively high density at high concentrations.2−5 Mixtures on the base of zinc chloride under certain conditions can be used as heavy oil drilling fluids in the oil industry to repair works in high pressure wells and perform nondamaging killing of the wells at maintenance.6,7 Its solutions had advantages in ease of preparation and long-time stability. Empirical choice of liquid phase composition with required properties is reasonable only in the case of low-dimension systems; therefore, it is necessary to compare values predicted by a one or another suitable model with an experiment for binary and ternary solutions. In the present work the Laliberte model was chosen due to a relatively simplicity and applicability to a wide range of system. Isothermal sections of phase diagrams of the ternary system were suggested by Bouchacourt et al.,8 Shevchuk and Moshinski,9 and Adiguzel et al;10 all experiments have been performed above 0 °C. To the best of our knowledge, any information about phase equilibria at subzero temperatures in ternary system are absent. Shevchuk and Moshinski9 and Adiguzel et al.10 provided density measurements of saturated solutions at 27, 25, and 0 °C (300.15, 298.15, and 273.15 K). The aim of this work was to expand the temperature range of NaCl−ZnCl2−H2O investigations concerning the phase equilibria and volumetric properties of the liquid phase.

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Table 1. Purity, Supplier, and CAS of the Compounds purity (%)

supplier

CAS

ZnCl2 NaCl

>98 (p.a.) >99.9 (puriss)

Reachim (Russia) Labtech (Russia)

7646−85−7 7647−14−5

carried out. The water used was previously distilled and degassed. The samples were prepared by adding water and NaCl to ZnCl 2 stock solutions. We checked Zn/Cl stoichiometry of the ZnCl2 probe: the Zn concentration was 0.03243 M, and Cl concentration 0.06492 M, with relative standard uncertainties ur = 0.003 and 0.009, respectively; the method will be described hereinafter. Impurities in the commercial ZnCl2 reagent were verified by ICP OES, giving the following values (in wt %): Ca, 0.012; Fe, 0.018; Na, 0.019; Si, 0.003. Concentrations of the stock solutions were determined by the complexometric titration with EDTA. Densities were determined with VIP-2MP vibrating-tube densimeter. The following expression was used to obtain densities of the solutions: ρ = A + Bτ 2

where τ is the oscillation period and A and B are coefficients, determined from calibration at the measurement temperatures (288.15, 298.15, 323.15 K) by known densities and oscillation periods of ambient air, ultrapure water and standard materials (produced and certificated by D. I. Mendeleyev Institute for Metrology, Russia, St. Petersburg, VNIIM) listed in Table 2. The temperature was maintained by built-in thermostat; the standard uncertainty of registered temperature was 0.02 °C.

METHODOLOGY

Received: January 17, 2016 Accepted: June 8, 2016

The names, CAS numbers, supplier, and mass fraction purities of salts used are listed in Table 1; no further purification was © XXXX American Chemical Society

compound

A

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pass glass cyclonic spray chamber (Agilent Technologies), a Seaspray concentric glass nebulizer (Glass Expansion), and Trident Internal Standard Kit (Glass Expansion). The concentration of Cl− was measured by potentiometric titration with 0.01 M AgNO3 standardized by NaCl 0.01 M solution with an Elis-131 ion-selective electrode (Research and Production Association Izmeritelnaya Tekhnika IT, Russian Federation) and Ag−AgCl reference electrode with 3 M KCl solution RE-10101/3.0 (Research and Production Association Izmeritelnaya Tekhnika IT, Russia). To determine the water content in mixed hydrates 2NaCl· ZnCl2·nH2O thermogravimetric measurements (TGA) were performed using NETZSCH TG 209 F1 in the temperature range 30−450 °C (303.15−723.15 K) in nitrogen flow (20 mL· min−1); the heating rate was 10 K·min−1. Additionally, the Schreinemaker’s method of moist residues13 was employed to analyze the composition of solid phase coexisting with saturated solution. Modeling of volume properties. To estimate density, we applied the Laliberte model.14,15 The density of multicomponent mixture (ρ) in this model is expressed as

Table 2. Density of VNIIM Standard Materials at Various Temperaturesa density, kg·m−3 tested sample

298.15 K (25 °C)

323.15 K (50 °C)

REP-2 REP-5 REP-7 REP-12

726.57 997.04 1315.56 1090.32

707.50 988.03

a Tested samples produced and certificated by D. I. Mendeleyev Institute for Metrology, Russia, St. Petersburg, VNIIM; density values are given according to certificates of REP-2, REP-5, REP-7, and REP12 solutions.

The standard deviation for measurement of solution density is 0.1 kg·m−3; however, due to uncertainty of ZnCl2 concentration in stock solution, the relative standard uncertainty of density was estimated as 0.002.11 Phase equilibria investigation have been performed with the method of isothermal solution saturation and wet residues analysis. We used 100 Ω Pt resistance thermometer TSPV-1 137 (Iztech, Russia) with a multichannel precise thermometric direct current bridge. The standard uncertainty of temperature registered in refrigerator camera during the experiment was 0.2 °C for −10.8 °C/262.35 K and 0.5 °C for −23 °C/250.15 K. The precision of temperature measuring was 0.05 °C. Raw mixtures were homogeneous, and precipitation appeared at decreasing of temperature. The samples were held during 2−3 days at subzero temperatures. The composition of solution over the solid phase was monitored throughout the experiment. As a result, we were sure that all samples achieved an equilibrium state at 2−3 days and simultaneously we estimated the reproducibility of measurements for a mixture with a fixed composition. The ratio of analyzed aliquots and solution volumes was such to neglect the changing of system composition during sampling. Zinc concentration of every data point is an average of three titrations, and standard deviation of these titrations was assumed as an error of zinc content in solution. The concentration of Zn2+ ion was analyzed by the complexometric titration method with 0.0500 M EDTA and eriochrome black as described by Schwarzenbach and H. Flaschka.12 Diluted probes with low ZnCl2 content were titrated with addition of diluted HNO3 (reagent grade) to prevent hydrolysis. The concentration of Na+ was analyzed by ICP OES; parameters of ICP OES equipment are listed in Table 3. An axial regime ICP-OES 5100 spectrometer (Agilent Technologies, USA) was used for measurements with a double-

⎛w HO ρ = 1/⎜⎜ 2 + ρ ⎝ H 2O

i

(1)

where ρH2O is water density, wH2O and wi are water and dissolved substance mass fractions, respectively, ρapp,i is an apparent density of dissolved substance, which is reciprocal of the specific volume (vi̅ ). The last one can be presented by eq 2: vi̅ = 1/ρapp, i = 1 ⎛ ⎞ (1 − wH2O) + c 2 + c3t ⎟ /⎜⎜ 2 ⎟ ⎝ (c0(1 − wH2O) + c1) ·exp(0.000001(t + c4) ) ⎠

(2)

where ck (k takes the value from 0 to 4) are parameters for the dissolved substance and t is temperature in °C. For the water density (ρH2O) calculation Laliberte and Cooper14,15 suggested using eq 3: ρH O = (999.83952 + 16.945176t − 0.0079870401t 2 2

− 4.6170461 × 10−5t 3 + 1.0556302 × 10−7t 4 − 2.8054253 × 10−10t 5)/(1 + 0.01687t )

(3)

This model is an empirical one and has limitations of this type of models. It describes rather a big data set for one salt− water systems in wide temperature ranges using only five parameters for a system. However, the model giving worse prediction for ternary and multicomponent systems with stronger interactions between components (complex formation, etc.).

Table 3. ICP OES Parameters

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conditions for all line registrations RF power (kW) plasma flow (L/min) axial flow (L/min) nebulizer flow (L/min) replicate read time (s) plasma stabilization delay replicates sample uptake delay (s) pump rate (rpm) emission lines (nm) Na

∑

wi ⎞⎟ ρapp, i ⎟⎠

RESULTS AND DISCUSSION ZnCl2−H2O System. Phase equilibria at low temperatures in this system were studied by Mylius and Dietz16 and Etard.17 There are some disagreements in salt solubility obtained in these works, so Etard17 reported lower concentrations of saturated solutions at subzero temperatures (−20/0 °C)/ (253.15/273.15 K) than Mylius and Dietz.16 According to Etard,17 the dihydrate ZnCl2·2H2O are stable at these temperatures, unlike the opinion of Mylius and Dietz16 who proposed ZnCl2·3H2O formation in temperature range ∼

0.7 12 1.0 0.70 5 15 3 25 12 588.995; 589.592 B

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Table 4. Mass Fraction Solubility of the Ternary NaCl−ZnCl2−H2O System at Temperature −10.8 °C/262.35 K and Pressure p = 0.1 MPaa initial (raw) composition, 100wc

composition of liquid phase, 100wd

composition of wet residue phase, 100w

no.

ZnCl2

NaCl

ZnCl2

NaCl

ZnCl2

NaCl

equilibrium solid phase

1 2 3 4 5 6 7 8 9

53.77 45.84 38.48 6.73b 5.10b 11.63 9.99 24.86 2.50b

6.50 12.01 20.01 8.01 10.84 39.36 27.63 30.86 34.93

54.70 45.95 37.52 9.08 5.21 15.36 11.21 28.52 3.13

6.72 10.67 14.59 9.96 11.88 21.40 21.95 20.81 21.91

44.15 43.60 43.73

38.47 37.40 37.63

2NaCl·ZnCl2·3H2O 2NaCl·ZnCl2·3H2O 2NaCl·ZnCl2·3H2O ice ice NaCl NaCl NaCl NaCl+ NaCl·2H2O

a

Standard uncertainties u are u(T) = 0.2 K, u(p) = 0.005 MPa, ur(w2) = 0.002. bur(w2) = 0.0003, u(w3) = 0.002. cw, mass fraction of component in raw solution. dw, mass fraction of component in equilibrium system.

Table 5. Mass Fraction Solubility of the Ternary NaCl− ZnCl2−H2O System at Temperature −23 °C/250.15 K and Pressure p = 0.1 MPaa initial (raw) composition, 100wc

composition of liquid phase, 100wc

no.

ZnCl2

NaCl

ZnCl2

NaCl

equilibrium solid phase

1

49.06

9.38

48.30

5.58

2 3 4 5 6 7 8 9 10 11 12

45.51 23.25 12.81 24.98 19.73 16.94 32.89 41.46 55.91 53.54 2.48b

15.19 24.32 29.69 5.03 9.97 14.96 22.74 17.90 4.46 9.05 63.07

45.97 23.93 14.97 28.57 23.05 18.01 31.63 41.19 55.15 54.26 4.23

7.85 19.82 20.95 5.75 11.65 15.90 17.35 11.07 2.92 2.77 20.21

2NaCl·ZnCl2·3H2O + ZnCl2· 3H2O 2NaCl·ZnCl2·3H2O NaCl NaCl ice ice ice 2NaCl·ZnCl2·3H2O + NaCl 2NaCl·ZnCl2·3H2O 2NaCl·ZnCl2·3H2O 2NaCl·ZnCl2·3H2O NaCl + NaCl·2H2O

Figure 1. Equilibrium phase diagram of the ternary system NaCl− ZnCl2−H2O at 262.3 K. ■, the composition of coexisting phases according to analysis data, red circles correspond to initial (raw) composition and red triangles correspond to the wet residue compositions; A, pure solid of ZnCl2; B, pure solid of NaCl; W, water; C pure solid dihydrate NaCl·2H2O (wNaCl = 61.86%), D, pure solid mixed hydrate 2NaCl·ZnCl2·3H2O (wNaCl = 38.04%, wZnCl2 = 44.37%), E, pure solid of ZnCl2·3H2O (wZnCl2 = 71.61%). Solubility of ZnCl2 in water; 65.41 wt %,15 solubility of NaCl in water; 24.93 wt %,17 cosaturated point of 30.6 wt % ZnCl2, and 21.5 wt % NaCl. Thick lines are phase boundaries, and thin lines are nodes. Numbers near red circles correspond to the numbers of mixtures in Table 4.

a

Standard uncertainties u(T) = 0.5 K, u(p) = 0.005 MPa, ur(w2) = 0.002. bur(w2) = 0.0003, ur(w3) = 0.002. cw, mass fraction of component in equilibrium system.

(−30/0 °C)/(243.15−273.15 K); the other hydrates with a lower water content exist at these temperature as metastable phase. Our experiments at −23 °C (250.15 K) are in good agreement with data of Mylius and Dietz.16 According to our data, the concentration with precipitation of ice is 33.02 wt % and with precipitation of ZnCl2 hydrate is 61.83 wt %, with relative standard uncertainties ur = 0.003 and 0.0014, respectively. Density measurements in the zinc chloride−water system were performed by Herrington et al.,2 Pogue and Atckinson,3 Rard and Miller,4 and Weingärtner et al.5 Those data have been used by Laliberte14,15 for modeling; data at the temperature range of 15−75 °C, and the concentration range−up to 52 wt % were approximated. Shevchuk and Moshinski9 and Adiguzel et al.10 reported density values for solutions with higher concentration: 80.12 wt % at 25 °C/298.15 K and 66.6 wt % at 0 °C/273.15 K, respectively. The Laliberte model prediction alters from these values, being an extrapolation for these concentrations. NaCl−ZnCl2−H2O System. Isothermal sections of phase diagrams in this system were studied by Bouchacourt et al. at 27

°C/300.15 K,8 Shevchuk and Moshinski9 at 25 °C/298.15 K, and Adiguzel et al.10 at 0 °C/273.1 K. We extended the temperature range by performing an experiment at −10.8 °C/ 262.35 K and −23 °C/250.15 K; results of chemical analysis of coexisting phases are presented in Table 4 and Table 5, respectively. The isothermal sections of ternary phase diagram at −10.8 °C/262.35 K and −23 °C/250.15 K are shown in Figures 1 and 2. The cosaturated point at −23 °C was determined directly from NaCl−2NaCl·ZnCl2·3H2O−liquid equilibria. As for −10.8 °C, it was calculated from intersections of extrapolated solubility curves. In binary NaCl−H2O system at subzero temperatures NaCl·2H 2O precipitates from saturated solutions,18 but in the ternary system (according to our data and Adiguzel et al.10) the field of dihydrate existence is C

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Figure 2. Equilibrium phase diagram of the ternary system NaCl− ZnCl2−H2O at 250.1 K. ■, the composition of coexisting phases according to analysis data, red circles correspond to initial (raw) composition of mixtures and red triangles correspond to the wet residue compositions; A, pure solid of ZnCl2; B, pure solid of NaCl; W, water; C pure solid dihydrate NaCl·2H2O (wNaCl = 61.86%), D, pure solid mixed hydrate 2NaCl·ZnCl2·3H2O (wNaCl = 38.04%, wZnCl2 = 44.37%), E, pure solid of ZnCl2·3H2O (wZnCl2 = 71.61%). Solubility of ZnCl2 in water (E); 61.83 wt %, solubility of NaCl in water; 0 wt %, cosaturated point of 31.63 wt % ZnCl2, and 17.35 wt % NaCl. Thick lines are phase boundaries, and thin lines are nodes. Numbers near red circles correspond to the numbers of mixtures in Table 5.

Figure 4. Liquidus shift in the temperature range (−23 to 30 °C)/ (250.15−303.15 K) of ternary NaCl−ZnCl2−H2O system. Black line and symbols: black dots, data at 250.1 K; blue dots, at 260.3 K (this work); purple dots, data at 273.1 K from ref 10; red dots, data at 298.1 K from ref 9; and red asterisks, data at 300.1 K from ref 8.

was determined with TG analysis. The TG curve is presented in Figure 3. According to TG analysis, the dehydration of sample proceeds into three steps. We suppose the first step corresponds to desorption of water up to 100 °C (∼0.5 mol of water per mole of salt), then partial dehydration (∼0.8 mol of water) and complete removal of water (∼2.3 mol of water) in the finishing stage. Due to the absence of pronounced plateau at TG curve above 100 °C, it is difficult to distinguish two last stages with the exact determination of mass loss. Additionally we analyzed the solution obtained from precipitate by titration and ICP OES, the result corresponds to hydrate formulas 2NaCl·ZnCl2·3H2O. The solubility of NaCl and NaCl·2H2O does not change considerably with temperature, whereas 2NaCl·ZnCl2·3H2O and ZnCl2 hydrates alter their

very narrow, and NaCl is the equilibrium solid phase for a wide concentration range. Bouchacourt et al.8 and Shevchuk et al.9 reported hydrate 2NaCl·ZnCl2·3H2O to precipitate at (25/27 °C)/(298.15− 300.15 K); according to Adiguzel et al.10 K another hydrate 2NaCl·ZnCl2·2H2O should be precipitated at 0 °C/273.15. We performed special “cold” filtration at −10.8 °C/262.3 K to separate the mother liquid and solid phase; after this procedure the water content (x) in the mixed hydrate 2NaCl·ZnCl2·xH2O

Figure 3. Experimental TG curve of mixed hydrate 2NaCl·ZnCl2·nH2O. HR = 10 K·min−1. D

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Table 6. Densities of Ternary Solutions in the NaCl−ZnCl2−H2O System at Various Temperatures and Pressure p = 0.1 MPaa composition, 100wb

a

density (ρ), kg·m−3

no.

ZnCl2

NaCl

exp

1 2 3 4 5 6

58.21 53.54 55.91 37.07 37.36 25.85

0.00 9.05 4.46 6.27 13.25 9.24

1702.7 1703.5 1703.2 1468.1 1505.5 1352.1

1 2 3 4 5 6

58.21 53.54 55.91 37.07 37.36 25.85

0.00 9.05 4.46 6.27 13.25 9.24

1692.5 1692.5 1692.6 1461.2 1495.4 1342.7

1 2 3 4 5 6

58.21 53.54 55.91 37.07 37.36 25.85

0.00 9.05 4.46 6.27 13.25 9.24

1666.6 1665.7 1666.1 1435.6 1471.9 1321.6

composition, 100wb

calc

no.

T = 288.15 K 1703.3 7 1744.7 8 1724.0 9 1444.1 10 1526.4 11 1332.3 T = 298.15 K 1696.3 7 1737.5 8 1716.8 9 1437.4 10 1519.2 11 1326.1 T = 323.15 K 1675.4 7 1719.0 8 1697.0 9 1418.5 10 1501.0 11 1308.4

density (ρ), kg·m−3

ZnCl2

NaCl

exp

calc

20.42 12.44 10.38 8.11 5.67

13.03 21.48 17.92 14.00 9.79

1316.4 1277.8 1225.2 1176.8 1121.7

1305.0 1292.1 1238.6 1182.3 1124.8

20.42 12.44 10.38 8.11 5.67

13.03 21.48 17.92 14.00 9.79

1307.9 1271.4 1218.8 1170.5 1116.2

1298.8 1285.7 1232.7 1177.1 1120.4

20.42 12.44 10.38 8.11 5.67

13.03 21.48 17.92 14.00 9.79

1287.9 1255.0 1203.2 1155.1 1101.6

1281.8 1269.6 1217.2 1162.5 1107.0

Standard uncertainties u(T) = 0.5 K, u(p) = 0.005 MPa, ur(w2) = 0.002, ur(w3) = 0.002, ur(ρ) = 0.002. bw, mass fraction.

Table 7. Parameters of Equation 2 from Laliberte Paper14 ZnCl2 NaCl

c0

c1

c2

c3

c4

2048.256171 −0.003241122

367.8993052 0.063635434

−0.006870805 1.013713995

0.001183555 0.014595102

505.0316629 3317.348544

Figure 5. Difference among the measured and calculated density values; numbers N = 1−10 correspond to data from ref 9 at 298.15 K, 11−43 (this work, at 288.1, 298.15, 323.15 K), 44−62 from ref 10 at 273.15 K.

solubility more and ice forming is noticeably influenced by

illustrates the transformation of solution boundaries with temperature; literature data8−10 and results of the present work were used for the phase diagrams construction. Moshinski and Shevchuk19 reported NaCl and ZnCl2 to form solid

temperature. For many practical applications of phase diagrams, it is very interesting to observe the trend in solubility changes. Figure 4 E

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solutions at 75 °C/348.15 K and higher temperatures, but there are not enough data about solid−solid and solid−liquid equilibria to construct a phase diagram at elevated temperatures. Thus, we have restricted the construction of isothermal sections below 30 °C/303.15 K. As was mentioned in the Introduction, Shevchuk and Moshinski9 and Adiguzel et al.10 provided density measurements of saturated solutions at 25 and 0 °C (300.15, 298.15, and 273.15 K). In the present work, we extended measurement range with different compositions including the ones staying liquid at lower temperatures and performed experiment at 15 °C/288.15 K, 25 °C/298.15 K, and 50 °C/323.15 K. The experimental results are shown in Table 6. These data were compared with densities calculated by the Laliberte model.14,15 Parameters of eq 2 for zinc chloride and sodium chloride are presented in Table 7. As can be seen from Table 6 and Figure 5, the description of ternary solution properties with the use of only binary parameters is not excellent, relative deviations reach 2% versus 0.02−0.09% in binary mixtures. Moreover, model provides mainly underestimated density values for the ternary aqua solution of zinc and sodium chloride.

Funding

The work was performed at User Facilities Center of M. V. Lomonosov Moscow State University. The investigations were partially supported by the URALCHEM OJSC. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors give thanks to the M. V. Lomonosov Moscow State University Program of Development. The authors wish to thank Mr. Ivan Mikheev who partially assisted with analytical part of work.

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(1) Chen, C.-C.; Mathias, P. M. Applied Thermodynamics for Process Modeling. AIChE J. 2002, 48, 194−200. (2) Herrington, T. M.; Roffey, M. G.; Smith, D. P. Densities of Aqueous Electrolytes MnCl2, CoCl2, NiCl2, ZnCl2 and CdCl2 from 25 to 72 °C at 1 atm. J. Chem. Eng. Data 1986, 31, 221−225. (3) Pogue, R. F.; Atkinson, G. Solution Thermodynamics of FirstRow Transition Elements. 3. Apparent Molal Volumes of Aqueous ZnCl2 and Zn(ClO4)2 from 15 to 55 °C and an Examination of SoluteSolute and Solute-Solvent Interactions. J. Solution Chem. 1989, 18, 249−264. (4) Rard, J. A.; Miller, D. G. Densities and Apparent Molal Volumes of Aqueous Manganese, Cadmium, and Zinc Chlorides at 25 °C. J. Chem. Eng. Data 1984, 29, 151−156. (5) Weingärtner, H.; Müller, K. J.; Hertz, H. G.; Edge, A. V. J.; Mills, R. Unusual Behavior of Transport Coefficients in Aqueous Solutions of Zinc Chloride. J. Phys. Chem. 1984, 88, 2173−2178. (6) Helvenston, E. P.; Cuevas, E. A. A Study of the System CaCl2ZnCl2-H2O (NaCl Saturated) at 15 °C. J. Chem. Eng. Data 1964, 9, 321−323. (7) Hudgins, C. M. Solubility and Density Studies of the CaCl2ZnCl2-H2O System at 0 and 25 °C. J. Chem. Eng. Data 1964, 9, 434− 436. (8) Bouchacourt, M.; Saugie, M. T.; Cohen-Adad, R. Sodium (+) Ion, Zinc 2q Ion, Sulfate (2+), chloride (−) Ion, Water Quaternary Reciprocal System: I. Limit Ternary Systems. Bull. Soc. Chim. Fr. 1977, 842−846. (9) Shevchuk, V. G.; Moshinski, A. S. The ZnCl2-ZnSO4-H2O and NaCl-ZnCl2-H2O Systems at 25 °C. Russ. J. Inorg. Chem. 1969, 4, 1316−1319. (10) Adiguzel, V.; Erge, H.; Alisoglu, V.; Necefoglu, H. Study of the solubility, viscosity and density in Na+, Zn2+/Cl− - H2O, Na+ - Zn2+ (H2PO2)− - H2O, Na+, Cl−/(H2PO2)− - H2O, and Zn2+, Cl−/ (H2PO2)− - H2O ternary systems, and in Na+, Zn2+/Cl, (H2PO2) reciprocal quaternary system at 273.15 K. J. Chem. Thermodyn. 2014, 75, 35−44. (11) Chirico, R. D.; Frenkel, M.; Magee, J. W.; Diky, V.; Muzny, C. D.; Kazakov, A. F.; Kroenlein, K.; Abdulagatov, I.; Hardin, G. R.; Acree, W. E., Jr.; et al. Improvement of Quality in Publication of Experimental Thermophysical Property Data: Challenges, Assessment Tools, Global Implementation, and Online Support. J. Chem. Eng. Data 2013, 58, 2699−2716. (12) Schwarzenbach, G.; Flaschka, H. Complexonometric titration (Russ. translation); Izdatel’stvo Chimija, 1970. (13) Schott, H. Mathematical Extrapolation for the Method of Wet Residues. J. Chem. Eng. Data 1961, 6, 324. (14) Laliberte, M.; Cooper, W. Model for Calculating the Density of Aqueous Electrolyte Solutions. J. Chem. Eng. Data 2004, 49, 1141− 1151. (15) Laliberte, M. A Model for Calculating the Heat Capacity of Aqueous Solutions, with Updated Density and Viscosity Data. J. Chem. Eng. Data 2009, 54, 1725−1760. (16) Mylius, F.; Dietz, R. Ü ber das Chlorzink. (Studien über die Löslichkeit der Salze XIV.). Z. Anorg. Chem. 1905, 44, 209−220.

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CONCLUSIONS Phase diagram of ternary NaCl−ZnCl2−H2O system was investigated at subzero temperatures with the method of isothermal solution saturation, wet residues, and thermogravimetric analysis. As a result, the compositions of saturated NaCl−ZnCl2−H2O solutions at 260.35 and 250.15 K and the composition of precipitated at these temperatures hydrate NaCl·ZnCl2·nH2O (n = 3) were determined. It was shown that the field of sodium chloride dihydrate stability in the ternary system at subzero temperatures seems to be rather short, sodium chloride precipitates at wider range of compositions. The solubility of NaCl and NaCl·2H2O does not change much with temperature, whereas 2NaCl·ZnCl2·3H2O and ZnCl2 hydrates alter their solubility, and ice forming is more influenced by temperature. It was shown that the boundary of ice crystallization is a more sensitive to the temperature than boundary of salts crystallization. The narrowing of the homogeneity area with the temperature decreasing is due to the greater expansion of ice crystallization area. The densities of ternary mixtures in 288.15−321.35 K temperature range were measured. The possibility of Laliberte model to predict densities of investigated ternary solution was checked. Unfortunately, the use of this model does not permit to give an adequate description of available experimental data with desirable precision. However, this method may be used in the case when high precision of data is not so essential. The situation might be improved by adding temperature-dependent ternary parameter to the Laliberte equation. These results allow determining concentrations of heavy solutions stable at low temperatures as to use them as a base for drilling liquids which can be transported and kept at these conditions.

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REFERENCES

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: +7-495-9392280. Fax: +7495-9391205. Author Contributions

The manuscript was written through equal contributions of all authors. F

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(17) Etard, A. Recherches Experimentales sur les Solutions Saturees. Ann. Chim. Phys. 1894, 7, 503−574. (18) Kogan, V. B.; Friedman, V. M.; Kafarov, V. V. Spravochnik po Rostvorimosti (Handbook on Solubility). 3. Binary systems; Izd. Akad. Nauk SSSR: Moscow, 1961. (19) Moshinski, A.; Shevchuk, V. G. The 2NaCl + ZnSO4 = Na2SO4 + ZnCl2 + H2O system at 75 °C. Russ. J. Inorg. Chem. 1970, 15, 1109− 1112.

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DOI: 10.1021/acs.jced.6b00048 J. Chem. Eng. Data XXXX, XXX, XXX−XXX