Solubility of Dilute SO2 in the Binary System Poly Ethylene Glycol 300

Aug 5, 2014 - Gas–liquid equilibrium (GLE) data were determined for dilute SO2 in the binary system poly ethylene glycol 300 (PEG) (1) + dimethyl su...
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Solubility of Dilute SO2 in the Binary System Poly Ethylene Glycol 300 + Dimethyl Sulfoxide at T = 298.15 K and p = 123.15 kPa and Mixtures’ Excess Properties at T = (298.15, 303.15, 308.15, 313.15, and 318.15) K Bo Guo, Jianbin Zhang,* Qiang Li, Lihua Li, Huiyan Ma, and Qiancheng Zhang* College of Chemical Engineering, Inner Mongolia University of Technology, Huhhot 010051, China S Supporting Information *

ABSTRACT: Gas−liquid equilibrium (GLE) data were determined for dilute SO2 in the binary system poly ethylene glycol 300 (PEG) (1) + dimethyl sulfoxide (DMSO) (2) at T = 298.15 K and p = 123.15 kPa, and SO2 partial pressures were found from (0 to 122) Pa. The GLE compositions were determined with ur(CSO2) = ± 0.6 % for the liquid phase SO2 concentration and ur(zSO2) = ± 5 % for the gas phase SO2 volume fraction. The measurement showed that dilute SO2 solubility in the PEG + DMSO mixtures decreased with the increasing PEG concentration. In the whole composition range, the pure DMSO showed the strongest solubility capability for dilute SO2 with 0.0756 mol·kg−1 and the solubility of SO2 in PEG was 0.0100 mol·kg−1 when the gas phase SO2 concentration (zSO2) was set at zSO2 = 5·10−4. In addition, the paper also reported densities and viscosities for the binary system PEG (1) + DMSO (2) as a function of composition. Based on the experimental density and viscosity data at T = (298.15 to 318.15) K, the excess molar volumes and viscosity deviations were calculated, and the calculated results were fitted to a Redlich−Kister equation to obtain the coefficients and estimate the standard deviations. Based on the kinematic viscosity values, enthalpy of activation for viscous flow and entropy of activation for the viscous flow were also calculated.

1. INTRODUCTION The combustion of coal with high sulfur content1 means that it is necessary to dedicate more attention to decreasing the resulting emission of SO2, which is an important atmospheric pollutant. Removal of SO2 from various flue gases is a significant environmental challenge: on the one hand, because of the lowering of the admissible emission limit and, on the other hand, due to the fact that a great number of scrubbing processes, such as limestone scrubbing processes that produce a huge volume of second solid waste. There are incremental interests in the use of organic solvents to remove SO2, and organic solvents had been seen as an optional absorbent among the regenerative processes2−6 because the processes can be carried out by use of a carrier gas, temperature increase, and pressure reduction. Of a great number of organic solvents, alcohol and its derivatives show favorable absorption and regeneration capabilities for various acid gases;7 therefore, Wei, Zhang, and their co-workers have paid more attention to dilute SO2 removal using the system containing alcohols for several years.8−16 Ethylene glycol (EG) and EG derivatives showed significant chemical uses in the absorption of SO2 due to their high chemical stability, low melting point, low vapor pressure, and low toxicity. In this work, as an EG derivative, the primary merits of polyethylene glycol 300 (PEG) may be also due to its high solubility © 2014 American Chemical Society

and desorption capability for dilute SO2, low-to-moderate vapor pressure below 373 K, and low toxicity. In flue gas desulfurization (FGD) processes, the knowledge of basal physicochemical properties of PEG (1) + DMSO (2) mixtures over a broad range of temperatures is very significant for practical applications; however, the mixing properties of PEG (1) + DMSO (2) have not been reported in the previous literature. Therefore, we have to carry out the measurements for dilute SO2 absorption in the system PEG (1) + DMSO (2) and densities and viscosities of PEG (1) + DMSO (2). The present study mainly covers the two aspects: (1) GLE data for mixture gas of SO2 + N2 with PEG (1) + DMSO (2) solution at T = 298.15 K and p = 123.15 kPa to develop the various EG derivative solutions and present the GLE data; and (2) density (ρ), viscosity (η), and excess properties for the binary system PEG (1) + DMSO (2) over the all solution compositions at T = (298.15 to 318.15) K and atmospheric pressure.

2. EXPERIMENTAL SECTION 2.1. Materials. A.R. grade PEG with the number-average molecular mass of 300 (280 to 320), was purchased from Beijing Received: January 21, 2014 Accepted: July 28, 2014 Published: August 5, 2014 2413

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of the liquid SO2 was estimated to be ur(CSO2) = ± 0.6 %. The gas phase concentrations of SO2 were determined using the Testo 350 flue gas analyzer (Testo Company, Germany). The overall uncertainty in the determination of the gas phase SO2 was estimated to be ur(zSO2) = ± 5 %. Data Analysis. Henry’s law constant (HLC) fitted from the experimental GLE data is often expressed as follows:24

Reagent Company (Beijing, China). PEG (≥ 99.4 %) was purified from PEG (A.R, ≥ 98.0 %, made in China) dehydrated by Na2SO4 and distilled. The purity of the final PEG, which was found using a gas chromatograph (GC), is better than 99.4 %. Meanwhile, A.R. grade DMSO was obtainted from Beijing Reagent Company (Beijing, China). DMSO (99.3 %) was purified from DMSO (A.R, ≥ 98.0 %, made in China) dried over 4A molecular sieves and degassed by ultrasound just before the experiment. The purity of the final DMSO, which was found by the GC, is better than 99.3 %. Completely specification of all chemical samples is listed in Table 1. The ρ and η values of PEG

HLC = pg /Cw

where Cw denotes the dissolved concentration (mol·m−3) and pg denotes the gas phase partial pressure (Pa). The dimensionless Henry’s law constant (H’) is obtained as follows:

Table 1. Specification of Chemical Samples chemical name sulfur dioxide/ nitrogen mixture nitrogen DMSO PEG ethanola

source

initial purityb (fraction)

purification method

Beijing Gas Center, Peking University, China

0.5 % (volume)

Beijing Gas Center, Peking University, China Beijing Reagent Co., Ltd., China Beijing Reagent Co., Ltd., China Beijing Tongguang Industry of Fine Chemicals Co., Ltd., China

99.9 % none (volume) 99.3 % (mass) desiccationc and degasificationd 99.4 % (mass) desiccationc and degasificationd 99.7 % (mass) desiccationc and degasificationd

(1)

H′ = HLC /RT

none

(2)

where T denotes the absolute temperature (K) and R denotes the ideal gas constant (8.314 Pa·m3·mol−1·K−1). Equation 1 may be written as eq 2 using the ideal gas law [p = (nRT)/V], in which SO2 partial pressure can be changed into mole per cubic meter (mol·m−3). Density and Viscosity. Solvent mixtures were prepared by mass method using a Sartorius BS 224S electronic analytical balance with a precision of ± 0.0001 g. The uncertainty in the mole fraction for each binary mixture was estimated to be ur(x1) = ± 0.0001. The ρ values of pure solvents and their mixtures were determined using a 10 cm3 bicapillary pycnometer. The volume of pycnometer was calibrated using bidistilled water at T = (298.15 to 318.15) K. A thermostatically controlled and wellstirred water bath, which was controlled to ± 0.01 K, was used to determine all the ρ and kinematic viscosity (ν) values. The pycnometer filled with solution was kept in the water bath for (25 to 30) min to attain thermal equilibrium. Each experimental ρ value was an average of at least three measurements; furthermore, the uncertainty of the ρ measurements was estimated to be ur(ρ) = ± 0.0002.

a

Chromatographic grade. bDeclared by the supplier. cMolecular sieve type 4A. dUltrasound.

at 298.15 K are found to be 1.1218 g·cm−3 and 69.0 mPa·s, which well agreed with the reported literature.17−21 The density and viscosity of DMSO at T = 298.15 K was found to be 1.0952 g·cm−3 and 2.00 mPa·s, which well agreed with the reported literature.22 The certified standard mixtures (SO2 + N2, the gas phase SO2 concentration (zSO2) is set at zSO2 = 5·10−4), which were obtained from the Beijing Oxygen Plant Specialty Gases Institute (Beijing, China), were used to determine the GLE data for dilute SO2 absorption in the system PEG (1) + DMSO (2). Bidistilled water was used in this work. 2.2. Measurements. GLE Data. The experimental apparatus used in this work is shown in Figure 1, which was based on the

Table 2. Comparison of Experimental Densities (ρ), Viscosities (η), and Kinematic Viscosities (ν) of PEG and DMSO with Literature Values at Various Temperatures and p = 0.1 MPa ρ/(g·cm−3) T/K

expt.

η/(mPa·s)

lit.

expt.

lit.

106ν/ (m2·s−1) expt.

lit.

PEG

Figure 1. Sketch of experimental apparatus. 1. jacketed vessel, 2. cold trap, 3. thermostatic bath, 4. gas circulatory pimp, 5. flue gas analyzer, 6. regulating valve, 7. thermometer, 8. pressure meter, 9. SO2/N2 gas cylinder, 10. buffer, 11. absorption apparatus, 12. liquid circulatory pump.

previous work.11 Especially, SO2 concentrations in the gas phase were determined by a Testo 350 flue gas analyzer (5), which were determined using a GC in the previous work.11 In the whole experimental processes, the overall uncertainty in the determination23

a

2414

298.15

1.1218

303.15 308.15

1.1186 1.1147

313.15 318.15

1.1115 1.1066

298.15 303.15 308.15 313.15 318.15

1.0952 1.0906 1.0859 1.0813 1.0753

1.12163415 1.1223616 1.1187715 1.1150515 1.11349716 1.1132817a 1.1135818,19a 1.1122115

69.0

61.5

53.7 41.3

48.1 37.0

31.5 25.7

28.3 23.3

DMSO 1.905420 2.00 1.090820 1.80 1.906220 1.61 1.44 1.33

1.98420 1.80120 1.65120

1.82 1.65 1.49 1.33 1.24

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Table 3. GLE Data for PEG + DMSO with Dilute SO2 at 298.15 K and 123.15 kPaa actual mass fraction of PEG %

CSO2/mol·kg−1

106zSO2b

pSO2/Pa

actual mass fraction of PEG %

CSO2/mol·kg−1

106zSO2b

pSO2/Pa

100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 60.00 60.00 60.00 60.00 60.00 60.00 60.00 60.00 60.00 60.00

0.00316 0.00336 0.00404 0.00503 0.00596 0.00648 0.00756 0.00804 0.0102 0.00954 0.00981 0.0111 0.0120 0.0131 0.0145 0.0148 0.0156 0.0161 0.00730 0.00856 0.00965 0.0111 0.0127 0.0137 0.0154 0.0174 0.0187 0.0202 0.0222 0.0250 0.0274 0.0296 0.0296 0.0321 0.00546 0.00780 0.00909 0.0129 0.0185 0.0213 0.0242 0.0284 0.0317 0.0406

31 58 102 180 200 286 344 368 405 471 502 570 635 699 774 836 900 971 49 95 140 186 240 288 346 437 468 530 600 667 780 828 905 990 37 82 128 199 275 335 411 480 566 660

3.82 7.14 12.5 22.2 24.6 35.2 42.3 45.3 49.8 58.0 61.8 70.2 78.2 86.0 95.3 103 111 120 6.03 11.7 17.5 22.9 29.5 35.5 42.6 53.8 57.6 65.3 73.9 82.1 96.1 102 112 122 4.55 10.1 15.8 24.5 33.8 41.2 50.6 59.1 69.7 81.3

60.00 60.00 60.00 60.00 60.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.0457 0.0462 0.0467 0.0498 0.0537 0.00417 0.00741 0.0101 0.0132 0.0187 0.0222 0.0271 0.0352 0.0431 0.0472 0.0511 0.0547 0.0628 0.0726 0.0772 0.00435 0.00821 0.0125 0.0180 0.0252 0.0335 0.0391 0.0514 0.0627 0.0694 0.0801 0.0869 0.100 0.105 0.00459 0.0069 0.0120 0.0178 0.0237 0.0333 0.0576 0.0959 0.135

742 795 843 903 940 35 88 139 208 267 312 380 459 525 580 635 705 782 853 937 43 91 151 206 272 339 398 483 563 625 701 778 869 905 34 60 119 170 208 279 402 610 863

91.4 97.9 104 111 116 4.31 10.8 17.1 25.6 32.8 38.4 46.8 56.5 64.6 71.4 78.2 86.8 96.3 105 115 5.29 11.2 18.6 25.3 33.5 41.7 49.0 59.5 69.3 76.9 86.3 95.8 107 111 4.19 7.39 14.65 20.9 25.6 34.4 49.5 75.1 106

a

Standard uncertainties u are ur(T) = ± 0.01 K, ur(x1) = ± 0.0001, ur(zSO2) = ± 0.05, ur(CSO2) = ± 0.006 and ur(pSO2) = ± 0.0011. bDetermined by gas chromatograph. z denotes the volume fraction of SO2 in the gas phase

The ν data in both the pure solvents and their mixtures were determined using a commercial capilary viscometer of Ubbelohde type with a capillary diameter of 0.90 mm, which was calibrated using bidistilled water and HPLC grade ethanol at the experimental temperatures whose ρ and ν values were well-known. Care was taken to decrease evaporation of solutions during the experimental processes. The flow time was measured using a hand-held digital stopwatch within ±0.01 s. All the measurements were carried out in the thermostatically controlled and well-stirred water bath. Each experimental ν value was an average of at least 18 measurements The ν value was obtained from the equation ν = At −

B t

where t denotes its flow time in the viscometer, and A and B denote viscometer constants, respectively. A and B are calculated from measurements with the calibrated ethanol and water. The absolute viscosity (η) was calculated by multiplying the ν values with density values as η = νρ. The uncertainty of ν measurement was estimated to be lower than ur(v) = ± 0.003. The experimental and reported ρ and ν values of pure PEG and DMSO at the expermiental temperatures are listed in Table 2.

3. RESULTS AND DISCUSSION GLE Data for PEG (1) + DMSO (2) with Dilute SO2. GLE experiments for dilute SO2 in the system PEG (1) + DMSO (2)

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were carried out at T = 298.15 K and p = 123.15 kPa, and the experimental data are listed in Table 3. From Table 3, the mass fraction of PEG in the binary system (w1) was performed in the actual operation, and PEG and DMSO were weighed to present accurate factual w1. The GLE data were determined with uncertainties of ur(CSO2) = ± 0.6 % for the liquid phase SO2 concentration and ur(zSO2) = ± 5 % for the gas phase SO2 concentration. In addition, zSO2 denotes the gas phase SO2 volume fraction as zSO2 ≈ VSO2/(VSO2 + VDMSO + VN2 + VPEG) = (VSO2/Vtotal), Vtotal and VSO2 respectively denote the total volume of GLE system the partial volume of the gas phase SO2, and CSO2 is the liquid phase SO2 concentration. The GLE curves of PEG (1) + DMSO (2) for dilute SO2 absorption at T = 298.15 K and p = 123.15 kPa are drawn in Figure 2, and SO2 partial pressure is found from (0 to 122) Pa.

Figures 2 and 3 indicated that the addition of DMSO increased the solubility of SO2 in PEG. In the whole composition range, the pure DMSO shows the maximum SO2 capability with 0.0756 mol·kg−1 at zSO2 = 5·10−4. Meanwhile, the pure PEG only dissolves 0.0100 mol·kg−1 SO2 at the same condition. The results may be related to the intermolecular interactions among PEG, DMSO, and SO2, and the intermolecuar interactions among PEG, H2O, and SO2 had been discussed in the previous work.25 Compared with the previous work,12,13 the SO2 solubility of in pure DEG is 0.00364 mol·kg−1 at zSO2 = 5·10−4, which is lower than in pure PEG 400 (0.0185 mol·kg−1) and is stronger than in pure EG (0.00180 mol·kg−1). The result presents important information for the near future SO2 absorption and desorption processes. From the GLE data, HLC values were fitted from the slope of the plot of gas phase partial pressure versus the liquid phase concentration of SO2 (Figure 4 and Table 4). The gas phase SO2 concentrations were determined in the range of zSO2 = 0−10−3, so the liquid phase SO2 concentrations for experimental runs can be assumed. Based on Figures 4A−F, the fitting HLC results were shown as solid line with coefficient of R2 > 0.99. HLC values were obtained from the slopes of the fitting lines and the results are listed in Table 4. Based in Figure 4 and Table 4, the pure DMSO showed the minimum HLC value, and the pure PEG showed the maximum HLC value. The high SO2 solubility is found in the solution with low HLC value, and the low SO2 solubility is found in the solution with high HLC value. HLC indicated that the adding of DMSO evidently boosted up the solubility of SO2. Density and Viscosity. Experimental ρ values of PEG (1) + DMSO (2) at T = (298.15 to 318.15) K throughout the entire concentrations are listed in Table 5 and plotted in Figure 5. Figure 5 shows that the ρ values increase with the increasing x1 values. Especially, the ρ values fast increase at x1 = (0 to 0.38). Meanwhile, the ρ values decrease with the increasing temperatures at the same solution concentration. The excess molar volume (VEm) was obtained from the ρ values according to the equation

Figure 2. GLE curves for PEG (1) + DMSO (2) + SO2 (3) + N2 (4): ×, w1 = 0; +, w1 = 0.20; ◇, w 1 = 0.40; Δ, w1 = 0.60; ○, w1 = 0.80; □, w1 = 1.00.

Solubility data of dilute SO2 in PEG (1) + DMSO (2) at zSO2 = 5·10−4 are shown in Figure 3. In Figure 3, if zSO2,1 is below 5·10−4 and zSO2,2 is above 5·10−4, CSO2 can be obtained from the equation as CSO2 = 5·10−4·(CSO2,2 − CSO2,1)/(ZSO2,2 − ZSO2,1) − (CSO2, 2·ZSO2, 1 − CSO2, 1·ZSO2, 2)/(ZSO2,2 − ZSO2,1).

VmE =

⎛ M x1M1 + x 2M 2 M ⎞ − ⎜⎜x1 1 + x 2 2 ⎟⎟ ρm ρ2 ⎠ ⎝ ρ1

(4)

where ρm denotes the density of the mixture, and x1, ρ1, M1, x2, ρ2, and M2 denote the mole fraction, density, and molecular weight of the pure PEG and DMSO, respectively. The VEm values are presented in Table 6, and the dependence of VEm at various experimental temperatures is shown in Figure 6. From Table 6 and Figure 6, all VEm values are negative, which indicates the solvents of PEG with DMSO are completely miscible. The minimum is found at about x1 = 0.38. Additionally, with the increasing temperatures, the VEm values show less negative. A Redlich−Kister relation is used to correlate the VEm values according to the equation n

VmE/cm 3·mol−1 = x1x 2 ∑ Ai (2x1 − 1)i i=o

(5)

where x2 is the mole fraction of DMSO and Ai is the polynomial coefficients. The standard deviation values (σ) between the experimental and calculated data are calculated by the equation Figure 3. Solubility of dilute SO2 in various PEG (1) + DMSO (2) system when SO2 concentration in the gas phase is at zSO2 = 5·10−4.

E σ VmE = [∑ (Vcalc − VmE)2 /(N − m)]1/2

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Figure 4. GLE data fitting lines for PEG (1) + DMSO (2) + SO2 (3) + N2 (4) at 298.15 K and under 123.15 kPa. A, w1 = 100 % PEG; B, w1 = 80 % PEG; C, w1 = 60 % PEG; D, w1 = 40 % PEG; E, w1 = 20 % PEG; and F, w1 = 0 % PEG.

Table 4. Henry’s Law Constants for PEG + DMSO + SO2 + N2 at 298.15 K and under 123.15 kPa w1( %)

100

80

60

40

20

0

HLC(103Pa·kg·mol−1)

8.44 ± 0.24

4.54 ± 0.081

2.28 ± 0.050

1.46 ± 0.033

1.03 ± 0.018

0.75 ± 0.024

The measured ν values of PEG (1) + DMSO (2) at T = (298.15 to 318.15) K are presented in Table 8 and shown in Figure 7. In all cases, the ν values decrease with the

where N denotes the total number of experimental points and m denotes the number of Ai coefficients considered. The Ai and σ values are listed in Table 7. 2417

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Table 6. Excess Molar Volumes (VEm) for PEG (1) + DMSO (2) at T = (298.15, 303.15, 308.15, 313.15, and 318.15) K

Table 5. Experimental densities (ρ) of PEG (1) + DMSO (2) at T = (298.15, 303.15, 308.15, 313.15, and 318.15) Ka and p = 0.1 MPa

VEm/(cm3·mol−1)

ρ/(g·cm−3)

T/K

T/K x1

298.15

303.15

308.15

313.15

318.15

0.0000 0.0134 0.0280 0.0438 0.0609 0.0797 0.1002 0.1227 0.1477 0.1754 0.2062 0.2411 0.2805 0.3255 0.3775 0.4382 0.5097 0.5956 0.7006 0.8316 0.9273 1.0000

1.0952 1.0971 1.0995 1.1013 1.1029 1.1051 1.1068 1.1084 1.1100 1.1115 1.1130 1.1144 1.1157 1.1169 1.1181 1.1190 1.1197 1.1203 1.1209 1.1213 1.1216 1.1218

1.0906 1.0921 1.0940 1.0959 1.0976 1.0997 1.1013 1.1032 1.1047 1.1066 1.1082 1.1096 1.1109 1.1122 1.1134 1.1144 1.1153 1.1160 1.1167 1.1171 1.1175 1.1177

1.0859 1.0877 1.0900 1.0918 1.0935 1.0958 1.0976 1.0992 1.1011 1.1029 1.1045 1.1061 1.1075 1.1089 1.1101 1.1112 1.1121 1.1130 1.1139 1.1144 1.1148 1.1150

1.0813 1.0832 1.0856 1.0878 1.0895 1.0916 1.0934 1.0951 1.0972 1.0990 1.1005 1.1021 1.1035 1.1049 1.1062 1.1073 1.1083 1.1093 1.1100 1.1108 1.1111 1.1113

1.0753 1.0773 1.0801 1.0821 1.0840 1.0861 1.0880 1.0900 1.0916 1.0936 1.0953 1.0968 1.0984 1.0998 1.1011 1.1022 1.1033 1.1042 1.1049 1.1056 1.1060 1.1063

x1

298.15

303.15

308.15

313.15

318.15

0.0000 0.0134 0.0280 0.0438 0.0609 0.0797 0.1002 0.1227 0.1477 0.1754 0.2062 0.2411 0.2805 0.3255 0.3775 0.4382 0.5097 0.5956 0.7006 0.8316 0.9273 1.0000

0.0000 −0.0410 −0.1188 −0.1591 −0.1878 −0.2650 −0.3084 −0.3474 −0.3894 −0.4265 −0.4681 −0.5030 −0.5314 −0.5514 −0.5739 −0.5577 −0.5084 −0.4320 −0.3384 −0.1800 −0.0776 0.0000

0.0000 −0.0126 −0.0532 −0.0968 −0.1290 −0.1945 −0.2247 −0.2837 −0.3115 −0.3804 −0.4271 −0.4569 −0.4794 −0.5048 −0.5203 −0.5098 −0.4822 −0.4147 −0.3320 −0.1658 −0.0806 0.0000

0.0000 −0.0267 −0.0898 −0.1207 −0.1466 −0.2215 −0.2615 −0.2879 −0.3434 −0.3952 −0.4327 −0.4735 −0.4968 −0.5231 −0.5264 −0.5156 −0.4720 −0.4193 −0.3544 −0.1888 −0.0906 0.0000

0.0000 −0.0309 −0.0987 −0.1567 −0.1809 −0.2381 −0.2754 −0.3074 −0.3785 −0.4280 −0.4527 −0.4898 −0.5089 −0.5302 −0.5409 −0.5242 −0.4891 −0.4464 −0.3369 −0.2215 −0.0955 0.0000

0.0000 −0.0350 −0.1291 −0.1702 −0.2069 −0.2618 −0.3048 −0.3606 −0.3838 −0.4485 −0.4898 −0.5128 −0.5505 −0.5682 −0.5745 −0.5525 −0.5267 −0.4605 −0.3410 −0.1920 −0.0781 0.0000

Standard uncertainties u are ur(T) = ± 0.01, ur(x1) = ± 0.0001, ur(ρ) = ± 0.0002.

a

Figure 6. Excess molar volumes for PEG (1) + DMSO (2): □, 298.15 K; ☆, 303.15 K; ○, 308.15 K; ×, 313.15 K; and Δ, 318.15 K.

Table 7. Coefficients and Standard Deviations of (VEm) for PEG (1) + DMSO (2)

Figure 5. Experimental densities with mole fraction for PEG (1) + DMSO (2): □, 298.15 K; ☆, 303.15 K; ○, 308.15 K; ×, 313.15 K; and Δ, 318.15 K.

increasing temperature and increase with the increasing PEG concentration. The η values of PEG (1) + DMSO (2) at T = (298.15 to 318.15) K are presented in Table 9 and shown in Figure 8. The η values were used to obtain the absolute viscosity deviation (Δη), which is defined by Δη = η − (x1η1 + x 2η2)

T/K

A0

A1

A2

A3

A4

σ/(cm3·mol−1)

298.15 303.15 308.15 313.15 318.15

−2.092 −1.920 −1.940 −1.999 −2.134

1.253 1.109 1.037 1.056 1.209

0.197 −0.408 −0.611 −0.479 0.037

0.114 −0.313 −0.136 −0.072 0.258

−0.787 0.959 0.678 −0.020 −0.576

0.014 0.014 0.015 0.015 0.017

where η1 and η2 denote the absolute viscosities of pure PEG and pure DMSO, respectively. The Δη values are presented in Table 10 and plotted in Figure 9.

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Table 8. Experimental Kinematic Viscosities (ν) of PEG (1) + DMSO (2)a and p = 0.1 MPa

Table 9. Experimental Viscosities (η) of PEG (1) + DMSO (2)a

ν/(m2·s−1)

η/(mPa·s)

T/K

T/K

x1

298.15

303.15

308.15

313.15

318.15

x1

298.15

303.15

308.15

313.15

318.15

0.0000 0.0134 0.0280 0.0438 0.0609 0.0797 0.1002 0.1227 0.1477 0.1754 0.2062 0.2411 0.2805 0.3255 0.3775 0.4382 0.5067 0.5956 0.7006 0.8316 0.9273 1.0000

1.82 2.28 2.76 3.27 3.82 4.65 5.52 6.55 7.85 9.36 11.0 13.2 15.8 19.1 23.1 27.9 34.6 40.9 47.6 54.8 59.1 61.5

1.65 1.94 2.29 2.77 3.15 3.75 4.43 5.28 6.21 7.43 8.82 10.6 12.6 15.1 18.1 21.6 25.8 30.6 35.6 41.2 45.2 48.1

1.49 1.69 1.99 2.35 2.70 3.21 3.75 4.41 5.20 6.16 7.26 8.60 10.2 12.0 14.2 16.9 19.9 23.4 27.3 31.8 34.7 37.0

1.33 1.51 1.75 2.06 2.34 2.75 3.22 3.73 4.37 5.09 5.91 6.95 8.22 9.55 11.3 13.2 15.4 17.9 20.9 24.3 26.6 28.3

1.24 1.39 1.58 1.87 2.13 2.50 2.92 3.41 3.96 4.58 5.31 6.13 7.11 8.22 9.51 10.9 12.5 14.5 16.8 19.7 21.6 23.3

0.0000 0.0134 0.0280 0.0438 0.0609 0.0797 0.1002 0.1227 0.1477 0.1754 0.2062 0.2411 0.2805 0.3255 0.3775 0.4382 0.5067 0.5956 0.7006 0.8316 0.9273 1.0000

2.00 2.50 3.04 3.61 4.22 5.15 6.11 7.27 8.72 10.4 12.3 14.8 17.7 21.4 25.8 31.3 38.8 45.8 53.4 61.4 66.3 69.0

1.80 2.11 2.50 3.04 3.46 4.13 4.88 5.83 6.90 8.23 9.77 11.8 14.0 16.9 20.2 24.2 28.8 34.1 39.8 46.1 50.6 53.7

1.61 1.84 2.18 2.57 2.96 3.52 4.12 4.84 5.73 6.79 8.02 9.51 11.2 13.3 15.8 18.8 22.1 26.0 30.5 35.5 38.7 41.3

1.44 1.64 1.90 2.24 2.55 3.00 3.52 4.08 4.79 5.59 6.50 7.66 9.07 10.5 12.4 14.6 17.0 19.9 23.2 26.9 29.5 31.5

1.33 1.51 1.72 2.03 2.33 2.73 3.18 3.72 4.32 5.01 5.82 6.74 7.81 9.04 10.4 12.0 13.8 16.0 18.6 21.8 24.0 25.7

Standard uncertainties u are ur(x1) = ± 0.0001, ur(T) = ± 0.01 and ur(ν) = ± 0.003.

Standard uncertainties u are ur(x1) = ± 0.0001, ur(T) = ± 0.01 and ur(η) = ± 0.003.

a

a

Figure 8. Experimental viscosities with mole fraction for PEG (1) + DMSO (2): □, 298.15 K; ☆, 303.15 K; ○, 308.15 K; ×, 313.15 K; and Δ, 318.15 K.

Figure 7. Experimental kinematic viscosities with mole fraction for PEG (1) + DMSO (2): □, 298.15 K; ☆, 303.15 K; ○, 308.15 K; ×, 313.15 K; and Δ, 318.15 K.

viscous flow (ΔS*), enthalpy of activation for viscous flow (ΔH*), and Gibbs energies of activation of viscous flow (ΔG*), were evaluated on the basis of Eyring’s approach to Andrade’s theory26 with the form

Table 10 and Figure 9 show that in all cases the Δη values keep decreasing from x1 = 0 to x1 = 0.2062, increasing from x1 = 0.2062 to x1 = 0.7006, and then decreasing from x1 = 0.7006 to x1 = 1. The Δη values are also fitted by the Redlich−Kister equation as follows:

ν=

n

Δη /mPa·s = x1x 2 ∑ Bi (2x1 − 1)i i=o

⎛ ΔG* ⎞ hNA ⎟ exp⎜ ⎝ RT ⎠ M

(9)

where M = ∑xiMi denotes the average molar mass, NA is the Avogadro number, and h is Planck’s constant. By applying the following equation:

(8)

The coefficients Bi and the Δη values are listed in Table 11. The thermodynamic parameters of activation of viscous flow of the binary mixtures, including entropy of activation for the

ΔG* = ΔH * − T ΔS* 2419

(10)

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Table 10. Viscosity Deviations (Δη) for PEG (1) + DMSO (2) Δη/(mPa·s) T/K x1

298.15

303.15

308.15

313.15

318.15

0.0000 0.0134 0.0280 0.0438 0.0609 0.0797 0.1002 0.1227 0.1477 0.1754 0.2062 0.2411 0.2805 0.3255 0.3775 0.4382 0.5067 0.5956 0.7006 0.8316 0.9273 1.0000

0.000 −0.394 −0.812 −1.32 −1.84 −2.18 −2.58 −2.96 −3.16 −3.35 −3.50 −3.35 −3.09 −2.41 −1.49 −0.0371 2.85 3.90 4.46 3.68 2.17 0.000

0.000 −0.386 −0.754 −1.034 −1.50 −1.81 −2.12 −2.34 −2.57 −2.67 −2.73 −2.62 −2.36 −1.84 −1.16 −0.153 0.652 1.22 1.59 1.24 0.673 0.000

0.000 −0.306 −0.545 −0.782 −1.07 −1.26 −1.47 −1.63 −1.75 −1.78 −1.79 −1.67 −1.55 −1.23 −0.7954 −0.164 0.377 0.849 1.08 0.833 0.385 0.000

0.000 −0.201 −0.380 −0.515 −0.719 −0.824 −0.930 −1.05 −1.08 −1.12 −1.14 −1.03 −0.83 −0.673 −0.386 −0.0111 0.330 0.607 0.701 0.542 0.226 0.000

0.000 −0.150 −0.295 −0.370 −0.489 −0.545 −0.595 −0.606 −0.610 −0.59 −0.537 −0.468 −0.358 −0.224 −0.0815 0.0393 0.120 0.194 0.225 0.193 0.101 0.000

Figure 10. Plots of Rln (ν/hNA) against 1/T for PEG (1) + DMSO (2) at various temperatures, the molar fractions corresponding to lines as follows: A, 0.0000; B, 0.0134 ; C, 0.0280 ; D, 0.0438 ; E, 0.0609 ; F, 0.0797 ; G, 0.1002; H, 0.1227; I, 0.1477; J, 0.1754; K, 0.2062; L, 0.2411; M, 0.2805; N, 0.3255; O, 0.3775; P, 0.4382 ; Q, 0.5067; R, 0.5956; S, 0.7006; T, 0.8316; U, 0.9273; V, 1.0000.

Figure 11. Gibbs energies of activation of viscous flow (ΔG*) about PEG (1) +DMSO (2). □, 298.15 K; ☆, 303.15 K; ○, 308.15 K; ×, 313.15 K; and Δ, 318.15 K.

Based on to the Eyring theory, the ΔH* and ΔS* values were obtained from eq 11. Plots of the term on the left-hand side of eq 926 against 1/T for each binary mixture are nearly linear, in Figure 10 and Figure 11. The ΔH* values so obtained, together with the ΔG* values calculate from eq 7,26 were used to calculate the corresponding ΔS* values by using eq 8.26 The ΔH* and ΔS* values are listed in the Supporting Information. The positive ΔH* values indicate that the binding force between two PEG molecules is weaker than between PEG and DMSO molecules or between DMSO and DMSO molecules. In addition, the negative ΔS* values indicate that the viscous flow is an ordered process involving contiguous liquid layers which may retain their structural configuration even moving in a stationary steady state.27

Figure 9. Viscosity deviations with mole fraction for PEG (1) + DMSO (2): □, 298.15 K; ☆, 303.15 K; ○, 308.15 K; ×, 313.15 K; and Δ, 318.15 K.

Table 11. Coefficients and Standard Deviations of (Δη) for PEG (1) + DMSO (2) T/K

B4

B3

B2

B1

B0

σ/(m2·s)

298.15 303.15 308.15 313.15 318.15

17.13 13.86 3.022 1.488 −1.554

−18.72 −2.555 −1.997 −0.148 4.1897

−23.21 −22.79 −11.95 −8.108 −3.754

47.20 22.28 15.04 8.951 2.412

7.715 2.054 1.153 1.125 0.478

0.012 0.048 0.040 0.028 0.022

4. CONCLUSION This paper reports the fundamental investigation results on GLE data of PEG (1) + DMSO (2) solutions with dilute SO2 at T = 298.15 K and p = 123.15 kPa and the densities, viscosities, and excess properties of the PEG (1) + DMSO (2) solutions at

it is possible to write ⎛ M ⎞ ΔH * R ln⎜ν − ΔS* ⎟= T ⎝ hNA ⎠

(11) 2420

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(9) Zhang, J. B.; Zhang, P. Y.; Chen, G. H.; Han, F.; Wei, X. H. Gas− Liquid Equilibrium Data for the Mixture Gas of Sulfur Dioxide/ Nitrogen with Ethylene Glycol at Temperatures from (298.15 to 313.15) K under Low Pressures. J. Chem. Eng. Data 2008, 53, 1479− 1485. (10) Zhang, J. B.; Zhang, P. Y.; Han, F.; Chen, G. H.; Deng, R. H.; Wei, X. H. Gas−Liquid Equilibrium Data for a Mixture Gas of Sulfur Dioxide + Nitrogen with Ethylene Glycol Aqueous Solutions at 298.15 K and 123.15 kPa. J. Chem. Eng. Data 2008, 53, 2372−2374. (11) Zhang, J. B.; Han, F.; Zhang, P. Y.; Chen, G. H.; Wei, X. H. GasLiquid Equilibrium Data for Mixture Gas of Sulfur Dioxide + Nitrogen with Poly(Ethylene Glycol) Aqueous Solutions at 298.15 K and 122.61 kPa. J. Chem. Eng. Data 2010, 55, 959−961. (12) Zhang, J. B.; Chen, G. H.; Zhang, P. Y.; Han, F.; Wang, J. F.; Wei, X. H. Gas-Liquid Equilibrium Data for Mixture Gas of Sulfur Dioxide + Nitrogen with Diethylene Glycol + Water at 298.15 K and 123.15 kPa. J. Chem. Eng. Data 2010, 53, 1446−1448. (13) Zhang, J. B.; Liu, L. H.; Huo, T. R.; Liu, Z. Y.; Zhang, T.; Wei, X. H. Absorption of Dilute Sulfur Dioxide in Aqueous Poly-Ethylene Glycol 400 Solutions at 308.15 K and 122.60 kPa. J. Chem. Thermodyn. 2011, 43, 1463−1467. (14) Zhang, N.; Zhang, J. B.; Zhang, Y. F.; Wei, X. H. Solubility and Henry’s law constant of Sulfur Dioxide in Aqueous Poly-Ethylene Glycol 300 Solution at Different Temperatures and Pressures. Fluid. Phase. Equilib. 2013, 348, 9−16. (15) Gao, F.; Niu, Y. X.; Zhang, J. B.; Sun, S. Y.; Wei, X. H. Solubility for Dilute Sulfur Dioxide in Binary Mixtures of N,N-dimethylformamide + Ethylene Glycol at T = 308.15 K and p = 122.66 kPa. J. Chem. Thermodyn. 2013, 62, 8−16. (16) Li, Q.; Zhang, J. B.; Li, L. H.; He, Z. Q.; Yang, X. X.; Zhang, Y. F.; Guo, Z. H.; Zhang, Q. C. Solubility Properties and Spectral Investigation of Dilute SO2 in Tri-ethylene Glycol + Water + La3+ System. J. Phys. Chem. B 2013, 117, 5633−5646. (17) Kinart, C. M.; Kinart, W. J.; Cwilinska, A.; Klimczak, M. Excess molar volumes of the binary mixtures of polyethylene glycol 300 with ethoxyethanols at various temperatures. J. Chem. Thermodyn. 2006, 38, 1017−1024. (18) Ayranci, E.; Sahin, M. Interactions of polyethylene glycols with water studied by measurements of density and sound velocity. J. Chem. Thermodyn. 2008, 40, 1200−1207. (19) Naidu, B. V. K.; Rao, K. C.; Subha, M. C. S. Densities and Viscosities of Mixtures of Some Glycols and Polyglycols in Dimethyl Sulfoxide at 308.15 K. J. Chem. Eng. Data 2002, 47, 379−382. (20) Bigi, A.; Comelli, F. Excess molar enthalpies of binary mixtures containing ethylene glycols or poly(ethylene glycols) + ethyl alcohol at 308.15 K and atmospheric pressure. Thermochim. Acta 2005, 430, 191− 195. (21) Comelli, F.; Ottani, S.; Francesconi, R.; Castellari, C. Excess Molar Enthalpies of Binary Mixtures Containing Glycols or Polyglycols + Dimethyl Sulfoxide at 308.15 K. J. Chem. Eng. Data 2003, 48, 995− 998. (22) Baragi, J. G.; Aralaguppi, M. I.; Aminabhavi, T. M.; Kariduraganavar, M. Y.; Kittur, A. S. Density, Viscosity, Refractive Index, and Speed of Sound for Binary Mixtures of Anisole with 2Chloroethanol, 1,4-Dioxane, Tetrachloroethylene, Tetrachloroethane, DMF, DMSO, and Diethyl Oxalate at (298.15, 303.15, and 308.15) K. J. Chem. Eng. Data 2005, 50, 910−916. (23) Rodriguez-Sevilla, J.; Alvarez, M.; Liminana, G.; Diaz, M. C. Dilute SO2 Absorption Equilibria in Aqueous HCl and NaCl Solutions at 298.15 K. J. Chem. Eng. Data 2002, 47, 1339−1345. (24) Bamford, H. A.; Poster, D. L.; Baker, J. E. Temperature Dependence of Henry’s Law Constant of Thirteen Polycyclic Aromatic Hydrocarbons between 4°C and 31°C. Environ. Toxicol. Chem. 1999, 18, 1905−1912. (25) He, Z. Q.; Liu, J. R.; Zhang, J. B.; Zhang, N. Spectroscopic Study on the Intermolecular Interaction of SO2 Absorption in Poly-Ethylene Glycol + H2O Systems. Korean J. Chem. Eng. 2014, DOI: 10.1007/ s11814-013-0249-7.

T = (298.15 to 318.15) K. The GLE results show that the system PEG (1) + DMSO (2) decreased the solubility of dilute SO2 with the increasing PEG concentration. Based on the density and viscosity data, the excess properties and thermodynamic parameters of activation of viscous flow of the system were calculated. The calculated VEm values were negative, while the viscosity deviations were positive. Furthermore, the ΔH* are all positive, while the ΔS* values are negative.

■

ASSOCIATED CONTENT

S Supporting Information *

Enthalpy of activation (ΔH*/J·mol−1) and entropy of activation (ΔS*/J·K·mol−1) for the viscous flow about PEG (1) + DMSO (2). This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Authors

*Tel.: +86-471-6575722. Fax: +86-471-6575722. E-mail: [email protected]. *E-mail: [email protected]. Notes

The authors declare no competing financial interest. Funding

This work was supported by the National Natural Science Foundation of China (21166017), Program for New Century Excellent Talents in University (NCET-12-1017), the Research Fund for the Doctoral Program of Higher Education of China (20111514120002), the Inner Mongolia Science and Technology Key Projects, the Program for Grassland Excellent Talents of Inner Mongolia Autonomous Region, Program for Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region (NJYT-12-B13), and the Inner Mongolia Talented People Development Fund, the foundation of the “western light” visiting scholar plan.

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REFERENCES

(1) Milani, M. R.; Cardoso, A. A. Construction and Performance of a Drop Cell for the Nephelometric Determination of Sulfur Dioxide. Microchem. J. 2003, 74, 75−82. (2) Esteve, X.; Conesa, A.; Coronas, A. Liquid Densities, Kinematic Viscosities, and Heat Capacities of Some Alkylene Glycol Dialkyl Ethers. J. Chem. Eng. Data 2003, 48, 392−397. (3) Ku, H. C.; Tu, C. H. Densities and Viscosities of Seven Glycol Ethers from 299.15 to 343.15 K. J. Chem. Eng. Data 2000, 45, 391−394. (4) Valtz, A.; Coquelet, C.; Richon, D. Vapor-Liquid Equilibrium Data for the Sulfur Dioxide (SO2) + 1,1,1,2,3,3,3-Heptafluoropropane (R227ea) System at Temperatures from 288.07 to 403.19 K and Pressures up to 5.38 MPa Representation of the Critical Point and Azeotrope Temperature Dependence. Fluid Phase Equilib. 2004, 220, 77−83. (5) Nagel, D.; de Kermadec, R.; Lintz, H. G.; Roizard, C.; Lapicque, F. Absorption of Sulfur Dioxide in N-formylmorpholine: Investigations of the Kinetics of the Liquid Phase Reaction. Chem. Eng. Sci. 2002, 57, 4883−4893. (6) De Kermadec, R.; Lapicque, F.; Roizard, D.; Roizard, C. Characterization of the SO2-N-Formylmorpholine Complex: Application to A Regenerative Process for Waste Gas Scrubbing. Ind. Eng. Chem. Res. 2002, 41, 153−163. (7) Schubert, C. N.; Echter, W. I. Method of Polymer Ethylene Glycol for Removal Pollution from Gases. CN. Patent. 1364096A. 2002. (8) Wei, X. H.; Zhang, J. B.; Zhang, P. Y.; Zhang, L. W.; Li, X. B.; Wan, M. J. Removal of SOx from Flue Gas by Ethylene Glycol. CN. Patent. 101053746. 2007. 2421

dx.doi.org/10.1021/je500067f | J. Chem. Eng. Data 2014, 59, 2413−2422

Journal of Chemical & Engineering Data

Article

(26) Corradini, F.; Marchetti, A.; Tagliazucchi, M.; Tassi, L.; Tosi, G. Viscosity Data and Viscous Flow Thermodynamics of 2-Methoxyethanol+Water Binary Mixtures. Aust. J. Chem. 1993, 46, 1711−1723. (27) Guo, Z. H.; Zhang, J. B.; Zhang, T.; Li, C. P.; Zhang, Y. F.; Bai, J. Liquid Viscosities, Excess Properties, and Viscous Flow Thermodynamics of Triethylene Glycol + Water Mixtures at T = (298.15, 303.15, 308.15, 313.15, and 318.15) K. J. Mol. Liq. 2012, 165, 27−31.

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