Density, Speed of Sound, Viscosity, and Surface Tension of

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Density, Speed of Sound, Viscosity, and Surface Tension of Dimethylethylenediamine + Water and (Ethanolamine + Dimethylethanolamine) + Water from T = (293.15 to 323.15) K Antonio Blanco, Alicia García-Abuín, Diego Gómez-Díaz, and José M. Navaza* PFPT Research Team, Department of Chemical Engineering, ETSE, Universidade de Santiago de Compostela, Rúa Lope Gómez de Marzoa s/n, E-15786 Santiago de Compostela, Galicia, Spain ABSTRACT: This work analyzes different physical properties with importance upon mass transfer processes (density, speed of sound, viscosity, and surface tension) for new chemical solvents for carbon dioxide capture (dimethylethylenediamine + water and ethanolamine + dimethylethanolamine + water). These solvents are composed of two different amino groups: a primary and a tertiary. In one solvent, it is achieved by the use of a diamine and for the other a mixture of two solutes is employed. Also excess properties have been studied in order to explain the behavior of previously commented properties on the basis of interactions between molecules. An increase in the amount of amine or amines in the mixtures generally causes a decrease in the analyzed properties but in speed of sound and viscosity a previous increase was observed. An increase in temperature also causes a decrease in all the physical properties. Also the diamine-based solvent shows higher molecular interactions than the amine mixture. These data allow one to perform a comparison between the properties of these solvents that can be useful information to choose one of them. On the basis of these properties, this kind of solvent (diamine + water) is better to be used in carbon dioxide chemical absorption



INTRODUCTION In the few last years, the development of new solvents for capture/separation of carbon dioxide by chemical absorption has been centered on different aspects that allow the optimization of the sequence absorption/regeneration: (i) high absorption rate and selectivity and (ii) high regeneration degrees with a low cost avoiding corrosion and degradation.1−3 Different studies tried to achieve these aims by using a mixture of amines, primary (or secondary) + tertiary ones. This kind of mixtures tries to improve absorption rate by using a nontertiary amine (high reaction rate), and on the other hand the tertiary one contributes to increasing the carbon dioxide loading (a 1:1 stoichiometry) and to enhancing the regeneration degree with low degradation and corrosion rates.4−6 The presence of more than one amine molecule in the solvent can cause undesirable behaviors related with parallel degradation reactions or high viscosity due to more complex interactions, and for these reasons the use of only one amine can be suitable to prepare the chemical solvent. The physical properties of these solvents can play a very important role in mass transfer operations and these properties can be influenced by the interaction with solute and solvent molecules. These properties can enhance7 or reduce8 mass transfer rate (e.g., a decrease in surface tension can cause interfacial turbulence enhancing mass transfer rate). Also, certain physical properties can affect the hydrodynamic behavior in multiphasic reactors/contactors (e.g., an increase in viscosity increases bubble size and the opposite behavior is © XXXX American Chemical Society

produced by a decrease in surface tension). Also, during the carbon dioxide chemical absorption changes in physical properties can be observed due to the formation of other product such as carbamates or carbonate/bicarbonate ions.9,10 The presence of this kind of substances tend to generally increase properties such as density, viscosity, and surface tension. For these reasons, present work analyzes the behavior corresponding to different physical properties of two solvents (dimethylethylenediamine + water and ethanolamine + dimethylethanolamine + water) with the same amine groups in order to obtain differences that allow to choose one of them to carry out absorption experiments.



EXPERIMENTAL SECTION Materials. Information about the reagents used in the present work is included in Table 1. Bidistilled water has been used to prepare the mixtures. When the mixture of amines is used in the mixture a molar ratio MEA/DMEA = 1 was employed. Samples were prepared by mass using an analytical balance (Kern 770). Methods. Density and Speed of Sound. The densities (ρ) and speed of sound (c) of pure components and the mixtures of different compounds were measured with an Anton Received: May 28, 2015 Accepted: November 4, 2015

A

DOI: 10.1021/acs.jced.5b00447 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 2. Comparison between Density ρ, Speed of Sound c, Viscosity η, and Surface Tension σ, Experimental and Literature Data for Pure Components at T = 298.15 K at p = 105 Paa

Table 1. Sample Description Table chemical name

CAS

molecular weight

source

DMEDAa

108-00-9

88.15 g·mol−1

MEAb

141-43-5

61.08 g·mol−1

DMEAc

108-01-0

89.14 g·mol−1

SigmaAldrich SigmaAldrich SigmaAldrich

initial mole fraction purity ≥ 0.98

lit

≥ 0.99 ρ/g·cm‑3

≥ 0.98

a

N,N-Dimethylethylenediamine. bEthanolamine or monoethanolamine. cN,N-Dimethylethanolamine.

c/m·s‑1

Paar DSA 5000 vibrating tube densimeter and sound analyzer. The transducer emits sound waves at a frequency of 3 MHz. Viscosity. The kinematic viscosity (ν) was determined from the transit time of the liquid meniscus through capillary Ubbelohde viscosimeters supplied by Schott. In this work, capillary number Ic has been used connected to a Schott-Geräte AVS 350 Ubbelohde viscosimeter. Equation 1 was employed to calculate the viscosity from the transit time

1300.8 0.895

σ/mN·m‑1

26.1

c/m·s‑1

DMEA 0.882714 0.8828 0.8838316 1335.9

η/mPa·s

3.7814

ρ/g·cm‑3

(1)

σ/mN·m‑1

wheret is the efflux time; K is the characteristic constant of the capillary viscosimeter; and θ is a coefficient to correct end effects. Both parameters were obtained from the capillaries supplier (Schott). An electronic stopwatch with an accuracy of ±0.01 s was used to measure efflux times. In the measurements, a Schott-Geräte AVS 350 Ubbelohde viscosimeter was used. The dynamic viscosity (η) was obtained from the product of the kinematic viscosity (ν) and the corresponding density (ρ) of the mixture, in terms of eq 2 for each mixture composition. η = ν·ρ (2)

31.517

lit

exp MEA

0.8143

η/mPa·s

ν = K · (t − θ )

exp DMEDA

3.690 31.3

1.0123011 1.0120 1.0123912 1719.213 1719.2 1717.712 18.6414 18.740 18.98015 49.016 49.1 48.489 Water 0.9970518 0.9971 0.9970412 1497.019 1496.7 1496.720 0.89018 0.891 0.890021 71.9822 72.1 72.0123

a

Standard uncertainties u are u(T) = 0.01 K, u(p) = 2 kPa, u(x) = 0.0008, and the combined expanded uncertainties Uc (level of confidence = 0.95, k = 2) are Uc(ρ) = 2 × 10−3 g·cm−3, Uc(c) = 0.7 m·s−1, Uc(η) = 0.002 mPa·s, and Uc(σ) = 0.3 mN·m−1.

water systems, respectively. Figure 1 shows the influence of amine/s concentration in aqueous solutions upon the value of density. For the system that includes the diamine, a monotonic decrease is observed when the solute concentration increases in the mixture. On the other hand, the behavior shown by the ternary mixture (MEA + DMEA + water) is quite different than the previously commented because at low amines concentration a maximum in the value of the density is observed. At higher amines concentration, a monotonic decrease in the value of density is reached. This behavior can be due to an important degree in the interactions between the amines molecules and water causing an important contractive behavior but it is similar than the corresponding one to DMEA + water system.24 The decrease in the value of density when amine concentration increases is higher when the diamine is used in the mixture. When examining the influence of temperature on the behavior corresponding to density, the experimental data show a typical behavior for all the systems used in the present work, that is, a monotonic decrease when temperature increases with a linear trend. The excess molar volume has been obtained from density data for both systems employing eq 3 and with a estimated uncertainty of ±0.002 cm3·mol−1.

Surface Tension. The surface tension (σ) was determined by employing a Krüss K-11 tensiometer using the Wilhelmy plate method. The plate employed was a commercial platinum plate supplied by Krüss. The platinum plate was cleaned and flame-dried before each measurement. Each surface tension value reported came from an average of five measurements. The samples were thermostated in a closed stirring vessel before the surface tension measurements. The highest temperature used in this study was avoided for surface tension measures because evaporation processes could influence upon measure uncertainty. Table 2 shows a comparison between experimental and literature data for pure components that shows a good agreement and indicates that the experimental procedures are suitable to determine these kinds of measurements.



RESULTS AND DISCUSSION As previously commented in Introduction and Experimental Section, several physical properties have been determined in the present work that correspond to the binary mixtures of water and dimethylethylenediamine and the ternary mixture of water, ethanolamine, and dimethylethanolamine. The diamine has the same amino groups as the mixture of both amines and this work compares the behaviors of both systems in order to obtain conclusions about the composition and temperature influence upon physical properties with importance in carbon dioxide absorption processes. The experimental data corresponding to density, speed of sound, viscosity, and surface tension are included in Tables 3 and 4 for dimethylethylenediamine + water and (ethanolamine + dimethylethanolamine) +

2

VE =

∑ xi·Mi ·(ρ−1 − ρi−1) i=1

(3)

where xi, Mi, and ρi are the molar fractions, molecular weights, and densities of pure components, respectively. Figure 2 shows the behavior of excess molar volume corresponding to the systems analyzed in present work (diamine versus amines mixture). Taking into account the calculated values for the system diamine + water, a contractive behavior is observed with a decrease in the value of excess B

DOI: 10.1021/acs.jced.5b00447 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 3. Density ρ, Speed of Sound c, Dynamic Viscosity η, and Surface Tension σ, of DMEDA (1) + Water (2) from T = (293.15 to 323.15) K at p = 105 Paa x1 0.0000 0.1002 0.2000 0.3002 0.3996 0.5035 0.5995 0.7007 0.8002 0.8999 1.0000 0.0000 0.1002 0.2000 0.3002 0.3996 0.5035 0.5995 0.7007 0.8002 0.8999 1.0000

T/K 293.15 0.998 0.975 0.952 0.920 0.895 0.874 0.858 0.844 0.833 0.825 0.819 1482.7 1773.4 1708.6 1605.4 1517.2 1456.6 1419.2 1387.2 1349.8 1328.0 1319.6

0.0000 0.1002 0.2000 0.3002 0.3996 0.5035 0.5995 0.7007 0.8002 0.8999 1.0000

0.993 6.830 12.660 10.498 6.463 3.875 2.743 1.965 1.464 1.162 0.988

0.0000 0.1002 0.2000 0.3002 0.3996 0.5035 0.5995 0.7007 0.8002 0.8999 1.0000

72.6 42.6 37.1 32.9 30.6 29.4 28.6* 27.9 27.4 26.9 26.4

T/K 303.15

T/K 313.15

ρ/g·cm−3 0.996 0.992 0.970 0.963 0.943 0.935 0.912 0.901 0.886 0.877 0.865 0.856 0.849 0.840 0.835 0.826 0.824 0.814 0.816 0.806 0.810 0.801 c/m·s−1 1509.3 1529.1 1743.6 1712.8 1672.8 1636.1 1568.6 1531.3 1480.2 1443.1 1419.2 1381.8 1381.6 1343.3 1349.0 1310.3 1305.2 1266.2 1288.7 1249.2 1279.3 1239.0 η/mPa·s 0.797 0.654 4.280 2.891 7.355 4.689 6.268 4.105 4.148 2.884 2.709 2.019 2.013 1.552 1.510 1.192 1.161 0.937 0.940 0.773 0.819 0.693 σ/mN·s−1 71.1 69.2 41.9 41.3 36.3 35.2 32.2 31.2 29.8 28.9 28.6 27.8 27.8 27.0 27.1 26.3 26.6 25.8 26.1 25.3 25.8 25.2

Table 4. Density ρ, Speed of Sound c, Dynamic Viscosity η, and Surface Tension σ of (MEA + DMEA) (1) + Water (2) from T = (293.15 to 323.15) K at p = 105 Pad

T/K 323.15

x1

0.988 0.955 0.926 0.893 0.868 0.847 0.831 0.817 0.806 0.797 0.791

0.0000 0.1003 0.1999 0.2994 0.3999 0.5001 0.5992 0.7014 0.7989 0.8993 1.0000

1542.6 1682.0 1598.4 1493.1 1411.3 1343.5 1305.1 1271.7 1227.0 1209.1 1199.3

0.0000 0.1003 0.1999 0.2994 0.3999 0.5001 0.5992 0.7014 0.7989 0.8993 1.0000

0.547 2.069 3.179 2.853 2.105 1.519 1.201 0.967 0.804 0.686 0.596 67.7 40.4 34.3 30.6 27.9 27.1 26.4 25.7 25.2 24.7 24.5

T/K 293.15 0.998 1.000 0.999 0.991 0.983 0.974 0.965 0.957 0.952 0.946 0.941 1482.7 1695.5 1737.1 1710.7 1669.6 1628.7 1592.7 1561.8 1538.7 1516.1 1498.1

0.0000 0.1003 0.1999 0.2994 0.3999 0.5001 0.5992 0.7014 0.7989 0.8993 1.0000

0.993 3.896 9.400 15.220 19.239 20.084 18.676 16.600 14.560 12.370 10.739

0.0000 0.1003 0.1999 0.2994 0.3999 0.5001 0.5992 0.7014 0.7989 0.8993 1.0000

72.6 46.7 42.1 39.0 36.8 35.2 34.5 33.7 33.1 32.6 32.4

T/K 303.15

T/K 313.15

ρ/g·cm−3 0.996 0.992 0.995 0.989 0.992 0.984 0.984 0.976 0.975 0.967 0.966 0.958 0.957 0.949 0.949 0.941 0.944 0.935 0.937 0.929 0.932 0.924 c/m·s−1 1509.3 1529.1 1684.2 1670.6 1710.8 1683.9 1680.5 1649.8 1637.9 1605.3 1596.1 1563.3 1559.9 1526.5 1528.4 1494.5 1504.9 1470.9 1482.0 1448.0 1463.7 1428.9 η/mPa·s 0.797 0.654 2.745 2.002 5.693 3.798 9.481 6.154 11.611 7.429 12.251 7.793 11.602 7.597 10.517 7.071 9.339 6.352 8.176 5.633 7.169 5.066 σ/mN·s−1 71.1 69.2 45.7 44.7 41.1 39.9 38.1 36.9 35.9 35.1 34.5 33.8 33.9 33.2 32.9 32.3 32.3 31.6 31.8 31.1 31.6 30.9

T/K 323.15 0.988 0.983 0.977 0.968 0.959 0.950 0.941 0.933 0.927 0.921 0.916 1542.6 1654.9 1656.1 1618.0 1572.2 1530.0 1492.6 1460.7 1436.7 1413.2 1394.1 0.547 1.565 2.727 4.197 4.985 5.232 5.218 4.882 4.502 4.037 3.517 67.7 43.6 39.0 36.1 34.2 33.2 32.6 31.6 31.0 30.5 30.3

a

Standard uncertainties u are u(T) = 0.01 K, u(p) = 2 kPa, u(x) = 0.0008, and the combined expanded uncertainties Uc (level of confidence = 0.95, k = 2) are Uc(ρ) = 2 × 10−3 g·cm−3, Uc(c) = 0.7 m·s−1, Uc(η) = 0.002 mPa·s, and Uc(σ) = 0.3 mN·m−1.

d

Standard uncertainties u are u(T) = 0.01 K, u(p) = 2 kPa, u(x) = 0.0008, and the combined expanded uncertainties Uc (level of confidence = 0.95, k = 2) are Uc(ρ) = 2 × 10−3 g·cm−3, Uc(c) = 0.7 m·s−1, Uc(η) = 0.002 mPa·s, and Uc(σ) = 0.3 mN·m−1.

molar volume in agreement with other amine + water systems.25 The maximum in this parameter is reached near to a diamine molar fraction of 0.3. The calculated values indicate that a low influence of temperature upon the molar excess colume is observed in the entire composition range.

The negative values indicate that there are interactions among unlike molecules. Taking into account the deviations’ sign and magnitude, it is possible to conclude that there are strong interactions (hydrogen bonding ones) in the blends studied in present work. Negative values for excess volume C

DOI: 10.1021/acs.jced.5b00447 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 5. Fit Parameters Corresponding to Redlich−Kister Equation for Excess Volume VE from T/K = 293.15 to 323.15 parameter A0 A1 A2 A3 δ/cm3· mol−1 A0 A1 A2 A3 δ/cm3· mol−1

Figure 1. Influence of temperature and composition upon density. System DMEDA (1) + water (2): ○, T = 293.15 K; ●, T = 313.15 K. System (MEA + DMEA) (1) + water (2): □, T = 293.15 K.

T/K = 293.15

T/K = 303.15

T/K = 313.15 T/K = 323.15

DMEDA (1) + water (2) 2.98 7.34 −28.038 −46.51 39.94 64.12 −33.09 −42.64 0.04 0.05

2.97 −29.63 42.01 −33.01 0.05

(MEA + DMEA) (1) + water (2) −6.36 −5.95 −6.36 18.82 16.60 18.80 −33.44 −29.82 −33.57 14.75 13.11 15.35 0.02 0.02 0.01

−5.63 14.86 −27.09 12.14 0.01

1.38 −21.06 30.43 −28.90 0.04

3

V E = x1·x 2· ∑ Aj ·x 2(j − 1)/2 j=0

(4)

Where x1 and x2 are amine and water mole fraction, respectively, and Aj are fitting parameters. In relation with the observed behaviors corresponding to speed of sound value in the mixtures analyzed in present work, Figure 3 shows the presence of a maximum at low amine(s)

Figure 2. Influence of composition and temperature upon the excess molar volume. System DMEDA (1) + water (2): ○, T = 293.15 K; ●, T = 303.15 K; □, T = 313.15 K; ■, T = 323.15 K. System (MEA + DMEA) (1) + water (2): △, T = 293.15 K. Solid line corresponds to DMEDA (1) + water (2) system at T = 293.15 K. Dashed line corresponds to (MEA + DMEA) (1) + water (2) system at T = 293.15 K. Figure 3. Effect of temperature and composition upon the speed of sound. System DMEDA (1) + water (2): ○, T = 293.15 K; ●, T = 313.15 K. System (MEA + DMEA) (1) + water (2): □, T = 293.15 K.

could be due to the amine protonated formation by reaction between water and amine, or the reaction between two molecules of amine forming a specie charged positive and negatively.26 Figure 2 also shows a comparison between the behavior obtained for dimethylethylenediamine + water system with the corresponding one for (ethanolamine + dimethylethanolamine) + water. Both systems show contractive behavior but the magnitude of it is quite different. A lower contractive behavior for the amines mixture system is observed than the values for diamine system. This fact indicates that the interaction between water and diamine are higher than in the ternary mixture. These data have been fitted using a Redlich−Kister equation (eq 4) and the fitting parameters are indicated in Table 5. Also, Table 5 shows low values of the standard deviation (δ) for excess volume fittings.

molar fraction. Once this maximum is reached and when the liquid mixture increases more and more its concentration in amine(s), a decrease in this property is observed. This behavior is in agreement with the previously one commented for excess molar volume because an important interactions exists when low water molecules are present in the mixture. The behavior shown for the influence of composition upon speed of sound is similar for both systems (diamine + water and amines mixture + water) though the maximum for the diamine system is reached at lower amine composition. In relation with the influence of temperature upon the speed of sound for these systems, in general an increase in this variable causes a decrease in the value of speed of sound but at very low amine(s) concentration the behavior is the opposite. D

DOI: 10.1021/acs.jced.5b00447 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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temperature. An increase in the amount of diamine in the mixture causes an increase in viscosity until a maximum is reached at a molar fraction near to 0.2. This fact is in agreement with previous conclusions about the interactions between different molecules using other calculated properties (i.e., excess molar volume). On the other hand, an increase in temperature causes a clear decrease in the value of viscosity that is a common behavior in this kind of mixture. Also, Figure 5 shows a comparison between both systems characterized in this work and an important difference is detected. Though both systems show a maximum in the value of viscosity when amine(s) concentration increases in the mixture, for the system based on amines blend this maximum is achieved at higher amines content (near to molar fraction of 0.5). But the main difference due to the high importance in mass transfer processes is the fact that the viscosity of ethanolamine + dimethylethanolamine + water reaches much higher than diamine aqueous solutions mainly at low water mole fraction. High liquid phase viscosity indicates that this solvent is less attractive to be used in chemical absorption processes because the mass transfer resistance increases (e.g., caused by a decrease in carbon dioxide diffusion) and causes flow pattern additional problems (e.g., decrease in gas−liquid interfacial area and mixture processes).29 The last physical property analyzed in present work for these solvents is surface tension with importance upon mass transfer processes between gas and liquid phases because it modifies the size of bubbles in bubbling reactors and the wettability in packed contactors. Examples of the behavior found for theses mixtures are shown in Figure 6 in relation with the influence of

Using the experimental values of density and speed of sound of the mixtures used in this work, the adiabatic compressibility was calculated (eq 5) under the different conditions of composition and temperature. Figure 4 shows the calculated

Figure 4. Influence of composition and temperature upon the adiabatic compressibility. System DMEDA (1) + water (2): ○, T = 293.15 K; ●, T = 303.15 K; □, T = 313.15 K; ■, T = 323.15 K.

results corresponding to the systems DMEDA + water. The observed behavior is the opposite than the previously one commented for speed of sound due to the important weight of this property upon the value of adiabatic compressibility. Analyzing the data included in Figure 4 is possible to conclude that there are a change about the influence of temperature upon the value of this parameter indicating the formation of a temperature-resistant structure27 1 κs = ρ ·c 2 (5) Also in this work, other physical properties with high influence upon mass transfer processes between different phases have been studies such as viscosity and surface tension.8,28 In relation with the first property (viscosity), Figure 5 shows the effect caused by mixture composition and

Figure 6. Effect of temperature and composition upon surface tension. System DMEDA (1) + water (2): ○, T = 293.15 K; ●, T = 313.15 K. □, x1 = 0.2000; ■, x1 = 0.3996; △, x1 = 0.5995; ▲, x1 = 0.7007; ◇, x1 = 0.8002. System (MEA + DMEA) (1) + water (2): *, T = 293.15 K.

composition and temperature. The effect of composition is based on a dramatic decrease in the value of surface tension with low additions of amines to water until a practically constant value is reached. This behavior is related with the accumulation of solutes at gas−liquid interface due to the presence of hydrophobic parts in the molecules and it is in agreement with previous studies using aqueous solutions of alkanolamines.30,31 This kind of molecules tends to form micelles or other type of aggregates such as dimers or trimers. A similar trend is observed when the amines blend is used in aqueous solution, but the diamine-based system allows it to reach lower surface tension values. This behavior can allow the

Figure 5. Influence of composition and temperature upon dynamic viscosity. System DMEDA (1) + water (2): ○, T = 293.15 K; ●, T = 303.15 K; □, T = 313.15 K; ■, T = 323.15 K. System (MEA + DMEA) (1) + water (2): △, T = 293.15 K. E

DOI: 10.1021/acs.jced.5b00447 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

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achievement of higher interfacial areas in certain types of gas− liquid contactors (bubbling type).32 The effect caused by temperature upon surface tension is also shown in Figure 6, and it consists in a linear decrease in the value of this physical property when temperature increases.



CONCLUSIONS This study has analyzed different physical properties of two chemical solvents that could be used for carbon dioxide chemical absorption: dimethylethylenediamine + water and (ethanolamine + dimethylethanolamine) + water. These systems were characterized on the basis of density, speed of sound, viscosity and surface tension. These physical properties allow to obtain information about properties with influence upon mass transfer processes and molecular interactions that causes these behaviors. Several properties indicate that high molecular interactions are produced at low diamine mole fraction. The diamine aqueous solutions show better characteristics to be used as chemical solvent than the mixture of amine attending to the behavior corresponding to viscosity and surface tension.



AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.



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DOI: 10.1021/acs.jced.5b00447 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

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DOI: 10.1021/acs.jced.5b00447 J. Chem. Eng. Data XXXX, XXX, XXX−XXX