The Solubilities and Physicochemical Properties of NaH2PO2âNaCl

Article pubs.acs.org/jced

The Solubilities and Physicochemical Properties of NaH2PO2−NaCl−H2O, NaH2PO2−Zn(H2PO2)2−H2O, and NaCl−Zn(H2PO2)2−H2O Ternary Systems and in NaH2PO2−NaCl−Zn(H2PO2)2−H2O Quaternary System at 298.15 K ̇ ,* ̇ ,† Vedat Adıgüzel,*,† and Ö mer Şahiṅ ‡ Sevilay Demirci †

Department of Chemical Engineering, Kafkas University, Kars 36100, Turkey Department of Chemical Engineering, Siirt University, Siirt 56100, Turkey

‡

S Supporting Information *

ABSTRACT: The physicochemical properties and solubilities of NaH2PO2− Zn(H2PO2)2−H2O, NaH2PO2−NaCl−H2O, and NaCl−Zn(H2PO2)2−H2O ternary systems and in NaH2PO2−NaCl−Zn(H2PO2)2−H2O quaternary system at 298.15 K were investigated via the isothermal method. Invariant point compositions represent the quaternary system were characterized as the following: 10.65% mass NaCl, 32.51% mass NaH2PO2, 6.50% mass Zn(H2PO2)2, and 50.34% mass H2O. In solid phases, the salts of Zn(H2PO2)2.H2O, NaCl and NaH2PO2·H2O were recognized. The crystallization area of the salts were obtained as (i) 79.04% Zn(H2PO2)2, (ii) 18.62% NaCl and (iii) 2.34% NaH2PO2. Being the least soluble salt, Zn(H2PO2)2 has the largest crystallization area when compared with other salts present in the medium. According to the results, the crystallization area of was the largest in comparison with those of other salts and at the same time it was the least soluble salt.

1. INTRODUCTION Hypophosphite salts have been using in many applications such as hydrogen1 and anticorrosive commercial paint production.2 Sodium hypophosphite is used as a reducing agent, a flameretardant in cotton fabrics, and electrodeposition of coppercoated graphite powders.3−5 Calcium hypophosphite has been generally used as an anticorrosive agent, a flame-retardant, a fertilizer, an assistant for Ni electroless plating, animal nutrition supplements, and a mild deamination reagent.6,7 Furthermore, calcium hypophosphite is used for treating obesity in humans.8 In the pharmacology and production of nylon carpet fibers and linear condensation polymers, manganese hypophosphite is highly valued.1 Metal hypophosphites have been gaining importance among the inorganic compounds thanks to their properties mentioned briefly above.9−14 Phase diagrams are used for separating salts and production of important chemicals.15 Hypophosphites are synthesized from the reactions of white phosphor and hot solutions of alkali metals (1).

reactions which increase the unit cost. For instance, Zn(H2PO2)2 synthesis was described below (2−4) (2)

Ba(H 2PO2 )2 + H 2SO4 → BaSO4 + 2H3PO2

(3)

10H3PO2 + 2ZnCO3·3Zn(OH)2 → 5Zn(H 2PO2 )2 + H 2O + CO2

(4)

Instead of this synthesis of Zn(H2PO2)2, a more useful and cheaper method of synthesis can be established with the A+, Zn2+//X−, (H2PO2)−−H2O (A = Na, K, NH4; X = NO3, Cl, Br) systems. In this case, Zn(H2PO2)2 can be obtained easier via differences of solubility of the salts used. There are some articles examining the solubility systems involving H2PO2 ion at various temperatures. Tan et al. studied the phase equilibria and density measurements of the Ca2+//H2PO2−,Cl−−H2O and Ca2+, Na+//H2PO2−−H2O systems. They found 6.23% Ca(H2PO2)2, 44.87% CaCl2, and density 1.4921 g/cm3 in the liquid phase in the invariant point of Ca2+//H2PO2−,Cl−−H2O ternary system, and Ca(H2PO2)2 and CaCl2·6H2O in the solid phase. Additionally, they found

2P4 + 3Ca(OH)2 + 6H 2O → 3Ca(H 2PO2 )2 + 2PH3 (1)

All the hydroxides compounds soluble in water give same reactions for obtaining the salts of NaH2PO2, Ca(H2PO2)2, and so forth.16 With regard to the use of water-insoluble hydroxide compounds, this process suffers from the requirement of multistep © XXXX American Chemical Society

8P + 3Ba(OH)2 + 6H 2O → 3Ba(H 2PO2 )2 + 2PH3

Received: November 20, 2015 Accepted: June 1, 2016

A

DOI: 10.1021/acs.jced.5b00988 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

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Table 1. Source and Property of the Chemicals Used chemical name

source

purity (in mass fraction)

NaCl NaH2PO2·H2O [Fe(C12H8N2)3]SO4 H3PO2 CuCl2·2H2O C10H14N2Na2O8·2H2O HCl K2Cr2O7 K2CrzO4 Zn(H2PO2)2

Merck Merck Merck RIė del-de Haen Merck RIė del-de Haen RIė del-de Haen Merck Merck synthesis

99% 99% 50% 98% 98% 37% 98% 98% 98%

analysis method

crystallization

standard ion and melting point analysis

same purity level of 98% of Zn(H2PO2)2. This information was supported from the melting point analyses which gave steady single point of temperature. A Stuart SMP30 melting point analyzer (accuracy ±2.5 K) was used for the analysis of the melting point. For the analysis of the density, a Mettler Toledo 30PX densitometer (accuracy ±0.001 g/cm3) was utilized and the viscosity was completed with the Brookfield DV2T viscometer (accuracy 1%). The viscometer with a calibrated spring operates a spindle immersed in a solution. The viscosity values are measured with the aid of the variation degree of the spring deflection. The rotational speed of the spindle limits the range of measurements. Titration measurements were carried out by using a 50 mL titration apparatus (Hirscmann Solarus, accuracy: 0.2%). In addition, stabilization of the temperatures applied was achieved by using a refrigerated circulator water bath (Polyscience, accuracy: ±0.05 K). 2.2. Experimental Methods. For the measurements of physicochemical property, solubility, and phase equilibrium at 298.15 K, solutions of ternary NaCl−NaH 2 PO 2 −H 2 O, NaH2 PO2 −Zn(H 2PO2 ) 2−H2 O, NaCl−Zn(H2 PO 2) 2 −H 2O, and quaternary NaH2PO2−Zn(H2PO2)2−NaCl−H2O systems in equilibrium were prepared. Additionally, 40 mL of the saturated NaCl solutions were used in waterproof and sealed tubes to form NaCl−NaH2PO2−H2O ternary system, then NaH2PO2 was added in the tubes in certain amounts until the invariant point would be found. Then all the tubes put into a disc were placed into heated circulating bath at 298.15 K (shown in Figure 1). The disc was shaken vigorously for 1 day and the

51.49 and 16.54% NaH2PO2, 0.03 and 3.03% Ca(H2PO2)2, and densities 1.3805 and 1.1837 g/cm3 in liquid phase in the invariant points of Ca2+, Na+//H2PO2−−H2O ternary system respectively, and Ca(H2PO2)2, NaCa(H2PO2)3, and NaH2PO2·H2O in solid phases.17 The Na2(NO3)2 + Na2(H2PO2)2 + Mn(H2PO2)2 + H2O system at 273.15 K was studied by Alisoglu and Necefoglu.18 Alisoglu had investigated the NaH2PO2−Mn(H2PO2)2−NaBr− MnBr2−H2O system at 278.15 K, and it was obtained that NaBr· 2H2O, MnBr2·4H2O, NaH2PO2·H2O, and Mn(H2PO2)·2H2O salts are in the solid phase.19 Alisoglu and Adiguzel have studied the KBr−MnBr2− KH2PO2−Mn(H2PO2)2−H2O system at 273.15 K and found that KBr, MnBr2·4H2O, KH2PO2, and Mn(H2PO2)2·H2O salts are in the systems.20 Erge et al. have investigated the solubility in NaCl−BaCl2− H2O, NaH2PO2−Ba(H2PO2)2−H2O, NaCl−NaH2PO2−H2O, BaCl2−Ba(H2PO2)2−H2O and NaCl−NaH2PO2−BaCl2−Ba(H2PO2)2−H2O systems at 273.15 K.21 According to the literature survey, there is no any article examining the solubility properties of both ions, Zn2+ and H2PO2−, except Adıgüzel’s study.22 In literature, the studies related to NaH2PO2 and Zn(H2PO2)2 compounds, saturated solubility values of NaH2PO2 were found as 51.95% and 51.25%, and invariant point compositions were found as 51.49% and 40.22% at 298.15 K.17,19 It was also found that the saturated solubility value of NaH2PO2 was 47.80% and invariant values were 42.88, 43.98, 44.02, and 45.27% at 273.15 K.18,21,22 It was investigated that the solubility value of Zn(H2PO2)2 was 13.79% at 273.15 K and 0.59%, 19.69% in invariant points.22 In this study, we focused on the solid−liquid phase equilibria of Zn(H2PO2)2, NaH2PO2, and NaCl containing systems; we also reported their SLE data and phase diagrams at 298.15 K.

2. EXPERIMENTAL SECTION 2.1. Materials. In Table 1, the chemicals of the study are described. Any purification methods had been applied to those chemicals. In the experiments, double-distilled deionized water of which pH is 6.6 and conductivity is less than 10−4 Sm−1 was used. Zinc hypophosphite was synthesized in accordance with below mentioned reaction 5 in our lab

Figure 1. Experimental apparatus of SLE: (1) heated circulating bath, (2) tube, (3) turning disc, and (4) mechanical stirrer.

mixture was waited until phase level changings were become fix. After getting the samples from the liquid and solid phase; the density, viscosity, and the composition of those phases were measured by using classical analytical methods. All these applications were employed to all ternary systems. In order to establish NaH2PO2−Zn(H2PO2)2−NaCl−H2O quaternary system, the other third salt was added to the invariant

10H3PO2 + 2ZnCO3·3Zn(OH)2 → 5Zn(H 2PO2 )2 + H 2O + CO2

purification method

(5)

The Zn(H2PO2)2 purity was controlled by using standard ion analyses of Zn2+and H2PO2− and melting point analysis (446.15 K22). Both Zn2+and H2PO2− analyses pointed out the B



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point of ternary systems until the quaternary system’s invariant point was seen. Stirring and other continuing processes were carried out as described above for the ternary systems. After converting the data into a tabular form, 100 mol mixtures of salt were calculated. Then, figures were drawn. The percent composition of the solid and liquid phases was calculated and the chemical structures of the salts were identified via Schreinemaker’s wet residue method21 (shown in Figures 2−5 and Tables 2−5). The 100 mol total salt compositions versus density and viscosity values graphs were plotted23 (shown in Figures 6−8).

Figure 4. Solubility diagram for the ternary NaH2PO2−Zn(H2PO2)2− H2O system at 298.15 K.

Figure 2. Solubility diagram for the ternary NaCl−NaH2PO2−H2O system at 298.15 K.

Figure 5. Phase diagram of quaternary NaCl−Zn(H2PO2 )2 − NaH2PO2−H2O system at 298.15 K.

The density and viscosity values and the percent compositions of the ternary and quaternary systems at the invariant points are as follows: The mass fraction of NaCl at the invariant point of NaCl− NaH2PO2−H2O ternary system was 1.83%. These values for NaH2PO2 and H2O were 46.43% and 51.74%, respectively. NaCl and NaH2PO2·H2O crystals were found to be in equilibrium with the liquid phase. The density of the invariant point was 1373 kg/m3 and the viscosity was 14.12 mPa·s (shown in Figure 2 and 6, Table 2). In the case of NaCl−Zn(H2PO2)2−H2O ternary system, invariant point compositions were calculated as 22.79% mass for NaCl, 19.8% mass for Zn(H2PO2)2, and 57.41% mass for H2O. Equilibrium state was also valid between Zn(H2PO2)2·H2O and NaCl crystal hydrates and the liquid phase while the density and the viscosity of the liquid phase at invariant point were 1369 kg/m3 and 3.7 mPa.s, respectively (shown in Figures 3 and 7 and Table 3). Mass fractions of our other ternary system, NaH2PO2− Zn(H2PO2)2−H2O, were as follows: 44.14% for NaH2PO2, 1.89% for Zn(H2PO2)2 and 53.97% for H2O. At the invariant point in this system, Zn(H2PO2)2·H2O and NaH2PO2·H2O crystal hydrates were in equilibrium with the liquid phase. Some

Figure 3. Solubility diagram for the ternary NaCl−Zn(H2PO2)2−H2O system at 298.15 K.

All tests were performed in triplicate. Results are expressed as mean value ± standard deviation. 2.3. Analytical Methods. The concentration of Zn2+, Cl−, and H2PO2− ions were determined by the titration with standard solutions of EDTA, AgNO3, and K2Cr2O7.10,24 The expanded uncertainties (ur) for Zn2+, Cl−, and H2PO2− analyses are 2%, 3%, and 0.8%, respectively (at the level of confidence of 0.95). Then, the concentration of Na+ ion was calculated by difference.

3. RESULTS AND DISCUSSION Binary systems’ solubilities were determined as 51.96% mass NaH2PO2, 18.61% mass Zn(H2PO2)2, and 26.42% mass NaCl at 298.15 K. C



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Figure 6. Viscosity (η/mPa·s) and density (ρ/kg/m3) diagram for the ternary NaCl−NaH2PO2−H2O system at 298.15 K.

Figure 7. Viscosity (η/mPa·s) and density (ρ/kg/m3) diagram for the ternary NaCl−Zn(H2PO2)2−H2O system at 298.15 K.

Figure 8. Viscosity (η/mPa.s) and density (ρ/kg/m3) diagram for the ternary NaH2PO2−Zn(H2PO2)2−H2O system at 298.15 K.

With respect to the NaH2PO2−Zn(H2PO2)2−NaCl−H2O quaternary system, compositions as mass fractions at the invariant point were found out as 10.65% for NaCl, 32.51% for NaH2PO2,

physicochemical properties such as density and viscosity were calculated as 1343 kg/m3 and 15.18 mPa·s (shown in Figures 4 and 8 and Table 4). D



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Table 2. Solubility, Viscosity (η), and Density (ρ) for the Ternary (NaCl−NaH2PO2−H2O) system at 298.15 K and P = 1.025 × 105 Paa

a

liquid phase (% mass)

solid phase (% mass)

density

viscosity

no

NaCl

NaH2PO2

NaCl

NaH2PO2

100 mol composition of salts NaCl

NaH2PO2

ρ (kg/m3)

η (mpa·s)

equilibrium saltb

1 2 3 4 5 6 7 8 9 10 11E 12E 13 14 15

26.42 24.38 22.18 19.43 15.96 14.25 13.60 8.55 5.58 3.20 1.83 1.83 1.22 0.80 0.00

0.00 3.60 7.58 12.79 18.76 22.65 22.80 33.92 39.60 44.38 46.43 46.43 47.98 49.81 51.96

92.24 91.48 90.65 89.47 88.24 86.97 85.79 84.54 83.38 82.13 61.51 8.54 1.12 0.47 0.00

0.00 1.02 2.03 3.25 4.12 5.67 5.70 7.12 8.23 9.11 29.40 71.50 76.83 78.12 79.56

100 91.04 81.50 69.60 56.17 48.70 47.35 27.49 17.43 9.84 5.60 5.60 3.67 2.35 0.00

0.00 8.96 18.50 30.40 43.83 51.30 52.65 72.51 82.57 90.16 94.40 94.40 96.33 97.65 100

1194 1204 1209 1216 1226 1238 1239 1276 1308 1350 1373 1373 1378 1386 1394

1.50 1.60 1.70 2.25 2.80 3.50 3.67 5.96 7.76 10.60 14.12 14.12 14.75 15.86 17.60

NC NC NC NC NC NC NC NC NC NC NC + NHyp NC + NHyp NHyp NHyp NHyp

Standard uncertainties u are ur(η) = 1%, u(ρ) = 0.001 g/cm3, u(T) = 0.05 K, ur(P) = 5%, and u(w) = 0.01 w. bNC: NaCl. NHyp: NaH2PO2·H2O

Table 3. Solubility, Viscosity (η), and Density (ρ) for the Ternary (NaCl−Zn(H2PO2)2−H2O) System at 298.15 K and P = 1.025 × 105 Paa liquid phase (% mass)

a

solid phase (%mass)

100 mol composition of salts

density

viscosity

no

NaCl

Zn(H2PO2)2

NaCl

Zn(H2PO2)2

NaCl

Zn(H2PO2)2

ρ (kg/m )

η (mPa·s)

equilibrium saltb

1 2 3 4 5 6 7E 8E 9 10 11 12 13 14 15

0.00 6.11 9.84 13.14 16.24 19.14 22.79 22.79 23.05 23.17 24.61 25.25 25.67 26.02 26.42

18.61 19.12 19.53 20.67 21.87 22.55 19.80 19.80 18.91 18.41 10.62 7.40 4.31 2.19 0.00

0.00 1.50 1.90 2.45 2.51 4.10 30.02 48.04 62.00 75.00 76.02 88.00 88.40 89.80 91.56

98.06 93.80 90.03 89.80 90.00 85.10 54.90 27.45 8.90 4.80 3.00 2.30 2.03 1.70 0.00

0.00 51.63 62.76 67.99 71.29 73.50 77.78 77.78 77.92 80.80 88.58 92.70 94.57 97.54 100

100 48.37 37.24 32.01 28.71 26.50 22.22 22.22 22.08 19.19 11.42 7.30 5.43 2.46 0.00

1157 1193 1226 1265 1309 1338 1369 1369 1367 1360 1324 1279 1246 1229 1214

2.04 2.92 3.21 3.40 3.56 3.65 3.70 3.70 3.57 3.33 2.79 2.34 2.05 1.85 1.70

NC NC NC NC NC NC NC + ZHyp NC + ZHyp ZHyp ZHyp ZHyp ZHyp ZHyp ZHyp ZHyp

3

Standard uncertainties u are ur(η) = 1%, u(ρ) = 0.001 g/cm3, u(T) = 0.05 K, ur(P) = 5%, and u(w) = 0.01 w. bNC: NaCl. ZHyp: Zn(H2PO2)2·H2O

When the system was approaching to the invariant point, the solubility of NaCl sharply decreased from 26.42% to 1.83% in the NaCl− NaH2PO2−H2O ternary system. The solubility of NaH2PO2 slightly decreased from 51.96% to 46.43% in the same system. With regard to the NaCl−Zn(H2PO2)2−H2O ternary system, it was observed that while the solubility of NaCl decreased from 26.42% to 22.79%, the solubility of Zn(H2PO2)2 increased from 18.61% to 19.80%. In the case of NaH2PO2−Zn(H2PO2)2−H2O ternary system, when the solubility of Zn(H2PO2)2 sharply decreased from 18.61% to 1.89%, the solubility of NaH2PO2 slightly decreased from 51.96% to 44.14%. When the results of this study are compared with the previous study at 273.15 K,22 it is seen that the solubility of NaCl and Zn(H2PO2)2 increased while the solubility of NaH2PO2 salt decreased in parallel with the temperature (shown in Figure 9). In the light of these results, first Zn(H2PO2)2 precipitate when the solution at the invariant point at 298.15 K falls to 273.15 K.

6.50% for Zn(H2PO2)2, and 50.34% for H2O. It is also found that NaCl, Zn(H2PO2)2·H2O and NaH2PO2·H2O crystals were present in equilibrium with the liquid phase at the invariant point (shown in Figure 5 and Table 5). In Figures 2−4, ABE, EDC, and EFG represent crystallization area of NaCl, NaH2PO2·H2O, and Zn(H2PO2)2·H2O, respectively. Additionally, BECW, BEFW, FECW denote unsaturated areas. It is seen that from Figures 2−4, B, C, and F represent the solubility of NaCl, NaH2PO2, and Zn(H2PO2)2 salts in water at 298,15 K, respectively. The calculations of crystallization areas of the salts were performed via the geometric rules from equilateral triangle with the values of 79.04% Zn(H2PO2)2, 18.62% NaCl, and 2.34% NaH2PO2. As it is understood from the experimental values and figures, having the largest crystallization field in comparison with the other salts, the crystallization of Zn(H2PO2)2 has occupied 79.04% of the general crystallization field. E



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Table 4. Solubility, Viscosity (η), and Density (ρ) for the Ternary (Zn(H2PO2)2−NaH2PO2−H2O) System at 298.15 K and P = 1.025 × 105 Paa density

viscosity

no

NaH2PO2

liquid phase (% mass) Zn(H2PO2)2

NaH2PO2

solid phase (%mass) Zn(H2PO2)2

100 mol composition of salts NaH2PO2

Zn(H2PO2)2

ρ (kg/m3)

η (mPa·s)

equilibrium saltb

1 2 3 4 5 6 7 8 9 10E 11E 12 13 14

0.00 10.65 18.52 24.73 30.21 30.81 36.98 40.34 43.90 44.14 44.14 45.60 47.40 51.96

18.61 10.85 7.28 5.48 4.00 3.83 2.17 1.86 1.85 1.89 1.89 1.19 0.64 0.00

0.00 1.90 2.31 2.62 11.25 16.04 22.61 13.12 15.01 42.51 58.22 60.13 70.03 82.80

88.31 83.02 83.10 81.00 59.57 46.80 37.25 62.95 62.27 29.23 29.00 0.50 0.30 0.00

0.00 68.55 84.98 90.85 94.36 94.72 97.42 97.93 98.06 98.12 98.12 98.83 99.39 100

100 31.45 15.02 9.15 5.64 5.28 2.58 2.07 1.94 1.88 1.88 1.17 0.61 0.00

1157 1165 1195 1223 1259 1262 1300 1320 1337 1343 1343 1353 1370 1394

2.04 2.40 2.65 3.11 3.90 3.96 5.69 8.36 13.28 15.18 15.18 14.57 14.45 17.60

ZHyp ZHyp ZHyp ZHyp ZHyp ZHyp ZHyp ZHyp ZHyp ZHyp + NHyp ZHyp + NHyp NHyp NHyp NHyp

Standard uncertainties u are ur(η) = 1%, u(ρ) = 0.001 g/cm3, u(T) = 0.05 K, ur(P) = 5%, and u(w) = 0.01 w. bZHyp: Zn(H2PO2)2·H2O. NHyp: NaH2PO2·H2O

a

Table 5. Solubility for the Quaternary (NaCl−NaH2PO2−Zn(H2PO2)2−H2O) System at 298.15 K and P = 1.025 × 105 Paa liquid Phase (% mass)

100 mol composition of salts

no

NaH2PO2

NaCl

Zn(H2PO2)2

H2O

NaH2PO2

NaCl

Zn(H2PO2)2

equilibrium saltb

1 2 3 4E 5 6 7 8 9E 10 11 12 13E

46.43 47.55 36.01 32.51 44.14 44.40 37.07 35.40 32.51 0.00 11.94 25.91 32.51

1.83 3.29 6.80 10.65 0.00 2.92 8.70 9.00 10.65 22.79 18.96 15.89 10.65

0.00 1.02 2.99 6.50 1.89 3.78 5.20 5.80 6.50 19.80 15.50 11.82 6.50

51.74 48.14 54.20 50.34 53.97 48.90 49.03 49.80 50.34 57.40 53.58 46.38 50.34

94.40 89.78 75.66 63.40 98.12 87.92 70.60 68.65 63.40 0.00 25.14 46.98 63.40

5.60 9.35 21.51 30.88 0.00 8.70 24.94 26.28 30.88 79.36 60.13 43.37 30.88

0.00 0.87 2.83 5.72 1.88 3.38 4.46 5.07 5.72 20.64 14.73 9.65 5.72

NHyp + NC NHyp + NC NHyp + NC NHyp + NC + ZHyp NHyp + ZHyp NHyp + ZHyp NHyp + ZHyp NHyp + ZHyp NHyp + NC + ZHyp NC + ZHyp NC + ZHyp NC + ZHyp NHyp + NC + ZHyp

Standard uncertainties u are ur(η) = 1%, u(ρ) = 0.001 g/cm3, u(T) = 0.05 K, ur(P) = 5%, and u(w) = 0.01 w. bNC: NaCl. NHyp: NaH2PO2·H2O. ZHyp: Zn(H2PO2)2·H2O

a

4. CONCLUSIONS In this study, some physicochemical properties such as viscosity, density, and percent mass compositions of saturated NaH2PO2− NaCl−H2O, NaH2PO2−Zn(H2PO2)2−H2O, and NaCl−Zn(H2PO2)2−H2O and quaternary NaH2PO2−Zn(H2PO2)2− NaCl−H2haO solutions were examined. The stable experimental phase diagrams were drawn as well as physicochemical properties vs compositions diagrams of the systems for the first time in the literature. For the all systems studied, three solid phases in equilibrium were identified including NaCl, Zn(H2PO2)2·H2O and NaH2PO2·H2O salts. In the ternary systems of NaH2PO2−NaCl−H2O and NaH2PO2−Zn(H2PO2)2−H2O, we concluded that NaH2PO2 has strong salting-out effect on both NaCl and Zn(H2PO2)2 salts. Obviously, in Table 5, the solubility value of Zn(H2PO2)2 at the invariant point of the quaternary system was 6.50% mass which is less than the other salts’ values. Zn(H2PO2)2 is precipitated near the invariant point as NaH2PO2 is added to

Figure 9. Compared phase diagram of quaternary NaCl−Zn(H2PO2)2− NaH2PO2−H2O systems at 273.15 and 298.15 K.

NaCl precipitate initially when NaH2PO2 is added to this new solution. In this way, a possible process may be designed in order to separate all these salts economically. F



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the nonsaturated solution containing NaCl, NaH2PO2 and Zn(H2PO2)2 salts. The results of this study reveals that a separation process for the salt of Zn(H2PO2)2 is feasible due to its relatively large area of crystallization with the value of 79.04%. The findings of this study can be applicable in various industrial and recycling processes. Zn(H2PO2)2, NaCl, and NaH2PO2 salts present in industrial wastes and natural salt compositions can be effectively separated each other using proposed method.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.5b00988. (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. Tel: +905332151650. Fax: +904742251282. *E-mail: [email protected]. Tel: +9053235893035. Fax: +904742251282. Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Funding

The authors gratefully thank to The Scientific and Technological Research Council of Turkey (TUBITAK) for the supporting this study with the Project No. 114Z651. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors gratefully thank Engin Zilkar for his invaluable technical support. ABBREVIATIONS E, invariant point; NC, NaCl; NHyp, NaH2PO2·H2O; ZHyp, Zn(H2PO2)2·H2O; SLE, solid−liquid equilibrium REFERENCES

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