Influence of Salt on the Solubility and Tie-Line Data for Water + Formic

Article pubs.acs.org/jced

Influence of Salt on the Solubility and Tie-Line Data for Water + Formic Acid + Methyl Isobutyl Ketone at T = 298.15 K Thanaporn Wannachod,† Milan Hronec,‡ Tomás ̌ Soták,‡ Katarína Fulajtárová,‡ Ura Pancharoen,*,† and Kasidit Nootong*,† †

Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Patumwan, Bangkok 10330, Thailand Department of Organic Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia

‡

ABSTRACT: The tie-line and solubility data for the systems containing formic acid (FA), water, and methyl isobutyl ketone (MIBK) + NaCl were determined experimentally at temperature 298.15 K and atmospheric pressure. The effect of salt 0.05−0.15 mass fraction (base on mass of initial water) was investigated. Binary interaction parameters were ascertained by comparing the experimental tie-line data with the nonrandom two-liquid model (NRTL) correlations. The tie-line data of the systems were analyzed using the Othmer−Tobias, Hand, and Bachman correlation equations. Separation factors and distribution coefficients were assessed. The results show that enlargement of the two−-hase region occurred when the concentration of salt increased in the initial aqueous phase; adding salt to the system proved beneficial in separating FA from water. The research provides sound solubility data for formic acid.19−21 Further studies on the extraction of formic acid from water involved the use of several organic solvents.22−24 However, more studies need to be undertaken. Methyl isobutyl ketone (MIBK) is a good solvent for extracting many organic acids from aqueous solutions.25,26 Although some research exists on separating carboxylic acids from aqueous solutions,19,27 so far no investigation has been done as regards the salt effect on FA with methyl isobutyl ketone. A summary of previous research on LLE of formic acid is shown in Table 1. In this work, the effect of salt on the tie-line and solubility data with methyl isobutyl ketone was investigated at temperature of 298.15 K and atmospheric pressure. From the tie-line data, separation factors and distribution coefficients were evaluated for the two-phase region. Validation of the experimental tie-line data was verified by the Othmer−Tobias,28 Hand,29 and Bachman30 correlation equations. In order to obtain the binary interaction parameters, the experimental LLE data were correlated using the NRTL activity coefficient model.31

1. INTRODUCTION Liquid−liquid extraction (LLE) consists in transferring solutes contained in a feed solution to another immiscible liquid (solvent). It is an extraction of a substance from one liquid into another liquid phase. Such extraction processes have proved to be highly effective leading to lower costs over other methods.1 In recent years, there has been increased interest in LLE, and there is a need for reliable data for this process as an efficient means of separation. LLE studies of organic solvents and carboxylic acids are important in the assessment of solvent extraction.2−5 The addition of salt to a mixture of solvents can bring about great changes in their composition.6 Adding salt has proved to be beneficial in separation, distillation, and solvent extraction processes. The purification of proteins, enzymes, and nucleic acids have come about due to the salt effect.7 Formic acid (HCOOH, FA) occurs naturally and is found in the venom of some ants. It is a colorless liquid which has a highly pungent smell. It is a strong corrosive material and can corrode equipment and pipelines. FA is extensively used in many areas such as pesticide, medicine, organic synthesis, and the tannery industry.8 A significant amount of FA is also produced as a byproduct in the manufacture of other chemicals, e.g., acetic acid. Formic acid is widely used to preserve animal feed for cattle.9 A prospective use of FA is in the hydrogenation process as a source of hydrogen. Formic acid forms an azeotrope with water (77.6% water, 22.4% FA).10 Many investigations on LLE11−17 and the salt effect on the LLE system6,18 have taken place. Among the first to report on the LLE system containing formic acid (FA) were Kumar and Das.1 © XXXX American Chemical Society

2. EXPERIMENTAL SECTION 2.1. Chemicals. All chemicals used are without further purification and are listed in Table 2. Gas chromatography (GC) analysis did not detect any appreciable impurities. For titration work, standardized sodium hydroxide was used. Received: February 4, 2016 Accepted: June 13, 2016

A

DOI: 10.1021/acs.jced.6b00109 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Summary of Previous Research on LLE of Formic Acid authors

formic acid

Kumar et al. Gilani et al. Zhang et al. Başlıoğlu et al. Bilgin et al. Demirel et al. Wannachod et al.

formic formic formic formic formic formic formic

acid acid acid + propionic acid acid or acetic acid acid

solvent

temperature (K)

effect of salt

ref.

MIBK 1-butanol, 1-pentanol, 1-hexanol, and 1-heptanol dibenzothiophene and butan-1-ol amyl acetate, diisobutyl ketone, and diisopropyl ether diethyl carbonate, diethyl malonate, and diethyl fumarate ethyl heptanoate MIBK

288.15, 298.15, and 308.15 298.2 278.15 and 333.15 298.15 298.15 288.15, 298.15, and 308.15 298.15

none none none none none none

1 2 13 23 24 32 this work

Table 2. Source and Mass Fraction of the Pure Components at 293.15 K and 101.3 kPa chemicals

source

purity/% mass

formic acid MIBK NaCl water

Sigma-Aldrich MicroChem Sigma-Aldrich

99.0 99.5 99.0 deionized and redistilled

Table 3. Experimental (Liquid + Liquid) Equilibrium Mass Fractions w at a Salt-Free Basis for the System Water (1) + Formic Acid (2) + Methyl Isobutyl Ketone (3) + Sodium Chloride (4) at Temperature T = 298.15 K and Pressure p = 101.325 kPaa,b

analytical method GC GC

ws = 0

2.2. Apparatus and Procedure. The solubility data (bimodal curves) were determined by the cloud point method33 in an equilibrium cell with a magnetic stirrer. All experiments were conducted under atmospheric pressure. The temperature of the mixtures at 298.15 K was checked using a digital thermometer; the cell temperature was measured within an accuracy of ±0.1 K. At the beginning of the experiments, water, FA, MIBK, and NaCl were added to the cell by mass at know ratios. The weights of these reagents were determined by an electronic balance with accuracy of ±0.1 g. The end-points were determined by observing the transition from an appearance to disappearance mixtures. The end-point of titration was achieved when the mixtures remained turbid for 5 min. All samples were three replicated. To determine the tie line data, the heterogeneous mixtures were stirred for 1 h with a magnetic stirrer and were allowed to settle for 8 h for complete phase separation. Samples were carefully taken from each phase and analyzed. Sample Analysis. Taken samples from each phase were weighed and titrated with 0.1 mol·kg−1 sodium hydroxide solutions, in the presence of phenolphthalein as the indicator. For each phase sample, the titration was repeated three times, and the average was used. Samples from the organic phase were then analyzed by a gas chromatograph (GC) (Hewlett-Packard 5890 Series II). A 1.4 m × 3 mm glass column was used to separate the components. The injection and the detector temperatures were T = 435 K. The carrier gas (helium) flow rate was maintained at 40 cm3·min−1. The external standard method was used to analyze the content of the three components.

3. RESULTS AND DISCUSSION 3.1. Experimental LLE and Tie-Line Data. LLE data for the system (water + formic acid + MIBK+ NaCl) were measured at T = 298.15 K and 101.3 kPa. Solubility data for water + FA + MIBK + NaCl system at mass fraction of NaCl of ws = 0, ws = 0.05, ws = 0.1 and ws = 0.15 are given in Table 3. The systems exhibited type-1 behavior.34 Thus, it is noted that water is most soluble with mass fraction of NaCl ws = 0, but least soluble with mass fraction of NaCl ws = 0.15: the two-phase region decreases as follows, i.e., mass fraction of NaCl 0.15 > 0.10 > 0.05. Thus, the influence of salt was more significant as the concentration of salt increased. It can be explained that salt

ws = 0.05

w1

w2

w3

w1

w2

w3

0.9845 0.9458 0.8872 0.8301 0.7915 0.7693 0.7540 0.7195 0.6956 0.6766 0.6555 0.6325 0.6052 0.5644 0.5075 0.4551 0.3914 0.3205 0.2268 0.0215

0.0000 0.0432 0.1023 0.1563 0.1891 0.2080 0.2185 0.2391 0.2498 0.2563 0.2615 0.2676 0.2709 0.2775 0.2805 0.2741 0.2461 0.1970 0.1309 0.0000 ws = 0.10

0.0155 0.0110 0.0105 0.0136 0.0194 0.0227 0.0275 0.0414 0.0546 0.0671 0.0830 0.0999 0.1239 0.1581 0.2120 0.2708 0.3625 0.4825 0.6423 0.9785

0.9990 0.9408 0.8943 0.8280 0.7950 0.7672 0.7444 0.7191 0.6987 0.6715 0.6352 0.6095 0.5740 0.5374 0.4628 0.4141 0.3608 0.2839 0.1985 0.0196

0.0000 0.0572 0.1033 0.1661 0.1993 0.2241 0.2431 0.2608 0.2746 0.2904 0.3035 0.3118 0.3130 0.3165 0.3118 0.3046 0.2798 0.2265 0.1470 0.0000 ws = 0.15

0.0010 0.0020 0.0024 0.0059 0.0057 0.0087 0.0125 0.0201 0.0267 0.0381 0.0613 0.0787 0.1130 0.1461 0.2254 0.2813 0.3594 0.4896 0.6545 0.9804

w1

w2

w3

w1

w2

w3

0.9990 0.8704 0.7622 0.6939 0.6134 0.5428 0.4602 0.3723 0.3047 0.2563 0.1942 0.1394

0.0000 0.1296 0.2378 0.3061 0.3758 0.4124 0.4198 0.4148 0.3982 0.3556 0.2786 0.1933

0.0010 0.0000 0.0000 0.0000 0.0108 0.0448 0.1200 0.2129 0.2971 0.3881 0.5272 0.6673

0.9990 0.8587 0.7577 0.6730 0.5521 0.4717 0.3989 0.3035 0.2268 0.1594 0.1069 0.0745

0.0000 0.1413 0.2423 0.3270 0.4429 0.5155 0.5463 0.5463 0.5356 0.4776 0.3876 0.2739

0.0010 0.0000 0.0000 0.0000 0.0050 0.0128 0.0548 0.1502 0.2376 0.3630 0.5055 0.6516

a ws is the mass fraction of sodium chloride in its initial mixture with water; bStandard uncertainties u are u(T) = 0.1 K, u(p) = 0.01 MPa, and u(w) = 0.005.

ions in the aqueous solution solvated: water being the preferred component for solvation. In hydration theory,35 it is assumed that each salt ion binds with water molecules. This bound water was then unavailable as solvent for formic acid. Therefore, formic acid tends to be less soluble in water. The tie-line data of these systems were measured at T = 298.15 K and atmospheric pressure. Mass fractions of NaCl in the salt B



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Figure 3. Diagram for the system formic acid + MIBK + water at mass fraction of NaCl ws = 0.10 and T = 298.15 K; gray ●, experimental solubility curve; blue ■, experimental tie-line data and red ▲, calculated NRTL data.

Figure 1. Diagram for the system formic acid + MIBK + water at mass fraction of NaCl ws = 0 and T = 298.15 K; gray ●, experimental solubility curve; blue ■, experimental tie-line data and red ▲, calculated NRTL data.



solutions were found to be 0, 0.05, 0.1, and 0.15, respectively. The corresponding triangular phase diagrams for these systems are shown in Figures 1−4. The slopes of the tie lines express the fact that formic acid is more soluble in MIBK than in water. This is due to the intermolecular interaction of formic acid with MIBK and water. In water, formic acid forms weak bonds with hydrogen atoms of water.36 Generally, the volume of a soluble component in water relies on its intermolecular vigor. 3.2. Correlation Models. The LLE data for each system were correlated using the NRTL model. Tables 4 and 5 show the experimental tie-line data for the systems at T = 298.15 K. The alpha value was fixed at α = 0.2. The binary interaction parameters (bij and bji) for the systems are shown in Table 6, respectively. The root-mean-square deviation (rmsd) value was determined accordingly as in eq 1: rmsd =

n 2 3 exp ∑k = 1 ∑ j = 1 ∑i = 1 (wijk

6n

−

where wexp is the experimental mass fraction, wcal is the calculated mass fraction, n is the number of tie-lines and subscript i is components, and j is phases and k = 1, 2, ..., n (tie-lines). The rmsd is shown in Table 6. 3.3. Reliability of Tie-Line Data. The experimental tie-line data was ascertained by the Othmer−Tobias,28 Hand,29 and Bachman30 correlation eqs 2−4, respectively:

cal 2 wijk )

⎡ 1 − w33 ⎤ ⎡ 1 − w11 ⎤ ⎥ = A + B⎢ ln⎢ ⎥ ⎣ w11 ⎦ ⎣ w33 ⎦

(2)

⎡w ⎤ ⎡w ⎤ ln⎢ 21 ⎥ = A′ + B′ ln⎢ 23 ⎥ ⎣ w11 ⎦ ⎣ w33 ⎦

(3)

w23 = A″ + B″

(1) C

w23 w11

(4) DOI: 10.1021/acs.jced.6b00109 J. Chem. Eng. Data XXXX, XXX, XXX−XXX


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Table 4. Experimental and NRTL Tie-Line Mass Fractions w at a Salt-Free Basis for the System Water (1) + Formic Acid (2) + Methyl Isobutyl Ketone (3) at Free Sodium Chloride, Temperature T = 298.15 K, and Pressure p = 101.325 kPaa,b

Table 5. continued Experimental: Water + Formic Acid + MIBK aqueous phase

Experimental: Water + Formic Acid + MIBK aqueous phase

organic phase

w1

w2

w3

0.9686 0.9620 0.9574 0.9528 0.9450 0.9287 0.9205 0.9100 0.8958 0.8827 0.8467 0.8185 0.7768 0.7238

0.0173 0.0248 0.0285 0.0356 0.0432 0.0604 0.0688 0.0795 0.0936 0.1084 0.1420 0.1659 0.2005 0.2338

0.0141 0.0132 0.0141 0.0116 0.0118 0.0109 0.0107 0.0105 0.0106 0.0089 0.0113 0.0156 0.0227 0.0424

w1

w2

w3

0.0804 0.1175 0.1506 0.1725 0.1932 0.2143 0.2358 0.2554 0.2862 0.3073 0.3474 0.3795 0.4159 0.4406

0.0392 0.0636 0.0848 0.0946 0.1125 0.1239 0.1401 0.1515 0.1683 0.1838 0.2123 0.2383 0.2538 0.2680

0.8804 0.8189 0.7646 0.7329 0.6943 0.6618 0.6241 0.5931 0.5455 0.5089 0.4403 0.3822 0.3303 0.2914

0.0766 0.1138 0.1470 0.1686 0.1913 0.2104 0.2335 0.2571 0.2902 0.3106 0.3398 0.3766 0.4108 0.4455

0.0380 0.0641 0.0818 0.0960 0.1102 0.1233 0.1387 0.1539 0.1708 0.1874 0.2111 0.2360 0.2537 0.2710

0.8854 0.8221 0.7712 0.7354 0.6985 0.6663 0.6278 0.5890 0.5390 0.5020 0.4491 0.3874 0.3355 0.2835

ws = 0

NRTL ws = 0 0.9681 0.9608 0.9572 0.9503 0.9435 0.9304 0.9198 0.9102 0.8948 0.8835 0.8489 0.8202 0.7802 0.7232

0.0171 0.0260 0.0291 0.0378 0.0453 0.0588 0.0695 0.0791 0.0945 0.1077 0.1388 0.1643 0.1998 0.2339

0.0148 0.0132 0.0137 0.0119 0.0112 0.0108 0.0107 0.0107 0.0107 0.0088 0.0123 0.0155 0.0200 0.0429

Experimental: Water + Formic Acid + MIBK

0.9038 0.8456 0.8033 0.7569 0.7359

0.0932 0.1500 0.1918 0.2318 0.2508

0.8555 0.8140 0.7553 0.7253

0.1438 0.1831 0.2431 0.2731

organic phase w3

w1

ws = 0.05 0.0030 0.6515 0.0044 0.4774 0.0049 0.3639 0.0113 0.2866 0.0133 0.2409 ws = 0.10 0.0007 0.1417 0.0029 0.1960 0.0016 0.2600 0.0016 0.3086

w2

w3

0.1993 0.2870 0.3548 0.4093 0.4493

0.1492 0.2356 0.2813 0.3041 0.3098

0.2005 0.2856 0.3598 0.3992

0.6578 0.5184 0.3802 0.2922

0.3109

0.8210 0.7480 0.6994 0.6636 0.6376

0.1780 0.2494 0.2995 0.3339 0.3614

0.8980 0.8400 0.7986 0.7515 0.7269

0.0985 0.1547 0.1968 0.2394 0.2560

0.8505 0.8110 0.7505 0.7208 0.6817

0.1483 0.1885 0.2478 0.2786 0.3177

0.8163 0.7406 0.6928 0.6554 0.6274

0.1821 0.2577 0.3066 0.3376 0.3706

i−j

Table 5. Experimental and NRTL Tie-Line Data Mass Fractions w at a Salt-Free Basis for the System Water (1) + Formic Acid (2) + Methyl Isobutyl Ketone (3) + Sodium Chloride (4) at Temperature T = 298.15 K and Pressure p = 101.325 kPaa,b

w2

0.6873

organic phase w3

w1

ws = 0.10 0.0018 0.3614 ws = 0.15 0.0010 0.0760 0.0026 0.1064 0.0011 0.1599 0.0025 0.2254 0.0010 0.2886 NRTL ws = 0.05 0.0035 0.2048 0.0053 0.2932 0.0046 0.3654 0.0091 0.4182 0.0171 0.4563 ws = 0.10 0.0012 0.1446 0.0005 0.199 0.0017 0.2639 0.0006 0.3108 0.0006 0.3660 ws = 0.15 0.0016 0.0763 0.0017 0.1090 0.0006 0.1650 0.0070 0.2299 0.0020 0.2912

w2

w3

0.4165

0.2221

0.2811 0.3941 0.4830 0.5331 0.5431

0.6429 0.4995 0.3571 0.2415 0.1683

0.1550 0.2371 0.2831 0.306 0.3155

0.6402 0.4697 0.3515 0.2758 0.2282

0.204 0.2881 0.3615 0.4030 0.4184

0.6514 0.5129 0.3746 0.2862 0.2156

0.2863 0.3958 0.4849 0.5388 0.5473

0.6374 0.4952 0.3501 0.2313 0.1615

Table 6. NRTL (α = 0.2) Binary Interaction Parameters (bij and bji) and rmsd Values for the Systems Investigated

ws is the mass fraction of sodium chloride in its initial mixture with water. bStandard uncertainties u are u(T) = 0.1 K, u(p) = 0.01 MPa, and u(w) = 0.005.

aqueous phase

w2

a ws is the mass fraction of sodium chloride in its initial mixture with water. bStandard uncertainties u are u(T) = 0.1 K, u(p) = 0.01 MPa, and u(w) = 0.005.

a

w1

w1

a

bija/K

1−2 1−3 2−3

851.85 1869.51 884.82

1−2 1−3 2−3

979.20 1914.53 655.82

1−2 1−3 2−3

989.23 1954.11 749.28

1−2 1−3 2−3

1015.32 1958.51 762.32

bija/K ws = 0 −510.42 331.59 −489.44 ws = 0.05 −651.18 348.03 −394.15 ws = 0.10 −658.11 448.44 −455.28 ws = 0.15 −685.12 485.41 −480.48

rmsd (%) 0.38

0.31

0.42

0.48

bij = (gij − gjj)/R.

where w11 is the mass fraction of water in the aqueous-rich phase, w33 is the mass fraction of the solvent in the organic-rich phase, and w21 and w23 are the mass fractions of formic acid in the aqueous-rich phase and the organic-rich phase. A, B, A′, B′, A″, and B″ are parameters of the Othmer−Tobias, Hand, and D



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Table 7. Othmer−Tobias, Hand, and Bachman Correlation Equation Data for Systems at Temperature T = 298.15 K and P = 101.325 kPa Othmer−Tobias correlation

Hand correlation

Bachman correlation

NaCl

A

B

R2

A′

B′

R2

A″

B″

R2

0 0.05 0.10 0.15

−2.0989 −1.5311 −1.3115 −1.1389

−2.0989 −1.5311 −1.3115 −1.1389

0.9987 0.9982 0.9974 0.9985

2.0124 1.468 1.345 1.254

1.4823 1.3129 0.9341 1.2685

0.9988 0.9979 0.9968 0.9981

2.5523 1.9058 1.4521 1.4578

1.8941 1.4854 1.2545 1.1241

0.9979 0.9981 0.9984 0.9988

Table 8. Separation Factors (S) and Distribution Coefficients (D) for Water (1) and Formic Acid (2) at Various Sodium Chloride Concentrations (s), Temperature T = 298.15 K, Pressure p = 101.325 kPaa ws = 0

a

ws = 0.05

ws = 0.10

ws = 0.15

D1

D2

S

D1

D2

S

D1

D2

S

D1

D2

S

0.281 0.308 0.352 0.369 0.391 0.420

1.58 1.64 1.81 1.91 1.98 2.10

5.62 5.54 5.25 5.18 5.10 5.00

0.021 0.024 0.026 0.029 0.031 0.034

1.48 1.55 1.58 1.62 1.65 1.68

70.48 64.58 60.76 55.86 53.22 49.42

0.012 0.016 0.02 0.022 0.026 0.027

1.11 1.18 1.12 1.10 1.08 1.00

92.50 73.75 56.00 50.00 41.54 37.04

0.005 0.008 0.009 0.015 0.018 0.021

0.75 0.77 0.72 0.85 0.87 0.88

150.00 96.25 80.00 56.66 48.33 41.90

Standard uncertainties u are u(T) = 0.1 K, u(p) = 0.01 MPa, u(D) = 0.01, and u(S) = 0.1.

declined accordingly: mass fractions of initial water of NaCl (ws) 0.15 > 0.10 > 0.05 > 0. Results show that, when the concentration of salt in the initial aqueous phase increased, enlargement of the two-phase region occurred. Adding salt to the system proved to be of benefit in the separation of FA from water.

4. CONCLUSION The tie-line and solubility data for the systems containing FA, water, and methyl isobutyl ketone (MIBK) + NaCl were obtained at T = 298.15 K and atmospheric pressure. The systems exhibited type-1 behavior. The NRTL model was used with the experimental LLE data. Binary interaction parameters were further determined. The NRTL model was analyzed and set against the experimental tie-line data. The NRTL model, it appeared, fitted in well with the experimental data. The distribution coefficients and separation factors for the MIBK were also ascertained. Consequently, the resultant separation factors proved that MIBK was most effective in separating FA from water and that the addition of salt to the system was most beneficial in separating FA from water.

Figure 5. Separation factors vs the mass fraction of formic acid in the aqueous phase, w21, at T = 298.15 K.

Bachman correlation equations. In Table 7, the values of parameters A and B at T = 298.15 K are given. The correlation values R2 show a good linear fit which proves that the experimental LLE data was most effective. 3.4. Separation Factors. The experimental data was used to assess the separation factors (S) and distribution coefficients (D) and the FA extraction by MIBK. The separation factor (S) and the distribution coefficients (D) were calculated as follows: S=

w /w D2 = 23 21 D1 w13/w11

■

APPENDIX A Thermodynamic models are explained in more detail here. A.1. NRTL model

The NRTL activity coefficient (γi) is given by 3

ln γi =

(5)

where w13 and w23 are the mass fractions of water as well as FA in the organic-rich phase, w11 as well as w21 are the mass fractions of water and FA in the aqueous-rich phase, as well as D1 and D2 are the distribution coefficients of water and FA. Distribution coefficients and separation factors for the systems are presented in Table 8. Variation of the experimental separation factor of FA, as a function of mass fraction of the solute in the aqueous phase for system, is shown in Figure 5. As can be seen, the separation factors proved to be more than 1 (S > 1) for the systems investigated. The separation factors

∑ j = 1 τjiGjixj 3

∑k = 1 Gkixk

3

+

∑ j=1

3 ⎛ ∑ xτG ⎞ ⎜τ − k = 1 k kj kj ⎟ ij 3 3 ∑k = 1 Gkjxk ⎟⎠ ∑k = 1 Gkjxk ⎜⎝

xjGij

(A-1)

where xi is the mole fraction of component i, the parameters τij, τji, τkj, Gij, Gji, Gij, and Gki are the adjustable parameters for each binary pair in the NRTL model and i, j, k are the indices for all components. The adjustable parameters can be calculated as follows: τij = aij + E

bij T

+ eij ln T

(A-2) DOI: 10.1021/acs.jced.6b00109 J. Chem. Eng. Data XXXX, XXX, XXX−XXX


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αij = αji = cij

(A-3)

Gij = exp( −αijτij)

(A-4)

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where aij, bij, cij, and eij are the NRTL coefficients for the binary interaction parameters and αij and αji are the nonrandom parameters.

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AUTHOR INFORMATION

Corresponding Authors

*Tel.: +66 22186891, +66 22186864. Fax: +66 22186877. E-mail addresses: [email protected] (U. Pancharoen). *E-mail address: [email protected] (K. Nootong). Notes

The authors declare no competing financial interest. Funding

The authors wish to thank the Thailand Research Fund and Chulalongkorn University under the Royal Golden Jubilee Ph.D. Program for their support (Grant No. PHD/0372/2552) as well as the Department of Organic Technology, Slovak University of Technology, Bratislava, Slovakia.

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REFERENCES

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Article

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Influence of Salt on the Solubility and Tie-Line Data for Water + Formic

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