Vapor Pressure Measurement for the Ternary System of Water, Lithium

Feb 20, 2018 - revealed that the experimental ternary system had lower vapor pressures, ... ratio = 3), and VLE data of the ternary system were measur...
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Vapor Pressure Measurement for the Ternary System of Water, Lithium Bromide, and 1‑Ethyl-3-methylimidazolium Acetate Xiangyu Zhang,† Neng Gao,*,‡ Yongping Wu,‡ and Guangming Chen† †

Key Laboratory of Refrigeration and Cryogenic Technology of Zhejiang Province, College of Energy Engineering, Zhejiang University, Hangzhou, 310027, P. R. China ‡ College of Mechanical and Energy Engineering, Ningbo Institute of Technology, Zhejiang University, Ningbo, 315100, P. R. China S Supporting Information *

ABSTRACT: To improve the performance of an absorption system, ionic liquids (ILs) have been chosen as additives to conventional working fluid (lithium bromide aqueous solution) in recent years. In this paper, 1-ethyl-3methylimidazolium acetate ([Emim]Ac) was added to lithium bromide aqueous solution (mass ratio LiBr/[Emim]Ac = 3) to measure the vapor− liquid equilibrium (VLE) data of the ternary system. The experiment was conducted by means of boiling point method, at temperatures between 303.94 K and 405.41 K and mass fractions of absorbent between 0.20 and 0.60. The experimental data were regressed using an Antoine-type equation, and the average absolute relative deviation (AARD%) between the experimental and calculated values was 0.34%, which showed excellent accuracy and consistency. The experimental ternary system was compared with the conventional LiBr + H2O system and two other ternary systems from the literature; the result revealed that the experimental ternary system had lower vapor pressures, which will benefit the process of releasing latent heat in absorption cycles. on ILs plus LiBr plus H2O systems. Dong et al.16 selected 1,3dimethylimidazolium dimethylphosphate ([Dmim]DMP) as an additive to LiBr aqueous solution (LiBr/[Dmim]DMP mass ratio = 3), and VLE data of the ternary system were measured. Li et al.17 studied two ternary systems H2O plus LiBr plus 1,3dimethylimidazolium chloride (mass ratio LiBr/[Dmim]Cl = 3), H2O plus LiBr plus 1,3-dimethylimidazolium tetrafluoroborate (mass ratio LiBr/[Dmim]BF4 = 2), and found that [Dmim]Cl is superior to [Dmim]BF4 on vapor pressure lowering of water. As a potential absorbent, an IL should accomplish three groups of chemical and physical properties, a large absorption capacity, a wide liquid range and a low vapor pressure.18 And the vapor pressure reduction of ILs is strongly influenced by the anion.19 Moreover, for the mutual solubilities between water and imidazolium-based ILs, the anion plays the central role on their phase behavior.20 Smaller hydrophilic anions (e.g., acetate, chlorine, and bromine) can enhance the mutual solubilities between water and ILs, and may have a strong moisture absorption property.21 In this work, we select 1-ethyl-3methylimidazolium acetate ([Emim]Ac) as an additive to the LiBr plus H2O system. The VLE data were measured at temperatures between 303.94 K and 405.41 K and mass fractions of absorbent were between 0.20 and 0.60. To make sure that the vapor pressure of the system was low enough, LiBr/[Emim]Ac

1. INTRODUCTION Lithium bromide aqueous solution has been widely used in absorption systems over the last decades for its superior physical and thermodynamic properties. However, affected by its connatural disadvantages of crystallization and corrosion, the further implementation of absorption systems was restricted. In that context, researchers have focused on additives to improve the performance of working fluids. Iyoki et al.1−3 have conducted a series of experiments on LiBr aqueous solution plus organic amine or inorganic salts since 1989. Ethanolamine was selected as an additive to lithium bromide aqueous solution by Kim et al.4,5 in 1996, and properties of the ternary system turned out to be better than the original system. Lucas et al.6−8 started in 2002 their property measurements on mixtures of LiBr aqueous solution and organic salts of sodium and potassium (sodium formate, potassium formate, potassium acetate and sodium lactates), they suggested HCOOK and HCOONa as effective and promising alternatives to lithium bromide aqueous solution based on thermodynamic evaluations. Tsai et al.9 measured the thermodynamic properties of ternary systems consisting of organic compounds (triethylene glycol and propylene glycol) plus lithium bromide aqueous solution, and pointed out that the performance of these systems were satisfactory, especially in dehumidification. Ionic liquids (ILs), with unique properties, have been extensively studied in various research fields. Abundant researches have been completed on ILs plus H2O systems as absorption working pairs,10−15 but little literature could be found © XXXX American Chemical Society

Received: November 1, 2017 Accepted: February 20, 2018

A

DOI: 10.1021/acs.jced.7b00951 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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mass ratio was set as 3.17 Previous VLE researches of [Emim]Ac were mostly on its mixtures with water, glycol, and ILs.19−26 By far, there is no literature on the VLE study of [Emim]Ac plus H2O plus LiBr system. To complete the VLE data of the ternary system and investigate its feasibility as an alternative working fluid in absorption cycles is the very motivation of our work.

was calibrated with the uncertainty of 0.05 K and the accuracy of silicon pressure sensor was ±0.064 kPa. To condense the vapor, water at room temperature is pumped to the condenser, so that the initial concentration of sample solution was kept. The temperature rise of water in the tank was no more than 2 degrees after each experimentation. In case the pressure fluctuated rapidly, a buffer bottle was connected to the vacuum pump. A sample solution with an approximate volume of 250 mL was stirred well and poured into the equilibrium vessel. The system was then evacuated to a certain vacuum degree of pressure. After that, the sample solution was heated and stirred vigorously with the magnetic stirrer to prevent super heating. When equilibrium is reached, the solution is boiling and the desired VLE data (the boiling point of the sample solution and it is corresponding saturated vapor pressure) can be read on the computer. By controlling the air inlet, the vacuum degree of pressure is changed and another equilibrium can be reached. 2.3. Verification of the System. To test the validity of system, pure water and sodium chloride aqueous solution (with mass fraction of 0.25) were used as standard solutions, and their vapor pressures were measured. The experimental data were compared with previous literature,27,28 and the average absolute relative deviation (AARD%) for vapor pressures of pure water was 0.35%, and 0.37% for that of NaCl aqueous solution. Figure 2

2. EXPERIMENT 2.1. Materials. All the chemicals used in this study were listed in Table 1. The 1-ethyl-3-methylimidazolium acetate ([Emim]Table 1. Source and Purity of Chemical Samples chemical name

CASRN

source

[Emim]Aca

143314-17-4

lithium bromide sodium chloride

7550-35-8

Lanzhou Green Chem ILS, Lanzhou Institute of Chemical Physics, China Aladdin Chemistry Co., Ltd., China Sinopharm Chemical Reagent Co., Ltd., China

a

7647-14-5

mass fraction purity

purification method

98%

none

99.9%

none

99.8%

none

[Emim]Ac = 1-ethyl-3-methylimidazolium acetate.

Ac) reagent was supplied by Lanzhou Green Chem ILS, Lanzhou Institute of Chemical Physics, China. LiBr reagent was supplied by Aladdin Chemistry Co., Ltd., China. NaCl reagent was supplied by Sinopharm Chemical Reagent Co., Ltd., China. No further purification of reagents above was conducted. The pure water used in this study was deionized and double-distilled. The required mass fraction of solutions were prepared on an electronic balance, of which the accuracy was 0.01 g. 2.2. Apparatus and Procedure. Considering the vapor pressure of absorbent can be neglected compared with that of water, the boiling point method was adopted to measure the VLE data of studied solutions. The experiment system can be divided into four parts, heating system, condensing system, vacuum system, and measuring system. Figure 1 is a schematic diagram of the system. The system comprises an equilibrium vessel (250 mL), an oil bath with a magnetic stirrer, a spherical condenser, a water tank, a water pump, a temperature sensor, a PTX50A2 type GE Druck silicon pressure sensor, a 34970A type Agilent dynamic signal analyzer, a computer, an air inlet, a vacuum pump, a high vacuum valve, and a buffer bottle. The temperature sensor

Figure 2. Relative deviations Δp/p = (pexp − pcal)/pcal of the experimental vapor pressures pexp from those calculated with the Antoine-type equation pcal for pure water27 and NaCl aqueous solution28 (with mass ratio of 0.25). ●, this work, pure water; ○, this work, NaCl aqueous solution (with mass ratio of 0.25).

shows the relative deviation of the two above liquids. It can be seen that the experimental data agree very well with data from previous literature. Therefore, the accuracy of the system is verified, and the apparatus can be used to measure the vapor pressure of the ternary system.

3. RESULTS AND DISCUSSION The vapor pressures for the ternary system ([Emim]Ac + LiBr + H2O) were measured at temperatures between 303.94 K and 405.41 K, at mass fraction of absorbent between 0.20 and 0.60. The experimental data were listed in Table 2. Besides, the vapor pressures over the absorbent mass fractions and temperatures were fitted to an Antoine-type eq 1.29,30

Figure 1. Schematic diagram of the experimental apparatus: 1, computer; 2, agilent dynamic signal analyzer; 3, oil bath with a magnetic stirrer; 4, silicon pressure sensor; 5, temperature sensor; 6, equilibrium; 7, spherical condenser; 8, water pump; 9, water tank; 10, buffer bottle; 11, air inlet; 12, high vacuum valve; 13, vacuum pump. B

DOI: 10.1021/acs.jced.7b00951 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 2. Experimental and Calculated Vapor Pressures for the Ternary System of LiBr (1) + [Emim]Ac (2) + H2O (LiBr: [Emim] Ac Mass Ratio = 3:1)a T/K

pexp/kPa

pcal/kPa

T/K

ARD%

pexp/kPa

303.94 325.12 334.77 349.64 356.07 361.38 365.11 368.05 371.67 373.59 375.53

4.699 13.049 20.069 37.469 48.457 59.512 68.72 76.742 87.695 94.014 100.896

307.38 337.80 345.23 354.45 360.53 365.71 369.73 374.19 377.56 379.88 381.68 332.16 355.89 370.78 376.19 381.54 387.16

pcal/kPa

ARD%

5.309 15.777 26.379 36.187 46.235 57.860 66.217 76.981 85.721 91.015 99.459

0.72 1.01 1.05 1.34 1.11 0.78 0.35 0.25 0.53 0.82 1.33

w1+2 = 0.30

w1+2 = 0.20 4.715 13.026 20.016 37.408 48.398 59.540 68.672 76.721 87.769 94.181 101.076

0.33 0.18 0.26 0.16 0.12 0.05 0.07 0.03 0.08 0.18 0.19

305.12 329.44 341.98 350.07 356.55 362.65 366.4 370.66 373.75 375.49 378.09

5.347 15.937 26.102 35.703 45.723 57.411 65.985 77.17 86.178 91.758 100.786

4.571 18.492 25.228 36.576 46.383 56.320 65.372 76.977 86.836 94.200 100.471

4.582 18.459 25.190 36.521 46.273 56.331 65.421 77.000 86.912 94.373 100.544

0.25 0.18 0.15 0.15 0.24 0.02 0.08 0.03 0.09 0.18 0.07

324.73 344.50 356.47 362.65 369.55 375.03 378.74 383.19 386.68 388.97 391.31

6.977 17.064 27.619 35.344 46.038 56.501 64.661 75.918 85.881 93.06 100.771

7.030 16.882 27.639 35.290 46.003 56.469 64.700 75.957 85.961 93.140 101.016

0.75 1.08 0.07 0.15 0.08 0.06 0.06 0.05 0.09 0.09 0.24

6.056 16.814 29.670 36.673 44.638 54.430

6.077 16.706 29.886 36.583 44.478 54.356

0.35 0.65 0.72 0.25 0.36 0.14

391.86 396.59 400.14 402.60 405.41

64.148 75.480 84.753 91.900 100.790

64.054 75.321 84.887 92.127 101.056

0.15 0.21 0.16 0.25 0.26

w1+2 = 0.40

w1+2 = 0.50

w1+2= 0.60

a

The vapor pressure was measured over the liquid phase. w is the mass fraction of all absorbent species. pexp and pcal are vapor pressures from experimentation and Antoine-type equation, respectively. ARD% = 100*|pexp − pcal|/pcal.. Standard uncertainties u are u(T) = 0.07 K, u(w) = 4 × 10−5, and u(p) = 0.529 kPa. The uncertainty of the mass ratio (LiBr: [Emim]Ac) was 1.3 × 10−5. 4

log(p) =

∑ [Ai + {1000Bi /(T /k − C)}]wi

temperature in Figure 3. Vapor pressures increase with temperature but decrease with mass fractions, and the decreasing range of pressures is larger with increasing mass fractions. Besides, Figure 4 shows the relative deviations between experimental and calculated data. Deviations for most points are very slight, which implies that the experimental data are in perfect agreement with calculated results. Furthermore, a comparison between vapor pressures of the measured system in this paper and [Dmim]BF4 + LiBr + H2O, [Dmim]DMP + LiBr + H2O together with LiBr + H2O systems was plotted in Figure 5. The mass fractions of all absorbent species containing IL were 0.60 and the mass ratios of [Emim]Ac/LiBr, [Dmim]BF4/LiBr, and [Dmim]DMP/LiBr were 3, 2, and 3, respectively. For a comparison, the mass fraction of LiBr in LiBr + H2O binary system was set as 0.45. As shown in the figure, the vapor pressures of IL + LiBr + H2O systems were all lower than the LiBr + H2O binary system, and the effect of absorbent species on the vapor pressure lowering of water follows the order [Emim]Ac + LiBr > [Dmim]BF4 + LiBr > LiBr > [Dmim]DMP + LiBr, which proves the superior hygroscopicity of [Emim]Ac. Uncertainty. The measurement uncertainty of temperature includes three parts, uncertainty of the calibrated temperature sensor UT1 = 0.05 K, uncertainty of the Agilent data acquisition

(1)

i=0

where p and T denote vapor pressure in kPa and temperature denote in K, w is the mass fraction of all absorbent species. Ai, Bi, and Ci are regressed parameters of Antoine-type equation and are listed in Table 3. The overall average absolute relative deviation (AARD%) value between the experimental data and calculated values was determined to be 0.34%, exhibiting excellent consistency and accuracy. The measured data and calculated fitted curves from the Antoine-type equation are plotted against Table 3. Regressed Parameters of Antoine-type Equation i

A

B

0 1 2 3 4 AARD%a

49.585012 −302.18807 1123.0300 −1755.2481 983.74411

−19.935219 128.51070 −472.42207 728.01429 −404.89103 0.34

C

−92.753755

AARD% = ∑i N= 1[|pexp − pcal|/pcal]/ N, where N is the number of measurement points, pexp and pcal are vapor pressures from experimentation and Antoine-type equation, respectively. a

C

DOI: 10.1021/acs.jced.7b00951 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Figure 3. Vapor pressure for [Emim]Ac + LiBr + H2O system (LiBr/ [Emim]Ac mass ratio = 3:1) at at temperatures from 303.94 to 405.41 K: ■, w = 0.20, experimental data; ●, w = 0.30, experimental data; ▲, w = 0.40, experimental data; ◆, w = 0.50, experimental data; ★, w = 0.60, experimental data; , calculated results from the Antoine-type equation.

Figure 5. Vapor pressure comparison between the measured system in this paper and other systems in the literature16,17,31 containing LiBr/ H2O: ■, [Dmim]DMP/LiBr/H2O (LiBr/[Dmim]DMP mass ratio = 3), w = 0.6; ●, LiBr/H2O, w = 0.45; ▲, [Dmim]BF4/LiBr/H2O (LiBr/ [Dmim]BF4 mass ratio = 2), w = 0.6; ◆, [Emim]Ac/LiBr/H2O (LiBr/ [Emim]Ac mass ratio = 3), w = 0.60.

⎛ ∂p ⎞2 UP = k ∑ ⎜ ⎟ (u Xi)2 ∂Xi ⎠ i=1 ⎝ 3

(3)

where Xi include all the variables in the derivation of vapor pressure, that is, the temperature T, mass fraction w, and vapor pressure p. k is the coverage factor and k ≈ 2 for 95% confidence interval. Therefore, the standard uncertainty of vapor pressure can be determined by eq 2 and eq 3. As for up, it comes from three parts, uncertainty of the silicon pressure sensor up1 = 0.064 kPa, uncertainty of the Agilent data acquisition unit up2 = 0.002 kPa, uncertainty from the reading fluctuations up3 = 0.02 kPa. Thus, up can be calculated by 2

up =

∑ upi2

= 0.067 kpa

i=1

Figure 4. Relative deviations Δp/p = (pexp − pcal)/pcal of the experimental vapor pressures pexp from those calculated with the Antoine-type equation pcal for [Emim]Ac + LiBr + H2O system (LiBr/ [Emim]Ac mass ratio = 3:1).

(4)

Taking these results into the calculation, the final Up was calculated to be 0.529 kPa (k = 2).

4. CONCLUSION The vapor pressure of the ternary system [Emim]Ac + LiBr + H2O (mass ratio LiBr/[Emim]Ac = 3) in the temperature range from (303.94 to 405.41) K and in the mass fractions of absorbent species range from 0.20 to 0.60 was measured by means of boiling point method. The experimental data were regressed using an Antoine-type equation and the result showed high accuracy and consistency. The ternary system [Emim]Ac + LiBr + H2O was also proven to have lower vapor pressures than the conventional LiBr + H2O system and two other ternary systems in the literature. Low pressure will surely benefit the process of dehumidification and releasing latent heat in absorption cycles. Therefore, the studied ternary system in this work might be used as a promising alternative working fluid in absorption systems upon more research.

unit UT2 = 0.006 K, and uncertainty from the reading fluctuations UT3 = 0.05 K. Therefore, the combined uncertainty of temperature can be calculated by 3

UT =

∑ UT2i = 0.07K i=1

(2)

For the uncertainty of mass fraction Uw, the accuracy of the electronic balance was 0.01 g. The chemical samples weighed between 300 g and 600 g. Therefore, the uncertainty of mass fraction can be determined and Uw was 4 × 10−5. According to the law of propagation of uncertainty, the expanded combined uncertainty of the vapor pressure Up can be obtained by D

DOI: 10.1021/acs.jced.7b00951 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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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.7b00951.



Experimental and calculated vapor pressures for pure water and sodium chloride aqueous solution (PDF)

AUTHOR INFORMATION

Corresponding Author

*Email: [email protected]. ORCID

Xiangyu Zhang: 0000-0001-6058-8537 Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS This work is financially supported by the National Key Research and Development Program of China (Grand No. 2016YFB0901404) and the Ningbo Science and Technology Bureau (No.2016B10003).



REFERENCES

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F

DOI: 10.1021/acs.jced.7b00951 J. Chem. Eng. Data XXXX, XXX, XXX−XXX